University of Babylon

College of Engineering
Department of
Chemical Engineering

Ethylene Glycol Production

Supervisor:
Asst. Prof. Dr .Shaker S. Babar

Prepared by :
Noor Ayad
Nawras Nabil
 ‫یم‬
‫الر ِح ِ‬ ‫الر َٰ‬
‫حْم ِن َّ‬ ‫س ِم اللَّ ِھ َّ‬
‫بِ ْ‬

‫ّللا الَّذِین آمنهوا ِم ْن هك ْم والَّذِین أهوتهوا ا ْل ِع ْلم درجات و َّ ه‬

‫ّللا بِما‬ ‫﴿ ی ْرف ِع َّ ه‬
‫ت ْعملهون خ ِبیر ﴾ [المجادلة‪]11 :‬‬

‫لل العظیم‬
‫صدق ه‬

‫‪-1-‬‬
 ‫أهداء‬

‫إلى كتفي الذي ال یمیل …‪.‬‬

‫إلى من كان سببا ً في حبي للھندسة‪.......‬‬

‫الی ِه الذي بذل الغالي والنفیس من اجل راحتي‬

‫الی ِه الذي أجھد نفسهه حتى ارتسمت مالمح التعب على وجھ ِه‬

‫وتوسم شعرهه بالبیاض في سبیل وصولي‬

‫الیك قدوتي ومھندسي األفضل والدي العزیز‪......‬‬

‫إلى من ازاحت عني ستار الھم وكانت السند في اجتیاز العقبات‬

‫إلى من أمست ابتسامتھا بھجتي وكلماتھا دلیالً لراحة قلبي‬

‫ي‬
‫إلیھا التي سھرت معي في اوقات دراستي وأستیقظت قبلي لتطمئن عل َّ‬
‫الیكِ یا نواة حیاتي التي أرتقي بھا والدتي العزیزة‪.........‬‬

‫إلى كل من اضاء بعلم ِه عقل غیره و هدى بالجواب الصحیح حیرة سائلیه‬

‫فأظھر بسماحته تواضع العلماء وبرحابته سماحة العارفین‬

‫إلیكم اساتذتي الكرام‬

‫أههدي إلیكم بحثنا هذا وأسال هللا العلي القدیر ان ینفعنا به ویمدنا بتوفیقه‬

‫نور أیاد‬

‫‪-2-‬‬
 ‫أهداء‬

‫إلیك أنت وحدك یا صاحب السیرة العطرة وصاحب الفكر المستنیر‬

‫ي ألبلغ التعلیم العالي‬

‫فأنت وحدك من كان له الفضل األول عل َّ‬
‫لك أنت والدي الحبیب الذي أتمنى من هللا أن یطیل عمره‪.‬‬

‫ت یا من وضعتني على طریق الحیاة‬

‫إلیك أن ِ‬

‫ت من جعلتیني موضع قوة واتزان وقومتیني بالرصانة‬

‫فأن ِ‬

‫ولك انت یا من راعیتیني في صغري حتى الكِبر‬

‫لك أنتي یا أمي الغالیة طیب هللا ثراكِ ‪.‬‬

‫وال یمكن أن أنسى أساتذتي الكرام الذین كان لھم الفضل الكبیر‬

‫والدور األول في مساندتي وتوضیح لي العدید من المعلومات الھامة والقیمة بالنسبة لي‪.‬‬

‫فأنا الیوم أقوم بإهداء لكم بحث تخرجي وأنا أتمنى من هللا أن یطیل لي في أعماركم ویرزقكم‬
‫دائ ًما بالخیرات‪.‬‬

‫نورس نبیل‬

‫‪-3-‬‬
 ‫كلمة شكر‬

‫بدایة الشكر لل عز وجل الذي أعاننا وشد من عزمنا إلكمال هذا البحث‬
‫والذي ألھمنا الصحة والعافیة والعزیمة‬

‫الحمد والشكر لل كثیرا‬

‫نتقدم بأجمل عبارات الشكر واالمتنان‬

‫من قلوب فائضة بالمحبة واالحترام والتقدیر له‬
‫ونقدم اجمل تحیاتنا وازكاها الى الدكتور المشرف (شاكر صالح الكالبي)‬
‫والذي كان ابا ً لنا في بحثنا هذا وسنوات دراستنا االربعة‬

‫شكرا له على كل ما قدمه لنا من معلومات قیمة‬

‫ساهمت في إثراء موضوع دراستنا‬

‫كما نشكر اساتذتنا الكرام الذین كانو خیر عون لنا خالل مسیرتنا الدراسیة‬

‫‪Abstract‬‬

‫‪-4-‬‬
- Objective: designing a project for production of ethylene glycol (mono,
di, tri, tetra ethylene glycol) with capacity of 75000 tons/years.

- Chapters details: the first chapter is to define ethylene glycol and its
physical and chemical properties, as well as, exploring production methods
and selecting the most suitable method and production capacity. The
second chapter is concerned with calculating the amounts of materials
required and material balance for each equipment, third chapter is
concerned with calculating the amount of energy required for all parts of
the plant.

