US3629096A - Production of technical white mineral oil - Google Patents
Production of technical white mineral oil Download PDFInfo
- Publication number
- US3629096A US3629096A US647628A US3629096DA US3629096A US 3629096 A US3629096 A US 3629096A US 647628 A US647628 A US 647628A US 3629096D A US3629096D A US 3629096DA US 3629096 A US3629096 A US 3629096A
- Authority
- US
- United States
- Prior art keywords
- hydrogen
- alumina
- catalyst
- oil
- platinum
- 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.)
- Expired - Lifetime
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- 239000002480 mineral oil Substances 0.000 title claims abstract description 15
- 235000010446 mineral oil Nutrition 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 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 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 239000010688 mineral lubricating oil Substances 0.000 claims abstract description 8
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 239000010687 lubricating oil Substances 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011959 amorphous silica alumina Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 230000001050 lubricating effect Effects 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000000017 hydrogel Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- -1 iron group metal oxides Chemical class 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- SPYRCJAMLFTYOB-UHFFFAOYSA-N (cyanatohexasulfanyl) cyanate Chemical compound S(SSSSSOC#N)OC#N SPYRCJAMLFTYOB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 108091034341 Gamma family Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 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
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000010779 crude oil Substances 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
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005057 refrigeration Methods 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
-
- 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
- C10G2400/14—White oil, eating oil
Definitions
- This invention relates to a process for the'production of technical grade white mineral oil from raw, waxy mineral oil distillates. More particularly, this invention concerns a hydrorefining, hydroisomerization-hydrocracking, aromatic saturation, catalytic conversion process for the production of technical grade white mineral oil in increased yields and at reduced operating costs.
- the present invention concerns a hydrorefining, hydroisomerization-hydrocracking, aromatic saturation process wherein a raw, waxy, lubricating oil distillate having a high pour point, and a high aromatic content is converted into a technical grade white mineral oil in increased yields and at reduced operating coats.
- the raw, waxy, lubricating oil distillate is contacted in a first stage 'with hydrogen in the presence of a desulfurization-denitrogenation type catalyst under hydrorefining conditions and treated in a second stage with hydrogen in the presence of a hydroisomerizationhydrocracking catalyst.
- the oil of lubricating viscosity in the second stage product is further contacted in a third stage with hydrogen under aromatic saturation conditions to produce high quality technical grade white mineral oil.
- the mineral lubricating oil distillates to be treated by the process of the present invention are raw, waxy lubricating oil distillates which may even represent the complete distillate lubricating oil fraction derived from a waxy crude oil.
- the lubricating oil distillates useful as feedstocks in the present invention often possess a viscosity in the range of about 35 to 90 SUS at 2 F., an aromatic carbon content of about to 30 percent, a pour point of atleast about 70 F., and boil primarily in the range of about 600 to 1,200 F.
- the hydrorefining treatment in the first stage of the present process is conducted at temperatures of about 600 to 800 F., preferably about 675 to 725 F
- the other reaction conditions generally can include pressures of about 500 to 3,000 p.s.i.g., preferably about 2,000 to 3,000 p.s.i.g., weight hourly space velocities (WHSV) of about 0.2 to 2, preferably about 0.25 to 0.5; and molecular hydrogen to feed oil ratios of about 1,000 to 5,000 SCF/B, preferably about 1,500 to 2,500 SCF/B.
- WHSV weight hourly space velocities
- the hydrogenated oil from the first hydrogenation stage is subjected to a second hydrogenation operation in which the catalyst is such that hydroisomerization and hydrocracking are effected.
- temperatures in the second stage range from about 600 to 950 F., with temperatures of about 650 to 800 F. being preferred.
- Other reaction conditions can include pressures of about 500 to 3,000 p.s.i.g., preferably about 2,000 to 3,000 p.s.i.g., weight hourly space velocities of about 0.25 to 2, preferably about 0.25 to 0.5, and molecular hydrogen to feed oilratio of about 1,000 to 5,000 SCF/B, preferably about 2,000 to 3,000 SCF/B.
- the aromatic saturation of the product of lubricating viscosity made in the second stage is in the third stage of the operation of this invention, and is conducted at a temperature of about 450 to 700 F., preferably about 550 to 600 F.
- Other reaction conditions can include a pressure of about 500 to 3,000 p.s.i.g., preferably about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.2 to 2, preferably about 0.25 to 0.5, and a hydrogen to feed oil rate of about 1,000 to 5,000 SCF/B, preferably about 2,000 to 3,000 SCF/B.
- the desulfurization-denitrogenation type catalysts used in the first stage of the present process can be the sulfur-resistant, nonprecious metal hydrogenation catalysts, such as those conventionally employed in the hydrogenation of heavy petroleum oils.
- suitable catalytic ingredients are tin, vanadium, members of Group VlB in the Periodic Table, i.e. chromium, molybdenum and tungsten, and metals of the iron group, i.e. iron, cobalt and nickel. These metals are present in catalytically effective amounts, for instance, about 2 to 30 weight percent, and may be in elemental form or in combined form such as the oxides or sulfides, the sulfides being preferred.
- Such mixtures or compounds are nickel molybdate, tungstate or chromate (or thiomolybdate, thio-tungstate or thiochromate) or mixtures of nickel or cobalt oxides with molybdenum, tungsten or chromium oxides,
- these catalytic ingredients are generally employed while disposed upon a suitable carrier of the solid oxide refractory type, e.g., a predominantly calcined or activated alumina or other base exerting little cracking effect.
- a suitable carrier of the solid oxide refractory type e.g., a predominantly calcined or activated alumina or other base exerting little cracking effect.
- Commonly employed catalysts have about 1 to 10 percent of an iron group metal and 5 to 25 percent of a Group VlB metal (calculated as the oxide).
- the catalyst is nickel molybdate supported on alumina.
- Such preferred catalyst can be prepared, for instance, by the method described in U.S. Pat. No. 2,93
- the platinum group metal-containing hydroisomerizationhydrocracking catalyst used in the second stage of the method of the present invention is not normally sulfur-resistant and contains a major amount of an amorphous silica-alumina composite, containing for instance, about 5 to 45, preferably about 10 to 20, weight percent alumina on a dry basis; about 3 to 25, preferably about 5 to 10, weight percent of a hydrogenexchanged crystalline alumino-silicate having a silica-to-alumina mole ratio greater than 3:1; and a catalytic amount, say about 0.1 to 5, preferably about 0.3 to 2, weight percent of a platinum group metal.
- an amorphous silica-alumina composite containing for instance, about 5 to 45, preferably about 10 to 20, weight percent alumina on a dry basis; about 3 to 25, preferably about 5 to 10, weight percent of a hydrogenexchanged crystalline alumino-silicate having a silica-to-alumina mole ratio greater than 3:1; and a catalytic
- the catalyst may also contain a small amount, e.g., less than about 1 weight percent of halide such as chloride or fluoride. If desired, a small amount, for instance about 5 to 20 or more weight percent of a suitable binder material, for example, alumina hydrogel, may be added to the second stage catalyst composition especially if the catalyst is formed by extrusion.
