Fischer-Tropsch Fuels Refinery Design

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Cite this: Energy Environ. Sci., 2011, 4, 1177
PERSPECTIVE
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FischerTropsch fuels refinery design

Arno de Klerk*
Received 19th November 2010, Accepted 21st December 2010
DOI: 10.1039/c0ee00692k
Carbon sources, such as coal, natural gas, biomass and waste, can be converted into transportation
fuels by combining appropriate gasification, FischerTropsch and refining technologies. Efficient
refining of the FischerTropsch synthesis derived syncrude requires a different approach to refinery
design than commonly applied to crude oil refinery design. The design of refineries to optimise the
production of on-specification motor-gasoline, jet fuel and diesel fuel respectively from both high
temperature FischerTropsch (HTFT) syncrude and low temperature FischerTropsch (LTFT) are
considered. Refinery designs are presented for the production of motor-gasoline and jet fuel with better
than 50% yield (better than 70% selectivity on transportation fuel), without resorting to very complex
designs. Only diesel fuel refining presented a problem, since the production of on-specification
EN590:2004 diesel fuel is limited by a FischerTropsch specific cetane-density-yield trade-off. The
compound classes that are required to produce diesel fuel in high yield that meet both minimum cetane
number and minimum density requirements are not abundant in FischerTropsch syncrude. Refinery
designs for diesel fuel production was limited to a yield of less than 25% EN 590 : 2004 compliant diesel
fuel. This yield restriction does not apply when diesel fuel specifications do not have a minimum density
requirement.
The refinery designs associated with the industrial application of Literature on the topic of FischerTropsch refinery design is
FischerTropsch synthesis to produce transportation fuels and rather limited and the studies over the past three decades can be
chemicals are quite varied.1 This is hardly surprising considering grouped as follows:
the changes that took place over time in terms of product types, (a) The United States Department of Energy sponsored
fuel specifications, refining technology and in the field of a research programme to evaluate the use of low temperature
FischerTropsch synthesis. One may learn from the historic FischerTropsch (LTFT) technology for the production of
FischerTropsch refinery designs, but it does not tell one how to transportation fuels. This study was conducted with industry
go about designing a present day refinery to convert Fischer collaboration and, amongst others, evaluated different strategies
Tropsch syncrude into on-specification transportation fuels. for refining LTFT syncrude to fuel.2
(b) The Shell Middle Distillate Synthesis (SMDS) process was
commercialised in the 1990s with the gas-to-liquids facility in
Department of Chemical and Materials Engineering, University of Alberta, Bintulu, Malaysia. The reasoning behind the development and
Edmonton, AB, T6G 2V4, Canada. E-mail: deklerk@ualberta.ca; Tel: +1 refinery design has been documented.3 It explains why the
780-248-1903
Broader context
FischerTropsch syncrude, like conventional crude oil, is not a useful product unless it is refined to consumer products, such as
transportation fuels, lubricants and petrochemicals. There is a significant body of literature on indirect liquefaction of alternative
carbon sources to synthesis gas (H2 + CO), as well as on the FischerTropsch conversion of synthesis gas into syncrude. However,
despite industrial implementation, there is no comprehensive work on FischerTropsch refinery design. The present work deals with
transportation fuel refinery design exclusively. It discusses the refining of FischerTropsch oil and aqueous product phases, the
impact of different types of FischerTropsch syncrude on refining, the refining of oxygenate-rich materials (also relevant to biomass
refining), environmental aspects and key elements pertinent to on-specification motor-gasoline, jet fuel and diesel fuel production
from syncrude. The design examples demonstrate that FischerTropsch refineries do not have to be overly complex in order to
produce on-specification fuels. A perspective is provided on efficient syncrude refining. The paper is not a literature review and as
such, it presents a new body of information on a topic that is crucial to the commercial success of FischerTropsch based facilities.
This journal is The Royal Society of Chemistry 2011 Energy Environ. Sci., 2011, 4, 11771205 | 1177
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syncrude is refined to a blending stock and chemicals only, rather

than to on-specification transportation fuels.
(c) Sasol has been operating commercial FischerTropsch
facilities since the 1950s, but the Sasolburg and Secunda refinery
designs were both licensor based. Some studies that drew on their
operating experience were published and these deal with both
chemicals and fuels refinery design.4,5
The design decisions associated with other FischerTropsch
Fig. 1 General configuration of feed-to-synthesis gas conversion,
facilities were not described and in general there has been little
FischerTropsch synthesis and product cooling/separation.
systematic study to guide FischerTropsch refinery design. Yet, it
has been made equally clear that FischerTropsch syncrude Solid carbon sources (coal, biomass and waste) must be
should be refined differently to crude oil6,7 and that refining gasified in order to produce synthesis gas. The selection of
catalysis should be approached differently.8 gasification technology depends on the nature of the feed, with
The aim of this work is to provide guidelines for Fischer properties such as ash behaviour, moisture content and fuel
Tropsch fuels refinery design. This will be illustrated by devel- reactivity limiting the choice.10 Gaseous carbon sources can be
oping refinery designs for motor-gasoline, jet fuel and diesel fuel. gasified or reformed to produce synthesis gas.
High temperature FischerTropsch (HTFT) and low tempera- Since the feed material usually contains heteroatoms such as
ture FischerTropsch (LTFT) syncrudes will be considered sulfur, the gas must be cleaned before it can be used as feed for
separately, and in all instances the objective will be to produce FischerTropsch synthesis. In the case of a gaseous feed, it may
final on-specification transportation fuels. be preferable to clean the gas before reforming. The gas cleaning
In order to develop the logic underlying FischerTropsch technology determines the quality of the synthesis gas and not
refinery design, it is important to demonstrate the feed-conver- the raw material used as carbon source.
sion-product relationship. In this way it can be shown how the The H2:CO ratio in the synthesis gas is largely determined by
properties of FischerTropsch syncrude as refinery feed must be the gasifier or reformer technology employed. The H2:CO ratio
transformed on molecular level to obtain the product properties must typically be adjusted to the usage ratio of the Fischer
being required by fuel specifications. Tropsch technology. The combination of gas recycle loops and
gas conversion technologies to achieve this is called the gas loop
and gas loop design is a topic in its own right.11
FischerTropsch technology After FischerTropsch synthesis the product is cooled and
Before delving into the topic of FischerTropsch refining, it is separated. The way and the extent to which separation is ach-
useful to have a quick look at FischerTropsch based technology ieved is of paramount importance for the refinery design. It
for indirect liquefaction (Fig. 1). forms part of the gas loop design and influences the overall
The feed material for synthesis gas (H2 and CO) production carbon efficiency of the process. Yet, due to its relevance to the
can in principle be any carbon source. Coal and natural gas are refinery, this aspect will be touched on as part of the refinery
presently the only raw materials that are industrially employed design.
for synthesis gas generation associated with FischerTropsch Different carbon sources may produce different pyrolysis
synthesis. Gasification of other carbon sources, such as biomass products during gasification, which can create co-refining
and waste, is less well developed.9 opportunities. In an analogous way associated liquids may be
recovered from natural gas before reforming. Such associated
products increase the carbon efficiency of the overall process.
Arno de Klerk is the Nexen The nature of the carbon source selected as raw material for
Professor of Catalytic Reaction synthesis gas production also affects the carbon efficiency
Engineering at the University of (and CO2 footprint) of the indirect liquefaction technology. In
Alberta in Canada. Born and this respect hydrogen-rich and heteroatom-poor materials are
educated in South Africa, he is preferred. This is a natural consequence of the atom balance over
a registered professional engi- indirect liquefaction. Heteroatoms are rejected with hydrogen
neer since 1999 and holds a PhD and in order to increase the H : C ratio from that of the feed to
in Chemical Engineering and that of the product, carbon is rejected as CO2. The conversion of
MSc in Chemistry. Before waste plastic (H : C z 2) and natural gas (H : C z 4) will
moving to academia in 2009, he
worked in both industry and
forensic science. Pertinent to The selection of feed-to-syngas conversion type may result in the
this paper is 14 years industrial co-production of non-syngas products. For example, in coal-to-syngas
conversion by low temperature gasification technology, some coal
Arno de Klerk experience with Sasol, since liquids are co-produced. Likewise, natural gas condensates may be
2001 leading the group in associated with the natural gas employed as feed for gas-to-syngas
FischerTropsch Refinery conversion. When these materials are co-refined with the
FischerTropsch syncrude, the refinery design is very different to that
Catalysis. In 2007 he received the South African Institution of
of a design based on FischerTropsch syncrude only. Co-refining of
Chemical Engineers Innovation Award for contributions in FischerTropsch materials is a topic in its own right, and it is not
FischerTropsch refinery design. covered by the present review.
1178 | Energy Environ. Sci., 2011, 4, 11771205 This journal is The Royal Society of Chemistry 2011
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therefore result in less CO2 production than biomass or coal Table 1 Generic FischerTropsch syncrude compositions on a mass
(H : C < 1 after heteroatom rejection). basis
Indirect liquefaction is inherently energy intensive, which Syncrude composition (mass %)a
reduces the conversion efficiency of FischerTropsch based
technology. Carbon efficiencies of coal-based indirect liquefac- Compound Fe-HTFT Fe-LTFT Co-LTFT
tion processes reported in literature are in the range 2834%.12
Gaseous product (C1-C4)
The overall efficiency depends on the refinery design too. Syn- methane 12.7 4.3 5.6
crude that are not refined to final products, but are used as fuel ethylene 5.6 1.0 0.1
gas, have a very high associated CO2 cost. In fact, any Fischer ethane 4.5 1.0 1.0
C3C4 olefins 21.2 6.0 3.4
Tropsch syncrude that is employed as fuel for an energy appli-
C3C4 paraffins 3.0 1.8 1.8
cation that could make direct use of the raw material itself, has 3 Naphtha (C5-C10)
times the CO2 footprint of the raw material! The efficient refining olefins 25.8 7.7 7.8
of syncrude is associated with a significant environmental paraffins 4.3 3.3 12.0
aromatics 1.7 0 0
responsibility. oxygenates 1.6 1.3 0.2
Distillate (C11-C22)
olefins 4.8 5.7 1.1
FischerTropsch syncrude paraffins 0.9 13.5 20.8
aromatics 0.8 0 0
For the purpose of this review, the generic properties of Fischer
oxygenates 0.5 0.3 0
Tropsch syncrude (Table 1)13 will be discussed. In this way the Residue/wax (C22+)
refinery designs are not intrinsically linked to a specific type of olefins 1.6 0.7 0
feed-to-synthesis gas conversion, FischerTropsch technology or paraffins 0.4 49.2 44.6
aromatics 0.7 0 0
gas loop design. oxygenates 0.2 0 0
The products have an Anderson-Schulz-Flory carbon number Aqueous product
distribution. The exact composition of an actual syncrude is alcohols 4.5 3.9 1.4
affected by the choice of FischerTropsch technology, state of carbonyls 3.9 0 0
carboxylic acids 1.3 0.3 0.2
FischerTropsch catalyst deactivation and operating conditions.
a
These variations in composition do not invalidate the present The syncrude compositions are based on the total syncrude, excluding
inert gases and water-gas-shift products (H2O, CO, CO2 and H2); zero
study. A similar principle is applied in the description of crude oil
values indicate low concentration and not necessarily complete absence.
for crude oil refinery design. Crude oil, just like FischerTropsch
syncrude, is affected by its exact origin. Yet, for the purpose of
refinery design a generic crude oil composition is selected that
represents the crude oil slate for which the refinery must be is around 2 : 14 : 1. The C4-material is even more linear, with
designed. The refinery design must be inherently robust enough a linear to branched ratio of around 10 : 1. Some cyclo-paraffins
to deal with the variations in crude oil composition that will be (naphthenes) are present, mostly in the naphtha fraction. The
found in practice. In this respect a FischerTropsch refiner is olefin composition over the whole carbon number range is
more fortunate, because the composition of the syncrude can be dominated by linear a-olefins. HTFT syncrude contains some
controlled within a narrow range of variation once the Fischer aromatics, with the aromatics content increasing with increasing
Tropsch technology has been selected. carbon number. The oxygenates display the opposite trend, with
the oxygenate content decreasing with increasing carbon
High temperature FischerTropsch (HTFT) syncrude number. The main oxygenate classes present in HTFT syncrude
are alcohols, aldehydes, carboxylic acids and ketones. Other
HTFT syncrude (Table 1) is characterised by a carbon number oxygenate classes, such as esters, furans and phenols are also
distribution that is very light and it is rich in olefins and present, but in much lower concentration.
oxygenates. It contains no sulfur or nitrogen, but has a large
associated aqueous product fraction that contains dissolved
short chain oxygenates. Some metals are present in the syncrude Low temperature FischerTropsch (LTFT) syncrude
(mainly Fe and Na)14 in the form of metal carboxylates. The About 50% of the hydrocarbon mass of LTFT syncrude is in the
residue fraction (boiling >360 C) is small and very aromatic C22 and heavier wax fraction (Table 1). The syncrude becomes
(>30%).15 more paraffinic with increasing carbon number and contains
The aliphatic hydrocarbons are predominantly linear. The very little aromatics and cyclo-paraffins.
ratio between linear and branched material in the naphtha range The olefin to paraffin ratio of the naphtha and distillate frac-
tions depends on the FischerTropsch technology, with the
The Anderson-Schulz-Flory (ASF) distribution provides an olefins increasing in the order: Co-LTFT fixed bed < Co-LTFT
approximation of the carbon number distribution from
a FischerTropsch process. In this work it is employed to give an slurry bed < Fe-LTFT fixed bed < Fe-LTFT slurry bed. The
indication of the straight run content as a function of a-value. This is LTFT syncrude composition employed for this study resembles
a qualitative indication and does not take deviations from the ideal that of Fe-LTFT.
ASF distribution into account. For example, the ASF model poorly
The olefin to paraffin ratio, as well as the carbon number
predicts the C1C2 content and for LTFT synthesis, the lighter and
heavier syncrude fractions seemingly have two different two different distribution changes over time as the FischerTropsch catalyst
a-values. deactivates. In this respect Fe-LTFT has a meaningful benefit for
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fuels refining, because it is the only FischerTropsch catalyst type a combination of catalyst compatibility, technology compati-
that deactivates in such a way that the refining efficiency is bility and environmental footprint.7,8
improved.16 (d) Carbon number based refinery design.5 Most refining
The LTFT syncrude contains no sulfur or nitrogen and has an technologies are designed with a specific feed range in mind. This
associated aqueous product fraction that contains dissolved limitation relates to the catalysis and the purpose of the
short chain oxygenates. The oxygenates are mainly alcohols and conversion process. By ordering refining choices in terms of their
carboxylic acids. feed range requirements, it is possible to have a logical selection
The nature and composition of metal containing organic based on carbon number. In crude oil refining this is what
compounds depend on the FischerTropsch technology and happens when the crude oil is fractionated to produce cuts with
FischerTropsch catalyst employed. As in the case of HTFT different boiling ranges. Each distillation cut (carbon number
syncrude, metals may be present due to corrosion, attrition and range) is prepared with a specific refining technology in mind.
catalyst dissolution.
The heavy hydrocarbons in LTFT syncrude usually have Design approach followed
a very high linear to branched ratio, typically higher than 20 : 1.
The wax fraction contains little branched paraffins. The olefins The conceptual refinery designs that are presented in this review
are mainly linear a-olefins. employed technology pre-selection to guide the design process.
The approach that was followed for each type of transportation
Refinery design fuel was to create robust refinery designs that maximised the
yield of the fuel that would meet international fuel specifications.
Refineries are complex systems and a purely mathematical Unfortunately motor-gasoline and diesel fuel specification are
approach to refinery design may yield optimal theoretical country dependent. In this review European EN228:2004
designs, but not necessarily operable practical designs. Real- (motor-gasoline) and EN590:2004 (diesel fuel) specifications are
world refinery designs, as opposed to conceptual studies, have used, since these are widely accepted standards. The DEFSTAN
the aim of producing a practical refinery design for a specific 91-91/Issue 6 specifications22 for aviation turbine fuel is the
purpose. There are many factors influencing real-world refinery internationally accepted standard for Jet A-1 and it includes
designs and when this added layer of detail is considered in the provision for semi-synthetic and fully synthetic jet fuels.
design process, the design becomes unique. It should be Synthetic jet fuel specifications are exceptionally restrictive in
emphasised that beyond the conceptual stage, there is no such terms of the refinery design, a requirement that makes little sense
thing as a generic or even general refinery design, despite many from a fundamental point of view. The jet fuel refinery designs
real refinery designs being close to each other. As a consequence are based on the synthetic Jet A-1 specifications, but ignores the
all designs that will be developed in this review should be seen as restrictions that limit the design to mimic the older Sasol
conceptual designs. operations.
For each fuel type two key aspects were considered in devel-
Conceptual refinery design oping the refinery design, namely:
Refinery design is essentially a creative process, but there are (a) How can the carbon number distribution of the syncrude
different tools and methodologies that can be followed to guide be manipulated in an efficient way to maximise the production of
conceptual refinery design. Some of the methodologies that can that specific fuel type?
be followed are: (b) How can be molecular composition be manipulated in an
(a) Linear programming.17 Design constraints such as fuel efficient way to ensure that the fuel type meets the relevant fuel
specifications and objective functions like minimum capital cost specifications?
or highest distillate yield, can be incorporated in a linear
programming model. This enables the mathematical solution of Motor-gasoline refining
a complex optimising problem. It nevertheless presupposes the
Fuel specifications
development of multiple refinery configurations.
(b) Hierarchical design.18 The design hierarchy that has been The motor-gasoline properties in Table 2 are only a subset of the
proposed for refinery debottlenecking, can also be used to guide full EN228:2004 specifications. These properties have been
refinery design. It is akin to the Michael Jackson programming highlighted, because they limit the composition of the fuel and set
approach,19 where the data flow of in being transformed to performance criteria that translates into requirements that can be
out determines the structure of the design. In the hierarchical related to the molecular properties of the fuel.
design approach, the feed flow is used to determine design Directive 2009/30/EC23 of the European specifications revised
bottlenecks and it can also be used for analysing sub-systems of the limitations placed on oxygenated motor-gasoline. The
the refinery. For example, hydrogen availability can be used to maximum oxygenate content has been increased to 3.7 mass % O
drive refinery design.20 and the limits on various oxygenates have been increased
(c) Technology pre-selection. An interesting approach to accordingly. For example, the limit on C4 derived ethers is 15%
refinery design has been followed by Nai Y. Chen, one of the and that on C5 and heavier ethers is 22%. The 2009/30/EC
ZSM-5 pioneers at Mobil research.21 Refining technology was directive also included distillation restrictions on motor-gasoline,
pre-selected based on its environmental footprint and the refinery namely, minimum E46 at 100 C (46 vol% evaporated at 100 C)
was then designed based on a logical ordering of the more limited and minimum E75 at 150 C. The maximum sulfur content of
set of technologies. Pre-selection can also be performed based on motor-gasoline has been set at 10 mg g1 by the directive.
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Table 2 Selected European EN228:2004 motor-gasoline specifications
EN228:2004 specification
Fuel property minimum maximum

