Simulation of Biomethanol Production from Green Syngas Through
Sustainable Process Design
Omar Y. Abdelaziz
1
, Mamdouh A. Gadalla
2
and Fatma H. Ashour
1
1
Department of Chemical Engineering, Cairo University, Giza 12613, Egypt
2
Department of Chemical Engineering, the British University, Cairo11837, Egypt
Keywords: Biomethanol, Process Simulation, Process Design, Rice Straw, Biorefinery.
Abstract: Methanol is considered an alternative energy source due to its various applicability and high octane. As a
fuel, it releases low emissions, and shows high performance and low risk of flammability. Egypt faces a
high population growth rate, which implies an increase in the agricultural production. At present, the
agriculture waste materials are burned leading to major environmental problems besides the loss of potential
resources. This work builds a design methodology for producing biomethanol fuel from green syngas. The
design methodology is based on rigorous model using the Aspen HYSYS® simulation software, and takes
into account both economics and environment. As a case study, the design methodology is applied to design
a plant that converts rice straw in Egypt into methanol. The raw materials for this process are selected from
the major regions in Egypt producing rice straw with a total capacity of 1.6 million tons per year. These
local regions are Kafr el Sheikh, Dakahlia and Sharkia governorates, located in northern part to Cairo. The
methanol produced from the process is estimated to be around 156 thousand metric tons per annum. The
process equipment capital costs are estimated to be 498 million dollars with total energy costs of 17 million
dollars per annum. On the other hand, an annual revenue of 537 million dollars is obtained. The simulation
model obtained in this study can be applied to any syngas coming from other gasification processes with
different biomass feedstock. In addition, the model provides a robust basis for further studies of process
integration leading to innovative and sustainable solutions to climatic and energy problems.
1 INTRODUCTION
Major environmental and economic problems as
global warming, climatic changes, and oil prices
fluctuating are caused by fossil fuels. These facts
drive the energy sector towards finding sustainable
and innovative solutions. Biofuels arose as an
effective alternative for the fossil fuels as a cleaner
renewable source of energy with fewer
environmental impacts. Thinking of new process
designs to reach sustainable goals is a challenge that
all industries must face.
Second generation biofuels derived from
lignocellulosic feedstocks are promising alternative
for energy that concerns environment (Damartzis
and Zabaniotou, 2011). Many innovative
technologies such as gasification and Fischer–
Tropsch synthesis created many opportunities for
thermochemical conversion of biomass into biofuels.
Gasification is considered as ancient as combustion,
although it is less developed since combustion is
dominant in its applications. Recently, the
significance of gasification has grown up to convert
biomass into gas or liquid valuable materials. The
motivating factors of gasification can be
summarized as its renewability, environmental
consciousness and sociopolitical benefits (Basu,
2010). As a result, different gasifier designs
differing in the biomass pyrolysis and tar cracking
mechanisms have been evolved. Researchers have
conducted different experimental setups and
changed various parameters via gasification on
different biomass feed stocks (Mertzis et al., 2014;
Olgun et al., 2011; Patil et al., 2011; Simone et al.,
2013; Xie et al., 2014).
It was stated by the Egyptian Central Agency for
Public Mobilization and Statistics (CAPMAS, 2012)
that the rice production in Egypt rose
31.2% in the
year 2011 reaching some 5.6 million tons, compared
with 4.3 million tons for 2010. Experts say that such
a production will generate more than 30 million tons
of waste per year. This will consequently lead to
major environmental problems as these wastes are
currently burned leading to what is called the black
677
Abdelaziz O., Gadalla M. and Ashour F..
Simulation of Biomethanol Production from Green Syngas Through Sustainable Process Design.
DOI: 10.5220/0005002906770684
In Proceedings of the 4th International Conference on Simulation and Modeling Methodologies, Technologies and Applications (SIMULTECH-2014),
pages 677-684
ISBN: 978-989-758-038-3
Copyright
c
2014 SCITEPRESS (Science and Technology Publications, Lda.)
cloud phenomena experienced in Egypt recently.
