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Methanol Production from Biomass
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Production of Methanol from
Biomass - PLANT DESIGN
CPD4702
By: Roseman Mphoswa
2015
Lecture: Dr James Fox

Production of Methanol from Biomass - PLANT DESIGN
Declaration
I hereby declare to have made the present work independently and

without assistance from third parties. Thoughts and quotes that I have
taken from other sources directly or indirectly are identified as such.
I hereby agree that the work can be made available to the public through
the department of Civil and Chemical Engineering of the University of
South Africa.
Roseman L Mphoswa
---------------------------
Page 1 of 111
Acknowledgments
This work has been carried out for CPD4702 for the department of Civil
and Chemical Engineering from the University of South Africa.
My gratitude goes to Dr. James Fox and the whole department, for
giving me the opportunity to be part of it and for their support and
patience.
Special consideration goes to my family, for sacrificing for me and

giving me so much. Without them nothing of this would be possible.
I want of course to thank all my friends, who were there whenever

needed without asking, helping me on difficult moments. Siviwe Cyril
Meveni, Malusi Mdletshe, Sithembiso Matthew Madela, thank you.
All Praise and Glory is to the Almighty who has guided me through this
achievement, and for the most precious and green earth he has gifted us
all.
Page 2 of 111
List of Tables
1. Table 3.1 Characteristics of gasifiers, taken from Williams et al. (1995).

2. Table 3.1 Estimated contaminant specifications for Methanol synthesis1), and
cleaning effectiveness of wet and dry gas cleaning.
3. Table 5.1: Composition of the product gas obtained from gasification of wood chips in
oxygen steam blown gasifier at 890°C and 25 bar.
4. Table 5.2: Power requirements of the methanol production process based on oxygen
steam blown biomass gasification.
5. Table 5.3 Streams table
6. Table 6.1 Equipment list
7. Table 8.1 Comparison of and k values
8. Table 9.1 Physical and Chemical Properties of fluid to be cooled using water at
ambient temperature (Methanol)
9. Table 10.1 Pump Data Sheet
10. Table 14.2.1 Half-lives (in days) of common fuel components, adapted from Howard.
11. Table 15.1 Total Capital Investment (TCI)
12. Table 15.2.1 Fixed and Variable Operational Costs
13. Table 15.2.2 Water fall illustration of the TCI
14. Table 15.3.1 CF and Cumulative CF table
15. Table 16.1 Instrument list
16. Table 17.1 Utility Requirement Schedule
Page 3 of 111
List of Figures
1. Figure 3.1: Key components in the conversion of biomass to methanol.

2. Figure 3.2 The directly heated, bubbling fluidised bed gasifier of IGT (Katofsky
1993).
3. Figure 2.3 The indirectly heated, twin bed gasifier of BCL (Katofsky 1993).
4. Figure 3.4 Three possible gas cleaning trains.
5. Figure 3.3 Methanol reactor types: adiabatic quench (left) and isothermal steam
raising (right).
6. Figure 3.4. Liquid phase methanol synthesis with three phases: slurry, gas and solid.
7. Figure 5.1 Process Flow Diagram
8. Figure 7.1 Fluidized Bed Gasifier
9. Figure 12.1 P&ID of a Circulating Fluidized Bed
List of Graphs
1. Graph 15.2.1 Water fall illustration of the TCI
Page 4 of 111
TABLE OF CONTENTS
1 INTRODUCTION ................................................................................................................ 9
2 DESIGN BASIS.................................................................................................................. 11
3 LITERATURE REVIEW .................................................................................................. 12
3.1 About Methanol ...................................................................................................... 12
3.2 Methanol Production ................................................................................................. 12
4 PROCESS DESCRIPTION ............................................................................................... 35

4.1 Drying ................................................................................................................. 35
4.2 Gasification ........................................................................................................... 35
4.3 Tar cracking .......................................................................................................... 35
4.4 Wet gas cleaning ...................................................................................................... 35
4.5 Autothermal reforming (ATR) ...................................................................................... 35
4.6 Water-gas-shift (WGS) ............................................................................................... 36
4.7 CO2 removal .......................................................................................................... 36
4.8 Methanol synthesis ................................................................................................... 36
5 PROCESS SIMULATION ................................................................................................ 38

5.1 Overview of heat and power requirements of the biomass based process ........................................ 41
6 EQUIPMENT LIST ........................................................................................................... 51

7 GASIFICATION ................................................................................................................ 52
7.1 Principles of Gasification ............................................................................................ 52
7.2 Fluidized Bed Gasifier................................................................................................ 53
8 DESIGN AND OPERATION OF THE CFB BIOMASS GASIFIER .............................. 55

8.1 Design calculations for the riser ..................................................................................... 56
8.2 Calculations for distributor plate ................................................................................... 60
8.3 Calculations for the Cyclone Separator ............................................................................. 61
8.4 Determination of optimum gasifier volume ........................................................................ 65
9 DESIGN OF A SHELL AND TUBE HEAT EXCHANGER ........................................... 70

9.1 Overview .............................................................................................................. 70
10 PUMP DATA SHEET ........................................................................................................ 77

11 CONTROL PHILOSOPHY .............................................................................................. 79
12 P&ID OF A CIRCULATING FLUIDIZED BED............................................................. 81
Page 5 of 111
13 HAZOP ............................................................................................................................... 82
13.1 Start-Up ............................................................................................................... 82
13.2 Feeding Biomass ...................................................................................................... 83
13.3 Gasifier Operation .................................................................................................... 84
13.4 Sampling .............................................................................................................. 87
13.5 Ash Removal .......................................................................................................... 87
13.6 Shutdown.............................................................................................................. 88
13.7 Startup ................................................................................................................ 88
13.8 Operation ............................................................................................................. 89
13.9 Cautionary Notes ..................................................................................................... 89
13.10 Adjusting the Air Feed Rate ......................................................................................... 89
13.11 Adjusting the Steam Feed Rate ...................................................................................... 90
13.12 Sampling .............................................................................................................. 90
13.13 Preparing for Shutdown ............................................................................................. 90
13.14 Shutdown.............................................................................................................. 90
13.15 MSDS’s ................................................................................................................ 91

13.15.1 Syngas 91
13.15.2 Methanol 92
14 OTHER IMPORTANT CONSIDERATIONS .................................................................. 94

14.1 Health & Safety ....................................................................................................... 94
14.2 Environmental ........................................................................................................ 94

14.2.1 Chemical Toxicity 96
14.2.2 Potential Safety Problems 96
14.2.3 Environmental Requirements for the Gasifier 96
15 COST ANALYSIS.............................................................................................................. 97
15.1 Total Capital Investment (TCI) ..................................................................................... 97
15.2 Fixed and Variable Costs ............................................................................................ 98

Table 15.2.1 Fixed and Variable Operational Costs 99
Table 15.2.2 Water fall illustration of the TCI 99
Graph 15.2.1 Water fall illustration of the TCI 100
15.3 Payback Period ......................................................................................................100

Table 15.3.1 CF and Cumulative CF table 101
16 INSTRUMENT LIST ....................................................................................................... 103
Page 6 of 111
16.1 Table 16.1 ............................................................................................................103
17 UTILITY REQUIREMENT SCHEDULE ...................................................................... 104

17.1 Table 17.1 ............................................................................................................104
18 CONCLUSION ................................................................................................................ 105

19 REFERENCES................................................................................................................. 107
20 APPENDICES .................................................................................................................. 108
20.1 Appendix A: Main modelling assumptions ........................................................................108
Page 7 of 111
SYNOPSIS
The importance of renewable fuel production has become significant in terms of supplying
energy carriers for the transportation sector and storing electricity overflows from intermittent
sources. Consequently, production of methanol from a biogas origin is investigated.
This design project covers a chemical process design for the production of 300000 metric tons
per year of Methanol from Biomass. Biomass is biological material derived from living, or
recently living organisms. In the context of biomass for energy this is often used to mean plant
based material, but biomass can equally apply to both animal and vegetable derived material.
The raw material to be considered in this design is Wood Chips with 50% moisture which will be
air dried to reduce the moisture content to 15% before gasification. There are several types of
gasification processes. Fluidized Bed Gasifier is used in this design.
Among several designs of gasifiers, the co-current downdraft design has been the most popular.
However, this design is suitable for units up to 250 kW capacity. Moreover, these gasifiers suffer
from shortcomings such as excessive tar formation, oxygen channeling, low carbon conversion
etc. Fuel specificity of these gasifiers is another impediment for their scale up to MW range. A
viable solution to these problems is offered by circulating fluidized bed biomass gasifier. In
general, fluidized bed processes have advantages of excellent gas-solid mixing and uniform
temperature within the bed. Presence of dense suspension provides a large thermal inventory for
flash pyrolysis of solid fuel particles. A cyclone or other type of separator is used for solid
capture and recycle in order to extend the solid residence time in the reaction zone. CFB systems
have earlier been employed for coal gasification.
CFB system suitable for biomass gasification is quite similar in principles with the coal
gasification systems. Although CFB biomass gasification is undergoing rapid commercialization,
fundamental studies, which will fill knowledge gaps in the underlying principles, are needed for
optimization and efficient scale-up. In this paper, we present a basic algorithm for design of
these gasifiers using basic hydrodynamics of fluidization and chemistry/ thermodynamics of
gasification.
Cost analysis is done and the Pay Back period is calculated using the Total Capital Investment
(TCI) and the price of Methanol. This is performed to evaluate the plant’s performance and to
see if it is a good business investment.
Page 8 of 111
1 INTRODUCTION
Methanol and hydrogen produced from biomass are promising carbon neutral fuels. Both are
well suited for use in Fuel Cell Vehicles (FCVs) which are expected to reach high efficiencies,
about a factor 2-3 better than current Internal Combustion Engine Vehicles (ICEVs). In addition
they are quiet and clean, emitting none of the air pollutants SOx, NOx, VOS or dust.
When methanol and hydrogen are derived from sustainably grown biomass, the overall energy
chain can be greenhouse gas neutral. Such a scheme could provide a major alternative for the
transport sector world-wide in a greenhouse gas constrained world (Katofsky 1993; E-lab 2000;
Ogden et al. 1999).
Methanol and hydrogen can be produced from biomass via gasification. Several routes involving
conventional, commercial, or advanced technologies, which are under development, are possible.
Methanol or hydrogen production facilities typically consist of the following basic steps: Pre-
treatment, gasification, gas cleaning, reforming of higher hydrocarbons, shift to obtain
appropriate H2:CO ratios, and gas separation for hydrogen production or methanol synthesis and
purification. Optional are a gas turbine or boiler to employ the unconverted gas, and a steam
turbine; resulting in electricity co-production.
Many process configurations are possible, however. Gasification can be atmospheric or

pressurized, direct or indirect, resulting in very different gas compositions; different options are
available for gas cleaning, processing and purification; generation of power is optional.
Altogether in theory a very large number of concepts to produce methanol or hydrogen is
possible.
Therefore, the key objective of this work is to identify biomass to methanol and hydrogen
conversion concepts that may lead to higher overall energy efficiencies and lower costs on longer
term. Improved performance may be obtained by:
 Applying improved or new (non-commercial) technologies. Examples are the use of

Autothermal Reforming (instead of steam reforming), improved shift processes, once
through Liquid Phase MeOH process, high temperature gas cleaning, high temperature
hydrogen separation and improved oxygen production processes.
 Combined fuel and power production by so-called ‘once through’ concepts. Combined
fuel and power production may lead to lower cost and possibly higher overall thermal
efficiencies because of cheaper reactor capacity and reduction of internal energy
consumption of the total plant.
Page 9 of 111
 Economies of scale; various system analyses have shown that the higher conversion
efficiencies and lower unit capital costs that accompany increased scale generally
outweigh increased energy use and costs for transporting larger quantities of biomass.
Furthermore, it should be noted that paper & pulp mills, sugar mills, and other facilities
operate around the world with equivalent thermal inputs in the range of 1000-2000
MWth. Such a scale could therefore be considered for production of energy/fuel from
(imported) biomass as well.
Page 10 of 111
2 DESIGN BASIS
If it is considered that the plant will run for the entire year with 31 days shutdown period.
Operating days will be 334 days but 333.33 days will be used as basis in this report assuming
that the plant will run for 8000 hours.
Thus production rate per hour will be:
𝑡𝑜𝑛 𝑘𝑔 1 𝑦𝑒𝑎𝑟 1
300000 ∗ 1000 ∗ ∗ = 37500.375 𝑘𝑔/ℎ𝑟
𝑦𝑒𝑎𝑟 𝑡𝑜𝑛 333.3 𝑑𝑎𝑦 24
This number will be rounded off to the nearest thousand, hence 38000 kg/hr will be used as basis
which then equate to 304000 tons in a year giving 1.3% allowance.
To ensure that the design specification is met, factors are included to give a margin of safety in
the design; safety in the sense that the equipment will not fail to perform satisfactorily, and that it
will operate safely: will not cause a hazard.
Over-design and safety factors will be applied in this design to ensure reliability as equipment
capacity decreases with time.
In this process design, tolerance of about 5% will be given on stream average flows and for
equipment design and piping. This factor will set the maximum flows for equipment,
instrumentation, and piping design.
Page 11 of 111
3 L I T E R AT U R E R E V I E W
3.1 About Methanol

Methanol was discovered in the mid 1800’s. Methanol (also known as wood alcohol or methyl
alcohol) is the simplest form of alcohol which is a light, colourless and flammable liquid with a
distinctive odour which is similar to that of ethanol. Methanol burns with a colourless flame and
is a liquid at normal temperature which is why it is used as an anti-freeze, solvent, fuel as well as
a denaturant.
Since its discovery, Methanol was put to use in a lot of applications. During the 1970’s, in the
event of the world oil crisis, methanol received a lot of attention as a motor fuel in the United
States but the demand soon came down when the prices for it went up a couple of years later.
Today the most expansive use of Methanol is in the chemical industry where it is being used to
make other chemicals such as plastics, paints and explosives. Apart from this, it is also being
used in other parts of the world to yield a form of biodiesel. Methanol is also used as an anti-
freeze in pipelines and windshield washer fluids in vehicles in the winter. The upcoming
application for methanol is in the manufacturing of fuel cells with many small versions of the
fuel cell already available today. Methanol is also the choice of fuel for many hikers, because of
its ability to burn well from an unpressurized container.
3.2 Methanol Production

The methanol industry is one of the world’s most dynamic and vibrant – producing a basic
chemical molecule that touches our daily lives in a myriad of ways. From the basic chemical
building block of paints, solvents and plastics, to innovative applications in energy,
transportation fuel and fuel cells, methanol is a key commodity and an integral part of our global
economy.
The methanol industry spans the entire globe, with production in Asia, North and South
America, Europe, Africa and the Middle East. Worldwide, over 90 methanol plants have a
combined production capacity of about 100 million metric tons (almost 33 billion gallons or 90
billion liters), and each day more than 100,000 tons of methanol is used as a chemical feedstock
or as a transportation fuel (60 million gallons or 225 million liters). Methanol is also a truly
global commodity, and each day there is more than 80,000 metric tons of methanol shipped from
one continent to another. But the methanol industry is not just those companies large and small
throughout the globe that produce methanol every day from a wide array of feedstocks –
including natural gas, coal, biomass, waste and even CO2 pollution – the industry is also made
Page 12 of 111
up of thousands of distributors, technology innovators, downstream manufacturers and service

providers.
Methanol is used to produce acetic acid, formaldehyde, and a number of other chemical
intermediaries that are utilized to make countless products throughout the global economy – and
by volume, methanol is one of the top 5 chemical commodities shipped around the world each
year. The global methanol industry generates $36 billion in economic activity each year, while
creating over 100,000 jobs around the globe.
Overview
Methanol is produced by a catalytic reaction of carbon monoxide (CO), carbon dioxide (CO 2)
and hydrogen (H2). These gasses, together called synthesis gas, are generally produced from
natural gas.
One can also produce synthesis gas from other organic substances, such as biomass. A train of
processes to convert biomass to required gas specifications precedes the methanol reactor. These
processes include pre-treatment, gasification, gas cleaning, gas conditioning and methanol
synthesis, as is depicted in Figure 3.5 and discussed in Sections 3.3.1 - 3.3.5:
Pre-treatment Gas cleaning Methanol

Biomass Gasifier Reformer Shift reactor Methanol
section section reactor
Figure 3.5: Key components in the conversion of biomass to methanol.
i. Pre-treatment
Chipping or comminution is generally the first step in biomass preparation. The fuel size
necessary for fluidised bed gasification is between 0 and 50 mm (Pierik et al. 1995). Total energy
requirements for chipping woody biomass are approximately 100 kJ/kg of wet biomass
(Katofsky 1993) down to 240 kW for 25 – 50 tonne/h to 3x3 cm in a hammermill, which gives
17 – 35 kJ/kg wet biomass (Pierik et al. 1995).
The fuel should be dried to 10 – 15 % depending on the type of gasifier. This consumes roughly
10 % of the energy content of the feedstock. Drying can be done by means of hot flue gas (in a
rotary drum dryer) or steam (direct/indirect), a choice that among others depends on other steam
demands within the process, and the extent of electricity co-production. Flue gas drying gives a
Page 13 of 111
higher flexibility towards gasification of a large variety of fuels. In the case of electricity
generation from biomass, the integration in the total system is simpler than that of steam drying,
resulting in lower total investment costs. The net electrical system efficiency can be somewhat
higher (van Ree et al. 1995). On the other hand, flue gas drying holds the risk of spontaneous
combustion and corrosion (Consonni et al. 1994). For methanol production, steam is required
throughout the entire process, thus requiring an elaborate steam cycle anyway. It is not a priori
clear whether flue gas or steam drying is a better option in methanol production. A flue gas dryer
for drying from 50 % moisture content to 15 or 10 % would have a specific energy use of 2.4 –
3.0 MJ/tonne water evaporated (twe) and a specific electricity consumption of 40 – 100
kWhe/twe (Pierik et al. 1995). A steam dryer consumes 12 bar, 200 °C (process) steam; the
specific heat consumption is 2.8 MJ/twe. Electricity use is 40 kWh e/twe (Pierik et al. 1995).
ii. Gasification
Through gasification solid biomass is converted into synthesis gas. The fundamentals have
extensively been described by among others Katofsky (1993). Basically, biomass is converted to
a mixture of CO, CO2, H2O, H2, and light hydrocarbons, the mutual ratios depending on the type
of biomass, the gasifier type, temperature and pressure, and the use of air, oxygen and steam.
Many gasification methods are available for synthesis gas production. Based on throughput, cost,
complexity, and efficiency issues, only circulated fluidised bed gasifiers are suitable for large-
scale synthesis gas production. Direct gasification with air results in nitrogen dilution, which in
turn strongly increases downstream equipment size. This eliminates the TPS (Termiska Processer
AB) and Enviropower gasifiers, which are both direct air blown. The MTCI (Manufacturing and
Technology Conversion International, affiliate of Thermochem Inc.) gasifier is indirectly fired,
but produces a very wet gas and the net carbon conversion is low. Two gasifiers are selected for
the present analysis: the IGT (Institute of Gas Technology) pressurised direct oxygen fired
gasifier, and the BCL (Battelle Columbus) atmospheric indirectly fired gasifier. The IGT gasifier
can also be operated in a maximum hydrogen mode, by increasing the steam input. Both gasifiers
produce medium calorific gas, undiluted by atmospheric nitrogen, and represent a very broad
range for the H2:CO ratio of the raw synthesis gas.
IGT gasifier
The IGT gasifier (Figure) is directly heated, this implies that some char and/or biomass are
burned to provide the necessary heat for gasification. Direct heating is also the basic principle
applied in pressurised reactors for gasifying coal. The higher reactivity of biomass compared to
coal permits the use of air instead of pure oxygen. This could be fortuitous at modest scales
because oxygen is relatively costly (Consonni and Larson 1994a). However, for the production
of methanol from biomass, the use of air increases the volume of inert (N 2) gas that would have
to be carried through all the downstream reactors. Therefore, the use of oxygen thus improves
Page 14 of 111
the economics of synthesis gas processing. Air-fired, directly heated gasifiers are considered not
to be suitable before methanol production.
Product
gas
Biomass Ash
Steam + oxygen
Figure 3.2 The directly heated, bubbling fluidised bed gasifier of IGT (Katofsky 1993).
This gasifier produces a CO2 rich gas. The CH4 fraction could be reformed to hydrogen, or be
used in a gas turbine. The H2:CO ratio (1.4 : 1) is attractive to produce methanol, although the
large CO2 content lowers the overall yield of methanol. The pressurised gasification allows a
large throughput per reactor volume and diminishes the need for pressurisation downstream, so
less overall power is needed.
The bed is in fluidised state by injection of steam and oxygen from below, allowing a high
degree of mixing. Near the oxidant entrance is a combustion zone with a higher operation
temperature, but gasification reactions take place over the whole bed, and the temperature in the
bed is relatively uniform (800 – 1000°C). The gas exits essentially at bed temperature. Ash,
unreacted char and particulates are entrained within the product gas and are largely removed
using a cyclone.
An important characteristic of the IGT synthesis gas is the relatively large CO 2 and CH4
fractions. The high methane content is a result of the non-equilibrium nature of biomass
gasification and of pressurised operation. Relatively large amounts of CO2 are produced by the
direct heating, high pressure, and the high overall O:C ratio (2:1). With conventional gas
processing technology, a large CO2 content would mean that overall yields of fluid fuels would
be relatively low. The synthesis gas has an attractive H2:CO ratio for methanol production, which
reduces the need for a shift reactor. Since gasification takes place under pressure, less
downstream compression is needed.
When operated with higher steam input the IGT gasifier produces a product gas with a higher
hydrogen content. This maximum hydrogen mode is especially useful if hydrogen would be the
desired product, but the H2:CO ratio is also better for methanol production. However, the gasifier
efficiency is lower and much more steam is needed.
Page 15 of 111
BCL gasifier
The BCL gasifier is indirectly heated by a heat transfer mechanism with as shown in Figure 6.3.
Ash, char and sand are entrained in the product gas, separated using a cyclone, and sent to a
second bed where the char or additional biomass is burned in air to reheat the sand. The heat is
transferred between the two beds by circulating the hot sand back to the gasification bed. This
allows one to provide heat by burning some of the feed, but without the need to use oxygen,
because combustion and gasification occur in separate vessels.
Offgas
Product gas
Biomass
Steam Air
Figure 6.3 The indirectly heated, twin bed gasifier of BCL (Katofsky 1993).
Because of the atmospheric pressure, the BCL gasifier produces a gas with a low CO2 content,
but consequently containing more heavier hydrocarbons. Therefore, tar cracking and reforming
are logical subsequent steps in order to maximise CO and H 2 production.
The reactor is fast fluidised allowing throughputs equal to the bubbling fluidised IGT, despite the
atmospheric operation. The atmospheric operation decreases cost at smaller scale, and the BCL
has some commercial experience (demo in Burlington USA, (Paisley et al. 1998)).
Because biomass gasification temperatures are relatively low, significant departures from
equilibrium are found in the product gas. Therefore, kinetic gasifier modelling is complex and
different for each reactor type (Consonni et al. 1994; Li et al. 2001). The main performance
characteristics of both gasifiers are given in Table .
Oxygen supply
Gasifiers demand oxygen, provided as air, pure oxygen or anything in between. The use of pure
oxygen reduces the volume flows through the IGT gasifier and through downstream equipment
which reduces investment costs. Also the Autothermal Reformer (see later) is, for the same
reason, preferably fired by oxygen.
Page 16 of 111
As the production of oxygen is expensive, there will likely be an economical optimum in oxygen
purity. Oxygen enriched air could be a compromise between a cheaper oxygen supply and a
reduced downstream equipment size.
Cryogenic air separation is commonly applied when large amounts of O 2 (over 1000 Nm3/h) are
required. Since air is freely available, the costs for oxygen production are directly related to the
costs for air compression and refrigeration; the main unit operations in an air separation plant. As
a consequence, the oxygen price is mainly determined by the energy costs and plant investment
costs (van Dijk et al. 1995; van Ree 1992).
The conventional air separation unit is both capital and energy intensive. A potential for cost
reduction is the development of air separation units based on conductive ionic transfer
membranes (ITM) that operate on the partial pressure differential of oxygen to passively produce
pure oxygen. Research and development of the ITM are in demonstration phase (DeLallo et al.
2000). Alternative options are membrane air separation, sorption technologies and water
decomposition, but these are less suitable for large scale application (van Ree 1992).
iii. Gas cleaning and contaminant limits
Raw gas versus system requirements
Table 3.1 Characteristics of gasifiers, taken from Williams et al. (1995).
IGT6) IGT max H27) BCL8)
bubbling fluidised bubbling fluidised Indirectly heated

