EP0728833A1 - Verfahren zur Herstellung von Brennstoff für Flugzeugturbinen - Google Patents
Verfahren zur Herstellung von Brennstoff für Flugzeugturbinen Download PDFInfo
- Publication number
- EP0728833A1 EP0728833A1 EP96101975A EP96101975A EP0728833A1 EP 0728833 A1 EP0728833 A1 EP 0728833A1 EP 96101975 A EP96101975 A EP 96101975A EP 96101975 A EP96101975 A EP 96101975A EP 0728833 A1 EP0728833 A1 EP 0728833A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- feedstock
- catalyst
- carrier
- weight
- turbine fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000446 fuel Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000004480 active ingredient Substances 0.000 claims abstract description 3
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910003294 NiMo Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 238000011021 bench scale process Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 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
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
Definitions
- the present invention is directed to the preparation of aviation turbine fuel, and, more particular, to a process for the preparation of such fuel by upgrading of FCC heavy gasoline.
- FCC heavy gasoline is produced by fluid catalytic cracking of vacuum distillates and boils in the range of 100-300°C.
- FCC heavy gasoline has a high content of aromatics and olefins, which makes it unsuitable for aviation turbine fuel.
- Aviation turbine fuel composition characteristics include a maximum content of aromatic compounds of 20 per cent by volume, a smokepoint of 20 at a minimum and a final boiling point of not higher than 300°C.
- Aviation turbine fuels are conventionally prepared by upgrading middle distillate feedstock, in particular kerosene by applying a two stage hydrogenation process.
- the conventional process consists of four main sections, initial hydrotreating, intermediate stripping, final hydrotreating and product stripping.
- the reactor will normally contain several beds of a metal sulphide catalyst, such as CoMo, NiMo or NiW on alumina. Most or all hydrogenation of olefins occurs in this stage. Quenching by treat-gas, make-up gas or by feedstock may be employed.
- the reactor effluent is cooled, and gas and liquid are separated.
- the liquid is passed to an intermediate stripper, where dissolved H 2 S and NH 3 are stripped off using either steam or recycle hydrogen.
- the final hydrotreating is performed using a process layout similar to that of the initial hydrotreater.
- the reactor contains typically several beds of a sulphur and nitrogen sensitive noble metal catalyst.
- Temperature control in the final hydrotreater can be achieved using interbed quenching by cold treat-gas, make-up gas, feed oil or product oil.
- the product stripper column removes H 2 S, dissolved gases and any naphtha formed in the process.
- catalytic hydrogenation may be applied for upgrading of low value FCC heavy gasoline to high value aviation turbine fuel, when employing in the final hydrotreating step of a hydrogenation process a Group VIII metal catalyst supported on a carrier comprising a crystalline alumina silicate.
- this invention provides a process for the hydrotreating of FCC heavy gasoline feedstock comprising the step of hydrogenating aromatic compounds in the feedstock by contacting the feedstock in the presence of hydrogen with a catalyst having at least one metal of group VIII in the Periodic Table as its active ingredient supported on a carrier comprising a crystalline alumina silicate.
- Group VIII metals being active as catalyst in the above process comprise preferably of platinum and/or platinum and palladium. Further active hydrogenation catalysts from Group VIII metals are ruthenium, rhodium, osmium, and iridium.
- a carrier being composed of 20-100% by weight of the crystalline alumina silicate and up to 80% by weight of alumina, silica alumina or clay minerals.
- most preferred catalysts consist of 0.2-0.8% by weight of palladium and 0.2-0.5% by weight of platinum supported on a carrier with 30-70% by weight of zeolitic material as the crystalline alumina silicate, the zeolitic material having a unit cell size of 24.30-24.40 ⁇ and 30-70% by weight of alumina.
- Suitable methods for preparing the above hydrogenation catalysts comprise any of the known methods for the preparation of supported catalysts, including impregnation or ion-exchange of the carrier or of the crystalline alumina-silica prior to incorporation in the carrier with a solution of salts of the active metal or metals and subsequent calcination of the carrier.
- a further advantage of the inventive process is a much lower sensitivity to sulphur and nitrogen compounds in the feedstock, which allows the process to be operated at less severe conditions and at high space velocity or reduced catalyst volume.
- FCC heavy gasoline feedstock is desulphurized and denitrogenated in an initial hydrotreating step to levels of less than 500 ppm by weight S and less than 50 ppm by weight N by contact with a conventional high activity desulphurization catalyst, as the known NiMo, NiW or CoMo catalysts mentioned above.
- a conventional high activity desulphurization catalyst as the known NiMo, NiW or CoMo catalysts mentioned above.
- the treated feedstock is then passed to the hydrotreating step and hydrogenated with hydrogen at a H 2 /oil ratio of between 100-1000 Nm 3 /m 3 and hydrogen partial pressure of 10-90 atm, preferably 20-50 atm.
- the feedstock is contacted with the catalyst arranged as fixed bed in the hydrogenation reactor at 190-340°C, preferably 210-290°C weight average bed temperature and a pressure of 25-60 atm.
- the calcined carrier was then impregnated by pore volume filling with an impregnation solution containing 0.6 g of Pt(NH 2 ) 4 (HCO 3 ) 2 and 1.4 g of Pd(NH 3 ) 4 (HCO 3 ) 2 and distilled water up to 60 ml. After impregnation, the catalyst was dried at room temperature for 16 hrs. The dried impregnated catalyst was then calcined in air at 310°C for 2 hours.
