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THE EFFECT OF ORGANIC IMPURITIES ON

THE PRECIPITATION OF ALUMINA TRIHYDRATE IN


THE BAYER PROCESS

by

Lakshman Dissanayake Jayaweera

A thesis submitted for the degree of


Doctor of Philosophy in Chemical Engineering

The University of New South Wales


Australia

November 1981
Form 1
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THE UNIVERSITY OF NEW SOUTH
WALES

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Candidate's Certificate

This is to certify the work presented in this

thesis was carried out in the School of Chemical Eng-

ineering and Industrial Chemistry at The University of

New South Wales, and has not been submitted previously

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degree or award.

~~~~
(Lakshman Dlssanayake Jayaweera)
ACKNOWLEDGEMENTS

I gratefully acknowledge the award of a research

scholarship by the Aluminium Development Council, which

supported me during this work.

I express my gratitude to Emeritus Professor J.S.

Ratcliffe, formerly of the School of Chemical Engineering,

The University of New South Wales, for glvlng me the

opportunity to undertake this work.

I am indebted very much to my supervisor, Associate

Professor R.G. Robins, for his guidance, encouragement and

constructive criticism which improved this work far beyond

that which would have been possible otherwise.

I also wish to thank Mr. A.G. Willard of the School

of Mining Engineering, The University of New South Wales,

for his help in size distribution analysis.

My sincere thanks are also due to Mrs. K. Nasev

of the School of Chemical Engineering & Industrial Chem-

istry, Miss Viera Piegerova, School of Metallurgy, Mrs. P.

Sirimanna, School of Chemistry, the Laboratory staff of the

Sydney Water Board, the Technical staff of the Queensland

Alumina Ltd., Gladstone, and all others associated with

this work, for their assistance.

Finally I would like to thank my wife for her

unfailing patience.

Dedicated to my parents.
ABSTRACT

The Bayer process has been the most successful

industrial process used in the extraction of alumina tri-

hydrate from bauxite. During the process, organic matter

accumulates in the recycled caustic liquor as impurities.

These impurities have a wide range of molecular weight

and are made up of degraded and oxidised vegetable matter.

The impurities are believed to have a deleterious effect

on the precipitation of alumina trihydrate, either by

adsorbing on to the surface of the seed particles of alumina

trihydrate or coprecipitating other compounds, thereby

preventing further crystal growth and leading to finer

particles. The rate of decomposition of the alumina tri-

hydrate in the subsequent calcination process is also

affected.

In this work studies were conducted in which an

attempt was made to separate and identify some of the

organlc impurities present in a particular solution of re-

cycle Bayer liquor from Queensland Alumina Limited. The


total organic content of this liquor was found to be ln the

range 25 - 30 g/1 expressed as carbon. Eighty percent of


the total carbon was below 1000 molecular weight; five to

seven percent was above 10,000 molecular weight. Of the


low molecular weight compounds (< 500) sodium formate,

'sodium acetate and sodium oxalate, with small quantities of

sodium propionate and sodium valerate were identified.

The adsorption properties of various organic salts

present in the Bayer liquor on alumina trihydrate seed was

investigated to explore whether such adsorption might be


linked with the crystallisation process. It was found,

however, that low molecular weight compounds such as sodium

oxalate, sodium formate, sodium acetate, sodium carbonate,

sodium succinate and sodium benzoate as well as the fractions

of molecular weight over 1000, were not significantly

adsorbed. There was evidence to suggest some of the inter-

mediate molecular weight compounds did adsorb onto the seed

but experimental difficulties hampered this examination.

The solubility of sodium oxalate in sodium

hydroxide, sodium aluminate, and Bayer Plant liquor was deter-

mined over a range of compositions and temperatures. Sodium

oxalate was found to be present in the Bayer Plant liquor at a

supersaturated level.

A series of batch crystalliser experiments to

determine the effects on the formation of alumina trihydrate

of the various organic impurities as additives was investi-

gated. Although no significant effects on the kinetics of

precipitation of alumina trihydrate were found, the particle

size of the crystals were finer for sodium aluminate solutions

supersaturated with sodium oxalate. The other low molecular

weight impurities and fraction with molecular weight greater

than 1000 had no deleterious effect on the crystallisation

process, but caused some variations ln the rate of reaction.


TABLE OF CONTENTS

Page

ACKNOWLEDGEMENTS

ABSTRACT
LIST OF TABLES

LIST OF FIGURES

INTRODUCTION 1

1. Aluminium production in Australia 1

2. Future process development in the 10

aluminium industry

PART I
CHAPTER 1

BAYER PROCESS PLANT OPERATION 13

1.1 The Basic Process 13

1.2 Plant Operation at Queensland Alumina Ltd., 16

Glad stone

1.3 Accumulation of Organic Impurities ln Bayer 24

Process Liquor

1.4 Removal of Organic Impurities from Bayer 28

Process Liquor in Plant Practice

CHAPTER 2

CHEMISTRY OF THE BAYER PROCESS 37

2.1 Occurrence of Bauxite 38

2.2 Structure of Alum9na Trihydrate 46

2.21 Nomenclature 47

2.22 Structure of Crystalline Alumina Trihydrate 47


2.221 Hydragillite 4-7

2.222 Bayerite 51

2.223 Boehmite 52
2.224- Diaspore 54-

2.3 Bayer Alumina Trihydrate and its Phase Trans- 55

formations

2.4- Extraction Stage in the Bayer Process 60

2.4-1 Factors Affecting the Extraction 64-


2.4-2 Effect of Organics on the Dissolution of 67
Bauxite

2. 5 Separation of Red Mud 68

2.6 Desilication 69

CHAPTER 3

ORIGIN, IDENTIFICATION, EFFECT AND REMOVAL 72

OF ORGANIC IMPURITIES IN THE BAYER PROCESS

3.1 Origin of Organic Impurities 1n Bayer Process 72


Liquor

3.2 Humic Substances 1n the Environment 74-


3.21 Theories on the Formation of Humic Substances 75
3.211 Felbeck's Hypothesis 76
a) Plant Alteration 77

b) Chemical Polymerization 77

c) Cell Autolysis 77

d) Microbial Synthesis 77

3.22 Occurrence of Humic Substances in Minerals 78

and its Relationship to Bauxite

3.23 Characterization of Humic Substances 79


3.231 Functional Groups in Humic Substances 80

a) Oxygen Containing Functional Groups 81

b) Nitrogen Containing Functional Groups 86

3.232 Use of Physical Methods for Characterization 86

of Humic Substances

a) Spectroscopic characterisation: 87

I Visible, spectroscopic method 88

II Ultra violet spectroscopic 89

method

III Infra-red (IR) spectrophoto- 90

metric method

IV Nuclear Magnetic Resonance 93

(N.M.R.) Spectrometry

V X-ray analysis 95

b) Molecular Method 96

I Vapour pressure osmometry 96

II Ultra centrifugation 97

III Gel filtration 97

IV Other methods 102

3.24 Chemical Structure and the Degradation of 102

Humic Substances

3.241 Various Models suggested for Chemical 102

Structure of Humic Substances

a) Flaig's Model 102

b) Felbeck's Model 102

c) Finkle's Model 105

d) Haworth's Model 105

e) Fulvic Acid Structure 105


3.242 Degradation of Humic Substances 107

3. 3 Identification and Characterization of 111

Organic Impurities ln Bayer Process Liquor

3.4 Effect of the Organic Impurities on the Rate 117

of Precipitation and the Particle Size

Distribution of Alumina Trihydrate

3. 5 Behaviour and Mechanism of Inhibition of 125

Organic Impurities in the Bayer Precipitation

3.6 Removal of Organic Impurities from Bayer Liquor 132

3.61 Activated Carbon Method 133

3.62 Ion Exchange Method 134

3.63 Oxidation Method 134

3.64 Heat Treatment 136

3.65 Seeding Method 136

CHAPTER 4

CRYSTALLISATION PROCESS OF ALUMINA TRIHYDRATE

4.1 Al o
2 3
- Na
2
o- H 0 System
2
138

4.11 Solubility of Alumina Trihydrate ln Pure Caustic 140

and Bayer Plant Liquor

4.12 Stability of Sodium Aluminate Solution 142

4.13 Super Solubility Concept 144

4.2 Spontaneous Precipitation of Alumina Trihydrate 145

from Sodium Aluminate Solution

4.3 Precipitation from Aluminate Solution Seeded 146

with Alumina Trihydrate (Bayer Process

Crystallisation)

4.31 Kinetics Relation for Seeded Precipitation 146

4.32 Mechanism of Bayer Process Crystallisation 149


4.321 Induction Period 1n Seeded Crystallisation 150

4.322 Nucleation 151

a) Kinetics Relation for Nucleation

4.323 Crystal Growth 155


4.324 Agglomeration 158
4.325 Crystal Breakage and Attrition 161
4.33 Major Factors which Affect the Over-all 162
Process of Crystallisation in the Bayer

Process

4.4 Summary of Crystallisation 162

PART II

CHAPTER 5

EXPERIMENTS RELATED TO THE SEPARATION, IDEN- 164

TIFICATION, ADSORPTION AND SOLUBILITY OF SOME

OF THE ORGANIC CONSTITUENTS OF RECYCLE BAYER

PROCESS CAUSTIC LIQUOR

5.1 Separation and Identification 164

5.11 Separation and Analysis of Organic Constitu- 165


ents Present in the Recycle Bayer Process

Liquor

5.112 Determination of Total Organic Carbon 1n the 168

Bayer Process Liquor

a) Using Beckman Carbon Analyser 168


b) Using Coleman Carbon Analyser and 171
Potassium Permanganate Titration Method

5.113 Use of Distillation Method 173


5.114 Use of Gas Chromatography 175
a) Direct Injection of Ether Extract

b) Injection of Esterified Ether Extract

5.115 Infra-Red Analysis 186

5.116 Use of Membrane Process for Characterization 191

5.12 Separation and Analysis of Organics which are 200


associated with the product Alumina Trihydrate

5.121 Methanol Treatment followed by Hot Water 201


De sorption

5.122 Cold Water Wash followed by Hot Water Desorption 203

5.2 Adsorptive Properties of Various Organic Corn- 209


pounds in the Bayer Process Liquor on the

Alumina Trihydrate Seeds

5.21 Preparation of Columns and Solutions 211

5.22 Equipment, Procedure and Results 212

5.3 Solubility of Sodium Oxalate in the Pure 226

Caustic and Aluminate Solutions at Varied

Temperature

5.4 Summary of Experiments discussed in 233

Chapter 5

CHAPTER 6

EXPERIMENTAL STUDIES ON THE EFFECT OF 237

ORGANIC IMPURITIES DURING THE CRYSTALL-

ISATION OF ALUMINA TRIHYDRATE

6.1 Batch Crystallisation Unit 237

6.2 Preparation of Caustic Aluminate Solution 240

6.3 Seed Preparation 241


6.4 Addition of Impurities 241

6.5 Procedure 242

6.6 Solution Analysis 243

6.7 Particle Size Analysis by Zeiss Type Micro 244

Videomat-2

6.8 Optical and Electronmicrograph y 244

6.9 Range of Conditions Studied 248

6.10 Results and Discussion 248

6.1~1 Effect of Sodium Oxalate 269


a) Induction period 272
b) Rate of decomposition 272
c) Particle size distribution 274
d) Optical and electron micrograph 275

6 .10.2 Effect of Organic Impurities Extracted from 276

the Bayer Process Liquor

a) Effect on the decomposition rate 277

b) Effect on the particle size distribution 278

6 .10.3 Effect of Sodium Acetate, Formate and 278

Succinate

CHAPTER 7

CONCLUSIONS 294

SUGGESTION FOR FURTHER WORK 295

REFERENCES 299

Appendix I 310

Thermodynamic Stability Diagrams for the Al-Fe-Si-H 2 o

System in Relation to the Bayer Process


Appendix II

a) Use of KMn0 Titration Method for Determination 321


4
of Total Organic Carbon Present in the Bayer Process

Liquor

b) Use of Coleman Carbon Analyser for Determination 327

of Total Organic Carbon Present in the Bayer Process

Liquor

Appendix III

Use of Zeiss Micro Videomat for Particle Size 330

Analysis of Product Alumina Trihydrate


List of Tables

1(a) Economic grade bauxite ln Australia


1(b) Known bauxite reserves in the world

2. Production details for bauxite, alumina and


aluminium metal in Australia
3. Alumina refineries in Australia and their
designed capacities
4. Aluminium consumption in Australia in comparison
with selected other countries
1.1 Composition of bauxite used at Q.A.L., Gladstone
1.2 Chemical composition of recycled caustic soda
obtained from the Queensland Alumina Ltd.,
plant
1.3 Chemical composition of product alumina
2.1 Mineralogical properties of bauxites
2.2 Aluminium bearing minerals present in the bauxite
and its Al 2o content
3
2.3 Composition of typical bauxites
2.4 Nomenclature of aluminium hydroxides
2.5 Crystalline form of product trihydrate obtained
from Sakamoto's decomposition experiments
3.1 Distribution of oxygen in humic substances
3.2 Main infra-red absorption bands of humic substances
3.3 Summary of molecular weights of humic substances
3.4 Percentage of total humic matter retained by each
ultra filtration membrane
3.5 "Building block" compounds (mg/1) identified ln
Bayer process liquor
3.6 Low molecular weight degradatio n products present
in low temperatu re digestion Bayer liquor

3.7 Sodium oxalate concentra tion after alumina trihydrat e


precipita tion

3.8 Crystallin e sodium oxalate ln product alumina tri-


hydrate

5.1 Results of the Beckman Carbon Analyser

5.2 Results of the Coleman Carbon Analyser

5.3 Results of the permangan ate titration method

5.4 Titration results and the formic acid content of


the distillate collected from the acidified
Bayer process liquor

5.5 Various condition s applied in the G.C. analysis


of methyl esters of Bayer process liquor

5.6 Results of G.C. analysis

5.7 Main I.R. absorptio n bands of the organic extract


from the Bayer process liquor

5.8 Relative intensitie s of selected absorption bands


for all systems

5.9 Total organic carbon compositio n of the Bayer


process liquor in relation to the various

molecular fraction

5.10 Total organic content 1n the extracts desorbed


from the product alumina trihydrate

5.11 Compariso n studies of the U.V. results of


different Bayer process liquor fractions
after passing through the alumina trihydrat e

seed column
6.1 Plant and laboratory crystallisation conditions
6.2 Details of experiments on crystallisation

6.3 Crystallisation yield

6.4 Summary of the results of crystallisation

experiments with oxalate impurity charge

Appendix I.1 Free energy data at 25°C for the various

species involved in the Al-Fe-Si-H 0 system


2
Appendix II.1 Results of the total organic carbon deter-

mination using permanganate titration method

Appendix II.2 do

Appendix III.1 Measuring facilities of Zeiss Micro-


videomat-2

Appendix III.2 Typical example of the results of the

particle size analysis of alumina trihydrate

using Zeiss microvideomat-2


List of Figures

Fig. 1 World and Australian alumina production

2 Application of aluminium

3 The reduced energy requirements 1n the smelting

of aluminium over 80 years

1.1 The Bayer process basic circuit

1.2 Process flow chart of Queensland Alumina Ltd.,

Glad stone

1.3 Sodium oxalate solubility in Bayer process liquor

1.4 Kaiser patent on control of sodium oxalate in the

Bayer process liquor

1.5 - do -
1.6 - do -

2.1 X-Ray diffraction patterns of bauxite

2.2 Structure of hydragillite

2.3 Model of hydragillite

2.4 Electron-micrograph of hydragillite crystal

2.5 Structure of bayerite

2.6 Structure of boehmite

2.7 Structure of diaspore

2.8 Diagram of equilibrium system of Al o -H 2 o at


2 3
higher pressure

2.9 Equilibrium ratios for trihydrated alumina over

a temperature range of 100 to 140°C

2.10 Equilibrium ratios for monohydrated alumina over


0
a temperature range of 100 to 260 C

2.11 Rate of dissolution of a) hydragillite b) boehmite

and c) diaspore
2.12 Silica cycle 1n the Bayer process

3.1 Formation of humic acids

3.2 Visible spectra of a) humic acid b) fulvic acid

3.3 Ultraviolet spectra of a) humic acid and

b) fulvic acid

3.4 Infrared spectra of a) humic acid and b) fulvic

acid
3.5 Infrared spectra of original humic acid obtained

from various sources

3.6 Infrared spectra of original fulvic acid

obtained from various sources

3.7 Flaig's model of structure of humic substances

3.8 Felbeck's model of the structure of humic

substances

3.9 Finkle's model of the structure of humic

substances

3.10 Structure of fulvic acid

3.11 Degraded carboxylic acids obtained under

alkaline permanganate oxidation

3.12 Process of transformation of organic substances

in soil

3.13 Influence of Bayer process liquor impurities

on rate of precipitation

3.14 Influence of organic matter on precipitate quality

3.15a Effect of glucoisosaccharinate on alumina tri-

hydrate yield (synthetic digest)

3.15b Effect of glucoisosaccharinate on alumina tri-

hydrate precipitation (synthetic digest)


3.15c Particle size distribution analysis. Effect of
glucoisosaccharina te on precipitation of alumina

trihydrate (synthetic digest).

3.15d Effect of glucoisosaccharina te on particle

size (synthetic digest)

3.16 The behaviour of sodium oxalate in a Bayer


plant over a period of one year

4.1 Phase diagrams in the Na 0-Al 0 -H 0 system


2 2 3 2
4.2 Mier's super solubility concept
4.3 Kossel model for crystal growth
4.4 Screw dislocation mechanism
5.1 Separations and analysis for the organic com-
pounds present in the Bayer process liquor

5.2 Separations and analysis for the organic com-


pounds present in the Bayer process liquor

5.3 Distillation of volatile organic acids from

acidified Bayer process liquor


5.4 Schematic diagram of the typical gas chroma-
tograph
5.5 Gas chromatogram of the Bayer process liquor -
direct injection of ether extract, Condition I

5.6 Gas chromatogram of the Bayer process liquor -

direct injection of ether extract, Condition II

5.7 Gas chromatogram of the Bayer process liquor-

methyl esters of impurities, Condition I

5.8 Gas chromatogram of the Bayer process liquor -

methyl esters of Bayer impurities, Condition II


5.9 Results of infrared analysis of the Bayer

process impurities in comparison with natural

humic and fulvic acids

5.10 Stirred cell used for the separation of organ1c

impurities over 1000 molecular weight

5.11 Immersible type of membrane used for the separ-

ation of organic impurities over 10,000 molecular

weight

5.12 Results of the pH - titration of the higher mole-

cular compounds greater than M.wt. 10,000 extracted

from the Bayer process liquor

5.13 Desorption and analytical methods used to deter-

mine the organic impurities contaminated with

the plant product alumina trihydrate

5.14 X-ray diffraction analysis of the alumina tri-

hydrate after a methanol wash

5.15 Infra-red analysis of the hot water desorbed

extract of the product alumina trihydrate

5.16a Sketch of the experimental unit used for the

adsorption studies

5.17a Laboratory equipment used for the adsorption

studies

5.17b Adsorption studies of sodium oxalate, succinate,

acetate and benzoate on alumina trihydrate seed

5.18 Adsorption studies of organic impurities

extracted from the Bayer process liquor on

alumina trihydrate seed

5.19 - do -
5.20 Adsorption studies of Bayer process liquor on

alumina trihydrate seed. Elementary sketch

of the experiment.

5.21 Adsorption of Bayer process liquor on alumina

trihydrate seed - comparison studies of the

collected fractions using the U.V. spectrometer

5.22 Solubility of sodium oxalate in the pure caustic

solution at different concentrations and

temperature

5.23a Solubility of sodium oxalate in caustic solution

and in the sodium aluminate solution

5.23b Solubility of sodium oxalate in distilled water

at elevated temperatures

6.1a Photograph of the laboratory batch crystalliser

6.1b Schematic diagram of laboratory batch crystalliser

unit

6.2 Effect of organic impurities on crystallisation

of alumina trihydrate. Experiment No. 1.

6.3a Effect of organic impurities on crystallisation

of alumina trihydrate. Experiment No. 2.

6.3b - do -

6.4a Effect of organic impurities on crystallisation of

alumina trihydrate. Experiment No. 3.

6.4b Effect of organic impurities on crystallisation

of alumina trihydrate. Experiment No. 4.

6.5a Effect of organic impurities on crystallisation

of alumina trihydrate. Experiment No. 5.

6.5b - do -
6.6a Effect of organic impurities on crystallisation

of alumina trihydrate - Experiment No. 6

6.6b - do -

6.7a Effect of organic impurities on crystallisation

of alumina trihydrate - Experiment No. 7

6.7b - do -

6.8a Effect of organic impurities on crystallisation

of alumina trihydrate - Experiment No. 8

6.8b - do -

6. 9a Effect of organic impurities on crystallisation

of alumina trihydrate - Experiment No. 9

6.9b - do -

6.10 Particle s1ze distribution of product alumina

trihydrate, from Experiment No. 1

6.11 - do - from Experiment No. 2

6.12 - do - from Experiment No. 3

6.13 - do - from Experiment No. 5

6.14- - do - from Experiment No. 6

6.15 - do - from Experiment No. 9

6.16 Microphotograph of product alumina trihydrate

without impurity charge (magnification 50X)

6.17a - do - (magnification 200X)

6.18 Microphotograph of product alumina trihydrate

with sodium oxalate impurity charge - from

Experiment No. 6 (magnification 50X)

6.19 - do - (magnification 200X)

6.20 Microphotograph of seed alumina trihydrate

(magnification 50X)
6.21 Microphotograph of product alumina trihydrate

with sodium acetate impurity charge from

Experiment No. 5 (magnification 50X)

6.22 - do - (magnification 200X)

6.23a Electron microscopic photograph of product

alumina trihydrate with sodium oxalate impurity

charge (magnification 150X)

6.23b - do - (magnification 300X)

6.24a Electron microscopic photograph of product

alumina trihydrate without any impurity charge

(magnification 150X)

6.24b - do - (magnification 300X)

6.25 Electron microscopic photograph of seed

alumina trihydrate (magnification 150X)

6.26 Electron microscopic photograph of product

alumina trihydrate with organic impurity charge

(M.wt.> 1000) (magnification 150X)

6.27 Electron microscopic photograph of product

alumina trihydrate with mixture of organic

impurities extracted from the Bayer process

liquor (magnification 150X)

Appendix I.1 Potential -pH diagrams for Al-Fe-H


2
o
system at 200°C

I.2 Potential -pH diagrams for Al-Fe-H D


2
at 150°C

I.3 Potential -pH diagrams for Al-Fe-H


2
o
at 100°C
I.4 Potential -pH diagrams for Al-Fe-Si-H 0
2
sys t em a t 25 oc

I.5 Temperature -pH diagram for Al-H 0 system


2
II.1 Stability field diagram for manganese species

at 25°C
INTRODUCTION

1. ALUMINIUM PRODUCTION IN AUSTRALIA

2. FUTURE PROCESS DEVELOPMENTS IN THE

ALUMINIUM INDUSTRY
1

INTRODUCTION

1. ALUMINIUM PRODUCTION IN AUSTRALIA

Although aluminium products have been manufac-

tured within Australia since 1914 in the form of die-cast,

rolled and extruded products, the source material was

either imported primary metal or secondary metal from local

scrap, and since domestic per capita consumption was low

there was no inducement to establish a primary metal

industry. The second world war became the main cause of

a great expansion in the use of aluminium, especially for

aircraft, and world supplies were inadequate and Australia

could not obtain more than a fraction of its requirements

of the metal from overseas.

In 1940 the Commonwealth Government proposed

the establishment of a combined aluminsrefinery and

aluminium smelter within Australia and selected Bell Bay in

Tasmania as a site which met the basic requirement of

adequate and reliable power, fresh water and an adjacent

deep water port. The plant came into production in 1955

with a capacity of 25,000 tonnes of aluminium per annum.

Bauxite as a plant raw material was totally

imported from Malaya, Indonesia and Indian sources but the

discovery of huge reserves of bauxite in Australia from

1955 onwards brought a dramatic change to the industry.

The opportunity to develop a full integration of the

industry from the mining of the basic resource to the pro-

duction of primary metal and the establishment of

secondary industries without reliance on overseas sources


2

saw the beginning of a mass1ve expansion which has attracted

a large investment, both financial and technological, and

established self-reliance for Australia, domestically,

and recognition as a major supplier of resources and end

products in export markets.

The various groups which had been responsible

for these bauxite discoveries had to look to the experienced

world producers to assist in development for two ma1n

reasons. Firstly, the technical complexity of production

which needed the know-how of experts and, secondly, because

of the huge scale of production from Australian deposits

which would have to be absorbed into world markets.

The world industry has had relatively few

large-scale integrated producers, with North American

companies producing about half of the world's total

aluminium. The four world giants in aluminium are Alcan

Aluminium Limited (Canada), Alcoa Aluminium Company of

America, Kaiser Aluminium and Chemical Corporation and

Reynolds Metals Company. Next in size come Swiss

Aluminium Limited and Pechiney (France). All of these

world leaders except Reynolds are now associated with the

industry in Australia.

Although the beginning of the Australian

aluminium industry was very small and difficult, today

Australia has built up a large and valuable industry

which is still expanding. Today, the contribution to the

Australian economy by the aluminium industry is consider-

able. In 1960 - 61 the total imports of bauxite,

unwrought aluminium waste and scrap, and of worked shapes

were valued at $21.8 million. By comparison, only


3

$1 million value of these commodities were exported in

1960 - 61. By 1965 - 66, this imbalance between imports

and exports had been reversed and in 1973, the aluminium

industry made a contribution exceeding $300 million to

Australis's overseas earnings. In the past years, the

growth in export earnings has been equally as dramatic and

the value of exports in 1979 exceeded $900 million.

The aluminium industry is also contributing to

the domestic economy of Australia. Australia stands in

first place in both the mlnlng of bauxite and the production

of alumina. The industry has a total value of production

of some $1,300 million which is based on an investment of

$2,200 million and provides direct employment to over

16,000 Australians.

As already mentioned, before 1950 there were no

known economic deposits of bauxite in Australia, then in

quick succession three major deposits were recognised;

one at Weipa in Queensland, another at Gove in the Northern

Territory and the third in the Darling Range in Western

Australia. The total of economic grade deposits in

Australia are estimated to be more than 4000 million

(see Table 1a).

The international importance of the discovery

of these reserves can be shown by taking into consideration

the world total known bauxite reserve (see Table 1b).

These figures are fairly speculative as all of the known

fields have not been thoroughly prospected or proven.


4

million tonnes
Weipa 2700

Darling Ranges 800

Gove 300

Kimberley District 200

TABLE 1a: Economic grade bauxite


in Australia (Ref.1)

Country Size of reserve


(million tonnes)

Australia 4000

Brazil 3000

Guinea 2400

China 1000

Jamaica 400

Switzerland 350

U.S.S.R. 300

Hungary 300

U.S.A. 300

Ghana 290

Guyana 290

India 190

Yugoslavia 188

Greece 100

Dominican Republic 40

TABLE 1b: Known bauxite reserves 1n


the world (Ref. 1)
5

Production (OOO's tonnes)

Year Bauxite Alumina Aluminium

1966 1827.1 307.0 92.0


1967 4243.6 854.4 92.3
1868 4955.1 1309.5 97.3
1969 7921.1 1931.0 132.1
1970 9256.3 2152.2 205.6
1971 12732.7 2712.6 223.6
1972 14437.0 3068.1 205.7
1973 17595.9 4088.9 207.3
1974 19994.3 4899.2 219.3
1975 21003.5 5128.9 213.9
1976 24083.5 6205.8 232.3
1977 26070.0 6659.0 247.6
1978 24299.2 6775.7 263.4
1979 27584.0 7416.0 269.6

TABLE 2: Production details for bauxite, alumina


and aluminium metal in Australia (Ref. 2)

Million
tonnes

30

20

10

1960 62 64 66 68 70 72 74 76 78 80 82

Fig. 1 World and Australian alumina production


6

Following the discovery of bauxite in Australia

the Australian aluminium industry has recorded a spectacular

growth in the last decade. Table 2 published by the

Aluminium Development Council illustrates the pattern taken

in the use of bauxite ln the aluminium industry in Australia.

Presently the Australian aluminium industry also

accounts for a sizeable fraction of the world's product as

shown in Fig. 1.

There are five major companies involved in the

aluminium industry in Australia.

1) Alcan Australia Ltd. (owned 70% by Alcan Aluminium Ltd.,

of Canada and 30% by Australian institutional investors)

produces aluminium and semi-fabricated and fabricated

products.

2) Alcoa of Australia Ltd. (owned 51% by Aluminium

Company of America, 20% by Westmines Investments

Pty.Ltd., 16.6% by B.H. South Ltd., 12% by North

Broken Hill Holdings Ltd., and 0.4% by AUC Nominees

Pty.Ltd., and Cushion Trust Ltd., Mines bauxite,

produces alumina, aluminium and semi-fabricated

products.

3) Comalco Ltd. (owned 45% by Kaiser Aluminium and

Chemical Corporation of U.S.A., 45% by Conzinc Rio-

tinto of Australia Ltd., and 10% by Australian and

New Zealand public shareholders), mines bauxite,

produces aluminium, semi-fabricated and fabricated

products.

4) Nabalco Pty.Ltd., (owned 50% by Swiss Aluminium

Australia Ltd., and 50% by Gove Alumina Ltd., a


7

consortium of Australian Companies headed by

CSR Ltd.), mines bauxite and refines alumina at

Gove, Northern Territory.

5) Queensland Alumina Ltd. (owned 21.4% by Alcan

Queensland Pty.Ltd., 20% by Aluminium Pechiney

Australia Pty.Ltd., 30.3% by Comalco Ltd., and

28.3% by Kaiser Alumina Australia Corporation,

refines bauxite into alumina.

Commercial mining has been ln operation at both

Weipa and ln the Darling Range since 1963 and in Gove

since 1971. The total bauxite mined in all of these

areas in 1977 was over 26 million tonnes.

There are four alumina refineries operating in

Australia at present. The first commenced production in

1963 at Kwinana in Western Australia. A second refinery,

now the world's largest, came into operation in March 1967

at Gladstone, Queensland. In 1972, Australia's third

alumina refinery came into operation at Pinjarra in Western

Australia, and the fourth of the refineries is located at

Gove in the Northern Territory and also began production in

1972. Present Australian capacity for alumina production

is more than 6.5 million tonnes and Australia is the

world's largest exporter of alumina. The design capacities

of the four major refineries are shown in Table 3.

Alumina production in Australia is forecast to

reach 10 million tonnes/year by 1980/83 with an aluminium

content of 5 million tonnes. The home market is unlikely

to reach more than 500,000 tonnes per year of aluminium by

1982/83. This surplus production would indicate that either


8

Company Capacity Outlets


(million tonnes)

Alcoa 1.4 Exported-and Alcoa


(Kwinana) Smelter at Point
Henry, Victoria

Alcoa 2. 2 Exported-and Alcoa


(Pinjarra) Smelter at Point
Henry, Victoria

Queensland 2. 0 225,000 tonnes to


Alumina Comalco, Bell Bay,
(Gladstone) 100,000 tonnes to
Alcan, Kurri Kurri,
balance exported

Nabalco 1.0 Exported


(Gove)

Total 6.6

TABLE 3: Alumina refineries in Australia and their


designed capacities.

Australia will have to depend on an export market or a

further development of integrated aluminium industry within

the country. However, home consumption of aluminium has

increased significantly as shown in Table 4.

The potential demand for aluminium ln the near

future shows good prospects of a significant increase.

The applications of aluminium are expanding immensely in

the various fields shown in Fig. 2. The 1976 model U.S.

passenger car had an average aluminium content of about

40 kg. By 1983, it is expected to be between 80 and

100 kg. This increase will represent an additional market

of 500,000 tonnes by 1983 in the U.S.A.


9

Building
and
Construction
22.0%

Fig. 2 Applications of aluminium

The other traditional markets for aluminium,

such as containers and packaging, building and construction

and electrical applications are expected to grow together

with the general worldwide increase of per capita consump-

tion. With their market potential, the world aluminium

industry is facing an excellent opportunity to bring the

supply versus demand balance in order.

Over the last 20 years, world aluminium con-

sumption has had an average growth rate of 9% per annum

which is approximately double the rate of growth of Gross

National Product in the main industrialised countries.

This has been the hard won result of the scale and quality

of the development and the effort applied, together with a

clear recognition of the marketing approach required,

which is an approach that is quite different from that


10

adopted in the marketing of most other metals. Aluminium

is essentially a new material, forcing its way into the

market by demonstrating its low cost and technical advan-

tages over existing materials and, in some cases, making

totally new applications possible. Proper price recovery

and the ability to maintain a profitable operation is the

key to the industry's ability to finance its future growth.

2. FUTURE PROCESS DEVELOPMENTS IN THE ALUMINIUM INDUSTRY

Although the aluminium industry has passed through

a very short history, the technical advancement made within

that short period is remarkable. The related research that

has been carried out throughout the world to bring this

industry up to the successful state of today is enormous,

but it cannot be said that the aluminium industry today has

completely achieved its technical capabilities. There are

many problems to be solved in the area of conservation of

energy in both alumina production and in aluminium smelting.

At the present time there are two major energy

sources available for use in the aluminium industry. The

first is electrical energy which is obtained either through

generation from hydro power or by burning coal. The

second is energy derived from oil in the form of fuel oil,

diesel oil and petrol, while in the medium to longer term,

other energy sources such as nuclear energy, may be devel-

oped on an economic basis. The aluminium industry claims

to have been continuously working to reduce the amount of

energy which is consumed in a production of aluminium.

Figure 3 shows the energy requirement in the

smelting stage of producing aluminium has been reduced


11

Kwh/Kg. of Al
50~----------------------------

401------------------------------
301\~~---------------------
~
20~~~~~~~====:-
101------------------------------ -
oL-----~----~----~--~~--~
1890 1910 1930 1950 1970 1980 years

Fig. 3 The reduced energy requirements in the


smelting of aluminium over 80 years (2).

since aluminium was first smelted on a commercial scale.

Further reduction of the consumption of energy is one of

the major tasks today that the aluminium producers are

facing. It is hoped that the figure can be reduced to

below eight kilowatt hours per kilogram of metal.

In order to reduce the energy requirement ln the

production of alumina, some technical ideas are now being

developed. The Germans have developed a tubular reactor

for the extraction process in which higher extraction

temperatures are used and very low reaction times can be

achieved and reduced capital and fuel costs are claimed (4).

Another area of further development is in

minimising the heavy losses of caustic incurred during the

separation of red-mud from the aluminate liquour, and

consumed by silica in the bauxite. According to the

information obtained from Queensland Alumina Ltd., consump-

tion (or loss) of caustic soda per tonne alumina produced

is about 0.15 tonne due to formation of various forms of

sodium alumina silicate. A challenging task is also ahead


12

for today's alumina producers to increase the output of

alumina trihydrate in the precipitation stage and also to

increase dissolution of bauxite in the extraction stage.

The availability of high grade (low silica content)

bauxite resources is limited. These resources will

probably last only for another 30 - 40 years depending on

the demand for aluminium, and then the alternatives will

be the relatively high silica content clay minerals. The

process that has been adopted for extraction of high grade

bauxite (the Bayer process) obviously cannot be used

economically for the low grade minerals. Although there

are several alternatives processes developed, these pro-

cesses are still economically not viable, but particularly

in the United States there is much research effort on

these alternative processes.


CHAPTER 1

BAYER PROCESS PLANT OPERATION


13

1.1 THE BASIC PROCESS

While many processes have been devised for the

production of pure alumina from bauxite, clay and other

minerals the one which is used predominantly and almost to

the exclusion of the others is the Bayer process invented

by Carl Joseph Bayer and patented by him in 1888.

In this process the bauxite is first digested

with caustic soda solution under pressure and at elevated

temperatures. The alumina is extracted in the form of

soluble sodium aluminate which leaves behind most of the

impurities such as iron oxide, titanium dioxide and silica

as an insoluble residue. The clear, filtered sodium

aluminate solution is diluted and cooled, and ''seed"

crystals of alumina trihydrate are added. The sodium


aluminate solution hydrolyses on the surface of the seed

to form crystalline alumina trihydrate. The alumina tri-


hydrate ~ finally filtered off and calcined to anhydrous

alumina.

The dissolution process for the var1ous con-

stituents of bauxite can be represented by the following

equation:

Monohydrate
(boehmite type)

2) Al 0 .3H 0 + 2Na0H + xNaOH Extraction> 2NaA1o +


2 3 2 2
<Decomposition

Trihydrate
(gibbsite type)
14

+ YA1 0 + 2Na o +
3) xS10
2 2 3 2
aH
2 0~xS10 2 yAl 2 o 3 .2Na 2 o.
aH
2
o

Irrespective of the type of bauxite (whether

predominantly boehmite or gibbsite) processed, it is the

trihydrate which is precipitated during decomposition of

the sodium aluminate solution and not the monohydrate.

Figure 1.1 shows a simplified flow-sheet of the

Bayer process which has not changed appreciably from the

time it was first developed in the 1890's.

The first plant came into operation 1n France

in 1895 and it was followed by one in the United Kingdom

1n 1896.
A more detailed account of the original process

is that the ore is crushed, ground and mixed with recycled

sodium aluminate solution and additional caustic soda and

the mixture then charged into autoclaves and heated to

dissolve the bauxite under pressure. The output slurry

from the autoclave system consists of a rich sodium

aluminate liqueur and an insoluble residue which is diluted

and cooled. The residue (known as red mud) is separated

by settling and filtration, washed free from caustic and

discarded. The clear filtered liqueur is further cooled

and passed to the precipitators for decomposition to pre-

cipitate alumina trihydrate. This was the basic method

covered by the original Bayer patent. Bayer also

investigated the effect of seeding a super saturated

liqueur of sodium aluminate, stirred with alumina tri-

hydrate as seed and as a result further deposition of


15

r- Soda make-up
Alumina
I

-'-- Evaporation

' Old
Calcination
I
Ore- Ore-
liquor
crushing crushinq

Hydrate
filtration
I

Seed
hydrate

Extraction Decomposition ~~

V
r-------------~ New
Mud 1 iquQJ:
Dilution ~ .r Cooling
separation

washing~
'-....- ~.....::!'---''IL-----,,-,
Water ... Mud
washings

' 11 Mud to
waste

Fig. 1.1 The Bayer process basic circuit


16

alumina trihydrate on the seed took place.

The alumina trihydrate produced in this operation

can therefore be regarded as being in two parts. A portion

of the slurry of trihydrate and "old" liquour is filtered

to give the product hydrate for conversion to alumina,

the remainder is separated from liquour either by settling

or filtration and returned to the system as seed hydrate.

The product hydrate is washed virtually free

from aluminate liquour and calcined in furnaces at 1200°C -

1300°C to give the final alumina. The remaining liquour

after the precipitation of trihydrate is recycled v1a an

evaporation plant to the bauxite extraction circuit.

All Bayer plants are based on this basic pattern

although there may be some differences in the technical and

engineering methods which vary according to the type of

raw material being used and individual factory preferences.

There are a number of separate cycles within this broad

process and these are considered later individually to show

how they lead to particular features of process and plant

design.

1.2 PLANT OPERATION AT QUEENSLAND ALUMINA LTD.,GLADSTONE

This plant also follows the same general pattern

of the basic Bayer cycle, but there are many technical and

engineering methods that have been adopted which differ to

some extent from those adopted elsewhere.

The raw material used in the plant is bauxite

from Weipa which typically consists of the two forms;

monohydrate boehmite (Al


2 o3 .3H 2 0) and the trihydrate
gibbsite (Al
2 o3 .3H 2 0). Alumina in the trihydrate form
17

1s much more readily soluble in sodium aluminate solution

of given soda concentration and temperature than the

monohydrate. Generally in the Bayer process, A10 .3H o


3 2
is attacked by concentrated caustic soda solution at 125°C,

where as Al o
2 3
.H 0 requires a temperature of over 200°C
2
but the solubility equilibrium for both types depends

mainly on the caustic soda concentration, temperature and

caustic ratio.

The bauxite used at the Queensland Alumina Ltd.,

plant has the composition shown in Table 1.1.

TCA- 55.21% (Total chemical alumina)

TAA- 49.21% (Total available


alumina extractable)

Total SiO - 5.3%


2

Quartz 1.0%

Reactable Si0 - 4.3%


2

TOOC 0.25% (Total oxidisable


organic carbon)

P205 0.08%

Moisture 13 - 15%

Ti0 2.6%
2

Table 1.1 Composition of bauxite used at


QAL Gladstone

The flow sheet shown in Figure 1.2 indicates

some of the more important conditions used in the process

as adopted at Gladstone. The whole process can be divided


hj
Water Water
1-'·
.
\.Q
Coal Steam
- - - - - - -7oo#1tis- -
.
I-'
N
Steam generation Caustic soda

0 ttJ
1-oi Evaporation
11 0
0 13,000 T.P.D.
l.l 0 (tl
Bauxites
P! 0 (/l
f-':;:l (/l
0 0 Digestion
~ (tl hj
f-':;:l I-' Grinding
P205
P! rt 0
rt 1-'l ~
f-'· P>
0 rt ()
:;:l 1-'· ::J'
(/l 0 P>
:;:l 1-oi 350 T.P.D.
t1 rt c~lBO g/
P> 0
(/l Ho 0
(tl 1-h
p, 0
P> lO 101°C Fresh
0 ~ ~ Lime
:::s (/l (]) Pregnant caustic liquor ;;at er
Filtration
rt (])
z"PJ 1-'·
0
:::s
(/l
Lime ~8,000 g.p.m
slaking - = 187 9 ;r
OA~
) I-'
0 (/l P> l
0 0 :::s
- - ---
0
) A. p,
P> 65°C ~-
:;,. Red mud
I-' C=l87 g/1

~ A/C=0.315 to waste
Precipitation
:;,. 1-'· 180 g. solids/l.
......_ :::s · 28,000 g.p.m .
0 P>
11 t-1
rt
:;,. p, Hot water

wa~w~:~i~~~e
1-' Primary
N
0
w G)
;;....._
I-' "'-...:-F_.....,..
t1 Pl
'< p, Filtrate
(/l Oxalate rich
~ rt Lime
(]) 0...,

LLJ
1-'· ,_,
\.Q (l)
::J'
rt
Cal::-iuxr: oxalate
to wa.st"'·

I-'
CXl
19

into the following major operations:

1) Grinding of bauxite and removal P o


2 5

2) Digestion (extraction)

3) Flashing stage to recover heat

4) Desilication and separation of red mud


(clarification)

5) Precipitation of alumina trihydrate

6) Classification and thickening

7) Filtration

8) Calcination of trihydrate

9) Concentration of recycled caustic liquor.

Bauxite is firstly ground to a particle s1ze of

-10 mesh and then mixed with lime slurry to remove P


2 o5 so
as to prevent phosphate being formed in the product

alumina. In the presence of lime, calcium phosphate is

formed which is settled with the red mud at a later stage.

Addition of lime at a later stage will also increase the

"strength" of caustic liquor by reacting with Na


2
co 3
present in the caustic liquor to form caustic soda. The

total input of bauxite 1s about 550 tons per hour.

After treating the bauxite with lime slurry it

1s passed into the digestor where it is leached with con-

centrated caustic soda solution at a pressure of 500 psl


0
and a temperature of 245 C. This caustic solution is a

mixture of recycled liquor recovered from the final stages

of the process and "make-up" caustic which is added to

increase the concentration to 230 g/litre soda (expressed

as Na
2
co 3 ). It also contains dissolved alumina up to a

ratio of Al 0 /Na co (A/C = 0.360 by weight). Steam at a


2 3 2 3
pressure of 700 psi is directly injected into the digestor to
20

attain the required temperature for extraction which

occurs during a retention time of about 15 minutes. These

conditions are controlled to suit the particular mixture

of both gibbsite and boehmite in the bauxite from Weipa.

Usually a weighed quantity of about 9 tons of bauxite

per minute is continuously mixed with about 20,000 US

gallons of caustic liquor. The reacted slurry which has

reached a caustic ratio, A/C (Al 0 /Na co ) of 0.65 after


2 3 2 3
digestion is now passed through a series of flash evapor-

ators, where steam and heat are recovered from the system.

The temperature is reduced down to the boiling point at

atmospheric pressure of about 105°C after passing through

the flash evaporators.

The liquor stream then passes through hydro-

cyclones where a sandy residue is separated and pumped

out and the undissolved fine mud is separated out of the

liquor by settling in single deck thickeners each 100 ft.

in diameter. The settled mud is re-washed in several

stages as shown in the flow sheet to recover part of the

caustic liquor in the mud. The concentration of caustic

in the feed to the thickener is reduced to 180 g/litre as

it will be mixed with low concentration caustic solution

which is recovered from the mud washing as shown in the

flow sheet. The dilution of the caustic concentration lS

optimised to separate soluble silica along with the red mud.

Usually the red mud is flocculated with a sorghum starch

solution added at the rate of 1 ton of starch for each

500 tons of Al o
2 3
produced.

The overflow from the mud settlers passes through

Kelly filters to remove the fine material carried over with


21

the liquor and the clear solution ("pregna nt mother liquor")

is further cooled to about 82°C.

The next stage of the process involves the pre-

cipitati on of alumina trihydra te from the mother liquor in

tall open topped tanks which stand 100 ft. high and 25 ft.

in diamete r. The precipi tation is aided by seeding with

crystals of previou sly precipi tated hydrate which are added

to the tank and agitated for about 36 hours. The seed

crystals are added in a slurry of 130g of solid hydrate

per litre of pregnan t liquor. It is essentia l at this point

to maintain the desired particle size of the alumina tri-

hydrate as it increase s during the decompo sition process .

Precipi tation occurs mainly by growth on existing particle s

to yield agglome rated polycry stals. The growth of the

crystals depends mainly on the tempera ture, the rate of

decompo sition and the supersa turation of the solution , the

particle size and the proporti on of seed hydrate , the

impurit ies present in the liquor and the rate of agitatio n.

The crystals formed are kept ln suspensi on by agitatio n.

The precipi tators consist of 11 tanks arranged in series,

each with a capacity to hold about 60,000 U.S. gallons.

The overflow passes through by gravity and the liquor passes

out from the last tank at 65°C with a caustic concent ration

of 187 g/litre and A/C = 0.375. Between tanks 4 and 5

there is a heat exchang er which brings about a tempera ture


0
drop of about 14 C.

The liquor from the precipi tators which contain

the final required particle size range of crystals is

settled and the trihydra te crystals separate d into three

size ranges in a series of three classifi cation tanks.


22

The primary classifier collects the coarse fraction

which becomes the product hydrate; the crystals from the

secondary and the tertiary classifier are returned to the

first precipitation tank as seed crystal after passing

through an oxalate removal stage.

The crystals which are settled in the tertiary

and secondary thickeners are contaminated with sodium

oxalate which retards the growth of alumina trihydrate

when these crystals are used for seeding, and as a result

an undesirably fine and slowly settling alumina trihydrate

precipitates. This situation is avoided by washing the

sodium oxalate from the hydrate seed crystals before they

are used in the first precipitation tank. The fine cry-

stalline seed containing sodium oxalate is filtered and

washed with hot water to dissolve the oxalate. The tri-

hydrate crystals from the final filter are then used for

seeding.

The overflow from the tertiary thickener which

has a concentration of 187g of caustic soda per litre

and A/C = 0.375 is mixed with fresh caustic soda and passed

through evaporators to build up the required concentration

of 230 g/1 and A/C is about 0.360. The chemical composition

of the spent liquor is as shown in Table 1.2.

The alumina trihydrate crystals which are

settled in the primary thickener contain mainly the coarse

particles. These are fed in to the hydrate washing system

which comprises a plurality of hydrate wash tanks and a

filter. After hydrate washing the alumina hydrate is

subjected to calcination.
23

g/litre
1. Alumina Al 0 84.3
2 3

2. Caustic soda (as Na


2
co 3 ) 234.5

3' Carbonate soda ( -do- ) 24.1

4. NaCl 16.19

5. Si0 0.53
2

6. P205 0.088

7. V205 0.74

8. Na
2
so 4 0.31

9. Sodium oxalate 5.51

10. Total organic soda (as carbon) 23.85

11. Fe
2 3
o .005

Table 1.2: Chemical composition of recycled


caustic soda obtained from the
Queensland Alumina Ltd. plant (5)

When alumina trihydrate lS calcined it first

loses its water of crystallisation, forming the active

y - type alumina at 400 - 600°C which will adsorb water.

Since moisture is undesirable in the alumina used in the

reduction furnace, calcination is carried to 1200 - 1350°C

in order to form the inert a - alumina. This operation

is carried out in oil-fired rotary kilns of about 200 ft.

long. Dust leaving the kiln is collected by an electro-

static precipitator and fed back to the kiln. The

alumina is finally cooled and conveyed to storage bunkers

and then despatched to the reduction factories.

The chemical composition of alumina produced is


24

shown 1n Table 1.3.

Maximum Typical
allowable

S10 0.030% 0.02%


2

Fe
2 3
o 0 . 0 3 0% 0.016%

Na
2
o 0 . 70% 0. 35%

Loss on ignition 0 . 8% 0.7-0.8%


(300-1000 oc)

Screen

+ 100 mesh 7.0% 2-3%

+ 325 mesh 90% 92%

Table 1.3 Chemical composition of product


alumina

1.3 THE ACCUMULATION OF ORGANIC IMPURITIES IN THE


BAYER LIQUOR

in all Bayer process plants one of the major

problems in the precipitation stage is the accumulation of

organic impurities. Most of the other impurities

originally present in the bauxite such as silica, iron

and titanium are easily separated from the liquor before

the precipitation of the alumina trihydrate. An explana-

tion of the separation of iron and aluminium is presented

in the form of thermodynamic stabilities in Appendix I.

As shown in Table 1.1, bauxite contains about

0.25% of organic carbon which is in the form of various

humic, fulvic and lignin materials mainly due to decayed

vegetation. These organics are extracted into the Bayer

liquor in the autoclave extraction. Some o£ these organics


25

altered by chemical reactions and many converted into the

sodium salts of various carboxylic acids. Furthermore a

certain percentage of starch added for the red mud floccu-

lation is also added to the Bayer liquor as a semi-soluble

organic compound. Because of the need to re-cycle caustic

liquor these organic compounds accumulate giving it a typical

brown coloration. In the Queensland Alumina Plant analysis

has shown that the total organic can reach about 160 -

190 g/litre as Na 2 co 3 , whereas the sodium oxalate would

reach about 3.0 to 5.00g per litre as Na 2 co 3 . Although it

is generally known that there are a great number of differ-

ent organic compounds present in the liquor apart from

sodium oxalate, no detailed quantitative or qualitative

study has been made to identify these compounds. Two

Bayer plants processing the same Jamaican bauxite, with

different temperature conditions of 135°C and 240°C have

shown an organic carbon content of 8.5 g/litre and

15 g/litre (as carbon) respectively in the recycled liquor.

Among the organic salts formed during the process . .some of

them are likely to reach saturated concentratio ns in the

pregnant liquor. For example, the solubility of sodium

oxalate decreases with an increase of pH. Yamada et.al.(6)

in their work, reported the solubility of sodium oxalate 1n

various concentration s of plant liquor as shown in

Figure 1.3. It was also shown from his work that sodium

oxalate is supersaturate d in the solution under the Bayer

process condition thus causing a tendency to crystallise

with the aluminium trihydrate as the concentratio n of sodium

oxalate in the Bayer liquor reaches about 3 to 4 g/litre.

The equilibrium solubility of sodium oxalate in the Bayer


26

liquor at 60°C is about 2 g/litre .

.-I 4.0
......... M.R . 3.0
0'>

()
~
3.0
0
()
2JJ 0
(\) 70C
n:l
so·c
:z; 1.0 9-o·c
0
0
u 1 0 140 160
120

Na
2
o concentration (g/1)

Fig. 1.3 Sodium oxalate solubility in Bayer process liquor (6).

The concentratio n of the total organic sub-

stances ln the Bayer process liquor reaches a certain level

after a period of time and such level is called the

"saturated concentratio n". Usually the saturated concen-

tration varies from plant to plant according to the

conditions applied and the type of bauxite treated. Yamada

et.al. (6) reported the following values of saturated con-

centration for the bauxite used in various plants in the

world.

Bauxite Digestion Saturated


temp. cone.
oc g/l
South East Asia 150 8.1

Australia - I 150 17.2

Australia - II 230 11.3

South Pacific Island 150 24.6

Africa 150 5. 5
27

Although there are no routine analyses to deter-

mine the various organic impurities in Bayer process liquor,

the total organic carbon analysis indicates the rate at

which the organics accumulate. These accumulated organic

impurities are known to cause several process problems. The


main problem is the inhibiting effect of the organics on

hydrate precipitation.

The organic impurities are reported to affect

trihydrate precipitation in the following ways:

a) they change the equilibrium solubility

values thus affecting both the rate of precipitation as well

as the precipitation yield.

b) Depending on the nature of the impurity

and the conditions of precipitation, they may increase or

decrease the nucleation rate. For example, it is widely

believed that sodium oxalate builds up to a critical super-

saturation and then gives rise to a finer precipitate of

trihydrate suggesting increased nucleation. The mechanism


of such fine formation is believed to be in the following

manner; after reaching the critical supersaturated level of

sodium oxalate it begins to crystallise as very fine

precipitate of sodium oxalate and thus interfere in the

agglomeration of alumina trihydrate in the precipitation

stage by acting as nuclei for trihydrate crystallisation.

c) Impurities are also believed to be inter-

fering with the induction period and the crystal growth,

for example, by getting adsorbed on the seed surface as

has been observed in other crystallisation systems.

A product of suitable size distribution lS

desirable for the subsequent reduction step. The slze


28

distribution is also important in the performance of the

settling, filtration and calcination operations of the

process where an unreasonable rate of fine recirculation

can cause considerable operational difficulties and loss of