- Conclusion: Ethylene glycol is colorless, practically odorless, low-

volatility, low-viscosity, hygroscopic liquid. It is completely miscible with
water and many organic liquids. The reactivity and solubility of ethylene
glycol provide the basis for many applications. The widespread use of
ethylene glycol as an antifreeze is based on its ability to lower the freezing
point when mixed with water. The physical properties of ethylene glycol-
water mixtures are therefore extremely important. The end-uses for
ethylene glycol are numerous.

-5-
Table of content
1.INTRODUCTION -------------------------------------------------------(8)

1.1 Historical Background --------------------------------------------(9)

1.2 Physical Properties ------------------------------------------------(10)

1.3 Chemical properties----------------------------------------------(12)

1.3.1Oxidation----------------------------------------------(12)
1.3.2 (1,3-Dioxolane Formation)-------------------------(13)
1.3.3 (1,4-Dioxane Formation)----------------------------(13)
1.3.4 Decomposition with Alkali Hydroxide-----------(13)

1.4 Uses-------------------------------------------------------------------(14)
1.5 Methods of production---------------------------------------------(14)
1.6 Selection of production method ----------------------------------(18)
1.7 PROCESS DESCRIPTION---------------------------------------(18)

2. Material balance------------------------------------------------------------(21)

2.1.Material Balance around Pressure Vessel-------------------------(25)

2.2.MATERIAL BALANCE AROUND PUMP---------------------(25)
2.3.MATERIAL BALANCE AROUND PREHEATER------------(26)
2.4.MATERIAL BALANCE AROUND REACTOR----------------(26)
2.5 MATERIAL BALANCE AROUND EVAPORATOR----------(27)
2.6 MATERIAL BALANCE AROUND DRYING COLUMN-----(30)
2.7 MATERIAL BALANCE AROUND EG REFINER-------------(31)

3. Energy balance ------------------------------------------------------------(33)

3.1.Mixer -------------------------------------------------------------------(34)
3.2.Pump -------------------------------------------------------------------(34)
3.3.Pre-heating ------------------------------------------------------------(35)
3.4.Heater ------------------------------------------------------------------(35)
3.5.Reactor -----------------------------------------------------------------(36)
3.6.Evaporator -------------------------------------------------------------(37)
3.7.Dryer -------------------------------------------------------------------(39)
3.8 Distillation colum------------------------------------------------------(41)

-6-
4. Equipment design -----------------------------------------------(43)
4.1. Hydrolysis reactor-----------------------------------------------(44)
4.2.Design calculation-----------------------------------------------(46)
4.3.Material of construction ----------------------------------------(46)
4.4.Mechanical design ----------------------------------------------(48)

-7-
CHAPTER ONE
INTRODUCTION

-8-
1.1 Historical Background

Ethylene glycol (EG) the simplest diol. was first developed in 1859 by a
French chemist Charles-Adolphe Wurtz—via saponification of ethylene
glycol diacetate with potassium hydroxide.1,2 In the early stages, though
EG was produced on a very small scale, its development created a
considerable revolution in coolant and explosives industries during World
War I. As the state-of-the-art invention by the Carbide Company of vapor-
phase oxidation of ethylene to ethylene oxide (EO)—a precursor for EG
synthesis via hydration—became cheaply available, the industrial
production of EG has been widespread since 1953. Currently, the global
production and consumption of ethylene glycol are about 20 million metric
tons in 2010 with an estimated increase of 5–10% per year.[1]
Ethylene glycol is a clear, colorless, odorless liquid with a sweet taste. It is
hygroscopic and completely miscible with many polar solvents, such as
water, alcohols, glycol ethers, and acetone. Its solubility is low, however,
in nonpolar solvents, such as benzene, toluene, dichloroethane, and
chloroform. The UV, IR, NMR. compounds containing two hydroxyl
groups attached to separate carbon atoms in an aliphatic chain. Although
glycols may contain heteroatoms, those discussed here are composed
solely of carbon, hydrogen, and oxygen. These are adducts of ethylene
oxide and can be represented by the general formula, CH_O_(OH)
Ethylene glycol, the adduct of water and ethylene oxide, is the simplest
glycol. Diethylene, tri ethylene, and tetra ethylene glycols are oligomers of
ethylene glycol.[2]
Ethylene glycol 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.
Ethylene Glycol brought changes to the vehicle industry. It made changes
to the technical model of airplanes and cars. It low freezing point and high
boiling point made it ideal for it to be used in engine of the vehicles. Today,
we have came up with many usages for the compound in our daily lives.
The technology and information on chemicals have made our lives easier.

