RECENT DEVELOPMENTS I N SASOL FISCHER-TROPSCH TECHNOLOGY

MARK E DRY
R & D DEPARTMENT
P 0 BOX 1
SASOLBURG 9570
REPUBLIC OF SOUTH AFRICA
When considering improvements i n the Fischer-Tropsch (FT) route f or producing
l i qui d fuels from coal, it i s important t o bear i n mind the rel ati ve costs o f
the various process steps. An approximate cost breakdown f or a typi cal plant i s
as follows:
Synthesis gas production 58 %
FT synthesis 18 % (pl ant 15 %; Catalyst 3 %)
Product separation 12 %
Refinery 10 % ( ol ef i n oligomerization 4 %)
Diverse 2 %
The advantage of a bi g improvement i n the s el ecti vi ty of the FT synthesis (an
ideal case would be one which only produces gasoline and diesel f uel ) i s that
thi s would lower the costs o f both the product separation and the refi nery
sections, which, together account f o r 22 % of the total . Obvious provisos,
however, are that the cost of the catal yst should not be markedly increased and
that i t s conversion acti vi ty should remain high otherwise the gains i n say the
refi nery would be negated by increased FT synthesis costs. El i mi nati on of
certai n products do not necessarily improve the economics. If the FT process
made no ethylene, the expensive cryogenic separation uni t could be replaced by a
cheaper process but thi s would not be a real gain as the market value of
ethylene rel ati ve t o that of l i qui d fuel s j us ti f i es i t s recovery. A si mi l ar
si tuati on holds f o r the alcohols and ketones produced i n the FT process. I f
these products were absent then the expensive process of f i r s t recovering them,
from .;he FT water and then ref i ni ng them would si gni fi cantl y lower the overal l
costs. (Note that these products would have to be completely absent and not j ust
lowered as the l atter would have l i t t l e impact on the economics of recovery as
the volume of water to be processed would remain unchanged.) These low molecular
mass alcohols and ketones, however, s el l at high prices and fur:hermore the
alcohols are valuable as gasoline octane boosters. Thus the production and
recovery of these components are j us ti f i ed.
A t Sasol -the aniount of methane produced f ar exceeds the need o f the l ocal fuel
gas market and so the CH i s reformed wi th steam and oxygen t o yi el d H and CO
which i s recycled to d e FT synthesis uni ts. This reforming i s o? course
thermally i nef f i ci ent and resul ts i n a (about 14 %) loss of hydrocarbon produced
from the reformed CH4. I n the Sasol process the bulk of the CH4 comes not from
Fischer-Tropsch but from the Lurgi coal gasi fi cati on process and so to eliminate
CH4 reforming would require an al ternati ve gasi fi cati on process. Confining the
issue to only the FT process, if a zero C1 to C3 sel ecti vi ty could be achieved
wi th only gasoline and diesel fuel being produced, it i s estimated that the
overal l cost of the process could be cut by about 5 %- Because the capi tal
outlay for a bi g commercial pl ant i s huge, the 5 % saving i s very si gni fi cant-
To date, however, the attainment o f a bi g improvement i n the FT s el ecti vi ty has
been an el usi ve goal. A l l the proposed mechanisms o f the reacti on involve the
concept of stepwise addi ti on o f si ngl e carbon enti ti es t o the growing
hydrocarbon chains on the catal yst surface ( 1) . This i nevi tabl y leads to a wide
di s tri buti on of products. By manipulating the catal yst's formulation and/or the
process conditions the probabi l i ty of chaingrowth can be varied but the resul t
i s simply that i f the production of C1 to c3 hydrocarbons 1s lowered the
(coal gasi fi cati on 53 %; CH4 reforming 5 %)
(cryogenic 4 %; Alcohols & ketones 4 %)
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production of the products heavier than di esel fuel i ncrease. The maximum of the
sum of gasol i ne plus di esel fuel l i es in the vi ci ni ty of 60 % ( 1) . To improve on
thi s appears to requi re ei ther a new kind of catal yst with a di f f erent mechanism
or to superimpose some secondary catal yti c acti on such as ol ef i n ol i gomeri zati on
and/or wax cracking.
