US20070021636A1 - Process to upgrade kerosenes and a gasoils from naphthenic and aromatic crude petroleum sources - Google Patents
Process to upgrade kerosenes and a gasoils from naphthenic and aromatic crude petroleum sources Download PDFInfo
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- US20070021636A1 US20070021636A1 US10/557,870 US55787005A US2007021636A1 US 20070021636 A1 US20070021636 A1 US 20070021636A1 US 55787005 A US55787005 A US 55787005A US 2007021636 A1 US2007021636 A1 US 2007021636A1
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- 239000003208 petroleum Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 58
- 125000003118 aryl group Chemical group 0.000 title description 13
- 239000003350 kerosene Substances 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 32
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 26
- 239000000779 smoke Substances 0.000 claims abstract description 20
- 238000012512 characterization method Methods 0.000 claims abstract description 19
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 18
- 239000011369 resultant mixture Substances 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims description 36
- 238000004821 distillation Methods 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims 24
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 238000002955 isolation Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 32
- 238000002156 mixing Methods 0.000 description 17
- 239000000446 fuel Substances 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
Definitions
- Crude petroleum sources featuring a value for the Watson characterisation factor K of in between 11 and 12 are also referred to as “naphthenic” crude. If the K factor below 11 the crude is also referred to as “aromatic” crude.
- the Watson characterisation factor K for hydrocarbons has been defined in the API technical data book (Section 2 Characterisation).
- Virgin naphtha fractions as distilled from Napthenic or Aromatic crudes are very suitable to prepare high octane motor gasoline components as they are easy convertable via Catalytic Reforming to high octane value reformates.
- virgin kerosenes and virgin gasoils produced from Naphthenic and/or Aromatic crudes are being characterised by certain quality properties which makes them unsuitable to meet certain environmentally driven fuels specifications as required by an increasing number of legislators in various Regions and Markets.
- Diesel quality gasoils produced from such naphthenic or aromatic crudes will typically feature a low cetane number (CN).
- CN cetane number
- the cetane number will be between 35-50 below the required international Cetane number specifications set for Diesel grades.
- the minimum Cetane Number requirement in the European Diesel specification (EN 590) has been increased to minimum of 51 from year 2000 onwards to meet the European Diesel fuel and emissions requirements set in the EU Fuels Directive 98/70 for Euro III fuels.
- EU Fuels Directive 98/70 for Euro III fuels.
- Global car manufacturers want to increase Diesel fuel Cetane Number requirements even further to minimum 55 as published in their World Wide Fuel Charter in year 2002.
- U.S. Pat. No. 3,775,297 describes a process wherein the gas oil fraction as isolated from a naphthenic crude is converted into a lubricating base oil and a motor gasoline.
- a disadvantage of blending with paraffinic crudes is that such crudes are not always available at the refinery location or only at a much higher price.
- Another disadvantage is, that it is not always possible to find a paraffinic crude to blend which will meet both kerosene and gas oil properties and volume demands of distillates to the qualities respectively quantities as specified.
- the object of the present invention is to obtain a process to prepare kerosene and gas oil from a naphthenic or aromatic crude wherein the product quality give away is being reduced and wherein special measures to reduce the naphthenic or aromatic hydrocarbon contents is not required.
- the process according to the invention provides a simple method to obtain kerosene and gas oil products having desired properties while avoiding the need to co-processing a paraffinic crude.
- Fischer-Tropsch products as blending components also facilitates the use of virgin kerosene and gas oil distilled from a naphthenic or aromatic crude type. This will thus reduce the need or even avoid hydroprocessing steps, which are normally applied to reduce the naphthenic or aromatics contents in these fractions.
- the petroleum crude source feature a value of the Watson characterisation factor K of equal or below 12.0. These K values are being calculated according to formulae and nomograms described in the API Technical Data Book (section 2 characterisation).
- K values are being calculated according to formulae and nomograms described in the API Technical Data Book (section 2 characterisation).
- Examples of crude petroleum sources having such a low K value are West African crudes, for example Forcados and Nigerian Light, Far East crudes, for example Champion Export, Labuan and Miri Light, North Sea crudes for example Danish (DUC), Troll, Gryphon and Alba crudes and South American crudes, for example Tia Juana Pesado, Bachequero and Maya.
- the petroleum derived fraction of the gas oil and kerosene products as obtained from the process according to the invention are for more than 50 wt %, more preferably more than 70 wt % and most preferably more than 90 wt % based on a crude having a K value equal or below 12.0.
