1. Production Of Di-Ethyl Ether By Vapor Phase Dehydration Of Ethanol
Project Supervisor : Miss Sidra Jabeen
Co-Adviser : Muhammad Usman

2. The Team 2010-Ch-08 Ruqia Mustafa
2010-Ch-32 Kamran Mohy-ud-Din(Group Leader)
2010-Ch-36 Ismail Zaidi
2010-Ch-76 Abbas Raza
2010-Ch-108 Irtiza Ali Butt
2010-Ch-120 Arslan Khan

3. Contents Introduction to DEE Uses Of DEE Production Of DEE
Methods to Prepare DEE
Selection Of Process
Capacity Selection
Process Description
Material Balance
Energy Balance

4. Introduction to DEE
Diethyl ether is an organic compound in the ether class with the formula C2H5—O—C2H5
Properties
It is a colorless
Highly volatile flammable liquid
It is commonly used as a solvent
Used as a general anesthetic. It has narcotic properties
It has a burning sweet taste
Its boiling point is 34.6 C at 1 atm

5. Uses Of DEE As a Fuel Laboratory uses Medical use Recreational use
Metabolism
Laboratory uses
Diethyl ether is a common laboratory solvent. It has limited solubility in water (6.05 g/100 mL at 25 °C.) and dissolves 1.5 g/100 mL water at 25 °C. Therefore, it is commonly used for liquid-liquid extraction. When used with an aqueous solution, the organic layer is on top as the diethyl ether has a lower density than the water. It is also a common solvent for the Grignard reaction in addition to other reactions involving organometallic reagents.

6. Companies producing DEE
Country
Production in Metric Tons/Year
Henan Golden Yangtze River Industry Co. Ltd.
China
10,800
Anhui Jin’ao Chemical Co. Ltd
5,000
Royal Exim
India
2,000
Chemical Point UG
Germany
7,000
SOHEUNG Chem Co. Ltd.
South Korea
7200

7. Contd…
Diethyl ether Imports by Countries in US Dollars

8. Contd.. Consumption in Pakistan
Pakistan Yearly Imports in US Dollars - Diethyl ether

9. Capacity Selection
5000 Metric Ton per year

10. Methods To Prepare DEE DEE is prepared from the following processes
Vapor-phase Dehydration Of Ethanol
Acid ether synthesis
Williamson ether synthesis
1. BY-PRODUCT OF ETHANOL PRODUCTION
This is the most common industrial route to generate diethyl ether. It follows the hydration reaction of ethylene to produce ethanol, which generates this compound as a by-product. The main advantage is that the reaction can be adjusted with phosphoric acid or sulphuric acid, acting as catalysts, to divert the production to more ethanol or more diethyl ether, according to requirements. This diversion can reach 95% production of diethyl ether, with minimal production of ethanol.
2. ACID ETHER SYNTHESIS
A second reaction to form diethyl ether, which can be used either in small scale laboratory procedures or large scale industrial applications, is through synthesis of acid ether. Ethanol (CH3CH2OH ) is mixed traditionally with sulphuric acid, but alternative strong acids can also be used. The acid generates H+ in solution, which protonates ethanol's negative oxygen, temporarily conferring ethanol a positive charge (CH3CH2OH2+, Reaction 1).
(Reaction 1) CH3CH2OH + H+ --> CH3CH2OH2+ + H2O
From an unprotonated ethanol, an oxygen atom is able to remove a water molecule from a protonated ethanol, generating water (H2O), a hydrogen ion (H+) and diethyl ether (CH3CH2OCH2CH3, Reaction 2)
(Reaction 2) CH3CH2OH2+ + CH3CH2OH --> H2O + H+ + CH3CH2OCH2CH3
It is vital that the method is carried out at temperatures under 150 degrees Celsius, to ensure that ethylene production is kept to a minimum. If the reaction is carried out at higher temperatures, ethylene will be generated by dehydration of ethanol. Usually temperatures around degree Celsius are used, as below this value the reaction will progress very slowly. Another aspect to consider is that diethyl ether needs to be removed from the reaction; otherwise equilibrium between reactants and products means generation of diethyl ether is blocked.
3. WILLIAMSON ETHER SYNTHESIS
A final way to synthesise diethyl ether is through the Williamson ether synthesis. This reaction starts with the production of an alkoxide by dissolving an alkali metal in alcohol, which is then used to carry out a bimolecular nucleophilic substitution of a primary alkyl halide (SN2 reaction) to generate diethyl ether. For example, this reaction can used sodium ethoxide (NaC2H5O) with chloroethane (C2H5Cl ) to form diethyl ether (CH3CH2OCH2CH3) and sodium chloride (NaCl, Reaction 3).
NaC2H5O + C2H5Cl --> CH3CH2OCH2CH3 + NaCl

