Department of Chemical Engineering, Government Engineering College

Energy Optimization
in Fischer-Tropsch
Process
Design Project

Abhinav N K, Adithya Raveendran T, Ajal Ramesh, Akash T, Amal

Rose.
11-17-2017
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Abstract

Fossil fuels is one of the most widely consumed source of energy for
industrial as well as personal uses. As it is widely understood, fossil fuels is
not a viable long term source of fuel as there is too much problems related
to it. And so, there needs to be a source of fuel which can be much more
environmentally friendly and also be less dependent on the fossil fuel that
was a result of millions of years of natural process.
FT synthesis can be a viable source of fuels which can used for various
applications in Industries as well as a fuel for vehicles and in engines. The
other products formed in this synthesis can be used as a feed material for
other chemical synthesis. The Study and optimization done in this project
is to make this promising field to more viable and more efficient. A study
of the different parts of the series of process is done and an optimum set
up is suggested for a source of biomass and then the setup is optimized by
utilizing the energy lost throughout the process.
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Introduction

Most of the problems facing the world has to do with energy. There is a
need for energy for all the different applications humans have found. And
the sources of energy are limited (Apart from Sun). One of the most
heavily utilized sources of energy are fossil fuels. The exhaustive use of
fossil fuels is one of the prime reasons for global warming which leads to
climate change. The worldwide energy usage is only second to that of the
industrial sector in terms of gross end-use energy consumption. According
to International Energy Outlook- 2011, the estimated fraction of global
transportation fuel consumption surges from 54% in 2008 to 60% in 2035
accounting for 82% of the total increase in world liquid fuel consumption.
Liquid fuel consumption increases at an average rate of 1% from 2008 to
2035 whereas total energy demand increases by 1.6% annually. Liquid
fuels are expected to continue dominating the transportation sector even
though the prices are rising. The current use of fossil fuels in different
sectors makes it so that sustainability is impossible.
The use of renewable energy is suggested to be the way to go because of
its lack of emission of greenhouse gases into the atmosphere when
compared to the fossil fuels since it is the main source of greenhouse gas
emissions. There have been steps taken to make sure that this emission of
greenhouse gases doesn’t continue through International agreements on
Climate change by various conventions. Another way to reduce
greenhouse gases is to find more useful fuel sources and especially
combustible liquid fuel sources as this is one of the most widely used form
of fuels.
Among these alternative sources of fuels, biomass is one which has the
most potential. It is the only natural, renewable source of carbon and is
considered as a replacement for fossil fuels. A wide range of biomass
based materials have been proposed to be used including crop residues,
agro-crops, and several tree species. These products can be directly burnt
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for energy or can be processed further for conversion to liquid fuels like
ethanol and diesel. Thermal processes offer an effective means for the
conversion of the energy content of various biomass. Biomass to Liquid
(BTL) is the best route to replace the fossil fuels and also in keeping the
environment clean. For 20% of the total liquid fuels produced from the
carbon neutral sources, like biomass, 15% CO2 emissions reduction could
be achieved by just fuel replacement.
There are various BTL possibilities including fast pyrolysis of biomass,
direct liquefaction of biomass, transesterification of vegetable oils to
produce diesel, production of bio-oil from algae and also Fischer-Tropsch
process which is the process focused on in this study.
The study that has been conducted here will involve a literature review
regarding the different aspects of the complete synthesis process and then
a process of design is submitted with the selection of design as well as the
future prospects of the project explained.
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Objectives

 To understand the process called Fischer-Tropsch Synthesis.

 Learn a brief history about the process.

 To understand the different steps involved in FT synthesis.

 To identify the importance and relevance of the process.

 To analyse the challenges involved in this process.

 Optimize the process so as to make it more efficient.