product by leading to the return of significant quantities

of hydrate to the digestion circuit.

There may also be some advantage to having

certain accumulated organic impurities in the Bayer process

liquor depending on the nature of the impurity. For

example, higher molecular compounds are believed to aid red

mud separation to sediment. Furthermore, as a result of

the rise of the solubility of sodium aluminate, premature

decomposition will be stopped by the presence of some

organlcs.

1.4 THE REMOVAL OF THE ORGANIC IMPURITIES FROM BAYER


LIQUOR IN PLANT PRACTICE

Although there are several works reported ln

regard to the removal of organics from Bayer process liquor

which will be discussed in a later chapter, only one method

has been adopted with some success in plant operation.

The Kaiser Aluminium Company of America (7)

has patented a method to remove some of the organlcs

present in Bayer process liquor (mainly the sodium oxalate).

This method has been adopted by several plants in the world

including Queensland Alumina Ltd., at Gladstone. The aim

of this method of control of organics lS to obtain the

desired particle SlZe of the alumina trihydrate as well as

to obtain a better recovery. Normally, during the

crystallisation of alumina trihydrate the sodium oxalate


29

and other organic salts having similar properties to sodium

oxalate is precipitated from the liquor as very fine

crystalline particles to provide active surface sites for

the nucleation of alumina trihydrate particles and/or

retard the agglomeration andgrowth of alumina trihydrate

particles thereby resulting in an undesirably fine and

slowly settling alumina trihydrate precipitate.

The Kaiser patent covers the procedure for wash-

ing seed crystals from the final sedimentation stages with

hot water prior to recycling to the crystallisers.

It is claimed that the removal of the sodium

oxalate contaminant from the seed fraction of the alumina

trihydrate promotes better particle size control during

precipitation, increased capacity of the precipitation system,

more efficient operation of the classification system, a

purer seed trihydrate and a purer product alumina. This

application also provides for treating the oxalate-rich

wash~ngs to precipitate all the oxalate as calcium oxalate

which can be further processed and also for recovery of

caustic soda which may be recycled in the process.

In the crystallisation stage the liquor is likely

to be saturated with respect to both alumina trihydrate and

sodium oxalate. The oxalate which crystallises tends to

nucleate a finely divided alumina trihydrate precipitate.

The Kaiser patent reports that the finer fractions of the

trihydrate particles from the classification stage are high

in sodium oxalate whereas the coarser fraction is substan-

tially lower in sodium oxalate. Therefore in plant practice

the sodium oxalate is removed only from a portion of the

finer fraction of alumina trihydrate particles which is


30

then used for seeding. The flow diagram for this oxalate

removal step which is basically the same in most of the

plants in the world, can be traced in Figs. 1.4 - 1.6 which

show a relationship of the washing techniques and the

oxalate removal system of the Kaiser patent with respect

to the precipitation and classification systems of the

Bayer process.

Figure 1.4 is a schematic drawing in which it

can be seen that the pregnant Bayer process liquor and alumina

trihydrate seed particles are added through lines 2 and 3

respectively to a precipitator tank No. 1. After the

precipitation cycle, the slurry containing alumina tri-

hydrate and solid sodium oxalate is fed to a coarse particle

thickening system No. 10 through lines 6 and 7. In the

No. 10 tank the fine particles are separated from the

coarse hydrate particles by elutriation and then fed to the

fine particle thickening system No. 30 with the major

portion of the spent liquor. Whereas the relatively

coarse hydrate slurry is fed to the hydrate washing system

No. 24 which is comprised of hydrate wash tanks and a

filter (not shown). After hydrate washing this product

alumina hydrate is subjected to calcination.

The fine particle thickening system No. 30 is

comprised of a plurality of thickeners or classifiers, from

which the fine alumina trihydrate particles are separated

from the major portion of the spent liquor. The overflow

of spent liquor, including some suspended solids, is recycled

to the digestion step of the process. The fine trihydrate

particles and the solid oxalate from the underflow are fed

to the seed washing system. The fine alumina trihydrate


Hydrate seed
Spent liquor recycled
3
to digestion of Bayer
process ....
'- Overflow

21
11
30
1
Coarse
Fine part-
particle
10 icle thick-
Precipita-
tor tank
thickening
system
ening systerr Overflow 1 0
.jJ .J-1
)..!
0
ctl
2 rcl-1-l
(J) ·.-!
.-I P.t
u ·.-!

y
7 22 40 :>;U
u (J)
(J) )..!
Seed p:; P.t
Seed
washing
Hydrate system
8
24 washing Ul
Ul
system ro (J)
(J) u
50 .-I 0
u l-1
:>;P.t
Oxalate Caustic u
(J) 0
precipita- solution I):; -I-)

26 Calcination tion system

Oxalate
Product
precipitate
alumina

Fig. 1.4 Kaiser patent on control of sodium oxalate in the Bayer process liquor
>=:
0
·.-l
.j.l
lJl
Q)
J tJ1
Hydra te seed ·.-l
'1J
lo-1
0 0
3 ;j.j.l
0'
·.-l '1J
r-l Q)
r-l
.j.l 0
>=: :>..
Q) 0
P-!aJ
Overfl ow Overfl ow lo-1

,I Overflow
U)

Precip ita-
tor tank L
t ~ L·
t ]
Tertia ry
Second ary (tray) !
thicke ner thicke ner
32 33 H
0 0
7 .j.l .j.l
m
6 '"(j.j.l lJl
8 22 Q) ·.-l lJl
r-l
0 ·.-l
P-i A
Ql
0

Secondary~ TT seed
:>..o
0
QJ
Q)
lo-1
e
P.!
Hydra te seed wash washin g ~ P-i
0
washin g ing syste system Seed .j.l

s stem lJl 41 42
'd
Q)
lJl r-l
24 Q) 0
0 :>..
0 0
lo-1
P-i lr &
0
.
.j...l
Oxala te Caust ic sol ution
'd I' t""\ precip ita-
Q)
r-l
-
0 tion
:>..
0
Q) 50 Oxala te ppt
~

Produ ct alumin a Seed


Recyc led to
prec~p~tator

w
N
Fig. 1. 5 Kaiser paten t (contin ued)
Cold water spray
Water spray

Slurry from tertiary


7 I
(tray) thickener

70 Dissolver
Filter
Repulper
Filter

Primary filtrate
recycled to
digestion

Recycle liquor to
Washed hydrate
keep hydrate fluid
in liquor to
precipitato r

To oxalate
precipitatio n system

Fig. 1.6 Kaiser patent - continued


w
w
34-

and solid oxalate are subjected to a series of washings in

hot water to dissolve sodium oxalate. Thus the alumina

trihydrate is separated from the liquor containing dissolved

sodium oxalate and the washed seed is recycled to the

precipitation step.

The liquor containing dissolved oxalate is

either discarded or is sent to an oxalate - precipitation

system where calcium oxalate is precipitated. This is

normally done by addition of lime thereby giving a caustic

solution which can be recycled to the process. The

precipitate of calcium oxalate lS converted by calcination

to regenerate the lime.

The flowsheet ln Figure 1.5 shows more detail

of the particle thickening system. Here it can be seen

that the product from thickeners 11,32 and 33 is progress-

ively smaller in particle size, and are referred to as

primary, secondary and tertiary thickener trihydrate. The

primary thickener trihydrate is of largest particle size

and is not normally used as seed material.

In Figure 1.6 there is shown diagrammatically a

seed washing system in more detail than in Figures 1.4 and

1.5 for washing the alumina trihydrate particles in the

tertiary or tray thickener underflow. The underflow is

fed to a rotary belt filter No. 70 wherein the spent liquor

is removed from the seed until the cake contains approx-

imately 80% solids by weight. Several water sprays wash


0
the filter cake with water (cold water, less than 32 C).

The amount of water used lS preferably just sufficient to

substantially remove all of the spent caustic liquor (the

primary filtrate) which can then be recycled in the process.


35

The filter cake from filter No. 70 is agitated with hot

water in tank No. 71 at a temperature of 50°C to 90°C, to

dissolve the oxalate. The resulting slurry is then

filtered on a second rotary belt type filter No. 72 after

which the filter cake is again washed with water to remove

substantially all of the dissolved oxalate. The washed

seed is fed to a repulper wherein the seed is reslurried

with liquor and returned to the precipitation tanks. The

filtrate from filter No. 72 is oxalate-rich and can be dis-

carded or suitably treated (for example, by adding lime to

precipitate calcium oxalate with the recovery of caustic

soda, or by evaporation to precipitate sodium oxalate). The

filtrate from filter No. 72 may be recycled to the dissolver

No. 71 to maintain the trihydrate fluid.

In extensive testing of washing, tertiary (tray)

thickener trihydrate in a system such as that depicted ln

Figure 1.6, it has been found that alumina trihydrate

particles containing 0.4 to 6.5% by weight of sodium

oxalate can be washed to yield a washed alumina seed having

only up to 0.25% by weight of sodium oxalate. The second-

ary filtrate from filter No. 72 in the flow sheet (Figure

1.6) contains in the range of 6-32 g/1 sodium oxalate.

The process described above is a typical

application in the Bayer process to reduce the concentra-

tion of sodium oxalate and some of the other organic salts

which reach the level of supersaturation after number

of process cycle. But this method does not remove all the

organic matter which can be poisonous to the crystallisation.

On the other hand, the effect of sodium oxalate on

trihydrate crystallisation is itself highly speculative.


36

It is essential to justify its poisonous effect, before

any development work is done to remove oxalate from the

Bayer process liquor on a commercial basis.


CHAPTER 2

CHEMISTRY OF THE BAYER PROCESS


37

The ma1n ore used for the production of aluminium

1s bauxite. The main compounds present in the bauxite are

aluminium oxide hydrates together with oxides and hydrates

of iron, silica, titanium and other elements.

Physically the bauxites could be represented

either as soft loose aggregates or hard massive rock deposits

with its colour changing with iron content from almost white

right through to a dark brown. Each bauxite deposit lS

distinctive depending on the way in which the var1ous elements

are combined and also the physical properties of the ore.

Therefore careful studies have to be conducted for each type

of deposit before the optimum conditions are chosen for the

stage of extraction and subsequent precipitation.

There are three main mineralogical forms of

alumina present in the world bauxite deposits. They are as

follows:

a) Gibbsite: (Al o
2 3
.3H 0) which is easily
2
extracted in the Bayer process

b) Boehmite: (yA1 o .H 0) which can be extracted


2 3 2
using higher temperatures and caustic concentrations in the

Bayer process

c) Diaspore: (aA1 o
2 3
.H 0) this phase is rare in
2
Australian bauxite and is only extracted under relatively

extreme extraction conditions.

In most of the bauxites of Europe and Northern


#

Asia the alumina monohydrate minerals predominate. Through-

out most of the rest of the world, the bauxites contain

alumina largely as the trihydrate gibbsite with varying but

relatively small proportions of the monohydrate boehmite.


38

Bauxite from Jamaica is principally gibbsitic but some of it

contains as much as 20% boehmite. Major impurities in bauxite

ores include iron oxides, aluminium silicates, quartz and

titanium dioxides.

Australian bauxites, depending on the deposits,

represent both gibbsitic and boehmitic forms. For example,

the bauxite mined from Weipa contain about 20% of boehmite,

whereas the bauxite from the Darling Ranges is mainly

gibbsitic, but low in the total available content of alumina

which is about 30 - 35%.

2.1 OCCURRENCE OF BAUXITE

It is estimated that about eight percent of the

earth's crust is aluminium, occurring mainly in combination

with silica in the form of various silicate minerals. Under

specific conditions these minerals are weathered to the

hydrous oxides from which alumina can be extracted.

The definition of bauxites from the refiner's

point of view is a mineral deposit of aluminium 1n which

aluminium is present predominantly as a hydrate or a mlx-

ture of hydrates and hydrous oxides. It also contains the

other oxides of iron, silicon and titanium and traces of

compounds of some other elements.

The silica is mainly present 1n the form of

hydrous aluminium silicate and a portion of it is found

as quartz.

Specific weathering conditions such as high

temperatures and seasonal variation in the weather is

believed to be the main requirement for the formation of

bauxite. Gently sloping land forms, minimal denudation,


39

tropical or sub-tropical vegetation, and a rock texture

which lS susceptible to leaching are considered as the

other requirements.

Under these conditions and with the increase 1n

acidity due to the presence of carbonic acid solutions

derived from rain, and organic acids supplied by plants,

the action of bacteria and other organisms leach out the

more soluble potassium, sodium, calcium and aluminium

silicates, thereby leaving behind a residue richer in the

more insoluble hydrous oxides of aluminium and iron.

Depending on the predominance of iron or aluminium oxides

the laterites are classified as ferruginous or aluminous.

If the laterite is rich in aluminium it is called bauxite.

From the mineralogical point of view, the residual

rocks, in which the alumina trihydrate and monohydrate

minerals gibbsite, boehmite and diaspore predominate are

classified as bauxite. Other residual minerals are

developed in a unique type of rock weathering which produces

bauxite, and these minerals, kaolinite, hallosite, goethite,

hematite, magnetite, anatase, quartz and some phosphatic

and manganiferrous minerals may form the lesser constituents

of bauxites.

As mentioned earlier. the bauxites form only

under special climatic, hydrological and biological con-

ditions. Bauxitization occurs only above the water level,

where there is alternating downward movement of acid

solutions and upward movement during drier periods of

alkaline solutions in rocks which contain sufficient sodium

and calcium aluminium silicates or calcaseous rocks contain-

ing small amounts only of soda, ferric oxide, silica and


40

alumina but with the latter oxides in the ratio 1 : 1. In

bauxites which are still being formed the predominant alumina

hydrate mineral is gibbsite. The tropics and sub-tropics

appear to provide the proper climatic conditions, since it

lS only in these areas that gibbsitic bauxites are known to

be forming today. In Malaya, where gibbsitic bauxites are

forming from metamorphose d acid volcanics and sediments on

a peneplained area, the annual range of temperature is from

68 to 94°F, the rainfall from 85 to 110 ln. and the moisture

content of the bauxites from 5 to 14%. In the Hawaiian

Islands, where gibbsitic bauxites are forming from alkaline

basalts and andesites on the wet side only of volcanic


0
domes, the annual range of temperature is from 62 to 77 F,

the rainfall from 60 to 150 in., and the moisture content of

the bauxites from 26 to 41%. While in Jamaica, where

gibbsitic bauxites are forming on karsted tertiary limestone

plateaux, the annual range of temperature is from 60 to 80°F,

the rainfall from 50 to 95 in., and the moisture content of

the bauxite from 20 to 23%.

Climatic variation and diastrophe, during or

after bauxitization probably account for subsequent mineral-

ogical changes of gibbsitic bauxites. Under a drier envir-

onment boehmite may be produced from gibbsite and hematite

from goethite, while under reducing conditions siderite,

marcasite, pyrite and chamoisite may develop from goethite,

hematite and magnetite and kaolinite from hallosite.

Summaries of the physical, crystallograp hic and

optical properties of the three alumina hydrate minerals,

gibbsite, boehmite and diaspore, have been published by


41

Hose (8) and are shown in Table 2.1. X-ray diffraction


patterns of typical bauxite are shown ln Figure 2.1.

X-ray diffraction patterns (a) and (b) Fig. 2.1

are of diasporic bauxites derived from limestones from

Greece. Pattern (b) shows the lines of hematite and

anatase, which are the normal lesser constituents in these

bauxites and (a) is of thermally metamorphosed low-grade

diasporic bauxite in which the kaolinite has been converted

to chlorite which was identified optically as daphnite.

X-ray diffraction pattern (c) is of boehmitic

bauxite derived from limestone from France, whereas

pattern (d) is of fine-grained red bauxite derived from

limestone in Jamaica. Pattern (e) of coarsely crystalline

gibbsite occurs as pods up to 4 ft. ln length in a

low-grade supergene manganese deposit in Minas Gerais.

These gibbsite crystals fluoresce yellow under short

wave ultraviolet light. These coarse gibbsite crystals


give a very strong d = 4.82 line and a weaker d = 4.34

than usual for gibbsite in gibbsitic bauxites.

Usual alumina bearing minerals present ln the

bauxites have been published by Kuznetsov and Derevyarn-

kin (9) with its formulas as shown in Table 2.2.

As the aluminium industry developed, bauxite

exploration was stimulated and resulted in the discovery

of immense deposits in tropical countries. Known


bauxites reserves throughout the world, including Australia,

are shown earlier in Table 1a and 1b.

Although the main components of all the ores are

identical, there are many variations in the percentage of

each compound according to the location. Table 2.3


4-2

{a)

(b)

B
B (c)

(d)

G A-anatase H-hallosyte
B-boehmite He-hematite
C-calcite K-kaolinite
Ch-chlorite M-magnetite
G-gibbsite P-phosphate (e)
Go-goethite Q-quartz
Diaspore
G GG
G G ""G9G.Ar-. GTG,.,
~VWV~\fk.-.1~

Fig. 2.1 X-Ray defraction patterns of bauxites


43

Mineral Gibbsite Boehmite Diaspore

Chemica l formula

65.4 85 85

34.6 15 15

Crystal system Monocli nic Orthorho mbic Orthorho mbic

Space group

Unit axis a8.62 2.85 4.40


lengths, A b5.06 12.2 9.39
c9.70 3.69 2.84
angle 85°
26 I

X-ray diffract ion 4.82 6.11 3. 9 9


d values in A 4.34 3.16 2. 56
and intensit ies 4.30 2. 3 5 2. 3 2
of stronge st 2.44 1. 86 2.13
lines 2.37 1.85 2.08
2.03 1. 45 1. 63
1.98 1.31 1. 48
1. 79

Index of refrac- 1.568 1. 649 1. 702


tion nD 1.568 1.659 1.722
1.587 1.665 1.750

Cleavage (001)pe rfect (010) (010)pe rfect

Hardnes s (Moh) 2.5-3.5 3.5-4 6.5-7

Density 2.42 3.01 3.44

Temp. of
decompo sition

TABLE 2.1 Minerol ogical propert ies of bauxites (8)


Mineral Formula Content of
Al o wt.%
2 3

1) Corundum Al o 100
2 3
2) Diaspore, boehmite AlOOH 85
3) Hydragillate, baerite Al(OH) 65.1+
3
I+) Kaolinite Al 2 o .2Si0 .2H o 39.5
3 2 2
5) Hallosyte Al o .2Si0 .1+H 0 31+.7
2 3 2 2
6) Pyrophyllite Al 2o .1+Si0 .H 0 28.3
3 2 2
7) Allophane mA1 2 o .nsio .pH o 2 3. 5 - 1+1.6
3 2 2
8) Muscorite K 0.3Al o .6Si0 .2H 0 38.5
2 2 3 2 2
9) Hydrous muscorite K<1Al 2 [CSi,Al) o 10 J[OHJ 2 .nH 20
4
25 - 33

10) Chamosite I+FeO.Al o .3Si0 .1+H 0


2 3 2 2
13 - 20.1

TABLE 2.2 Aluminium bearing minerals present in the bauxite and its
Al o content (9).
2 3
Composition %
Grade of
Ore Proportion of
Country % Trihydrate or Monohydrate Silica Loss on
Available (Gibbsite) Ignition
(Boehmite Reactive Free Iron
Alumina Diaspore)

Australia

Darling Range 30-35 Major Nil 1-2 18-22 15-20 20


Mitchell Plateau 40-45 Major Small 2-5 20 20
Gove 50 Major Small 2-6 0.4 13-18 26
Weipa 52 40% 10% 3 2.5 7 26
Guinea 50 Major Small 1.2 0.8 24 25
Jamaica 46-50 Major Small 2. 5 17-22 26-27
Suriname 46-50 Major 4-5 1-2 8-11 26-28
Yugoslavia 58-64 Major 2-3 16-22
Hungary 50-60 Major 1-8 15-20 13-20

Greece 35-60 Major 0.5-5 15-30

Dominican 46-48 Major &mall 1-5 20 23-26


Republic
United States 50 Major 11-13 4-7 27

India 50-55 Major 1-3 7-10 28-29


-1="
CJ1
TABLE 2. 3 Composition of typical bauxites
46

published by Kirke (10) shows the composition of bauxite

taken from throughout the world.

The relative degree of hydration is an important

economic feature of bauxite. The extraction of alumina

from bauxite containing boehmite and diaspore (alumina

monohydrate) is more difficult and costly than from those

consisting largely of gibbsite (alumina trihydrate). As

shown in Table 2.3, most of the deposits from the tropical

reg1ons, including Australian deposits, can be considered

as the most economical deposits due to the higher percent-

age of gibbsite.

The higher content of silica will also decide

the economy of the bauxite deposits. For example,the

bauxite from the Darling Range has 1 - 2% reactive silica

and 18 - 22% free silica. This would also increase the

cost of operation in the process.

Other factors such as the location of the

deposits, for example, whether it is a surface deposit or an

interior deposit, will affect the quality of bauxite.

Normally surface deposits contain relatively high levels

of organic materials and their decomposition products

during the refining process tend to be compounded by the

low grade.

2.2 STRUCTURE OF ALUMINA TRIHYDRATE

There are three forms of aluminium hydroxide

which are the amorphous, gel and crystalline forms. There


are two groups of the crystalline aluminium hydroxide that

have been identified as follows:


47

Group 1 - alumina trihydrate, which exists in three

different crystalline modifications

Group 2 - alumina monohydrate (oxide-hydroxide -

AlO(OH)) which exists in two crystalline

modifications.

2.21 NOMENCLATURE

There is some confusion as to the nomenclature

relating to aluminium hydroxide. Table 2.4 summarises

various names which have been ascribed to the hydroxides.

This table is a result which evolved by some agreement at a

symposium in West Germany in 1957 (11).

2.22 STRUCTURE OF CRYSTALLINE ALUMINA TRIHYDRATE

2.221 Gibbsite (hydragillite)

Most of the bauxite deposits found in the

tropical regions of the world contain gibbsite as the major

component. This is in the form of trihydrate which is

crystallised as product during precipitation in tbe Bayer

process.
Megaw et.al.(12), Saalfeld et.al.(13) and

Wells (14) have independently investigated the structure of

gibbsite.

In Wells' work, he has described the alumina

trihydrate as a tri-clinic structure, whereas in Megaw's

work it has been described as a monoclinic (pseudo-hexagonal)

structure. The products usually obtained from the Bayer

process precipitation support Megaw's conclusion.

Kuznetsov (9) has reported that the structure of gibbsite

is very similar to the structure of brucite Mg(OH) 2 ,


Symposium (15) Weiser & Milligan (16) Edwardsi Frary and Haber Other names
1957 1934 Jeffries (17) 1930 (18)1925

UJ
(])
'Cl Aluminium hydroxide
·.-I Hydrargillite Gamma alumina Alpha alumina
~ Alumina trihydrate
0 or
!-l
'Cl Gibbsite trihydrate trihydrate Orthoaluminic acid
;:;..,
.£:
·.-I
!-l
.j.l

·.-I
s
>::
Bayerite
Alpha alumina
trihydrate
Beta alurnina UJ
(!)
·.-I
!-l
Aluminium hydroxide
Alumina trihydrate
·.-I
trihydrate (!)
E UJ
Bauxite dihydrate
::s ro
.-I
~ro
~<!;

Nordstrandite Randomite
(.9
Baverite I I
UJ Bohmite Gamma alumina Alpha alumina Bauxite
(J)
'0 (or Boehmite) monohydrate monohydrate Alurnina monohydrate
E ·.-I
::s X
·.-I 0
~ l-4
·.-I 'Cl
E ;:;.., Alpha alurnina ro
UJ
;:1 ::r:I cEJl.aspore Beta alurnina (J)
Meta alumina acid
.-I .£: ·.-!
~<!; (!) monohydrate monohydrate Pl!-l
'Cl .-I (])
·.-I ~<!; UJ
X
0

TABLE 2.4 Nomenclature of aluminium hydroxides (11)

+
CD
49

except for minor differences.

The basic structural unit of gibbsite is a layer

consisting of two sheets of closely packed, negatively

charged, hydroxyl ions bound together by positively charged

aluminium ions which occupy two-thirds of the interstices

between the hydroxyl sheets as shown in Fig. 2.2. Growth

occurs by superposition of other layers and lateral extension

of the layers. Figure 2.3 shows a model of the gibbsite

structure in which it can be seen that there are no alumin-

ium ions between the second and third layers of the hydroxyl

ions and the hydroxyl ions of the third layer are directly

over rather than lying in the depression of the second layer.

The stacking arrangement of the double sheet layers can be


1 I I

described by the symbol: AB : BA : AB : BA and so on,


I

where A and B denote the hydroxyl sheets in different

positions as shown in Figure 2.2, and the vertical dashes

represent the boundaries between the layers. In the

"c" -plane the large hydroxyl ions are approximately hexa-

gonal close packed. The small hexagonally distributed

aluminium ions are surrounded by six hydroxyl ions, three

above and three below. A characteristic of the structure

is the hole in the centre of each hexagon of the aluminium

ions.

According to Van Nordstrand et.al.(19) gibbsite

grows as hexagonal platelets aligned parallel to the layer

in the lattice. According to Oomes et.al.(20) gibbsite


0 0
crystallises as hexagonal plates below 40 C, and above 60 C

as hexagonal bars. Hence the rate of growth on the direc-

tion of the C - axis apparently depends more on temperature


so

B
.B

-----A

Al at 1/3 2/3

Al at 1/6 5/6

Fig. 2.2 Structure of hydragillit e

c- plane

Fig. 2. 3 Models of hydrogillit e

Fig. 2.4 Electron-mi crograph of hydragillit e crystal


51

than the rate of growth in the direction of the other axis.

The hexagonal plate structure is easily recognised in

Figure 2.4 which is an electron micrograph of a small

gibbsite crystal.

According to Megaw et.al.(12), Betexin (21) and

Ormont (22) (who reported separately) the unit cell of

gibbsite consists of eight ions of aluminium and twenty-

four of hydroxyl which corresponds to eight units of

The dimensions of the unit cell lattice have been


0
reported by Betexin et.al. as a= 8.624°A, b = 5.060A ,

0 0 ~
c = 9.7A , S = 94 34 (21) whereas according to Ormont

s = 85° 26~.

2.222 Bayerite

The hydroxide bayerite was named after the founder

of the Bayer process, K.J. Bayer. Unlike gibbsite, bayerite

lS not found ln nature (except for a very few, rare

occurrences) . The existence was first reported by

Fricke (23). Aranderenko et.al. (24) reported the possible

formation of bayerite by passing carbondioxid e through a

solution of sodium aluminate containing 200 g/litre of

A1 0 at room temperature without any seeding. Bayerite


2 3
also can be produced by heating gibbsite to 200°C under
2
pressures in the vicinity of 30,000 kg/cm (25).
According to Fricke (23), bayerite can also be

found ln an intermediate form between bayerite and gibbsite.

According to Montoro (26), bayerite is also

crystallised in a hexagonal form in which the unit cell

consists of two ions of aluminium and six hydroxyl lons,

and the cell dimensions are a 0 = 5.01°A and c 0 = 4.76°A.


52

Funaki et.al. (27) has reported similar results with a

difference of 0.01°A in all dimensions. Sasvari (28)

has suggested that the structure of bayerite is monoclinic,

but that the unit cell consists of four molecules of

Al(OH) instead of two. Belov (29) has suggested the


3
structure of the crystal of bayerite as shown in Figure 2.5.

Fig. 2.5 Structure o£ bayerite (29)

2.223 Boehmite

This mineral was named after Byoma who was the

first person to discover it. Boehmite is usually found

in nature as diaspore boehmite or as the boehmite

hydragillite type bauxite. Crystals of boehmite can be

obtained by heating either hydragillite, bayerite or


53

- alumina, with water in an autoclave or in a hydro-

thermal bomb (30,31,32). Formation of boehmite has also

been reported by Diana et.al. (33) as a result of heating a

mixture of aluminium nitrate and nitric acid at 320 -

360°C under a pressure of 200 - 300 atm.

Boehmite crystallises in the rhombic system.

The structure of the crystal of boehmite is believed to be

as shown in Figure 2.6 (9).

Fig. 2. 6 Structure of boehmite

In boehmite the refractive index was found

to be in the range of 1.654 - 1.661 (34) and the density


. -3 0
of pure boehm1te 3.014 gm cm at 20 C (35).

Cryst~l structure was reported by Betexin (21)

and Diana et.al. (33) as having a unit cell with dimensions:


54

a
0
= 3.78 0 A c
0
= 2.85A0
The crystalline structure of boehmite is very similar to

the structure of lenidocktrite (goethite) FeOOH as shown in

Figure 2.6. Every F e +3 ('ln b oe h mlte


. Al +3 lon
. ) lS

surrounded octahedrally by six ions of oxygen (21).

2.224 Diaspore

Diaspore has a similar composition to boehmite

and it is normally found in diaspore or in the mixture of

diaspore-boehmitic type bauxites. It is also found as the


mineral in a pure form in the Naksos region of Greece and

Koksoi Brod (Sverdlovski region) and Aktas (Republic of

Usbekistan) of U.S.S.R., where it is combined with corundum

and aluminium silicate.

The artificial preparation of diaspore was first

reported by Laubengayer and Weisz (31) and it can be formed

from boehmite or y-kaolinite by heating at temperature

of 280°C - 450°C, for a time interval of 50 - 200 hours

ln the presence of natural or artificial diaspore (2%) as

seed material.

Diaspore as boehmite crystallises in the rhombic

system in a rhombo-dipyramidal habit. The structure

(which corresponds to the formula H Al o ) is reported to


4 4 8
have the following unit cell dimensions:

a
0
= 4.40 0 A b0 = 9.39A0 c
0
= 2.84A
0
(21,33).

The typical structure lS represented diagrammatically ln

Figure 2.7.
55

Fig. 2.7 Structure of diaspore

2.3 BAYER ALUMINIUM TRIHYDROXIDE AND ITS PHASE


TRANSFORMATIONS

The crystalline aluminium hydroxide obtained

under Bayer process conditions is essentially the tri-

hydroxide gibbsite (mono-clinic form),but in some work it

has been reported that there are other compounds (boehmite

and diaspore) precipitated in the process.

A portion of the phase diagram of the Al o


2 3
-

H 0 system taken from Kennedy (36) is shown in Figure 2.8.


2
Kennedy reported that at one atmospheric pressure hydrag-

illite slowly breaks down to boehmite at about 90°C.

However, he states that the transition probably takes place

at much lower temperatures but at rates which are much

slower. According to Laubengayer and Weisz (31) this

transition occurs at 155°C whereas Ginsberg et.al. (37)

have reported temperatures in the range of 150 - 200°C

for the transition.


56

3
As shown in Figure 2.8, at pressures of 26 x 10
2
to 40 x 10 3 kg/cm , and with heating up to 260°C, hydragill-

ite can be transformed to diaspore, but at lower pressures

hydragillite is first converted into boehmite and then to

diaspore.

2
kg/cm
40,788
Hydragillite
(Gibbsite) Diaspore + Water
Al 0 .3H 0
2 3 2
30,591

20,394

Metastable
Boehmite
0~----~----~~--~~----_. _______
100 200 300 400 500 600°C

Fig. 2.8 Diagram of equilibrium system of


Al o - H 0 at higher pressures (36)
2 3 2

In the Bayer process it is usually assumed that

the primary product obtained in the precipitation is

gibbsite, but there are also some conflicting reports

regarding the possibility of forming boehmite during pre-

cipitation at the higher temperatures in the range of

temperature where precipitation occurs. Thermodynamic

stability calculations also indicate that both gibbsite

and boehmite are stable under Bayer process conditions.


57

The use of thermodynamic stability diagrams to explain

stabilities under Bayer process conditions is reported in

Appendix I.

Sakamotos (38) has reported in his work that

crystallisation studies carried out under conditions close

to those employed in the Bayer process yielded products

containing both gibbsite and bayerite (at both 30°C and

50°C), but bayerite was not formed at 80°C. Bayerite was

formed at the initial stage of the experiments where the

temperature was kept constant at 30 0 C or 50 0 C, but later

the proportion of bayerite to gibbsite decreased with time.

More bayerite formed at 30°C than at 50°C.

Furthermore, almost an equal amount of gibbsite

and bayerite was obtained in this work when bayerite was

used as the seed at 30°C up to a time limit of 24 hours.

Bayerite seeds for Sakamoto's experiments were prepared by

bubbling carbon dioxide into sodium aluminate solution at

Boehmite seeds were produced by treating Bayer

process gibbsite hydrothermally for 2 hours at 200 0 C. The

results obtained in his experiments are presented in

Table 2.5.

According to Sakamoto's results, the ratio of

gibbsite : bayerite changes slightly with the type of seed

added. For example, when bayerite seed is added, the

quantity of bayerite formed during the early stages

increases and when gibbsite is added, the quantity of

bayerite formed decreases. However, the precipitated

hydrate is not all bayerite when bayerite seed is added.

When alumina monohydrate (boehmite) is added, there is no

great change in the ratio of the two hydrates, but the rate
58

Temp. Time Decompn., Amount precipitated


oc hr. %

Gibbsite Seed
30 24 16
48 40 G > B
72 55 G > B
96 60 G>> B

50 24 36 G>> B
48 50 G>> B
72 55 G>> B

80 24 16 G
48 22 G
96 27 G
Bayerite Seed
30 24 22 G B
48 50 G > B
72 62 G > B

50 24 30 G > B
48 51 G>> B
72 57 G>> B
Boehmite Seed
30 24 3
48 19 G = B
72 32 G > B
96 55 G>> B

60 24 6 G>> B
48 29 G>> B
72 53 G>> B
96 56 G>> B
No Seed
30 72 0
96 11
120 33 G > B
144 48 G >>B
168 58 G >>B

80 72 0
96 12 G
120 18 G
144 21 G

TABLE 2.5 Crystalline forms of product trihydrate


obtained from Sakamoto's decomposition
experiments.
G gibbsite B bayerite
59

of precipitation decreases. It can therefore be concluded

that the kind of seed has a definite effect on the rate of

precipitation but does not have a great effect on the

crystalline form of the precipitated trihydrate.

Chistyakova (39) has shown that bayerite is the

stable solid phase in equilibrium with a solution correspond-

ing to Bayer process concentration at 20°C. With increas-

lng temperature there was an increase in the proportion of

gibbsite.

According to Arakelyan et.al. (40), only gibbsite

is precipitated from sodium aluminate solutions at 65°C,

regardless of the nature of seed (boehmite or gibbsite ).


·
However, a t t emperat ures Of 95 °c , b oe h ml"t e lS a 1 so preclp-

itated when boehmite seed is used and gibbsite when gibbsite

seed is used.

Kavina et.al. (41) have detected a small amount

of bayerite in an industrial Bayer process precipitation.

According to them, the presence of bayerite in Bayer process

precipitate plays a significant role in the increase in the

relative amount of fines in the product. They consider the

action of atmospheric carbon dioxide on the cold solution

to be a major factor in the formation bayerite under indus-

trial conditions.

In summary it can be concluded that there have

been many conflicting reports regarding the conditions of

formation and the stability of the three different forms of

crystalline aluminium hydroxide. However, the results of

most of the work suggest that gibbsite is the stable

crystalline form under. Bayer process precipitation conditions.


60

Although the formation of bayerite takes place at the

initial stage of precipitation, most of the workers cited

believe that there is a rapid transformation of this bayer-

ite into gibbsite under the usual Bayer process precipitation

conditions, thus explaining the absence of bayerite in the

Bayer process precipitation product.

2.4 THE EXTRACTION STAGE IN THE BAYER PROCESS

Generally, alumina occurring in bauxite ln the

trihydrate form is readily attacked at low temperatures by

liquors of relatively low soda concentration, while mono-

hydrate alumina is economically extracted only at higher

temperatures using liquors of higher soda concentration.

Notable in modern practice lS the increasing importance of

mixed ores with alumina present in both trihydrate and

monohydrate form.

The extraction conditions are normally chosen to

be suitable for the economics of the plant as a whole and

not as dictated solely by the extraction of alumina.

For mixed monohydrate and trihydrate ores as

found in Jamaica, Queensland or Ghana, economic factors

such as plant site, determine whether they should be treated

for recovery of the gibbsite only or whether the generally

more expensive recovery of the boehrnite is justified. If


the latter, then two processes are available. In the
first, the ore is considered as being boehrnite alone and

the extraction conditions arranged accordingly. In the


second, gibbsite is extracted ln a first extraction step

and the residue re~worked for extraction of the boehrnite.

This is particularly applicable where the proportion of


61

monohydrate is small but the ore cost is high due to the

long distance of transport. This latter procedure is the

normal practice in the United Kingdom when using Ghana ore

although a plant in Ghana would probably use a single

gibbsite extraction process alone. The Queensland and

Jamaican ores contain much higher proportions of monohydrate

and the single high-temperature process is used in their pro-

cessing.

Extraction conditions are usually chosen to

facilitate the process of removal of silica. Silica corn-

bined as clay and other silicates dissolves early in the

extraction process. Silica present in the bauxite as quartz

is generally not attacked during extraction at lower tern-

peratures but is attacked to an increasing extent at higher

temperatures. Silica dissolved during the extraction

process must be eliminated from the solution as sodium

alumino silicate, and is therefore responsible for loss of

soda from the circulating liquor and for reduced recovery

of alumina from the ore. The choice of extraction condi-

tions is usually such that quartz attack is at an economic

minimum, and that optimum desilication of the product liquor

lS affected.

Extraction conditions must also be selected so

that the product liquor can readily be recycled into the

feed liquor. Furthermore, the extraction conditions must

be chosen, in such a way so that premature decomposition

will not take place.

Generally, for economic operation, extraction of

monohydrate is carried out at temperatures above 180 0 C,

and with relatively concentrated solutions containing up to


62

320 g/litre free of caustic Na 2 o. The solubility of

trihydrate is higher and extraction can be carried out at

lower temperatures up to 150°C using weaker solutions. At


0
temperatures above about 140 C, and at a rate increasing

with temperature and soda concentration, trihydrate is

converted to monohydrate, so that a solution prepared under

trihydrate conditions, if containing alumina in excess of

that soluble under monohydrate conditions, if heated above

140°C, will deposit monohydrate.

The solubilities of alumina under extraction

condition for both trihydrate and monohydrate in the form of

equilibrium ratio (weight Al 2 o3 /weight Na 0) curves are shown


2
in Figures 2.9 and 2.10. Pearson (43) has reported that

extraction obeys a kinetic law similar to that governing

decomposition. In practice extraction is based on the

attainment of the required extraction efficiency under produc-

tion conditions for the particular ore, and also desilication

of the solution after alumina extraction. Pearson's

equation for extraction rate is as follows:

2
dx (xt - xoo)
-dt = kAt-----------
(aoo + xoo)2

where K is a parameter dependent on temperature only; At is


2
the area of solid bauxite surface, m /litre at time t,

hours : xt and X 00 are the molar concentrations of NaAl0 2

at time t and at equilibrium, respectively; and a 00 is the

molar concentration of NaOH at equilibrium.

Kuznetsov and Derevyarnkin (9) in this work have

recommended a very similar rate formula for extraction as


63

0
N
~ 1.55
......._
("')
0
N
r-1
.:1!
--:- 1. 35

!
0
:j 1.15
('(j
l-1

~
·~ 0.95
,.Q
·.-!
r-1
·.-!
&o. 75
fil 0 40 80 120 160 200 240
Free soda concentration g/1 Na o
2

Fig. 2.9 Equilibrium rates for trihydrated alumina


0
over a temperature range of 100 to 140 C (42)

1.45
0
N
('(j

~ 1.25
("')
0
N
r-1
.:1!
--:- 1. 05 -
! 0
·.-!
~ 0.85
l-1

•.-!
~
~ 0.65
·.-!
r-1
·.-!

i 0.45 0 50 100 150 200 250


Free soda concentration g/1 Na
2
o

Fig. 2.10 Equilibrium ratios for monohydrated


alumina over a temperature range of
100 to 250°c (42)
64

follows:

dx
= KA ( y - x)
dt

where A = area of the solid phase

y = concentration of Al o
2 3
in the inter-

mediate phase

X = concentration of Al o
2 3
in the whole mass

of the solution

K = constant.

By considering A and to be constant for a short interval

of time, the equation could be formulated as follows:

dx
dt = K1 ( y - X)

and by integrating the above formula:

X =y
1
K has the units of t- . This formula lS well in agree-
1
ment with the results of the experiments conducted by

Herrman ( 44).

2.41 FACTORS AFFECTING THE EXTRACTION

According to Kuznetsov and Derevyarnkin (9) the

following are the main factors affecting the rate of ex-

traction of aluminium from bauxite.

1) The physical structure of the bauxite

2) The mineralogical composition of bauxite

3) The surface properties of the bauxite,

including surface area

4) Temperature

5) Stirring rate

6) Activating substances

Kuznetsov and Derevyarnkin have reported that (as shown 1n


65

Figures 2.11 (a,b,c) the rate of extraction is not greatly

dependent on temperature, but basically more dependent on

diffusion, and he gives the following equation:


dx DA
= -- (x s - x)
dt = KA (x s - x) 0

where dx
dt = rate of dissolution of bauxite

K = coefficient of the rate of dissolution

which is equal to the ratio of diffusion

coefficient (D) and the thickness of the

diffusion layer (o)

A = surface area of the crystals of gibbsite

in bauxite which are in contact with the

solution

= equilibrium concentration of Al 2 o3 ln

the caustic solution

X = concentratio n of Al 2 o3 in the solution at

the given time.

Kuznetsov and Derevyarnkin have also shown diffusion to be

related to temperature by the equation


RT
. 1
D = N 311dll
R = gas constant

N = avagadro number

11 = viscosity of solution

d = diameter of particles.

With an increase ln temperature, viscosity de-

creases and therefore the diffusion increases. Furthermore,

when the temperature is increased, solubility of aluminium

hydroxide is also increased, thereby the difference of

But it should also be considered that with the

increase of concentratio n of the aluminate solution (at


Dissolution %
100
0- 150°C

d- 175°C

80 e- 210°C
X- 230°C

60

40 ~/
.
0-

-
120°C

·-
150°C
0
0- 150 c
210°C
11 x- 210°c
20
v- 0
11s c

D- 230°C

0 1
J
2
I0
I I
1 2 2
0 1
TIME (Hours)
a b c

Fig. 211 Rate of dissolution of a) gibbsite b) boehmite c) diaspore.

m
m
67

constant caustic ratio), viscosity is increased, and so the

rate of diffusion is decreased. However, in this process

as the Xs - X is increased, the isotherm will be increased

and in this manner XS - X increases faster than the change

of viscosity, and so will keep the rate of dissolution

increasing.

Kuznetsov and Derevyarnkin have also reported

from other literature the effect of some of the mineral

impurities on the rate of dissolution. The effect of

silicates, iron, sulphide, titanium and carbonate bearing

minerals and lime on the dissolution of bauxite are reported.

Impurities such as silicagel and kvartz have a negative

effect on the rate of dissolution but the presence of iron

containing minerals favour the dissolution.

2.42 EFFECT OF ORGANICS ON THE DISSOLUTION OF BAUXITE

Accumulated organic material in the recycle

caustic liquor is also believed to affect the extraction

rate. Kuznetsov and Derevyarnkin (9) have reported in

their publication some of the work done in relation to this

proposition. According to them some of the organic corn-

pounds present in the recycled caustic liquor promote the

extraction. It was found that aluminate solution taken

from the plant and used to leach bauxite is more effective

than the synthetic solution. Organic impurities with

hydroxyl radicals appear to activate the dissolution,

whereas the rest of the organic is believed to be increas-

ing the solubility of bauxite in the aluminate solution.

Sodium salts of oxalic and acetic acids have no effect on

the dissolution. However, organic impurities which are


68

soluble 1n benzene reduce the rate of dissolution.

It has also been found that different fractions

of similar organic compounds have different effects on the

dissolution of bauxite in caustic soda. For example,

higher molecular weight compounds reduce the rate at 210°C

whereas they accelerate the rate over 230°C. Sodium

oxalate reduces the rate of dissolution considerably between


0
210 and 230 C.

According to Kuznetsov and Derevinkin (45) the

electronmicroscopic observation of crystals of aluminium

hydroxide indicates a uniform dissolution of the particles in

the solution during the extraction in the presence of

organic impurities. They believe that this may be due to

adsorption of some of the organic on to the surface of the

hydroxide crystals, thereby preventing further contact

between the caustic and the hydroxides crystals.

2.5 SEPARATION OF RED MUD

Separation of the red mud from the alumina rich

liquor from the Bayer process is carried out by sedimenta-

tion followed by classification and filtration. This part

of the process has an enormous influence on the plant cost

and product quality. Firstly to produce a rich aluminate

liquor sufficiently free from suspended solids to prevent

contamination of the hydrate deposited later. The second

objective is to remove as much as practicable the adhering

caustic liquor from the mud before disposal, using a

minimum amount of wash water.

The efficiency or the rate of sedimentation

depends on many factors such as the mineralogical composi-


69

tion of the solids, the conditions that were applied in

the extraction stage) the dispersion and other conditions

in the sedimentation stage itself.

The mud always possesses some degree of

flocculation depending on the type of ore and the extraction

conditions but it is universal practice to increase this by

the addition of starch ln some form (for example, bran,

potato starch or maize starch) pre-treated with caustic

solution.

2.6 DESILICATION

The control of silica in the Bayer process

circuit is most important to ensure that the required

purity of the alumina is obtained. Adamson (4) in his

report, has illustrated the role of silica in the form of a

silica cycle in the Bayer process as is shown here in Fig. 2.12.

Silica normally exists ln bauxite in two main

forms: firstly as reactive silica and as minerals of the

kaolinite type which are rapidly attacked by caustic liquor

under the extraction conditions; secondly, silica exists

as quartz which is not readily attacked by caustic liquors

at low temperatures but increasingly attacked at higher

temperatures causing corresponding loss of alumina and

caustic soda.

Simultaneously with the solution of the silica,

desilication of the solution occurs by deposition of rela-

tively insoluble triple compound (xA1 o


2 3
.y Na 2 0.z Si0 2 ).

The rate of deposition is accelerated by the presence of

the triple compound in the solid phase acting as a seed

and by high temperature.


70

Si0 in ore
2

Extraction &
l I I
I Evaporation I
Dilution

solid
3Na o
2
3Al 0 Extract
5Si0
2H 0
2 3
2
15-30g Si0
2 I Decomposition
I
I
Hydrat e
2 0.012% Sio
2
in Al o
2 4

Conditioning
Retention
at 105°C
Hot
Solid
I
liquor J
0 . 55g.Sio l
Cooler I
I
2
Triple compound per 100g NA20
discarded with
red mud

Fig. 2.12 Silica cycle in the Bayer process

It is essential in the process control of a

Bayer plant to reduce the silica in the liquor passing to

the crystalliser to such a value that contamination of

the hydrate produced during crystallisation is minimised.

This desilication process is only partially completed in

the extraction plant and hence it is necessary to have a

conditioning step in the process. According to Adamson (4),

the desilication of sodium aluminate solutions appears to

follow a monomolecular rate law of the form

where S is the concentration of silica in the solution.

The equilibrium silica S 00 is independent of temperature,

but is proportional to the alumina and free soda concen-

trations.
71

The primary desilication product is believed

to be the triple compound itself. Hence the best desili-

cation conditions are to dilute the extraction slurry to

the new liquor strength and ratio thereby keeping the silica

deposition potential at a maxlmum and maintaining a high

temperature as practicable until the silica content is

reduced to the desired level. In practice the alm lS a

figure of not greater than 0.55 - 0.60 Si0 per 100 g of


2
free soda in the solution.

The role of silica in the Bayer process can be

explained by the use of the stability diagrams calculated

by the author and presented in Appendix I.


CHAPTER 3

ORIGIN, IDENTIFICATION, EFFECT AND REMOVAL OF


THE ORGANIC IMPURITIES IN THE BAYER PROCESS
72

It is commonly accepted in the alumina industry

that organic impuritie s adversely affect the precipita tion of

alumina trihydrat e. These observatio ns are, however, mostly

based indirectly on plant operating experienc e and very little

direct informatio n is available on actual identifica tion and

effects of these impuritie s.


It was firstly Pearson (43) who discussed the

poisoning effect of impuritie s on the seed and the consequen t

slowing down and even bringing to a complete stoppage the

precipita tion rate of alumina trihydrat e. He also stated

that effective poisons are high molecular weight organic

substance s containing hydroxyl groups like saponin, green

arabic, cane sugar~ etc., but that sodium oxalate appeared

to have little effect. Dissolved calcium and iron salts

are the most common inorganic impuritie s which cause poison-

ing according to Pearson who also stated that the effective -

ness of poisons decrease with increasing temperatu res.

However, his statement s in regard to this matter were with-

out any experimen tal evidence and were merely based on

conjecture relating to plant experienc e.

3.1 ORIGIN OF ORGANIC IMPURITIES IN BAYER PROCESS LIQUOR

Organic matter enters the recycled caustic liquor

from two main sources.


1) Organic matter present in the bauxite

2) Starch added as a flocculati ng agent in

the red mud separation stage.

Bauxite usually contains from 0.1 to 0.3% by

weight of organic carbon, but occasiona lly up to 0.6% is


73

found when surface bauxites are mined. It is generally

believed that the organic carbon is present in the form of

humic substances.

Uteley (46) has reported on the or1g1n and

nature of organic matter found in Arkansas bauxite. He

believes that the bulk of the organic matter comes from the

overburden, and especially from the lignitic clays. It is

believed to be composed mostly of humic acids, humates and

their oxidation products. The oxidation products of these

humic acids, after extraction with sodium hydroxide, may be

degraded into many different compounds. However, these con-

clusions were not based on any direct experimental results.

Other possible sources of organic carbon in

Bayer process liquor are the flocculants and antifoams used

in the process. The contribution of these organics to the

total organics present in the liquor is believed to be small

and this presentation will therefore concentrate only on the

organic matter originating from the bauxite.

Kirke (10) has reported on the likely organic

impurities in the Darling Range bauxite and their behaviour

in the Bayer process. He believes that their organic

material is derived largely from decomposed vegetation and

roots and consists of many substances, such as humus, lignin,

cellulose and protein. Under the alkaline oxidative condi-

tions existing in the Bayer process these complex organic

compounds break down through a series of stages as outlined

below to simple compounds such as the sodium salts of

succinic, acetic and oxalic acids and carbon dioxide. Pre-

dominant among these salts is sodium oxalate .


74

Humus cellulose etc.

!
Humates + co 2
l
Coloured Humic Acids + co 2
l
Polyhydroxy Compounds + co 2
~
Oxalic, Acetic Acids + C0 2

l
C0 2 + H2 0

These suggestions by Kirke are based only on

the behaviour of humic substances in the environment as

described by previous workers.

3.2 HUMIC SUBSTANCES IN THE ENVIRONMENT

Humic substances are probably the most widely

distributed natural products on the earth's surface, occurr-

ing in soils, lakes, rivers and 1n the sea. In spite of

their extensive distribution, much remains to be learned

about their origins) synthesis, chemical structure and

reactions.

The organ1c matter of soils and waters consists

of a mixture of plant and animal products in various stages

of decomposition, and of substances synthesized biologically

and/or chemically from their breakdown products and of

microorganisms and small animals and their decomposing

remains.

Schnitzer and Khan (47) have classified the


75

organic compounds ln soil into two groups:

(a) non-humic substances, and

(b) humic substances.

Non-humic substances include compounds that

exhibit still recognizable chemical characteristics. To this

class of compounds belong carbohydrates, proteins, peptides,

amino acids, fats, waxes, resins, pigments and other com-

paratively low-molecular-weight organic substances.

The bulk of the organic matter in most soils and

waters consists of humic substances. These are amorphous,

brown or black, hydrophilic, acidic, polydisperse substances

with molecular weights ranging from several hundreds to tens

of thousands. Based on their solubility in alkali and acid,

humic substances are usually divided into three main fractions:

(a) humic acid, which is soluble in dilute alkaline solution

but is precipitated by acidification of the alkaline extract,

(b) fulvic acid, which is that humic fraction which remains

in the aqueous acidified solution, i.e. it is soluble in both

acid and base, (c) the humic fractions that cannot be extract-

ed by dilute base or acid, which are referred to as humins.

3.21 THEORIES ON THE FORMATION OF HUMIC SUBSTANCES

The mechanism of formation of humic substances is

still a highly speculative matter. It has been suggested

that they result from bacterial and chemical degradation of

plant tissue followed by secondary processes in the soil.

These latter processes include polymerization of the plant

polyphenols, condensation of these with amino acids and meta-

bolites from soil micro-organisms and finally complexing


76

with sesqui-oxides and silica. A diagrammatic repres-

entation of these processes is shown in Figure 3.1.

Lignin and lignin:--like Plant polyphenols


materials acting as reacting with amino
polyphenols to complex acids in the plants
with amino acids and soils

Humic Acids

Lignin oxidation products Cellulose polysacharides


being de-polymerized and ~sugar utilizable by
eo-polymerized with other micro-organisms-- ---
plant phenols and amino shikimic acids--~~
acids polyphenols which react
with amino acids

Fig. 3.1 Formation of Humic Acids

3.211 FELBECK'S HYPOTHESIS

Felbeck (48) in 1971 suggested four possible

mechanisms for the synthesis of humic substances.


77

a) Plant Alteration

According to this hypothesis, fractions of plant

tissue (especially lignified tissue) are changed to form

humic substances at or near the soil surface. The higher

molecular weight fractions, humins, are formed first, then

bacterial degradation takes place to form humic acids, fulvic

acids and finally carbon dioxide and water.

b) Chemical Polymerizatio n

This hypothesis assumed that plant materials are

attacked by bacteria to form small molecules. These mole-

cules are used by microbes to synthesise products such as

phenols and am1no acids which are then excreted. Humic sub-

stances are formed as products of chemical oxidation and

polymerizatio n of these excretions.

