CN105209580A - 制备重基础油的方法 - Google Patents
制备重基础油的方法 Download PDFInfo
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- CN105209580A CN105209580A CN201480024800.5A CN201480024800A CN105209580A CN 105209580 A CN105209580 A CN 105209580A CN 201480024800 A CN201480024800 A CN 201480024800A CN 105209580 A CN105209580 A CN 105209580A
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- 239000002199 base oil Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 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 abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 239000005864 Sulphur Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 17
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 47
- 239000004215 Carbon black (E152) Substances 0.000 claims description 34
- 239000011820 acidic refractory Substances 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 41
- 239000003921 oil Substances 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 230000001050 lubricating effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229910003294 NiMo Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013058 crude material Substances 0.000 description 2
- 238000007324 demetalation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
本发明提供一种制备重基础油的方法,包括如下步骤:(a)提供含烃原料,所述含烃原料包含至少50wt%的沸点高于460℃的烃、800-2500ppmw的氮和1.5-4.0wt%的硫;(b)在加氢处理条件下在含氢气体存在下用加氢处理催化剂加氢处理所述含烃原料,以获得氮含量为30-80ppmw和硫含量为200-450ppmw的加氢处理后产品;(c)脱除在步骤(b)获得的加氢处理后产品中存在的至少50%的NH3和H2S;(d)在催化脱蜡条件下在含氢气体存在下用脱蜡催化剂使步骤(c)获得的至少部分加氢处理后产品催化脱蜡,以获得脱蜡产品,所述脱蜡催化剂包含第VIII族金属加氢组分、脱铝的铝硅酸盐沸石晶体和基本不含氧化铝的低酸性耐高温氧化物粘结剂材料;(e)在加氢精制条件下在含氢气体存在下用加氢精制催化剂使步骤(d)获得的至少部分脱蜡产品加氢精制,以获得重基础油;和(f)回收所述重基础油。
Description
技术领域
