AU2003252879B2 - Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process - Google Patents
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- 239000000446 fuel Substances 0.000 title claims description 112
- 238000000034 method Methods 0.000 title claims description 65
- 239000000047 product Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 54
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 31
- 239000002283 diesel fuel Substances 0.000 claims description 25
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000000994 depressogenic effect Effects 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- 238000010626 work up procedure Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000005194 fractionation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010454 slate Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Regulation 3.2
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A DIVISIONAL PATENT
ORIGINAL
Name of Applicant: Sasol Technology (Pty) Ltd Actual Inventor: Luis Pablo Dancuart Address for Service: MADDERNS, 1st Floor, 64 Hindmarsh Square, Adelaide, South Australia, Australia Invention title: PROCESS FOR PRODUCING SYNTHETIC NAPHTHA FUEL AND SYNTHETIC NAPHTHA FUEL PRODUCED BY THAT PROCESS The following statement is a full description of this invention, including the best method of performing it known to us.
(PatAU132) This invention relates to naphtha fuels useable in Compression Ignition (CI) combustion engines as well as to a process for production of such naphtha fuels. More particularly, this invention relates to naphtha fuels produced from a mainly paraffinic synthetic crude which is produced by the reaction of CO and H 2 typically by the Fischer-Tropsch (FT) process.
Background to the invention Products of a FT hydrocarbon synthesis process, particularly the products of a cobalt and/or iron based catalytic process, contain a high proportion of normal paraffins. Primary FT products provide notoriously poor cold flow properties, making such products difficult to use where cold flow properties are vital, e.g. diesel fuels, lube oil bases and jet fuel. It is known in the art that octane number and cetane number are normally inversely related i.e. a higher octane number is typically associated with a lower cetane number. It is also known that naphtha fractions intrinsically have low cold flow characteristics like congealing and cloud points. There is thus an incentive for a process to produce a synthetic naphtha fuel obtained from the FT process which has good cold flow characteristics and a Cetane number compatible with CI engine fuel requirements. Additionally, such synthetic naphtha fuel may have acceptable biodegradability properties.
The synthetic naphtha fuel described in this invention is produced from a paraffnic synthetic crude (syncrude) obtained from synthesis gas (syngas) through a reaction like the FT reaction. The FT primary products cover a broad range of hydrocarbons from methane to species with molecular masses above 1400; including mainly paraffnic hydrocarbons and smaller quantities of other species such as olefins, and oxygenates.
The prior art teaches in US 5,378,348 that by hydrotreating and isomerizing the products from a Fisher-Tropsch reactor one can obtain a jet fuel with freezing point of -34°C or lower due to the isoparaffinic nature of this fuel. This increased product branching relative to the waxy paraffin feed corresponds with a Cetane rating (combustion) value less than that for normal (linear) paraffins, depicting that an increase in branching reduces the Cetane value ofparaffinic hydrocarbon fuels.
Surprisingly, it has now been found by the applicant, that a hydroprocessed synthetic naphtha fuel may be produced having a Cetane number, typically in excess of 30, as well as good cold flow properties.
The synthetic naphtha fuels of the present invention could be used on their own or in blends in CI In engines, typically where diesel fuels are presently used. This would lead to the more 0 stringent fuel quality and emission specifications being satisfied. The synthetic 1C naphtha fuels of the present invention may be blended with conventional diesel fuels 4 to have lower emissions, good cold flow characteristics, low aromatics content and 00 C 5 acceptable cetane numbers.
SUMMARY OF THE INVENTION 00 Thus, according to a first aspect of the invention, there is provided a process for the 0 production of a synthetic naphtha fuel suitable for use in CI engines, the process including at least the steps of: a) hydrotreating at least a fraction of a Fischer-Tropsch (FT) synthesis reaction product of CO and H 2 or a derivative thereof; b) hydrocracking at least a fraction of the FT synthesis product or a derivative thereof; and c) fractionating the process products to obtain a desired synthetic naphtha fuel characteristic.
The process may include the additional step of blending the fractionated process products in a desired ratio to obtain a synthetic naphtha fuel having desired characteristics for use in a CI engine.