Finding solutions to such problem is a critical issue.
Methanol is considered as a liquid fuel that can
be used in fuel cells and as a chemical feed-stock in
addition to its use as a transportation liquid fuel
(Yang et al., 2004). Most methanol plants built all
over the world use natural gas for generation of
syngas to produce methanol. The scope of process
system engineering is increasing so as to achieve
more sustainable processes (Jegatheesan et al.,
2009). Design of plants converting biomass to
methanol is challenging; most existing design
approaches are just in the form of simulations to the
process and have not been commercialized yet. Few
researches (Abu Bakar et al., 2013; Bula et al., 2012;
Kumabe et al., 2008; Shabangu et al., 2014) have
simulated the methanol production from different
biomass feed stocks. The syngas required to produce
biomethanol could be attained from the process that
includes pre-treatment of the biomass, gasification
according to the biomass physical characteristics,
cleaning of the gas produced, and the final methanol
catalytic synthesis (Minteer, 2006). It is obvious that
tackling the environmental problems of biomass
residues is essential and requires design
methodologies and procedures.
The objective of this work is to build a design
methodology for producing methanol from biomass.
The new design methodology is rigorous simulation-
based and applicable to methanol production from
any source of biomass. Aspen Hysys simulator
(Hysys User Guide, 2004) is adopted to model the
production plant. The simulation model achieved in
the study is robust and can help for further
investigation studies, such as optimization, process
integration, dynamic control, sensitivity analysis,
scaling, etc. As a case study, the design
methodology is applied to design a plant that
produces methanol from rice straw in Egypt.
2 DESIGN AND SIMULATION
METHODOLOGY
Conventionally biomethanol is produced from the
synthesis gas that is rich in hydrogen and carbon
monoxide through a heterogeneous catalysis
mechanism. Figure 1 shows the ordinary process
flow schematic diagram for biomethanol production
from biomass gasification (Ohlstrom, 2001). In this
study some critical points are identified during the
process design: The low purity of H
2
in the waste
gas stream seems to be unsuitable for reuse. Thus,
purification of this H
2
stream can be considered.
Also, the CO
2
circulating in the process demands
high amount of energy. This calls for removal from
the syngas stream. Further, the presence of water
circulating in the process leads to high energy
wastage. This also calls for purification of the
syngas stream. Hence, the following structural
modifications are proposed based on the above
recommendations: installation of a separation unit to
improve the H
2
purity in the waste gas stream and
purification of the syngas feed stream by removing
CO
2
and water components.
In this design the Aspen HYSYS Ver. 7.3
process simulator is used to model the given
process. Other process simulators can be employed
such as Aspen Plus, PRO/II, VMG, etc. The given
process is simulated on the basis of converting a
certain amount of syngas into green methanol fuel.
In this stage the feed streams are specified, and the
flow process design is described, further mass and
energy balances are performed. Finally individual
process equipments are designed. As a result of this
stage, temperatures, pressures, and flows of all
process streams and products are obtained in
addition to equipment dimensions, and heat and
cooling duties.
Process economics is considered in the
proceeding stage. Equipment capital costs, total
utilities costs, and raw material costs are estimated.
Finally the total profit is calculated. CAPCOST, a
powerful tool for evaluating full process economics
and profitability is used (Turton et al., 2009). In this
stage it is easy to assess the process feasibility.
After reaching a base case design with the
associated economics, the environmental
implications of the process is to be considered
consciousnessly. In this stage of design emissions
from the process is to be estimated also the potential
characterization of waste water is to be considered.
The aim of this stage is to reduce the local and
global CO
2
emissions in addition to minimizing the
release of harmful compounds from the process to
the atmosphere.
While the environment is considered in the
earlier phase, the energies of all process streams are
to be integrated with the objective of minimizing the
energy demands of all the process. Pinch Analysis
and heat integration principles are to be applied to
attain the best heat exchanger network (HEN) where
minimum amount of utility requirements are
required. An ideal solution of this phase is an
optimum heat integrated process.
