RELATED LITERATURE

Derivatives of Mono Ethylene Glycol

In addition to Oligomers ethylene glycol dervative classes include

monoethers, diethers, esters, acetals, and ketals as well as numerous other organic

and organometalic molecules. These derivatives can be of ethylene glycol,

Diethylene 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.

a. Diethylene Glycol

Diethylene glycol is similar in many respects to ethylene glycol, but contains an

ether group. It was originally synthesized at about the same time by both Lourenco

and Wurtz in 1859, and was first 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 Diethylene glycol. Approximately 14% is blended into

antifreeze. Triethylene glycol from the ethylene oxide hydrolysis does not meet

marketrequirements, which leads to 12% of the Diethylene glycol being converted

with ethylene oxide to meet this market need. About 10% of Diethylene glycol is

converted to morpholine. Another significant use is natural gas dehydration, which

uses 6%. The remaining 13% is used in such applications as plasticizers for paper,

fiber finishes, and compatiblizers for dye and printing ink components, latex paint,

antifreeze, and lubricants in a number of applications.

 b. Triethylene Glycol

Triethylene glycol is a colorless, water-soluble liquid with chemical properties

essentially identical to those of Diethylene 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.

Triethylene 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 %) Triethylene 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 Triethylene glycol is

the basis for its use in heat-transfer fluids.

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

plasticizer. Triethylene 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 Triethylene glycol are used as emulsifiers, emulsifiers, and lubricants.

Polyesters derived from Triethylene glycol are useful as low pressure laminates for

glass fibers, asbestos, cloth, or paper. Triethylene glycol is used in the manufacture

of alkyd resins used as laminating agents and adhesives.

c. Tetra ethylene Glycol

Tetra ethylene glycol has properties similar to Diethylene and Triethylene

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, such as silicone rubber, poly (Vinyl

acetate), and cellulose triacetate. Ceramic materials utilize tetra- ethylene glycol as

plasticizing agents in resistant refractory plastics and molded ceramics. It is also

employed to improve the physical properties of cyanoacrylate and polyacrylonitrile

adhesives, and is chemically modified to form Polyisocyanate, polymethacrylate, and

to contain silicone compounds used for adhesives.

Tetra ethylene glycol has found application in the separation of aromatic

hydrocarbons from nonromantic hydrocarbons (BTX 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 Diethylene

glycol. Hence, at a given temperature, tetra ethylene glycol tends to exact the higher

alkyl benzenes at a greater capacity than a lower polyglycols.

Storage and Transportation

Pure anhydrous ethylene glycol is not aggressive toward most metals and

plastics. Since ethylene glycol also has a low vapor pressure and is non caustic. It

can be handled with out any problems: it is transported in railroad tank cars, tank

trucks, and tank ships. Tanks are usually made of steel: high grade materials are only

required for special quality requirements. Nitrogen blanketing can protect ethylene

glycol against oxidation.

At ambient temperature, aluminum is resistant to pure glycol. Corrosion

occurs, however, above 100oC and hydrogen is evolved. Water air and acid
producing impurities (aldehydes) accelerate this reaction. Great care should be taken

when phenolic resins are involved, since they are not resistance to ethylene glycol.

Environmental Protection and Ecology

Ethylene glycol is readily biodegradable, thus disposal of waste water

containing this compound can proceed without major problems. The high LC 50value

of over 10000 mg/lit account for its low water toxicity.

Product Safety

When considering the use of ethylene glycol in any particular application,

review and understand our current Material Safety Data Sheet for the necessary

safety and environmental health information. Before handling any products you

should obtain the available product safety information from the suppliers of those

products and take the necessary steps to comply with all precautions regarding the

use of ethylene glycol. No chemical should be used as or in a food, drug, medical

device, or cosmetic, or in a product process in which it may come in contact with a

food, drug, medical device, or cosmetic until the user has determined the suitability of

the use. Because use conditions and applicable laws may differ from one location to

another and may change with time, Customer is responsible for determining whether

products and the information are appropriate for Customers use.

COMPARISON BETWEEN PROCESSES AND SELECTION OF PROCESS:

Hydration of ethylene oxide is an industrial approach to glycols in general, and ethylene

glycol in particular. Ethylene glycol is one of the major large-scale products of industrial organic

synthesis, with the world annual production of about 15.3 million t/yr in 2000. Hydration of

ethylene oxide proceeds on a serial-to-parallel route with the formation of homologues of glycol.