To date Sasol has excl usi vel y used i ron based catal ysts in the FT process not
only because iron i s cheap but al so because the products are ri cher i n ol ef i ns
than those normally produced by other metals acti ve i n the FT reacti on. The
l i ghter, C to C , ol ef i ns are readi l y oligomerized to ei ther gasol i ne or di esel
thus gi vi n6 the $vera11 process a high degree o f f l exi bi l i ty regarding the rati o
of gasol i ne to di esel fuel produced. A major drawback of i ron catal ysts at
temperatures above say 270 "C i s that carbon deposi ti on occurs. This, f or mainly
mechanical reasons (eg, di si ntegrati on of the parti cl es) resul ts in shorter
reactor on-l i ne times which means both a higher catal yst consumption rate and
more reactors requi red per uni t of gas converted. A t the temperatures at which
metals l i ke cobal t or ruthenium are acti ve i n the FT synthesi s, very l i ttl e
carbon i s deposited and so these metals have attracted attenti on as al ternati ve
catal ysts. On a uni t mass basi s the cost of cobal t i s about 250 times that of
the i ron used at Sasol while t hat o f ruthenium i s about 20 000 times that of
i ron. To make coba1.t competitive wi t h i ron, a much lower mass per volume of
catal yst wi l l have to be employed, the catal yst l i f e wi l l have to be longer
(with i ts acti vi ty and sel ecti vi ty as good or better than that of i ron) and the
spent catal yst wi l l have t o be regenerated f or re-use. While these obj ecti ves
may well be met with cobal t, the case f or ruthenium i s bleak. Putti ng asi de the
pri ce, i t can be shown that f or only a si ngl e Sasol commercial pl ant one would
requi re more than the enti re avai l abl e world stock of ruthenium to produce the
needed catal yst charge which would only contai n 0,5 mass % of Ru on a typi cal
support. The production of Ru and other noble metals such as Rh, i s enti rel y
linked to the demand f or P t -
While Sasol remains committed to developing catal ysts with longer l i ves and
improved sel ecti vi ti es these obj ecti ves are seen as longer termed. In the short
term i nvesti gati ons have concentrated on i ncreasi ng the production per reactor,
developing lower cost reactors and optimizing the product spectrum by improving
the processes downstream of the FT reactors. Several of these new developments
are in the process of bei ng commercialized.
Ki neti c inves.Ligations had i ndi cated and pi l ot pl ant tests had confirmed that
f or both fi xed bed tubul ar and fl ui di sed bed reactors the production per uni t
volume of catal yst could be rai sed by simultaneously i ncreasi ng the operati ng
pressure and the volume of feed gas thus maintaining a fi xed l i near vel oci ty, i e
a fi xed residence time i n the reactors ( 1) . Sasol recentl y decided to bui l d an
addi ti onal commercial fi xed bed tubul ar r<actor.to i ncrease the production of FT
waxes. This reactor wi l l operate at a pressure consi derabl y higher than the
reactors currentl y i n use.
The Synthol reactors, which are the "work horses" of the Sasol FT process, are
ci rcul ati ng fl ui di zed bed (CFB) types with catal yst flowing down a standpi pe on
one si de and up a ri ser on the other si de (see Figure 1 ) . These uni ts are
al ready very l arge and there are doubts whether .they could be scal ed up f urther
by ei ther i ncreasi ng thei r diameter or rai si ng the operati ng pressure. As an
al ternati ve Sasol has been i nvesti gati ng f or some time the fi xed f l ui di zed bed
(FFB) system. I n thi s reactor the catal yst i s not ci rcul ated but remains
"stati onary" as an ebul ati ng bed with the gas enteri ng at the bottom. This
reactor i s considerably smal l er and so should be cheaper to construct, si mpl er
to operate and i ncreasi ng the operati ng pressure presents no mechanical
problems. An addi ti onal advantage of higher pressure in the case of i ron
catal ysts operating at high temperatures i s that the rate of carbon deposi ti on
on the catal yst decreases ( 1) which f or the reasons already mentioned, should
resul t in longer l i f e catal y?ts. A demonstration FFB uni t has been operati ng at
the Sasolburg pl ant f or some time and vari ous design aspects have been
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investigated. The design of a l arge commercial si ze uni t i s currentl y underway
for cost estimating purposes and hopefully f or implementation i n the near
future.
Another reactor version being investigated i s the sl urry phase reactor. I n
concept thi s i s s i mi l ar to the FFB reactor but the f i nel y divided catal yst i s
suspended i n a sui tabl e l i qui d, eg molten FT wax. Compared to the fi xed bed
reactor it i s cheaper t o construct and because of thi s it may be a viable
al ternati ve process f or producing FT waxes. A potenti al advantage of the sl urry
phase system i s that wi th i ron catal ysts it can operate i n the temperature range
260 t o 290 "C. I n thi s temperature region a fi xed bed would plug up due t o
carbon deposition whi l e a "dry" fl ui di zed bed would "defl ui di ze" because of
catal yst parti cl e agglomeration due t o wax formation. To date the experimental
investigations a t Sasol have been confined to 5 cm ID pi l o t pl ant reactors. The
nex t planned phase i s the construction of a l arger pi l ot reactor i n order to
investigate the system at hydrodynamic conditions l i kel y t o exi st i n a
commercial scale reactor.
