Untitled
Untitled
Untitled
by
November 1981
Form 1
WAIVER
THE UNIVERSITY OF NEW SOUTH
WALES
' J
Date.......lJ.j /J:j J:,/ ...................................................
.
Candidate's Certificate
degree or award.
~~~~
(Lakshman Dlssanayake Jayaweera)
ACKNOWLEDGEMENTS
unfailing patience.
Dedicated to my parents.
ABSTRACT
affected.
supersaturated level.
Page
ACKNOWLEDGEMENTS
ABSTRACT
LIST OF TABLES
LIST OF FIGURES
INTRODUCTION 1
aluminium industry
PART I
CHAPTER 1
Glad stone
Process Liquor
CHAPTER 2
2.21 Nomenclature 47
2.222 Bayerite 51
2.223 Boehmite 52
2.224- Diaspore 54-
formations
2.6 Desilication 69
CHAPTER 3
b) Chemical Polymerization 77
c) Cell Autolysis 77
d) Microbial Synthesis 77
of Humic Substances
a) Spectroscopic characterisation: 87
method
metric method
(N.M.R.) Spectrometry
V X-ray analysis 95
b) Molecular Method 96
II Ultra centrifugation 97
Humic Substances
CHAPTER 4
4.1 Al o
2 3
- Na
2
o- H 0 System
2
138
Crystallisation)
Process
PART II
CHAPTER 5
Liquor
Temperature
Chapter 5
CHAPTER 6
Videomat-2
Succinate
CHAPTER 7
CONCLUSIONS 294
REFERENCES 299
Appendix I 310
Liquor
Liquor
Appendix III
molecular fraction
seed column
6.1 Plant and laboratory crystallisation conditions
6.2 Details of experiments on crystallisation
Appendix II.2 do
2 Application of aluminium
Glad stone
1.5 - do -
1.6 - do -
and c) diaspore
2.12 Silica cycle 1n the Bayer process
b) fulvic acid
acid
3.5 Infrared spectra of original humic acid obtained
substances
substances
in soil
on rate of precipitation
weight
adsorption studies
studies
5.19 - do -
5.20 Adsorption studies of Bayer process liquor on
of the experiment.
temperature
at elevated temperatures
unit
6.3b - do -
6.5b - do -
6.6a Effect of organic impurities on crystallisation
6.6b - do -
6.7b - do -
6.8b - do -
6.9b - do -
(magnification 50X)
6.21 Microphotograph of product alumina trihydrate
(magnification 150X)
at 25°C
INTRODUCTION
ALUMINIUM INDUSTRY
1
INTRODUCTION
industry in Australia.
16,000 Australians.
million tonnes
Weipa 2700
Gove 300
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
Million
tonnes
30
20
10
1960 62 64 66 68 70 72 74 76 78 80 82
shown in Fig. 1.
products.
products.
products.
Total 6.6
Building
and
Construction
22.0%
This has been the hard won result of the scale and quality
Kwh/Kg. of Al
50~----------------------------
401------------------------------
301\~~---------------------
~
20~~~~~~~====:-
101------------------------------ -
oL-----~----~----~--~~--~
1890 1910 1930 1950 1970 1980 years
achieved and reduced capital and fuel costs are claimed (4).
alumina.
equation:
Monohydrate
(boehmite type)
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
1n 1896.
A more detailed account of the original process
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
design.
of the basic Bayer cycle, but there are many technical and
where as Al o
2 3
.H 0 requires a temperature of over 200°C
2
but the solubility equilibrium for both types depends
caustic ratio.
Quartz 1.0%
P205 0.08%
Moisture 13 - 15%
Ti0 2.6%
2
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
2) Digestion (extraction)
7) Filtration
8) Calcination of trihydrate
as Na
2
co 3 ). It also contains dissolved alumina up to a
ators, where steam and heat are recovered from the system.
500 tons of Al o
2 3
produced.
tall open topped tanks which stand 100 ft. high and 25 ft.
out from the last tank at 65°C with a caustic concent ration
hydrate crystals from the final filter are then used for
seeding.
and A/C = 0.375 is mixed with fresh caustic soda and passed
subjected to calcination.
