CHE4049F

CHEMICAL ENGINEERING DESIGN

PROJECT 1

SYNTHESIS OF BUTYRALDEHYDES BY THE HYDROFORMYLATION PROCESS

UCT PEOPLESOFT # 1814799

TABLE OF CONTENTS

1. PROCESS DESCRIPTION...............................................................................................1

2. STEP 1: CHEMICAL REACTION......................................................................................2

3. STEP 2: MIXING AND RECYCLES..................................................................................3

4. STEP 3: SEPARATION.....................................................................................................4

5. STEP 4:TEMPERATURE, PRESSURE AND PHASE CHANGE......................................5

6. STEP 5: PROCESS FLOW DIAGRAM (PFD).................................................................6

7. EQUIPMENT LIST............................................................................................................7

8. STREAM TABLE...............................................................................................................8

9. RATIONALE....................................................................................................................10

10. THINKING ABOUT THE PROCESS...........................................................................11

11. REFERENCES............................................................................................................12

12. PLAGIARISM REPORT..............................................................................................13

13. APPENDIX A – ARTIFICIAL INTELLIGENCE DECLARATION..................................14

i
 1. PROCESS DESCRIPTION
In this process, butyraldehydes are manufactured via the hydroformylation process which
uses propylene and syngas containing hydrogen and carbon monoxide in the presence
rhodium/TPP in a CSTR. The reaction takes place at 15 bar and 90 °C with a conversion of
85% propylene and selectivity of 95%. In these conditions propylene also forms propane.
The reactions are as follows:

C 3 H 6 + H 2 +CO → n−C 4 H 8 O

C 3 H 6 + H 2 +CO → i−C 4 H 8 O

C 3 H 6 + H 2 →C 3 H 8

In the reactor the catalyst is in a different phase, organic phase, whilst the reactants and
products remains in the aqueous phase. The ratio of n-butanal to i-butanal is 92:8. The
propylene in the propylene stream fed to the reactor is at 99.5 wt% and the balance is
propane, whilst the CO in the syngas stream is 93.7 wt% and the balance being hydrogen.
The products at 15 bar and 90 °C, are sent to a 3-phase decanter. In this stage the catalyst is
recovered back to the reactor with 5% of it being taken purged for regeneration. The
unreacted CO,H2 leaves as vapor and is purged with 1% being recycled back to reactor.

The n-butanal, i-butanal, propane, propene, are recovered in the aqueous phase and sent to
a stripping column at 15 bar, 34°C. In this stream the fresh syngas is used to absorb most of
the propene recovering 99% and 2.4% of propane, the syngas concentrated with propene is
then sent to the reactor. The aldehydes and unabsorbed propane leaves as liquid then sent
to a low-pressure flash. The stream enters the flash drum at 10 bar, 28 °C, propane, and
propene leaves as vapor whilst n-butanal, i-butanal leaves with as liquid at 10 bar 28°C and
sent to a distillation column. In the distillation column the i-butanal leaves at the top at 1.2 bar
and 64.5°C with 100 wt% and a flowrate of 906 kg/h. The n-butanal leaves at the bottom at
1.2 bar, 75.5°C flowrate of 12081 kg/h with a purity of 98.8 wt%, this stream contains
propane as well, at a flowrate of 147 kg/h and 1.2 wt%.

1
 A
2. STEP 1: CHEMICAL REACTION
B C D E F G H I J

1 1

PROPYLENE: PROPYLENE:
2 16951 kg/h 2543 kg/h 2

PROPANE: PROPANE:
94 kg/h 7145 kg/h
3 3

REACTOR RHODIUM SOLUTION

13,2 kg/h
SYNGAS: 90 OC, 15 bar
CO: 25211 kg/h
4 H2 : 1695 kg/h Catalyst: RhH(CO)(P(C6H5)3)3 4
X = 0,85 CARBON MONOXIDE
200093 kg/h

WATER
43818 kg/h
5 5
CH3CH=CH2 + H2 + CO CH3CH2CH2CHO
RHODIUM SOLUTION
13,2 kg/h n-BUTANAL
CH3CH=CH2 + H2 + CO CH3CH(CH3)CHO 12108 kg/h

CH3CH=CH2 + H2 CH3CH2CH3
6 6

i-BUTANAL
1053 kg/h

7 7

8 8

Figure 1: Block Flow diagram for step 1.