With regards t o process improvements downstream of the FT reactors two catal yti c
processes are being developed. FT waxes produced a t low temperatures are
essenti al l y straight-chained containing no aromatics and are sulphur and
nitrogen-free. Because of these factors the wax can be hydrocracked under
rel ati vel y mi l d conditions io yi el d up to 80 % o f high qual i ty diesel fuel .
These resul ts have been independantly veri fi ed by fi rms speci al i zi ng i n
hydrocracking and no problems are foreseen i n commercializing the process.
Li ght ol ef i n oligomerization to gasoline and di esel fuel has been commercially
practiced by Sasol f o r many years but the process which uti l i z es a supported
phosphoric acid catal yst produces a l i ght diesel fuel which has a lowish
vi scosi ty and a very poor cetane number, the l atter being due t o the high degree
of skeletal branching. Because of thi s the amount o f thi s fuel which can be
added t o the overal l pool i s l i mi ted and so res tri cts the f ul l uti l i z ati on of
ol ef i n oligomerization t o maximise diesel fuel production. The- new generation
ZSM-5 type zeol i tes can completely remove the above-mentioned l i mi tati ons.
Because of the hi gh strength of the zeol i te acid sites, a higher degree of
oligomerization occurs which resul ts i n a higher molecular mass product wi th a
higher vi scosi ty. Because o f the unique size o f the zeol i te pores, it i s
physically impossible t o produce hi ghl y branched oligomers and consequently the
product diesel fuel has a high cetane number. This process has been thoroughly
evaluated on pi l o t pl ant scale wi th FT feedstocks both at Sasolburg and abroad.
The bui l di ng of a f ul l scale commercial pl ant i s presently under consideration
as p a r t of a debottlenecking process at Sasol's Secunda complex. A new zeol i te
oligomerization plan-c would not only process additional ol efi ns but should also
be able to improve the yi el d and qual i ty of the overal l diesel fuel pool.
Table 1 i l l us trates the s el ecti vi ti es (on a carbon atom basis) typi cal l y
obtained i n the two types of commercial FT reactors used by Sasol, namely, the
high temperature Synthol process (geared at making l i ght ol efi ns and gasolene)
and the lower temperature fi xed bed process (geared at making waxes). Applying
to each of chese product streams, the secondary processes previously discussed,
namely, oligomerization of the C to C ol efi ns t o yi el d 75 % diesel fuel and
hydrocracking of the wax to yie?d 80 % diesel fuel , the overal l l i qui d fuel
si tuati on obtained i s shown i n Table 2. As can be seen high qual i ty diesel fuel
at high yi el ds can be obtained i n both processes. When both maximum l i qui d fuel
yi el d and maximum di esel fuel to gasolene rati o i s required, the low temperature
Arge FT process has the greater potenti al .
REFERENCE
(1) Catalysis Science and Technology, Vol 1, Ch. 4, Ed. by J R Anderson &
M Boudart Springer Verlag 1981
290
TABLE 1
COMPARISON OF THE STRAIGHT-RUN FT PRODUCTS FROM THE SYNTHOL AN0 ARGE REACTORS
cut ISynthol high temperature IArge low temperature
c1 + c* I 16.0 I 5.4
C3 t o C 6 paraffi ns I 5.0 I a. 4
C 7 - 160 "C I 17. 2 I 8.0
+350 "C I 7.8 I 48.1
C3 to C6 ol ef i ns I 33.5 I 7. 6
160 - 350 "C I 14.0 I 19.5
Water soluble oxygenated
compounds I 6.5 I 3.0
TABLE 2
COMPARISON OF THE TWO DIESEL PRODUCING SCHEMES
cut I Synthol I Arge
Total f i nal l i qui d product I 80 I a7
% diesel o f l i qui d fuel I 55 I 75
Diesel source:
- From oligomerization I 58 I 9
- S trai ght run I 31 I 30
Wax cracking I 11 I 61
Cetane number o f diesel pool I 53 I 67
( Al l fi gures are percentages except f or the cetane number)
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TAIL GAS c-
SETTLING HOPPER
HEAT EXCHANGERS
GAS AND CATALYST
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