Simulation and Optimization of a Green

Process for Methanol Production via

Hydrogenation of Carbon Dioxide

Presented by: Eng. Diala Alwan

Supervised by: Dr. Jean Claude
Defended on 30 September 2022 in front of the jury:
Dr. Jean Chamoun
Dr. Rami Nader
Outline
Process Simulation,
Validation & Environmental analysis
Optimization & HAZOP study

01 02 03 04 05

Conclusion &
State of Art Process design Perspectives

2
Introduction
Energy Demand

Methanol Climate change

Essential energy
3
Aim of Project
CO2 from

CO2 viable compound

Simulation, Modelling, and
Optimization of a methanol production
process via the direct hydrogenation of
CO2 using Aspen HYSYS.
An and environmental study.
4
Methanol Uses & Market Size
Excellent fuel

Starting materials for

hydrocarbon products
Used as both solvent
and reactant
Found in many
household products The market size of
methanol in the US is
forecast to grow to over
8.4 MMT by 2027. 5
Methanol Process via CO2 Hydrogenation

CO2 H2 Methanol

6
H2 Sources

7
CO2 Sources

Global emissions
in 2020, by sector
(in billion metric
tons)

8 8
Methanol Production process
This process includes three units:
• The H2 production unit by which H2 is generated through a Water Gas
Shift Reaction,
• The CO2 capture unit by which carbon dioxide is seized from the flue
gases of power plant stacks,
• and finally the CO2 hydrogenation unit by which methanol is produced.

9
H2 Production Methods
Natural Gas
Reforming

Efficiency Efficiency Efficiency

70-85% 60-75% 60-75%
Autothermal
Steam reforming Partial Oxidation
reforming

CO
Water Gas
shift reaction 𝐇𝟐 10
Capture Methods
CO2 Capture
from power
plants

Absorption Membrane
Adsorption Technology

Chemical Physical

MEA DEA

11
Selected Route for Methanol
Production via CO2 hydrogenation

CO2 from MEA chemical absorption of flue gases

H2 from WGS reaction Methanol

using CO as a byproduct
from steam reforming

12
 Process Simulation,
Validation & Optimization

13
Carbon Dioxide source via a CO2 capture unit

14
Hydrogen source via  a Water Gas Shift Reaction

15
The buildup of the CO2 hydrogenation process

Purity
99.5%

16
Effect of Feed’s inlet Temperature on the Methanol Flow
Rate for multiple H2:CO2 ratios

300
Methanol's Molar Flow rate (kgmole/h)

250

200

150
H2:CO2 = 2
H2:CO2 = 3
100 H2:CO2 = 4

50

0
150 200 250 300 350 400 450 500 550 600
Feed's inlet Temperature

17
Methanol Flow Rate (kgmole/h) versus Feed’s inlet
Temperature (°C) for multiple Pressures (kPa)

350

300
Methanol's flow rate (kgmol/h)

250

200 P = 3000 kPa

P = 4000 kPa
P = 5000 kPa
150
P = 6000 kPa
P = 7000 kPa
100
P = 8000 kPa
P = 9000 kPa
50

0
150 200 250 300 350 400 450 500 550 600
Feed's inlet temperature (C)

18
Effect of Pressure of Sour Gas entering the Absorber on
the fraction of CO2 in sweet gas

0.012
0.01104689041364
92
0.01
Fraction of CO2 in sweet gas

0.008

0.006

0.004

0.002 [X VALUE],
0.0000073651
0
1890 1900 1910 1920 1930 1940 1950 1960
Pressure of Sour Gas entering the Absorber (kPa)

19
Optimization of process’s heating and cooling
duties
7000000000

6000000000
% of energy % of savings
5000000000
saved after
Heat
Utilities (kJ/h)

4000000000 Integration
3000000000
Total 22.16% 7%
Utilities
2000000000 Heating 15.61% 2.9%
1000000000
Utilities
Cooling 38.14% 17%
0
Total Utilities Heating Utilities Cooling Utilities Utilities

20
Pinch Analysis

Heat Energy Saved (kJ/h)

Exchanger
1 16.35× 107
2 1.482 × 108
3 6.048 × 107
4 3.983 × 107

21
Mass & Energy Balances
Separators
1,2,3,4,5

PFR Desorber

Distillation
Column
22
Mass Balance for the Separators
Component Streams MATLAB Aspen HYSYS Error (%)
V11

Flash Separator 1 CO2 1111.247839 1111 0.022308

H2O-1 2938.752161 2939 0.008433
Flash Separator 2 H2-Cold 4068.01 4067 0.024834
Flash Bottom 6511.99 6509 0.045936
Flash Separator 3 Comp-3-In 5178 5178 0
H2O-2 0 0 -
Flash Separator 4 Flash-4-Overhead 365545.9207 3.656×105 0.014792

Flash-4-Bottom 854.0792541 859.3 0.607558

Flash Separator 5 Vent-1 24.65657388 24.64 0.067264
Flash-5-Bottom 834.6434261 834.6 0.005203 23
Mass Balance for Desorber & Distillation
Column

Component Streams MATLAB Aspen HYSYS Error (%)

V11
Desorber CO2-H2O 13026.39594 1.247×104 4.461876
Lean MEA from 353573.6041 3.541×105 0.148657
Desorber

Component Streams MATLAB Aspen HYSYS Error (%)

V11

Distillation Methanol 332.4979296 332.5 0.000622

Column H2O-3 502.1020704 502.1 0.000412

24
Energy Balance for PFR

Component Aspen MATLAB Error (%)

HYSYS
V11
Q for PFR 3.387×109 3341251732.075062 1.35070174
reactor kJ/h kJ/h

25
Methanol Production
Process Design

26
Process Design
Rich/Lean
Heat
Exchanger

Separators
Desorber
1,2,3,4,5

27
Rich/Lean Heat Exchanger Design
tube outer 0.02m
diameter
tube length 3m

∆𝑇𝑚 15.447 ℃

𝐴𝑡𝑜𝑡𝑎𝑙 60.255 𝑚2

𝐴𝑡𝑢𝑏𝑒 0.1884 𝑚2

𝑁𝑡𝑢𝑏𝑒 320 tubes

28
Desorber Design

Desorber Design Description

Material Stainless Steel
Selection Type 304
Diameter 64 m
Height 4m
Packing Weight 120 tons

29
Separators Design

Separator-1 Separator-2 Separator-3 Separator-4 Separator-5

Material Stainless Stainless Stainless Stainless Stainless

Selection Steel Type Steel Type Steel Type Steel Type Steel Type
304 304 304 304 304
Diameter 1.88 m 1.048 m 1.7 m 10.653 m 0.343 m

Height 3m 3m 3m 3m 3m

30
Novel Catalysts

Cu-ZnO-Al2O3

Pd (or Ni or Co)
is supported on
ZnO or ZnAl2O3

31
Economical Analysis &
HAZOP Study

32
HAZOP Study

HAZOP

• It is a study made for the assessment of Distillation

the whole system and risk management Reactor
• The different parts integrated in a Column
HAZOP study are: guide words,
deviations, causes, effects and
recommendations
33
Economical Study
Total Operating Total Capital
Costs: $13,307,500 Cost: $18M
Annual Revenue:
$31,841,846.4
Profability:
$16,494,346.4

Total Utility Cost:

Payoff Period:
$2,040,000 2.097 years
34
Conclusion & Perspectives

35
Conclusion

Eco- Reasonable
CO2 friendly operating Economically
recycling & Clean conditions Feasible

01 02 03 04

36
Perspectives

37
Thank you!

38