FISCHER-TROPSCH EFFICIENCY & PERFORMANCE

Comparing liquid transportation fuels production from coal gasification to fuels

from traditional production methods is a difficult undertaking because of the vastly
diverse configuration options available for gasification processing. Traditionally,
fuels like gasoline and diesel are refined from crude oil, a (comparatively) more
uniform feedstock than coal or, for that matter, biomass, petcoke, refinery waste,
etc. Each potential feedstock, even between different coal ranks, has variable
characteristics that can necessitate design changes (ash content, sulfur
concentration, feed handling issues, etc.). Additionally, as a relatively new
approach to producing liquid fuels, gasification has not had years of refinement to
develop a "best," most productive or cost-efficient approach, in part, due to the
aforementioned flexibility in choosing feedstock, product, synthesis gas (syngas)
cleaning and conditioning units. In fact, besides multiple gasifier options and
configurations, the liquid fuel synthesis component itself can be approached
multiple ways: methanol-to-gasoline or Fischer-Tropsch (FT) synthesis, to name
the two most important. Essentially, comparing petroleum-refinery produced
transportation fuels and gasification-derived fuels requires design assumptions and
limiting the scope of the comparison in order to arrive at meaningful conclusions.
Fischer-Tropsch Diesel from Domestic Coal
NETL has issued several reports evaluating diesel fuel production via gasification
and FT synthesis of coal and biomass. One of the more recent studies is
"Production of Zero Sulfur Diesel Fuel from Domestic Coal: Configurational
Options to Reduce Environmental Impact" released in 2011. This study evaluated
the economic viability and environmental impact of producing diesel fuel via FT
synthesis from coal or coal supplemented with biomass in the form of switchgrass
(which can be grown on marginal land unsuitable for food crops), and considered
two facility design approaches: 1) fuels production only and 2) the co-production
of fuels and electricity. The commercial-scale plant assumed in this evaluation
would produce 50,000 barrels per day fuels (700 million gallons per year) using
commercially available technologies. Study results indicate that diesel fuel can be
produced from coal that has a lower life-cycle greenhouse gas (GHG) emissions
profile than conventional petroleum-derived diesel fuel on a well-to-wheels basis,
assuming that CO2 produced at the facility is sequestered, and possibly requiring
methane mitigation practices in the case of certain bituminous coals which are
particularly high in methane content. The coal-derived diesel will be economically
viable when crude oil prices are as low as $94 per barrel, corresponding to a
petroleum-derived diesel price of $2.70 per gallon.

If sufficient biomass resources are available to co-convert with the coal, the GHG
emissions profile of the diesel fuel can be significantly reduced at a minimal
increase in cost. For example, replacing 15 percent of the coal feedstock with
switchgrass will result in diesel fuel which produces up to 34% less life-cycle
GHG emissions than petroleum-derived diesel. Such a facility would be
economically viable at crude oil prices as low as $104 per barrel, increasing the
diesel fuel price by $0.26 to $0.46 per gallon.
The co-production of fuels and electricity has the potential to produce less overall
GHG emissions than conventional pathways, but these benefits are highly sensitive
to the methodology utilized to evaluate emissions. The economic viability is
somewhat sensitive to the price at which electricity can be sold a 10% change in
the electric sale price results in a 1% change in the required selling price of the
fuel.
Study results show that FT synthesis is a near-term technology pathway which
could be leveraged to produce large volumes of transportation fuels from domestic
coal and biomass at reasonable cost. This pathway enables improvement of
Americas energy security, and at the same time addresses climate change
concerns.
Market Potential for Coal-based Liquid Fuels
While coal to liquid fuels technology has been commercialized in South Africa (by
Sasol) for decades, a market for coal-based F-T liquid fuels in the United States
would probably only successfully emerge in the case of concurrent and sustained
high oil prices and high natural gas prices. Although high crude oil prices have
made production of gasoline and diesel fuel from coal more economical, because
natural gas is also a suitable feedstock for liquid fuels synthesis, natural gas prices
would have to reach a certain threshold (considerably higher than current natural
gas prices in the United States) before coal-based fuels synthesis would be
economically competitive. Also, while gasification can currently meet
all environmental standards, carbon capture may need to be more fully
implemented to ease public concerns about greenhouse gas emissions in the
context of large-scale implementation of liquid fuels production from coal.
FISCHER-TROPSCH SYNTHESIS
Liquid transportation hydrocarbon fuels and various other chemical products can
be produced from syngas 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