11. Per Pass Conversion (%)
Selection Of Process
Process
Yield(%)
Per Pass Conversion (%)
Catalyst
Purity (%)
Vapor-phase dehydration of Ethanol 95 80
Al2O3
(Alumina)
99.5
Acid Ether Synthesis 75 70
H2SO4
(sulphuric acid)
Williamson Ether Synthesis 55 Na
(sodium metal) 90

12. Process Description

13. Distillation Column-I Feed Drum
Ethylene Fuel Gas
Fresh Ethanol Feed
Diethyl Ether Product
Distillation Column-I
Feed Drum
Distillation Column-II
3 Phase separator
Reactor
Waste Water
Ethanol Recycle Stream

14. Process Flow Diagram

16. Contd… Chemical Reactions Main Reaction
(C2H5 )2O (g) C2H4 (g) + H2O (g)
Ethanol DEE water
Side Reaction
(C2H5 )2O (g) C2H4 (g) + H2O (g)
DEE Ethene water

17. Material Balance

18. Basis 596 kg/hr DEE with purity 99.5 %
8.054 kgmole/hr DEE with purity 99.5 %

19. Overall Material Balance
Component
Mole
fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
Overall Material Balance
Component
Mole fraction
Moles
(kgmole)
Mass (kg)
Ethanol
0.7
16.401
754.44
Water
0.3
7.029
126.52
DEE
Ethene
Total flow
23.43
880.96
component
mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
0.995
Ethene
Total flow
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow

20. Cond… Total Mass Balance: stream 1 = stream 4 + stream 7 +stream 12=
kg = kg

21. Material Balance across feed vessel
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
Component
Mole fraction
Moles
(kgmole)
Mass(kg)
Ethanol
0.7
16.401
Water
0.3
7.029
DEE
Ethene
Total flow
23.43
Component
Mole fraction
Moles
(kgmole)
Mass(kg)
Ethanol
Water
0.2763
DEE
0.0142
Ethene
Total flow

22. Cond…. Total Mass Balance: stream 1 + stream 11 = stream 2=
kg = kg

23. Material balance across Reactor
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow

24. Cond.. Total Mass Balance: stream 2 = stream 3
kg = kg

25. Material Balance across 3 phase separator
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
Component
Mole fraction
Moles (kgmole)
mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
component
Mole fraction
Moles
(kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
E-05
Total flow

26. Cond…. Total Mass Balance: stream 3 = stream 4 + stream 5 +stream 6=
kg = kg

27. Material Balance across 1st distillation column
Component
Mole fraction
Moles
(kgmole)
Mass(kg)
Ethanol
Water
DEE
0.995
Ethene
Total flow
component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
component
Mole fraction
Moles
(kgmole)
Mass
(kg)
Ethanol
Water
DEE
Ethene
E-05
Total flow
Component
Mole fraction
Moles
(kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow

28. Cond.. Total Mass Balance: stream 5 + stream 6 = stream 7 + stream 8=
kg = kg

29. Material Balance across 2nd distillation column
Component
Mole fraction
Moles (kgmole)
Mass(kg)
Ethanol
Water
DEE
0.0142
Ethene
Total flow
Component
Mole fraction
Moles
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow
Component
Mole fraction
Moles
(kgmole)
Mass(kg)
Ethanol
Water
DEE
Ethene
Total flow

30. Cond.. Total Mass Balance: stream 8 = stream 11 + stream 12=
kg = kg

31. Reference conditions
Temperature 30 C
Pressure kPa

32. energy Balance

33. Energy Balance across feed vessel
Stream 1 11 2
Temperature(C) 30 88 42
Pressure(kpa)
1500
1450
Enthalpy of Ethanol (kJ/hr)
Enthalpy of DEE (kJ/hr)
Enthalpy of water (kJ/hr)
Enthalpy of Ethene (kJ/hr)
Total Enthalpy (kJ/hr)

34. Cond… Total Energy Balance: stream 1 + stream 11 = stream 2=
kJ/hr = kJ/hr

35. Energy balance across Reactor
Stream 2 3
Temperature(C)
200
Pressure(kpa)
1450
1300
Total enthalpy

36. Cond… Total Energy Balance: Enthalpy of reaction = Hr = -190057 kJ
Heat removed = Hrev = kJ
enthalpy of stream 2 + Hr = enthalpy of stream 3 =
kJ/hr = kJ/hr

37. Energy balance across throttle valve
Stream 3
3(a)
Temperature(C) 40
39.96
Pressure(kpa)
1250
200
Enthalpy of Ethanol (kJ/hr)
Enthalpy of DEE (kJ/hr)
Enthalpy of water (kJ/hr)
Enthalpy of Ethene (kJ/hr)
Total Enthalpy (kJ/hr)
32166

38. Cond… Total Energy Balance: stream 3 = stream 3(a)
kJ/hr = kJ/hr

39. Energy balance across 3 phase seperator
Stream
3(a) 4 5 6
Temperature(C)
39.96 40
Pressure(kpa)
200
Enthalpy of Ethanol (kJ/hr)
809.54
Enthalpy of DEE (kJ/hr)
709.88
Enthalpy of water (kJ/hr)
7220.3
Enthalpy of Ethene (kJ/hr)
0.0965
Total Enthalpy (kJ/hr)
32166
8739.8

40. Cond… Total Energy Balance:
stream 3(a) = stream 4 + stream 5 + stream 6
32166 =
32166 kJ/hr = kJ/hr

41. Energy balance across 1st distillation column
Stream
5&6 7 8
Temperature(C) 40 45 97
Pressure(kpa)
200
165
195
Enthalpy of Ethanol (kJ/hr)
Enthalpy of DEE (kJ/hr)
Enthalpy of water (kJ/hr)
Enthalpy of Ethene (kJ/hr)
Total Enthalpy (kJ/hr)
121634

42. Cond… Total Energy Balance: stream 5&6 + Qr = Qc + stream 7 + stream 8=
kJ/hr = kJ/hr

43. Energy balance across 2nd distillation column
Stream 8 11 12
Temperature(C) 97 88
116
Pressure(kpa)
195
170
175
Enthalpy of Ethanol (kJ/hr)
Enthalpy of DEE (kJ/hr)
Enthalpy of water (kJ/hr)
Enthalpy of Ethene (kJ/hr)
Total Enthalpy (kJ/hr)
121626

44. stream 8 + Qr = Qc + stream 11 + stream 12
Total Energy Balance:
stream 8 + Qr = Qc + stream 11 + stream 12 =
kJ/hr = kJ/hr

45. Duties of Heat Exchangers
Duty (kJ/hr)
E-1201(vaporizer)
E-1202(cooler)
E-1203(condenser)
353648
E-1204(reboiler)
463620
E-1205(cooler)
11741
E-1206(condenser)
149271
E-1207(reboiler)
160054
E-1208(cooler)
88075