ftsynthesis | netl.doe.gov https://www.netl.doe.gov/research/coal/energy-systems/gasification/gas...

| | | |

Research Coal Energy Systems Gasification Gasifipedia

News FISCHER-TROPSCH SYNTHESIS

Liquid transportation hydrocarbon fuels and various other chemical products can be produced from syngas
Gasifipedia via the well-known and established catalytic chemical process called Fischer-Tropsch (FT) synthesis, named
after the original German inventors, Franz Fischer and Hans Tropsch in the 1920s. During World War II, FT
Gasifier Optimization synthesis provided the needed liquid hydrocarbon fuels for the German war effort. Later, facing isolation
during the apartheid era, South Africa turned to FT synthesis from coal gasification to supply significant
Feed Systems quantities of its hydrocarbon fuel and chemical needs. Since then, many refinements and adjustments to
the technology have been made, including catalyst development and reactor design. Depending on the
Syngas Processing source of the syngas, the technology is often referred to as coal-to-liquids (CTL) and/or gas-to-liquids
(GTL). Examples of current operating CTL plants include Sasol's Sasolburg I and II plant, and an example of
a GTL FT process is Shell's plant in Bintulu, Malaysia. Several world-class GTL and CTL plants are currently
Systems Analyses
at various stages of engineering, construction, and production in Nigeria, Qatar and China, and most
recently in the United States as well with the announcement of front-end engineering and design on
Gasification Plant
Sasol's Lake Charles Gas-to-Liquid (GTL) and Ethane Cracker Complex in Louisiana.
Databases
Figure 1 shows a simplified block flow diagram of a process incorporating FT synthesis. The gasification
Program Plan island consists of all the supporting process technologies of coal handling & feed preparation, heat
recovery, syngas cleanup and conditioning, water-gas-shift, sulfur recovery, etc. The clean syngas leaving
the gasification island is sent onto the FT synthesis island, where the clean shifted syngas is converted into
Project Portfolio
primary products of wax, hydrocarbon condensate, tail gas, and reaction water. The wax is sent on to an
upgrading unit for hydrocracking in the presence of hydrogen, where it is chemically split into smaller
Project Information
molecular weight hydrocarbon liquids. A hydrogen recovery unit is used to extract the required quantity of
hydrogen from the tail gas as shown, or alternatively from the feed syngas stream. The reaction products,
Publications along with that from the upgrading section, are fractionated into the final products of diesel, naphtha, and
other light ends, depending on the desired product mix. The production facility is supported by several
Conferences and Workshops utility plants, including the power train.

NETL R&D

FAQs

Figure 1: Simplified F-T Synthesis-based Production Scheme

Chemistry
The Fischer-Tropsch process is a catalytic chemical reaction in which carbon monoxide (CO) and hydrogen
(H2) in the syngas are converted into hydrocarbons of various molecular weights according to the following
equation:

(2n+1) H2 + n CO Cn H(2n+2) + n H2O

Where n is an integer. Thus, for n=1, the reaction represents the formation of methane, which in most CTL
or GTL applications is considered an undesirable byproduct. The Fischer-Tropsch process conditions are
usually chosen to maximize the formation of higher molecular weight hydrocarbon liquid fuels which are
higher value products. There are other side reactions taking place in the process, among which the water-
gas-shift reaction

CO + H2O H2 + CO2

is predominant. Depending on the catalyst, temperature, and type of process employed, hydrocarbons
ranging from methane to higher molecular paraffins and olefins can be obtained. Small amounts of low
molecular weight oxygenates (e.g., alcohol and organic acids) are also formed. The Fischer-Tropsch
synthesis reaction, in theory, is a condensation polymerization reaction of CO. Its products obey a
well-defined molecular weight distribution according to a relationship known as Shultz-Flory distribution.

Catalysts

1 of 3 14-May-17 12:16 PM
ftsynthesis | netl.doe.gov https://www.netl.doe.gov/research/coal/energy-systems/gasification/gas...

Catalysts considered for Fischer-Tropsch synthesis are based on transition metals of iron, cobalt, nickel and
ruthenium. FT catalyst development has largely been focused on the preference for high molecular weight
linear alkanes and diesel fuels production. Among these catalysts, it is generally known that:

Nickel (Ni) tends to promote methane formation, as in a methanation process; thus generally it is not
desirable
Iron (Fe) is relatively low cost and has a higher water-gas-shift activity, and is therefore more suitable
for a lower hydrogen/carbon monoxide ratio (H2/CO) syngas such as those derived from coal
gasification
Cobalt (Co) is more active, and generally preferred over ruthenium (Ru) because of the prohibitively
high cost of Ru
In comparison to iron, Co has much less water-gas-shift activity, and is much more costly.

