Additional Examples and Exercises:

Chapter 14: Bio-Oil Refining I: Fischer-Tropsch Liquid and Methanol Synthesis

1. Description of bio-oil integrated gasification system for the production of methanol

This example assumes that the feed specification if bio-oil is known and the objective is to

synthesise a flowsheet in tandem with the establishment of basic mass and energy balances.

The current case considers a bio-oil input of 1350 MW.

Step 1

Chemical components - Table shows a list of chemicals involved in conversion of bio-oil

feed into syngas and fuel products (methanol). Bio-oil can be modelled using three chemical

constituents, i.e. acetic acid, acetol and guaiacol1-3. The methodology for selecting a set of

suitable representative components to model bio-oil can be found in chapter 10, Gibbs free

energy minimisation model.

Table 1. List of components involved in the process modelling for bio-oil integrated

gasification with methanol synthesis.

Category Component

C2H4O2 (Acetic acid)

Feed
C3H6O2 (Acetol)
(Bio-oil)
C7H8O2 (Guaiacol)

H2

H2O
Intermediate Product
CO
(Syngas)
CO2

CH4

1
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
 Gasifying medium O2

Main Product (Fuel) CH3OH

Physical property package - Since the modelling of integrated gasification system only

involves homogenous gaseous reactions and separation, the choice of suitable physical

property package is rather straightforward. Most of the common physical property package

such as Non-Random Two Liquids (NRTL) and Peng-Robinson can be applied. Most

importantly, the results obtained from the simulation should be compared and validated to

confirm the suitability of the physical property method.

Step 2 and Step 3

The three main reactors in an integrated gasification system are:

 Gasifier

 Water-gas shift reactor

 Synthesis reactor (methanol)

Select equilibrium reactor models, if there is no kinetic data available. There are four types of

equilibrium reactor models in Aspen Plus: Stoichiometric reactor (RStoic), Equilibrium

reactor (REquil), Gibbs reactor (RGibbs) and Yield reactor (RYield). Which reactor should

be chosen for gasifier, water-gas shift reactor and synthesis reactor, depends on what

information is available. In most cases, operating parameters such as temperature and

pressure are known. However, chemical reactions may not always be easy to define. Table

shows the reactor models adopted in Aspen Plus and the rationale for choosing the respective

models. It should be reminded that the choice of models is case-specific depending on the

desired level of details of the model and the need for subsequent analysis.

Table 2. The reactor models and the rationale of model selection.

2
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
 Reactor Aspen Rationale

Plus

model

Gasifier RGibbs Gasification reactions are complex (r.f. Chapter 9). REquil and

RStoic require input of chemical reactions. There are too many

possibilities of reactions and hence choosing the other two reactor

types is not practical. RYield can be chosen when the yield of

product gas is known. However, RYield model restricts the

flexibility of changing the operating conditions. Hence, RGibbs is

more suitable, so that all possible products are considered.

However, this model depends strongly on the feed specification

(see Chapter 10).

Water-gas REquil It can be assumed that only one reversible reaction occurs in the

shift reactor, i.e. water-gas shift. RGibbs can also be used when the

reactor product constituents are known. RYield is not suitable, since it

restricts the flexibility of changing the operating conditions. RStoic

is also not a choice since the conversion rate has to be specified.

Therefore, REquil is the preferred model so that H2/CO molar ratio

can be modified conveniently by altering the temperature or steam

flow rate.

Methanol REquil For modelling methanol synthesis reaction, REquil is the most

synthesis suitable choice, since the synthesis reaction involves three main

reactor reversible reactions. RStoic and RYield are not appropriate in this

case, unless the conversion rate or product yield is specified.

3
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
 RGibbs may not be a right choice, because the product is generated

according to the lowest free energy pathway and by this model,

undesired product slate may be generated.

1. Gasification modelling

RGibbs model in Aspen Plus is used to model the bio-oil gasification process (GASIFIER),

shown in Figure . Two operating parameters are needed in RGibbs, i.e. temperature and

pressure. In this case, use a temperature of 1112°C and pressure of 30 bar. HE1 is used for

preheating oxygen, use 480°C at 30 bar.

Figure 1. Gasifier model in Aspen Plus.

The bio-oil feed stream and oxygen stream are specified according to the values shown in

Table , and then connected to the RGibbs reactor as shown in Figure .

Table 3. Feed specification.