- a suitable binder material for example, alumina hydrogel
- the platinum group metals include such group VlIl metals as, for example, platinum, palladium, rhodium, or iridium.
- the platinum group metal may be present in the metallic form or as a sulfide, oxide or other combined form, The metal may interact with other constituents of the catalyst, but if during use the platinum group metal is present in the metallic form, then it is preferred that it be so finely divided that it is not detectable by X-ray defraction means, i.e. that it exists as crystallites of less than about 50 A. in size.
- the amorphous silica-alumina composite employed in the second stage catalyst of the process of the invention is usually synthetically precipitated.
- the silica-alumina can be prepared by any desired method and several procedures are known in the art.
- a hydrogel can be prepared by coprecipitation or sequential precipitation by either component being the initial material precipitated with at least the principal part of the silica or alumina being made in the presence of the other, Generally the alumina is precipitated in the presence of a silica gel.
- the silica-alumina hydrogel be made by forming a silica hydrogel by precipitation from an alkali metal silicate solution and an acid such as sulfuric acid. Then alum solution may be added to the silica hydrogel slurry.
- the alumina is precipitated by raising the pH into the alkaline range by the addition of an aqueous sodium aluminate solution or by the addition of a base such as ammonium hydroxide.
- a base such as ammonium hydroxide.
- Other techniques for preparing the silica-alumina are well known in the are, and these techniques may be used.
- the silica-alumina is present in xerogel or catalytically active form due to treatment at elevated temperatures as by calcination of the hydrogel.
- the crystalline aluminosilicate component of the second stage catalyst may be synthetic or naturally occurring and has a pore size of about 8 to 15 A., preferably about 10 t 14 A. Usually, with a given material, the pores are relatively uniform in size and often the crystalline alumino-silicate particles used to make the catalyst are primarily less than about 15 microns in size, preferably less than about microns. 1n the crystalline aluminosilicate, the silica-to-alumina mole ratio is greater that 3:1 and is usually not above about 12:1, preferably being about 4 to 6:1.
- the aluminosilicate is at least about 50 percent, preferably at least about 75 percent, hydrogenexehanged.
- Hydrogen exchange is commonly carried out by exchange of the cations of the synthetic or naturally occurring aluminosilicates with ammonium ions, for instance through contact with an aqueous solution of ammonium chloride or other water-soluble ammonium compound and subsequently calcining the aluminosilicate.
- One method of preparing the second stage catalyst is by combining the silica-alumina hydrogel and the hydrogenexchanged crystalline aluminosilicate and drying the mixture, for instance at temperatures of about 230 to 600 F., to con vert the silica-alumina hydrogel to the xerogel form.
- the crystalline aluminosilicate may, if desired, be hydrogenexchanged after it is combined with the silica-alumina hydrogel.
- the dried material can be calcined, for instance, at a temperature of the order of about 700 to 1500 F., preferably about 800 to 1,100" F.
- the platinum group metal may be added before or after the calcination, by, for example, ion exchange or impregnation, 1n any event, after the platinum group metal is added, the catalyst can be dehydrated and activated at the calcination temperature described above.
- An available method for adding the platinum group metal by ion exchange comprises treating the silica-aluminacrystalline alumino-silicate mixture with an aqueous solution containing complex water-soluble, metal-amine cations, both organic and inorganic, of the metal to be deposited in the crystal structure. These complex cations ion-exchange with the cations present in the crystalline aluminosilicate.
- the exchange material is then removed from the solution, dried and activated or calcined, for example, by heating the material up to a temperature of about 250 C. in a flowing stream ofinert dry gas or vacuum. The activation may be effected at a temperature below the temperature at which the complex cations are destroyed.
- the activated material may then be subjected to heat treatment to a temperature not exceeding about 650 C. and preferably not exceeding about 500 C. in vacuum or inert atmosphere whereby the complex cation is destroyed and the platinum group metal is reduced in the material.
- heat treatment to be insufficient to reduce the metal of the complex cations to the elemental state, chemical reduction either alone or in combination with thermal reduction may be employed.
- Alkali metals such sodium are suitable reducing agents for this purpose. Throughout the operation excessive temperatures and extremes of acidity are to be avoided since they may tend to destroy the crystal structure ofthe silica-alumina-crystalline aluminosilicate mixture.
- the platinum group metal may also be added by impregnation.
- the silica-alumina-crystalline aluminosilicate mixture for example, either with or without previous evacuation, may be soaked in either a dilute or concentrated solution, usually aqueous chloroplatinic acid, ammonium hexathiocyanoplatinate (1V) or hexathiocyanate platinic acid, often in an amountjust sufficient to wet the material and be completely absorbed. Also, ifdesired, the solution may be incorporated into the silica-a1umina-crystalline aluminosilicate during the formation ofthe latter.
- the catalyst can, if desired, be formed into macrosized particles by -inch or extruding. Generally, these particles are about l/32 inch to k inch in diameter and about l/16-inch to l-inch or more in length. Although these macrosized particles are usually formed after dehydration and before calcination, this, of course is optional and can be done at any time found most convenient.
- the catalyst employed in the third, or aromatic-saturation stage of the present invention is a platinum group metal-containing hydrogenation catalyst.
- This catalyst like the catalysts of the second stage, is distinguished from the catalysts of the first stage in that it is not normally considered to be sulfur-resistant.
- the catalyst includes catalytically effective amounts of the platinum group metals mentioned above. Often, the platinum group metal is present in an amount, for example, of about 0,01 to 2 weight percent, preferably about 0.1 to 1 weight percent.
- the platinum group metal may be present in the metallic form or as a sulfide, oxide, or other combined form.
- the metal may interact with other constituents of the catalyst but if during use the platinum group metal is present in metallic form, then it is preferred that it be so finely divided that it is not detectable by X-ray diffraction means, i.e. that it exists as crystallites ofless than about 50 A. size. Of the platinum group metals, platinum is preferred.
- the catalysts employed in the third stage of the process of the invention can be prereduced prior to use by heating in the presence of hydrogen, generally at temperatures of about 600 to 800 F.
- the preferred supports have no substantial cracking effect on the hydrocarbon feeds.
- the support is composed predominantly of alumina of the activated or calcined type.
- the alumina base is usually the major component of the catalyst, generally constituting at least about 75 weight percent on the basis of the catalyst and preferably at least about to 99.8 percent.
- the alumina catalyst base can be an activated or gamma family alumina, especially gamma or eta alumina, such as those derived by calcination of amorphous hydrous alumina, alumina monohydrate, alumina trihydrate or their mixtures.
- a catalyst base advantageously used is a mixture predominating in, or containing a major proportion of, for instance about 65 to weight percent, of one or more of the alumina trihydrates, bayerite, nordstandite or gibbsite, and about 5 to 35 weight percent of alumina monohydrate (boehmite), amorphous hydrous alumina or their mixtures.
- the alumina base can contain small amounts of other solid oxides such as silica, magnesia, natural or activated clays (such as kaolinite, montmorillonite, halloysite, etc.), Titania zirconia, etc., or their mixtures.