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Literature Survey
There have been a lot of studies involving the various aspects of FT
synthesis including that of the syngas production, Fischer-Tropsch process,
syngas clean-up, etc. Fischer-Tropsch Synthesis can be defined as a series
of processes through which biomass is converted into various hydrocarbon
products such as diesel, naphtha, olefins etc. There are various steps
involved in a large scale synthesis plant of this type.
The processes involved in this synthesis are (1) Gasification, (2) Syngas
Clean up and cooling, (3) Fischer-Tropsch Process, (4) Upgradation of
Waxes and liquids.
According to a review on Biomass gasification technology, by Antonio
Molino, Simeone Chianese and Dino Musmarra, Gasification is defined as a
thermochemical process in which a biomass or a solid/liquid organic
compound undergoes conversion into a gas phase usually called “syngas”,
which has a high heating power and also a solid phase called “char”, which
includes organic unconverted fraction and inert materials present in the
treated biomass. This conversion represents a partial oxidation of the
carbon in the feeding material and is generally carried out in presence of a
gasifying carrier such as air, oxygen, steam or carbon dioxide. Biomass
gasification is considered as a way to increase the use of biomass for
energy production allowing widespread biomass utilization. The
development of biomass gasification is pushed up by the growing
awareness of the possible effects of fossil fuels on the climate and by the
continuous increase in oil prices. The syngas produced is a gas mixture of
carbon monoxide (CO), hydrogen (H2), methane (CH4) and carbon dioxide
(CO2) as well as light hydrocarbons, such as ethane and propane, and
heavier hydrocarbons, such as tars, that condense at temperatures
between 250 and 300 °C. Undesirable gases, such as sulphidric (H2S) and
chloridric acid (HCl), or inert gases, such as nitrogen (N2), can also be
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present in the syngas. Their presence depends on the biomass treated and
on the operational conditions of the gasification process.
The principle reactions of the gasification are endothermic and the
necessary energy for their occurrence is, generally, granted by the
oxidation of part of the biomass. The main steps in gasification process are
1. Oxidation (Exothermic stage).
2. Drying (Endothermic stage).
3. Pyrolysis (Endothermic stage).
4. Reduction (Endothermic stage).
An additional step consisting in tar decomposition can also be included in
order to account for the formation of light hydrocarbons due to the
decomposition of large tar molecules. The study also gives an idea about
the various gasification technologies. The main reactors used in the
biomass gasification process are:
1. Entrained flow reactor.
2. Fixed bed reactor.
3. Fluidized bed reactor.
4. Rotary kiln reactor.
5. Plasma reactor.
A study into these reactors have suggested that these reactors have
different advantages and disadvantages and that can be summarized in
the table:
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Thus for a plant that needs to have a syngas conversion system, there
needs to be a reactor with enough capacity to produce the syngas on a
commercial level and then be able to clean it up properly.
The studies conducted by P. De Filippis, M. Scarsella, B. de Caprariis on the
Biomass gasification plant and syngas clean-up system gives a basic idea
on what happens after the syngas is produced in the gasifier. For their
study they used an updraft gasifier and even though there will be
difference between individual gasifiers, the basic product from all gasifiers
will have a hot syngas of around 800oC and it will need to be cooled to
300oC so as to use for the downward processes in FT synthesis. This
cooling is currently done by heating the gasifying air and passes through a
cyclone to remove dragged particulates. A water direct contact heat
exchanger is used to further purify the syngas from the residual tar. There
will be another various other cleaning technologies including sulphur
removal and ammonia removal and both these are done by spray towers.
Even though there are various ways to use biomass for energy production
as specified above, gasification and producing syngas is likely the best
thanks to the lesser amount of charring and also the high temperatures it
attains.
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After gasification, there are two ways to approach the energy production.
One is to use this hot syngas for electrical power generation with the help
of internal engines. This has been done in large scale for electricity
generation and thermal applications. It is only recently that research is
concentrated on converting biomass derived syngas into higher
hydrocarbons via FT process. Advanced research work on biomass
gasification systems by the combustion and gasification group at the
Indian Institute of Science has resulted in the development of state of the
art biomass gasification technology using variety of biomass fuels. They
use a downdraft gasifier in their studies and this involves the gasifying
agent as air.
There have been studies conducted by Solar Energy Research Institute
under the U S Department of Energy Solar Technical Information Program.
These studies suggest that syngas of higher carbon monoxide and
hydrogen composition can be attained by high temperature gasification
with oxygen as the gasifying agent rather than air itself. The main
difference in this would be the controlled flow of oxygen which will double
the energy that is stored by a unit volume of syngas. The SERI studies have
suggested the use of downdraft gasifiers as it gives more overall stability in
terms of temperature and conversion rate and also produce less tar
compared to the other gasifiers.
Among the downdraft gasifiers, Imbert gasifier is one which has been the
most popular because of its design and on how effective it is. The main
problem with the Imbert gasifier is the scaling up although this too have
been solved a lot by readjusting the dimensions and could be further
modified by future studies.
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The figure above is an Imbert type gasifier which is a downdraft gasifier