c) Cell Autolysis

Humic substances are formed from plant and

bacterial cell autolysis as the products of random conden-

sation and free radical polymerizatio n of cellular debris.

These reactions are assisted by autolytic enzymes.

d) Microbial Synthesis

This hypothesis assumes that plant tissue is

used as a source of carbon and energy by microbes to produce

high molecular weight humic-like substances. These sub-

stances are syntherized by microbes intercellula rly and

only released into the soil when microbes die and their cells

are lysed. This stage is followed by extracellula r

degradation to form humic acids, fulvic acids and finally

carbon dioxide and water.


78

3.22 OCCURRENCE OF HUMIC SUBSTANCES IN MINERALS AND ITS

RELATIONSHIP TO BAUXITE

Humic substances are accumulated in surface and

sub-surface soil layers, in and beneath marsh deposits, 1n-

shore and in beach sands. It is believed that the humic

materials are leached from decaying plant materials or humus

on the land surface and transported by surface and sub-surface

waters 1n a soluble or colloidally dispersed form to sub-

surface sand environments or to brackish or saline waters

where flocculation or precipitation of the humic substances

is triggered by various physical-chemical mechanisms. One

or probably a combination of the following mechanisms may

be responsible for precipitation:

a) the adsorption or complexing of dissolved cations such


as Al+ 3 , Fe+ 3 and Mg 2 +

b) complexing with clay minerals and

c) a lowering of pH.

Dissolved aluminium is involved in the important

processes of rock weathering and soil development, but there

has not been much literature available to explain the

occurrence of these humic substances in the clay minerals

such as bauxite. However, supporting evidence to this

question can be gained from the work done on the association

of humic substances with aluminium in soil and natural water.

Pauli (49) described strong complexes formed by humic acid

and aluminium. Kavrichev et.al. (50) demonstrated the

possible binding of a measurable amount of dissolved alumin-

ium with dissolved organic matter, in soil water in the

normal pH range.
79

Lind and Hem (51) reported the possibility of

forming aluminium complexes with naturally occurring organic

compounds, such as humic substances, in natural water. The

functional groups in these humic substances are most likely

to be involved in metal complexation reactions, since protons

are released during such reaction (47). The extent of com-

plexation of a metal thus depends not only on the stability

constant of the metal-ligand complex but also on the acid

dissociation constant of the acidic functional group which

serves as the complexing ligand.

Hoefs (52) in his book went so far as to say that

"many geological model cases which have been treated as pure

inorganic systems are not realistic at all, because, especially

in sedimentary geology, there are no pure systems without

organic matter or micro-organisms". Also Schnitzer (53)

stated that there is increasing evidence that the most impor-

tant component of soil solution is fulvic acid, as it is

likely it affects practically all reactions occurring 1n

soils.

There is strong evidence to suggest that the

humic substances present in bauxite are 1n a very complex

form a part of which is associated with both aluminium and

iron present in the bauxite. During the Bayer process

extraction, these humic substances are leached into the

caustic liquor producing a brown colouration, probably in

a very different structure to the occurrence in the mineral

before processing.

3. 2 3 CHARACTERIZATION OF HUMIC SUBSTANCES

Schnitzer and Khan (47) have reported on the


80

distribution of the major constituent elements in humic

compounds. Functional groups analyses shed light on the

occurrence of major functional groups ( -co 2H, -OH, and

=C =0 ). The predominant elements are carbon and oxygen

with the carbon content of humic substances ranging from

50 - 60%, oxygen content from 30 - 35% and percentages of

hydrogen and nitrogen ranging from approximately 4 - 6% and

2 - 4% respectively. The sulphur content may vary from

close to zero to between 1 - 2%.

3.231 FUNCTIONAL GROUPS IN HUMIC SUBSTANCES

The literature available on humic substances in

the environment and in bauxite in particular indicate that

these substances are very complex in structure and properties.

The structure and properties of these humic substances

depend on the location, geographical and geological condi-

tions such as climate, weathering, and soil conditions and

also on the vegetation of the area. The analytical results

obtained on humic substances from the same location differ

in structure and properties due to the wide range of

complexity.
Therefore most of the reports made ln the last

decade on this subject have been speculative. However, it

is generally accepted that humic substances are complex

polymers which possess both carboxyl, phenolic, hydroxy

and acidic functional groups.

In normal systematic organlc analysis and in

instrumental analysis, very often the sample has to be chem-

ically treated, so that it suits the particular method of

analysis, but in doing so, the structure of these humic


81

organics are likely to be changed. Due to such complexity

of humic substances, many workers have given priority to

determining the functional groups quantitatively, as such

determination is a useful guide for further investigation of

the structure, but most of this work has been limited to

humic substances in natural waters and soils.

(a) Oxygen containing functional g~oups

The most possible oxygen containing functional

groups believed to be present in humic substances are the

carboxylic and phenolic groups. There have been varlous

methods used in determining the functional groups in humic

substances. Many workers in the early stage used poten-

tiometric titration methods to characterize acidic functional

groups to determine the concentration of carboxyl and phen-

olic hydroxyl groups, but this method was not successful due

to the complexity of the humic substances, and particularly

due to 1the presence of components in the humic substances

which may take a longer period to complete full oxidation.

Therefore the end point of potentiometric titration is

always inaccurate.

The concentration of carboxyl and phenolic

hydroxyl groups in humic substances is more often determined

using a calcium acetate exchange reaction and the barium

hydroxide total acidity reaction. The specificity of

these reactions however has been questioned. The author

believes that these methods can be successfully applied only

after the humic substance is extracted as a separate fraction,

as otherwise the other low boiling carboxylic acid groups and

the inorganic acid groups such as sulphate and chloride

could interfere.
82

The calcium acetate method is based on the reaction

between calcium acetate and humic acids as follows:

Before the reaction a total acidity of the humic acids is

detected by the barium hydroxid e method and then after the

addition of calcium acetate , the acetic acid is titrated

with a standard solution of sodium hydroxid e. In this

method there is an error claimed to be due to the reaction

of calcium acetate with some of the more weakly acidic

phenolic groups.
Perdue (54) claimed from his work that calori-

metric titratio n is the most accurate method of determin ing

the carboxy lic and phenolic content in humic substan ces.

The method of titratio n calorim etry was recently used by

Perdue to charact erize the acidic function al group of humic

acids. This work was done as part of an overall evaluati on

of techniqu es for· charact erizatio n of acid-bas e and metal-

ligand reaction s of humic substanc es in river water. Perdue

has determin ed by this method the concent ration of carboxy l

and titrable phenolic hydroxy l groups, their respecti ve

average enthalpi es of ionizati on (~H),


a
and the average

pK of the titrable phenolic hydroxy l groups. His studies


a
have been limited to river water humic substanc es.

Accordin g to Perdue, the thermom etric titratio n

curves, in which the amount of heat evolved is determin ed

for a series of titrant addition s (sodium hydroxid e

solution s), were establis hed. In these curves the initial

slope of approxim ately -56 kJ/mol has clearly indicate d

that carboxy l groups are being titrated , while the non


83

linear portion of the titrati on has indica ted weaker acidic

functio nal groups (presum ably phenol ic hydrox yl groups ) as

being titrate d in the latter part of the titrati on.

Althou gh these method s have been used satisfa ctor-

ily to charac terise the humic substan ces in natura l water,

they must be furthe r extend ed for examin ing the organi c

materi als presen t in such as clay minera ls.

For determ ining the total hydrox yl in humic

substa nces, acetyl ation with acetic anhydr ide in pyridin e

has been recomm ended by Brooks et.al.( 55). This method

which is being widely used can be represe nted by the

equatio ns:
ROH + (CH 3 C0) 2 0 CH COOR + CH 3 COOH
3

H 0 + (CH 3 C0) 2 0· 2CH COOH


2 3

The excess anhydr ide is hydroly zed to acetic acid, which is

titrate d with standa rd base. The phenol ic hydrox yls are

calcula ted as follow s: Total acidity - carbox yl group

acidity = phenol ic hydrox yl group acidity . There is no

direct method to determ ine alcoho l hydrox yls consid ered

that alcoho l hydrox yl groups are less reactiv e than

phenol ic hydrox yl groups . Estima tes of alcoho lic hydrox yl

groups can be obtaine d indire ctly by taking (total hydrox yl -

phenol ic hydrox yl= alcoho l hydrox yl).

The determ ination of carbon yl CC = 0) groups

presen t in humic substan ces is reporte d by Fritz et.al.( 56).

This proced ure was based on the reactio n of humic substan ces

in methan ol - 2 - propan ol with an excess of hydrox ylamin e.


84

R1 R1
~ ~
C =0 + NH 2 0H.HC1 --~- C - NOH + HCl + H 0
- 2
/
R 2
R/ 2

The unreacted hydroxylam ine is titrated with standard

perchlori c acid solution. Brown (57) has developed a method

for estimating the carbonyl group which is based on their

reduction to - CH 2 0H with sodium boro hydride (NaBH 4 ).

The reduction is carried out in alkaline solution and the

hydrogen liberated from the unused NaBH 4 is estimated

manometr ically.

However, the most widely used method for carbonyl

group determina tion is based on the formation of derivativ es,

especially oximes and phenyl-hy drazones (58).

From various functiona l group analyses, the value

of the proportion of oxygen in the functiona l groups of humic

substances was collected and published by Schnitzer and

Khan ( 4 7). Table 3.1 indicates that between 68% and 91%

of the oxygen in humic acids and humins can be accounted for

1n the functiona l groups, whereas more than 90% of oxygen

1n fulvic acids is similarly distribute d. In general, most

of the oxygen in humic substance s, especiall y 1n fulvic acid,

is present 1n -co 2 H groups, phenolic -OH and C =0 groups

accounting for most of the remaining oxygen. Most of the


Oxygen
Oxygen Carboxyl Phenolic Alcoholic Carbonyl Methoxyl accounted
OH OH for

% of oxygen

Soil HA 1 s

32.9 43.8 10.2 13.6 21.4 1.5 90.5


a
36.8 26.1 24.9 15.2 7.8 - 74.0
a
35.4 13.6 38.0 12.7 4.1 - 68.4
a
35.6 42.2 24.7 0.9 23.4 - 91.2
a
33.6 44.8 17.1 - 14.8 1.4 78.1
Coal HA
a
28.7 49.1 16.2 - -a 9.4 74.4
Soil FA 1
S

47.3 57.5 19.3 11.5 5.8 -a 94.1


44.8 65.0 11.8 12.9 11.1 1.7 102.5
47.7 61.0 9.1 16.4 3.7 1.0 91.2
Soil humins
a
33.8 36.0 9.9 - 22.7 1.9 70.5
31.8 26.1 12.1 -a 28.7 1.5 68.4

~ot determined
TABLE 3.1 Distribution of oxygen in humic substances {47)
CO
(]1
86

systematic errors that occurred in the determinatio ns of the

individual oxygen-conta ining functional groups are accumu-

lated in these values. However, the available data show

that most of the oxygen in humic substances occurs in

functional groups such as -co 2H, -OH and C = 0.


(b) Nitrogen Containing Functional Groups

There has been a complete review on the distribu-

tion and nature of nitrogen in humic substances by Bremner

(59,60).
The nitrogen content of humic substances ranges

from about 1 - 6%. The presence of amino acids, amino

sugars and ammonium compounds was observed by Sowden (61)

using a "Technicon" amino acid auto analyzer. There is also

evidence to show that after acid hydrolysis of humic

substances about 20 - 55% of the nitrogen consists of amino

acid nitrogen, and that 1 - 10% is amino sugar nitrogen

(61- 65). However, the nature of the solutions used for

the extraction of humic material may have significant effects

on the total nitrogen content and on the nitrogen distribu-

tion in acid hydrolyzates . For example, Bremner (64 - 65)

found that humic acids extracted by 0.5 N sodium hydroxide

and by 0.1 M sodium pyrophosphat e (pH 7) differed markedly

from each other in total nitrogen content and in nitrogen

distribution after acid hydrolysis, the former having the

higher nitrogen content and higher proportion of acid soluble

and amino acid nitrogen.

3.232 THE USE OF PHYSICAL METHODS FOR CHARACTERIZATION OF

HUMIC SUBSTANCES

The characteriza tion of humic substances using


87

physical methods such as spectroscopy, electrometric titra-

tion and molecular weight measurements, has become more

attractive due to the complexity of other chemical procedures.

The use of the following main methods of character-

ising humic substances have been discussed by Schnitzer and

Khan (47).

a) Spectroscopic methods:

i) Visible spectroscopic method

ii) Ultra violet spectroscopic method

iii) Infra red method

iv) Nuclear magnetic resonance (NMR) spectrometric

method

v) Electron spin resonance (ESR) spectrometric method

vi) X-ray analysis

b) Molecular methods:

i) Vapor pressure osmometry

ii) Ultracentrifugatio n

iii) Gel filtration

a) Spectroscopic characterisation

The different regions of electromagnetic spectrum

were used by soil scientists for the characterisation of

humic substances. These methods have a number of attrac-

tive features: (a) they are non-destructive (b) only small

sample weights are needed (c) they are experimentally simple

and do not require special manipulative skills.

Some of the disadvantages in these methods were

the overlapping of the results due to the similar character-

istics of some of the functional groups. Secondly, these

methods are very much limited to qualitative determination


88

for the same reason.

i) Visible Spectroscopic Method

Humic substances, like many relatively high mole-

cular weight materials, yield generally uncharacter,isTic

spectra in the visible region (4u0 - 800~m ) as shown ln

Figure 3.2. Absorption spectra or neutral, alkaline and

acidic aqueous solution of humic acids and fulvic acids are

featureless showing no maxlma or mlnlma.

Light absorptlon of humic substances appears to

increase wiTh increases in (a) the degree of condensation of

the aromatic rings that they contain (b) the ratio of carbon

in aromatic "nuclei 11 to carbon in alipnatic or alicyclic

side clJ.ains (c) total car·bon content and (d) molecular

weight. Usually~ adsorption spectra of humlc substances

in the visible region of tne spectrum do not provide

detailed lnformation on their chemical structure. However,

Konova (66) has approached this problem by using a ratio of

optical densities at 465 and 665 m~ wavelength. According

to him this ratio, referred to as E 4 /E 6 is independent of the

concentration of the humic compound, but varies for humic

substan8es from different soil type. Brown humic acids

have an E /E 6 ratio of about 5, whereas the ratio for grey


4
humic acids ranges from 2.2 to 2.8. He claims that the

progressive humification and increased condensation are

indicated by a decrease in the E4 /E 6 ratio so that the

ratio could serve as an lndex of humification. This method

of characterisation received a great deal of attention as

a successful ntethod of separation as some differences of

various humic substances could be determined even though the


89

two separate groups could not be identified 1n molecular

terms.

1.6

1.4

:>,1.2
-!J
·.-I
~ 1.0
Q)
'D
r-1
r1)
0
·.-I
-!J 0.6
0..
0

0.4

0.2

400 500 600 700


Wave length mlJ
Fig. 3.2 Visible spectra of (A) Humic
Acid and (B) Fulvic Acid

ii) Ultraviolet Spectroscopic Method (200 to 400 IDlJ)

Absorption in the UV region normally occurs due

to the presence of multiple bonds and of unshared electron

pairs in the humic substances. Among those linkages which

confer the colour to the organic substance are those called

chromophores and the linkages which by themselves do not

confer colour but which increase the colour of chromophores

are referred to as auxochromes. The typical chromophores

known to occur in humic substances are C = C and C = 0,

auxochromes that are likely "LO be present are C - OH,

C - NH and others. The use of UV absorbtion spectra has


2
not been wide because the interpre~ation of the spectra is
90

difficu lt due to the presence of more than one chromop hore.

Ultra-v iolet spectra of most humic substanc es are

feature less, because there is no sharp maximum in the absorp-

tion spectra. In most cases, a broad peak lS obtained

probably due to the whole complex mixture . It is also

reported that the optical density decrease s as the wavelen gth

increase s as in Figure 3.3 (47). Occasio nally an indicati on

of a maximum lS observed in the U.V. region but this cannot

be used as an accurate method for charact erisatio n without

separati ng the mixture of humic substanc es to some extent.

:>, 0.5
+-'
·rl
(})
!=: 0.4
(])
'\j

rl 0.3
rU
0
·rl
+-' 0. 2
p_,
0
0.1

200 250 300 350 400


Wave length, fill

Fig. 3.3 Ultravi olet spectra of (A) HA and


(B) FA

iii) Infra-re d (IR) Spectrop hotomet ric Method: (4000 to


1
650 cm- or 2.5 to 15.4 fill)

Infra-re d methods have been very attracti ve ln

yielding useful informa tion on the structur e of humic

substanc es. These methods are based on the followin g

princip le. The masses of atoms, and the forces holding

them togethe r, are of such magnitud e that the usual vibra-


91

tions of organic molecules interact with electromagnetic

energy so as to absorb and radiate in the I.R. region of the

electromagnetic spectrum. Some of the vibrational bonds

are associated with specific groupings in the molecule such

as the carbonyl group carboxylate anions, hydrogen bonded -

OH groups, aromatic C =C groups, etc., thus producing a

peak at a characteristic wavelength (67). The position and

intensity of an absorption bond can be used to confirm the

presence of a particular group and to obtain information on

its molecular structure. Conversely, the absence of a

strong absorption group is often indicative of the absence

of that group in the molecule, provided that no other effects

operate which could shift the absorbtion bond to other

regions of the spectrum.

Schnitzer (53) has reported on the infra-red

spectra obtained from humic acids and fulvic acids as

shown in Figure 3.4. The absorption bonds are listed ln

Table 3.2. These bonds appear to be broad and Schnitzer

claims that this is because of extensive overlapping of

individual absorption peaks.

~
0
·rl
00
00
·rl~----------------------------------------,
s
00
~
~
~
~

~
~
~
0
~
~
~

4000 3200 2400 1800 1400 1000 700


Wave Number cm- 1

Fig. 3.4 Infra red spectra of (A) HA and


(B) FA (53)
92

-1
Frequency cm Assignment

3400 Hydrogen-bonded OH

2900 Aliphatic C-H stretch

1725 C =0 of co 2 H, C =0 stretch of

ketonic carbonyl

1630 Aromatic C =C
Hydrogen - bonded C =0 of carbonyl,

conjugated with carbonyl, COO

1450 Aliphatic C - H

1400 COO , aliphatic C - H

1200 C - 0 stretch or OH deformation

of co 2H
1050 Si - 0 of silicate impurity

TABLE 3.2 Main infra-red absorption bands of


humic substances
93

Other workers have also reported similar results

(68) for soil humic compounds as are shown in Figures 3.5

and 3.6. In most of those reported works sharp peaks were

not obtained due to the overlapping as mentioned earlier.

This has been a prime drawback to using I.R. analysis for

structural determination. I.R. analysis, however, has given

a lead to the determination of functional groups present in

soil humic substances.

As shown in Figures 3.4, 3.5 and 3.6, the most

striking difference between the two spectra of humic acids

and fulvic acids lies in the intensities of the bonds in


1
the 2900 - 2800 cm- region and in the 1725 cm- 1 bond.

The humic acids appear to contain more aliphatic C - H groups


-1
than do fulvic acids. The 1725 cm bond is very strong

in the case of fulvic acids, but only a shoulder for humic

acids, and so substantiates the chemical data which shows

that fulvic acids contain considerably more co 2 H groups

than do humic acids.

The I.R. spectra reflect the preponderance of

oxygen - containing functional groups, that is, co 2 H, OH,

and C =0 in humic substances which may, at least 1n part,

be responsible for the relatively poor definition of the

I.R. spectra of these compounds. However, it is evident

that, in general, spectra of humic substances of diverse

origin are very similar, which may indicate the presence of

essentially similar chemical structures, differing mainly

in the contents of functional groups.

iv) Nuclear Magnetic Resonance (NMR) Spectrometry

There has been work reported by Barton and

Schnitzer (69) on the use of N.M.R. spectrometric methods ln


94

4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency (ern )
Fig. 3.5 Infrared spectra of original humic acids (A) humic
acid-I (B) humic acid-II (C) sodium salt of "A" (68)

4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600

Fig. 3.6 Infrared spectra of original fu1vic acid


(A) fulvic acid type I (B) fulvic acid type II
(C). sodium salt of "A" (68).
95

studying humic substances. The application of N.M.R. to

organic molecules is concerned largely with proton resonance.

The resonance frequency varies slightly for hydrogen in

different molecules, and for hydrogens in the different

environments in the same molecule, so that different types of

hydrogen in an unknown structure can be distinguishe d in a

N.M.R. spectrum. It is only in the liquid or dissolved

state that fine structure, due to the chemical shift, can be

observed. The most widely used solvents for this purpose

are CC1 and CDC1 3 . However, pure humic substances are not
4
soluble in these solvents, unless they are chemically

treated. Therefore the use of N.M.R. spectroscopy has been

limited to methylated fractions or to the degradation

products of humic substances soluble in organic solvents.

However, there has been useful information reported by Barton

and Schnitzer by producing the N.M.R. spectra of methylated

fulvic acids fraction dissolved in CC1 4 and CDC1 3 . The most

remarkable fact about these spectra was the absence of

aromatic and olefinic protons.

Schnitzer and Skinner (70) recorded N.M.R. spectra

of methylated fulvic acid fractions separated by gel filtra-

tion. These spectra do not exhibit aromatic protons,

indicating that either the aromatic "nuclei" or cores of the

fulvic acid fraction are fully substituted by atoms other

than hydrogen or that the relaxing effects of the spins of

impaired electrons (free radicals) interfere with the N.M.R.

measurements .

v) X-Ray Analysis

X-ray defraction analysis has been used to charac-

terise carbon arrangement in humic substances as to whether


96

it occurs predominantly in condensed "nuclei" or in loose

open structural arrangements. Kasatochkin et.al. (71)

reported from X-ray studies that humic substances contain

flat condensed aromatic networks to which side chains and

functional groups are attached. There has been more work

reported on this aspect by Kononova in 1956 (72), Tokudome

and Kanno (73), Kodama and Schnitzer (74) in their independ-

ent work.

It was claimed in the above work that the diffrac-

tion patterns suggest structural similarities between soil

humic materials and carbon black and coal of various ranks.

A structure of condensed aromatic networks of humic material

was suggested after comparing some of the lines of the

X-ray diffraction pattern with high ranks of coal in which

some bonds occur due to ordering of condensed aromatic layers

normal to their carbon planes. Since naturally occurring

humic substances are non-crystalline, the use of this X-ray

diffraction method was found to have only limited application

in structure determination.

b) Molecular Weight Method

Molecular weights ranging from a few hundred to

several million have been reported for humic substances.

Among the methods used in determining molecular weight are

vapour pressure osmometry, ultra centrifuge and gel filtra-

tion. Membrane separation has also been applied very

recently ( 7 5) .

i) Vapour Pressure Osmometry

Vapour pressure osmometry lS being used increas-

ingly for measuring number - average molecular weight (Mn)


97

of water-sol uble humic substance s, especially fulvic acids,

but when measured in water, number-av erage molecular weight

values for polyfunct ional substance s like fulvic acid may

be erroneous because of the dissociati on of any acidic

functiona l groups. Although this dissociat ion can be mini-

mized by measureme nt in organic solvents, humic substance s

are usually insoluble or only slightly soluble in these media.

These difficult ies have been overcome by Hansen and

Schnitzer (76) by a correction system for experimen tally

determine d values of Mn and pH, which makes possible calcu-

lation of accurate Mn values in aqueous solution.

ii) Ultracent rifuge

The ultracent rifuge method is used to measure

molecular weight, size and shape of high-mole cular weight

organic substance s such as proteins. Attempts to use this

technique on humic materials have, so far, met with only

limited success. Many of the technique s that have been

developed for proteins did not work well with humic

materials ( 4 7) . The cause is mainly due to the complexit y

of humic substance s.

iii) Gel Filtration (Gel Permeatio n Chromatog raphy)

Gel filtration has been very successfu l in measur-

ing weight - average molecular weights (Mw ) of humic sub-

stances. This method is being widely used due to the

inexpensiv eness of the apparatus and the use of small

sample size.
Gel permeatio n chromatog raphy (GPC) is a type of

liquid partition chromatog raphy in which the chromatog raphic

medium is made up of particles of a gel, the pores of which

are filled with a liquid (the stationary phase). The mobile


98

phase is also liquid, and when a mixture of solutes is

passed through the column it is found that the sequence of

emergenc e of the compone nts of the mixture from the column

is in order of their decreasi ng molecul ar size. For

practic al purpose s, this method is used for determin ing the

molecul ar weight of similar compone nts in similar environ -

ments.
Three mechanis ms have been suggeste d for the

separati on processe s involved in G.P.C. (77) based on:


a) the steric exclusio n theory

b) the restrict ed diffusio n theory

c) thermody namic theories .

G.P.C. has been used both for fraction ation

and measurem ent of molec1.1 lar weights of humic substan ces.


In early work carried out before 1967, it was

found that charged and mainly aromatic humic acid molecul es

are adsorbed by the gels used, making it impossi ble to

deduce reliable molecul ar weights from elution curves.

Several eluants were suggeste d by Swift and Posner (78)

to overcome this difficu lty. They showed that fraction a-

tion of humic substanc es solely on a molecul ar weight basis

can be obtained on sephadex gels using 0.025 M Na 2 B4 o 7

solution or an alkaline buffer solution contain ing a large

amino cation to depress gel solute inter-ac tion. Khan and

Friesen (79) also obtained molecul ar weight fraction ation

of humic acids on sephadex gels using a glycine - NaOH

buffer at pH 10 as eluant.
The applica tion of G.P.C. to the measurem ent

of molecul ar weights of humic substanc es in sedimen ts, soils

and natural waters has been reported . The data show that
99

the molecular weights of humic substances in sediments

range from 700 to over 200,000 in soils from 300 to over

200,000 and in natural waters from 700 to over 50,000.

Schnitzer and Skinner (70) point out that

molecular weights of humic materials measured by gel filtra-

tion may be between 2 and 10 times higher than those

measured by other methods such as vapour pressure osmometry

and freezing point depression. This disagreement was

found to be very high in the case of the upper range of

molecular weight fractions. Gels are usually calibrated

with carbohydrates or proteins of known molecular weight

and shape. Many workers have assumed that these calibra-

tions were also valid for humic substances of which the

molecular dimensions were not known. The basic error

could originate from the above assumption, as the proteins

and carbohydrates differ very much from humic substances.

There have been suggestions to overcome this difficulty by

calibrating gels with humic fractions of accurately known

molecular weight, size and shape.

Cameron et.al. in 1972 (80) calibrated sephadex

G-100 for humic acids. They used humic acid fractions of

very low polydispersity obtained by preparative gel permea-

tion chromatography and measured the molecular weight of

each fraction by ultracentrifugation. The published

calibration curves were regarded as being approximately

equivalent to curves obtained with a series of truly mono-

disperse macromolecular species. However, the application

of such a calibration curve to broadly polydisperse

unfractionated humic materials requires the further assump-

tion that such a system is made up of a series of monodis-


100

perse species. Alderdice et.al. (81) ln 1978 calibrated

sephadex G.200 for humic acids by a cross calibration

procedure. Darmutji (77) in 1978 in her work fractionated

humic acid samples by gel permeation chromatography, and the

relationship between average molecular weight and optical

absorptivity in the visible - ultraviolet region was

determined. Humic acid samples were satisfactorily frac-

tionated by the gel permeation chromatographic method in

this work. Absorption spectra were measured for each

fraction and it was found that absorptivities increase with

decreasing molecular weight. The molecular weight results

were established using a similar calibration curve to that

published by Cameron et.al. (80).

Lever (75) used gel permeation methods to

characterise the organic matter present in Bayer process

liquor. His work also was limited to the gel filtration

curves due to the non availability of suitable known

compounds for calibration.

Gel filtration appears to have good application

prospects to the problem of identifying the organics in

Bayer process liquor but it needs additional development

before it can be used confidently for measuring the molecu-

lar weight of these substances. The method is based on

the assumption that molecular size is proportional to

molecular weight for similar compounds in similar environ-

ments. It would be useful to investigate this proportion

in regard to the humic substances, as they are so complex

ln structure. However, until that stage is reached, it is

advisable to determine molecular weight of humic materials

by at least two different but independent methods.


101

Value Method Reference

-1000 Isothermic (82)

distillation

984-1294 End group analysis (83)

1336 Equivalent weight (84)

1350 Equivalent weight (85)

1235-1445 Equivalent weight (86)

1624 Freezing point (87)

1392 X-ray (88)

5000-7000 Dialysis (89)

4500-26,000 Diffusion (90)

14,000-20,000 GPC (91)

5000-100,000 GPC (92)

10,000-200,000 GPC (93)

25,000 Sedimentation, (94)

viscosity

36,000 Viscosity (95)

47,000-53,000 Osmometry (96)

53,000 Sedimentation (97)

6600-100,000 GPC (98) & (81)

500 to over 10,000 Ultra filtration (75)

membrane

TABLE 3.3 Summary of Molecular Weights of


Humic Substances
102

iv) Other methods

There have been other methods such as end-group

analysis, viscometry) isothermic distillation, equivalent

weight, dialysis and diffusion, used for measuring molecular

weights of humic substances. Table 3.3 summarises the

available information on the various molecular weight deter-

mination of humic substances.

3.24 CHEMICAL STRUCTURE AND THE DEGRADATION OF HUMIC

SUBSTANCES

3.241 Various Models suggested for Chemical Structure of

Humic Substances

In regard to the structure of humic substances

various models have been suggested 1n the past decade

which are discussed below.

Flaig's Model

Flaig 1n 1960 (89) suggested that this source of

humic substances in soil is plant liquor which is depoly-

merized, demethylated, oxidized and eo-polymerized with

amino acids to form a heteropolymer as given in Fig. 3.7.

Felbeck's Model

Felbeck (48) concluded from his experiments, which

were based on hydrogenolysis of humic acid from muck soil,

that a significant part of the humic macromolecule has a

heterocyclic structure containing both oxygen and nitrogen

as the principal hetero-atoms. A partial structure is

given in Figure 3.8.


103

! 0~
-y~OH
y
----AocH3
~~V
~H~ ~H~
HC~ HC~
I I
CH CH3
3

-oOH 11
0
0

H C ---·---C-CH 3
4 H .

R represents an amino acid residue

Fig. 3. 7 Flaig's model of the structure of humic


substances.
104

l
0
CH30o~"'OCH3
H·--- 0 r./
_,., o
11
H---0
,

6-?it o~c(') o-('~ /


AN)l c H~Y,,0)l.c H 4Jl~1)l.c H{
C-R
l
C=O
I
N-H
I I
R-C-H
I
c=o
l

R and R1 represent alkyl groups

Fig. 3.8 Felbeck's model of the structure


of humic substances.

CH==CH-COOl-1

OH
OH
\
H
.............- - + - - - C C

A 6H
R~OH
OH
n
R represents H, OH or COOH

Fig. 3.9 Finkle's model of the structure of


humic substances.
105

Tinkle's Model

Finkle in 1965 (99) suggested that humic acids

are formed in soils by a sequence of reactions which begin

with the liberation and/or synthesis of hydroxycinnamic

acid from the decay of plant litter. Micro-organisms de-

carboxylate these substances, producing hydroxystyrenes

which are converted to humic acids by oxidation, polymeriza-

tion and eo-polymerization reaction as shown in Figure 3.9.

Haworth's Model

Recently, Haworth (100) in 1971 suggested that

the typical humic acid molecule has a complex aromatic core

with chemically or physically attached polysaccharides,

proteins, metals and phenols, as shown below:

Peptides)-- -- - - - --- --?'Carbohydrates


, ... ,
'

....
" , I

: ',1 core(
I , ,
I , ', I
/ ',
I ," 'I .
~Pheno
l 'lC acids
Metals .,_-- - - - - - - - -

The mode of attachment is uncertain. The pro-

tein core attachment appears to be stable towards chemical

and biological attack. Haworth suggested that humic

substances are linked to polypeptides by hydrogen bonds,

which can be broken by hot water.

Fulvic Acid Structure

Ogner and Schnitzer in 1971 (101) and Khan and

Schnitzer in 1971 (102) suggested that fulvic acid is made

up of phenolic and benzene carboxyl acids linked by hydrogen

bonds to form a polymeric structure of considerable stability.

The proposed structure is given in Figure 3.10 (47 and 103).


106

Th~ structure is characterized by voids or

holes of different dimensions where organic molecules,

such as alkanes, fatty acids, inor'ganic compounds, metal

lons and oxides can be accommodated. Any weakening of

hydrogen bonds breaks up the structure and liberates both

the building units and any included compounds (47).

0
0 OH ~
0 o~-1 OH 11 I C-oH 0
HO-~ oH----o=c*c-OH·-··O=C*CtDH
0 c--Y
0
o==c .OH·---o=c
/ /OH
c:::::::- 0
HO
I OH
'ow· I C-C>H
1
OH OH
I I OH 11 I
I
I
I I 0 I
I I I
I I I

0 --70
c-oH I

HO-C*OHC=O····HO-~0
11

...
H
0

OH
HO-C
8 C=-0
I
OH

Fig. 3.10 Structure of fulvic acids


107

3.242 The Degradation of Humic Substances

The chemical structure of humic substances has

been the subject of numerous investigations over a long

period of time. Because of the chemical complexity of

humic materials) many workers have used degradative methods,

hoping to produce compounds that could be identified and

whose structures could be related to those of the starting

materials. However, very few approaches have been

successful.

The major methods that have been and are being used

1n structural investigations on humic substances were hydrol-

ysis with H 0, acid hydrolysis, alkaline hydrolysis, oxida-


2
tive degradation and reductive degradation (47).

Hydrolysis of humic substances with water means

boiling with water and analysing the extract for organics,

similar to the method in which polysaccarides yield

glucuronic acid (47) as acid hydrolysis.

The boiling water also extracts small amounts of

ether soluble materials which contain (a) p-hydroxy benzoic,

(c) vanillic acids and vanillin as shown below (47).

HC=O

~OCH3 ~
COOH

Q OH
~OH
OH OH OH
OCH
3

(a) (b) (c) (d)

Under acid hydrolysis, it was claimed that in

addition to the p-hydroxy benzoic, vanillic acids and

vanillin, there are also small amounts of syringic acid:


108

C0 H
2
OCH
3

HC0 OCH 3 .
3
OH

Jakab et.al. (104) has reported the degraded products ob-

tained when a humic substance is leached with 5NaOH at 170°C.

They have detected over thirty phenolic compounds by

chromatographic methods and suggested that these compounds

obtained in the alkaline hydrolysis is shown as follows:

~OH ~OH HA ~OH ~H OH~H


OH
OH

The conditions applied in the Bayer process are,

1n fact, alkaline hydrolysis and alkaline oxidation.

Schnitzer and Khan (47) have reported on the oxida-

tion of humic substances by potassium permanganate under

alkaline conditions. They have identified the presence of

aliphatic mono- and di- carboxylic and benzoic carboxylic

acids. Aliphatic monocarboxylic acids that have been

isolated and identified include acetic, propionic, isobu-

tyric, isovaleric, n-valeric, isocaproic, n-caproic and

n-heptanoic acids. Aliphatic dicarboxylic acids resulting

from the alkaline permanganate oxidation of humic

substances include oxalic, malonic, succinic, glutaric,

adipic, pimelic and suberic acids. The following benzene


109

T02H T02H TH3 TH3 Y02H yH3 C0 H yo 2 H


I 2
CH TH2 ?HC0 2 H yH.CH co 2 H TH2 TH(CH2)2C02H I(CH2) 4 (CH2) 5
3 2 I
CH CH CH CH CH CH
3 3 3 TH2 3 3 3
CH
3

(1) (2) (3) (4) (5) (6) (7) (8)

CO H T02H T02H ?0 2 H T02H T02H T02H


I 2
C0 H I(CH2) 2 (CH2) 3 fCH) 4 I(CH2) 5 (CH2) 6
2 TH2
I
co H co H bo H C0 H C0 H C0 H
2 2 2 2 2 2

(9) (10) (11) (12) (13) (14) (15)

6co2H6 Q (Xco2H2lco2:6 C0 H
2
C0 H
2
H0 C
2
C0 H
2
QtC02H
C0 H
2
C0 H C0 H C0 H
2 2 2
(16) (17) (18) (19) (20) (21) (22)

CO H

Ho2yYco2H
HOM02H C0 H
2
(23) (24) (25) (26)

(1) Acetic (13) Adipic (25) Benzene penta carboxylic


(2) Propionic (14) Pimelic (26) Benzene hexa carboxylic
(3) Iso-butyric (15) Suberic
(4) Iso-valeric (16) 0-phthalic
(5) N-va1eric (17) M-phthalic
(6) I so-caproic (18) P-phthalic
(7) N-caproic (19) 1,2,3 -benzene tri carboxylic
(8) N-heptanoic (20) 1,2,4 -benzene tri carboxylic
(9) oxalic (21) 1,3,5 -benzene tri carboxylic~
(10) Malonic (22) 1,2,3,4 - benzene tetra carboxylic
(ll) Succinic (23) 1,2,3,5 - benzene tetra carboxylic
(12) Glutaric (24) 1,2,3,5 - benzene tetra carboxylic

Fig. 3.11 Degraded carboxylic acids obtained under alkaline


permanganate oxidation.
Carbohydrates (Cellulose) Protein Lignin
50-60% 1-3% 10-30%
I
Oxidation & degradation
Energy supply and
growing of microorganisms of high molecular parts

Lignin degradation products

autolysis
I
Oxidation & dehydrogenation

NH Amino acids
3

~----------------------~ Decomposition of Polymers


the side chain
C-linkages mostly
in the side chain
I
Dehydrogenation &
demethylation
Oxidation, dehydrogenation Polymers
and demethylation
-C,-H,-OCH
,I ,
(-C -H -OCH )
3
3

~ a=r=o=m~at=~=·c~~~~~=-
Oxidation
Polymers
I

Aliphatic compounds Polymers


I C-linkages between the rings
I
Energy supply for microorganisms Oxidation
C0 + H o
2 2 --------------~~co +
2 H
2
o
Fig. 3.12 Process of transformation of organic substances in soil (105) •
111

carboxylic acids have been identified among the oxidation

products~ o-phthalic acid, m-phthalic acid, p-phthalic

acid, 1,2,3 -benzene-tricarbo xylic acid, 1.2.4 -benzene-

tricarboxylic acid, 1,3,5 -benzene-tricarbo xylic acid,

1,2,3,4 -benzene-tetra carboxylic acids, 1,2,3,5 -

benzene-tetra carboxylic acid, benzene-penta carboxylic

acid and benzene hexacarboxylic acid. Excluding oxalic

acid, the aliphatic and aromatic compounds identified

account for up to 4.3% of the original weight of humic

substances. The structure of the degraded compounds

obtained under alkaline permanganate oxidation are

illustrated ln Figure 3.11.

The degradation of organic matter in the soil has

been reported by many workers as a very complex process.

It could vary greatly according to the conditions applied.

The complexity of the processes that may be involved in

transformation of organic materials in soil is illustrated

ln Figure 3.12 originating in the work of Flaig (105).

It is evident from the above collected work that

the organic matter present in bauxite shows a similar type

of complex system during its degradation when attacked by

the caustic liquor in the Bayer process. The degraded

products obtained in the Bayer process are also believed

to be similar to the products illustrated in Figure 3.11.

3.3 IDENTIFICATION AND CHARACTERISATION OF ORGANIC

IMPURITIES IN BAYER PROCESS LIQUOR

There has been very little work reported ln rela-

tion to the identification of organic materials present in

Bayer process liquor.


112

One of the earliest studies of the organics present

ln Bayer process liquor was carried out in 1954 by Breuer

(106). He identified the presence of eight organic com-

pounds, but the technique he employed was not sufficiently

modern to give accurate results, although his findings were

important.

In most alumina plants, any organic materials

which reach supersaturation and can be oxidised by potassium

permanganate are termed oxalate. Therefore, most methods


of control of organic matter in the process assume that it

is sodium oxalate.

Sata and Kazama (107) have identified formic,

acetic and oxalic acids in Bayer process liquor. They have

used steam distillation to separate these organic acids

with low boiling point and column chromatographic methods

for oxalic acid. The details were not mentioned in their

work, therefore it was difficult to assess the reliability

of their results. They have also reported the presence

of oxalic acid in a sample of scale taken from a precipita-

tor in an alumina plant by x-ray diffraction methods.

The most detailed and up-to-date work is reported

by Lever (75) on the subject of identification of organics

ln Bayer process liquor. In Lever's work the major organic

constituents in Bayer process liquor have been classified

in the following three groups: (a) the humic matter,

consisting of the coloured high molecular weight organics

extracted from the bauxite and their initial degradation

products (b) the humic "building block" organic compounds

which are mainly the benzene carboxylic acids and phenolic

acids and (c) the low molecular weight degradation products


113

such as formic and oxalic acids.

The organics in group (a) (humic matter) were

characterized by measuring their molecular weight distri-

butions by ultrafiltrati on and gel filtration chromato-

graphy. Firstly, the Bayer process liquor was acidified

to pH= 2, and the organic matter was extracted into

n-butanol, after which the butanol extract was subjected

to a number of washings in order to make the extract almost

salt free. It was then fractionated by ultrafiltrati on,

successively , through the PMIO, DM5, UM2 and UM05 membranes

(Amicon Ultrafiltrati on membranes). Lever used two types


of Bayer process liquor for his investigatio ns. These were
from the Bayer process plants processing Jamaican bauxite;

one from a low temperature (135°C) digestion plant and the

other from a high temperature (240°C) digestion plant.

The results obtained are reported in Table 3.4 below.

Membrane M.W. cut off Liquor Digestion Temp.


135°C 240°C
PM10 10,000 2 0
DM5 5,000 14 12
UM2 1,000 75 76
UM05 500 9 12

TABLE 3.4 Percentage of Total Humic Matter


Retained by each Ultrafiltrati on
Membrane
114

In his gel filtration chromatographic method, Lever

has only been able to use the shape of the gel filtration

curve as a fingerprint to characterise the humic material.

Because of the polydispersity of the fractions, calibration

by this method could not be used for any accurate molecular

weight distribution measurements.

The organics in group (b), or the suspected

organ1c compounds which are mainly the benzene carboxylic

acids and phenolic acids, were separated by using gas

chromatography and identified by their retention times and

comparison of their infra-red spectra to those of known

compounds. Firstly, the Bayer process liquor was acidified

to pH = 2 and then extracted with diethyl ether. The extract

was then methylated with diazomethane. The methylated

sample was subjected to gas chromatography using a Perkins

Model 3920 flame ionisation detector, 1.82m x 3.18mm O.D.

stainless steel column containing 3% OV-17, 80 - 100 mesh

Gaschrom Q, programmed from 100° to 320°C at 8°C/min and

nitrogen flow of 30 ml/min. The results obtained are

illustrated in Table 3.5.

The organics 1n group (c) 1.e. the Low Molecular

Weight Degradation Products, were extracted into butanol

and then butylated. The butyl esters were subjected to

gas chromatographic analysis. Butyl esters were used

since the methyl esters of the low molecular weight degrad-

ation products were found to be highly volatile. These

results are given in Table 3.5.

The work done by Lever is considered to be the

most up-to-date and successful in identification of organic


115

Liquor Digestion
Temperature
No. Compound 135°C 240°C

1 Glutaric acid 10 20
2 Pentanedicarboxylic acid 540 100
3 2-Hydroxy benzoic 10 70
4 Hexanedicarboxylic acid 150 250
5 Dihydroxybenzoic acid 10 10
6 Pentanetricarboxylic acid* 340 10
7 Hydroxybenzenedicarboxylic acid 70 470
8 1,2,4-benzenetricarboxylic acid 70 260
9 1,3,5-benzenetricarboxylic acid 50 410
10 Methyl-benzenetricarboxylic acid 25 250
11 Ethyl-benzenetricarboxylic acid
150 360
12 Dihydroxybenzenedicarboxylic acid
13 Hydroxybenzenetricarboxylic acid lOO 10
14 1,2,4,5-benzenetetracarboxylic acid 140 490
15 1,2,3,5-benzenetetracarboxylic acid 120 990
16 Methyl-benzenetetracarboxylic acid 40 200
17 Benzenepentacarboxylic acid 460 1580
18 Benzenehexacarboxylic acid 640 570

* Tentatively identified
Identified 2925 6050
Total from integrator count 3600 6500
% of compound identified 81 93

TABLE 3.5 "Building Block" compound (mg/1) identified in


Bayer process liquor (Ref. 75).
116

impurities in Bayer process liquor, but there are limitations

to Lever's methods which are described below.

Compound Concentration (mg/1)

Formic acid 2290


Acetic acid 4440
Lactic acid 180
Oxalic acid 2530
Succinic acid 1420

TABLE 3.5 Low Molecular Weight Degradation


Products Present in Low Temperature
Digestion Bayer Liquor

In characterisation of the organ1cs 1n group (a),

the Bayer process liquor was first acidified to pH =2


and later extracted into butanol. By doing this, there

could be changes in the molecular structure of the humic

matter present in the Bayer process liquor caused by change

of pH. These could have been polymerization of the

organic matter resulting in different quantitative results

for the higher molecular compounds. Secondly, there is

the question as to whether all of the particular organic

matter enters the ether extract. A survey of the solubil-

ity of benzene carboxylic acids indicates that they are less

soluble in ether than in aqueous solution. Therefore

quantitative results obtained by Lever in identifying the

organics of group (b) could be in error.

The most recent work on identifying organics in

Bayer process liquor has been by Paul (108) who claims the

presence of sodium oxalate and an organic compound similar

to glucoissaccharinate in the Bayer process liquor. He has

not given details of the analytical methods used in identify-

ing this compound, but he considers that the starch added


117

to the Bayer process liquor is the main source of organic

impurity. Therefore a close relationship between the

organic compounds present in the Bayer process liquor

and the degraded products of starch under alkaline attack

has been brought to attention in his work. According to

Paul, starch consists of amylase and amylopectin. Amylase,

the labile fraction of starch and cellulose compounds,

undergoes degradation in hot sodium hydroxide solution,

generating saccharinates as the main degradation products

(109).

3.4 EFFECT OF THE ORGANIC IMPURITIES ON THE RATE OF

PRECIPITATION AND THE PARTICLE SIZE DISTRIBUTION OF

ALUMINA TRIHYDRATE

There have been several works reported on the

investigation of the behaviour of organic impurities of

Bayer process liquor and its effect on the crystallisation

of alumina trihydrate. However, the literature has

revealed that there has not been a complete work to deter-

mine the actual mechanism of those organics in the precipi-

tation system. Furthermore, some of the workers have

looked into the kinetics of precipitation, by using some

organics which were not even present in the Bayer process

liquor. For example, Ivekovic and the others(110) have

examined the rate of precipitation of alumina trihydrate ln

the presence of isopropyl alcohol, n-butyl alcohol,

isovaleryl alcohol, glycol and glycerol. The same workers

have also investiated the effect of the presence of starch.

According to them only glycol accelerated the precipitation

of alumina trihydrate at concentrations covered by the


118

~experiments, the other substances retarded precipitation.

Glycerol in a concentration of about 0.2 M/1, glucose in a

concentration of 6.7 g/1 and starch in a concentration of

6.7 g/1 prevented the precipitation.

Sato (111) has examined the decomposition rate of

sodium aluminate solution with the addition of glucose,

sugar and starch. It was revealed from his experiments

that the addition of glucose or sugar retards the decompo-

sition, and that an increase ln the amount of starch added

promotes decomposition. Further, it was found that the

retarding action of glucose is stronger than that of sugar.

In the Bayer operation starch is added to the

process as a flocculant in the separation of red mud.

Therefore the above workers have conducted their experi-

ments on the basis that the starch is present ln the

pregnant Bayer process liquor as an impurity. However, it

is important to note that the amount of starch added is

negligible. Usually it is only about one ton of starch

that is added to every 500 tons of Al 2 o3 produced. That

means it is only about 0.1 gm of starch that is present in

1 litre of Bayer process liquor. Furthermore, 80% of the

starch added is carried away by the red mud during the

separation of red mud. Consequently it is very unlikely

that .02 gm of starch per litre could affect the rate of

precipitation, but there could also be argument for the

accumulation of starch in the Bayer process liquor after a

series of recycles. The starch would then not be retained

as starch because it has to go through an extraction con-

dition at high temperatures and pressure in an alkaline

solution and would be converted into a degraded product.


119

Kuznetsov et.al. (112) has investigated the decom-

position of aluminate solutions in the presence of aluminium

salts, iron salts, iron hydroxide and oxalic acids. He

found that oxalic acid, iron salts, Feso , Fe Cso ) and


4 2 4 3
Fe o accelerate decomposition of aluminate solutions. He
2 3
explained the above mechanism in the following manner.

Crystals of aluminium salts and oxalic acid react with the

aluminate solution in their vicinity and render it neutral.

During this process, colloidal aluminium hydroxide is formed,

its particles becoming crystallisation centres. Therefore

the aluminium hydroxide gel formed in the solution areas

adjoining the crystals of aluminium salts and oxalic acid

(and evidently on their surfaces) serves as the actual seed.

According to Kuznetsov et.al., the above mechanism is only

applied to aluminium salts and oxalic acid and the mechanism

for iron impurities has not been investigated. The amount

of salts of aluminium and iron present in the Bayer process

liquor was negligible when compared to the amount of organics

present in the liquor as impurities.

There has been detailed work on the effect on the

crystallisation of alumina trihydrate by Kelly (113). His

studies covered the influence of sodium oxalate on the

induction periods, initial decomposition rate, equilibrium

concentration and crystal shape. Micro-photographs of the

products were presented. His major conclusion was that the

sodium oxalate does not affect the kinetics of crystallisa-

tion.
Another interesting work was carried out by Sato

and Kazama (107) who investigated the influence of organic

matter, sodium carbonate and sodium chloride on precipitation


120

of alumina trihydrate. His experiments were carried out

with the addition of different charges of organic impurities

from 0 - 8 gm per litre, Na


2
co 3 from 0 - 90 gm per litre

and NaCl from 8 - 30 g/litre. He has obtained the organic

impurities by extraction using n - butanol under the H so


2 4
acid phase thus neutralised by means of NaOH. Results
from his experiments prove that the precipitation yield de-

clines with the lncrease of addition of impurities.

However, it was not clear how the rate of crystallisation

was affected in the presence of impurities. It was not


possible to obtain a clear idea as to the actual effect of

the impurities on the rate of crystallisation because details

of figures and experimental and analytical methods applied

were not available. Some of his results are illustrated

in Figures 3.13 and 3.14.

In his investigation he has also analysed the

particle size of the products obtained in crystallisation.

Figure 3.14, which was taken from his work, indicates the

organic matter causes the particle size of the precipitate

to become fine and increase the fixed Na o content in the


2
crystals. He also believes that those organic matters

were probably included within the crystals.

The most recent work on the effect of impurities

on the Bayer precipitation was carried out by Paul (108)

who studied the effect of glucoisosaccharinate on Bayer

precipitation. Glucoisosaccharinate has been synthesized

in the laboratory. He claims that the addition of this

compound to a concentration of 0.8 g/litre as organlc

carbon has lowered the precipitation yield by 17% and

increased the quantity of particles finer than 20 um by 23%.


Organic Matter

a,o Carbon
ro equivalent
.-I 45
(!)
·r-l
:>..
s::
0
·r-l
.j.l
rtl
.j.l
·r-l 40
Cl
·r-l
u
(!)
1>-1
p.,

35

0 20 40 60 80 100 0 2 4 6 8
Concentration of impurities (g.p.l.)

NaCl Minor Inorganic Impurities


50

o'P

ro
.-I
(!) 45
·r-l
:>..
s:: 46.5 hrs.
0
·r-l
.j.l
rtl
.j.l
·r-l 40
0!
·r-l
u hrs.
(!)
1>-1
p.,

35

10 20 30 40 1st 2nd 3rd (level)


Concentration of impurities (g.p.l.)

Fig. 3.13 Influence of Bayer process liquor


impurities on rate of precipitation.
122

(!) Particle size Fixed Na


2
o impurity
N
·r-1
Ul 100
l--1
(!) 0.31
5
4-1 80
0
0.30
o\O

.jJ
..c:tJl 60 0.29
·r-1 olo
(!)
:s: .jJ
..c:
-~0.28
(!)
:> (!)
·r-1
.jJ
40 :3:
ro 200 mesh
,...;
§ 0 0.27
N
::s ro
u 20 z
0.26
mesh

0 0.25
0 2 4 6 8 0 2 4 6 8

Concentration of Organic Matter


(carbon equivalent: g.p.l.)

