EP0104807A2 - Emploi de haute pression pour l'amélioration de la qualité de produit et l'augmentation de la longueur du cycle dans le déparaffinage catalytique des lubrifiants - Google Patents
Emploi de haute pression pour l'amélioration de la qualité de produit et l'augmentation de la longueur du cycle dans le déparaffinage catalytique des lubrifiants Download PDFInfo
- Publication number
- EP0104807A2 EP0104807A2 EP83305125A EP83305125A EP0104807A2 EP 0104807 A2 EP0104807 A2 EP 0104807A2 EP 83305125 A EP83305125 A EP 83305125A EP 83305125 A EP83305125 A EP 83305125A EP 0104807 A2 EP0104807 A2 EP 0104807A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- raffinate
- dewaxing
- dewaxed
- catalyst
- pour point
- 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.)
- Granted
Links
- 230000003197 catalytic effect Effects 0.000 title claims description 19
- 239000010457 zeolite Substances 0.000 claims abstract description 58
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 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 16
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 239000010779 crude oil Substances 0.000 claims abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 description 22
- 239000013078 crystal Substances 0.000 description 14
- 239000001993 wax Substances 0.000 description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 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
- 239000011159 matrix material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical group 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
- 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
- 239000007788 liquid Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Chemical group 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse 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
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 2
- 239000012634 fragment Substances 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
- 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
- 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
- 238000002156 mixing Methods 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000036619 pore blockages Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect 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
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052677 heulandite Inorganic materials 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 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
- 238000012552 review Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052678 stilbite Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 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
- 238000010977 unit operation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C10G45/58—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
- C10G45/60—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 characterised by the catalyst used
- C10G45/64—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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Definitions
- This invention relates to the manufacture of high qrade viscous oil products from crude petroleum fractions, particularly high quality lube base stock oils from crude stocks of high wax content, commonly classified as “wax base” as compared with the “naphthenic base” crudes.
- the latter crudes are relatively lean in straight chain paraffins and yield viscous fractions which inherently possess low pour points.
- a process for preparing high quality lube base stock oil from waxy crude oil which comprises separating from the waxy crude a distillate fraction thereof having an initial boiling point of at least 232°C (450°F) and a final boiling point less than 566°C (1050°F), extracting the distillate fraction with a solvent selective for aromatic hydrocarbons to yield a raffinate from which undesirable compounds have been removed, catalytically dewaxing the raffinate in the presence of hydrogen to a pour point not higher than -1°C (+30°F) by contacting theraffinate at a temperature of 260° to 385°C (500° to 725°F) at a hydrogen partial pressure of 10,350 kPa (1,500 psia) in the absence of hydrotreating catalyst with a dewaxing catalyst comprising an aluminosilicate zeolite having a silica/alumina ratio above 12 and a constraint index between 1 and 12 thereby forming dewaxed raffinate and lower boiling
- High quality lube base stock oils are conventionally prepared by refining distillate fractions or the residuum prepared by vacuum distilling a suitable crude oil from which the lighter portion has been removed by distillation in an atmospheric tower.
- the charge to the vacuum tower is commonly referred to as a "long residuum,” and the residuum from the vacuum tower is distinguished from the starting material by referring to it as the “short residuum.”
- the vacuum distillate fractions are upgraded by a sequence of unit operations, the first of which is solvent extraction with a solvent selective for aromatic hydrocarbons.
- This step serves to remove aromatic hydrocarbons of low viscosity index and provides a raffinate of improved viscosity index and quality.
- Various processes have been used in this extraction stage, and these employ solvents such as furfural, phenol, sulfur dioxide and others.
- the short residuum because it contains most of the asphaltenes of the crude oil, is conventionally treated to remove these asphalt-like constituents prior to solvent extraction to increase the viscosity index.
- the raffinate from the solvent extraction step contains paraffins which adversely affect the pour point.
- the waxy raffinate regardless of whether prepared from a distillate fraction or from the short residuum, must be dewaxed.
- Various dewaxing procedures have been used and the art has gone in the direction of treatment with a solvent such as methyl ethyl ketone (MEK)/toluene mixtures to remove the wax and prepare a dewaxed raffinate.
- MEK methyl ethyl ketone
- the dewaxed raffinate may then be finished by any of a number of sorption or catalytic processes to improve color and oxidation stability.