- platinum group metal to the alumina or other solid refractory type carrier
- the platinum-group metal hydrogenation catalysts used in the third stage of the process of the invention may be employed in the form of macrosized particles generally having a diameter of about 1/32-inch to zfi-inch and a length of about l/l 6-inch to linch or more.
- the catalyst which contained 2.3 percent nickel and 15.6 percent molybdenum as the oxide, was pretreated with hydrogen sulfide at 350 F.
- the hydrotreated product thus formed was flashed to remove light gaseous products and further treated in a second stage at a temperature of 750 F., a pressure of 2,500 p.s.i.g., a weight hourly space velocity of 0.35 and a hydrogen rate of 2,500 SCF/B of feed in the presence of a calcined platinum-containing, silica-alumina-crystalline aluminosilicate extrudate catalyst.
- the catalyst contained about 0.5 weight percent platinum, about 7 weight percent of about 90 percent hydrogen-exchanged crystalline aluminosilicate having a pore size of about 13 A. and a silica-to-alumina mole ratio of about 4 to 1, about 82.5 weight percent silica-alumina xerogel containing about 13 weight percent alumina, and about weight alumina added as a hydrogel.
- the effluent product from the second stage was steam stripped to remove hydrocracked components boiling below the lubricating oil range, and contacted with hydrogen at a temperature of 550 F., a pressure of 2,500 p.s.i.g., a weight hourly space velocity of 0.25 and a hydrogen rate of 2,7500 SCF/B of feed in the presence of a platinum on alumina catalyst containing 0.6 weight percent platinum.
- Technical grade white mineral oil was recovered in a yield of about 30 percent by weight.
- a process of producing a technical white mineral oil which comprises contacting a raw, waxy mineral lubricating oil distillate having a viscosity of about 35 to 90 SUS at 210 F., an aromatic carbon content of about 15 to 30 percent, a pour point of at least about 70 F., and boiling primarily in the range of about 600 to 1,200 F., with hydrogen in the presence of a sulfur-resistant hydrogenation catalyst at a temperature of about 600 to 800 F.
- a hydroisomerization-hydrocracking catalyst comprising a major amount of amorphous silica-alumina composite containing about 5 to 45 weight percent alumina on a dry basis about 3 to 25 weight percent of an at least about 50 percent hydrogen-exchanged crystalline aluminosilicate having a pore size of about 8 to 15 A., and a silica-to-alumina mole ratio greater than 3:1.
- a platinum group metal at a temperature of about 600 to 950 F., removing components boiling below the lubricating oil range from the resulting product, and further contacting resulting hydroisomerized-hydrocracked product fraction of lubricating viscosity with hydrogen in the presence of a hydrogenation catalyst comprising a platinum group metal on a support having no substantial cracking effect on said hydroisomerization-hydrocracked product fraction, at a temperature of about 450 to 700 F. to saturate aromatics and produce technical white mineral oil.
- a process of producing a technical white mineral oil which comprises contacting in a first stage a raw, waxy mineral lubricating oil distillate having a viscosity of about 35 to 90 SUS at 210 F., an aromatic carbon content of about 15 to 30 percent, and a pour point of at least about F., and boiling primarily in the range of about 600 to 1,200 F., with hydrogen in the presence of a catalytic amount of a sulfided nickel molybdate supported on alumina catalyst at a temperature of about 675 to 725 F., a pressure of about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 0.5 and a hydrogen feed rate of about 1,500 to 2,500 SCF/B to provide a hydrorefined oil, contacting said hydrorefined oil in a second stage with hydrogen at a temperature of about 650 to 800 F.
- a hydroisomerizationhydrocracking catalyst which comprises a major amount of amorphous silica-alumina composite containing about 10 to 20 weight percent alumina on a dry basis, about 5 to 10 weight percent of at least about percent hydrogen-exchanged crystalline aluminosilicate having a pore size of 10 to 14 A., a crystal size of less than about 10 microns and a silica-to-alumina mole ratio of about 4 to 6:1, and about 0.3 to 2 weight percent of platinum, removing components boiling below the lubricating oil range from the resulting product, and further contacting the fraction of the oil of lubricating viscosity from said second stage with hydrogen in the presence of a platinumalumina catalyst containing about 0.1 to 1 weight percent platinum at a temperature of about 550 to 600 F., a pressure of about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 0.5 and a hydrogen to feed oil rate of about 2,000 to
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Abstract
Technical grade white mineral oil is produced by a series of steps including treating a mineral lubricating oil distillate with hydrogen in the presence of a sulfur-resistant catalyst (e.g., nickel molybdate on alumina) under hydrorefining conditions. The hydrogenated oil is hydroisomerized and hydrocracked by contact with hydrogen in the presence of a silica-alumina and crystalline-aluminosilicate-containing catalyst having about 0.1 to 5 weight percent of a platinum group metal. The resulting product is further contacted with hydrogen under aromatic saturation conditions in the presence of a platinum group metal-containing hydrogenation catalyst (e.g., platinum on alumina).
Description
United ,States Patent 1 3,629,096
72 Inventor JosephM.Divljak,Jr. 3,301,917 1/1967 Wise 260/683.65
Grifiith, Ind. 3,308,052 3/1967 lreland et al. 208/27 [21] Appl. No. 647,628 3,459,656 8/1969 Rausch 208/57 [22] Filed June 21, 1967 2,779,713 1/1957 Cole et al... 208/57 [45] Patented Dec. 21, 1971 2,967,147 1/1961 Cole 208/144 [73] Assignee Atlantic Richiield Company 3,340,181 9/1967 Diringer et al 208/210 Primary Examiner-Delbert E. Gantz [541 PRODUCTION or TECHNICAL WHITE MINERAL 4mm"! Examiner-Q Crasanakis 01L Attorney-Morton, Bernard, Brown, Roberts & Sutherland 8 Claims, No Drawings Technical grade white mineral is produced 208/210 by a series of steps including treating a mineral lubricating oil [51] lnt.Cl ..C10g3l/ 14, di ill t ith hydrogen in the presence of a sulfur-resistant g l5/02 catalyst (e.g., nickel molybdate on alumina) under hydrorefin- 0 Search l8, conditions The hydrogenatgd is hyd oisomerized and 57. 46 260/633-65 hydrocracked by contact with hydrogen in the presence of a silica-alumina and crystalline-aluminosilicate-containin [56] References cued catalyst having about 0.1 to 5 weight percent of a platinun? UNITED STATES PATENTS group metal. The resulting product is further contacted with 3,487,005 12/1969 Egan et al. 208/59 hydrogen under aromatic saturation conditions in the 3,125,51 1 3/1964 Tupman et al. 208/264 presence of a platinum group metal-containing hydrogenation 3,268,439 8/1966 Tupman et a1 208/1 [2 catalyst (e.g., platinum on alumina).
