1.

2 Literature Review
1.2.4 Fischer-Tropsch Process of Syngas to Diesel
The Fischere-Tropsch (FT) synthesis has been investigated over decades
as an alternative route to obtain synthetic fuels from synthesis gas. FT is a high-
performance synthesis based on metallic catalysis, mainly using ruthenium, cobalt
and iron catalysts, which converts syngas in hydrocarbons and chemical precursors.

Fig. Syngas conversion into fuels and energy

(Source: Santos, 2016)

Subsequently, Fischer and Tropsch described the production of synthetic oil

from CO and H2. Fischer-Tropsch Synthesis (FTS) produces a mixture of
hydrocarbons (syncrude) with different chain lengths. The catalytic conversion of
H2 and CO to hydrocarbons is described as stepwise reaction. CH2 intermediates
are formed from H2 and CO. Although the reaction is exothermic, FT reaction needs
a fairly high temperature (about 200 oC) and high pressure (about 15 bar).
2H2 + CO → (CH2) + H2O
(2n + 1)H2 + nCO → CnH2n+2 + nH2O ΔH = -159.2 kJ/mol
(2n) H2 + nCO → CnH2n + nH2O
 The Fischere-Tropsch synthesis is a highly exothermic process, requiring
a heat exchange system. These characteristics make feasible the coupling of an FT
plant with a heat recovery system to the temperature control. The reaction
temperature is a crucial process parameter influencing the Fischere-Tropsch
synthesis. The temperature increasing can lead to the production of a greater
methane amount because of the higher propagation and termination reaction rates
at high temperatures. The FT represents essentially a biomass to liquid (BTL)
process, which can be divided into three main sections: (1) Syngas production, (2)
FT reaction, and (3) product upgrading and separation. The Fischer-Tropsch
synthesis can be carried out through a set of reaction ways, which uses different
types of reactors and follows an assortment of chemical kinetics, thereby resulting
in a wide range of products that includes hydrocarbons and oxygenates. Fixed bed,
fluidized bed, and slurry bed are the main types of reactors used in the Fischere-
Tropsch synthesis.

Fig. FT reactor types

(Source: Rauch, 2015)

The fixed bed reactor has the advantage to be more flexible for different
scale applications and it does not require a separation step to recover the catalyst
from the product mixture. These characteristics become the fixed bed the most used
reactor for both small-scaled studies and industrial purposes. For fixed bed reactor,
cooling fluid (frequently water) flow is generally required to remove the reaction-
released heat to maintain the reactor isothermal conditions. The reactants are fed by
the reactor top, passing through tubes containing the catalysts, and the final reaction
mixture flows out by the reactor bottom. The fixed bed can be designed as a multi-
tubular arrangement in which a set of catalyst containing tubes are arranged inside
a shell. The number of tubes must be very big, increasing the reaction productivity.
Fluidized bed reactors operate at a higher temperature and higher-pressure
conditions on a design that leads to improved efficiency. The fluidized bed allows
reaching superior heat transfer, easier catalyst handling, and improved temperature
control on the highly exothermic FT reactions. Commercial fluidized bed reactors
can be set mainly as bubbling bed (BFB) or circulating bed (CFB). A sort of reactor
designs has been experienced and modeled. Fixed bed multi-tubular reactor has
been applied for the Fischer-Tropsch synthesis using cobalt catalyst attached to a
particulate silica carbide and ruthenium as a promoter of Co catalysts.
The chemical reaction between hydrogen and carbon monoxide requires a
high quantity of energy to be over. Therefore, catalysts are crucial to guarantee
chemical conversion to appreciable quantities of products. The chemical
composition of the products obtained from the Fischer-Tropsch synthesis depends
to a large extent on the catalyst selectivity and on the reaction extension related to
the process thermodynamics.
Group VIII elements, especially ruthenium (Ru), iron (Fe), cobalt (Co) and
nickel (Ni), are surely eligible a catalyst in FT synthesis since they have activity
enough for commercial applications, although that only Fe and Co interest indeed
for industrial-scale FT processes. Nickel catalysts display usually high surface
activity, but they have a limited chain growth. Despite the high selectivity,
Ruthenium usage is almost impeditive for industrial scale application because of its
high cost and low availability. On another hand, iron catalysts have been preferred
for a large-scale usage due to its low cost, even so their fast oxidation with water
contact. Cobalt catalysts have shown a balance between the selectivity and catalytic
activity that allows its usage on a large scale.
 The main catalysts used in the reaction of Fischer-Tropsch are metallic,
because of their ability to form a complex with carbon monoxide and to dissociating
it into ethylene monomer. FT metal catalysts are often supported on metal oxides,
commonly alumina or silica, to increase their stability. Unsupported metal activity
raises as Fe > Co > Ni > Ru, while supported metal activities change to Ru > Fe >
Ni > Co on alumina and to Co > Fe > Rh > Ni on silica. Nevertheless, specific
characteristics must be required of the catalyst used in FT synthesis, explicitly:
 High resistance to the process conditions, allowing a viable life for the process.
 High resistance to water, as some FT secondary reactions are prone to generate
water.
 High resistance to temperature.
 The catalyst must have extensive selectivity to the desired product.
The FischereTropsch catalytic reaction faces problems regarding the
existing impurities. The major impurities encountered during the FischereTropsch
synthesis, which cause damage to the process are:
 The HCl that can be generated during the process, causing reactor tubing
corrosion and damaging the catalyst.
 Alkali metals deposited on the catalyst surface, (iii) impurities derivate from
reactants and catalysts.
 Sulphonate compounds derived through the biomass affecting the catalyst life.
The catalysts may lose activity and decrease the reaction rate. The main
causes of catalyst deactivation are related to the sintering (loss of catalyst surface
activity due to crystal growth), the conversion of active parts of the catalyst into
inactive parts (oxidation of the metal, for example), the carbon deposition on the
catalyst surface and surface poisoning (related to strong interactions established
between the active site and contaminants).
2.1 Process Selection
2.1.1 Gasification Reactor
There are several different generic types of gasification technology that
have been demonstrated or developed for conversion of biomass feedstocks. Most
of these have been developed and commercialized for the production of heat and
power from the syngas, rather than liquid fuel production. The brief description of
each types had been presented in the previous sections.

