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Chaudhari Ethylene Glycol PDF
Chaudhari Ethylene Glycol PDF
3) Hydraulic fluids :
Hydraulic brake and shock absorber fluids contain ethylene glycol to
improve inhibitor solubility, prevent rubber swelling, and inhibit foam formulation.
Ethylene glycol is mixed with polyalkylene glycols and water to produce hydro lubes ,
which have extensive application as nonflammable, low viscosity hydraulic fluids.
4) Capacitors :
Ethylene glycol is a solvent and suspending medium for ammonium
perborate , which is used in most electrolytic capacitors.
5) Other Uses :
Ethylene glycol is an intermediate in the manufacture of glyoxal, which is
used to treat cotton polyester fabrics to make the permanent press.
It is added to water dispersions of urea formaldehyde and melamine -
formaldehyde to stabilize them. It is also used as a humectants for paper, textile fibers,
leather, and adhesives, and in addition makes these products softer and more pliable
and improves their durability.
First we will consider the Ethylene oxide hydration process then we will shift to
other process alternatives.
Process chemistry
The chemistry of the hydration reaction is quite simple. It consists of the reaction
of the ethylene oxide with water to form Monoethylene Glycol ( MEG ).
The above reaction is followed by the reaction of the MEG with the remaining
Ethylene Oxide to form higher derivatives of the glycol.
The most Important variable affecting the glycol distribution is the water to
oxide ratio. In commercial plants, the production of di and tri ethylene glycol can be
effectively reduced by using a large amount of excess water.
As an example, at water to oxide ratios in excess of 20 : 1 , the heavier glycols
will comprise less then 10 weight percent of the total glycol produced. In the design of a
commercial glycol plant, the improvement in MEG yields that can be achieved by
increasing water recycle are balanced against the increase in capital and utility costs for
optimal economics.
The glycol distribution from the reactor is essentially unaffected by changes in
pressure and temperature over the ranges that are normally of commercially interest ( 1
to 30 bars, 90 to 2000C. ). Under neutral or acidic conditions, the product distribution
is essentially unchanged. However, Basic catalysts ( or a high pH ) will substantially
increase the production of higher glycols.
The rate of the hydration reaction is however strongly dependent on the
temperature and is catalyzed by acids, bases are only about 1 percent as effective as
acids. While the use of acid catalysts permit’s the hydration reaction to proceed at
lower temperatures and pressures than those required for unanalyzed conditions, the
reaction solution becomes corrosive and requires acid removal.
Process Description :
In a free standing glycol plant, the feeds are refined ethylene oxide and pure
water. These are mixed with the cold recycle water in a feed tank to produce a dilute
oxide - water solution containing 8 to 12 percent ethylene oxide. The solution is
pumped through preheaters ( hot recycle water and steam ) into an adiabatic reactor
where the ethylene oxide is hydrated ( non catalytically ) to produce a MEG and a small
amount of higher derivatives. The glycol reactor is designed to provide sufficient
residence time to react ( non catalytically ) essentially all the ethylene oxide. The reactor
pressure is controlled at a level that avoids vaporization of ethylene oxide from the
aqueous solution and will depend on the initial concentration of the oxide and the
reaction temperature. Published information shows that commercial reactors operating
at temperatures of 190 to 2000C will be at a pressure around 14 to 22 bars.
The glycol water mixture from the reactor is fed to the first effect of a multiple
effect evaporator. The first effect is operated at a medium pressure level and is reboiled
using high pressure steam. The following effects of the evaporator operate at
progressively lower pressures, with the final stage at low pressure or even under
vacuum. The evaporated water is recovered as an overhead condensate is recycled
back to the glycol reaction fed tank after heat exchange with cold reactor feed. If the
feed to the plant is a crude oxide water solution from an EO plant, the recycled water is
sent back to the ethylene oxide recovery section.
The concentrated crude glycol solution leaving the final evaporation effect is
stripped of its remaining water and light impurities in the light ends column. The water
free glycol mixture is then distilled in a series of vacuum towers to produce fiber grade
MEG and high purity higher derivatives. The final column produces a small bottoms
stream that contains heavier glycol and is usually used for fuel, but does have potential
commercial value.
The main problem where lot of research is going on is the selectivity of the
ethylene oxide. The selectivity is low which is around 90%. The rest being the
polyethylene glycol. This is a very low selectivity for a product made in such large
quantities.
New synthetic paths for the glycol will make this intermediate much less
important.
Process description :
To produce ethylene chlorohydrin by a continuous process, ethylene is passed
under a pressure of 200 atm at 200C in to a tower. A solution of hydrated lime is then
charged in to the tower, so that under the stated temperature and pressure about 28 g
of ethylene per lit. of alkali results. The solution is pumped under pressure in to the
mixer, where it meets a stream of chlorine at the rate of 1 mole chlorine per lit. of alkali
solution. The chlorine reacted with hydrated lime to form calcium ox chloride , which is
immediately decomposed to form hypochlorous acid and calcium chloride.
The HOCl reacts with the ethylene in the solution to give ethylene chlorohydrin.
The reaction takes place at essentially room temperature and at about 200 atm.
Pressure. The solution is treated with the sodium bicarbonate solution at 70 to 800C in a
closed steam jacket kettle fitted with an efficient agitator. After 4 to 6 hrs. evolution of
the carbon dioxide ends, and the crude glycol solution is passed in to a vacuum still.
Here under reduced , the solution is concentrated and separated from the salt by
distillation.
* Direct Reaction :
This procedure is at first glance the most straightforward, but really is not since
practically every bond in the product molecule has to be formed. It consists of the
rhodium catalyzed condensation of syngas at 3400 atm. As shown in the following
equation;
2CO + 3H2 → Purified Syngas → HOCH2CH2OH → Purified EG.
* Carbonization :
In this process formaldehyde is reacted with more CO. This is followed by a
reduction as shown. This is the oldest of the syngas EG synthesis. The process requires
2000C temperature and 700 atm of pressure. A copper oxide - magnesia catalyst is
required for the reaction to carry out.
Material required :
For one ton of Ethylene Glycol
Formaldehyde 1300 lb Hydrogen 150 lb
Carbon Monoxide 1250 Sulfuric Acid 90 lb.
* Hydroformylation :
The hydroformylation is the reaction of the formaldehyde with CO and
hydrogen, followed by hydrogenation. This procedure, where HCHO is subjected to
hydroformylation conditions, is discussed in a review by Dombek ( 1986 ). Normally
the substrate is an olefin.
* Reductive Hydroformylation :
In this reaction, reduction and the hydroformylation are combined in one
reactor. The catalyst used is Rh( CO )2 ( Acetylacetonate ) in N - Methyl pyrrolidone.
HCHO + H2 + CO → HOCH2CH2OH
The first step uses a palladium catalyst. The Pd has to be reoxidized. Copper salts are
used for this , as well as alkyl nitrite.
References :
1) Industrial Organic Chemistry By K. Weissermel, H. - J. Arpe.
2) Riegel’s Handbook Of Chemistry ( Seventh Edition )
3) Chemical Process Analysis : Mass & Energy Balances By William Luyban &
Leonard Wenzel.
4) Handbook Of Chemicals Production Processes By Robert Meyers.
5) Industrial Chemicals By W. L. Faith, Donald Keyes & Ronald Clark.
6) Industrial Organic Chemistry By Harold Wittcoff & Bryan Reuben.
7) Introduction to Industrial chemistry By Howard White.
8) Encyclopedia Of Chemical Engineering By Kirk & Othmer.