bed bed fast fluidised bed
Biomass input dry basis1) 80 80 80

(tonne/hr)
Initial moisture content (%) 30 30 30
Dry moisture content (%) 15 15 10
HHVdry biomass (GJ/tonne) 19.28 19.28 19.46
LHVwet biomass2) 11.94 11.94 12.07

(GJ/tonne)
Steam demand drier3) 26.2 26.2 tonne/hr 33.0 tonne/hr
Page 17 of 111
(tonne/hr)
Thermal Biomass input HHV 428.4 / LHV HHV 428.4 / LHV HHV 432.4 / LHV
(MW) 379.0 379.0 383.2
Steam (kg/kg dry feed) 0.3 0.8 0.019
Steam4) (tonne/hr) 24 64 1.52
Oxygen (kg/kg dry feed) 0.3 0.38 0
Air (kg/kg dry feed) 0 0 2.06
Product temperature (°C) 982 920 863
Exit pressure (bar) 34.5 25 1.2
Gas yield (kmol/dry tonne) 82.0 1215) 45.8
Wet gas output kmol/hour 6560 9680 3664
Composition: mole fraction on wet basis (on dry basis)
H2O 0.318 (-) 0.48 (-) 0.199 (-)
H2 0.208 (0.305) 0.24 (0.462) 0.167 (0.208)
CO 0.15 (0.22) 0.115 (0.221) 0.371 (0.463)
CO2 0.239 (0.35) 0.16 (0.308) 0.089 (0.111)
CH4 0.0819 (0.12) 0.005 (0.009) 0.126 (0.157)
C2H4 0.0031 (0.005) 0 0.042 (0.052)
C2H6 0 0 0.006 (0.0074)
O2 0 0 0
N2 0 0 0
Σ 1 (1) 1 (1) 1 (1)
Page 18 of 111
LHVwet synthesis gas 6.70 3.90 12.7

3
(MJ/Nm )
Thermal flow (MW) HHV 352 /LHV HHV 309 / LHV HHV 348 / LHV
296 231 316
1)
640 ktonne dry wood annual, load is 8000 h.
2)
Calculated from LHVwet = HHVdry  (1 - W) - Ew  (W + Hwet  mH2O); with E w the
energy needed for water evaporation (2.26 MJ/kg), Hwet the hydrogen content on wet basis (for
wood Hdry = 0.062) and mH2O the amount of water created from hydrogen (8.94 kg/kg).
3)
Wet biomass: 80/0.7 = 114 tonne/hr to dry biomass 80/0.85 = 94.1 tonne/hr for IGT
evaporate water 20.2 tonne/hr at 1.3 ts/twe in Niro (indirect) steam dryer. Calculation for BCL is
alike. The steam has a pressure of 12 bar and a temperature of minimally 200 °C (Pierik et al.
1995).
4)
Pressure is 34.5, 25 or 1.2 bar, temperature is minimally 250, 240 or 120 °C.
5)
Calculated from the total mass stream, 188.5 tonne/hr.
6)
Quoted from OPPA (1990) by Williams et al. (1995).
7)
Knight (1998).
8)
Compiled by Williams et al. (1995).
The raw synthesis gas produced by gasification contains impurities. The most typical impurities
are organic impurities like condensable tars and BTX (benzene, toluene, and xylenes), inorganic
impurities (NH3, HCN, H2S, COS, and HCl), and furthermore volatile metals, dust, and soot
(Tijmensen 2000; van Ree et al. 1995). These contaminants can lower catalyst activity in
reformer, shift and methanol reactor, and cause corrosion in compressors, heat exchangers and
the (optional) gas turbine.
The estimated maximal acceptable contaminant concentrations are summarised in Table 3.2,
together with the effectiveness of wet and dry gas cleaning, as described below.
The gas can be cleaned using available conventional technology, by applying gas cooling, low
temperature filtration, and water scrubbing at 100 – 250 °C. Alternatively, hot gas cleaning can
be considered, using ceramic filters and reagents at 350 – 800 °C. These technologies have been
described thoroughly by several authors (Consonni et al. 1994; Kurkela 1996; Tijmensen 2000;
van Dijk et al. 1995; van Ree et al. 1995). The considered pressure range is no problem for either
of the technologies. Hot gas cleaning is advantageous for the overall energy balance when a
Page 19 of 111
reformer or a ceramic membrane is applied directly after the cleaning section, because these
processes require a high inlet temperature. However, not all elements of hot gas cleaning are yet
proven technology, while there is little uncertainty about the cleaning effectiveness of low
temperature gas cleaning. Both cleaning concepts are depicted in Figure
Tar removal
Table 3.2 Estimated contaminant specifications for Methanol synthesis1), and cleaning
effectiveness of wet and dry gas cleaning.
Gas phase Treatment method & remarks

Specification
Existing technologies Dry gas cleaning3)
Contaminant
Soot (dust, char, 0 ppb Cyclones, metal filters, moving beds,

ash)
candle filters, bag filters, special soot scrubber
Specifications are met.
Alkaline (halide) < 10 ppb Active coal bed meets Sorbents

metals specification2)
Under development
Tar Below dew All tar and BTX: All tar and BTX:
point
Thermal tar cracker, Catalytic tar cracker,
Oil scrubber4), other catalytic

Catalyst operations.
Specifications are met
poisoning
Under development.
compounds <
1 ppmV
BTX Below dew

point
Halide compounds
HCl (HBr, HF) < 10 ppb Removed by aqueous scrubber In-bed sorbents or in-
stream
Active coal bed meets
Page 20 of 111
specification sorbents
Absorbed by dolomite in tar < 1 ppm

cracker (if applicable)
Guardbeds necessary
Nitrogen Total N <1 All nitrogen:

compounds ppmV
catalytic decomposition,
NH3 Removed by aqueous scrubber
combined removal of
Removed to specification
NH3/H2S
HCN Active coal bed
Selective oxidation
possibly preceded by hydrolysis
Under development
to NH3
Sulphur compounds Total S <1 All sulphur:

ppmV2)
In-bed Calcium sorbents
H2S ZnO guard bed
Metal oxide sorbents
in case of high sulphur loads a
< 20 ppm
special removal step, e.g. Claus
unit
COS active coal bed
possibly preceded by hydrolysis

to H2S
1)
Most numbers are quoted from Fischer-Tropsch synthesis over a cobalt catalyst (Bechtel
1996; Boerrigter et al. 2003; Tijmensen 2000). Gas turbine specifications are met when FT
specifications are.
2)
Cleaning requirements for MeOH synthesis are 0.1 (van Dijk et al. 1995) to 0.25 ppm
H2S (Katofsky 1993). Total sulphur <1 ppmV (Boerrigter et al. 2003). For Fischer-Tropsch
synthesis requirements are even more severe: 10 ppb (Tijmensen 2000).
Page 21 of 111
3)
Hot gas cleaning was practiced in the Värnamo Demonstration plant, Sweden (Kwant
2001). All data on dry gas cleaning here is based on the extensive research into high temperature
gas cleaning by Mitchell (Mitchell 1997; Mitchell 1998).
4)
Bergman et al. (Bergman et al. 2003).
Especially in atmospheric gasification larger hydrocarbons are formed, generally categorised as

‘tars’. When condensing, they foul downstream equipment, coat surfaces and enter pores in
filters and sorbents. To avoid this, their concentration throughout the process must be below the
condensation point. On the other hand, they contain a lot of potential CO and H 2. They should
thus preferably be cracked into smaller hydrocarbons. Fluidised beds produce tar at about 10
g/mNTP3 or 1 – 5 wt% of the biomass feed (Boerrigter et al. 2003; Milne et al. 1998; Tijmensen
2000). BTX, accounting for 0.5 volume % of the synthesis gas, have to be removed prior to the
active carbon filters, which otherwise sorb the BTX completely and quickly get filled up
(Boerrigter et al. 2003).
Three methods may be considered for tar removal/cracking: thermal cracking, catalytic cracking,
and scrubbing. At temperatures above 1000 – 1200 °C, tars are destroyed without a catalyst,
usually by addition of steam and oxygen, which acts as a selective oxidant (Milne et al. 1998).
Drawbacks are the need for expensive materials, the soot production and the low thermal
efficiency. Catalytic cracking (dolomite or Ni based) is best applied in a secondary bed, and
avoids the mentioned problems of thermal cracking. However, the technology is not yet fully
proven (Milne et al. 1998). It is not clear to what extent tars are removed (Tijmensen 2000) and
the catalyst consumption and costs are matters of concern. Per kg dry wood (15 % moisture),
0.0268 kg dolomite. Part of the H2S and HCl present adsorb on dolomite (van Ree et al. 1995).
The tar crackers can be integrated with the gasifier.
Page 22 of 111
Aqueous
Hydrolysis
scrubbing
Removes NH3, HCl,

metals, part HCN, H2S
Residual
Gasifier Tar cracker Gas cooling Methanol
Cyclones Dust removal contaminants Conditioning Guard beds
850 ºC 1300 ºC 100 ºC reactor
wet cleaning
HP steam
Tar+oil
Residual
Gasifier Gas cooling Oil scrubber Methanol
Cyclones contaminants Conditioning Guard beds
850 ºC 400 ºC 100 ºC reactor
wet cleaning
HP steam
Residual
Gasifier Tar cracker Gas cooling Gas cooling Methanol
Cyclones Candle filters contaminants Conditioning Guard beds
850 ºC 1300 ºC 400 ºC 20 ºC reactor
dry cleaning
HP steam
base acid Sulphur Active carbon

absorption absorption absorption + ZnO guardbeds
Removes Removes Removes Removes traces