PRODUCTION OF TECHNICAL WHITE MINERAL OIL This invention relates to a process for the'production of technical grade white mineral oil from raw, waxy mineral oil distillates. More particularly, this invention concerns a hydrorefining, hydroisomerization-hydrocracking, aromatic saturation, catalytic conversion process for the production of technical grade white mineral oil in increased yields and at reduced operating costs.
Conventional refining techniques employed in producing technical grade white lubricating oils from raw, waxy distillates involve, for example, solvent treating, solvent dewaxing, and severe acid treating. These conventional refining techniques suffer from many shortcomings. For example, acid treating and solvent extraction have the inherent disadvantage of producing relatively low value byproduct sludge or extracts, and solvent dewaxing is a relatively costly operation due to high refrigeration requirements and low filter rates. Other techniques, such as urea adduction, encounter great difficulties as a continuous process for refining raw, waxy lubricating oil distillates.
The present invention concerns a hydrorefining, hydroisomerization-hydrocracking, aromatic saturation process wherein a raw, waxy, lubricating oil distillate having a high pour point, and a high aromatic content is converted into a technical grade white mineral oil in increased yields and at reduced operating coats. According to the process of the present invention the raw, waxy, lubricating oil distillate is contacted in a first stage 'with hydrogen in the presence of a desulfurization-denitrogenation type catalyst under hydrorefining conditions and treated in a second stage with hydrogen in the presence of a hydroisomerizationhydrocracking catalyst. The oil of lubricating viscosity in the second stage product is further contacted in a third stage with hydrogen under aromatic saturation conditions to produce high quality technical grade white mineral oil.
The mineral lubricating oil distillates to be treated by the process of the present invention are raw, waxy lubricating oil distillates which may even represent the complete distillate lubricating oil fraction derived from a waxy crude oil. The lubricating oil distillates useful as feedstocks in the present invention often possess a viscosity in the range of about 35 to 90 SUS at 2 F., an aromatic carbon content of about to 30 percent, a pour point of atleast about 70 F., and boil primarily in the range of about 600 to 1,200 F.
The hydrorefining treatment in the first stage of the present process is conducted at temperatures of about 600 to 800 F., preferably about 675 to 725 F, The other reaction conditions generally can include pressures of about 500 to 3,000 p.s.i.g., preferably about 2,000 to 3,000 p.s.i.g., weight hourly space velocities (WHSV) of about 0.2 to 2, preferably about 0.25 to 0.5; and molecular hydrogen to feed oil ratios of about 1,000 to 5,000 SCF/B, preferably about 1,500 to 2,500 SCF/B.
According to my method the hydrogenated oil from the first hydrogenation stage is subjected to a second hydrogenation operation in which the catalyst is such that hydroisomerization and hydrocracking are effected. Thus, temperatures in the second stage range from about 600 to 950 F., with temperatures of about 650 to 800 F. being preferred. Other reaction conditions can include pressures of about 500 to 3,000 p.s.i.g., preferably about 2,000 to 3,000 p.s.i.g., weight hourly space velocities of about 0.25 to 2, preferably about 0.25 to 0.5, and molecular hydrogen to feed oilratio of about 1,000 to 5,000 SCF/B, preferably about 2,000 to 3,000 SCF/B.
The aromatic saturation of the product of lubricating viscosity made in the second stage is in the third stage of the operation of this invention, and is conducted at a temperature of about 450 to 700 F., preferably about 550 to 600 F. Other reaction conditions can include a pressure of about 500 to 3,000 p.s.i.g., preferably about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.2 to 2, preferably about 0.25 to 0.5, and a hydrogen to feed oil rate of about 1,000 to 5,000 SCF/B, preferably about 2,000 to 3,000 SCF/B.
The desulfurization-denitrogenation type catalysts used in the first stage of the present process can be the sulfur-resistant, nonprecious metal hydrogenation catalysts, such as those conventionally employed in the hydrogenation of heavy petroleum oils. Examples of suitable catalytic ingredients are tin, vanadium, members of Group VlB in the Periodic Table, i.e. chromium, molybdenum and tungsten, and metals of the iron group, i.e. iron, cobalt and nickel. These metals are present in catalytically effective amounts, for instance, about 2 to 30 weight percent, and may be in elemental form or in combined form such as the oxides or sulfides, the sulfides being preferred. Mixtures of these materials or compounds of two or more of the oxides or sulfides can be employed, for example, mixtures or compounds of the iron group metal oxides or sulfides with the oxides or sulfides of Group VlB constitute very satisfactory catalysts. Examples of such mixtures or compounds are nickel molybdate, tungstate or chromate (or thiomolybdate, thio-tungstate or thiochromate) or mixtures of nickel or cobalt oxides with molybdenum, tungsten or chromium oxides, As the art is aware and as the specific examples below illustrate, these catalytic ingredients are generally employed while disposed upon a suitable carrier of the solid oxide refractory type, e.g., a predominantly calcined or activated alumina or other base exerting little cracking effect. Commonly employed catalysts have about 1 to 10 percent of an iron group metal and 5 to 25 percent of a Group VlB metal (calculated as the oxide). Advantageously, the catalyst is nickel molybdate supported on alumina. Such preferred catalyst can be prepared, for instance, by the method described in U.S. Pat. No. 2,938,002.
The platinum group metal-containing hydroisomerizationhydrocracking catalyst used in the second stage of the method of the present invention, unlike the catalyst employed in the first stage, is not normally sulfur-resistant and contains a major amount of an amorphous silica-alumina composite, containing for instance, about 5 to 45, preferably about 10 to 20, weight percent alumina on a dry basis; about 3 to 25, preferably about 5 to 10, weight percent of a hydrogenexchanged crystalline alumino-silicate having a silica-to-alumina mole ratio greater than 3:1; and a catalytic amount, say about 0.1 to 5, preferably about 0.3 to 2, weight percent of a platinum group metal. The catalyst may also contain a small amount, e.g., less than about 1 weight percent of halide such as chloride or fluoride. If desired, a small amount, for instance about 5 to 20 or more weight percent of a suitable binder material, for example, alumina hydrogel, may be added to the second stage catalyst composition especially if the catalyst is formed by extrusion.
The platinum group metals include such group VlIl metals as, for example, platinum, palladium, rhodium, or iridium. The platinum group metal may be present in the metallic form or as a sulfide, oxide or other combined form, The metal may interact with other constituents of the catalyst, but if during use the platinum group metal is present in the metallic form, then it is preferred that it be so finely divided that it is not detectable by X-ray defraction means, i.e. that it exists as crystallites of less than about 50 A. in size.
The amorphous silica-alumina composite employed in the second stage catalyst of the process of the invention is usually synthetically precipitated. The silica-alumina can be prepared by any desired method and several procedures are known in the art. For instance, a hydrogel can be prepared by coprecipitation or sequential precipitation by either component being the initial material precipitated with at least the principal part of the silica or alumina being made in the presence of the other, Generally the alumina is precipitated in the presence of a silica gel. It is preferred that the silica-alumina hydrogel be made by forming a silica hydrogel by precipitation from an alkali metal silicate solution and an acid such as sulfuric acid. Then alum solution may be added to the silica hydrogel slurry. The alumina is precipitated by raising the pH into the alkaline range by the addition of an aqueous sodium aluminate solution or by the addition of a base such as ammonium hydroxide. Other techniques for preparing the silica-alumina are well known in the are, and these techniques may be used. In the final catalyst the silica-alumina is present in xerogel or catalytically active form due to treatment at elevated temperatures as by calcination of the hydrogel.