Direct restrictions on boiling range

Final boiling point ( C) 210
Indirect restrictions on boiling range
density at 15 C (kg m3) 720 775
Reid vapour pressure (kPa) 60a
Direct restrictions on composition
olefin content (vol %) 18
aromatic content (vol %) 35
oxygenate content (mass % O) 2.7
sulfur content (mg g1) 50/10
benzene content (vol %) 1 Fig. 2 Effect of the FischerTropsch catalysts a-value on the yield of
C5+ derived ethers (vol %) 15 C5C10 straight run naphtha. (The yield is based on C3 and heavier
C4 derived ethers (vol %) 10
syncrude calculated from the Anderson-Schulz-Flory distribution).
Indirect restrictions on composition
research octane number 95
motor octane number 85
a
Dependent on the climate of the region where the fuel will be used.
Carbon number distribution
The carbon number range of motor-gasoline is directly and

indirectly regulated. The upper limit is set by the final boiling
point specification (210 C; C11/C12), while the lower limit is set
indirectly by the vapour pressure specification. In practice
motor-gasoline typically covers the carbon number range
Fig. 3 Octane number contributions and limitations on the composition
C5C10, with the amount of C4 being determined by the vapour
of EN 228 : 2004 motor-gasoline, showing paraffin quality as key.
pressure of the base fuel.
The carbon number distribution is indirectly regulated by both
the density requirements and vapour pressure limit. In order to explain the refining challenges related to the
In order to maximise the yield of motor-gasoline from composition of motor-gasoline, it is useful to look at the different
compound classes in relation to the octane number requirements
a FischerTropsch refinery, the syncrude that falls outside of the
C5C10 range has to be converted in some way to change its of motor-gasoline (Fig. 3).
carbon number distribution. The amount of straight run Aromatics and fuel oxygenates are octane positive, since
syncrude that is already in the correct carbon number range, is they have higher octane numbers than are required by motor-
determined by the chain growth probability (a-value) of the gasoline specifications. Olefins generally are almost octane
FischerTropsch technology employed (Fig. 2). It is clear that neutral, being close to the octane numbers required by motor-
HTFT synthesis has an advantage over LTFT synthesis in terms gasoline specifications. It should be noted though, that the
of straight run syncrude that is in the C5C10 range. octane numbers of olefins are structure dependent, with linear
a-olefins having lower octane numbers than branched internal
olefins. Aromatics, oxygenates and olefins are all regulated and it
Composition
implies that motor-gasoline must contain at least 32% paraffins.
The composition is regulated by compound class, as well as by The octane values of paraffins are very structure sensitive,
specific compound in some instances (Table 2). The composition making the quality of the paraffins the key to motor-gasoline
must be manipulated in the refinery to comply with these limi- refining. Blending calculations indicate that the paraffins must
tations, as well as to meet the performance criteria of the fuel. have a RON around 70 and a MON around 65 to meet motor-
The key performance criteria for motor-gasoline are research gasoline specifications, when mid-range values for the RON and
octane number (RON) and motor octane number (MON). RON MON of aromatics, oxygenates and olefins are used at their
and MON are measures of a fuels resistance to autoignition respective blending limits.
under different driving and load conditions and are directly Paraffin octane number increases with increasing degree of
related to the molecular properties of the fuel. branching and decreasing carbon number. This is illustrated with
European specifications require motor-gasoline to have some RON values for C3C8 paraffins (Table 3).24 It is in prin-
a minimum RON and a minimum MON value, while countries ciple possible to produce high octane paraffins, but it requires
like the United States regulate only the road octane number very specific conversion technologies. Furthermore, the paraffins
( RON + MON) as a single value. The latter is easier to are seldom segregated in a refinery and some conversion tech-
achieve by refining, since there is no octane give-away to meet the nologies co-produce low octane paraffins in mixtures with high-
constraining octane number, RON or MON. octane compounds, for example, catalytic reforming. This makes
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Table 3 Research octane numbers of selected C3C8 paraffins Technology selection
Research octane number Carbon number based refining is a useful concept for designing
a motor-gasoline refinery, especially when it is combined with
Carbon number linear 2-methyl 2,3-dimethyl 2,2,3-trimethyl
technology pre-selection.
3 112 (a) C2 hydrocarbons. Olefin oligomerisation, olefin hydration
4 93.8 101.3 and aromatic alkylation are technologies that can be considered
5 61.7 92.3 for motor-gasoline production from ethylene. There are no clear
6 24.8 73.4 103.5
7 0 42.4 91.1 112 fuels refining pathway for ethane and it is unlikely that typical
8 <0 20.6 71.3 109.6 ethane technologies, such as steam cracking, will be considered to
produce fuels. Ethane will therefore be used as fuel gas, or be
recycled to the gas loop.
it difficult in practice to achieve a high-octane value for all the (b) C3 hydrocarbons. The HTFT derived C3 hydrocarbons
paraffins in a refinery. have a propylene to propane ratio of 87 : 13 and constitutes
about 15% of the syncrude. This makes it the most abundant
carbon number in HTFT syncrude. Propylene can typically be
HTFT motor-gasoline refining
converted into olefinic motor-gasoline by an appropriate olefin
Let us now consider the development of an HTFT refinery for oligomerisation technology (solid phosphoric acid), or by
the production of maximum EN228:2004 compliant motor- aromatic alkylation into high-octane motor-gasoline and jet fuel.
gasoline. Both processes indirectly facilitate the separation of propylene
It has already been shown that the a-value of HTFT synthesis and propane and can be combined in a single unit.25 Propane is
(Fig. 2) is close to the optimum for the highest yield of straight a product in its own right and can be sold as such. It may also be
run naphtha material. In order to increase the overall production converted into motor-gasoline by processes such as aromatisa-
of naphtha range material, three strategies can be followed: tion.
(a) Convert the C2C4 gaseous syncrude fraction into naphtha (c) C4 hydrocarbons. The C4 hydrocarbon fraction of HTFT
range material. This not only transforms normally gaseous syncrude contains about 85% olefins. Olefin oligomerisation by
products into liquid products, but targets 3035% of the total a motor-gasoline selective technology, such as solid phosphoric
syncrude production. Some conversion technologies immediately acid based oligomerisation, is a natural choice. The motor-
come to mind, namely olefin oligomerisation, aliphatic alkyl- gasoline thus produced can be hydrogenated to produce an
ation, aromatic alkylation and aromatisation. Olefin oligomer- alkylate-equivalent product.26 The remaining butanes can be
isation and aromatic alkylation can only be used to refine the directly blended into the motor-gasoline and their inclusion is
C2C4 olefins, not paraffins. Aliphatic alkylation can convert only limited by the vapour pressure constraints placed on the
C3C4 olefins and C4 paraffins. Aromatisation can employ C3C4 final fuel. Other upgrading pathways that can be considered are
olefins and paraffins as feed. aliphatic alkylation and etherification. However, these pathways
(b) Convert the C11 and heavier syncrude into naphtha range are less attractive for HTFT syncrude due to the olefin to paraffin
material. It does not make sense to convert HTFT distillate that (85 : 15) imbalance, high degree of linearity (n-C4:iso-C4 z 9 : 1)
can easily be refined to jet fuel and diesel fuel into naphtha. The and large volume (13% of HTFT syncrude).
C22 and heavier (residue) fraction may be considered though, but (d) C5 naphtha. The straight run C5 HTFT naphtha has an
it represents only 3% of the total syncrude production. octane number of around 9095 on account of its high olefin
(c) Recover and incorporate the oxygenates present in the content (85%) and can be blended directly into motor-gasoline.
aqueous product into the motor-gasoline. Only the alcohols can The pentenes can also be skeletally isomerised and used as feed
be used as direct blending components (Table 2). This suggests for etherification, as is the case at the Sasol Synfuels refineries
strategies such as selective partial hydrogenation and acid cata- where it is used for tertiary amyl methyl ether (TAME)
lysed conversion. production. More importantly, there is little octane penalty when
Producing maximum naphtha is not all that is required. The the C5 naphtha is hydroisomerised before it is blended into
naphtha must also meet the motor-gasoline specifications before motor-gasoline, which has the advantage of not limiting the
it can be sold as motor-gasoline. For the material that is not inclusion of other olefins into the fuel. The C5 naphtha would
already in the naphtha range, quality can be addressed while normally be hydrotreated first, but it is possible to feed the
manipulating the carbon number distribution. For the straight olefinic naphtha directly to beneficially employ the heat of
run naphtha material, the quality must be adjusted preferably hydrogenation during hydroisomerisation.27
without affecting the carbon number distribution. (e) C6 naphtha. Although this cut has a low straight run octane
Environmentally responsible refinery design extends beyond number, there are many ways to refine it to good quality motor-
technology selection. It requires that the least amount of work gasoline. The most obvious refining pathway is hydro-
necessary be performed on a molecule to achieve the required isomerisation, but alumina-based isomerisation of the olefinic
product properties. This implies that a molecule should pass product has in the past been employed with success.1 Another
through the least number of units. It also implies that one would option is to refine it to aromatics over a non-acidic Pt/L-zeolite
ideally want the products from any primary conversion to have based reforming technology. This is especially well-suited to
acceptable properties to be included in the final product, namely, HTFT C6 naphtha and in combination with aromatic alkylation
on-specification transportation fuel. it produces a high quality reformate.
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(f) C7 naphtha. In syncrude, like in crude oil refining, this is the

most difficult naphtha cut to upgrade. It is poorly converted by
catalytic reforming (C7 conversion is low and the N + 2A of
HTFT syncrude is low, <25),14 unless non-acidic Pt/L-zeolite
based technology is considered. Due to its cracking propensity

hydroisomerisation is inefficient and its hydrogenated straight
run octane number (RON < 50) makes it a poor motor-gasoline
component. Catalytic cracking can be used, but since the mate-
rial is already in the correct boiling range, it is an inefficient
refining pathway.
(g) C8 naphtha. This fraction is traditionally upgraded by
catalytic reforming. Non-acidic Pt/L-zeolite based and standard
Pt/Cl/Al2O3 based technologies can be considered. However, as
noted before, the N + 2A of HTFT syncrude is very low, making
Fig. 4 HTFT refinery design maximising motor-gasoline production.
the former more efficient.
(h) C9C10 naphtha. Like C8 naphtha, this naphtha fraction is
usually refined by catalytic reforming to produce aromatics. HTFT motor-gasoline refinery design
Despite its low N + 2A value, the Sasol and PetroSA HTFT
An important advantage of a FischerTropsch refinery is that the
refineries make use of this approach.1 The main drawback of this
syncrude feed to the refinery is pre-fractionated as a consequence
approach is that aromatics production is limited, since this
of the stepwise cooling of the product from FischerTropsch
fraction constitutes only 5% of the HTFT syncrude. The inclu-
synthesis (Fig. 1). It is consequently possible to design the cooling
sion of more than one aromatics producing technology would be
steps in such a way that it not only fits the gas loop design, but
costly and add unnecessary complexity. As straight run motor-
also serves the refinery.
gasoline, the C9C10 naphtha has a low octane value, which
The HTFT motor-gasoline refinery design presented in Fig. 4,
becomes worse after hydrogenation. It can be mildly hydro-
requires stepwise cooling similar to that employed commercially
isomerised, but only to further improve its already good cold
by the Sasol and PetroSA HTFT facilities. The beneficial use of
flow properties. Oligomerisation would result in a distillate range
the C2 hydrocarbons also implies cryogenic separation. One of
product, thereby reducing the motor-gasoline yield and still
the most important benefits of cryogenic separation in the
leaving the low octane C9C10 paraffins to be dealt with. After
FischerTropsch gas loop is the ability to separate and recycle
hydrogenation it can be used as jet fuel component, but this
hydrogen and methane. This improves the carbon efficiency of
reduces the motor-gasoline yield of the refinery.
the overall process. However, if an economic analysis of the gas
(i) C11C14 kerosene. The straight run kerosene fraction from
loop design contra-indicates cryogenic separation, the same basic
HTFT can be hydrogenated/hydroisomerised in order to be used
design can be retained (Fig. 4), but employing combined oligo-
for jet fuel.28 Optionally this fraction can be cracked to produce
merisation and alkylation in the C3 solid phosphoric acid (SPA)
more lower boiling material to increase motor-gasoline produc-
oligomerisation unit.25 The latter approach has been used
tion.
recently to illustrate the design of a typical modern HTFT
(j) C15C22 distillate. Since HTFT material is sulfur free and
refinery (not shown here).7
low in polynuclear aromatics, the traditional refining approach
The design intent, namely to produce mainly motor-gasoline,
would be to hydrogenate this material and incorporate it into
has been met (Table 4), with 70% of the transportation fuel being
diesel fuel. The hydrogenated product has a good cetane number,
motor-gasoline. The transporation fuels from the refinery
typically >51, and meets all diesel fuel specifications (including
(Fig. 4) meet fuel specifications and selected fuel properties are
density) when appropriately cut and hydrotreated.15 Optionally
given in Table 5.
it may be considered to use a carbon number reduction tech-
The stepwise cooling of the FischerTropsch product allows
nology to crack this material into lower boiling material and
the broad cut light oil and decanted oil to be hydroprocessed
thereby increase the motor-gasoline production.
first.x By doing so, it not only eliminates the atmospheric distil-
(k) Residue (C23 and heavier). HTFT syncrude contains
lation unit (ADU) that one typically finds in a refinery, but also
about 3% material boiling above 360 C. Using the low sulfur
overcomes the stability problems associated with the distillation
residue as a fuel oil is tempting from a design perspective, since
of unrefined HTFT syncrude. Due to the olefin and oxygenate
it avoids the inclusion of any residue upgrading units.
rich nature of HTFT syncrude, thermal decomposition in the
However, if the aim is to maximise motor-gasoline, some form
reboiler of an ADU is a problem. The reboiler temperature
of cracking is required to reduce the average carbon number of
should consequently not exceed 300320 C, which makes it
the residue.
(l) Aqueous product. The oxygenates in the aqueous product
can be recovered and purified. The lower alcohols can be blended x The decanted oil from HTFT synthesis contains much higher levels of
into the motor-gasoline,29 or used as feed to an etherification solids (catalyst particles carried over from synthesis) and dissolved metals
unit. Refining can be simplified by partial hydrogenation of the (metal carboxylates) than the lighter fractions. If standard fixed bed
carbonyls to alcohols, optionally followed by dehydration to hydroprocessing technology is considered for the conversion of this
fraction, appropriate feed pretreatment must be considered.
produce olefins.30 The olefins thus produced can be co-refined Alternatively it would be better to consider a moving or ebullated bed
with the other HTFT olefins. technology or even slurry phase hydroprocessing for this application.
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Table 4 Product distribution from the HTFT motor-gasoline refinery Table 5 Selected transportation fuel properties from the HTFT refinery
shown in Fig. 4 that incorporates cryogenic separation to recover the C2 design shown in Fig. 4
hydrocarbons. The transportation fuel yield is 74.0%
Fuel property Refinery product Specification
Total producta Transportation
Product description (mass %) fuels (vol %) Motor-gasoline EN228