2.1.2 Gasifying Agent

The gasifying agent is an indispensable medium for biomass gasification.
The selectivity of the gasification reactions varies with different gasifying agents,
thus affecting the composition and LHV of produced gas. The brief description of
each process will be presented in the following sections.
2.1.2.1 Steam
If steam is used as the gasification agent, the product gas contains more
hydrogen per unit of carbon, resulting in a higher H/C ratio. Some of the
intermediate-reaction products like CO and H2 also help to gasify the solid carbon.
Steam as a gasifying agent leads to a product gas with a heating value in the range
10–18 MJ/Nm3 and with higher H2 concentration, despite the energy required by
the process increases due to endothermic step of gasification.
2.1.2.2 Air
Air has gained popularity as the most practical gasifying agent in biomass
power plants due to its low cost and availability. However, the LHV of the product
gas is quite low with air gasification due to the dilution of nitrogen. Air gasification
leads to a syngas with a heating value in the range 4–7 MJ/Nm3 and with lower
concentrations of CO and H2. Moreover, combustion of H2 and CO takes place,
resulting in CO2 concentration increase.

2.1.2.3 Oxygen

If oxygen is used as the gasifying agent, the conversion path moves toward
the oxygen corner. Its products include CO for low oxygen and CO2 for high
oxygen. When the amount of oxygen exceeds a certain (stoichiometric) amount, the
process moves from gasification to combustion, and the product is “flue gas”
instead of “fuel gas.” Neither flue gas nor the combustion product contains residual
heating value when cooled. O2 gasification leads to a syngas with a heating value
up to 28 MJ/Nm3, with higher concentrations of CO and H2 and low concentration
of tar. Gasification with oxygen will reduced nitrogen dilution, reduce gasifier and
downstream equipment size, improve carbon conversion efficiency in the gasifier,
and improve combustion efficiency in downstream power generation devices. This
gasifying agent commonly used in pressurized gasification.

2.1.2.4 Steam-O2 Mixture

A combination of steam and oxygen can also be used to enhance syngas

quality while providing the needed energy for the exothermic nature of biomass
burning. Steam-O2 mixture can also reduce the nitrogen content of the produced gas
and will increase its heating value. CO content was higher than H2 content below
the temperature of about 830 °C and H2 content exceeded CO content when
temperature was higher than about 830 °C.

Scoring method is used for the process selection to find the best process
based on several criteria. There are 4 criteria considered on process selection. They
are H2 to CO ratio, energy consumption, economic value, and availability. Each
criterion will has the same weight and will be scored from 1 to 3. The detail of each
criterion is shown on Table 2.4. and the result of process selection using scoring
method is shown on Table 2.5

Table 2.4. Criteria Detail for Gasifiying Agent Selection

Criteria 1 2 3

H2/CO 0.7-1.2 1.2-1.4 1.4-1.8

Energy consumption High Medium Low

Economic value High Cost Medium Low Cost

Availability Scarce Moderate Abundant

Table 2.5. The Result of Gasifiying Agent Selection

 Gasification
Gasification Gasification Gasification
Criteria with Steam-
with Steam with Air with O2
O2 Mixture

H2 to CO
3 1 2 2
ratio

Energy
2 3 1 3
consumption

Economic 1 2 3 2

Availability 1 2 3 3

Total 7 8 9 10

2.1.3 Fischer-Tropsch Reactor

Commercially available FT reactors nowadays have two different temperature
ranges. The high temperature FT (HTFT) reactor runs with iron catalysts at around
340 °C, and is used to produce olefins and gasoline. The low temperature FT
(LTFT) reactor uses iron or cobalt based catalysts at around 230 °C, and is used to
produce diesel and linear waxes. Generally, commercially established FT reactors
can be divided into three main categories: fixed bed, fluid bed and slurry FT
reactors. The critical features of FT reactors, such as heat transfer and mass transfer,
are summarized and compared in table below.
 Feature Fixed bed Fluid bed (circulating) Slurry
Temperature Poor Good Good
Heat exchange surface 240 m2 per 1000 m3 feed 30 m2 per 2000 m3 feed 50 m2 per 1000 m3 feed
CH4 formation <0.08 m Large Large
Flexibility Low High Low
Product Intermediate Little High
Space-time yield Full range Low mol. Weight Full range
Catalyst affectivity >1000 kg/m3 day 4000-12000 kg/m3 day 1000 kg/m3 day
Back-mixing Little Intermediate Large
Minimum H2/CO
As slurry or higher Highest Simplest
Construction
2.1.4 Catalyst Selection