EP0273592B1 - Procédé de déparaffinage en continu des huiles d'hydrocarbures - Google Patents
Procédé de déparaffinage en continu des huiles d'hydrocarbures Download PDFInfo
- Publication number
- EP0273592B1 EP0273592B1 EP19870310491 EP87310491A EP0273592B1 EP 0273592 B1 EP0273592 B1 EP 0273592B1 EP 19870310491 EP19870310491 EP 19870310491 EP 87310491 A EP87310491 A EP 87310491A EP 0273592 B1 EP0273592 B1 EP 0273592B1
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- European Patent Office
- Prior art keywords
- catalyst
- hydrogen
- oxygen
- process according
- regenerated
- 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.)
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- 238000000034 method Methods 0.000 title claims description 37
- 230000008569 process Effects 0.000 title claims description 33
- 239000003921 oil Substances 0.000 title claims description 23
- 229930195733 hydrocarbon Natural products 0.000 title claims description 22
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims description 65
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims 1
- 239000010457 zeolite Substances 0.000 description 54
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 34
- 229910021536 Zeolite Inorganic materials 0.000 description 31
- 230000007420 reactivation Effects 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- -1 brewsterite Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical group 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000036619 pore blockages Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/66—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins with moving solid particles
Definitions
- This invention relates to a process for dewaxing hydro carbon oils.
- Dewaxing is required when highly paraffinic oils are to be used in products which need to remain mobile at low temperatures, e.g., lubricating oils, heating oils, jet fuels.
- the higher molecular weight straight chain normal and slightly branched paraffins which are present in oils of this kind are waxes which are the cause of high pour points in the oils and, if adequately low pour points are to be obtained, these waxes must be wholly or partly removed.
- the catalyst has usually been a shape-selective zeolite having a pore size which admits the straight chain n-paraffins either alone or with only slightly branched chain paraffins, but which excludes more highly branched materials, cycloaliphatics and aromatics.
- Zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 have been proposed for this purpose in dewaxing processes, and their use in described in U. S. Patent Nos. 3,894,938; 4,176,050; 4,181,598; 4,222,855; 4,229,282 and 4,247,388.
- the zeolite catalyst utilized When dewaxing is effected, as is customary, in a fixed bed reactor, the zeolite catalyst utilized ages, loses activity and/or becomes deactivated with time. The rate of aging or deactivation depends, to a great exent, on the nature of the feedstock being dewaxed. Loss of activity is evidenced by the fact that it is necessary to raise the temperature within the reactor to achieve the degree of reaction desired. After a time, the temperature is raised to a point where undesirable side reactions, which detrimentally affect the nature of the product and/ or catalyst efficiency, increase to a value which makes it impractical to continue. Dewaxing is then discontinued and the catalyst is reactivated by treatment with hydrogen at an elevated temperature or regenerated by burning with oxygen in an oxygen-containing gas. An obvious disadvantage of such reactivation/ regeneration is that the dewaxing process cannot be carried out while the catalyst is undergoing reactivation/regeneration.
- This invention provides a continuous process for the shape-selective catalytic hydrodewaxing of a hydrocarbon oil which comprises introducing the hydrocarbon oil, shape-selective dewaxing catalyst and hydrogen at an upper portion of a moving bed reactor, removing dewaxed hydrocarbon oil, partially spent catalyst, and unconsumed hydrogen at a lower portion of the moving bed reactor, separating the dewaxed hydrocarbon oil and the unconsumed hydrogen, reactivating the partially spent catalyst and returning the reactivated catalyst to an upper portion of the moving bed reactor at a rate such that the temperature within the reactor remains constant.
- reactivation of the spent catalyst is with hydrogen at an elevated temperature or by burning with oxygen in an oxygen-containing gas.
- both forms of reactivation may be utilized sequentially or in parallel, taking care that hydrogen-containing and oxygen-containing streams are not mixed and that the oxygen-regenerated catalyst is essentially free of oxygen gas before being returned to the dewaxing reactor.
- Fig. 1 is a flowchart illustrating overall operation of the process of the invention
- Fig. 2 is a flowchart illustrating an oxygen regeneration system for use in conjunction with the process illustrated in Fig. 1.