Stream BIO-OIL O2

Temperature (°C) 25 25

Pressure (bar) 1.013 1.013

Molar flow (kmol s−1) 2.10 1.14

Component Mole fraction Mole fraction

4
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
 Acetic Acid 0.109

Acetol 0.109

Guaiacol 0.109

H2O 0.673

O2 1.0

The product composition is calculated based on Gibbs free energy minimisation method

(chapter 10). By default, RGibbs considers all the components as possible products. Simulate

the reaction. The product flow rate and composition is calculated, shown in Table .

Table 4. Simulated results of product from gasification.

Stream SYNGAS

Temperature (°C) 1112

Pressure (bar) 30

Molar flow (kmol s−1) 3.1

Component Mole fraction

H2 0.307

H2O 0.251

CO 0.318

CO2 0.124

2. Syngas Conditioning Modelling

In a bio-oil integrated gasification system, the syngas should be free (or has negligible

amount) of contaminants. Syngas needs to be cooled in SYNGCOOL for the subsequent

5
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
reaction. This high level of heat can be recovered to generate steam and the steam can be

flown through to back pressure steam turbine to generate power. Water-gas shift (WGS)

reaction is important for adjusting the H2/CO molar ratio of the syngas, so that it is suitable to

be used in the synthesis reaction. The stoichiometric number for methanol synthesis, R

defined as (H2 − CO2) / (CO + CO2) should be manipulated to 2. Water-gas shift reaction is

also vital in concentrating CO2 in the outlet stream so that it can be removed by CO2 capture

unit (CO2SEP) more economically. Water removal unit (H2OREM) should be in place to

reduce the water content in the syngas, before the CO2 capture and synthesis reaction. This

unit can be modelled by using flash separators. The degree of water-gas shift, degree of water

removal as well as the degree of CO2 capture are three major factors in determining the

stoichiometric number, R and hence the yield of methanol from the synthesis reaction. After

capturing, CO2 is compressed to supercritical condition (~74 bar and 32°C), 80 bar and 35°C

are used in the modelling. This condition is needed to reduce the volume of CO2 to ease

transportation through pipeline and storage. The syngas conditioning system is shown in

Figure .

Figure 2. Syngas conditioning model in Aspen Plus.

6
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
Table shows the model specification for each unit operation in the syngas conditioning

system.

Table 5. Model specification for syngas conditioning system.

Process Aspen Plus model Input Specification

SYNGCOOL Heater Temperature = 450°C

(syngas cooler) Pressure = 30 bar

WGS REquil Temperature = 450°C

(water-gas shift Pressure = 30 bar

reactor) Reaction: CO + H2O ↔ CO2 + H2

HE2 Heater Temperature = 50°C

(WGS product Pressure = 30 bar

cooler)

H2OREM Flash2 Temperature = 50°C

(water removal) Pressure = 30 bar

CO2SEP Sep Split ratio for CO2 to storage = 0.85

(CO2 capture)

CO2COMP Compr Model: Compressor

(CO2 compressor) Type: Isentropic

Discharge pressure = 80 bar

Isentropic efficiency = 0.9

HE3 Heater Temperature = 35°C

(CO2 cooler) Pressure = 80 bar

7
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
3. Methanol Synthesis Reaction Modelling

Methanol reaction is carried out at 100 bar and 250°C. Due to the high pressure requirement

in the methanol reactor, the syngas stream (SYN3) needs to be compressed in SYNGCOMP

from 30 bar to 100 bar. After reaction, the product is a mixture of light gases (e.g. H2, CO)

and methanol. The pressure of the product stream (METPOUT) is lowered in SYNGEXP to

40 bar (minimum pressure to maintain the stream at gaseous phase since presence of liquid

has an adverse effect on the expander) and subsequently separated into gas and liquid streams

in METSEP. The liquid can be sent to distillation column for further methanol purification.

Gases can be combusted in gas turbine to generate power. Methanol synthesis reactor model

is shown in Figure .

Figure 3. Methanol synthesis model in Aspen Plus.

Table shows the model specification for each unit operation in the methanol synthesis

process.

8
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
Table 6. Model specification for methanol synthesis process.