- FCC heavy gasoline having a composition as summarized in Table 1 below was in a first step subjected to desulphurization and denitrogenation by hydrotreating in an isothermal bench-scale reactor being loaded with 75 cc of a NiMo based conventional HDS catalyst, commercial available from Haldor Tops ⁇ e A/S under the tradename TK-525.
- the product collected was used for aromatics saturation using the catalyst as prepared under Example 1.
- the hydrodearomatization was conducted in an isothermal bench-scale reactor with a volume of 50 cc.
- Table 4 The conditions for aromatics saturation and the corresponding properties are shown in Table 4 and Table 5, respectively.
- Table 4 Test Conditions Temperature, °C 242 Pressure, ato 35 LHSV, h -1 1.0 H 2 /oil ratio, Nl/l 600
- Table 5 Product Properties HPLC Aromatics, vol% Mono- 5.5 Di- 0.1 Tri- 0 Simulated TBP Dist, °C 10% 145 30% 172 50% 189 70% 204 90% 231 Smoke Point, mm 23
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DK20195 | 1995-02-24 | ||
DK201/95 | 1995-02-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0728833A1 true EP0728833A1 (de) | 1996-08-28 |
Family
ID=8090895
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96101975A Withdrawn EP0728833A1 (de) | 1995-02-24 | 1996-02-12 | Verfahren zur Herstellung von Brennstoff für Flugzeugturbinen |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0728833A1 (de) |
JP (1) | JPH08245968A (de) |
AU (1) | AU4567996A (de) |
BR (1) | BR9600798A (de) |
CA (1) | CA2170220A1 (de) |
NO (1) | NO960740L (de) |
NZ (1) | NZ280999A (de) |
ZA (1) | ZA961474B (de) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2179880A1 (de) * | 1972-04-10 | 1973-11-23 | British Petroleum Co | |
US4240900A (en) * | 1979-05-18 | 1980-12-23 | Exxon Research & Engineering Co. | Process for the hydrogenation of olefins and aromatic compounds |
EP0042461A1 (de) * | 1980-06-23 | 1981-12-30 | Exxon Research And Engineering Company | Verfahren zur katalytischen Hydrierung hydrierbarer Verbindungen in einer Kohlenwasserstofffraktion und hydrierte Kohlenwasserstoffprodukte |
EP0303332A1 (de) * | 1987-08-14 | 1989-02-15 | Shell Internationale Researchmaatschappij B.V. | Hydrierverfahren für Kohlenwasserstofföle |
EP0519573A1 (de) * | 1991-06-21 | 1992-12-23 | Shell Internationale Researchmaatschappij B.V. | Hydrierungskatalysator und Verfahren |
WO1994026846A1 (en) * | 1993-05-10 | 1994-11-24 | Akzo Nobel N.V. | Hydrogenation of aromatics in hydrocarbonaceous feedstocks |
-
1996
- 1996-02-12 EP EP96101975A patent/EP0728833A1/de not_active Withdrawn
- 1996-02-16 NZ NZ280999A patent/NZ280999A/en unknown
- 1996-02-22 AU AU45679/96A patent/AU4567996A/en not_active Abandoned
- 1996-02-23 CA CA002170220A patent/CA2170220A1/en not_active Abandoned
- 1996-02-23 JP JP8036415A patent/JPH08245968A/ja not_active Withdrawn
- 1996-02-23 NO NO960740A patent/NO960740L/no not_active Application Discontinuation
- 1996-02-23 ZA ZA961474A patent/ZA961474B/xx unknown
- 1996-02-23 BR BR9600798A patent/BR9600798A/pt active Search and Examination
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2179880A1 (de) * | 1972-04-10 | 1973-11-23 | British Petroleum Co | |
US4240900A (en) * | 1979-05-18 | 1980-12-23 | Exxon Research & Engineering Co. | Process for the hydrogenation of olefins and aromatic compounds |
EP0042461A1 (de) * | 1980-06-23 | 1981-12-30 | Exxon Research And Engineering Company | Verfahren zur katalytischen Hydrierung hydrierbarer Verbindungen in einer Kohlenwasserstofffraktion und hydrierte Kohlenwasserstoffprodukte |
EP0303332A1 (de) * | 1987-08-14 | 1989-02-15 | Shell Internationale Researchmaatschappij B.V. | Hydrierverfahren für Kohlenwasserstofföle |
EP0519573A1 (de) * | 1991-06-21 | 1992-12-23 | Shell Internationale Researchmaatschappij B.V. | Hydrierungskatalysator und Verfahren |
WO1994026846A1 (en) * | 1993-05-10 | 1994-11-24 | Akzo Nobel N.V. | Hydrogenation of aromatics in hydrocarbonaceous feedstocks |
Also Published As
Publication number | Publication date |
---|---|
NO960740D0 (no) | 1996-02-23 |
BR9600798A (pt) | 1997-12-23 |
NZ280999A (en) | 1997-02-24 |
CA2170220A1 (en) | 1996-08-25 |
NO960740L (no) | 1996-08-26 |
JPH08245968A (ja) | 1996-09-24 |
ZA961474B (en) | 1996-10-03 |
AU4567996A (en) | 1996-09-05 |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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17P | Request for examination filed |
Effective date: 19970228 |
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17Q | First examination report despatched |
Effective date: 19981201 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 19990612 |