NH3 HCl, HCN H2S and COS HCN, H2S, NH3, COS
Figure 3.4 Three possible gas cleaning trains.
Top: tar cracking and conventional wet gas cleaning; middle: tar scrubbing and conventional wet
gas cleaning; and bottom: tar cracking and dry gas cleaning.
Tars can also be removed at low temperature by advanced scrubbing with an oil based medium
(Bergman et al. 2003; Boerrigter et al. 2003). The tar is subsequently stripped from the oil and
reburned in the gasifier. At atmospheric pressures BTX are only partially removed, from about 6
bar BTX are fully removed. The gas enters the scrubber at about 400 °C, which allows high
temperature heat exchange before the scrubber.
Wet gas cleaning
When the tars and BTX are removed, the other impurities can be removed by standard wet gas
cleaning technologies or advanced dry gas cleaning technologies.
Wet low temperature synthesis gas cleaning is the preferred method on the short term (van Ree et
al. 1995). This method will have some energy penalty and requires additional waste water
treatment, but on the short term it is more certain to be effective than hot dry gas cleaning.
A cyclone separator removes most of the solid impurities, down to sizes of approximately 5 m
(Katofsky 1993). New generation bag filters made from glass and synthetic fibres have an upper
temperature limit of 260 °C (Perry et al. 1987). At this temperature particulates and alkali, which
condense on particulates, can successfully be removed (Alderliesten 1990; Consonni et al. 1994;
Page 23 of 111
Tijmensen 2000; van Ree et al. 1995). Before entering the bag filter, the synthesis gas is cooled
to just above the water dew point.
After the filter unit, the synthesis gas is scrubbed down to 40 °C below the water dew point, by
means of water. Residual particulates, vapour phase chemical species (unreacted tars, organic
gas condensates, trace elements), reduced halogen gases and reduced nitrogen compounds are
removed to a large extend. The scrubber can consist of a caustic part where the bulk of H 2S is
removed using a NaOH solution (van Ree et al. 1995) and an acid part for ammonia/cyanide
removal. Alkali removal in a scrubber is essentially complete (Consonni et al. 1994).
With less than 30 ppm H2S in the biomass derived synthesis gas a ZnO bed may be sufficient to
lower the sulphur concentration below 0.1 ppm. ZnO beds can be operated between 50 and 400
°C, the high-end temperature favours efficient utilisation. At low temperatures and pressures less
sulphur is absorbed, therefore multiple beds will be used in series. The ZnO bed serves one year
and is not regenerated (Katofsky 1993; van Dijk et al. 1995). Bulk removal of sulphur is thus not
required, but if CO2 removal is demanded as well, a solvent absorption process like Rectisol or
Sulfinol could be placed downstream, which also removes sulphur. H 2S and COS are reduced to
less than 0.1 ppm and all or part of the CO2 is separated (Hydrocarbon Processing 1998).
Dry / hot gas cleaning
In dry / hot gas cleaning, residual contaminations are removed by chemical absorbents at
elevated temperature. In the methanol process, hot gas cleaning has little energy advantages as
the methanol reactor operates at 200 – 300 °C, especially when preceding additional compression
is required (efficient compression requires a cold inlet gas). However, dry / hot gas cleaning may
have lower operational costs than wet gas cleaning (Mitchell 1998). Within ten years hot gas
cleaning may become commercially available for BIG/CC applications (Mitchell 1998).
However, requirements for methanol production, especially for catalyst operation, are expected
to be more severe (Tijmensen 2000). It is not entirely clear to what extent hot gas cleaning will
be suitable in the production of methanol.
Tars and oils are not expected to be removed during the hot gas cleaning since they do not
condense at high temperatures. Therefore, they must be removed prior to the rest of the gas
cleaning as discussed above.
For particle removal at temperatures above 400 °C, sliding granular bed filters are used instead
of cyclones. Final dust cleaning is done using ceramic candle filters (Klein Teeselink et al. 1990;
Williams 1998) or sintered-metal barriers operating at temperatures up to 720 °C; collection
efficiencies greater that 99.8 % for 2 – 7 m particles have been reported (Katofsky 1993). Still
better ceramic filters for simultaneous SOx, NOx and particulate removal are under development
(White et al. 1992).
Page 24 of 111
Processes for alkali removal in the 750 – 900 °C range are under development and expected to be
commercialised within few years. Lead and zinc are not removed at this temperature
(Alderliesten 1990). High temperature alkali removal by passing the gas stream through a fixed
bed of sorbent or getter material that preferentially adsorbs alkali via physical adsorption or
chemisorption was discussed by Turn et al. (1998). Below 600 °C alkali metals condense onto
particulates and can more easily be removed with filters (Katofsky 1993).
Nickel-based catalysts have proved to be very efficient in decomposing tar, ammonia and
methane in biomass gasification gas mixtures at about 900 °C. However, sulphur can poison
these catalysts (Hepola et al. 1997; Tijmensen 2000). It is unclear if the nitrogenous component
HCN is removed. It will probably form NO x in a gas turbine (Verschoor et al. 1991).
Halogens are removed by sodium and calcium-based powdered absorbents. These are injected in
the gas stream and removed in the dedusting stage (Verschoor et al. 1991).
Hot gas desulphurisation is done by chemical absorption to zinc titanate or iron oxide-on-silica.
The process works optimally at about 600 °C or 350 °C, respectively. During regeneration of the
sorbents, SO2 is liberated and has to be processed to H2SO4 or elemental sulphur (Jansen 1990;
Jothimurugesan et al. 1996). ZnO beds operate best close to 400 °C (van Dijk et al. 1995).
Early compression would reduce the size of gas cleaning equipment. However, sulphur and
chloride compounds condense when compressed and they may corrode the compressor.
Therefore, intermediate compression to 6 bar takes place only after bulk removal and 60 bar
compression just before the guardbed.
iv. Gas conditioning
Reforming
The synthesis gas can contain a considerable amount of methane and other light hydrocarbons,
representing a significant part of the heating value of the gas. Steam reforming (SMR) converts
these compounds to CO and H2 driven by steam addition over a catalyst (usually nickel) at high
temperatures (Katofsky 1993). Autothermal reforming (ATR) combines partial oxidation in the
first part of the reactor with steam reforming in the second part, thereby optimally integrating the
heat flows. It has been suggested that ATR, due to a simpler concept could become cheaper than
SMR (Katofsky 1993), although others give much higher prices (Oonk et al. 1997). There is
dispute on whether the SMR can deal with the high CO and C+ content of the biomass synthesis
gas. Where Katofsky writes that no additional steam is needed to prevent coking or carbon
deposition in SMR, Tijmensen (2000) poses that this problem does occur in SMR and that ATR
is the only technology able to prevent coking.
Steam reforming is the most common method of producing a synthesis gas from natural gas or
gasifier gas. The highly endothermic process takes place over a nickel-based catalyst:
Page 25 of 111
CH4 + H2O  CO + 3H2 Equation 1
C2H4 + 2H2O  2CO + 4H2 Equation 2
C2H6 + 2H2O  2CO + 5H2 Equation 3
Concurrently, the water gas shift reaction (see below) takes place, and brings the reformer
product to chemical equilibrium (Katofsky 1993).
Reforming is favoured at lower pressures, but elevated pressures benefit economically (smaller
equipment). Reformers typically operate at 1 – 3.5 MPa. Typical reformer temperature is
between 830 °C and 1000 °C. High temperatures do not lead to a better product mix for
methanol production (Katofsky 1993). The inlet stream is heated by the outlet stream up to
nearby the reformer temperature to match reformer heat demand and supply. In this case less
synthesis gas has to be burned compared to a colder gas input, this eventually favours a higher
methanol production. Although less steam can be raised from the heat at the reformer outlet, the
overall efficiency is higher.
SMR uses steam as the conversion reactant and to prevent carbon formation during operation.
Tube damage or even rupture can occur when the steam to carbon ratio drops below acceptable
limits. The specific type of reforming catalyst used, and the operating temperature and pressure
are factors that determine the proper steam to carbon ratio for a safe, reliable operation. Typical
steam to hydrocarbon-carbon ratios range from 2:1 for natural gas feeds with CO 2 recycle, to 3:1
for natural gas feeds without CO2 recycle, propane, naphtha and butane feeds (King et al. 2000).
Usually full conversion of higher hydrocarbons in the feedstock takes place in an adiabatic pre-
reformer. This makes it possible to operate the tubular reformer at a steam to carbon ratio of 2.5.
When higher hydrocarbons are still present, the steam to carbon ratio should be higher: 3.5. In
older plants, where there is only one steam reformer, the steam to carbon ratio was typically 5.5.
A higher steam:carbon ratio favours a higher H2:CO ratio and thus higher methanol production.
However, more steam must be raised and heated to the reaction temperature; this decreases the
process efficiency. Neither is additional steam necessary to prevent coking (Katofsky 1993).
Pre-heating the hydrocarbon feedstock with hot flue gas in the SMR convection section, before
steam addition, should be avoided. Dry feed gas must not be heated above its cracking
temperature. Otherwise, carbon may be formed, thereby, decreasing catalyst activities, increasing
pressure drop and limiting plant throughput. In the absence of steam, cracking of natural gas
occurs at temperatures above 450 °C, while the flue gas exiting SMRs is typically above 1000 °C
(King et al. 2000).
Nickel catalysts are affected by sulphur at concentrations as low as 0.25 ppm. An alternative
would be to use catalysts that are resistant to sulphur, such as sulphided cobalt/molybdate.
However, since other catalysts downstream of the reformer are also sensitive to sulphur, it makes
the most sense to remove any sulphur before conditioning the synthesis gas (Katofsky 1993).
Page 26 of 111
The lifetime of catalysts ranges from 3 years (van Dijk et al. 1995) to 7 years (King et al. 2000).
The reason for change out are typically catalyst activity loss and increasing pressure drop over
the tubes.
Autothermal reforming (ATR) combines steam reforming with partial oxidation. In ATR, only
part of the feed is oxidised, enough to supply the necessary heat to steam reform the remaining
feedstock. The reformer produces a synthesis gas with a lower H 2:CO ratio than conventional
steam methane reforming (Katofsky 1993; Pieterman 2001).
An Autothermal Reformer consists of two sections. In the burner section, some of the preheated
feed/steam mixture is burned stoichiometrically with oxygen to produce CO2 and H2O. The
product and the remaining feed are then fed to the reforming section that contains the nickel-
based catalyst (Katofsky 1993).
With ATR considerably less synthesis gas is produced, but also considerably less steam is
required due to the higher temperature. Increasing steam addition hardly influences the H 2:CO
ratio in the product, while it does dilute the product with H 2O (Katofsky 1993). Typical ATR
temperature is between 900 °C and 1000 °C.
Since autothermal reforming does not require expensive reformer tubes or a separate furnace,
capital costs are typically 50 – 60 % less than conventional steam reforming, especially at larger
scales (Dybkjaer et al. 1997; quoted by Pieterman 2001). This excludes the cost of oxygen
separation. ATR could therefore be attractive for facilities that already require oxygen for
biomass gasification (Katofsky 1993).
The major source of H2 in oil refineries, catalytic reforming, is decreasing. The largest quantities
of H2 are currently produced from synthesis gas by steam-reforming of methane, but this
approach is both energy and capital intensive. Partial oxidation of methane with air as the oxygen
source is a potential alternative to the steam-reforming processes. In methanol synthesis starting
from C1 to C3, it offers special advantages. The amount of methanol produced per kmol
hydrocarbon may be 10 to 20 % larger than in a conventional process using a steam reformer (de
Lathouder 1982). However, the large dilution of product gases by N2 makes this path
uneconomical, and, alternatively, use of pure oxygen requires expensive cryogenic separation
(Maiya et al. 2000).
Reforming is still subject to innovation and optimisation. Pure oxygen can be introduced in a
partial oxidation reactor by means of a ceramic membrane, at 850 – 900 °C, in order to produce a
purer synthesis gas. Lower temperature and lower steam to CO ratio in the shift reactor leads to a
higher thermodynamic efficiency while maximising H2 production (Maiya et al. 2000).
Water gas shift
Page 27 of 111
The synthesis gas produced by the BCL and IGT gasifiers has a low H 2:CO ratio. The water gas
shift (WGS) reaction (Equation 4) is a common process operation to shift the energy value of the
carbon monoxide to the hydrogen, which can then be separated using pressure swing adsorption.
If the stoichiometric ratio of H2, CO and CO2 is unfavourable for methanol production, the water
gas shift can be used in combination with a CO2 removal step. The equilibrium constant for the
WGS increases as temperature decreases. Hence, to increase the production to H 2 from CO, it is
desirable to conduct the reaction at lower temperatures, which is also preferred in view of steam
economy. However, to achieve the necessary reaction kinetics, higher temperatures are required
(Armor 1998; Maiya et al. 2000).
CO + H2O  CO2 + H2 Equation 4
The water gas shift reaction is exothermic and proceeds nearly to completion at low
temperatures. Modern catalysts are active at as low as 200 °C (Katofsky 1993) or 400 °C (Maiya
et al. 2000). Due to high catalyst selectivity, all gases except those involved in the water-gas shift
reaction are inert. The reaction is independent of pressure.
Conventionally, the shift is realised in a successive high temperature (360 °C) and low
temperature (190 °C) reactor. Nowadays, the shift section is often simplified by installing only
one CO-shift converter operating at medium temperature (210 °C) (HaldorTopsoe 1991). For
methanol synthesis, the gas can be shifted partially to a suitable H 2:CO ratio, therefore ‘less than
one’ reactor is applied. The temperature may be higher because the reaction needs not to be
complete and this way less process heat is lost.
Theoretically the steam:carbon monoxide ratio could be 2:1. On lab scale good results are
achieved with this ratio (Maiya et al. 2000). In practice extra steam is added to prevent coking
(Tijmensen 2000).
CO2 removal
The synthesis gas from the gasifier contains a considerable amount of CO 2. After reforming or
shifting, this amount increases. To get the ratio (H 2-CO2)/(CO +CO2) to the value desired for
methanol synthesis, part of the carbon dioxide could be removed. For this purpose, different
physical and chemical processes are available. Chemical absorption using amines is the most
conventional and commercially best-proven option. Physical absorption, using Selexol, has been
developed since the seventies and is an economically more attractive technology for gas streams
containing higher concentrations of CO2. As a result of technological development, the choice
for one technology or another could change in time, e.g. membrane technology or still better
amine combinations could play an important role in future.
Chemical absorption using amines is especially suitable when CO 2 partial pressures are low,
around 0.1 bar. It is a technology that makes use of chemical equilibria, shifting with temperature
rise or decline. Basically, CO2 binds chemically to the absorbent at lower temperatures and is
Page 28 of 111
later stripped off by hot steam. Commonly used absorbents are alkanolamines applied as
solutions in water. Alkanolamines can be divided into three classes: primary, secondary and
tertiary amines. Most literature is focused on primary amines, especially monoethanolamine
(MEA), which is considered the most effective in recovering CO 2 (Farla et al. 1995; Wilson et al.
1992), although it might well be that other agents are also suitable as absorbents (Hendriks
1994). The Union Carbide “Flue Guard” process and the Fluor Daniel Econamine FG process
(formerly known as the Dow Chemical Gas/Spec FT-1 process) use MEA, combined with
inhibitors to reduce amine degradation and corrosion. The cost of amine based capture are
determined by the cost of the installation, the annual use of amines, the steam required for
scrubbing and the electric power. There is influence of scale and a strong dependence on the CO 2
concentration (Hendriks 1994). The investment costs are inversely proportional to the CO 2
concentration in the feed gas when these range from 4 to 8 %. MEA is partly entrained in the gas
phase, this results in chemical consumption of 0.5 – 2 kg per tonne CO2 recovered (Farla et al.
1995; Suda et al. 1992). The presence of SO2 leads to an increased solvent consumption
(Hendriks 1994).
When the CO2 content makes up an appreciable fraction of the total gas stream, the cost of
removing it by heat regenerable reactive solvents may be out of proportion to the value of the
CO2. To overcome the economic disadvantages of heat regenerable processes, physical
absorption processes have been developed which are based on the use of essentially anhydrous
organic solvents which dissolve the acid gases and can be stripped by reducing the acid-gas
partial pressure without the application of heat. Physical absorption requires a high partial
pressure of CO2 in the feed gas to be purified, 9.5 bar is given as an example by Hendriks (1994).
Most physical absorption processes found in literature are Selexol, which is licensed by Union
Carbide, and Lurgi’s Rectisol (Hendriks 1994; Hydrocarbon Processing 1998; Riesenfeld et al.
1974). These processes are commercially available and frequently used in the chemical industry.
In a counter current flow absorption column, the gas comes into contact with the solvent, a 95 %
solution of the dimethyl ether of polyethylene glycol in water. The CO 2 rich solvent passes a
recycle flash drum to recover co-absorbed CO and H2. The CO2 is recovered by reducing the
pressure through expanders. This recovery is accomplished in serially connected drums. The CO 2
is released partly at atmospheric pressure. After the desorption stages, the Selexol still contains
25 - 35 % of the originally dissolved CO2. This CO2 is routed back to the absorber and is
recovered in a later cycle. The CO2 recovery rate from the gas stream will be approximately 98
to 99 % when all losses are taken into account. Half of the CO 2 is released at 1 bar and half at
elevated pressure: 4 bar. Minor gas impurities such as carbonyl sulphide, carbon disulphide and
mercaptans are removed to a large extent, together with the acid gases. Also hydrocarbons above
butane are largely removed. Complete acid-gas removal, i.e. to ppm level, is possible with
physical absorption only, but is often achieved in combination with a chemical absorption
process. Selexol can also remove H2S, if this was not done in the gas-cleaning step.
Page 29 of 111
It has been suggested by De Lathouder (1982) to scrub CO2 using crude methanol from the
synthesis reactor that has not yet been expanded. The pressure needed for the CO 2 absorption
into the methanol is similar to the methanol pressure directly after synthesis. This way only a
limited amount of CO2 is removed, and the required CO2 partial pressure is high, but the desired
R can be reached if conditions are well chosen. The advantage of this method is that no separate
regeneration step is required and that it is not necessary to apply extra cooling of the gas stream
before the scrubbing operation. The CO2 loaded crude methanol can be expanded to about
atmospheric pressure, so that the carbon dioxide is again released, after which the methanol is
purified as would normally be the case.
Physical adsorption systems are based on the ability of porous materials (e.g. zeolites) to
selectively adsorb specific molecules at high pressure and low temperature and desorb them at
low pressure and high temperature. These processes are already commercially applied in
hydrogen production, besides a highly pure hydrogen stream a pure carbon dioxide stream is co-
produced. Physical adsorption technologies are not yet suitable for the separation of CO 2 only,
due to the high energy consumption (Ishibashi et al. 1998; Katofsky 1993).
Methanol synthesis
Methanol is produced by the hydrogenation of carbon oxides over a suitable (copper oxide, zinc
oxide, or chromium oxide-based) catalyst:
CO + 2H2  CH3OH Equation 5
CO2 + 3H2  CH3OH + H2O Equation 6
The first reaction is the primary methanol synthesis reaction, a small amount of CO 2 in the feed
(2-10%) acts as a promoter of this primary reaction and helps maintain catalyst activity. The
stoichiometry of both reactions is satisfied when R in the following relation is 2.03 minimally
(Katofsky 1993). H2 builds up in the recycle loop, this leads to an actual R value of the combined
synthesis feed (makeup plus recycle feed) of 3 to 4 typically.
H 2  CO2
R
CO  CO2 Equation 7
The reactions are exothermic and give a net decrease in molar volume. Therefore, the
equilibrium is favoured by high pressure and low temperature. During production, heat is
released and has to be removed to keep optimum catalyst life and reaction rate. 0.3 % of the
produced methanol reacts further to form side products as dimethyl ether, formaldehyde or
higher alcohols (van Dijk et al. 1995).
The catalyst deactivates primarily because of loss of active copper due to physical blockage of
the active sites by large by-product molecules; poisoning by halogens or sulphur in the synthesis
Page 30 of 111
gas, which irreversibly form inactive copper salts; and sintering of the copper crystallites into
larger crystals, which then have a lower surface to volume ratio.
Conventionally, methanol is produced in two-phase systems: the reactants and products forming
the gas phase and the catalyst being the solid phase. The production of methanol from synthesis
gas was first developed at BASF in 1922 Germany. This process used a zinc oxide / chromium
oxide catalyst with poor selectivity, and required extremely vigorous conditions—pressures
ranging from 300–1000 bar, and temperatures of about 400 °C. In the 1960s and 70s the more
active Cu/Zn/Al catalyst was developed allowing more energy-efficient and cost-effective plants,
and larger scales. Processes under development at present focus on shifting the equilibrium to the
product side to achieve higher conversion per pass. Examples are the gas/solid/solid trickle flow
reactor, with a fine adsorbent powder flowing down a catalyst bed and picking up the produced
methanol; and liquid phase methanol processes where reactants, product, and catalyst are
suspended in a liquid. Fundamentally different could be the direct conversion of methane to
methanol, but despite a century of research this method has not yet proved its advantages.
Fixed bed technology
Two reactor types predominate in plants built after 1970 (Cybulski 1994; Kirk-Othmer 1995).
The ICI low-pressure process is an adiabatic reactor with cold unreacted gas injected between the
catalyst beds (Figure 3.7, left). The subsequent heating and cooling leads to an inherent
inefficiency, but the reactor is very reliable and therefore still predominant. The Lurgi system
(Figure 3.7, right), with the catalyst loaded into tubes and a cooling medium circulating on the
outside of the tubes, allows near-isothermal operation. Conversion to methanol is limited by
equilibrium considerations and the high temperature sensitivity of the catalyst. Temperature
moderation is achieved by recycling large amounts of hydrogen rich gas, utilising the higher heat
capacity of H2 gas and the higher gas velocities to enhance the heat transfer. Typically a gas
phase reactor is limited to about 16 % CO gas in the inlet to the reactor, in order to limit the
conversion per pass to avoid excess heating.
Page 31 of 111
Hot synthesis gas Methanol
Catalyst beds
Cool Steam
synthesis
gas
Water
Methanol Hot synthesis gas
Figure 3.7 Methanol reactor types: adiabatic quench (left) and isothermal steam raising
(right).
The methanol synthesis temperature is typically between 230 and 270 °C. The pressure is
between 50 and 150 bar. Higher pressures give an economic benefit, since the equilibrium then
favours methanol. Only a part of the CO in the feed gas is converted to methanol in one pass
through the reactor, due to the low temperature at which the catalyst operates. The unreacted gas
is recycled at a ratio typically between 2.3 and 6.
The copper catalyst is poisoned by both sulphur and chlorine, but the presence of free zinc
oxides does help prevent poisoning.
Liquid phase methanol production
In liquid phase processes (Cybulski 1994; USDOE 1999), the heat transfer between the solid
catalyst and the liquid phase is highly efficient, and therefore the process temperature is very
uniform and steady. A gas phase delivers reactants to the finely divided catalyst and removes the
products swiftly. This allows high conversions to be obtained without loss of catalyst activity.
The higher conversion per pass (compared to fixed bed technology) eliminates the need for a
recycle loop, which implies less auxiliary equipment, less energy requirements, smaller
volumetric flow through the reactor (Katofsky 1993). An additional advantage is the ability to
withdraw spent catalyst and add fresh catalyst without interrupting the process.
Page 32 of 111
Methanol
+ unreacted gas
Gas bubbles
H2
CH3OH
CO
Slurry with catalyst

Synthesis gas
Figure 3.8 Liquid phase methanol synthesis with three phases: slurry, gas and solid.
Different reactor types are possible for liquid phase methanol production, such as a fluidised
beds and monolithic reactors. Air Products and Chemicals, Inc. invented a slurry bubble column
reactor in the late 1970s, which was further developed and demonstrated in the 1980s and 1990s.
From 1997 tot 2003, a 300 tonne/day demonstration facility at Eastman Chemical Company in
Kingsport TN produced about 400 million litres methanol from coal via gasification (Heydorn et
al. 2003).
In the slurry bubble column reactor (Figure 3.8), reactants from the gas bubbles dissolve in the
liquid and diffuse to the catalyst surface, where they react. Products then diffuse through the
liquid back to the gas phase. Heat is removed by generating steam in an internal tubular heat
exchanger.
Commercial Cu/Zn/Al catalysts developed for the two-phase process are used for the three-phase
process. The powdered catalyst particles typically measure 1 to 10 m and are densely
suspended in a thermostable oil, chemically resistant to components of the reaction mixture at
process conditions, usually paraffin. Catalyst deactivation due to exposure to trace contaminants
is a point of concern (Cybulski 1994).
Conversion per pass depends on reaction conditions, catalyst, solvent and space velocity.
Experimental results show 15 – 40 % conversion for CO rich gases and 40 – 70 % CO for
balanced and H2 rich gases. Computation models predict future CO conversions of over 90 %, up
to 97 % respectively (Cybulski 1994; Hagihara et al. 1995). Researchers at the Brookhaven
National Laboratory have developed a low temperature (active as low as 100 °C) liquid phase
catalyst that can convert 90 % of the CO in one pass (Katofsky 1993). With steam addition the
reaction mixture becomes balanced through the water gas shift reaction. USDOE claims that the
initial hydrogen to carbon monoxide ratio is allowed to vary from 0.4 to 5.6 without a negative
effect on performance (USDOE 1999).
Page 33 of 111
The investment costs for the liquid phase methanol process are expected to be 5 – 23 % less than
for a gas phase process of the same methanol capacity. Operating costs are 2 – 3 % lower; this is
mainly due to a four times lower electricity consumption (USDOE 1999).
Page 34 of 111
4 PROCESS DESCRIPTION
4.1 Dr ying
The biomass pre-treatment is identical to that described by Isaksson et al. (2012), i.e. chipping
followed by drying using a low temperature air drier. The biomass is assumed to initially have a
moisture content of 50 wt% and being dried to a moisture content of 15 wt%. The biomass is
then fed to the gasifier.
4.2 Gasification
It is advantageous to use elevated pressure and oxygen instead of air as the oxidizing media.
Elevated pressure makes it possible to use smaller equipment downstream of the gasifier. Using
oxygen instead of air also has the advantage of avoiding dilution of the syngas with nitrogen,
which is especially important if the purpose is to convert the syngas to chemical products. In this
thesis O2/steam-blown fluidized-bed gasification is assumed.
4.3 Tar cracking

Tars and other hydrocarbons will form during gasification of biomass, and must be removed
prior to methanol synthesis. It is possible to either use “hot gas”, e.g. catalytic tar cracking, or
“cold gas”, scrubbing, cleaning. Catalytic tar cracking is assumed in this thesis, as outlined in
Isaksson et al. (2012). Catalytic tar cracking has the advantage that heat can be recovered at high
temperatures. Furthermore, the tars are catalytically cracked into e.g. CO and H2, which is
beneficial for the downstream methanol synthesis. Forest logging residues Drying Gasification
Tar cracking Gas cleaning Autothermal reforming Water-gas-shift CO2 removal Methanol
synthesis Purification Methanol.
4.4 Wet gas cleaning

Removal of particulates and other impurities in the product gas is necessary since particulates
can poison the methanol synthesis catalyst. As in the study by Isaksson et al. (2012), wet gas
cleaning is assumed for removal of particulates and other impurities from the product gas. Solid
particles are first removed with a cyclone. Particulates and alkalis, which condense on particles,
are removed in a bag filter before the gas passes through a wet scrubber and a sulfur guard bed.
Using a ZnO bed makes it possible to lower the sulfur concentration to below 0.1 ppm
(Hamelinck & Faiij, 2001).
4.5 Autothermal reforming (ATR)

The methane content in the product gas is relatively large. In order to avoid accumulation of
methane in downstream processes it is important to reform the gas prior to methanol synthesis.
This can be accomplished using a steam-methane-reformer (SMR) or an autothermal reformer
Page 35 of 111
(ATR). In this study an oxygen-blown ATR is assumed. In the ATR, hydrocarbons such as
methane, ethane and ethylene are reformed into carbon monoxide and hydrogen. The reforming
is based on equilibrium reactions and operating parameters found in the literature (Rostrup-
Nielsen, 2002; Rostrup Nielsen, 1993; Hiller, et al., 2006). In order to provide heat to the highly
endothermic reforming reactions, carbon dioxide and water is also formed by oxidizing part of
the feed product gas. The temperature range of the ATR is typically 900 to 1100˚C. A water to
carbon ratio of 1.5 – 2.5 moles of steam per mole of carbon is possible.
4.6 Water-gas-shift (WGS)

The final step before the methanol synthesis is to adjust the hydrogen to carbon monoxide ratio
to obtain higher methanol yields in the methanol synthesis, which is based on equilibrium
reactions. This can be done by utilizing the water-gas-shift reaction by adding steam to the shift
reactor, according to 2-1. 2-1 The desired hydrogen to carbon monoxide ratio is defined by the
downstream reaction, and the specified ratio can be met by by-passing the shift reactor with a
sub-stream. In the case for methanol synthesis the ratio between hydrogen and carbon monoxide
to maximize the methanol yield is 2.1:1 (Hamelinck & Faiij, 2001).
4.7 CO2 removal

To further increase the methanol yield in the methanol synthesis, CO2 can be removed from the
syngas. The closer the (H2-CO2)/(CO+CO2) ratio is to 2.1, the greater is the conversion of the
syngas to methanol. It is however advantageous to have some CO2 in the feed to the reactor to
promote the methanol formation from CO, i.e. the CO2 content of the gas affects the equilibrium
reactions within the methanol synthesis. CO2 in the gas is also advantageous to avoid too much
deactivation of the catalyst. A volume fraction of CO2 of 2  10% is suitable (Air Products and
Chemicals, Inc, 1998). CO2 removal from the syngas can e.g. be achieved via amine absorption
(Götz, et al., 2012). The syngas containing CO2 enters the absorber and contacts an aqueous
solution of amine that flows counter-currently to the syngas stream. CO2 is a weak base and
reacts exothermically with the amines, which is a weak acid, and forms water soluble salt. The
stream containing the absorption solution and the salt, exits the absorber at the 8 bottom of the
absorption column. This stream is then regenerated and recycled back to the absorption column.
The “clean” syngas exits at the top of the absorption column (Alie, et al., 2005). When utilizing
internal heat exchanging for the absorber and regeneration processes, the required energy input
for the absorption of CO2 can be approximated by the energy requirement for the reboiler in the
desorber (Götz, et al., 2012).
4.8 Methanol synthesis

