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Esterification:
Ethylene glycol can be produced by reaction of formaldehyde with carbon monoxide.
This route first produces glycolic acid which is converted by esterification and
hydrogenolysis to ethylene glycol.
HOCH2COOH
HOCH2COOH +ROH
HOCH2COOR + H20
HOCH2COOR + 2H2
HOCH2CH2OH + ROH
An expensive rhodium based catalyst catalyzes the reaction. The process is yet to be
commercialized. Union Carbide has already started work on a modified process in association
with Ube Industries. It plans to set up a commercial scale plant soon.
Oxidation of Ethylene:
This process involves the oxidation of ethylene to ethylene glycol in an aqueous
medium using an iron copper catalyst to produce Ethylene Glycol as represented in the
reaction below.
Fe-Cu
CH2=CH2 + O2 + H20
HOCH2CH2OH
(TEG) can be reduced by using a large excess of water. A 90 percent yield is realized when
the ethylene oxide/water molar ratio is 1:5-8.
The advantage of the acid-catalyzed reaction is no high pressure, however the thermal
reaction needs no corrosion resistance and no acid separation step.
The crude glycols are dehydrated and then recovered individually as highly pure
overhead streams from a series of vacuum-operated purification columns. Ethylene glycol
(boiling point: 197.6oC) is readily vacuum distilled and separated from the diethylene glycol
(boiling point: 246oC, density: 1.118, flash point: 124oC) and triethylene glycol (boiling
point: 288oC, density: 1.1274, flash point: 177oC).
Since ethylene glycol is produced in relatively high purity, differences in quality are
not expected. The directly synthesized product meets the high quality demands (polyester
grade glycol).
Other Alternatives:
Other Possible catalyst for this reaction includes quaternary ammonium and
phosphonium salts. A more recently developed catalyst system is based on use of Pd (II)
complexes. A mixture of PdCl2, LiCl and NaNO3 in acetic acid and acetic anhydride has
been shown to give a 95% selectivity
During this process, Pd(II) is reduced to Pd(0). If PdCl 2-CuCl2-CuOCOCH3 is used,
reaction proceeds under mild conditions without formation of a precipitate. A yield of over
90% is obtained.
The crude Ethylene produced from the reactor is dehydrated and recovered as highly
pure overhead stream from a distillation column with a partial condenser. The Distillate from
the partial condenser is mainly water and is recycled back to the reactor and mixed with
incoming water. The flow sheet for this sequence is shown below
Fig: Shows the Flow sheet for the Production of Ethylene Glycol Simulated on Aspen
Hysis
Therefore
Amount of water left unconverted = Total Water fed Amount that took part in the reaction =
4.64x10-4kmol 5.97x10-5kmol = 4.04x10-4kmol
=4.04x10-4kmol x 18kg/kmols = 7.27x10-3kg/sec of Water
=7.27x10-3/1000 = 7.27x10-6m3/sec of Water
ENERGY BALANCE FOR THE REACTOR
Equation of the reaction
C2H4(g) + H20(g) = C2H6O2(l)
Standard Heat of formation data for this condition
Ethylene Oxide = -52.6kj/mol
Water = -241.8kj/mol
Ethylene glycol = - 460kj/mol
Heat of reaction = Summation of the heat of formation for product summation of the heat of
formation of the reactants
= (1 x -460) ((1 x -52.6) + (1 x -241.8)) = -165.6kj/mol
Therefore DHR (Heat of the reaction) = +165.6kj/mol
The reaction is exothermic so a cooler is incorporated take out the heat produced/mol as the
reaction progresses.
Heat generated by the reaction (Q) = Heat taken by cooling water (Q)
Q = mCPDT of water
Heat generated by the reaction (Q) = 165.6 x 5.38x10-5 (moles of Ethylene oxide produced) =
8.91x10-3kj/s
Where
Where 250c the Temperature of water available
Degree of approach is taken as 100c
CP of water = 4.180kj/kgk
Thus
8.91x10-3kj/s = mCPDT = m x 4.180 x (35-25) +273k
Where 250c the Temperature of water available
Degree of approach is taken as 100c
CP of water = 4.180kj/kgk
m = 8.91x10-3 / 1162.04= 7.67 x 10-6 kg/s
Thus 7.67 x 10-6 kg/s of water must be feed into the cooler system around the reactor to
maintain at operational temperature.
DISTILLATE ESTIMATE
BOTTOMS ESTIMATE