- the present process may be used to dewax a variety of hydrocarbon oil feedstocks ranging from relatively light distillate fractions up to high boiling stocks, such as whole crude petroleum, reduced crudes, vacuum tower residua, fluid catalyst cracking (FCC) tower bottoms, gas oils, vacuum gas oils, deas- phalted residua and other heavy oils.
- the feedstock will normally be a C + 16 feedstock, since lighter oils will usually be free of significant quantities of waxy components.
- the process is particularly applicable to waxy distillate stocks, such as gas oils, kerosenes, jet fuels, lubricating oil stocks, heating oils and other distillate fractions, whose pour point and viscosity need to be maintained within certain specification limits.
- the feedstock will normally contain paraffins, olefins, naphthenes, aromatics and heterocyclic compounds and with a substantial proportion of higher molecular weight n-paraffins and slightly branched paraffins which contribute to the waxy nature of the feedstock.
- n-paraffins and slightly branched chain paraffins undergo limited cracking or hydrocracking to form liquid range materials, thereby both reducing the pour point and lowering the viscosity of the feedstock being dewaxed.
- Some isomerization of straight chain and slightly branched chain paraffins to more highly branched aliphatics may also take place, and contribute to lowering the pour point.
- the preferred catalysts for hydrodewaxing are those shape-selective zeolites having a Constraint Index within the range of 1 to 12. These zeolites retain a degree of crystallinity for long periods, in spite of the presence of steam at high temperature, which induces irreversible collapse of the framework of other zeolites, e.g., of the X and A type. Furthermore, carbonaceous deposits, when formed, may be removed by burning at higher than usual temperatures to restore activity. In many environments, the zeolites of this calss exhibit very low coke-forming capability, conducive to very long times on stream between burning regenerations.
- the crystal structure of this class of zeolites provides constrained access to, and egress from, the intracrystalline free space by virtue of having a pore dimension greater than 5 Angstroms, and pore windows of a size such as would be provided by 10-membered rings of oxygen atoms. It is to be understood, of course, that these rings are those formed by the regular disposition of the tetrahedra making up the anionic framework of the crystalline aluminosilicate, the oxygen atoms themselves being bonded to the silicon or aluminum atoms at the centers of the tetrahedra.
- the preferred type zeolites useful in this invention possess, in combination, a silica-to-alumina mole ratio of at least 12, and a structure providing constrained access to the crystalline free space.
- the zeolite will have a silica/alumina ratio greater than 12.
- the silica-to-alumina ratio referred to may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zeolite crystal and to exclude aluminum in the binder or in cationic or other form within the channels.
- Such zeolites after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e., they exhibit "hydrophobic" properties. It is believed that this hydrophobic character is advantageous in the present invention.
- the type of zeolites described freely sorb normal hexane and have a pore dimension greater than 5 Angstroms.
- the structure must provide constrained access to large modules. It is sometimes possible to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of oxygen atoms, then access by molecules of larger cross-section than normal hexane is excluded, and the zeolite is not of the desired type. Windows of 10-membered rings are preferred, although, in some instances excessive puckering or pore blockage may render these zeolites ineffective.
- a simple determination of the "Constraint Index" may be made by passing continuously a mixture of an equal weight of normal hexane and 3-methylpentane over a sample of zeolite at atmospheric pressure, according to the following procedure.
- a sample of the zeolite, in the form of pellets or extrudate, is crushed to a particle size about that of coarse sand and mounted in a glass tube.
- the zeolite Prior to testing, the zeolite is treated with a stream of air at 1000 ° F (538 ° C) for at least 15 minutes.
- the zeolite is then flushed with helium and the temperature adjusted between 550 ° to 950 ° F (288 ° -510 ° C) to give an overall conversion of between 10 and 60%.
- the mixture of hydrocarbons is passed at 1 liquid hourly space velocity (i.e., volume of liquid hydrocarbon per volume of zeolite per hour) over the zeolite with a helium dilution to give a helium to total hydrocarbon mole ratio of 4:1.
- a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining unchanged for each of the two hydrocarbons.
- Constraint Index approximates the ratio of the cracking rate constants for the two hydrocarbons.
- Zeolites suitable for the present invention are those having a Constraint Index in the range of 1 to 12.
