6th International Conference on

Sustainable Solid Waste Management

(NAXOS 2018)

Simulation of methanol synthesis from

syngas obtained through biomass
gasification using Aspen Plus®
M. Puig-Gamero, J. Argudo-Santamaria, J. L. Valverde, P. Sanchez, and L. Sanchez-Silva

Department of Chemical Engineering, University of Castilla-La Mancha, Spain

*maria.puig@uclm.es
Naxos Island, 15th June 2018

1
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

2
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

3
Simulation of methanol
synthesis from syngas Energy demand Fossil fuels
obtained through
biomass gasification
using Aspen Plus®

TABLE OF CONTENTS

 1. Introduction

 2. Aspen plus modelling

 2.1. Gasification process Disadvantages Advantages
 2.2. Syngas cleaning: Pressure Problems derived from
swing adsorption (PSA)
their use
 2.3. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model Renewable Energies
 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4.Optimal process improvement

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

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis process

Second-generation biomass
 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

Third-generation biomass
 3.4.Optimal process improvement

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

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis process

Syngas
 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation • Methanation

 3.3. Gas emission
Uses of syngas • Fischer-Tropsch
 3.4.Optimal process improvement

• 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

 2. Aspen plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA) Reactions involved in gasification process:
 2.3. Methanol synthesis process

 3. Results Water Gas: ⇌

 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation Water gas shift: ⇋

 3.3. Gas emission

 3.4.Optimal process improvement Steam reforming: ⇌ 3

Boudouard: ⇌2
Tar forming: 6 9 ⇌6

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

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis process Syngas composition:

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

2,1
 3.3. Gas emission

 3.4.Optimal process improvement

2,4 2,5

0,13 0,14

8
Simulation of methanol
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® Aspen Plus®

TABLE OF CONTENTS SPEED

 1. Introduction
 2. Aspen plus modelling
 2.1. Gasification process
 2.2. Syngas cleaning: Pressure
swing adsorption (PSA)
PRICE
The main objetive of this research was the simulation
of three integrated process: pine gasification, syngas
cleaning and metanol synthesis using Aspen Plus®
Pilot plant

 2.3. Methanol synthesis process

Simulation process
 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation • Blocks

 3.3. Gas emission

 3.4.Optimal process improvement

• Streams

• Design specifications, codes

Pilot plant
9
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

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

 2. Aspen plus modelling V-1 PSA2 30 V-3

C-2 37
31 38
22 23 24 32

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

swing adsorption (PSA) 2 SEP-1 Q-1

C-3 SPLIT-1

HEATX-2 39 40
28

 2.3. Methanol synthesis process

14 13 V-6
41 C-4 COOLER-1
R-5 MIXER-2 45 METSEP
47 49 50
5

 3. Results 7
HEATX-1
25
MIXER-3
46
R-6

53
6 8

 3.1. Gasification simulation model

9

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4.Optimal process improvement

48

52

11
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

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

 3.2. Methanol synthesis simulation

 3.3. Gas emission 6 8

 3.4.Optimal process improvement

Thermodynamic equilibrium model (reaction kinetics are unknown)

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.

SEP-1: Separator of the amount9 of char necessary to

achieve the gasification temperature.

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

 2.2. Syngas cleaning: Pressure

2. Air flow HEATX-2
swing adsorption (PSA)
14 13
 2.3. Methanol synthesis process
R-5
R-5
 3. Results
 3.1. Gasification simulation model 5
 3.2. Methanol synthesis simulation
7
 3.3. Gas emission
Heatx-1
HEATX-1
 3.4.Optimal process improvement

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

 2.2. Syngas cleaning: Pressure 14 13

swing adsorption (PSA)
R-5
 2.3. Methanol synthesis process
5
 3. Results
 3.1. Gasification simulation model
R-3 (RGIBBS): It simulated
7
the gasifier.
HEATX-1
 3.2. Methanol synthesis simulation

 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

 2.2. Syngas cleaning: Pressure HEATX-2

swing adsorption (PSA) 14 13
 2.3. Methanol synthesis process
R-5
 3. Results
5
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation 7

HEATX-1
 3.3. Gas emission

 3.4.Optimal process improvement

The main blocks of6 gasification
8 process were integrated
energy through Q-1, Q-2 and Q-3.
9

Energy requirements = 0

17
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

18
Simulation of methanol Syngas cleaning: Pressure swing adsorption (PSA)
synthesis from syngas
obtained through
biomass gasification Specifications:
using Aspen Plus®
V-5

2,1 2,4 2,5 0,13 0,14 PSA4

34 35
TABLE OF CONTENTS
29

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

 2.2. Syngas cleaning: Pressure

SEP-3 SEP-4
C-1
swing adsorption (PSA)
18 19 21 27
 2.3. Methanol synthesis process PSA1 33 42