with a constricted hearth and the inner chamber is simply a magazine for
the wood chips or other biomass. During operation, the spring loaded
cover is opened to charge the gasifier and then closed for operation. It also
functions as a safety valve. About one third of the way up from the
bottom, there is a set of radiall directed air nozzles that permit air to be
drawn into chips as they move down to be gasified. As the gasification
process occurs in the V shaped hearth, the syngas syngas formed will
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move down and will go out through the outer shell and into cooling and
cleaning systems. In Imbert type gasifier, tar production is very low and
the ash produced will have temperatures around 600oC. The main
peculiarity of the Imbert type gasifier is its throat which allows for a better
conversion and its self-adjusting combustion. The way syngas produced
and is going out of the system is also an aspect of the system that can be
useful.
The syngas which is cleaned is then used to produce various solid products
through Fischer-Tropsch process. Fischer-Tropsch process or FT process is
a heterogeneous catalytic reaction which converts the synthesis gas into
long chain hydrocarbons. The overall reaction is given by –
(2n + 1)H2 + n CO CnH2n+2 + n H2O; n=Integer
M. Dry has called this process a surprising phenomenon in heterogeneous
catalysis that attracts the interests of world experts: CO and H2 enters the
reactor as gases and hydrocarbon solids and liquids exits as products. The
interest in Fischer-Tropsch technology has been increasing rapidly. This is
due to the recent improvements to the technology and the realisation that
it can be used to obtain value from stranded natural gas as well as syngas.
The industry is often called Gas to Liquid Industry and the main potential
advantage of a GTL industry is the ability to diversify further from fuels to
higher value chemical products. Some advantages of the FT hydrocarbons
compared to crude oil as a feedstock for fuel production are the absence
of sulphur, nitrogen or heavy metal contaminants, and the low aromatic
content. Linear olefins required in the chemical industry can be produced
either directly in the FT process or by dehydrogenation of the paraffinic
cuts.
Potential co-products may also utilise materials and energy that is not
directly associated with the FT hydrocarbons. For example, waste heat
may be converted to electrical power and nitrogen produced in air
separation unit may be used to make ammonia which may be further
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reacted with waste carbon dioxide to make urea. Before surveying the
literature for the mechanism, a short history of the process is found.

A Short History of Fischer-Tropsch Process

Franz Fischer and Hans Tropsch were two chemists working at the Kaiser
Wilhelm Institute for Coal Research in Mulheim, Ruhr. The institute was
created in 1913, but the work on which Fischer and Tropsch were jointly
engaged started producing results only in the 1920s. Their aim was to
produce hydrocarbon molecules from which fuels and chemicals could be
made, using coal-derived gas.
The first Industrial FT reactor was the Ruhrchemie atmospheric fixed bed
reactor (1935). It consisted of a box which was divided into sections by
vertical metal sheets, the catalyst being loaded between sheet and tube.
Water was used as the cooling medium and is converted to steam at a
uniform temperature that corresponds to the boiling point of water at the
prevailing pressure. Fischer and Pichler then developed the ‘cobalt
medium pressure synthesis with the main products being middle distillates
and wax. This was the most important technology used in Germany during
the Second World War. By November 1935, less than three years after
Germany’s Nazi government came to power and initiated a push for
petroleum independence, four commercial size Ruhrchemie licensed FT
plants were under construction. Their total annual capacity was 100000-
120000 metric tons of motor gasoline, diesel fuel, lubricating oil and other
preoleum chemicals. The other chemical products included alcohols,
aldehydes, soft waxes and heavy oil.
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FT synthesis: Further literature survey