9 9

Reaction table
Notes: Sheet: 00/00 Flowsheet title
Insert notes, abbreviations and brief explanations here
Date: 99/99/2020 DRAWING No.

Drawn: XX 000

A B C D E F G H I J

Components In (kmol/h) React Out (kmol/h)

Propene 404 -343 60,5

CO 900 -183 718

H2 848 -343 504

Propane 2,13 160 162

n-Butanal 168 168

i-Butanal 14,6 14,6

Assumptions for step 1

1. Rhodium modified by triphenylphosphine was selected as the catalyst for this

process, this favours the production of n-butyraldehyde over i-butyraldehyde, 92:8. [1]
2. A propene conversion of 85% was assumed aligning with the rhodium catalyst [1].
3. A selectivity of 95% was assumed [1]
4. Reactor conditions were at 90°C and 15 bar that favour high conversion and still
maintain longevity of catalyst [1].
5. Concentration of catalyst was assumed to be 200 ppm [2].

2
 A
3. STEP 2: MIXING AND RECYCLES
B C D E F G H I J

1 1

PROPYLENE:
14433 kg/h
PROPYLENE:
2 PROPANE: 25,4 kg/h 2
72,5 kg/h

PROPANE:
7124 kg/h
3 3

HYDROGEN
REACTOR 999 kg/h

90OC, 15 bar Separator

PROPYLENE
4 CARBON MONOXIDE 4
RHODIUM PROPANE
CARBON 19 892 kg/h
SOLUTION
0,659 kg/h MONOXIDE
n-BUTANAL RHODIUM
I-BUTANAL SOLUTION
RHODIUM 0,659 kg/h
5 5
SOLUTION
RHODIUM SOLUTION n-BUTANAL
12108 kg/h

n-BUTANAL
6 SYNGAS: 12108 kg/h 6
CO: 25010 kg/h
H2 : 1685 kg/h i-BUTANAL
1053 kg/h

7 7

8 8

Figure 2: Block Flow Diagram for Step 2

9 9
Assumptions for step 2
Notes: Sheet: 00/00 Flowsheet title
Insert notes, abbreviations and brief explanations here
Date: 99/99/2020 DRAWING No.
1. 99% of unreacted carbon monoxide and hydrogen is purged while 000
Drawn: XX 1% is recycled
A B C D E F G H I J
back to the reactor.
2. Assumed 99% of catalyst is recycled whilst 1% is sent to for regeneration.
3. Assumed 99% of unreacted propylene is recycled back to the reactor.
4. 98% of unreacted carbon monoxide and hydrogen are purged while 2% is recycled
back to reactor.

3
 4. STEP 3: SEPARATION
A B C D E F G H I J

1 1

PROPYLENE:
14433 kg/h
2 PROPANE: CARBON MONOXIDE 2
72,5 kg/h 19 892 kg/h
15 bar
34 oC PROPANE
PROPENE
CO
H2
3 3
REACTOR
DECANTER 15 bar
90OC, 15 bar 90 oC 60 oC
15 bar

15 bar RHODIUM
4 SOLUTION 4
RHODIUM 34 oC STRIPPING
SYNGAS: 0,659 kg/h
SOLUTION COLUMN
CO: 25010 kg/h
H2 : 1685 kg/h
15 bar
30 oC
5 10 bar 5
RHODIUM PROPANE:
28 oC 7124 kg/h
SOLUTION
0,659 kg/h PROPYLENE:
25,4 kg/h

6 FLASH 6
n-BUTANAL
I-BUTANAL 1 bar
PROPANE 64,5 oC
PROPENE i-BUTANAL
1053 kg/h
7 7
10 bar
28 oC

DISTILLER

8 8

1 bar n-BUTANAL
75,5 oC 12108 kg/h
1 bar
9 75,5 oC 9

Notes: Sheet: 00/00 Flowsheet title

Figure 3: Block Flow Diagram of Step 3.

Insert notes, abbreviations and brief explanations here
Date: 99/99/2020 DRAWING No.

Drawn: XX 000

A B C D E F G H I J

Assumption for step 3

1. Since the catalyst is soluble in aqueous phase and not in organic phase, we assume
no catalyst carry over to the stripping column from the decanter.
2. Assumed the stripping column operates at 10 bar, 34°C, at this temperature propene
is a saturated liquid [3] while propane is liquid [4], thus most of the propene will be
absorbed into the syngas stream under these conditions.