After the CO2 absorption process, the gas is transferred to a methanol synthesis unit. There exist
different processes for methanol synthesis, e.g. gas-phase methanol synthesis and liquid phase
methanol synthesis. The methanol synthesis reaction method assumed in this thesis is the triple-
phase methanol synthesis with the trademark LPMEOHTM , which is referred to as a liquid
phase methanol synthesis (Air Products and Chemicals, Inc, 1998). The reactor used in this
Page 36 of 111
catalytic reaction is a slurry bubble column. Catalyst used is Cu/Zn/Al (Air Products and
Chemicals, Inc, 1998; Heydorn & Diamond, 2003). Typical reaction temperature for the
LPMEOHTM reaction is in the range of 230 to 270˚C (Heydorn & Diamond, 2003). The
pressure of the LPMEOHTM reaction is in the range of 35 to 90 bar, where higher pressures
results in higher conversions (Air Products and Chemicals, Inc, 1998). The reactions taking place
during the methanol synthesis are according to 2-2, 2-3 and the water-gas-shift reaction 2-1. 2-2
2-3 Reaction 2-3, methanol formation from CO2, occurs only to a minor extent. The methanol
synthesis is an exothermic reaction. An advantage with the three-phase reactor is that the liquid-
phase oil that the catalyst particles are dispersed in serves as a heat removal medium, and permits
isothermal operation of the synthesis reaction (Heydorn & Diamond, 2003). The LPMEOHTM
process is very flexible when it comes to variations in the syngas composition. It is very
advantageous, compared to other technologies, for syngas that is rich in CO. This is due to the
ability to control the temperature within the reactor with the heat removal medium. In an
ordinary gas-phase reaction, a circulating H2 rich gas is often required to be able to control the
temperature within the reactor. Despite that it is possible to use a CO rich syngas in the
LPMEOHTM process, the closer the (H2-CO2)/(CO+CO2) ratio is to 2.1, the greater is the
conversion. Another method of increasing the degree of conversion is to cool down the reaction
mixture, resulting in methanol condensation, and to recycle part of the reactor effluent back to
the reactor inlet (Air Products and Chemicals, Inc, 1998). This is necessary since the methanol
synthesis reaction is limited by chemical equilibrium (Graaf & Beenackers, 1996). According to
Air Products and Chemicals (1998), a recycle to fresh feed ratio of 1:1 is usually quite effective
when optimizing the methanol production. However, the recycle ratio depends upon whether the
syngas is rich in CO or if the syngas is more balanced, H2/CO=2.1. As long as neither the CO
nor the H2 is entirely consumed, the overall conversion into methanol is increased with an
increased recycle ratio. If for example using a CO rich syngas where most of the H2 is consumed
in the reactor, it is claimed that little is gained with a recycle ratio above 2:1 (Air Products and
Chemicals, Inc, 1998). If this is the case and a higher conversion is desired it is necessary to 9
generate additional H2, e.g. via a water-gas-shift reaction prior to the methanol synthesis, as
assumed in this thesis. It can also be done by adding additional water to the syngas before
passing it through the reactor resulting in that the water-gas-shift equilibrium within the
methanol synthesis reactor goes towards the H2 product (Air Products and Chemicals, Inc,
1998). The alternative of not having a separate WGS reaction would require one less process
unit. However since the WGS reaction is an exothermic reaction, and the heat formed during
reaction can be recovered, the alternative of not having a separate WGS reactor would affect the
opportunities for heat recovery. Unreacted gas, which is not recycled back to the methanol
synthesis reactor, is assumed to be combusted in a steam-boiler. After the methanol has been
flashed out a first time, another flash is used at a lower pressure to separate methanol from
unreacted gas. After the second flash, the methanol is further purified using two distillation
columns, reaching a final purity of 99.8 wt% (Isaksson, et al., 2012).
Page 37 of 111
5 P R O C E S S S I M U L AT I O N
This section presents the mass and energy balance of a methanol production process based on
oxygen-steam blown pressurized gasification with 450 MWLHV biomass input consisting of
wood chips at 50% moisture. This corresponds to a biomass intake of 189 360 kg∙h⁻¹,
corresponding to around 1 514 kt∙y⁻¹ assuming 8000 hours of operation per year.
Mass and energy balances of the biomass conversion to methanol were estimated by process
modelling using published models developed at the Div. of Heat and Power Technology
Chalmers (Isaksson, Pettersson et al. 2012). The main assumptions for the gasification system
were taken from published literature data and in particular from the results of activities
conducted by the Finnish VTT Technical Research Center (Hannula and Kurkela 2010, Hannula
and Kurkela 2013).
This system for biomass based methanol differs from the concept based on indirect gasification
investigated in the first system configuration only for the gasification technology and on the gas
cleaning section.
The process simulation for this design was achieved using ASPEN HYSIS version 7 simulation
software.
Here biomass is gasified in pressurized conditions (at 25 bar) and in presence of oxygen and
steam. Pressurization of the whole gas production process through a pressurized biomass feeding
system introduces significant savings in the subsequent gas compression required to achieve the
optimal synthesis pressures both in terms of capital and operating costs. However, since
combustion and gasification occur in the same reactor, to avoid large amount of inert nitrogen
the direct gasification concepts necessitates a pure oxygen stream. Gasification occurs also in
presence of steam which is required as a reforming agent. These latter endothermic reactions
require energy to be provided by combustion and therefore the consumption of oxygen increases
with the steam input. As reported in Ref. (Hannula and Kurkela 2012) the optimal ratio between
oxygen and steam for a temperature around 886°C and for a pressure of around 25 bar is around
1:1.
The biomass is converted into around 176 981 kg∙h⁻¹ of gas with the composition reported in
Table 5.1. The higher heating value (HHV) of this gas is 9.191 MJ∙kg⁻¹, the lower heating value
(LHV) is 7.790 MJ∙kg⁻¹.
Page 38 of 111
𝐻𝐻𝑉
𝑚̇𝑔𝑎𝑠 ∗ 𝐻𝐻𝑉𝑔𝑎𝑠
𝜂𝐶𝐺 = = 82.4%
𝑚̇𝑏𝑖𝑜𝑚𝑎𝑠𝑠 ∗ 𝐻𝐻𝑉𝑏𝑖𝑜𝑚𝑎𝑠𝑠
𝐿𝐻𝑉
𝑚̇𝑔𝑎𝑠 ∗ 𝐿𝐻𝑉𝑔𝑎𝑠
𝜂𝐶𝐺 = = 85.1%
𝑚̇𝑏𝑖𝑜𝑚𝑎𝑠𝑠 ∗ 𝐿𝐻𝑉𝑏𝑖𝑜𝑚𝑎𝑠𝑠
Table 5.1: Composition of the product gas obtained from gasification of wood chips in oxygen
steam blown gasifier at 890°C and 25 bar.
Component Mol. Frac. (%)
H2 20.1
CO 15.8
CO2 21.9
H2O 34.1
CH4 5.4
N2 0.027
O2 -
Acetylene 0.035
Ethylene 1.476
Ethane 0.377
Propane 0.017
Benzene 0.328
Naphthalene 0.364
Ammonia 0.050
H2S 0.003
HCl 0.005
Page 39 of 111
The gasification is followed by an isothermal (890°C) catalytic bubbling fluidized bed in which
the tar compounds are reformed in presence of the abundant steam content of the product gas.
Data about such a reformer were obtained from publications by the US NREL (Spath, Aden et al.
2005). Tar compounds such as Naphthalene, light hydrocarbons such as propane and ethane as
well as ethylene and acetylene are found in the product gas from the gasifier and are largely
reformed into H2 and CO by catalytic cracking. Methane is also partially cracked although about
half of that still remains in the gas at the reformer outlet. The heat for reforming is provided by
circulating the bed and the catalyst from a side combustor which is fuelled by a certain quantity
of product gas (about 10% of the total product gas) that is by-passed prior the reformer and
therefore does not contribute to methanol production.
At the outlet of the tar cracker, particulate matter, alkali materials, and sulphur compounds are
still present in the gas and must be removed prior to the gas upgrading and synthesis reactions. In
this second system configuration, this is done by hot gas cleaning technologies and in particular
by candle filters. The sulphur, assumed here completely in the form of H2S, is removed through
a guard bed based on metal oxides.
In order to finally convert the remaining hydrocarbons that would otherwise remain as inert in
the methanol synthesis process, a catalytic autothermal reformer was considered as in the first
system alternative. Here, however, enough steam is present in the gas after the gasification and
the tar cracker, and steam injection is not required as the steam to carbon ratio is already higher
than 1.
The syngas at the reformer outlet is then cooled to a temperature around 350°C and sent to a high
temperature water gas shift reactor where the final ratio between H2 and CO is obtained. A
certain amount of gas is also bypassed so that only the required amount of gas is shifted. The gas
is subsequently cooled to ambient temperature and most of the CO2 is removed by a Rectisol
process where methanol is used as a physical absorbent. A final CO2 concentration of 3% in the
dry syngas is obtained as it is the optimal concentration for subsequent methanol synthesis. The
syngas is finally compressed up to the synthesis pressure of 90 bar.
A certain amount of hydrogen is recovered from a purge stream after the methanol synthesis
which is mixed to the fresh syngas feed to reach the final synthesis ratio14 of around 2.05 with a
3% CO2 molar fraction. The syngas is then mixed with the synthesis loop gas obtained at the top
of the flash drum right after the reactor. Here the synthesis loop is assumed to be 3:1 in volume
with respect to the fresh syngas.
Methanol synthesis occurs in a fixed bed reactor where steam is produced by reactor cooling.
The reaction products are subsequently cooled leaving a two-phase stream. The crude methanol
is obtained at the bottom of the flash drum and is then sent to distillation after the pressure has
been released to atmospheric values. A stripper is used to evaporate the remaining gases
Page 40 of 111
entrained in the raw methanol. The methanol rich liquid still present a large quantity of water
which is removed in a two column system.
The purge gases are burnt thus producing additional heat that can be used for steam production.
More details about the modelling assumptions and stream composition and characteristics in the
different process steps are given in the Appendix.
Overall, a biomass input of 450 MWLHV (548.7 MWHHV) yields a production of 53 534 kg∙h⁻¹
of methanol (336.8 MWHHV15, 295.6 MWLHV), which corresponds to a conversion efficiency
of 61.3% HHV basis (65.7% LHV basis).
The production of methanol from biomass through an oxygen steam blown gasifier requires a
large amount of high purity oxygen at high pressure. The biggest share of the oxygen is used for
the gasification itself. Some oxygen is also used for the catalytic reforming of hydrocarbons
(mostly methane) prior to the water gas shift, in order to further recover them in form of H2 and
CO which can be subsequently used for synthetizing methanol.
Oxygen is considered to be delivered by an air separation unit (ASU). Based on Aspen Plus
simulations, the specific work consumption for delivering an oxygen stream at atmospheric
pressure (95%mol O2, 2%mol N2, 3%mol Ar) is 0.263 kWh∙kg⁻¹, which is in agreement with
the value of 0.23 kWh∙kg⁻¹ reported in Ref. (Fu and Gundersen 2011) and 0.25 to 0.35 kWh∙kg⁻¹
reported in Ref. (Hamelinck and Faaij 2002). Additional work is required by further compression
of the oxygen stream up to the desired process pressure, here around 30 bar. The total specific
work consumption has been estimated to be around 0.43 kWh∙kg⁻¹ kg⁻¹oxygen.
The total oxygen demand in this second system alternative amounts to 42 747 kg∙h⁻¹, of which
32 835 kg∙h⁻¹ for the gasifier and 9 914 kg∙h⁻¹ for the autothermal reforming. This results in a
total power demand for the ASU and further oxygen compression of around 18.3 MW.
Although pressurized gasification helps to reduce the gas compression (at least for operating
pressures up to 25 to 30 bar) compared to the indirect gasification concept, power is still required
for compressing the gas up to the synthesis pressure of 90 bar. In addition, power is required by
the recirculation blowers in the methanol synthesis loop.
5.1 Overview of heat and power requirements of the biomass based

process
Heat recovery opportunities from the biomass to methanol process were estimated based on the
results of process simulation and by including the hot and cold thermal streams (cooling and
heating process steps).
Page 41 of 111
Most of the heat from the methanol synthesis reactor is recovered in form of steam at around 25
bar which is used for gasification and water gas shift. The remaining heat can be used for
producing steam to run the first distillation column.
Abundant heat is available instead from syngas cooling, which can be used for high pressure
steam production.
Note that heat is required by the first distillation column which is run at 10 bar as well as for
biomass drying. Still, no other large heat demand appears in the biomass to methanol process
which opens the opportunity for condensing steam turbine in case power shall be maximized or
for steam export to the nearby pulp and paper plant.
The production of methanol from biomass through an oxygen steam blown gasifier requires a
large amount of high purity oxygen at high pressure. The biggest share of the oxygen is used for
the gasification itself. Some oxygen is also used for the catalytic reforming of hydrocarbons
(mostly methane) prior to the water gas shift, in order to further recover them in form of H2 and
CO which can be subsequently used for synthetizing methanol.
Oxygen is considered to be delivered by an air separation unit (ASU). Based on Aspen Plus
simulations, the specific work consumption for delivering an oxygen stream at atmospheric
pressure (95%mol O2, 2%mol N2, 3%mol Ar) is 0.263 kWh∙kg⁻¹, which is in agreement with
the value of 0.23 kWh∙kg⁻¹ reported in Ref. (Fu and Gundersen 2011) and 0.25 to 0.35 kWh∙kg⁻¹
reported in Ref. (Hamelinck and Faaij 2002) . Additional work is required by further
compression of the oxygen stream up to the desired process pressure, here around 30 bar. The
total specific work consumption has been estimated to be around 0.43 kWh∙kg⁻¹ kg⁻¹oxygen.
The total oxygen demand in this second system alternative amounts to 42 747 kg∙h⁻¹, of which
32 835 kg∙h⁻¹ for the gasifier and 9 914 kg∙h⁻¹ for the autothermal reforming. This results in a
total power demand for the ASU and further oxygen compression of around 18.3 MW.
Although pressurized gasification helps to reduce the gas compression (at least for operating
pressures up to 25 to 30 bar) compared to the indirect gasification concept, power is still required
for compressing the gas up to the synthesis pressure of 90 bar. In addition, power is required by
the recirculation blowers in the methanol synthesis loop.
Table 5.2: Power requirements of the methanol production process based on oxygen steam
blown biomass gasification.
Page 42 of 111
Equipment Power (KW)
Biomass feeding system (piston) 2 250
Pumps 146
Main gas compressor before synthesis 9 120
Air compressor to tar reformer combustor 8 783
Synthesis loop recirculation blower 1 021
H2 recirculation compressor 735
Rectisol refrigeration 3 804
ASU 11 255
O2 compressor 7 053
Total 44 167
Compression is also required for pressurizing the air needed for the catalyst regenerator
combustor and bed reheating for the tar reformer.
A piston-type biomass feeding system is assumed for biomass injection in pressurized

gasification conditions and 5 kW electricity consumption per 1 MW fuel (LHV basis) is
considered.
CO2 removal is achieved through physical absorption in a Rectisol process with methanol as
solvent. Absorption is favoured by high pressures and low temperatures which are obtained
through refrigeration. In addition, steam is required in the stripper for further separation of CO2
from methanol in order to regenerate the solvent.
Other ancillaries such as pumps and small compressors are also power consumers.
A breakdown of the process power requirement is given in Table 5.1. Overall, a total power
consumption of around 44.2 MW is estimated.
Page 43 of 111
11 12
4 8 9 Q6 Q7
3A 5
3B Q2 6
Q3
Q102
Q4
Q103
7
10
1 Q1
W4
2
Q5
13 21
W3 30
24 28
20 Q101
19
W2 Q100
18 Q15 Q17 Q21

22
Q11 Q14 27
Q9
Q12
14 Q8 15 16 17
Q19
24 29
Q18
Q13
26 Q20
Q10 23 Q16
W1
Figure 5.1 PROCESS FLOW DIAGRAM Page 44 of 111

Table 5.2 Streams table
Stream 1 2 3 3b 3a 4 5 6
Mass flow 32 833 32 833 176 981 18 583 158 398 158 398 158 398 158 377
(kg∙h⁻¹)
Temp (°C) 200 228 886 886 886 886 300 700
Pressure (atm) 24.7 24.7 24.7 24.7 24.7 24.5 24.0 24.0
Molar flow 1 026 1 822 7 775 816 6 959 8 180 8 180 8 180
(kmol∙h⁻¹)
Mol frac. (%)
H2 - - 20.1 20.1 20.1 32.0 32.0 32.0
CO - - 15.8 15.8 15.8 27.2 27.2 27.2
CO2 - - 21.9 21.9 21.9 14.6 14.6 14.6
H2O - 100.0 34.1 34.1 34.1 23.4 23.4 23.4
CH4 - - 5.4 5.4 5.4 2.6 2.6 2.6
N2 - - 0.027 0.027 0.027 0.042 0.0 0.0
O2 100.0 - 0.000 - - - - -
Acetylene - - 0.035 0.035 0.035 0.003 0.003 0.003
Ethylene - - 1.476 1.476 1.476 0.126 0.126 0.126
Ethane - - 0.377 0.377 0.377 0.003 0.003 0.003
Propane - - 0.017 0.017 0.017 0.000 0.000 0.000
Benzene - - 0.328 0.328 0.328 0.003 0.003 0.003
Naphthalene - - 0.364 0.364 0.364 0.000 0.000 0.000
Ammonia - - 0.050 0.050 0.050 0.004 0.004 0.004
H2S - - 0.003 0.003 0.003 0.003 0.003 -
HCl - - 0.005 0.005 0.005 0.004 0.004 -
Methanol - - - - - - - -
Page 45 of 111
Stream 7 8 9 10 11 12 13 14
Mass flow 9 914 168 291 74 754 36 311 111 065 204 575 59 644 60 141
(kg∙h⁻¹)
Temp (°C) 200 1 001 350 400 503 50 59 264
Pressure (atm) 30.0 23.6 23.6 29.6 23.5 23.5 23.5 88.8
Molar flow 311 8 616 3 828 2 016 5 843 10 631 5 301 5 547
(kmol∙h⁻¹)
Mol frac. (%)
H2 - 31.2 31.200 - 34.200 32.900 65.900 67.416
CO - 28.0 28.000 - 4.500 15.100 29.700 28.390
CO2 - 14.2 14.300 - 23.100 19.100 3.100 2.936
H2O - 26.3 26.300 100 37.900 32.700 0.800 0.804
CH4 - 0.2 0.200 - 0.100 0.200 0.300 0.281
N2 2.0 0.1 0.100 - 0.100 0.100 0.200 0.173
O2 98.0 0.0 - - - - - -
Acetylene - 0.0 - - - - - 0.000
Ethylene - 0.0 - - - - - 0.000
Ethane - - - - - - - -
Propane - 0.0 - - - - - 0.000
Benzene - 0.0 - - - - - -
Naphthalene - 0.0 - - - - - -
Ammonia - 0.0 - - - - - -
H2S - - - - - - - -
HCl - - - - - - - -
Methanol - - - - - - - -
Page 46 of 111
Stream 15 16 17 18 19 20 21 22 23
Mass flow 130 599 130 599 58 950 71 649 70 456 1 192 497 2 475 56475
(kg∙h⁻¹)
Temp (°C) 250 250 50 50 57 50 408 18 66
Pressure (atm) 88.8 83.9 83.9 83.9 88.8 83.9 88.8 1.0 1
Molar flow 22 190 18 830 1 904 16 925 16 643 281.67 246.5 70.5 1834
(kmol∙h⁻¹)
Mol frac. (%)
H2 85.936 82.791 0.000 92.109 92.109 92.109 100 0.001 0.0
CO 9.191 2.543 0.328 2.792 2.792 2.792 - 8.855 0.0
CO2 1.823 1.514 2.064 1.452 1.452 1.452 - 55.781 0.0
H2O 0.219 0.892 8.611 0.023 0.023 0.023 - 0.003 8.9
CH4 0.657 0.774 0.702 0.782 0.782 0.782 - 18.962 0.0
N2 1.621 1.910 0.195 2.103 2.103 2.103 - 5.259 0.0
O2 - - - - - - - - 0.0
Acetylene 0.000 0.000 0.000 0.000 0.000 0.000 - 0.000 0.0
Ethylene 0.000 0.000 0.000 0.000 0.000 0.000 - 0.000 0.0
Ethane - - - - - - - - 0.0
Propane 0.000 0.000 0.000 0.000 0.000 0.000 - 0.000 0.0
Benzene - - - - - - - - 0.0
Naphthalene - - - - - - - - 0.0
Ammonia - - - - - - - - 0.0
H2S - - - - - - - - 0.0
HCl - - - - - - - - 0.0
Methanol 0.554 9.575 88.100 0.738 0.738 0.738 - 11.139 91.1
Page 47 of 111
Stream 24 25 26 27 29 28 30
Mass flow 56475 38564 17911 17911 2941 14970 53534

(kg∙h⁻¹)
Temp (°C) 120 137 143 40 98 65 40
Pressure (atm) 10 10 10 1 1 1 1
Molar flow 1834 1204 630 630 162 468 1672