Fig. 3.14 Influence of organic matter on precipitate quality.

His results suggest that, unlike pure sodium oxalate,

certain types of organic compounds similar to glucoiso-

saccharinate exist in Bayer process liquor, which have an

adverse effect on the precipitation of alumina trihydrate.

Paul also claims that the glucoisosaccharinate,

which has a molecular structure similar to glucose (or

sugar) interacts with aluminate molecules on the surface of

the trihydrate to form soluble compounds thereby stabilizing

the aluminate liquor around the alumina trihydrate seed

crystal surface. It is known that when an induction period


123

80

70

Al
2 3
o
yield
g/1 60

50

0 0.2 0.4 0.6 0.8 1.0


Glucoisosaccharinate cone. as organic carbon/L

Fig. 3.15(a) Effect of glucoisosaccharinate on


A1 o yield (synthetic digest) •
2 3

0.36

0.34

Finish
ratio
0.32
Al 0/TC
2
0.30
0 0.2 0.4 0.6 0.8 1.0

Glucoisosaccharinate concentration as organic


carbon/L

Fig. 3.15(B) Effect of glucoisosaccharinate on


alumina trihydrate precipitation
(synthetic digest)
124

100

90
0 ::: control
80
H rJ ::: 0. 4 g/1 Org .Carbon
QJ
~ 70
0.8 g/1 Org .Carbon
~ 60
·ri
A -.:::

<0

@50
..c:
.j.l

H
QJ
40
r-1
r-1
~ 30
UJ

.j.l 20
..c:
tJ'l
·ri
~ 10
dP
0
1 10 100
Diameter in microns

Fig. 3.15(c) Particle size distribution analysis


Effect of glucoisosaccharinate on
precipitation of Al(OH) (synthetic digest)
3

• = 30..}Jm
H
QJ 0 = 20 ,,
.j.l
QJ
sctJ
80
jj, =10 ,,
·ri
<0
~
ctJ 60
:5
H
QJ
r-1
r-1
ctJ
sUJ
.j.l
..c:
tJ'l
·ri 20
QJ
;;:
cr.o

0 0.2 0.4 0.6 0.8 1.0


Glucoisosaccharinate concentration as organic
carboh/L
Fig. 3.15(d) Effect of glucososaccharinate on particle
size (synthetic digest)
125

precedes precipitation, outgrowths appear on the seed

crystal surfaces. Inter-particle collisions, caused by

mixing, will dislodge and break them to form secondary

nuclei, resulting in the generation of excessive fines

and lower precipitation yield. His work has been largely

concentrated on the effect of precipitation yield and the

particle size and some of the results are illustrated 1n

Figures 3~15a,b,c and d. However, no mention is made of

the effect of this compound on the rate of precipitation.

3.5 BEHAVIOUR AND MECHANISM OF INHIBITION OF ORGANIC

IMPURITIES IN THE BAYER PRECIPITATION

Most of the work carried out has been related to the

effect of organics on the rate, yield and particle size in

the Bayer precipitation. Results were interpreted either

as precipitation curves, yield or particle size distribution.

There has been little attempt to explain the behaviour and

the mechanism that takes place within the precipitation

system in the presence of organic impurities.


Kelly (113) in his work made an attempt to explain

the role of impurities in the precipitation systems. He

looked into the effect, and the behaviour, of the following

three impurities; sodium oxalate, soluble starch and

magnes1um ions. The rate of precipitation was studied by

using the electrical resistance vs time data. He reported

from his work the impurities influence on the induction

period, initial decomposition rates, equilibrium concentra-

tion and crystal sizes.

Kelly suggests that the role of sodium oxalate on

the crystallisation is unimportant. Although the size


126

distribution is not affected by sodium oxalate, it is

suggested that the increased induction period results from

the dissolution of sodium oxalate which tends to inhibit and

retard the decomposition of sodium aluminate molecules.

Consequently, the increase in stability of the molecules

acts on the increased induction period.

Additional starch would appear to affect

crystallisation resulting in a prolonged induction period,

decreased decomposition rates, higher equilibrium concen-

tration and coarser products. Kelly believes these results

are attributable to the shielding or enveloping of potential

growth surfaces by the starch.

It was claimed in his work that the presence of

magnesium added as 4MgC0 .Mg(OH) .5H 0 tends to retard the


3 2 2
decomposition rates and cause a marked 1ncrease in alurnina

equilibrium concentrations. No effects on induction periods

and product crystal size were noted. These results are

interpreted to arise from the adsorption of magnesium ions

by colloidal Al(OH) particles with consequent interfering


3
effects on the conversion of this colloidal material to the

crystalline product.

Yamada and others (6) have looked into the

behaviour of sodium oxalate and measured the solubility of

sodium oxalate in a Bayer plant liquor at different concen-

trations and temperatures. Their results were previously

illustrated in Figure 1.3. It is clear that the sodium

oxalate represents a very low solubility value under the Bayer

precipitation conditions, therefore there is always a

tendency for supersaturation of Bayer process liquor with

sodium oxalates.
127

In their work, eo-precipitation of sodium oxalate

with alumina trihydrate was reported. Their observations

were mainly based on the variation of sodium oxalate content

in the plant liquor after the addition of seeds and also

the sodium oxalate analysis done on product alumina

trihydrate itself. Their test results are listed in

Table 3.7.

Na c o initial
2 2 4 ln Al(OH)
3
(%)
cone. ( g/1) 0.05 0.3 0.6 0. 9

3.0 2. 8 2. 4 2.3 2.3


2. 5 2. 5 2. 5 2. 2 2.15
2. 3 2. 3 2•3 2. 0 2•0

Precipitation time 48 hr.

TABLE 3.7 Na 3 c2 o cone. after alumina trihydrate


4
precipitation

According to Yamada and others (Fig. 1.3) the

solubility of sodium oxalate in the Bayer plant liquor

under the Bayer precipitation conditions is analysed to be

1. 8 g/li tre. However, as shown in Table 3.7, from his

experimental results the sodium oxalate concentration in

the Bayer liquor lS higher than the solubility value

(1. 8 g/litre). He claims that the codeposition rate of

sodium oxalate with the alumina trihydrate, increases with

the increase of the oxalate content in the liquor and also

in the seed. He also observed that when the sodium oxalate

content in the alumina trihydrate is lower than 0.3%, and

the oxalate concentration in the liquid is lower than

2.5 g/1, the sodium oxalate does not precipitate with the

alumina hydrate for 48 hours.


128

Brown and Cole (114) reported the behaviour of

sodium oxalate in the Burntisland Bayer plant in Scotland

with special emphasis on (a) the cyclic nature of the sodium

oxalate behaviour (b) the distribution of crystalline sodium

oxalate in the alumina trihydrate produced, and the effect

of crystalline sodium oxalate on the calcination of the

trihydrate to alumina.

According to them, the driving force for crystalli-

sation of sodium oxalate from Bayer process liquor is the

oxalate supersaturation which is defined as follows:

c c c
oxalate oxalate equilibrium
supersaturation concentration solubility
in liquor

They arrived at an equation which satisfactorily

describes the equilibrium solubility of sodium oxalate in

Burntisland spent liquor following the experimental work

carried out to determine the equilibrium solubility of

sodium oxalate.

C . .b .
equl 1 l rlum
= 7.62 exp.(.012T- 0.016FS- 0.011 co 3 2 - )
solubility

where T is liquor temperature in °C

FS is liquor free soda concentration expressed

as g/1 Na
2
o
co 3 2 - lS liquor carbonate concentration expressed

as g/1 Na
2
o
They have established the equilibrium solubility

of sodium oxalate at 50°C as 1.2 g/litre for a typical plant

spent liquor of the following composition:


129

Alumina 75 g/litre

Free Soda 145 g/litre

Carbonate 15 g/litre

The behaviour of sodium oxalate ln the alumina

plant was monitored over a period of one year by analysing

weekly composite samples of

a) spent liquor for dissolved sodium oxalate

concentration

b) hydrate seed for crystalline sodium oxalate,

and

c) kiln feed (product hydrate) for crystalline

sodium oxalate.

The results of their monitoring experiments are

illustrated in Figure 3.16. As the dissolved sodium

oxalate in spent liquor rises, there is a corresponding

decrease in the solid sodium oxalate present in the hydrate

and in the kiln feed. These trends are reversed when the

dissolved sodium oxalate reaches a critical concentration.

Over the monitoring period of one year this behaviour pattern

was repeated three times.

They examined the crystalline sodium oxalate within

the hydrate particles and it was claimed that the finer end

of the hydrate seed distribution would be most contaminated

with crystalline sodium oxalate. They observed the presence

of sodium oxalate needles amongst the final hydrate, using

the scanning electron microscope. According to them the

product trihydrate, when fractionated, has shown the follow-

ing distribution of crystalline sodium oxalate within the

hydrate particle.
130

Spent liquor
Dissolv ed 4
sodium
oxalate
-----~
(g/1)
1

H drate seed

Solid
sodium
oxalate
(wt.%)
0.3
0.2
0.1
-----L
I

Kiln feed (Produ ct Hydrate )


.04
Solid
.03 -----~
sodium
.02
oxalate
.01
(wt.%)

Time (one year period)

Fig. 3.16 The behavi our of sodium oxalate in a


Bayer plant over a period of one year
131

Size Weight Percent


Fraction Sodium Oxalate
(~m) %

0-32 .046

32-63 .033

63-90 .032

90 .027

TABLE 3.8 Crystalline Sodium Oxalate in


product alumina trihydrate

They suggest that the increasing concentration of

sodium oxalate towards the fine end of the distribution is

consistent with the greater trapping of the oxalate crystals

by the finer hydrate particles during precipitation, but

the evidence seems insufficient to conclude that the oxalate

promotes fine formation. There is no clear indication

given from this result as to the effect on the particle s1ze

distribution of the product trihydrate in the presence of

sodium oxalate.

Solymar and Zsindely (115) also investigated the

behaviour of organic impurities in the Bayer liquor. Their

work was done by extracting the organic impurities 1n the

following manner. The Bayer liquor was acidified by adding

HCl and some of the organic matter was precipitated during

the acidification which was graded as the humic fraction.

Model tests were carried out by adding the precipitated

humic matter and they claimed decreased precipitation rates

with increased organic impurities. They also reported the

diminution of the digestion effect due to a carbon content

from 2 to 3 g/1. During a further increase 1n the organic

substance concentration, however, the degree of digestion


132

was not diminished further. However, the above report

on digestion effect was not based on any det;ailed experimental

evidence. They also reported on the influence of the humic

acid fraction on the sedimentation of red mud and on the

precipitation. According to them the unfavourable effects

are only noticeable after attaining the critical carbon

~-------content of 2 to 3 g/1. It is also claimed that the increase

of viscosity of aluminate liquor, containing sodium carbonate,

is noticeable with small amounts of organic substances, but

when the amount of organic is increased, the viscosity

decreases again. They syggest that this appearance depends

on the influence of the humic acids increasing the soda

solubility. They also suggest organic substances increase

not only the solubility of soda, but also other salts,

thereby increasing the stability of aluminate liquor, thus

reducing precipitation yield. However, it was not quite


clear from their experimental results as to the increase

of the solubility of the other salts.

Tikhonov et.al. (116) reported that high content of

organic impurities in the Bayer process liquor increase the

induction period to about 4 - 6 hours. They explained that


the action of organic substances is due to adsorption on the

surface of the trihydrate seeds, leading to partial break-

down of contact between the hydroxide crystals and the liquid

phase, so that crystal growth is hindered.

3.6 REMOVAL OF ORGANIC IMPURITIES FROM BAYER LIQUOR

There have been few workers who report on the

problem of removing organic impurities from Bayer process

liquor. Most of the studies have been limited to laboratory


133

scale investigations and no commercial application has

taken place. The only method used in industry was that

based on the Kaiser patent described in Chapter I. This

may have been due to the fact that firstly there has been

no complete investigation to justify the poisoning effect

of the organic impurities, and, secondly, most of the remain-

ing methods are costly and the economics of such an operation

would not be sound. The present method of removal (i.e.

Kaiser patent (7)) has been quite successful but it removes

only the organic which reaches supersaturation and adheres

onto the fine trihydrate particles.

The following methods were suggested by various

workers to remove the organic impurities in the Bayer process

liquor:
1) use of activated carbon and pulverised coal as adsorp-

tion material

2) ion exchange method

3) oxidation method, anodic oxidation, oxidation under

pressure

4) heat treatment

5) seeding method.

3.6.1 ACTIVATED CARBON METHOD

Early in 1936, Iskolsky et.al. (117) reported the

removal of organic impurities from Bayer liquor using

activated carbon and they claimed that the activated carbon

adsorbed the organic present in the liquor. Their findings

were not used commercially as the economics of such operation

were doubtful. Further, it was necessary to investigate the

after-effects of the activated carbon itself (by contamina-


134

tion) on the precipitation of alumina trihydrate. They

also claimed that the stability of aluminate solution was

affected by the addition of activated carbon resulting 1n

premature precipitation. The premature precipitation

is also believed to be due to the nucleation effect of

carbon particles.

Recently (1971) Loeffler (118) examined various

adsorption methods for the removal of organic impurities.

Dolomite, active bauxite, active alumina, carbon and

active carbon, were subjected to the examination as adsor-

bants. Active carbon proved to be very effective. He had

also looked into the use of pulverised and granulated coal

for their activity. The economics of using coal as an

adsorbant to remove organic impurities were studied.

3. 6. 2 ION EXCHANGE METHOD

Romanov et.al. (119) reported from his findings that

an1on type ion exchange resins could successfully remove

organic impurities from Bayer process liquor. He stated

(Cl-) type ion exchange resins are capable of remov1ng 30%

of the organic impurities present in the Bayer liquor,

whereas the strong (OH-) base ion exchange resins could

remove almost 70% of the organics. Both types of resins

used were stable in caustic medium and the complete decol-

ouration of the Bayer process liquor was observed with the

(OH-) base ion-exchange. However, it was not clear whether

the sorption could be carried out successfully above 60°C,

under Bayer conditions, as his experiments were limited to


0
only 40 C.

3. 6. 3 OXIDATION METHOD

This method is based on oxidation of the organic


135

matter to C0 under various conditions. Lapp and Kuznet-


2
sov (120) investigated electrolytic oxidation of humic

substances in alkali and soda solution which was carried

out in glass electrolyzers equipped with nickel and nickel

plated anodes, and, in some cases, with stainless steel

anodes. They determined the optimum conditions for, and

the composition of final products of the electrolytic

oxidation of humic substances in alkali and soda solutions.

It was concluded that the oxidation of humic substances

takes place much more effectively in soda solutions than ln

alkaline solutions.

Loeffler (121) reported on his tests on the anodic

oxidation of organic impurities using a cell which was

previously designed for electrolytic purification of waste

water. Pb0 - stratified anodes were used. The tests


2
2
were carried out at current densities of 10 - 100 amp/m

and resulted in a consumption of 10 kwh/t Al o , for a


2 3
0
brightening of 15% during a liquor temperature of 83 C.
2
At current densities of about 1000 Amp/m , an energy con-

sumption of 140 Kwh/t Al o


2 3
resulted with a new anode.

However, Loeffler pointed out that in order to use the cell

to decolour Bayer process liquor, the cell would have to be

reconstructed.

According to a Japanese patent (122) the oxidation

of humic substances could be carried out with oxygen under

high pressure. A similar type of work was repeated by

Loeffler (123) and the oxidation of the organic substance

in the Bayer liquor was suggested to be carried out under

digestion conditions of bauxite under pressure and tempera-

ture with oxygen. He claims that it is possible to achieve


136

a satisfac tory discolo uration of the Bayer liquor uslng

this method. He pointed out, however , that at the reaction

a corrosio n may occur on the autoclav es so that it will be

necessar y to execute corrosio n investig ations prior to the

technic al applica tion of the process.

3.6.4 HEAT TREATMENT

There have been suggesti ons by various workers (9)

that if the recycled caustic liquor is heated to 400°C,

most of the organic impurit ies will decompo se into co 2 .


Although this method is simple, the economi cs of the process

would requlre further investig ation.


Jung abd Loeffle r (124) suggeste d from their find-

ing that the organic impurit ies could success fully be removed

directly within the bauxite itself by roasting before the

digestio n stage within the tempera ture range of 400 - 500°C.

However , any structu ral changes of the bauxite which could

affect the extracti on conditio ns have to be studied further.

For example , during such operatio n, hydrag illite, which

could have been extracte d at low tempera ture, may be con-

verted to boehmite which can be extracte d only at high

tempera tures.

3.6.5 SEEDING METHOD

The methods mentione d earlier do not find commer-

cial applica tion due to the heavy cost involved . However ,

the method based on the Kaiser patent (7) has been

success fully applied in the industry to remove the organics

which reach supersa turation and tend to copreci pitate with

alumina trihydra te. This method has been describe d in

detail in Chapter 2.
137

Yamada et.al. (6) reported from their findings

that removal of sodium oxalate could be performed by adding

sodium oxalate as seeds to precipitate sodium oxalate and

some of the humic acids which have low solubility values

in Bayer liquor. They have not investigated the possible

coprecipitat ion of alumina trihydrate along with the sodium

oxalate crystals as seeds, thereby again the problem of

possible fine formation arises.


CHAPTER 4

CRYSTALLISATION PROCESS OF ALUMINA TRIHYDRATE


138

The crystallis ation (precipita tion) of alumina tri-

hydrate is one of the most important steps in the productio n

of alumina from bauxite. The process is also known as the

decomposi tion of sodium aluminate liquor. The process is

controlled under the two prime criteria of a high recovery

of product and a desirable product size distributi on. In

practice, it is always found that those criteria are contrad-

ictory to each other since when the condition s are selected

to obtain a high recovery of product then the product con-

tains a large percentag e of fines. On the other hand, if

the condition s are chosen to obtain the best particle size

distributi on, then the product yield is very poor. Therefore

in the industry the process lS optimised on the basis of

past experienc e.

The mechanism of alumina trihydrat e precipita tion

has been extensive ly studied by a great number of authors

who have tried to evaluate the importanc e of the measurabl e

factors such as temperatu re, caustic concentra tion, degree

of supersatu ration, nature and quantity of seed, impuritie s

in the liquor and agitation speed as well as to establish

mathemati cal expressio ns to describe the kinetics of the

trihydrate precipita tion.

In the Bayer process the condition s for both the

extraction process and the precipita tion stage can be clearly

delineated from phase diagrams relating to the Na 2 o -


Al o - H2 0 system. One of the most applicabl e phase
2 3
diagrams was published by Wefers (125), illustrate d in

Figure 4.1, in which is plotted equilibriu m curves using the


40
Bayer Extraction

~ Bayer Precipitation
35
0
Temperature C
30

(Y)
0
1:\1
rl 25
-<
.J-l
~
([)
C)
H
([)
20
p_,
.J-l
,.>::;
bO
·rl 15
([)
:s

rv.(J/
/
/
/
/

0 5 10 15 20 25 40
Weight percent NA 2 0 I-'
Figure 4.1 Phase Diagrams in the NA 2 0 - Al 2 0 3 - H2 0 system w
tD
140

data obtained from the past workers. The range of condi-

tions usually applied in the extraction and precipitation

step of the Bayer process are shown as shaded areas in

Figure 4. L

4.11 SOLUBILITY OF ALUMINA TRIHYDRATE IN PURE CAUSTIC

AND BAYER PLANT LIQUOR

Process optimisation of the extraction or the

crystallisation steps of the Bayer process requires accurate

information on the solubility of alumina trihydrate 1n

sodium hydroxide solution. Although many studies of the

Al o - Na 2 o - H2 0 system have been reported there are


2 3
discrepancies in the solubility values obtained.

Misra (11) reviewed the solubility determination

published by previous workers and also some additional

solubility data which was obtained from several alumina

producers.

Various equilibrium equations have been proposed

in the past to interpret the solubility data. Pearson (43)

suggested the following empirical equilibrium constant

to represent solubility data.

[cNaOH + cNaA1o 1j
2
K =
[cNaA1o 2][ a H2o] n

where C represents the molar concentration of the subscripted

species and a H is the activity of water. The exponent


0
2
of the activity term was g1ven by n = 2.67 - 0.0133t,
0
where t = temperature C.

The above equation does not clearly explain the


14-1

fundamental solubility relationship and is only a useful

form for data correlation. Pearson did not give a value

for the equilibrium constant K or clearly explain how

successfully this correlation fitted experimental data.

Russell et.al. (126) used the following equation

to represent the equilibrium constant:

Employing the equation he defined the equilibrium constant

as follows:

K =

The symbols have the same meaning as previously and the

equilibrium constant is related to temperature by the

Vant Hoff equation:

- 734-0
log K = 4-.574-T + 4-.11

where T is the temperature in °K.

The most recent empirical relation to correlate

solubility data was proposed by Misra (11) in 1970 for

the temperature range of 25 - 100°C and for the caustic

concentration of range of 30- 320 g/litre (Na 2 0):

ln Re = 6.2106- 24-86.7/T + 1.0875 CNa


20
/T

where =
= NaOH concentration g/1 Na
2
o

T = temperature °K

He claimed that the solubility of hydragillite in caustic

solution is dependent on the caustic concentration and the


142

temperature. Furthermore~ impurities such as Na


2
co 3 , NaCl

and organic impurities tend to increase the solubility value.

For example, in Bayer plant liquor with the same caustic

concentration the solubility values are typically 15 percent

higher than that of the pure solutions.

Adamson et.al. (127) suggested a relationship to

interpret the solubility data 1n plant liquor but in the

temperature range of 40 - 60°C:


"i'~
log C
Al 2 0
=- 2.4186 + 0.02113t + (1.788- 0.004t). log
3

0
where t = temperature C

= initial concentration g/1

= equilibrium concentration g/1.

Juhasz (128) proposed a relation for plant liquor

which is applicable to the temperature range of 40 - 68°C

and for caustic concentrations of 80 - 196 g/1 Na 2 o as

follows:

i'
log CAl o =
2 3

where concentration is in g/1 and temperature is in °C,

but which is applicable only to particular plant liquors.

4.12 STABILITY OF SODIUM ALUMINATE SOLUTION

The various phase diagrams for the Al 2 o3 - Na 2 o -


H o (Fig. 4.1) system gives information about the stability
2
of the sodium aluminate solution under given conditions.
143

Using these it is possible to predict whether the solution

is supersaturated with Al 2 o and also the amount of Al 2 o3


3
which will be precipitated at a given temperature.

Kuznetsov (9) suggested the following formula 1n

relation to the degree of supersaturation

Caustic ratiot
s = = Caustic rat1o
eq

where

S = degree of supersaturation

= concentration of Al o
2 3
in super-

saturated solution at the given time

Al o
2 3
eq = concentration of Al o
2 3
at equilibrium

Caustic ratio =

He also suggested that the stability of the sodium aluminate

solution depends very much on the degree of supersaturation.

Stability decreases with the increase of S. The other

factors on which the stability will depend are the caustic

ratio (Al 2 0 /Na 0), temperature, seed, impurities and


3 2
agitating speed. However, the apparent stability of highly

supersaturated caustic aluminate solution is shown by the

prolonged induction periods (up to several days) for precip-

itation from unseeded liquors of Bayer process composition

(in the absence of alumina trihydrate seed). Furthermore,

the high solid to solution interfacial tension of


-2
1,250 ergs. cm (129) suggests that the possibility of

spontaneous homogenous nucleation occurring in the industrial

process is remote.
144

4.13 SUPER SOLUBILITY CONCEPT

In order for crystallisation to take place, there

should be a state of imbalance with a decrease in chemical

potential between the bulk of the solution and the crystall-

ine surface. In other words, the solution should be super-

saturated.
Miers (130) postulated that the region of super-

saturation can be divided into two parts as shown in

Figure 4.2. According to the theory, crystal growth occurs

when the concentration lies above line A and nucleation takes

place only in the labile region (above line B). Referring

to Figure 4.2, any point below the saturation curve A (for

example, point E) is unsaturated and will not promote or

yield crystal material. Point D in the metastable region

will promote crystal growth and will drop to concentration E

if seed is added, but will remain unchanged at point D if

no such seed crystals are present. Concentrations above

the supersaturation curve such as point C will spontaneously

crystallise to ultimately yield concentration E by both nuclea-

tion and growth mechanisms.

/B
Labile
region c 0 /
/
A

>::: I
0 ,/
·o-1
+l ......
m /
.,....D
f..l
, ..... 9
+l
>:::
Q)
0
>:::
0
-- - Stable
region
u I
I
I
F 0

Temperature

Fig. 4.2 Miers supersolubility concept


145

4.2 SPONTANEOUS PRECIPITATION OF ALUMINA TRIHYDRATE


FROM SODIUM ALUMINATE SOLUTION

Generally sodium aluminate solution will remain

stable even at the higher levels of supersaturation for long

periods so that crystallisation of alumina trihydrate has a

very long induction period.

Vrbasky et.al. (131) studied the kinetics of the

spontaneous precipitation of alumina trihydrate from

unseeded aluminate solution. He suggested that the

spontaneous precipitation system shows an auto-catalytic

characteristic nature with a pronounced induction period,

during which no precipitation occurs then a steady state and

a period of delayed precipitation. These authors also

developed an empirical equation for calculating the maximum

precipitation rate for the time when this precipitation takes

place and for the amount of the precipitate at equilibrium for

glven aluminate solutions. They also reported that during

the spontaneous precipitation system there can exist a very

long induction period depending on the caustic ratio

The induction period becomes longer with

the decrease of the caustic ratio Al o


2 3
/Na
2
o.
According to Vrbasky and others the spontaneous

precipitation behaves more like an autocatalytic reaction

at lower caustic ratio and less so at higher caustic ratio,

thus the precipitation rate seems to follow a simple

logarithmic law which is of first order relationship. This

is to be expected since in a higher caustic ratio solution

(high supersaturation), there is a very rapid nucleation at

the beginning of precipitation and then the rate. is con-


146

trolled by growth and therefore appears to follow a first

order relation.

4.3 PRECIPITATION FROM SODIUM ALUMINATE SOLUTIONS SEEDED

WITH ALUMINA TRIHYDRATE (BAYER PROCESS CRYSTALLISATION

During the production of alumina trihydrate us1ng

the Bayer process, it is the usual practice that the previously

pre·pared alumina trihydrate is added to the supersaturated

solution of sodium aluminate to act as a seed crystal. In

fact, Bayer, in his original work, showed that the rate of

decomposition could be accelerated by adding some seed

material to act as nuclei as well as by providing new surface

for crystal growth. In his patent, he recommended only

alumina trihydrate and possibly isomorphic chemical compounds

to be used as the seed material for the crystallisation of

alumina trihydrate. Although it is now known that many

other compounds such as other aluminium salts, iron hydroxide,

titanium oxides and cryolite can be used as seed. However,

in plant practice, for the sake of purity and economy,

alumina trihydrate is used as the seed material.

4. 3 1 KINETICS RELATION FOR SEEDED PRECIPITATION

There have been several relationships proposed by

various workers 1n the past to interpret the kinetics of

crystallisation of alumina trihydrate with seeding, but most

of these relationships have been unable to explain all the

stages in the crystallisation systems including the induction

period.
The rate equations suggested by past workers were

mainly based on the change in weight of trihydrate precipi-


147

tated with time as follows:

dW
dt = K f (S)

where

S lS the supersaturation of the aluminate solution

given by R - R
e
or CAl
0 - c* and K is the rate constant
2 3
dependent on the temperature, surface area of the seed and

caustic concentration of the solution.

A simple first order reaction equation was proposed


by Hermann and Stipetic (129) for the kinetics of precipita-

tion of alumina trihydrate 1n the Bayer process:

dW ~':

dt = K (C - C )

An identical type of equation was suggested by

Kuznetsov (9) in his work. Shimosato (132) suggested


the effect of seed as one of the factors in his equation to

explain the kinetics of seeded precipitation as follows:

dC
- dt = K/Cs + r

Where cs the seed concentration

r the activity ratio of alumina trihydrate

precipitated to seed trihydrate

the initial alumina concentration


I
K &K reaction rate constants dependent on

temperature and the caustic concentration.

Pearson (43) suggested the following equation for

the kinetics of precipitation:

dX
dt =
148

(The same equation was suggested for the extraction

stage as mentioned in Chapter 2 of this thesis). Where K


1s a parameter dependent upon temperature, At is the area

of seed surface (m 2 /litre) at timet (hours), xt and x*

are the mole concentration of NaA10 at time t and at


2
equilibrium respectively and a * is the molar concentration

of NaOH at equilibrium. It has been shown that the rate of

reaction is proportionate to the total surface area of the

trihydrate particles present at any given time.

Solymar and Zambo (133) presented some express1ons

for the kinetics of precipitation, using experimental results

from different sources. They showed that in the tempera-

ture range of 30 - 80 0 C the rate of precipitation in the

initial part of the process is proportional to the square

and later to the first power of supersaturation.

Jamey (134) from his isothermal precipitation

experiments suggested two distinct stages for the crystall-

isation. In the first stage, at the beginning of the

precipitation where the ratio of Al o /Na 2 o of the solution


2 3
is higher than 0.92 or (Al o /Na co >0.54), the rate of
2 3 2 3
precipitation was constant and, in the second stage, the rate

was decreasing according to the law,

dC
dt =

where C is the alumina concentration in which n 1s rather high,

comprised between 8 and 10. He suggested that 1n the first


stage in the hydrolysis of the sodium aluminate plays an

essential part, while the second stage represents probable

polymerisation of the aluminate ions followed by crystal

growth.
149

In most of the previous works the induction period

is neglected from the crystallisation system in the equations

that have been developed. For example, Jamey described

two stages of the precipitation system without mentioning

the induction period in the system.

Misra (11) constructed a mathematical model for the

precipitation process by combining appropriate population,

mass and energy balance relations with kinetic models for

the various crystallisation mechanisms. His model was

solved for a batch unit and the solution has been shown to

agree with the results obtained from a laboratory precipita-

tor which was used to study the effect of different variables

on the product rate and size distribution.

4. 3 2 MECHANISM OF THE BAYER PROCESS CRYSTALLISATION

The mechanism of the crystallisation stage in the

Bayer process is highly speculative. It is not known

whether it is a physical or chemically controlled reaction,

but, at present, there is more evidence to conclude that it

is a chemical reaction.

The crystallisation of alumina trihydrate with

seeding is usually followed by an induction period, nuclea-

tion, crystal growth, agglomeration and crystal breakages,

and therefore it is regarded as a complex system.

Misra (11) explained the precipitation of alumina

trihydrate as a process involving new crystal formation by

nucleation, and crystal breakage and growth of the crystals

by agglomeration and deposition from the super-saturated

caustic aluminate solution.

Maricic and Markovcic (135) explained from their


150

work that the decomposition of sodium aluminate solution by

seeding with hydragillite crystals occurs simultaneously in

the following ways:

a) crystal growth

b) formation of firm binded agglomerates, and

c) creation of new crystallites.

They claimed that the formation of new crystallites 1s

characteristic for the beginning of the decomposition while

the crystal growth is predominant at the latter stage.

An investigation of the decomposition of sodium

aluminate solutions or the crystallisation process, must be

separated into the above-mentioned partial processes, the

kinetics of which in relation to various physico-chemical

factors must be first studied separately. As a result it

should be possible to select favourable conditions for

acceleration of the overall process with greater precision

and better utilization of the accelerating factors.

Lj.. 3 21. Induction Period in Seeded Precipitation

A very long induction period is usually noted in

the case of spontaneous precipitation, but a considerably

decreased induction period is found with the use of seeding.

Tikhonov et.al. (116) carried out some systematic

work of the induction periods in seeded crystallisation of

alumina trihydrate. They claimed that the following major

factors will affect the duration of the induction period.

a) Temperature: induction period decreases

appreciably with increasing temperatures

b) Initial ratio (Al 0 /Na 0) of the solution:


2 3 2
induction periods decrease with increased initial ratio
151

c) Seed surface area: induction period decreases

with increased seed surface area

d) The purity of the solution: impurities such

as organic substances accumulated in the Bayer process liquor

increase the induction period.

They also suggested that 1n plant practice where a

high caustic ratio and high seed surface are applied, the

induction period can be regarded as being negligible.

4. 3 22 Nucleation

Several workers have studied nucleation in caustic

aluminate solutions in the presence of seed. Formation of

nucleus in the seeded crystallisation process is known as

secondary nucleation, and secondary nucleation of alumina

trihydrate can occur during the crystallisation step of the

Bayer process. Therefore for effective control of product

size distribution, it is necessary to be able to control the

rate of secondary nucleation or the formation of new crystals.

Maricic and Markovcic (135) reported that the

crystallisation of alumina trihydrate in the presence of

seed occurs simultaneously in the following three different

ways:-
a) creation of new crystallites (secondary nuclea-

tion)

b) crystal growth

c) formation of firm-binded agglomerates (inter-

crystallisation).

They also claimed from their experiments that the

secondary nucleation is characteristic for the beginning of

the decomposition while the crystal growth is predominant at


152

the later stage.

They also investigated the nucleation 1n the

presence of different size ranges of seeds and reported

that the creation of new crystallites is caused only by

fine seed particles and independently from the coarser one

which plays quite a passive role.

Hlobik et.al. (136) later revised their prev1ous

work by adding that the nucleation can be induced even with

coarse grained alumina trihydrate. They also reported

that the induced nucleation is greater the more supersatur-

ated the decomposition solution. Some approach to the

actual mechanism of induced nucleation was made in their

work.

Scott (137) concluded from the results of previous

workers that the crystallisation process has the following

stages:

a) growth on the surface of the parent crystals

b) formation of dendrites at the surface of the crystals

c) breaking away of the dendrites to give new particles.

The new nuclei so formed tend to form large loosely bound

flocculates which can be broken under very slight mechanical

pressure.

Misra and White (138) suggested that broken frag-

ments formed by attrition of the seed crystals could be one

of the sources for new crystals formation, when there is a

high agitation rate in the crystalliser, but that it was not

the case at lower agitation rates. They also reported that

the number of fine particles generated decreased progressively

with increasing temperatures from 40°C to 70°C. At 75°C

and above there was negligible nucleation. Furthermore,


153

they noted that nuclei will not form readily when seed

particles are about, but will form copiously when they are

present. This would suggest a secondary nucleation

mechanism in the Bayer process.

Brown (139) reported that the secondary nucleation

of alumina trihydrate in seeded caustic aluminate solutions

of industrial composition is closely associated with the

crystal growth process via a surface nucleation mechanism.

When crystallisation is preceded by an induction period, the

seed crystals develop and give birth to large numbers of

secondary nuclei. However, under the condition of high

supersaturation and absence of impurities, the initial crop

of secondary nuclei grow dendritically. These dendrites

then break away from crystal surfaces to form an additional

crop of secondary nuclei. Brown also reported that in

the caustic aluminate solution of industrial composition, the

crystal counts obtained under more vigorous conditions of

agitation indicated that the number of secondary nuclei formed

is directly proportional to the length of the induction

period. According to his results, at sufficiently large


0
seed charge (300 g.p.l. at 60 C), where there was no measur-

able induction period, the secondary nucleation was not noted.

Scanning electron microscopy was used in Brown's experi-

mental studies to identify the secondary nucleation. He

also suggested that in the industrial Bayer precipitation

step, the impurities can adsorb on the faces of the seed

crystal and suppress crystal growth by a surface nucleation

mechanism and divert the nucleation process to slower

growing, but presumably less contaminated crystal surfaces.

Exactly how the impurities act was not clearly explained


154

ln his studies, but he suggests that the impurities may

alter the characteristics of the adsorbed layer of the

solute molecules and interface with the reaction which must

take place at crystal surfaces to convert the aluminate ions

into the neutral Al(OH) 3 molecules prior to incorporation in

the crystal lattice.

a) Kinetic relationships for nucleation

A generalised nucleation rate equation for the

industrial Bayer crystallisation system was suggested by

Branson et.al. (142) as follows:

dNo
Rate = B
0 = dt =
f (S,T,X,Y,Z)

where = total number of particles

t = time

T = temperature °C
~~
s = supersaturation cc - c )
X = some property representing the presence

of solid crystalline material

Y = some properties connected with the history

of the solution

Z = hydro-dynamic conditions (agitation,

geometry, etc.)

A quantitative consideration of factors such as Y

and Z are usually omitted and the suggested relationship for

nucleation rate is as follows:


dN
0
B
0 = dt = f (S,T,X)

A form of nucleation rate was suggested (11) after

representing property X as the total surface area as follows.


dN
Rate = B0 = dt0 =
155

when s = supersaturat ion (C - c*)


KN = rate constant dependent on the temperature

A = total crystal surface area.

4. 32 3 Crystal Growth

Growth of alumina trihydrate particles in super-

saturated caustic aluminate solutions is considered to be

entirely surface reaction controlled. Qualitative evidence

for this is provided by the very low growth rate and the

negligible effect of agitation on growth.

Usually growth occurs by deposition of the solute

from the supersaturate d solution on to the surface of the

crystal seed including both the newly formed crystallites

and the added seed crystals.

The overall process of crystal growth on a seed

crystal or nucleus surrounded by the supersaturate d solution

can be considered basically as a mass transfer with surface

reaction operation and treated as a diffusional step in

series with a surface reaction step. In the first stage the

solute molecules diffuse through the solution to the surface

of the growing crystal. In the second stage, after reaching

the surface they must be incorporated into the crystal lattice.

It is believed that the supersaturat ion is the driving force

for both the steps.

Lyapunov and Kholmogortse va (14) determined the

growth of alumina trihydrate particles in an aluminate

solution by the linear growth of the crystal faces. Some

quantitative growth rate measurements were reported, but the

data is very limited. This method eliminated the error

caused by increase of the particle size owing to aggregation


156

of the particles. They also reported that the growth rate of

alumina trihydrate particles in aluminate solution of equal

degrees of supersaturation greatly increases with an

increase of temperature from 50 to 65°C. The rate of

growth of the alumina trihydrate particles increases with

increase of the degree of supersaturation of the aluminate

solution to a greater extent at 65°C than at 50°C.

Misra and White (138) reported that the growth is

found to depend on the square of the supersaturation and it

also increased with increasing temperature, but was independ-

ent of particle size. They developed the following kinetic

relationship for growth rate.

dL
G = dt =

The effect of temperature on the rate constant KG was

correlated by an Arrhenius type relation.


6 3
= 1.96 x 10 Exp.(- 14.3 x 10 /RT)

Then the growth rate can be re-written as follows:


6 3
G = 1.96 x 10 Exp.(-14.3 x 10 /RT)(c-c*)

The activation energy was found to be 14.3 K.cal/g-mole

and this value suggests that a surface reaction mechanism

is rate controlling step for crystal growth in this system.

In an attempt to relate the variation of nucleation

with growth conditions, Misra and White suggested the following

possibility in the crystallisation system. If nucleation

occurs by the growth of small crystallites on the crystal,

which then break off) the nucleation rate would be propor-

tional to growth rate. Thus a dependence of nucleation on

the second power of supersaturation (as with growth) is a


157

Figur e 4.3 Kosse l Mode l for Crys tal Growt h

Figur e 4.4 Screw Dislo catio n Mecha nism


158

possibility. However, their experimental data did not fit

this proposition closely.

Two types of growth mechanism models are suggested

in the literature (11). First is the Kosel model of crystal

growth and second the screw dislocation mechanism. Accord-

ing to the Kosel model, crystal growth occurs by the deposition

unit by unit of successive strips (Figure 4.3). This con-

tinues until the particular layer is completed. In order for

growth to continue a new layer must then be initiated. This

is accomplished by a process of two dimensional surface

nucleation which provides the starting point for continued

growth on a new plane.

The screw dislocation mechanism takes place when

the supersaturation level is in the region of one per cent

higher than saturation~ the growth pattern may be initiated

by a screw dislocation method (141) as shown in Figure 4.4.

Therefore, in the Bayer precipitation system, the possible

mechanism is that crystal growth first occurs by filling the

Kosel sites. As the step reaches the low supersaturation

level, a spiral growth pattern results and the dislocation

is continually regenerated as each surface layer is corn-

pleted. This obviates the need for surface nucleation to

initiate a new layer.

4. 324 Agglomeration

In the precipitation of alumina trihydrate it is

generally recognised that under certain favourable conditions

(e.g. low agitation rate) the finer particles (< 20~m size)

agglomerate into larger particles in addition to the ordinary

crystal growth mechanism. Pearson (43) suggested that


159

agglomeratio n occurs through flocculates followed by cement-

ation, and the occurrence of some such phenomenon is con-

firmed by the fact that the agglomerate can be split, at

least partly into their component crystals by treatment with

sodium hydroxide solution. He also claimed that the

agglomeration is favoured by (i) fine seed (ii) high seed

concentration (iii) high temperature and (iv) slow stirring

rate, but no quantitative evidence was given to confirm this.

Agglomeratio n is usually desirable since it results

1n the coarsening of the product at the expense of the

unwanted fines, although there are some trial and error

techniques being applied in the industry to promote the

agglomeratio n, there are no basic studies related to this

mechanism.
Maricic and Markovcic (135) observed the formation

of firmly bound agglomerates in the crystallisati on system

which they named "intercrysta llisationtr. They also claimed

that this mechanism is exclusively characterist ic for the

particle size-range <20 microns (especially for the particle

s1ze 10 microns).

Scott (137) reported considerable agglomeratio n of

particles less than 20 ]Jm in the size under plant supersat-

uration conditions and found that the extent of agglomeratio n

is inversely proportional to the number of particles

originally present.
The process of agglomeratio n is generally accepted

to be composed of the following three steps.

1) Firstly, relative motion between the particles allows

them to collide, but this need not occur provided the

particles are within a range of influence.


160

2) Secondly, attractive forces between the particles allow

the particles to remain attached (but again, it is not necess-

ary to be in direct contact). During this process the

particles may also separate again due to agitation of the

precipitate.

3) Finally, ln the suspension ln which the particles are

simultaneously growing by deposition (e.g. crystallisation)

deposition can cement the particles together. Such deposi-

tion could occur by growth in the space between the two

particles and also possibly by the bridging action of the

growth layer extending from the surface of one particle to

the other.

The process of agglomeration is believed to take

the following form in its actual set-up.

Reversible
original individual
particles of
suspension
-... (surface
_

forces)
Aggregate

Irreversible
Agglomerate
(Cementation by
crystallisation)

As shown ln the process, aggregation or the initial cluster-

ing step is reversible. In an aggregate the force which

holds the particles together is weak so that the breakdown

of the aggregate to the initial constituent particles is


161

easily achieved with little energy requirement. Furthermore

the aggregate retains the identity of the individual con-

stituent particles, but an agglomeration is formed by the

cementing action of additional deposition by crystallisation

and therefore the agglomeration is not reversible.

4.325 Crystal Breakage and Attrition

It is generally believed in the Bayer crystallisation

system that crystal breakage can be significant enough to

affect the crystal size distribution during the precipitation,

which is usually undesirable. A high degree of agitation

promotes the crystal breakage and the breakage is closely

related to the properties of crystals mainly hardness,

crystal habit and crystal growth pattern (for example, den-

drite growth is more easily broken).

The laws governing the crystal breakage can be

compared to processes such as grinding, but the limiting

case of such comparison with the grinding mechanism is the

attrition which takes place in the crystallisation system.

Attrition means the chipping off of a small fragment from

the parent crystal, but this leaves the parent crystal prac-

tically unaltered in s1ze. For example, 200 small particles

of 2 ~m size or 1000 particles of 1 Vm size can be generated

from a 50 ~m crystal without significantly changing the size

of the parent crystal (i.e. 50 ~m particle). This effect

will generate a number of fine particles without changing the

larger particles to any significant extent, but gross break-

age takes place with the complete change in the present crystal

size by breaking into a number of small ones.

Although the operating conditions can be chosen to


162

avoid particle breakages, attrition is a difficult one to

avoid. Furthermore, attrition cannot be differentiated

from secondary nucleation, which is a function of super-

saturation. However, the mechanism of attrition has not

been investigated to any extent.

4. 3 3 MAJOR FACTORS WHICH AFFECT THE OVERALL KINETICS OF

DECOMPOSITION

The major factors that affect the overall kinetics

of crystallisation are as follows:


1) Temperature

2) Caustic concentration

3) Initial and final caustic ratio

4) Quality and quantity of seed

5) Method and rate of agitation

6) Main impurities present in the Bayer

process liquor.

The selection of optimum conditions in the crystall-

isation process in order to obtain the desired particle size

distribution and the maximum product output should be con-

trolled by studying the effect of the above major factors, on

the induction period individually: nucleation crystal

growth, agglomeration, crystal breakage and attrition. The

effect of organic impurities on the crystallisation process

has been widely discussed in Chapter 3.

4.4 SUMMARY OF CRYSTALLISATION

The main objective in the crystallisation stage is

to select optimum conditions in order to obtain desired

particles and the maximum output of product. The major

driving force in the crystallisation of alumina trihydrate


163

is the degree of supersaturation. The industrial Bayer

crystallisation process is followed by secondary nucleation,

crystal growth, agglomeration, breakage and attrition which

takes place simultaneously. An induction period has also

been noted at the beginning of the process.

Secondary nucleation is accepted as the principal

mechanism by which new crystals are generated in an agitated

suspension. The crystal growth is a surface controlled

mechanism, the main driving force for which is the degree of

supersaturation, and also the increase of temperature.

Agglomeration is a process which depends very much as

a) particle size of the seed b) seed concentration

c) temperature and d) agitation. The process of agglomer-

ation takes place through a stage of aggregation and then to

the final stage of agglomeration. The process of aggregation

is reversible whereas the agglomeration is irreversible.

The major variables for the overall crystallisation

process are: temperature, caustic concentration, caustic

ratio, quantity and quality of seed, the method and rate of

agitation and finally the major impurities present in the

Bayer process liquor.


CHAPTER 5

EXPERIMENTS RELATED TO THE SEPARATION, IDENTIFICATION~

ADSORPTION AND SOLUBILITY OF SOME OF THE ORGANIC CON-.

STITUENTS OF RECYCLE BAYER PROCESS LIQUOR


164

In this project the experimental work was con-

ducted in the following four areas:

1) Separation and identification of the organics

present ln both recycle caustic liquor and product alumina

trihydrate crystals.

2) Adsorption on alumina trihydrate seed crystals

of various pure organic compounds as well as different

molecular weight fractions separated from Bayer liquor.

(Since it is most likely that molecules adsorbed to the seed

crystal surface will effect crystal growth on that surface).

3) Solubility of sodium oxalate ln sodium alum-

inate liquor. (It has been shown that sodium oxalate at

concentrations near saturation play a significant role as an

impurity in the crystallisation process and possibly inhibit

crystallisation of alumina trihydrate due to coprecipitation

of sodium oxalate on the seed crystals).

4) Crystallisation studies were performed in a

batch crystallisator using pure sodium aluminate solutions

seeded with clean seed crystals under conditions where the

suspect organics were both present and absent.

This chapter describes the experiments relating

to 1,2 and 3 above, and Chapter 6 covers the crystallisation

experiments.

5.1 SEPARATION AND IDENTIFICATION OF THE ORGANICS PRESENT

IN BOTH RECYCLE CAUSTIC LIQUOR AND PRODUCT ALUMINA

TRI-HYDRATE CRYSTALS

Samples for the investigation work were obtained

from the Bayer process operation at Queensland Alumina Ltd.,

in Gladstone. The recycled Bayer liquor which was taken


165

after the precipitation stage was used as sample. It was

dark brown in colour and the composition is given 1n

Table 1.2. The pH of this liquor was greater than 14.

Samples were obtained of alumina trihydrate at the

thickening stage and before washing and were collected from

both the secondary and tertiary thickeners. These were

the samples most likely to be contaminated with organics 1n

the Bayer liquor either by coprecipitation or by adsorption.

5.11 SEPARATION AND ANALYSIS OF ORGANICS IN THE RECYCLE

BAYER PROCESS LIQUOR

Recycled Bayer liquor was subjected to various

methods of analysis and the main methods are given in

Figures 5.1 and 5.2.

There are many difficulties to overcome in attempt-

ing to separate the organics from the Bayer process liquor.

The primary problem was that the liquor was highly caustic

and most of the organic impurities had much greater solu-

bility in the caustic solution than in any organic solvent

chosen for extraction. Secondly, much of the organic

present in the liquor was in the form of the sodium salt

of the organic acid and in such form a limited range of

extraction and separation procedures is available. It is

difficult to extract the organic sodium salts into an

organic solvent, so in order to overcome this it was necess-

ary to convert the caustic solution to acidic conditions.

However, in doing this, some of the complex type organic

impurities may undergo various changes in structure as dis-

cussed in Chapter 3 1 but this method was adopted in some

cases in this work when the analysis was only limited to the
166

r-::=-~d caustic Total organic


28.15 gms/litre as C
~~~quor analysis
... using Beckman carbon
analyser

