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Ethylhexanol From Propylene and Synthesis Gas

The document describes a design project to produce 40,000 metric tons per year of 2-ethylhexanol from propylene and synthesis gas. The key steps are: 1) A hydroformylation reaction produces n-butyraldehyde and isobutyraldehyde. 2) Isobutyraldehyde is cracked to produce recycled gases and n-butyraldehyde is converted to 2-ethylhexanol. 3) The task is to design the process, including a distillation column to separate the aldehydes.

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John Callous
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351 views4 pages

Ethylhexanol From Propylene and Synthesis Gas

The document describes a design project to produce 40,000 metric tons per year of 2-ethylhexanol from propylene and synthesis gas. The key steps are: 1) A hydroformylation reaction produces n-butyraldehyde and isobutyraldehyde. 2) Isobutyraldehyde is cracked to produce recycled gases and n-butyraldehyde is converted to 2-ethylhexanol. 3) The task is to design the process, including a distillation column to separate the aldehydes.

Uploaded by

John Callous
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© © All Rights Reserved
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F DESIGN PROJECTS II

The design exercises given in this appendix are somewhat more structured than those
given in Appendix E. They have been adapted from design projects set by the
Institution of Chemical Engineers as the final part of the Institution’s qualifying
examinations for professional chemical engineers.

F.1 ETHYLHEXANOL FROM PROPYLENE AND SYNTHESIS GAS

The Project
Design a plant to produce 40,000 metric tons (tonnes)/year of 2-ethylhexanol from
propylene and synthesis gas, assuming an operating period of 8,000 hours on stream.

The Process
The first stage of the process is a hydroformylation (oxo) reaction from which the
main product is n-butyraldehyde. The feeds to this reactor are synthesis gas (CO/H2
mixture) and propylene in the molar ratio 2/1, and the recycled products of isobutyr-
aldehyde cracking. The reactor operates at 1308C and 350 bar, using cobalt carbonyl
as catalyst in solution. The main reaction products are n- and isobutyraldehyde in the
ratio of 4:1, the former being the required product for subsequent conversion to
2-ethylhexanol. In addition, 3% of the propylene feed is converted to propane while
some does not react.
Within the reactor, however, 6% of the n-butyraldehyde product is reduced to
n-butanol, 4% of the isobutyraldehyde product is reduced to isobutanol, and other reac-
tions occur to a small extent yielding high molecular weight compounds (heavy ends) to
the extent of 1% by weight of the butyraldehyde/butanol mixture at the reactor exit.
The reactor is followed by a gas-liquid separator operating at 30 bar from which
the liquid phase is heated with steam to decompose the catalyst for recovery of cobalt
by filtration. A second gas-liquid separator operating at atmospheric pressure subse-
quently yields a liquid phase of aldehydes, alcohols, heavy ends, and water, which is
free from propane, propylene, carbon monoxide, and hydrogen.
This mixture then passes to a distillation column which gives a top product
of mixed butyraldehydes, followed by a second column which separates the two

F -1
F-2 APPENDIX F DESIGN PROJECTS II

butyraldehydes into an isobutyraldehyde stream containing 1.3% mole n-butyralde-


hyde and an n-butyraldehyde stream containing 1.2% mole isobutyraldehyde.
A cracker converts isobutyraldehyde at a pass yield of 80% back to propylene,
carbon monoxide, and hydrogen by passage over a catalyst with steam. After separa-
tion of the water and unreacted isobutyraldehyde the cracked gas is recycled to the
hydroformylation reactor. The isobutyraldehyde is recycled to the cracker inlet. The
operating conditions of the cracker are 2758C and 1 bar.
The n-butyraldehyde is treated with a 2% w/w aqueous sodium hydroxide and
undergoes an aldol condensation at a conversion efficiency of 90%. The product of
this reaction, 2-ethylhexanol, is separated and then reduced to 2-ethylhexanol by
hydrogen in the presence of a Raney nickel catalyst with a 99% conversion rate.
In subsequent stages of the process (details of which are not required), 99.8% of the
2-ethylhexanol is recovered at a purity of 99% by weight.

Feed Specifications
i. Propylene feed: 93% propylene, balance propane.
ii. Synthesis gas: from heavy fuel oil, after removal of sulfur compounds and
carbon dioxide:
H2 48.6%; CO 49.5%; CH4 0.4%; N2 1.5%.
Utilities
i. Dry saturated steam at 35 bar.
ii. Cooling water at 208C.
iii. 2% w/w aqueous sodium hydroxide solution.
iv. Hydrogen gas: H2 98.8%; CH4 1.2%.