research octane number 97 95 min
hydrogen 0.0 motor octane number 89 85 min
methane 12.7 density at 15 C (kg m3) 741 720775
fuel gas 5.9 Reid vapour pressure 55 60 maxa
liquid petroleum gas 3.0 olefin content (vol %) 17.6 18 max
motor-gasoline (EN228) 50.9 70.1 aromatic content (vol %) 25.5 35 max
jet fuel (Jet A-1) 16.1 21.2 oxygenate content (vol %) 5.6 15 max
diesel fuel (EN590) 7.0 8.7 benzene content (vol %) 0.3 1 max
unrecovered organics 2.8 Jet fuel Jet A-1
water 1.6 density at 15 C (kg m3) 775 775840
a
aromatic content (vol %) 24.8 825
Excludes H2, CO, CO2 and H2O from HTFT synthesis. Diesel fuel EN590
cetane number 61 51 min
density at 15 C (kg m3) 820 820845
a
impossible to achieve distillate-residue separation of HTFT Dependent on the climate of the region where the fuel will be used.
syncrude in a conventional ADU.
Another advantage of hydroprocessing the syncrude first,
can be achieved at the expense of carbon efficiency of the overall
before an ADU, is that distillation range broadening is avoided.
facility, for example, by eliminating cryogenic separation from
Distillation broadening occurs due to deoxygenation in
the gas loop and treating the total aqueous product as waste-
downstream refining units. On a carbon number basis oxygen-
water (as in recent LTFT designs, such as Oryx GTL).1 Such
ates co-boil with hydrocarbons that are 24 carbon numbers
a simplified refinery design (Fig. 5) can produce mainly motor-
longer. When the oxygenates are deoxygenated to become
gasoline, but at lower overall yield (Table 6).k
hydrocarbons, there is a significant shift in their boiling point.
The design shown in Fig. 5 produces motor-gasoline and jet
This reduces the efficiency of refinery units and their associated
fuel that meet specifications, but the distillate fails the density
separations.
specification of diesel fuel (Table 7). The inherently low density
The separation of the C2C4 hydrocarbons in their respective
of FischerTropsch distillates is a recurring theme in Fischer
carbon number cuts is implied by the inclusion of cryogenic
Tropsch refining.13,33 In HTFT refining this can be rectified by
separation in the gas loop design. This separation has been dis-
appropriate selection of the hydroprocessing unit15 and the
cussed in texts dealing with the upgrading of light hydrocarbon
design in Fig. 5 can in principle be modified to yield on-specifi-
gases, such as that by Chavel and Lefebvre.31
cation diesel fuel.
The technology selection has already been discussed and
Implicit in the design shown in Fig. 5, is a more efficient
variations on the design in Fig. 4 will yield equally viable refin-
product cooling section, but without cryogenic separation. The
eries. From Table 5 it is clear that the motor-gasoline is not
product from HTFT synthesis is washed at higher temperature
specification constrained, making it a robust design. There is
than found in current commercial HTFT designs in order to
significant octane number give away and the motor-gasoline is
minimise the loss of carbon to the heavy oil (industrially called
far from the blending limits with respect to high octane
decanted oil, as shown in Fig. 4). The condensed oil in Fig. 5 is
components (aromatics and oxygenates).{ Some of the light-end
therefore not the same as light oil, but contains a significant
kerosene material can therefore be blended into the motor-
portion of the heavier fraction. In practice, this type of modifi-
gasoline to increase the yield of motor-gasoline further. No fuel
cation to the stepwise cooling of HTFT product can benefit
oil or black products are produced.
HTFT refinery designs in general (including Fig. 4).
In conventional refinery design, the hydrogen balance of the
The olefin and oil hydrotreaters (Fig. 5) can with clever design
refinery is critical.20 Although this is less critical in a Fischer
be combined in a single unit, but from an operability point of
Tropsch refinery due to the availability of hydrogen from the gas
view, it is better to have two separate units. Different hydroge-
loop, it should be noted that hydrogen production and
nation catalysts are required for olefin hydrogenation and
consumption in the design shown in Fig. 4 is well-balanced.
hydrotreating of oxygenate-rich HTFT syncrude.
The design of FischerTropsch motor-gasoline refineries can
There is a significant difference in complexity between the two
be simplified, by making use only of the key conversion units
HTFT motor-gasoline refinery designs (Fig. 4 and 5). This
identified for such a refinery, namely, olefin oligomerisation,
aromatic alkylation, aromatisation (catalytic reforming), iso-
merisation, hydrotreating and cracking.32 Further simplification k Simplification of a FischerTropsch refinery by excluding cryogenic
separation and aqueous product work-up is accompanied by
a significant loss in carbon efficiency. There is consequently an
{ The direct use of alcohols in the FischerTropsch aqueous product as opportunity for the development of a refining technology that can
fuel alcohols simplifies the refinery design. However, from convert the full-range FischerTropsch aqueous product into a liquid
a motor-gasoline blending and distribution point of view, alcohols are product that can easily be separated from the water. There is likewise
not preferred oxygenates due to their de-mixing tendency in the an opportunity for the development of a refining technology that can
presence of water. It may therefore be preferable to etherify the convert the C2 and lighter tail gas from FischerTropsch synthesis into
alcohols with the C5 olefins and rather produce fuel ethers. a liquid product that can be recovered from the remaining tail gas.
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Considering that the refinery cost is typically only 1015% of the

total cost of a FischerTropsch facility, it is unlikely that a saving
in refinery capital cost will be able to offset the cost associated
with the lower product yield.
LTFT motor-gasoline refining

In this section we consider the design of an LTFT refinery for the
production of maximum EN228:2004 compliant motor-gasoline.
Compared to HTFT syncrude, LTFT syncrude has some
drawbacks for motor-gasoline refining. There is less straight run
naphtha material, the gaseous fraction is less olefinic, the degree
of branching of aliphatic material is lower and there are no
Fig. 5 HTFT motor-gasoline refinery without cryogenic separation and
aqueous product refining to simplify the refinery design. aromatics. On the flip side some advantages can be noted too.
Alcohols are the dominant LTFT oxygenates, the syncrude is
thermally more stable and distillation range broadening is less of
Table 6 Product distribution from the HTFT motor-gasoline refinery an issue. Alcohols are easier to refine than the other oxygenate
shown in Fig. 5 that excludes cryogenic separation and aqueous product
recovery. The transportation fuel yield is 60.0% classes and the stability of the syncrude allows atmospheric
distillation.
Total producta Transportation In order to maximise motor-gasoline production, material
Product description (mass %) fuels (vol %) outside the naphtha boiling range must be converted in such
a way that it increases the naphtha yield. Although one can apply
hydrogen 0.2
methane 0 similar thinking as for HTFT syncrude, it would not be efficient.
fuel gas 23.8 Yet, it has been pointed out that the key conversion technologies
liquid petroleum gas 3.1 for HTFT and LTFT syncrude conversion to motor-gasoline are
motor-gasoline (EN228) 45.0 76.1
jet fuel (Jet A-1) 13.0 20.9 the same, namely, olefin oligomerisation, aromatic alkylation,
diesel fuel (EN590) 2.0 3.0 aromatisation (catalytic reforming), isomerisation, hydro-
unrecovered organics 12.6 treating and cracking.32
water 0.3 One particular aspect that is on the next level of detail, but
a
Excludes H2, CO, CO2 and H2O from HTFT synthesis. must be highlighted, is the impact of LTFT catalyst deactivation
on product selectivity.16 This has a significant impact on motor-
gasoline refining and on refinery design in general.**
The following strategies are suggested for converting LTFT
difference in complexity must be economically justified by
syncrude into mainly naphtha range material:
a difference in the product yield and product quality. The more
(a) The C1C2 hydrocarbons in the LTFT tail gas are less than
complex design (Fig. 4) had a transportation fuel yield of 74 mass
for HTFT and current commercial LTFT gas loop designs do not
% and all fuels met specifications. The less complex design
include cryogenic separation. The C1C2 material would typi-
(Fig. 5) had a transportation fuel yield of only 60 mass % and the
cally not be converted to naphtha and the refining approach
distillate did not meet EN590:2004 diesel fuel specifications.
depends strongly on the type of LTFT technology and the
location of the facility. In locations where there are infrastructure
and market for synthetic natural gas (SNG), this would be the
Table 7 Selected transportation fuel properties from the HTFT refinery preferred application. Co-LTFT is especially well suited for this
design shown in Fig. 5 application, since gradual deactivation of a Co-LTFT catalyst is
** Low temperature FischerTropsch (LTFT) catalysts, like all catalysts,
Motor-gasoline EN228 deactivate with time on stream. This may introduce transience into
research octane number 98 95 min refinery operation, depending on the type of FischerTropsch
motor octane number 90 85 min technology that is employed. The faster deactivation of Fe-LTFT
density at 15 C (kg m3) 740 720775 catalysts led to the development of slurry bed technology that allows
Reid vapour pressure 54 60 maxa the on-line addition and removal of catalyst. In such cases the refinery
olefin content (vol %) 16.3 18 max can be designed for a steady state syncrude composition. For
aromatic content (vol %) 31.8 35 max Fe-LTFT fixed bed technology the design must make provision for the
oxygenate content (vol %) 0 15 max transience, although multiple fixed beds in parallel with different
benzene content (vol %) 0.3 1 max catalyst ages can reduce variation somewhat. Co-LTFT catalysts
Jet fuel Jet A-1 present an interesting conundrum. Since Co-LTFT catalysts have
density at 15 C (kg m3) 777 775840 a longer lifetime and they deactivate slower, on-line catalyst
aromatic content (vol %) 23.8 825 replacement does not have the same clear-cut benefit as for Fe-LTFT.
Diesel fuel EN590 It may consequently be necessary to design the refinery in such a way
cetane number 57 51 min that it caters for the slow, albeit inexorable change in syncrude
density at 15 C (kg m3) 813 820845 composition related to Co-LTFT catalyst deactivation. The same
arguments apply with respect to operating temperature changes to
a
Dependent on the climate of the region where the fuel will be used. counteract activity loss due to deactivation. The syncrude composition
depends on the operating temperature.
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typically accompanied by an increase in methane yield34 and it production, cracking is preferred. However, if hydrocracking is
inherently has a low selectivity to ethylene (0.05%).35 The situa- employed, it may be difficult to recycle this fraction to extinction.
tion with Fe-LTFT is different. When Fe-LTFT catalysts deac- (c) C11C14 kerosene. Although kerosene and distillate can be
tivate, the yield of methane levels out around 4%.36 In parallel the treated in the same way, there is one important difference. LTFT
yield of C2C4 and oil increases significantly at the expense wax kerosene can more easily be refined to jet fuel than LTFT
yield. In order to employ the C1C2 tail gas for SNG, reactive distillate can be refined to diesel fuel. The cold flow properties
recovery or hydrogenation of the ethylene may be necessary. can be corrected by hydroisomerisation. Producing jet fuel is
(b) Convert the gaseous C3C4 hydrocarbons, which can be more efficient than forcing this material into the naphtha boiling
recovered from the LTFT tail gas, to naphtha range material. range.
The same conversion technologies suggested for HTFT are (d) C9C10 naphtha. The discussion on technology selection
applicable, but the actual technology selection may be different for refining HTFT syncrude to motor-gasoline is applicable.
on account of the olefin to paraffin ratio and the possibility to Depending on the refining approach for the C11C14 cut, jet fuel
co-refine the C3C4 material with the naphtha. In the case of production may be more efficient, although this comes at the
Fe-LTFT, this fraction almost doubles due to deactivation of the expense of motor-gasoline yield. In order to maximise motor-
FischerTropsch catalyst. The yield of C3C4 syncrude may gasoline, catalytic reforming to produce aromatics may be the
therefore in practice be far more than is suggested by the LTFT preferred refining pathway. The lack of aromatics in LTFT
syncrude composition in Table 1. syncrude is a serious deficiency for fuel production.
(c) Convert the C11 and heavier syncrude into naphtha range (e) C7C8 naphtha. This cut is ideally refined to aromatics by
material. The bulk of LTFT syncrude is in this fraction. In order catalytic reforming. The preferred technology for catalytic
to maximise motor-gasoline production, the C11 and heavier reforming is non-acidic Pt/L-zeolite based.
material must be converted to naphtha range products. Unlike (f) C6 naphtha. If non-acidic Pt/L-zeolite based reforming is
HTFT syncrude, the distillate is not easily refined to diesel employed, the C6 material is best refined to aromatics. It can also
fuel.13,33 The application of some form of cracking technology is be hydroisomerised to produce a good paraffinic motor-gasoline
indicated. blending component. The olefin conversion technologies, as
(d) Aqueous product oxygenates (mainly alcohols) can be suggested for HTFT, may be less applicable to LTFT. Straight
recovered and incorporated into the motor-gasoline. The alco- run Fe-LTFT material is very olefinic, but Co-LTFT is less
hols may also be employed in conversion processes such as olefinic. Furthermore, if hydrocracking is employed for
etherification. upgrading of the heavier fractions, the naphtha produced will be
A high yield of naphtha does not necessarily imply a high yield paraffinic. Etherification has been suggested in conjunction with
of on-specification motor-gasoline. The quality of the naphtha FCC of LTFT wax to produce methyl ethers from the branched
must still be adjusted to meet motor-gasoline specifications. Here C4C6 olefins.39 However, it has been reported that not all methyl
the technology selection becomes critical. hexyl ethers have high blending octane numbers in a Fischer
Tropsch matrix.40
(g) C5 naphtha. The two most promising refining pathways are
Technology selection
etherification and hydroisomerisation. Etherification with alco-
As in the case of HTFT motor-gasoline refining, carbon number hols that may be obtained from the aqueous product, will supply
based refining is a useful concept. Considering that the heavier a high-octane motor-gasoline blending component. It may be
(wax) material is dominant, it makes more sense to start the desirable to increase the branched olefin content by skeletal
discussion from the heavier side. isomerisation of the n-pentenes. The C5 olefins from FCC of wax
(a) Residue/wax (C23 and heavier). There are three types of already contain 6570% branched material, but straight run
cracking technology that can be considered to adjust the carbon LTFT C5 olefins are mainly linear. Part or all of the C5 naphtha
number distribution. Historically, thermal cracking has been can be hydroisomerised to a good paraffinic motor-gasoline
considered for upgrading LTFT waxes to motor-gasoline.37 blending component. Hydrogenation is not a required feed
Thermal cracking produces a product with high linearity that is pretreatment step.27 The amount of isopentane that can be
rich in a-olefins. It has been pointed out that in comparison to blended into the motor-gasoline is limited by the vapour pressure
hydrocracking, the high linear a-olefin content from thermal specification. One would therefore prefer to rather include the
cracking makes it better suited for chemicals production, while C5 olefins as fuel ethers.
hydrocracking is better for fuels production.38 However, when (h) C3C4 hydrocarbons. The best refining pathway for this
hydrocracking is compared to fluid catalytic cracking (FCC), the fraction is dependent on the technology selection employed for
latter seems to be better suited, especially for motor-gasoline the heavier material. If non-acidic Pt/L-zeolite based reforming is
production.2 The selection of the cracking technology directly used for C6 upgrading, the resultant benzene must be alkylated
influences the selection of the other refining units. Hydrocracking before it can be included in the motor-gasoline. For this purpose,
yields a paraffinic product, while FCC yields a mixture of the C3 olefins are ideal. One can also consider SPA based
paraffins, olefins and aromatics. oligomerisation with combined benzene alkylation for the whole
(b) C15C22 distillate. Straight run LTFT distillate has a high C3C4 cut.25 This does not address the upgrading of the paraffins.
cetane number, low density and poor cold flow properties. The Depending on the cracking technology used to convert the
main design decision that has to be made, is whether this material heavier LTFT material, a significant amount of C3C4 paraffins
should be retained as distillate, or if it should be cracked with the may be produced. This material can be sold as LPG and some of
C23 and heavier fraction. In order to maximise motor-gasoline the butanes can be blended into the motor-gasoline. However, it
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is also possible to consider Ga- or Zn/H-ZSM-5 aromatisation, is transformed into a product that bears resemblance to HTFT
which can be employed instead of catalytic reforming for syncrude. On a philosophical level one has to question the
aromatics production. The use of H-ZSM-5 has been studied rationale of selecting an LTFT technology if motor-gasoline
extensively as method for the upgrading of the total LTFT refining benefits from HTFT syncrude. However, the trans-
syncrude, excluding wax, in order to improve the quality of the portation fuel yield (Table 10) and quality (Table 11) is high,
resulting naphtha for motor-gasoline production.41 despite the simplicity of the refinery design.
(i) Aqueous product. The alcohols in the LTFT aqueous This design (Fig. 6) again emphasises the robustness of the
product can be recovered and used in conjunction with an basic configuration that was employed for motor-gasoline
etherification technology. The alcohols may also be included production. As anticipated, the inclusion of an FCC improved
directly as a blending component in the motor-gasoline, but on the motor-gasoline yield (Table 10). The motor-gasoline is
account of the high methanol fraction, etherification is vapour pressure constrained, but meets all other specifications
a preferred strategy. (Table 11).
The kerosene (Table 11) is very aromatic and it is rich in
LTFT motor-gasoline refinery design cumene specifically, on account of the cumene unit. In order to
produce jet fuel from the kerosene, about half the aromatics must
The basic refining steps needed to ensure appropriate fuel be exported as chemicals. The significant aromatic production
quality, are not intrinsically linked to the steps required to also resulted in a large hydrogen excess in the refinery. These are
maximise quantity. The HTFT motor-gasoline refinery design in not drawbacks per se, but it points to an imbalance in the refinery
Fig. 5 can be employed without change for refining of LTFT design.
syncrude. The yield of motor-gasoline is much less (Table 8), A balanced refinery design must avoid the high vapour pres-
since residue/wax upgrading has not been included in the design. sure of the motor-gasoline, avoid the excessive aromatics
Nevertheless, the motor-gasoline and jet fuel are on-specification production and make use of the aqueous product. All of these
products (Table 9). actions would improve the volumetric motor-gasoline yield by
A direct comparison of Table 7 and Table 9 shows that HTFT allowing more butane to be blended into the motor-gasoline,
syncrude yields a better quality motor-gasoline than LTFT reducing the density and exploiting the alcohols in the aqueous
syncrude for the same refining effort. A salient point that needs
product.
to be highlighted, is the importance of olefins in the naphtha, The LTFT motor-gasoline refinery design presented in Fig. 7 is
without which it would not have been possible to meet the fuel more balanced and it exploits the syncrude and FCC product
specifications. This implies that Fe-LTFT will have a benefit over properties. Etherification of the branched C5 olefins in the FCC
Co-LTFT for motor-gasoline refining and that the deactivation naphtha reduced the vapour pressure of the motor-gasoline and
of the Fe-LTFT catalyst36 is actually beneficial from a syncrude made beneficial use of the alcohols from the aqueous product. In
quality perspective in this regard. Considering that half the this design only tertiary amyl methyl ether (TAME) was
LTFT syncrude has been excluded from this example, it is clear produced, but in principle a mixed ether product would take
that the selection of the residue (wax) conversion technology will better advantage of the LTFT alcohols. The more branched C6
significantly influence the syncrude composition that has to be naphtha from the FCC was hydroisomerised to reduce the feed
refined. Following on the previous observation, an olefin to the non-acidic Pt/L-zeolite based reformer. With less C6
producing conversion technology, such as FCC, would be better
reformer feed, benzene production was reduced, thereby making
for motor-gasoline production, corroborating the conclusions of more propylene available for oligomerisation. The FCC material
Choi and co-workers.2 increased the isobutene content of the C4 fraction and thereby
The LTFT refinery design shown in Fig. 6 is essentially the
same design as shown in Fig. 5, but includes FCC of the wax as
residue upgrading technology. By doing so, the LTFT syncrude Table 9 Selected transportation fuel properties of the products from
LTFT syncrude refining in the HTFT refinery design shown in Fig. 5