- the quality of the lube base stock oil prepared by the sequence of operations outlined above depends on the particular crude chosen as well as the severity of treatment for each of the treatment steps. Additionally, the yield of high quality lube base stock oil also depends on these factors and, as a rule, the higher the quality sought, the less the yield. In general, naphthenic crudes are favored because less loss is encountered, particularly in the dewaxing step. In many cases, however, waxy crudes are more readily available and it would be desirable to provide a process for preparing high quality lube base stock oils in good yields from such waxy crude oils.
- That fraction is solvent refined by counter current extraction with at least an equal volume of a selective solvent such as furfural.
- the furfural raffinate is subjected to catalytic dewaxing by mixing with hydrogen and contacting at 260°-357°C (500°-675°F) with a catalyst containing a hydrogenation metal and zeolite ZSM-5 or other aluminosilicate zeolite having a silica/alumina ratio above 12 and a constraint index of 1 to 12 and space velocity (LHSV) of 0.1 to 2.0 volumes of charge oil per volume of catalyst per hour.
- LHSV space velocity
- the effluent of catalytic dewaxing is then cascaded into a hydrotreater containing, as catalyst, a hydrogenation component on a non-acidic support, such as cobalt-molybdate or nickel-molybdate on alumina.
- the hydrotreater operates at 218° to 316°C (425° to 600 0 F), preferably 246 0 to 288°C (475 to 550°F), and space velocity like that of the catalytic dewaxing reactor.
- the reactions are carried out at hydrogen partial pressures of 1035-10350 kPa (150-1500 psia), at the reactor inlets, and preferably at 1725-3450 kPa (250-500 psia), with 89 to 890 1/1 (500 to 5000 standard cubic feet) of hydrogen per barrel of feed (SCF/B), preferably 267 to 445 1/1 (1500 to 2500 SCF/B).
- the hydrotreating step of the process of U.S. Patent No. 4,137,148 is essential if a lube base stock oil possessing adequate oxidation stability is to be obtained.
- the present process results in a significant lowering of the line-out temperature thereby extending catalyst life and reducing the frequency with which the dewaxing catalyst must be regenerated.
- the wax base crudes (sometimes called “paraffin base") from which the charge stock is derived by distillation constitute a well recognized class of crude petroleums.
- Many scales have been devised for classification of crude, some of which are described in Chapter VII Evaluation of Oil Stocks of "Petroleum Refinery Engineering," W.L. Nelson, McGraw-Hill, 1941.
- a convenient scale identified by Nelson at page 69 involves determination of the cloud point of the Bureau of Mines "Key Fraction No. 2" which boils between 275°C and 300°C (527°F and 572°F) at 40 mm pressure. If the cloud point of this fraction is above -15°C (5°F), the crude is considered to be wax base.
- a propane deasphalted short residuum fraction or a fraction having an initial boiling point of at least 232°C (450°F) and a final boiling point less than 566°C (1050°F) is prepared by distillation of such wax base crude. That fraction is solvent refined by counter current extraction with at least an equal volume (100 vol.%) of a selective solvent such as furfural. It is preferred to use from 1.5 to 3.0 volumes of solvent per volume of oil.
- the furfural raffinate is subjected to catalytic dewaxing by mixing with hydrogen and contacting at 260°-385°C (500°-725°F) and a hydrogen partial pressure of above 10350 kPa (1,500 psia) and preferably.at least 13800 kPa (2,000 psia) with a catalyst containing a hydrogenation metal and zeolite ZSM-5 or other aluminosilicate zeolite having a silica/alumina ratio above 12 and a constraint index of 1 to 12 and preferably a hydrogenation component, using a liquid hourly space velocity (LHSV) of 0.1 to 2.0 volumes of charge oil per volume of catalyst per hour.
- the preferred space velocity is 0.5 to 1.0 LHSV.
- the higher melting point waxes so removed are those of higher market value than the waxes removed in conventionally taking the product to a still lower pour point below -12°C (10°F).
- cracked (and hydrogenated) fragments from cracking wax molecules in the catalytic dewaxer will have adverse effects on flash and fire points of the dewaxed raffinate product and are therefore removed by distillation of the product to meet flash and fire point specifications.
- the catalyst employed in the catalytic dewaxing reactor and the temperature in that reactor are important to success in obtaining good yields and very low pour point product.
- the hydrotreater catalyst may be any of the catalysts commercially available for that purpose but the temperature should be held within narrow limits for best results.
- the solvent extraction technique is well understood in the art and needs no detailed review here.
- the severity of extraction is adjusted to the composition of the charge stock to meet specifications for the particular lube base stock and the contemplated end-use. This severity will be determined in practice of this invention in accordance with well established practices.