The main part of Fischer Tropsch process is the FT reactor and the
catalysts. The strong relationship between FT catalyst and catalytic
reactors has resulted in the design of various types of heterogeneous gas
solid catalytic vapour phase reactors for such a multiproduct reaction
system. Most common reactors include multi-tubular fixed-bed reactor,
the slurry reactor, three phase fluidized bed reactor, fluidized bed
reactor, and circulating fluidized-bed reactor. Currently, there
are two operating modes for the FT reactors – high temperature
mode (300–350 °C) and low temperature mode (200–240 °C). Iron
catalysts are employed in high temperature mode for the synthesis
of gasoline and linear low molecular olefins. On the other hand,
low temperature processes utilize either iron or cobalt catalyst for
the production of high molecular mass linear waxes. In case of
fluidized bed reactors, the bed being more isothermal compared to
fixed bed reactors, it can be operated in the temperature range of
320–350 °C which is 100 °C higher than the operating temperature range
used with the tubular fixed bed reactor and slurry phase
reactors.
Low Temperature FT reactor-LTFT
Modern FT processes employ low temperature processes for
the production of liquid fuels. In these reactors synthesis gas,
liquid products, and solid catalysts co-exist. The primary aim of
any FT reactor is to remove the large heat of reaction produced
during the FT process and maintain uniform temperature profile
within the catalyst bed. Guettel et al grouped the
various possibilities for LTFT reactors as follows:
1. Cooling with internal tubes, where coolant fluid circulates in the
tubes, within suspended or fixed bed reactors.
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2. External cooling- this is enabled by recycling of gas or liquid

into the catalyst bed.
3. Direct cooling by dispersing the feed of inlet synthesis gas in stacked
fixed bed reactors.

Most common type of fixed bed reactor is a multi-tubular

reactor, with the catalyst placed within the tubes and cooling
medium on the shell side. The short span between the catalyst
particles and the tube walls and high gas linear velocities significantly
augments heat transfer from the catalyst particles to the
cooling medium, maintaining steady FT temperature range. Syngas
recycling aids in improved heat transfer and also in increased
overall conversion. Similarly, recycling of liquid hydrocarbon
products also enhances the temperature profile in the fixed bed
reactors. Due to the similarity in behaviour of the parallel
tubes in multi-tubular reactors they are easy to handle and design.
Some of the other advantages of the multi-tubular fixed bed
reactors include the absence of catalyst–wax separator since the
heavy wax products trickle down the bed and gets collected in the
receiver pot. Most importantly, the behaviour of large scale reactors
can be predicted accurately based on the performance of pilot
scale plants. Limitations of the fixed bed FT reactor include
the pressure drop constraint; and hence catalysts in fixed bed
reactors have diameters greater than about 1 mm. Intraparticle
diffusion plays limiting factor for the overall reaction rate for
catalysts with sizes greater than 1 mm. Consequently, intraparticle
diffusion is an important factor that needs to be accounted for
while choosing catalyst particle size and shape for a fixed-bed FT
process. The second type of commercial LTFT reactor is the slurry
phase bubble column reactors where catalyst powders with
dimensions of 10– 20 0 μ m are used. As a result, the effect of
internal mass transfer resistances is negligible resulting in optimal
activity and
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selectivity. Also, the efficient heat removal system allows nearly

isothermal operation of the catalytic bed. Productivity in a slurry
bubble column reactor is higher than in a fixed bed reactor due to
increased catalyst utilization and greater average reactor
temperature. Difficulty in scale up of slurry bubble column reactors
and solid catalyst separation posed issues towards the
commercialization of slurry bubble columns for FT process.

High temperature FT reactor- HTFT

High temperature FT processes operate in the temperature range of

300–350 °C utilizing Fe catalysts and producing gasoline
or linear olefins. The high temperatures vaporize all the
products under reaction conditions, maintaining just two phases
throughout the process. These are called 2-phase fluidized
bed systems. Two types of high temperature fluidized bed systems
are in commercial use – fixed fluidized bed reactors and circulating
fluidized bed (CFB) reactors. Fixed fluidized bed reactors are also
called Sasol Advanced Synthol (SAS) reactors. The high
temperature FT technology exercised by Sasol in the Synthol
process, South Africa, is the largest commercial scale application of
the FT process. SAS reactors that were successfully used for
30 years at Sasol are more economic compared to the CFB –
primarily due to lesser structural complexity (like the suspended
reactor–hopper–standpipe system of CFB). Duvenhage and Shingles
[119] list major advantages of SAS over CFB as higher pass per
conversion; lower catalyst consumption; uniform product selectivity
with products in the range of slightly heavier hydrocarbons;
less maintenance and easier construction. Cyclone separators of
SAS very effectively retain the catalyst within the reactor. However,
in case of CFB reactors, scrubber towers need to be used
downstream of the cyclones to remove the last traces of catalyst
before the product stream can be condensed.
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FT Catalysts