(kmol∙h⁻¹)
Mol frac. (%)
H2 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CO 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CO2 0.0 0.0 0.0 0.0 0.0 0.0 0.0
H2O 8.9 0.1 25.8 25.8 99.1 0.3 0.2
CH4 0.0 0.0 0.0 0.0 0.0 0.0 0.0
N2 0.0 0.0 0.0 0.0 0.0 0.0 0.0
O2 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Acetylene 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Ethylene 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Ethane 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Propane 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Benzene 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Naphthalene 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Ammonia 0.0 0.0 0.0 0.0 0.0 0.0 0.0
H2S 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HCl 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Methanol 91.1 99.9 74.2 74.2 0.9 99.7 99.8
Page 48 of 111
Heat Q1 Q2 Q3 Q4 Q5 Q6 Q7 Q8 Q9
sink/source
Tin (°C) 15 886 300 1000 25 437 159 109 250
Tout (°C) 200 300 700 350 200 50 160 250 249
Heat load 1629 49620 33146 57798 466 83191 1008 26215 45141
(kW)
Heat Q10 Q11 Q12 Q13 Q14 Q15 Q16 Q17+Q Q18
sink/source 21
Tin (°C) 250 25 54 66 91 137 143 65 143
Tout (°C) 50 200 18 66 120 136 144 40 40
Heat load 52315 460 1249 2279 3206 10478 21482 13957 2083
(kW)
Heat Q19 Q20 Q100 Q101 Q102 Q103

sink/source
Tin (°C) 66 100 1000 1000 20 1000
Tout (°C) 65 101 999 150 70 150
Heat load 10095 10687 3651 3638 76978 23066

(kW)
Power demands Power (kW)
W1 9120
W2 1021
W3 735
W4 8783
Rectisol 3804
Biomass feeding 2250
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ASU 11255
O2 compress to 30 bar 7053
Ancillaries 146
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6 EQUIPMENT LIST
Table 6.1 The main process areas require the following equipment:
Equipment Heat Duty (kW) Construction Materials

1. Air Drier 76978 Stainless steel 308L
2. Fluidized Bed Gasifier 51249 Stainless steel 308L
3. TAR Reformer 49620 Stainless steel 308L
4. Filter Stainless steel 308L
5. Guard Bed Stainless steel 308L
6. Heat Exchangers 128115 Stainless steel 308L
7. ATR 33146 Stainless steel 308L
8. Shift Reactor 57798 Stainless steel 308L
9. Rectisol 3804 Stainless steel 308L
10. Compressor 7053 Stainless steel 308L
11. Blower 52313 Stainless steel 308L
12. MEOH Reactor 71356 Stainless steel 308L
13. Membrane Stainless steel 308L
14. Furnace 3651 Stainless steel 308L
15. Stripper 3528 Stainless steel 308L
16. Storage 23077 Stainless steel 308L
Page 51 of 111
7 G A S I F I C AT I O N
Thermochemical gasification involves the conversion of a carbonaceous feedstock such as

biomass or coal at elevated temperature into a gaseous energy carrier. The gaseous product
generally contains carbon monoxide, carbon dioxide, hydrogen, methane, trace amounts of
higher hydrocarbons such as ethane and ethene, water, nitrogen (if air is used as the oxidizing
agent) and various contaminants such as small char particles, ash, tars and oils. The partial
oxidation can be carried out in the presence of air, oxygen, steam or a mixture of these.
If air is used as the gasification medium, a poor-quality gas is produced in terms of heating value
(4-7 MJ/m3 higher heating value). This type of gas is suitable for boiler, engine and turbine
operation, but not for pipeline transportation due to its low energy density. A better-quality gas is
produced with oxygen (10-18 MJ/m3 higher heating value) which is suitable for limited pipeline
distribution and for use as synthesis gas for conversion, for example, to methanol and gasoline.
Gas of this quality can also be produced by steam gasification, with the process energy being
supplied by combustion of by-product char in a second reactor.
7.1 Principles of Gasification

Gasification occurs in different steps as listed below:
 Evaporation of moisture by drying,
 Pyrolysis resulting in the production of gas, vaporized tars or oils and a solid char
residue,
 Gasification or partial oxidation of the solid char, tars and gases.
Subjecting a solid fuel to heated (35 to 5000oC) in the absence of an oxidizing agent, results in
pyrolysis of the fuel to solid char, tar (condensable hydrocarbons), and gases.
As mentioned before, the relative yields of gas, liquid and char depend on the rate of heating and
the final temperature. Generally the pyrolysis or devolatillisation step is much more rapid than
gasification, and consequently the latter is the rate-controlling step. The interaction and reaction
of the gas, liquid and solid products of pyrolysis with the oxidizing agent give permanent gases
(CO, CO 2, H2,) and lesser quantities of hydrocarbon gases. Char gasification is the interactive
combination of several gas-solid and gas-gas reactions in which solid carbon is oxidized to
carbon monoxide and carbon dioxide, and hydrogen is generated through the water-gas shift
reaction. The gas-solid reactions of char oxidation are the slowest and limit the overall rate of the
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gasification process. Many factors such as feed composition, water content, and reaction
temperature influence the gas composition.
Due to the physical and geometrical limitations of the reactors and also the limitations imposed
by the chemical reactions that take place, it is not possible to convert all of the liquid products
generated in the pyrolysis stage. As a result, the product gas always contains contaminants in the
form of tar.
7.2 Fluidized Bed Gasifier

Figure 7.1 Fluidized Bed Gasifier
The simplicity of single fluidized beds makes them attractive for gasification of biomass. Gases
produced by a fluid bed gasifier vary widely depending on several parameters. Fuel moisture,
bed temperature, bed depth, gasification rate, bed particle size, char re-injection, air temperature
and location of fuel inlet all affect the gas composition.
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If oxygen is present, some of the solid carbon and most of the hydrocarbon vapours are oxidized.
However solid particles can be satisfactorily removed and unburned carbon particles can be
returned to the bed and oxidized or gasified. The gas temperature can be reduced to a
manageable level. Fluid bed gasifiers can be designed to have bed temperatures lower than
500°C or higher than 900°C. The pyrolysis of biomass is rapid and occurs at whatever
temperature the bed is maintained. Selecting the optimum bed temperature depends on what the
optimum desirable product is.
The fluid bed process is unique among the biomass gasifiers in one important capability, biomass
fuel in any particle size range, any moisture content, and any ash or grit content can be gasified.
A typical product gas composition obtained from the steam gasification of biomass (almond
shells) in a fluidized bed reactor is shown in figure (Rapagna and Latif, 1997). The authors have
investigated the gasification of biomass in a fluidized bed reactor over the temperature range of
600 — 850 °C. They have shown that for small particle sizes, the differences in the product yield
and distribution becomes negligible at high temperatures (around 850 °C). However for larger
particles (dr > 1mm), although the total yield continues to increase over the temperature range
studied, but quantitatively it does not reach that obtained with the smaller particles.
This suggests the significance of heat transfer limitations as the particle increases in size. The
authors have also reported that char production is negligible for very small biomass particle feed
size and high temperatures. For larger biomass feed particles (d = 1mm), the char yield decreases
over the temperature range but still maintains a significant quantity.
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8 D E S I G N A N D O P E R AT I O N O F T H E C F B B I O M A S S
GASIFIER
The basic unit of circulating fluidized bed biomass gasifier system comprises of following
components:
(1) Riser,
(2) Cyclone separator,
(3) Burner-blower system for hot air generation,
(4) Biomass hopper and screw feeder,
(5) Gas cooling system (either quench or heat exchanger type),
(6) Particulate filter system (either single or double stage) and
(7) Dual fuel generator.
The operation of the CFB biomass gasifier can be described in brief as follows:
Hot air (at a temperature of about 700 – 1000oC) is generated by the burner-blower system. This
system could be either diesel or natural gas or LPG fired, depending on application. The exhaust
of the burner-blower system is admitted into the bottom of the riser section of the gasifier
through a distributor plate. Biomass is admitted in to the gasifier via a screw feeder system at a
specified rate. A hopper is used for storage of biomass. In the riser section, contact between hot
air and biomass takes place which results in oxidation of the biomass yielding gases such as
carbon monoxide, carbon dioxide, hydrogen, methane and water, along with un-reacted oxygen
(if any) and nitrogen. In many situations, sand is used as an inert bed material.
Purpose of sand is two-fold: (1) it increases the residence time of the light biomass particles
introduced in the riser by causing friction and (2) it increases the heat transfer characteristics of
the fluidized bed due to its inherent high heat capacity. The exhaust of the riser section is
introduced in a cyclone separator at high velocity. The cyclone separator disengages the
particulate solids from gas (sand as well as unconverted biomass particles), which are returned at
the bottom of the riser section.
The gas from the cyclone separator is first taken to a heat recovery exchanger, in which the
incoming air for burner-blower system is preheated with the exhaust of the gasifier. The
producer gas is then further cooled (to approximately room temperature, before admitting it to
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the dual fuel generator) by spraying water in it. This is called quench cooling in which the latent
heat of vaporization of water is utilized for rapid cooling of hot gas. This leaves the producer gas
saturated with vapor; however, the vapor pressure of water at ambient conditions is rather small
(~ 3000 Pa) and the gas can still be used in a dual fuel engine. To remover suspended droplets of
water from the gas, a small cyclone separator is used. The gas is then filtered in two steps; first
with a sawdust filter, and secondly, using a fiber reinforced bag for removal of ash particles.
Depending on scale of operation, either single stage or double stage filters are used. As noted
earlier, tar formation problem is less marked in case of CFB gasifiers. However, to further
eliminate tar formation, in-bed catalyst such as calcined dolomite or sintered olivine can be used.
Three crucial factors affect the quality and quantity of producer gas obtained from biomass
gasification, viz. temperature of gasification, equivalence (air to fuel) ratio and moisture content
of biomass. In addition, several other factors such as type of biomass, particle size of biomass,
pressure of gasification etc. also affect the composition of producer gas. In subsequent section,
we shall discuss effect of these variables in greater detail. Higher moisture content of biomass
results in formation of methane. If composition of methane is significant, in-bed steam reforming
catalyst can also be used. In some situations where methane formation is desired, steam is mixed
with gasification air in certain molar ratio.
Hydrodynamic Calculations for Circulating Fluidize d Bed Gasifier
We start with the hydrodynamic calculations of the fluidized bed (i.e. the riser and the cyclone).
Aiming at capacity of 5 kWe. Assuming that the overall efficiency of conversion of thermal
energy to electrical energy is 20%, we should aim at a design of 25 kWth capacity gasifier.
8.1 Design calculations for the riser

To start with we need to decide upon three important design parameters of the riser section of the
gasifier, viz. height, diameter and material of construction. Main factors that affect the choice of
these parameters are capacity and operating conditions of the gasifier, typical dimensions of the
pipes available in market and the dimensions of the room in which the gasifier will be installed
(since this is a lab scale gasifier). After significant pondering on literature survey, in addition to
consideration of the conditions of gasification and limitations of the room available, it was
decided upon these parameters as follows: diameter = 4 in. (or 0.1016 m), height = 2 m and
MOC = SS 308. It should be noted that decisions on MOC was based on recommendations from
the literature on fabrication of high temperature equipment.
The particles of biomass are rather light and are easily drifted out of the rise even with small
velocities of gas. Therefore, in order to ensure effective and uniform distribution of the biomass
particles in the riser, the biomass will be mixed with sand particles of proper size and shape.
Friction with the sand particles will help distribute the biomass uniformly in the riser. Sand
particles will also help effective distribution of heat through the riser section due to their high
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heat capacity. Given below is a step-by-step calculation for the riser section of the gasifier along
with the distributor plate.
Particles size of sand: dp1 = 0.271 mm = 271 μm
Sphericity of sand particles: φs = 0.86
Density of sand particles: ρs1 = 2600 kg/m3
Take wood chips as the representative biomass. As far as hydrodynamics of the CFB gasifier is
concerned, the relevant properties are particle size and density.
Particle size of biomass: dp2= 270 μm
Density of biomass: ρs2 = 235 kg/m3
Fluidizing gas is taken to be air at 700oC (or 973.16 K). As noted earlier, hot air is generated by
the burner-blower system (presumed to be supplied by third party at required specifications). The
pressure of hot air exhaust is sufficiently high to overcome the pressure drops in different
sections of the gasifier unit. As air is being heat in an internal flow, the rise in temperature is
compensated by rise in pressure, and no significant reduction is seen in the density of air. As a
conservative estimate, therefore, we take the density of air as 1.1 kg m-3, which is slightly less
than the corresponding value for ambient conditions (1.2 kg m-3). The viscosity of air is taken at
700oC.
Density of air: ρair = 1.1 kg m-3
Viscosity of air: μair= 3.547 ×10-5 Pa-s
Voidage at minimum fluidization εmf1 = 0.4
Minimum fluidization velocity for sand (umf1):

2 (
𝑑𝑝1 𝜌𝑠1− 𝜌𝑎𝑖𝑟 ) ∈3𝑚𝑓 𝜑𝑠2
𝑈𝑚𝑓1 = = 0.028𝑚/𝑠
150𝜇𝑎𝑖𝑟 (1 − 𝜖𝑚𝑓 )
Minimum fluidization velocity for biomass (umf2):
2 (
𝑑𝑝2 𝜌𝑠2− 𝜌𝑎𝑖𝑟 ) ∈3𝑚𝑓 𝜑𝑠2
𝑈𝑚𝑓2 = = 0.00251𝑚/𝑠
150𝜇𝑎𝑖𝑟 (1 − 𝜖𝑚𝑓 )
Particle Reynolds no. of sand (Re p, sand) = 0.233

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Particle Reynolds no. of biomass (Rep,biomass) = 0.021
To determine the actual air velocity required for having the pneumatic conveying regime, we
determine non-dimensional terminal settling velocity (Ut*) and the non-dimensional diameter of
the particle (d*p) for sand particles. It needs to be mentioned that the sand particles (denoted by
subscript 1 in the following formulae), being denser, are taken as basis for choosing the gas
velocity. The fluidization velocity for the biomass particles is one order of magnitude smaller.
Thus, the biomass particles will be assured to be in pneumatic conveying regime for these
velocities.
Non-dimensional particle diameter:
1
∗
𝜌𝑎𝑖𝑟 (𝜌𝑠2− 𝜌𝑎𝑖𝑟 ) 3
𝑑𝑝1 = 𝑑𝑝1 ( ) = 6.548
𝜇𝑎𝑖𝑟
Non-dimensional terminal settling velocity:
∗
18 2.335 − 1.744𝜑𝑠
𝑈𝑡1 = ∗2 + [ ] = 1.34
𝑑𝑝1 ∗
√𝑑𝑝1
Actual terminal settling velocity:

1
∗
𝜇𝑎𝑖𝑟 (𝜌𝑠2− 𝜌𝑎𝑖𝑟 )𝑔 3
𝑈𝑡1 = 𝑈𝑡1 [ 2 ] = 1.649𝑚/𝑠
𝜌𝑎𝑖𝑟
Given the non-dimensional range of superficial velocity, which gives pneumatic transport
regime, is 𝑈𝑔∗ = 4 to 12.
The actual fluidizing velocity is then:

1
𝜇𝑎𝑖𝑟 (𝜌𝑠2− 𝜌𝑎𝑖𝑟 )𝑔 3
𝑈𝑔 = 𝑈𝑔∗ [ 2 ] = 1.649𝑚/𝑠
𝜌𝑎𝑖𝑟
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Taking into consideration the fact that the difference in the minimum fluidization velocity of
sand and biomass particle is large, it is quite clear that the gas velocities for which these particles
will enter fast fluidization regime will also be different. Similar calculations for biomass particles
shows that fast fluidization is encountered for air velocities between 1.63 to 4.88 m/s. Therefore
a velocity of 5m/s for fluidizing medium was chosen, which would give pneumatic conveyance
regime for all biomass particles, while the sand particles will be in fast fluidization / pneumatic
conveying regime.
Riser diameter dbed: 4 in. (101.6 mm).

2
𝜋𝑑𝑏𝑒𝑑
Bed cross-sectional area: 𝐴𝑏𝑒𝑑 = = 0.008107𝑚2
4
𝑚3
Airflow rate: = 𝐴𝑏𝑒𝑑 ∗ 𝑈𝑔 = 0.0405 (145 m3/h) at operating temperature of 700oC and 1
𝑠
bar (approx) pressure. We now calculate various pressure drops in the system:
Fixed bed voidage εm = 0.4
Height of fixed bed Lm= 0.2 m

𝑊
Weight of solid per unit area of bed = 𝐴 = 𝐿𝑚 (1 −∈𝑚 )𝜌𝑠1𝑔 = 3058 Pa ≈ 3.1 kPa
𝑏𝑒𝑑
𝑊
Adding up the pressure drop due to friction in the bed: ∆𝑃𝑏𝑒𝑑 = 1.2 (𝐴 ) = 3.72 kPa
𝑏𝑒𝑑
Distributor plate pressure drop is given by following expression (for a perforated plate type
distributor operating at superficial gas velocities much higher than minimum fluidizing
velocities:
−𝐷
∆𝑃𝑑 = ∆𝑃𝑏 [0.01 + 0.2 (1 − 𝑒𝑥𝑝 ( ))] = 168 Pa
2𝐿𝑚
Another major contributor to the pressure drop is the cyclone separator. The pressure drop in
cyclone separator comprises of five components:
(1) Inlet contraction,

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(2) Particle acceleration in the cyclone,
(3) Barrel friction,
(4) Gas flow reversal in the barrel and
(5) Exit contraction.
The detailed calculation procedure for these components is explained by Pell and Dunson.
However, for the preliminary design purpose, we take the net pressure drop in the cyclone
separator as 50% of the pressure drop in the bed as 1.5 kPa. Other miscellaneous pressure drops
in the system such as pipes and bends would another 15-20% (approximately 0.5 kPa). Thus, we
take the total pressure drop of cyclone and piping (denoted as ∆P misc ) as 2 kPa.
Thus, the total pressure drop in the system is:
∆Ptotal = ∆Pbed + ∆Pd + ∆Pmisc = 6.1 kPa
8.2 Calculations for distrib utor plate

The distributor plate of the riser section of gasifier is an important component. The distributor
plate is responsible for proper introduction of gasification medium (hot air) into the riser. It
essentially affects the proper contacting of biomass and the medium so as to achieve maximum
conversion of biomass. Effective design of distributor plate also eliminates problem of formation
of jets which could cause erosion of the system. We consider a perforated type distributor which
offers sufficient pressure drop so as to achieve uniform distribution of fluidizing medium in the
riser.
Distributor plate pressure drop ∆Pd = 168 Pa
Thickness of distributor plate = 5 mm = 0.005m
Diameter of orifice dor = 4 mm = 0.004 m
2∆𝑃𝑑
Gas velocity through distributor plate is given as 𝑈𝑑,𝑜𝑟 = 𝐶𝑑,𝑜𝑟 √ 𝜌 = 14.74m/s
𝑎𝑖𝑟
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𝑡 0.13
Where the orifice discharge coefficient is 𝐶𝑑,𝑜𝑟 = 0.82 ( ) = 0.8441
𝑑𝑜𝑟
𝑈𝑎𝑖𝑟 4
Number of orifices per m2 of the distributor Nor = ∗ 2 = 26990𝑚−2
𝑈𝑜𝑟 𝜋𝑑𝑜𝑟
Total number of holes on the distributor plate: Nor × Ab = 218.82 ≈ 220 holes
𝜋 2
Open area in the distributor plate = 4 𝑑𝑜𝑟 ∗ (𝑁𝑜𝑟 × 𝐴𝑏 ) = 0.00275m−2
Percent open area: 0.0025/0.008107 = 33.9%
8.3 Calculations for the Cyclone Separator