Process Aspen Plus model Input Specification

SYNGCOMP Compr Model: Compressor

(syngas compressor) Type: Isentropic

Discharge pressure = 100 bar

Isentropic efficiency = 0.9

HE4 Heater Temperature = 270°C

(syngas cooler) Pressure = 100 bar

METHANOL REquil Temperature = 250°C

(methanol synthesis reactor) Pressure = 100 bar

SYNGEXP Compr Model: Turbine

(METHANOL product Type: Isentropic

expander) Discharge pressure = 40 bar

Isentropic efficiency = 0.9

HE5 Heater Temperature = 40°C

(product cooler) Pressure = 24 bar

METSEP Flash2 Temperature = 40°C

(methanol separator) Pressure = 24 bar

A complete integrated gasification and methanol synthesis flowsheet is shown in Figure ,

comprising a gasifier unit, syngas cleaning and processing and methanol synthesis reactor.
The stream results are shown in

Table .

9
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
Final Flowsheet and Stream Results

Figure 4. Integrated gasification and methanol synthesis flowsheet in Aspen Plus.

10
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
Table 7. Stream results for integrated gasification and methanol synthesis model.

Stream Name

Component

Mole BIO-OIL O2 SYNGAS SYN1 SYN2 WATER SYN3 SYNGIN METPOUT METGAS METLIQ CO2

Fraction

Acetic acid 0.109

Acetol 0.109

Guaiacol 0.109

H2 0.305 0.459 0.513 0.001 0.687 0.687 0.473 0.734 0.001

H2O 0.673 0.253 0.099 0.004 0.912 0.005 0.005 0.007 0.020

CO 0.320 0.166 0.185 0.005 0.248 0.248 0.073 0.112 0.003

CO2 0.122 0.276 0.298 0.082 0.060 0.060 0.102 0.138 0.037 1.000

CH3OH 0.343 0.014 0.938

O2 1.000

CH4 0.001 0.002

Molar flow 2.10 1.14 6.20 6.20 5.55 0.65 4.14 4.14 2.46 1.58 0.88 1.41

11
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
 rate

(kmol s−1)

Mass flow
303.76 131.32 435.08 435.08 387.87 47.22 164.92 164.92 164.92 63.64 101.28 222.95
−1
rate (t h )

12
Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis, First Edition.
Jhuma Sadhukhan, Kok Siew Ng and Elias Martinez Hernandez.
© 2014 John Wiley & Sons, Ltd. Published 2014 by John Wiley & Sons, Ltd.
2. Description of bio-oil integrated gasification system for the production of FT liquids

Using the same analogy as in the methanol synthesis process, develop a simulation model of

an integrated gasification and Fischer-Tropsch (FT) synthesis system. The current case

considers a bio-oil input of 1350 MW.

Step 1

Chemical components –The current model assumes that FT product consists of C1-C30

straight-chain paraffinic components. More components can be added depending on the

desired level of detail of the model. The component list is updated and shown in Table .

Table 8. List of components involved in the process modelling for bio-oil integrated

gasification with FT synthesis.

Category Component

C2H4O2 (Acetic acid)

Feed
C3H6O2 (Acetol)
(Bio-oil)
C7H8O2 (Guaiacol)

H2

H2O
Intermediate Product
CO
(Syngas)
CO2

CH4

Gasifying medium O2

Main Product (Fuel) C1-C30 straight-chain paraffins

Physical property package – Same as methanol synthesis process.

13
Step 2 and Step 3

The fundamental modelling technique for gasification is same as in the methanol synthesis

process. Only the differences in terms of conditioning the syngas composition and FT

synthesis reactor models are shown here.

Figure shows the integrated gasification and FT synthesis flowsheet, consisting of a gasifier
unit, syngas cleaning and conditioning and FT synthesis reactor. The stream results are
shown in

Table . The model specification for the integrated gasification and FT synthesis system is

shown in Table .

14
Final Flowsheet and Stream Results

Figure 5. Integrated gasification and FT synthesis flowsheet in Aspen Plus.