Either the base case design or the environmental
based design is to be optimized by manipulating the
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operating and design parameters of the process to
minimize multiple objectives. These optimization
objectives may include the total costs, utility
requirements, CO
2
emissions or any other objective.
The sections below detail the new design
methodology.
Figure 1: Schematic for biomethanol production from
biomass.
2.1 Simulation Procedure and
Algorithm
Figure 2 summarizes the simulation algorithm for
biomethanol production from biomass. As shown in
the figure the algorithm illustrates the main phases
of simulation design. It starts by the biomass
gasification reaching the green syngas production,
and then follows to the process simulation part
through the model validation, analysis, costing and
optimization. More details will be presented in the
following sections.
Figure 2: Simulation algorithm for methanol production
from biomass.
2.2 Syngas Adjustment Stage
Methanol is one of the most important basic
chemicals that can be produced using synthesis gas
(a mixture of CO, CO
2
and H
2
). The typical
methanol process involves a reaction of syngas in
the presence of metal catalyst followed by
purification of the methanol. Here the feed is syngas
produced from biomass gasification which totally
differs from the syngas coming from the natural gas
in properties and conditions. The high percentage of
nitrogen found in the gas has to be separated first,
and then the syngas is sent to the reformer to convert
the existing methane to extra syngas. Water gas shift
reactor adjusts the reactor feed requirements by
providing the required amount of hydrogen through
the water gas shift reaction. Water and CO
2
are
removed, and then the make-up stream is ready to be
mixed with the recycle stream, and further fed to the
reactor. In one pass only, thermodynamic
equilibrium is reached before achieving 50%
conversion of the synthesis gas, therefore, after
methanol and water are condensed out and removed,
the remaining synthesis gas must be recycled to the
reactor. Adjustment stages are discussed in this
section.
2.2.1 Nitrogen Separation
Pressure swing adsorption (PSA) can be a cost-
effective method of onsite nitrogen generation for a
wide range of purity and flow requirements. So it is
used to separate 97.5 mole% of nitrogen that exists;
separation is assumed to be ideal in which the
separated nitrogen stream is pure nitrogen.
2.2.2 Methane Reformer
Since most biomass gasifiers produce significant
amount of methane and small amounts of other light
hydrocarbons, it is wise to use them to produce extra
amount syngas through steam reforming. The
reaction is carried out according to the following
highly endothermic reaction:
CH
H
O↔CO3H
(1)
Acceptable conversion is achieved only at
relatively high temperatures (>800°C), conventional
steam reformers operate at temperature of up to
1000°C. Since the total number of moles of gas
increases significantly throughout the reaction,
reforming is also favored at lower pressures (1-
3.5MPa). Methane conversion in biomass systems
varies from 60-90% using Ni-based catalyst. Steam
is required not only for promoting the reaction but
START
END
O
p
timization
Process
Simulation
Biomass Feedstock
(Rice straw, Rice husk, Wood, etc.)
Gasification Model
Model
Validation
Anal
y
sis of Results
Costing
Yes
No
S
y
n
g
as
Air
CO
2
Biomas
N
2
Distillation
Pretreatment
Steam
reformed
Gasification
Methanol S
y
nthesis
Removal of
CO
2
, H
2
O,
and H
2
S
WGSR
HRSG
PSA
Steam
O
2
Ash
O
2
SimulationofBiomethanolProductionfromGreenSyngasThroughSustainableProcessDesign
679
also to prevent carbon formation (coking), for that
steam to carbon ratio are recommended to be 3:1
which is achieved in the model.
