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1
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
2
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
3
Simulation of methanol
synthesis from syngas Energy demand Fossil fuels
obtained through
biomass gasification
using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model Renewable Energies
3.2. Methanol synthesis simulation
4
Simulation of methanol
synthesis from syngas BIOMASS
obtained through
biomass gasification “All organic material including trees, crops, algae and residues which are
using Aspen Plus®
susceptible to be converted into energy”
TABLE OF CONTENTS
Types of biomass
1. Introduction
First-generation biomass
2. Aspen plus modelling
2.1. Gasification process
Fourth-generation biomass
Pine
bark
5
Simulation of methanol
synthesis from syngas
obtained through • Pyrolysis
biomass gasification
using Aspen Plus® Thermochemical process • Combustion
• Gasification
TABLE OF CONTENTS Energy conversion of • Licuefaction
biomass
• Alcoholic fermentation
1. Introduction Biochemical process
2. Aspen plus modelling • Anaerobic digestion
2.1. Gasification process
• Methanol synthesis
• Intermedies (Toluene, isobutane)
6
Simulation of methanol
synthesis from syngas
obtained through
biomass gasification Gasification can be defined as the conversion of biomass into a gaseous fuel
using Aspen Plus® by heating in a partial oxidation atmosphere
TABLE OF CONTENTS
Biomass
Gasifying agent Syngas
(steam) (CO, H2, CO2, CH4)
1. Introduction
7
Simulation of methanol
synthesis from syngas
Methanol synthesis
obtained through
biomass gasification Feedstock Reactions
using Aspen Plus®
• CO 2 ⇌
TABLE OF CONTENTS • H2 3 ⇌
Syngas • CO2
1. Introduction
• CH4 Low conversion
2. Aspen plus modelling • Traces Catalys: Cu/ZnO
2.1. Gasification process
0,13 0,14
8
Simulation of methanol
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® Aspen Plus®
PRICE
1. Introduction The main objetive of this research was the simulation
2. Aspen plus modelling
2.1. Gasification process
of three integrated process: pine gasification, syngas
2.2. Syngas cleaning: Pressure cleaning and metanol synthesis using Aspen Plus®
Pilot plant
swing adsorption (PSA)
Pilot plant
9
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
10
Simulation of methanol
synthesis from syngas Aspen Plus® flowsheet process
obtained through
biomass gasification
using Aspen Plus®
TABLE OF CONTENTS
Syngas purification
V-5
34 35
PSA4
29
Gasification process PSA3
1. Introduction 26
36
V-4
SPLIT-2 MIXER-4
11
2.1. Gasification process R-2 MIXER-1 SEP-3 SEP-4
C-1
R-1 3 4
SEP-2
R-3 R-4
16 18 19 21
PSA1
27
33 42
Methanol synthesis
2.2. Syngas cleaning: Pressure 1 Q-2
10 12 15
V-2
Q-3 17 20
HEATX-2 39 40
28
3. Results 7
HEATX-1
25
MIXER-3
46
R-6
53
6 8
52
11
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
12
Simulation of methanol Gasification process
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® R-2
11 MIXER-1 SEP-3
SEP-2
R-1 3 4 16 18
TABLE OF CONTENTS R-4
R-3
1 Q-2
10 12 15
Q-3 17
1. Introduction
2 SEP-1 Q-1
2. Aspen plus modelling
HEATX-2
2.1. Gasification process
14 13
2.2. Syngas cleaning: Pressure
swing adsorption (PSA) R-5
2.3. Methanol synthesis process 5
3. Results 7
3.1. Gasification simulation model
HEATX-1
13
Simulation of methanol Gasification process
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus®
11 MIXER-1
R-2 SEP-3
TABLE OF CONTENTS SEP-2
R-1 3 4 16 18
R-3 R-4
1 Q-2
10 12 15
1. Introduction
Q-3 17
2. Aspen plus modelling
2.1. Gasification process 2 SEP-1 Q-1
2.2. Syngas cleaning: Pressure
HEATX-2
swing adsorption (PSA)
14 13
2.3. Methanol synthesis process
R-1 (RYIELD):
R-5 Biomass pyrolysis reactor, it decomposed
3. Results
3.1. Gasification simulation model
the5 biomass into its compounds and ash.