- the dewaxing catalyst is a composite of hydrogenation- metal, preferably a metal of Group VIII of the Periodic Table,- associated with the acid form of a novel class of aluminosilicate zeolite having a silica/alumina ratio of at least about 12 and a constrained access to the intracrystalline free space, as more fully described hereinbelow.
- zeolites An important characteristic of the crystal structure of this class of zeolites is that it 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 about 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 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.
- zeolites with a silica to alumina ratio of at least 12 are useful, it is preferred to use zeolites having higher ratios of at least 30. 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 zeolites useful in this invention freely sorb normal hexane and have a pore dimension greater than about 5 Angstroms.
- the structure must provide constrained access to larger molecules. 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 small sample, approximately 1 gram or less, of catalyst 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 538°C (1000°F) for at least 15 minutes.
- the zeolite is then flushed with helium and the temperature adjusted between 288°C and 510°C (550°F and 950°F) to give an overall conversion between 10% and 60%.
- the mixture of hydrocarbons is passed at 1 liquid hourly space velocity (i.e., 1 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 chromotography, to determine the fraction remaining unchanged for each of the two hydrocarbons.
- the "constraint index” is calculated as follows:
- the 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 approximate range of 1 to 12.
- Constraint Index (CI) values for some typical zeolites are:
- the above constraint index values typically characterize the specified zeolites but that such are the cumulative 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 constraint index while affording a highly useful means for characterizing the zeolites of interest-is approximate, taking into consideration the manner of its determination, with probability, in some instances, of compounding variable extremes. However, in all instances, at a temperature within the above-specified range of 288° to 510°C (550°F to 950°F), the constraint index will have a value for any given zeolite of interest herein within the approximate range of 1 to 12.
- 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 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 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 538°C (1000°F) for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 38°C (100°F) 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 at about 538°C (1000°F) 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 ferrerite, brewsterite, stilbite, dachiardite, epistilbite, heulandite, and clinoptilolite.
- the preferred crystalline aluminosilicates are ZSM-5, ZSM-11, ZSM-12, ZSM-38 and ZSM-35, with ZSM-5 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 from 1 to 12, a silica to alumina ratio of at least about 12 and a dried crystal density of not less than about 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 page 19 of the article on Zeolite Structure by W.M.
- 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 about 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 about 1.5 percent by weight 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, for example, nickel, copper, zinc, palladium, calcium or rare earth metals.
- Such matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, 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, McNamee-Georgia and Florida clays or others in which the main mineral constituent is haloysite, 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-berylia, 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 1 to 99 percent by weight and more usually in the range of from 5 to 80 percent by weight of the composite.
- the effluent of the dewaxing unit is topped by distillation, i.e., the most volatile components are removed, to meet flash and fire point specifications.
- a hydrotreating step such as that described in U.S. Patent No. 4,137,148, supra, is ordinarily not required to provide a lube base stock oil having a suitable level of oxidation stability, in some cases it may be desirable to conduct such a step herein.
- the catalytic dewaxing effluent is introduced into a hydrotreater containing, as catalyst, a hydrogenation component on a non-acidic support, such as cobalt-molybdate or nickel-molybdate on alumina.
- Hydrotreating is effected therein at a temperature of from about 218 0 to 316°C (425° to 600 0 F), hydrogen partial pressures of 1035-10350 kPa (150-1500 psia), at the reactor inlets, and preferably 1725-3450 kPa (250-500 psia), with 89 to 890 1/1 (500 to 5000 standard cubic feet) of hydrogen per barrel of feed (SCF/B), preferably 267 to 445 1/1 (1500 to 2500 SCF/B).
- Examples 1 to 4 illustrate of the high-pressure catalytic dewaxing process of the present invention carried out upon two heavy neutral lube stocks, designated Raffinate A and Raffinate B, and EXample 5 illustrates a low-pressure combined catalytic dewaxing/hydrotreating process such as described in U.S. Patent No. 4,137,148. In all examples, a nickel-containing HZSM-5 catalyst was employed.