- a petroleum derived kerosene and gas oil is isolated, preferably by distillation. Such distillation is preferably carried out in an atmospheric distillation column by well known processes for the person skilled in refinery operations.
- the fractions isolated by distillation and which have not been subjected to another conversion process are referred to as virgin distillate fractions.
- the petroleum derived kerosene fraction will preferably have an ASTM D 86 distillation IBP of between 140 and 200° C. and a final boiling point of between 200 and max 300° C.
- the petroleum derived gas oil fraction should preferably have an ASTM D 86 IBP of between 250 and 300° C. and a FBP of between 340 and 380° C.
- Fischer-Tropsch derived kerosene and gas oil fractions are suitably obtained from the (hydrocracked) Fischer-Tropsch synthesis product.
- Fischer-Tropsch derived kerosene and gas oils are described in EP-A-583836, WO-A-9714768, WO-A-9714769, WO-A-011116, WO-A-011117, WO-A-0183406, WO-A-0183648, WO-A-0183647, WO-A-0183641, WO-A-0020535, WO-A-0020534, EP-A-1101813, U.S. Pat. No. 5,766,274, U.S. Pat. No. 5,378,348, U.S. Pat. No. 5,888,376 and U.S. Pat. No. 6,204,426.
- the Fischer-Tropsch derived kerosene will consist of at least 90 wt %, more preferably at least 95 wt % of iso and linear paraffins.
- the weight ratio of iso-paraffins to normal paraffins will suitably be greater than 0.3. This ratio may be up to 12. Suitably this ratio is between 2 and 6. The actual value for this ratio will be determined, in part, by the hydroconversion process used to prepare the Fischer-Tropsch derived kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
- the Fischer-Tropsch derived kerosene will suitably have a smoke point of higher than 25 mm and preferably above 50 mm and the ASTM D 86 distillation curve which will for its majority be within the typical kerosene range: between about 150 and 200° C., a density of about 740 kg/m 3 at 15° C., and zero sulphur and aromatics levels (below detection limits).
- the Fischer-Tropsch derived gas oil will consist of at least 90 wt %, more preferably at least 95 wt % of iso and linear paraffins.
- the weight ratio of iso-paraffins to normal paraffins will suitably be greater than 0.3. This ratio may be up to 12. Suitably this ratio is between 2 and 6. The actual value for this ratio will be determined, in part, by the hydroconversion process used to prepare the Fischer-Tropsch derived kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
- the Fischer-Tropsch derived gas oil will suitably have a cetane number of higher than 60 and preferably above 70 and an ASTM D 86 distillation curve which will for its majority be within the typical gas oil range: between about 200 and 400° C.
- the Fischer-Tropsch gas oil will suitably have a T90% vol of between 300-400° C., a density of between about 0.76 and 0.79 g/cm 3 at 15° C., and a viscosity between about 2.5 and 4.0 centistokes at 40° C.
- Blending can either be performed by so-called in-line blending, on-line blending or batch blending. This depends on the level of automation.
- in batch blending the petroleum derived fraction and the Fischer-Tropsch derived fraction are first mixed and subsequently supplied to a storage vessel and than supplied to a ship, rail or road car or other means of transport of the final blend.
- the desired product quality, i.e. smoke point or cetane number, of the feed to the storage vessel is measured and the quantity of the blending components is adjusted such that the property value is maintained within a pre-determined range in order to minimise quality give-away.
- the invention will be illustrated with the following non-limiting examples.
- the Examples are based on calculations using known blending rules.
- a naphthenic crude having a UOPK value of 11.5 is distilled into a naphtha fraction, a kerosene fraction and a gas oil fraction.
- the properties of the different fractions are listed in Table 1.
- TABLE 1 Distillates properties of a typical Naphthenic crude Kerosene Gas oil Yield on 12.2 36.9 naphthenic crude (% woc) Initial boiling 165 235 point (° C.) Final boiling 235 350 point (° C.) Density 840 887 (spec ⁇ 845 kg/m 3 Diesel EN 590) Smoke point 18 — (spec >25 mm) Aromatics (% vol) 21 43 Sulphur (% wt) 0.02 0.07 Cetane number 33 38.5 (spec >51
- Example 1 is repeated.
- an paraffinic crude having a Watson K characterisation factor value of 12.3 was distilled to obtain blending components to improve the kerosene and gas oil properties of the fractions listed in Table 1.
- the amount of paraffinic crude that was used was enough to obtain a kerosene and gas oil mixture to adjust the respective fraction of Table 1 to meet the desired specification.
- the properties of the blends are reported in Table 2.
