Introduction

Across this report, the major aim is to synthesise a design that is best suited to the needs that we
are required to achieve, which is to produce bio-methanol. We carefully analyse the varied
feedstock that we have the choice of using. We then also follow the basic steps into the design
synthesis. We justify all the equipment used and the operating conditions. We then compile all
the collected data and henceforth produce a complete process block diagram describing the
whole process.
Feedstock
The chosen biomass being palm oil gives us the choice of three separate feedstock. We have the
empty fruit bunch, the fiber and the shell. The following table gives us a simple comparison of
the three.
Table 1. Comparison of Palm Oil Material Analysis (A. Bula, 2012)
Mat

Energy(kJ/kg
)

Volatile
Ash (%)
Carbon
Sulfur
Humidity
Matter
Fixed (%) Total (%)
Initial
(%)
(%)
EFB
19599
71.9
5.3
16.1
0.12
60
Fiber
18711
70.7
3.3
18.6
0.15
39
Shell
21490
71.2
2.1
19.3
0.08
19
The majority of companies tend to use the empty fruit bunch as their chosen biomass. However,
based on this analysis we have chosen the palm shell as our chosen biomass. Not only is the
energy per kilogram higher, the use of the shell reduces the costs we have when it comes to the
conversion of biomass to syngas. The processing of the feedstock has a considerably lower cost.
For the biomass to be processed in a gasifier, the humidity of the feedstock must be between 1015%. As you can see, the information in the table has highlighted the fact that the initial humidity
of the shell is as low as 15%. This means the drying time can be significantly reduced for the
processing of the biomass whereas the other two materials have significantly higher water
content. This would mean a greater expenditure for the drying cost.

Table2. Weight Percentage of Palm Material

Material
EFB
Fiber
Shell

Weight (%)
41
32
27

The average weight of an oil palm fruit bunch is between 15 and 23 kg. As you can tell, the
greatest component by weight percentage is the empty fruit bunch. This is why most tend to use
the EFB as their source of biomass from oil palm. However even though, this is the case, the
difference in weight with a maximum weight fruit bunch is about 3 kgs. However, the energy per
kg of biomass is greater for the shell than the EFB, so this fact can be easily overcome.

We have also listed the chemical characteristics of the of the oil palm kernel shell.

Table3. Composition of Oil Palm Kernel Shell (Ndoke, 2006)

Property
Chemical

Structural Carbohydrates

Parameter
C (%)
H (%)
O (%)
N (%)
S (%)
Cl (ppm)
Hemicellulose (%)
Cellulose (%)
Lignin (%)

Value
46.75
5.92
37.97
0.68
<0.08
84
26.18
6.92
53.85

Distribution of Chemicals for Palm Shell Gasification

Solid impurities,

Palm shell:
H, C, S, N,
O, Ash

Dryer
200C
12 bar

Crusher
25C
1bar

Gasifier
Gas cleaning
910 Raw
C 24 syngas:
bar
24
barCO2, H2O, CO, CH4, O2
H2,

Impurities, H2S, N2

Unreacted gas:

Steam reforming 900C, 30bar

Water gas shift reaction 360C
Methanol synthesis reactor 250
C 75 bar
Nickel catalyst
Removal of 40C, 30bar
30 bar
CU-Zn catalyst

Estimate composition differences for methanol separation:

Effluent from methanol synthesis reactor needs further separation into methanol.
Normal boiling points of chemicals involved are:
Component

Boiling
Point/C
64.7

Methanol,
CH3OH
Water, H20
100
Hydrogen, H2
-252.9
Carbon dioxide, -57
CO2
Carbon
-191.50
monoxide, CO
Methane, CH4
-161.5
Possible routes for separation:
A=flue gas, B=methanol, C=water
Boiling point of C B A
Route (1):

Route (2):
A

A
B

A, B

B, C
C

C
Route (1):
For the 1st route, flue gas is separated from methanol and water by using
flash drum separator. Methanol and water can then be separated by a
distillation column .It is easy to separate the liquid and gas phase component
by using flash drum .since the temperature differences between flue gas and
methanol is large .liquid mixture of methanol and water can be separated by
multistage distillation to improve the purity of methanol product.
Route (2):
Water is first separated out from flue gas and methanol by flash drum, where
the bottom product is water and top product is the mixture of methanol and
slue gas.