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US42584282A | 1982-09-28 | 1982-09-28 | |
US425842 | 1982-09-28 |
Publications (3)
Publication Number | Publication Date |
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EP0104807A2 true EP0104807A2 (fr) | 1984-04-04 |
EP0104807A3 EP0104807A3 (en) | 1986-08-13 |
EP0104807B1 EP0104807B1 (fr) | 1990-04-04 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19830305125 Expired EP0104807B1 (fr) | 1982-09-28 | 1983-09-05 | Emploi de haute pression pour l'amélioration de la qualité de produit et l'augmentation de la longueur du cycle dans le déparaffinage catalytique des lubrifiants |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0104807B1 (fr) |
JP (1) | JPS5980491A (fr) |
AU (1) | AU561968B2 (fr) |
BR (1) | BR8305306A (fr) |
CA (1) | CA1228563A (fr) |
DE (1) | DE3381413D1 (fr) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0161833A2 (fr) * | 1984-05-03 | 1985-11-21 | Mobil Oil Corporation | Déparaffinage catalytique d'huiles légères et lourdes dans deux réacteurs parallèles |
US5098551A (en) * | 1989-05-30 | 1992-03-24 | Bertaux Jean Marie A | Process for the manufacture of lubricating base oils |
FR2785617A1 (fr) * | 1998-11-06 | 2000-05-12 | Inst Francais Du Petrole | Procede flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite |
WO2000027950A1 (fr) * | 1998-11-06 | 2000-05-18 | Institut Francais Du Petrole | Procede flexible de production d'huiles medicinales et eventuellement de distillats moyens |
FR2797270A1 (fr) * | 1999-08-02 | 2001-02-09 | Inst Francais Du Petrole | Procede et flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite |
AU2012211757B2 (en) * | 2011-02-04 | 2015-09-03 | Cosmo Oil Co., Ltd. | Method for producing hydrocarbon oil |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06916B2 (ja) * | 1984-06-01 | 1994-01-05 | 東燃株式会社 | 低流動点潤滑油基油の製造方法 |
US9796936B2 (en) * | 2015-09-09 | 2017-10-24 | Chevron U.S.A. Inc. | Production of heavy API group II base oil |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2010321A (en) * | 1977-12-20 | 1979-06-27 | Mobil Oil Corp | Manufacture of lube base stock oil |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4137148A (en) * | 1977-07-20 | 1979-01-30 | Mobil Oil Corporation | Manufacture of specialty oils |
US4357232A (en) * | 1981-01-15 | 1982-11-02 | Mobil Oil Corporation | Method for enhancing catalytic activity |
-
1983
- 1983-09-05 EP EP19830305125 patent/EP0104807B1/fr not_active Expired
- 1983-09-05 DE DE8383305125T patent/DE3381413D1/de not_active Expired - Fee Related
- 1983-09-08 CA CA000436263A patent/CA1228563A/fr not_active Expired
- 1983-09-14 AU AU19109/83A patent/AU561968B2/en not_active Ceased
- 1983-09-27 BR BR8305306A patent/BR8305306A/pt unknown
- 1983-09-28 JP JP17835783A patent/JPS5980491A/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2010321A (en) * | 1977-12-20 | 1979-06-27 | Mobil Oil Corp | Manufacture of lube base stock oil |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0161833A2 (fr) * | 1984-05-03 | 1985-11-21 | Mobil Oil Corporation | Déparaffinage catalytique d'huiles légères et lourdes dans deux réacteurs parallèles |
EP0161833A3 (en) * | 1984-05-03 | 1988-01-20 | Mobil Oil Corporation | Catalytic dewaxing of light and heavy oils in dual parallel reactors |
US5098551A (en) * | 1989-05-30 | 1992-03-24 | Bertaux Jean Marie A | Process for the manufacture of lubricating base oils |
FR2785617A1 (fr) * | 1998-11-06 | 2000-05-12 | Inst Francais Du Petrole | Procede flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite |
WO2000027950A1 (fr) * | 1998-11-06 | 2000-05-18 | Institut Francais Du Petrole | Procede flexible de production d'huiles medicinales et eventuellement de distillats moyens |
FR2797270A1 (fr) * | 1999-08-02 | 2001-02-09 | Inst Francais Du Petrole | Procede et flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite |
AU2012211757B2 (en) * | 2011-02-04 | 2015-09-03 | Cosmo Oil Co., Ltd. | Method for producing hydrocarbon oil |
US9487713B2 (en) | 2011-02-04 | 2016-11-08 | Japan Oil, Gas And Metals National Corporation | Method for producing hydrocarbon oil |
Also Published As
Publication number | Publication date |
---|---|
DE3381413D1 (de) | 1990-05-10 |
AU561968B2 (en) | 1987-05-21 |
BR8305306A (pt) | 1984-05-08 |
AU1910983A (en) | 1984-04-05 |
CA1228563A (fr) | 1987-10-27 |
EP0104807A3 (en) | 1986-08-13 |
EP0104807B1 (fr) | 1990-04-04 |
JPS5980491A (ja) | 1984-05-09 |
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