An ideal FT catalyst should possess a high hydrogenation

activity to catalyze the hydrogenation of CO to higher hydrocarbons. There
are four transition metals that possess sufficiently high hydrogenation
activity for use in the FT synthesis process –
iron, cobalt, nickel and ruthenium. Iron catalysts are the most
common catalysts, primarily due to easy availability and low costs
in comparison to other metals. Ruthenium has the highest activity
for the FT reaction but is an expensive catalyst compared to Fe and
Co. Nickel too has got very high activity for hydrogenation.
However, it produces much more methane than Fe or Co. Also, it
forms volatile carbonyl resulting in continuous loss of the metal at
the temperatures and pressures at which practical FT plants
operate. Hence, Fe and Co are the only two ideal metals that can be
used for practical application of FT synthesis. Overall, as far as the
commercially viable metals are concerned, Co appears to be more
active than Fe. The FT turnover rates on Co catalysts are significantly larger
than on Fe catalysts. Intrinsic rates of FT reaction on the catalyst surface,
and the rates of diffusion of reactants and products across the porous
catalyst particles dictate the overall reaction rates. In particular,
the diffusion rates depend on the porosity and pore sizes, catalyst
particle size, species concentration, and on the presence of higher
hydrocarbons, especially liquid waxes, within the catalyst particles. As
seen in the Thiele–Wheeler plot, the catalyst effectiveness drops less than
one as the Thiele modulus, ϕ, rises above unity. Clearly, intra-particle
diffusion plays a crucial factor for FT catalyst particle with diameters
relatively greater than 0.5 mm, thus making intra-particle diffusion a
critical parameter
for consideration while selecting catalyst particle size and shape
for a fixed-bed FT process.
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Iron Catalyst
Fe catalyst, owing to its relatively low costs and easy availability, is the
most common catalysts used for the FT process.
Initial FT processes employed catalysts that were synthesized by
precipitation method. Zimmerman et al. synthesized catalyst
using continuous precipitation method. During the prevailing reaction
conditions, Fe catalyst can exist in form of magnetite, or in the form of Fe-
carbide. The existence of these phases during the FT reaction have a direct
consequence on the FT product distribution. It is necessary to reduce the
Fe catalyst prior to use in FT reactor. The need to reduce the catalyst is to
achieve active catalysts with high metallic surface areas. Promoters are
added to Fe catalyst for increased activity and
improved stability. The addition of potassium enhances CO chemisorption
and reduces H2 chemisorption due to electron donating
nature of potassium to iron, thus aiding CO chemisorption since CO
readily accepts an electron from Fe. Furthermore, hydrogen donates
electrons to Fe, and the existence of electron-donating alkali
weakens the iron-hydrogen bond, boosting the Fe–C bond and
reducing the strength of the C–O and Fe–H bonds. Tao et al. used
manganese as a promoter for their Fe catalyst in a slurry
reactor. They concluded that initial FT synthesis activity reduced
with increased Mn content due to weak carburization. However, Mn
was able to restrict the re-oxidation of iron carbides to Fe3O4 and
augment additional carburization of the catalyst, maintaining stability
during FT reaction. At the same time, Mn promotion
restricted CH4 formation and increased light olefin selectivity.
With Fe catalysts, FT reactions exist over wide temperature
ranges (210–350 °C). Schulz et al. further claimed that the active
Fe catalyst for FT synthesis is “constructed” in several stages of
“self-organization”, during which conversion, selectivity, catalyst
composition and structure change, concluding that Fe in its zero
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valent state is not the active phase. FT activity develops when iron
carbide are formed. Use of Fe catalysts produces broad range
of hydrocarbon products including paraffins and olefins. The products vary
from fractions of methane to high molecular weight
waxes. Fe catalysts show varying WGS activities and, in some
cases, leading to rejection of 30–50% carbon feed in as CO2. α-
olefins are the primary products formed over iron catalysts.
However, olefins can undergo secondary reactions resulting in
isomerization or hydrogenation. In experiments conducted by
Rao Pendyala et al., the effect of the addition of varying
amounts of water on selectivity and activity of alkali promoted
precipitated Fe catalysts was investigated. Increased addition of
water in feed gas reduced the selectivity to C5 þ hydrocarbons due
to increased WGS activity and simultaneously increased the
selectivity to oxygenates. Fe catalysts are designed for operations
in high temperature FT reactions (340°C), for the production of
low molecular weight olefinic hydrocarbons, and for operations at