Given these constraints, commercially available FT catalysts are either cobalt or iron based. In addition to
the active metal, the Fe catalysts at least typically contain a number of promoters, including potassium and
copper, as well as high surface area binders/supports such as silica and/or alumina.

Only iron-based FT catalysts are currently used commercially for converting coal-derived syngas into FT
liquids, given Fe catalyst's inherent water gas shift capability to increase the H2/CO ratio of coal-derived
syngas, thereby improving hydrocarbon product yields in the FT synthesis. Fe catalysts may be operated in
both high-temperature regime (300-350C) and low-temperature regime (220-270C), whereas Co
catalysts are only used in the low-temperature range. This is a consequence of higher temperatures causing
more methane formation, which is worse for Co compared to Fe.

Co catalysts are 230 times more expensive than Fe but are a useful alternative to Fe catalysts for FT
synthesis because they demonstrate activity at lower synthesis pressures, so higher catalyst costs can be
offset by lower operating costs. Also, coke deposition rate is higher for Fe catalyst than Co catalyst;
consequently, Co catalysts have longer lifetimes. Co catalysts have a long lifetime/greater activity; i.e., Co
catalysts are replaced less frequently.

Although there are differences in the product distribution of Co and Fe catalysts at similar temperatures and
pressures (e.g. at 30 atm and 240C a Co catalyst has somewhat higher selectivity for heavier
hydrocarbons than Fe would have) the product distribution is primarily driven by the choice of operating
temperature: high temperature results in gasoline/diesel ratio of 2:1; low temperature results in
gasoline/diesel 1:2 more or less no matter if the catalyst if Fe or Co. Higher temperatures shift selectivity
towards lower carbon number products and more hydrogenated products; branching increases and
secondary products such as ketones and aromatics also increase. This is reflected in the following graphic1

(click to enlarge)

So, in short it is observed that low temperatures yield high molecular mass linear waxes while high
temperatures produce gasoline and low molecular weight olefins. If maximizing the gasoline product
fraction, it is best to use an iron catalyst at a high temperature in a fixed fluid bed reactor. If maximizing
the diesel product fraction, a slurry reactor with a cobalt catalyst is the best choice (see following discussion
on reactor types).

Both Fe and Co FT catalysts are sensitive to the presence of sulfur compounds in the syngas and can be
poisoned by them. However, the sensitivity of the catalyst to sulfur is higher for Co-based catalysts than for
their iron counterparts. This is one reason why Co catalysts are preferred for FT synthesis with natural gas
derived syngas, where the syngas has a higher H2:CO ratio and is relatively lower in sulfur content; Fe
catalysts are preferred for lower quality feedstocks such as coal.

F-T Reactors
The Fischer-Tropsch reaction is highly exothermic; therefore heat removal is an important factor in the
design of a commercial reactor. In general, three different types of reactor design might be used for FT
synthesis:

Fixed bed reactor

Fluidized bed reactor
Slurry bed reactor.

All three types of reactors are in use commercially. The multitubular fixed-bed reactors, known as Arge
reactors, were developed jointly by Lurgi and Ruhrchemie and commissioned in the 1955. They were used
by Sasol to produce heavy FT liquid hydrocarbons and waxes in Sasolburg, in what Sasol called it now their
Low-Temperature FT Synthesis Process, aiming for liquid fuels production. Most, if not all, of these types of
Arge reactors are now be replaced by slurry-bed reactors, which is considered the state-of-the-art
technology for low temperature FT synthesis. Slurry-bed FT reactors offer better temperature control and
higher conversion. Slurry-bed FT reactors are also being developed by other Fischer-Tropsch technology
vendors, namely Exxon and Shell.

2 of 3 14-May-17 12:16 PM
ftsynthesis | netl.doe.gov https://www.netl.doe.gov/research/coal/energy-systems/gasification/gas...

Fluidized-bed FT reactors were developed for high temperature FT synthesis to produce low molecular
gaseous hydrocarbons and gasoline. It was originally developed in a circulating mode, e.g., Sasol's Synthol
reactors, and they have since been replaced by a fixed fluidized bed type of design called Advanced Synthol
reactors. These types of reactors have high throughputs.

References/Further Reading

Short history and present trends of FischerTropsch synthesis in Applied Catalysis A: General (Vol.
186), Elsevier Publication

1. Mark Crocker, ed., Thermochemical Conversion of Biomass to Fuels and Chemicals, (2010) Royal Society
of Chemistry.

Liquid Fuels

Gasoline & Diesel

Fischer-Tropsch Synthesis
Commercial Use of Fischer-Tropsch Synthesis
Fischer-Tropsch Efficiency & Performance
Syngas Conversion to Methanol
Conversion of Methanol to Gasoline
Indirect Liquefaction Processes
Direct Liquefaction Processes
DOE Supported R&D for Liquid Fuels/Advanced Fuels Synthesis

3 of 3 14-May-17 12:16 PM