 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

 3.4.Optimal process improvement MIXER-2 41 C-4

45

MIXER-3
25

Temperature and pressure of adsorbers: 35 ºC and 30 atm

19
Simulation of methanol Syngas cleaning: Pressure swing adsorption (PSA)
synthesis from syngas V-5
obtained through
34 35
biomass gasification PSA4

using Aspen Plus® 29

SEP-3 separates the char PSA1

PSA3 separates the H2
TABLE OF CONTENTS 36
26 PSA2 separates the CO
SEP-4 separates the water V-4
MIXER-4
condensed SPLIT-2
V-1 PSA2
PSA2 MIXER-2
V-3 mix the H2 and
C-2 37
 1. Introduction CO 31 38
22 23 24 32
 2. Aspen plus modelling
SEP-3 SEP-4
SPLIT-1 separates the CO to
 2.1. Gasification process C-1
achieve the H2/CO ratio
 2.2. Syngas cleaning: Pressure
18 19 21 27
swing adsorption (PSA) PSA1
PSA1 33 42
 2.3. Methanol synthesis process

 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

 3.4.Optimal process improvement

MIXER-2
MIXER-2 41
45
C-4

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

 2.3. Methanol synthesis process 18 19 21 27

PSA1 33 42
 3. Results PSA4 separates the CH4
 3.1. Gasification simulation model V-2
17 20
 3.2. Methanol synthesis simulation C-3 SPLIT-1
 3.3. Gas emission
28 39 40
 3.4.Optimal process improvement

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

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

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)

 2.3. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model R-6 simulates the metanol synthesis
 3.2. Methanol synthesis simulation

 3.3. Gas emission 2 ⇌

 3.4.Optimal process improvement
3 ⇌
Catalyst: Cu/ZnO

METSEP separates the crude methanol, gas-phase and impurities

23
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

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

 2. Aspen plus modelling Compound Experimental composition * Predicted composition

 2.1. Gasification process (vol.% db) (vol.% db)
 2.2. Syngas cleaning: Pressure
swing adsorption (PSA)
H2 45-55 57
 2.3. Methanol synthesis process

 3. Results CO 21-25 20
 3.1. Gasification simulation model
CO2 18-22 18
 3.2. Methanol synthesis simulation

 3.3. Gas emission CH4 2-4 2,2

 3.4.Optimal process improvement
*(British Columbia University)

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

CO (vol.% dry basis)

H 2 (vol.% dry basis)
TABLE OF CONTENTS
40 40

20 20
 1. Introduction

 2. Aspen plus modelling

 2.1. Gasification process 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
 2.2. Syngas cleaning: Pressure
S/B mass
S/B ratio
(ratio) S/B
S/Bmass ratio
(ratio)
swing adsorption (PSA)
80 80
 2.3. Methanol synthesis process c) 800 ºC d) 800 ºC
CO2 900 ºC 70
CH4 900 ºC
 3. Results 1000 ºC 1000 ºC
60 60
 3.1. Gasification simulation model
CO 2 (vol.% dry basis)

CH 4 (vol.% dry basis)

 3.2. Methanol synthesis simulation 50

 3.3. Gas emission

40 40
 3.4.Optimal process improvement
30

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

CO (vol.% dry basis)

H 2 (vol.% dry basis)
TABLE OF CONTENTS
40
CO y CH4 40

20 20
 1. Introduction

 2. Aspen plus modelling

 2.1. Gasification process 0
Water Gas: ⇌ 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
 2.2. Syngas cleaning: Pressure
S/B mass
S/B ratio
(ratio) S/B
S/Bmass ratio
(ratio)
swing adsorption (PSA)
80 Water gas shift: 80 ⇋
 2.3. Methanol synthesis process c) 800 ºC d) 800 ºC
CO2 900 ºC 70
CH4 900 ºC
 3. Results
 3.1. Gasification simulation model
60 Steam reforming: 1000 ºC
60 ⇌ 3 1000 ºC
CO 2 (vol.% dry basis)

CH 4 (vol.% dry basis)

 3.2. Methanol synthesis simulation 50

 3.3. Gas emission

40
Boudouard: ⇌2 40

 3.4.Optimal process improvement
30

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 mole ratio

TABLE OF CONTENTS
6 9 ⇌6
40
2.5

H2/CO = 2,4

20
 1. Introduction 2.0

 2. Aspen plus modelling

 2.1. Gasification process
0 1.5
 2.2. Syngas cleaning: Pressure 0.5 0.6 0.7 0.8 0.9 1.0 0.6 0.8 1.0
0,9
swing adsorption (PSA) S/BS/B (ratio)
mass ratio S/B mass ratio
 2.3. Methanol synthesis process 50
800 ºC
 3. Results CH3OH 900 ºC
 3.1. Gasification simulation model 1000 ºC
40
 3.2. Methanol synthesis simulation

 3.3. Gas emission

CH3OH (kg/h)

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

Gas composition (vol.% dry basis)

CO2
40
CH4
60
TABLE OF CONTENTS C6H6

CH 3OH yield (kg/h)

CH3OH
30 H2, CO and CH3OH
40

 1. Introduction 20
CO2, CH4 and C6H6
 2. Aspen plus modelling
20
 2.1. Gasification process 10

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)
0 0
 2.3. Methanol synthesis process 800 900 1000
3.5
 3. Results Temperature (ºC)
800 ºC
 3.1. Gasification simulation model 900 ºC
1000 ºC
 3.2. Methanol synthesis simulation
3.0
 3.3. Gas emission