The process as described above may produce a synthetic naphtha wherein some of the desired characteristics include; having a high Cetane number in excess of having a low sulphur content below about having good cold flow properties; and having more than 30% isoparaffins, wherein the isoparrafins include methyl and/or ethyl branched isoparaffins.
rn According to yet another aspect of the invention, there is provided a process for producing a synthetic naphtha fuel having a Cetane number higher than 30, the IC process including: 4 separating the products obtained from synthesis gas via the FT 00 C 5 synthesis reaction into one or more heavier fraction and one or more lighter fraction; r catalytically processing the heavier fraction under conditions which 00 Syield predominantly distillates; separating a naphtha product fraction of step from a heavier product fraction which is also produced in step and optionally, blending the naphtha product obtained in step with at least a portion of the one or more lighter fraction of step or products thereof.
The catalytic processing of step may be a hydroprocessing step, for example, hydrocracking or mild hydrocracking.
The process for producing a synthetic naphtha fuel may include one or more additional step of fractionating at least some of the one or more lighter fraction of step or products thereof, prior to step The process for producing a synthetic naphtha fuel may include the additional step of hydrotreating at least some of the one or more light fraction of step or products thereof, prior to step The one or more heavier fraction of step may have a true boiling point (TBP) in the range of about 70'C. to 700 0 however, it may be in the range of 80°C. to 650 0
C.
The one or more lighter fraction may have a true boiling point (TBP) in the range -70'C. to 350 0 typically in the range -10°C. to 340 0
C.
S The product of step may boil in the range 30'C. to 200 0 C. The product of step (d) may boil in the range 40'C. to 155 0 as measure by the ASTM D86 method.
4 The product of step may be a naphtha fuel.
00 The product of step may have a Cloud Point below typically 40'C. and even below -50 0
C.
00 The product of step may be obtained by mixing the naphtha product fraction LO obtained in step with at least a portion of the one or more lighter fraction of step or products thereof, in a volume ratio of between 1:24 and 9:1, typically 2:1 and 6:1, and in one embodiment, in a volume ratio of 50:50.
The invention extends further to a process for the production of synthetic naphtha fuels suitable for CI engines, from FT primary products, comprising predominantly short chain linear and branched paraffins.
In this process, the waxy product from the FT process is separated into at least two fractions, a heavier and at least one lighter fraction. The lighter fraction may be subjected to mild catalytic hydrogenation to remove hetero-atomic compounds such as oxygen and to saturate olefins, thereby producing material useful as naphtha, diesel, solvents, and/or blending components therefor. The heavier fraction may be catalytically hydroprocessed without prior hydrotreating to produce products with good cold flow characteristics. This hydroprocessed heavier fraction could be blended with all or part of the hydrogenated and/or unhydrogenated light fraction to obtain, after fractionation, naphtha fuel characterised by an acceptable Cetane number.
The catalysts suitable for the hydroprocessing steps are commercially available and can be selected towards an improved quality of the desired final product.
t According to a further aspect of the invention there is provided a process for the production of a synthetic naphtha fuel suitable for use in CI engines, the process C including at least the steps of: 4 a) hydrotreating at least a condensate fraction of a Fischer-Tropsch (FT) 00 C 5 synthesis reaction product of CO and H 2 or a derivative thereof; b) hydrocracking at least a wax fraction of the FT synthesis product or a derivative thereof; 00 c) fractionating the hydrocracked fraction of step b) to obtain desired Ssynthetic naphtha fuel components; and SLO d) blending said components of step c) with the hydrotreated fraction of step a) in a desired ratio to obtain a synthetic naphtha fuel having desired characteristics for use in a CI engine.
The wax fraction of step b) may have a true boiling point (TBP) in the range of about 70 0 C. to 700 0
C.
The condensate fraction of step a) generally has a true boiling point (TBP) in the range -70 0 C. to 350 0
C.
The fuel of step d) generally boils in the range 30 0 C. to 200 0 as measured by the ASTM D86 method.
The fuel of step d) may be obtained by mixing the components obtained in step c) with at least a portion of the hydrotreated condensate of step or products thereof, in a volume ratio of between 1:24 and 9:1.
The invention extends yet further to a process for the production of a synthetic fuel suitable for use in CI engines, the process including at least the step of blending a synthetic naphtha fuel with a diesel fuel.