2.2 g/litre Forw~c Acid


Concentrate d Distillatio n Presence of acetic acid
acidified liquor identified

Direct G.C.

l
Presence of:
Ether extract analysis
~----------~----------~·1) Acetic Acid Sg/litre
1---....------.~-----' 2) Propionic acid .06 g/litre
3) Valeric acid .02 g/litre

Diazomethan e
esterificat ion G.C.Analysi s 3 Peaks obtained
not identified

Infra red analysis Presence of carboxylic


Evaporated to of solids h acid groups and aromatic
dryness rings

Figure 5.1 Separations and Analysis for the Organic Compounds


present in Bayer liquor.
167

Total organ ic carbon


Recyc led Caust ic ~----------------~~~ 28.15 g/litr e using
Liquo r Beckm an Carbon Analy ser

Carbo nation with C0 2


to neutr alise the
soluti on and separa te
Alumin ium Hydro xide

I Precip itated
T.O.C. 5% by weigh t

I Alumin ium Hydro xide


of solid trihyd rate

Filter ed Liquo r T.O.C .30.6 g/litr e


pH 9 of the origin al liquo r

Membra ne separat~io::1
with Millip ore type
molec ular cut off.lOO O

1Conce ntrate of the high er} I


molec ular compo unds over 1000

Membrane separa tion


with Millip ore type .Total Organ ic Analy sis
molec ular cut off with Beckman Carbon
10,000 A.."lalyser

Resul ts.T.O .C.


6.20 g/litr e of
origin al liquor
Conce ntrate M.W.
over 10,000

T.O.C .
1. 23 g/litr e of
origin al liquor

Figure 5.2 Separ ation and analy sis of organ ic compo unds presen t in
the Bayer proces s liquor .
168

stable lower molecular organic impurities.

5.112 Determination of Total Organic Carbon Present in

the Bayer Liquor

The organic impurities present in the liquor were

very complex in nature and it was decided that some prelim-

inary approach had to be made by determining the total

organic content present in the liquor. Three methods were

used for this purpose:

a) Using Beckman carbon analyser

b) Using Coleman carbon analyser

c) Titration with potassium permanganate and

oxalate to determine the total oxidisable

amount in the liquor.

a) Using Beckman carbon analyser

The Beckman carbon analyser is very much based on

the Van Hall (143) principle of catalytic conversion of the

carbon to a substance (usually C0 2 ) which is the measurement

by a sensitive detector. Usually this method was very

accurate for organics in water and dilute aqueous solution.

The Beckman carbon analyser is used as a standard equipment

for the determination of the organic level in water. In

this work the Bayer liquor was diluted 10 times in order to

get the conditions suitable for the equipment.

This system essentially involves vapourizing the

sample and oxidizing it in a stream of oxygen on a contact

catalyst bed. The resulting co 2 is swept by oxygen (via a

condenser and water trap) through a non-dispersive infrared

analyser (sensitised to C0 2 ) which, in turn, relays a signal

to a recorder.
169

Two combustion furnaces are employed, one that


. 0
oxidizes only organlc carbon at 950 C and the other that

oxidizes only inorganic carbon at 150°C. Two micro-volume

injections of sample (between 20 and 200 microlitres, depend-

ing on the range of analysis) are required, and the total

organic carbon (TOC) is determined by subtracting the inor-

ganic carbon (TIC) from the total carbon value (TCV). The

high-temperature combustion tube contains cobalt-oxide

impregnated asbestos packing, while the low temperature

combustion tube holds quartz chips wetted with 85 percent

phosphoric acid. In the latter tube the acid-treated pack-

ing causes the release of co 2 from inorganic carbonates and

the water is vapourized, but the temperature at 150°C is too

low for the oxidising of organic matter.

Usually determination of soluble organic and

inorganic carbon in water can be made by analysis of a sample

portion that has been filtered through a glass fibre filter

of approximately 0.3 ~m porosity. Particulate carbon levels

ln the sample can then be obtained by subtraction of the

soluble carbon values from the total values. Where water

samples contain particulate material of sufficient size to

prohibit injection of the sample via a microlitre syringe,

particles with a dimension greater than 100 ~m are unlikely

to pass through an ordinary microlitre syringe needle. The

total carbon levels are determined after reduction of particle

size via treatment with a high-speed blender or in a sonic

bath. Sample dilution before analysis is required only

when concentrations greater than 4000 mg/1 are present or

when samples with high salt, acid or base content are to be

analysed.
170

Bayer liquor was diluted 10 times and acidified

to pH2 by adding HCl, so that the precipitated Al(OH) 3 is

re-dissolved and also Na 2 co 3 present in the solution would

evolve C0 2 . The acidified sample was injected into the

equipment after filtering through the glass filter. The

samples were injected in 100 microlitres. Firstly, it was

only heated to 150°C to determine any inorganic carbon

content, then a fresh sample was put in the 950°C chamber

to determine the total organic carbon content. After a few

runs it was noticed the deposition of inorganic salts was

interfering.

The total organlc carbon analyses for the recycle

Bayer process liquor using the Beckman Analyser are shown in

Table 5 .1.

Test Sample Reading at 150°C Reading at 950°C Total


dilution chamber mg/litre chamber mg/litre organic
carbon
@ g/1

1 10 X 120 2870 28.7

2 10 X 100 2890 28.9

3 10 X 150 2830 28.3

TABLE 5.1 Results of Beckman Carbon Analyser

During the calculation of total organic carbon the

author has not subtracted the value obtained at 150°C from

the total value at 950°C(Table 5.1). Usually the figure

obtained at 150°C should be accounted as inorganic carbon or

the co 2 evolved due to the presence of carbonate. However,in

this method the samples were acidified to pH2. Therefore

any co 2 from the inorganic carbonates had already been

evolved, before the test.


171

However, the end results showed that there was

about 1000 - 1500 PPM of inorganic carbon present in the


f

liquor. Theoretically, such an amount of inorganic carbonate

cannot be present at pH2. The author suggests the following

explanation for the inaccuracy of the results obtained.

i) Some of the organic compounds present in the Bayer

liquor after acidification are decomposed before 150°C and

have been interpreted as inorganic carbonate figures.

ii) Although the carbonate in the liquor has reacted with

acid and evolved co 2 , there has been a supersaturation of

C0 at this stage.
2
One of the major drawbacks of the Beckman

Carbon Analyser is that it has not been improved and cannot

differentiate and compute separately the inorganic carbon

from the unstable organics which could be decomposed before

150°C.

b) Using Coleman Carbon Analyser and Potassium Permanganate

titration method

Details of the above two methods are provided

ln Appendix II. Both methods were unsatisfactory for Bayer

process liquor.
In using the Coleman Carbon Analyser, sodium

carbonate in the liquor overestimates the results, but in

order to eliminate carbonate the sample has to be acidified

and later it should be in dried form to be used in the

equipment. By so doing it is always possible that some of

the volatile acids present in the liquor are lost during

evaporation.
172

A major drawback in the potassium permanganate

titration method is the difficulty in obtaining an accurate

end-point due to complexity in nature of the humic sub-

stances and also the formation of a number of compounds of

manganese. This is extensively described 1n Appendix II.

The results obtained from both methods are

summarised in Tables 5.2 and 5.3.

Sample Total organ1c


(as carbon)

I Bay er process liquor 27.6 g/litre


11
II -do- 27.3
11
III -do- 26.5

Table 5.2 Results of the Coleman Carbon


Analyser

Sample Total organic


oxidised by
permanganate
(as carbon)

I Bay er process liquor 9.08 g/litre

II -do- 10.59 11

11
III -do- 11.51
11
IV -do- 9. 5
11
V -do- 6.85

VII -do- 6.37 11

Table 5.3 Results of the potassium permanganate


titration method
173

5.113 Use of Distillation Method to Identify s6me of the

Volatile Organic Compounds in the Bayer liquor

The distillation method has assisted in obtaining

some useful information about volatile organic compounds in

the form of acids by acidifying.

250 ml of Bayer liquor was concentrated down to

150 ml and it was acidified to almost pH 1, by adding con-

centrated hydrochloric acid. During the acidification heat

is evolved therefore precautions were taken not to heat the

sample over 60°C as volatile organic acids present in the

sample may be evolved. This was done by adding HCl in a

very small quantity in a cold water bath. Aluminate in the

solution is precipitated as alumina trihydrate and it was

redissolved in the acidic medium. The sample was now ready

for distillation.

A 1-litre distillation flask with a distillation

column, cooled by cold water, was used, as shown in Fig. 5.3.

The receiver was immersed in an ice bath in order to minimize

any loss of acid vapour. The sample in the flask was heated

to the boiling point of the solution (approx. 100°C).

However, prior to the water vapour, HCl vapour was evolved.

The liquor was boiled and some of the vapour condensed and

collected in the collecting flask. The condensed liquid

had a strong smell which could be due to the presence of

either organic acids or hydrochloric acids. Heating continued

until the solution in the flask was almost thick. The quan-

tity of condensed liquid was measured and the sample was

checked with the U.V. absorption, showing absorption at

210 )lffi,, The U.V. peak was determined with various dilutions.
174

water

Gentle Acidified
heating Bayer liquor

Fig. 5.3 Distillation of volatile acids from acidified


Bayer process liquor.

It was noticed that the condensed solution was

discoloured with KMno 4 . The above result is an indication

of the presence of organic acids in the sample.

In order to determine the amount of organic present

in the condensate, permanganate value was determined by

titrating a known quantity of the sample of condensate with

a standard solution of KMn0 4 in the acidic medium, as

described in Appendix II. The results obtained are as

follows:

Total quantity of Bayer liquor treated 250 ml

Volume after concentration 150 ml

Total volume after acidification 250 ml

Volume of condensed solution collected- 50 ml


175

Molarity Volume Volume Molarity of Formic acid


of KMn0 (distillate) (KMnO ) distillate content in the
4 4 Bayer process
titrated (calculated
from results) liquor
Ml M1 g/1

.031 5 39.5 .2449 2.25

.031 1 8 .248 2.28

.031 1 7.7 .238 2.18

Table 5.4 Titration results and the formic acid content


of the distillate collected from the acidified
Bayer process liquor

Usually in the Bayer process liquor, salts of

acetic acid and formic acid are suspected to be present as

impurities. These two acids have low boil~ng points and

with steam they could easily vaporise and condense with

water.

Acetic and formic acids have max1mum absorption 1n

the U.V. range at 210 ~m which is similar to the results

obtained from the sample. Furthermore, neutral solution

of the sample gave a deep red colouration with ferric chloride

confirming the presence of either acetate or formate. Only formic

acid is oxidised by KMn0 4 in acidic medium, therefore the

figures obtained from the KMn0 4 titration are taken to be

the amount of formic acid in the Bayer liquor.

5.114 Use of Gas Chromatography to analyse the Organics 1n

the Bayer liquor

Gas chromatography lS a quick and easy method of

determining the organic compounds in a solution which is vola-

tile at high temperatures. The main requirement is that the

organ1c compounds are stable in their gaseous form.


176

The basic principle of gas chromatograp hy involves

the preferential absorption and subsequent desorbtion of

volatile materials on to an absorbant substance. In the

G.C. Method the vapour of the organic compound to be analysed

is mixed with a carrier gas, usually nitrogen or argon, and

the gas mixture is known as the moving phase. It is then

passed into a column of absorbent material, the stationary

phase, which can be either a solid silicate material or a

non-volatile liquid absorbed into a porous solid.

A small sample of the gas to be analysed is injected

into the carrier gas stream and the gaseous components are

selectively absorbed on to a long column (about 2m) of

stationary phase material. They are then eluted one at a

time. The presence of the components in the eluent gas

is then detected and measured by a device which gives an

output on a chart recorder. The peaks can then be identi-

fied by subjecting known standard gases to the same condi-

tions as those used when analysing the test sample. The main

variables in gas chromatograp hy are the carrier gas flow

temperature and the sample quantity. Stationary phase

columns may also be changed.

A schematic diagram of a typical gas chromatograp h

1s given in Figure 5.4.

The organic impurities in the Bayer liquor are

usually in the form of organic salts, therefore they cannot

be detected as volatile unless these compounds are converted

into the acidic form

A 100 ml of Bayer process liquor was first concen-

trated to 70 ml by boiling and then acidified to pH 1 by

adding concentrated HCl. It was noticed during the acid-


177

Differential
Flow

To waste or
fraction
collector

I
Sample
injection

Column

ics Recorder
Column

Fig. 5.4 A schematic diagram of the typical gas


chromatograph.

ification that some of the organic present in the solution

was precipitated as brown material. The solution was

filtered, transferred to a quick-fit liquid/liquid extractor

and extracted with 400 ml of diethyl ether (analytical grade),

added in small quantities over about ten hours. The

brownish-yellow colour of the Bayer solution was gradually

transferred to the ether extract, which was then concentrated

to 100 ml in a water bath.