- Example 1 is repeated. To the kerosene and gas oil fractions of Table 1 an amount of Fischer-Tropsch kerosene and gas oil (having the properties as listed in Table 3) respectively is added in an amount sufficient to meet the smoke point and cetane number specifications. The resulting properties are listed in Table 4.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
Abstract
A process to prepare a kerosene and a gasoil product from a crude petroleum source having a Watson characterization factor K value of equal or below 12.0 by (a) isolation of a petroleum derived kerosene fraction and a petroleum derived gasoil fraction from said crude petroleum source, wherein the petroleum derived kerosene fraction has a smoke point of below 25 mm or below 19 mm if naphthalenes content of the kerosene fraction is below 3% vol and the petroleum derived gas oil has a cetane number of below 50 or a density higher than 845 kg/m3, ( ) adding a Fischer-Tropsch derived kerosene fraction to the petroleum derived kerosene fraction in an amount sufficient to obtain a mixture having a smoke point value of above 25 mm or above 19 mm if the naphthalenes content of the mixture is below 3% vol and (c) adding a Fischer-Tropsch derived gas oil fraction to the petroleum derived gasoil fraction such that the resultant mixture has a cetane number value of above 51.
Description
- Process to upgrade low quality kerosenes and gasoils from Naphthenic and Aromatic crude petroleum sources, featuring a value for the Watson characterisation factor K of equal of below 12.
- Crude petroleum sources featuring a value for the Watson characterisation factor K of in between 11 and 12 are also referred to as “naphthenic” crude. If the K factor below 11 the crude is also referred to as “aromatic” crude. The Watson characterisation factor K for hydrocarbons has been defined in the API technical data book (Section 2 Characterisation).
- Virgin naphtha fractions as distilled from Napthenic or Aromatic crudes are very suitable to prepare high octane motor gasoline components as they are easy convertable via Catalytic Reforming to high octane value reformates. However virgin kerosenes and virgin gasoils produced from Naphthenic and/or Aromatic crudes are being characterised by certain quality properties which makes them unsuitable to meet certain environmentally driven fuels specifications as required by an increasing number of legislators in various Regions and Markets.
- Aviation kerosenes produced from naphthenic and/or aromatic crudes by distillation and treating will typically have a smoke point far below the required international specification (min. 25 mm) set for Aviation Turbine Fuels (Avtur) in Checklist No. 19 of Aviation Fuel Quality Requirements for Jointly Operated Systems (AFQRJOS), or does not meet the alternative specification of maximum smokepoint (min. 19 mm) if naphthalenes content of the kerosene is below 3% vol. Sometimes naphthalenes levels are too high in kerosenes produced from these crudes in case of high final boiling points of the kerosenes. Also other specification requirements set for Aviation kerosenes like a minimum Total Acid Number of 0.015 mg KOH/g, a maximum specified aromatics level 25% vol and Thermal stability requirements (JFTOT) are difficult to be met with kerosenes directly distilled from Naphthenic and/or Aromatic crude sources.
- Diesel quality gasoils produced from such naphthenic or aromatic crudes will typically feature a low cetane number (CN). Typically the cetane number will be between 35-50 below the required international Cetane number specifications set for Diesel grades. Internationally there is a clear drive to increase Cetane number of Diesel fuels to reduce vehicle emissions. For example the minimum Cetane Number requirement in the European Diesel specification (EN 590) has been increased to minimum of 51 from year 2000 onwards to meet the European Diesel fuel and emissions requirements set in the EU Fuels Directive 98/70 for Euro III fuels. Global car manufacturers want to increase Diesel fuel Cetane Number requirements even further to minimum 55 as published in their World Wide Fuel Charter in year 2002.
- Gas oils produced from naphthenic or aromatic crudes also feature high densities. Maximum density limits of international Diesel qualities are currently being reduced to meet Dieselcar emissions requirements. Again in EU the maximum specification for Diesel fuels in EU 590 has been reduced in 2000 to a maximum of 845 kg/m3 as set in the EU Fuels Directive 98/70.
- The consequence of these emission driven fuel requirements is that middle distillate fuels produced from naphthenic or aromatic crudes may not be suitable to meet the severe environmental driven fuels specification requirements being set for Avtur and Diesel. This will result in “off-spec” Diesel or Kerosene qualities if these crudes are being processed in so-called Hydroskimming refineries. Hydroskimming refineries are relatively simple refineries consisting of crude distilling and hydrotreating processes.