H2/CO mole ratio

 3.4.Optimal process improvement

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

 2. Aspen plus modelling Water gas shift: ⇋

 2.1. Gasification process
Exothermics
 2.2. Syngas cleaning: Pressure
swing adsorption (PSA) Tar forming: 6 9 ⇌6
 2.3. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

H2, CO and CH3OH
 3.4.Optimal process improvement

Temperature = 900ºC CO2, CH4 and C6H6

30
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

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

 1. Introduction Pressure and temperature influence on metanol production

 2. Aspen plus modelling
 2.1. Gasification process

 2.2. Syngas cleaning: Pressure

50
swing adsorption (PSA)
220 ºC CH3OH Pressure
 2.3. Methanol synthesis process 240 ºC
260 ºC
 3. Results 40
CH3OH production (kg/h)

 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation 30 Working at high pressures:

 3.3. Gas emission

 3.4.Optimal process improvement

• Operational risks
20

• High costs
10
• Human danger
0
40 50 60 70 80
Pressure (atm)

Industrial plants 55 atm

33
Simulation of methanol Pressure and temperatura influence on metanol production
synthesis from syngas
obtained through
P= 55 atm
biomass gasification
using Aspen Plus® CH3OH Temperature
32 kg/h
TABLE OF CONTENTS

 1. Introduction
9 kg/h
 2. Aspen plus modelling
 2.1. Gasification process

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis 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

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

34
Simulation of methanol Capture and gas emissions
synthesis from syngas
obtained through
biomass gasification
using Aspen Plus® Capture:

TABLE OF CONTENTS  80% CO2

 95% CH4
 1. Introduction

 2. Aspen plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis process

 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

 3.4.Optimal process improvement

 Low NH3 and H2S emission

36
Simulation of methanol synthesis from syngas obtained
through biomass gasification using Aspen Plus®

TABLE OF CONTENTS
 1. Introduction

 2. Aspen Plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure swing adsorption (PSA)

 2.2. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4. Optimal process improvement

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

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model
 3.2. Methanol synthesis simulation
 3.3. Gas emission
 3.4.Optimal process improvement
 Combustion chamber:
H2 reacted with O2 to produce H2O
and decrease CO2 formation.

Caudal másico
 NH3 and H2S were kept

Caudal másico (Kg/h)

(Kg/h)

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

Gasification process PSA3

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

 2.2. Syngas cleaning: Pressure 1

R-1 3 4

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

 2.3. Methanol synthesis process

HEATX-2 28
14 13 V-6
MIXER-2 41 C-4 COOLER-1 METSEP
R-5 45
47 49 50
5

 3. Results 7
HEATX-1
MIXER-3
46
R-6
25 53
6 8
 3.1. Gasification simulation model
9

 3.2. Methanol synthesis simulation

 3.3. Gas emission

 3.4.Optimal process improvement

48

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

 2. Aspen plus modelling

 2.1. Gasification process

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)
Spanish Ministry of Education, Culture and Sports for FPU grant
 2.3. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model
Thanks you very much for your attention!
 3.2. Methanol synthesis simulation

 3.3. Gas emmission

 3.4.Optimal process improvement

39
 6th International Conference on
Sustainable Solid Waste Management
(NAXOS 2018)

Simulation of methanol synthesis from

syngas obtained through biomass
gasification using Aspen Plus®
M. Puig-Gamero, J. Argudo-Santamaria, J. L. Valverde, P. Sánchez, and L. Sanchez-Silva

Department of Chemical Engineering, University of Castilla-La Mancha, Spain

*maria.puig@uclm.es
Naxos Island, 15th June 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

was 900ºC and a S/B mass ratio of 0.9.

- 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

the gasification process.

41 42
REACTING AND
GAS ANALYSIS
Thermogravimetric analysis:
UNITS Thermogravimetric analyzer TGA-DSC 1 (METTLER Toledo)

Mass spectrometric analysis:

Mass spectrometer Thermostar-GSD 320/quadrupole mass analyzer
(PFEIFFER VACUUM)

Mineral content determination:

Inductively coupled plasma (ICP) (Liberty Sequential. Varian)
CHARACCTERIZATION

Proximate analysis:
Standard Procedure Volatile matter (VM): UNE-EN 15148
Ash content (AC): UNE-EN 14775
Moisture content (MC): UNE-EN 14774

Fixed Carbon*dab = 100 – (VM+AC+MC)*dab

Ultimate analysis:
CHNS/O analyzer (LECO CHNS-932)
O*dab= 100-(C+H+N+S)*dab

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

Primary process: Optimization of gasifier and operating conditions

Removal
 1. Introduction
Secondary process: Catalytic process. DOLOMITE
 2. Aspen plus modelling
 2.1. Gasification process

 2.2. Syngas cleaning: Pressure

swing adsorption (PSA)

 2.3. Methanol synthesis process

 3. Results
 3.1. Gasification simulation model

 3.2. Methanol synthesis simulation

 3.3. Gas emission S/B= 0.6

 3.4.Optimal process improvement
T = 800 ºC

→ 2 6 →3 12

3 →2
31