‫ﺑﺳم ﷲ اﻟرﺣﻣن اﻟرﺣﯾم‬

University of AL-Qadisiyah
College of Engineering
Department of Chemical
Engineering

production of Ethylene glycol from ethylene oxide

Prepared by:
 Ziad ahmed
 Ali A. Amosh
 Yasser sahab

supervisor:
Directed by Dr. Mohamed mutter

1
 ‫ِﯾم‬
‫اﻟرﺣ ِ‬‫اﻟر ْﺣ َﻣ ٰـ ِن ﱠ‬‫ِﺑ ْﺳ ِم اﻟﻠﱠـ ِﮫ ﱠ‬
‫﴿ﻗَﺎﻟُﻮا ُﺳ ْﺒ َﺤﺎﻧَﻚَ َﻻ ِﻋ ْﻠ َﻢ ﻟَﻨَﺎ إِ ﱠﻻ َﻣﺎ َﻋﻠﱠ ْﻤﺘَﻨَﺎ ۖ إِﻧﱠﻚَ أَﻧﺖَ ا ْﻟ َﻌﻠِﯿ ُﻢ ا ْﻟ َﺤ ِﻜﯿ ُﻢ﴾‬
‫ﺳورة اﻟﺑﻘرة‪ :‬اﻵﯾﺔ ‪٣٢‬‬
‫ﺻدق ﱠ‬
‫ﷲُ اﻟﻌظﯾم‬

‫‪2‬‬
 ‫اﻻھداء‪:‬‬

‫اﻟﻰ ﻣن ﻋﻠﻣﻧﻲ اﻟﻘﯾم واﻻﺧﻼق‬

‫اﻟﻰ ﻣن ﻛﺎن ﻋوﻧﺎ وﺳﻧدا ﻟﻲ )واﻟدي اﻟﻌزﯾز(‬

‫اﻟﻰ ﻣن أرﺿﻌﺗﻧﻲ اﻟﺣب واﻟﺣﻧﺎن‬

‫اﻟﻰ رﻣز اﻟﺣب وﺑﻠﺳم اﻟﺷﻔﺎء‬

‫اﻟﻰ اﻟﻘﻠب اﻟﻧﺎﺻﻊ ﺑﺎﻟﺑﯾﺎض)واﻟدﺗﻲ اﻟﺣﺑﯾﺑﮫ(‬

‫اﻟﻰ اﻟﻘﻠوب اﻟطﺎھره اﻟرﻗﯾﻘﺔ واﻟﻧﻔوس اﻟﺑرﯾﺋﺔ اﻟﻰ رﯾﺎﺣﯾن ﺣﯾﺎﺗﻲ )اﺧوﺗﻲ(‬

‫اﻟﻰ اﻻرواح اﻟﺗﻲ ﺳﻛﻧت ﺗﺣت ﺗراب اﻟوطن اﻟﺣﺑﯾب )اﻟﺷﮭداء اﻟﻌظﺎم(‬

‫‪3‬‬
 ‫ﺷﻜﺮ وﺗﻘﺪﯾﺮ‪:‬‬

‫ﻛن ﻋﺎﻟﻣﺎ ‪ ...‬ﻓﺈن ﻟم ﺗﺳﺗطﻊ ﻓﻛن ﻣﺗﻌﻠﻣﺎ‪ ،‬ﻓﺈن ﻟم ﺗﺳﺗطﻊ ﻓﺄﺣب اﻟﻌﻠﻣﺎء ﻓﺈن ﻟم ﺗﺳﺗطﻊ ﻓﻼ‬
‫"ﺗﺑﻐﺿﮭم"‬

‫ﻻﺑد ﻟﻧﺎ وﻧﺣن ﻧﺧطو ﺧطواﺗﻧﺎ اﻷﺧﯾرة ﻓﻲ اﻟﺣﯾﺎة اﻟﺟﺎﻣﻌﯾﺔ ﻣن وﻗﻔﺔ ﻧﻌود إﻟﻰ أﻋوام‬

‫ﻗﺿﯾﻧﺎھﺎ ﻓﻲ رﺣﺎب اﻟﺟﺎﻣﻌﺔ ﻣﻊ أﺳﺎﺗذﺗﻧﺎ اﻟﻛرام اﻟذﯾن ﻗدﻣوا ﻟﻧﺎ اﻟﻛﺛﯾر ﺑﺎذﻟﯾن ﺑذﻟك‬

‫ﺟﮭودا ﻛﺑﯾرة ﻓﻲ ﺑﻧﺎء ﺟﯾل اﻟﻐد ﻟﺗﺑﻌث اﻷﻣﺔ ﻣن ﺟدﯾد ‪....‬‬

‫دﻣﺗم ﺷﻣﻌﺔ ﻣﺿﯾﺋﺔ وﻣﻧﺎرة ﺗﺿﻲء درب طﺎﻟﺑﻲ اﻟﻌﻠم‬

‫وﻗﺑل أن ﻧﻣﺿﻲ ﻧﻘدم أﺳﻣﻰ آﯾﺎت اﻟﺷﻛر واﻻﻣﺗﻧﺎن واﻟﺗﻘدﯾر واﻟﻣﺣﺑﺔ إﻟﻰ اﻟذﯾن ﺣﻣﻠوا‬

‫أﻗدس رﺳﺎﻟﺔ ﻓﻲ اﻟﺣﯾﺎة إﻟﻰ اﻟذﯾن ﻣﮭدوا ﻟﻧﺎ طرﯾق اﻟﻌﻠم واﻟﻣﻌرﻓﺔ ‪.‬‬

‫إﻟﻰ ﺟﻣﯾﻊ أﺳﺎﺗذﺗﻧﺎ اﻷﻓﺎﺿل ‪.‬‬

‫ﺷﻛر وﺗﻘدﯾر ﻻﺳﺗﺎذ اﻟﻣﺷرف ﻋﻠﻰ اﻟﺑﺣث ‪ :‬د‪.‬ﻣﺣﻣد ﻋﻠﻲ ﻣطر‬

‫ورﺋﯾس اﻟﻘﺳم د‪.‬ﺻﺎﻟﺢ ﻋﺑد اﻟﺟﺑﺎر ﺻﺎﻟﺢ‬

‫‪4‬‬
Abstract:

ethylene glycol is synthetic organic liquid used for manufacturing of

polyester fiber and as anti-freezing agents. The polyester staple fiber
industry developed during the last decade in response to growing
demand for man-made fiber for the production of blended yarn and
fabrics Due to increasing demand of polyester the demand of EG has
grown tremendously.
This design report is about the "Production of ethylene Glycol'
Detailed description of process of "Production of ethylene Glycol"
Afterwards material and energy balance for each equipment is
presented. In preceding chapters, introduction to different equipments
of plant along with their selection criteria, designing procedure and in
the next chapter we discussed HAZOP study of Storage tank.
Instrumentation & Control of the distillation column is presented;
Material safety data sheet is also included in the project report.

5
Table of content
1.Introduction ……………………………………………[5-28]
1.1.HISTORY
1.2.CHEMISTRY
1.3.PHYSICAL PROPERTIES
1.4.CHEMICAL PROPERTIES AND REACTIONS
1.4.1.Dehydration

1.4.2.Oxidation
1.4.3.Other reactions
1.5.Production
1.6.Applications for ethylene Glycol
1.6.1.Antifreeze
1.6.2.Polyester Resins.
1.6.3.Chemical Intermediates
1.6.5.Hydraulic Fluids
1.6.6.Heat Transfer Fluids
1.6.7.Capacitor
1.6.8.Explosives
1.6.9.Other Applications.
1.7. DERIVATIVES OF MON0 ETHYLENE GLYCOL
1.7.1. Di ethylene Glycol
1.7.2 Tri ethylene Glycol
1.7.3.Tetra ethylene Glycol

1
1.8. Storage and Distribution
1.8. 1 Toxicity
1.8.2. Impact of ethylene glycol on humans and animals

1.8.3. In the environment

1.9. MARKET SURVEY

1.9.1 ECONOMIC ASPECTS

1.9.2. LEADING PRODUCERS IN WORLD

1.9.3. Mono ethylene glycol in sudan

1.10. QUALITY SPECIFICATION

2 . PROCESS SELECTION AND DESCRIPTION……………….[29-38]

2. 1. Process selection:-
2.1.1 Types of Manufacturing Processes
2.1.1.1 Ethylene Carbonate Process:-
2. 1. 1.2 Halcon Acetoxylatin Process
2. 1 .1.3 Teijin Oxychlorination Processes
2.1.1.4 Union Carbide Syngas Process
2.1.1.5 DuPont Formaldehyde process:-
2.1.1.6 Hydrolysis of Ethylene Oxide
2.1.2: Chemistry of the Reaction
2.2: Process Description of Ethylene Glycol Plant