- To improve the quality of the distillates produced from these crudes to meet the specified Product Qualities these refineries have two options:
- 1) As a first option, further improvement of the inferior distillate qualities can be achieved by more applying more severe hydroprocessing or hydrocracking. This option may need however expensive investment for those refineries not equipped with these processing units.
- In these processes by catalytic ring opening of the naphthenic components in the kerosene fraction as described in U.S. Pat. No. 3,607,729, the smoke point of the kerosene fraction can be improved. Also the cetane values of gasoils can be improved in these processes due to hydrogenation and ringopening reactions.
- U.S. Pat. No. 3,775,297 describes a process wherein the gas oil fraction as isolated from a naphthenic crude is converted into a lubricating base oil and a motor gasoline.
- More recent developments as illustrated in U.S. Pat. No. 5,107,056, involve processes wherein the undesired naphthenic compounds are removed by membrane separation from the oil.
- 2) A second option to improve the kerosene and gas oil properties is to blend and co-process these inferior quality types of naphthenic and aromatic crudes with more paraffinic type of crudes. The final distillate yields of this crude blend can be calculated from the crude blend ratio multiplied by the distillate yields obtainable for each crude.
- A disadvantage of blending with paraffinic crudes is that such crudes are not always available at the refinery location or only at a much higher price. Another disadvantage is, that it is not always possible to find a paraffinic crude to blend which will meet both kerosene and gas oil properties and volume demands of distillates to the qualities respectively quantities as specified.
- Normally crude blending will result in quality give-away for example it is either the kerosene blend or the gas oil blend which will meet the smoke point respectively the cetane number specification after blending such crudes. The other blend will have a property value exceeding the specification while the property value of said blend will be the same or near a blend having a property closer to the specification. This so-called quality give away is preferably to be avoided for obvious reasons. Nevertheless, as explained above, when optimizing both kerosene and gas oil products in a refinery blending environment such quality give-away cannot always be avoided. Co-processing of a paraffinic crude will also result in more crude storage and handling, blending, crude distilling and processing requirements.
- In Cookson David J et al., “Observed and predicted properties of jet and diesel fuel formulated from coal liquefaction and Fischer-Tropsch feedstocks”, Energy Fuels 1992, 6, pages 581-585, it is described how the kerosene and gas oil fraction as obtained from a non-crude source, namely a coal liquefaction process are blended with respective Fischer-Tropsch derived kerosene and gas oil.
- The object of the present invention is to obtain a process to prepare kerosene and gas oil from a naphthenic or aromatic crude wherein the product quality give away is being reduced and wherein special measures to reduce the naphthenic or aromatic hydrocarbon contents is not required.
- This object is achieved with the following process. Process to prepare a kerosene and a gasoil product from a crude petroleum source having a Watson characterisation factor K value of equal or below 12.0 by (a) isolation of a petroleum derived kerosene fraction and a petroleum derived gasoil fraction from said crude petroleum source, wherein the petroleum derived kerosene fraction has a smoke point of below 25 mm or below 19 mm if naphthalenes content of the kerosene fraction is below 3% vol and the petroleum derived gas oil has a cetane number of below 50 or a density higher than 845 kg/m3, (b) adding a Fischer-Tropsch derived kerosene fraction to the petroleum derived kerosene fraction in an amount sufficient to obtain a mixture having a smoke point value of above 25 mm or above 19 mm if the naphthalenes content of the mixture is below 3% vol and (c) adding a Fischer-Tropsch derived gas oil fraction to the petroleum derived gasoil fraction such that the resultant mixture has a cetane number value of above 51.
- The process according to the invention provides a simple method to obtain kerosene and gas oil products having desired properties while avoiding the need to co-processing a paraffinic crude. The use of Fischer-Tropsch products as blending components also facilitates the use of virgin kerosene and gas oil distilled from a naphthenic or aromatic crude type. This will thus reduce the need or even avoid hydroprocessing steps, which are normally applied to reduce the naphthenic or aromatics contents in these fractions.
- Additional advantages are that also other product characteristics of the kerosene will be improved. E.g. the Hydrogen content will be increased due to a higher heating value of the kerosene. The thermal stability will also be improved.