The naphtha fuel and diesel fuel may be blended in substantially equal proportions lt The synthetic naphtha fuel used in the process may be produced according to a O process including at least the steps of: a) hydrotreating at least a condensate fraction of a Fischer-Tropsch (FT) 00 N 5 synthesis reaction product of CO and H 2 or a derivative thereof; b) hydrocracking at least a wax fraction of the FT synthesis product or a derivative thereof; 00 c) fractionating the hydrocracked fraction of step b) to obtain desired
C
synthetic naphtha fuel components; and S0 d) blending said components of step c) with the hydrotreated fraction of step a) in a desired ratio to obtain a synthetic naphtha fuel having desired characteristics for use in a CI engine.
According to a further aspect of the invention, there is provided a synthetic naphtha fuel having a Cetane number above 30 and a Cloud Point below -30 0 said naphtha fuel having an isoparaffinic content substantially as described above.
The synthetic naphtha fuel having a Cetane number above 30, a Cloud Point of below 0 more than 30% isoparaffins, may have a Final Boiling Point (FBP) of less than 160 0
C.
The synthetic naphtha fuel may have an Initial Boiling Point (IBP) of at least 49 0
C.
In one embodiment, the synthetic naphtha fuel is a FT product.
The invention extends to a fuel composition including from 10% to 100% of a synthetic naphtha fuel as described above.
Typically, the fuel composition may include from 0 to 90% of one or more diesel fuels.
Vr The fuel composition may include at least 20% of the synthetic naphtha fuel, the composition having a Cetane number greater than 40 and a Cloud Point below 2 0
C.
Using the synthetic naphtha as Cloud Point depressor may result in at least 2 0
C.
4 depression in Cloud Point of the fuel composition.
00 N The fuel composition may include at least 30% of the synthetic naphtha fuel, the S composition having a Cetane number greater than 40 and a Cloud Point below 0°C.
oO 00 Using the synthetic naphtha as Cloud Point depressor may result in at least 3 0
C.
(Ni N depression in Cloud Point for the fuel composition.
.0 The fuel composition may include at least 50% of the synthetic naphtha fuel, the composition having a Cetane number greater than 40 and a Cloud Point below 0°C., more typically below -4 0 C. Using the synthetic naphtha as Cloud Point depressor may result in at least 4 0 C. depression in Cloud Point for the fuel composition, or more typically at least 8 0 C. depression.
The fuel composition may include at least 70% of the synthetic naphtha fuel, the composition having a Cetane number greater than 40 and a Cloud Point below more typically below -15 0 C. Using the synthetic naphtha as Cloud Point depressor may result in at least 13 0 C. depression in Cloud Point for the fuel composition, or more typically at least 18 0 C. depression.
The blend composition may further include from 0 to 10% additives to improve other fuel characteristics.
kn The additives may include a lubricity improver. The lubricity improver may 0 comprise from 0 to 0.5% of the composition, typically from 0.00001% to 0.05% of the c composition. In some embodiments, the lubricity improver comprises from 0.008% 4 to 0.02% of the composition.
00 Ni The fuel composition may include, as the diesel, a crude oil derived diesel, such as US 2-D grade (low sulphur No. 2-D grade for diesel fuel oil as specified in ASTM oO 00 (1 D 975-94) and/or CARB (California Air Resources Board 1993 specification) diesel (Ni fuel, and/or a South African specification commercial diesel fuel.
1 0 The invention extends to a Fischer-Tropsch derived Cloud Point depressant for a diesel fuel containing fuel composition, the Cloud Point depressant having a Cetane number above 30, a Cloud Point of below more than 30% isoparaffins, and a Final Boiling Point (FBP) of less than 1601C.
The Fischer-Tropsch derived Cloud Point depressant may have an Initial Boiling Point (IBP) of at least 49 0
C.
BRIEF DESCRIPTION OF THE FIGURES FIG. 1 depicts an example of a process in accordance with the invention.
DETAILED DESCRIPTION This invention describes the conversion of primary FT products into naphtha and middle distillates, for example, naphtha fuels having a Cetane number in excess of 30, while also having good cold flow properties, as described above.