4
 5. STEP 4:TEMPERATURE, PRESSURE AND PHASE CHANGE
A B C D E F G H I J

1 1

ΔT
PROPYLENE: 15 bar
14433 kg/h 90 oC
2 ΔP CO 2
PROPANE: 19 892 kg/h
72,5 kg/h ΔP 1 bar
9,2 bar 15 bar 25 oC 1 bar
21oC 34 oC 25 oC
15 bar
21 oC
15 bar 15 bar
3 90 oC 34 oC 15 bar 3
REACTOR
ΔT ΔT 60 oC
Decanter
15 bar 90OC, 15 bar
90 oC
RHODIUM
SOLUTION
15 bar
4 0,659 kg/h 4
15 bar 15 bar 34 oC
STRIPPING 15 bar 90 oC
SYNGAS 90 oC 34 oC COLUMN
1 bar, 25 oC:
CO: 25010 kg/h
H2 : 1685 kg/h ΔP 15 bar PROPANE:
1 bar 15 bar ΔT 30 oC 7124 kg/h
5 15 bar 5
25 oC 25 oC 70 oC
RHODIUM
SOLUTION 10 bar 10 bar PROPYLENE:
ΔT
28 oC 21 oC 25,4 kg/h
0,659 kg/h 15 bar 15 bar ΔT
15 bar, 90 oC 90 oC 34 oC
6 FLASH 6
ΔP
10 bar
28oC ΔT ΔPh 1 bar i-BUTANAL:
64,5 oC 906 kg/h
10 bar 1 bar
7 28 oC 25 oC 7
ΔT
1 bar
25 oC
ΔP
DISTILLER
2 bar
26 oC
8 8

ΔPh n-BUTANAL:
ΔT 12108 kg/h
1 bar i-BUTANAL:
75,5 oC 1 bar
ΔT 147 kg/h
9 9
25 oC 1 bar, 25 oC

A B C D E F G H I J

Assumptions for step 4

1. Assumed propene and propane is purchased at 9.2 bar and 21°C [5]
2. Assumed rhodium solution is prepared and made available at 90 °C and 15 bar,
these are the conditions of the reactor.
3. Since the top and bottom streams of the distillation column have high purity, it was
therefore assumed that they are at their boiling points of purest state.
4. It was assumed that propane was sent back to the supply chain as pressurised liquid
vapour at 10 bar 21°C.

5
6. STEP 5: PROCESS FLOW DIAGRAM (PFD)

A B C D E F G H I J

E-101 R-101 E-102 E-105 E-107 D-101 S-101 EX-101 F-102 E-108 TC-101 P-102 A/B E-109
Hydrocarbons Hydroformylation Syngas-propene Reactor Syngas Reactor Propylene Syngas Propane Propane i-Butanal i-Butanal i-Butanal
1 heater product heat recycle heat products Stripping column 1
heater reactor expander flash heat Total pumps Heat
exchanger exchanger decanter tank exchanger condenser exchanger
9,2 bar 21oC 15 bar LPS
Hydrocarbons 1 90 oC 11
E-102 EX-101
2 Propylene: LPS 1 bar To be used as fuel gas 2
14433 kg/h 21 23 25 oC 24 CO, H2
12
Propane: 15 bar 15 bar
72,5 kg/h P-101 90 oC E-107 15 bar 34 oC CO: 19 892 kg/h
A/B 34 oC 19 H2 : 999 kg/h
From 15 bar
3 supply Reactor at 15 bar 34 oC Rhodium 3
90 OC, 15 bar 35 solution
chain 34 oC
15 bar To regeneration
15 bar 2 15 bar 34 oC
25 oC 90 oC E-105 15 bar 0,659 kg/h
RW
13 14 D-101 60 oC 10 bar
LPS R-101 28 oC 27 28 propane
4 E-101 10 bar 4
CW
E-108 21 oC To supply chain
15 bar 22
15 bar 15
3 10 34 oC
90 oC 18 Propane:7124 kg/h
E-106 F-102 cw Propene:25,4 kg/h
Rhodium 26
5 4 17 16 TC-101 5
solution S-101
15 bar, 15 bar
90 oC 34 oC 10 bar
0,659 kg/h LPS 20 28 oC L-101
15 bar, 90 oC 15 bar,
From supply chain 34 oC V-102 10 bar P-102
29 To other
6 28 oC A/B processes 6
C-101 E-103 C-102 E-104 E-109
25 31 32 i-Butanal
0
Syngas 5 6 7 8 9
V-103 RW
15 bar TK-101 1,2 bar 1,2 bar 906 kg/h
5 bar CW 15 bar 25 oC
7 1 bar,25 Co 5 bar CW 15 bar 30 oC 64,5 oC 7
40 oC 70 oC 30
255 oC 95 oC
CO: 25010 kg/h 26 oC
H2 : 1685 kg/h 2 bar 0
From storage RB-101 1,2 bar To storage
25 oC
RW
8 n-Butanal 8
33 34
1,2 bar E-110
75,5 oC n-Butanal: 12081 kg/h
C-102 i-Butanal: 147 kg/h
P-101 A/B C-101 E-103 E-106 E-104 V-102 V-103 TK-101 RB-101 L-101 E-110
1st Syngas Catalyst- 2nd Syngas Propane-Aldehydes Aldehyde n-Butanal n-Butanal n-Butanal
Hydrocarbons 1st Syngas nd
2 Syngas Aldehydes
9 feed heat recovery feed valve Distillation reboiler Liquid exchanger 9
Pumps feed feed heat valve
heater compressor tank storage
compressor exchanger exchanger
drum
Notes: Sheet: 1/1 Hydroformylation Process
LPS - Low Pressure Steam
CW - Cooling Water Date: 28/01/2024 DRAWING No. 1
RW - Refrigerated Water
NG - Natural Gas Drawn: 1814799