23
g/litre
1. Alumina Al 0 84.3
2 3
4. NaCl 16.19
5. Si0 0.53
2
6. P205 0.088
7. V205 0.74
8. Na
2
so 4 0.31
11. Fe
2 3
o .005
Maximum Typical
allowable
Fe
2 3
o 0 . 0 3 0% 0.016%
Na
2
o 0 . 70% 0. 35%
Screen
has shown that the total organic can reach about 160 -
Figure 1.3. It was also shown from his work that sodium
.-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)
world.
Africa 150 5. 5
27
hydrate precipitation.
organlcs.
then used for seeding. The flow diagram for this oxalate
Bayer process.
can be seen that the pregnant Bayer process liquor and alumina
particles and the solid oxalate from the underflow are fed
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-)
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
~
w
N
Fig. 1. 5 Kaiser paten t (contin ued)
Cold water spray
Water spray
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
precipitation step.
of process cycle. But this method does not remove all the
with its colour changing with iron content from almost white
follows:
a) Gibbsite: (Al o
2 3
.3H 0) which is easily
2
extracted in the Bayer process
Bayer process
c) Diaspore: (aA1 o
2 3
.H 0) this phase is rare in
2
Australian bauxite and is only extracted under relatively
titanium dioxides.
as quartz.
other requirements.
of bauxites.
{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~
Chemica l formula
65.4 85 85
34.6 15 15
Space group
Temp. of
decompo sition
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
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
age of gibbsite.
low grade.
modifications.
2.21 NOMENCLATURE
process.
Megaw et.al.(12), Saalfeld et.al.(13) and
gibbsite.
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
+
CD
49
ium ions between the second and third layers of the hydroxyl
ions and the hydroxyl ions of the third layer are directly
ions.
B
.B
-----A
Al at 1/3 2/3
Al at 1/6 5/6
c- plane
gibbsite crystal.
0 0 ~
c = 9.7A , S = 94 34 (21) whereas according to Ormont
s = 85° 26~.
2.222 Bayerite
2.223 Boehmite
a
0
= 3.78 0 A c
0
= 2.85A0
The crystalline structure of boehmite is very similar to
2.224 Diaspore
seed material.
a
0
= 4.40 0 A b0 = 9.39A0 c
0
= 2.84A
0
(21,33).
Figure 2.7.
55
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-
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
Appendix I.
Table 2.5.
great change in the ratio of the two hydrates, but the rate
58
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
gibbsite.
seed is used.
trial conditions.
monohydrate form.
cessing.
lS affected.
2
dx (xt - xoo)
-dt = kAt-----------
(aoo + xoo)2
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
1.45
0
N
('(j
~ 1.25
("')
0
N
r-1
.:1!
--:- 1. 05 -
! 0
·.-!
~ 0.85
l-1
•.-!
~
~ 0.65
·.-!
r-1
·.-!
follows:
dx
= KA ( y - x)
dt
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.
dx
dt = K1 ( y - X)
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).
4) Temperature
5) Stirring rate
6) Activating substances
where dx
dt = rate of dissolution of bauxite
solution
= equilibrium concentration of Al 2 o3 ln
N = avagadro number
11 = viscosity of solution
d = diameter of particles.
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
m
m
67
increasing.
solution.
2.6 DESILICATION
caustic soda.
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
trations.
71
the new liquor strength and ratio thereby keeping the silica
humic substances.
believes that the bulk of the organic matter comes from the
!
Humates + co 2
l
Coloured Humic Acids + co 2
l
Polyhydroxy Compounds + co 2
~
Oxalic, Acetic Acids + C0 2
l
C0 2 + H2 0
reactions.
remains.
acid and base, (c) the humic fractions that cannot be extract-
Humic Acids
a) Plant Alteration
b) Chemical Polymerizatio n
phenols and am1no acids which are then excreted. Humic sub-
c) Cell Autolysis
d) Microbial Synthesis
only released into the soil when microbes die and their cells
RELATIONSHIP TO BAUXITE
c) a lowering of pH.
normal pH range.
79
soils.
before processing.
complexity.
Therefore most of the reports made ln the last
olic hydroxyl groups, but this method was not successful due
always inaccurate.
could interfere.
82
phenolic groups.