15
Table 9. Stream results for integrated gasification and FT synthesis model.

Component’s Stream Name

mole fraction O2 BIO-OIL SYNGAS WATER1 WATER2 SYN CO2 SYNGIN FTOUT FTLIQ RECYC FTGAS

Acetic acid 0.109

Acetol 0.109

Guaiacol 0.109

H2 0.307 0.001 0.001 0.679 0.618 0.459 0.002 0.561 0.561

H2O 0.673 0.251 0.986 0.864 0.001 0.002 0.161 0.866 0.003 0.003

CO 0.318 0.005 0.007 0.314 0.301 0.237 0.014 0.288 0.288

CO2 0.124 0.008 0.128 0.004 1.000 0.007 0.009 0.006 0.010 0.010

O2 1.000

CH4

C1-C4 paraffins 0.050 0.092 0.095 0.095

C5+ paraffins 0.022 0.042 0.113 0.043 0.043

Molar flow
1.14 2.10 6.20 0.56 0.30 3.89 1.45 8.06 6.13 1.12 4.18 0.83
−1
rate(kmol s )

16
Table 10. Model specification for integrated gasification and FT synthesis system.

Process Aspen Plus model Input Specification

CO2COMP Compr Model: Compressor

Type: Isentropic

Discharge pressure = 80 bar

Isentropic efficiency = 0.9

CO2SEP Sep Split ratio for CO2 to storage = 0.99

FTREACT RStoic Temperature = 240°C

Pressure = 25 bar

Reactions are shown in Table 11.

GASIFIER RGibbs Temperature = 1111°C

Pressure = 30 bar

H2OREM1 Flash2 Temperature = 155°C

Pressure = 30 bar

H2OREM2 Flash2 Temperature = 25°C

Pressure = 30 bar

HE1 Heater Temperature = 480°C

Pressure = 30 bar

HE2 Heater Temperature = 400°C

Pressure = 30 bar

HE3 Heater Temperature = 35°C

Pressure = 80 bar

HE4 Heater Temperature = 220°C

Pressure = 25 bar

HE5 Heater Temperature = 40°C

17
 Pressure = 25 bar

M1 Mixer Pressure = 25 bar

M2 Mixer Pressure = 14 bar

S1 FSplit Split fraction to RECYC = 0.835

SYNGCOOL Heater Temperature = 155°C

Pressure = 30 bar

VLFLASH Flash2 Temperature = 40°C

Pressure = 25 bar

WGS REquil Temperature = 400°C

Pressure = 30 bar

Reaction: CO + H2O ↔ CO2 + H2

Note: Process enhancement through recycling the FT offgas is considered in this case. In

order to result in an overall conversion of CO of 80%, discussed later, the split ratio to

RECYC on S1 is manipulated to 0.835.

Syngas conditioning modelling

The H2/CO molar ratio required in the FT reaction is approximately 2. WGS is used to adjust

the ratio. In this case, 2 water removal units are used. One of them is placed before the WGS

(H2OREM1) to manipulate the steam required by the water-gas shift reaction while the

second water removal unit (H2OREM2) is used to reduce the amount of water content in

syngas which may influence the FT reaction.

FT synthesis reaction modelling

It is assumed that only the straight-chain paraffins C1 to C30 are produced from FT synthesis

reactor. Stoichiometric reactor (RStoic) is selected for modelling FT reaction in Aspen Plus.

18
There are 30 reactions in total, inputs to the reaction list for the reactor model. The general

paraffin reaction occurs in FT reactor is shown as n CO + (2n + 1) H2 → CnH2n+2 + n H2O,

where n = 1, 2, 3,….., 30, is the carbon number. The fractional conversion of each reaction is

required in each of the reaction input. These are estimated based on the weight distribution of

each FT product obtained via Anderson-Schulz-Flory (ASF) distribution model given by wn =

αn-1 (1−α)2 n, where α the chain growth probability has a value between 0.7-0.9.

Song et al. shows an empirical model to relate α with temperature, as in Equation 11. This

creates a more flexible reactor model. α responds to different temperature and hence provides

a sensible prediction on the FT product distribution. α value in this case is 0.76, which

corresponds to the operating temperature of 240°C.

 
 B 1  0.0039T  533
yCO
 A (1)
 y H 2  yCO 
 

where

A and B are parameters with values of 0.2332±0.0740 and 0.6330±0.0420, respectively.

yCO and y H 2 denote the mole fraction of CO and H2, respectively at the inlet stream into FT

reactor.

T is the operating temperature of FT reactor, K.

Figure shows the modelling approach for estimating product distribution from FT synthesis.

19
 Fractional conversion (30 reactions)

ASPEN Plus
Syngas
Stoichiometric Reactor
(CO, H2) Simulate Product
model (RStoic) for FT
reaction distribution

T
Match

T-α correlation Assume constant α Anderson-Schulz- Product distribution Calculate fractional

Flory (ASF) conversion for each
distribution model reaction

Excel environment

Link with Excel

Figure 6. Modelling approach for Fischer-Tropsch reactor using combined Aspen Plus

simulation and Excel.