The crystalline aluminosilicate component of the second stage catalyst may be synthetic or naturally occurring and has a pore size of about 8 to 15 A., preferably about 10 t 14 A. Usually, with a given material, the pores are relatively uniform in size and often the crystalline alumino-silicate particles used to make the catalyst are primarily less than about 15 microns in size, preferably less than about microns. 1n the crystalline aluminosilicate, the silica-to-alumina mole ratio is greater that 3:1 and is usually not above about 12:1, preferably being about 4 to 6:1. The aluminosilicate is at least about 50 percent, preferably at least about 75 percent, hydrogenexehanged. That is about 50 percent of the metal cations, e.g. sodium, present in the aluminosilicate are replaced by hydrogen. Hydrogen exchange is commonly carried out by exchange of the cations of the synthetic or naturally occurring aluminosilicates with ammonium ions, for instance through contact with an aqueous solution of ammonium chloride or other water-soluble ammonium compound and subsequently calcining the aluminosilicate.
One method of preparing the second stage catalyst is by combining the silica-alumina hydrogel and the hydrogenexchanged crystalline aluminosilicate and drying the mixture, for instance at temperatures of about 230 to 600 F., to con vert the silica-alumina hydrogel to the xerogel form. The crystalline aluminosilicate may, if desired, be hydrogenexchanged after it is combined with the silica-alumina hydrogel. The dried material can be calcined, for instance, at a temperature of the order of about 700 to 1500 F., preferably about 800 to 1,100" F. The platinum group metal may be added before or after the calcination, by, for example, ion exchange or impregnation, 1n any event, after the platinum group metal is added, the catalyst can be dehydrated and activated at the calcination temperature described above.
An available method for adding the platinum group metal by ion exchange comprises treating the silica-aluminacrystalline alumino-silicate mixture with an aqueous solution containing complex water-soluble, metal-amine cations, both organic and inorganic, of the metal to be deposited in the crystal structure. These complex cations ion-exchange with the cations present in the crystalline aluminosilicate. The exchange material is then removed from the solution, dried and activated or calcined, for example, by heating the material up to a temperature of about 250 C. in a flowing stream ofinert dry gas or vacuum. The activation may be effected at a temperature below the temperature at which the complex cations are destroyed. The activated material may then be subjected to heat treatment to a temperature not exceeding about 650 C. and preferably not exceeding about 500 C. in vacuum or inert atmosphere whereby the complex cation is destroyed and the platinum group metal is reduced in the material. Should the thermal treatment be insufficient to reduce the metal of the complex cations to the elemental state, chemical reduction either alone or in combination with thermal reduction may be employed. Alkali metals such sodium are suitable reducing agents for this purpose. Throughout the operation excessive temperatures and extremes of acidity are to be avoided since they may tend to destroy the crystal structure ofthe silica-alumina-crystalline aluminosilicate mixture.
The platinum group metal may also be added by impregnation. The silica-alumina-crystalline aluminosilicate mixture, for example, either with or without previous evacuation, may be soaked in either a dilute or concentrated solution, usually aqueous chloroplatinic acid, ammonium hexathiocyanoplatinate (1V) or hexathiocyanate platinic acid, often in an amountjust sufficient to wet the material and be completely absorbed. Also, ifdesired, the solution may be incorporated into the silica-a1umina-crystalline aluminosilicate during the formation ofthe latter.
Either before of after dehydration, the catalyst can, if desired, be formed into macrosized particles by -inch or extruding. Generally, these particles are about l/32 inch to k inch in diameter and about l/16-inch to l-inch or more in length. Although these macrosized particles are usually formed after dehydration and before calcination, this, of course is optional and can be done at any time found most convenient.
The catalyst employed in the third, or aromatic-saturation stage of the present invention is a platinum group metal-containing hydrogenation catalyst. This catalyst, like the catalysts of the second stage, is distinguished from the catalysts of the first stage in that it is not normally considered to be sulfur-resistant. The catalyst includes catalytically effective amounts of the platinum group metals mentioned above. Often, the platinum group metal is present in an amount, for example, of about 0,01 to 2 weight percent, preferably about 0.1 to 1 weight percent. The platinum group metal may be present in the metallic form or as a sulfide, oxide, or other combined form. As in the case of the second stage catalyst, the metal may interact with other constituents of the catalyst but if during use the platinum group metal is present in metallic form, then it is preferred that it be so finely divided that it is not detectable by X-ray diffraction means, i.e. that it exists as crystallites ofless than about 50 A. size. Of the platinum group metals, platinum is preferred. If desired, the catalysts employed in the third stage of the process of the invention, like the catalysts used in the first stage, can be prereduced prior to use by heating in the presence of hydrogen, generally at temperatures of about 600 to 800 F.
Although various solid refractory type carriers known in the art may be utilized as a support for the third stage platinum group metal, the preferred supports have no substantial cracking effect on the hydrocarbon feeds. Most advantageously, the support is composed predominantly of alumina of the activated or calcined type. The alumina base is usually the major component of the catalyst, generally constituting at least about 75 weight percent on the basis of the catalyst and preferably at least about to 99.8 percent. The alumina catalyst base can be an activated or gamma family alumina, especially gamma or eta alumina, such as those derived by calcination of amorphous hydrous alumina, alumina monohydrate, alumina trihydrate or their mixtures. A catalyst base advantageously used is a mixture predominating in, or containing a major proportion of, for instance about 65 to weight percent, of one or more of the alumina trihydrates, bayerite, nordstandite or gibbsite, and about 5 to 35 weight percent of alumina monohydrate (boehmite), amorphous hydrous alumina or their mixtures. The alumina base can contain small amounts of other solid oxides such as silica, magnesia, natural or activated clays (such as kaolinite, montmorillonite, halloysite, etc.), Titania zirconia, etc., or their mixtures.
The addition of the platinum group metal to the alumina or other solid refractory type carrier can be accomplished employing, for example, the impregnation methods described above in connection with the second stage hydroisomerization-hydrocracking catalyst. Also, as in the case of the catalyst of the second stage, the platinum-group metal hydrogenation catalysts used in the third stage of the process of the invention may be employed in the form of macrosized particles generally having a diameter of about 1/32-inch to zfi-inch and a length of about l/l 6-inch to linch or more.
The process of the present invention is illustrated in detail by the following example.