Since mixture of methanol and flue gas is in gas phase, it is hard to separate
two gas phase mixture.
So, route (1) is chosen.
Justification on the choice of Units
Drying
Drying is an essential process for production of bio-methanol from palm shell. In this process,
the biomass used is dried moisture content to lower than 10-15%. With this process, it can lower
down the heat requirement for the following gasification process and also the moisture content of
the syngas. Nowadays, there are two types of drying processes that being applied in the industry
which is flue gas drying and steam drying. The operating condition is at 12bar and 2000C for
both of the dryer. Drying process has to be held under high temperature and pressure is to ensure
that all the biomass used has been dried to the desired moisture content. Otherwise, it will cause
some corrosion on the crusher in the following process because of the high moisture content.
Flue gas drying has a higher flexibility of a variety fuel gasification, lower total investment cost
and higher net electrical efficiency as compare with steam dryer which is a simple drying
process. However there are some consequences in the flue gas drying process. Flue gas drying is
not encourage for industry purposes because of the risk of spontaneous combustion and
corrosion as compared with steam dryer which have less corrosion. The energy and electricity
consumption for fuel gas dryer to dry the biomass to 10-15% are 2.4-3.0MJ/twe and 40-100
KWh/twe . But for steam dryer, the energy and electricity consumption are much lesser than flue
gas dryer which are 2.8 MJ/twe and 40 KWh/twe. After considering the pros and cons of these
two drying process, decision is concluded by saying that steam dryer is an applicable drying
process for industry and plant used due to its less energy and electricity consumptions.
(Barannon D.C.C, 2006)

Gasification
In the production of bio-methanol process, gasification is a process that produces syngas from
the palm shell. In this process, there are two types of gasifier which are commonly used in the
methanol production; fixed bed and fluidized bed gasifiers.
In fixed bed gasifier, it can be separated into updraft and downdraft gasifier with their own
applications. In general, fixed bed gasifier required the small size raw material to centimeter
which prevents the blockage of the gas flowing through the bed and this process is very costly.
Thus, to summarize this fixed bed gasifier, it can only work for the small piece wood pieces. On
the other hand, fluidized bed gasifier are more commonly been used in the industry for biomass
gasification. Besides fluidized bed gasifier is easy to be scaled from small to large size which is
appropriate to electrical power production. In general, fluidized bed gasifier is highly suitable for
those biomass which contain high ash melting point which is between 7500C to 10000C.( Carlo
N. Hamelinck, 2001)
Thus, after comparing two type of the gasifier, the gasifier that has been chosen is fluidized bed
gasifier. This is because it can be used to process a wider range of biomass including those with

high moisture content, and appropriate electrical power production as compared with the fixed
bed which is highly selected for wood pieces process.
There are some operating conditions used for fluidized bed gasification process. The operating
condition used in this gasification process is 9100C and 24 bar but not the others that are 9820C,
34.5bar and 8630, 1.2bar. This is mainly due to the hydrogen to CO ratio produced. For 9100C
and 24bar, the hydrogen to CO ratio is 2:1 in the syngas production as compared with others
which is less than 2:1 and this 2:1 ratio is highly suitable for gasification to produce quality
syngas. . Temperature used must be more than 8000C to achieve high carbon conversion and
achieve reasonable high gasification rate in the gasification process.

Gas cleaning
Gas cleaning is a process used to remove the contaminants that are in the syngas produced that
might be harmful to the catalyst or plant by corrosion, erosion or fouling. There are two type of
gas cleaning:

Wet low temperature gas cleaning

Dry high temperature gas cleaning
Table4: Comparison between wet low temperature and dry high temperature gas
cleaning

Wet low temperature gas cleaning

Dry high temperature gas cleaning

Low operating temperature (2250C)- low

energy consumption
Used of Scrubber- Residual particulate,
reduced halogen gases and nitrogen
compound are eliminated to a large extend.
The concentration of H2S in the scrubbed
syngas is less than 30ppm and no need
further treatment of S.

High operating temperature (9000C)-high

energy consumption.
Nil used of scrubber- Nickel based catalyst
is used in this process with high efficiency
in removing tar, ammonia, and methane in
the syngas at around 9000C. However, the
sulphur that is still present in the syngas will
poison these catalyst and deactivate them.

After considering two of the cleaning process mentioned above, wet low temperature gas
cleaning is selected because of the reason mentioned above as compared with dry high
temperature gas cleaning which has more cons .(Barann onD.C.C, 2006)

Syngas conditioning
Syngas produced from gasification of biomass is composed of H2, CO2, CO, CH4. Syngas
conditioning processes are set to adjust the ratio of syngas for desired amount of methanol
production. Syngas conditioning consists of 3 continuous steps:
1. Reforming
2. Water-gas shift reaction
3. Removal of carbon dioxide

1. Reforming
There are 2 options for the selection of methane reformer reactors:

Steam methane reformer (SMR)

Autothermal reformer (ATR); which is a combination of steam reforming with partial
oxidation of CH4 reactants. Partial oxidation is undergone to supply sufficient heat to
reform the remaining reactants.