Perdue (54) claimed from his work that calori-
equatio ns:
ROH + (CH 3 C0) 2 0 CH COOR + CH 3 COOH
3
This proced ure was based on the reactio n of humic substan ces
R1 R1
~ ~
C =0 + NH 2 0H.HC1 --~- C - NOH + HCl + H 0
- 2
/
R 2
R/ 2
manometr ically.
Khan ( 4 7). Table 3.1 indicates that between 68% and 91%
% of oxygen
Soil HA 1 s
~ot determined
TABLE 3.1 Distribution of oxygen in humic substances {47)
CO
(]1
86
(59,60).
The nitrogen content of humic substances ranges
HUMIC SUBSTANCES
Khan (47).
a) Spectroscopic methods:
method
b) Molecular methods:
ii) Ultracentrifugatio n
a) Spectroscopic characterisation
the aromatic rings that they contain (b) the ratio of carbon
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
:>, 0.5
+-'
·rl
(})
!=: 0.4
(])
'\j
rl 0.3
rU
0
·rl
+-' 0. 2
p_,
0
0.1
~
0
·rl
00
00
·rl~----------------------------------------,
s
00
~
~
~
~
~
~
~
0
~
~
~
-1
Frequency cm Assignment
3400 Hydrogen-bonded OH
1725 C =0 of co 2 H, C =0 stretch of
ketonic carbonyl
1630 Aromatic C =C
Hydrogen - bonded C =0 of carbonyl,
1450 Aliphatic C - H
of co 2H
1050 Si - 0 of silicate impurity
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
are CC1 and CDC1 3 . However, pure humic substances are not
4
soluble in these solvents, unless they are chemically
measurements .
v) X-Ray Analysis
ent work.
in structure determination.
recently ( 7 5) .
of humic substance s.
sample size.
Gel permeatio n chromatog raphy (GPC) is a type of
ments.
Three mechanis ms have been suggeste d for the
buffer at pH 10 as eluant.
The applica tion of G.P.C. to the measurem ent
and natural waters has been reported . The data show that
99
distillation
viscosity
membrane
SUBSTANCES
Humic Substances
Flaig's Model
Felbeck's Model
! 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 .
l
0
CH30o~"'OCH3
H·--- 0 r./
_,., o
11
H---0
,
CH==CH-COOl-1
OH
OH
\
H
.............- - + - - - C C
A 6H
R~OH
OH
n
R represents H, OH or COOH
Tinkle's Model
Haworth's Model
....
" , I
: ',1 core(
I , ,
I , ', I
/ ',
I ," 'I .
~Pheno
l 'lC acids
Metals .,_-- - - - - - - - -
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
successful.
The major methods that have been and are being used
HC=O
~OCH3 ~
COOH
Q OH
~OH
OH OH OH
OCH
3
C0 H
2
OCH
3
HC0 OCH 3 .
3
OH
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)
autolysis
I
Oxidation & dehydrogenation
NH Amino acids
3
~ a=r=o=m~at=~=·c~~~~~=-
Oxidation
Polymers
I
important.
is sodium oxalate.
has only been able to use the shape of the gel filtration
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
Bayer process liquor has been by Paul (108) who claims the
(109).
ALUMINA TRIHYDRATE
tion.
Another interesting work was carried out by Sato
Figure 3.14, which was taken from his work, indicates the
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.)
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
.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
80
70
Al
2 3
o
yield
g/1 60
50
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
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
• = 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
crystalline product.
sodium oxalates.
127
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
2.5 g/1, the sodium oxalate does not precipitate with the
trihydrate to alumina.
c c c
oxalate oxalate equilibrium
supersaturation concentration solubility
in liquor
sodium oxalate.
C . .b .
equl 1 l rlum
= 7.62 exp.(.012T- 0.016FS- 0.011 co 3 2 - )
solubility
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
Alumina 75 g/litre
Carbonate 15 g/litre
concentration
and
sodium oxalate.
and in the kiln feed. These trends are reversed when the
the hydrate particles and it was claimed that the finer end
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
0-32 .046
32-63 .033
63-90 .032
90 .027
sodium oxalate.
may have been due to the fact that firstly there has been
liquor:
1) use of activated carbon and pulverised coal as adsorp-
tion material
pressure
4) heat treatment
5) seeding method.
carbon particles.