The FT process is used industrially to convert synthesis gas, derived from coal, natural gas, biomass or heavy oil streams, into hydrocarbons ranging from methane to species with molecular masses above 1400.
k3n While the main products are linear paraffinic materials, other species such as 0 branched paraffins, olefins and oxygenated components may form part of the Sproduct slate. The exact product slate depends on reactor configuration, operating [4 conditions and the catalyst that is employed, as is evident from e.g. Catal. Rev.-Sci.
00 c 5 Eng., 23 (1 265-278 (1981).
r- Preferred reactors for the production of heavier hydrocarbons are slurry bed or 00 C-I tubular fixed bed reactors, while operating conditions are preferably in the range of Cc 160°C 280°C, in some cases 210-260°C, and 18-50 bar, in some cases 20-30 bar.
0 Preferred active metals in the catalyst comprise iron, ruthenium or cobalt. While each catalyst will give its own unique product slate, in all cases the product slate contains some waxy, highly paraffinic material which needs to be further upgraded into usable products. The FT products can be converted into a range of final products, such as middle distillates, naphtha, solvents, lube oil bases, etc. Such conversion, which usually consists of a range of processes such as hydrocracking, hydrotreatment and distillation, can be termed a FT work-up process.
The FT work-up process of this invention uses a feed stream consisting of C, and higher hydrocarbons derived from a FT process. This feed is separated into at least two individual fractions, a heavier and at least one lighter fraction. The cut point between the two fractions is preferably less than 300°C and typically around 270"C.
The table below gives a typical composition of the two fractions, with 10% accuracy: Table 1: Typical Fischer-Tropsch product after separation into two fractions (vol% distilled) FT Condensate FT Wax 270*C fraction) 270*C fraction)
C
5 -160C 44 3 160-270"C 43 4 270-370"C 13 370-500°C 500*C 28 The >160"C fraction, contains a considerable amount of hydrocarbon material, which boils higher than the normal naphtha range. The 160°C to 270 0 C fraction may be regarded as a light diesel fuel. This means that all material heavier than 270'C needs to be converted into lighter materials by means of a catalytic process often referred to as hydroprocessing, for example, hydrocradcig.
Catalysts for this step are of the bifunctional type; i.e. they contain sites active for cracking and for hydrogenation. Catalytic metals active for hydrogenation include group VIII noble metals, such as platinum or palladium, or a sulphided Group VIII base metals, e.g. nickel, cobalt, which may or may not include a sulphided Group VI metal, e.g. molybdenum. The support for the metals can be any refractory oxide, such as silica, alumina, titania, zirconia, vanadia and other Group III, IV, VA and VI oxides, alone or in combination with other refractory oxides. Alternatively, the support can partly or totally consist of zeolite. However, for this invention the preferred support is amorphous silicaalumina.
Process conditions for hydrocracking can be varied over a wide range and are usually laboriously chosen after extensive experimentation to optimise the yield of naphtha. In this regard, it is important to note that, as in many chemical reactions, there is a trade-off between conversion and selectivity. A very high conversion will result in a high yield of gases and low yield of naphtha fuels. It is therefore important to painstakingly tune the process conditions in order to optimise the conversion of >160°C hydrocarbons. Table 2 gives a list of the preferred conditions.
Table 2: Process conditions for hydrocrackirm CONDITION BROAD PREFERRED RANGE RANGE Temperature, *C 150-450 340-400 Pressure, bar-g 10-200 30-80 Hydrogen Flow Rate, M 3 .m 3 feed 100-2000 800-1600 Conversion of >3700C material, mass 30- 80 50-70 Nevertheless, it is possible to convert all the >3700C material in the feedstock by recycling the part that is not converted during the hydrocracking process.
As is evident frm table 1, a large proportion of the fracton boiling below 1 60-C (light condensate) iS already in the typical boiling range for naphtha, i.e. 50 160*C. This fraction may or may not be subjected to hydrotreating. By hydrotreating, hetero-atosns are removed and unsaturated compounds are hydrogenated. Hydroteatig is a well-known indtistriai process, catalysed by any catalyst having a hydrogenation function, e-g. Group VII noble metal or suiphided base metal or Group VI metals, or combinations thereof. Preferred supports are alumina and silica.