2.2. 1. 1. Reactor
2.2.1.3 Drying
2.2.1.4 Distillation

2
3.Material Balance ……………………………………………[39-51]
3.1. Material Balance around Pressure Vessel
3.2. MATERIAL BALANCE AROUND PUMP:
3.3. MATERIAL BALANCE AROUND PREHEATER:
3.4. MATERIAL BALANCE AROUND REACTOR: .
3.4.1. MATERIAL ENTERING THE REACTOR
MATERIAL LEAVING THE REACTOR
3.5. MATERIAL BALANCE AROUND EVAPORATOR. .
3.6. MATERIAL BALANCE AROUND DRYING COLUMN:.
3.7. MATERIAL BALANCE AROUND EG REFINER:

4. Energy balance: …………………………………………………..[52-60] .

4.1. Mixer
4.2. Pump
4.3. Pre-heating
4.4 .Reactor
4.5.Evaporator
4.6.Dryer
4.7. Distillation column
4.7.1: Balance around Re-boiler
4.7.2: Balance around Condenser
5.Equipment design………………………………………[61-67]
5.1.Hydrolysis reactor
5.2.Design calculation

3
 5.3.Material of construction
5.4.Mechanical design

6.Economical Evaluation……………………………….[68-77]
6.1 introduction
6.2 The specification of plant
6.3Cost Estimation
6.3.1 . Total Capital Investment
6.3.2. Purchased equipment cost
6.3.3. Total production cost
6.3.4. Gross earnings

6. 3.5. Net present value

6.3.6: Internal rate of return

6.3.7: Probability index :- (PI)

Reference…………………………………………..[78-81]

4
 Chapter 1
Introduction

5
1. Introduction
1.1.HISTORY:

Ethylene Glycol(1, 2 – ethanediol),HOCH2CH2OH usually called

glycol is the humblest Diol. Diethylene glycol then Triethylene glycol
are Oligomers of Mono ethylene glycol.

Ethylene glycol was primary prepared by Wurtz in 1859; treatment of

1,2 dibromoethane with silver acetate yielding ethylene glycol diacetate
via saponification with potassium hydroxide and in 1860 from the
hydration of ethylene oxide. There to have been no commercial
manufacture or application of ethylene glycol prior to World War-I
when it was synthesized from ethylene dichloride in Germany and used
as substituted for glycerol in the explosives industry and was first used
industrially in place of glycerol during World War I as an intermediate
for explosives (ethylene glycol dinitrate) but has since developed into a
major industrial product.

The use of ethylene glycol as an antifreeze for water in automobile

cooling systems was patented in the United States in 1917, but this
commercial application did not start until the late 1920s. The first
inhibited glycol antifreeze was put on the market in 1930 by National
Carbon Co. (Now Union Carbide Corp.) under the brand name
“prestone”.

6
Carbide continued to be essentially the sole supplier until the late 1930s.
In 1940 DuPont started up an ethylene glycol plant in Belle, West
Virginia based on its new formaldehyde methanol process. In 1937
Carbide started up the first plant based on Lefort’s process for vapor
phase oxidation of ethylene oxide.

The worldwide capacity for production of Ethylene Glycol via

hydrolysis of ethylene oxide is estimated to be 7×106 ton/annum [1]

1.2.CHEMISTRY:

Compound contains more than one –oly group is called Polyhydric

Alcohol (Dihydric alcohol) or polyols (Diols). Diols are commonly
known as Glycols, since they have a sweet taste (Greek, glycys= Sweet).

Dihydric alcohols because compounds contain two –OH groups on one

carbon are seldom encountered. This is because they are unstable and
undergo spontaneous decomposition to give corresponding carbonyl
compound and water.

7
According to IUPAC system of nomenclature, IUPAC name of glycol is
obtained by adding suffix Diol to the name of parent alkanes.

HO OH H H H H

H--C---C--H HO--C---C--OH H--C---C--H

H H H H HO OH

1, 2 Glycol 1, 3 Glycol 1, 4 Glycol

(α- Glycol) (β- Glycol) (γ- Glycol)

Glycols are Diols. Compounds containing two hydroxyl groups attached

to separate carbon in an aliphatic chain. Although glycols may contain
heteroatom can be represented by the general formula C2nH4nOn-
1(OH)2.[2]

Formula Common name IUPAC name

CH2OHCH2OH Ethylene Glycol Ethane-1, 2-Diol

8
1.3.PHYSICAL PROPERTIES:

 Monoethylene glycol and its lower polyglycols are clear, odorless,

colorless, syrupy liquid with a sweet taste.
 It is a hygroscopic liquid completely miscible with many polar
solvents, such as water, alcohols, glycol ethers, and acetone.
 Its solubility is low however in non polar solvents, such as
benzene, toluene, dichloroethane, and chloroform. It is miscible in
ethanol in all proportion but insoluble in ether, completely miscible with
many polar solvents, water, alcohols, glycol ethers and acetone. Its
solubility is low, however in nonpolar solvents, such as benzene,
toluene, dichloromethane and chloroform.
 It is a toxic as methyl alcohol when taken orally.
 Ethylene glycol is difficult to crystallize, when cooled; it forms a
highly viscous, super-cooled mass that finally solidifies to produce a
glasslike substance.
 The widespread use of ethylene glycol as an antifreeze is based
on its ability to lower freezing point when mixed with water. [3]

9
Sr. Physical Properties
no.
1. Molecular formula C2H6O2
2. Molecular weight 62
3. Specific gravity at 20/20oC 1.1135
4. Boiling point oC at 101.3 KPa 197.60
5. Freezing point oC -13
6. Heat of vaporization at 101.3 KPa; KJ/mol 52.24
7. Heat of combustion (25oC) MJ/mol 19.07
8. Critical Temp. oC 372
9. Critical pressure, KPa 6513.73
10. Critical volume, L/mol 0.1861
11. Refractive index, ŋ 1.4318
12. Cubic expansion coefficient at 20 oC, K-1 0.62 × 10-3
13. Viscosity at 20oC; mPa S 19.83
14. Liquid density (20oC) gm/cm3 1.1135
15. Flash point, oC 111

10
1.4.CHEMICAL PROPERTIES AND REACTIONS:

Ethylene Glycol contains two primaries –OH groups. Its chemical

reactions are therefore, those of primary alcohols twice over.
Generally, one –OH group is attacked completely before other reacts.

1.4.1Dehydration:

 With Zinc chloride, it gives Acetaldehyde

HOCH2CH2OH CH3CHO + H2O

(Ethylene Glycol) (Acetaldehydes)

 On hea ng alone at 500 oC, it gives Ethylene oxide.

 With H2SO4 it gives dioxane which is important industrial solvent.

1.4.2.Oxidation:

Ethylene glycol is easily oxidized to form a number of aldehydes and

carboxylic acids by oxygen, Nitric acid and other oxidizing agents.

The typical products derived from alcoholic functions are Glycol

aldehyde (HOCH2CHO), Glycolic acid (HOCH2COOH), Glyoxylic acid
(HCO-COOH), Oxalic Acid (HOOCCOOH), formaldehyde & formic acid.[4]

11
 With HNO3 oxidation it yields nos. of substance as one or both
primary –OH groups may be oxidized to aldehydes and these carboxylic
groups.
HNO3 [O] [O]

HOCH2CH2OH HOCH2CHO HOCH2CH2COO CHOCOOH

(Ethylene Glycol) (Glycol aldehydes) (Glycolicacid) (Glyoxylic acid)

[O]

HOOC-COOH

(Oxylic acid)

[O]

HNO3 [O] [O]

HOCH2CH2OH HOCH2CHO CHOCHO CHOCOOH

(Ethylene Glycol) (Glycol aldehydes) (Glyoxal) (Glyoxylic

acid)

1.4.3.Other reactions:

The hydroxyl groups on glycols undergo the usual alcohol chemistry

giving a wide variety of possible derivatives. Hydroxyls can be

12
converted to aldehydes, alkyl halides, amides, amines, azides,
carboxylic acids, ethers, mercaptans, nitrate esters, nitriles, nitrite
esters, organic esters, peroxides, phosphate esters, and sulfate esters.

 Reac on with sodium at 50 oC to form monoalkoxide and

dialkoxide when temperature is raised.
Na at 50 oC Na at 160 oC

HOCH2CH2OH HOCH2CH2ONa NaOCH2CH2ONa

(Ethylene Glycol) (Mono Alkoxide) (Di Alkoxide)

 Reaction with Phosphorus pentahalide (PCl5) it first gives Ethylene

chlorohydrins and then 1, 2 Di Chloro ethane. PBr5 reacts in same way.
PCl5 PCl5

HOCH2CH2OH HOCH2CH2Cl ClCH2CH2Cl

(Ethylene Glycol) (Ethylene chlorohydrins) (1, 2-Dicholorochlorohydrins)

 With Phosphorus trihalide (PBr3) to form responding dihalide

PBr3 PBr3

HOCH2CH2OH HOCH2CH2Br BrCH2CH2Br

(Ethylene Glycol) (Ethylene Bromohydrins) (1, 2-Dibromohydrins)

13
 With HCl in two step reaction, form ethylene chlorohydrins at
160oC and second forms 1, 2 dichloroethane at 200oC.
160 oC 200 oC

HOCH2CH2OH HOCH2CH2Cl ClCH2CH2Cl

(Ethylene Glycol) (Ethylene chlorohydrins) (1, 2-Dicholorochlorohydrins)

 Ethylene glycols is stable compound, but special care is required

when ethylene glycol is heated at a higher temperature in presence of
NaOH, which is exothermic reaction at temperature above 250 oC of
evolution of H2 (-90 to -160 KJ/Kg).