本发明涉及制备重基础油的方法。
背景技术
基础油的主要用途是用于润滑油如车用机油中以保护机动车辆中的内燃机。润滑油通常由主要的基础油和各种添加剂组成以获得理想特性。
轻润滑基础油主要用于汽车应用,而重润滑基础油则用于重负载应用如船用发动机和工业过程。
用于润滑油中的基础油大规模地通过如下过程制备:首先使真空瓦斯油馏出物和/或脱沥青油加氢处理,和随后使加氢处理后的液体产品或加氢处理后液体产品的370℃+馏分催化脱蜡和加氢精制。通常在催化脱蜡步骤中应用贵金属脱蜡催化剂。公知的是有机氮和有机硫化合物会使贵金属脱蜡催化剂中毒,因此为了充分降低加氢处理器的370℃+产品中有机氮和有机硫化合物浓度,必须应用苛刻的加氢处理步骤。
加氢处理器中较高的处理深度通常会提高用作基础油装置原料的370℃+加氢处理后产品的质量。但较高的加氢处理深度意味着370℃+加氢处理后产品的收率变低和全部加氢处理后产品变轻(由于深度加氢处理发生沸点转移),作为后果,这明显降低了重润滑基础油与轻润滑基础油之间的比。
当重基础油需求高时,重润滑基础油的收率降低是不希望的。
因此,本发明的目的是提供含烃原料的提质方法,其中将获得重润滑基础油的高收率。
发明内容
当含烃原料经受包括特定序列的工艺步骤的提质过程时,实现了上述目的。
因此,本发明涉及一种制备重基础油的方法,包括如下步骤:
(a)提供含烃原料,所述含烃原料包含至少50wt%的沸点高于460℃的烃、800-2500ppmw的氮和1.2-4.0wt%的硫;
(b)在加氢处理条件下在含氢气体存在下用加氢处理催化剂或加氢处理催化剂包加氢处理所述含烃原料,以获得氮含量为30-80ppmw和硫含量为200-450ppmw的加氢处理后产品;
(c)脱除在步骤(b)获得的加氢处理后产品中存在的至少50%的NH3和H2S;
(d)在催化脱蜡条件下在含氢气体存在下用脱蜡催化剂使步骤(c)获得的至少部分加氢处理后产品催化脱蜡,以获得脱蜡产品,所述脱蜡催化剂包含第VIII族金属加氢组分、脱铝的铝硅酸盐沸石晶体和基本不含氧化铝的低酸性耐高温氧化物粘结剂材料;
(e)在加氢精制条件下在含氢气体存在下用加氢精制催化剂使步骤(d)获得的至少部分脱蜡产品加氢精制,以获得重基础油;和
(f)回收所述重基础油。
按照本发明,可以获得重润滑基础油的高收率。所获得的重润滑基础油包括具有高的重润滑基础油与轻润滑基础油比的第II种和第III种润滑基础油。这种重润滑基础油具有高的粘度,使得它们对于重负载应用很有吸引力。
具体实施方式
步骤(a)提供的含烃原料优选包含大于65wt%但至少50wt%的沸点高于460℃的烃。合适地,步骤(a)提供的含烃原料含有在100℃下粘度高于12cSt、优选至少14cSt的370℃+馏分。
含烃原料的氮含量为800-2500ppmw,优选为1000-1500ppmw,和硫含量为1.2-4.0wt%,优选为1.5-3.0wt%。
在步骤(a)提供的含烃原料中,沸点为370-460℃的烃馏分与沸点为460-800℃的烃馏分之间的比优选小于10。
用于本发明的含烃原料的例子有直馏瓦斯油、加氢裂化瓦斯油、热裂化瓦斯油、焦化瓦斯油、减压瓦斯油、轻或重循环油、脱沥青油(DAO)或它们中两种或更多种的组合。烃原料也可以是溶剂提取后的蜡质残液。步骤(a)提供的含烃原料至少部分可以合适地为通过使至少一种馏出物馏分(优选为减压馏出物馏分)和脱沥青油(DAO)掺混而获得的掺混物。可以应用的DAO合适地通过使渣油烃油(优选为减压渣油)脱沥青而获得。所述脱沥青步骤可以按任何常规方式实施。公知且合适的脱沥青方法为溶剂脱沥青,包括用提取溶剂逆流处理渣油烃油原料。这种提取溶剂通常为包含具有3-8个碳原子的链烷烃化合物如丙烷、丁烷、异丁烷、戊烷、异戊烷、己烷和它们中两种或更多种的混合物的轻烃溶剂。优选的链烷烃为具有3-5个碳原子的那些,其中丙烷、丁烷、戊烷以及它们的混合物是最优选的。溶剂脱沥青处理方便地在转盘接触器或板式塔中实施,渣油烃油原料进入顶部区域而提取溶剂进入底部区域。渣油烃油中存在的较轻烃溶解于提取溶剂中,并从设备的顶部抽出。在回收提取溶剂后由该顶部馏分得到DAO。不溶于提取溶剂的沥青质从设备的底部抽出。实施脱沥青的条件在本领域中是已知的。合适地,在总的提取溶剂与渣油烃油的比为1.5-8wt/wt、压力为1-50bar和温度为50-230℃下实施脱沥青。