3.2. Methanol synthesis simulation 7
3.3. Gas emission R-2 (RGIBBS): It HEATX-1models chemical equilibrium
3.4.Optimal process improvement minimizing the Gibss free energy. It was used to produce
CO2, CO, CH6 4, H2S and NH
8
3.
14
Simulation of methanol Gasification process
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® R-5 (RSTOIC): Char combustion reactor.
11 MIXER-1
R-2 SEP-3
SEP-2
Heatx-1: Exchange heat between the outlet stream from R-5 and the
TABLE OF CONTENTS R-1 3 4
air inlet stream. 16 18
R-4 R-3
1 Q-2
10 12 15
1. Introduction Q-3 1. Amount of char for combustion 17
2. Aspen plus modelling
Design
2 specifications:
SEP-1 Q-1
2.1. Gasification process
6 8
15
Simulation of methanol Gasification process
synthesis from syngas
obtained through
biomass gasification 11 MIXER-1
R-2 SEP-3
using Aspen Plus® SEP-2
R-1 3 4 16 18
R-3
R-3 R-4
R-4
TABLE OF CONTENTS
1 Q-2
10 12 15
Q-3 17
1. Introduction
2 SEP-1 Q-1
2. Aspen plus modelling
Heatx-2
HEATX-2
2.1. Gasification process
3.3. Gas emission R-4 (RSTOIC): It was used to model the tar
3.4.Optimal process improvement 6 8
reforming using Dolomite as a catalyst.
9
Heatx-2: Heater to warm up the gasifying
agent (water steam).
16
Simulation of methanol Gasification process
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus®
11 MIXER-1
R-2 SEP-3
SEP-2
TABLE OF CONTENTS R-1 3 4 16 18
R-3 R-4
1 Q-2
10 12 15
1. Introduction Q-3 17
2. Aspen plus modelling
2 SEP-1 Q-1
2.1. Gasification process
Energy requirements = 0
17
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
18
Simulation of methanol Syngas cleaning: Pressure swing adsorption (PSA)
synthesis from syngas
obtained through
biomass gasification Specifications:
using Aspen Plus®
V-5
PSA3
36
26
V-4
1. Introduction SPLIT-2
MIXER-4
PSA2 V-3
2. Aspen plus modelling V-1 C-2 37
31 38
2.1. Gasification process 22 23 24 32
3. Results
V-2
17 20
3.1. Gasification simulation model
C-3 SPLIT-1
3.2. Methanol synthesis simulation
28 39 40
3.3. Gas emission
MIXER-3
25
19
Simulation of methanol Syngas cleaning: Pressure swing adsorption (PSA)
synthesis from syngas V-5
obtained through
34 35
biomass gasification PSA4
3. Results V-2
17 20
3.1. Gasification simulation model C-3 SPLIT-1
SPLIT-1
3.2. Methanol synthesis simulation
CO
3.3. Gas emission
Water 28 39 40
H2
MIXER-3
25
20
Simulation of methanol Syngas cleaning: Pressure swing adsorption (PSA)
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® V-5
PSA4 PSA4
34 35
TABLE OF CONTENTS
29
PSA3PSA3
36
26
V-4
1. Introduction
V-3
SPLIT-2
SPLIT-2 CH4 MIXER-4
2. Aspen plus modelling V-1 C-2
PSA2
37
2.1. Gasification process 31 38
22 23 24 32
2.2. Syngas cleaning: Pressure
SEP-3
PSA3 separates the CO2
SEP-4
CO2
swing adsorption (PSA) C-1
MIXER-2 41 C-4
45
MIXER-3
25
21
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
22
Simulation of methanol Methanol synthesis process
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® V-6
C-4 COOLER-1 METSEP
45
TABLE OF CONTENTS 47 49 50
46
R-6
1. Introduction MIXER-3
2. Aspen plus modelling 53
2.1. Gasification process
METHANOL
2.2. Syngas cleaning: Pressure
swing adsorption (PSA)
3. Results
3.1. Gasification simulation model R-6 simulates the metanol synthesis
3.2. Methanol synthesis simulation
23
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