By applying ASF relation, the weight and molar distribution of each FT product are obtained.

An overall conversion of the syngas (assume CO) is assumed to be 0.8. The consumption of

CO for each reaction can be determined by solving Equation 2, where the total molar flow

rate of paraffin produced, Fp is determined using “Solver” function in Excel. Ultimately, the

fractional conversion based on CO for each reaction (CO consumption for a reaction divided

by the total CO converted, then multiplied by 0.8) is determined.

n 30
Total CO converted = y n 1
p ,n  Fp  n (2)

where

yp,n is the mole fraction of paraffin with carbon number n produced

Fp is the total molar flow rate of paraffin produced, kmol s-1

n is the carbon number

20
After specifying all the fractional conversion for each reaction into the reactor model (refer to

Table ), the simulation is thereby completed. The simulation results of the weight and molar

distribution are featured in Figure (a) and (b), respectively.

Table 11. Reaction specification in RStoic (Aspen Plus) for modelling Fischer-Tropsch

reaction.

Reaction Fractional conversion Reaction

No. (80% conversion of CO)

1 0.0405 3 H2 + CO → H2O + CH4

2 0.0659 5 H2 + 2 CO → 2 H2O + C2H6

3 0.0772 7 H2 + 3 CO → 3 H2O + C3H8

4 0.0796 9 H2 + 4 CO → 4 H2O + C4H10

5 0.0765 11 H2 + 5 CO → 5 H2O + C5H12

6 0.0704 13 H2 + 6 CO → 6 H2O + C6H14

7 0.0630 15 H2 + 7 CO → 7 H2O + C7H16

8 0.0551 17 H2 + 8 CO → 8 H2O + C8H18

9 0.0474 19 H2 + 9 CO → 9 H2O + C9H20

10 0.0403 21 H2 + 10 CO → 10 H2O + C10H22

11 0.0339 23 H2 + 11 CO → 11 H2O + C11H24

12 0.0283 25 H2 + 12 CO → 12 H2O + C12H26

13 0.0234 27 H2 + 13 CO → 13 H2O + C13H28

14 0.0193 29 H2 + 14 CO → 14 H2O + C14H30

15 0.0158 31 H2 + 15 CO → 15 H2O + C15H32

16 0.0129 33 H2 + 16 CO → 16 H2O + C16H34

21
 17 0.0104 35 H2 + 17 CO → 17 H2O + C17H36

18 0.0085 37 H2 + 18 CO → 18 H2O + C18H38

19 0.0068 39 H2 + 19 CO → 19 H2O + C19H40

20 0.0055 41 H2 + 20 CO → 20 H2O + C20H42

21 0.0044 43 H2 + 21 CO → 21 H2O + C21H44

22 0.0035 45 H2 + 22 CO → 22 H2O + C22H46

23 0.0028 47 H2 + 23 CO → 23 H2O + C23H48

24 0.0022 49 H2 + 24 CO → 24 H2O + C24H50

25 0.0018 51 H2 + 25 CO → 25 H2O + C25H52

26 0.0014 53 H2 + 26 CO → 26 H2O + C26H54

27 0.0011 55 H2 + 27 CO → 27 H2O + C27H56

28 0.0009 57 H2 + 28 CO → 28 H2O + C28H58

29 0.0007 59 H2 + 29 CO → 29 H2O + C29H60

30 0.0006 61 H2 + 30 CO → 30 H2O + C30H62

12

10
Weight distribution (wt %)

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Carbon number, n

(a)

22
 25

20
Molar distribution (mol %)

15

10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Carbon number, n

(b)

Figure 7. (a) Weight distribution of FT products predicted using ASF model. (b) Molar

distribution of FT products predicted using ASF model. Operating condition of FT reactor:

T=240°C which corresponds to α=0.76.

Sensitivity analysis of FT synthesis reaction

By adopting Equation 1, a sensitivity analysis of the effect of temperature on product

distribution can be evaluated, as shown in Figure . These figures show that higher diesel

range product can be attained at lower temperature.