- Similarly also other gas oil properties apart from Cetane Number will be improved after blending virgin napthenic gasoils with Fischer-Tropsch derived Gasoils. E.g. Thermal Stability will be increased, density will be reduced, as well as Sulphur and Aromatics contents will be reduced as required by Motor manufacturers in their World Wide Fuels Charter (Revised in 2002) for Category 4 Diesel grades
- The petroleum crude source feature a value of the Watson characterisation factor K of equal or below 12.0. These K values are being calculated according to formulae and nomograms described in the API Technical Data Book (section 2 characterisation). Examples of crude petroleum sources having such a low K value are West African crudes, for example Forcados and Nigerian Light, Far East crudes, for example Champion Export, Labuan and Miri Light, North Sea crudes for example Danish (DUC), Troll, Gryphon and Alba crudes and South American crudes, for example Tia Juana Pesado, Bachequero and Maya. Preferably the petroleum derived fraction of the gas oil and kerosene products as obtained from the process according to the invention are for more than 50 wt %, more preferably more than 70 wt % and most preferably more than 90 wt % based on a crude having a K value equal or below 12.0.
- From the petroleum crude source a petroleum derived kerosene and gas oil is isolated, preferably by distillation. Such distillation is preferably carried out in an atmospheric distillation column by well known processes for the person skilled in refinery operations. The fractions isolated by distillation and which have not been subjected to another conversion process are referred to as virgin distillate fractions.
- The petroleum derived kerosene fraction will preferably have an ASTM D 86 distillation IBP of between 140 and 200° C. and a final boiling point of between 200 and max 300° C.
- The petroleum derived gas oil fraction should preferably have an ASTM D 86 IBP of between 250 and 300° C. and a FBP of between 340 and 380° C.
- The Fischer-Tropsch derived kerosene and gas oil fractions are suitably obtained from the (hydrocracked) Fischer-Tropsch synthesis product. Examples of Fischer-Tropsch derived kerosene and gas oils are described in EP-A-583836, WO-A-9714768, WO-A-9714769, WO-A-011116, WO-A-011117, WO-A-0183406, WO-A-0183648, WO-A-0183647, WO-A-0183641, WO-A-0020535, WO-A-0020534, EP-A-1101813, U.S. Pat. No. 5,766,274, U.S. Pat. No. 5,378,348, U.S. Pat. No. 5,888,376 and U.S. Pat. No. 6,204,426.
- Suitably the Fischer-Tropsch derived kerosene will consist of at least 90 wt %, more preferably at least 95 wt % of iso and linear paraffins. The weight ratio of iso-paraffins to normal paraffins will suitably be greater than 0.3. This ratio may be up to 12. Suitably this ratio is between 2 and 6. The actual value for this ratio will be determined, in part, by the hydroconversion process used to prepare the Fischer-Tropsch derived kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
- The Fischer-Tropsch derived kerosene will suitably have a smoke point of higher than 25 mm and preferably above 50 mm and the ASTM D 86 distillation curve which will for its majority be within the typical kerosene range: between about 150 and 200° C., a density of about 740 kg/m3 at 15° C., and zero sulphur and aromatics levels (below detection limits).
- Suitably the Fischer-Tropsch derived gas oil will consist of at least 90 wt %, more preferably at least 95 wt % of iso and linear paraffins. The weight ratio of iso-paraffins to normal paraffins will suitably be greater than 0.3. This ratio may be up to 12. Suitably this ratio is between 2 and 6. The actual value for this ratio will be determined, in part, by the hydroconversion process used to prepare the Fischer-Tropsch derived kerosene or gas oil from the Fischer-Tropsch synthesis product. Some cyclic-paraffins may be present.
- The Fischer-Tropsch derived gas oil will suitably have a cetane number of higher than 60 and preferably above 70 and an ASTM D 86 distillation curve which will for its majority be within the typical gas oil range: between about 200 and 400° C. The Fischer-Tropsch gas oil will suitably have a T90% vol of between 300-400° C., a density of between about 0.76 and 0.79 g/cm3 at 15° C., and a viscosity between about 2.5 and 4.0 centistokes at 40° C.
- Blending can either be performed by so-called in-line blending, on-line blending or batch blending. This depends on the level of automation. In batch blending the petroleum derived fraction and the Fischer-Tropsch derived fraction are first mixed and subsequently supplied to a storage vessel and than supplied to a ship, rail or road car or other means of transport of the final blend. The desired product quality, i.e. smoke point or cetane number, of the feed to the storage vessel is measured and the quantity of the blending components is adjusted such that the property value is maintained within a pre-determined range in order to minimise quality give-away.
- When in line blending is being applied no intermediate storage vessel is being applied but the blending ratio/volumes are adjusted automatically in line by Quality Measuring Instruments (QMI) and blends are directly discharged into the ship, rail or roadcar. The measurement and control of the quality or property of the blend in line can be performed by well known techniques, for example near infrared (NIR). Examples of a suitable method is describe in WO-A-0206905.
- The invention will be illustrated with the following non-limiting examples. The Examples are based on calculations using known blending rules.