3. 6. 3 OXIDATION METHOD
alkaline solutions.
reconstructed.
ing that the organic impurit ies could success fully be removed
tempera tures.
detail in Chapter 2.
137
past experienc e.
~ 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
Figure 4. L
producers.
[cNaOH + cNaA1o 1j
2
K =
[cNaA1o 2][ a H2o] n
as follows:
K =
- 734-0
log K = 4-.574-T + 4-.11
where =
= NaOH concentration g/1 Na
2
o
T = temperature °K
0
where t = temperature C
follows:
i'
log CAl o =
2 3
Caustic ratiot
s = = Caustic rat1o
eq
where
S = degree of supersaturation
= concentration of Al o
2 3
in super-
Al o
2 3
eq = concentration of Al o
2 3
at equilibrium
Caustic ratio =
process is remote.
144
saturated.
Miers (130) postulated that the region of super-
/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
order relation.
period.
The rate equations suggested by past workers were
dW
dt = K f (S)
where
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
dW ~':
dt = K (C - C )
dC
- dt = K/Cs + r
dX
dt =
148
dC
dt =
growth.
149
solved for a batch unit and the solution has been shown to
is a chemical reaction.
a) crystal growth
high caustic ratio and high seed surface are applied, the
4. 3 22 Nucleation
ways:-
a) creation of new crystallites (secondary nuclea-
tion)
b) crystal growth
crystallisation).
work.
stages:
pressure.
they noted that nuclei will not form readily when seed
particles are about, but will form copiously when they are
dNo
Rate = B
0 = dt =
f (S,T,X,Y,Z)
t = time
T = temperature °C
~~
s = supersaturation cc - c )
X = some property representing the presence
of the solution
geometry, etc.)
4. 32 3 Crystal Growth
for this is provided by the very low growth rate and the
dL
G = dt =
4. 324 Agglomeration
(e.g. low agitation rate) the finer particles (< 20~m size)
mechanism.
Maricic and Markovcic (135) observed the formation
s1ze 10 microns).
originally present.
The process of agglomeratio n is generally accepted
precipitate.
the other.
Reversible
original individual
particles of
suspension
-... (surface
_
forces)
Aggregate
Irreversible
Agglomerate
(Cementation by
crystallisation)
the parent crystal, but this leaves the parent crystal prac-
age takes place with the complete change in the present crystal
DECOMPOSITION
2) Caustic concentration
process liquor.
trihydrate crystals.
experiments.
TRI-HYDRATE CRYSTALS
The primary problem was that the liquor was highly caustic
cases in this work when the analysis was only limited to the
166
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
I Precip itated
T.O.C. 5% by weigh t
Membra ne separat~io::1
with Millip ore type
molec ular cut off.lOO O
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
to a recorder.
169
ganic carbon (TIC) from the total carbon value (TCV). The
analysed.
170
interfering.
Table 5 .1.
C0 at this stage.
2
One of the major drawbacks of the Beckman
150°C.
titration method
process liquor.
In using the Coleman Carbon Analyser, sodium
evaporation.
172
II -do- 10.59 11
11
III -do- 11.51
11
IV -do- 9. 5
11
V -do- 6.85
for distillation.
any loss of acid vapour. The sample in the flask was heated
The liquor was boiled and some of the vapour condensed and
until the solution in the flask was almost thick. The quan-
210 )lffi,, The U.V. peak was determined with various dilutions.
174
water
Gentle Acidified
heating Bayer liquor
follows:
water.
into the carrier gas stream and the gaseous components are
tions as those used when analysing the test sample. The main
Differential
Flow
To waste or
fraction
collector
I
Sample
injection
Column
ics Recorder
Column
this method was to track the most volatile organic acids and
acidification.
Chromatograph
conditions:
Type of column:
injected.
were as follows:
2) Acetic acid
3) Lactic acid
4) Propionic acid
5) Butonic acid
6) Pivalic acid
7) Valeric acid
180
Conditions I Conditions II
Rate of temp.
Final temp.
Temperature
at detector
Temperature
at injecting
port
ing and comparing again with the known samples. The peak
~
·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)
(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.