Table 3 gives typical operating conditions for the hydrotreating process.
Table 3: Operating conditions for the bwdotepqting Rrocess.
CONDITION BROAD PREFERRED RANGE RANGE Temperature, OC 150-450 200-400 Pressure, bar(g) 10-200 30-80 Hydrogen Flow Rate, M1./m 3 feed 100-2000 400-1600 While the hydrotreated fr-action may be fractionated into paraffinic materials useful as solvents, the applicant has now surprisingly found that the hydrotreated fracion may be directly blended with the products obtained fromn hydrocracking the wax. Although it is possible to hydroisomerise the material contained in the condensate stream, the applicant has found that this leads to a small, but significant loss of material in the naphtha boiling range to lighter material. Furthermore, isomerisation leads to the formation of branched isomers, which leads to Cetane ratings less than that of the corresponding normal paraffins.
Important parameters for a FT work-up process are maximization of product yield, product quality and cost. While the proposed process scheme is simple and therefore cost-effective, it produces synthetic naphtha fuels suitable for CI engines, having a Cetane number >30 in good yield. In fact, the process of this invention is able to produce a naphtha for use in a CI engine of hitherto unmatched quality, which is characterized by a unique combination of both acceptable Cetane number and excellent cold flow properties.
It is the unique composition of the synthetic naphtha fuel, which is directly caused by the way in which the FT work-up process of this invention is operated, that leads to the unique characteristics of said fuel.
The described FT work-up process of Figure 1 may be combined in a number of configurations. The applicant considers these an exercise in what is known in the art as Process Synthesis Optimisation.
However, the specific process conditions for the Work-up of FT primary products the possible process configurations of which are outlined in Table 4, were obtained after extensive and laborious experimentation and design.
Table 4 Possible Fischer-Tropsch Product Work-up Process Configurations Process Step Process Scheme A B C D 1 FT Synthesis Reactor X X X X 2 Light FT Product Fractionator X 3 Light FT Product Hydrotreater X X X X 4 Light HT FT Product Fractionator X X Waxy FT Product Hydrocracker X X X X 6 Product Fractionator X X X X Numbers
FT
reference numerals of Figure 1 Fischer-Tropsch The basic process is outlined in the attached Figure 1. The synthesis gas (syngas), a mixture of Hydrogen and Carbon monoxide, enters the FT reactor 1 where the synthesis gas is converted to hydrocarbons by the FT reaction.
A lighter FT fraction is recovered in line 7, and may or may not pass through fractionator 2 and hydrotreater 3. The product 9 from the hydrotreater may be separated in fractionator 4 or, alternatively, mixed with hydrocracker products 16 sent to a common fractionator 6.
A waxy FT fraction is recovered in line 13 and sent to hydrocracker 5. If fractionation 2 is considered the bottoms cut 12 are to be sent to hydrocracker 5. The products 16, on their own or mixed with the lighter fraction 9a, are separated in fractionator 6.
Depending on the process scheme, a light product fraction, naphtha 19, is obtained from fractionator 6 or by blending equivalent fractions 10 and 17. This is a typically C,-160"C fraction useful as naphtha.
A somewhat heavier cut, synthetic diesel 20, is obtainable in a similar way from fractionator 6 or by blending equivalent fractions 11 and II. This cut is typically recovered as a 160-370'C fraction useful as diesel.
The heavy unconverted material 21 from fractionator 6 is ecycled to extinction to hydrocracker Alternatively, the residue may be used for production of synthetic lube oil bases. A small amount of
CI-C
4 gases are also separated in fractionators 4 and 6.
The following examples 1-9 will serve to illustrate further this invention.
Nomenclature used in examples LTFT Low Temperature Fischer-Tropsch. A Fischer-Tropsch synthesis completed at temperatures between 160*C and 280*C using the basic process conditions as described previously in this patent, at pressures of 18 to 50 bar in a tubular fixed bed or slurry bed reactor.
SR Straight Run. A product obtained directly from LTFT that has not been subjected to any chemical transformation process.
HT SR Hydrogenated Straight Run. A product obtained from LTFT SR products after being hydrogenated using the basic process conditions as described previously in this patent.
HX Hydrocracked. A product obtained from LTFT SR products after being hydrocracked using the basic process conditions as described previously in this patent.