Stairmand’s design data is used for the high efficiency cyclone. The cyclone can be designed for
the maximum gas flow rate Qm = Ug × Ab = 0.0405 m3/s.
An important parameter in the design of a cyclone separator is the barrel diameter. This factor
depends on the design velocity for the cyclone inlet. We take the inlet velocity of the cyclone as
15 m/s, (3× the velocity in the riser, 5 m/s) so as to have efficient separations of the particulates
from producer gas.
With this, we have completed the preliminary mechanical design of the circulating fluidized bed
biomass gasifier.
Determining the amount of electrical power required
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Given spherical particles, and the char to be mainly composed of carbon, then the char-steam
reaction can be primarily represented as:
1 𝑑𝑛𝑐 1 𝑑𝑛𝐻2 𝑂
− 2
= − (𝑚𝑜𝑙𝑠 −1 𝑚−2 )
4𝜋𝑟𝑐 𝑑𝑡 4𝜋𝑟𝑐2 𝑑𝑡
1 𝑑𝑛𝑐 𝑑𝑟𝑐
− 2
= −𝑝̈𝑐 (𝑚𝑜𝑙𝑠 −1 𝑚−2 )
4𝜋𝑟𝑐 𝑑𝑡 𝑑𝑡
= 𝑘𝑐𝑠 𝑐𝐻2 𝑂
Where 𝑝̈𝑐 is the molar density of the char (mol/m3), k is the char gasification surface rate
constant, r is the radius of the char particle, and 𝑐𝐻2 𝑂 is the concentration of the gaseous reactant
(steam). The density of the wood char formed has been roughly calculated as 296 kg/m3. So
12𝑔
𝑀𝑐 =
𝑚𝑜𝑙
0.012𝑘𝑔
𝑀𝑐 =
𝑚𝑜𝑙
𝜌𝑐
𝑝𝑐̈ =
𝑀𝑐
0.012 𝑚𝑜𝑙
𝑝𝑐̈ = = 2.47 ∗ 104 ( 3 )
296 𝑚
It is required to find an overall rate coefficient, 𝑘𝑐 (𝑠 −1 ), assuming a reaction mass of 1g of

carbon and spherical particle.
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4𝜋 𝑑𝑐 3 1
𝑉𝑜𝑙𝑢𝑚𝑒 = ( ) =
3 2 𝑝𝑐
𝜋𝑑𝑐2 1
=
6 𝑝𝑐
1
6 3
Therefore: 𝑑𝑐 = (𝜋𝑝 )
𝑐
The density of the char produced from the wood chips is 296 kg/m3
Surface area/ mass (g) = 𝜋𝑑 2
1 2
6 3
= 𝜋 ⌊( ) ⌋
𝜋𝑝𝑐
2
6 3
= 𝜋( )
𝜋𝑝𝑐
2
𝐴𝑟𝑒𝑎 𝜋 6 3
= ( )
𝑔 1002 𝜋0.296
−3
𝑚2
= (1.10 ∗ 10 )
𝑔
𝐴𝑟𝑒𝑎 𝑚2 𝑔
= (1.10 ∗ 10−3 ) ∗ 12
𝑚𝑜𝑙 𝑔 𝑚𝑜𝑙
𝐴𝑟𝑒𝑎 𝑚2
= (1.32 ∗ 10−2 )
𝑚𝑜𝑙 𝑚𝑜𝑙
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𝑚𝑜𝑙 𝑚2
𝑘𝑐 (𝑠 −1 ) = 1.32 ∗ 10−2 𝑚𝑜𝑙
𝑚 2𝑠
𝑚𝑜𝑙 1
2
= 75.7 ∗
𝑚 𝑠 𝑠
𝑚 𝑚𝑜𝑙 1
∗ 3 = 75.7 ∗
𝑠 𝑚 𝑠
The steam concentration at the surface of the char at 800 °C has been evaluated as 6.78 mol/ m3.
𝑚 75.7 1
= ∗
𝑠 6.78 𝑠
1 𝑚
= 0.09 ∗ (at 800°C)
𝑠 𝑠
1 𝑐𝐻2 𝑂
= ∗𝑘
𝑠 75.7 𝑐𝑠
The above relationship is used to convert the char gasification surface rate constants into an
overall rate coefficient, k, at the corresponding temperature and the values are reported below in
Table 8.1.
Table 8.1 Comparison of and k values.
Temperature [°C] P [kPa] 𝒌𝒄𝒔 (𝐦/𝐬) 𝒌𝒄 (𝒔−𝟏 )
712 101.3 5. 14 ∗ 10−5 5.03∗ 10−6
753 101.3 7.76∗ 10−5 7.21∗ 10−6
806 101.3 1.26 ∗ 10−4 1.13∗ 10−5
The char gasification rate constants calculated are compared with those published in literature.
The value of the rate constants obtained (wood chips) are in good agreement with those for
coconut shell as shown. Wood char has rate constant much high than the nut chars and thus
indicate a higher char reactivity.
All the rate constant are compared with that obtained from the gasification of graphite which is a
very inert material and thus it would be expected to have rate constants much lower than the coal
and biomass chars.
Page 64 of 111
Effect of temperature
The temperature dependence of the reaction rate can be investigated from the Arrhenius
relationship:
𝐸𝑎
𝑘𝑐 = 𝐴 𝑒𝑥𝑝 (− )
𝑅𝑇𝑏
𝐸𝑎
ln(𝑘𝑐 ) = ln 𝐴 −
𝑅𝑇𝑏
From a plot of ln(k) against 1/Tb
𝐸𝑎
𝑠𝑙𝑜𝑝𝑒 = − 9213.3 = −
𝑅
Therefore
𝑘𝐽
𝐸𝐴 = 76.6
𝑚𝑜𝑙
The activation energy for the biomass char gasification obtained here is lower than those for coal
derived char-steam gasification reported in literature although the latter have not been derived
from a fluidized bed. However, this suggests that the chars derived from biomass may be more
reactive than those of coal.
8.4 Determination of optimum gasifier volume

The intention here is to use the rate constant results to evaluate the optimum gasifier volume
required for the particular conversion of the char. Assuming that devolatillization stage is rapid
and once the biomass particle has passed through the bed and surfaced at the top, it has lost all its
volatiles and is fully carbonized. Defining the extent of conversion during the gasification of
biomass as:
Page 65 of 111
𝑊𝐶0 − 𝑊𝐶𝑡
( ) = (1 − 𝑋 )
𝑊𝐶0
Since the particles stay in the reactor for different length of times, this leads to a variation in the
conversion level. From Kunii and Levenspiel (1991) for shrinking core and reaction-controlling
kinetics.
∞
(1 − 𝑋̅ ) = ∫ (1 − 𝑋)𝑃𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝐸 (𝑡)𝑑𝑡
𝑡=0
Where the solids age distribution in the fluidized bed is
1 𝑡
𝐸 (𝑡 ) = exp ( )
𝑡̅ 𝑡̅
And
𝑡 3
(1 − 𝑋) = (1 − )
𝜏𝑐
Combining the two equations you get:
2 3
𝑡̅ 𝑡̅ 𝑡̅ 𝜏
(1 − 𝑋̅ ) = 1 − 3 ( ) + 6 ( ) − 6 ( ) (1 − 𝑒𝑥𝑝 (− ))
𝜏𝑐 𝜏𝑐 𝜏𝑐 𝑡̅
Assuming that the gasifier is operating at 850 °C with biomass feed rate of 550 kg/hr and feed
𝑐𝐻2𝑂
particles of 1mm in diameter, using Equation (𝑘𝑐 (𝑠 −1 ) = 𝑘𝑐𝑠 (m/s)) and Equation (
75.7
76.6∗103
𝑘𝑐 = 0.06 𝑒𝑥𝑝 (− )), we can derive a surface rate constant as:
𝑅𝑇𝑏
Page 66 of 111
76.6 ∗ 103
𝑘𝑐 = 0.06 𝑒𝑥𝑝 (− )
8.314 (273 + 850)
𝑘𝑐 = 1.64 ∗ 10−5 𝑠 −1
And
75.7 𝑚
𝑘𝑐𝑠 = = 1.93 ∗ 10−4 ( )
6.42 𝑠
The conversion time is related to the surface rate constant by the expression of Kimura et al.
(1982):
𝜌̈ 𝑐 𝑑𝑐0
𝜏𝑐 =
2𝑏𝑘𝑐𝑠 𝐶𝐻2 𝑂
3.33 ∗ 104 ∗ 1000 ∗ 10−6

𝜏𝑐 = = 166 𝑚𝑖𝑛
2 ∗ 1.93 ∗ 10−4 ∗ 6.42
If we allow 70% conversion of the char before circulating to the combustor, then:
(1 − 𝑋̅ ) = (1 − 0.7) = 0.3
𝑡̅ 𝑡̅ 2
Inserting the values of 𝜏𝑐 and (1 − 𝑋̅) into Equation ((1 − 𝑋̅) = 1 − 3 (𝜏 ) + 6 (𝜏 ) −
𝑐 𝑐
𝑡̅ 3 𝜏
6 (𝜏 ) (1 − 𝑒𝑥𝑝 (− 𝑡̅ ))) and solving for the mean residence time, 𝑡̅.
𝑐
𝑡̅
= 0.6
𝜏𝑐
Page 67 of 111
𝑡̅ = 0.6 ∗ 166 = 99.6 𝑚𝑖𝑛
Assuming a solids circulation rate of 176 981 kg/hr (= 200 kg/mm). Now:
𝑊
𝑡=
𝐹
W = 200x99 =19800kg
The bulk density of the sand is approx. 1560 kg/m3 (= 2600 x 0.6). Therefore the bed volume is
given by:
VG = 176981/1560 = 113.15 m3
A design safety factor of at least 5% needs to be added in this calculation to ensure better
efficiency and reliability.
And that gives VG = 119.12 m3
Assuming a bed height of 2 times the diameter:
𝜋𝐷𝐺2
119.12 = ∗ 𝐷𝐺 ∗ 2
4
𝜋𝐷𝐺3
59.56 =
4
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3 59.56 ∗ 4
𝐷𝐺 = √
𝜋
𝑫𝑮 = 𝟒. 𝟐𝟑 𝒎
And
𝑯𝑮 = 𝟐 ∗ 𝟒. 𝟐𝟑 𝒎
𝑯𝑮 = 𝟖. 𝟒𝟔 𝒎
Page 69 of 111
9 D E S I G N O F A S H E L L A N D T U B E H E AT E X C H A N G E R
9.1 Overview
After distillation, heat transfer is the most important operation in a process plant. Most of the
heat transfer in chemical plants and petroleum refineries takes place in shell-and-tube heat
exchangers.
A wide variety of heat exchangers are available, some of which you may have seen: plate, spiral,
and coil to name just three. But 99 percent of the heat exchangers are ordinary shell-and-tube
exchangers, the design of which has not changed since the 1920s.
Before considering the process aspects of heat transfer, let’s look at the mechanical components
of the heat exchanger shown in Fig. 9.1. This shell-and-tube heat exchanger is actually a
compromise between four aspects of heat-exchanger design:
 Allowance for thermal expansion
 Efficient heat transfer
 Ease of cleaning
 Mechanical robustness
Page 70 of 111
Figure 9.1: Shell-and-tube heat exchanger. Tube support baffles 90 from true orientation.
Table 9.1 Physical and Chemical Properties of fluid to be cooled using water at ambient
temperature (Methanol)
Physical State: Liquid

Appearance: clear, colorless
Odor: alcohol-like - weak odor
pH: Not available.
Vapor Pressure: 128 mm Hg @ 20 deg C
Vapor Density: 1.11 (Air=1)
Evaporation Rate: 5.2 (Ether=1)
Viscosity: 0.55 cP 20 deg C
Boiling Point: 64.7 deg C @ 760.00mm Hg
Freezing/Melting Point: -98 deg C
Auto-ignition Temperature: 464 deg C ( 867.20 deg F)
Flash Point: 11 deg C ( 51.80 deg F)
Decomposition Temperature: Not available.
NFPA Rating: (estimated) Health: 1; Flammability: 3; Reactivity: 0
Explosion Limits, Lower: 6.0 vol %
Upper: 36.00 vol %
Solubility: miscible
Page 71 of 111
Specific Gravity/Density: 7910g/cm3

Molecular Formula: CH3OH
Molecular Weight: 32.04
9.3 Design Calculations
𝑄 = 𝑀𝐶𝑝∆𝑇
𝑄 = 5659 ∗ 2.51 ∗ 200
𝑄 = 2840818 𝑊
𝑄 = 28404 𝑘𝑊
Heat transfer area calculation:
𝑄 = 𝑈𝐴∆𝑇𝑙𝑚
𝑄
𝐴=
𝑈∆𝑇𝑙𝑚
Assuming overall heat transfer coefficient (U) of 900 𝑊/𝑚2 ℃
(𝑇1 − 𝑡1 ) − ( 𝑇2 − 𝑡2 )
∆𝑇𝑙𝑚 =
𝑙𝑛[(𝑇1 − 𝑡1 )/ ( 𝑇2 − 𝑡2 )]
Where T1 and T2 are 250 and 50 degC
And t1 and t2 are 120 and 25 degC
⋰⋱ ∆𝑇𝑙𝑚 = 63.69
𝑄
𝐴=
𝑈∆𝑇𝑙𝑚
28404 ∗ 1000
𝐴=
900 ∗ 63.69
𝐴 = 495.53 𝑚2
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Length of a tube 𝐿 = 4.88𝑚 − (2 ∗ 25𝑚𝑚) (𝑎𝑙𝑙𝑜𝑤𝑖𝑛𝑔 𝑓𝑜𝑟 𝑡𝑢𝑏𝑒 𝑠ℎ𝑒𝑒𝑡 𝑡ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠)
Therefore 𝐿 = 4.83𝑚
Area of a tube is given by 𝐴𝑡 = 𝜋𝐷𝐿
Assuming a tube diameter of 20mm:
𝐴𝑡 = 𝜋 ∗ 0.02 ∗ 4.83
𝐴𝑡 = 0.303𝑚2
Number of tubes:
𝐴
𝑁𝑡 =
𝐴𝑡
495.53
Nt =
0.303
Nt = 1636 tubes required
Recalculating
If were to upscale the surface area by 5%, A becomes 520.31m2 and the new Nt becomes 1718
tubes required.
The heat exchanger 1 Shell pass with 2 Tube passes, giving 859 tubes per pass.
Mass flow rate of cooling water required:
𝑄
𝑀𝑤 =
𝐶𝑝∆𝑇
28404
𝑀𝑤 =
4.2 ∗ 95
𝑀𝑤 = 71.19𝑘𝑔/𝑠
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Tube side heat transfer coefficient
120 − 25
𝑀𝑒𝑎𝑛 𝑤𝑎𝑡𝑒𝑟 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 =
2
𝑀𝑒𝑎𝑛 𝑤𝑎𝑡𝑒𝑟 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 47.5
𝜋𝐷2
𝑇𝑢𝑏𝑒 𝑐𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎 =
4
𝑇𝑢𝑏𝑒 𝑐𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎 = 0.000201𝑚2
𝑇𝑜𝑡𝑎𝑙 𝑓𝑙𝑜𝑤 𝑎𝑟𝑒𝑎 = 0.000201 ∗ 859 = 0.173𝑚2
71.19
𝐺𝑡 =
0.173
𝐺𝑡 = 411.50
411.50
𝐿𝑖𝑛𝑒𝑎𝑟 𝑣𝑒𝑙𝑜𝑠𝑖𝑡𝑦 =
1000
𝐿𝑖𝑛𝑒𝑎𝑟 𝑣𝑒𝑙𝑜𝑠𝑖𝑡𝑦 = 0.412𝑚/𝑠
4200(1.35 + 0.02 ∗ 47.50)0.4120.8

ℎ𝑖 =
160.2
ℎ𝑖 = 2729.88 𝑊/𝑚2 𝑜 𝐶
Page 74 of 111
Shell side heat transfer coefficient
As the shell-side fluid is relatively clean use 1.25 triangular pitch.

1
1718 2.207
Bundle diameter 𝐷𝑏 = 0.02 (0.249 )
𝐷𝑏 = 1.097𝑚
Use a split-ring floating head type.
Bundle diametrical clearance = 0.068 m,
Therefore 𝐷𝑠 = 1.097 + 0.068 = 1.165𝑚
Tube pitch = 1.25*20 = 25 mm
𝐷𝑠 1.165
Choose baffle spacing of = = 0.233𝑚
5 5
(0.025 − 0.020)
𝐴𝑠 = ∗ 1.165 ∗ 0.233 = 0.054𝑚2
0.025
Flow rate of methanol in stream 16 = 130599 kg/h and therefore:
130599 1 𝑘𝑔
𝐺𝑠 = ∗ = 671.81
3600 0.054 𝑠 𝑚2
De = 0.014 m
Mean shell side temperature = (250+50)/ 2 = 150
Methanol density = 635 kg/m3
Viscosity = 0.113 mNs/m2
Heat capacity = 2.40 kJ/kgoC
Thermal conductivity = 0.16 W/moC
Page 75 of 111
𝐺𝑠 𝐷𝑒 671.81 ∗ 0.014
𝑅𝑒 = ∗ = 83233
𝜇 0.113 ∗ 10−3
𝐶𝑝𝜇 3.96 ∗ 103 ∗ 0.113 ∗ 10−3

𝑃𝑟 = ∗ = 2.797
𝑘𝑓 0.16
Choose 25 per cent baffle cut,
Jh = 3.3 * 10-3
0.16 1
ℎ𝑜 = ∗ 3.3 ∗ 10−3 ∗ 83233 ∗ 2.7973 = 4421.30 W/m2 𝑜 C
0.014
Overall heat transfer coefficient
20
1 1 1 20 1 1 0.02 ln (16)
= + ∗ + + +
𝑈𝑜 4421.30 2729.88 16 4230 2850 2 ∗ 48.28
1
= 0.0013176
𝑈𝑜
𝑈𝑜 = 758.97 W/m2 𝑜 C
This overall heat transfer coefficient is fairly lower than the initial assumption. This simple
means total area for tubes is lower than the one previously calculated and outlet temperature of
water can be reduced to lower than 100oC using the calculated number of tubes.
Page 76 of 111
10 P U M P D ATA S H E E T
PUMP DATA SHEET
PUMP NAME Centrifugal pump
TAG NUMBER
PUMP SPEED rpm 2900
Liquid properties
Temperature degC 20
Density kg/m3 996.00
Viscosity cP 0.9
Vapour pressure at
Vapour Pressure bar(a) 0.02 operating temperature
Flowrates
Total Mass Flow kg/h 300,000
Total Volumetric Flow m3/h 301.20
Total Volumetric Flow US gpm 1326.16
Volumetric Flow (per pump) m3/h 150.6
Volumetric Flow (per pump) US gpm 663.1
Suction Side Hydraulics
Suction Vessel Operating Pressure bar(a) 1.01
Elevation of Suction Vessel from

Grade m 1.3
Vessel low liquid level m 0.0
m 0.7
Pump centerline elevation from
Page 77 of 111
grade
Static Pressure Low Liquid Level to

Pump bar 0.06
Suction Side Pressure Drop bar 0.00
Pump Suction Pressure bar(a) 1.07
Discharge Side Hydraulics
Maximum Termination Pressure bar(g) 1.00
Elevation of Terminal Point m 22.1 - above pump centreline
Discharge Side Pressure Drop bar 0.00
Pump Discharge Pressure bar(g) 3.16
Pump NPSH
NPSH Required at the Pump m 5.1
NPSH Safety Margin m 1.0
Total NPSH Required m 6.1
Head at Pump Entry m 10.9
NPSH Available m 10.8 Sufficient NPSH Available
Pump Design Data
Pump Differential Pressure bar 3.10
Pump Differential Head m 31.8
Estimated Pump Efficiency % 69
Estimated Pump Power Required kW 18.92
Page 78 of 111
11 CONTROL PHILOSOPHY
Gasifier control and simulation
Process control equipment must be utilized to operate the process equipment within design
specifications and to handle possible plant upsets.
Process control equipment monitors the temperatures and pressures of reactors, the effectiveness
of the equipment, and all process streams throughout the plant to ensure safe and on-spec
operation. Deviations from set-point should provide signals to the controller, and appropriate
action(s) must be taken to prevent endangerment of human life, destruction and/or damage of
process units, and production of off-spec product.
Even though many advanced control algorithms are proposed for complex process and systems,
the authors are strongly of the opinion that PID control will also meet the control requirements
using appropriate controller constants and feed forwards if necessary. Hence the PID controller is
considered as a tool for gasifier control and simulation.
Here PID controller is used to vary the steam and biomass inputs for syngas pressure and
biomass and air is varied for syngas temperature.
Gasifier: Input and Output Variables
The controllable input variables to the gasifier are
 Ash off-take (kg/s)
 Air flow rate (kg/s)
 Biomass flow rate (kg/s)
 Steam flow rate (kg/s)
 limestone flow rate (kg/s)
Page 79 of 111
The controlled output variables are:
 Gas calorific value (J/kg)
 Bed mass (kg)
 Fuel gas pressure (N/m2 )
 Fuel gas temperature (K)
Load Demand on Gasifier
The flow rate of syngas to gas turbine is controlled through a valve at the inlet of turbine (also
referred as controlled input disturbance to the gasifier). The pressure at the inlet of turbine called
is the controlled variable. The control problem is to study the transient behavior of gasifier
process variables such as pressure, temperature of the syngas for typical variations in gas flow
drawing rate to gas turbine through appropriate changes in the throttle valve. Any proposed
control system should control the pressure and temperature of the syngas at the inlet of gas
turbine for any variation in gas turbine load – which in turn will affect throttle valve moment-
without undue overshoots and undershoots.
The most important parameters to be controlled being the pressure and the flowrate. Pressure is
measured using pressure transmitters and the reading is sent to the PLC module.
If the pressure reading higher than the operating pressure, the signal will be sent through and
intermediate device (IM) to the PLC module and from the PLC module through an IM to the
inlet flow control valve and the nitrogen supply control valve. Inlet control valve will shut-off
and the nitrogen supply stream will open to purge the reactor until the operating pressure is
reached. In case of low pressure the inlet control valve will be triggered and flow will be
increased.
The same goes for higher temperatures or flow.
Page 80 of 111
12 P & I D O F A C I R C U L AT I N G F L U I D I Z E D B E D
Page 81 of 111
13 HAZOP
HAZOP study is one of the most widely used hazard identification methods and has found
applications in many different industries. Many potential problems can be identified by the
examination of new, modified or existing designs, procedures and operations using the
systematic and structured approach of HAZOP.
13.1 Start-Up
1: What if the blow torch ignites the insulation or other material besides the biomass?
Likelihood: Low
Hazard: Medium
Safeguards: Two people will always be present during gasifier operation. For start-up
specifically, one person will observe and ensure that the blow torch is being operated with
necessary caution. A fire extinguisher will also be nearby.
2: What if the flame travels down the flare tube?
Likelihood: Low
Hazard: Medium
Safeguards: A flame arrestor is installed just prior to the flare. This acts as a heat sink, which
prevents ignition upstream of this device.
3: What if the reactor gets too hot before steam is produced?
Likelihood: Medium
Hazard: High
Safeguards: Temperature will be closely monitored during start-up. During the initial start-up
and subsequent runs if necessary, the water will be pre-heated using a heating element to produce
steam more quickly. If the temperature exceeds 800°C before the water is boiling, we will choke
the reaction by decreasing the air feed to the gasifier.
4: What if flare ignition causes a burst of flame?
Likelihood: Medium
Page 82 of 111
Hazard: Low
Safeguards: A propane torch will be used to provide a pilot light during startup and if at any time
the flame goes out. If it is difficult to maintain a flame, small pieces of steel wool will be used as
tinder.
5: What if combustible gases from previous operations build up inside the reactor and ignite
when the blow torch is used to start the reaction?
Likelihood: Medium
Hazard: High
Safeguards: The venturi will be turned on and air will be flushed through the reactor for two
space times (about 2.5 minutes) before the reaction is started.
6: What if the flame travels out the port hole while it is open for start-up?
Likelihood: Low
Hazard: High
Safeguards: The port hole will be open only for a few moments during start-up. Combustible
gases will not be present at appreciable levels during this time, so the flame is extremely unlikely
to travel out of the reactor. Operators will wear personal protective equipment and stay out of the
line of the port hole. The insulation will also be covered with material sprayed with flame
retardant. In addition, a check valve will be installed in the port hole to ensure that the flame
does not travel out.
13.2 Feeding Biomass