EXAMPLE A raw, waxy, mixed base lubricating oil distillate having an AP1 gravity of 23.8; a flash point of5 10 F., a viscosity of 82.4 SUS at 210 F., a pour point of F. and an aromatic carbon content of about 21 percent, was contacted with hydrogen in the presence of a calcined nickel molybdate on alumina catalyst at a temperature of 700 F., a pressure of 2,500 p.s.i.g., a weight'hourly space velocity of 0.25 and a hydrogen rate of 1,500 SCF/B of oil. The catalyst, which contained 2.3 percent nickel and 15.6 percent molybdenum as the oxide, was pretreated with hydrogen sulfide at 350 F. for two hours using one SCF-H SIhrJ 100 grams of catalyst. The hydrotreated product thus formed was flashed to remove light gaseous products and further treated in a second stage at a temperature of 750 F., a pressure of 2,500 p.s.i.g., a weight hourly space velocity of 0.35 and a hydrogen rate of 2,500 SCF/B of feed in the presence of a calcined platinum-containing, silica-alumina-crystalline aluminosilicate extrudate catalyst. The catalyst contained about 0.5 weight percent platinum, about 7 weight percent of about 90 percent hydrogen-exchanged crystalline aluminosilicate having a pore size of about 13 A. and a silica-to-alumina mole ratio of about 4 to 1, about 82.5 weight percent silica-alumina xerogel containing about 13 weight percent alumina, and about weight alumina added as a hydrogel.
The effluent product from the second stage was steam stripped to remove hydrocracked components boiling below the lubricating oil range, and contacted with hydrogen at a temperature of 550 F., a pressure of 2,500 p.s.i.g., a weight hourly space velocity of 0.25 and a hydrogen rate of 2,7500 SCF/B of feed in the presence of a platinum on alumina catalyst containing 0.6 weight percent platinum. Technical grade white mineral oil was recovered in a yield of about 30 percent by weight.
it is claimed:
1. A process of producing a technical white mineral oil which comprises contacting a raw, waxy mineral lubricating oil distillate having a viscosity of about 35 to 90 SUS at 210 F., an aromatic carbon content of about 15 to 30 percent, a pour point of at least about 70 F., and boiling primarily in the range of about 600 to 1,200 F., with hydrogen in the presence of a sulfur-resistant hydrogenation catalyst at a temperature of about 600 to 800 F. to provide a hydrorefined oil, contacting said hydrorefined oil with hydrogen in the presence of a hydroisomerization-hydrocracking catalyst comprising a major amount of amorphous silica-alumina composite containing about 5 to 45 weight percent alumina on a dry basis about 3 to 25 weight percent of an at least about 50 percent hydrogen-exchanged crystalline aluminosilicate having a pore size of about 8 to 15 A., and a silica-to-alumina mole ratio greater than 3:1. and about 0.1 to 5 weight percent of a platinum group metal at a temperature of about 600 to 950 F., removing components boiling below the lubricating oil range from the resulting product, and further contacting resulting hydroisomerized-hydrocracked product fraction of lubricating viscosity with hydrogen in the presence of a hydrogenation catalyst comprising a platinum group metal on a support having no substantial cracking effect on said hydroisomerization-hydrocracked product fraction, at a temperature of about 450 to 700 F. to saturate aromatics and produce technical white mineral oil.
2. The process of claim 1 wherein the contact of said mineral lubricating oil distillate with hydrogen and a sulfur-resistant hydrogenation catalyst is conducted at a pressure of about 500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.2 to 2 and hydrogen feed rate of about 1,000 to 5,000 SCF/B.
3. The process of claim 2 wherein the contact of said hydroisomerized-hydrocracked product fraction with hydrogen is conducted at a pressure of about 500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.2 to 2 and a hydrogen feed rate of about 1,000 to 5,000 SCF/B.
4. The process of claim 3 wherein the contract of said oil with hydrogen and the hydroisomerization-hydrocracking catalyst is conducted at a pressure of about 500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 2 and a hydrogen feed rate of about 1,000 to 5,000 SCF/B 5. The process of claim 1 wherein the platinum group metal of the hydroisomerization-hydrocracking catalyst and of the platinum group metal hydrogenation catalyst is platinum.
6. The process of claim 5 wherein the sulfur-resistant catalyst contains molybdenum and an iron group metal supported on alumina.
7. The process of claim 6 wherein the iron group metal is nickel.
8. A process of producing a technical white mineral oil which comprises contacting in a first stage a raw, waxy mineral lubricating oil distillate having a viscosity of about 35 to 90 SUS at 210 F., an aromatic carbon content of about 15 to 30 percent, and a pour point of at least about F., and boiling primarily in the range of about 600 to 1,200 F., with hydrogen in the presence of a catalytic amount of a sulfided nickel molybdate supported on alumina catalyst at a temperature of about 675 to 725 F., a pressure of about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 0.5 and a hydrogen feed rate of about 1,500 to 2,500 SCF/B to provide a hydrorefined oil, contacting said hydrorefined oil in a second stage with hydrogen at a temperature of about 650 to 800 F. in the presence of a hydroisomerizationhydrocracking catalyst which comprises a major amount of amorphous silica-alumina composite containing about 10 to 20 weight percent alumina on a dry basis, about 5 to 10 weight percent of at least about percent hydrogen-exchanged crystalline aluminosilicate having a pore size of 10 to 14 A., a crystal size of less than about 10 microns and a silica-to-alumina mole ratio of about 4 to 6:1, and about 0.3 to 2 weight percent of platinum, removing components boiling below the lubricating oil range from the resulting product, and further contacting the fraction of the oil of lubricating viscosity from said second stage with hydrogen in the presence of a platinumalumina catalyst containing about 0.1 to 1 weight percent platinum at a temperature of about 550 to 600 F., a pressure of about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 0.5 and a hydrogen to feed oil rate of about 2,000 to 3,000 SCF/B to saturate aromatics in said fraction, and recovering resulting technical white mineral oil.
Claims (7)
- 2. The process of claim 1 wherein the contact of said mineral lubricating oil distillate with hydrogen and a sulfur-resistant hydrogenation catalyst is conducted at a pressure of about 500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.2 to 2 and hydrogen feed rate of about 1,000 to 5,000 SCF/B.
- 3. The process of claim 2 wherein the contact of said hydroisomerized-hydrocracked product fraction with hydrogen is conducted at a pressure of about 500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.2 to 2 and a hydrogen feed rate of about 1,000 to 5,000 SCF/B.
- 4. The process of claim 3 wherein the contract of said oil with hydrogen and the hydroisomerization-hydrocracking catalyst is conducted at a pressure of about 500 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 2 and a hydrogen feed rate of about 1,000 to 5,000 SCF/B
- 5. The process of claim 1 wherein the platinum group metal of the hydroisomerization-hydrocracking catalyst and of the platinum group metal hydrogeNation catalyst is platinum.
- 6. The process of claim 5 wherein the sulfur-resistant catalyst contains molybdenum and an iron group metal supported on alumina.
- 7. The process of claim 6 wherein the iron group metal is nickel.