-9-
1.2 Physical Properties [1]
Table 1.1

Properties Scientific

Molecular formula C2H6O2

Molecular Weight 62.07 g/mol

Boiling point at 1 atm 197.60 ◦C

Density at 20 ◦C 1.1135 g/cm3

Refractive index 1.4318
Heat of vaporization at 101.3 kPa 52.24 kJ/mol
Heat of combustion 19.07 MJ/kg
Critical Pressure 6515.73 kPa
Critical Temperature 372 ◦C

Critical Volume 0.186L/mol

Flash point 111 ◦C
Ignition temperature 410 ◦C

Lower explosive limit 3.20 vol %

Upper explosive limit 53 vol %

Viscosity at 20 ◦C 19.83 mPa ·s

Cubic expansion coefficient at 20 ◦C 0.62×10−3 K−1
Specific grafity at 20 ◦C 1.1135

Solubility in Water at 20°C 100 wt %

Freezing point -13 ◦C

- 10 -
Table 1.2 :- Solubilities of Various Materials in Ethylene
Glycol
Solubility, g/100 ml of Ethylene Glycol at 25°C

Materials Solubilities
Animal Glue (Dry) Slightly Soluble
Benzene 6.0
Carbon Tetrachloride 6.6
Castor Oil Insoluble
Cellulose Acetate Insoluble
Chlorobenzene 6.0
Coconut Oil Insoluble
Cottonseed Oil Insoluble
Dextrin (10% in water) soluble
Dextrin Slightly Soluble
Dibutyl Phthalate 0.5
Di chloroethyl Ether 11.8
Diethanolamine Completely Soluble
Ethyl Ether 8.9
Gum Damar Slightly Soluble
Heptane Slightly Soluble
Hydrous Wool Fat Slightly Soluble
Kauri Gum Slightly Soluble
Acetone Completely Soluble
Lard Oil Insoluble
Linseed Oil Insoluble
Methanol Completely Soluble
Methyl Orange 1.8
Nitrocellulose Insoluble
Olive Oil Insoluble
Phenol Completely Soluble
Urea 44.0
Toluene 3.1

- 11 -
1.3 Chemical properties [1]
Ethylene glycol, undergoes the reactions typical of its hydroxyl groups,
which are described elsewhere (→ Alcohols, Aliphatic). Thus, only the
special chemical characteristics and industrially important reactions of
ethylene glycol are considered here. The two adjacent hydroxyl groups
allow cyclization, and polycondensation; one or both of these functional
groups may.

1.3.1Oxidation
Ethylene glycol is easily oxidized to form a number of aldehydes and
carboxylic acids by oxygen, nitric acid, and then oxidizing agents. The
typical products derived from the alcoholic functions are glycol aldehyde
(HOCH2CHO) glycolic acid (HOCH2COOH) glyoxal (CHOCHO)
glyoxylic acid (HCOCOOH) oxalic acid (HOOCCOOH) formaldehyde
(HCHO) and formic acid (HCOOH).Variation of the reaction conditions
can lead to the selective formation of a desired oxidation product. Gas-
phase oxidation with air in the presence of copper catalysts is of industrial
importance for the production of glyoxal (→ Glyoxal and → Glyoxylic
Acid). Glycol cleavage occurs in acidic solution with certain oxidizing
agents such as permanganate, periodate, or lead tetraacetate.[5]

1.3.2 (Dioxolane Formation):-

1. By Reacting

- 12 -
 2. By Trans acetalization

1.3.3 (Dioxane Formation):- By dehydration

1.3.4 Decomposition with Alkali Hydroxide.

Glycol is a relatively stable compound, but special care is required when
ethylene (or diethylene) glycol is heated at a higher temperature in the
presence of a base such as sodium hydroxide. Fragmentation of the
molecule begins at temperatures above 250 ◦C and is accompanied by the
exothermic evolution of hydrogen (Δ H = −90 to −160 kJ/kg). This leads
to a buildup of pressure in closed vessels.

- 13 -
1.4 Uses [5] :-

1. Ethylene glycol lowers the freezing point of water.

2. Protection against freezing is directly related to the glycol concentration;
60 % glycol prevents freezing down to a temperature of −55 ◦C.
3. Ethylene glycol is also a commercially important raw material for the
manufacture of polyester fibers, chiefly poly (ethylene terephthalate)
4. Other minor uses of ethylene glycol are as a humectant (moisture retaining
agent), plasticizer, softener hydraulic fluid, and solvent.
5. Ethylene glycol derivatives, mainly the ethers and esters, are frequently
employed as reaction media, as absorption fluids, and as solvents for dyes,
and cellulose products (cellulose esters, ethers, and nitrocellulose).
6. Brake and shock absorber fluid formulation.
7. All-weather automotive antifreeze and coolants.
8. Humectant :- • Textile fibers • Paper • Leather • Adhesives • Glue

1.5 Methods of production [1] :-

Although ethylene glycol has been known since 1859 (Wurtz) it was not
produced industrially until World War I. Its synthesis was then based on
the hydrolysis of ethylene oxide produced by the chlorohydrin process.
Production from formaldehyde and carbon monoxide was also used
commercially from 1940 to 1963. Neither of these methods is now used,
however; the older literature should be consulted for details. Direct
oxidation of ethylene to ethylene glycol was also employed commercially
for a short time but was abandoned, probably due to problems caused by
corrosion.