In the first step of syngas conditioning, steam methane reforming (SMR) is selected instead of
ATR due to the result of a higher H2: CO ratio production from SMR.
Methane reforming reaction is endothermic and is taken place over nickel-based catalyst:
CH4 + H2O

CO + 3H2

Steam is supplied to prevent carbon formation during the process and is used as a conversion of
H2O vapour reactant. A higher steam to carbon ratio favours a higher hydrogen to carbon
monoxide ratio and thus higher methanol production. The commercial steam to carbon ratio is
2:1 which determines the operating conditions to be 900C and 30bar. The inlet stream to
reformer is heated from 185C to 400C by a heater or heat exchanger. Additional heating is
taken place in the reformer to reach 900C.
2. Water gas-shift reactor
In water-gas shift reaction, the ratio of H2:CO is adjusted to 2:1 with the following chemical
reaction which is exothermic and is independent of pressure:
CO + H2O

CO2 + H2

There are 2 conventional shift reactions known as:

High temperature water-gas shift reactor operating at 360C by using iron oxidechromium oxide catalyst.

Low temperature water-gas shift reactor operating at 190C by using zinc oxide-copper
oxide catalyst.

Shift reactors have simple design structures and have lower capital cost especially when
compared to reformers and methanol synthesis reactors.
High temperature shift reactor is selected due to the consideration of a longer catalyst
lifespan, catalyst service life of high temperature shift is 5-7 years while low temperature shift
catalyst service life is only 3-5 years (King and Bochow Jr. 2000).
A cooler is placed after steam reformer to reduce the temperature from 900 to 360C before
entering shift reactor. The operating pressure is set to be 30bars to ensure shift catalyst to last at
least 1-3 years.

3. CO2 removal
In this process, CO2 produced from gasification and water-gas shift reaction is reduced to an
optimum H2: CO2 ratio to improve the efficiency of methanol production in the methanol
synthesis reactor.
CO2 removal from syngas can be done by various methods, which are:

Chemical absorption using amines as solvent

Physical absorption using Selexol
Physical adsorption on porous zeolites
Diffusion of CO2 due to pressure difference through thin layer membranes

Chemical absorption also known as scrubbing is selected for the following carbon dioxide
removal process due to its application on a wide range of carbon dioxide containing stream.
Chemical absorption using amines is currently existed as one of the commercially proven
technology in refining as well as in methanol production industry.
CO2 is chemically absorbed to amines operating at a lower temperature than water-gas shift
reaction, the bind CO2 and amine mixture exiting from scrubber is then strip-off at high
temperature (Beychok et al), scrubbing is applicable to operate at a wide range of pressure from
5-208bar.
Hence the selected operating condition for CO2 scrubber is at 40C, 30bar. A cooler is added
after the water-gas shift reactor to reduce the temperature of outlet gas stream from 360 to 40C
before being transported to CO2 scrubber.

Methanol Synthesis Reactor

There are mainly 2 different technologies for methanol synthesis reactor:

Low pressure methanol synthesis by using fixed bed catalyst

Liquid phase methanol synthesis by using fluidised beds and monolithic reactors
Low pressure methanol synthesis reactor is chosen in this process. Methanol is
produced in two-phase systems: reactants and products are in gas phase reacts with fixed
bed solid copper/zinc catalyst pellets.
The fixed bed catalyst is placed in the tubes where syngas stream is in contact with the
catalyst for reaction to occur:
CO + 2H2
CO2 + 3H2

CH3OH
CH3OH + H2O

Since both reactions are exothermic, cooling water is circulated on the shell of tubes or
outside the tubes to keep optimum catalyst life and reaction rate.
The methanol synthesis temperature is selected to be 250C to accommodate with the
activation of copper/zinc catalyst. A pressure of 75bar is chosen to favour the conversion
of methanol beyond equilibrium which is economically beneficial.
A compressor is added after CO2 scrubber to increase the pressure of synthesis gas from
30 to 75bar before entering methanol synthesis reactor. Further heating on syngas is done
by a heater from 85 to 250C.
Methanol, water vapour produced and the remaining unreacted synthesis gas exits the
reactor in gas phase. Further separation between methanol, water vapour and remaining
syngas is needed to obtain higher purity of methanol.

Methanol separator
Methanol and water is first separated from flue gas (CO, CO2, H2, CH4) in a flash drum. The
remaining methanol and water is then separated in a distillation column.
Methanol and water vapour produced from methanol synthesis reactor (MSR) is at 250C and
75bar. The stream out from MSR passes through two continuous pressure release valve to reduce
pressure to20bar, the stream then passes a cooler to further set the inlet temperature of flash drum
to 40C. Methanol and water are in liquid phase at 40C, which allow flue gas to be separated
upwards and outwards of the flash drum. Subsequently, the entrained liquid methanol and water
mixture is sent to distillation column operating at 75C, 1bar; where methanol is evaporated up
to the condenser and water is separated out from the bottom of the column.
Water separated from distillation column is reused at the scrubber for syngas cleaning. Methanol
is totally condensed through to give a liquid phase methanol product while is easier for storage
and transport purposes.

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Milton Beychok (2011), Amine gas treating, Available from: http://www.eoearth.org/view/article/170697/

retrieved from: 1st March 2015