Table
Comparison of different Processes

PROCESSES PARAMETER CATALYST ADVANTAGES/

DISADVANTAGES
Hydrolysis of Non-catalytic Non-catalytic -Use large excess water
Ethylene Oxide Yield: 98% to increase the yield
Selectivity: 98% Catalytic which leads to high
Temp:1050C Sulfonic acids, energy consumption
Pressure:1.5MPa Carboxylic acids and -Use less excess water
Catalytic salts, Ion exchange which leads to low
Yield: 95% resins, Acidic zeolites, energy consumption
Selectivity: 90% halides, Metal oxide and -High yield & selectivity
Temp:200oC Metal salts. -Permit use of low
Pressure :1-30 bar temp & pressure
-Acid catalyst makes
the reaction solution
highly corrosive.
Ethylene Glycol Yield: 50% Non- catalytic -Very low yield &
Ethylene Selectivity: 75% selectivity
chlorohydrins -Very costly
Ethylene glycol Yield: 90-95 % Cromate -High pressure process
From CO,H2, Temp: 200 0C Catalyst -Discontinued now a day
CH3OH & Pressure: 100 atm -Low selectivity
Formaldehyde
Ethylene Glycol Yield: 98% Alkali halide or -Give high yield and
from Ethylene Selectivity: 95% ammonium selectivity
Carbonate Temp: 1800C salt -Utility saving
Pressure: 13 bar -Extra purification cost
Transesterificati Low yield Zirconium and Titanium -Produce large amount
on of Ethylene compound of by products
Esterification of Yield : 70% Copper catalyst -High conversion but
Oxalic acid and Selectivity: 90% Catalyst removal is
Reduction with H2 very difficult.
Direct one stage Selectivity: 65% Rhodium -As crude prices
 synthesis of Temp: 190-2300C catalyst increase this process
Ethylene glycol Pressure: 3400 atm (Homogeneous will become more
from Syngas catalyst route.) economical.
-Use of very high
pressure
-Not prove to be
indirectroute may be
viable or not.
-Catalyst is very
Sensitive and
expensive.
Hydrolysis of Yield: 90% Pd complexes -Very Low conversion
Glycol diacetate Selectivity: 95% PdCl2 + NanO3
Temp.: 1600C
Pressure: 2.4 Mpa

3.1 PROCESS DESCRIPTION

This process produced mono 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 mono ethylene glycol (MEG). The

process is devided in to five different sections.

3.1.1 MEG reaction unit

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 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.
3.1.2 MEG evaporation unit

The glycol evaporation system consists of multiple effect evaporation system(three

effects). The reactor effluent flows by difference in pressure from one evaporator to the next the

water content of glycol is reduced to about 15% in the evaporators. The remaining water is

removed in drying column, the pressure of the system is such that the reactor effluent is

maintained as a liquid and is fed as such in to the vapor portion of the first effect evaporator.

Evaporation in the first effect is accomplished by 12Kg/cm2 (g) pressure steam. The overhead

vapor from the first effect is used as heating media in the second effect. The steam condensate

from the first effect is goes to the medium pressure condensate header.

The overhead vapor from the second effect is used as heating media in the third effect.

The third effect operated under vacuum. The vacuum is maintained by using steam jet ejector.

The bottom of the third effect containing 15% water is fed to crude glycol tank via glycol pump,

which is then fed to the drying unit. The condensate from first two effects and the vapor from

third effect containing water and some amount of glycol are fed to the glycol recovery unit.

3.1.3 MEG drying unit

The concentrated glycol from the third effect 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 MEG refining column. Where the

MEG 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).

3.1.4. MEG Refining unit

Drying column bottoms essentially free of water are fed to the MEG refining column.

(PACKED COLUMN). About 15% of the feed to the MEG column enters as vapor due to

flashing. MEG product is withdrawn from the top of the column. Some MEG is purged in the

overhead to the vacuum jets to reduce the aldehydes in the product. The MEG column bottoms

primarily di-ethylene glycols are pumped from the column bottom to the storage tank. The MEG

column operates at a pressure of 10mmHg (A). The vacuum is maintained by MEG column

ejector system. The MEG column condenser is mounted directly on the top of the MEG column.

3.1.5 MEG Recovery unit

The MEG leaving along with water from the Top of the multiple effect evaporator & drying

column are recovered in the MEG Recovery Column (PLATE COLUMN). The column is

operated under Atmospheric pressure.MEG leaving from the bottom of the column and the

water leaving from the top of the column are Recycle to reactor.