1: What if the flame front travels quickly up the reactor?
Likelihood: Low
Hazard: Low
Safeguards: We will ensure that the entrance to the hopper is tightly sealed. The lid will only be
opened for short periods of time (less than 30 seconds) while feeding biomass to the reactor. If
the flame front does begin to travel upward, the lid will be immediately placed on the hopper and
sealed.
2: What if the flame reaches the biomass hopper?
Likelihood: Very low

Page 83 of 111
Hazard: Low
Safeguards: The lid will be placed on the hopper as soon as possible. In any case, the gasifier
will be shut down until the biomass is finished combusting and has cooled.
13.3 Gasifier Operation

1: What if the reactor gets too hot?
 Thermocouple Reading Above 1100 °C (Maximum Expected Temperature, at which Tar

Cracking Occurs)
Likelihood: Medium
Hazard: Low
Safeguards: We will choke the reaction by lowering the air feed rate via the venturi vacuum
system and purge the contents using Nitrogen as it is an inert. More steam produced using the
heating element will also be admitted to the reactor to decrease temperature.
 Thermocouple Reading Above 1300 °C (Integrity of Stainless Steel Compromised)
Likelihood: Low
Hazard: Medium-High
Safeguards: The venturi vacuum will be inactivated, preventing air from being fed, effectively
cooling the combustion zone of the reactor. The steam valve will be fully opened. We will move
away from the area. This event is unlikely because prior measures will be taken if the
temperature exceeds 1100 °C.
2: What if the entire reactor bursts into flames?
Likelihood: Very Low
Hazard: High
Safeguards: The venturi vacuum will be immediately inactivated. The compressed air valve for
this will be located at least 10 feet away from the reactor so that it can be shut down despite the
fire. A fire extinguisher will also be kept near the reactor during operation to douse the flames.
3: What if a dangerous amount of carbon monoxide or hydrogen gas leaks out of the reactor?
Likelihood: Low
Hazard: High
Page 84 of 111
Safeguards: The reactor will be welded to prevent leaks and will be operated under a vacuum, so
gas cannot leak out. If the reactor does leak, air will leak in, rather than synthesis gas leaking out.
Additionally, a carbon monoxide detector will be kept nearby to monitor atmospheric carbon
monoxide levels. If the alarm goes off, the team will shut the reactor down by turning off the
vacuum. The team will then exit the area and allow the carbon monoxide to dissipate before
reentering.
Operating the gasifier outdoors will also allow higher levels of carbon monoxide without danger
to operators or others nearby.
4: What if the gasifier explodes?
Likelihood: Low
Hazard: High
Safeguards: The gasifier might explode if liquid water is fed to the reactor. In order to avoid this,
a hole has been placed in the heater in order to leak any liquid water before it enters the reactor
and avoid the possibility of explosion.
5: What if the synthesis gas is unable to exit the reactor?
Likelihood: Low
Hazard: None
Safeguards: Because the vacuum is generated on the back-end of the pilot plant, closing a valve
after the reactor will cut off the vacuum to the reactor, effectively shutting down the reactor.
6: What if insulation is touched?
Likelihood: High
Hazard: None
Safeguards: According to our calculations, due to its low thermal conductivity, the outside of the
gasifier’s insulation should be less than 150 °C and therefore will be safe to touch for short
periods of time.
7: What if another portion of the reactor is touched?
Likelihood: Low
Hazard: High
Page 85 of 111
Safeguards: The manifold system, the synthesis gas exit pipe, and the flare will be too hot to
touch.
All hot surfaces, including manifold system, synthesis gas exit pipe and flare, will be painted red
and labeled appropriately. The high temperature of the manifold system could present dangers
only while feeding biomass. Anyone loading the feed hopper will wear gloves.
Question 8: What if the flare is extinguished?
Likelihood: High
Hazard: Low
Safeguards: A carbon monoxide detector will be placed near the reactor. Some carbon monoxide
might be leaked to the atmosphere. Synthesis gas typically contains approximately 18% carbon
monoxide, but this will be diluted using compressed air from the venturi vacuum system. The
carbon monoxide output should not be dangerous if the flare is extinguished, especially given
that the gasifier will be under supervision at all times while it is running.
9: What if the synthesis gas produced is outside the flammability range?
Likelihood: Low
Hazard: Low
Safeguards: The synthesis gas will never be near the UFL value because the reactor uses an air
feed, so it is diluted with nitrogen gas. The team is aware of the LFL value and will monitor this
closely until a better understanding of the reactor’s operation is obtained. In a worst case
scenario, the gas will be too dilute to ignite at the flare and the air dilution valve on the venturi
vacuum will be closed to reduce the vacuum.
Synthesis Gas Lower Flammability Limit Calculations (Matheson Gas Products, 2001)
10: What if the flame travels out the port hole?
Likelihood: Low
Hazard: High
Safeguards: The port hole will be never be open except during start-up. A check valve will also
be installed.
Page 86 of 111
11: What if there is a significant air leak that causes the reactor temperature to increase and
cannot be located and/or fixed to cool the reactor?
Likelihood: Low
Hazard: High
Safeguards: The soapy water test will be performed periodically. A significant mechanical
failure might not allow the reactor to be salvaged. If the temperature cannot be decreased, all
operators will move away from the reactor and it will run using only air provided via leaks until
all the biomass has combusted.
13.4 Sampling
1: What hazards are present when collecting a sample?
Likelihood: High
Hazard: Medium-High
Safeguards: To avoid potential burns while collecting a sample, heat-resistant gloves will be
worn during this process along with usual PPE. The sampling station will be a few feet from the
reactor, but the unit will be insulated and hot pipes will be labeled.
2: What if the sample leaks?
Likelihood: Medium
Hazard: Low
Safeguards: Air must leak in to dilute the sample before any hazardous gas is released to the
atmosphere. If air did leak in to equilibrate the pressure between the sample and the atmosphere,
the sample might leak. However, in the event that gases did leak to the atmosphere, it would be a
small amount. A carbon monoxide detector will be near the gasifier to ensure that hazardous
levels are not reached.
13.5 Ash Removal

1: What if toxic gases build up in the reactor before ash is removed?
Likelihood: Low
Hazard: High
Safeguards: Ash will be removed only after the gasifier has cooled and been flushed with air for
two space times to prevent build-up of combustible or toxic gases.
Page 87 of 111
13.6 Shutdown
1: How will the gasifier be shutdown?
Air feed will be closed, the compressor hose will be disconnected, and the reactor will be
allowed to cool to 150 °C outside the engineering building before it is transported inside and
stored.
2: After shutdown, when can the gasifier be operated again without the danger of explosion due
to build-up of combustible gases?
The gasifier can be flushed with air for two space times (about 2.5 minutes) and operated again
once the temperature is below 250 °C, which is the auto-ignition temperature.
13.7 Startup
Startup is time sensitive. Once this list of steps is begun, it is important to act quickly and
efficiently and complete the steps below within 15 minutes if possible. Make sure that you
completely understand and are able to complete each step before beginning start up. Unnecessary
delay between startup steps could lead to overheating in the reactor. One person should be
watching the temperature reading in the combustion zone and be ready to control the temperature
as described in the operating section.
The gasifier should only be started up with two or more team members present. The first member
should be responsible for closely monitoring the temperature of the reactor and actively watching
for any potential dangers. This operator should also operate all valves and controls. The second
member should be responsible for ensuring that the flare remains lit and for recording the reactor
temperature, synthesis gas temperature, reactor pressure, flow rates, valve positions (100% open,
50% open, etc), and flare status (not burning, burning yellow, burning white) every 2 minutes.
 Turn on water heater
 Wait for water to begin boiling (up to 30 minutes)
 Open compressed air valve fully
 Watch the flare, waiting for a continuous flow of smoke and a temperature in the
combustion zone of 400°C
 Using the butane torch try to light the flare for a duration of 3 seconds every 3 minutes
until it maintains a self-sustained flame
 Set the air feed rotameters according to the experimental plan

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 Throttle the compressed air valve to achieve 4-6” water vacuum exiting the reactor (this
is the expected value as cited in the literature (ALL Power Labs, 2014))
 Adjust the steam valve following the temperature control guidelines in the operating
section
13.8 Operation
Once the gasifier has been started up, reduce the oxygen feed to the desired operating level
(~0.25 equivalence) so that the combustion zone temperature does not become excessively high.
During operation, monitor the combustion zone temperatures. If this temperature ever exceeds
1100℃, the compressed air feed to the venturi vacuum should be reduced using the venturi
needle valve. If the temperature continues to climb or does not begin to decrease, steam should
be added using the heating element. The steam causes an endothermic reaction, which will drop
the reactor temperature. If the temperature ever exceeds 1300℃, the compressed air feed to the
venturi vacuum should be completely closed (venturi needle valve) and the steam feed valve
should be opened completely (steam valve) until the temperature drops below 1100℃. The first
thermocouple should give an accurate approximation of the combustion zone temperature
because it is inserted directly in the biomass bed.
A second thermocouple can be moved to other regions of the reactor to obtain a temperature
gradient. It will typically be used to measure the temperature of the bottom combustion zone.
13.9 Cautionary Notes

While the gasifier is operating, the outside of the insulation will be near 150℃. One can safely
touch this surface for one second without feeling pain. With that being said, this surface should
never be intentionally touched without an insulated glove, but if it is touched momentarily, no
harm will come to the individual.
The synthesis gas pipe exiting the reactor is extremely hot (up to 800℃) and should never be
touched during operation. This pipe has been painted red with cautionary words inscribed on the
surface to warn users. The pipe cannot be insulated because the synthesis gas should be cooled
by the surrounding air. The high temperature portions of the pilot plant have purposely been
positioned on the opposite side as the sampling valves, rotameters, and digital temperature
readout so that the team will not be near the hottest parts of the system during operation.
13.10 Adjusting the Air Fee d Rate

Air is pulled into the reactor by a venturi vacuum pump located near the flare. The total air feed
rate should be adjusted primarily by opening or closing the venturi needle valve near the flare,
which modifies the vacuum on the system. The air distribution to the top and bottom combustion
zones can be modified by adjusting the air feed valves located on the rotameters connected to the
bottom two manifolds. One valve controls the air feed to the top combustion zone, while the
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other controls the air feed to the bottom combustion zone. The rotameters near these valves
should be used to measure how much air is being fed to each region. Under normal operating
conditions, more air will be fed to the top combustion zone than the bottom to thermally crack
the tars at higher temperatures. It is important to understand the relationship between air feed and
reactor temperature. Combustion is an exothermic reaction that generates a lot of heat. The more
air fed to the reactor, the hotter the reactor will get.
However, this is a tradeoff because too much air will cause complete combustion of the biomass
and less synthesis gas will be produced. Gasifier literature states that air should be fed at
approximately 25% of the amount required for complete combustion of the biomass to obtain the
best quality synthesis gas. A material balance should be calculated to determine the total air feed
based on a 25% equivalence ratio.
13.11 Adjusting the Steam Feed Rate

Steam is fed to the bottom of the reactor by cracking the steam valve. The steam rotameter near
this valve will be used to measure the steam flow rate. As was stated earlier, steam causes an
endothermic reaction (water shift reaction) that cools the reactor. This will be one of the primary
means of controlling the reactor temperature, along with the air feed rate.
13.12 Sampling
In order to take continuous samples, the valves on either side of the sampling apparatus should
both be open. The synthesis gas product should be allowed to flow through the sampling
apparatus for a few minutes to ensure that the previous sample is evacuated and that the current
sample is representative. After the sample is obtained, the valves will be closed to divert the flow
back through its normal exit path. The unions will be unscrewed to remove the sampling vial.
The sample will be cooled using an ice bath. Then the apparatus will be reattached to the unions
and operation will continue as described above until a sample is again obtained. The sample for
the Orsat should be collected through the metal pipe, fed to the instrument, and analyzed.
13.13 Preparing for Shutdown

During shutdown there must be two people present. The team will ensure that they have excess
flare material on hand as it is likely that the flare will extinguish multiple times while shutting
down the reactor.
13.14 Shutdown
To shut down the gasifier the next step will be to close the valve on the venturi. This will choke
the reactor and prevent air from feeding into the reactor. At this time there will be carbon
monoxide and other gasification byproducts coming out of the manifold system and therefore the
team must not be within 10 meters of the reactor. During this time the team will carefully
monitor the temperature for the upper combustion zone. The steam valve will also be opened to
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promote cooling in the reactor. The team will wait until the core combustion zone temperature of
the reactor is below 400 °C.
13.15 MSDS’s
13.15.1 Syngas
MATERIAL SAFETY DATA SHEET

1. Chemical Identification
Product Name Syngas
Chemical Name Mixture
Chemical Family N/A
Formula Mixture
Synonym Syn Gas (Synthesis Gas)
2. Company Identification Union Carbide Corporation

3. Emergency Telephone Number 1-800-424-9300
4. Composition Information
Component CAS# Amount (%W/W)
Carbon Monoxide 630-08-0 >= 50 <= 9 %
Carbon Dioxide 124-38-9 <= 20%
Water 7732-18-5 <= 20%
Hydrogen 1333-74-0 >= 5 <= 9%
Methane 74-82-8 <= 3%
5. Hazard Identification
5.1 Emergency Overview
Appearance Transparent colorless
Physical state Gas
Odor Odorless
Hazards of product Extremely flammable liquid and gas under
pressuer.
May form mixtures with air.
Harmful or fatal if inhaled.
Can Cause Rapid Suffocation
May cause dizziness and drowsiness
May cause nervous system damage
5.2 Potential Health Effects
Inhalation Duration of exposure may cause headache,
drowsiness, dizziness, excitation, rapid
breathing, excess salivation, rapid breathing,
nausea, vomiting, hallucinations, confusion,
convulsions and unconsciousness. With well-
established poisoning, the mucosal surfaces will
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be bright red (cherry red) in colour. Lack of

oxygen can cause death.
Effects of Repeated Over-exposure Repeated hypoxia from carbon monoxide
exposure will cause gradually increasing central
nervous system (CNS) damage, with loss of
sensation in the fingers, poor memory, positive
Romberg’s sign mental deterioration. Chronic
exposure may facilitate the development of
atherosclerosis.
6. Medical conditions Aggravated Due to the hypoxia from carboxyhemoglobin

formation, may aggravate established heart and
celebral circulation diseases.
7. First Aid Measures
Inhalation Remove to fresh air. Give artificial respiration if
not breathing
Eye contact Flush eyes thoroughly with water for several
minutes
Skin contact
8. Fire Fighting Measures Do not extinguish due to possible hazard of
explosive reignition. Use water spray to cool
containers and structures and to protect
personnel attempting to shut-off flow.
9. Handling and Storage
Use equipment rated for pressure
Keep away from heat, sparks and flame
Keep container tightly closed
Use with adequate ventilation
Cylinder temperature should not exceed 52oC
13.15.2 Methanol
MATERIAL SAFETY DATA SHEET

1. Chemical Identification
Product Name Methanol
Chemical Name Methanol
Chemical Family Alcohol
Formula CH3OH
Synonym Methyl Alcohol
2. Company Identification ScienceLab

3. Emergency Telephone Number 1-800-901-7247
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4. Composition Information
Component CAS# Amount (%W/W)
Methyl Alcohol 67-56-1 100%
5. Hazard Identification
5.1 Emergency Overview
Appearance colorless
Physical state Liquid/ Gas
Odor Alcohol like. Pungent when crude
Hazards of product Flammable liquid and gas under pressure.
Skin irritant.
Eye irritant
Skin permeator
Carcinogenic effect.
Mutagenic effects
May cause dizziness and drowsiness
May cause nervous system damage
6. First Aid Measures
Inhalation Remove to fresh air. Give artificial respiration if
not breathing
Eye contact Flush eyes thoroughly with water for several
minutes
Skin contact Immediately flush skin with plenty of water
7. Fire Fighting Measures Do not extinguish due to possible hazard of
explosive reignition. Use water spray to cool
containers and structures and to protect
personnel attempting to shut-off flow.
8. Handling and Storage
Keep locked up
Keep away from heat, sparks and flame
Keep container cool
Use with adequate ventilation
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14 O T H E R I M P O R TA N T C O N S I D E R AT I O N S
14.1 Health & Safety

Human health and safety is an important consideration in the presence of flammable materials
such as methanol.
Methanol is produced in small amounts in the human body as part of the metabolic process, and
occurs naturally in some fruits. At high enough concentrations it is poisonous. Ingestion of 10 ml
can cause blindness and 60-100 ml can be fatal if the condition is untreated. [Toxicity] US
OSHA permissible exposure limit for general industry in air (40 h/week) is 1900 mg/m³ for
ethanol, 900 mg/m³ for gasoline, and 260 mg/m³ for methanol. When methanol is blended in
gasoline, although the overall vapor pressure increases (see section VI), the partial vapor
pressures of some gasoline compounds with high toxicity, such as benzene and 1,3 butadiene,
decreases. It is difficult to smell methanol in air at methanol concentrations less than 2,000 ppm
(1500 mg/m3).
For exposure to toxic chemicals, the most common measurement of prompt toxicity is the
median lethal dose, LD50, defined as the dose at which 50% of the test population is killed. For
methanol there are three primary methods of exposure: ingestion, inhalation and dermal contact.
[Stark] The toxicity of chemicals is determined by observing following exposure the response of
a population of test animals (commonly mice and rats, but in some cases, rabbits and dogs),
compared with a similar population that is not exposed. The duration of exposure and the time of
50 observation are not uniform across investigators, but there are well known rules to adjust for
variations.
Monitoring of fugitive emissions is especially important since methane is colorless and odorless
and is therefore not readily identifiable. Although methane and methanol do not pose high
hazards to health, effective measures must be taken to ensure the integrity of plant personnel
health and safety.
Methanol and methane are both flammable and present fire and explosive hazards. Methanol
should be handled in a confined area, which must be well ventilated. Respirators must be used
while working in an area where methanol vapor concentration is high. Also, gloves and other
protective equipment must be used while working in areas of high methanol concentration.
14.2 Environmental
Methanol, like ethanol but unlike hydrocarbon fuels, is water soluble. As a consequence, it is
transported through diffusion and convection through the environment at much faster rate than
hydrocarbons. A ground spill migrates substantially through the subsurface water, while
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hydrocarbon’s mobility is much lower (gasoline agglomerates above the water table, forming
Non-Aqueous Liquid Phase pockets). In addition to fast migration, methanol bio-degrades much
faster than hydrocarbons. Fast transport and degradation result in short lifetimes. Hydrocarbons,
on the other hand, comprise many stable compounds, which include some, such as aromatics,
that are highly toxic to bio-organisms and degrade slowly.
Table 14.2.1. Half-lives (in days) of common fuel components, adapted from Howard.
Soil Air Surface Water Ground Water

MeOH 1-7 3-30 1-7 1-7
EtOH 0.1-1 5-5.1 0.25-1 0.5-2.2
Benzene 5-16 2-21 5-16 10-710
Toluene 4-22 0.4-4.3 4-22 7-28
Table 14.2.1 shows the half-life of common fuels in soil, air and water. Compared to
hydrocarbon based fuels, methanol lifetime is substantially shorter. Ethanol degrades even faster
than methanol and has comparable transport properties to methanol. In the case of a large
methanol spill, the environment is likely to recover quickly. A catastrophic failure is the case of
methanol dispersion in surface water. While most hydrocarbon components would float on the
surface, methanol would dissolve in the water. In the case of a river with limited water
throughput, the methanol would form a “plug” that would flow down river and may prevent
human consumption of the water until the methanol flows downstream or degrades. The
concentration of the methanol “plug” decreases fast due to dilution/mixing by diffusion and
turbulent mixing with upstream/downstream waters while degrading [Jamali], and the
environment recovers quickly. One of the consequences of this scenario is that barge transport of
methanol in rivers should be carefully monitored and precautions taken. On the other hand,
releases in open waters results in very quick decrease of methanol from the source of the spill
[Katsumata] according to the International Programme on Chemical Safety of the World Health
Organization (WHO) the LC50 values (contamination where half the population dies) in aquatic
organisms range from 1300 to 15900 mg/liter for invertebrates (over 48 and 96 hr exposures),
and 13000 to 29000 mg/liter for fish (over 96 hour exposure) [WHO]. Even in the event of a
large scale spill these times of exposure are unlikely to occur due to the rate at which methanol
dissipates.
Syngas is a very toxic chemical. It should not escape. Vapors form from this product and may
travel or be moved by air currents and ignited by pilot lights, other flames, smoking, sparks,
heaters, electrical equipment, static discharges or other ignition sources at locations distant from
product handling point.
To prevent this, the area of handling point should be ventilated and atmosphere should be
checked with appropriate gas detecting devices to ensure that volume of gas in air is within the
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limits. Use of spark-proof tools and explosion-proof equipment should be considered to prevent
possible explosion.
14.2.1 Chemical Toxicity