 Ketones and aldehydes react with ethylene glycol under acidic

condi ons to Form 1, 3-dioxolanes cyclic ketals and acetals.
O
+ R'
H
HOCH2CH2OH + RCOR+ + H2O (7)
R
O

 Ethylene glycol reacts with ethylene oxide to form di, tri, tetra
and polyethylene glycols.

14
1.5.Production:

Mono Ethylene Glycol is produced by the oxidation of ethylene at a

high temperature in the presence of a silver oxide catalyst. The
ethylene oxide is then hydrated to yield mono ethylene glycol with di
and tri ethylene glycols as co-products.

C2H40 + H20 —¥ HO-CH2CHŽ-OH

Figure 1 : Overall process block diagram

Global demand for MEG is strong with demand es mated at 18 million
tons in 2008 and forecasts sugges ng that this demand could rise to 25
million tons by 2015. Demand is strongest in China where
approximately 70% of the world's MEG output is consumed.

15
1.6.Applications for ethylene Glycol:

1- Antifreeze
2- Polyester Resins.
3- Chemical Intermediates
4- Hydraulic Fluids
5- Heat Transfer Fluids
6- Capacitor
7- Explosives
8- Other Applications.

1.6.1.Antifreeze:

A major use of ethylene glycol is as antifreeze for internal combustion

engines. Solutions containing ethylene glycol have excellent heat
transfer properties and higher boiling points than pure water.
Accordingly, there is an increasing tendency to use glycol solutions as a
year-round coolant. Ethylene glycol solutions are also used as industrial
heat transfer agents.
 Mixtures of ethylene glycol and propylene glycol are used for
defrosting and de-icing aircraft and preventing the formation of frost
and ice on wings and fuselages of aircraft while on the ground.

16
Ethylene glycol-based formulations are also used to de-ice airport
runways and taxiways as de-icing agent.
 Asphalt-emulsion paints are protected by the addition of ethylene
glycol against freezing, which would break the emulsion. Carbon
dioxide pressurized fire extinguishers and sprinkler systems often
contain ethylene glycol to prevent freezing.[5]

1.6.2.Polyester Resins:
Ethylene glycols are used as a reactant in the manufacture of
polyester resins. Ethylene glycols use to produce polyester fiber,
films and polyethylene terephthalate (PET) resin production, as well
as alkyd resins used in paints. The uses for polyester resins are
extremely varied, and include boat and marine, construction
materials, automotive and aircraft bodies, luggage, furnishings,
appliances, textiles and packaging.
Polyester fibers are commonly found in textile applications including
clothing and carpets. Polyester films arc frequently used in packaging
and wraps for consumer goods, as well as video, audio and computer
tapes. PET is widely used in the manufacturing of beverage bottles and
containers, and other consumer goods packaging. It is estimated that
70-80% of all the MEG consumed is used as a chemical intermediate in
these polyester production processes.

17
 1.6.1 Chemical Intermediates:
Ethylene glycols including ethylene glycol (EG). Di ethylene glycol
(DEG), tri ethylene glycol (TEG) and tetra ethylene glycol (TETRA EG)
are versatile chemical intermediates used to produce a variety of
products for commercial and industrial use:

Adhesives and coatings.

Emulsifiers.
Lubricants.
Plasticizers.
Polyurethane foams.
Solvents.
Silicone compounds.
Thermoplastics.
Unsaturated polyester resins

1.6.4.Hydraulic Fluids:
 Ethylene glycol is used in hydraulic, brake and shock absorber
fluids to help dissolve inhibitors, prevent swelling of rubber, and inhibit
foam formation.
 Hydro lubes, which are water-based mixtures of polyalkylene
glycols and presses and die casting machines, and in airplane hydraulic
systems because of their relatively low viscosity at high pressure. An
added advantage of primary importance is that these hydro lubes

18
1.6.5. Heat Transfer Fluids:
ethylene glycol (EG), di ethylene glycol (DEG), tri ethylene glycol
(TEG) and tetra ethylene glycol (TETRA EG), due to their low point.
freezing point depressant and high boiling point are predominantly used
in heat transfer fluids.

1.6.6. Capacitors:

 Ethylene glycol is used as a solvent and suspending

medium for ammonium perborate, which is the conductor
in almost all electrolytic capacitors.
 Ethylene glycol, which is of high purity (iron and chloride
free), is used because it has a low vapor pressure, is non-
corrosive to aluminum and has excellent electrical
properties.

1.6.7.Explosives:
 Ordinary dynamite will freeze at low temperatures and
cannot then be detonated. Ethylene glycol dinitrate, which

19
 is an explosive itself, is mixed with dynamite to depress its
freezing point and make it safer to handle in cold weather.
 Mixtures of glycerol and ethylene glycol are nitrated in the
presence of sulfuric acid to form solutions of nitroglycerin
in ethylene glycol dinitrate, which are added to dynamite
in amounts ranging from 25 to 50%.

1.6.8.Other Applications:
Ethylene glycol is used to stabilize water dispersions of urea-
formaldehyde and melamine formaldehyde from gel formation and
viscosity changes. It is used as humectants (moisture retaining agent)
for textile fibers, paper, leather and adhesives and helps make the
products softer, mole pliable and durable.
Tri ethylene glycol (TEG) and tetra ethylene glycol (TETRA EGD may
be used as a plasticizer or modified by esterification. As a plasticizer,
TEG and TETRA EG are used in the manufacture of: Safety glass,
Separation membranes (silicone rubber, polyvinyl acetate, and
Cellulose triacetate), Ceramic materials (resistant refractory plastics,
molded ceramics).

Demand for tetra ethylene glycol is strong in the area of BTX (benzene,
toluene, xylene) extraction to separate aromatic hydrocarbons from
non-aromatic hydrocarbons.[6]

20
ethylene glycol (EG), Di ethylene glycol (DEG) are often used in water-
based paints, drywall compounds, glass cleaners, dyes, waxes and
adhesives as a freezing point depressor to avoid damage by low-
temperature

It is also a used as a dehydration agent in natural gas pipelines where it

inhibits the formation of natural gas clathrates before being recovered
from the gas and reused.
In addition, ethylene glycol and Di ethylene glycol are also used as
binders for foundry sand molding, and a lubricant for glass- and
cement-grinding. In addition, both homologs are also used as
humectants in textile fiber, paper, leather, adhesive and glue
applications.

1.7. DERIVATIVES OF MON0 ETHYLENE GLYCOL:

In addition to Oligomers ethylene glycol dervative classes include

mono ethers, Di ethers, esters, acetals, and ketals as well as
numerous other organic and organometalic molecules. These
derivatives can be of ethylene glycol, Di ethylene glycol, or higher
glycols and are commonly made with either the parent glycol or with
sequential addition of ethylene oxide to a glycol alcohol, or
carboxylic acid forming the required number of ethylene glycol
submits.

21
 1.7.1. Di ethylene Glycol:

Physical properties of Di ethylene glycol are listed in Table. Di

ethylene glycol is similar in many respects to ethylene glycol, but
contains an ether group. It was originally synthesized at about the
same me by both Lourenco and Wurtz in 1859, and was rst
marketed, by Union Carbide in 1928. It is a co product (9 - 10%) of
ethylene glycol produced by ethylene oxide hydrolysis. It can be made
directly by the reaction of ethylene glycol with ethylene oxide, but
this route is rarely used because more than an adequate supply is
available from the hydrolysis reaction. Manufacture of unsaturated
polyester resins and polyols for polyurethanes consumes 45% of the
Di ethylene glycol. Approximately 14% is blended into an freeze.

1.7.2 Triethylene Glycol:

Tri ethylene glycol is a colorless, water-soluble liquid with chemical

properties essentially identical to those of Di ethylene glycol. It is a co
product of ethylene glycol produced via ethylene oxide hydrolysis.
Significant commercial quantities are also produced directly by the
reaction of ethylene oxide with the lower glycols.

22
Tri ethylene glycol is an efficient hygroscopicity agent with low
volatility, and about 45% is used as a liquid drying agent for natural gas.
Its use in small packaged plants located at the gas wellhead eliminates
the need for line heaters in field gathering systems as a solvent (11 %)
Tri ethylene glycol is used in resin impregnants and other additives,
steam-set printing inks, aromatic and paraffinic hydrocarbon
separations, cleaning compounds, and cleaning poly (ethylene
Terephthalate) production equipment. The freezing point depression
property of Tri ethylene glycol is the basis for its use in heat-transfer
fluids.