low reaction temperatures (230°C), for the production of paraffin waxes,
which can be further hydrocracked for producing high
quality diesel.
Cobalt catalyst
Cobalt catalysts possess high activity with 60–70% conversion
in a single pass, along with high selectivity and stability in the
synthesis of linear hydrocarbons. Cobalt catalysts exhibit good
resistance to attrition in slurry bubble column reactors. Due to
negligible WGS activity over cobalt catalysts, there is no effect of
water on CO conversion. Excessive CH4 formation at higher temperatures
over cobalt catalysts restricts its use to lower temperatures. Cobalt
catalysts show high methane and C2–C4 selectivities at temperatures
above 250 °C. At temperatures below 200 °C, CH4 selectivities are less
than 15% along with low metal and site-time yields. Another unfavourable
aspect of cobalt catalyst is the difficulty in the regeneration of deactivated
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catalysts,
which requires sequential hydrogen and steam treatments or a
solvent wash. Relative high costs of cobalt based catalysts make the study
of catalyst deactivation a major challenge. The synthesized catalysts need
to have apart from good activity and selectivity, long life. Oxidation of
cobalt to its oxide form by water and CO2 is the main cause of
deactivation of the catalyst though long term effect on cobalt based
catalysts due to CO2 is very small. The addition of copper reduces the
temperature required to
reduce cobalt oxide to metallic cobalt, which is the active phase for
FT synthesis. But, the presence of copper decreases the cobalt
catalyst activity. Hence, alternative promoters need to be used
[83]. Noble metal promoters such as Pt, Ru and Re are often added
to cobalt catalysts. These metals catalyse cobalt reduction by H2
spillover from the promoter surface, thus reducing the temperature at
which reduction occurs. Also, textural promoters are used
to increase dispersion, improve attrition resistance, build up a
sulphur tolerance or electronically modify the active metal site.
These metals include Zr, La, B and K. Experiments by Thiessen et al.
showed considerable higher C5 þ selectivity, lower methane selectivity
and higher olefin to paraffin ratio, compared to an un-promoted catalyst
for Mn promoted carbon nanotubes supported cobalt catalysts.
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The tables above give a basic summary of the various reactors available
and a comparison on the two most popular catalysts in FT synthesis.
The primary products from FT reactor will be wax, liquid hydrocarbons, tail
gas and reaction water. These products are then further processed by a
upgrading unit which will consist of phase separation equipments as well
as distillation equipments. The main process done to produce diesel from
these waxes are Hydrocracking.
Hydrocracking is a catalytic cracking process assisted by the presence of
added hydrogen gas. Unlike a hydro-treater, where hydrogen is used to
cleave C-S and C-N bonds, hydrocracking uses hydrogen to break C-C
bonds (hydro treatment is conducted prior to hydrocracking to protect the
catalysts in a hydrocracking process). The hydrocracking process depends
on the nature of the feedstock and the relative rates of the two competing
reactions, hydrogenation and cracking. Heavy aromatic feedstock is
converted into lighter products under a wide range of very high pressures
(1,000-2,000 psi) and fairly high temperatures (750°-1,500 °F, 400-800 °C),
in the presence of hydrogen and special catalysts.
Another means of converting long chain hydrocarbons into shorter chain
hydrocarbons is a process called hydrous pyrolysis which is the process of
thermal decomposition which takes place when organic compounds are
heated to high temperatures in the presence of water. Many hydrous
pyrolysis processes use superheated water in the liquid phase, whereas
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steam cracking uses water in the gas phase. Steam cracking is used in the
petroleum industry to produce lighter alkenes. It is suggested that hydrous
pyrolysis had a significant effect on the formation of fossil fuels. There
have been successful experiments such as Zhang et al. at the University of
Illinois, report on a hydrous pyrolysis process in which swine manure is
converted to oil by heating the swine manure and water in the presence of
carbon monoxide in a closed container. For that process they report that a
temperatures of at least 275 °C (527 °F) is required to convert the swine
manure to oil, and temperatures above about 335 °C (635 °F) reduces the
amount of oil produced. The Zhang et al. process produces pressures of
about 7 to 18 MPa (1000 to 2600 psi - 69 to 178 atm), with higher
temperatures producing higher pressures. Zhang et al. used a retention
time of 120 minutes for the reported study, but report at higher
temperatures a time of less than 30 minutes results in significant
production of oil.
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Challenges involved in FT synthesis