Table 8 Product distribution from refining LTFT syncrude in the HTFT
motor-gasoline refinery shown in Fig. 5. The transportation fuel yield is Motor-gasoline EN228
36.5% (compared to 60% for HTFT with the same refinery design) research octane number 95 95 min
motor octane number 89 85 min
Total producta Transportation density at 15 C (kg m3) 721 720775
Product description (mass %) fuels (vol %) Reid vapour pressure 60 60 maxa
olefin content (vol %) 17.8 18 max
hydrogen 0 aromatic content (vol %) 19.7 35 max
methane 0 oxygenate content (vol %) 0 15 max
fuel gas 6.8 benzene content (vol %) 0.4 1 max
liquid petroleum gas 2.3 Jet fuel Jet A-1
motor-gasoline (EN228) 9.6 27.8 density at 15 C (kg m3) 775 775840
jet fuel (Jet A-1) 13.8 37.2 aromatic content (vol %) 18.8 825
diesel fuel (EN590) 13.1 35.0 Diesel fuel EN590
unrecovered organics 54.1 cetane number 82 51 min
water 0.3 density at 15 C (kg m3) 777 820845
a
a
Excludes H2, CO, CO2 and H2O from LTFT synthesis. Dependent on the climate of the region where the fuel will be used.
Published on 03 February 2011. Downloaded by Norwegian University of Science and Technology on 17/10/2017 07:24:38. View Article Online
Fig. 6 LTFT motor-gasoline refinery based on an HTFT design (Fig. 5),

with a fluid catalytic cracker added for C9 and heavier upgrading. The
benzene and propylene feed is balanced and the C3 SPA unit is operated Fig. 7 Balanced LTFT motor-gasoline refinery that exploits the syn-
in cumene-mode, rather than alkylation-oligomerisation-mode. crude and FCC product properties.
Table 10 Product distribution from the LTFT motor-gasoline refinery In neither of the LTFT designs (Fig. 6 and 7) was any diesel
shown in Fig. 6. The transportation fuel yield is 81.4% fuel produced. This has been deliberate, since LTFT syncrude is
on a molecular level unsuited for EN590:2004 diesel fuel
Product description (mass %) fuels (vol %) production.13 This is a consequence of the FischerTropsch
density-cetane-yield triangle that makes it difficult to produce
hydrogen 0.9 on-specification diesel fuel in high yield. This topic will be dis-
methane 0 cussed in more detail in the section dealing with diesel fuel
fuel gas 8.5
liquid petroleum gas 4.4 refining.
jet fuel (Jet A-1) 31.8 37.3 Jet fuel refining
diesel fuel (EN590) 0 0
unrecovered organics 4.6 Fuel specifications
water 0.2
a
Excludes H2, CO, CO2 and H2O from LTFT synthesis.
The jet fuel properties listed (Table 14) are only a subset of the
full DEFSTAN 91-91/Issue 6 specifications.22 With minor
differences, a similar set of Jet A-1 specifications can be found in
ASTM D1655.42 The properties that have been highlighted are
Table 11 Selected transportation fuel properties from the LTFT refinery those that affect refinery design the most. These properties can be
design shown in Fig. 6 related to the molecular properties of the fuel that must be
produced by the refinery.
Two types of FischerTropsch derived jet fuel were qualified
Motor-gasoline EN228 for use as Jet A-1. Semi-synthetic jet fuel is a mixture of refined
research octane number 100 95 min FischerTropsch derived and refined crude oil derived
motor octane number 93 85 min components. Fully synthetic jet fuel consists of only refined
density at 15 C (kg m3) 742 720775
Reid vapour pressure 61 60 maxa
aromatic content (vol %) 34.9 35 max Table 12 Product distribution from the balanced LTFT motor-gasoline
oxygenate content (vol %) 0 15 max refinery shown in Fig. 7 that incorporates aqueous product work-up. The
benzene content (vol %) 0.5 1 max transportation fuel yield is 86.8%
Jet fuel Jet A-1
density at 15 C (kg m3) 801 775840 Total producta Transportation
aromatic content (vol %) 44.1 825 Product description (mass %) fuels (vol %)
a
hydrogen 0.4
methane 0
fuel gas 8.2
liquid petroleum gas 2.9
improved the quality of the hydrogenated motor-gasoline from motor-gasoline (EN228) 61.2 71.8
SPA oligomerisation.26 jet fuel (Jet A-1) 25.6 28.2
diesel fuel (EN590) 0 0
The motor-gasoline yield (Table 12) from the refinery design unrecovered organics 3.2
shown in Fig. 7 is higher than that of the design shown in Fig. 6 water 0.2
(Table 10). This was achieved with only a small increase in refinery methanol (imported) -1.7
complexity. The fuel quality issues were also resolved and the a
motor-gasoline and jet fuel meet specifications (Table 13).
View Article Online
Table 13 Selected transportation fuel properties from the balanced Carbon number distribution
LTFT motor-gasoline refinery design shown in Fig. 7
The carbon number range of jet fuel is directly and indirectly
Fuel property Refinery product Specification regulated. The upper limit is set by the final boiling point spec-
ification (300 C; about n-C17), while the lower limit is set indi-
Motor-gasoline EN228
research octane number 99 95 min rectly by the density and viscosity specifications. In refining
motor octane number 91 85 min practice the kerosene boiling range is typically 160260 C, which
density at 15 C (kg m3) 728 720775 covers the carbon number range C10C15 and overlaps with both
olefin content (vol %) 5.6 18 max naphtha and distillate. The specifications allow a wider cut to be
aromatic content (vol %) 21.2 35 max employed, which is useful for maximising jet fuel production.
oxygenate content (vol %) 14.8 15 max The viscosity limit, rather than boiling range restriction, limits
benzene content (vol %) 0.1 1 max the inclusion of heavier boiling material.
Jet fuel Jet A-1
density at 15 C (kg m3) 776 775840 The fraction of straight run FischerTropsch syncrude that is
aromatic content (vol %) 24.0 825 already in the correct carbon number range, is determined by the
a chain growth probability (a-value) of the FischerTropsch
technology (Fig. 8). The amount of straight run material is quite
sensitive to the broadness of the kerosene cut and the Fischer
Tropsch a-value.
Table 14 Selected properties of Jet A-1 turbine aviation fuel as specified The jet fuel yield can be maximised by converting gaseous
by DEFSTAN 91-91/Issue 6 products, naphtha, distillate and residue into kerosene. In
FischerTropsch context, one of the key components of synthetic
Jet A-1 specifications jet fuel is isoparaffinic kerosene (IPK). IPK is the hydrogenated
Fuel property minimum maximum kerosene produced from oligomerisation of C3C4 olefins over
a SPA catalyst. This product is a good source of highly branched
Direct restrictions on boiling range C8C12 aliphatic hydrocarbons and demonstrates how the jet fuel
distillation T10 ( C) 205
yield can be increased by the conversion of lighter material into
Final boiling point ( C) 300
distillation T40 T10 ( C)a 20 kerosene. Naphtha can also be converted into kerosene by
distillation T90 T10 ( C)a 40 technologies such as oligomerisation and aromatic alkylation.
Indirect restrictions on boiling range Heavy distillate (gas oil) and residue can likewise be converted
flash point ( C) 38 50a into kerosene by technologies such as hydrocracking.
viscosity at 20 C (cSt) 8
Direct restrictions on composition Composition
aromatic content (vol %)b 8a 25
sulfur content (mass %) 0.3 Jet fuel specifications (Table 14) are not very restrictive in terms
mercaptan content (mass %) 0.003
of molecular composition. The key composition related criteria
total acidity (mg KOH/g) 0.015c
Indirect restrictions on composition for jet fuel refining from FischerTropsch are the freezing point
freezing point ( C) 47 and the aromatic content.
net heat of combustion (MJ kg1) 42.8 Although density would normally be distillation range
smoke point/mm 25d
dependent in a crude oil refinery, the composition plays an
a
Only applicable to synthetic jet fuel blends. b As determined by important role in meeting the density specification of synthetic jet
standard test methods IP156 or ASTM D1319. c Maximum acidity in fuel. This is related to the low abundance of cyclo-paraffins and
ASTM D1655 is 0.10 mg KOH/g. d Alternatively a minimum smoke
point of 19 mm (18 mm in ASTM D1655) and maximum naphthalene aromatics in FischerTropsch syncrudes. There are some cyclic
content of 3% is allowed.
FischerTropsch derived components. In addition to the

