PRODUCTION OF ETHYLENE GLYCOL

Manufacturing process Discrimination
The different processes followed for the production of ethylene glycol includes:
Ethylene carbonate process:
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 1970s, but this process was replaced later by combined
ethylene oxide-glycol plants.
Halcon Acetoxylatin Process:
Two reaction steps were used in the Oxirane plant. In the first, ethylene glycol
diacatate is 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, proceeds via a telluriumbromoethylene complex. The oxidation, which is carried out at 90-200 C and 20-30 atm
pressure, results in a mixture of acetates due to partial 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The reaction liquid effluent is withdrawn and processed to recover glycol acetates and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 is obviously relatively more complex and will amount to huge capital
cost and Literature also shows that it has operating difficulties. A plant started at Channelview
in United State to produce 800 million lb/yr of ethylene glycol was shut down after
difficulties in start up.

This route first produces glycolic acid which is converted by esterification and hydrogenolysis to ethylene glycol. Glycerol and propylene oxide are the major byproducts. Uses synthesis gas for the production of ethylene glycol. HCHO +CO + H20 HOCH2COOH HOCH2COOH +ROH HOCH2COOR + H20 HOCH2COOR + 2H2 HOCH2CH2OH + ROH Teijin Oxychlorination Process: This process produces ethylene glycol by the reaction of ethylene with thallium salts in the presence of water and chloride or bromide ions. The process is yet to be commercialized. Methanol. Inc. Union Carbide has already started work on a modified process in association with Ube Industries. Union Carbide Syngas Process: The following process developed by Union Carbide. 2CO + 3H2 → HOCH2CH2OH An expensive rhodium based catalyst catalyzes the reaction. The Teijin process is still in the works and yet to be commercialized. It plans to set up a commercial scale plant soon. methyl formate and water are also produced as shown below. .Esterification: Ethylene glycol can be produced by reaction of formaldehyde with carbon monoxide. 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.

0% sulphuric acid (H2SO4) catalyst is used at 50 to 70oC for 30 minutes or.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. and then further reacts with ethylene glycol and higher homologues in a series of consecutive reactions as shown in the following equations: CH2CH2O + H2O → HOCH2CH2O ethylene glycol 2CH2CH2O + H2O → HOCH2CH2OCH2CH2OH diethylene glycol 3CH2CH2O + H2O → HOCH2CH2OCH2CH2OCH2CH2O triethylene glycol Production Process Description In the process either a 0. The most important variable is the water-to-oxide ration. It is summarized as follows: ethylene oxide reacts with water to form ethylene glycol. a temperature of 195oC and 185 psi for 1 hour will form the diol. and the production of diethylene glycol (DEG) and triethylene glycol . it is either acid or thermally catalyzed. The formation of higher glycols is inevitable because ethelene oxide reacts faster with ethylene glycols faster than with water.5 to 1. in the absence of the acid. Fe-Cu CH2=CH2 + ½ O2 + H20 HOCH2CH2OH Hydrolysis of Ethylene Oxide: The reaction chemistry is quite simple.

Since ethylene glycol is produced in relatively high purity. The crude glycols are dehydrated and then recovered individually as highly pure overhead streams from a series of vacuum-operated purification columns.(TEG) can be reduced by using a large excess of water. Ethylene glycol (boiling point: 197. density: 1. however the thermal reaction needs no corrosion resistance and no acid separation step. The directly synthesized product meets the high quality demands (polyester grade glycol). The advantage of the acid-catalyzed reaction is no high pressure. flash point: 177oC).6oC) is readily vacuum distilled and separated from the diethylene glycol (boiling point: 246oC.118.1274. A 90 percent yield is realized when the ethylene oxide/water molar ratio is 1:5-8. density: 1. flash point: 124oC) and triethylene glycol (boiling point: 288oC. differences in quality are not expected. .