A B C D E F G H I J

6
 7. EQUIPMENT LIST
Table 1: Equipment list of Process Flow

Code Equipment Description

R-101 Hydroformylation reactor P = 15 bar, T = 90°C, Stainless steel
E-101 Hydrocarbons heater Tin = 25°C, Tout = 90°C, stainless steel
E-102 Syngas-propene heater Tin = 60°C, Tout = 90°C, stainless steel
1st Syngas feed heat
E-103 exchanger Tin = 255°C, Tout=40°C, stainless steel, utility= cw
2nd Syngas feed heat
E-104 exchanger Tin = 95°C, Tout = 70°C, stainless steel, utility= cw
Reactor product heat
E-105 exchanger Tin = 90°C, Tout = 34°C, stainless steel, utility= cw
Catalyst recycle heat
E-106 exchanger Tin = 34°C, Tout = 60°C, stainless steel, utility= LPS
Syngas recycle heat
E-107 exchanger Tin = 60°C, Tout = 90°C, stainless steel, utility= LPS
Tin = 28°C, Tout = 21°C, stainless steel, utility=
E-108 Propane heat exchanger refrigerated water
Tin = 75°C, Tout = 25°C, stainless steel, utility=
E-109 n-Butanal heat exchanger refrigerated water
Tin = 64.5°C, Tout = 25°C, stainless steel, utility=
E-110 i-Butanal heat exchanger refrigerated water
1st Syngas feed
C-101 compressor Pin = 1 bar, Pout = 5 bar, stainless steel
nd
2 Syngas feed
C-102 compressor Pin = 5 bar, Pout = 15 bar, stainless steel
P-101 Hydrocarbons feed
A/B pumps Pin = 9.2 bar, Pout =15 bar
P-102
A/B i-Butanal distillate pumps Pin = 1 bar, Pout = 1.2 bar
D-101 Reactor product decanter P =15 bar, T = 34°C, stainless steel
V-101 Propane-Aldehydes valve Pin = 15 bar, Pout = 10 bar
EX-101 Purge syngas expander Pin = 15 bar, Pout = 1 bar, stainless steel
Propylene stripping
S-101 column P = 15 bar, T = 34°C, stainless steel
F-101 Propane flash tank P = 10 bar, T=28 °C, stainless steel
Aldehyde
TK-101 Distillation tank P = 2 bar, T= 75.5 °C, stainless steel
RB-101 n-Butanal reboiler P = 1.2 bar, T= 75.5°C, stainless steel
n-Butanal liquid storage
L-101 drum P =1.2 bar, T= 64.5°C, stainless steel
TC-101 i-Butanal total condenser Tin = 64.5°C, T= 64.5°C, stainless steel