property specifications, there is also a limitation on the actual
refining processes that may be used. This limits synthetic jet
fuel production to a technology selection and operation that
reflects the older Sasol Syncrude operation. With the changes
that were subsequently made,1 it is not clear whether even
Sasol still meets the requirements for synthetic jet fuel
production.
Since there is no scientific basis for a restriction to limit the
actual refining processes, this aspect of the DEFSTAN 91-91/
Issue 6 specifications will be ignored in the development of jet
fuel refineries. Fundamentally there is no reason why LTFT Fig. 8 Effect of the FischerTropsch catalysts a-value on the yield of
syncrude and other refining strategies cannot be employed to straight run kerosene. (The yield is based on C3 and heavier syncrude
produce on-specification jet fuel. calculated from the Anderson-Schulz-Flory distribution).
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material in HTFT syncrude, but LTFT syncrude contains very (a) Adjust the carbon number distribution to maximise
little cyclic material. kerosene.
Selected properties of some kerosene range hydrocarbons are (b) Synthesise appropriate kerosene range aromatics and/or
given in Table 15.24,43 From this data it is clear that cyclic cyclo-paraffins to meet aromatics and density specifications.
hydrocarbons are essential to meet the lower density limit (775 kg (c) Skeletally isomerise the linear hydrocarbons to lower their
m3) of the jet fuel specification. It is also quite apparent that freezing point.
aliphatic hydrocarbons in the kerosene boiling range requires (d) Hydrogenate the kerosene to reduce the olefin and
some branching to meet the maximum freezing point (47 C) oxygenate content.
specification. Mono-methyl branching is usually sufficient to These steps are common to all FischerTropsch derived feed
lower the freezing point of the mixture sufficiently for jet fuel use. materials. In principle it should be possible to design a refinery
Carboxylic acids must be removed from the kerosene, as well for maximum jet fuel production with only four conversion
as oxygenate classes that may result in gum formation, such as steps.44 This disregards aqueous product work-up and the quality
carbonyl compounds. The jet fuel specifications discuss requirements of other fuel types.
contamination of jet fuel with fatty acid methyl esters (FAME)
and make provision for maximum 5 mg g1 FAME. Unless Technology selection
pre-qualified, like phenolic antioxidants, the jet fuel specifica-
tions disallow oxygenates. The key conversion technologies that have been identified for jet
Olefins are detrimental to fuel stability and although jet fuel fuel refining from FischerTropsch syncrude are aromatic
may contain olefins, olefins are not deliberately included. alkylation, oligomerisation, hydrotreating, aromatisation (cata-
lytic reforming) and hydrocracking (and by implication associ-
ated hydroisomerisation).44 Many of the comments made when
HTFT jet fuel refinery design technology selection was discussed for motor-gasoline refining
The production of jet fuel is the least demanding of the three are valid for jet fuel refining too.
main transportation fuels and does not require much refining (a) C2 hydrocarbons. Aromatic alkylation with ethylene can be
effort to achieve specification. The basic refining steps that are employed to shift the boiling range of naphtha range aromatics
needed to produce maximum jet fuel from syncrude are: to the kerosene range. Such a conversion would typically operate
at higher olefin to aromatic feed ratio than is normally found in
aromatic alkylation processes. There is no convenient refining
pathway to convert ethane to jet fuel.
Table 15 Physical properties relevant to jet fuel production of selected
kerosene range hydrocarbon compounds.24,43 (b) C3 hydrocarbons. Oligomerisation of propylene over SPA
and in combination with aromatics, is ideal for jet fuel produc-
Boiling Density, Freezing Flash tion.25 An added advantage of this technology is that it increases
Compound point ( C) 15 C (kg m3) point ( C) point ( C) refinery flexibility. The light kerosene range material can also be
Linear paraffins used as a high-octane motor-gasoline blending component.
n-nonane 150.8 721.9 53.5 31.1 Other oligomerisation technologies may be considered too.
n-decane 174.2 734.2 29.6 46.1 Propane can be sold directly, or converted to aromatics with an
n-undecane 195.9 744.5 25.6 65.0 appropriate aromatisation technology.
n-dodecane 216.3 752.7 9.6 73.9
n-tridecane 235.2 761.7 5.4 (c) C4 hydrocarbons. Butene oligomerisation over SPA is
n-tetradecane 253.8 763.3 5.9 100.0 useful for the production of high-octane hydrogenated motor-
n-pentadecane 270.7 772.2 9.9 gasoline. Some kerosene is co-produced during this process, but
Branched paraffins
2-methyloctane 143.3 717.7 80.4
it is not a preferred technology to maximise kerosene. For
2-methylnonane 167.0 730.6 74.7 maximum kerosene production, the butenes should rather be
2-methyldecane 189.9 736.9a 49.5 oligomerised over other types of acid catalysts, such as amor-
2-methylundecane 210.2 745.6a 46 phous silica-alumina (ASA) or H-ZSM-5 to boost the kerosene
2-methyldodecane 229.4 753.3a 26
2-methyltridecane 247.4 760.4a 26.5 production. The motor-gasoline quality from ASA is better than
2-methyltetradecane 264 766a 8.9 that of H-ZSM-5 and may therefore be preferred. The tech-
Cyclo-paraffins nology selection for C4 olefins is very important, since it consti-
propylcyclohexane 156.7 793.6a 94.9
tutes around 10% of HTFT syncrude. Aromatic alkylation is
butylcyclohexane 177 799a 79
pentylcyclohexane 203 804a 57.5 a less preferred refining pathway.
hexylcyclohexane 224 808a 43 (d) C5 naphtha. The C5 hydrocarbons are primarily motor-
Aromatics gasoline components, with hydroisomerisation yielding high-
n-propylbenzene 159.2 868.3 99.5 30.0
n-butylbenzene 183.3 866.0 88.0 71.1 octane C5 isomerate. However, in order to increase kerosene
n-pentylbenzene 205.4 862.9 75.0 production it may be preferable to oligomerise the pentenes, or to
n-hexylbenzene 226.1 862.1 61.0 82.9 employ them for aromatic alkylation.
cumene 152.4 868.5 96.0 43.9 (e) C6 naphtha. The two obvious upgrading pathways for the
p-cymene 177.1 860.7 67.9 47.2
sec-butylbenzene 173.3 866.2 75.5 52.2 C6 naphtha are hydroisomerisation and aromatisation. The
p-diethylbenzene 183.8 866.3 42.8 56.7 former results in a product destined exclusively for motor-
a gasoline, while the latter results in the production of aromatics
Density at 20 C.
that can be refined to jet fuel. Since the aim is to produce
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maximum jet fuel, aromatisation over a non-acidic Pt/L-zeolite

based catalyst is preferred. Olefin oligomerisation and aromatic
alkylation technologies may also be considered to increase
kerosene production.
(f) C7C8 naphtha. The inclusion of C7C8 naphtha in jet fuel

is limited by the minimum flash point specification, while its
inclusion in motor-gasoline is limited by its poor straight run
octane number. The bulk of this fraction must therefore be
upgraded and aromatisation (non-acidic Pt/L-zeolite based) is
a sensible refining pathway. The olefins may also be oligomerised
to convert some of this material into kerosene boiling range
products.
(g) C9C10 naphtha. This heavy naphtha fraction overlaps
with the kerosene range. It can be co-refined with the C11C14
kerosene in a hydroisomerisation or in a mild hydrocracking
Fig. 9 HTFT refinery design maximising jet fuel production.
unit. Depending on the concentration of the linear C10 material
in the final jet fuel, it may not be necessary to hydroisomerise the
C9C10 naphtha. If this is indeed the case, this fraction need only increases the refinery complexity. The combined oligomerisation
be hydrotreated, gaining two benefits. The flash point is not of C3C5 olefins in a single conversion unit simplifies the
lowered and no material is lost to lighter products. The inclusion design.
of the C9C10 naphtha in jet fuel effectively rules out standard When this approach is employed for a refinery design to
catalytic reforming (chlorided Pt/Al2O3) as technology to maximise jet fuel (Fig. 9) it is easy to meet both the yield and
produce aromatics. quality requirements for jet fuel. Meeting motor-gasoline speci-
(h) C11C14 kerosene. Straight run HTFT kerosene does not fications is more difficult. The refinery design is rich in aromatics
meet jet fuel specifications, but can easily be converted to a jet to compensate for the lack of high-octane paraffinic motor-
fuel component by hydroisomerisation. gasoline. This is a direct consequence of selecting ASA
(i) C15C22 distillate. The technology selection for the C15C22 oligomerisation technology instead of including a C4 SPA
cut, will also determine how the residue fraction is upgraded. oligomerisation unit. Although the design (Fig. 9) illustrates the
After mild hydroprocessing this material can be sold as diesel concept, it is complex and some carbon numbers have inefficient
fuel,15 but with maximum jet fuel production in mind, hydro- refining pathways. For example, the C6 product from ASA
cracking is preferable. oligomerisation passes through three further conversion steps
(j) Residue (C22 and heavier). Despite the HTFT residue before it ends up as a product. What is not immediately apparent,
fraction being small, the need to hydroisomerise the kerosene is that the main design constraint is ethylene refining. Ethylene
range material and the possibility to convert heavy distillate into constitutes about 5% of the HTFT syncrude and refining
kerosene, argues for the inclusion of a hydrocracker. ethylene to fuel has a knock-on effect on the yield requirements
(k) Aqueous product. Much of this material can be incorpo- of other conversion units.
rated into the kerosene by partial hydrogenation of the carbonyls The design (Fig. 9) requires atmospheric distillation before
to alcohols, followed by alcohol dehydration.30 The acid cata- hydrotreating. The bottom fraction contains C9 and heavier
lysed conversion of the oxygenates can also be considered. material, which implies that the reboiler temperature is low and
Depending on the oligomerisation technology that is employed, thermal decomposition can be avoided. However, this will not
it may be possible to co-refine the alcohols directly. prevent carbon range broadening that will occur during
oxygenate conversion in the downstream refinery units.
Jet fuel refinery design Nevertheless, the design is successful in terms of product yield
(Table 16) and product quality (Table 17). However, it has little
As in the case of motor-gasoline refinery design, the carbon blending flexibility and it is not a practical refinery design. Many
efficiency and complexity of a jet fuel refinery are influenced by of the fuel properties are at their specification limits.
the gas loop design. The carbon efficiency is greatly increased if
the gas loop contains cryogenic separation. The carbon efficiency
is also increased if the aqueous product is refined, albeit at the Although it may seem preferable on paper to select a single technology
for olefin oligomerisation, in practice it is unlikely that the conversion can
cost of increased refining complexity. take place in a single reactor. The heat release associated with olefin
In order to maximise kerosene production it is critical to oligomerisation is very high and employing multiple reactors in parallel
convert the C3C5 olefins appropriately. About 30% of the total with paraffin (LPG) quenching is a likely engineering solution.
HTFT syncrude is C3C5 olefins and the oligomerisation Selecting different catalysts for different reactors will increase the unit
complexity somewhat, but may improve refining efficiency
technology selection is very important. considerably. There are also flexibility considerations. For example, if
When cryogenic separation and aqueous product refining are a refinery employs C3 SPA oligomerisation in combination with
both included in the refinery, ethylene becomes the preferred ethylene aromatic alkylation and another oligomerisation technology,
the C3 SPA oligomerisation can be used to co-process aromatics, or
olefinic feed for aromatic alkylation. Although C3 SPA-based
C4C5 olefins when either of those units experience problems. The
oligomerisation is an ideal technology for jet fuel production, trade-off between complexity and efficiency/flexibility must be carefully
employing two different olefin oligomerisation technologies evaluated.
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Furthermore, the aromatic rich nature of the motor-gasoline and Table 17 Selected transportation fuel properties from the HTFT jet fuel
jet fuel causes these fuels to have a high density and thereby it refinery design shown in Fig. 9
reduces the volumetric yield of the refinery. The density is further Fuel property Refinery product Specification
increased by the product from ASA oligomerisation, which
contains some cyclo-paraffins. This affects the economics of the Motor-gasoline EN228
refinery, since fuels are sold on a volumetric basis and not research octane number 97 95 min
a gravimetric basis. The carbon efficiency benefit derived from density at 15 C (kg m3) 767 720775
cryogenic separation and aqueous product refining is therefore Reid vapour pressure 56 60 maxa
only partially translated into an economic benefit. olefin content (vol %) 6.5 18 max
When cryogenic separation and aqueous product work-up are aromatic content (vol %) 35.0 35 max
oxygenate content (vol %) 10.9 15 max
omitted to simplify the refinery at the expense of carbon effi- benzene content (vol %) 1.0 1 max
ciency, a less constrained design is possible (Fig. 10). Combined Jet fuel Jet A-1
SPA alkylation and oligomerisation favours jet fuel production density at 15 C (kg m3) 791 775840
and it improves the quality of the C8 and lighter motor-gasoline
a
fraction. Dependent on the climate of the region where the fuel will be used.
The product yield (Table 18) indicates that jet fuel is the main
product, with both the motor-gasoline and jet fuel meeting fuel
specifications (Table 19).
No diesel fuel is produced in either jet fuel refinery designs
(Fig. 9 and 10). It is possible to produce some diesel fuel if
required, by lowering the hydrocracking severity and not recy-
cling material in the C15C22 range to the hydrocracker. As
a natural consequence of the carbon number distribution of the
HTFT syncrude, the diesel fuel yield will be low, but it can meet
EN590:2004 diesel fuel specifications.
Fig. 10 HTFT jet fuel refinery without cryogenic separation and

LTFT jet fuel refinery design
aqueous product refining in order to simplify the refinery design, albeit at
The four basic steps in jet fuel refining that has been listed for the the expense of carbon efficiency.
conversion of HTFT syncrude to jet fuel are equally applicable to
LTFT syncrude. A comparison of HTFT and LTFT syncrude on
the basis of these refining steps indicates that is should be easier distribution to maximise kerosene, introduce branching into the
to refine LTFT syncrude to jet fuel. product that result in kerosene with low freezing point.
(a) LTFT syncrude has more straight run material in the (d) LTFT syncrude has less olefins and oxygenates and
kerosene boiling range (Fig. 8) and less work has to be performed requires less hydrotreating effort than HTFT syncrude.
to maximise kerosene.
(b) Although HTFT syncrude contains more aromatics than
LTFT syncrude, there is little difference in the effort required
to convert more material to aromatics, as long as non-acidic Technology selection for jet fuel production must necessarily also
Pt/L-zeolite based technology is employed. take into consideration the quality of the other fuel types. Some
(c) Oligomerisation and hydrocracking technologies that are of the comments pertaining to LTFT motor-gasoline refining is
typically employed to adjust the LTFT carbon number consequently also applicable to jet fuel, despite the change in
Table 16 Product distribution from the HTFT jet fuel refinery shown Table 18 Product distribution from the HTFT jet fuel refinery shown in
in Fig. 9, which includes cryogenic separation and aqueous product Fig. 10, which does not include cryogenic separation or aqueous product
work-up. The transportation fuel yield is 69.4% work-up. The transportation fuel yield is 61.2%
Total producta Transportation Total producta Transportation

Product description (mass %) fuels (vol %) Product description (mass %) fuels (vol %)
hydrogen 0.1 hydrogen 0.1

methane 12.7 methane 0.0
fuel gas 5.2 fuel gas 23.8
liquid petroleum gas 6.1 liquid petroleum gas 4.1
motor-gasoline (EN228) 17.2 25.3 motor-gasoline (EN228) 18.2 30.7
jet fuel (Jet A-1) 52.2 74.7 jet fuel (Jet A-1) 43.0 69.3
diesel fuel (EN590) 0.0 0.0 diesel fuel (EN590) 0.0 0.0
unrecovered organics 5.1 unrecovered organics 10.5
water 1.6 water 0.3
a a
Excludes H2, CO, CO2 and H2O from HTFT synthesis. Excludes H2, CO, CO2 and H2O from HTFT synthesis.
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Table 19 Selected transportation fuel properties from the HTFT jet fuel and H-ZSM-5 catalysts are able to convert this feed material to
refinery design shown in Fig. 10 mainly distillate range products. However, the straight run
LTFT syncrude contains little C6C8 olefins. The additional
C6C8 material form hydrocracking of the heavier syncrude
Motor-gasoline EN228 fractions is paraffinic. It is therefore better to consider aromati-

research octane number 98 95 min sation that can convert olefins and paraffins. Although catalytic
density at 15 C (kg m3) 746 720775 reforming employing a non-acidic Pt/L-zeolite based catalyst is
Reid vapour pressure 59 60 maxa a good technology fit, the overall aromatics requirements of the
olefin content (vol %) 17.0 18 max refinery may suggest the use of an aromatisation technology that
aromatic content (vol %) 31.0 35 max can also convert lighter paraffins. Selecting a technology based
benzene content (vol %) 0.7 1 max on metal promoted H-ZSM-5 may not be the most efficient for
Jet fuel Jet A-1 C6C8 conversion, but it allows a single conversion unit to
density at 15 C (kg m3) 778 775840 upgrade the lighter paraffinic products from both hydrocracking
and straight run syncrude.
a
Dependent on the climate of the region where the fuel will be used. (f) C5 naphtha. When motor-gasoline is co-produced with jet
fuel, the conversion of the C5 naphtha may be dictated by motor-
gasoline quality rather than jet fuel production. There is not
focus. It has also been pointed out that the same conversion a single conversion technology that can be singled out as the best.
technologies that are important for HTFT syncrude refining to Hydroisomerisation, etherification, aromatic alkylation, oligo-
jet fuel are important for LTFT syncrude, namely aromatic merisation, aromatisation and direct inclusion of the straight run
alkylation, oligomerisation, hydrotreating, aromatisation and material should all be evaluated within the context of a specific
hydrocracking/hydroisomerisation.44 refinery design.
(a) Residue/wax (C23 and heavier). Hydrocracking is a tech- (g) C3C4 hydrocarbons. Aromatic alkylation with C3C4
nology that is ideally suited for jet fuel production. It adjusts the olefins is important to reduce refinery benzene and to shift
carbon number distribution by cracking and it hydoisomerises aromatics into the kerosene boiling range. The process for
(hydrogenates and isomerises) the linear hydrocarbons to combined aromatic alkylation and olefin oligomerisation
introduce branching and reduce the olefin and oxygenate emerged as an useful technology for this purpose.25 The amount
content. The level of hydroisomerisation activity is determined of C3C4 paraffins in the refinery is typically more than suggested
by the hydrocracking catalyst, which should be judiciously by the composition of the LTFT syncrude. During hydro-
selected. It has been shown that a branched to linear paraffin cracking C3C4 paraffins are inevitably produced. Aromatisation
ratio in the kerosene range of around 1 : 1 to 2 : 1 is sufficient to of this material is a convenient way of converting the liquid
meet the freezing point specification of jet fuel, but that a more petroleum gas fraction into aromatics-rich liquid products.
isomerised kerosene allows more and heavier material to be (h) Aqueous product. The alcohols in the LTFT aqueous
included.45 product can be recovered and co-refined if an appropriate oli-
(b) C15C22 distillate. In order to maximise the production of gomerisation technology has been selected.
kerosene, this fraction can be hydrocracked with the wax. A high
hydroisomerisation activity of the hydrocracking catalyst is
Jet fuel refinery design
critical to the refining of this fraction, which can easily be over-
cracked to naphtha. With a very isomerising catalyst, material up It does not require a complicated refinery design (Fig. 11) to
to C17/C18 can be included in the jet fuel, as illustrated by the produce jet fuel in high yield (Table 20) from LTFT syncrude.
Syntroleum S-5, whereas a low level of isomerisation limits The two main jet fuel components, namely branched paraffins
inclusion to C13/C14, as in the case of Sasol Slurry Phase Distil- and alkyl aromatics, are easily produced. However, in the
late derived kerosene.45 absence of a high-octane paraffinic base stock for motor-gasoline
(c) C11C14 kerosene. The same comments as for C15C22 production, the design in Fig. 11 yields an aromatic rich naphtha
distillate applies. This material should only be isomerised and not (Table 21) that is better suited for chemicals production than for
cracked. Although hydroisomerisation can be performed in fuels refining.
a hydrocracking unit, it is important that the feed be introduced A different refining approach is called for if both the jet fuel
closer to the bottom of the hydrocracking catalyst bed in order to and the motor-gasoline are to be on-specification products. This
reduce cracking losses. is a motor-gasoline refining challenge and changes in the refinery
(d) C9C10 naphtha. Mild hydroisomerisation is beneficial for design should focus on the production of high-octane paraffins.
this fraction, but not essential for the C9 naphtha. The same Analysis of the design in Fig. 11 shows that 68% of the jet fuel is
comments as for C11C14 kerosene applies and when the produced by hydrocracking. The kerosene yield from this unit
hydroisomerisation is performed in a hydrocracker, the feed dictates the aromatics requirement in order to meet the jet fuel
must be introduced close to the bottom of the catalyst bed. density and aromatics specifications. The other units that
(e) C6C8 naphtha. The two main technologies that can be produce aliphatic components for jet fuel are minor contributors.
considered are oligomerisation and aromatisation. In both Selecting different technologies for naphtha upgrading is there-
instances, the specific technology selection is important. The fore unlikely to cause a significant change in kerosene yield.
choice depends on the olefin content and aromatics deficiency of The same refinery design as shown in Fig. 10, but with
the refinery design. Oligomerisation technologies based on ASA a slightly different separation configuration, was employed with
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Table 22 Product distribution from the LTFT jet fuel refinery shown in
Fig. 12, which is very similar to the HTFT design in Fig. 10. The trans-
portation fuel yield is 76.6%