Pd(II) is reduced to Pd(0). A mixture of PdCl2. A yield of over 90% is obtained. reaction proceeds under mild conditions without formation of a precipitate.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. LiCl and NaNO3 in acetic acid and acetic anhydride has been shown to give a 95% selectivity During this process. If PdCl 2-CuCl2-CuOCOCH3 is used.

and then further reacts with ethylene glycol and higher homologues in a series of consecutive reactions as shown in the following equations: Step 1 CH2CH2O + H2O → HOCH2CH2O ethylene glycol Step 2 2CH2CH2O + H2O → HOCH2CH2OCH2CH2OH diethylene glycol Step 3 3CH2CH2O + H2O → HOCH2CH2OCH2CH2OCH2CH2O triethylene glycol The aim of this work is the yield of Ethylene Glycol not those of higher glycol does this reaction is modified in such a way as to favour reaction step one and disfavour the other two steps and this is achieved by using excess of water for the reaction to dilute the concentration of the ethylene glycol produced to discourage the formation of higher glycols. For this Project design there is a modification to the common Flow sheet used for the Hydrolysis of Ethylene Oxide process that has been shown above. simple reliable and can be used in plants that manufacture ethylene oxide and glycol together. It is relatively economical. . This modified unit arrangement will still achieve the production of Ethylene Glycol at a lower Capital cost.ETHYLENE GLYCOL PRODUCTION The production of ethylene glycol by the hydrolysis of ethylene oxide has been selected in the following Design Thesis because it is by far the most widely used method for the production of ethylene glycol. As stated above this reaction can be acid or based catalysed but for this work a choice of a neutral and high pressure and temperature reaction is made because it has the economic advantage of having no need for corrosion resistance and no acid separation step. The chemistry of the reaction is summarized as follows: ethylene oxide reacts with water to form ethylene glycol.

This is done by using a large excess of water. This Plant is designed to produced 10000kg/yr of Ethylene Glycol.Production Process Description Ethylene Oxide and water a passed into a Continous Stirring Tank Reactor which operates a temperature of 195oC and pressure 185 psi for 1 hour will form the diol. Since the formation of higher glycols is inevitable because ethelene oxide reacts faster with ethylene glycols faster than with water then the water-to-oxide ration must be manipulated to reduce if not eliminate the production of diethylene glycol (DEG) and triethylene glycol (TEG). The flow sheet for this sequence is shown below P Fig: Shows the Flow sheet for the Production of Ethylene Glycol Simulated on Aspen Hysis . In this work. 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 ethylene oxide/water molar ratio is 1: 7 and the yield of Ethylene glycol is 90%. The Distillate from the partial condenser is mainly water and is recycled back to the reactor and mixed with incoming water.

9kmol/yr = 5.38x10-5kmol/moles of ethylene oxide = 0.33x10-5/0.6x10-6kmol/moles Material balance for Water: From Literature.000kg/yr of HOCH2CH2O = 10.64x10-4kmol = 8.38x10-5kmol/moles = 6.38x10-5kmol/sec of ethylene glycol must be produced from the reactor to be feed into the column.9 = 6. From Literature.000kg/yr 10.97x10-5/0.33x10-5kmol/sec HOCH2CH2O The Ethylene glycol/Water splitter column can only achieve a 99% separation for the ethylene glycol thus 5. therefore the amount of water reacting = amount in moles of ethylene oxide=5.64x104 kmols Mass flow rate of water required = 18kg/kmols x 4. moles of ethylene oxide = 5.35x10-6m3/sec of water Unconverted Water The reacting moles are same for water and ethylene oxide.97x10-5kmol.9 Therefore.92x10-3kg Unreacted Ethylene oxide = 6.MATERIAL BALANCE FOR THE REACTOR Reaction Stoichiometry: CH2CH2O + H2O → HOCH2CH2O ethylene glycol Molecular weight of Species: CH2CH2O = (12x2+1x4+16) = 44kg/kmol HOCH2CH2O = (12x2+1x6+16x2) =62kg/kmol Material Balance for Ethylene Oxide: The target is 10.38x10-5/0. the yield of Ethylene Glycol in the reactor is 90% Yield of 90% implies Moles of ethylene oxide used up in the reaction/total moles of ethylene Oxide = 90/100 5.35x10-3kg/sec Taking density of water = 1000kg/m3 The volume of water required per year = 8.97x10-5kmol of ethylene Oxide is used up during the reaction but 5.000/62 = 1612. . Since the feed ratio is 1: 7 therefore the moles of water feed = 7 x 6.99 = 5.63x10-5kmols = 4.63x10-5kmol/sec .63x10-5kmol = 2.9 = 5.35x10-3/1000 = 8.5.63x10-5kmol/sec of Ethylene is actually feed into the reactor Mass of ethylene Oxide required per second = 44kg/kmol x 6.