Example 1 A Straight Run (SR) naphtha was produced by fractionation of the light FT Condensate. This product had the fuel characteristics indicated in Table 5. The same table contains the basic properties of a petroleum based diesel fuel.
Example 2 A Hydrogenate Straight Run (HT SR) maphtha was produced by hydrotrating and fractionation of the light FT Condensate. This product had the fuel characteristics indicated in Table Example 3 A Hydrocracked O(X) naphtha was produced by hydrocracking and fractionation of the heavy FT wax. This product had the fuel characteristics indicated in Table Example 4 A LTFT Naphtha was produced by blending of the naphthas described in examples 2 and 3. The blending ratio was 50:50 by vohune. This product had the fuel characteristics indicated in Table Table 5 Tale SCharacteristics of the LTFT Naphbthas Synthetic FTF Naphathas Commeciaj oti] I SA Diese aim n I NK I fl~K ILTVT ASTM D96 -I IBP, -C 53 60 49 54 182 TIO, -C 94 83 79 a1 223 C 11& 101 101 101 292 -C 141 120 120 120 358 FEP, OC 159 133 131 131 382 Desity, kgIL (2kC) 0.7101 0.6825 0.6977 0.6352 0.3493 Cetane Number W/a 42,7 30,0 39,6 50,0 'Heat ofCombustion, 45625 48075 46725 46725 45520 note 2 HHV, kJik__ Acid Nuber, mng 0.36 1 0.001 0.011 0.006 0.040 KOWg Total sulphur, mg/L <1 <1 <1 4242 Composition, iiM a-puaffins 53,2 90,1 22,6 59,0 n/a Lqso-perfnS 1,2 3,3 66,7 39,2 a Naphthenics ala Aromnatics 0,1 0,5 0,3 Olefins 35,0 1,5 4,2 2,5 a/a alcohols 10,7 aa Clou Pont -C -51 -54 -35 -33 4 Flash Point, OC -9 -13 -21 -20 57 foe VisCOsuty u/a u/a a/a 0,50 3,97 I Th~pe -AJ W A I I.Ezz'r r q'~;..Lnztd(e:H e 97p 1 -FOCCLW= 14AI.3; 3. Correlated (ref.: Bp Sep 1997 p. 81) Example The SR Naphtha, described in example 1, was tested for emissions obtaining the results indicated in table 6. A Mercedes Benz 40T Diesel engine was used for the test, with the characterstics also 1u indicated in table 6. The emissions measured during the test were 21,6% less CO, 4,7% less C0 2 and 20,0% less NOx than that those measured for the conventional diesel fuel Additionally, the Particulates emission measured by the Bosch Smoke Number was 52% lower than that observed for the conventional diesel fuel. The specific fuel consumption was 0,2% lower than that observed for the conventional diesel.
Example 6 The HT SR Naphtha, described in example 2, was tested for emissions obtaining the results indicated in table 6. A Mercedes Benz 407T Diesel engine was used for the test, with the characteristics also indicated in table 6. The emissions measured during the test were 28,8% less CO, 3,5% less C0 2 and 26,1% less NQx than that those measured for the conventional diesel fuel. Additionally, the Particulates eniission measured by the Bosch Smoke Number wvas 45%,0 lower than that observed for thi, conveiltlofla! diesel Tht: specific fuel consumption was 4.9% lowver than that obser-\ed for die conventional diesel- Example 7 The HN Naphtha. described in examiple 3. was tested for emissions obtaining thc results indicated in table 6. A Mcrcedes Benz 407T Diesel engine was use-d for the lest, with the characteristics also Indicated In table 6. The emissions measured during the test were 7_2% less CO. 0_3% less CO,. and i) 26-6'a less NO, than that those measured for the conventional diesel fuel. Additionallv. the Particulates emissioni measured by the Bosch Smokc Number was. 54% lower than that observed for dhe conventional diesel fuel. The specific fuel consunption was 7.1% lower than that observed for the conventional diesel- Example 8 T1he LTFT Naphtha, described in example 4. wmas tested for emissions obtaining the results indicated in table 6. An unm-odified Mercedes Benz 407T Diesl engine was used for the test- with the characteristics also indicated in table 6- The emissions mneasured during the test were 25,2% less CO.