Scope of Design Work Required


1. Process Design
a. Prepare a material balance for the complete process.
b. Prepare a process diagram for the plant showing the major items of equipment.
Indicate the materials of construction and the operating temperatures and
pressures.
c. Prepare energy balances for the hydroformylation reactor and for the isobu-
tyraldehyde cracking reactor.
2. Chemical Engineering Design
Prepare a chemical engineering design of the second distillation unit, i.e., for the
separation of n- and isobutyraldehyde. Make dimensioned sketches of the column, the
reboiler, and the condenser.

3. Mechanical Design
Prepare a mechanical design with sketches suitable for submission to a drawing office
of the n- and isobutyraldehyde distillation column.
APPENDIX F DESIGN PROJECTS II F -3

4. Control System
For the hydroformylation reactor prepare a control scheme to ensure safe operation.

Data
1. Reactions

CH3  CH ¼ CH2 þ H2 ! CH3 CH2 CH3 DH298 ¼ 129:5 kJ=mol


CH3 CH ¼ CH2 þH2 þCO ! CH3 CH2 CH2 CHO DH298 ¼ 135:5 kJ=mol
or ! CH3 CHCH3
j
CHO DH298 ¼ 141:5 kJ=mol
C3 H7 CHO þ H2 ! C4 H9 OH DH298 ¼ 64:8 kJ=mol
2CO þ 8CO ! CO2 (CO)8 DH298 ¼ 462:0 kJ=mol
2CH3 CH2  CH2  CHO ! CH3 CH2 CH2 CH ¼ C  CHO þ H2 O
j

C2 H5 DH298 ¼ 262:0 kJ=mol
C4 H8 ¼ C  CHO þ 2H2 ! C4 H9  CHCH2 OH
j j
C2 H5 C2 H5 DH298 ¼ 433:0 kJ=mol

2. Boiling Points at 1 bar

Propylene  47.78C
Propane  42.18C
n-Butyraldehyde 75.58C
Isobutyraldehyde 64.58C
n-Butanol 117.08C
Isobutanol 108.08C
2-Ethylhexanol 184.78C

3. Solubilities of Gases at 30 Bar in the Liquid Phase of the First


Gas-Liquid Separator

H2 0.08  103 kg dissolved/kg liquid


CO 0.53  10 3 kg dissolved/kg liquid
Propylene 7.5  103 kg dissolved/kg liquid
Propane 7.5  103 kg dissolved/kg liquid
F-4 APPENDIX F DESIGN PROJECTS II

4. Vapor-Liquid Equilibrium of the Butyraldehydes at 1 atm


(Reference 7)

T8C x y
73.94 0.1 0.138
72.69 0.2 0.264
71.40 0.3 0.381
70.24 0.4 0.490
69.04 0.5 0.589
68.08 0.6 0.686
67.07 0.7 0.773
65.96 0.8 0.846
64.95 0.9 0.927

where x and y are the mole fractions of the more volatile component (isobutyralde-
hyde) in the liquid and vapor phases, respectively.

REFERENCES

1. Hancock, E. G. (ed.) (1973) Propylene and Its Industrial Derivatives (New York: John
Wiley & Sons) Chapter 9, pp. 333–367.
2. Carbon Monoxide in Organic Synthesis. (1970) (New York: Falbe-Springer Verlag) pp. 1–
75.
3. Physical and thermodynamic properties of CO and CO2. (September 30, 1974) Chemical
Engineering, 81, pp. 115–122.
4. Physical and thermodynamic properties of H2/N2/O2. (January 20, 1975) Chemical
Engineering, 82, pp. 99–106.
5. Physical and thermodynamic properties of C2H4/C3H6/iC4H8. (March 31, 1975) Chem-
ical Engineering, 82, pp. 101–109.
6. Physical and thermodynamic properties of CH4/C2H6/C3H8. (May 12, 1975) Chemical
Engineering, 82, pp. 89–97.
7. Wojtasinski, J. G. (July 1963) Measurement of total pressures for determining liquid-
vapour equilibrium relations of the binary system isobutyraldehyde-n-butyraldehyde.
J Chem Eng Data, pp. 381–385.
8. Weber, H. and FALBE, J. (April 1970) Oxo Synthesis Technology. Ind Eng Chem. pp. 33–
37.
9. Hydrocarbon Processing (November 1971) p. 166.
10. Hydrocarbon Processing (November 1975) p. 148.

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