During this method of preparation it was possible

that some of the organics in the Bayer liquor could change 1n

structure during acidification. However, the objective of

this method was to track the most volatile organic acids and

usually those acids are not expected to be affected by the

acidification.

Sample injection was carried out in two ways. In

the first method the ether sample was injected directly to

the gas chromatograph, whereas in the second method the ether


178

extract was evaporated to dryness and the residue dissolved

in methanol and methylated using an etheral solution of

diazomethane. Diazomethane was ~prepared in the laboratory

from diazald. Methyl esters are more volatile than its

carboxylic acids, therefore some of the organic acid which

cannot be trapped in the G.C. in acid form (due to the high

boiling points) is expected to be trapped when it is methy-

lated to methyl esters.

a) Direct Method of injecting Ether Extract to the Gas

Chromatograph

The equipment used was Hewlett Packard Model 5710A

which has facilities to programme the temperature. The out-


going gases are detected either by the flame ionising detector

or refraction index detector.

A sample of the ether extract in 5 ~1 was injected

into the gas chromatograph equipment with the following

conditions:

Type of column:

4 ft. x 18" I.D. stainless steel column

packed with Poropak Q. Mesh size 80-100.


Temperature programming:

Initially holding at 100°C for 16 minutes

then with the rising rate of 4°C/min to

250°C holding for 10 minutes.

Temperature of the detector - 300 0 C

Temperature of the injecting port - 100°C

Detector - flame ioniser.

Nine peaks were obtained and to identify them reten-

tion time was compared by injecting known compounds such as

acetic acid, formic acid, lactic acid, propionic acid, butonic


179

acid, valeric acid and pivalic acid, with different concen-

trations. The same conditions were applied as previously

in the gas chromatograph when the reference samples were

injected.

In order to confirm the identify of the peaks, the

samples were injected with slightly changed conditions so

that the retention times of the peaks were also changed

slightly, then, under the same conditions, the known corn-

pounds were injected.

b) Injection of methyl esters of the extract

The sample was prepared as mentioned previously.

5 ]Jl of the sample was injected with the conditions as set

out in Table 5.5.

The type of chromatograms obtained from both

methods of injection are shown in Figures 5.5, 5.6, 5.7 and

5.8. Figures 5.5 and 5.6 illustrate the peaks obtained

from the direct analysis of ether extract under different

conditions. Retention times obtained were compared with

the known carboxylic acids which have a boiling point in

the range 100 - 250 0 C. The known carboxylic acids injected

were as follows:

1) Formic acid (formic acid cannot be detected by

the flame ioniser)

2) Acetic acid

3) Lactic acid

4) Propionic acid

5) Butonic acid

6) Pivalic acid

7) Valeric acid
180

Conditions I Conditions II

Column 6'x1/8" stainless 10'x1/8" stainless


steel column packed steel packed with
with liquid phase SE 30-20%
O.V-17,-mesh gas-
chrom Q
Temperature
programming

Initial temp. 54°C held for 100°C held for


16 mins. 8 mins.

Rate of temp.

Final temp.

Temperature
at detector

Temperature
at injecting
port

Table 5.5 Various conditions applied in the G.C.analysis


of methyl esters of Bayer process liquor.

The reference samples were chosen out of the

carboxylic acids which are normally stable in the volatile

phase. Identifications were made by comparing the reten-

tion time with the reference samples. The identified sub-

stances were confirmed by changing the temperature programm-

ing and comparing again with the known samples. The peak

heights were compared with the peak heights of different

concentration of the known samples in the ether mixture.

Such calibrations give an approximate value of the concen-

tration of the identified organic impurities.

Table 5.6 summarises the results and the confirm-

ation arrived at from the chromatogram of ether extract

illustrated in Figures 5.5 and 5.6.

From the results only the presence of acetic,

propionic and valeric acids were confirmed. The presence


Conditions:- Poropak column
Initial temperature at 100°C
Holding time - 16 min.
Rate - 4°C/min.
Final temperature - 250°C
Sample vol. - 5 ~1.

~
·M
u
~

u ~
·ri ·ri
~ 0
w ~
0
~ ~ 0
w ·M
~ (1) ~ ~
~ 0 ~ ·ri
w ·ri ·M u
0 ~
%~
m
~ 0
·ri
~
(2) 0
m
M

Fig. 5.5 Gas chromatogram of the Bayer process liquor - direct injection of the ether
extract, - condition - I.
Condition s:- Poropak. column
Initial temperatu re - 100°C
Holding time - 32 mins.
Rate - 4°C/min.
Final temperatu re - 250°C
sample vol. - 5 ~1.

'tl
·.-!
()
m
()
·.-! 'tl
.j.l ·.-!
(J) ()
l-l () m
(J) m
'tl
:5
(J)
(1)
()
·.-!
~
·.-!
()
0 m
·.-!
0; ()
0 ·.-!
l-l l-l
0; (J)
(2) r-i
m
:>
(3)

Fig. 5.6 Gas chromatog ram of the Bayer process liquor - direct injection of
the ether extract and condition -II
I-'
CO
N
Conditions:- Column - 3% OV-17 mesh gas chrom. Q
Initial temperature - 54°C
Holding time - 16 min.
Rate - 4°C/min.
Final temperature - 290°C
Sample volume - 5 ~1.

(1) - (7) - unidentified compounds

(1)

(6)
(7)

Fig. 5.7 Gas chromatogram of the Bayer process liquor- methyl esters of
the extract - Condition I
Conditions:- Column SE - 30 - 20%
Initial temperature - 100°C
Holding time - 8 mins.
Rate - 4°C/min.
Final temperature - 290°C
Sample volume - 5 ~1.

(1) - (6) - unidentified compounds

(2)

(5)

(6)

Fig. 5.8 Gas chromatogram of the Bayer process liquor - Methyl-esters


of the extract - Condition II
Sample:- Direct Analysis of Ether Extract

Conditions Column Peak No. Sensitivity Retention Peak Reference sample Calculated
time or chart Height which has similar concentration
Distance retention time in the Bayer
cm. cm. li uor
(1)
Initial Temg. Poropak 1 100x128 13.4 4 Acetic acid 5 g/litre
held at 100 c 2 10x128 17 1.5 Propionic 0.06 g/litre
for 16 minutes 3 do 21.7 1.0 Lactic acid
Rate 4°C/min. 4 do 22.4 2.0
to 250°C 5 do 23.5 2.1 Valeric .02 g/litre
(Fig. 5 • 5) 6 do 26.7
7 do 28.4 2.0
8 do 31.2 2.6&4.5
9 do 33.6

{2)
Initial Temg. 1 100x128 20.8 Acetic
held at 100 c 2 10x128 37.1 Propionic
for 32 minutes 3 do 47.1 Valeric
Rate 4°C/min.
to 250°C

TABLE 5.6 Results of G.C. Analysis


186

of lactic acid was noticed in some of the G.C. analyses

when compared to the retention time of the standard sample

of lactic acid as shown in Table 5.6. However, it was not

reproducible when the temperature programming condition was

altered for confirmation.

Peaks obtained from the methyl ester samples

were not identified due to the difficulty of methylating

each reference sample to be injected for comparison.

However, it was noted that some of the carboxylic acids in

the extract which are not volatile and cannot be trapped by

direct injection, are trapped in the form of methyl esters.

5.115 Infra Red Analysis

A sample of the Bayer process liquor was first

acidified and extracted into the ether as prepared for

G.C. analysis. The ether extract was then evaporated to

dryness in the water bath and a brown wavy type solid material

was obtained. An infra-red spectra of the material was

obtained on KBr plate.

The spectrum obtained is illustrated in

Figure 5.9. Although infra-red analysis of such an organlc

mixture would not characterise it, it definitely did suggest

at least some of the functional groups in this mixture.

The major absorption bands from Figure 5.9 are

listed in Table 5.7. These bands are broad presumably

because of extensive overlapping of individual absorptions.

For comparison studies, the infra-red spectra

of humic acids and fulvic acid published by Schnitzer (53)

lS illustrated in Figure 5.9.


Fulvic acid
(previously
published)(53)

Humic acids
(previously published)
(53)

Sample

4000 3000 2500 2000 1600 1400 1200 1000


-1
Frequency (cm )
Figure 5.9 Results of the Infra-red analysis of desorbed material from the
trihydrate seed.
188

Major absorption bands Possible functional groups


of the Bayer liquor sample
-1
Frequency cm

3400 - 3100 Hydrogen-bonded OH at


1
3400 cm-

3000 - 2900 Aliphatic C-H stretch


1
2900 cm-

1750 - 1700 C=O of co 2H, C=O stretch of


ketonic carbonyl group at
1
1725 cm-

1650 - 1600 Aromatic C=C, hydrogen bonded


C=O of carbonyl, conjugated
1
with carbonyl, coo- at 1630 cm-

-1
1450 - 1400 Aliphatic C-H at 1400 cm

1
1300 - 1260 e-o at 1200 cm-

Table 5.7 Main infra-red absorption bands of the


Bayer liquor sample.
189

Major absorption bands occur at about 3400 cm -1

(OH-stretching), 2900 cm- 1 (aliphatic C-H stretching),

1720 cm- 1 CC= 0 stretching of COOH and ketones), 1620 cm-1

(aromatic C = C and/or H- bonded C = 0). Referring to the

spectra of the humic and fulvic acid, spectra of the organic

extract used in the experiment is very similar to the spectra

of the humic acids. A unique feature of the spectra of the

organic extract from the Bayer liquor is the absorption in

the 3400 cm- 1 which is weak and centred in the range 3100 -
-1
2900 cm . This feature can be explained as a result of the

presence of considerably more aliphatic C - H stretching

than does humic acid extracted from the soil. Alternatively,


it is due to the small amount of OH - stretching in the

organic extract. It is also noteworthy that the absorption

band at 1720 cm- 1 1s stronger in the case of organic extract

than the humic acids which is mainly due to the presence of

more -COOH groups. The absorption band at 1620 cm- 1 which

is due to the aromatic C = 0 and/or H - bonded C = 0 is

weaker than in the humic acids, possibly indicating the

presence of less aromatic. The absorption at 1440 cm -1


which is prominent in both organic extract and humic acid

samples is again due to the presence of H-bending of C-H

aliphatic groups. The broad absorption band between


1
1260 - 1300 cm- appeared in the spectra of organic sample,

whereas in the spectra of both humic and fulvic acid, this

band is not shown. This band is usually due to the C-0


-1
stretching vibration at 1200 cm However, the broad
absorption in this region is possibly increased due to the

C-0 stretching from diethyl-ether found in the dried sample

as impurities. This was initially prepared by extracting


3400 2940 - 1800 1720 1640 - 1440 1250
Sample
2800 1600
-1 -1 -1 -1 -1 -1
cm- 1 cm cm cm cm cm cm

Humic acid Strong Very Absent Strong Moderate Weak Absent


weak

Strong Very Absent Very Moderate Weak Absent


Fulvic acid
weak strong

Organic Strong Strong Absent Very Moderate Moderate Very


extract from shifted to strong strong
Bayer liquor 3200 cm-1

Table 5. 8 Relative intensit ies of selected absorpti on bands for


all spectra

I-'
tO
0
191

the organics ln the Bayer liquor into an ethereal solution.

Table 5.8 summarises the relative intensities of

humic acids, fulvic acids and the organic extract from the

Bayer liquor.

In general, the results indicate that the spectra

of organic extract is very similar to the spectra of humic

acids and fulvic acids, suggesting the presence of essentially

similar chemical structures, differing mainly in the contents

of functional groups. The presence of carboxylate lons

(COO-) indicates that the organic impurities in the Bayer

liquor are found as salts of carboxylic acids.

5.116 Use of Membrane Process for Characterisa tion

The main objective of the work done in this

section was to determine the presence of any higher molecular

weight fraction. The Bayer liquor was passed through the

ultra filtration type membranes with specific molecular cut

off. The concentrates so obtained were examined for total

organic carbon to get an idea about the higher molecular

compound content in the Bayer liquor. The content of this

work and the results are summarised briefly in Figure 5.2.

Usually the membranes used for ultrafiltrati on

have the following characterist ics:

a) the size of solute retained in the concentrate are over

the molecular weights 1000 and 10,000

b) the effect of osmotic pressure of feed solution on the

efficiency of the ultrafiltrati on membrane is negligible

c) the mechanism of the separation is based on the molecu-

lar screening and the proper pore size, and the pore size

distribution in the membrane play an important role.


192

The Bayer liquor had to be treated before

passing through any membrane as most of the commercial type

ultrafiltration membranes are affected by highly caustic

solutions. Therefore the pH of Bayer liquor was gradually

brought down to pH 9. This was achieved by bubbling C0 2

through the solution. Sodium hydroxide in the solution is

converted into Na
2
co 3 during the process. Sodium carbon-

ate has the pH range of 9.

A 1-litre sample of Bayer liquor was poured

into a beaker and co 2 was bubbled through it for about

20 hours. The pH of the liquor which was 14 initially was

dropped down to pH 9. During this process aluminate ions

in the liquor were precipitated as aluminium hydroxide due

to the change of pH.

The precipitate was filtered and washed and

the filtrate was measured for the volume change. One litre

of the liquor was changed into 750 ml of filtrate after

precipitating aluminium hydroxide. 100 gm of aluminium

hydroxide was obtained from one litre. The precipitated

aluminium hydroxide was dried and tested for total organlc

carbon content using a Coleman carbon analyser.

The filtrate was first passed through a membrane

which has a nominal molecular cut-off 500,000 fitted

in a stirred cell, thereby obtaining a solution free of fine

solid and colloidal material. The filtrate is now ready

for membrane separation.

a) Separation of molecular weight over 1000

The apparatus used was a stirred cell with a

capacity of 100 ml fabricated from clear plastic material,

as shown in Figure 5.10. The membrane is fitted to the


193

Figure 5.10 Stirred cell type membrane used for


the separation of organic impurities,
M.wt. > 1000.
194

bottom of the cell and the pressure is applied to the cell

from a nitrogen cylinder connected to it with a regulator.

The membrane used was a millipore type ultrafiltration

membrane, type PSAC, with the nominal molecular weight cut

off 1000.
100 ml of the filtrate was poured into the cell

and nitrogen pressure was regulated at 25 lbs/sq.in. The

flux was very slow, only about 1 ml per minute. It was

noticed that the colour of flux was lighter than the original

and also the concentrate in the cell, indicating that most of

the brown colour retains as higher molecular compounds in

the cell. When the level of liquor in the cell was dropped,

it was refilled with distilled water. The addition of dis-

tilled water was continued until only the distilled water

was passed through the membrane. This was tested by check-

ing the U.V. absorption of the flux at different times,

using an ultra violet spectrophotometer. When there was no

absorption in the U.V. range by the flux sample it was

decided that the separation was complete. The concentrate

was diluted to 100 ml in order to equalise back to the

original volume taken. The concentrate and the original

solution were examined for the total organic carbon content

using the Beckman carbon analyser.

b) Separation of organic impurities over 10,000

The membrane used in this work was millipore

type PTGC membrane with the nominal molecular cut off 10,000.

The filter kit included 5 filter units. Each


2
unit consisted of 11 cm of Pellicon type filtration mem-

brane permanently sealed to a cylindrical plastic core.

The retentive surface of the membrane faces outward.


195

Pigure 5.11 Immersibl e type membrane used for


the separatio n of organic impuritie s,
M. wt > 10, 0 0 0 •
pH
Original pH of the organic material
Concentration of high molecular compound 0.805 g/1.
Total volume 100 ml.
- - - - - (1)
Concentration of HCl = 0.1 N
Horizontal dotted line - equilibrium line

---- (3)
4

1 2 4 6 8 10 12 14 16 18 20 22
Volume of 0.1 HCl

Fig. 5.12 pH - titration of the high molecular compound M wt. over 10,000
197

In use, the device is lowered into the solution to be pro-

cessed and is then connected to any convenient vacuum source.

Filtrate passes through the membrane into the core, and thus

flows via the vacuum line to a suitable trap. Retained

molecules (the retontate) remain in the original sample vessel.

100 ml. of the Bayer process liquor was taken into

a beaker and the membrane was immersed fully as shown in

Fig. 5.11. When the vacuum was applied the lower molecular

solutes and water pass through the membrane into the collect-

ing flask. Higher molecular solutes over 10,000 were concen-

trated in the beaker. The concentrate in the beaker was

mixed up with distilled water in order to keep the membrane

fully immersed in the solution for successful performance.

The addition of distilled water was continued until the

absorption of spectra for filtrate in the ultraviolet region

was blank. After the separation was completed, the concen-

trate was made to 100 ml. and it was tested for total organic

carbon content. The sample was later evaporated until the

dryness in. the oven settled at 100°C. The solid brown

coloured waxy compound was obtained and weighed. A known

concentration of this material was titrated against a solution

of 0.1 molar hydrochloric acid us1ng a pH meter to obtain a

titration curve. The curves obtained are shown in Fig. 5.12.

Although the curve obtained was not clear, the results show

the formation of numbers of equilibrium points indicating the

presence of different compounds act separately in the mixture.

The suspected equilibrium points are outlined by the dotted

line. Different functional groups in this complex mixture

have reached an equilibrium with HCl at different levels of pH.


198

The determination of total organic carbon content

after each membrane separation suggests an idea of the quan-

tity of higher molecular compounds present in the Bayer liquor.

The results obtained from both types of separation are summar-

ised in Table 5.9.

as carbon

Re cycled caustic liquor 28.75 g/litre

Re cycled caustic liquor 30.6 g/litre

after carbonisation

Molecular wt. over 1,000 6. 2 g/litre

Molecular wt. over 10,000 1. 735 g/litre

Molecular wt. below 1,000 24.4 g/litre

Table 5.9 Total organic carbon composition of


the Bayer process liquor in relation
to the various molecular fractions
(determined as carbon g/litre)

During the carbonation of the Bayer process liquor,

some of the organlc impurities in the Bayer liquor are

adsorbed on to the crystals of precipitated aluminium

hydroxide. The total organic carbon analysis on the pre-

cipitated aluminium hydroxide using a Coleman carbon analyser


199

indicate that it contains about 5% (by weight) of organic

impurities contaminated with aluminium hydroxide. Whether

these organics are adsorbed or eo-precipitated due to the

decrease in pH is a question for further investigation. How-

ever, the quantitative results obtained for the higher molecular

compounds present in the Bayer process liquor cannot be con-

sidered as the most accurate due to the loss of some of the

organic impurities along with the aluminium hydroxide precip-

itated previously during the carbonation.

The millipore type membrane used for this work was

designed and specified by the manufacturers to produce a mole-

cular cut off at 1000 and another at 10,000 based on the pore

size of the membranes. The accuracy of these results is

questionable due to the following drawbacks.

1) The pore size of the membrane cannot be considered as the

main basis for different molecular cut off because different

organic compounds have different shapes. For example, long

carbon chain could easily pass through a small pore slze.

2) During the membrane separation of higher molecular

compounds, some of the organic compounds also could go through

a structural change, such as polymerisation, colloidal forma-

tion, breakages due to the change in the pH.

3) In the stirred cell as well as in the immersible type

membranes, there is a possibility of forming a concentrated

layer of the organic impurities on the top of the existing

membrane, thus changing the function of the membrane. Such

a formation could easily alter the pore size of the membrane,

furthermore the organic compounds concentrated near the

membrane as a layer could act as a new membrane. However,


200

the above possibilities are minimised by continuous stirr-

lng to a certain extent.

4) Usually the flux of both stirred cell and the immer-

sible type membrane are very slow. It was almost in the

range of 10 ml - 15 ml per hour. A complete separation takes

even longer than 8 hours. Due to the prolonged period of

contact of membranes with the organics, the membranes are

liable to be changed in their properties at a later stage.

5.12 SEPARATION AND IDENTIFICATION OF ORGANICS WHICH ARE

ASSOCIATED WITH THE ALUMINA TRIHYDRATE PRODUCT

It is believed that the organic impurities in

recycled Bayer process liquor inhibit the crystallisation

process either by coprecipitating with the alumina trihydrate

or by adsorbing onto the seed crystal surfaces and thus

affecting crystal growth. In order to assess the extent

of association with the growing crystal, samples were

obtained of alumina plant product at the final stages of

crystallisation and before the washing stage. These

samples which were provided by Queensland Alumina Ltd., from

the tertiary thickener of their Gladstone plant, contained

adherent plant liquor which was thoroughly washed from the

crystals prior to each of the tests carried out.

Various methods of desorption were applied to extract

the organics from the product trihydrate. Figure 5.13 out-

lines various methods applied and summarises the results

obtained thereafter.
2Q1

There were two major methods applied to desorb

and characterise the organics contaminated with the product

alumina trihydrate. The two methods are as follows:

1) Methanol treatment followed by hot water desorption

2) Cold water wash followed by hot water desorption.

5.121 Methanol treatment followed by hot water desorption

The alm of this method of desorption was firstly to

dissolve and separate most of the inorganic contaminants

and caustic from the product alumina trihydrate without

hindering the organic impurities contaminated in the crystals

of alumina trihydrate. Later the organics are extracted

from the crystals. Most of the inorganic salts, such as

caustic and sodium carbonate are dissolved in the methanol.

Usually organic salts are less and sparingly soluble in the

methanol.
After the methanol wash the product was dried and

the X-ray defraction analysis was performed. The XRD

analysis usually indicates if there are any crystalline

organic salts deposited along with the alumina trihydrate

seed during the precipitatio n. The results are discussed

later in this section.

A weighed quantity of the dried sample was extracted

into the hot water. The extract was divided into two

portions, A and B, portion A was evaporated until dryness at

100°C. The dried sample from A was weighed to determine

the amount of impurities extracted into the hot water.

An infra-red spectrum of dried sample of A was


202

Wet crystals from


tertiary thickener

Cold water
wash & filter

Hot water
extraction

Aqueous extract

Methanol Evap. to
wash and dryness
crystals
dried
~xy brown 81 g solid organics
L__solid per kg of crystals
Membrane
separation I.R. Presence of aromatic rings
of 1000 MW ana.lys1.s phenolic compounds. No
solutes carbohydrate.
Aqueous concen- Evaporate 3.44 g solid organic per
trate 1000 MW kg of crystals

Crystals still Presence of sodium oxalate


containing x-ray diffraction
confirmed. Many unidenti-
methanol Analysis fied diffraction lines.
insolubles

Hot water
extraction

Evap. to
Aqueous extract ~ 61 g per kg crystals
dryness

Membrane concentration Compounds over MW 1000


of 1000 MW solutes 10 g per kg crystals

Fig. 5.13 "Desorption" of organics from Bayer plant


crystalliser product.
203

taken to study the functional groups present in the sample.

The results are discussed later in the section.

The portion B of the hot water extract was first

filtered through a membrane with the pore size of about


0
140A with the nominal molecular weight cut off about

500,000, to separate any fine solid particles from the

solution such as alumina trihydrate particles. Then the

filtrate was passed through a millipore type membrane with

the nominal molecular weight cut off 1000 in a stirred cell

as shown in Figure 5.10. The liquid ln the stirred cell

was washed with distilled water until it was concentrated

in the cell with the compounds over 1000 molecular weight

cut off. The concentrate was dried and weighed to measure

the quantity.

5.122 Cold water wash followed by the hot water desorption

The method adopted here differs only from the

previous method by the choice of the washing reagent used.

Methanol was used in the previous method.

The aim of the previous method was to wash the

caustic and sodium carbonate from the surface of the alumina

trihydrate leaving behind most of the contaminated salts of

carboxylic acids with the seeds as they are not soluble in

the methanol. Later when the product is desorbed with hot

water carrying most of the undissolved organic salts to the

hot water extract. In this present method, the methanol

wash is eliminated from a cold water wash. The cold water

wash usually removes even some of the organic salts along

with the caustic and inorganic salts, leaving behind the corn-

pounds which were mostly adsorbed on to the surface of

alumina trihydrate.
204

A weighed quantity of alumina trihydrate was

washed several times with cold water at 10°C until no

caustic is present in the washed water. The washed liquor

was checked by a pH meter until the pH came down to about 8.

However, allowance had to be made for some of the eo-

precipitated organic contaminants being washed away with the

cold water leaving the organics which were adsorbed onto the

surface of trihydrate products.

After the cold water wash the sample was drained

and poured into boiling water which was stirred for about

30 mins. whilst boiling. The hot water extract was then

filtered and divided into two portions, namely A and B.

Portion A was evaporated until dry 1n an oven


0
where the temperature was fixed at 100 C. The dried sample

had a waxy brown appearance and infra-red analysis was made

on it using paraffin oil as the base.

Portion B of the extract was passed through a

membrane with the molecular weight cut off of about 500,000

to separate any fine solid particles. It was then passed

through a millipore type membrane with a nominal molecular

weight cut off of 1000. The resulting concentrate was

then dried and weighed.

The results obtained from both methods of desorption

experiments were not very conclusive. The poisoning effect

of the organics in the Bayer process liquor are usually

divided into two groups on the basis of its behaviour.

1) The organic impurities which reach supersaturation

during crystallisation of alumina trihydrate and eo-

precipitates with the product. In this case it is believed

that the organic precipitates on the surface of alumina


A = Gibbsite
B = Sodium Oxalate
A A
A

A
A
A A A A
A

Fig. 5.14 X-ray diffraction analysis of the product alumina trihydrate


after the methanol wash.

N
0
(Jl
206

trihydrate. However, methanol may also have dissolved some

of this brown coloured humic acid fraction.

X-ray diffraction patterns take on the above dried

sample of alumina trihydrate after the methanol wash has

indicated the presence of sodium oxalate. Sodium oxalate

is crystallised with the trihydrate. The XRD patterns

obtained are illustrated in Figure 5.14. In addition to

the peaks obtained due to alumina trihydrate and sodium

oxalate, there were a number of peaks due to unknown com-

pounds which cannot be identified from the available charts.

It is suggested that those unknown peaks are due to some

organic compounds which were crystallised with alumina

trihydrate.

The results of the XRD patterns also reveal that

the sodium oxalate, and some unknown organics, crystallise

along with the alumina trihydrate after reaching the level

of supersaturation. Usually XRD analysis detects only

crystalline forms of a compound and not the adsorbed layer

on to solid surface.

Analysis of the hot water extract of the alumina

trihydrate samples indicate it contains about 1% by weight

higher molecular compounds over nominal molecular weight

1000. This was revealed from the membrane filtration.

Results obtained from the second method of treat-

ment (cold water wash) are compared with the previous method

in Table 5.10. However, an error is encountered in both

methods by the inorganic contaminants which were computed to

the total organic per kg. of product trihydrate, as it was

measured by weight.
207

Methanol wash Cold water wash


followed by hot followed by hot
water desorption water desorption

TOC per kg of
seeds of the 81 g 61 g
extract

Molecular wt.
> 1000 per kg 3.44 g 10 g
seeds

Table 5.10 Total organic content in the


extract (by weight) desorbed
from the product alumina trihydrate.

In order to justify the possible adsorption of

organic impurities onto the alumina trihydrate surface,

the following simple calculations were made to determine

the amount of organic impurities required to form a complete

monolayer on the total surface area of solid alumina tri-

hydrate.

The surface area of alumina trihydrate was deter-

mined and varied in the range of 0.1 - 0.2 m2 /g. The

highest value of the surface area was taken for these

calculations.

The following assumptions were made ln the calcula-

tions.
2
The density of organic materials were taken as 1.2 g/cm

The thickness of a mono-layer of organlc

material-50°A
2
Surface area of alumina trihydrate .2 m /g

The weight of organic required to form a] 1.2 g per Kg


of alumina
mono-layer of organic impurities per =
( trihydrate

Kg of seed
Paraffin

Paraffin

(1)

Paraffin

3500 3000 2500 2000 1800 1600 1400 1200 1000 800

Wave number

Fig. 5.15 Infra-red analysis of the hot water desorbed extract of the product
aluroina trihydrate.

N
0
(X)
209

When the above results are compared with Table 5.10,

it is clear that the formation of more than a monolayer of

organlc on the surface is possible.

Infra red spectra taken on a sample of hot water

extract after membrane filtration is shown in Figure 5.15.

The IR analysis was performed for the sample after mixing

with paraffin oil. The peaks obtained due to the paraffin

oil is marked "Paraffin" and the rest of the peaks are due

to the sample. These peaks were studied by using published

charts for the frequencies of characteristic groups. The

peaks obtained were in the following region of frequencies:


1) 3700 = 3400 ern -1

2) 1000 - 1050 ern -1

3) 700 - 800 ern -1

These results indicate that the IR pattern does not

show any similarity towards the humic acids (Fig. 5.9).

However, the sample used for the IR tests was the filtrate

after the membrane separation. It is possible, therefore,

that humic acid fractions are not present in it.

From the IR results it is suggested that the hot

water extract contains phenolic and polynuclear aromatics ln

the mixture as the frequencies obtained are in the same

visuality and vicinity of the frequencies obtained for the

said organic compounds. However, the peaks are not very

accurate and not sharp enough to confirm this judgment as it

has overlapped and formed very broad peaks due to the complex-

ity of the mixture.

5.2 ADSORPTIVE PROPERTIES OF VARIOUS ORGANIC COMPOUNDS IN

THE BAYER PROCESS LIQUOR ON THE ALUMINA TRIHYDRATE SEEDS

When crystallising alurnina trihydrate from the Bayer


210

process liquor it is always suspected that some of the organic

impurities are adsorbed onto the surface of seed alumina tri-

hydrate. As a result it could modify many surface properties.

This behaviour was explained as one of the major reasons for

the retardation of crystal growth of alumina trihydrate and

its fine formation. Brown (139) has explained that the

build-up of a mono or multilayer on the surface of seed

alumina trihydrate by some of the surface active organic

impurities in the Bayer process liquor will eventually prevent

further deposition of alumina trihydrate on the seed surface.

The above predictions were not supported by any experimental

evidence.

In this work, the author has made an attempt to

justify the above possibilities. An investigation was

carried out to characterise the organic impurities in the

Bayer process liquor according to its adsorption properties.

Alumina trihydrate seed crystals (obtained from

Queensland Alumina Ltd.) were packed into adsorption columns

and solutions of various pure organics and also specific

molecular weight fraction organics separated from the plant

liquor was passed through them. As the adsorptive proper-

ties depend on the level of pH and temperatures, the conditions

were made similar to the Bayer crystallisation conditions in

the experiments. The organic compounds to be tested were

dissolved in the NaAl0 solutions and the temperature was set


2
up at 60°C which was very close to the process conditions.

The fractions collected were analysed and the concentrations

of organics were determined to compare with the original

concentration. The plant liquor was also passed directly

through the column to investigate the adsorptive materials


211

present in the liquor.

5.21 PREPARATION OF COLUMNS AND SOLUTIONS


The plant seeds were washed thoroughly ln hot

caustic liquor and then in hot water to remove any contam-

inants. The seeds were agaln washed in cold water until

the washed liquor failed to absorb any wavelengths of the

U.V. spectra when it was checked by the U.V. spectrophoto-

meter. The seeds were dried at 100°C. Care had to be

taken that the seed was not dried over 120°C as it could be

transferred into monohydrate.

70 gms. of trihydrate seeds were weighed and

densely packed into a glass column of internal diameter l!!


2 •

A solution of caustic liquor was prepared using analar

grade sodium hydroxide and the concentration was made up to

0. 5M. A weighed quantity of aluminium failings with a


purity of 99% was dissolved in the solution for a few hours
0
at 70 C. The solution was then filtered and cooled. The

proper Bayer concentrations could not be used for these

experiments as the trihydrate seeds in the columns can be

easily dissolved at higher concentrations of caustic. The

higher concentrations of aluminium could deposit some of the

trihydrate on the seeds.

The organic salts known to be present in the liquor,

i.e. sodium oxalate, sodium acetate, sodium formate, sodium

succinate, sodium benzoate and sodium carbonate were dissolved

separately, in the previously prepared solution of sodium

aluminate and it was made up to the concentration of

.145 g/litre.

The organic compounds extracted from the Bayer

process liquor were also made up to the similar concentration


212

1n the caustic aluminate solution. The group of organ1c

impurities selected for adsorption studies were as follows:

a) Mixture of organics extracted from the ether in which

both the higher and lower molecular compounds

are present

b) Higher molecular compounds over 10,000 separated us1ng

membrane filtration as described in section 5.115

c) Higher molecular compounds over 1000 separated using

the same method as in (b)

d) Organic impurities below the molecular cut off 10,000

(a filtrate after passing through the 10,000

molecular cut off membrane).

5.22 Equipment Procedure and Results

A schematic diagram and photograph of the experl-

mental unit are shown in Figures 5.16 a and b. As shown 1n

Figure 5.16, the storage funnel is connected to a glass

column packed with alumina trihydrate seed. The funnel

and the column are packetted to pass hot water at 60°C in

order·to keep the temperature closer to the Bayer prec1p1-

tation conditions.

Fractions are collected from the bottom of the

column into a fraction collector which is set up to collect

one at each 5 minutes.

The hot water system in the jacket was maintained

at 60°C by connecting the tube into a hot water tap in the

laboratory. From the hot water tap it is connected to a

copper coil immersed in a water bath before it reaches the

jacket inlet. This method was adopted to boost the temper-


0
ature to 60 C as normal tap hot water is not always able to
0
produce the temperature of 60 C. The temperature in the
213

Hot water --rf--


outlet

Hot Caustic solution


water of organic salts

- "'\.
,_~ -
. ·:,.
- ..
.....
- "!:'"-
-
- ;i
--~~-+---+---~
--..:~
_-

Inner tube packed


4=: - with alumina trihydrate
f'·- 'l--
....
Jacket
- :·:-
,..
- •'"1 -

,•.
- -
- ·....... -
\ ~

-
--t!=:
....._ - -
...
~- r-
- ......

Hot water at 60°C

~
- ~,. .:_., . . .
:r.·n.---
u
It,. .. ____ )I
Fraction collector

Fig. 16(a) Sketch of the experimenta l unit used for the


adsorption studies.
214

Fig. 5.16(b) Laboratory equipment used for the adsorption


studies.
215

jacket was controlled at 60°C by m1x1ng with cold water from

the tap where necessary. However, once the temperature had

achieved a steady state, it was kept constant for 6 to 7 hours

until the experiments were completed.

A solution of organic compounds to be tested on the

trihydrate column was prepared as previously described 1n

this section. It was then passed through the column. The

solution level in the funnel was kept constant by adding

solution when necessary in order to keep the flow rate con-

stant. The solution drained from the column was collected

as fractions using a fraction collector which was programmed

to collect fractions every 5 minutes. The flow rate was

determined by measuring the volume collected every five

minutes. The samples collected were compared for concentra-

tion with the original organic solution.

A calibration chart was established using the original

solution prepared at different dilutions. Absorption in the

U.V. spectra was taken as the measurement. There is also the

possibility that the C0 which is absorbed into the caustic


2
aluminate solution should also absorb the U.V. region. In

order to avoid this effect, a sample of the original pure

caustic aluminate solution was used as the blank solution 1n

the U.V. spectrophotometer. The wavelength was set at

210 ~m. In some cases where the U.V. determination was

difficult, the total organic value was determined for each

fraction by titrating with a standard solution of KMn0 .


4
Although the flow rate was kept constant by keeping

the solution level constant, there were small variations

from one run to another. This behaviour is explained as

being due to the difficulty in obtaining equally packed


216

columns for each run. A separate column was used for

each run.
The following organic compounds were subjected

to investigation:

1) Sodium Oxalate 0.146 g/litre

2) Sodium Formate 0.145 11

3) Sodium Acetate 0.145 11

4) Sodium Carbonate 0.146 11

5) Sodium Benzolate 0.144 11

6) Sodium Succinate 0.146 11

7) Mixture of organic impurities extracted

from Bayer process liquor 0.146 g/litre

8) Higher molecular fraction of nominal

molecular weight over 1,000 present

in the Bayer process liquor 0.146 g/litre

9) Higher molecular fraction of nominal

molecular weight over 10,000 present

in the Bayer process liquor 0.145 g/litre

10) Recycle Bayer process liquor diluted x 10

In the case of recycle Bayer process liquor, the

objective was to make an approach to the selective adsorp-

tive properties of the impurities present in the liquor by

the alumina trihydrate seeds.

The original Bayer process liquor, after diluting

ten times, was passed through the column and the fractions

collected were tested by U.V. spectrophotometer. A sample

of the original liquor (10 x diluted) was kept in the

'sample' side of the U.V. photometer and the fractions

collected were kept in the blank side, and was scanned

through the whole range of U.V. spectrum to detect whether


217

any wavelengths had been absorbed. It was anticipated that

the appearance of such absorption peaks would indicate that

some of the organics were adsorbed by the seeds. Later the

adsorption column was regenerated and desorbed with 3M

solution of sodium hydroxide and the fractions were collected

as desorbed materials.

The result of the adsorption as a function of con-

centration of the solution and the volume was plotted. The


curves obtained are illustrated in Figures 5.17 - 5.19. The
results indicate that none of the following compounds were

adsorbed on to the surface of trihydrate: sodium salts of

acetic, formic, benzoic and succinic acids and sodium carbon-

ate. Sodium oxalate being adsorbed very slightly. However,


the calculations indicate that the amount of sodium oxalate

adsorbed onto the surface is hardly sufficient to form even

amono-layer on the surface of trihydrate seeds. The

higher molecular fractions with the N.M.W. over 1000 and

10,000 acted in a similar manner as sodium oxalate.

The above results indicate that usually the higher

molecular fraction generally known as humic fractions, do

not act like a poisoning agent in the crystallisation stage

as a result of adsorbing onto the seed crystals. If it


has any poisoning effect, it may be due to other reasons

which have to be further investigated, possibly by eo-

precipitating with alumina trihydrate.

Figure 5.19 illustrates the adsorption results

obtained from the mixture of higher and lower molecular

compounds before and after passing through the membrane

filtration with cut off 10,000 are adsorbed on to the

alumina trihydrate. From the results the calculations were


218

made to determine the amount of organics adsorbed by 1 gm

of alumina trihydrate, as shown ln the~ection 5.122. An

approximate assumption was made as follows:

2
Surface area of trihydrate ::0.15m/g
2
Density of organic materials = 1.2 g/cm

Thickness of monolayer of

organic material

The amount of organic adsorbed by the seeds was

calculated from the adsorption curves by integrating the

area in the adsorbed region. The calculation was limited

to the curves in Figure 5.17.

The amount of organic adsorbed = 0.114 gm per

by the seed (integrated from 70 gm of seed (or

Figure 5.17) 1.6 X 10- 4 gm/gm

of seeds)

Volume of the adsorbed layer = 1. 33 3 X 10- 4 cm 2

Thickness of the layer = 8.88 X 10 -8 cm


0
= 8. 8 A

The results from the above calculation indicate

that the adsorbed layer is not sufficient to form even a

monolayer if it is assumed that the thickness of a mono-


o
layer is about 50A.

When the results are summarised it was found that the

lower molecular compounds such as the salts of aliphatic

carboxylic acids, as well as higher molecular compounds, do

not adsorb onto the surface of trihydrate seed, but there was

an indication that some intermediate compounds present in the


g/1 ~--------------------------------------------------------------------------------~
cone.

Initial concentration 0.146 g/1


0.15

(1) 0---0 Sodium oxalate


0.1 (2) o---0 Sodium succinate

(3) x---x Sodium acetate

(4) V---V Sodium benzoate

0.05

6 12 18 24 30 36 42 48 54 Vol.ml.

Fig. 5.17 Adsorption studies of sodium oxalate, succinate, acetate and


benzoate on alumina trihydrate seed column.
cone.
g/1

0.15 Initial concentration 0.146 g/1.

(1)V---V Higher molecular extract


m.wt.> 1000
(2) o--0 Higher molecular extract
m.wt.> 10,000
0.1

0.0

6 12 18 24 30 36 42 48 54 volume ml.

Fig. 5.18 Adsorption studies of organic impurities extracted from the


Bayer process liquor on alumina trihydrate column. N
N
0
cone.
g/1 (1) o-o Organic impurity extract before molecular
membrane separation
(2) v-v Filtrate of the above extract after passing
0.15 through membrane cut of~lO,OOO
0.146 g/1 initial concentration for No. 1

0.1

-0.082 g/linitialconcentration for No. 2

0.05
V

50 100 150 200 250 volume ml.

Fig. 5.19 Adsorption studies of organic impurities extracted from the Bayer
process liquor.
222

organlc materials (extracted from the Bayer process liquor)

adsorb onto the surface, when passed through the seed column.

The above statement was supported by the adsorption curves

appearing in Figure 5.19 i.e. the organic extract after

passing through the membrane. However, there is doubt


about the curves in Figure 5.19 as chemical changes may have

occurred in the method of preparation of these organic

extracts. The organic extract for this experiment appearing

in Figure 5.19 was prepared as described in section 5.115.

The Bayer process liquor sample was acidified and extracted

into the ether solution. This organic mixture was re-


dissolved in the caustic aluminate solution for this experi-

ment. During this process it is questionable whether there

was any change in the properties of these organics, but this

error does not arise for the curves obtained in Figure 5.18

as those higher molecular compounds were directly separated


from the Bayer process liquor using the membrane filtration,

without acidifying the liquor.

It was found that when the plant liquor containing

impurities was passed directly through the column, some of

the organics were adsorbed onto the trihydrate seeds. This


was evident from the different U.V. adsorption peaks

obtained from the fractions collected when compared with the

original solution in the U.V. spectrophotometer.

Furthermore, some useful information was collected

when the column was regenerated with pure caustic liquor

(Figure 5.20). The fractions so collected were compared


with the original caustic liquor in the U.V. spectrophoto-

meter indicating some U.V. absorption peaks. The first few


fractions so collected were brown in colour and the later
223

Adsorption
Collection of fractions (first fraction

- 1.6 (brownish)
to be obtained from
the bottom)
1.5 (brownish)

1.4 (brownish)

---;o.. 1.3 (brownish)

1.2 (slightly brownish)

..... 1.1 (colourless)

Alumina tri-hydrate adsorption column

De sorption
J_
Collection of fractions

2.6 (colourless)

2.5 (colourless)
alumina tri-
hydrate column ~------ 2.4 (slightly brownish)

2.3 (slightly brownish)

2.2 (brownish)

2.1 (brownish)

3m
Ng.OH
solution

Fig. 5.20 Adsorption studies of recycled Bayer process liquor


on seed alumina trihydrate.
Elementary sketch of the experiment.
224

Wavelengths of the peaks 11m Fractions

~~!~i:a!f the
recycle Bayer
1-------.... l 265 [_:__
.
1_._1_ _ . . ~1
i
process liquor r-----------·~ ~-------2_6_2------~~-----1-·-2-----~

262 I
N.B. Fractions were
placed in the blank
I 1.3 I
side of the double beam
262
U.V.spectrophotometer , 1.4
whereas the original
sample of the recycle
Bayer process liquor 260 I
was placed in the
1.5
sample side.
260 I
1.6
I

Desorption with caustic liquor


N.B. Regenerated 272
fractions were 2.1
f
placed in the 272
sample side of
the equipment.
[ 2.2
J
3 M
NaOH Sol.
r-
1-----
- 2.3
:
I
I 220
[:: 2.4 i
220

218
l
I
2.5 l
I
1 2.6 j

'---·
270 & 220
L 2.7 l
270 & 230
2.8

Fig. 5.21 Comparison studies of the collected fractions


using the U.V. spectrophotometer.
Original sample used Sample used for the com-
for the studies parison studies (placed
(placed in the sample in the blank side of the Absorption Peak Remarks
side of the u.v. U. V. equipment) 1Jm
equipment)

1) Original Bayer Colourless solution was


liquor Fraction 1.1 265 obtained as the fraction
(brown colour indicating f the compound
solution) with above peak is being
adsorbed by the column
2) -do- Fraction 1.2 262 Slightly coloured
3) -do- Fraction 1.3 262 Coloured fraction
4) -do- Fraction 1.4 262 Coloured fraction
5) -do- Fraction 1.5 260 Coloured fraction
6) -do- Fraction 1.6 260 Coloured fraction

Desorbed after passin9: caustic liquor


7) Fraction 2.1 Caustic liquor (colourless) 272 Brown colour fractions
8) -do- 2.2 -do- 272 -do-
9) -do- 2.3 -do- tested Medium brown
10) -do- 2.4 -do- 220 Slightly brown
11) -do- 2.5 -do- 220 Yellow colour
12) -do- 2.6 -do- 218 Colourless
13) -do- 2.7 -do- 270 & 220 - do -
14) -do- 2.8 -do- 270 & 230 - do -
15) -do- 2.9 -do- 270 & 230 - do -

TABLE 5.11 Comparison studies of the U.V. results of different Bayer process liquor fractions after
passing through the trihydrate column.
226

ones colourless. The results obtained in these experi-

mental studies are summarized in Table 5.11 and Figure 5.21.