As previously stated, humans are most commonly exposed to methanol through skin contact and
vapor inhalation. Although carcinogenicity of methanol has not been determined, exposure to
methanol has been linked to reproductive defects in rats. Methanol is known to cause headaches,
dizziness, giddiness, insomnia, nausea, gastric disturbances, conjunctivitis, blurred vision, and
blindness in humans. High doses of methanol may be fatal. OSHA’s regulatory concentration of
methanol for human exposure without adverse effects in an 8 hour day is 260mg/m3 or 198 ppm.
14.2.2 Potential Safety Problems

Methanol is readily degraded in the environment by photo oxidation and biodegradation
processes.
Half-lives of 7 – 18 days have been reported for the atmospheric reaction of methanol with
hydroxyl radicals. Methanol is readily degradable under both aerobic and anaerobic conditions in
a wide variety of environmental media including fresh and salt water, sediments and soils,
ground water, aquifier material and industrial wastewater. Methanol is of low toxicity to aquatic
and terrestrial organisms, and effects due to environmental exposure to methanol are unlikely to
be observed except in the case of a spill.
14.2.3 Environmental Requirements for the Gasifier

The primary environmental requirement of the biomass gasifier involved the handling of
synthesis gas and other products in a safe and environmentally friendly way.
The gasifier shall:
1. Not release appreciable amounts of synthesis gas to the environment during operation by
completely combusting the synthesis gas product in a flare. Produce less than 600g of Carbon
monoxide per kilowatt hour (United States Environmental Protection Agency, 2012)
2. Be free from leaks -Synthesis gas burns with a clear flame, which can only be seen at night.
The gasifier will be run at night periodically to check for leaks.
3. Be operated outside in a well-ventilated area to avoid hazardous buildup of carbon monoxide

gas.
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15 C O S T A N A LY S I S
Chemical plants are built to make profit, and an estimate of the investment required and the cost
of production, are needed before the profitability of a project can be assessed. Since the net profit
equals total income minus all expenses, it is essential to be aware of the various types of costs
associated with each manufacturing step (Peters, 2003). In the economic analysis of a chemical
plant, the costs for the plant are divided into investment cost and operating cost. In the following
section these costs are considered for the methanol plant.
Before an industrial plant can be put into operation, a large sum of money must be available to
purchase and install the required equipment. Land must be obtained, service facilities must be
made available, and plant must be erected complete with all piping, controls and services. In
addition, funds are required to pay the expenses involved in the plant operation before sales
revenue becomes available. The capital needed to supply the required manufacturing and plant
facilities is called the fixed-capital investment, FCI, while that needed for the operation of the
plant is called working capital, WC. The sum of the fixed capital investment and the working
capital is known as the total capital investment, TCI (Peters, 2003).
Costs estimates were obtained from US DOE Biomass Program Plan.
15.1 Total Capital Investment (TCI)

Capital cost
Item Cost
Gasification $ 43,250 000.00
Tar Reforming and Quench $ 26,940 000.00
Acid gas and Sulfur removal $ 28,490 000.00
Syngas Compression and Expansion $ 60,630 000.00
Methanol Synthesis $ 41,420 000.00
Separation $ 20,320 000.00
Steam System and Power $ 45,840 000.00
Cooling water and other Utilities $ 9,560 000.00
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Total $ 276, 450 000.00
Total Capital Investment (TCI) (Including $ 367, 253 151.00

Operational Costs, land and basic
infrastructure)
15.2 Fixed and Variable Costs
The variable costs of production include the costs of
 Raw materials
 Utilities
 Consumables
 Effluent disposal
 Shipping
The fixed costs of production include the costs of
 Operating labour
 Supervision
 Direct salary overhead
 Maintenance
 Property taxes and insurance
 Rent of land/buildings
 General plant overhead
 Allocated environmental charges
 Running license fees and royalty payments
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 Capital charges
 Sales and marketing costs
Table 15.2.1 Fixed and Variable Operational Co sts

Item Cost
Management and Liability $ 1,694 000.00

Insurance
Marketing and other $ 1,000 000.00
Operational (Raw material and $ 47,560 000.00

utilities)
Employee Benefits and $ 20,548 151.00

Utilities
Total $ 70,802 151.00
Table 15.2.2 Wat er fall illustration of the TCI

Water fall illustration of TCI
Cooling water and other Utilities $0.00 $9,560,000.00
Land and Basic Infrastructure $9,560,000.00 $20,001,000.00
Separation $29,561,000.00 $20,320,000.00
Tar Reforming and Quench $49,881,000.00 $26,940,000.00
Acid gas and Sulfur removal $76,821,000.00 $28,490,000.00
Methanol Synthesis $105,311,000.00 $41,420,000.00
Gasification $146,731,000.00 $43,250,000.00
Steam System and Power $189,981,000.00 $45,840,000.00
Syngas Compression and Expansion $235,821,000.00 $60,630,000.00
Operational Costs $296,451,000.00 $70,802,151.00
TCI $367,253,151.00
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Graph 15.2.1 Water fall illustration of the TCI
This graph shows that Operational Costs is the biggest bucket, and the top five being Operational
Costs, Syngas Compression and Expansion, Steam System and Power, Gasification and
Methanol Synthesis.
15.3 Payback Period

The Payback Period represents the amount of time that it takes for a Capital Budgeting project to
recover its initial cost. The use of the Payback Period as a Capital Budgeting decision rule
specifies that all independent projects with a Payback Period less than a specified number of
years should be accepted. When choosing among mutually exclusive projects, the project with
the quickest payback is preferred.
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Given that Methanol sells for USD0.557/liter, which is equivalent to USD0.441/kg and
USD441.00 per ton.
300000 metric could sell for: 300000*441 = USD132, 300 000.00 per year
Table 15.3.1 CF and Cumulative CF table

Year CF Cumulative CF
0 367253151 367253151
1 132300000 234953151
2 132300000 102653151
3 132300000 -29646849
4 132300000 -161946849
5 132300000 -294246849
6 132300000 -426546849
7 132300000 -558846849
8 132300000 -691146849
9 132300000 -823446849
10 132300000 -955746849
11 132300000 -1088046849
12 132300000 -1220346849
13 132300000 -1352646849
14 132300000 -1484946849
15 132300000 -1617246849
16 132300000 -1749546849
17 132300000 -1881846849
18 132300000 -2014146849
19 132300000 -2146446849
20 132300000 -2278746849
The first three Cumulative values (highlighted in red) are negative even though they appear as
positive.
It can be clearly seen from the table that Total Capital Investment will be recovered after two
years.
The values highlighted in Yellow apply to the formula for calculation of payback period.
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Payback Period becomes: = 2 + (102653151/132300000)
= 2 + 0.776
=2.776 years Equivalent to 2 years and 9 Months
If salvage/ residual value of 14 percent is assumed.
Giving: 0.14*$276, 450 000.00 = $38, 703 000.00 (salvage value).
The plant’s useful life span is 20 years. Given that the plant will run from the beginning of a
year.
Depreciation after year 1 = Cost - Residual value) / Useful life
= ($367, 253 151.00 - $38, 703 000.00)/ 20
= $16, 427 507.55
Net Cash Flow in in year 1: = $132, 300 000.00 - $367, 253 151.00
= -$234,953,151.00
The plant depreciation is not factored in the Payback Period calculation, but it is shown that even
when the plant’s useful life span is reached the Salvage/ Residual Value will still be high.
Ones this period is over the plant can still be refurbished or sold as it has a potential to make a
good annual return.
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16 INSTRUMENT LIST
16.1 Table 16.1

Instrument Where used Purpose
High Temp. Electrical Element Inside the gasifier and main streams To measure temperature
PID Controllers Central control panel Process control
Solenoid Valves In all streams For better control
PLC Module Central control panel Process control
Auto Igniter Gasifier To ignite flame
Level Sensor Inside the gasifier To detect level
Gas Analyzer Gasifier outlet To analyse gas from Gasifier
Pressure Meter In all streams Pressure measuring
Flow Meter In all streams Flow measuring
Cascade Impactor Stream between Gasifier and Filter Air sampling device
Page 103 of 111

17 UTILITY REQUIREMENT SCHEDULE
17.1 Table 17.1

Utility Condition Where used
Biomass (Wood chips) 50% moisture Gasifier feed
Power (Electricity) Across the plant
Steam from boiler Superheated steam @ 6 bar Autothermal reforming, Rectisol, Methanol synthesis, HE
Boiler water pretreated water at ambient Boiler
Cooling water Cold water Heat exchanging
Air ambient Air drier
Compressed air Hot air
Causting Soda 70% For cleaning and passivation
Catalyst Methanol synthesis/ Gasification/ Autothermal reforming
Process water ambient Through out the plant
Page 104 of 111

18 CONCLUSION
A high temperature fluidized bed reactor was designed to study the gasification and combustion
of biomass and the subsequent char at temperatures of up to 890°C.
This Biomass-steam gasification has also been seen to increase strongly with temperature giving
rate constant of 5.03E-6, 7.21E-6 and 1.13E-5 for temperatures of 712, 753, and 806 °C
respectively.
The fast fluidization and continuous circulating of char feature the circulating fluidized bed
gasifier, which benefit the gasification process dramatically. The features enhance heat and mass
transfer, raise reaction rate, strengthen fast pyrolysis, reduction and shift as well as other gas-
solid reactions etc. which make the productivity of the CFB much higher and gas quality much
better than other kinds of air blown gasifiers. They reach 2000 kg/m² .h and 7000 kJ/m³
respectively.
In operating the CFBG, reaction temperature can be easily adjusted by altering the air
equivalence ratio; and the load is flexible in wide range under conditions of steady operation and
the gas quality can be maintained in favorable range under different conditions. These are the
advantages in operating the CFBG.
In order to get higher heat efficiency, the following parameters recommended will favor the fast
pyrolysis, reduction, shift and secondary reactions.
Fluidized Bed Gasifier has the following advantages and disadvantages
Advantages:
 High maximum efficiency
 Can be scaled to produce over 10 MW (Solar Energy Research Institute, 1988)
 Most cost effective for production of over 15 MW (Chopra & Jain, 2007)
 Decreased potential for bridging
Disadvantages:
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 Complicated design
 Impractical for small scale production
Given the plant Payback Period of 2.776 years, it shows that the plant is capable and offers a
good business value and accomplishes the purpose of its design.
Page 106 of 111

19 REFERENCES
 Bergman, P.C.A.; van Paasen, S.V.B.; Boerrigter, H. The novel "OLGA" technology for
complete tar removal from biomass producer gas. In Pyrolysis and Gasification of Biomass and
Waste; Bridgwater, A.V. (Ed.); CPL Press: Newbury UK, 2003; 347-356.
 Katofsky, R.E. The production of fluid fuels from biomass; Princeton University/Center for
Energy and Environmental Studies: Princeton NJ USA, 1993.
 Methanol.org. (2014). The Methanol Industry - Methanol Institute. Retrieved 10 March 2014,
from http://www.methanol.org/Methanol-Basics/The-Methanol-Industry.aspx
 Fritz Ullmann’s et. Al, 2003, Ullmann’s Encyclopedia of Industrial Chemistry: Methanol, vol. 11,
John Wiley & Sons Inc.
 Graboski, M.S. and Brogan, T.R., (1988), Development of a Downdraft Modular Skid
 Mounted Biomass/ Waste Gasification System, Energy from Biomass and Waste XI,
Chicago, Institute of Gas Technology.
 Poongodi, P., S. Victor Genetic algorithm based PID controller design for LTI system via reduced
order model, International Conference on Instrumentation, Control & Automation ICA2009
October 20-22, 2009, Bandung, Indonesia.
 Rapagna, S., Tempesti, E., Foscolo, P.U. and Parodi, E., (1992), Continuous Flash Pyrolysis of
Biomass at High Temperature in a Fluidized Bed Reactor, Journal of Thermal Analysis, 38, 2621-
2629.
 Journal of Sustainable Bioenergy Systems, 2012, 2, 160-169
 M. Siedlecki, K. Van der Nat, E. Simeone and W. De Jong, “The First Results of Gas and Solids
Characterization Obtained during Steam-Oxygen Gasification of Biomass in a 100kWth CFB
Gasifier,” World Renewable Energy Congress IX, Florence, 19-25 August 2006.
 A. N. Hayhurst and A. D. Lawrence, “The Devolatilization of Coal and a Comparison of Chars
Produced in Oxidizing and Inert Atmospheres in Fluidized Beds,” Combustion and flame, Vol.
100, No. 4, 1995, pp. 591-604.
 C. Franco, F. Pinto, I. Gulyurtlu and I. Cabrita, “The Study of Reactions Influencing the Biomass
Steam Gasification Process,” Fuel, Vol. 82, No. 7, 2003, pp. 835-842
 Grace, J.R., (1986), Contacting Modes and Behaviour Classification of Gas-Solid and
Other Two-Phase Suspensions, The Canadian Journal of Chemical Engineering, 64,
(3), 353-363.
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20 APPENDICES
20.1 Appendix A: Main modelling assumptions

General assumptions
Biomass input: 15°C, 1 atm, moisture 50% at the drier inlet, reduced to 15% before gasifier.
Wood chips (% mass):
ash 0.156, C 51.9, O2 41.8, H2 6, N2 0.12, Cl 0.015, S 0.009.

Property models: Redlich Kwong Soave, NRTL is used for vapour liquid equilibria when
necessary.
10% excess of air in gas combustions, 20% excess of air in solid fuel combustions.
Exhaust gas stack temperature: 150°C

Pumps, compressors, turbine eff.: 0.75
Mechanical and electrical driver eff.: 0.98
Compression intercooling end temp.: 50°C (water is separated with flash)
Pressure drops in reactors: 0.2 bar unless specified
No pressure drops in heat exchangers
Air-drier
Inlet biomass moisture: 50%
Outlet biomass moisture: 15%
Max air temperature: 70
Out air temperature: 20
Oxygen steam blown pressurized fluidized bed gasification

The model has been taken from (Hannula and Kurkela 2012).
Temperature Tgas: 886°C
Pressure: 25 bar
Page 108 of 111

Steam to Oxygen ratio: 1

Carbon conversion: 99%
Steam injection is adjusted to obtain extra heat (loss) equal to 1% of the input biomass chemical
energy rate in HHV which corresponds to a steam to biomass ratio of around 0.5 (biomass
moisture excluded).
Methane molar fraction in product gas: 7.074 mol∙kg⁻¹ – 0.0155 Tgas
Acetylene molar fraction in product gas: 0.06454 mol∙kg⁻¹ – 0.00004 Tgas
Ethylene molar fraction in product gas: 2.987 mol∙kg⁻¹ – 0.002 Tgas
Ethane molar fraction in product gas: 1.196 mol∙kg⁻¹ – 0.001 Tgas
Propane molar fraction in product gas: 0.150921 mol∙kg⁻¹ – 0.000155 Tgas
Benzene molar fraction in product gas: 0.27 mol∙kg⁻¹
Naphthalene molar fraction in product gas: 0.3 mol∙kg⁻¹
Ammonia molar fraction in product gas: 0.04154 mol∙kg⁻¹
Biomass S is fully converted in H2S.

Biomass Cl is fully converted in HCl.
Biomass N2 not yielding Ammonia is inert.
CO, H2O, CO2, H2, reacting C, are all considered at equilibrium.
Catalytic tar reformer

Tar reforming temperature is set equal to temperature of incoming gasifier product gas (here
886°C). Methane reforming and water gas shift reaction are assumed at equilibrium (WGS with
40 K of temperature approach).
Hydrocarbon conversion higher than methane is set according to (Spath, Aden et al. 2005).
The following conversions are assumed:
Acetylene 50%, Ethylene 50%, Ethane 90%, Propane 90%, Benzene 70%, Naphthalene 95%,
Ammonia 70%.
Entrained flow gasification

Temperature: 890°C
Pressure: 25 bar
Page 109 of 111

H2, CO, CO2, H2O are considered at equilibrium with the exception for methane which
concentration is set at 1%-mol in dry product gas.
All biomass sulphur ends up in H2S, all biomass chlorine ends up in HCl, all biomass nitrogen
ends up in NH3.
Autothermal reforming (for biomass syngas)

Adiabatic reactor with steam and O2 injection.
Steam to carbon (in hydrocarb.) ratio: 1 (this is achieved by steam injection, if enough steam is
present in the gas, no steam is injected)
Exiting temperature: 1000°C
All species are considered at equilibrium.
Water-gas-shift reactor
Adiabatic reactor with steam injection to avoid carbon deposition.
Steam to CO ratio: 3
Inlet temperature: 330 / 350°C
water-gas-shift at equilibrium with 10°C temperature approach.
Methanation (SNG plant)

Adiabatic reactor with steam injection to avoid carbon deposition.
H2O molar fraction in fresh syngas: 20%
All species are considered at equilibrium.
MDEA CO2 removal (SNG plant)
Modelled as a 99.5% CO2 selective separation.
Stripper heat demand assumed to be 3.3 MJ/kg at 150°C.
Rectisol CO2 removal

Modelled as a CO2 selective separation to achieve the desired CO2 content in the syngas.
Syngas inlet temperature: 30°C
Syngas outlet temperature: 10°C
Refrigeration work: 0.55 kWh∙kmol-1 CO2 removed
Steam demand at 6 bar: 3.4 kg∙kmol-1 CO2 removed
Page 110 of 111

Methanol Synthesis
Temperature: 250°C
Pressure: 90 bar
Pressure drop: 5 bar
Synthesis loop ratio: 3

Stoichiometric equilibrium reactor with temperature approach of 27°C according to data found in
(DOE 1998) for both reactions:
Methanol synthesis of CO: CO + 2H2  CH3OH
Water gas shift: CO + H2O  CO2 + H2
Methanol separation and upgrading

Stripper is modelled as equilibrium column with 10 stages, 1.6 reflux ratio, bottom to feed ratio
around 0.9 (depending on the composition of the incoming raw methanol stream).
Distillation of methanol from water is simulated using a shortcut distillation model (Winn,
Underwood, Gilliland methods) considering 20 stages and limiting the water concentration in
distillate to 0.1%. Methanol recovery is imposed in the first column to obtain a balanced heat
demand between the condenser of the first column and the reboiler of the second column, while
in the second column it is imposed to obtain 99.9% recovery.
Page 111 of 111
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Methanol Production from Biomass

Conference Paper · November 2015

Methanol Production from Biomass View project

The user has requested enhancement of the downloaded file.

Lecture: Dr James Fox

I hereby declare to have made the present work independently and

Special consideration goes to my family, for sacrificing for me and

I want of course to thank all my friends, who were there whenever

1. Table 3.1 Characteristics of gasifiers, taken from Williams et al. (1995).

1. Figure 3.1: Key components in the conversion of biomass to methanol.

1. Graph 15.2.1 Water fall illustration of the TCI

3.2 Methanol Production ................................................................................................. 12

4 PROCESS DESCRIPTION ............................................................................................... 35

4.2 Gasification ........................................................................................................... 35

4.3 Tar cracking .......................................................................................................... 35

4.4 Wet gas cleaning ...................................................................................................... 35

4.5 Autothermal reforming (ATR) ...................................................................................... 35

4.6 Water-gas-shift (WGS) ............................................................................................... 36

4.7 CO2 removal .......................................................................................................... 36

4.8 Methanol synthesis ................................................................................................... 36

5 PROCESS SIMULATION ................................................................................................ 38

6 EQUIPMENT LIST ........................................................................................................... 51

7.2 Fluidized Bed Gasifier................................................................................................ 53

8 DESIGN AND OPERATION OF THE CFB BIOMASS GASIFIER .............................. 55

8.2 Calculations for distributor plate ................................................................................... 60

8.3 Calculations for the Cyclone Separator ............................................................................. 61

8.4 Determination of optimum gasifier volume ........................................................................ 65

9 DESIGN OF A SHELL AND TUBE HEAT EXCHANGER ........................................... 70

10 PUMP DATA SHEET ........................................................................................................ 77

13.2 Feeding Biomass ...................................................................................................... 83

13.3 Gasifier Operation .................................................................................................... 84

13.4 Sampling .............................................................................................................. 87

13.5 Ash Removal .......................................................................................................... 87

13.7 Startup ................................................................................................................ 88

13.8 Operation ............................................................................................................. 89

13.9 Cautionary Notes ..................................................................................................... 89

13.10 Adjusting the Air Feed Rate ......................................................................................... 89

13.11 Adjusting the Steam Feed Rate ...................................................................................... 90

13.12 Sampling .............................................................................................................. 90

13.13 Preparing for Shutdown ............................................................................................. 90

13.15 MSDS’s ................................................................................................................ 91

14 OTHER IMPORTANT CONSIDERATIONS .................................................................. 94

14.2 Environmental ........................................................................................................ 94

15.2 Fixed and Variable Costs ............................................................................................ 98

15.3 Payback Period ......................................................................................................100

16 INSTRUMENT LIST ....................................................................................................... 103

16.1 Table 16.1 ............................................................................................................103

17 UTILITY REQUIREMENT SCHEDULE ...................................................................... 104

18 CONCLUSION ................................................................................................................ 105

Many process configurations are possible, however. Gasification can be atmospheric or

 Applying improved or new (non-commercial) technologies. Examples are the use of

Thus production rate per hour will be:

3.1 About Methanol

3.2 Methanol Production

up of thousands of distributors, technology innovators, downstream manufacturers and service

Pre-treatment Gas cleaning Methanol

Figure 3.5: Key components in the conversion of biomass to methanol.

iii. Gas cleaning and contaminant limits

Raw gas versus system requirements

Table 3.1 Characteristics of gasifiers, taken from Williams et al. (1995).

IGT6) IGT max H27) BCL8)

bubbling fluidised bubbling fluidised Indirectly heated