7
 8. STREAM TABLE
Stream 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Temperature (°C) 21,1 25 90 90 25 255 40 95 70 90 90 90 90 34 34 34 90
Pressure (bar) 9,2 15 15 15 1,0 5,0 5,0 15 15 15 15 15 15 15 15 15 15
Phase L l V L V V V V V V V V V/L V/L L L L
kmol/h
Propene 344 344 344 - - - - - - 404 59,9 - 60,5 60,5 - - -
CO 7,18 7,18 7,18 - 893 893 893 893 893 893 893 7,18 718 718 - - -
H2 5,04 5,04 5,04 - 842 842 842 842 842 842 842 5,04 504 504 - - -
Propane 1,65 1,65 1,65 - - - - - - 2,13 0,482 - 162 162 - - -
n-Butanal - - - - - - - - - - - - 168 168 - - -
i-Butanal - - - - - - - - - - - - 14,6 14,6 - - -
Rhodium solution - - - 0,00646 - - - - - 0,129 0,129 0,129 0,129 0,123 0,123
Total 358 358 358 0,01 1736 1736 1736 1736 1736 2142 1796 12,2 1628 16278 0,129 0,123 0,123
mol%
Propene 0,96 0,96 0,96 - - - - - - 0,19 0,03 - 0,04 0,04 - - -
CO 0,020 0,020 0,020 - 0,51 0,51 0,51 0,51 0,51 0,42 0,50 0,59 0,44 0,44 - - -
H2 0,014 0,014 0,014 - 0,49 0,49 0,49 0,49 0,49 0,39 0,47 0,41 0,31 0,31 - - -
Propane 0,0046 0,0046 0,0046 - - - - - - - - - 0,10 0,10 - - -
n-Butanal - - - - - - - - - - - - 0,10 0,10 - - -
i-Butanal - - - - - - - - - - - - - - - -
Rhodium solution - - - 1,00 - - - - - - - - - - 1,0 1,0 1,0
Total 1,0 1,0 1,0 0,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 0,0 0,0 0,0
kg/h
Propene 14433 14433 14433 - - - - - - 16951 2517 - 2543 2543 - - -
CO 201 201 201 - 25010 25010 25010 25010 25010 25010 25010 201 20093 20093 - - -
H2 10,1 10,1 10,1 - 1685 1685 1685 1685 1685 1685 1685 10 1009 1009 - - -
Propane 72,5 72,5 72,5 - - - - - - 93,8 21,2 - 7145 7145 - - -
n-Butanal - - - - - - - - - - - - 12108 12108 - - -
i-Butanal - - - - - - - - - - - - 1053 1053 - - -
Rhodium solution - - - 0,659 - - - - - 13,2 - - 13,2 13,2 13,2 12,5 12,5
Total 14717 14717 14717 0,659 26695 26695 26695 26695 26695 43753 29233 211 43964 43964 13,2 12,5 12,5
wt%
Propene 0,98 0,98 0,98 - - - - - - 0,39 0,086 - 0,058 0,058 - - -
CO 0,014 0,014 0,014 - 0,94 0,94 0,94 0,94 0,94 0,57 0,86 0,95 0,46 0,46 - - -
H2 0,00069 0,00069 0,00069 - 0,063 0,063 0,063 0,063 0,063 0,039 0,058 0,048 0,023 0,023 - - -
Propane 0,0049 0,0049 0,0049 - - - - - - - - 0,16 0,16 - - -
n-Butanal - - - - - - - - - - - - 0,28 0,28 - - -
i-Butanal - - - - - - - - - - - - 0,024 0,024 - - -
Rhodium solution - - - 1,0 - - - - - 0,00030 - - - - 1,0 1,0 1,0
Total 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0