The first part of the results indicated that some

of the components in the Bayer process liquor are adsorbed

by the seed column. They have the U.V. absorption in the

region of 260 to 265 ~m.

The fractions collected from the regeneration stage

were regarded as some of the components which were actually

adsorbed by the trihydrate column and now being desorbed by

the caustic. The major peaks of these fractions were

obtained in the region of 270 - 272 vm and 218 to 230 vm.

The first few regenerated fractions were dark brownish ln

colour and the later ones gradually became colourless.

5.3 SOLUBILITY OF SODIUM OXALATE IN THE PURE CAUSTIC AND

ALUMINATE LIQUOR AT VARIED TEMPERATURE

Solubility curves for sodium oxalate in aluminate

solution at different temperatures and concentrations were

established in order to study the saturation level of sodium

oxalate at varied Bayer process conditions. These results

would also lead to gaining of knowledge as to the behaviour

of sodium oxalate in the Bayer process liquor, such as the

possible coprecipitation of sodium oxalate with alumina

trihydrate. Yamada et.al.(6) had already reported the

solubility data for sodium oxalate in the Bayer process

liquor at different temperatures.

The experimental work carried out in this thesis

has been limited to pure caustic and pure sodium aluminate

solutions. Previous work performed by Yamada could be

affected by other impurities in the Bayer process liquor

which is not the case in these experiments.


227

In the case of solubility in pure caustic solu-

tions a saturated solution of sodium oxalate was prepared

by dissolving an excess of sodium oxalate in the caustic

liquor at different concentrations, initially at room

temperature. The concentrations of the solutions were deter-

mined by titrating with a standard solution of KMn0 . The


4
same beakers containing the samples were kept in an oil bath

controlled by a thermostat and then the concentration of


0
oxalate was determined at elevated temperatures up to 8 0 C.
In the case of solubility in sodium aluminate

solutions the solutions of sodium aluminate were prepared by

dissolving different weights of aluminium in a previously

prepared 4m solution of caustic liquor. Sodium oxalate in

excess was dissolved ln the aluminate liquor and the concen-

trations were determined as discussed ln the previous method

at room temperature and also at elevated temperatures. These

experiments were not conducted in the higher range of caustic

ratio, although it was important to do so. Solutions of high


caustic ratio were not prepared for the tests as this could

lead to the deposition of aluminium hydroxide as a result of

supersaturation.

Figure 5.22 illustrates solubility curves plotted

for the pure caustic liquor at different concentrations and

temperatures.

It was noticed that in the case of pure caustic

solution the solubility decreases with the increase of caustic

concentration. This behaviour can be explained by looking

at the equation for the solubility products of sodium oxalate

as follows:
228

Solubility
g/1

30 0-0 23°C
x-x 40°C
Cl-Cl 70°C
28
~-A
80°C

26

24

22

18

16 -

14

12

10 -

8 -

0 1 2 3 4 molar cone.
NaOH
Fig. 5.22 Solubility of sodium oxalate in the pure
caustic solution at varied concentration
and temperature.
229

solubility
g/1
5

(1)· 0-0 Pure sol'n of NaOH - 4M


2591
(2) v--V Sodium aluminate sol'n 4M, Al 0 /Na o-0·
2 3 2
(3) X--X Sodium aluminate sol'n 4M, Al 0 /Na 0-0.1159
2 3 2
(4) 0---a Bayer plant liquor of 4M cone. of NaOH
(previously published by Yamada et.al.)

4
Oxalate level in the recycle
Bayer process liquor

3 -

20 30 40 50 60 70 80 oc
temp.

Fig. 5.23(a) Solubility of sodium oxalate in the pure


caustic and the caustic aluminate solution.
230

The increase of the sodium 1on concentration in the

solution by increasing the caustic concentration tends to low

down the oxalate ion concentration 1n the solution resulting

1n a low solubility value for oxalate in the solution. The


solubility of sodium oxalate in the caustic aluminate solu-

tion at different temperatures was plotted and illustrated 1n

Figure 5.23(a). The prepared caustic aluminate solutions

had the following composition.

1) 4 Molar sodium hydroxide with the caustic ratio

(Al 0 /Na 0) by weight 0.2591


2 3 2
2) 4 Molar sodium hydroxide with the caustic ratio

Solubility
g/1

40

30

10 20 30 40 50 60 70 80
0
T~.c

Fig. 5.23(b) Solubility of sodium oxalate in distilled water


at varied temperature.
231

The solubility values obtained for the pure caustic

solution of 4 Molar concentrations at different temperatures

(previously obtained from Figure 5.22) are also plotted here

in Figure 5.23 for comparison studies. The results indicate

that at the lower temperatures (near room temperature), the

solubility values are similar in both cases. At elevated

temperatures solubility values are higher in caustic alumin-

ate solutions than in the caustic solutions for a given

temperatu~e value. The above behaviour could be explained

by considering this system in the form of a solid-liquid

equilibrium. Any decrease in the activity of the solute

species in the equilibrium system is accompanied by an

increase in solubility. Hence in dilute solutions where the

ionic strength (I < 1) is less than the unity, the solubility

of a salt is enhanced in the presence of inert electrolyte.

It is suggested here that the aluminate species is most

likely to behave as inert electrolyte, resulting in higher

solubility values for oxalate in the system.

Solubility curves for sodium oxalate ln the Bayer

plant liquor at different caustic concentrations and tempera-

tures were studied by Yamada et.al. (6). The results have

been previously outlined in Figure 1.3. Using these values,

the solubility versus temperature was plotted for the Bayer

process liquor with a caustic strength of 4 molar sodium

hydroxide. The results are shown in the curve 4 of Figure

5.23. Those results are compared with the experimental

results obtained by the author using 4 molar concentration of

NaOH with different caustic ratio (Al 2 0 /Na 2 0). Curve 1


3
indicates the solubility of sodium oxalate in 4 molar pure

sodium hydroxide solution, Curve 2 indicates the solubility


232

v~lues 4 Molar sodium hydroxide with the caustic ratio

(Al
2 3
o /Na
2
o wt.) of .2591~ whereas Curve 3 indicates the

caustic ratio of 0.1159. However, it is interesting to

note that Curve 4 is similar to Curve 1 which is for pure

caustic solution. The Bayer plant liquor usually contains

Al0 in the caustic ratio range of (Al 0 /Na 0) 0.2 - 0.3.


2 2 3 2
According to results obtained by Yamada (Figure 1.3) the

aluminate does not have any effect on the solubility of sodium

oxalate in the Bayer process liquor.

Some workers have reported the following figures

being analysed as sodium oxalate in the recycle Bayer process

liquor.

1) 3.7 g/litre Ref. (75)

2) 4 g/litre If If
Ref. ( 144)

The analysis was performed at room temperature.

The recycle Bayer process liquor usually contains

about 3.5 molar concentration of caustic liquor and alumin-

ate with the caustic ratio of about 0.25. When these

analytical results are compared with the actual solubility

values of sodium oxalate under those conditions, the values

are much higher than the solubility figures. These results

indicate that the sodium oxalate in the Bayer process liquor

has reached the supersaturation level. The following exper-

iments by the author contribute very much to the above

argument.
After determining the solubility values at higher

temperatures the solutions were brought down to room temper-

atures and thereaften the concentration of oxalate in the

samples was measured. The final concentration values

obtained were very much closer to the values obtained for


233

elevated temperatures~ thus indicating that no crystallisa-


tions of sodium oxalate had taken place instead it was in

the form of supersaturation. This supersaturation behav-


iour of sodium oxalate in the Bayer process liquor can lead

to various effects on the precipitation of alumina trihydrate,

such as eo-precipitation with alumina trihydrate, when

trihydrate seed acts like nuclei.

5.4 SUMMARY OF THE EXPERIMENTS DISCUSSED IN CHAPTER 5

Results of the experiments carried out in Chapter 5

indicate that the organics present in the Bayer process liquor

are complex in nature. It was found to be a mixture of


low molecular compounds and higher molecular compounds.

Total organic carbon content in the Bayer process

liquor was analysed and it is usually built up to about

25 - 30 g/litre based on carbon.

Various methods were applied ln an attempt to

analyse the organic impurities present in the Bayer process

liquor. Distillation method suggested that it contains

sodium formate and acetate, whereas its formate content was

analysed to be in the range of 2.0 - 2.5 g/litre (as formic

acid).

The Bayer process liquor was subjected to various

extraction methods. Ether extract of the acidified

solution of Bayer process liquor was analysed using gas

chromatography. The direct analysis of the ether extract


indicated the presence of sodium acetate, propionate and

valerate. The ether extract was methy.lated and was

injected through a G.C. Although there were some distinct


peaks in the chromatogram, it was unable to identify as
234

there were no suitable reference samples available. The

infra red analysis performed on the ether extract from the

Bayer process liquor suggested the presence of carboxylic acid

radicals and aromatic rings in the organic impurities.

Furthermore, I.R. spectra obtained from the said extract

was found to be very similar to the I.R. spectra of the

natural humic and fulvic acids reported elsewhere.

Membrane separation was used to characterise the

organ1c present in the Bayer process liquor according to the

molecular weight range. Two types of membrane were used,

one with the molecular weight cut off at 1000, the other with

10,000. The membrane with cut off 1000 was not operable

at high pH. Therefore the Bayer process liquor sample was

carbonated with C0 2 to bring down the pH to 9. The follow-

lng analyses of the Bayer process liquor were obtained from

the membrane separation.

Molecular wt. over 10,000 - 1.8 g/litre (as carbon)

Molecular wt. over 1,000 - 6.2 g/litre (as carbon)

Molecular wt. below 1,000 - 24.4 g/litre (as carbon)

An attempt was made to characterise the organic

impurities accumulated with the plant trihydrate product

either in the form of adsorbed or coprecipitated material.

Various methods were applied to desorb the contaminated

organics selectively from the product trihydrate. The first

extract was obtained by washing with methanol and thereafter

the dried samples were extracted with hot water. The dried

trihydrate before the hot water desorb, was tested with x-ray

defraction analysis and it indicated the presence of sodium

oxalate and some other unknown compounds in the crystalline

form suggesting that they are crystallised with trihydrate


235

product. The hot water desorb of the product trihydrate

was fractionated using membrane separation and it was

found to contain about 20% of higher molecular organic

greater than 1000 M.wt.

The second extract was obtained by washing the

alumina trihydrate first with cold water and extracted with

hot water. In this extract higher molecular organic

greater than 1000 M.wt. was found to be only about 3% out of

the total organic content. Furthermore, infra red analysis

of the desorb suggest the presence of aromatic rings and the

phenolic compounds in the extract.

Experiments were conducted to investigate the

adsorptive properties of some of the known organic compounds

believed to be present in the Bayer process liquor on alumina

trihydrate seed. Among them were sodium oxalate, formate,

acetate, carbonate, benzolate, succinate and different

molecular weight fractions of the organics extracted from

the Bayer process liquor. Adsorption properties of the

recycled Bayer process liquor was also investigated by

passing through the trihydrate column. The results indica-

ted that the oxalate, formate, acetate, carbonate, benzolate,

succinate and the organic molecular fractions over 1000 were

less adsorptive, whereas the intermediate molecular weight

fraction below 1000 was considerably adsorptive. When the

recycle Bayer process liquor was passed through the trihydrate

column, it was found that some of the organics do get

adsorbed on to the trihydrate seed.

Solubility of sodium oxalate 1n the pure caustic

and aluminate solution was studied at varied caustic concen-

trations and temperatures. It was noticed that in the case


236

of pure caustic solution the solubility decreased with the

increase of caustic concentration. The solubility value

1n the aluminate liquor at ambient temperature was identical

to the value obtained in the pure caustic liquor of equal

caustic strength. However, at elevated temperatures it

was higher in the aluminate liquor than in the pure caustic

solution as shown in Fig. 5.23(a).

The plant analysis of sbdium oxalate concentration

1n the Bayer process liquor was compared with the solubility

values obtained in these studies and revealed that the sodium

oxalate in the Bayer process liquor was present in the super-

saturated level.
CHAPTER 6

EXPERIMENTAL STUDIES ON THE EFFECT OF ORGANIC IMPURITIES


DURING THE CRYSTALLISATION OF ALUMINA TRI-HYDRATE
23 7

INTRODUCTION

Studies were carried out to determine the effect of

various organic compounds on the crystallisati on of alumina

trihydrate. The individual effect on the kinetics, crystal


habit~ particle size distribution and the crystal mass by
major organic impurities found to be present in the Bayer

process liquor were investigated . The above kinetic studies


mainly involved the effect on the induction period, the

crystal growth and the rate of decompositio n.

An isothermal batch crystallisati on was selected as

the most appropriate method for these studies. Although


the continuous process was the most suitable method as it

reproduced the nearest possible plant condition, it was not

possible under these circumstance s. The precipitatio n runs


were carried out under isothermal conditions. Most of the
other conditions, i.e. temperature, caustic ratio, caustic

concentratio n, seed charge and the impurity charge were very

similar to the Bayer plant conditions. The data obtained


were interpreted as rate kinetics, particle size distribution ,

and those results were compared with those of crystallisat ion

runs without any impurities.

6.1 BATCH CRYSTALLISATION UNIT

A photograph of the laboratory batch crystalliser is

displayed in Figure 6.1a and a sketch of the unit is in

Figure 6.1b. The crystalliser was a 5 nos. of stainless


steel beakers of 750 ml capacity and 500 ml working capacity.

The beakers were closed with PVC type lids which can be

lifted easily. The closed operation kept evaporation loss


to the minimum and also minimised the contaminatio n of caustic
238

Fig. 6.1a Photograph of the laboratory batch


crystalliser.
with atmospheric co 2 . Propeller type stainless steel

stirrers enter through each beaker, as shown in Figures

6.1 a and b. The stirrers were mechanically rotated by

connection into a universal axle coupled to an electric

motor through a gear box. All the stirrers were rotating

at a speed of 30 r.p.m. which was continually checked by a

tachometer.

The crystallisers were kept immersed ln a constant

temperature bath (± 0.3 accuracy) and all the runs were

carried out isothermally. The temperature in the water

bath was controlled by a thermostat and the water bath was

insulated from every side, including the top of the tank,

during the run. The temperature of the bath and the beakers

was checked during each run and the products were kept in
.
,
r'l 11 111
J Mf

-" iY .c w
!-

TI T
Stirrers-
p lastic

Insula tion .
cover

... .. . lt .. . . .
!l s . . . . . ... ..... "" ... "
I
I 'tto . . . . . . . . .. 1 . ..
I

Il
~ . . . .. . rh •<6 . . . . . ll .,.
.
,.,.
I

I
l
Thermoline with
contact thermo-
meter

.. I
-
·:
-·4. <
..... - - -
-
-
~ )
...__

-
\
-- • - - - -- - j• • .~

I
-- - I - - r:....
-
±
....
.. -- - I
Stainl ess . - -
.. - - -I -- --- -- i
t:J In
beaker s - ... -
- - t:..
-
--l -- ~ --
~ ~
steel
'
.
- - - -
- --
- -- - - - -- - ~.: 6
~
...•
- - - - -- - - - -- - - - - - - -- - -
- - - J~ I

FIGURE 6.lb Schematic diagram of the laboratory batch crystalliser unit

N
w
tO
240

suspension by stirring.

6.2 PREPARATION OF CAUSTIC ALUMINATE SOLUTION

Caustic aluminate solution for precipitation studies

can be prepared 1n two ways. The first is to dissolve pure

aluminium metal 1n NaOH solution. The reaction is exothermic

with the evolution of hydrogen. The second is by dissolving

alumina trihydrate in a caustic solution in a stainless steel

autoclave at elevated temperatures in the range 150°C - 175°C.

In this work the first method was used to prepare

the caustic aluminate solution. There were some difficul-

ties, such as premature precipitation before the ratio was

reached. This was mentioned by Misra (11) when using the

same method. However, the premature precipitation was not

observed in this work, as a result of the exothermic

reaction, usually the caustic concentration was increased

due to the evaporation, while keeping the required

Therefore, during the prepara-

tion, solubility value was high due to the high concentra-

tion of caustic. When all the aluminium was dissolved the

solution was brought up to the correct concentration of caustic

by adding water. For each run 3 litres of NaOH solution of

appropriate Bayer process concentration (equivalent to

187 g/litre in Na co 3 ) was prepared in a stainless steel


2
container. Aluminium foils (equivalent to a caustic ratio

Al o /Na co of 0 .. 65) were added to the solution little by


2 3 2 3
little. The aluminium metals used had the purity of 99%

which was obtained from Alcan Ltd., in Sydney. During the

addition of aluminium, H2 was evolved and the boiling was

noticed in the solution due to the heat. When the addition


241

of aluminium was completed the volume of the solution was

almost reduced to about 2300 ml. and water was added to make

up a quantity of 3 litres. The caustic aluminate solution

was black in colour due to the presence of solid carbon as an

impurity. When the solution was passed through a glass

fibre filter it was separated and the filtrate became very

clear. Special care was taken to avoid even the slightest

contamination of solid particle in the container as they

could act as nuclei to precipitate alumina trihydrate.

6.3 SEED PREPARATION

The seed was obtained from the Queensland Alumina

Co. Ltd., in Gladstone, and was an industrial type used in

their plant for seeding purposes. It was the product

alumina trihydrate obtained from the tertiary and secondary

thickeners of the Bayer process plant. The average particle

size was in the range of 10 - 20 ~m. The seed was washed

in cold and also in hot water and then dried for about 6 - 8
0
hours at 100 C. Weighed amounts of seed were usually pre-

warmed to the test temperature before addition to the

crystalliser.

6.4 ADDITION OF IMPURITIES

Impurities used in these studies include most of the

organ1c salts commonly present in the Bayer process liquor,

i.e.
a) sodium oxalate

b) sodium acetate

c) sodium formate

d) sodium succinate

e) higher molecular organic impurities,


242

molecular weight over 1000

f) mixture containing all the organic impurities

present in the Bayer process liquor.

The impurity charge was based on the quantities

present in the Bayer process liquor, but, ln some runs,

sodium oxalate was added at a higher than normal level of con-

centration to investigate the effect of supersaturation.

The organic impurities over the molecular weight

1000 used for this experiment were extracted from the Bayer

process liquor according to the method described in

section 5.116. The organic impurity concentrate so collected

after passing through the membranes was oven dried at 100°C

before using for this work.

The mixture containing all the organlc impurities

present in the Bayer process liquor was extracted using the

method adopted in section 5.115.

6.5 PROCEDURE

The crystalliser unit was filled with water and the

required temperature was maintained. It was allowed to run


for a few hours until it was stabilised at the required

temperature. (Most of the runs were at 64°C).

The stainless steel beakers were filled with 500 ml

of sodium aluminate liquor and placed in the crystalliser

bath until it reached the equilibrium temperature. Weighed


quantities of organic compounds were added to the beakers

as the impurities and allowed to dissolve. Seed was also

prewarmed to the required temperature separately.

Weighed quantities of warmed-up seed were charged

into the beakers and stirring began immediately. Every


243

batch of experiments included one or two units (beakers)

in the crystalliser without any impurity charge for corn-

parison studies.

The precipitation experiments were continued for

24 - 26 hours. When the experiments were terminated, the

product trihydrate was separated from the remaining liquor

by sedimentation and filtration and the volume of the rema1n-

ing liquor was measured. The product was washed and dried

at 101°C.

6.6 SOLUTION ANALYSIS

Analysis of Al o
2 3
and Na
2
o concentration 1n the

solution was required for obtaining kinetic data. Although

the variation in the Na o concentration was slight, the


2
change in Al 0 concentration is regarded as the main
2 3
variable in order to plot the precipitation curves.

The atomic absorption method was used for

estimating alumina concentration of periodic samples. The

samples of aluminate liquor were taken us1ng a syringe at

different intervals, usually at 1 or 2 hours. However,

in some cases, the intervals were shortened to ~ hr.,

especially at the initial stag.es of some runs, in order to

investigate the induction period. Samples were filtered

and diluted 100 times as they were too strong in Al o


2 3
concentration to be tested by atomic absorption method.

Solutions for calibration were prepared using different

dilutions of standard solution of aluminium nitrate used for

atomic absorption. A fresh batch of calibration was done

for every run as the conditions of the atomic absorption

unit can be changed easily.


244

6.7 PARTICLE SIZE ANALYSIS BY ZEISS. TYPE MICRO VIDEOMAT 2


The determination of accurate kinetic data from

batch crystallisation depends considerably on the accuracy of

the particle counting sizing techniques employed. Fairly


fast analysis and good resolution were desirable features.

The micro-videomat used for this work has many of these

features. Details of the micro-videomat used ln these

experiments are described in Appendix III.

Particle sizes in the range of 1 - 120 ~m were


measured using the videomat. A major problem in this analy-

sis was to obtain a sample of uniform particle size distribu-

tion to be placed on the slide. Larger particles were con-


centrated on one side of the slide and the smaller particles

on another side. This problem was overcome by mixing the

product to be analysed in a glycerine - water mixture with a

ratio of 1 : 1. In this manner the product was kept ln a

uniform suspension due to the high viscosity. A portion of


the suspension was transferred on to the slide to be analysed

in the videomat.

6.8 OPTICAL AND ELECTRONMICROGRAPHY


The products obtained from the experiments were

studied uslng the optical microscope and the electron micro-

scope. These studies were aimed at looking at the crystal

habit, size and the shape of the products trihydrate due to the

presence of impurities. Products from several runs were

photographed with an optical microscope and using a 35 mm

reflex camera.

Micrographs of the samples of various products were

taken using the scanning electron microscope. The samples

were properly washed and dried, then coated with a gold film.
245

Variables Plant Laboratory

Caustic concentration 185 - 190


185 - 190
(gm/litre Na co )
2 3

Caustic ratio by weight 0.65 -0.36 0.6 - 0.3


(Al o /Na co )
2 3 2 3

0
Temperature ( C) 80 - 60 60 - 65
varying at constant
temperature

Seed charge 100 - 150 80 - 130


(Al(OH) g/litre)
3

24 negligible

Impurities · Organic Individual


impurities organic com-
(inc.sodium pounds and
oxalate), pure runs &
NaCl, and also various
Na so Trace fractions of
2 4
organics ex-
tracted from
the liquor

Residence time 40 - 60 24 - 26
hrs.or more hours

Type of operation continuous batch type

Type of agitation air mechanical


agitation stirring

TABLE 6.1 Plant and laboratory crystallisation


conditions.
246

Exp. Cryst- Impurities addition Seed Temp. Dura-


No. alliser addi- range tion of
No. tion Expt.
g/litre g/1 oc hrs.

1 1 Pure solution 130 65-66 24

2 -do- " " "


3 Sodium oxalate 3 " " "
4 -do- 5 " " "
5 Sodium acetate 5 " " "
2 1 Pure solution " 64-65 24

2 -do- 11 11
"
3 Sodium oxalate 5 " 11 11

4 Sodium formate 5 11 11 11

11
5 Sodium succinate 5 " 11

3 1 Pure solution 80 63.5-65 23.5

2 -do- 130 11 11

3 Organic extract from 4 130 11 11

Bayer process liquor


M.Wt.> 1000

4 Sodium succinate 5 130 11 11

5 Sodium oxalate 5 80 11
"
4 1 Pure solution 130 26 24

5 1 Pure solution 130 63.5-64 23

2 Sodium oxalate 10 11 11
"
3 Sodium succinate 10 11 11 11

11
4 Sodium formate 10 11
"
5 Sodium acetate 10 11
" "
6 1 Pure solution 130 66-68 24

2 Sodium oxalate 8 11 11 11

3 Organic extract from 10 11 11


"
Bayer process liquor
M.Wt.> 1000
247

Exp. Cryst- Impurities addition Seed Temp. Dura-


No. alliser addi- range tion of
No. tion Expt.
g/litre g/1 oc hrs.
4 Pure solution 130 66-68 24
(Unwashed
seed)

5 Sodium acetate 8 130 " "

7 1 Pure solution 130 64.5-65 29

2 Sodium oxalate 6 " " "


3 -do- 6 " 11
"

4 -do- 6 " 11
"
5 Pure solution 11
" "
8 1 Sodium oxalate 10 130 63.5-64 24

2 Pure solution " 11


"
3 Sodium oxalate 10 11
" 11

4 Pure solution 11
" 11

5 Sodium oxalate 10 11 11
"
9 1 Pure solution 130 63-63.5 24

11
2 Mixture of organic 5 11 11

impurities extracted
from Bayer process
liquor (without any
molecular fraction-
ation)

3 Pure solution " 11


"
11
4 Mixture of organic 5 " 11

impurities extracted
from Bayer process
liquor (without any
molecular fraction-
ation)

11
5 Pure solution 11 11

TABLE 6.2 Details of experiments on crystallisation


248

During coating the spec1mens were rotated and tilted.

The specimens were carefully examined by a scanning

microscope with magnifications of 150 and 300 and compared

with the seed products obtained from the pure solutions. As

many of the samples were similar only representative samples

of different results obtained were selected to be micro-

photographed.

6.9 RANGE OF CONDITIONS STUDIED

The conditions employed 1n the studies were based

on the normal operating conditions of Bayer plants. Few

changes had to be made to suit laboratory scale experiments.

Table 6.1 compares industrial operations at Queensland

Alumina Plant with the conditions used in this study. Details

of the crystallisation runs are summarised in Table 6.2 indi-

cating the number of runs, type and quantity of impurities

added, seed change and the temperature ranges for each run.

6.10 RESULTS AND DISCUSSION OF CRYSTALLISATION STUDIES

The atomic absorption results were used to plot the

precipitation curves based on the aluminium content in the

solution against time. The results obtained for each run

are illustrated in Figures 6.2 to 6.9. Table 6.3 summarises

the kinetics of all the crystallisation experiments.

As shown in Figures 6.2 to 6.9, the precipitation

curve of each experimental run differs due to the change in

the conditions applied i.e. initial caustic concentration)

caustic ratio and the temperatures which were not identical

throughout the series of experiments. This error is caused

because the aluminate liquor was prepared batchwise for


249

each run. The temperatures also varied slightly by at least

1 - 2°C in each run. Therefore the study of impurity can be

treated more intelligently if a basis for comparison is avail-

able. For this reason it was decided to run at least one unit

out of the five crystalliser units without any impurity charge.

It was felt that this would prove to be a valuable standard

against which the effects of impurities could be better

treated.

Particle slze distribution of the products and seed

trihydrate were analysed and are shown in Figures 6.10 - 6.15

as cumulative oversize against the particle size using the

micro videomat (image analyser). The analyser is able to

produce only the particle size count and it was not possible

to obtain the weight distribution.

The product obtained from the experimental runs was

analysed by the optical microscope and the scanning electron

microscope. The microphotographs were taken only from the

experiment which indicated some different results and they

are shown ln Figures 6.16 - 6.25.

On the basis of the experimental results a number

of aspects of the precipitation may be analysed. These

include the following factors: induction period, initial and

general decomposition rate, equilibrium concentration, crystal

growth, crystal habit and particle size distribution.

a) Induction period

Induction period lS defined as that interval between

the time that seed is added to the supersaturated solution

and the time that decomposition is first noted. Many workers

in the past have neglected the induction period ln modelling

the crystallisation system of the Bayer process. Past


250

workers were not able to obtain an equation for the complete

precipitation curve, including the induction period, and it

was limited to only the crystal growth.

The induction period is a measure of the stability

of the given sodium aluminate solution. This stability is

related to the tendency for the aluminate lons to decompose

to colloidal aluminium hydroxide, which, in turn, depends on

the tendency for the conversion from c6lloidal to crystalline

material and deposition of this material on an existing crystal

surface. The induction period usually depends on the surface

area of the seed, the greater the seed surface the shorter

will be the induction period. Wherever possible the induction

period was evaluated in these runs.

(b) Initial decomposition rate

This rate is determined at the end of the induction

period, i.e. at the beginning of the decomposition period.

The initial decomposition rate is analysed as the grams of

dissolved Al o per hour at the initial stage.


2 3

(c) Total decomposition rate

The assumption made for the initial decomposition

stage is not valid for the entire curve. The total

decomposition rate is based on the overall drop in dissolved

alumina.
(d) Equilibrium concentration

The alumina concentration at the termination of

the runs is designated as "equilibrium concentration".

Theoretical equilibrium concentration can be calculated for

a given temperature and the caustic and alumina concentration

using the solubility values of Al 2 o in the caustic liquor.


3
Expt. Cryst- Impurity charge Seed Induction Initial Total Original Equilibrium Source of
No. alliser charge period decomposi- decomposition concentration concentration reference
No. Type of Impurity tion rate rate of Al of Al
Impurity cone.
g/1 '4!~ hr. g/hr g/hr g/1 g/1

1 1 Pure - 130 0 1.0 0.78 59 34 Fig. 6.2


2 -do- - 130 0 1.0 0.78 59 34 -do-
3 Sodium 3 130 0 0.5 0.43 59 38 -do-
oxalate

4 -do- 5 130 0 0.6 0.55 59 32.5 -do-


5 Sodium 5 130 0 0.9 0.516 59 34.2 -do-
acetate

2 1 Pure - 130 0 10.0 0.97 70 23 Fig. 6.3a


2 -do- - 130 0 10.0 0.975 70 23.2 -do-
3 Sodium 5 130 0 10.0 0.96 70 24 -do-
oxalate

4 Sodium 5 130 0 6.2 1.02 70 29 Fig. 6.3b


formate

5 Sodium 5 130 0 5.7 0.92 70 33 -do-


succinate

3 1 Pure - 80 1.0 3.5 0.60 57.5 32 Fig. 6.4a


2 -do- - 130 1.0 4.25 0.63 57.5 31 -do-
3 Organic 4 130 1.2 4.0 0.55 57.5 33 Fig. 6.4b
extract
M.Wt>lOOO

4 Sodium 5 130 1.2 3.5 0.54 57.5 33.5 -do-


succinate

5 Sodium 5 80 1.2 2.0 0.57 57.5 34.7 -do-


oxalate

N
(Jl
I-'
Expt. Cryst- Impurity charge Seed Initial Total Original Equilibrium Source of
Induction
No. alliser charge period decomposi- decomposition concentration concentration reference
No. Type of Impurity tion rate rate of Al of Al
Impurity cone.
g/1 hr.

5 l Pure - 130 1.2 3.0 0.47 57 36 Fig. 6.5a


2 Sodium 10 130 1.4 0.36 57
1.2 41 -do-
oxalate

3 Sodium 10 130 2.5 0.41 57


1.2 39 -do-
succinate

4 Sodium 10 130 1.62 0.41 57


1.3 39 Fig. 6.5b
formate

5 Sodium 10 130 2.0 0.40 57


1.3 39.5 -do-
acetate

6 l Pure - 130 1.5 0.42


1.0 56 36.5 Fig. 6.6a
2 Sodium 8 130 1.0 0.75 0.41 56 37 -do-
oxalate

3 Organic 10 130 2.0 1.15 0.39 56 37 -do-


extract
M.Wt>lOOO

4 Pure - 130 0.5 0.5 0.36 56 38.5 Fig. 6.6b


(unwashed)
5 Sodium 8 130 0.25 0.625 0.40 56 36.5 -do-
acetate

7 1 Pure - 130 0.25 0.75 0.61 54 34 Fig. 6.7a


2 Sodium 6 130 1.0 0.45 54
1.0 32 -do-
oxalate

3 -do- 6 130 1.0 0.5 0.47 54 33 Fig. 6.7b


4 -do- 6 130 0.5 1.0 0.47 54 33 -do-
5 Pure - 130 0.4 1.1 • 0.47 54 33 -do-

N
c.n
N
Expt.
No.
Cryst-
alliser
Impurity charge Seed Inductio n Initial . Total Original Equilibr ium source of
charge period decompo si- decompo sition concentr ation concentr ation referenc e
No. Type of Impurity rate of Al of Al
Impurity cone.
g/1 g/1 hr.

8 1 Sodium 10 130 2.5 \ 0.48


1.5 57 34 Fig.6.Ba
oxalate

2 Pure 10 130 1.5 3.5 0.48 57 34 -do-


3 Sodium 10 130 1.5 3.5 0.5 57
oxalate 33 Fig. 6.8b

4 Pure - 130 1.5 2.5 0.48 57 34 -do-


5 Sodium 10 130 1.5 3.0 0.49 57 33.5 -do-
oxalate

9 1 Pure - 130 0.5 1.0 0.57 57 34 Fig. 6.9b


2 Total organ- 5 130 0.2 1.1 0.56 57 30 Fig. 6.9a
ic extract
from Bayer
liquor

3 Pure - 130 0.5 1.0 0.62 57 32 Fig. 6.9b


4 Total organ- 5 130 0 1. 75 0.56 57 30 Fig. 6.9a
ic extract
from Bayer
liquor

5 Pure - 130 0 1.1 0.57 57 34 Fig. 6.9b

Table 6.3 Results of the crystall isation experime nts

N
(.T1
w
60
[Al] 0-0 Pure sodium aluminate liquor
g/1 0--I:l Sodium oxalate 3 g/1

x-x Sodium oxalate 5 g/1

A-IJ. Sodium acetate 5 g/1

Time (hours)

FIGURE 6.2 Crystallisation experiment No. 1


'

[Al]
gl 0-0 Pure sodium aluminate solution
70

X-X Pure sodium aluminate solution

60 V-'V Sodium oxalate 5 g/1

50

40

30

20

10

0
0 25
Time (hours)
FIGURE 6.3a Crystallisation experiment No. 2
[Al]
g/1 0-0 sodium succinate 5 g/1
70
o- a sodium formate 5 g/1

60

50

40

Time (hours)

FIGURE 6.3b Crystallisation experiment No. 2


N
c.n
m
60
[Al] o-o Pure sodium aluminate solution
g/1 Seed charge 80 g/1
o-n - do - Seed charge 130 g/1

50

40

0
0

0 25
Time (hours)

FIGURE 6.4a Crystallisation experiment No. 3


N
(J1
-...J
0-.-0 Organic impurity M wt.> 1000 4 g/1.
X-K Sodium succinate - 5 g/1

a-o sodium oxalate - 5 g/1

50

40

30
0 25
Time (hours)
FIGURE 6.4b Crystallisation experiment No. 3
60
[Al] 0-•0 Pure sodium aluminate solution
g/1
a-D Sodium oxalate 10 g/1

X- X Sodium succinate 10 g/1

50

40

30
0 5 10 15 20 25
Time (hours)
FIGURE 6.5a Crystallisation experiment No. 5
N
(Jl
tD
60
[A1]
g/1 0-0 Sodium formate 10 g/1

h.-A Sodium acetate 10 g/1

50

40

30
0 20 25
Time (hours)
FIGURE 6.5b Crystallisation experiment No. 5

N
(J)
0
60r-------------------------------------------------------------------------------------~

[Al]
0-0 Pure sodium aluminate solution
g/1
IJ-0 Sodium oxalate 8 g/1

X-X Organic impurity M.wt.> 1000; 10 g/1

50

40

Time (hours)
FIGURE 6.6a Crystallisation experiment No. 6
60---------- ------------- ------------- ------------- ------------- ------------- ------------- -.
[Al]
g/1
Pure sodium aluminate solution
0 0 Sodium acetate 8 g/l

50

40

----------------~0

30
0 5 10 15 20 25
Time (hours)
FIGURE 6.6b Crystallisation experiment No. 6
60
[Al] o-o Pure sodium aluminate solution
g/1
X-X Sodium oxalate 6 g/1

50

40

Time (hours)

FIGURE 6.7a Crystallisation experiment No. 7

N
(5)
w
60
[Al] 0-0 Sodium oxalate 6 g/1
g/1
x->< - do -

Pure sodium aluminate solution

50

40

Time (hours)
FIGURE 6. 7b Crystallisation experiment No. 7
60
[AI"] 0-0 Sodium oxalate 10 g/1
g/1
1:.-A Pure sodium aluminate solution

50

40

Time (hours)

FIGURE 6.8a Crystallisation experiment No. 8


N
m
(J1
60
Q-0 Sodium oxalate 10 g/1

O-D Pure sodium aluminate solution

x-x Sodium oxalate 10 g/1

50

40

30L--J--~--L--L--~~--~--L--L--J-~~~--L-~--J-~~~--~~--~--~~--~~--~
0 5 10 15 20 25
Time (hours)
Fig. 6.8b Crystallisation experiment No. 8

N
0)
0)
60
[Al] 0-0 Mixture of organic impurities extracted from the Bayer
g/1 process liquor, 5 g/1
A-!::. - do -

50

40

0 5 10 15 20 25
Time (hours)
FIGURE 6.9a Crystallisation experiment No. 9
60
[Al]
0-0 Pure sodium aluminate solution
g/1
o-P -do-

A-A -do-

50

40

20 25
Time (hours)
FIGURE 6.9b Crystallisation experiment No. 9
269

Usually it was found that the practical values are different

from the theoretical values.

(e) Crystal Growth

The theoretical aspect of a crystal growth is widely

explained in Chapter 4. The crystal growth in these runs lS

started from the initial decomposition stage down to the

reach of equilibrium concentration. However, during this

process, because the mechanism of the crystal growth is com-

bined with other factors such as secondary nucleation,

crystal breakages and agglomeration, a proper independent

crystal growth analysis is not possible. Furthermore, it

was found that the effect of impurities on the above men-

tioned factors is not an easy task in these studies.

(f) Crystal size distribution

In crystallisation systems one of the prime interests

is to characterise the population according to Slze. The

results obtained from these experimental runs gives a lead

to the effect of individual organic impurities on the particle

size of the product. In these studies the results with

impurity charges are compared with the particle size distri-

bution of the original seed and also the product obtained

without the influence of impurities.

6.10.1 Effect of Sodium Oxalate

Few batches of experiments were performed to invest-

igate the effect of sodium oxalate in the precipitation

system. A summary of the results obtained from the experi-

ments is given in Table 6.4. In this section the effect of

sodium oxalate on the induction period, decomposition rate,

equilibrium concentration, crystal growth and habit and the


Expt. Crystalliser Oxalate Method applied Effect on kinetics Particle size distribution
No. Unit No. change in charging (Comparison of (Comparison of rate with
sodium oxalate rate with standard) standard)
impurity

1 3 3 Supersaturated* T.D.R. is low Finer particles


Fig.6.2 with sodium oxalate DP= 5.5 ~ whereas Dstd= 15.5 ~

4 5 Supersaturated plus T.D.R. is low Fine formation


Fig.6.2 sodium oxalate pre-
cipitate in excess

2 3 5 - do - No difference Fine formation


Fig.6.3a Dp= 5 ~ whereas Dstd= 45 ~

3 5 5 - do - I.D.R. is low No difference in the average


Fig.6.4b C is slightly particle size but less coarse
eq high particles in the product

5 2 10 - do - I.D.R. is low Less fine formation


Fig.6.5a and C is low Dp= 23 ~m whereas Dstd= 40 ~
eq

6 2
Fig.6.6a 8 - do - - do - Dp = 16 ~m whereas Dstd= 39 ~m

fine formation

7 2 6 Supersaturated plus I.D.R. low Particle size distribution was


Fig.6.7a sodium oxalate in detected by the image analyser
excess but fine formation was observed
using the optical microscope
3 -do- Saturated only No difference
Fig.6.7b
4 -do- - do - - do -
Fig.6.7b N
--.:1
0
Expt. Crystalliser Oxalate Method applied Effect on kinetics Particle size distribution
No. Unit No. change in charging (Comparison of (Comparison of rate with
sodium oxalate rate with standard) standard)
impurity

8 1 10 Saturated only No difference Fine formation


Fig.6.8a

3
Fig.6.8b 11
-do- -do-

5 11
-do- -do-
Fig.6.8b

* Supersaturated solution of sodium oxalate was prepared by heating the aluminate solution with oxalate up to
95°C and then the temperature was brought down to operating temperature range in the crystalliser.

Notation:- I.D .R. = Initial decomposition rate


T.D.R. Total decomposition rate
c eq = Aluminium concentration at the equilibrium in the experiment
D = Average particle size of the product trihydrate with the impurity charge
p
Dstd = Average particle size of the product trihydrate obtained from the
standard solution (without any impurity charge)

TABLE 6.4: Summary of the results of the crystallisation experiments with oxalate
impurity charge.
272

particle size distribution are discussed.

a) Induction period

Misra (11) suggested that prolonged induction

periods can be due to the presence of sodium oxalate impurity.

Kelly (113) in his work contributed to the above suggestion.

However, the results obtained in this work are contradictory

to Kelly's findings as any evidence_ of prolonged induction

periods was not noticed at any time due to sodium oxalate

impurity. A drawback in Kelly's experiments was found to

be that his standard crystallisation runs (experiments with-

out any impurities) were performed at a different time and

were not parallel to the runs with the impurity charge.

In the author's experiments it was noticed that slightly

different precipitation curves were obtained for the experi-

ments under the same conditions, when it was carried out at

different times, therefore the results indicate that the

slightest change in the conditions could easily change the

precipitation results.

b) Rate of decomposition

The results show that there is a slight effect,

mainly on the initial decomposition rate, by the sodium

oxalate impurity. This effect seems to be very much

dependent on the degree of supersaturation of sodium oxalate

in the aluminate liquor.

It was notice in experiment No. 1 (Fig. 6.2)

that the total decomposition rate has been affected compared

to the standard. However, due to the lack of sufficient

point at the beginning of the experimental curve, it is not

possible to show clearly which step of the crystallisation 1s

being affected~ whether the induction period, the initial


273

decompositio n rate or the crystal growth.

In Experiment No. 2 (Fig. 6.3a), although

sufficient points have been taken at the initial stage, due

to the high content of aluminium in the solution, there lS

a very high initial decompositio n rate in all five units of

the experiment, therefore it seems to have overruled any

effect of impurity on the crystallisati on. For this reason

the effect of sodium oxalate cannot be properly detected in

this batch of experiments.

In Experiment No. 3 (Figs. 6.4 a and b), Experiment

No. 5 (Fig. 6.4a), Experiment No. 6 (Fig. 6.6a) and Experi-

ment No. 7 (Fig. 6.7a), it was noticed that the initial decom-

position rate is slightly affected. All these experiments

were conducted in the solution supersaturate d with sodium

oxalate and many of the experiments showed sodium oxalate was

present in excess in insoluble form.

The following experiments were carried out only in

the saturated solution of sodium oxalate with excess insoluble.

They are Experiment No. 7 (Fig. 6.7b) and Experiment No. 8

(Figs. 6.8 a and b). It was noticed that in these crystall-

isation runs, the initial decompositio n rate is not affected

very much by the sodium oxalate impurity.

The results of the experiments suggest that the

initial decomposition rate is affected only when the sodium

oxalate in the aluminate liquor reaches the level of super-

saturation.
Furthermore, there is also a possibility for sodium

oxalate to deposit on the alumina trihydrate seed particle

at the initial stage of precipitatio n, thus slightly retarding

the initial decompositio n rate of alumina trihydrate in the


274

system. When the sodium oxalate reaches its equilibriu m

concentra tion 1n the aluminate solution, the rate of

decomposi tion of alumina trihydrate takes the normal

pattern as in the standard solution. It was also investi-

gated in the previous studies (author's experimen t, section

5.122) that the product trihydrate obtained from the indus-

trial precipita tion system analysed to be containin g

deposited sodium oxalate from the X.R.D. analysis.

In a supersatu rated solution of sodium oxalate,

the driving force for crystallis ation of sodium oxalate has

been reported as follows (114):

c = c c
oxalate oxalate equilibriu m
supersatu ration concentra tion solubility
in liquor

They have also reported that the following

equation satisfacto rily described the equilibriu m solubility

of sodium oxalate in industria l condition s:

-2 )
c = 7.62 exp.(0.01 2T- 0.016FS- 0.011C0 3
equilibriu m
solubility

(Further details 1n section 3.5).

c) Particle size distributi on

The oxalate appear to have some effect on the final


275

size distribution of the product trihydrate. This con-

elusion has been made on the basis of the particle slze

analysis found as shown in Figs. 6.10, 6.11, 6.12, 6.13

and 6.14.
In most of the runs the product trihydrate was

very much finer than the product obtained from the pure

aluminate solution.

