Production of Methanol from Biomass - PLANT DESIGN

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.
Plant Capacity

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.

According to the market demand 38000 kg/hr will be used as basis which
then equate to 304000 tons in a year .

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.

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.

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 madeup 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),
carbondioxide (CO2) 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

Key components in the conversion of biomass to methanol.

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
. Total energy requirements for chipping woody biomass are approximately
100 kJ/kg of wet biomass down to 240 kW for 25 – 50 tonne/h to 3x3 cm in a
hammermill, which gives 17 – 35 kJ/kg wet biomass .
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.

Gasification

Through gasification solid biomass is converted into synthesis gas. .

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.

IGT gasifier

The IGT gasifier 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. However, for the production of methanol from biomass, the
use of air increases the volume of inert (N2) gas that would have to be carried
through all the downstream reactors. Therefore, the use of oxygen thus
improve the economics of synthesis gas processing. Air-fired, directly heated
gasifiers are considered not to be suitable before methanol production.
 The directly heated, bubbling fluidised bed gasifier of IGT

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 CO2
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.

Gas cleaning and contaminant limits

Raw gas versus system requirements

Table 3.1 Characteristics of IGT gasifier

IGT6)
bubblin fluidise
g bed d

Biomass input dry 80

basis1) (tonne/hr)
Initial moisture 30
content (%)
Dry moisture content 15
(%)
HHVdry biomass 19.28
(GJ/tonne)
LHVwet biomas 11.94
(GJ/tonne) s2)

Steam drier3) 26.2

dem
and

(tonne/hr)
Therm Biomas inpu HHV 428.4 /
al s t LHV 379.0
(MW)

Steam (kg/kg dry 0.3

feed)
Steam4) (tonne/hr) 24
Oxygen (kg/kg dry 0.3
feed)
Air (kg/kg dry feed) 0

Product temperature 982

(°C)
Exit pressure (bar) 34.5
Gas yield (kmol/dry 82.0
tonne)
Wet gas output 6560
kmol/hour
Composition: mole fraction on wet
basis (on dry basis)
H 2O 0.318 (-)
H2 0.208 (0.305)
CO 0.1 (0.22)
5
CO2 0.239 (0.35)
CH4 0.0819 (0.12)
C2H4 0.0031 (0.005)
C2H6
O2 0
N2 0
Σ 1 (1)

640 ktonne dry wood annual, load is 8000 h.

2)
Calculated from LHVwet = HHVdry × (1 - W) - Ew × (W + Hwet × mH2O);
with Ew 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
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.

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 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 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.

Tar removal
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 . 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 . It is not clear to what extent tars are removed 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
The tar crackers can be integrated with the gasifier.
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 . 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 μm .New generation bag filters made from glass and
synthetic fibres have an upper temperature limit of 260 °C .At this
temperature particulates and alkali, which condense on particulates, can
successfully be removed 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
H2S 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).

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 .
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 μm particles have been reported . Still better ceramic
filters for simultaneous SOx, NOx and particulate removal are under
development .

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 .
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 although others give much higher prices .

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:
CH4 + H2O → CO + 3H2 Equation 1

C2H4 + 2H2O → 2CO + 4H2 Equation 2

C2H6 + 2H2O → 2CO + 5H2 Equation 3

Concurrently, the water gas shift reaction takes place, and brings the
reformer product to chemical equilibrium .

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 .
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.

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 .

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 H2:CO ratio in the product, while it does dilute
the product with H2O . Typical ATR temperature is between 900 °C and 1000
°C.

Water gas shift

The synthesis gas produced by the IGT gasifiers has a low H2: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 H2 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 °or 400 °C
. Due to high catalyst selectivity, all gases except those involved in the water-
gas shift reaction are inert. The reaction is independent of pressure.

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 (H2-
 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.

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 Equation6

The first reaction is the primary methanol synthesis reaction, a small amount
of CO2 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.

Figure: 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 , 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 . An additional advantage is the ability to
withdraw spent catalyst and add fresh catalyst without interrupting the
process.

PROCESS DESCRIPTION
Drying
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.

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.

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.

Wetgas 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).

Auto thermal reforming ( A T R )

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

(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.

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).

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 (G⎞tz, 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).
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 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).

Process flow diagram of Methanol production

 PROCESS SIMULATION

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.

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.

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.

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.
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

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
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.
 EQUIPMENT L IST
The main process areas require the following equipment:
Equipment Heat Duty (kW) Construction
Materials
1. Air Drier 76978 Stainless steel
308L
2. Fluidized Bed 51249 Stainless steel
Gasifier 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

GASIFICATION
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.