- 8. A process of producing a technical white mineral oil which comprises contacting in a first stage a raw, waxy mineral lubricating oil distillate having a viscosity of about 35 to 90 SUS at 210* F., an aromatic carbon content of about 15 to 30 percent, and a pour point of at least about 70* F., and boiling primarily in the range of about 600* to 1,200* F., with hydrogen in the presence of a catalytic amount of a sulfided nickel molybdate supported on alumina catalyst at a temperature of about 675* to 725* F., a pressure of about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 0.5 and a hydrogen feed rate of about 1,500 to 2,500 SCF/B to provide a hydrorefined oil, contacting said hydrorefined oil in a second stage with hydrogen at a temperature of about 650* to 800* F. in the presence of a hydroisomerization-hydrocracking catalyst which comprises a major amount of amorphous silica-alumina composite containing about 10 to 20 weight percent alumina on a dry basis, about 5 to 10 weight percent of at least about 75 percent hydrogen-exchanged crystalline aluminosilicate having a pore size of 10 to 14 A., a crystal size of less than about 10 microns and a silica-to-alumina mole ratio of about 4 to 6:1, and about 0.3 to 2 weight percent of platinum, removing components boiling below the lubricating oil range from the resulting product, and further contacting the fraction of the oil of lubricating viscosity from said second stage with hydrogen in the presence of a platinum-alumina catalyst containing about 0.1 to 1 weight percent platinum at a temperature of about 550* to 600* F., a pressure of about 2,000 to 3,000 p.s.i.g., a weight hourly space velocity of about 0.25 to 0.5 and a hydrogen to feed oil rate of about 2,000 to 3,000 SCF/B to saturate aromatics in said fraction, and recovering resulting technical white mineral oil.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64762867A | 1967-06-21 | 1967-06-21 | |
| CA113,786A CA953233A (en) | 1967-06-21 | 1971-05-25 | Production of technical white mineral oil |
| GB2779571 | 1971-06-14 | ||
| NL7108226A NL7108226A (en) | 1967-06-21 | 1971-06-15 | |
| DE19712131227 DE2131227A1 (en) | 1971-06-18 | 1971-06-18 | Three stage hydrotreatment - of oils with hydropurification - hydrocracking - hydroisomerisation and hydrogenation |
| FR7122475A FR2142583B1 (en) | 1967-06-21 | 1971-06-21 | |
| BE768821A BE768821A (en) | 1967-06-21 | 1971-06-21 | WHITE MINERAL OIL PRODUCTION PROCESS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3629096A true US3629096A (en) | 1971-12-21 |
Family
ID=27560797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US647628A Expired - Lifetime US3629096A (en) | 1967-06-21 | 1967-06-21 | Production of technical white mineral oil |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3629096A (en) |
| FR (1) | FR2142583B1 (en) |
| GB (1) | GB1310320A (en) |
| NL (1) | NL7108226A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3852207A (en) * | 1973-03-26 | 1974-12-03 | Chevron Res | Production of stable lubricating oils by sequential hydrocracking and hydrogenation |
| US3915843A (en) * | 1972-12-08 | 1975-10-28 | Inst Francais Du Petrole | Hydrocracking process and catalyst for producing multigrade oil of improved quality |
| US3962071A (en) * | 1973-05-19 | 1976-06-08 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for producing lubricating oils |
| US4263127A (en) * | 1980-01-07 | 1981-04-21 | Atlantic Richfield Company | White oil process |
| US4515681A (en) * | 1982-09-08 | 1985-05-07 | Exxon Research & Engineering Co. | Catalytic dewaxing using collapsed large pore zeolites |
| US4810355A (en) * | 1985-12-12 | 1989-03-07 | Amoco Corporation | Process for preparing dehazed white oils |
| US4900707A (en) * | 1987-12-18 | 1990-02-13 | Exxon Research And Engineering Company | Method for producing a wax isomerization catalyst |
| US4906601A (en) * | 1988-12-16 | 1990-03-06 | Exxon Research And Engineering Company | Small particle low fluoride content catalyst |
| US4923588A (en) * | 1988-12-16 | 1990-05-08 | Exxon Research And Engineering Company | Wax isomerization using small particle low fluoride content catalysts |
| US4937399A (en) * | 1987-12-18 | 1990-06-26 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils using a sized isomerization catalyst |
| US4992159A (en) * | 1988-12-16 | 1991-02-12 | Exxon Research And Engineering Company | Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization |
| US5019662A (en) * | 1988-05-19 | 1991-05-28 | Uop | Process for the production of white oil from heavy aromatic alkylate |
| US5057206A (en) * | 1988-08-25 | 1991-10-15 | Uop | Process for the production of white oils |
| US5158671A (en) * | 1987-12-18 | 1992-10-27 | Exxon Research And Engineering Company | Method for stabilizing hydroisomerates |
| US5320811A (en) * | 1991-07-15 | 1994-06-14 | The United States Of America As Represented By The Department Of Health And Human Services | Thin layer chromatography direct sample application manifold |
| US5997732A (en) * | 1997-12-22 | 1999-12-07 | Chevron U.S.A. Inc. | Clay treatment process for white mineral oil |
| WO2000029511A1 (en) * | 1998-11-16 | 2000-05-25 | Shell Internationale Research Maatschappij B.V. | Catalytic dewaxing process |
| JP3062701B2 (en) | 1990-03-12 | 2000-07-12 | アトランティック リッチフィールド カンパニー | Formulation of food grade quality white mineral oil |
| US6274029B1 (en) | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6309432B1 (en) | 1997-02-07 | 2001-10-30 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US20070149723A1 (en) * | 2005-12-23 | 2007-06-28 | Goldschmidt Gmbh | Silicone-containing graft copolymers based on styrene oxide-based silicone polyethers |
| US20090166251A1 (en) * | 2007-12-28 | 2009-07-02 | Hantzer Sylvain S | All catalytic medicinal white oil production |
| US20150315493A1 (en) * | 2013-11-06 | 2015-11-05 | Axens | Process for the production of white oils meeting the cfr standard from waste oils |
| CN107880932A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst grading method and heavy oil hydrogenation treatment method |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7713122A (en) * | 1977-11-29 | 1979-05-31 | Shell Int Research | PROCESS FOR THE PREPARATION OF HYDROCARBONS. |
| US4474618A (en) * | 1983-08-08 | 1984-10-02 | Mobil Oil Corporation | Overnight cloud and color in lube dewaxing using platinum zeolite catalyst |
| US5453176A (en) * | 1993-10-13 | 1995-09-26 | Narloch; Bruce A. | Process for preparing white oil containing a high proportion of isoparaffins |
| US6051127A (en) * | 1996-07-05 | 2000-04-18 | Shell Oil Company | Process for the preparation of lubricating base oils |
| EA000850B1 (en) * | 1996-07-16 | 2000-06-26 | Шеврон Ю.Эс.Эй. Инк. | Base stock lube oil manufacturing process |