(2)
(5)
(6)
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
dryness in the water bath and a brown wavy type solid material
Humic acids
(previously published)
(53)
Sample
-1
1450 - 1400 Aliphatic C-H at 1400 cm
1
1300 - 1260 e-o at 1200 cm-
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
I-'
tO
0
191
humic acids, fulvic acids and the organic extract from the
Bayer liquor.
lar screening and the proper pore size, and the pore size
converted into Na
2
co 3 during the process. Sodium carbon-
the filtrate was measured for the volume change. One litre
off 1000.
100 ml of the filtrate was poured into the cell
noticed that the colour of flux was lighter than the original
the cell. When the level of liquor in the cell was dropped,
type PTGC membrane with the nominal molecular cut off 10,000.
---- (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
Filtrate passes through the membrane into the core, and thus
Fig. 5.11. When the vacuum was applied the lower molecular
solutes and water pass through the membrane into the collect-
trate was made to 100 ml. and it was tested for total organic
Although the curve obtained was not clear, the results show
as carbon
after carbonisation
cular cut off at 1000 and another at 10,000 based on the pore
obtained thereafter.
2Q1
methanol.
After the methanol wash the product was dried and
into the hot water. The extract was divided into two
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
Hot water
extraction
Evap. to
Aqueous extract ~ 61 g per kg crystals
dryness
the quantity.
with the caustic and inorganic salts, leaving behind the corn-
alumina trihydrate.
204
cold water leaving the organics which were adsorbed onto the
and poured into boiling water which was stirred for about
A
A
A A A A
A
N
0
(Jl
206
trihydrate.
on to solid surface.
ment (cold water wash) are compared with the previous method
measured by weight.
207
TOC per kg of
seeds of the 81 g 61 g
extract
Molecular wt.
> 1000 per kg 3.44 g 10 g
seeds
hydrate.
calculations.
tions.
2
The density of organic materials were taken as 1.2 g/cm
material-50°A
2
Surface area of alumina trihydrate .2 m /g
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
oil is marked "Paraffin" and the rest of the peaks are due
However, the sample used for the IR tests was the filtrate
has overlapped and formed very broad peaks due to the complex-
evidence.
taken that the seed was not dried over 120°C as it could be
.145 g/litre.
are present
tation conditions.
- "'\.
,_~ -
. ·:,.
- ..
.....
- "!:'"-
-
- ;i
--~~-+---+---~
--..:~
_-
,•.
- -
- ·....... -
\ ~
-
--t!=:
....._ - -
...
~- r-
- ......
~
- ~,. .:_., . . .
:r.·n.---
u
It,. .. ____ )I
Fraction collector
each run.
The following organic compounds were subjected
to investigation:
ten times, was passed through the column and the fractions
as desorbed materials.
2
Surface area of trihydrate ::0.15m/g
2
Density of organic materials = 1.2 g/cm
Thickness of monolayer of
organic material
of seeds)
not adsorb onto the surface of trihydrate seed, but there was
0.05
6 12 18 24 30 36 42 48 54 Vol.ml.
0.0
6 12 18 24 30 36 42 48 54 volume ml.
0.1
0.05
V
Fig. 5.19 Adsorption studies of organic impurities extracted from the Bayer
process liquor.
222
adsorb onto the surface, when passed through the seed column.
error does not arise for the curves obtained in Figure 5.18
Adsorption
Collection of fractions (first fraction
- 1.6 (brownish)
to be obtained from
the bottom)
1.5 (brownish)
1.4 (brownish)
De sorption
J_
Collection of fractions
2.6 (colourless)
2.5 (colourless)
alumina tri-
hydrate column ~------ 2.4 (slightly brownish)
2.2 (brownish)
2.1 (brownish)
3m
Ng.OH
solution
~~!~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
218
l
I
2.5 l
I
1 2.6 j
'---·
270 & 220
L 2.7 l
270 & 230
2.8
TABLE 5.11 Comparison studies of the U.V. results of different Bayer process liquor fractions after
passing through the trihydrate column.
226
supersaturation.
temperatures.
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
4
Oxalate level in the recycle
Bayer process liquor
3 -
20 30 40 50 60 70 80 oc
temp.
Solubility
g/1
40
30
10 20 30 40 50 60 70 80
0
T~.c
(Al
2 3
o /Na
2
o wt.) of .2591~ whereas Curve 3 indicates the
liquor.
2) 4 g/litre If If
Ref. ( 144)
argument.