2.2.3 Water Gas Shift Reactor
Syngas out of the reformer is then cooled before
being sent to a shift reactor that converts CO to H
2
via the water-gas shift reaction:
CO H
O⇄CO
H
(2)
For methanol synthesis, the shift reactor is used
to increase H
2
to CO ratio which is found to be
essential in this process. Since the shift reaction is
exothermic, higher conversion levels are achieved at
lower temperatures. The reaction nearly proceeds to
completion with modern catalysts (ZnO-CuO) at
temperatures as low as 200°C. In this process, only
60% conversion is required to achieve the purpose
of having proper hydrogen amount in the make-up
gas. The water gas shift reactor (WGSR) operates at
200°C, design parameters is adjusted to reach the
required conversion. In this model no steam was
added to the shift reactor, the amount of steam in the
feed was already sufficient due to the extra steam
added in the reformer.
2.2.4 Water Removal
To reduce the water content in the syngas stream, a
condensation-separation process was proposed. At
pressure of 13 bar cooling the water to 110
o
C is
necessary so as to condense only the water rather
than other compounds flowing in the stream.
2.2.5 CO
2
Removal
The CO hydrogenation reaction is considered to be
the primary reaction in methanol formation. CO
2
hydrogenation reaction results in the loss of some of
the hydrogen as water that is why in ideal
circumstances there would be no CO
2
in the feed.
However small amount of CO
2
(1-2%) acts as a
promoter of the primary methanol synthesis and
helps maintain catalyst activity. As a matter of fact,
the use of membrane process for CO
2
removal from
syngas has been commercially available (Membrane
Technology & Research, 2010a). Using such
technology, CO
2
recovery with up to 80% at 95%
purity on volume basis can be obtained. In this
process 85% of the CO
2
found in the gas stream out
of the separator is assumed to be removed.
2.2.6 Compression
After leaving the carbon-dioxide membrane, dry
syngas enters the syngas compressor at 13 atm
where it is compressed to 50 atm, the pressure at
which the proposed low pressure Lurgi methanol
synthesis reactor operates. Inter-cooling appears
between the two compressors so as to decrease the
net power consumption.
2.2.7 Pre-reactor Heating
After the make-up stream in compressed and mixed
with the recycle stream, and before sending the
syngas to the methanol reactor, it is heated close to
the temperature in the methanol reactor (260
o
C).
This is necessary as temperatures lower than this
reaction temperature has the problem of low
equilibrium constants (slow reactions). Also catalyst
activity drops off sharply below 230°C (Katofsky,
1993).
2.3 Reaction Modeling
Feed syngas enters methanol reactor at temperature
of 260
o
C and pressure of 50 atm in the presence of
metal catalyst most common commercially is the
(Cu–ZnO–Al
2
O3). Two successive reactions take
place in the reactor:
CO 2H
⇌CH
OH
(3)
CO
3H
⇌CH
OH H
O
(4)
Since all of the above reactions are exothermic
reactions, heat removal from the reactor is a critical
issue. Water gas shift reaction may slightly occur
during the methanol synthesis which is ignored in
this design. Single pass conversion in the methanol
reactor ranges from 40 to 60 percent of CO and CO
2
.
To increase the conversion, the un-reacted gases
after methanol condensation are recycled back to the
reactor, in which up to 99.5 percent overall
conversion can be achieved (Vaswani, 2000).
Although modern methanol synthesis catalysts are
highly selective, some side reactions are possible,
such as:
2CH
OH CH
OCH
H
O
(5)
CO H
⇄CH
O
(6)
2nH
nCOC
H

OH n 1H
O
(7)
The formation of these species is limited by the
selectivity of the catalyst and the kinetics at the
reactor conditions. For simplicity, this model
considers dimethyl-ether as the only side product in
the system; the amount of dimethyl-ether produced
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is typically equal 2% wt of the methanol produced.
The make-up gas should be slightly hydrogen rich to
compensate the hydrogen consumed by reactions
and also that is lost in the purge stream. The quantity
of hydrogen in the make-up gas stream must satisfy
the stoichiometry of both methanol synthesis
reactions, and this could be typically determined by
the R-value which should be 2 or more:
R
H
CO
CO CO
2
(8)
Due to hydrogen build up, the actual combined
R-value (make-up + recycle) reached more than 4 in
this model. Table 1 summarizes all reactors data.