- A naphthenic crude having a UOPK value of 11.5 is distilled into a naphtha fraction, a kerosene fraction and a gas oil fraction. The properties of the different fractions are listed in Table 1.
TABLE 1 Distillates properties of a typical Naphthenic crude Kerosene Gas oil Yield on 12.2 36.9 naphthenic crude (% woc) Initial boiling 165 235 point (° C.) Final boiling 235 350 point (° C.) Density 840 887 (spec <845 kg/m3 Diesel EN 590) Smoke point 18 — (spec >25 mm) Aromatics (% vol) 21 43 Sulphur (% wt) 0.02 0.07 Cetane number 33 38.5 (spec >51 - Example 1 is repeated. In addition an paraffinic crude having a Watson K characterisation factor value of 12.3 was distilled to obtain blending components to improve the kerosene and gas oil properties of the fractions listed in Table 1. The amount of paraffinic crude that was used was enough to obtain a kerosene and gas oil mixture to adjust the respective fraction of Table 1 to meet the desired specification. The properties of the blends are reported in Table 2.
TABLE 2 Distillates properties of Paraffinic and Naphthenic crudes and blend Crude Blend Naphthenic Paraffinic (31/69 % w/w crude crude N/P) Kero Gasoil Kero Gasoil Kero Gasoil Yield on 12.2 36.9 17.1 28.6 15.5 31.3 paraffinic crude (% woc) Initial 165 235 165 235 165 235 boiling point (° C.) Final 235 350 235 350 235 350 boiling point (° C.) Density 840 887 790 826 0.806 0.845 (kg/m3) (spec <845 kg/m3 Diesel EN 590) Smoke point 18 — 26 — 24 (spec >19 mm) Aromatics 21 43 16 14 17 24 (% vol) Sulphur 0.02 0.07 0.01 0.04 0.01 0.05 (% wt) Cetane 33 38.5 52 62.8 47 55 number (spec >51 - As can be seen from Table 2 a quality give away is observed for Smokepoint of the Kero produced from the blend and some of the Gasoil qualities like Cetane and Density.
- Example 1 is repeated. To the kerosene and gas oil fractions of Table 1 an amount of Fischer-Tropsch kerosene and gas oil (having the properties as listed in Table 3) respectively is added in an amount sufficient to meet the smoke point and cetane number specifications. The resulting properties are listed in Table 4.
TABLE 3 FT Distillates properties Fischer-Tropsch Fischer-Tropsch derived kerosene derived Gas oil Initial boiling 150 200 point (° C.) Final boiling 200 345 point (° C.) Density (kg/m3) 738 775 Smoke point (mm) >50 — Cetane number 60 76 Sulphur (ppmwt) <1 (below <1 (below detection limits) detection limits) Aromatics (% vol) <0.1 <0.1 -
TABLE 4 Blends of FT distillates with Naphthenic crude distillates Gasoil Kerosene Kerosene Gasoil Blend from Blend from with Naphthenic with FT Napthenic FT Gas crude kerosene crude oil Fraction of 0 5 0 34 Fischer-Tropsch derived components in blend (% wt) Initial boiling 165 162 235 220 point (° C.) Final boiling 235 230 350 348 point (° C.) Density kg/m3 840 834 887 845 (spec <845 kg/m3 EU 590 Diesel) Smoke point mm 18 19.6 — — (spec >19 mm) Cetane number 33 35 38.5 52 (spec >51 EU 590) Sulphur (% wt) 0.02 0.019 0.07 0.046 Aromatics (% vol) 21 20 43 27
Claims (36)
1. A process to prepare a kersosene and a gasoil product from a crude petroleum source having a Watson characterization factor K value of equal to or below 12.0 comprising:
(a) isolating a petroleum derived kerosene fraction and a petroleum derived gasoil fraction from said crude petroleum source, wherein the petroleum derived kerosene fraction has a smoke point of below 25 mm if the naphthalenes content of the petroleum derived kerosene fraction is at least 3% vol, or below 19 mm if the naphthalenes content of the petroleum derived kerosene fraction is below 3% vol, and the petroleum derived gasoil fraction has a cetane number of below 50 or a density higher than 845 kg/m3;
(b) adding a Fischer-Tropsch derived kerosene fraction to the petroleum derived kerosene fraction in an amount sufficient to obtain a mixture having a smoke point value of above 25 mm if the naphthalenes content of the mixture is at least 3% vol, or above 19 mm if the naphthalenes content of the mixture is below 3% vol; and,
(c) adding a Fischer-Tropsch derived gasoil fraction to the petroleum derived gasoil fraction such that the resultant mixture has a cetane number value of above 51, wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffins to normal paraffins weight ratio of greater than 0.3.