After determining the solubility values at higher
acid).
one with the molecular weight cut off at 1000, the other with
10,000. The membrane with cut off 1000 was not operable
the dried samples were extracted with hot water. The dried
trihydrate before the hot water desorb, was tested with x-ray
saturated level.
CHAPTER 6
INTRODUCTION
The beakers were closed with PVC type lids which can be
tachometer.
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
N
w
tO
240
suspension by stirring.
almost reduced to about 2300 ml. and water was added to make
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-
crystalliser.
i.e.
a) sodium oxalate
b) sodium acetate
c) sodium formate
d) sodium succinate
1000 used for this experiment were extracted from the Bayer
6.5 PROCEDURE
parison studies.
ing liquor was measured. The product was washed and dried
at 101°C.
Analysis of Al o
2 3
and Na
2
o concentration 1n the
in the videomat.
habit, size and the shape of the products trihydrate due to the
reflex camera.
were properly washed and dried, then coated with a gold film.
245
0
Temperature ( C) 80 - 60 60 - 65
varying at constant
temperature
24 negligible
Residence time 40 - 60 24 - 26
hrs.or more hours
2 -do- 11 11
"
3 Sodium oxalate 5 " 11 11
4 Sodium formate 5 11 11 11
11
5 Sodium succinate 5 " 11
2 -do- 130 11 11
5 Sodium oxalate 5 80 11
"
4 1 Pure solution 130 26 24
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
4 -do- 6 " 11
"
5 Pure solution 11
" "
8 1 Sodium oxalate 10 130 63.5-64 24
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)
impurities extracted
from Bayer process
liquor (without any
molecular fraction-
ation)
11
5 Pure solution 11 11
photographed.
added, seed change and the temperature ranges for each run.
able. For this reason it was decided to run at least one unit
treated.
produce only the particle size count and it was not possible
a) Induction period
area of the seed, the greater the seed surface the shorter
alumina.
(d) Equilibrium concentration
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.
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.
N
(.T1
w
60
[Al] 0-0 Pure sodium aluminate liquor
g/1 0--I:l Sodium oxalate 3 g/1
Time (hours)
[Al]
gl 0-0 Pure sodium aluminate solution
70
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)
50
40
0
0
0 25
Time (hours)
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
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
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
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)
N
(5)
w
60
[Al] 0-0 Sodium oxalate 6 g/1
g/1
x->< - do -
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)
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
6 2
Fig.6.6a 8 - do - - do - Dp = 16 ~m whereas Dstd= 39 ~m
fine formation
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.
TABLE 6.4: Summary of the results of the crystallisation experiments with oxalate
impurity charge.
272
a) Induction period
precipitation results.
b) Rate of decomposition
ment No. 7 (Fig. 6.7a), it was noticed that the initial decom-
saturation.
Furthermore, there is also a possibility for sodium
c = c c
oxalate oxalate equilibriu m
supersatu ration concentra tion solubility
in liquor
-2 )
c = 7.62 exp.(0.01 2T- 0.016FS- 0.011C0 3
equilibriu m
solubility
and 6.14.
In most of the runs the product trihydrate was
very much finer than the product obtained from the pure
aluminate solution.
trihydrate on it.
The results are compared with the standard run (Fig. 6.9b)
reveals that the final products were not being affected by the
Figures 6.10, 6.13 and 6.14. The fine formation was also
and 6.Sa show the curve obtained for sodium succinate impurity.
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 -
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
~
()
0 150
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-
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
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"'
*
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.. (j'· "i!
'tit
*
.,
Zl
"
4
" 'i
--
-:-:.
~
!i \
$ .At ..fJ.
"
·:>b ,,£(} .
~·:~
·~
·~
Q) ;:; ;~
"""
~· ~
<I¥" 0
,p $ it\ '*"
"JP &
~ ..
t
4. ..'· 4t '*' 1%
'* .Af ''-f
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t
"'
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¥
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"'
"" ""''
'*
(;)),
11
%
''* ~
if
,.
Q 1f
$'
(a)
(b)
(a)
(b)
FIGURE 6. 24 Electron microscopic photograph of the product
alumina trihydrate without any impurity charge.