2.4 Product Purification
Stream out of the reactor is cooled to 45°C. CH
3
OH,
DME and H
2
O condense out of the product gases. It
is assumed that a complete condensation of these
components takes place. Other components entering
the condenser leave as gases. Uncondensed gases
like CH
4
, N
2
, un-reacted CO, un-reacted CO
2
and
un-reacted H
2
are removed in a flash drum at the top
as a purge.
Then part of it (molar recycle ratio
approximately 4 of the makeup feed) is recycled
back to the reactor and the other part is used to
produce the pure hydrogen. The liquid fraction is
taken out at the bottom and it mainly consists of
CH
3
OH, DME and H
2
O. A membrane process for
H
2
purification has also been widely used in the
refineries. The process has been claimed to be able
to recover up to 95% of H
2
at 99% purity on volume
basis (Membrane Technology & Research, 2010b).
Hence, these alternatives were implemented in the
HYSYS model of the base case process simulation.
In pre-distillation pressure relief valve, the pressure
of the outlet stream from the condenser is reduced
from 41.4 atm to 11.2 atm for the removal of
uncondensed gases and to allow the separation of the
DME tower at this operating pressure. Liquid out
from the separator post the reactor enters a relief
valve in which the pressure is reduced from 41.4 atm
to 11.2 atm for the removal of uncondensed gases
and to allow the separation of the DME tower at this
operating pressure feed to the distillation column is
at the boiling point of DME (45
o
C) at 11.2 atm. It is
assumed that complete recovery of DME takes place
in the top product. Water and methanol are assumed
to leave as bottoms of DME distillation column at
45
o
C. Fifteen trays, and with reflux ratio of 20 are
able to perform the distillation process. The bottom
exit from the DME distillation column consists of
CH
3
OH and H
2
O at 11.6 bar and 157.2
o
C, the
pressure of this stream is first reduced to 3.4 atm
(the pressure at which methanol distillation occurs),
and then it is cooled to 45°C.The exit stream from
pre-methanol distillation column valve enters
methanol distillation column at 45
o
C and 3.4 atm. It
is assumed that 99.9 percent recovery of methanol in
top product takes place producing 99.9 percent pure
methanol on weight basis. Water with a trace
quantity of methanol is recovered at the bottom.
Forty-five trays, and with reflux ratio of 1.5 are able
to perform the distillation process.
The above algorithm and simulation procedure
will be applied to address a local environmental
problem in north Egypt. A case study will be
considered in the following section.
3 CASE STUDY
The raw materials for the case study are selected
from the major regions in Egypt producing rice
straw with a total capacity of 1.6 million tons per
year. These local regions are Kafr el Sheikh,
Dakahlia and Sharkia governorates, located in
northern part to Cairo (Bakker, 2011). After
gasification, the amount of volatile matter which is
mainly syngas represents about 60% of the biomass
feed (Basu, 2010), so that the synthetic gas feed to
methanol synthesis process (from gasifier) can be
calculated to be 0.96 million tons per year. In this
study 300 operational days are assumed per year.
Table 2 and Table 3 show an approximation for the
Table 1: Reactor simulation data.
Reaction Reactions equations Conversion (%) Reactor
Steam Reforming CH
4
+H
2
O CO+3H
2
85 Steam Reforming
WGSR CO+H
2
O CO
2
+H
2
60 WGSR
CO to Methanol CO+2H
2
CH
3
OH 50
Methanol Reactor
CO
2
to Methanol CO
2
+3H
2
CH
3
OH+H
2
O 50
DME formation 2CO+4H
2
CH
3
OCH
3
+H
2
O 5
SimulationofBiomethanolProductionfromGreenSyngasThroughSustainableProcessDesign
681
syngas compositions and conditions coming from
the gasification process respectively (Patil et al.,
2011). It is assumed to use Peng-Robinson Fluid
package which is commonly used with
petrochemical compounds, but it is not
recommended by HYSYS when using dimethyl-
ether. So the SRK-Twu Fluid package is adopted in
the model instead.