1- Direct Oxidation of Ethylene

2- Synthesis from C1 Units
3- Ethylene carbonate process [3]
4- Ethylene Oxide Hydrolysis

- 14 -
1.5.1 production of ethylene glycol by Direct Oxidation of Ethylene

catalytic oxidation of ethylene with oxygen in acetic acid has already been
used on an industrial scale, but this method was soon abandoned due to
problems caused by corrosion. The yield of ethylene glycol (>90 %) was
much higher than that obtained in the more indirect route via ethylene
oxide.

1.5.2 production of ethylene glycol by Synthesis from C1 Units

The long-term shortage and increased price of crude oil have led to an
intensive search for methods of producing organic intermediates from C1
units (i.e., methods based on coal). Many publications have appeared on
the synthesis of ethylene glycol by this approach. at a high pressure, carbon
monoxide and hydrogen react directly to produce ethylene glycol.
However, the reaction is slow and the catalyst is both sensitive and
expensive.

1.5.3 production of ethylene glycol by Ethylene carbonate process [3]

In this method, ethylene oxide is converted to an intermediate, ethylene
carbonate, by reaction with carbon dioxide, which is then hydrolyzed by
water to give ethylene glycol. This process was in use in the 1970, but this
process was replaced later by combined ethylene oxide-glycol plants.

1.5.4 production of ethylene glycol by Ethylene Oxide Hydrolysis

Only one method is currently used for the industrial production of ethylene
glycol. This method is based on the hydrolysis of ethylene oxide obtained
by direct oxidation of ethylene with air or oxygen (→ Ethylene Oxide).
The ethylene oxide is thermally hydrolyzed to ethylene glycol without a
catalyst. The ethylene oxide – water mixture is preheated to 200 ◦C,
whereby the ethylene oxide is converted to ethylene glycol. Di-, tri-, tetra-
, and glycols are also produced. The formation of these higher homologues
is inevitable because ethylene oxide reacts with ethylene glycols more
quickly than with water their yields can, however, be minimized if an
excess of water is used – a 20-fold molar excess is usually employed.
(Figure 1) shows the composition of the resulting product mixture as a

- 15 -
function of the ratio of water to ethylene oxide. Although the values were
determined by using sulfuric acid as a catalyst, they also apply as a good
approximation for the reaction without a catalyst. Thus, in practice almost
90 % of the ethylene oxide can be converted to mono ethylene glycol, the
remaining 10 % reacts to form higher homologues:

Main reaction:
C2H4O + H2O → C2H6O2

Side reaction:
C2H4O + C2H6O2 → C4H10O3
2C2H4O + C2H6O2 → C6H14O4
3C2H4O + C2H6O2 → C8H18O5

1.5.5 Possible Developments

The glycol production method described in Section 1.5.4 is the only one of
current industrial importance. but has some major drawbacks:

1) The selectivity of the first step – the production of ethylene oxide – is low
(ca. 80 %).
2) The selectivity of ethylene oxide hydrolysis is low – ca. 10 % is converted
to di- and tri and tetra ethylene glycol.
3) Energy consumption for the distillation of the large amount of excess water
is high.

- 16 -
Figure 1: composition of the product obtained on hydrolysis of ethylene
oxide (EO) as a function of the water to ethylene oxide ratio
a) Mono ethylene glycol; b) Di ethylene glycol; c) Tri ethylene glycol; d)
tetra ethylene glycols

- 17 -
1.6 Selection of production method
Selection of production method of ethylene glycol by Ethylene Oxide
Hydrolysis Because the conversion of the basic material in this method is
high compared to the previous methods. 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 current Design project and will hence be dealt in detail

1.7 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

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

- 18 -
1.7.1 Reactor:
Ethylene oxides mixed with recycle water and pumped to glycol
reactor where it is reacted with water at 105◦C &1.5 MPa in the
presence of catalyst. The Reactor is Continuous stirred-tank reacto
type

1.7.2 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

The Evaporators are three or four columns in series with each

operating at a lower pressure. The overhead vapor is used to provide
heat for the succeeding evaporator re-boilers. There are five
evaporators in the section. The third effect bottoms contain
approximately 15% water

1.7.3 drying 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).

- 19 -
1.7.4 Distillation 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,
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

- 20 -
 CHAPTER 2
Material balance

- 21 -
2.Material balance:

Plant capacity = 75000 tons/ year

Production per hour = (75000*1000) /(300*24)= 10416.6667 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 TEG

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]

- 22 -
Reactions:

CH2OCH2 + H2O HOCH2CH2OH (EG).

CH2OCH2+HOCH2CH2OH HOCH2CH2OCH2CH2OH (DEG).

HOCH2CH2OCH2CH2OH+CH2OCH2 HOCH2CH2OCH2CH2OCH2CH2OH (TEG).