- Constraint Index (CI) values for some typical zeolites are:
- Constraint Index values typically characterize the specified zeolites, but that such are the cummulative result of several variables used in determination and calculation thereof.
- the Constraint Index may vary within the indicated approximate range of 1 to 12.
- other variables such as the crystal size of the zeolite, the presence of possible occluded contaminants and binders intimately combined with the zeolite may affect the Constraint Index.
- the class of zeolites defined herein is exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-38 and other similar materials.
- U. S. Patent No. 3,702,886 describes and claims ZSM-5.
- ZSM-11 is described in U.S. Patent No. 3,709,979.
- ZSM-12 is described in U. S. Patent No. 3,832,449.
- ZSM-35 is described in U. S. Patent No. 4,016,245.
- ZSM-38 is more particularly described in U. S. Patent No. 4,046,859.
- the specific zeolites described, when prepared in the presence of organic cations, are catalytically inactive, possibly because, the intracrystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 1000 ° F (538 ° C) for 1 hour, for example, followed by base-exchange with ammonium salts followed by calcination at 1000 ° F (538 ° C) in air.
- the presence of organic cations in the forming solution may not be absolutely essential to the formation of this type zeolite; however, the presence of these cations does appear to favor the formation of this special type of zeolite. More generally, it is desirable to activate this type catalyst by base-exchange with ammonium salts followed by calcination in air or about 1000 ° F (538 ° C) for from 15 minutes to 24 hours.
- Natural zeolites may sometimes be converted to this type zeolite catalyst by various activation procedures and other treatments, such as base-exchange, steaming, alumina extraction and calcination, in combinations.
- Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiard- ite, epistilbite, heulandite, and clinoptilolite.
- the preferred crystalline aluminosilicates are ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38, with ZSM-5 being particularly preferred.
- the zeolites hereof are selected as those having a crystal framework density, in the dry hydrogen form, of not substantially below 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired. Therefore, the preferred zeolites of this invention are those having a Constraint Index as defined above of 1 to 12, a silica-to-alumina ratio of at least 12 and a dried crystal density of not less than 1.6 grams per cubic centimeter.
- the dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on paper 19 of the article on Zeolite Structure by W. M. Meier.
- the crystal framework density may be determined by classical pycnometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which is not sorbed by the crystal. It is possible that the unusual sustained activity and stability of this class of zeolites is associated with its high crystal anionic framework density of not less than 1.6 grams per cubic centimeter. This high density, of course, must be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, is important as the locus of catalytic activity.
- Crystal framework densities of some typical zeolites are:
- the zeolite When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammonium form as a result of ammonium ion-exchange and calcination of the ammonium form to yield the hydrogen form.
- the hydrogen form In addition to the hydrogen form, other forms of the zeolite, wherein the original alkali metal has been reduced to less than 1.5 wt %, may be used.
- the original alkali metal of the zeolite may be replaced by ion-exchange with other suitable ions of Groups IB to VIII of the Periodic Table, including, by way of example, nickel, copper, zinc, palladium, calcium or rare earth metals.
- crystalline aluminosilicate zeolite in another material resistant to the temperature and other conditions employed in the process.
- matrix materials include synthetic or naturally occurring substances, as well as inorganic materials such as clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides.
- Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as dixie, Mc-Namee-Georgia and Florida clays, or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite.
- Such clays can be used in the raw state, as originally mined, or initially subjected to calcination, acid treatment or chemical modification.
- the zeolites employed herein may be composited with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-ber- ylia, silica-titania, as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia, zirconia.
- the matrix may be in the form of a cogel.
- the relative proportions of zeolite component and inorganic oxide gel matrix may vary widely, with the zeolite content ranging from between 1 to 99 wt %, and more usually in the range of 5 to 80 wt % of the composite.
- the catalysts employed in this invention are constituted by a zeolite, as described above, in intimate combination with a hydrogenating component, such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as platinum or palladium.
- a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as platinum or palladium.
- a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal, such as platinum or palladium.
- a noble metal such as platinum or palladium
- Such component can be exchanged into the composition, impregnated therein or physically intimately admixed therewith.
- Such component can be impregnated in or onto ze
- the compounds of the useful platinum or other metals can be divided into compounds in which the metal is present in the cation of the compound and compounds in which it is present in the anion of the compound. Both types of compounds which contain the metal in the ionic state can be used.