Approximately 13% Tri ethylene glycol is used in some form as a vinyl

plasticizer. Tri ethylene glycol esters are important plasticizers for poly
(vinyl butyral) resins,

Nitrocellulose lacquers, vinyl and poly (vinyl chloride) resins, poly

(vinyl acetate) and synthetic rubber compounds and cellulose esters. The
fatty acid derivatives of Tri ethylene glycol are used as emulsifiers,
emulsifiers, and lubricants. Polyesters derived from Tri ethylene glycol
are useful as low pressure laminates for glass fibers, asbestos, cloth, or
paper. Tri ethylene glycol is used in the manufacture of alkyd resins
used as laminating agents and adhesives.

23
1.7.3.Tetra ethylene Glycol:

Tetra ethylene glycol has properties similar to Di ethylene and

Tri ethylene glycols and may be used preferentially in
applications requiring a higher boiling point, higher molecular
weight, or lower hygroscopicity.

Tetra ethylene glycol is miscible with water and many organic

solvents. It is a humectants that, although less hygroscopic than
the lower members of the glycol series, may find limited
application in the dehydration of natural gases. Other
possibilities are in moisturizing and plasticizing cork, adhesives,
and other substances.

Tetra ethylene glycol may be used directly as a plasticizer or

modified by esterification with fatty acids to produce
plasticizers. Tetra ethylene glycol is used directly to plasticize
separation membranes,

Tetra ethylene glycol has found application in the separation of

aromatic hydrocarbons from nonromantic hydrocarbons (BTX

24
extraction). In general, the critical solution temperature of a
binary system, consisting of a given alkyl-substituted aromatic
hydrocarbon and tetra ethylene glycol, is lower than the critical
solution temperature of the same hydrocarbon with Triethylene
glycol and is considerably lower than the critical solution
temperature of the same hydrocarbon with Di ethylene glycol.

25
1.8. Storage and Distribution
Ethylene Glycol can be stored in stainless steel, aluminium, or lined
drums, tank cars, or tank trucks. It has a specific gravity of 1.115 and a
flash point of 100C(closed cup). It is not regulated for transport on
road, rail, air, or sea but it is classified as harmful, and is harmful if
swallowed [8]

1.8. 1 Toxicity
1.8.2. Impact of ethylene glycol on humans and animals

Ethylene glycol is moderately toxic with an oral Lowest dose of a toxic

material at which the death of the exposed test animal occurs (LDLO)
= 786 mg/kg for humans. The major danger is due to its sweet taste.
Because of that. children and animals are more inclined to consume
large quantities of it than of other poisons. Upon ingestion, ethylene
glycol is oxidized to glycolic acid which is, in turn, oxidized to oxalic
acid, which is toxic. It and its toxic byproducts first affect the central
nervous system, then the heart, and finally the kidneys. Ingestion of
sufficient amounts can be fatal if untreated.

Antifreeze products for automotive use containing propylene glycol in

place of ethylene glycol are available, and are generally considered
safer to use, as it possesses an unpleasant taste in contrast to the
perceived "sweet" taste of toxic ethylene glycol-based coolants, and
only produces lactic acid in an animal's body, as their muscles do when
exercised.

26
The Department of Health and Human Services (DHHS), the
International Agency for Research on Cancer (IARC), and the EPA
have not classified ethylene glycol for carcinogenicity [9]

1.8.3. In the environment

Ethylene glycol breaks down in air in about ten days, and in water or
soil in a few weeks. It enters the environment through the disposal of
ethylene glycol-containing products, especially at airports where it is
used in deicing agents for runways and airplanes [10]

27
1.9. MARKET SURVEY

1.9.1 ECONOMIC ASPECTS:

Ethylene glycol is one of the major products of the chemical industry.
Its economic importance is founded on its two major commercial uses as
antifreeze and for fiber production. Since Ethylene glycol is currently
produced exclusively from ethylene oxide production plant are always
located close to plant that produce ethylene oxide. The proportion of
ethylene oxide that is convened to Ethylene glycol depends on local
condition, Such as market situation and transport facilities. About 60%
of total world production is converted to ethylene glycol . About 50% of
the ethylene glycol that is used as antifreeze, another 40% is used in
fiber industry. Consequently the ethylene glycol demand is closely
connected to the development of these two sectors In view of the
increasing price of crude oil, alternative production method based on
synthesis gas is likely to become more important and increasing
competitive.

28
1.9.2. LEADING PRODUCERS IN WORLD:

 BASF, Geismer, La. (America).

 DOW, Plaquemine, La (America)
 OXYPETROCHEMICALS, Bayport, Tex (America)
 PD Glycol ,Beaumont, Tex. (America)
 SHELL, Geismer ,La. (America)
 TEXACO ,Port Neches, Tex. (America)
 BP Chemicals, Belgium, (West Europe)
 IMPERIAL Chemicals Ind. United Kingdom, (West
Europe)
 BPC , (West Europe)
 STATE COMPLEXES USSR, (West Europe)
 PAZINKA, Yugoslavia, (West Europe)
 EASTERN PETROCHEMICAL CO. Saudi Arabia,
(Middle East)
 National Organic Chemical, India, (Asia).
 Mitsubishis Petrochemicals, (Japan)
1.9.3. Mono ethylene glycol in sudan:
In Sudan many local authorities importing ethylene glycol to use it in
many fields next table 1.3 shows year and amount of ethylene glycol
imported 1 1 41
Table I .3: amount of ethylene glycol Sudan import in different
years[11]
Year EG (kg)
1997 10206
1998 5850
1999 14625
2000 53955
2001 36275
2002 59925
2003 209187
2004 342250
2005 286593
2006 563207
2007 908784
2008 979408
2009 804136
2010 582490
2011 1200103
2012 893435

27
1.10. QUALITY SPECIFICATION:
Since ethylene glycol is produce in relatively high purity difference in
quality are not accepted. The directly synthesized product meets high
quality demands. The ethylene glycol produce in the wash water that is
use during ethylene oxide production IS normally of a somewhat
inferior quality. The quality specifications far mono ethylene glycol are
compiling in table2.2
Table I -4: Quality Specification OF Ethylene Glycol[12]
DESCRIPTION FIBER INDUSTRIAL
GRADE
GRADE
Color, Pt-Co, max 10
Suspended matter Substantially Substantially free
free
Di ethylene glycol, wt. % 0.08 0.6
max
Acidity, as acetic acid, wt% 0.005 0.02
max
Ash, wt% max 0.005 0.005
Water, max 0.08 0.3
Iron, ppm wt max 0.07 0.05
Chlorides, ppm wt max
Distillation range, ASTM at
760mm

28
Hg
IBP, C min 196 196
DP, C max 200 199
Odor Practically none
UV transmittance, % min at:
220 nm 70 700
250 nm 900
275 nm 90 950
350 nm 98 990
Specific gravity, 20/200C 1.1151-1.1156 1.1 151-1.1156
Water solubility, 25 C Completely miscible

29
 Chapter 2
PROCESS
SELECTION AND
DESCRIPTION

30
2.PROCESS SELECTION AND DESCRIPTION

In this section we will discuss different processes for production of

ethylene glycol. Then we will select the most suitable process. The
economics of the various processes for the manufacture of ethylene
glycol are strongly dependent on the price of the feed stock used.
Since 1960 the liquid phase oxidation of ethylene oxide has been the
process of choice. However, there is still commercial production by
some other processes.

2.1 MANUFACTURING PROCESSES:

Up to the end of 1981, only two processes for manufacturing ethylene
glycol have been commercialized. The first, the hydration of ethylene
oxide, is by far the most important, and from 1968 through 1981 has
been the basis for all of the ethylene glycol production. Manufacturing
process involves laboratory methods and industrial methods

2.1.1Laboratory methods:

 By passing Ethylene in to cold dilute Alkaline permanganate

solution i.e. Oxidation of Ethylene to Glycol
 By hydrolysis of Ethylene Bromide by boiling under reflux with
aqueous sodium carbonate solution. This reaction mixture is refluxed

31
till an oily globule of ethylene bromide disappears. The resulting
solution is evaporated on a water bath and semi solid residue is
extracted with ether-alcohol mixture. Glycol is recovered from solution
by distillation. The best yield of glycol (83-84%) can be obtained by
heating ethylene bromide with potassium acetate in Glacial acetic acid.
 Ethylene glycol can be produced by an electro hydro Di
merization of formaldehyde.
 An early source of glycols was from hydrogenation of sugars
obtained from formaldehyde condensation. Selectivity to ethylene
glycol was low with a number of other glycols and polyols produced.
Biomass continues to be evaluated as a feedstock for glycol production.