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| US2779713A (en) * | 1955-10-10 | 1957-01-29 | Texas Co | Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions |
| US2967147A (en) * | 1958-01-24 | 1961-01-03 | Texaco Inc | Method of processing lubricating oil |
| US3125511A (en) * | 1960-10-28 | 1964-03-17 | Treatment of hydrocarbon fractions to | |
| US3268439A (en) * | 1962-01-26 | 1966-08-23 | British Petroleum Co | Conversion of waxy hydrocarbons |
| US3301917A (en) * | 1964-09-22 | 1967-01-31 | Mobil Oil Corp | Upgrading of paraffinic hydrocarbons in the presence of a mixed aluminosilicate, platinum metal catalyst |
| US3308052A (en) * | 1964-03-04 | 1967-03-07 | Mobil Oil Corp | High quality lube oil and/or jet fuel from waxy petroleum fractions |
| US3340181A (en) * | 1965-08-05 | 1967-09-05 | Chevron Res | Two-stage hydrotreatment for white oil manufacture |
| US3459656A (en) * | 1966-08-16 | 1969-08-05 | Sinclair Research Inc | Making a white oil by two stages of catalytic hydrogenation |
| US3487005A (en) * | 1968-02-12 | 1969-12-30 | Chevron Res | Production of low pour point lubricating oils by catalytic dewaxing |
-
1967
- 1967-06-21 US US647628A patent/US3629096A/en not_active Expired - Lifetime
-
1971
- 1971-06-14 GB GB2779571A patent/GB1310320A/en not_active Expired
- 1971-06-15 NL NL7108226A patent/NL7108226A/xx unknown
- 1971-06-21 FR FR7122475A patent/FR2142583B1/fr not_active Expired
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2779713A (en) * | 1955-10-10 | 1957-01-29 | Texas Co | Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions |
| US2967147A (en) * | 1958-01-24 | 1961-01-03 | Texaco Inc | Method of processing lubricating oil |
| US3125511A (en) * | 1960-10-28 | 1964-03-17 | Treatment of hydrocarbon fractions to | |
| US3268439A (en) * | 1962-01-26 | 1966-08-23 | British Petroleum Co | Conversion of waxy hydrocarbons |
| US3308052A (en) * | 1964-03-04 | 1967-03-07 | Mobil Oil Corp | High quality lube oil and/or jet fuel from waxy petroleum fractions |
| US3301917A (en) * | 1964-09-22 | 1967-01-31 | Mobil Oil Corp | Upgrading of paraffinic hydrocarbons in the presence of a mixed aluminosilicate, platinum metal catalyst |
| US3340181A (en) * | 1965-08-05 | 1967-09-05 | Chevron Res | Two-stage hydrotreatment for white oil manufacture |
| US3459656A (en) * | 1966-08-16 | 1969-08-05 | Sinclair Research Inc | Making a white oil by two stages of catalytic hydrogenation |
| US3487005A (en) * | 1968-02-12 | 1969-12-30 | Chevron Res | Production of low pour point lubricating oils by catalytic dewaxing |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915843A (en) * | 1972-12-08 | 1975-10-28 | Inst Francais Du Petrole | Hydrocracking process and catalyst for producing multigrade oil of improved quality |
| US3852207A (en) * | 1973-03-26 | 1974-12-03 | Chevron Res | Production of stable lubricating oils by sequential hydrocracking and hydrogenation |
| US3962071A (en) * | 1973-05-19 | 1976-06-08 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for producing lubricating oils |
| US4263127A (en) * | 1980-01-07 | 1981-04-21 | Atlantic Richfield Company | White oil process |
| US4515681A (en) * | 1982-09-08 | 1985-05-07 | Exxon Research & Engineering Co. | Catalytic dewaxing using collapsed large pore zeolites |
| US4810355A (en) * | 1985-12-12 | 1989-03-07 | Amoco Corporation | Process for preparing dehazed white oils |
| US4900707A (en) * | 1987-12-18 | 1990-02-13 | Exxon Research And Engineering Company | Method for producing a wax isomerization catalyst |
| US4937399A (en) * | 1987-12-18 | 1990-06-26 | Exxon Research And Engineering Company | Method for isomerizing wax to lube base oils using a sized isomerization catalyst |
| US5158671A (en) * | 1987-12-18 | 1992-10-27 | Exxon Research And Engineering Company | Method for stabilizing hydroisomerates |
| US5019662A (en) * | 1988-05-19 | 1991-05-28 | Uop | Process for the production of white oil from heavy aromatic alkylate |
| US5057206A (en) * | 1988-08-25 | 1991-10-15 | Uop | Process for the production of white oils |
| US4906601A (en) * | 1988-12-16 | 1990-03-06 | Exxon Research And Engineering Company | Small particle low fluoride content catalyst |
| US4923588A (en) * | 1988-12-16 | 1990-05-08 | Exxon Research And Engineering Company | Wax isomerization using small particle low fluoride content catalysts |
| US4992159A (en) * | 1988-12-16 | 1991-02-12 | Exxon Research And Engineering Company | Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization |
| JP3062701B2 (en) | 1990-03-12 | 2000-07-12 | アトランティック リッチフィールド カンパニー | Formulation of food grade quality white mineral oil |
| US5320811A (en) * | 1991-07-15 | 1994-06-14 | The United States Of America As Represented By The Department Of Health And Human Services | Thin layer chromatography direct sample application manifold |
| US6607568B2 (en) | 1995-10-17 | 2003-08-19 | Exxonmobil Research And Engineering Company | Synthetic diesel fuel and process for its production (law3 1 1) |
| US6296757B1 (en) | 1995-10-17 | 2001-10-02 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6274029B1 (en) | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
| US6669743B2 (en) | 1997-02-07 | 2003-12-30 | Exxonmobil Research And Engineering Company | Synthetic jet fuel and process for its production (law724) |
| US6309432B1 (en) | 1997-02-07 | 2001-10-30 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
| US5997732A (en) * | 1997-12-22 | 1999-12-07 | Chevron U.S.A. Inc. | Clay treatment process for white mineral oil |
| US6576120B1 (en) | 1998-11-16 | 2003-06-10 | Shell Oil Company | Catalytic dewaxing process |
| WO2000029511A1 (en) * | 1998-11-16 | 2000-05-25 | Shell Internationale Research Maatschappij B.V. | Catalytic dewaxing process |
| US20070149723A1 (en) * | 2005-12-23 | 2007-06-28 | Goldschmidt Gmbh | Silicone-containing graft copolymers based on styrene oxide-based silicone polyethers |
| US7594991B2 (en) | 2007-12-28 | 2009-09-29 | Exxonmobil Research And Engineering Company | All catalytic medicinal white oil production |
| US20090166251A1 (en) * | 2007-12-28 | 2009-07-02 | Hantzer Sylvain S | All catalytic medicinal white oil production |
| US20150315493A1 (en) * | 2013-11-06 | 2015-11-05 | Axens | Process for the production of white oils meeting the cfr standard from waste oils |
| US10174264B2 (en) * | 2013-11-06 | 2019-01-08 | Axens | Process for the production of white oils from waste oils |
| CN107880932A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst grading method and heavy oil hydrogenation treatment method |
| CN107880932B (en) * | 2016-09-29 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst grading method and heavy oil hydrogenation treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7108226A (en) | 1972-12-19 |
| GB1310320A (en) | 1973-03-21 |
| FR2142583A1 (en) | 1973-02-02 |
| FR2142583B1 (en) | 1975-07-11 |
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