Product description (mass %) fuels (vol %)
hydrogen 0.0
methane 0.0
fuel gas 7.4
Fig. 11 Uncomplicated LTFT jet fuel refinery. motor-gasoline (EN228) 19.6 26.4
jet fuel (Jet A-1) 57.0 73.6
diesel fuel (EN590) 0.0 0.0
unrecovered organics 4.3
water 0.3
Table 20 Product distribution from the uncomplicated LTFT jet fuel
refinery shown in Fig. 11. The transportation fuel yield is 84.5% a

H-ZSM-5 was specifically developed for the conversion of LPG
hydrogen 0.5
into aromatics.)
methane 0.0
fuel gas 9.8
liquid petroleum gas 1.6 Diesel fuel refining
jet fuel (Jet A-1) 62.7 74.7 Fuel specifications
unrecovered organics 4.3 The sub-set of the EN590:2004 diesel fuel specifications pre-
water 0.3
sented in Table 24 highlight properties that can easily be related
a
Excludes H2, CO, CO2 and H2O from LTFT synthesis. to refinery design.
Table 23 Selected transportation fuel properties from the LTFT jet fuel
Table 21 Selected transportation fuel properties from the uncompli- refinery design shown in Fig. 12
cated LTFT jet fuel refinery design shown in Fig. 11
Motor-gasoline EN228 research octane number 95 95 min
research octane number 92 95 min motor octane number 88 85 min
motor octane number 84 85 min density at 15 C (kg m3) 744 720775
density at 15 C (kg m3) 807 720775 Reid vapour pressure 62 60 maxa
Reid vapour pressure 16 60 maxa olefin content (vol %) 2.9 18 max
olefin content (vol %) 9.1 18 max aromatic content (vol %) 34.2 35 max
aromatic content (vol %) 62.7 35 max oxygenate content (vol %) 0.0 15 max
oxygenate content (vol %) 0.0 15 max benzene content (vol %) 0.7 1 max
benzene content (vol %) 0.2 1 max Jet fuel Jet A-1
Jet fuel Jet A-1 density at 15 C (kg m3) 777 775840
density at 15 C (kg m3) 784 775840 aromatic content (vol %) 18.3 825
a
a
LTFT syncrude as feed. The resulting design (Fig. 12) was

sensitive to the routing of the C6 hydrocarbons from the
hydrocracker, but it was possible to produce a high yield of jet
fuel (Table 22) and achieve specification for both motor-gasoline
and jet fuel (Table 23). The vapour pressure of the motor-gaso-
line was a constraining property, since naphtha hydro-
isomerisation has been employed as the main source of
high-octane paraffinic motor-gasoline.
The transportation fuel yield of Fig. 12 was lower than that of
Fig. 11. This is mainly due to the production of LPG during
hydrocracking and the inability of non-acidic Pt/L-zeolite based
catalytic reforming technology to convert the LPG into Fig. 12 LTFT jet fuel refinery design similar to the HTFT jet fuel
aromatics. (Aromatisation technology based on metal promoted refinery design shown in Fig. 10.
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Directive 2009/30/EC23 that was published in June 2009,

amended some specifications. The limit on the polycyclic
aromatic content has been lowered to 8 vol% and the maximum
allowable fatty acid methyl ester (FAME) content has been
increased to 7 vol%. The most significant change in 2009/30/EC

for FischerTropsch refiners is the omission of a minimum
density limitation, as will become apparent from the subsequent
discussion.
The fuel specifications that ensure fuel compatibility with the
engine are generically similar in all countries, since these fuel
properties are determined by engine requirements, for example,
lubricity. The cold flow properties depend on the climate where
the fuel will be used. Fuel specifications that relate to emission
standards may differ considerably between countries, for Fig. 13 Effect of the FischerTropsch catalysts a-value on the yield of
C11C22 straight run distillate and C15C22 heavy distillate (the yield is
example, sulfur content.
based on C3 and heavier syncrude calculated from the Anderson-Schulz-
Flory distribution).
Carbon number distribution
The distillate range material that can be included in diesel fuel is
directly regulated through the maximum T95 boiling point, 24). This is a direct consequence of the high acyclic aliphatic
which determines the upper limit of the carbon number distri- hydrocarbon content of the FischerTropsch derived distillate.
bution (about C22). The lower limit is regulated only indirectly Acyclic aliphatic hydrocarbons in the distillate range have
and diesel fuel typically includes material in the C11C22 carbon densities of less than 800 kg m3 at 15 C. Density generally
number range. decreases with carbon number. Including FischerTropsch
The amount of straight run FischerTropsch syncrude in derived distillate in the kerosene range (C11C14), which typically
the distillate range is determined by the chain growth probability has a density of less than 770 kg m3, exacerbates the problem
(a-value) of the FischerTropsch technology employed with low density.13
(Fig. 13). LTFT syncrude contains significantly more straight
run distillate than HTFT syncrude. In this respect LTFT Composition
syncrude has an advantage over HTFT syncrude. The direct restrictions on diesel fuel composition (Table 24) has
The distillate range material can be maximised by cracking the little impact on FischerTropsch syncrude refinery design.
residue/wax fraction and oligomerising, alkylating or aromatis- Although HTFT distillate contains 2025% aromatics, these
ing the naphtha range material. However, these strategies may aromatics are mainly alkylated mononuclear aromatics,15 while
not all be practical. LTFT distillate contains essentially no aromatics. Fischer
In practice the lower carbon number limit of the Fischer Tropsch syncrudes are inherently sulfur free and FischerTropsch
Tropsch derived distillate that can be included in diesel fuel is derived products only contain sulfur when sulfur-compounds are
severely constrained by the minimum density requirement (Table added during refining. Hence the strong case for employing
unsulfided, rather than sulfided catalysts for hydroprocessing of
FischerTropsch syncrude.7
Table 24 Selected European EN590:2004 diesel fuel specifications for The composition of FischerTropsch derived diesel fuel is
temperate climates. Values for arctic climates are different mainly with
respect to cold flow properties, distillation range and density mainly determined by the need to satisfy both the minimum
density and minimum cetane number specifications. There exists
EN590:2004 specification a FischerTropsch density-cetane-yield triangle13,33 that governs
the yield-quality relationship during diesel fuel refining from
Fuel property minimum maximum
FischerTropsch syncrude. It has been pointed out that it is not
Direct restrictions on boiling range possible to produce on-specification EN590:2004 diesel fuel in
T95 boiling point ( C) 360 high yield from FischerTropsch syncrude, contrary to the
Indirect restrictions on boiling range
perceptions about the suitability of FischerTropsch technology
flash point ( C) 55 for maximum diesel fuel production. On a molecular level
Direct restrictions on composition FischerTropsch syncrude is unsuitable for EN590:2004 diesel
polycyclic aromatic content (vol %) 11 fuel production, although it is a good feed material for the
sulfur content (mg g1) 10
fatty acid methyl ester content (vol %) 5 production of high cetane number, low density distillate. The
Indirect restrictions on composition tremendous impact of directive 2009/30/EC with respect to the
cetane number 51 density requirements of diesel fuel is therefore clear.
cetane index 46 In a homologous series of hydrocarbons, density, viscosity and
viscosity at 40 C (cSt) 2.0 4.5
lubricity, wear scar diameter (mm) 460 cetane number increases with increasing carbon number.
cold filter plugging point ( C) +5 to 20a Conversely, cold flow properties become worse with increasing
a carbon number. Linear hydrocarbons have poor cold flow
properties, but this deficiency can be corrected by introducing
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Table 25 Combined hydroisomerisation-hydrotreating of straight run HTFT vacuum gas oil (VGO), which contains both distillate and residue (C10
C36) and heavy vacuum gas oil (HVGO), which is the heavier VGO fraction, but still contains 64% distillate. The operating conditions were 5 MPa and
liquid hourly space velocity of 0.5 h1, with the different operating temperatures being indicated. The different hydroisomerisation catalysts are indicated
Description HTFT hydroisomerisation-hydrotreating configurations, yields and product properties

Operating conditions
hydroisomerisation catalyst M/ZSM-5a M/ZSM-5a M/ZSM-5a NiMo/ASA NiW/zeo1a NiW/zeo2a PtMo/ASA PtMo/ASA PtMo/ASA
HTFT feed VGO VGO VGO HVGO HVGO HVGO HVGO HVGO HVGO
pre-hydrotreating T/ C 250 250 250 200b 200b
hydroisomerisation T/ C 350 360 370 370 370 370 390 390 390
post-hydrotreating T/ C 290 290 310 200b
Product yield structure
naphtha, <190 C (mass %) 26 30 36 25 30 47 16 9 12
distillate, 190360 C 59 54 51 70 65 53 74 78 82
(mass %)
residue, >360 C (mass %) 15 16 13 5 5 0 15 17 11
Distillate (190360 C)
properties
density at 20 C (kg m3) 817.4 821.6 832.1 820.1 814.5 806.5 829.0 828.8 824.3
cetane number 56 55 49 61 60 61 56 55 63
viscosity at 40 C (cSt) 2.34 2.34 2.36 2.71 2.46 2.32 2.83 2.86 3.07
lubricity, wear scar 486 488 363 458 422 357 340 330 414
diameter (mm)
cold filter plugging point ( C) 11 12 13 11
cloud point ( C) 14 27 64 9 10 10 15 12 9
T95 boiling point ( C) 363 358 353 333 325 319 325 334 326
a b
Metal promotor or zeolite support not disclosed by the different catalyst suppliers. Hydrotreating with low acidity PtPd/SiO2Al2O3 catalyst;
operating temperature not explicitly stated in conjunction with hydroisomerisation.
branching, which may have the added benefit of increasing the A detailed discussion on the molecular requirements for
density somewhat. Introducing branching, rather than obtaining diesel fuel and strategies to produce diesel fuel from Fischer
a specific degree of branching, is usually sufficient to improve the Tropsch syncrude has been presented in literature.13 The
cold flow properties of distillate. compound classes that are desirable from this point of view are
Straight run syncrude inherently has good lubricity, which is alkyl cyclo-paraffins and oxygenates. Diesel fuel quality is also
lost on severe hydrotreating. This may be corrected by reducing improved by co-producing jet fuel, but clearly at the expense of
the severity of hydroprocessing, or by making use of lubricity diesel yield, as indicated by the density-cetane-yield triangle.
additives. The strategies involving alkyl aromatics that were suggested for
jet fuel refining are not necessarily as applicable to diesel fuel
refining, since the accompanying decrease in the cetane number
HTFT diesel fuel refinery design
is difficult to offset.
The refinery designs presented for maximum motor-gasoline and
maximum jet fuel production, co-produced little if any diesel Technology selection
fuel. Only the HTFT motor-gasoline refinery shown in Fig. 4 was
able to co-produce on-specification diesel fuel. There are no commercially available refining technologies with
Distillate can be produced in high yield from HTFT syncrude the specific aim of increasing distillate density while retaining an
by oligomerisation of the olefin-rich gaseous (C3C4) and acceptable cetane number. This is less of a problem for refining of
naphtha (C5C10) fractions. The overall distillate yield may be HTFT syncrude, since the straight run distillate and residue
further improved by converting the aqueous product to olefins fractions possess sufficient density on account of their high
and cracking the HTFT residue. However, this only addresses aromatic content.
yield, not quality. (a) Distillate (C11C22) and residue (C23 and heavier). Some of
The FischerTropsch density-cetane-yield triangle suggests the hydroisomerisation-hydrotreating configurations that were
that diesel fuel yield and quality are intrinsically linked. Here the reported (Table 25)15 are able to produce on-specification diesel
challenge emerges. In crude oil refining the aim is to decrease fuel from HTFT syncrude. This is the only report in literature
distillate density and increase cetane number, which can be that shows how HTFT syncrude can be refined to EN590:2004
achieved by a combination of hydrodearomatisation (HDA) and
selective ring opening.46 These two effects are synergistic. In Most alkyl benzenes have densities around 860870 kg m3 and
a paraffinic distillate typically has a density around 770780 kg m3. In
FischerTropsch refining the aim is to increase the density, but order to meet the EN590:2004 minimum density specification of 820 kg
not at the expense of cetane number. These effects are opposing. m3, an equal volume blend is required. Unless the cetane number
When diesel yield is not maximised, it is possible to produce deficiency of the alkyl benzenes are less than the cetane number surplus
of the paraffinic distillate, the blend will not meet the EN590:2004
diesel fuel meeting EN590:2004 specifications by hydro-
minimum cetane number specification of 51. This is applicable to
isomerisation-hydrotreating of the HTFT distillate and residue distillates from olefin oligomerisation of HTFT and LTFT syncrude, as
fractions (Table 25).15 well as straight run and hydrocracking derived LTFT distillate.
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diesel fuel without resorting to blending or co-refining with Table 27 Selected fuel properties of some alkyl aromatics produced by
non-HTFT feed material. alkylation with C2C4 olefins
(b) C9C10 naphtha. The most efficient refining pathway for Density Cetane
this cut is to convert it into jet fuel. The C9 fraction only needs to Compound (kg m3)a number RON MON
by hydrotreated, while the C10 fraction can benefit from some