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 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 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 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 Sasol's Lake Charles Gasto-Liquid (GTL) and Ethane Cracker Complex in Louisiana.
Figure 1 shows a simplified block flow diagram of a process incorporating FT
synthesis. The gasification 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 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 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, 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 utility plants, including the power train.

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
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 coalderived 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 (220270C), 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 FischerTropsch technology vendors, namely Exxon and Shell.
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.
COMMERCIAL USE OF FISCHER-TROPSCH SYNTHESIS
Operating Facilities - Sasol
Production of liquid fuels and chemicals from coal on a large scale has been a
reality in South Africa for decades. Sasol Synfuels owns and operates Sasol II and
Sasol III, which are two Fischer-Tropsch (FT) synthesis-based fuels production
plants in Secunda, South Africa. The Sasol plants represent the most significant
example of commercialized FT synthesis in the world. Construction of Sasol II

began in the mid-1970s, with operation of the two plants commencing in the early
1980s. The two plants contain 80 Sasol-Lurgi Fixed Bed Dry Bottom (FBDB)
gasifiers, and total output from both of the plants is approximately 150,000 barrels
per day (bpd), reaching 160,000 bpd in 2006. The feedstock for the plants is subbituminous coal supplied by Sasol Mining, a sister company of Sasol Synfuels.
Natural gas is also used as a supplemental feedstock. A proprietary iron-based FT
process is used to convert the synthesis gas (syngas) produced by the gasifiers to
gasoline, light olefins (alkenes), and a variety of other products.

SASOL II and III, Secunda, S. Africa. FTL Facility. source: SASOL

Project Participants
The South African Coal Oil and Gas Corporation was founded in 1950, amid the
realization that South Africa lacked crude oil reserves. The company was formed to
protect against the country's increasing imports of crude oil. Today, Sasol Limited
is headquartered in Johannesburg, South Africa, and is engaged in commercial
production and marketing of chemicals and liquid fuels, in addition to developing
interests in oil and gas exploration. The company is now comprised of a diverse
group of businesses, including Sasol Synfuels, with a total of 50 entities
worldwide.
Sasol had previously operated Sasol I, in Sasolburg, South Africa, which was also a
coal-to-liquids facility. It used 17 Lurgi Fixed Bed Dry Bottom gasifiers, and subbituminous coal to feed FT processes for liquid fuel and chemical production. In
2004 however, this facility retired the gasifiers in favor of natural gas autothermal
reformers.
Plant Description
Coal produced by Sasol Mining is sent to the Secunda petrochemical plant. The
coal is converted in the Lurgi gasifiers into a raw product gas with the addition of
steam and oxygen. The produced syngas is then cooled, cleaned and conditioned as
it leaves the gasifier, producing the first level of co-products as they condense or
are recovered from the stream: tars, oils and pitches, ammonia, sulfur and phenols.
Once purified, the syngas is sent to a suite of nine Sasol Advanced Synthol (SAS)
reactors where it is reacted in the presence of a fused iron based catalyst at elevated
pressure (~ 350 psi) and a temperature of about 350C, producing hydrocarbons

along with reaction water and oxygenated hydrocarbons. The reaction water and
oxygenated hydrocarbons are recovered, purified, and then marketed as
byproducts.
The hydrocarbons from the SAS reactors are cooled until most of the components
are liquefied before fractionation is used to separate the various hydrocarbon-rich
fractions. Methane rich gas is also produced in this process and is converted to
syngas via autothermal reforming for process recycle and sale as pipeline gas. The
recovered product hydrocarbons are then converted into a wide range of saleable
products, as shown in the following process diagram. Note that the Secunda plants
use the High Temperature Syngas Conversion technology.