24
Simulation of methanol Model validation
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® Condicions: Biomass:
Temperature: 831ºC
TABLE OF CONTENTS Wood pellets
Pressure: 1 atm
1. Introduction
3. Results CO 21-25 20
3.1. Gasification simulation model
CO2 18-22 18
3.2. Methanol synthesis simulation
Error: 5-7 %
25
Simulation of methanol Effect of the S/B mass ratio on the syngas composition
synthesis from syngas
obtained through 80 80
biomass gasification a)
800 ºC
800 ºC
H2 900 ºC b) CO 900 ºC
using Aspen Plus® 1000 ºC
1000 ºC
60 60
20 20
1. Introduction
20 20
10
0 0
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
S/B
S/B (ratio)
mass ratio S/Bmass
S/B (ratio)
ratio
26
Simulation of methanol Effect of the S/B mass ratio on the syngas composition
synthesis from syngas
obtained through 80 80
biomass gasification a)
800 ºC
800 ºC
H2 900 ºC b) CO 900 ºC
using Aspen Plus®
60
H2 y CO2
1000 ºC
60
1000 ºC
20 20
1. Introduction
20
Tar forming: 6 9 ⇌6 20
10
0 0
0.5 0.6 0.7 0.8 0.9 1.0 0.5 0.6 0.7 0.8 0.9 1.0
S/B
S/B (ratio)
mass ratio S/Bmass
S/B (ratio)
ratio
27
Simulation of methanol Effect of the S/B mass ratio on the syngas composition
synthesis from syngas
80
obtained through 800 ºC 3.5
e) C 6H 6 900 ºC 800 ºC
biomass gasification
1000 ºC 900 ºC
using Aspen Plus® 60 1000 ºC
3.0
C 6 H 6 (vol.% d ry b asis)
H2/CO = 2,4
20
1. Introduction 2.0
30
3.4.Optimal process improvement
S/B = 0,9
20
10
0
0.5 0.6 0.7 0.8 0.9 1.0
S/B mass ratio
28
Simulation of methanol Effect of gasification temperature
synthesis from syngas
obtained through
biomass gasification 80 50
H2
using Aspen Plus® CO
1. Introduction 20
CO2, CH4 and C6H6
2. Aspen plus modelling
20
2.1. Gasification process 10
2.5
2.0
1.5
0.6 0.8 1.0
S/B mass ratio 29
Simulation of methanol Effect of gasification temperature
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® Water Gas: ⇌
Endothermics
TABLE OF CONTENTS Steam reforming: ⇌ 3
Boudouard: ⇌2
1. Introduction
3. Results
3.1. Gasification simulation model
30
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
31
Simulation of methanol Methanol synthesis: validation
synthesis from syngas
obtained through
biomass gasification Stoichiometric Equilibrium % Error
using Aspen Plus® reactor reactor
CH3OH (kg/h) 16.5 15.4 7.1
TABLE OF CONTENTS
• High costs
10
• Human danger
0
40 50 60 70 80
Pressure (atm)
1. Introduction
9 kg/h
2. Aspen plus modelling
2.1. Gasification process
3. Results
3.1. Gasification simulation model
3.2. Methanol synthesis simulation - At high temperatures, the catalyst can be damaged.
3.3. Gas emission
3.4.Optimal process improvement - At low temperatures can reduce the reaction rate55 atm
Optimal conditions for metanol synthesis :
220 ºC
34
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
34
Simulation of methanol Capture and gas emissions
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® Capture:
95% CH4
1. Introduction
3. Results
3.1. Gasification simulation model
CO2 produced from the
Emisión de gases
3.2. Methanol synthesis simulation
combustión chamber
(Kg/h)
3.3. Gas emission
36
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
36
Simulation of methanol Optimal process improvement
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus®
Char to combustion chamber:
40% 10%.