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

Fluidized Bed Gasifier

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.
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.

DESIGN AND OPERATION OF THE CFB

BIOMASS GASIFIER
The basic unit of circulating fluidized bed biomass gasifier system comprises of
following components:

• Riser,

• Cyclone separator,

• Burner-blower system for hot air generation,

• Biomass hopper and screw feeder,

• Gas cooling system (either quench or heat exchanger type),

• Particulate filter system (either single or double stage) and

• 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 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. However, to 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 gasifie.In designing of riser, 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).

For 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:

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.

Where the solids age distribution in the fluidized bed is

And

Combining the two equations you get:

Assuming that the gasifier is operating at 850 °C with biomass feed rate of 550 kg/hr and feed
particles of 1mm in diameter, using Equation

And

we can derive a surface rate constant as:

And

The conversion time is related to the surface rate constant by the expression of
Kimura et al. (1982):
If we allow 70% conversion of the char before circulating to the combustor, then:

Inserting the values of Ʈ c and (1-X) and solving for mean residence time,we get

Assuming a solids circulation rate of 176 981 kg/hr (= 200 kg/mm). Now:

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:

 𝑫𝑮 = 𝟒. 𝟐𝟑 𝒎

𝑯𝑮 = 𝟐 ∗ 𝟒. 𝟐𝟑 𝒎
𝑯𝑮 = 𝟖. 𝟒𝟔 𝒎

DESIGN OF A SHELL AND TUBE HEAT EXCHANGER

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.

Before considering the process aspects of heat transfer, let’s look at the
mechanical components of the heat exchanger shown in figure given below.
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
Figure : Shell-and-tube heat exchanger. Tube support baffles 90 from true orientation.

Table :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
Specific Gravity/Density: 7910g/cm3
 Molecular Formula: CH3OH
Molecular Weight: 32.04

Design Calculations
𝑄 = M𝐶𝑝∆𝑇

𝑄 = 5659 ∗ 2.51 ∗ 200

𝑄 = 2840818 𝑊

𝑄 = 28404 𝑘𝑊

Heat transfer area calculation:

𝑄 = 𝑈𝐴∆𝑇𝑙𝑚
𝐴 =Q/𝑈∆𝑇𝑙𝑚
Assuming overall heat transfer coefficient (U) of 900 𝑊/𝑚2℃
∆𝑇𝑙𝑚 = (𝑇1 − 𝑡1) − ( 2 − 𝑡2) /[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
𝐴 =Q/𝑈∆𝑇𝑙𝑚

2
A = 28404 ∗ 1000/[900*63.69]= 495.53 𝑚

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:

N= A/At
N = 495.53
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:

𝑀𝑤 = Q/ 𝐶𝑝∆𝑇

𝑀𝑤 = 28404/[42*95]

𝑀𝑤 = 71.19𝑘𝑔/𝑠

Tube side heat transfer coefficient

120−25
M𝑒𝑎𝑛 𝑤𝑎𝑡𝑒𝑟 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 =
2

M𝑒𝑎𝑛 𝑤𝑎𝑡𝑒𝑟 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 47.5

𝑇𝑢𝑏𝑒 𝑐𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎 =𝜋𝐷2 4

𝑇𝑢𝑏𝑒 𝑐𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛𝑎𝑙 𝑎𝑟𝑒𝑎 = 0.000201𝑚2

𝑇𝑜𝑡𝑎𝑙 𝑓𝑙𝑜𝑤 𝑎𝑟𝑒𝑎 = 0.000201 ∗ 859 = 0.173

71.19
Gt=
0.173
𝐺𝑡 = 411.50

L𝑖𝑛𝑒𝑎𝑟 𝑣𝑒𝑙𝑜𝑠𝑖𝑡𝑦 =411.50/1000

L𝑖𝑛𝑒𝑎𝑟 𝑣𝑒𝑙𝑜𝑠𝑖𝑡𝑦 = 0.412𝑚/𝑠
 ℎ𝑖=4200(1.35 + 0.02 ∗ 47.50)0.4120.8
0.2
16

ℎ𝑖 = 2729.88 𝑊/𝑚2 𝑜𝐶
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
Bundle diametrical clearance = 0.068 m,

Therefore 𝐷𝑠 = 1.097 + 0.068 = 1.165𝑚

Tube pitch = 1.25*20 = 25 mm

Choose baffle spacing of Ds /5 = 1.165/ 5= 0.233𝑚

(0.025 − 0.020)
As= * 1.165 * 0.233 = 0.054 m2
0.025

Flow rate of methanol in stream 16 = 130599 kg/h and therefore:

130599 1
G= * 0.054 = 671.81 kg/s m2
3600
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

−3
𝑅𝑒 = 𝐺𝑠𝐷𝑒 /µ = ( 671.81 ∗ 0.014)/( 0.113 ∗ 10 )= 83233

3.96 ∗ 103 ∗ 0.113 ∗ 10−3

𝑃𝑟 =Cp µ/Kf = = 2.797
0.16
Choose 25 per cent baffle cut,
 Jh = 3.3 * 10-3

0.16
ℎ𝑜 = * 3.3 ∗ 10−3 ∗ 83233 ∗ 2.797 1/3
0.014

ho = 4421.30 W/m2 𝑜C
Overall heat transfer coefficient

1 1 1 1
1/U0 = + + + + [0.02ln(20/16)]/(2*48.28)
4421.30 2729.88 4230 2850

1/𝑈𝑜= 0.0013176
𝑈𝑜 = 758.97 W/m2 𝑜C

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.

MSDS’

S y n g as

MATERIAL SAFETY DATA SHEET

1. Chemical Identification
Product Name Syngas
Chemical Name Mixture
Chemical Family N/A
Formula Mixture
Synonym Syn Gas (Synthesis Gas)
4. Composition Information
Compone Amount (%W/W)
nt
Carbon Monoxide >= 50 <= 9 %
Carbon Dioxide <= 20%
Water <= 20%
Hydrogen >= 5 <= 9%
Methane <= 3%

5. Hazard Identification
5.1 Emergency Overview
Appearance
Physical state
Odor
Hazards of product
5.2 Potential Health Effects
Inhalation
Transparent colorless
Gas
Odorless
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
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

be bright red (cherry red) in colour. Lack of

Effects of Repeated Over-
exposure
oxygen can cause death.
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 Due to the hypoxia from

Aggravated 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

1 3 . 1 5 . 2M e t h a n o l

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 1-800-901-7247
Number
 4. Composition Information
Compon CAS Amount
ent # (%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
 COST ESTIMATION AND ECONOMICS
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. 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.

CAPITAL COST

Gasification 320 crore

Tar Reforming and Quench 190 crore

Acid gas and Sulfur removal Rs 2 200 crore

Syngas Compression and Expansion 44 crore

Methanol Synthesis 300 crore

Separation 140 crore

Cooling water and other Utilities 66 crore

Total 1260 crore

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
• Sales and marketing costs
Fixed and Variable Operational Costs

Management and Liability Insurance 11 crore

Marketing and other 7 crore

Operational (Raw material and utilities) 350 crore

Employee Benefits and Utilities 140 crore

Total 508 crore

TOTAL CAPITAL INVESTMENT - 1260 + 508 = 1768 CRORE

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.

Given that Methanol sells for INR 35/kg and INR 35000 per ton.

300000 metric could sell for: 300000*35000 = INR 1050,00,00,000per year

= INR 1050 CRORE per year

Year CF (in crore ) Cumulative CF (in crore)

0 1768 1768

1 1050 718

2 1050 -332

3 1050 -1382

It can be clearly seen from the table that Total Capital Investment will be recovered after 1 year

Payback period :- = 1 + ( 718/1050)

= 1.683 years

This is equivalent to 1 year and 8 months

OTHER IMPORTA NT CONSIDERATIONS

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.
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 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: 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

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.

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.

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:

• 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)

• 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.

• Be operated outside in a well-ventilated area to avoid hazardous buildup of

carbon monoxide gas.

STORAGE

Storage of methanol is subject to substantially the same provisions as thoseUsed for

gasoline storage. Methanol is routinely stored in tank farms consisting of above-ground,
floating roof tanks and smaller, internally baffled floating baffle tanks.Tanks must be grounded
to avoid hazards associated with static discharge. Ignition control may be by nitrogen
padding, natural gas padding or by designation of a hazard zone with ignition control.
Because methanol is commonly stored with other solvents andfeed stocks, all piping and
valves subject to carrying methanol should be consistently labeled, and direction of flow
should be indicated. All storage materials, including totes and drums, require berming and
adequate ventilation. Berming should be stabilized by compacting, by use of suitable
methanol resistant fabric, or with concrete. Because of the solvent properties of methanol,
hydrocarbon residuum, asphalt, and road oil are not suitable as berm cover/stabilization
materials.Methanol burns with a non-luminescent flame, which may beinvisible in bright
sunlight. Responders should be equipped with infrared devices that allow remote heat and
relative temperature detection. It is highly desirable to have this capability overhead in
an emergency response helicopter, if at all possible.