The main challenges in FT synthesis is the nature of the complex reaction
and dependency on a lot of factors. The performance of the FT synthesis
depends on the gas composition (feed/product component partial
pressures), catalyst formulation and operating temperature. The effects of
these variables are interrelated. Furthermore, the catalysts used
undergoes chemical changes during FT synthesis and that further
complicate s reactor design and optimization. Another facet that requires
optimization is the energy balance. Both the generation of synthesis gas
and the FT process involves tremendous amounts of heat exchange. The
application of FT synthesis deals primarily with the conversion of a source
of fossil fuel or biomass into a more convenient, user friendly fuel. Then
there is the problems of the temperature since increasing the temperature
favours the increased methane production which isn’t favourable. But on
the other hand, rate of reaction increases the quality of steam produced
by the reactor heat removal system improves which are both desirable.
Hence the application of FT technology involves a number of compromises
and optimizations. To complicate matters further, the FT reactor/catalyst
system cannot be designed in isolation. There is a strong interaction
between the design for FT reactor and the choice of technology to provide
the synthetic gas fed to the FT reactor. Separation technologies are also
important to isolate various product components from the broad range of
liquid hydrocarbon products formed. The FT process is fairly unique in the
field of heterogeneous in that there is not a single desired product but the
emphasis is rather on the avoidance of undesirable by-products. The
separated primary products generally require further processing to
produce the variety of desirable end product fuels and chemicals.
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Process of design
For the optimization of Fischer-Tropsch synthesis, first there is a need to
set a specific set up for the synthesis plant as there are more than a few
setups. And for that reason, the following set up is assumed and then the
design modifications are proposed for the set up.
1. Feed Preparation: In this setup, the feed preparation involves a
rotary dryer for making the feed of suitable moisture content which
is ideally <20 % and is then with the help of a cutter, made into
average diameters between 5mm-30mm. Then the feed is stored in a
hopper and from the hopper is fed into the gasifier by a screw
conveyor.
2. Imbert Gasifier: The gasifier used in this set up is an Imbert type
gasifier with oxygen as gasifying agent and will be working with an
average temperature of 800oC. The syngas will be leaving the gasifier
through the outer shell and the syngas will have a temperature of
around 700oC. The hot ash from the gasifier will leave at a
temperature of 650oC which will be removed with the help of a
conveyor.
24 Department of Chemical Engineering, GEC Kozhikode Design Project

3. Synthesis gas clean up system: The syngas leaving the gasifier will be
very hot and should be cleaned so as to remove tar, sulphur and
nitrogen content and this can be done by the first cooling the gas and
then passing through a cyclone separator and then being cleaned in a
scrubber.
4. FT reactor: The popularly used slurry bed reactor is used here since it
offers better temperature control and uniformity in temperature
control and also has the advantage of getting better conversion. The
slurry bed reactor will use water as coolant. The reactor will use Co
catalysts rather than Fe because of its different properties that can
give a better yield.
5. The upgrading unit: The upgrading unit will involve a separator and a
hydrocracking unit that is the standard in every FT synthesis plant.
25 Department of Chemical Engineering, GEC Kozhikode Design Project

Fig: Basic Scheme of the FT synthesis plant

Selection of Process
The Only optimization possible within the scope of our study is energy
optimization. And this can be done so as to use the various energy loss or
to optimize the various usage of energy.
The main three design modification suggested in this design project are
1. Modified Imbert Gasifier
2. Fluidized ash bed Heat exchanger.
3. Parallel hydrous pyrolysis of waxes.