通过使包含沸点至少460℃的烃的渣油馏分(优选减压渣油馏分)脱沥青可以获得脱沥青油。
在步骤(b)中,在加氢处理条件下在含氢气体存在下用合适的加氢处理催化剂或加氢处理催化剂包加氢处理所述含烃原料,以获得氮含量为30-80ppmw和硫含量为200-450ppmw的加氢处理后产品。
在步骤(a)中在第一反应区中应用的加氢处理催化剂或催化剂包可以合适地为脱硫催化剂或脱硫催化剂组合(包括在脱硫步骤前可能的脱金属催化剂或脱金属催化剂组合)。所述脱硫催化剂可以为本领域已知的任何加氢脱硫催化剂或加氢处理催化剂组合,它将输出具有预期氮和硫浓度的加氢处理流出物。通常,这些催化剂包含在多孔催化剂载体(通常为氧化铝或无定形二氧化硅-氧化铝)上作为加氢组分的元素周期表第VIII族金属和第VIB族金属的化合物。加氢化合物的合适组合的公知例子包括钴-钼、镍-钼、镍-钨和镍-钴-钼。包含镍和/或钴和钼的化合物作加氢化合物的加氢脱硫催化剂是优选的。步骤(b)获得的加氢处理后产品包含30-80ppmw的氮和200-450ppmw的硫,这表明步骤(b)的加氢处理不是深度加氢处理过程。因此,合适地应用不是活性太强的加氢处理催化剂或加氢处理催化剂组合。因此,优选应用氧化铝基加氢处理催化剂。催化剂优选基本不含裂化组分。包含在氧化铝上载带的镍和/或钴和钼但不含沸石裂化化合物的催化剂或催化剂组合是特别优选的。
在步骤(b)中也可以应用其中两种或更多种加氢处理催化剂堆叠的堆叠床构造。
加氢处理步骤的温度合适地为250-480℃,优选为280-450℃,和更优选为350-420℃。
合适的加氢处理压力为30-250bara。加氢处理压力优选为110-180bara,更优选为120-170bara。
重时空速合适地为0.2-10hr-1,优选为0.2-2.0hr-1,和更优选为0.2-1.0hr-1。
将会理解的是步骤(a)中精确的加氢处理条件尤其取决于所应用的催化剂以及烃原料的硫含量和氮含量。
步骤(b)获得的加氢处理后产品中氮含量与硫含量的比(N/S)合适地为0.1-0.3,优选为0.12-0.28。
在步骤(c)中,将步骤(b)获得的加氢处理后产品中存在的至少50%的NH3和H2S脱除。合适地,通过汽提、优选通过蒸汽汽提将步骤(b)获得的加氢处理后产品中存在的至少部分NH3和H2S脱除。汽提合适地在100-350℃、优选130-240℃的温度和1-50bar、优选1.5-10bar的压力下实施。在步骤(c)中,优选将步骤(b)获得的加氢处理后产品中存在的至少80%、更优选至少90%和最优选至少95%的NH3和H2S从加氢处理后产品中脱除。优选地,在步骤(c)中还从步骤(b)获得的加氢处理后产品中分离出沸点低于370℃的烃。
优选使步骤(b)获得的全部加氢处理后产品经受步骤(c)。
在步骤(d)中,在催化脱蜡条件下在含氢气体存在下用脱蜡催化剂使步骤(c)获得的至少部分加氢处理后产品催化脱蜡,以获得脱蜡产品,所述脱蜡催化剂包含第VIII族金属加氢组分、脱铝的铝硅酸盐沸石晶体和低酸性耐高温氧化物粘结剂。
优选使步骤(c)获得的全部加氢处理后产品经受步骤(d)。
催化脱蜡在这里指通过选择性地将赋予高倾点的油原料组分转化为不赋予高倾点的产品而降低润滑基础油产品倾点的方法。赋予高倾点的产品为具有高熔点的化合物。这些化合物被称为蜡。蜡化合物包括例如高温熔化的正链烷烃、异-链烷烃和单-环化合物。优选将倾点降低至少40℃和更优选降低至少60℃。因此,在本发明方法中含烃原料含有赋予不想要的高倾点的蜡质分子。少量的这些化合物就可以明显影响倾点。原料合适地包含小于2%和至多80%的这些蜡质化合物。