(a) (lSOX) magnification
(b) (300X) magnification
292
CONCLUSIONS
294
7.1 CONCLUSIONS
compounds.
more, the infra red spectra of the Bayer liquor extract was
1000 molecular weight and about 20% was greater than 1000
a supersaturation level.
supersaturated region.
affected.
gation.
using a membrane.
practice.
8) Organic impurities used for the crystallisation studies
poisonous material.
I
299
REFERENCES
and 1980
(3) Hellidge Forberg, National South Wise Aluminium Co.,
Division
(7) British Patent 1,039,985 published 24 August (1966) by
(1934) p.1175
627 - 630
p. 249 - 256
Metallurgy)
p.123 - 129
p 501 - 541
p 134 - 148
s 287 - 308
(40) Arakelyan O.I., and others, Trvetnye Metally 33, No. 11,
(1960) 54
302
3 (1955)
U.S.S.R. (1960) pp 47 - 57
Springer-Verlag (1969) p 6 - L - 1 to 6 - L - 30
1351 - 8
Proc . , 2 9 ( 19 6 5 ) 4 0 0
Wisconsin (1965)
(62) Khan S.U. and Sowden F.J., Can.J.Soil Sci., 51 (1971) 185
(63) Khan S.U. and Sowden F.J. Can.J.Soil Sci. 52 (1972) 116
~B) Stevenson F.G. and Goh, K.M., Soil Sci. 113, 334- 345
(1972)
304
(69) Barton, D.H.R. and Schnitzer M., Nature, 198, 217 (1963)
(73) Tokudome S. and Kanno, I., Soil Sci. Plant Nutri., 11,
(1965) 193
(78) Swift, R.S. and Posner, A.M., J.Soil Sci., 22 (1971) 237
(79) Khan, S.U. and Friesen, D., Soil Sci. 114 (1) (1972) 73
(1930) 96
(1971) 259
(94) Piret, E.L., White R.G., Walther, H.C. and Madden, A.J.,
(1971) p 2302
306
(104) Jakab, T., Dubach, P., Mehta N.C. and Deuel, H.,
z. Pflanzenernahr.Dung.Bodenk, 97(1963) p 8
Aechen (1954)
p 289 - 329
University (1962)
307
1964
(134) Jamey, M., Paper presented at the 95th A.I.M.E.
163 - 169
(140) Lyapunov, A.N. and Kholmogo rtseva, E.P. Journal of
p 1306 - 1535
309
liquor
Oct. 1972
Tokyo
310
Appendix I
seed crystals.
The Criss and Cobble (150,151) method was used to plot the
in Table I .1.
I.1, I.2, I.3, I.4 and 1.5 and the equations relevant to the
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
be precipitated.
studies.
Al - H2 0 System
(1) Al 0 + H2 0 = Al0 - + H+
2 3 2
(2b)
Fe - H 0 System
2
( 3) FeOOH + e = HFe0
2
( 5) Fe o + H 0 + 2e = 2HFe0
2 3 2 2
2
25°C E = - 1.149 - 0.0296 log (HFe0 -)
2
( 6) HFe0 - + 3H+ + 2e = Fe + H 0
2 2
(7) Fe
3 4
o + 8H+ + 8e = 3Fe + 4H 0
2
( 8) Fe o + 2H 0 + 2e = 3HFe0 - + H+
3 4 2 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)
-2 -212 148
Si0 "
3
H 0 (liquid)
2 - 56.688 " 146
Fe 0 " 146
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
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
2 1-
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
APPENDIX II
titration.
+ e - -2
but if the solution is not strongly basic, Mn0 will
4
disproportionate as follows:
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:
Figure II.1.
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
6) Mn0 + e = Mn0 -2
4 4
15) Mn(OH)
2- + H+
= Mn(OH) - + H 0
4 3 2
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
I II III IV V VI
1 .031 .099 1 20 80 8. 3
4 .031 .099 1 20 80 9. 5
I Molarity of KMn0
4
II Molarity of sodium oxalate
Total oxidisable
organic in terms
A B c D of carbon g/litre
Among the solid and ionic species reactions Nos. 5,17,18 and
co 2 or water.
determined.
APPENDIX III
ALUMINA TRIHYDRATE
inscribed hexagon
longest dimension
(with structure analyzer)
intercept count
linear erosion with D 13
follows:
counts).
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.