67 x 10-6 kg/s Thus 7. .04x10-4kmol =4.27x10-6m3/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 Therefore –DHR (Heat of the reaction) = +165.8)) = -165.Therefore Amount of water left unconverted = Total Water fed – Amount that took part in the reaction = 4.38x10-5 (moles of Ethylene oxide produced) = 8.64x10-4kmol – 5.460kj/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 -52.04= 7.97x10-5kmol = 4.6kj/mol The reaction is exothermic so a cooler is incorporated take out the heat produced/mol as the reaction progresses.91x10-3kj/s Where Where 250c – the Temperature of water available Degree of approach is taken as 100c CP of water = 4.180kj/kgk m = 8.6) + (1 x -241.91x10-3kj/s = mCPDT = m x 4.27x10-3kg/sec of Water =7.8kj/mol Ethylene glycol = .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 Thus 8.6 x 5.67 x 10-6 kg/s of water must be feed into the cooler system around the reactor to maintain at operational temperature.27x10-3/1000 = 7.04x10-4kmol x 18kg/kmols = 7.91x10-3 / 1162.6kj/mol Water = -241. Heat generated by the reaction (Q) = Heat taken by cooling water (Q) Q = mCPDT of water Heat generated by the reaction (Q) = 165.

38x10-6kmol/s=4.5x4.04x10-6kmol/s = 5.5D = 2.33x10-5kmol/s 1% water with flow rate of 4.01 = 4.5D=1.07x10-4kmol/s L+D=T Where L=Flow of Condensate returned to the column D=Flow of condensate taken out as Distillate T=Flow of vapour leaving the first stage of the column Reflux Ration = L/D At 2.734x10-5kmol/s = 4.MATERIAL BALANCE FOR THE DISTILLATION COLUNM Ethylene Glycol has a boiling point of 197.64x10-4kmol/s . Relative volatility of Ethylene glycol versus water α = 15.734x10-5kmol/s Distillate (D) Specification 100% Water Distillate (D) = F – B = 4.6x10-6kmol/s+5. the theoretical number of trays can be calculated with relative volatility of Ethylene glycol versus water α = 15. From Literature.5D+D=3.01 moles Bottoms (B) Specification 99% Ethylene Glycol with flow rate of 5.02x10-3kmol/s T=2.5reflux. L/D=2.99 = 5.64x10-4kmol/s Which implies that Water – 0.60c while water has a boiling point of 1000c showing that water will boil over first leaving the Ethylene glycol in the bottoms.33x10-5kmol/s + 4.1 Using Fenske’s Equation .04x10-4x0.07x10-4kmol/s = 1.1 Specification for the column Feed rate=F=Amount of water unconverted + Unreacted Ethylene oxide + Ethylene glycol F=4.38x10-5x0.87 moles Ethylene Glycol – 0.04x10-6kmol/s Therefore Bottoms (B) = 5.5.12 moles Ethylene Oxide – 0.5 L=2.4x10-3kmol/s At total Reflux.04x10-4kmol/s+6.

Peng Robinson was used as the fluid package and the specification of the composition of ethylene glycol in the bottoms was specified as 0.60 = 6.46 – 1 =1.46 Using Gillilands rule of thumb.108= 7 trays SIMULATION OF THE DISTILLATION COLUNM The column was simulated using ASPEN HYSIS with the main aim of obtaining the energy balance of the system and the reboiler and condenser duties.908/1.01)/log15. The above calculated value for the Feed rate and mole composition of the species.12 x 0.98/0.65trays Correcting for Tray Efficiencies assuming the efficiency to be 60% = 3.1 Nm= (2.99/0. The result of the simulation is shown below along with the condenser and heater duties. ETHYLENE GLYCOL/WATER SPLITTER FLOW SHEET .178) – 1 = 2.Nm+1 = log (XD/1-XD 1-XB/XB)/logα =log(0. reflux ratio. It was noted that the HYSIS Estimate of the other Distillate flow. and number of trays were inputed into the software.99. the actual number of tray = 2. Distillate flow rate.5x1.5xNm = 2. Bottoms flow etc were very close to the manual calculations made for them.46 =3.65/0.

SPECIFICATION FOR THE REACTOR EFFLUENT (COLUMN INPUT) .

DISTILLATE ESTIMATE .

BOTTOMS ESTIMATE .