2.1.2 Industrial methods:

2.1.2.1Ethylene Carbonate Process:

The production of ethylene glycol by the hydration of ethylene oxide is

simple, and can be summarized as follows: ethylene oxide reacts with
water to form glycol, and then further reacts with ethylene glycol and
higher homologues in a series of consecutive

32
2.1.2.2Union Carbide Syngas Process:
The process developed by Union Carbide, Inc. Uses symthesis for the
production of ethylene glycol. Glycerol and propylene oxide are the
major byproducts. Methanol, methyl format and water are also
produced. An expensive rhodium based catalyst catalyzes the reaction.
The process is yet to be commercialized

2.1.2.3HalconAcetoxylatin Process:
Two reaction steps were used in the plant. In the first, ethylene glycol
diacatate was obtained by the oxidation of ethylene in an acetic acid
solution, catalyzed by tellurium and a bromine compound. The reaction
complex, which is quite complicated, is believed to pmeeed via a
tellufium-bromoethylene complex. The oxidation, which is carried out
at 90-200 oc and 20-30 atm pressure, in a mixture of acetates due to
panial hydrolysis of the diacetate. The reaction liquid effluent is
withdrawn and processed to recover glycol acetates and glycol and
provide the recycle streams back to oxidation. In the second step of the
process, the glycol acetates are hydrolyzed to ethylene glycol and acetic
acid. The process however is not popular due to opelating difficulties.
A plant started at Channelview to produce 800 million lb/yr of ethylene
glycol was shut down after difficulties in startup

33
 2.1.2.4 Hydrolysis of Ethylene Oxide:
This method is by far the most widely used method for the
production of ethylene glycol. The simplicity and reliability of the
process makes it popular. Furthermore, it can be used in plants that
manufacture ethylene oxide and glycol together. This process has
been selected in lhccurrent Design project and will hence be dealt in
detail

2.1.2.5 Teijin Oxychlorination Processes:

The Teijin process, which has not been commercialized yet,
produces ethylene glycol by the reaction of ethylene with
thallium salts in the presence ol' water and chloride or
bromide ions. A redox metal compound (such as copper)
oxidizable with molecular oxygen is added to the reaction
medium to permit the regeneration of the thallium salt.

2.2 PROCESS DESCRIPTION:

This process produced ethylene glycol by the catalytic hydrolysis of
ethylene oxide in the presence of less excess of water. After the
hydrolysis reaction is completed the glycol is separated from the

34
excess water and then refined to produce ethylene glycol (EG). The
process is devided in to five different sections.[13]

2.2.1 Reactor:

Ethylene oxides mixed with recycle water and pumped to glycol

reactor where it is reacted with water at 1050C &1.5 MPa in the
presence of catalyst. The Reactor is Catalytic Plug flow Fixed bed type.
The reaction volume consists of two phase, the liquid phase and ionite
(catalyst) phase. The liquid streams through catalyst bed in a plug flow
regime. The catalytic and non catalytic ethylene oxide hydration takes
place in the ionite phase, and only non catalytic reaction takes place in

35
the liquid phase. The distribution of the components of the reaction
mixture between liquid and ionite phases is result of the rapid
equilibrium. The glycol reactor operate at approximately
1.5MPa.pressure which is supplied by the reactor feed pump. The
reactor effluent goes to the evaporation unit for the evaporation of
excess water. [14]

2.2.2 Evaporator:
Multiple-effect evaporators which are defined, an apparatus for
efficiently using the heal from steam to evaporate water. In a multiple-
effect evaporator, water is boiled in a sequence of vessels, each held
at a lower pressure than the last. Because the boiling temperature of
water decreases as pressure decreases, the vapor boiled off in one
vessel can be used to heat the next, and only the first vessel(at the
highest pressure) requires an external source of heat. While in theory,
evaporators may be built with an arbitrarily large number of stages,
evaporators with more than four stages are rarely practical except in
systems where the liquor is the desired product such as in chemical
recovery systems where up to seven effects are used and it has
advantages, At first sight : it may seem that the multiple effect
evaporator has all the advantages, the heat is used over and over
again and we appear to be getting the evaporation in the second and
subsequent effects for nothing in terms of energy costs. Closer
examination shows, however, that there is a price to be paid for the
heat economy. The Evaporators are three or four columns in series
with each operating at a lower pressure. The overhead vapor is used to

36
provide heat for the succeeding evaporator re-boilers. There are five
evaporators in the section. The third effect bottoms contain
approximately 15% water and the[15]

2.2.3drying unit:

The concentrated glycol from the third e ect is containing approximately 15%
water. Essentially all the water is removed from the aqueous ethylene glycol
solution in the drying column. Normally the drying column is fed from the crude
glycol tank. The drying column operated under vacuum which is maintained by
steam jet ejector. Drying column bottom which are free from water are
transferred by column bottom pump to EG refining column. Where the EG is
separated from the higher glycol, Water vapors leaving the top of the drying
column are fed to MEG recovery unit for glycol recovery. (An inert gas line is
provided at the base of the drying column for breaking the vacuum).

2.2.4Distillation column:
The EG is separated from the heavier glycols in the EG refiner column.
The EG is taken overhead and the bottoms which contain an
appreciable amount of EG are sent to a Splitter Column. In the Splitter
Column, the remaining MEG is removed overhead and mixed with the
feed to the Refiner Column The heavy glycols are removed from the
Splitter bottoms and sent to storage as byproduct in another process
heavy product sent to DEG Column where the DEG is taken overhead,

37
The DEG Column bottoms are sent to the TEG Column where the TEG
is distilled overhead. The TEG bottoms are stored and sold as scrap
[16]

Figure 2 PFD

38
2.3 Equipment in the process:
Mean equipment:

1. Pressurizing vessel
2.Reactor (plug ow reactor)
3.Evaporator ( three effect )
4.Dis lla on column

Auxiliary equipment:
1.Pumps
2. Pre-heater
3.Heater
4.Condenser
5.Dryer (distillation column)

39
 Chapter 3
Material balance

40
3.Material balance:

Plant capacity = 100000 tons/ year

Production per hour = (100000 *1000)(333*24) = 12512.51 kg.hr

Basis: Unit hour operation

Further we will use the notations as under:

Ethylene oxide EO
Mono-ethylene Glycol MEG or EG
Di-ethylene Glycol DEG

Tri-ethylene Glycol DEG

If we use 12 fold molar excess of water, then from literature selectivity of

different products is as

under:

EG = 85 %, DEG = 14 % TEC = 1% [17]

41
Reactions:

CH20CH2 + H20 HOCH2CH20H (EG).

CH2OCH2+HOCH2CH20H HOCH2CH20 CH2CH20H (DEG).

HOCH2CH2OCH2CH20H+CH20CH2 HOCH2CH2OCH2CH2OH2CH20H (TEG).

EG from the top of distillation column =12512.51 kg/hr and its purity is 99%

Total amount of EG from distillation column =12638.9 kg/hr

Suppose 1 % of MEG is lost during evaporation and distillation then

EG = 12765.25 kg/hr.

From selectivity of different products

DEG =(12765.25 /0.85)* 0.14=2102.512 kg/hr.

TEG = (12765.25/0.85)*0.01= 150.1794 kg/hr.

Molecular weights:
EO= 44.05 g/mol , EG= 62.0 g/mole, DEG= 106.12 g/mol , TEG= 150.17 g/mole

water=18.02 g/mole [18]

EG =205.659 kmoles/hr, DEG =19.813 kmoles/hr , TEG=1.00 kmoles/hr.

EO = 205.659 + 19.813 = 248.285 kmoles/hr.

Water/EG= 12.

Water = 248.285*12 = 2979.42 kmoles/hr.

42
Water required for reaction = 205.659 * 1 + 19.813 + 1.00 * 1
=226.472kmoles/hr.

Excess water =2979.42 - 226.472 = 2752.948 kmoles/hr.

Interring EO=248.285 kmoles/hr =248.285*44.05= 10936.954 kg,/hr

Interring water= 2979.42 kmoles/hr =2979.42*18.02= 53689.1484kg/hr

By applying principle of mass balance, material balance across each equipment is

as under

Input = output +accumulation disturbance [19]

3.1.Material Balance around Pressure Vessel.

Input = output – accumulation + disturbance

Accumulation=0

Disturbance =0

input vessel output

43
 Mass (kg/hr) Mass Fraction Mass Mass
(kg/hr) OUT Fraction OUT
IN

Ethylene 10936.954 0. 1692 10936.954 0. 1692

Oxide

Fresh Water 53689.1484 0.8308 53689.1484 0.8308

Total 64626.1024 1.0 64626.1024 1.0

3.2.MATERIAL BALANCE AROUND PUMP:

Input = output +accumulation + disturbance

Accumulation=0

Disturbance=0

pump
Input output

Mass Mass Mass Mass

(kg/'hr) fraction (kg/'ht) fraction
Out out
Ethylene 10936.954 0.1692 10936.954 0.1692
Oxide

Water 53689.1484 0.8308 53689.1484 0.8308

Total 64626.1024 1.0 64626.1024 1.0

44
3.3.MATERIAL BALANCE AROUND PREHEATER:

Input = output +accumulation + disturbance

Accumulation=0

Disturbance =0

PREHEATER
Input Output

Mass Mass Mass Mass

(kg/hr) fraction (kg/hr) fraction
Out out
Ethylene 10936.954 0. 1692 10936.954 0.1692
Oxide

Water 53689.1484 0.8308 53689.1484 0.8308

Total 64626.1024 1.0 64626.1024 1.0

45
3.4.MATERIAL BALANCE AROUND REACTOR:
Input =output - accumulation + disturbance

Accumulation=0

Disturbance=0

All EO is converted to glycols with reason of using a large amount of water.