2. The process of claim 1 , wherein the petroleum derived kerosene fraction and the petroleum derived gasoil fraction are isolated from the crude petroleum source in a hydroskimming refinery.
3. The process of claim 1 , wherein the petroleum derived gasoil fraction and the petroleum derived kerosene fraction are each more than 50 wt % based on a crude having a Watson characterization factor K value equal to or below 12.0.
4. The process of claim 1 , wherein the petroleum derived kerosene fraction has an ASTM D86 distillation initial boiling point of between 140° C. to 200° C. and a final boiling point of between 200 CC to 300° C.
5. The process of claim 1 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
6. The process of claim 1 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
7. The process of claim 2 , wherein the petroleum derived gasoil fraction and the petroleum derived kerosene fraction are each more than 50 wt % based on a crude having a Watson characterization factor K value equal to or below 12.0.
8. The process of claim 2 , wherein the petroleum derived kerosene fraction has an ASTM D86 distillation initial boiling point of between 140° C. to 200° C. and a final boiling point of between 200° C. to 300° C.
9. The process of claim 2 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
10. The process of claim 2 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
11. The process of claim 3 , wherein the petroleum derived kerosene fraction has an ASTM D86 distillation initial boiling point of between 140° C. to 200° C. and a final boiling point of between 200° C. to 300° C.
12. The process of claim 3 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
13. The process of claim 3 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
14. The process of claim 4 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
15. The process of claim 4 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
16. The process of claim 5 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
17. A process to prepare a kerosene product from a crude petroleum source having a Watson characterization factor K value of equal to or below 12.0 comprising:
(a) isolating a petroleum derived kerosene fraction from said crude petroleum source, wherein the petroleum derived kerosene fraction has a smoke point of below 25 mm if the naphthalenes content of the petroleum derived kerosene fraction is at least 3% vol, or below 19 mm if the naphthalenes content of the kerosene fraction is below 3% vol; and,
(b) adding a Fischer-Tropsch derived kerosene fraction to the petroleum derived kerosene fraction in an amount sufficient to obtain a mixture having a smoke point value of above 25 mm if the naphthalenes content of the mixture is at least 3% vol, or above 19 mm if the naphthalenes content of the mixture is below 3% vol, wherein the Fischer-Tropsch derived kerosene fraction has an iso-paraffin to normal paraffin weight ratio of greater than 0.3.
18. The process of claim 17 , wherein the petroleum derived kerosene fraction is isolated from the crude petroleum source in a hydroskimming refinery.
19. The process of claim 17 , wherein the petroleum derived kerosene fraction is more than 50 wt % based on a crude having a Watson characterization factor K value equal to or below 12.0.
20. The process of claim 17 , wherein the petroleum derived kerosene fraction has an ASTM D86 distillation initial boiling point of between 140° C. to 200° C. and a final boiling point of between 200° C. to 300° C.
21. The process of claim 17 , wherein the Fischer-Tropsch derived kerosene fraction has an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
22. A process to prepare a gasoil product from a crude petroleum source having a Watson characterization factor K value of equal to or below 12.0 comprising:
(a) isolating a petroleum derived gasoil fraction from said crude petroleum source, wherein the petroleum derived gasoil fraction has a cetane number of below 50 and/or a density higher than 845 kg/m3; and
(b) adding a Fischer-Tropsch derived gasoil fraction to the petroleum derived gasoil fraction such that the resultant mixture has a cetane number value of above 51, wherein the Fischer-Tropsch derived gasoil fraction has an iso-paraffin to normal paraffin weight ratio of greater than 0.3.
23. The process of claim 22 , wherein the petroleum derived gasoil fraction is isolated from the crude petroleum source in a hydroskimming refinery.
24. The process of claim 22 , wherein the petroleum derived gasoil fraction is more than 50 wt % based on a crude having a Watson characterization factor K value equal to or below 12.0.