在本发明的催化脱蜡步骤中,在催化脱蜡条件下使加氢处理后原料与包含第VIII族金属加氢组分、脱铝的铝硅酸盐沸石晶体和低酸性耐高温氧化物粘结剂的催化剂组合物接触。
已经发现这类脱蜡催化剂即使当油原料中存在高的硫和氮含量时也很稳定。这种催化剂的例子在WO-A-9641849中有述。
铝硅酸盐沸石晶体优选具有直径为0.35-0.80nm的孔。该直径指最大孔径。正如通常所认识到的,分子筛中的孔为具有最小和最大孔径的多边形通道。针对本发明的目的,最大孔径为关键参数,因为它确定了可进入孔的蜡质分子的尺寸。
适合在本发明中应用的铝硅酸盐沸石的例子有镁碱沸石、ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35、ZSM-38、ZSM-48、ZSM-57、SSZ-23、SSZ-24、SSZ-25、SSZ-26、SSZ-32、SSZ-33和MCM-22及这些中两种或更多种的混合物。沸石组分优选为ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35或ZSM-48。
以脱蜡催化剂的总重量为基准,脱蜡催化剂中的沸石组分优选以10-50wt%的量存在。
优选的铝硅酸盐沸石为MFI-拓扑结构如ZSM-5。
为获得最优催化活性,优选应用小晶体。优选应用小于10微米和更优选小于1微米的晶体。实际下限合适地为0.1微米。
脱蜡催化剂还包含基本不含氧化铝的低酸性耐高温氧化物粘结剂材料。例子有低酸性耐高温氧化物如二氧化硅、氧化锆、二氧化钛、二氧化锗、氧化硼、以及这些中两种或更多种的混合物。最优选的粘结剂为二氧化硅。改性分子筛与粘结剂的重量比合适地为05/95至95/05。
铝硅酸盐沸石的脱铝会造成在沸石中存在的氧化铝部分数量减少,并因而造成氧化铝摩尔百分比减少。在此应用的术语"氧化铝部分"指Al2O3单元,它是铝硅酸盐沸石骨架的一部分,即它与铝硅酸盐沸石骨架中的其它氧化物部分如二氧化硅(SiO2)通过共价键结合。铝硅酸盐沸石中存在的氧化铝的摩尔百分数被定义为相对于组成铝硅酸盐沸石(脱铝前)或改性分子筛(脱铝后)的氧化物总摩尔数的Al2O3的摩尔百分数。
优选地,使沸石晶体的表面选择性脱铝。选择性的表面脱铝会造成沸石晶体的表面酸性位点数减少,但不会影响沸石晶体的内部结构。
可以通过本领域中公知的方法实现脱铝。特别有用的方法为其中脱铝选择性发生或不管如何选择性发生在分子筛晶体表面上的那些。脱铝方法的例子在前述WO-A-9641849中有述。
优选地,通过其中沸石与氟硅酸盐的水溶液接触的方法实施脱铝,其中所述氟硅酸盐由如下通式表示:(A)2/bSiF6,其中'Α'为具有化合价'b'的金属或非H+的非金属阳离子。这种处理也被称为AHS处理。阳离子'b'的例子有烷基铵、NH4 +、Mg++、Li+、Na+、K+、Ba++、Cd++、Cu+、Ca++、Cs+、Fe++、Co++、Pb++、Mn++、Rb+、Ag+、Sr++、Tl+和Zn++。'Α'优选为铵阳离子。沸石材料可以与pH合适地为3-7的氟硅酸盐接触。这种脱铝方法例如在US-A-5157191中有述。所述脱铝处理也称作AHS-处理。
用于本发明的脱蜡催化剂优选通过如下过程制备:首先挤出铝硅酸盐沸石和粘结剂,然后使所述挤出物经受脱铝处理,优选经受上述的AHS处理。已经发现当按照这种步骤顺序制备时,可以获得机械强度增加的催化剂挤出物。
通过已知技术如离子交换技术向包含脱铝的铝硅酸盐沸石晶体的催化剂挤出物中合适地加入周期表的第VIII族金属。典型的离子交换技术要求所选的沸石与想要替换的阳离子的盐接触。虽然可以采用多种盐,但特别优选氯化物、硝酸盐和硫酸盐。代表性的离子交换技术在包括US-A-3140249、US-A-3140251和US-A-3140253的多个专利中有述。