hydroisomerisation. This can be achieved by co-processing this ethylbenzene 874.4 8 107.4 97.9
m-diethylbenzene 868.3 9 >115 97.0
material with the heavier fraction. cumene 868.5 15 113 99.3
(c) C2C4 hydrocarbons and C5C8 naphtha. Technology p-cymene 860.7 2 110.5 97.7
selection for these fractions are determined by balancing two sec-butylbenzene 866.2 6 106.8 95.7
different objectives. The first objective is to produce additional tert-butylbenzene 870.7 1 >115 107.4
distillate range material that can be blended with the base stock a
Density at 15 C.
diesel fuel (Table 25) to increase diesel fuel yield while still
meeting diesel fuel specifications. For this purpose refining
technologies can be selected based on either the cetane number or
Diesel fuel refinery design
the density benefit. The second objective is to ensure that the
other fuel types are of sufficient quality to meet motor-gasoline The refining of diesel fuel from HTFT syncrude has the advan-
and jet fuel specifications. Judicious selection of technologies tage that the diesel fuel derived from hydroprocessing of the
that are also important for motor-gasoline and jet fuel produc- straight run distillate and residue fractions meets EN590:2004
tion from C2C8 material are therefore key to maximising diesel density and cetane number specifications. This attribute was
fuel yield without undermining the quality of the other trans- exploited to produce on-specification diesel fuel in the design
portation fuel types. These technologies are olefin oligomerisa- shown in Fig. 4.
tion and aromatic alkylation. The properties of the products Unless new refining technology is developed specifically for
from olefin oligomerisation depend on the catalyst and in some FischerTropsch syncrude to overcome the restrictions of the
instances on the feed (Table 26).14,47 The trade-offs are complex, density-cetane-yield triangle, or an external source of distillate is
since motor-gasoline and jet fuel quality do not necessarily go blended in, the FischerTropsch derived diesel yield can only be
hand-in-hand with diesel fuel quality. Furthermore, no oligo- increased by adding distillate that is deficient in either density or
merisation technology has a clear cetane number or density cetane number until the specification limit is reached. The
benefit. Aromatic alkylation products generally have good volume of distillate that can be blended increases as the deficient
motor-octane and jet fuel properties and have a consistently high property of the distillate is closer to the specification limit. The
density, but low cetane numbers (Table 27). Technology selection design of an HTFT diesel fuel refinery therefore relies heavily on
is consequently driven by the selection of the alkylating olefin. the application of the lever-rule for density and cetane number.
Alkylation with longer chain olefins are possible and should in For example, when cumene (Table 27) is employed to increase
principle improve the cetane number of the alkyl aromatics, but the density of H-ZSM-5 distillate (Table 26), it is not possible to
it is doubtful whether it would ever make economic sense to produce a blend that is not deficient in either density or cetane
synthesise linear alkyl benzenes (LABs) for use as diesel fuel number. Unless this deficiency can be offset against the diesel fuel
extenders. At best one may consider adapting standard aromatic base stock, this combination of technologies cannot be used to
alkylation technology for use with C5C6 olefins, which are the increase diesel fuel yield.
longest chain olefins with a low cracking propensity. There is consequently limited scope to increase diesel yield
(d) Aqueous product. The refining of the aqueous product is with the refining technologies that would typically be considered
mainly linked to the refining requirements for meeting motor- for HTFT refining (Fig. 14). Nevertheless, the base stock that can
gasoline and jet fuel specifications. be produced by different hydroprocessing configurations (Table
25) can be selected in such a way that a combination of H-ZSM-5
Table 26 Olefin oligomerisation technologies evaluated with HTFT
oligomers and alkyl benzenes can be blended in (Fig. 15). Co-
feed. Depending on the unit configuration, a distillate yield of around production of jet fuel is critical to the success of such a refinery
70% is possible design, since it reduces the density and cetane number deficiency.
Ethylene is beneficially employed for aromatic alkylation
Property ASA SPAa H-ZSM-5
(Fig. 15), which makes the propylene available for oligomerisa-
Technology attributes tion. In order to make use of the ethylene the gas loop includes
sensitivity to feed Moderate High Moderate cryogenic separation. Refining the aqueous product further
suitability for distillate Good Poor Good increases the availability of material for H-ZSM-5 oligomerisa-
feed range in C2C8 cut C3C8 C3C5 C3C8
Distillate properties tion and further improves the carbon efficiency of the design. The
density at 20 C (kg m3) 809-816 765 780801 C3 and heavier alcohols can either be used directly, or may be
cetane number 2837 34 5156 dried/dehydrated before use. The amount of heavy distillate from
viscosity at 40 C (cSt) 2.83.6 1.2 2.42.5 H-ZSM-5 oligomerisation contributes to the overall diesel yield
a
SPA oligomerisation with heavier feed materials have been evaluated, that can be obtained (Table 28).
but SPA is mechanistically poorly suited for the conversion of such The upgrading of the C5 naphtha is central to meeting the
feed and is very sensitive to the oxygenate content of the feed. The
motor-gasoline specifications, since the H-ZSM-5 derived
distillate properties are those reported for commercial operation with
C3C5 feed. naphtha has poor motor-gasoline properties compared to SPA
derived naphtha.47 The naphtha from hydroisomerisation and
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Table 28 Product distribution from the HTFT diesel fuel refinery shown
in Fig. 15. The transportation fuel yield is 68.7%

hydrogen 0.1
methane 12.7
fuel gas 6.3
jet fuel (Jet A-1) 15.0 21.8
water 1.6
imported FAME 0.9
Fig. 14 Density and cetane number relationship of different HTFT (-), a
LTFT (,) and coal liquid (O) derived distillates to indicate blending Excludes H2, CO, CO2 and H2O from HTFT synthesis.
opportunities for meeting EN590:2004 diesel fuel specifications. The
lever-rule applies and blends that meet specification will have connecting
lines that intersect the diesel fuel specification block.
included 5% FAME and that the design in Fig. 15 is dependent
on FAME in order to meet the diesel fuel specifications.xx
Although there are opportunities for further increasing the
diesel fuel yield, with presently available refining technology
these are limited mainly to blending with distillates from other
sources. There are two blending materials that have a natural fit
with HTFT technology, namely coal liquids and/or LTFT
syncrude.
In a coal-to-liquids (CTL) facility where synthesis gas is
generated from coal, some coal types are well matched with low
temperature gasification technology9,10 that co-produce liquids
from coal pyrolysis in the colder regions of the gasifier. When
these coal liquids are hydrotreated, as is industrially practised by
the Sasol Synfuels facilities, coal distillate of high density and
Fig. 15 HTFT refinery for maximising EN 590 : 2004 diesel fuel moderate cetane number is obtained.48 Although such hydro-
production. The design includes cryogenic separation in the Fischer treated coal distillate requires some cetane number improvement,
Tropsch gas loop, as well as aqueous product refining. All transportation it provides a significant density surplus for blending with low
fuels meet specifications.
density, high cetane material (Fig. 14).
In the original Sasol 1 design, HTFT and LTFT synthesis was
mild hydrocracking of the heavier fraction is likewise not a very combined within a single gas loop and the products were co-
good paraffinic motor-gasoline. The design therefore has scope refined.1 The LTFT derived distillate has a high cetane number,
for improvement, but it met all the transportation fuel specifi- but low density. This creates blending opportunities with both
cations (Table 29). It should be pointed out that the diesel fuel HTFT distillate and some refining technologies that are typically
be associated with FischerTropsch fuels refining (Fig. 14). It has
Table 29 Selected transportation fuel properties from the HTFT diesel been reported that such a combined HTFT-LTFT refinery are
fuel refinery design shown in Fig. 15 being considered for the new South African Mafutha CTL
facility,49 which is intended to produce mainly diesel fuel.
In gas-to-liquids (GTL) facilities, natural gas liquids may also
Motor-gasoline EN228 be employed as a high cetane number, low density blending
research octane number 96 95 min material, as is practised by PetroSA in their HTFT facility.1 The
principle is similar to HTFT-LTFT co-refining.
density at 15 C (kg m3) 751 720775
Reid vapour pressure 60 60 maxa In conclusion, without blending or the development of new
olefin content (vol %) 18.0 18 max technologies to convert FischerTropsch material into distillate
aromatic content (vol %) 34.8 35 max with adequate density and cetane number, little can be done to
benzene content (vol %) 0.4 1 max improve HTFT derived diesel fuel yield while meeting
Jet fuel Jet A-1 EN590:2004 specifications. The refinery design in Fig. 15
density at 15 C (kg m3) 777 775840
Diesel fuel EN590 xx The use of energy from renewable sources is actively being promoted
cetane number 51 51 min by governing bodies like the European Parliament through directives
density at 15 C (kg m3) 820 820845 such as 2009/28/EC. The mandated inclusion of oxygenated fuel
components derived from renewable sources will out of necessity have
a an impact on the design, operation and blending in fuels refineries. It
will also impose a dependence on an external supply of such materials.
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illustrates this limitation, although it also demonstrates that hydroisomerisation-hydrotreating of LTFT syncrude produces
some on-specification diesel fuel can be obtained from HTFT a distillate with low density (<780 kg m3) and high cetane
syncrude. This restriction on diesel fuel yield does not apply number (>70). The distillate base stock is consequently available
when the diesel fuel specification does not include a minimum in good yield, but requires densification to meet the
density specification. It has been shown that a distillate yield of EN590:2004 specifications.
4050% on total syncrude is possible with only oligomerisation Of the refining technologies that are commercially available,
and hydrocracking.13,50 only alkyl benzene synthesis in combination with jet fuel
production can potentially yield on-specification EN590:2004
LTFT diesel fuel refinery design LTFT diesel fuel (refer to Fig. 14, applying the lever-rule). This
requires the synthesis of sufficient aromatics and olefins for
Not a single LTFT refinery presented thus far (Fig. 6, 7, 11 and
aromatic alkylation. The final diesel blend would have to contain
12) was designed produced diesel fuel as a product. These were
around 4050% alkyl aromatics. The LTFT syncrude does not
deliberate design decisions that were motivated by the constraint
have sufficient naphtha range material for this and the technology
imposed by the FischerTropsch density-cetane-yield triangle.
selection must therefore take this deficiency into consideration.
This may seem surprising considering the commonly held
(a) Residue/wax (C23 and heavier). In all modern LTFT-based
perception that LTFT technology is ideally suited for diesel fuel
gas-to-liquids facilities, hydrocracking is employed for wax
production. This is unfortunately a consequence of the inter-
refining.1 The resulting distillate is a blending material for diesel
changeable colloquial use of the terms distillate (boiling range)
fuel. In order to produce on-specification EN590:2004 diesel fuel,
and diesel fuel (distillate meeting legislated fuel specifications).
the volume of LTFT distillate must be balanced with the volume
Producing a high yield of distillate from LTFT syncrude is not
of alkyl aromatics that is required to meet both diesel fuel and jet
difficult. It has been shown that a distillate yield of 6070% on
fuel specifications. Fluid catalytic cracking (FCC) of the wax is
a total syncrude basis is achievable with only two conversion
consequently preferred over hydrocracking, because it generates
units, oligomerisation and hydrocracking.13 In order to produce
olefins for alkylation and sufficient naphtha for aromatisation.
EN590:2004 compliant diesel fuel in high yield, the challenge is to
When the minimum density specifications for diesel fuel is less
meet the quality requirements of the distillate. In this respect it is
demanding, the FCC can be operated at lower severity, or
necessary to increase the density of the distillate without
hydrocracking can be considered for some or all of the C23 and
decreasing the cetane number too much.
heavier material.
On a molecular level the compound classes that will result in
(b) C11C22 distillate. The straight run distillate has to be
improved density are cyclo-paraffins, oxygenates and alkyl
hydroisomerised to improve its cold flow properties and
aromatics. Of these, the alkyl aromatics are the least preferred,
stability. The isomerised C15C22 fraction then forms the
due to its negative impact on the cetane number of the resulting
distillate base stock for diesel fuel production, while the C11
diesel fuel blend. The refining strategies that were suggested to
C14 fraction forms the base stock for jet fuel production. Mild
meet EN590:2004 diesel fuel specifications in many instances
hydrocracking can also be considered, with some of the lighter
require technology development or blending with non-Fischer
waxy material being co-fed. Mild hydrocracking is especially
Tropsch feed materials:13
attractive when the refinery design targets diesel fuel specifica-
(a) Cyclo-paraffin synthesis. Not a commercial technology
tions that is less restrictive in terms of minimum density
from LTFT syncrude.
requirements.
(b) Alkyl benzene synthesis. Requires aromatics that have to
(c) C9C10 naphtha. This cut can be hydroisomerised with the
be produced in the refinery. Alkylation with longer chain olefins
straight run distillate to form part of the base stock for jet fuel
is preferred to reduce the cetane number penalty. Yet, it is
production. Depending on the choice of aromatisation tech-
unlikely that linear alkyl benzene synthesis can be justified for
nology, this cut may also be employed as feed for the catalytic
fuels use.
reformer.
(c) Alcohol recovery and conversion. Alcohols and ethers can
(d) C6C8 naphtha. The preferred aromatisation technology is
be used as diesel fuel extenders,51 but have insufficient density to
non-acidic Pt/L-zeolite based catalytic reforming and this is an
meet EN590:2004 specifications.xx
ideal feed for conversion into aromatics. The high benzene
(d) Jet fuel production. This comes at the expense of diesel fuel
selectivity from C6 naphtha is beneficial, since it facilitates alkyl
yield, but helps to improve the density and cetane number of the
benzene production. The volume of straight run naphtha is
distillate base stock.
augmented by the C6C8 products from wax cracking.
(e) Oligomerisation. This has little value for LTFT diesel fuel
(e) C5 naphtha. The refining pathway will be dictated mainly
production, since it exacerbates the quality problem.
by motor-gasoline refining needs. Etherification of the branched
(f) Co-refining of pyrolysis liquids. Only an option in a coal-to-
pentenes from fluid catalytic cracking of wax is a preferred
liquids facility with low temperature coal gasification.
technology. It not only produces a high-octane motor-gasoline
(g) Biofuel addition. Beneficial, but like all blending solutions,
blending component, but also a C5 raffinate rich in n-pentenes,
it requires access to a non-FischerTropsch feed.xx
which may be beneficially employed as alkylating olefin for alkyl
benzene production. The remainder of the C5 fraction can be
hydroisomerised to produce a high-octane motor-gasoline
Much of the discussion on technology selection for diesel fuel component.
refining from HTFT syncrude also applies to LTFT syncrude. (f) C3C4 hydrocarbons. The C3C4 olefins are useful for the
The main difference is that the combined hydrocracking- production of alkyl benzenes. Although cumene and butyl
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Table 31 Selected transportation fuel properties from the LTFT diesel

fuel refinery design shown in Fig. 16

research octane number 95 95 min
density at 15 C (kg m3) 739 720775
aromatic content (vol %) 24.3 35 max
benzene content (vol %) 0.7 1 max
Jet fuel Jet A-1
density at 15 C (kg m3) 775 775840
Fig. 16 LTFT refinery to maximise EN 590 : 2004 diesel fuel, producing
Diesel fuel EN590
on-specification motor-gasoline, jet fuel and diesel fuel (recovery of cetane number 51 51 min
methanol from aqueous product not shown). density at 15 C (kg m3) 820 820845
a
benzenes have low cetane numbers, they can be blended into
diesel fuel to increase the diesel density. These alkyl aromatics are
also useful as high-octane motor-gasoline and jet fuel compo-
nents. The preferred refining pathway for C3C4 olefins is employing the C11C14 kerosene fraction as jet fuel component
consequently aromatic alkylation. Depending on the refining and not for diesel fuel. By doing so, the base stock quality
needs, some of the olefins can be oligomerised with an appro- was sufficiently improved to allow blending of high density,
priate technology. low cetane number alkyl aromatics. Only a narrow range of
(i) Aqueous product. The C1C2 alcohols in the LTFT blending ratios allowed the production of diesel fuel. Normally
aqueous product can be recovered and used as feed for C5 this would undermine refinery flexibility, but the alkyl
etherification. aromatics were selected for their compatibility with the other
transportation fuel types. Flexibility is thus retained, since
Diesel fuel refinery design fluctuations in the LTFT distillate to alkyl benzene ratio can
be absorbed by blending more or less alkyl benzene into the jet
When there is no lower limit on the density of diesel fuel, fuel or motor-gasoline.
maximum diesel fuel can be produced by employing only The diesel fuel yield (Table 30) is less than that of the other
hydrocracking and oligomerisation. However, such a design does transportation fuel types, but more than was obtained with the
not yield on-specification motor-gasoline or jet fuel. The design HTFT design in Fig. 15 (Table 28). This indicates that LTFT
challenge is to produce on-specification fuels, which requires at syncrude is somewhat better suited for maximum diesel fuel
least some aromatics production in order to meet jet fuel speci- production than HTFT syncrude, even though the straight run
fications. Refinery complexity will further increase in order to LTFT distillate does not meet EN590:2004 specifications. All
meet motor-gasoline specifications. transportation fuels were on-specification (Table 31), but it
The design in Fig. 16 has been devised to meet the EN590:2004 should be pointed out that the diesel fuel included 5% FAME
diesel fuel specifications that has a minimum density requirement and that some imported methanol was needed to produce fuel
of 820 kg m3 (Table 24). The quality of the low density, high ethers (TAME).
cetane number LTFT distillate was further improved by Further improvements in LTFT diesel fuel refinery design can
be made by balancing the distillate and alkyl benzene produc-
tion. However, for diesel fuels where there is no minimum density
Table 30 Product distribution from the LTFT diesel fuel refinery shown
in Fig. 16. The transportation fuel yield is 86.0%
specification, or a less stringent minimum density requirement,
the diesel fuel yield can be increased dramatically. This can be
Total producta Transportation achieved by splitting the wax feed and hydrocracking some of the
Product description (mass %) fuels (vol %) wax instead of converting all wax by fluid catalytic cracking.
Nevertheless, the basic refinery design elements remain the same.
hydrogen 0.8
methane 0.0
fuel gas 8.0 Discussion
motor-gasoline (EN228) 32.8 39.9 Capital cost
jet fuel (Jet A-1) 28.4 33.0
diesel fuel (EN590) 24.8 27.2 In a FischerTropsch facility, the refinery is only part of the
overall process. The refinery constitutes only 1015% of the total
water 0.3
imported methanol 0.3 capital cost. Capital cost savings in the refinery design of
imported FAME 1.2 a FischerTropsch facility have a minor impact on the overall
a
project cost. Clever designs to save cost at the expense of
operability, flexibility, efficiency or product quality are
View Article Online
Table 32 Benefit-cost analysis of investments in FischerTropsch and crude oil refining. The refinery cost is expressed as a fraction (x) of the total cost
of feed-to-syncrude conversion (C). The feed (z) and product (y) prices are expressed in terms of the crude oil price (B)
Cost Benefit Incremental D(Benefit)/D(Cost)