TABLE OF CONTENTS
C available CO
methanol.
1. Introduction
CO CO2 CO2
2. Aspen plus modelling
capture
2.1. Gasification process
3. Results
3.1. Gasification simulation model Combustion chamber:
3.2. Methanol synthesis simulation H2 reacted with O2 to produce H2O
3.3. Gas emission and decrease CO2 formation.
3.4.Optimal process improvement
Caudal másico
NH3 and H2S were kept
38
Simulation of methanol Final simulation
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus®
TABLE OF CONTENTS
T = 900ºC
S/B mass ratio = 0.9 Syngas cleaning
V-5
34 35
PSA4
1. Introduction
29
26
36
T = 220ºC
2. Aspen plus modelling
V-4
SPLIT-2 MIXER-4
22
V-1
23
C-2
24
PSA2 30 V-3
31
32
37
38 P = 55 atm
2.1. Gasification process R-2
11 MIXER-1 SEP-3 SEP-4
SEP-2 C-1
Q-2
R-3 R-4
16 18 19 21
PSA1
27
33 42 Methanol synthesis
10 12 15
V-2
swing adsorption (PSA) Q-3 17 20
C-3 SPLIT-1
2 SEP-1 Q-1
39 40
3. Results 7
HEATX-1
MIXER-3
46
R-6
25 53
6 8
3.1. Gasification simulation model
9
52
Recycle
39
Simulation of methanol Acknowledgement
synthesis from syngas
obtained through
biomass gasification Authors acknowledge the financial support from the Spanish Ministry of
using Aspen Plus®
Education, Culture and Sports for FPU grant (FPU15/02653).
TABLE OF CONTENTS
1. Introduction
3. Results
3.1. Gasification simulation model
Thanks you very much for your attention!
3.2. Methanol synthesis simulation
39
6th International Conference on
Sustainable Solid Waste Management
(NAXOS 2018)
40
Conclusions
- The gasification process was simulated using a thermodynamic equilibrium model which is based on the minimization of the
Gibbs free energy of the system. A double chamber gasifier, which allows the separation of the gasification and combustion
zones to obtain a high-quality gas, was considered. The influence of the steam to biomass (S/B) mass ratio and the temperature
on the gas product composition and methanol production was studied. The best calculated operational condition of the process
- One of the main technical barriers for the syngas production is the presence of tar coming from the gasification process.
According to the simulation performed, tar production was hindered with increasing temperatures and steam flow rates.
grant
Dolomite was used as the catalyst in the decomposition of tar due to its low cost.
- A pressure swing adsorption (PSA) process was considered to clean the syngas and simultaneously capture the greenhouse
gases. Therefore, about 80% of the CO2 and 95% of the CH4 were sequestered.
- Once the H2/CO molar ratio of the clean syngas was fitted, the methanol synthesis proceeded. Although the methanol production
is favoured at high pressures and low temperatures, a pressure of 55 atm was selected to avoid operational issues. Thus, 220ºC
and 55 atm were selected as the optimal operation conditions for the methanol synthesis.
- Finally, to improve the process yield, the methanol synthesis waste stream is recycled to the combustion chamber. With this
recycle, the carbon required to burn is reduced from 40 to 10%. Thus, there is a higher amount of carbon available to be used in
Proximate analysis:
Standard Procedure Volatile matter (VM): UNE-EN 15148
Ash content (AC): UNE-EN 14775
Moisture content (MC): UNE-EN 14774
42
Simulation of methanol Tar craking
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® C3H8, C6H6, Operating issues due to tar
Tar C7H8, C8H8, condensation
C4H10, C6H12
TABLE OF CONTENTS
3. Results
3.1. Gasification simulation model
→ 2 6 →3 12
3 →2
31