EG from the top of distillation column =10416.6667 kg/hr

and its purity is 99%

Total amount of EG from distillation column =10521.8856 kg/hr

Suppose 1 % of MEG is lost during evaporation and distillation

Then EG =10628.16727 kg/hr.

From selectivity of different products

DEG =(10628.16727/0.85)* 0.14= 1750.5216 kg/hr.

TEG = (10628.16727/0.85)*0.01= 125.03262 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 =10628.16727 (kg/hr) / 62 (g/mol)=171.42205 kmoles/hr

DEG=1750.5216 (kg/hr) / 106.12 (g/mol)=16.4956 kmoles/hr

TEG=125.03262 (kg/hr) /150.17 (g/mol)=0.8326 kmoles/hr

EO =EG+DEG=171.42205 +16.4956 =187.91765 kmoles/hr

Water/EO=12

- 23 -
Water=12*187.91765=2255.0118 kmoles/hr

Water required for reaction =n EG + n DEG +n TEG

=(1* 171.42205 )+(1*16.4956 )+(1*0.8326 )

=188.75025 kmoles/hr

Excess water = 2255.0118 – 188.75025=2066.26155 kmoles/hr

Interring EO = 187.91765(kmoles/hr) * 44.05(g/mol)

= 8277.7724 kg,/hr

Interring water = 2255.018(kmoles/hr ) * 18.02(g/mol)

= 40635.31264 kg/hr

By applying principle of mass balance, material balance across each

equipment is as under

Input = output +accumulation disturbance [19]

- 24 -
2.1.Material Balance around Pressure Vessel:

Input = output + accumulation

Accumulation=0

Mass IN Mass fraction Mass OUT Mass fraction

Material
(kg/hr) IN (kg/hr) Out
Ethylene Oxide 8277.7724 0.1692 8277.7724 0.1692

Fresh Water 40635.31264 0.8308 40635.31264 0.8308

Total 48913.08504 1 48913.08504 1

2.2.MATERIAL BALANCE AROUND PUMP:

Input = output +accumulation

Accumulation=0

Mass IN Mass fraction Mass OUT Mass fraction

Material
(kg/hr) IN (kg/hr) Out
Ethylene Oxide 8277.7724 0.1692 8277.7724 0.1692
Water 40635.31264 0.8308 40635.31264 0.8308
Total 48913.08504 1 48913.08504 1

- 25 -
2.3.MATERIAL BALANCE AROUND PREHEATER:

Input = output +accumulation

Accumulation=0

Mass IN Mass fraction Mass OUT Mass fraction

Material
(kg/hr) IN (kg/hr) Out
Ethylene Oxide 8277.7724 0.1692 8277.7724 0.1692
Water 40635.31264 0.8308 40635.31264 0.8308
Total 48913.08504 1 48913.08504 1

2.4.MATERIAL BALANCE AROUND REACTOR:

Input =output + accumulation

Accumulation=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

- 26 -
2.4.1.MATERIAL ENTERING THE REACTOR:

Material Mass (kg/hr) Mass fraction Kmol/hr Mole fraction

Ethylene Oxide 8277.7724 0.1692 187.9176 0.077

Water 40635.31264 0.8308 2255.0118 0.923

Total 48913.08504 1 2442.9294 1

2.4.2.MATERIAL LEAVING REACTOR:

MEG =171.42205 kmole/hr

MEG =171.42205*62 =10628.1671 kg/hr

Material MASS (kg/hr) Mass fraction Kmol/hr Mole fraction

WATER 36409.35908 0.7443 2020.497174 0.9145
EG 10628.1671 0.2172 171.42205 0.0775
DEG 1750.5216 0.0357 16.4956 0.00746
TEG 125.037262 0.0025 0.8326 0.000376
TOTAL 48913.08504 0.9997~1 2209.2474 0.999~1

2.5 MATERIAL BALANCE AROUND EVAPORATOR:

Input= output+ accumulation

Accumulation=0

• Suppose EG is concentrated from 21.72% to 72.25 % in this long

tube vertical falling film evaporator.

- 27 -
 • So glycols concentrated from 23.24% to 85% [20]

Glycols amount = EG + DEG + TEG

=10628.1671+1750.5216+125.037262
=12503.72596 kg/hr.

Glycols present 0.85 of output stream and water

present 0.15 water amount at output stream

so water amount = (12503.72596 /0.85) * 0.15=2206.5398 kg/hr

Evaporated water = interring water - output water

= 36409.35908 - 2206.5398
= 34202.8192 kg/hr

Mass IN Mass OUT

Material Mass IN % Mass OUT%
(kg/hr) (kg/hr)
Water 36409.35908 74.43 2206.5398 15
EG 10628.1671 21.72 10628.1671 72.25
DEG 1750.5216 3.57 1750.5216 11.899
TEG 125.037262 0.25 125.037262 0.85
TOTAL 48913.08504 99.97~100 14710.26576 99.999~100
Evaporated water = 34202.8192 kg/ht.