21 4.4' less CO:_ and 26.1% less NO-K than that those measured for the conventional diesel fuel.
Additionallv, the Particulates emission measured by the Bosch Smoke Number wvas 45%7 lower tha that obscrved for the conv entional diesel fuel. The specific fuel consumption wvas 4.6%/e lower than that observed for the conventlonal diesel.
Table 6 CI Enine and Emissions Performance of the Synthetic Nahthas S-.mheti NapthasConventional SR I LT I Diesel Benz407 Engine 1 400 rMm Test condition Contaplon k/h17.55 16,72 16.34 16.7 C .P h0.70-79 1._03 0.83 1l CC:. gk~h 668-1 676.1 698.9 670.1-0~ NO uikwh 13.59) 12.' ;5 12-47 12.55 16,9(
I
Bosh Smoke Number 0.32 0.37 0.3 U. 2# 1 U Example 9 The LTFT Naphtha was blended in a 50:50 proportion (volume) with a commercial South African diesel to produce a fuel suitable for cold weather environments. The fuel characteristics of this fuel and its components are included in Table 7. In Table 8 the performance of this fuel blend, and that of its components, in a Compression Ignition (CI) Engine are shown. The 50:50 blend shows 10% lower specific fuel consumption, 19% lower NOx emissions and 21% lower Bosch Smoke Number. Other parameters are also significant.
The commercial diesel fuel is a conventional non-winter fuel grade. Conventionally petroleum refiners producing diesel fuels for cold weather environments are forced to reduce the final boiling points of their products. By doing this, they reduce the cold flow characteristics, making it more compatible with low temperature operation and reducing the possibility of freezing. This results in lower production levels, not only for diesel fuels but also for jet fuel and other products like heating oils.
The blend of the LTFT Naphtha and the commercial South African Diesel is a fuel suitable for cold weather environments that can be prepared without reducing production of conventional fuel. The blend retains the advantages of conventional fuels, including acceptable cetane number and flash points, and can be used in cold conditions without additives or loss of performance. Additionally the blend might have environmental advantages in respect to emissions.
Some of the results included in Tables 7 and 8 are illustrated graphically in the attached figures at the end of the Examples.
Table 7: Fuel Characteristics of the Commercial Diesel-Synthetic Naphtha Blends LTFT Naphtha in Blend 50% 100% ASTM D86 IBP 182 50 53 Distillation TI0 223 87 79 °C T50 292 129 100 358 340 120 FBP 382 376 129 Specific Gravity 0.8483 0.7716 0.6848 Flash Point °C 77 47 Viscosity cSt 40 0 C 3.97 1.19 0.50 Cetane Number 50,0 41,8 39,6 Cloud Point (DSC) 0 C 4 -5 CFPP 0 C -6 -16 T~hI. R' CI En2me and Emissions Perfonnance of the Commercial Diesel-Synthetic Nanhtha Tahlo Be Blends LTFT Naphtha in Blend %50%A 100% Engine tested Mercedes Benz 4071T Test cndition 1400 rpm Engine load 553 Nm Fuel Consumption, kg/h 17,53 16,7 1 16,77 CO, g/kIVh 1,11 1,21 0,3 C0 2 gkwh 700,9 711,6 670,1 NOx, g&"w 16,99 13,15 12,55 Bosch Smoke Number 0,67 0,53 0,37 Combustion and Emissions Performance of the Synthetic Naphthas SR HT SR LTFT HX Diesel SR HT SR LTFT HX Diesel Bosch Smoke Number Base -261I% -26.1% -25.6% SR HT SR LTFT HX Diesel i E-) Specific Fuel Consumption, glkWh 0 W I all, Combustion and Emissions Performance of the LTFT Synthetic Naphtha and Commercial Diesel Blend Flash Point 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%I/ Naphtha Fraction In Blend, vol 0.85 -Specific Gravity 0.8u0.75 0.7 0.65 0.6 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% Naphtha In Blend, vol 17 0% 10% 20% 30% 40% 50% 60% 70% 80% Naphtha In Blend, vol 90% 100% 20 30 40 50 60 70 80 90 100 Naphthia In Blend, vol 0 1 0
U)-
20 30 40 50 Naphtha In Blend, vol 60 70 80 90 100
Claims (9)
1. A process for the production of synthetic fuel suitable for use in CI engines, -4 the process including at least the step of blending a synthetic naphtha fuel with 00 C 5 diesel fuel, wherein the synthetic naphtha fuel is produced according to a process including at least the steps of: a) hydrotreating at least a condensate fraction of a Fischer-Tropsch (FT) 00 C synthesis reaction product of CO and H 2 or a derivative thereof; b) hydrocracking at least a wax fraction of the FT synthesis product or a derivative thereof; c) fractionating the hydrocracked fraction of step b) to obtain desired synthetic naphtha fuel components; and d) blending said components of step c) with the hydrotreated fraction of step a) in a desired ratio to obtain a synthetic naphtha fuel having desired characteristics for use in a CI engine.