23
 50

45

40
Weight distribution (wt%)

35
T = 160°C, α = 0.98
30
T = 200°C, α = 0.87
25 T = 240°C, α = 0.76
T = 300°C, α = 0.60
20
T = 400°C, α = 0.32
15

10

0
0 5 10 15 20 25 30 35
Carbon number, n

Figure 8. Variation of product distribution with temperature, with constant H2/CO molar

ratio of approximately 2.1.

Research in Bio-oil

Aston University (UK) and Dynamotive (Canada) undertakes extensive research and

development of biomass pyrolysis technologies for the production of bio-oil. The Energy

research Centre of the Netherlands (ECN) focuses on the thermochemical production routes

from biomass to syngas and FT diesel production. Other specialist biomass gasification and

pyrolysis research centres include BTG. Gasification of bio-oil and bio-oil and char (bio-

slurry) has received considerable interest and research has been carried out extensively by

FZK, Dynamotive, Future Energy and BTG.

24
Test your skills with the following questions.

1. The offgas from methanol synthesis reactor in a bio-oil integrated gasification and

methanol synthesis system is to be utilised to generate power by expanding through gas

turbine2. Using the simulation model and specification in methanol synthesis process as the

basis, develop and simulate the models for power generation within the system using a

simulation package. Estimate the power generated from the expansion of the offgas through

gas turbine. Assume a discharge pressure of 2 bar and an isentropic efficiency of 90% for the

gas turbine. A combustor is required, operating at 1200°C and 14 bar. Include a heat recovery

steam generator (HRSG) to recover the heat from the exhaust gas of gas turbine, given that

the outlet temperature from the HRSG is 100°C. Air and an auxiliary fuel such as natural gas

can be used to help the combustion of offgas. Report results appropriately, including energy

efficiency.

2. Alternative process enhancement can be done on the bio-oil integrated gasification

and methanol synthesis system2 generated in Question 1 to improve the yield of methanol, by

implementing a recycle stream within the methanol synthesis reactor. However, this will

result in a reduction in power generation. Assume that 90% of the offgas from methanol

synthesis reactor can be recycled to obtain higher yield of methanol, while 10% of the offgas

can be sent to the gas turbine power generation system. Determine the amount of methanol

and power produced and compare the results with those from the methanol synthesis process

and Question 1. The same assumptions can be made for the power generation section as in

Question 1.

3. The amount of products generated from the integrated gasification and methanol

synthesis system varies with the type of feed used. Bio-oil can come from different types of

25
biomass feedstocks. The methanol synthesis process and Questions 1-2 used the bio-oil from

poplar wood as the feedstock. Estimate the yields of products (methanol and electricity) if a

different biomass, miscanthus is used. Carry out a simulation study to investigate this, using a

once-through 1350 MW system as in Question 1. The proximate and ultimate analyses of

miscanthus are shown in Table . The bio-oil feed can be represented using acetic acid, acetol

and guaiacol. Refer to a study by Ng and Sadhukhan for the procedure of defining the feed

composition3.

Table 12. Proximate and ultimate analyses of miscanthus.

Heating Proximate analysis Ultimate analysis (wt%)

value (wt%)

(MJ kg−1) Fixed Moisture C H O

Carbon

30.7 89.9 10.1 64.2 8.3 27.5

4. The operating conditions of the gasifier impose an impact on the downstream

processes such as methanol synthesis and power generation. Carry out a process simulation

using a different operating condition of the gasifier, i.e. 1400°C and 20 bar. Report results.

Discuss the differences in terms of operating conditions.

5. CO2 capture unit is important in an integrated gasification and methanol synthesis

system in terms of removing CO2 from the system and also manipulating the stoichiometric

number for optimum yield of methanol. Comment, qualitatively, the impact on energy, yield

of product and the environment, if there is no CO2 capture unit.

26
References

1. H.S. Song, D. Ramkrishna, S. Trinh, H. Wright, Operating strategies for Fischer-Tropsch

reactors: A model-directed study, Korean J. Chem. Eng., 21, 308-317 (2004).

2. K.S. Ng and J. Sadhukhan, Process integration and economic analysis of bio-oil platform

for the production of methanol and combined heat and power, Biomass Bioenergy, 35, 1153-

1169 (2011).

3. K.S. Ng and J. Sadhukhan, Techno-economic performance analysis of bio-oil based

Fischer-Tropsch and CHP synthesis platform, Biomass Bioenergy, 35, 3218-3234 (2011).

27