The total evaporated water with the total output

= 14710.26576+34202.8192
=48913.08504
So its equal the total input

- 28 -
Steam stream:

For three stage evaporator to evaporate 1 kg water

we need 0.4 kg steam[21]

Steam amount = Evaporated water *0.4

= 34202.8192 * 0.4
= 13681.12768 kg/hr.

Assume each stage of evaporator evaporate the same amount

Stage one vapor stage two vapor stage three vapor (11400.973 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 = 34202.8192 kg/hr.

Condensate water for stage one = stage two = stage three

= 11400.93973 kg/hr

- 29 -
2.6 MATERIAL BALANCE AROUND DRYING COLUMN:

Input = output + accumulation

Accumulation=0

We need to remove remaing water :

Mass IN Mass OUT Mass

Material (kg/hr)
Mass IN %
(kg/hr) OUT%
Water 2206.5398 15 - 0.0
EG 10628.1671 72.25 10628.1671 85
DEG 1750.5216 11.899 1750.5216 14
TEG 125.037262 0.85 125.037262 1
TOTAL 14710.26576 99.999~100 12503.72696 100
Removed water = 2206.5398

- 30 -
2.7 MATERIAL BALANCE AROUND EG REFINER:
Input= output +accumulation

Accumulation=0

Reminding we assume there is lost in EG = 1%

=10416.6667*0.01
=104.166667 kg/hr

So output ethylene glycol = input EG - lost EG

=10628.1671 -104.166667

=10524.00043 kg/hr

Top stream
MASS IN MASS IN MASS OUT MASS OUT
Material (kg/hr) % (kg/hr) %

EG 10628.1671 85 10524.00043 99
DEG&TEG 1875.558862 15 104.166667 1
TOTAL 12503.72596 100 10628.1671 100

- 31 -
 BOTTOM STREAM
MASS OUT
Material (kg/hr)
MASS OUT %

EG 104.166667 5.554
DEG&TEG 1771.392193 94.446
TOTAL 1875.55886 100
Recycle water = evaporated water + condensate water from evaporator

Recycled vapor is just the third evaporator vapor =11400.9397 kg/hr

Recycled condensate water is condensate water from stage tow and

three=(11400.9397 +11400.9397) kg/hr

Recycle water =34202.8191 kg/hr

Using recycle will decrease interring Geed water from

(40635.31264 kg/hr) to (6432.49354 kg/hr) [22]

- 32 -
 CHAPTER 3
Energy balance

- 33 -
3.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]

3.1.Mixer:

Ethylene oxide temperature inlet= 25 0c at 1 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

Tin = Tout=250c
CP=3.78 kj/kg.k ,
M=48913.08504 kg/hr[13]
T out vessel=35 0c
Q out=o kj/hr

3.2.Pump:
Qin =0 kj/hr
Assume the pump head =0.0027 m
Energy done by the pump=m*g*h
g=9.81g m/s M=48913.08504 kg/hr
Q =48913.08504*9.81*0.0027
= 1295.560883 kj /hr

- 34 -
3.3.Pre-heating:
Q out=Q In + Q getting

Q lose by hot liquid = Q getting by cool liquid

T IN (0c) T OUT (0c) CP mean (kj/kg.k)

Hot steam from
Tmean=35.1 30 4.19
evaporator
Cold liquid
30 95 3.81
(feed)

Q getting =M*cp*ΔT
=48913.08504*3.81*(95-30)
= 12113325.51 kj/hr
Q out =1295.560883+12113325.51

= 12114621.07 kj/hr

3.4.Heater:

T IN (0c) T OUT (0c) CP mean (kj/kg.k)

Hot steam 650 250 4.19
Cold liquid
95 160 3.81
(feed)

Qfeed = m*cp* ΔT

= 48913.08504*3.81*(160-95)

= 121125.51 kj/kg

- 35 -
3.5.Reactor:

Assume constant temperature of the reactor

Tin =160 0c =Tout Tmean=160 0c
Pin= 18 atm Pout=16 atm

Heat of formulations kj/kmol

Ethylene oxide -129000
Water -242000
EG -386000
DEG -571000
TEG -397740

1 St reaction EO+H2O EG
ΔH=-386000-[ (-129000)+( -242000) ]
= -15000 kj/kmol

2ndreaction EG+EO DEG

ΔH = -571000-[(-386000)+(-129000)]
= -56000 kj/kmol

3rd reaction DEG+EO TEG

ΔH =-397740-[(-571000)+(-129000)]
= 302250 kj/kmol
Heat generated in the reaction=ΣΔH=ΣMi(kmol/hr)*ΔHi

=[171.42205*(-15000)]+[16.4956*(-56000)]+[0.8326*302260]
=-3243422.674 kj/hr

- 36 -
Total out let heat = entering energy +generation
= 1211325.51+(-3243422.674)
= 8869902.836 kj/hr
Cpmean=4.05 kj/kg.hr
Qremoved in reactor = Qout- Qin
= 8869902.836-12113325.51
= -3243422.674 kj/hr

ΔT=Q/Mcp
=-3243422.674/48913.08504
=-16.37281934 0c
so we need heating source around the reactor to keep constant temperature
because there are endo-thermal reaction