2. A Fischer-Tropsch derived synthetic naphtha fuel having a Cetane number above 30, a Cloud Point of below -30 0 more than 30% isoparaffins, and a Final Boiling Point (FBP) of less than 160 0 C.
3. A synthetic naphtha fuel as claimed in claim 2, having an Initial Boiling Point (IBP) of at least 49 0 C.
4. A fuel composition including from 1% to 100% of a synthetic naphtha fuel as claimed in claim 2. A fuel composition including from 1% to 100% of a synthetic naphtha fuel as claimed in claim 3.
6. A fuel composition as claimed in claim 4, which includes from 0 to 99% of one or more diesel fuels. in 7. A fuel composition as claimed in claim 4, which includes at least 20% of the Ssynthetic naphtha fuel, the composition having a Cetane number greater than 40 and a Cloud Point below 2 0 C. 00 oO C 5 8. A fuel composition as claimed in claim 4, which includes at least 30% of the synthetic naphtha fuel, the composition having a Cetane number greater than 40 and a Cloud Point below 0 0 C. oO
9. A fuel composition as claimed in claim 4, which includes at least 50% of the 0 synthetic naphtha fuel, the composition having a Cetane number greater than and a Cloud Point below -4C. A fuel composition as claimed in claim 4, which includes at least 70% of the synthetic naphtha fuel, the composition having a Cetane number greater than 40 and a Cloud Point below -13 0 C.
11. A fuel composition as claimed in claim 6, which includes equal volumes of the synthetic naphtha fuel and the diesel fuel and has a Cetane number greater than 40 and a Cloud Point below -5 0 C.
12. A Fischer-Tropsch derived Cloud Point depressant for a diesel fuel containing fuel composition, the Cloud Point depressant having a Cetane number above a Cloud Point of below -30 0 more than 30% isoparaffins, and a Final Boiling Point (FBP) of less than 160 0 C.
13. A Fischer-Tropsch derived Cloud Point depressant as claimed in claim 12, the Cloud Point depressant having an Initial Boiling Point (IBP) of at least 49 0 C. Dated this 28 t day of February, 2005 Sasol Technology (Pty) Ltd by its Patent Attorneys MADDERNS r
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| AU2003252879A AU2003252879B2 (en) | 1999-04-06 | 2003-10-09 | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
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| US60/128036 | 1999-04-06 | ||
| ZA99/02789 | 1999-04-19 | ||
| AU22263/00A AU769078B2 (en) | 1999-04-06 | 1999-12-23 | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
| AU2003252879A AU2003252879B2 (en) | 1999-04-06 | 2003-10-09 | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248794B1 (en) * | 1999-08-05 | 2001-06-19 | Atlantic Richfield Company | Integrated process for converting hydrocarbon gas to liquids |
| US6274029B1 (en) * | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6475375B1 (en) * | 1999-04-06 | 2002-11-05 | Sasol Technology (Pty)Ltd. | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6274029B1 (en) * | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6475375B1 (en) * | 1999-04-06 | 2002-11-05 | Sasol Technology (Pty)Ltd. | Process for producing synthetic naphtha fuel and synthetic naphtha fuel produced by that process |
| US6248794B1 (en) * | 1999-08-05 | 2001-06-19 | Atlantic Richfield Company | Integrated process for converting hydrocarbon gas to liquids |
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