Literature selectivity of different products is:

EG=0.85 DEG=0.14 TEG=0.01

INPUT OUTPUT
REACTOR

3.5.MATERIAL ENTERING IHE REACTOR:

Mass (kg/hr) Mass KMole/hr Mole

Fraction Fraction

Ethylene 10936.954 0.1692 248.285 0.077

Oxide

Water 53689.1484 0.8308 2979.42 0.923

Total 64626. 1024 1.0 3227.705 1.0

46
3.6.MATERIAL LEAVING REACTOR:

MEG =205.659 kmole/hr

MEG =205.659*106.12=12765.254 kg/hr

Mass Mass kmole/hr Mole

(kg/hr) Fraction Fraction

Water 49608.123 0.7676 2752.948 0.924

EG 12765.254 0.1975 205.659 0.069

DEG 2102.556 0.0325 19.813 ().00665

TEG 150.17 0.0023 1.00 0.000336

Total 64626.1 1.0 2979.42 1.0

47
3.7.MATERIAL BALANCE AROUND EVAPORATOR.
Input= output- accumulation + disturbance

Accumulation=0

Disturbance =0 WATER

INPUT EVAPORATER OUTPUT

Suppose EG is concentrated from 19.75% to 72.25 % in this

long tube vertical falling film evaporator.

So glycols concentrated from 23.24% to 85% [20]

Glycols amount = EG + DEG + TEG =12765.254+2102.556 + 150.17

=15017.98 kg/hr.

Glycols present 0.85 of output stream and water

present 0.15 water amount at output stream = (
15017.98 /0.85) * 0.15=2650.232 kg/hr

Evaporated water = interring water - output water= 49608.123 - 2650.232

= 46957.89 kg/hr

48
 Mass Mass 0/0 Mass(kg/hr) Mass %
(kg/hr) OUT
OUT
Water 49608.123 76.76 2650.232 15
EG 12765.254 19.75 12765.254 72.25
DEG 2102.556 03.25 2102.556 1 1.9
TEG 150.17 0.23 150.17 0.85
Total 64626.1 100 19242.62 100
Evaporated water = 46957.89 kg/ht•.
Steam stream:

For three stage evaporator to evaporate 1 kg water we need 0.4 ka steam

[21]
Steam amount = 18783.16 kg/hr.
Assume each stage of evaporator evaporate the same amount
Stage one vapor stage two vapor stage three vapor — 15652.63 kg/hr
Steam gives its lateen heat to hot liquid to be evaporated and the steam
became liquid
Condensate water:
For the first effect evaporator condensate water return back to steam unit.
For the second and third evaporator effect condensate water return back
and mix with fresh interring water.
Condensate water in each stage = interring vapor amount
Condensate water =46957.89 kg/hr.
Condensate water for stage one = stage two = stage three 15652.63 kg/hr

49
3.8.MATERIAL BALANCE AROUND DRYING COLUMN:
Input = output - accumulation + disturbance

Accumulation=0

Disturbance =0 Water

INPUT DRYER OUTPUT

We used dryer to remove remaining water.

Mass (kg/hr) Mass % Mass(kg/hr) Mass %

IN OUT OUT

Water 2650.232 15 0.0

EG 12765.254 72.25 12765.254 85

DEG 2102.556 11.9 2102.556 14

TEG 150.17 0.85 150.17

Total 1924262 100 15017.98 100

Removed water =2886.392 kg/hr.

50
3.9.MATERIAL BALANCE AROUND EG REFINER

Top stream
EG REFINER

input Bottom stream

Input= output -accumulation + disturbance

Accumulation=0

Disturbance=0

Reminding we assume there is lost in EG = 1% =125.1251kvhr

So output ethylene glycol = input EG - lost EG

=12765.254-125.1251 =12512.51 kg/hr

Top stream

Mass Mass % Mass(kg/hr) Mass %

(kg/hr) OUT
IN OUT
IN
EG 12765.254 85 12512.51 99

DEG & 2252.726 15 125.1251 1

TEG
Total 15017.98 100.0 12638.9 100.0

51
Bottom stream
Mass(kg/hr) Mass %
OUT OUT
EG 125.1251 0.056
DEG & 2127.601 0.944
TEG

Total 2252.726 1.0

Recycle water = evaporated water + condensate water from evaporator

Recycled vapor is just the third evaporator vapor =15652.63 kg/'hr

Recycled condensate water is condensate water from stage tow and

three=(15652.63 +15652.63) kg/hr
Recycle water = 46957.89 kg/hr

Using recycle will decrease interring Geed water from (53689.1484kg/hr)

to (6731.258kg/hr) [22]

52
 Chapter4
Energy balance

53
4.Energy balance

According to law of conservation of energy

[Rate of Accumulation of Energy within system =Rate of Energy entering
the system-Rate of energy leaving the system + Rate of Energy generation]
[23]
4.1.Mixer:
Ethylene oxide temperature inlet=25 0c at 2 atm
T water=33 0c at 1 atm and recycle water at 30 0c
Assume the vessel work at 25 0c and at 8 atm
Accumulation =0=generation
So: energy enter=energy leave the system , Qin=Qout =M*cp*ΔT
CP=cp(mean inlet)=xw*cpw+xe*cpe=3.78 kj/kg.k , M=64626.1 hg/h[24]
T out vessel=30 0c
Q out=o kj/h
4.2.Pump:
Qin =0 kj/h
Assume the pump head =0.0027 m
Energy done by the pump=m*g*h
g=9.g m/s, M=64926.1 kg/hr
Q=615602.38 kj/h
4.3.Pre-heating:
Q out=Q In + Q getting

54
 Q lose by hot liquid = Q getting by cool liquid

T in 0c Tout 0c Cp mean kj/kg.k

Hot stream from Tmean=123.09 30 4.19

evaporater
Cold liquid(feed) 30 95 3.81

Q getting =M*cp*ΔT=64926.1*3.81*(95-30)= 16004653.67 kj/hr

Q out =16620256.05 kj/h
4.4.Heater:
T in 0c T out 0c C mean kg/kg
.k
Hot steam 160 160 4.19
Cold liquid( feed) 95 160 3.81
8291.1kg/h= Q/latent heat= Latent heat of steam=1939.3 kj/kg ,Msteam
Q feed=Mcp(Tout-Tin)=16078948.67 kj/kg
4.5.Reactor:
Assume constant temperature of the reactor
Tin =160 0c =Tout ,Tmean=160 0c
P= 18 atm , Pout=16 atm
Heat of formulations kj/kmol
Ethylene oxide -129000

Water -242000

EG -386000

55
DEG -571000

TEG -397740

1 St reaction EO+H2O----EG ΔH=-386000-((-129000)+( -242000))= -

15000 kj/kmol
2ndreaction• . EG+EO---DEG ΔH = -56000 kj/kmol
3rd reaction • DEG+EO---TEG ΔH =302260 kj/kmol
Heat generated in the reaction=∑ΔH=∑M(kmol/hr)i*ΔHi
=201.597*(-15000)+11.79*(-56000)+0.9258*302260=-3404362.692 kj/hr
Total out let heat= entering energy +generation= 12674585.71 kj/hr
Cp mean=4.05 kj/kg.hr
Q removed in reactor = Q out- Q in = -3404362.692 kj/h
T=Q/Mcp=-12.9 0cΔ
so we need heating source around the reactor to keep constant temperature
because there are endo-thermal reaction

4.6.Evaporator:

ΔT all=Tin-Tout=159-105=54 0c
Assumption:
The steam loses its latent heat to vapor the water so it will change from
saturated steam to saturated liquid at the same temperature.
1kg of steam or vapors will vapor 1 kg of water[25]
Equal areas of the evaporators. The vapor from 1st stage will used to heat
the 2nd stage and so on[26]

56
 1st stage: at p=0.41 Mpas
Cp mean T in 0c T out 0c X for Kj/kgλ M kg/hr
water
Feed inlet 3.2 145 76.6 - 64626.1
Outlet 3.25 - 159 69.11 - 48973.47
steam
(calculated)
Vaporized - - 153 1 2104.32 15657.89
water
Steam - 160 160 1 2082 15657.89
required at
2 bar
X mass fraction
Tout will calculated from energy balance equation
Ms*λ=F*cp*(Ti-Tf)+Mv1*λv1=Q1=32599726.98 kj/hr

Second stage: p= 0.17 Mpas

Cp mean Tin 0c Tout 0c X kj/kgλ M kg/ hr
Feed inlet 3.25 159 - 69.1 1 - 48973.47
Outlet 3.1 - 136 54.68 - 3331 5.58
stream
Vaporized - - 130 1 2173.7 15657.89
water
Vapors from - 153 153 1 2104.32 15657.89
Iststage
Q2=Mv1*λ1=(F-V1)*cp*(T2-T1)+Mv2*λ2=32949211.08 kj/hr