在步骤(d)中,应用了包含第VIII族金属加氢组分的脱蜡催化剂。第VIII族金属组分包括基于贵金属和非贵金属的那些组分。因此特别合适的第VIII族金属组分为硫化物、氧化物和/或元素形式的钯、铂、镍和/或钴。以载体的总量为基础按元素计,周期表第VIII族金属的总量合适地不超过10wt%,和优选为0.1-5.0wt%,更优选为0.2-3.0wt%。如果铂和钯都存在,铂与钯的重量比可以在宽范围内变化,但合适地为0.05-10,更合适地为0.1-5。包含钯、铂和镍作为加氢组分的催化剂是优选的。第VIII族金属加氢组分优选为铂或钯,更优选为铂。
在本发明方法的步骤(d)中,催化脱蜡条件为典型的催化脱蜡条件。因此,温度合适地为300-400℃,优选为320-390℃,和更优选为330-380℃。合适的脱蜡压力为80-240bara。脱蜡压力优选为100-180bara,更优选为120-170bara。步骤(d)的重时空速合适地为0.4-7hr-1,优选为0.5-2.5hr-1,和更优选为0.65-2.25hr-1。
步骤(d)在氢存在下实施。氢合适地以350-1500Nl/kg原料的速率提供给第二反应区。
步骤(d)获得的脱蜡产品具有能够生产高VI润滑基础油的粘度指数(VI)。步骤(d)获得的脱蜡产品的硫含量合适地小于350ppmw,优选小于300ppmw,和氮含量小于80ppmw,优选小于60ppmw。脱蜡产品在100℃下粘度合适地为10-17cSt,优选为10-15cSt。
在步骤(e)中,在加氢精制条件下在含氢气体存在下用加氢精制催化剂使步骤(d)获得的至少部分脱蜡产品加氢精制,以获得重基础油。
优选使步骤(d)获得的全部脱蜡产品经受步骤(e)。
加氢精制在本领域中是已知的,和合适的加氢精制步骤的例子例如在US-A-5139647、WO-A-9201657和WO-A-9201769中进行了公开。通常,加氢精制包括在相对温和的条件下使烃原料(在这种情况下为包含脱蜡润滑基础油的原料)与加氢催化剂接触,从而使脱蜡基础油中仍存在的至少部分芳烃饱和。合适的催化剂为那些通常用于此目的的贵金属基催化剂,如在无定形二氧化硅-氧化铝载体上载带的包含Pt和/或Pd的催化剂。在本发明的一个替代实施方案中,在步骤(b)的加氢处理步骤中,应用非贵金属加氢精制催化剂,即所谓的基础金属加氢精制催化剂如在氧化铝载体上的镍-钼。
按本发明,加氢精制条件包括:操作温度至多390℃,和优选为300-380℃,更优选为330-370℃;操作压力为80-200bara,优选为100-170bara;和重时空速为0.3-2.5hr-1,优选为0.5-1.5hr-1。
当与应用加氢裂化和催化脱蜡步骤的制备基础油的已知方法相比时,步骤(e)中重基础油的收率更高。重基础油的这种高收率可以表示为在步骤(e)中获得的重基础油与轻基础油的比。例如重基础油的高收率可以表示为在步骤(e)中获得的500N基础油与150N基础油的比。500N基础油为在100℃下粘度通常为10.0-12.9cSt的重第II类基础油,而150N基础油为在100℃下粘度通常为4.8-6.8cSt的轻第II类基础油。合适地,步骤(e)中获得的500N基础油与150N基础油的比为至少1.0,优选为至少1.5,更优选为至少2.5,和最优选为至少3.0。
重基础油的这种高收率建立在工艺步骤(a)-(e)的特殊顺序和应用特定催化剂和/或催化剂组合上,和构成对制备基础油的已知方法的主要改进,特别是站在今天对重基础油的需求日益增长的角度来看。
在步骤(f)中回收重基础油。例如通过常规方法如常压精馏或减压精馏可以将步骤(e)获得的重基础油与加氢精制过程流出物的其它组分(包括轻基础油)分开。在这些当中,在减压下精馏(包括减压闪蒸和真空精馏)是最合适应用的。选择馏出物馏分的分割点,从而所回收的每种产品馏出物均具有对于其预期用途理想的重基础油特性。