- hydrodewaxing is accomplished by contacting a waxy lube base stock with hydrogen and catalyst in a moving-bed reaction zone containing a mixture of reactivated and/or regenerated catalyst.
- reactivation generally refers to treatment with hydrogen and regeneration to burning with oxygen. However, in practice, those terms are often used interchangeably.
- Catalyst is continuously or intermittently removed from the bottom of the hydrodewaxing reactor and passed to a reactivation section, where catalyst is either contacted with a hot hydrogen stream to volatilize and strip entrained and adsorbed hydrocarbons or, alternatively, contacted with an oxygen-containing gas to burn off coke and other accumulations or hydrocarbons.
- Reactivat- ed/regenerated catalyst is returned to the dewaxing zone.
- a small segment of the total catalyst inventory can be continuously or periodically removed and replaced by fresh catalyst to maintain overall catalyst activity.
- Figs. 1 and 2 describe certain configurations for practicing the process of the present invention. In order to simplify the description, furnaces, heat exchangers, pumps and other conventional heat integration equipment are not shown.
- liquid feed is fed to the top of reactor 4 through line 1 along with recycle and makeup hydrogen, typically at a pressure in the range 2170 to 8375 kPa (300 to 1200 psig), from lines 2 and 3, respectively.
- the mixed phase stream passes downward through the catalyst bed and exits the reactor through lines 5 and 6 into the high temperature separator 7.
- the liquid product is removed through line 8 and the vapor stream, containing primarily hydrogen, light hydrocarbons, ammonia and hydrogen sulfide, is removed through line 9.
- the stream is further split in the low temperature separator 10 into a liquefied light hydrocarbon stream exiting through line 11, and a hydrogen-rich stream in line 12.
- the hydrogen stream may be further purified in an amine adsorption system (not shown), and additionally may have water removed by molecular sieve adsorption (not shown) before pressuring back to process conditions in the recycle gas compressor 13.
- Pressurized hydrogen in line 14 is used as recycle hydrogen in line 2, as preliminary catalyst deoiling gas in lines 15 and 16, for pressurizing lock hopper 35 via line 39 and for transporting catalyst via line 17.
- Fresh catalyst is intermittently fed to the top of reactor 4 from storage vessel 18 by way of lock hopper 19, where the catalyst charge is brought up to reactor pressure.
- fresh catalyst mixes with recirculated catalyst transferred from the reactivation/regeneration section through line 20.
- the mixture of reactivated-regenerated and fresh catalyst from the storage vessel is passed to the reactor at a rate such that the temperature within the reactor remains constant at a predetermined value, generally in the range 288 ° to 427 ° C (550 to 800 ° F), chosen, in part, depending on the nature of the feedstock being dewaxed.
- the temperature within the reactor is adjusted by adjusting the feed rate of catalyst being supplied to the reactor.
- reactivation with hydrogen involves treating or contacting the catalyst to be reactivated with hydrogen at elevated temperatures, most generally in the range of 427 ° to 538 ° C (800° to 1000 ° F). Such treatment results in removal of a portion of the carbonaceous deposits formed on the catalyst during dewaxing, and in striping various volatile materials adsorbed onto the catalyst.
- reactivation is effected continuously, or in a batch operation, in reactor 26 with hydrogen from compressor 27 fed through lines 28 and 29. Hydrogen exits the reactor through line 30 to knock-out pot 31 for removal, via line 32, of any liquids stripped from the catalyst.
- a separate stream of hydrogen 33 may also be used as transport gas in line 25.
- Reactivated catalyst leaving reaction 26 via line 34 enters lock hopper 35, where it reduces until it is transported back to reactor 4 through line 36, star valve 37 and lines 38 and 20. Pressure in lock hopper 35 is equalized by hydrogen from line 39.
- the catalyst is regenerated with oxygen, as required.
- regeneration with oxygen involves burning off carbonaceous and other deposits with oxygen in an oxygen-containing gas at elevated temperatures. Since burning with oxygen is exothermic, regeneration generally initiated at a lower temperature, such as 316 ° C (600 ° F), with 1 to 10% oxygen (the oxygen in air is diluted with an inert gas, such as nitrogen), and the temperature and concentration of oxygen are gradually increased until all of the carbonaceous deposits have been oxidized. This generally occurs at a temperature of 48 2° to 538 ° (900 ° to 1000 ° F), with an oxygen concentration of 1 to 20% (air contains about 21 vol % of oxygen).