57
Third stage : p=0.03 Mpas
Cp Tin 0c Tout 0c X kj/kg M kg/hr

Feed inlet 3.1 136 54.68 33315.58

Outlet stream 3.04 105 15 17657.69

Vaporized 90 2282.5 15657.89

water

Vapors from 2nd 130 130 2173 7 15657.89

stage

Q3=Mv2*λ2=(F-V1-V2)*cp*(T3-T2)+Mv3*λ3=34035555.49 kj/hr
From calculation:
the temperature will be decrease because the decreasing in pressure in 2nd
and 3rd stages.
Overall energy in evaporator = Q in+∑Q from evaporator= 112259079.3
kj/hr
4.7.Dryer:
In let energy=112259079.3 kj/hr
105 0c , p=0.009 Mpas saturated liquidat
In distillation column energy balance is made around Re-boiler and
Condenser.
4.7.1.Balance around Re-boiler:
Latent heat to vaporize the three components by(kj/kg) as:

58
 EG 1396476
DEG 215581 4
TEG 273569.7

Hot stream: Inlet Temp Of steam=160 c

Outlet Temp of steam=160
Mass flow rate of steam=2650.23 Kg/h
Latent heat of steam=1939.3 KJ/Kg [27]
Q=m*lalent heat=3336948.23 which getting vaporize water
cold liquid: feed=17668.21 kg/h , T out=131.75 c , T in=T
out=Q/Mcp=61.83c
Heat getting by water=M* latent heat at
P=0.009=2640.23*2394=6320710.62 kj/h
Q out=33369948.23-6320710.62=2709237.61 kj/h
4.7.2.Balance around Condenser
Cold liquid: Feed to condenser=2650.23 kg/hr
Tin= 30 c , T out=43.7c , Q getting =151404.99 kj/h
Hot stream: feed=15415.4S kg/hr , Tout-43.7 0c, T in=T out =(Q cold-
Qw)/Mcp =150 c
Q getting by water =M* latent heat at 43.7 0c = 2650.23 *2394=6344650.62
kj/hr
Feed of distillation column : at 105 0c
Tin 0c Tout 0c Q kj/hr
Re-boiller 61.8 131.75 2709237.61
Condenser 150 43.7 6344650.62

59
4.8.Distillation column:
In let energy=2709237.61 kj/hr , T=131.75 0c , p=0.003 Mpas , saturated
liquid.
In distillation column energy balance is made around Re-boiler and
Condenser.

4.8.1.Balance around Re-boiler

Latent heat to vaporize the three components by (kj/kg) as:
EG 5132.2497
DEG 4338863.9
TEG 6975220. I

Hot stream: Inlet Temp of steam=160 0c and Outlet Temp of steam=160 0c

Mass flow late of steam=12765.25 Kg/h
Latent heat of steam=1939.3 KJ/Kg
Q=m*latent heat=33369948.23 which getting vaporize water
cold liquid: feed=15017.976 kg/hr , Tout=147.1 0c , Tin=Tout = Q/Mcp =
61.83 0c
Heat getting by EG=M*cp(Tout-Tin)=12765.254*1.8*(237-
147.1)=2065673.4 kj/hr
Q out= 3336994-2065673.4=1271320.6 kj/h
4.8.2.Balance around Condenser:
Cold liquid: Feed to condenser= 12765.245 kg/hr
T in=30 0c , T out=1130c , Q getting =4418182.062 kj/hr

60
Hot stream: feed=12765.245 kg/hr , Tout=113 0c , Tin=Tout=(Q cold-
Qw)/Mcp =2370c
Q getting by water=M*latent heat at 43.70c = 5132.2497 *12765.245
=65513148.3 kj/h
Feed of distillation column: at 105 oc
T in 0c Tout oc
Re-boiler 61.8 131.75 1271320.6
Condenser 150 43.7 65513148.3

61
 Chapter5
Equipment design

62
5.1. Hydrolysis reactor
5.1.1.Introduction:-
The reactor is the heart of a chemical process. It is the only place in the process
where raw materials are converted into products, and reactor design is a vital step
in the overall design of the process.
The design of an industrial chemical reactor must satisfy the following
requirements:
l . The chemical factors: the kinetics of the reaction. The design must provide
sufficient residence time for the desired reaction to proceed to the degree of
conversion.
2. The mass transfer factors: with heterogeneous reactions the reaction rate may
be controlled by the rates of diffusion of the reacting species; rather than the
chemical kinetics.
3. The heat transfer factors: the removal, or addition, of the heat of reaction.
4. The safety factors: the confinement of hazardous reactants and products, and the
control of the reaction and the process conditions.
The need to satisfy these interrelated, and often contradictory {actors, makes
reactor design a complex and difficult task. However, in many instances one of the
factors will predominate and will determine the choice of reactor type and the
design method [28]
5.1.2Reactor is selected On the basis of following parameters.
1-Conversion.
2-Selectivity.
3-Productivity.
4-Safety.
5-Economics.
6- Availability.

63
7-Flexibility.
8-Compatibility with processing.
9-Energy utilization.
10- Feasibility.
11- Investment operating cost.
12- Heat exchange and mixing.

5.1.3.The plug flow reactor has been selected according to:-

1 . Mostly used for EG production.
2-High conversion.
3-No back mixing.
4-Less volume than CSTR.
5-Economical.[29]

Fig (3)Plug flow reactor

64
0perating condition:-
1- Temperature 160 0С
2- Pressure 18 atm
5.2.Design calculation
Chemistry of reaction:
(CH2)20 + H2O (CH2OH)2 ΔH=-21.8 Kcal

M0nethyIene Glycol
(СН2)2О + (СН2ОН)2 НОСН2СН2ОСН2СН20Н

Diethylene Glycol
(СН2)20 + НОСН2СН2ОСН2СН20Н НОСН2СН2ОСН2СН20СН2СН20Н

Triethylene Glycol
The ethylene oxide reacts with water to produce three products however the target
product is mono - ethylene glycol (which has the highest yield )
The reaction is second order which obey the following equation:-
-rEO=K CE0Cw
Where:-
-rEO =rate of reaction.
k = constant of reaction.
CEO= concentration of ethylene oxide .
Cw=concentration of water. [29]
5.3.Material of construction:-
Stainless steel because the reaction in high pressure [28]
From material and energy balance:-

65
material balance for reactor:
Mass Mass kmoles /hr Mole
(kg/hr) Fraction
Fraction
Ethylene 10936.954 0.1692 248.285 0077
Oxide
Water 53689.1484 0.8308 2979.42 0.923

Total 64626.1024 1.0 3227.705 1.0

Ci=Mi/Vmix
Vmix=Mmix/ρmix =3.325 m3
ρ mix=∑Xi*ρi =970.5 kmol/m3
• By substitinting in equation ( l)
CEO = 74.7 Kmol/m3
Cw = 895.8 Kmol/m3
As the concentration of water is large enough to be considered as constant so the
reaction order will become pseudo first order, as following :
rEO=k* CEO
Where: -

66
K= kCw
K=A* EXP(-E/RT)
Where:-
A = frequency = 338 (m3)3 kmol-3S-1
E = activation energy = 18880 cal /g. mol.
R = ideal gas constant
By substituting in eq (4):
As K=5.62 * 10-8 (m3)3 kmol-3S-1 =2*10-4 (m3)3 kmol-3hr-1
K= 0.305 m6/kmol2hr-1
The rate of reaction (from eq ()):
-rEo= 6.521 m3/kmol.hr
The plug flow reactor obeys the following equation:-
V/FEO = - 1/CEO * 1/K * Ln (Ceo0/Ceof )
t=30
Ceof =(1-Xeo) =0.01
Vr = 50.2 m3
5.4.Mechanical design:-
Generally the ratio of length to diameter (L/D) for reactors has range (1 -3)
So, it has been selected 1. L/D=1.5
V= π D2/4 * L
By substituting:
D = 6.6 m =L 9.8 m

67
For a cylindrical shell the minimum thickness required to resist internal pressure
can be determined by equation:-
e = Pi*Di/2f-Pi
e = thickness of cylindrical shell
Pi = pressure of reactor = 2.23 N/mm2
f = design stress = 135 CO N/mm2 [30]
By substitute these value.
e=32.173 mm

68
 Chapter 6
Economical
Evaluation

69
6.1 introduction

Economical evaluation is a major component of chemical plant design that decides

whether the design is economically feasible. An acceptable plant design must
present a process that is capable of operating under conditions which will yield a
profit. Since net profit equals total income minus all expenses, it is essential that
the chemical engineer be aware of the many different types of costs involved in
manufacturing processes. The total investment needed lar a project is the sum of
the fixed and working capital. Fixed capital IS the total cost of the plant ready for
startup. It is the cost paid to the contractors. Working capital is the additional
investment needed, over and above the fixed capital, to start the plant up and
operate it to the point when income is earned. Most of the working capital is
recovered at the end of project.
Factors Affecting Investment and Production Costs:-
To accomplish costs determination the engineer must have a complete
understanding of the many factors that can affect costs, as example of these
factors:
1.Sources of equipment
2.Price Fluctuations
3.company Policies.
4.Operating Time and Rate of Production.
5.Governmental policies.