步骤(f)回收的重基础油的硫含量合适地小于300ppmw,优选小于200ppmw,和氮含量小于80ppmw,优选小于50ppmw。重基础油在100℃下的粘度合适地为10-15cSt,优选为10-13cSt。
实施例
下面通过如下非限定性实施例描述本发明
在步骤(a)中提供巴士拉(Basrah)轻质蜡质馏出物原料。
表1:原料的主要特性
实验室溶剂脱蜡温度 | ℃ | -20 |
蜡含量 | wt% | 9.2 |
过滤油 | ||
运动粘度 | ||
40℃ | cSt | 272.22 |
100℃ | cSt | 17.16 |
粘度指数 | 53.6 | |
硫含量 | wt% | 2.93 |
碱性氮含量 | ppmw | 414 |
芳烃(UV方法) | ||
单环 | mmol/100g | 47.8 |
双环 | mmol/100g | 9.3 |
多环 | mmol/100g | 47.1 |
在步骤(b)中,对原料进行加氢处理。
实施例1(本发明)
用常规的氧化铝上的NiMo加氢处理催化剂(对于本实施例用来自Criterioncatalystportfolio的C-424)对表1中描述的原料进行加氢处理,目标是产生含约50ppm氮和约300ppm硫的加氢处理后流出物(370℃+馏分)。
加氢处理步骤的操作条件和主要结果在下表2中给出。
表2:在本发明步骤(b)中生产加氢处理后流出物
实施例2(对比例)
以常规方式对相同的原料(如表1)进行加氢处理,以明显降低氮和硫含量分别至<5ppmw和<50ppmw,从而符合目前实践中二级贵金属异构化-脱蜡和加氢精制催化剂的典型要求。对于此,需要高活性的NiMo/Al2O3-II类加氢处理催化剂(例如来自Criterioncatalystportfolio的DN-3100)。加氢处理步骤的操作条件和主要结果在表3中给出。
表3:以常规方式生产加氢处理后流出物
步骤(b)总结表
步骤(b) | 流出物-实施例1 | 流出物-实施例2 |
催化剂 | 常规NiMo/Al2O3 | 高活性NiMo/Al2O3 |
氮,ppmw | 50 | 2 |
硫,ppmw | 275 | 55 |
370℃+收率,wt% | 85.8 | 70.7 |
460℃+,% | 71 | 63 |
Vk100,cSt | 10.41 | 8.30 |
粘度指数 | 101 | 115 |
倾点,℃ | +48 | +44 |
在步骤(c)中,由实施例1和2获得的流出物中汽提出H2S和NH3杂质和轻质产品。随后,在步骤(d)中,使步骤(c)获得的产品经受本发明的脱蜡步骤和常规的脱蜡步骤。
实施例3(本发明)
应用从Shell商购的脱蜡催化剂SLD-800对实施例1的370℃+馏分进行催化脱蜡,所述催化剂是针对严重污染原料进行脱蜡的特别开发的基础金属(Ni)催化剂。
催化脱蜡步骤的操作条件和主要结果在表4中给出。
表4:按本发明生产催化脱蜡产品
实施例4(对比例)
应用从Shell商购的脱蜡催化剂SLD-821对实施例2的370℃+馏分进行催化脱蜡,所述催化剂是为了生产基础油II和III针对使深度加氢处理原料脱蜡而特别开发的贵金属(Pt)催化剂。
催化脱蜡步骤的操作条件和主要结果在表5中给出。
表5:以常规方式生产催化脱蜡产品
步骤(d)总结表
步骤(d) | 实施例3 | 实施例4 |
催化剂 | SLD-800 | SLD-821 |
370℃+收率,wt%(步骤2) | 83.3 | 87.0 |
370℃+收率,wt%(步骤1+2) | 71.5 | 61.5 |
Vk100,cSt | 10.30 | 8.81 |
粘度指数 | 91 | 106 |
倾点,℃ | -12 | -12 |
在步骤(e)中,使按本发明步骤(d)获得的脱蜡产品加氢精制。
实施例5(本发明)