8
Table 2: Continuation of stream table

Stream 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35
Temperature (°C) 90 34 34 34 34 34 35 30 28 28 21,1 28 26 64,5 25 75,5 25 43
Pressure (bar) 15 15 15 15 15 15 1,0 15 10 10 60 10 2,0 1,2 1 1,2 1,0 15
Phase L V L V V V V L V/L V V L L L L L L L
kmol/h
Propene - - 61 - 344 - - 0,61 0,61 0,61 0,61 - - - - - - -
CO - 718 - 7,18 7,18 710 710 - - - - - - - - - - -
H2 - 504 - 5,04 5,04 499 499 - - - - - - - - - - -
Propane - - 162 - 1,65 - - 162 162 162 162 - - - - - - -
n-Butanal - - 168 - - - - 168 168 - - 168 168 - 168 168 -
i-Butanal - - 14,6 - - - - 14,6 14,6 - - 14,6 14,6 12,6 12,6 2,04 2,0 -
Rhodium solution 0,129 - - - - - - 0,01 0,01 - - 0,01 0,01 0,01 0,01 - - -
Total 0,129 1222 406 12,2 358 1210 1210 345 345 163 163 183 183 13 13 170 170 -
mol%
Propene - - 0,15 - 0,96 - - 0,0018 - 0,0037 0,0037 - - - - - - -
CO - 0,59 - 0,59 0,020 0,59 0,59 - - - - - - - - - - -
H2 - 0,41 - 0,41 0,014 0,41 0,41 - - - - - - - - - - -
Propane - - 0,40 0,0046 0,47 0,47 1,0 1,0 - - - - - - -
n-Butanal - - 0,41 - - - - 0,49 0,49 - - 0,92 0,92 - - 0,99 0,99 -
i-Butanal - - 0,036 - - - - 0,042 0,042 - - 0,08 0,08 1,0 1,0 0,012 0,012 -
Rhodium solution 1,0 - - - - - - 0,00 - - - - - - 1,00
Total 0,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 0,0
kg/h
Propene - - 2543 14433 - - 25 25 25 25
CO - 20093 - 201 201 19892 19892 - - - - - - - - - - -
H2 - 1009 - 10,1 10,1 999 999 - - - - - - - - - - -
Propane - - 7145,3 - 72,5 - - 7124 7124 7124 7124 - - - - - - -
n-Butanal - - 12108 - - - - 12108 12108 - - 12108 12108 - - 12108 12108 -
i-Butanal - - 1053 - - - - 1053 1053 - - 1053 1053 906 906 147 147 -
Rhodium solution 13,2 - - - - - 0,626 0,626 - - 0,626 0,626 0,626 0,626 - - 0,659
Total 13,2 21102 22849 211 14717 20891 20891 20311 20311 7149 7149 13161 13161 906 906 12255 12255 0,659
wt%
Propene - - 0,111 - 0,98 - - 0,0013 0,0013 0,0036 0,0036 - - - - - - -
CO - 0,95 - 0,95 0,014 0,95 0,95 - - - - - - - - - - -
H2 - 0,048 - 0,048 - 0,048 0,048 - - - - - - - - - - -
Propane - - 0,31 - - - - 0,35 0,35 1,0 1,0 - - - - - - -
n-Butanal - - 0,53 - - - - 0,60 0,60 - - 0,92 0,92 0,99 0,99 -
i-Butanal - - 0,046 - - - - 0,052 0,052 - - 0,080 0,080 1,0 1,0 0,012 0,012 -
Rhodium solution 1,0 - - - - - - - - - - - - - 1,0
Total 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0

9
9. RATIONALE
1. Propylene with propane is purchased as a liquid at 9,2 bar and 21 °C [5]. And sent
back to supply chain at the same conditions.
2. Rhodium modified with triphenylphosphine (TTP) was selected as the catalyst as it
has a very high n:i butanal ratio, 92:8 [1]. The target is to produce more n-butanal and
have as less i-butanal as possible.
3. The normal operating temperature at which the catalyst is active ranges from 85°C to
115°C. Since this is an exothermic reaction[6]. Lower temperatures favour higher
conversions on the flip side very low temperatures the reaction rate is slow, therefore
a temperature of 90°C was chosen.
4. Rhodium catalyst operate effectively at 15 bar to 20 bar, although high pressure tends
to favour formation of n-butanal than i-butanal, but for the durability and longevity of
the catalyst [7], lower pressure was selected. Therefore, CSTR was assumed to
operate at 90°C,15 bar.
5. Catalyst recovery was made to be 99% as the decanter was assumed to have three
phases: H2 and CO as vapor, aldehydes, propene, and propane in the aqueous
phase, while the catalyst remains in the organic phase. From this, a 3-phase decanter
was chosen, and it was assumed that there would be no catalyst carry-over to the
aqueous phase. Additionally, the 1% of catalyst was assumed to be purged to catalyst
activation, in case of deactivation. All this was done for the longevity of the catalyst.
6. The stream fed to the stripping column was cooled to 34°C, 15 bar, at these
conditions, propene is at saturation while propane is a liquid [4]. Therefore, propene
recovery in the absorption was assumed to be 99% and 2.4%.
7. Decreasing pressure decreases the boiling point of component, therefore the stream
to a flash was expanded to lower pressure thus propane at 34°C, 10 bar is vapour
therefore low-pressure flash was selected. And the aldehydes are liquids.
8. Required concentration of rhodium catalyst in the reactor was assumed to be 200
ppm as a typical concentration range was 40 ppm to 200 ppm of rhodium in
hydroformylation process. Higher concentration was selected to increasing reaction
time [2].
9. 98% of unreacted carbon monoxide and hydrogen are purged to be use as fuel gas
as the 2% is recycled back to reactor.
10. It was assumed that there’s pressure drop of 0.8 bar in the distillation column.