6.2 The specification of plant:-

There are some general assumption assumptions in this chapter:-
a. The plant life is fifteen years.
b. the price of raw material is fixed [ 1]

70
 Raw material Price($/ton) Amount( ton/ Cost $/year
year)
Ethylene oxide 900 87408.14 78667326

price of product (ethylene glycol):-

Uses Price($/ton) Amount Annualprofit($/year)

Polyester 800 50*10^3 8*10^7

Anti-freeze 800 50*10^3 8*10^7

Di- 780 16.8*10^3 13.1*10^6

ethylene
glycol
Tri- 1400 1.2810^3 16.8*10^5
ethylene
glycol
Total 3780 11.8*10^4 17.48*10^7

6.3Cost Estimation:-

Cost estimation is a specialized subject and a profession in its own right. -The
design engineer, however, needs to be able to make quick, rough, cost estimates to
decide between alternative designs and for project evaluation. Chemical plants are
built to make a profit, and an estimate of the investment required and the cost of
production are-needed before the profitability of a project can be assessed

6.3.1 . Total Capital Investment:

total capital investment (TCI) fixed capital investment (FCI) + working capital
(WCI)

71
Purchased equipment = 15-40 % TCI.
Working capital investment =10 - 20 %TCI
6.3.2. Purchased equipment cost:-
The present capital cost of the equipment related to capacity by the equation:-

Ce =a + b * Sn (6.1)

C2=C1 *(index of 2006/index of 2018)

For all materials:

Index in 2018 = 1296.2
Index in 2006 = 478.6

(A)-For reactor
a b s N I2\I1
14000 15400 50 0.7 2.7

C1= 25.2 8 10 4 $
C2 =68.3*104 $

(B)=For evaporator:-
A b s n I2\I1

-17000 13500 470 6 2.7

C1=52.45 * 104 $
C2=42.6 * 105 $

(C)-For distillation (trays):-

a b s N I2\I1

72
 100 120 3.4 2 2.7

C1=3*103 $
C2=16.12*104 $
(D)- For vessel:-
A b s N I2\I1
-400 230 3984 0.6 2.7

C1=32.8* 103 $
C2=88.99*103 $

(E)-heat exchanger:
A b S n I2\I1
1000 88 77 1 2.7

C1=16.78*103 $
C2=45.43*103 $
• Summary:-
Equipment Cost ($/year)
I- Reactor 68.3*104 $
2- Evaporators 42.6 * 105 $
(multi-effect evaporator)
3- Distillations 16.12*104 $
4- Vessel 88.99*103 $
5- Heat exchangers 46.23*105 $

73
( heater and pre-heater )
6- Condenser 6.95*103 $
8 – Furnace 3.5*103 $
Total purchased equipment cost 1.0022* 107 $

TCI=(total purchased equipment/0.25)

= (1.002 * 107 / 0.25) =4 *107 $
WCI= 4* 107 * 0.15 = 60.13 * 105 $
FCI = 0.85 * 4 *107 = 3.4* 107 $
fixed capital cost = direct cost + indirect cost

Direct cost %

Purchased equipment 20%

Equipment installation 10%

Control 5%

Piping 5%

Electrical 5%

Buildings 5%

Yard 5%

Land 2%

Services facilities

Indirect cost %
Engineering and supervision 10%

74
Construction expense 10%

Contractor 3%

Contingency 10%

6.3.3. Total production cost

(TPC) =manufacturing cost +general expense
(1) - Manufacturing Cost

(a)- Direct production costs:

Type % Cost $/ year
1 - raw material 50 % of TPC 78.667*106
2- operating labor 13% of TPC 20.45*106
3- Direct supervisory 15% of 2.36*106
and clerical labor 0perating labor
4- Utilities 15% of TCP 23.6 * 106
5- Maintenance and repairs 3% of FCI 1.703*106

75
 6- Operation supplies 0. 6% of FCI 3.4 * 105

7- Laboratory charges 11% 0f 1.73*106

operating labor

8- Patents and royalties 1% 0f TCP 3.147*l06

Total 13* 107

TCP= ( 78.667 * 106 /0.5) =15.733* 106 ($/year)

(b)- Fixed charges:-

Type % Cost ($/year)

l- Depreciation 10% of FCI and 5.7*106

1% of building
2- Local taxes 1% of FCI 34*103

3- Insurance 0.4 % of FC1 17*104

Total 5.9*106

(c) - Plant overhead cost:-

0.05 * TCP = 7.87*106 ( $/year )

(2) General Expenses

Type % Cost ($/year)

1-Administrative costs 2.5% of TCP 6.29*106
2-Distribution and selling 2% of TCP 4.72*106

76
costs
3-Research and 4% of TPC 7.87*106
development costs
4- Furnace 0% of TCI 0
Total 13.37*106

TPC = manufacturing cost + general expense = 15.74*107

6.3.4. Gross earnings:-

Net annual profit = total income - TCP

=17.48*10 7- 15.74 * 107 =1.74 * 107
Gross earnings:-
Net profit - taxes*net profit
1.74 - (0.3*1.74)= 1.22 * 107
Total cost investment
Payback period = = 3.2 ~ 4 years.
gross earings

6. 3.5. Net present value:-

NPV =∑0n(Cfn/(1+i)n- FCI

n = useful life of the project = 15

years

i=annual interest rate = 10 %

Cfn = Cash flow for year n.

77
NPV= 7.84*106

6.3.6: Internal rate of return:

NPV = O
NPV =∑0n(Cfn/(1+i)n- FCI

6.3.7: Probability index :- (PI)

Summary:-

TCI 4*107
TPC 15.74 * 107
NPV 7.84*106
Annual profit 17.48 * 107
Payback period 4 years
IRR 11.5 %
PI 1.2
Gross earrings 1.22* 107

Since project is under budget, IRR more than i and NPV positive
• Project is acceptable.

78
REFERENCES

[1] Kirk &Othmer,“Encyclopedia of Chemical Technology”, John Wiley & Sons,

New York, Toronto; fourth Edition;1996; vol-12 (p-696 - 714).
[2] Organic Chemistry by P L Soni, p-2.159
[3] http://www.meglobal.biz]media./product ouides/MEGlobal_MEG.pdf
[4]http://www.sbioinformaties.com/design_thesis/Ethylene Glycol/Ethyleneglycol
Methods
[5] -http://uw.v.dow.com/ethyleneglycol/prodimeg.htm

[6]- http://ww.v.dow.com/ethyleneglycol/prod/meg.htm

[7] - http://www.ncbi.nlm.nih.gov/pubmed/17637146

[8]-http:.i/www.solventis.net/glycols/mono-ethylene-glycol

[9]-http://en.wikipedia.org/wiki/Ethylene_glycol
[10]-http://en.wikipedia.org/wiWEthylene_glycol#In the environment

[11]-Sudan customs police/ dep. Of statistics / headquarters Khartoum (5/2/2013)

[12] - http://vvvo.v.mehtatraders.in/industrial-glycol.html

[13]-http://uww.sbioinforrnatics.eom/design_thesis/Ethylene_Glycol 25200f-
2520Production.pdf

[14]- Schmidt, Lanny D. (1998). The Engineering or Chemical Reactions. New

York: Oxford University Press.

79
 [15]-http://en.wikipcdia.01Vwiki/Multiple-effect
evaporator
[16]-Chemical Engineering Design: Chemical
Engineering, Volume 6 2005 Elsevier Coulson and
Richa Klson's
[17] http://www.doestoc.com/docs/72724000/Plant-Design-for-Production-of-
Polyester-Grade--
[18]http://www.lenntech.eom/ealculators/moleeular/moleeular-weight-
calculator.htm.

[19]OctaveLevenspiel "Chemical Reaction Engineering" Copyright 0 1999 John

Wiley & Sons, Inc.

[20]http://w„w.ippe.com/p1ant0600593/EG_PPT.pdñ
[21]http://wuw.unido.org/fileadmin/user
Kit english/PR-Volume 04/PR-4-Examples-4.pdf.

[22] - "PROCESSINTEGRATION", ed, vol 7, Mahmoud M.E1-Ha1awgi, 2006.

[23][l] simulation program chemcad

[24] process heat transfer Donald Q, kern,Tokyo ,21 st,198
[25]thcrmodynamic and engineering approach ,yunus A. cengel, micheal A.
boles,5th , 1991.
[26]Coulson and Richardson's CHEMICAL. ENGINEERING, VOLUME 2, ,2002
.
[27]PROCESSINTEGRATION", ed, vol 7, Mahmoud M.E1-Ha1awgi, 2006.

80
[28][1]Sinnot, RK., "Coulson and Richardson's Chemical Engineering", 2ndcd, vol
6, Butterwold Heinemann, 1993.

[29]Levenspiel, O. , "Chemical Reaction Engineenng:, 2nded, John Wiley and

Sons Inc., 1972.

81