(1) The Modified Imbert Gasifier:

26 Department of Chemical Engineering, GEC Kozhikode Design Project

The modified Imbert gasifier is the optimization of the reactor by

providing a tubular plug flow reactor between the inner shell and
outer shell of the Imbert gasifier. This reactor will be used to
superheat the water in the mixture flowing through it and pyrolyze
the wax and water mixture that will be flowing through it. Since the
next step after gasification is to cool and clean the syngas, it is
preferred to use the heat energy that the syngas possess to heat the
tubular plug flow reactor and there by using the energy more
effectively.
The Imbert gasifier with oxygen as the gasifying agent will be a
downdraft gasifier and since the syngas moves into the shell space
between the two shells, if there is a plug flow reactor of the coil type
there, the utilization of the heat will be better. Another important
fact is that even after the syngas pass over the reactor the heat can
be further utilized by the syngas cooling unit where the rest of the
heat can be transferred into a steam generation unit with the help of
a heat exchanger.

(2) Fluidized ash bed heat exchanger:

27 Department of Chemical Engineering, GEC Kozhikode Design Project

The hot ash from the gasifier can be collected through a grit into a
fluidizable bed through which pipes pass through and can act as a
fluidized bed heat exchanger. The hot ash has a temperature of
about 650oC and this heat can be transferred to the water and
thereby used for steam generation.

(3) Parallel Hydrous Pyrolysis of waxes:

The plug flow reactor in the modified Imbert gasifier can be used to
help with the upgrading of the Fischer-Tropsch products which will
mainly be waxes and liquid hydrocarbons. In the upgrading unit,
there needs to be a separator as well as a hydrocracking unit to get
the required products. So, after the products are separated in the
separator, part of the wax is mixed with water in a mixed and is fed
into the PFR, where it will undergo hydrous pyrolysis. This will break
down the long chain hydrocarbons into shorter chain hydrocarbons
which is the desired products. The water-wax mixture in the reactor
is superheated and under high pressure. This will have the same
effect as steam cracking but in the liquid phase.
28 Department of Chemical Engineering, GEC Kozhikode Design Project
29 Department of Chemical Engineering, GEC Kozhikode Design Project

Future Applications
The future implications of such a modification will be the cheaper cost of
making the fuel such as FT Diesel and also the speciality chemicals. As the
technology becomes more and more efficient, the more bio-waste of high
moisture content can be processed and could play an important role in
promoting sustainability and making the a better place. This system could
also be combined with a wastewater treatment facility to form a waste
management treatment facility there by making a single sector for waste
treatment. With further studies, even the sludge formed and all could be
utilized as a source of heat transfer bed or even make the whole process
more sustainable. The water treated by the waste water treatment plant
could be used as the source water for the whole process. The other future
application of FT synthesis will be to act as a waste management facility
and energy source for small localities as this is feasible if further
developments are made.
30 Department of Chemical Engineering, GEC Kozhikode Design Project

Conclusion
Fischer-Tropsch synthesis is a process with a large potential to replace
fossil fuels to produce liquid fuel. It has a lot of applications that can make
the life better. It is a very old field with a huge potential for the future
because of the basic requirement of the feed. Although bio-waste haven’t
been used much as feed, it can be in the future because of the various
advances in the gasification & FT technology. This project had aimed to
optimize the process called FT synthesis and the energy optimization
suggested here is of large importance. This is mainly because in the
current environment, the major constraint facing the FT technology is the
cost and the amount of energy saved here will be of great effect in the
large scale. Even the optimization of the catalysts by providing a feedback
loop to ensures that some sort of economic and environmental profit. And
hence Fischer-Tropsch technology is one of the fields that will be in the
forefront of fuel production and chemical production in a world where
climate change and greenhouse effect is increasing.
31 Department of Chemical Engineering, GEC Kozhikode Design Project

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