10
 10. THINKING ABOUT THE PROCESS
In the hydroformylation process rhodium and cobalt are the two main catalysts used.
However, rhodium catalyst was selected over cobalt in this process because it is more active
than cobalt therefore it has more active sites available for reaction hence conversion is
higher, 80% [1]. Also, in using rhodium catalyst we achieve high selectivity towards n-
butanal over the i-butanal 92:8 [1]. The rhodium is water soluble, therefore easy separation
from the products as it dissolves in aqueous phase and the products being in organic phase,
hence we can recover it back. However, it must be noted that rhodium is expensive than
cobalt, but it is standard to use is rhodium modified with triphenylphosphine (TPP).

The proposed process configuration addresses the size of optimisation as there is a decanter
before the stripping column. This decanter removes hydrogen and carbon monoxide, thus
decreasing the amount of vapor going into the stripping column. This decreases the vapour
loading in the column thus ensuring diameter of the stripping column is optimum. It therefore
essential to have a flash off vapor before the stripping column.

Optimisation is also met in the low-pressure flash and distillation column. The flash tank
flashes unabsorbed vapour from the stripping column ensuring there is no vapour coming to
the distillation column. Having vapour coming in the distillation column would increasing the
reflux ratio, thus there will be flooding and as a consequence the diameter of the column
should be increased. Hence having no vapour coming in the distillation ensures an optimum
diameter of trays and column. Flashing off the vapor also ensures there is minimal vapour
loading in the distillation column, thus without vapour coming into the distillation ensures
minimum diameter with respect to process configuration.

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 11. REFERENCES
[1] “fullc40_982596.pdf.” Accessed: Feb. 28, 2024. [Online]. Available:
https://www.scientificbulletin.upb.ro/rev_docs_arhiva/fullc40_982596.pdf
[2] “US6946580.pdf.” Accessed: Feb. 28, 2024. [Online]. Available:
https://patentimages.storage.googleapis.com/a3/fe/de/49b9d0817c7252/US6946580.pdf
[3] “Propene | Gas Encyclopedia Air Liquide.” Accessed: Feb. 24, 2024. [Online]. Available:
https://encyclopedia.airliquide.com/propene#properties
[4] “Propane | Gas Encyclopedia Air Liquide.” Accessed: Feb. 28, 2024. [Online]. Available:
https://encyclopedia.airliquide.com/propane#properties
[5] “Gas_Innovations-Product_Catalog-rev.02.02.2024_Propylene.pdf.” Accessed: Feb. 25,
2024. [Online]. Available:
https://gasinnovations.com/wp-content/uploads/Gas_Innovations-Product_Catalog-
rev.02.02.2024_Propylene.pdf
[6] “Industrial Operation of Hydroformylation - Chempedia - LookChem.” Accessed: Feb. 28,
2024. [Online]. Available:
https://www.lookchem.com/Chempedia/Chemical-Technology/Organic-Chemical-
Technology/7505.html
[7] R. Paciello, “High Pressure Hydroformylation in the Chemical Industry”.

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 12. PLAGIARISM REPORT

I know that plagiarism is wrong. Plagiarism is to use another’s work and pretend that it is our
own.

I have used the IEEE system for citation and referencing. In this report, all contributions to,
and quotations from, the work(s) of other people have been cited and referenced.

This report is our own work. I have not allowed and will not allow anyone to copy my work.

Signed ____________________ Date: 29 February 2024

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 13. APPENDIX A – ARTIFICIAL INTELLIGENCE DECLARATION
I have not used artificial intelligence (AI) tools in the preparation of this report.

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