Table 2: Syngas composition (Mole percent).
Component Mole %
CO 22.2
Hydrogen 10.9
Methane 4.5
CO2 11.5
Nitrogen 50.9
Table 3: Syngas conditions.
T (°C) 866
P (atm) 1
Mass Flow rate (kg/hr) 133,333
4 RESULTS AND DISCUSSION
Figure 3 shows the process flow diagram designed
in this study for methanol production from synthesis
gas generated from the biomass gasification process.
The figure shows the most important stages made on
the gasifier syngas so as to reach the desired
biomethanol product, such as the methane reforming
reactor, the water gas shift reactor and the methanol
synthesis reactor. The process is rigorously
simulated starting from the syngas adjustment stage
and reaching to the final product purification stage.
This simulation model provides a robust basis for
further studies of process integration, environmental
assessment, and optimization studies leading to
innovative solutions to the energy scarcity problems.
Moreover, it can be applied on any type of biomass
reaching to liquid methanol production as a
sustainable model of a biorefinery. Table 4 shows
the methane reformer steam conditions used in the
process necessary to convert the methane to syngas
with required R-value. The flow rate is adjusted so
as there is no need to enter steam in the WGSR.
Also, the pressure and temperature conditions are set
favoring the methane reforming reaction.
Table 4: Reformer steam conditions.
Flow rate (kgmole/hr) 5770
P (bar) 15
T (°C) 198.5
Economic analysis has been performed for this
case with the aid of CAPCOST tool. The methanol
obtained is estimated to be around 156 thousand
metric tons per year. The process equipment capital
costs are estimated to be 498 million dollars with
total utilities costs of 17 million dollars per year. On
the other hand, revenue of 537 million dollars is
obtained per year. Table 5 shows a summary of the
costs including capital and energy costs. It is
obvious that the operating costs of the process are
much lower than its raw material costs. This can
show an indication of the profitability of the process.
Table 6 shows a summary of the annual revenue
obtained from each product production.
Table 5: Summary of costs.
Total Cost of Equipment (MM$) 498
Annual Utilities Cost (MM$/Yr) 17
Cost of Raw Material (MM$) 41.5
Cost of Land (M$) 875
The annual revenue achieved from the methanol
which is the main product is estimated to be 81
million dollars. This value covers both the annual
operating and raw material costs. Also, the high
quantity of nitrogen can be useful if it is sold to
nearby plant that can use it in liquefaction purposes
as an example. Integration between hydrogen and
nitrogen products to produce ammonia (NH
3
) can be
useful as ammonia serves as an essential precursor
to food and fertilizers industries. Finally Figure 4
shows the cash flow diagram for this case
illustrating the tremendous increase in the project
value after around 4 years from the project life
implementation.
Table 6: Summary of revenues.
Material
Name
Price
($/kg)
Flowrate
(kg/h)
Annual
Revenue
(MM$)
Methanol 0.52 21593 81
Nitrogen 0.85 69972 428
Hydrogen 3.50 670 17
Carbon
Dioxide
0.02 50980 7.5
Dimethyl
Ether
0.68 655 3.5
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-1,0
0,0
1,0
2,0
3,0
4,0
5,0
6,0
012345678910111213141516171819202122232425
Project Value (millions of dollars)
Project Life (Years)
Figure 3: Biomethanol production process flow diagram.
Figure 4: Cash flow diagram (Acquired from CAPCOST).
5 CONCLUSIONS
In the present study, a design methodology was
developed for producing biomethanol out of the
green syngas coming from the biomass gasification
route. The design methodology is rigorous
simulation-based and can be applied to any source of
biomass for methanol production. The design
methodology was applied to design a plant that
produces methanol from rice straw in Egypt as a
case study. In addition, the economic analysis for the
case study was investigated. The simulation model
achieved is robust; Hence, as a recommendation
further investigation studies, such as optimization,
process integration, dynamic control, sensitivity
analysis, scaling, etc. have to be performed.
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