The above results contradict the results reported

by Kelly (113) in his work. He found that oxalate have

little effect on the particle size distribution.

It was previously found by the author that sodium

oxalate is not adsorbed onto the surface of alumina tri-

hydrate seed (section 5.2). Therefore it is suggested

that due to the level of supersaturation of sodium oxalate

in the solution, some of the sodium oxalate is likely to be

deposited on the surface of the seed, thus retarding the

crystal growth. As a result there is a possibility towards

the formation of secondary nucleation, followed by the

increase of the fine formation. However, fine formation was

also noticed in some of the experiments where the solution

was only saturated with sodium oxalate. This behaviour can

be explained as due to the presence of excess insoluble sodium

oxalate, they act as nuclei for the deposition of alumina

trihydrate on it.

d) Optical and Electron Micrograph

Microphotographs of the product trihydrate with the

sodium oxalate impurity charge are shown in Figs. 6.18 and

6.19. The fine formation, due to the sodium oxalate, is


276

also noticed ln these photographs.

The same samples were analysed by the electron

scannlng microscope. Some of the photographs are displayed

in Fig. 6.23. It can be seen from these photographs that due

to the presence of sodium oxalate, some incomplete crystal

growth (appearance of small size crystallite) has taken place

in these products. However, in the product crystals obtained

from the crystallisation experiment without any impurity

appeared to be in complete form of growth (crystallites are

large). No observation was made of any deposited sodium

oxalate crystals along with the product trihydrate. Brown


and Cole (114) have identified the presence of needle-shaped

sodium oxalate in the product alumina trihydrate obtained in

the industrial precipitation system, using the scanning electron

microscope. Such eo-precipitation of sodium oxalate was

not observed in the author's work.

6.10.2 EFFECT OF ORGANIC IMPURITIES EXTRACTED FROM THE

BAYER PROCESS LIQUOR

The organic impurities tested in the crystallisation

experiment are grouped into two categories based on the method

of preparation. They are as follows:

1) Organic impurities extracted from the Bayer process liquor

with M.wt. > 1000.

2) Mixture of organic impurities extracted from Bayer process

liquor composed of lower molecular fraction, intermediate

fraction as well as the higher molecular weight fraction.

The organic impurity mentioned in Group 1 was

extracted as described in Section 5.116, whereas the organics

in Group 2 were extracted as described in Section 5.115.

However, most of the dibasic acids such as oxalic acids,


277

succinic acids~ etc., do not enter the organic extract

Group 2 because they are sparingly soluble in ether.

a) Effect on the decomposition.. rate

The results of the precipitation curves obtained in

the presence of organic compounds Group 1 (Experiments Nos. 3

and 6) are plotted in Figs. 6.4b and 6.6a.

The results indicate that 4g/litre of organ1c corn-

pound of M.Wt.> 1000 (Group 1) have no effect on the rate of


~

crystallisation (Fig. 6.4b) whereas the experiment with

10 g/litre of the same material has slightly prolonged the

induction period (Fig. 6. 6a). However, later it seems to

follow the same pattern curve as the standard crystallisation

curve performed at the same time.

Furthermore, the product yield is also not much

different from the standard run (Table 6.3).

The precipitation curves obtained with the addition

of organic impurity Group 2 type are illustrated in Fig. 6.9a.

The results are compared with the standard run (Fig. 6.9b)

which was performed at the same time. It was noticed that

the induction period decreased due to the presence of this

group of organic impurities. Furthermore, a sharp increase 1n

the initial decomposition rate is noticeable, but from the

second hour of the process until the fifth hour, there is a

sudden drop in the decomposition rate. After the fifth hour

again it takes the normal pattern of the precipitation curve,

as in the standard c~rve. This behaviour seems to be some-

what unusual compared to the other crystallisation experiments.

The equilibrium concentration of these curves has reached the

same level of the standard at the end of the experiment.

The adsorption experiments conducted by the author,


278

described in Section 5.2 have revealed that the same group

of organic extracts (Group 2) of the Bayer process liquor,

were moderately adsorptive onto the seed of alumina trihydrate.

Therefore the coincidence of the results of the total experi-

ments suggests that the Group 2 organic extract has some

poisonous effect on the rate of decomposition, although it lS

not very severe. Furthermore, the results of both experi-

ments suggest that it is an intermediate molecular fraction

of organic compound M.Wt. <1000 that is most likely to play

this role in the precipitation system. It was revealed in

these experiments that most of the lower molecular compounds

and the higher molecular compounds (M.Wt. >1000) known to be

present 1n the Bayer process liquor were already individually

tested and they are playing a neutral part in the rate of

decomposition, as well as in the adsorption experiments.

b) The particle size distribution

The particle size distribution of final product tri-

hydrate obtained from the crystallisation experiments No. 3 ~

Unit 3, No. 6 - Unit 3 and No. 9- Units 2 and 4, are displayed

in Figures 6.12, 6.14 and 6.15 respectively. The analysis

reveals that the final products were not being affected by the

presence of either type of organic impurity extracted from the

Bayer process liquor.

The optical microscopic and electron microscopic

photograph taken of the final products suggests that the experi-

ments with organic impurity charge shows no difference to the

products from the standard experiment. Scanning electron micro-

scopic photographs are illustrated in Figures 6.26 and 6.27.

6.10.3 EFFECT OF SODIUM ACETATE; FORMATE AND SUCCINATE

The results of the crystallisation experiments in the


279

presence of sodium acetate are displayed in Figures 6.2,

6.5b and 6.6b. The results indicate that there is no

evidence as to any poisonous effect caused by sodium acetate.

The particle size analysis of the produce trihydrate

obtained from the same experiments, suggest a slight tendency

towards the formation of fine particles as shown in

Figures 6.10, 6.13 and 6.14. The fine formation was also

observed when the same products were examined through optical

microscope (Fig. 6.21).

It was noticed from the crystallisation experiments

that the effect of sodium formate and succinate on the

crystallisation kinetics is negligible. Figures 6.3b and

6.5b display the shape of the precipitation curves obtained

with the presence of sodium formate and Figures 6.3b, 6.4b

and 6.Sa show the curve obtained for sodium succinate impurity.

The examination of the results of the particle slze distribu-

tion of product trihydrate obtained from these runs also

reveal nothing particularly striking or unique about these

impurities had no effect on the precipitation of alumina

trihydrate in the Bayer process.


100

0-0 Seed
o-o Pure product
x-x Sodium acetate impurity charge
v-\7 Sodium oxalate impurity charge

mo
(])
N
·.-l
tll 50
~
(])

5
(])
:>
·.-l
.jJ
m
r-1
~
::l
u

0
0 50 100 150 N
(X)
(~) Particle size) 0

FIGURE 6.10 Particle size distribution of product alumina trihydrate obtained from Expt.No. 1
0-0 Sodium succinate impurity charge
A-A Sodium formate impurity charge
Q-0 Sodium oxalate impurity charge
X--X Pure product
0-0 - do -

(~) particle size 150


Fig. 6.11 Particle size distribution of product alumina trihydrate obtained
from Experiment No. 2
lOO

0-0 Pure product

0--P Sodium oxalate impurity


x--X Organic extract molecular Wt.> 1000
~-ll. Sodium succinate impurity

o\o
(])
N
·r-1
!il
1-l
(])
:>
0 50
(])
:>
·r-1
+l
m
r-l
~::I
u

0 50 lOO 150
Particle size (micron)

FIGURE 6.12 Particle size destribution of product alumina trihydrate obtained from Expt.No. 3
100

0-0 Sodium formate impurity


Cl-0 Sodium acetate impurity
1<-X Sodium oxalate impurity
A-A Sodium succinate impurity
0-0 Pure product
dP
(!)
1:\1
·r-1
!Jl
l-1
(!)
>
0
(!)
> 50
·r-1
+l
ctl
.-l

~
()

0 150
N
Particle size (micron) CO
w
FIGURE 6.13 Particle size distribution of product alumina trihydrate obtained from Expt.No.S
100
X->< Pure product
V-'if Sodium oxalate impurity
G-0 Organic impurity molecular wt.> 1000
o_o Pure product
Sodium acetate impurity

o'l'
Q)
N
·.-l
Ul

f..!
Q)
i>
0
50
Q)
i>
·.-l
.J-l
eO
r-l
§
::l
u

0 100 150
Particle size (micron) N
OJ
FIGURE 6.14 Particle size distribution of product alumina trihydrate obtained from Expt.No. 6 +
100
X-X Pure product
0-0 -do-

A- A Organic impurity mixture previously extracted


from the Bayer process liquor
o-o -do-

0 100 150
Particle size (micron)
N
FIGURE 6.15 Particle size distribution of product alumins trihydrate obtained from Expt. No. 9 (X)
en
286

FIGURE 6.16 Microphotograph of the product alumina trihydrate


without impurity charge (magnification SOX)

FIGURE 6.17 Microphotograph of the product alumina trihydrate


without impurity charge (magnification lOOX)
287

flif V

..0~6
4

_,&
.,. . 4
Q
~
4
,@

.,4\,
•:'?
Ill "·. ,, 'iP

6 10
lif.i
~
.,

'e
>\
c;

0
#
'.?
~-41 "
.
#

'I'

lJ •jp

'
:;;»
%
4
1

s"'

*

.. (j'· "i!
'tit
*
.,
Zl

"
4

" 'i

--
-:-:.
~
!i \
$ .At ..fJ.

FIGURE 6.18 Microphotograph of the product alumina trihydrate


with sodium oxalate charge (Expt. 6)
(Magnification SOX)

FIGURE 6.19 Microphotograph of the product alumina trihydrate


with sodium oxalate charge (Expt. 6)
(Magnification 100X)
288

"
·:>b ,,£(} .
~·:~

·~
·~

Q) ;:; ;~
"""

FIGURE 6.20 Microphotograph of the seed alumina trihydrate


(Magnification SOX)
289

..,. ' . . . . . . jli"


•• ~
ff
it

~· ~
<I¥" 0
,p $ it\ '*"
"JP &

~ ..
t
4. ..'· 4t '*' 1%
'* .Af ''-f
' 4
t
"'
'
¥

G... %

* f '
~.
"'
"" ""''
'*
(;)),
11
%

''* ~
if
,.
Q 1f
$'

FIGURE 6.21 Microphotograph of the product alumina trihydrate


with sodium acetate charge (Expt. 5)
(MagnificationSWX)

FIGURE 6. 22 Microphotograph of the product alumina trihydrate


with sodium acetate charge (Expt. 5)
(Magnification 100X)
290

(a)

(b)

FIGURE 6.23 Electron microscopic photograph of the product


alumina trihydrate with sodium oxalate impurity charge
(a) (150X) magnification
(b) (300X) magnification
291

(a)

(b)
FIGURE 6. 24 Electron microscopic photograph of the product
alumina trihydrate without any impurity charge.
(a) (lSOX) magnification
(b) (300X) magnification
292

FIGURE 6.25 Seed alumina trihydrate used in the crystallisation


experiments (150X) magnification.
293

FIGURE 6. 26 Electron microscopic photograph of the product


alumina i::J;:'ihydrate with the organic impurity charge
M.Wt. > extracted from the Bayer process liquor.

FIGURE 6. 27 Electron microscopic photograph of the product


alumina trihydrate with organic impurity charge
(mixture .extracted from the Bayer process liquor).
CHAPTER 7

CONCLUSIONS
294

7.1 CONCLUSIONS

Organic impurities present in the Bayer process

liquor are very complex in nature. These organics were

found to originate from the humic substances present in the

soil. During bauxite leaching the organics are also

extracted into the caustic solution. Some of the organics

are degraded into low molecular carboxylic and intermediate

compounds.

Sodium formate, acetate and oxalate were found to be

present as major low molecular compounds. Propionate and

valerate were found in very small quantities. Although there

were many other low molecular compounds, it was not possible

to identify them due to the lack of required techniques.

There was also evidence of the presence of aromatic carboxylic

and phenolic compounds in the Bayer process liquor. Further-

more, the infra red spectra of the Bayer liquor extract was

found to be very similar to the spectra of the natural humic

and fulvic acids reported elsewhere. The total organic con-

tent was found to be in the range of 25 - 30 g/litre (based

on carbon). 80% of the total organic present was below

1000 molecular weight and about 20% was greater than 1000

whilst 5 - 7% was over 10,000. Any attempt to identify

these organics over 500 molecular weight is not advisable as

it would involve a very complicated procedure. Furthermore,

with a slight change in the medium of the solution rapid

change of the structure of these organfcs can be expected.

It was found that some of the organics were adsorbed

on to the product alumina trihydrate seed. Sodium oxalate

and other groups of unidentified organics were found to be

crystallised with product alumina trihydrate after reaching


295

a supersaturation level.

The experiments on the adsorptive properties of

individual organic compounds present in the Bayer process

liquor on the product alumina trihydrate, reveal that low

molecular organic compounds such as sodium oxalate, formate,

acetate, carbonate, succinate and benzolate were less

adsorptive. Molecular weight fractions over 1000 were also

less adsorptive. Evidence was found to suggest that some

intermediate compounds were comparatively adsorptive on the

alumina trihydrate seed.

Experiments on the solubility of sodium oxalate in

the sodium aluminate liquor at varying temperatures reveal

that the oxalate in the Bayer plant liquor is present in the

supersaturated region.

It was found from the crystallisation experiments

that the presence of sodium oxalate has no adverse effect on

the kinetics of precipitation. However, it was noticed

that the particle size was slightly affected resulting in

fine formation especially when the sodium aluminate solution

was supersaturated with sodium oxalate. Sodium formate,

acetate,succinate, benzolate and the organic fraction

> 1000 M.wt. has no poisonous effect on the crystallisation

process. Some intermediate organic impurities below

1000 M.wt. have a very slight poisonous effect on the rate

of decomposition, but the size of the particles was not

affected.

7.2 SUGGESTION FOR FURTHER WORK

The studies conducted in this project were aimed at

exploring the role of organic impurities and their effect


296

on the precipitation system with a broad v1ew as there has

not been much literature reported elsewhere. Detailed

study of each individual problem was not possible in this

work as it can be seen as a very complex problem. For this

reason the results of these studies can only be used as a

guide for further investigation which should eventually lead

to some solution in the alumina industry. The following


areas of work are therefore recommended for further investi-

gation.

1) The characterisation studies of the organics present

1n the Bayer process liquor were not carried out in systematic

order as the author was unable to obtain the ultra-filtration

type membranes with varying range of molecular cut-off

which should also be stable in highly caustic medium. It is


suggested, therefore, that future work be carried out us1ng

such membranes. The separation must be performed in the

caustic medium as the slight change of the medium could alter

the structure of organics present in the Bayer process liquor.

2) The analysis of the low molecular compounds in this

project was not successful. Some of the results (peaks)

obtained from the gas chromatographic method could not be

identified as there was no full range of reference samples

readily available. Further detailed work undertaken in

relation to the analysis of the low molecular compounds

present in the liquor should perhaps be carried out using a

G.C. mass spectrometer.

3) Similar work is also recommended for the organic

impurities extracted from the product alumina trihydrate

obtained from the plant.


297

4) There are no records whatsoever available on the solu-

bility of the various fractions of the organics impurities

in the caustic or Bayer process liquor~ Any data on such

work would assist in evaluating which fractions of the

organics reach supersaturation during the precipitation of

alumina trihydrate. Further work on that aspect may be

worthwhile for further studies.

5) Adsorptive properties of various organlc impurities on

seed alumina trihydrate were studied, however, they were

limited to some low molecular compounds and higher molecular

compounds M.wt. over 1000. It was impossible to study the

adsorptive effect of the intermediate organics between 200

and 1000 M.wt. separately. It is suggested that further work

might be carried out if such separation can be achieved

using a membrane.

6) In the crystallisation studies undertaken by the author

a major drawback was the quality of the seed trihydrate used.

Seed with a very narrow range of particles should have been

used. In any future work on crystallisation serious consider-

ation should be given to this aspect as the slight change of

particle size itself can alter the kinetics of the system.

7) The crystallisation studies in this project were batch

operation. It could be worthwhile considering the possibil-

ity of using continuous type crystallisation experiments

when the results could be very applicable to industrial

practice.
8) Organic impurities used for the crystallisation studies

were the material extracted from the Bayer process liquor,

however, in future work it is suggested organic impurities


298

desorbed from the product alumina trihydrate obtained

from the plant be used. These organics could be very

poisonous material.

I
299

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(123) Loeffler, Chr. Martinswerk Ltd., Report No. 70/12

17 July 1970 (in German)

(124) Jung, M. and Loeffler, Chr. Martinswerk GmbH Report

No. 71/8 19 March 1971 (in German)

(125) Wefer, K., Metall. 21 (5) (1967) p 422

(126) Russell, A.S., Edwards, J.D. and Taylor, C.S.,

J. Metals (1955) p 1123 - 1235

( 12 7) Adamson, A. N. , Bloore, E. J. , Carr. A .R . , Gerard G. ( ed) .

Basic Principles of Bayer Process Design.

Extractive Metallurgy of Aluminium, Vol. 1,


308

New York. Interscien ce Publisher s 1963

(128) Juhasz~ A. Paper presented at the A.I.M.E. Annual

Meeting, Washingto n, February, 1969


(129) Hermann, E.~ and Stipetic, J. z. Anorg. Alleg.Che m.,
262 (1950) 258

(130) Miers, Sir H.A., Journal of Institute of Metals,

Vol. 37, (1927) p 331

(131) Vrbasky, T., Ivekovic, H. and Pavlovic D., Can. J.

Chem. , 3 6 ( 19 58) p 1410

(132) Shimosato , J., Kogyo Kogaku Zasshi, 66 (1963) 172

(133) Solymar, K., and Zambo, J. Paper presented at the

symposium on Reaction Engineeri ng, Amsterdam ,

1964
(134) Jamey, M., Paper presented at the 95th A.I.M.E.

Annual Conferenc e, New York, 1966


(135) Maricic, S. and Markovcic , I. Arhiv, Kern. 27 (1955) 41

(136) Hlobik z., Jungman - Horvart, Maricic, s., Croatica


Chimica Acta, (1960) 32

(137) Scott, J., Effect of Seed and Temperatu re on the

Particle Size of Bayer Hydrate. Extractiv e Met-


allurgy of Aluminium , Vol. 1 Alumina Interscien ce

Publisher s, New York 1963


(138) Misra, C. and White, E.T. Journal of Crystal Growth

8 (1971) p 172 - 178


(139) Brown, N., Journal of Crystal Growth, 16 (1972)

163 - 169
(140) Lyapunov, A.N. and Kholmogo rtseva, E.P. Journal of

Applied Chemistry of the U.S.S.R., v. 30 (1957)

p 1306 - 1535
309

(141) Walton, A.G. The formation and properties of

precipitates, Interscience Publishers,

New York 1967

(142) Branson, S.H., Brown, D.E., Healey, G.P. Paper

presented at the symposium on Industrial

Crystallisation, Institution of Chemical

Engineers, London, April 1969

(143) Van Hall) C.E., Safaranko, J. and Stenger, V.A.

Anal. Chem., 35 (1963) p 315

(144) Private correspondence with the Technical Manager of

Queensland Alumina Ltd., Gladstone, 1977,

Analytical report of the recycle of Bayer Process

liquor

(145) Lowson, R.T., Potential -pH Diagrams at temperatures


0
above 298.16 K. Part 3 Australian Atomic Energy

Commission Research Establishment, Lucas Heights,

Oct. 1972

(146) N.B.S. Technical Note 270 - 4

(147) O.J. Kwok, Ph.D. Thesis, University of New South

Wales, Australia (1974)

(148) Pourbaix, M., Atlas of Electrochemical Equilibria

in Solution, Pergamon (1966)

(149) Hardwick, B.A. Ph.D. Thesis, University of New South

Wales, Australia (1972)

(150) Criss, C.M. and Cobble, J.W., J.Am.Chem.Soc., 86,

(1964) 5385 - 5390 and 5390 - 5393

(151) Cobble, J.W. J.Am.Chem.Soc. 86 (1964) 5394 - 5401

(152) Blaedel, W.J., Meloche, V.W. Elementary Quantitative

Analysis, Theory and Practice, 2nd Ed. p.837 - 841

Harper & Row, New York and John Weatherhill, Inc.

Tokyo
310

Appendix I

THERMODYNAMIC STABILITY DIAGRAMS .FOR THE Al~Fe~si-H


20
SYSTEM IN RELATION TO THE BAYER PROCESS

The Bayer process lS based on hydrometallurgical re-

actions wherein the first step bauxite is leached with caustic

liquor at elevated temperatures (between 150 - 225°C). In

the second stage the temperature of the leached sodium alumin-

ate solution is reduced to 60 - 80°C to precipitate alumina

trihydrate, by adding previously prepared alumina trihydrate

seed crystals.

An attempt is made in this section to explain the

course of reactions in the Bayer process using thermodynamic

stability diagrams. Potential -pH, or Pourbaix (148)

diagrams provide a useful means of summarizing a large amount

of thermodynamic data in relation to a system composed of metal

species in an aqueous environment. These diagrams can be

used as a tool to understand the basic principles of various

hydrometallurgical processes. The utility of published

diagrams is unfortunately somewhat limited as they have been

constructed mostly for simple Metal - Water systems and the

single temperature of 25°C. Since many important processes

occur at elevated temperatures, it is desirable to have dia-

grams available to depict the different equilibria that exist

at those temperatures. In cases where thermodynamic data

are not available the problem is either a) measuring the

necessary high temperature equilibria, or b) computing those

equilibria by a reliable means.

Criss and Cobble (150, 151) have advanced a


311

technique that allows the second alternative which was the

one used in the present study. This technique is based on a

correspondence principle relating ionic entropies at room

temperature to those at higher temperature.

In the present study, data for the Al-H 0 system at


2
elevated temperatures were available from Lowson's work (145).

The Criss and Cobble (150,151) method was used to plot the

diagrams for the Fe-H o system at elevated temperatures. The


2
values of free energy data used in these diagrams are listed

in Table I .1.

The stability diagrams are illustrated in Figures

I.1, I.2, I.3, I.4 and 1.5 and the equations relevant to the

Bayer process are shown later in this appendix.

The main constituents in the bauxites are the

hydroxides and oxides of aluminium, iron, silica and titanium,

in which aluminium is predominant. In the Bayer process

bauxite is first leached with strong caustic liquor over

It is clearly seen from Fig. I.1 that aluminium

present ln the bauxite (in this case alumina monohydrate is

considered as the type of bauxite) enters the solution as the

equilibrium line between Al o


2 3
2
o and Al0 2 lies just below
.3H

pH 14. As shown from the diagrams iron does not enter the

caustic solution as Fe o
2 3
or FeOOH is more stable in that

reglon under the conditions applied during the leaching.

At elevated temperatures, the equilibrium line

between Si0 and Si0 - 2 (Fig. I.4) will be shifted towards


2 3
the left, although it is not shown ln the diagrams plotted

for elevated temperatures. Presence of soluble silica which

create the scaling problems in the Bayer process can be

explained clearly from these diagrams.


312

In the crystallisation stage, the temperature is

reduced to about 60°C. Although the stability diagrams for

60°C are not illustrated here, the equilibrium of the species


0
can be predicted from the stability diagrams of 25 C and

100°C which are shown in Figures I.3 and I.4 respectively.

It is shown from those diagrams that alumina trihydrate is

crystallised at just over pH 14. In order to avoid

eo-precipitation of Si0 , the desilication is carried out


2
before the crystallisation stage, as such soluble silica will

be crystallised before alumina trihydrate.

Hydragillite has been considered for low temperature

diagrams, as it is the most stable hydrate below 100°C.

Therefore during the crystallisation stage, irrespective of

the raw material leached, it is the hydragillite which will

be precipitated.

The metallic aluminium region has not been consid-

ered in the diagrams as it was not relevant to the author's

studies.

Al - H2 0 System

(1) Al 0 + H2 0 = Al0 - + H+
2 3 2

25°C Log [Al0 -J = - 15.644 + pH (hydragillite)


2

100°C Log [A10 -J = - 13.964 + pH (hydragillite)


2

150°C Log [Al0 -J = - 13.576 + pH (boehmite)


2

200°C Log [Al0 2 -J = - 13.490 + pH (boehmite)


313

Calculations for elevated temperatures are not

presented in this work due to unavailability of sufficient

thermodynamic data for the Si - H 0 system. However, it is


2
understood that in general at elevated temperatures equili-

brium lines will be shifted towards the left.

(2b)

25°C Si0 + H 0 = Si0 - 2 + 2H+


2 2 3

Log [Si0 - 2 J = - 27.21 + 2pH


3

Fe - H 0 System
2

( 3) FeOOH + e = HFe0
2

25°C E = - 0.982 - 0.0591 log (HFe0 -)


2

100°C E = - 1. 033 - 0.074 log (HFe0 - )


2

(4) FeOOH + 3H+ + 3e = Fe + 2H 0


2

25°C E = 0.004 - 0.0591 pH

100°C E = 0.0344 - 0.0740 pH

( 5) Fe o + H 0 + 2e = 2HFe0
2 3 2 2

2
25°C E = - 1.149 - 0.0296 log (HFe0 -)
2

150°C E = -1. 2 7 8 - 0.042 log (HFe0 - ) 2


2

200°C E = - 1. 396 - 0.0469 log (HFe0 - ) 2


2
314

( 6) HFe0 - + 3H+ + 2e = Fe + H 0
2 2

25°C E = 0.496 + 0.0296 log (HFe0 -) 0.0887 pH


2
100°C E = 0.568 + 0.0370 log (HFe0 -) 0.1110 pH
2

150°C E = 0.618 + 0.0420 log (HFe0 -) 0.1259 pH


2

200°C E = 0.676 + 0.0469 log (HFe0 -)


2 - 0.1408 pH

(7) Fe
3 4
o + 8H+ + 8e = 3Fe + 4H 0
2

150°C E = 0.053 0.0839 pH

200°C E = 0.055 0.0939 pH

( 8) Fe o + 2H 0 + 2e = 3HFe0 - + H+
3 4 2 2

25°C E = 1. 842 0.0296 log (HFe0 - ) 3 + .0296pH


2

150°C E = 2.068 - 0.0420 log (HFe0 -) 3 + . 0. 0420pH


2

200°C E = - 2. 2 5 - 0.0469 log (HFe0 - ) 3 + 0.0469pH


2

( 9) =

E = 0.3 - 0.0839 pH

E = 0.31 - 0.0939 pH
315

0
Formula !'J.Go Temp. C Ref.
f
K.cal.mol -1

Al o .H 0 -377.5 25 145
2 3 2
(boehmite)

Al o .3H 2 0
2 3
-382.4 " 145
(hydragillite)

A1o; -196.8 " 145

Si0 (quartz 192.4 " 148


2 silica)

-2 -212 148
Si0 "
3

Hsio; -228.36 " 148

FeOOH -113.166 " 147

HFe0 2 - 90.3 " 146

Fe o -117.4 " 146


2 3

Fe o -242.7 " 146


3 4

H 0 (liquid)
2 - 56.688 " 146

Fe 0 " 146

TABLE I.1 Free Energy Data at 25°C for


the various species involved
Eh-------------------------------------------------------------------------i
3

110-2 (1)
2
I

1
I Al203.H20

I
I

0 -
I
I
---- -- I
(9)

-- --- 5
--- HF 0
------~2...
--
-2

Fe

8 9 10 11 12 13 14 15 16 17 18 19 20
pH
Fig. I.l Potential -pH diagram for Al-Fe-H o system at 200°c
2
2 f-
10- 2 10°
10- 4 I
I
I
1 - I I (1)
I I
I -
I Al o
2 3
.H
2
o Al0
2
0 f-. l I
I I
I
-
- - ~
I
_(7j
- _I __ Fe:f
4
(9)
Fe o
2 3 10- 4
-1
I
I
I -
- - - - (8)
(5)
-
10°

~
I
-2 1-
I I
I I Fe
1 I
I I
I
I I I I I I l I I I I I

8 9 10 11 12 13 14 15 16 17 18 19 20
pH

Fig. I.2 Potential -pH diagram for Al-Fe-H o system at 150°C


2
Eh
3

2 f-

10- 2 10°
10- 4 I
1 - I
I 1
I
I I -
I I A1203.3H20 Al0
2
I I
0 f--
I I
(4) I I
I I FeOOH 10- 4

-1 - I (1) 10°
I I (6) HFe0
-
I 2
I 10°
I
-2 - I
I
I Fe
-
I
I
I
I
I
I, I I I I

8 9 10 11 12 13 14 15 16 17 18 19 20

Fig. I.3 Potential -pH diagram for A1-Fe-H o system at 100°C


2
w
~
CO
El
3

2 1-

10- 4 10- 2 10°


I I
I I
1 - I I
I I -
I I Al203. 3H20 Al0
2
I I (1)
0 - I
I
I I
I (2b) (2)
loo- ( 4)
I I
_j I
-1 r- 11 (3) 10°
I
I (fil HFeO..., 10°
I
I I
I I -
HS 03
-2 '-
I Sio lsio - 2 Fe
I 2
I 3
I I
I I j_
I I
I I lL _t ..1 I I I I
8 9 10 11 12 13 14 15 16 17 18 19 20
pH
Fig. I.4 Potential -pH diagram for Al-Fe-si-H o system at 25°c
2
320

oC
200
I -2
10- 4
I
I 1 10 10°
I I
180 I I
I I

160
' I
I
\
'
I
I I
I
\ I
\ I A10
140 I Al203 .H20 2
\
I

120 '\ \
\
\ \
\
\ '\
lOO
\ \

80 ''
\
\
\
\Al
2 3
o • 3H 0
2
\ \
\
60
\ \
\ \
\ \
\ \
\ \
40
\ \
\
\
\ \
\ \
20
10 11 12 13 14 15 16 17

Fig. I.5 Temperatures -pH diagram for Al-H


2
o system
321

APPENDIX II

DETERMINATION OF TOTAL ORGANIC CARBON "PRESENT

IN THE BAYER PROCESS LIQUOR

a) Potassium Permanganate Titration Method

This method was used to determine the total

oxidisable organic content in Bayer process liquor, but due

to the complex nature of the organic matter, the results

obtained were not conclusive. The organic material in the

Bayer process liquor was not completely oxidised during the

normal period of titration. It was noticed that some of the

organic present in the liquor was oxidised after the final

end-point reading was noted even with very slow rates of

titration.

This method is usually used to determine the

total oxidisable organic in the water (149) and is based on

the oxidation-reduction titration with potassium permanganate

solution. Firstly, the organic substance is oxidised

with excess standard potassium permanganate (KMn0 ) in 1 m


4
sodium hydroxide for about 10 minutes at room temperature

(longer times will cause permanganate to decompose slowly to

When permanganate acts as an oxidant in strongly

basic solution, the product is the manganate ion (Mno -2 ):


4

+ e - -2
but if the solution is not strongly basic, Mn0 will
4
disproportionate as follows:

3Mn0 -2 + H 0 ---Mn0 + 2Mn0 + 4PH -


4 2 2 4

Many organic compounds of low molecular weight containing


322

C =C , C- OH, C = NH 2 , C =0 and -CHO

are oxidised to carbonate by permangan ate, but some

organic compounds such as the humic substance s are not

oxidised quantitat ively to carbonate but yield oxalate and

other intermedi ates. Therefore in the titration of Bayer


liquor the solution was first acidified and a sufficien t

excess of standard sodium oxalate added to reduce all the

manganate and permangan ate still present to Mn +2 The


excess of oxalate then present in the acid solution was

titrated with a standard solution of potassium permangan ate.

In this way all of the original compound was converted to

CO an d a ll o f th e permangan a t e to Mn + 2 . Th e ea l cu l a t•lOn
2
of total oxidisabl e carbon could then be completed as follows:

(A) (B) (C) (D)


(equivalen t = Eq.of KMn0
of organic 4 + (Eq.of KMn0 4
added before
(Eq.of oxalate
used in added before
compound) oxidation titration ) titration )

From the results obtained it was clear that this

method was unsuitabl e for determinin g the oxidisabl e organic

carbon content for any accurate purpose. This was mainly


due to the complexit y of the reaction of potassium perman-

ganate in the basic medium.

The stability fields on Eh-pH diagrams for man-

ganese water were studied to understan d the role of potassium

permangan ate in the reaction with organic matter in Bayer

process liquor. The stability field diagram for manganese


species at 25°C constructe d by Pourbaix (148) is shown in

Figure II.1.

The boundarie s of the various species are


323

numbered to correspond to the reaction mechanism given below

(only the reactions which are relevant to this work are

mentioned here).

1) Mno + H+ + e = MnOOH
2

2) 3MnOOH + H+ + e = Mn o + 2H 0
3 4 2

3) Mn o
3 4
+ 2H+ + 2e - 3Mn0 + H 0
2

4) Mn0 + 4H+ + 3e = Mn0 + 2H 0


4 2 2

5) Mn0 + 4H+ + 2e = Mn+ 2 + 2H 0


2 2

6) Mn0 + e = Mn0 -2
4 4

7) Mn0 + 8H+ + Se = Mn+ 2 + 4H 0


4 2

8) Mn0 -2 + 4H+ + 4e = Mn(OH) -2


4 4

9) Mn0 -2 + 5H+ + 4e = Mn(OH) -1 + H 0


4 3 2
-2 + 6H+ + 4e 0
10) Mn0
4 = Mn(OH)
2
+ 2H 0
2
-2 + 7H+ + 4e +
11) Mn0
4
= MnOH + 3H 0
2

12) MnOH+ + H+ = Mn+ 2 + H o


2
0 + H+
13) Mn(OH) = MnOH+ + H 0
2 2

14) Mn(OH) - + H+ = Mn(OH)


0
+ H 0
3 2 2

15) Mn(OH)
2- + H+
= Mn(OH) - + H 0
4 3 2

16) Mn(OH) + 2H+ = Mn+ 2 + 2H o


2 2

17) MnOOH + 3H+ + e = Mn+ 2 + 2H o


2

18) Mn o + 8H+ + 2e = 3Mn+ 2 + 4H 0


3 4 2
324

1.6

1.2-

0.8-

Mn ++
0.4

--
-- -
(16)

-1.2·~------------------------------------------~~

-1.6

-2 0 2 4 6 8 10 12 14 16
pH

Fig. II.1 Potential -pH diagram for the system


Manganese - water at 2soc.
325

I II III IV V VI

1 .031 .099 1 20 80 8. 3

2 .031 .099 1 21 80 15.5

3 .031 .099 1 21 80 18.0

4 .031 .099 1 20 80 9. 5

5 .031 .099 1 21 81 4.5

6 .031 .099 1 21 80 4.2

TABLE II.1 Titration results

I Molarity of KMn0
4
II Molarity of sodium oxalate

III Volume of Bayer liquor used for titration (ML)

IV Volume of sodium oxalate added before titration


(ML)

V Volume of KMn0 added in excess


4
VI Volume of KMn0 used for titration
4
326

Total oxidisable
organic in terms
A B c D of carbon g/litre

1 0.7513 2.48 .2573 1.98 9.08

2 0.8815 2.48 .4805 2.079 10.578

3 0.959 2.48 .558 2.079 11.508

4 0.7945 2.48 .2945 1. 98 9. 5

5 0.571 2.511 .139 2.079 6.852

6 0.531 2.48 .130 2.079 6.372

TABLE II.2 Calculation of Organic Content

A Equivalent of organic compound

B Equivalent of KMn0 added ln excess


4
c Equivalent of KMn0
4
used for titration

D Equivalent of oxalate added before titration


327

It is evident from the diagram that in the basic

medium a number of consecutive reactions are taking place.

The main reaction is the reduction of Mn0 - to Mn0 - 2 (No.6),


4 4
but the diagram shows that reactions Nos. 1,2,3,4,8,9,10 and

11 are also possible. As a result Mno , MnOOH, Mn o and


2 3 4
Mn(OH) can also be formed. Furthermore the following
2
. -2
intermediate ionic specles are also stable, Mn(OH) 4 ,

Mn(OH) -2 , Mn(OH) -1 and MnOH + . However, formation of such


2 2
intermediate compounds are also dependent on the properties

of the organic compounds in the Bayer process liquor.

In the second stage of the titration (after the

solution is acidified) the following reactions will take

place among the ionic species- Nos. 7,12,13,14 and 15.

Among the solid and ionic species reactions Nos. 5,17,18 and

16 will take place.

At the end of the titration the product is ex-


+2
pected to be Mn and co , but due to these intermediate
2
reactions, the end-point of the titration cannot be properly

identified. Tables II.1 and II.2 indicate some of the

results obtained. It is noticeable that the results are not

reproducible. Therefore the above method is not useful

and cannot be recommended for the determination of total

organic content in the Bayer process liquor.

(b) Using Carbon-Hydrogen Analyzer - Coleman Model 33

The Coleman Model 33 Carbon-Hydrogen Analyzer is

an automated combustion instrument for the laboratory deter-

mination of carbon and hydrogen ln materials dissociable at

temperatures below 1100°C.


The instrument is comprised of a combustion train
328

and an absorption train. The combustion train consists of

a vertically mounted combustion tube and motor-driven

electric furnaces. The furnaces move to specified positions

during each phase of the instrument's operating cycle.

The absorption train consists of four glass absorption tubes

containing chemical packings which contain absorption media

for C0 .H 0 and interfering substances. One tube pretreats


2 2
the oxygen sweeping gas to remove possible contamination by

co 2 or water.

The operating cycle of the instrument is function-

ally divided into purge, combustion and absorption. During


purge, a stream of oxygen displaces atmospheric gases trapped

in the combustion train. During combustion, the sample is


broken down into its elemental constituents which combine

with the oxygen stream. During absorption, the gaseous

combustion products are swept into the absorption train where

carbon (as carbon dioxide) and hydrogen (as water vapour)

are selectively absorbed. Carbon and hydrogen content of

the sample are determined by weighing the respective

absorption tubes. In this case only the carbon content was

determined.

A measured sample of Bayer liquor was first acid-

ified by adding hydrochloric acid and then evaporated until

dryness in the oven, which was set at 11S°C. The amount


obtained was then weighed. A portion of the weighed dried

sample was fed into the analyser. The co 2 absorption tube


was weighed before and after the experiments and the differ-

ence in weight indicated the carbon content as carbon dioxide.

The results obtained are as follows:


329

I Bay er liquor sample 27.5 g/litre (as carbon)

II -do- 27.2 g/litre -do-


III -do- 26.5 g/litre -do-

These results indicate that the total organic

values obtained by this method are somewhat lower than the

results obtained when using the Beckman Carbon Analyser.

The difference can be explained as being due to the loss of

volatile organic acids such as formic and acetic, during the

evaporation in the oven. However, the sample must be

acidified and dried in order to eliminate the carbonate which

is also present in the sample. Therefore this method is

not useful as a satisfactory method for determining total

organic carbon present in Bayer liquor.


330

APPENDIX III

THE USE OF A ZEISS MICROVIDEOMAT-2 FOR THE

ANALYSIS OF PARTICLE SIZE DISTRIBUTION OF

ALUMINA TRIHYDRATE

The Zeiss Microvideomat-2 provides a rapid means

of analysing the size of particulate material. This method

has been found to be less time consuming and more efficient

compared to the other commonly used methods for determining

particle size such as the use of sieves, sedimentation

equipment, cyclosizer or Coulter counter.

The Zeiss Microvideomat-2 quantitatively analyses

the images taken either with the optical microscope or with

the electron microscope. The objects which are to be

measured are discriminated according to their brightness.

Objects which are not required to be measured can be suppress-

ed. During the analysis the input is supplied from the

microscope. The TV line scans the aerial image from the

microscope. The operator manually selects the discriminat-

ing levels. When the brightness deviates from this level, a

square wave pulse is produced with the length of the scan

line within the discriminated image proportional to the time

parameter of the square wave. This discriminated signal

pulse selected from the continuous background oscillator pulse

is further processed if required before being fed to the

digital output stage. The combination of vertical oscilla-

tor pulses and horizontal TV scan line produces picture

prints, which are scanned 1n 40 milliseconds.

Stereological and photometric parameters can be


331

Parameter Required measuring parameters

Classification with erosion with D 13


inscribed hexagon (with structure analyzer)
particle count

Surface area absolute object surfaces


classification feature selector

Perimeter classifi- perimeter surface


cation (with structure analyzer)
feature selector

Linear analysis in linear erosion with D 13


X2 direction particle count

Proximate analysis linear dilatation with D 14


in X2 direction particle count

Linear analysis in linear erosion with D 13 in each


three directions hexagonal direction
(with structure analyzer)
particle count

Linear proximate linear dilatation with D 14 in each


analysis in three hexagonal direction (with structure
directions analyzer) particle count

Hexagonal analysis erosion with D 13 or opening with


D 13 and D 14 (with structure
analyzer) particle count

Hexagonal proximate dilatation with D 14 or closing


analysis in three with D 14 and D 13 (with structure
directions analyzer) particle count

Transmittance intensity measurements with D 12

Reflectance intensity measurements with D 12

Total absorbance intensity measurements with D 12


surface area measurement
feature selector

Brightness classifi- gray threshold given with D 12


cation particle count
332

Parameter Required measuring parameters

Absolute object relative object surface


surface reference field size

Volume percentage relative area percentages of the


of a phase different object phases

Weight percentages relative area percentage and specific


of a phase weights of the required phases

Specific surface intercept count


particle count

Projection length particle count


reference field height

Chord length in linear erosion with D13


X2 direction

Inscribed hexagon erosion with D 13


(with structure analyzer)

Longest dimension with D 13 (with structure analyzer)

Perimeter perimeter measurement


(with structure analyzer)

Average fibre relative object surface


thickness (measurement in measuring slit, if
necessary)
reference field size

Average grain size intercept count


reference field height
particle count

Dilatation factor intercept count with


Shape factor 90° object rotation

inscribed hexagon
longest dimension
(with structure analyzer)

intercept count
linear erosion with D 13

Classification with longest dimension with D 13


longest dimension (with structure analyzer)
particle count

TABLE III.1 Measuring facilities of the Microvideomat-2


333

determined with the microvideoma t-2 e.g. absolute and

relative surfaces of specific areas, lengths and distances

of image areas, relative frequency and sizing of particles,

intensities and brightness classificatio ns.

Depending on specimen and problem the required

measuring parameter can be determined directly by conversion

or by a combination of several instrument parameters as

follows:

1) The primary measuring parameters are the characterist ic

measuring results, which are directly supplied by the instru-

ment and can be interpreted without conversion (e.g. particle

counts).

2) By mathematical relationship s, a number of other measur-

ing parameters can be derived and or calculated from the

primary measuring parameters, such as average diameter via

intercept counts. This requires the calibration of the


corresponding instrument parameters.

3) Only the combination of the primary or derived measuring

parameters and different instrument parameters offers the

great variety of measuring facilities (e.g. sizing).

Table III.1 illustrates most important stereologica l and

photometric measuring facilities available using videomat-2.

The particle size distribution of the product alu-

mina trihydrate obtained from the crystallisati on experiments

in this project were analysed using the videomat-2. The


maJor problem in these studies was the difficulty in obtain-

ing a uniform particle distribution on the slide which is to

be analysed by the microscope. However, this problem was


overcome by dispersing the product to be analysed in a

glycerine - water solution.


334

Particle counts

Field
Particle
oversize 1 2 3 4
j.lm

1 43 53 32 45

5 38 50 30 41

10 36 47 26 38

15 31 45 25 39

20 29 43 20 37

25 28 42 18 34

30 24 38 18 30

35 22 35 17 28

40 16 30 13 24

45 15 28 10 21

50 12 22 6 19

55 10 18 5 13

60 9 15 5 10

65 8 13 4 10

70 6 11 2 8

75 4 9 2 5

80 3 8 3 4

85 2 8 2 3

90 2 7 0 0

95 3 5 0 0

100 0 0 0 0

Total count: 43 53 31 46

TABLE III.2 Particle size count of product alumina


trihydrate
335

The particle count of oversize and the average

size of the product trihydrate were determined using the

microvideomat and an example of the results is shown ln

Table III.2.

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