3.6.Evaporator:

ΔTall=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[14]
Equal areas of the evaporators. The vapor from 1st stage will used to heat
the 2nd stage and so on[19]

- 37 -
1st stage: at p=0.41 Mpas
CP mean T OUT
(kj/kg.k)
T IN (0c) (0c)
λ(kj/kg) M (kg/hr)
Feed
3.2 145 - - 48913.08504
inlet
Outlet
steam 3.25 - 159 - 34202.8192
calculated
Vaporized
water - - 153 2104.32 11400.93973

Tout will calculated from energy balance equation:

Ms*λ=M*cp*(Ti-Tf)+Mv1*λv1=Q1

Ms*λ = 48913.08504*3.2*(145-159)+11400.93973*2104.32

Q1 =21799919.28 kj/kg

Second stage: p= 0.17 Mpas

CP mean T OUT
(kj/kg.k) T IN (0c) (0c) λ(kj/kg) M (kg/hr)
Feed
3.25 159 - - 34202.8192
inlet
Outlet
steam 3.1 - 136 - 22801.87947
Vaporized
water - - 130 2173.7 11400.93973

Q2=M*cp*(T2-T1)+Mv2*λ2

= 34202.8192*3.25*(136-159)+11400.93973*3173.7

= 22225561.96 kj/kg

- 38 -
Third stage : p=0.03 Mpas
CP mean T OUT
(kj/kg.k)
T IN (0c) (0c)
λ(kj/kg) M (kg/hr)
Feed
3.1 136 - - 22801.87947
inlet
Outlet
steam 3.04 - 105 - 11400.93974
Vaporized
water
- - 90 2282.5 11400.93973

Q3=M*cp*(T2-T1)+Mv3*λ3

= 22801.87947*3.1*(105-136)+1140093973*2282.5

= 2383138.32 kj/kg

From calculation:
the temperature will be decrease because the decreasing in pressure in 2nd
and 3rd stages.
Overall energy in evaporator = Q in+ΣQ from evaporator
=8869902.836+[ 21799919.28+22225561.96+2383138.32]
= 7672768.4 kj/hr

3.7.Dryer:

In let energy=7672768.4 kj/hr

saturated liquid at
T =105 0c p=0.009 Mpas
In distillation column energy balance is made around Re-boiler and
Condenser.

- 39 -
3.7.1.Balance around Re-boiler:

Latent heat to vaporize the three components by(kj/kg) as:

EG 1396476
DEG 2155814
TEG 273569.7

Hot stream:
Inlet Temp Of steam=160 0c
Outlet Temp of steam=160 0c
Mass flow rate of steam=2206.5398 Kg/hr
Latent heat of steam=1939.3 KJ/Kg [20]

Q=m*lalent heat
=2206.5398*1939.3
=4279142.63 kj/hr

which getting vaporize water

Heat getting by water =M* latent heat at (P=0.009)
=2206.5398*2394=5282456.28 kj/hr
Qout=5282456.28 -4279142.63 =1003313.65 kj/hr

- 40 -
3.7.2.Balance around Condenser

Q getting by water =M* latent heat at( 43.7 0c)

= 2206.5398 *2394
=5282456.28 kj/hr

3.8 Distillation column:

In distillation column energy balance is made around Re-boiler and

Condenser.

3.8.1.Balance around Re-boiler

Latent heat to vaporize the three components by (kj/kg) as:

EG 5132.2497
DEG 4338863.9
TEG 6975220.1

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

Mass flow late of steam=10628.1671 Kg/hr

Latent heat of steam=1939.3 KJ/Kg
Q = m*latent heat
= 10628.1671*1939.3
= 20611204.5 kj/hr

- 41 -
which getting vaporize water
Heat getting by EG=M*cp(Tout-Tin)
=10628.1671*1.8*(237-147.1)
=171950 kj/hr
Q out=20611204.5 -171950 =1587848.16 kj/hr

3.8.2.Balance around Condenser:

Cold liquid:
Feed to condenser = 10628.1671kg/hr
T in=30 0c T out=1130c

Q getting = M*cp(Tout-Tin)

=10628.1671*1.8*(113-30)

= 1587848.16 kj/hr

Q getting by water =M*latent heat at (43.70c)

= 10628.1671* 5132.2497
=54546407.4 kj/h

- 42 -
 CHAPTER 4
Equipment design

- 43 -
4.1. Hydrolysis reactor

4.1.1.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 [21]

4.1.2Reactor is selected On the basis of following parameters.

1-Conversion.
2-Selectivity.
3-Productivity.
4-Safety.
5-Economics.
6- Availability.
7-Flexibility.

- 44 -
8-Compatibility with processing.
9-Energy utilization.
10- Feasibility.
11- Investment operating cost.
12- Heat exchange and mixing.

4.1.3.The CSTR has been selected according to:-

1-Mostly used for EG production.