使汽提出所有气体的实施例3的370℃+馏分经受加氢精制步骤,该步骤应用基础金属加氢精制催化剂(高活性的NiMo/Al2O3-类催化剂)如实施例5a,或者应用贵金属加氢精制催化剂(如CriterionLN-5)如实施例5b,已知后一催化剂具有高的加氢能力和对硫和氮中毒高的耐受力。
加氢精制步骤(e)的操作条件和主要结果在表6中给出。
表6:按本发明的步骤(e)生产加氢精制产品
实施例6(对比例)
应用获自Criterion的贵金属加氢精制催化剂(LN-5)使汽提出全部气体的对比例4的370℃+馏分经受加氢精制步骤(e)。
加氢精制步骤(e)的操作条件和主要结果在表7中给出。
表7:以常规方式生产加氢精制产品
从以上所述内容可清楚地看出本发明方法改进了制备重基础油的常规方法。
Claims (15)
1.一种制备重基础油的方法,包括如下步骤:
(a)提供含烃原料,所述含烃原料包含至少50wt%的沸点高于460℃的烃、800-2500ppmw的氮和1.5-4.0wt%的硫;
(b)在加氢处理条件下在含氢气体存在下用加氢处理催化剂加氢处理所述含烃原料,以获得氮含量为30-80ppmw和硫含量为200-450ppmw的加氢处理后产品;
(c)脱除在步骤(b)获得的加氢处理后产品中存在的至少50%的NH3和H2S;
(d)在催化脱蜡条件下在含氢气体存在下用脱蜡催化剂使步骤(c)获得的至少部分加氢处理后产品催化脱蜡,以获得脱蜡产品,所述脱蜡催化剂包含第VIII族金属加氢组分、脱铝的铝硅酸盐沸石晶体和基本不含氧化铝的低酸性耐高温氧化物粘结剂材料;
(e)在加氢精制条件下在含氢气体存在下用加氢精制催化剂使步骤(d)获得的至少部分脱蜡产品加氢精制,以获得重基础油;和
(f)回收所述重基础油。
2.权利要求1的方法,其中步骤(a)中提供的含烃原料包含大于65wt%的沸点高于460℃的烃。
3.权利要求1或2的方法,其中步骤(a)中提供的含烃原料包含至少50wt%的100℃下粘度大于14cSt的烃。
4.权利要求1-3任一项的方法,其中步骤(b)获得的加氢处理后产品中氮含量与硫含量的比(N/S)为0.1-0.3。
5.权利要求1-4任一项的方法,其中在步骤(c)中通过汽提从步骤(b)获得的加氢处理后产品中脱除NH3和H2S。
6.权利要求1-5任一项的方法,其中在步骤(c)中脱除步骤(b)获得的加氢处理后产品中存在的至少90%的NH3和H2S。
7.权利要求1-6任一项的方法,其中以脱蜡催化剂的总重量计,步骤(d)的脱蜡催化剂中的沸石组分以10-50wt%的量存在。
8.权利要求7的方法,其中所述沸石组分为ZSM-5、ZSM-11、ZSM-12、ZSM-22、ZSM-23、ZSM-35或ZSM-48。
9.权利要求1-8任一项的方法,其中步骤(b)中的加氢处理条件包括250-480℃的温度、30-250bar的压力和0.2-10hr-1的重时空速;步骤(d)中的脱蜡条件包括350-460℃的温度、80-240bar的压力和0.4-7hr-1的重时空速;和步骤(e)中的加氢精制条件包括300-390℃的温度、80-200bar的压力和0.5-2.5hr-1的重时空速。
10.权利要求1-9任一项的方法,其中步骤(e)中的加氢精制催化剂为贵金属基加氢精制催化剂。
11.权利要求1-9任一项的方法,其中步骤(e)中的加氢精制催化剂为基础金属加氢精制催化剂。
12.权利要求1-11任一项的方法,其中在步骤(c)中还从步骤(b)获得的加氢处理后产品中分离出沸点低于370℃的烃。
13.权利要求1-12任一项的方法,其中使在步骤(b)获得的全部加氢处理后产品经受步骤(c)。
14.权利要求1-13任一项的方法,其中使在步骤(c)获得的全部加氢处理后产品经受步骤(d)。
15.权利要求1-14任一项的方法,其中使在步骤(d)获得的全部脱蜡产品经受步骤(e)。
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