- Regeneration with oxygen can be done either continuously or an be alternated with hydrogen reactivation.
- a separate oxygen regeneration system is installed in parallel or in series with a hydrogen reactivation system, illustrated in Fig. 1.
- the oxygen regeneration system illustrated in Fig. 2 includes a double valve isolation system 61, 61', 62 and 62' upstream and downstream, respectively, to separate the oil/hydrogen atmosphere of the reactor system from the oxygen-containing atmosphere of the regeneration system.
- the catalyst to be regenerated by treatment with oxygen is passed through initial isolation valve system 61 and 61' into lock hopper 63 and purged free of hydrogen (purge system not shown).
- the purged catalyst is then fed by valve 70 to regenerator 64, where it is contacted with recycle gas stream 65 containing combustion gas mixed with makeup air 66.
- Combustion gases exit the regenerator via line 71 and are passed to separator-cooler 67, where water separates and is removed.
- the catalyst passed downflow via valve 72 to catalyst cooler/lock hopper 68, where oxygen-containing gases are purged (purge system not shown).
- the purged catalyst passes through isolation valves 62 and 62' to transfer line 69 for return to catalyst storage vessel 18 (shown in Fig. 1).
- the reactivation vessel 26 (shown in Fig. 1) is used for both hydrogen reactivation and oxygen regeneration (the system is run in alternating modes for treatment with hydrogen and oxygen). As before, care should be taken to ensure that the oxygen-containing and hydrogen-containing gas streams do not mix and oxygen-regenerated catalyst is stripped of adsorbed oxygen prior to return to the dewaxing process.
- the dewaxing process of the present invention involves more than the conversion of a batch process to a continuous one.
- the present process permits operation at lower temperature (in conventional processes, the temperature is progressively raised to compensate for loss in catalyst activity until it becomes necessary to stop dewaxing and reactivate and/or regenerate the catalyst).
- the temperature is progressively raised to compensate for loss in catalyst activity until it becomes necessary to stop dewaxing and reactivate and/or regenerate the catalyst.
- a catalyst of uniform activity there is obtained, starting with a particular feedstock, a uniform dewaxed product.
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US93809486A | 1986-12-04 | 1986-12-04 | |
US938094 | 1986-12-04 |
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EP0273592A1 EP0273592A1 (fr) | 1988-07-06 |
EP0273592B1 true EP0273592B1 (fr) | 1990-06-27 |
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Application Number | Title | Priority Date | Filing Date |
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EP19870310491 Expired EP0273592B1 (fr) | 1986-12-04 | 1987-11-27 | Procédé de déparaffinage en continu des huiles d'hydrocarbures |
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Country | Link |
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EP (1) | EP0273592B1 (fr) |
JP (1) | JPS63159495A (fr) |
CA (1) | CA1299131C (fr) |
DE (1) | DE3763419D1 (fr) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU581439B2 (en) * | 1984-07-05 | 1989-02-23 | Mobil Oil Corporation | Method of adding zsm-5 containing catalyst to moving bed catalytic cracking units |
EP0188898B1 (fr) * | 1984-12-21 | 1990-09-19 | Mobil Oil Corporation | Procédé de déparaffinage en cascade |
US4600700A (en) * | 1984-12-28 | 1986-07-15 | Mobil Oil Corporation | Regeneration of platinum-containing zeolite catalysts which includes oxidation of coke in the presence of water |
-
1987
- 1987-11-16 CA CA000551915A patent/CA1299131C/fr not_active Expired - Lifetime
- 1987-11-27 EP EP19870310491 patent/EP0273592B1/fr not_active Expired
- 1987-11-27 DE DE8787310491T patent/DE3763419D1/de not_active Expired - Fee Related
- 1987-12-04 JP JP30848787A patent/JPS63159495A/ja active Pending
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JPS63159495A (ja) | 1988-07-02 |
EP0273592A1 (fr) | 1988-07-06 |
CA1299131C (fr) | 1992-04-21 |
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