2-High conversion.
3-No back mixing.
4-Economical.
5- Temperature control is easily maintained
6-Continuous Stirred Tank Reactor behavior is well understood, including
in mixing, dosing options and chemical kinetics.
7-Less expensive and easier to construct than dedicated specialty flow
systems.
8-Multiple units can be easily joined for cascade operation or integration
in more complex flow systems with PFR, etc. [22]

0perating condition:-
1- Temperature 160 0С
2- Pressure 18 atm

- 45 -
4.2.Design calculation

Chemistry of reaction:

(CH2)2O + H2O (CH2OH)2 Monoethylene Glycol

(СН2)2О + (СН2ОН)2 НОСН2СН2ОСН2СН2OН

Diethylene Glycol

(СН2)2O + НОСН2СН2ОСН2СН2OН НОСН2СН2ОСН2СН2OСН2СН2OН

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 CEOCw
Where:-
-rEO =rate of reaction.
k = constant of reaction.
CEO= concentration of ethylene oxide .
Cw=concentration of water. [29]

4.3.Material of construction:-

Stainless steel because the reaction in high pressure [21]

From material and energy balance:-

- 46 -
 Mass Mass Mole
Kmole/hr
(kg/hr) fraction Fraction
Ethylene 8277.7724 0.1692 187.9176 0.077
Water 40635.31264 0.8308 2255.0118 0.923
Total 48913.08504 1 2442.9294 1
ρ water= 997.0479 kg/m3
ρ EO= 882 kg/m3

ρ mix= Σ Xi* ρ i
= (0.1692*882)+(0.8308*997.0479)
= 977.5817953 kmol/m3

Vmix= Mmix/ρ mix

= 48913.08504 / 977.5817953
= 50.03476439 m3

Ci = Mi / Vmix

CEO =187.9176481 / 50.03476439

= 3.755741641 Kmol/m3
CW = 2255.0118 / 50.03476439
= 45.06890015 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 CEOCw
Where:-
K=A* EXP(-E/RT)

Where:-
A = frequency = 338 (m3)3 kmol-3S-1
E = activation energy = 1888 cal /g. mol
R = ideal gas constant
By substituting in the eq :

- 47 -
K = 338 * EXP[-1888/(1.987*433)]

= 37.6617 m3/kmol.s

= 0.01046158386 m3/kmol.hr

The rate of reaction:

-rEO=K CEOCw

-rEO = 0.01046158386 * 3.755741641* 45.06890015

= 1.770802432 m3/kmol.hr

X =0.9 (conversion)

The CSTR obeys the following equation:-

V = (FA * X) / - rEO

= (187.9176*0.9) / 1.770802432

= 95.50802332 m3

4.4.Mechanical design:-

Generally the ratio of length to diameter (L/D) for reactors has range (1-3)
So, it has been selected

L/D=1.5

V= (π/4 ) D2* L

By substituting:

D = 4.328 m

L= 6.493 m

- 48 -
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/mm 2 [30]

By substitute these value:

e = (2.23*4.328*103)/((2*135)-2.23)
e=36.0437 mm

- 49 -
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]design_thesis/Ethylene Glycol/Ethyleneglycol Methods
[4]glycols/mono-ethylene-glycol
[5]-wikipedia.org/wiki/Ethylene_glycol
[6]-Ethylene_glycol#In the environment
[7]-Sudan customs police/ dep. Of statistics / headquarters Khartoum
(5/2/2013)
[8] - mehtatraders.in/industrial-glycol.html
[9]-design_thesis/Ethylene_Glycol 25200f-2520Production.pdf
[10]- Schmidt, Lanny D. (1998). The Engineering or Chemical Reactions.
NewYork: Oxford University Press.
[11]en.wikipcdia.01Vwiki/Multiple-effect evaporator
[12]-Chemical Engineering Design: Chemical Engineering, Volume 6
2005 Elsevier Coulson and Richa Klson's
[13]Plant-Design-for Production-of- Polyester-Grade--
[14]OctaveLevenspiel "Chemical Reaction Engineering" 1999 John
Wiley & Sons, Inc.
[15] Kit english/PR-Volume 04/PR-4-Examples-4.pdf.
[16] - "PROCESSINTEGRATION", ed, vol 7, Mahmoud M.E1-Ha1awgi,
2006.
[17] simulation program chemcad
[18] process heat transfer Donald Q, kern,Tokyo ,21 st,198
[19]thcrmodynamic and engineering approach ,yunus A. cengel, micheal
A.boles,5th , 1991.

- 50 -
[20]Coulson and Richardson's CHEMICAL. ENGINEERING, VOLUME
2, ,2002
[21]PROCESSINTEGRATION", ed, vol 7, Mahmoud M.E1-Ha1awgi,
2006.

[22]Sinnot, RK., "Coulson and Richardson's Chemical Engineering",

2ndcd, vol 6, Butterwold Heinemann, 1993.
[23]Levenspiel, O. , "Chemical Reaction Engineenng:, 2nded, John Wiley
and Sons Inc., 1972.

- 51 -