25. The process of claim 22 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
26. The process of claim 22 , wherein the Fischer-Tropsch derived gasoil fraction has an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
27. A process to prepare a hydrocarbon product from a crude petroleum source having a Watson characterization factor K value of equal to or below 12.0 comprising:
(a) isolating a petroleum derived kerosene fraction and a petroleum derived gasoil fraction from said crude petroleum source, wherein the petroleum derived kerosene fraction has a smoke point of below 25 mm if the naphthalenes content of the petroleum derived kerosene fraction is at least 3% vol, or below 19 mm if the naphthalenes content of the petroleum derived kerosene fraction is below 3% vol, and the petroleum derived gasoil fraction has a cetane number of below 50 and/or a density higher than 845 kg/m3; and
(b) adding a Fischer-Tropsch derived kerosene fraction to the petroleum derived kerosene fraction in an amount sufficient to obtain a mixture having a smoke point value of above 25 mm if the naphthalenes content of the mixture is at least 3% vol, or above 19 mm if the naphthalenes content of the mixture is below 3% vol; and/or,
(c) adding a Fischer-Tropsch derived gasoil fraction to the petroleum derived gasoil fraction such that the resultant mixture has a cetane number value of above 51, wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of greater than 0.3.
28. The process of claim 27 , wherein the petroleum derived kerosene fraction and/or the petroleum derived gasoil fraction are isolated from the crude petroleum source in a hydroskimming refinery.
29. The process of claim 27 , wherein the petroleum derived gasoil fraction and the petroleum derived kerosene fraction are each more than 50 wt % based on a crude having a Watson characterization factor K value equal to or below 12.0.
30. The process of claim 27 , wherein the petroleum derived kerosene fraction has an ASTM D86 distillation initial boiling point of between 140° C. to 200° C. and a final boiling point of between 200° C. to 300° C.
31. The process of claim 27 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
32. The process of claim 27 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
33. The process of claim 28 , wherein the petroleum derived gasoil fraction and the petroleum derived kerosene fraction are each more than 50 Wt% based on a crude having a Watson characterization factor K value equal to or below 12.0.
34. The process of claim 28 , wherein the petroleum derived kerosene fraction has an ASTM D86 distillation initial boiling point of between 140° C. to 200° C. and a final boiling point of between 200° C. to 300° C.
35. The process of claim 28 , wherein the petroleum derived gasoil fraction has an ASTM D86 distillation initial boiling point of between 250° C. to 300° C. and a final boiling point of between 340° C. to 380° C.
36. The process of claim 28 , wherein the Fischer-Tropsch derived kerosene fraction and the Fischer-Tropsch derived gasoil fraction each have an iso-paraffin to normal paraffin weight ratio of between 2 and 6.
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EP03076566 | 2003-05-22 | ||
EP03076566.3 | 2003-05-22 | ||
PCT/EP2004/050819 WO2004104142A1 (en) | 2003-05-22 | 2004-05-17 | Process to upgrade kerosenes and a gasoils from naphthenic and aromatic crude petroleum sources |
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US (1) | US20070021636A1 (en) |
EP (1) | EP1627028B1 (en) |
JP (1) | JP5478806B2 (en) |
CN (1) | CN100362085C (en) |
AT (1) | ATE380855T1 (en) |
DE (1) | DE602004010648T2 (en) |
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WO (1) | WO2004104142A1 (en) |
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US20070205137A1 (en) * | 2005-12-22 | 2007-09-06 | Clark Richard H | Fuel composition |
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WO2018077976A1 (en) * | 2016-10-27 | 2018-05-03 | Shell Internationale Research Maatschappij B.V. | Process for preparing an automotive gasoil |
WO2020128545A1 (en) * | 2018-12-19 | 2020-06-25 | Mol Magyar Olaj- És Gázipari Nyilvánosan Működő Részvénytársaság | Colliodal disperse system suitable for phase inversion to stimulate hydrocarbon production wells |
US11555144B2 (en) | 2018-12-19 | 2023-01-17 | Mol Magyar Olaj- És Gázipari Nyilvánosan Müködö Részvénytársaság | Colloidal disperse system suitable for phase inversion to stimulate hydrocarbon production wells |
US11248176B2 (en) | 2019-08-28 | 2022-02-15 | Saudi Arabian Oil Company | Low-sulfur aromatic-rich fuel oil blending component |
Also Published As
Publication number | Publication date |
---|---|
DK1627028T3 (en) | 2008-03-17 |
WO2004104142A1 (en) | 2004-12-02 |
ATE380855T1 (en) | 2007-12-15 |
JP5478806B2 (en) | 2014-04-23 |
DE602004010648D1 (en) | 2008-01-24 |
EP1627028A1 (en) | 2006-02-22 |
DE602004010648T2 (en) | 2008-12-11 |
CN1795258A (en) | 2006-06-28 |
CN100362085C (en) | 2008-01-16 |
JP2007502899A (en) | 2007-02-15 |
EP1627028B1 (en) | 2007-12-12 |
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