Investment FT crude FT crude FTa crude
Nothing 0 0
No refinery C 0 (1 z)$B 0 (1 z)$B/C
Refinery (1 + x)$C x$C (y z)$B (y 1)$B (y 1)$B/x$C (y 1)$B/x$C
a
For the overall FischerTropsch facility relative to no investment the incremental D(Benefit)/D(Cost) (y z)$B/(1 + x)$C.
consequently misguided. To put this another way, 8590% of the reformer. Depending on the tail gas composition it may be
capital cost in a FischerTropsch facility is required to transform employed either as reformer feed, or as fuel gas.
the carbon source (natural gas, coal, biomass, waste) into Since the gas loop determines the extent of H2 and methane re-
synthetic crude oil. Saving capital cost in the refinery design at use, refining efficiency cannot be completely decoupled from gas
the expense of carbon efficiency has to be offset against the loop design. In order to establish at least some reasonable basis
capital cost that was required to produce that carbon in the for comparison, the yield of transportation fuels from the
syncrude. This is a very different situation to crude oil refinery different refinery designs have been expressed on a hydrogen-
design, where the total capital cost of the facility is that of the and methane-free basis when the gas loop includes cryogenic
refinery. Engineering decisions in FischerTropsch refining must separation (Table 33). Irrespective of whether cryogenic sepa-
take cognisance of this difference. ration forms part of the gas loop or not, all designs generated
To illustrate the point, it is useful to refer to benefit-cost some fuel gas and its potential beneficial effect has not been taken
analysis theory.52 Benefit-cost analysis (Table 32) of Fischer into account in the same way.
Tropsch and crude oil refining indicates that the same incre- From Table 33 it is clear that HTFT syncrude refineries require
mental benefit-cost relationship applies to both refinery types if both cryogenic separation and aqueous product workup to ach-
the investment in syncrude production is disregarded, but not ieve good carbon efficiency. In this respect refining of LTFT
when the total project is considered. syncrude has an inherent benefit. Purely on a transportation fuel
The same principle can be employed to express the refinery yield basis, it seems that LTFT syncrude has better refinery carbon
capital cost that can be justified as fraction of the capital cost of efficiency than HTFT syncrude. However, this does not take the
FischerTropsch based feed-to-syncrude conversion. It is the energy efficiency of the conversion units into account. Conversion
ratio of the benefit obtained during refining (price difference units that are energy demanding may reduce the overall carbon
between transportation fuel and crude oil) and the benefit efficiency. Likewise, the separation complexity implied by each
obtained during syncrude production (price difference between refinery design may have an impact on the overall carbon effi-
crude oil and raw material, e.g. coal). ciency. Furthermore, the yield of transportation fuels should not
be confused with the overall product yield, since products such as
Carbon efficiency liquid petroleum gas have not been reported in Table 33.
During the discussion of individual refinery designs, reference

HTFT versus LTFT
has been made to carbon efficiency and the importance of the gas
loop design. Since the carbon efficiencies of the refinery designs Technologies and commercial facilities for HTFT and LTFT
are dependent on the gas loop designs, a quantitative analysis of have co-existed for many decades and there is no historic pref-
the refinery designs in isolation was not justified. erence for any particular FischerTropsch technology. The
Qualitatively, three aspects related to the carbon efficiency thermal efficiencies of various FischerTropsch based feed-to-
can be highlighted: the refinery H2 consumption, recovery and syncrude gas loop designs were calculated, with values ranging
use of the aqueous product and the impact of gas loop design from 46.1 to 53.3% being reported.11 There was overlap between
on tail gas (H2, CO, CO2, H2O and C1C2 hydrocarbons) HTFT and LTFT based technologies and consequently not
recovery and use. The per pass synthesis gas conversion during a clear preference for either based on syncrude production alone.
FischerTropsch synthesis is also important, but with a gas It can be stated that with proper design, a transportation fuel
loop design involving recycle, the overall CO conversion is yield in the region of 1.01.1 m3$t1 syncrude is realistic for both
generally high. HTFT and LTFT. However, the present work is not detailed
About 30% of HTFT syncrude and around 10% LTFT syn- enough to confidently discriminate between the efficiencies of
crude are contained in the aqueous product and tail gas. In closed HTFT and LTFT based fuels refineries.
gas loop designs, most of the tail gas can be recycled and From a transportation fuels perspective some refining prefer-
reformed to synthesis gas. Some tail gas is purged to get rid of ence can be indicated, but the preference is dependent on the
inert gases and the conversion of the remainder of the tail gas is main refining objective. HTFT syncrude yields a better quality
subject to the same carbon losses as natural gas reforming for motor-gasoline than LTFT syncrude for the same refining effort.
gas-to-liquids applications. In open gas loop designs, tail gas Conversely, it is easier to refine LTFT syncrude to jet fuel than
recycling is restricted by the feed and product requirements of the HTFT syncrude. In all instances the differences are not huge.
Table 33 Summary of fuels refinery designs and yields, taking the impact of FischerTropsch gas loop on recycling of hydrogen and methane into account. The influence of imported fuel chemicals,
such as methanol, ethanol and FAME have also been reported
Conversion units Transportation fuel yield on total syncrude basisb Import/exportc
1202 | Energy Environ. Sci., 2011, 4, 11771205

total
gasoline jet fuel diesel H2 chemicals
a
Refinery design total units unit types Cryogenic separation Aqueous product work-up (mass %) (m3$t1) (m3$t1) (m3$t1) (m3$t1) (mass %) (mass %)
Motor-gasoline
HTFT, Fig. 4 10 8 Yes Yes 84.7 1.12 0.79 0.24 0.10 0.0 0.0
HTFT, Fig. 5d 6 5 No No 60.0 0.80 0.61 0.17 0.02 0.2 0.0
LTFT, Fig. 5d 6 5 No No 36.5 0.48 0.13 0.18 0.17 0.0 0.0
LTFT, Fig. 6d 7 6 No No 81.4 1.07 0.67 0.40 0.00 0.9 0.0
LTFT, Fig. 7 8 7 No Yes 85.7 1.13 0.83 0.33 0.00 0.4 1.7
Jet fuel
HTFT, Fig. 9 8 8 Yes Yes 79.5 1.01 0.26 0.76 0.00 0.1 0.0
HTFT, Fig. 10 6 5 No No 61.2 0.80 0.24 0.55 0.00 0.1 0.0
LTFT, Fig. 11d 4 4 No No 84.5 1.07 0.27 0.80 0.00 0.5 0.0
LTFT, Fig. 12 6 5 No No 76.6 1.00 0.26 0.73 0.00 0.0 0.0
Diesel fuel
HTFT, Fig. 15 8 7 Yes Yes 77.9 1.02 0.53 0.22 0.25 0.1 0.9
LTFT, Fig. 16 8 7 No No 84.8 1.11 0.44 0.36 0.30 0.8 1.5
a
When two units perform the same task and can theoretically be combined into a single unit, it is considered a single unit type, for example hydrogenation of naphtha and olefins. Partial hydrogenation
and complete hydrogenation are seen as different unit types, since it cannot be combined in the same unit. b Transportation fuel yield is calculated on methane- and hydrogen-free basis when cryogenic
separation is employed, since it allows complete recycle in the FischerTropsch gas loop. The use of fuel gas for reforming is possible in all designs. c Import into the refinery is negative and export is
positive. d Non all transportation fuels were on-specification.
This journal is The Royal Society of Chemistry 2011

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Chemicals, co-refining and blending treated as a wastewater, the CO2 footprint is large, because every
carbon atom that is not refined to a final product is equivalent to
Chemicals production, co-refining and blending of other fuel
three times its carbon content in CO2 emissions (due to the
types (apart from FAME), have not been explored, although
carbon efficiency of indirect liquefaction).12 Refining pathways
some benefits have been pointed out. In many instances there

for dealing with the aqueous product have been suggested.30 The
are synergistic effects. Some literature on this subject can be
unrecovered oxygenates (mainly carboxylic acids) can be con-
found4,5 and exploring these possibilities is a topic in its own
verted by aerobic biological degradation, or in anaerobic
right. It will suffice to mention that in many instances it is
digesters to produce methane, as is applied at the PetroSA HTFT
possible to improve the efficiency of refinery designs when
refinery. Finding an efficient refining pathway for carboxylic acid
chemical co-production, co-refining and blending of imported
recovery from a dilute aqueous medium is one of the main
materials are considered. In real-world refinery designs, these
environmental challenges associated with FischerTropsch
opportunities will be exploited.
refining.
(c) Gaseous waste. Overall, most of the gaseous waste from
Waste treatment a FischerTropsch based indirect liquefaction process comes
As with any production process, the production of fuels and from synthesis gas generation and FischerTropsch synthesis.
chemicals in a FischerTropsch based facility is associated with Volatile metals, S and N compounds need to be captured by
the co-production of some waste. An overview of the nature of appropriate gas cleaning technologies. The large CO2 footprint is
the waste products was given by Dry.53 inherent of indirect liquefaction. With proper design, the
Two of the major products from indirect liquefaction by FischerTropsch refinery is a small contributor to the overall
FischerTropsch synthesis are H2O and CO2. This is a natural gaseous waste. Refinery emissions can be of the same order or
consequence of synthesis gas based chemistry, where synthesis less than in a conventional crude oil refinery, because a Fischer
gas generation, water-gas-shift and FischerTropsch synthesis Tropsch refinery is not burdened with S and N containing
reject H2O and CO2 to drive liquefaction: compounds. This requires proper selection of catalysts,8 in order
to avoid the on-purpose introduction of sulfur in the refinery.
2 C + 2 H2O + O2 / (CH2) + H2O + CO2 + 180 kJ Most of the potential refining wastage comes from the syncrude
recovery section, which forms part of the FischerTropsch gas
It should be clear that little can be done to prevent H2O and loop. If there is no light gas recovery, the lighter gaseous product
CO2 as major by-products from FischerTropsch based facilities. becomes a fuel gas stream, with a very high associated CO2
In addition to these products, other heteroatoms and metals that footprint (as discussed before).
may be present in the raw material (e.g. S, N, Hg and mineral
matter) will also be liberated. The waste treatment associated
Conclusions
with FischerTropsch based facilities must therefore deal with
three categories of waste: Guidelines were provided for FischerTropsch refinery design to
(a) Solid waste. Solid waste produced during gasification is maximise the production of on-specification transportation fuels:
related to the raw material used. The waste may be in the form of motor-gasoline (EN 228 : 2004), jet fuel (DEFSTAN 91/91 Issue
an ash or slag depending on the gasifier type and disposal is 6) and diesel fuel (EN 590 : 2004). For each fuel type the fuel
analogous to that in the power generation industry. There is also specifications were related to the molecular property require-
solid catalyst waste. Deactivated iron-based FischerTropsch ments. The carbon number distribution and composition
catalyst can be disposed via landfill or reused for catalyst requirements were translated into technology selection and
production, but deactivated cobalt-based catalysts are poten- refinery design strategies. These were illustrated by the devel-
tially harmful to the environment and the metals must be opment of refinery designs for the upgrading of high temperature
recovered from the deactivated catalyst.54 The fate of refining FischerTropsch (HTFT) and low temperature FischerTropsch
catalysts is similar to that in conventional crude oil refineries, (LTFT) syncrudes. Some of the main points are:
where catalysts are regenerated and reused, or disposed of. (a) Transportation fuel refinery designs for both HTFT and
FischerTropsch refining technologies should be selected to LTFT syncrude were presented with a volumetric motor-gasoline
minimise the solid waste. Refining catalysts can also be selected selectivity of better than 70%. The motor-gasoline yields were
based on their environmental footprint. For example, solid better than 50% on a total syncrude mass basis.
phosphoric acid has a very low environmental footprint and the (b) As in the case of crude oil, the refining of FischerTropsch
spent catalyst can be reused as fertiliser in agricultural applica- syncrude to on-specification motor-gasoline requires more
tions.55 The onus is on the refinery design engineer to select conversion units than are required for the production of other
catalysts and technologies responsibly to minimise refinery transportation fuel types.
waste. (c) HTFT syncrude yields a better quality motor-gasoline than
(b) Liquid waste. The liquid waste products are dominated by LTFT syncrude for the same refining effort.
wastewater produced during synthesis gas generation and (d) Fe-LTFT technology is better suited for motor-gasoline
FischerTropsch synthesis. Wastewater from synthesis gas refining than Co-LTFT technology.
generation, such as gas liquor from coal gasification, can be used (e) Deactivation of Fe-LTFT catalysts causes a selectivity
as source of chemicals, the remainder being an industrial change in the syncrude production that is actually beneficial for
wastewater stream. The FischerTropsch aqueous product forms transportation fuel production. The same does not hold true for
part of the syncrude (Table 1). Although this fraction can be the deactivation of Co-LTFT catalysts.
View Article Online
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FischerTropsch fuels refinery design

syncrude is refined to a blending stock and chemicals only, rather

Table 2 Selected European EN228:2004 motor-gasoline specifications

Fuel property minimum maximum

Direct restrictions on boiling range

Carbon number distribution

The carbon number range of motor-gasoline is directly and

Table 3 Research octane numbers of selected C3C8 paraffins Technology selection

(f) C7 naphtha. In syncrude, like in crude oil refining, this is the

based technology is considered. Due to its cracking propensity

Product description (mass %) fuels (vol %) Motor-gasoline EN228

Considering that the refinery cost is typically only 1015% of the

LTFT motor-gasoline refining

Fuel property Refinery product Specification

Fig. 6 LTFT motor-gasoline refinery based on an HTFT design (Fig. 5),

FischerTropsch derived components. In addition to the

maximum jet fuel, aromatisation over a non-acidic Pt/L-zeolite

(f) C7C8 naphtha. The inclusion of C7C8 naphtha in jet fuel

Fig. 10 HTFT jet fuel refinery without cryogenic separation and

Total producta Transportation Total producta Transportation

hydrogen 0.1 hydrogen 0.1

Motor-gasoline EN228 fractions is paraffinic. It is therefore better to consider aromati-

Total producta Transportation

Product description (mass %) fuels (vol %)

Total producta Transportation

LTFT syncrude as feed. The resulting design (Fig. 12) was

Directive 2009/30/EC23 that was published in June 2009,

increased to 7 vol%. The most significant change in 2009/30/EC

Description HTFT hydroisomerisation-hydrotreating configurations, yields and product properties

by hydrotreated, while the C10 fraction can benefit from some

Total producta Transportation

Table 31 Selected transportation fuel properties from the LTFT diesel

Fuel property Refinery product Specification

Cost Benefit Incremental D(Benefit)/D(Cost)

Investment FT crude FT crude FTa crude

During the discussion of individual refinery designs, reference

Conversion units Transportation fuel yield on total syncrude basisb Import/exportc

1202 | Energy Environ. Sci., 2011, 4, 11771205

This journal is The Royal Society of Chemistry 2011

some benefits have been pointed out. In many instances there

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