CN108102698B - Method for producing lubricating oil base oil - Google Patents
Method for producing lubricating oil base oil Download PDFInfo
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- CN108102698B CN108102698B CN201611051788.4A CN201611051788A CN108102698B CN 108102698 B CN108102698 B CN 108102698B CN 201611051788 A CN201611051788 A CN 201611051788A CN 108102698 B CN108102698 B CN 108102698B
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- molecular sieve
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- 239000002199 base oil Substances 0.000 title claims abstract description 27
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000002808 molecular sieve Substances 0.000 claims description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 230000001588 bifunctional effect Effects 0.000 claims description 40
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 4
- 230000000881 depressing effect Effects 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 17
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G65/046—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being an aromatisation step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for producing lubricating oil base oil. The invention generates alkylbenzene from the Fischer-Tropsch wax as the raw material under the action of the catalyst, thus achieving the purposes of reducing the pour point of the Fischer-Tropsch wax and producing the high-viscosity index lubricating oil base oil. The method not only improves the selectivity of the pour point depressing process, but also improves the yield of the lubricating oil base oil produced by the Fischer-Tropsch wax.
Description
Technical Field
The invention relates to a method for producing lubricating oil base oil. In particular to a method for producing lubricating oil base oil by using Fischer-Tropsch wax as a raw material and adopting hydrocarbon conversion.
Background
To ensure the low temperature flow properties of lubricant base oils, it is desirable to reduce the pour point of the base oil feedstock. The base oil pour point depressing process mainly includes solvent dewaxing, catalytic dewaxing and isomerization dewaxing. The solvent dewaxing is to separate the high pour point wax component from the low pour point wax component in the material by physical separation to reduce the pour point of the base oil. The catalytic dewaxing (hydrodewaxing) is that under the action of ZSM-5 containing molecular sieve catalyst and hydrogen gas the lubricating oil fraction is undergone the process of shape-selective cracking treatment to crack its normal paraffin hydrocarbon into small molecular hydrocarbon so as to reduce freezing point. The isomerization dewaxing process is to convert the normal paraffin with high freezing point into isoparaffin through shape selective isomerization under the action of molecular sieve catalyst containing SAPO-11, ZSM-22, ZSM-23, ZSM-48 and the like and hydrogen, thereby achieving the purpose of reducing the pour point.
CN200710063010.X, CN201010615901.3 and CN201210143102.X all adopt a hydroisomerization (isodewaxing) process to reduce the freezing point of Fischer-Tropsch wax to produce lubricating oil base oil. U.S. Pat. No. 4,943,672 uses a combined hydroisomerization (isodewaxing) and solvent dewaxing process to reduce the Fischer-Tropsch wax pour point to produce lubricant base oils. US7,198,710 proposes a process for producing high viscosity index lubricant base oils from fischer-tropsch wax. Firstly, Fischer-Tropsch wax is fractionated to obtain a light component and a heavy component, and then hydrogenation isodewaxing is respectively carried out to reduce the pour point of the raw material, so that the light lubricating oil base oil with the pour point meeting the requirement can be obtained. And (3) because the pour point of the hydroisomerization dewaxing heavy component is unqualified, the pour point of the heavy component is further reduced by adopting a solvent dewaxing method, and finally the heavy lubricant base oil product with the pour point meeting the requirement is obtained.
The prior art technology for reducing pour point, such as Fischer-Tropsch wax isodewaxing or solvent dewaxing, is limited by process selectivity, and the yield of the lubricant base oil product is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for producing lubricating oil base oil by using Fischer-Tropsch wax as a raw material. In the method, the Fischer-Tropsch wax is converted into alkylbenzene, so that the pour point of the Fischer-Tropsch wax is reduced, and the product yield is high.
The invention provides a method for producing lubricating base oil, which comprises the following steps:
(1) mixing Fischer-Tropsch wax and hydrogen, then entering a first reaction zone, and carrying out dehydrocyclization reaction under the action of a bifunctional catalyst;
(2) carrying out gas-liquid separation on the reaction effluent obtained in the step (1), mixing the liquid phase effluent obtained by separation with hydrogen, then entering a second hydrogenation reaction zone, and carrying out hydrofining reaction under the action of a hydrofining catalyst;
(3) and (3) carrying out gas-liquid separation on the hydrofining effluent obtained in the step (2), and distilling the liquid-phase product obtained by separation to obtain the lubricating oil base oil with different viscosity grades.
In the method, the Fischer-Tropsch wax refers to Fischer-Tropsch product full fraction or heavy components of the Fischer-Tropsch product obtained by synthesis gas through a Fischer-Tropsch synthesis process, and the distillation range of the heavy components is 350-700 ℃.
In the process of the present invention, the gaseous phase separated in step (2) may be partially or completely recycled to the first reaction zone.
In the process of the present invention, the bifunctional moiety described in step (1)The catalyst comprises a TON type molecular sieve, a metal component and an inorganic refractory oxide; wherein the TON type molecular sieve is a TON type molecular sieve containing rare earth elements; the inorganic refractory oxide is one or more of alumina, titanium oxide, boron oxide, silicon oxide, zirconium oxide and magnesium oxide, and the metal component is noble metal, and can be platinum and/or palladium. The bifunctional catalyst comprises the following components in percentage by weight of the catalyst: 10-95 wt% of TON type molecular sieve containing rare earth elements; the metal component is 0.05wt% -5.0 wt% calculated by metal, and the inorganic refractory oxide is 15wt% -40 wt%. The rare earth element is calculated by oxide (RE)2O3) The content in the catalyst is 1wt% to 15wt%, preferably 3wt% to 10 wt%. The specific surface area of the bifunctional catalyst is 200-350 m2The pore volume is 0.3 to 0.5 mL/g.
In the method, the TON type molecular sieve is one or more of a ZSM-22 molecular sieve, a Nu-10 molecular sieve, a KZ-2 molecular sieve and an ISI-1 molecular sieve, and is preferably a ZSM-22 molecular sieve. The TON type molecular sieve has a Si/Al molar ratio of 50-200, preferably 80-160.
In the method of the present invention, the rare earth element is one or more of lanthanum, cerium, praseodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, yttrium and lutetium, and preferably lanthanum and/or cerium. The precursors are water soluble salts such as chlorides, nitrates and acetates, preferably nitrates.
In the method, the rare earth element-containing TON type molecular sieve is obtained by directly mixing a rare earth element compound with the TON type molecular sieve, drying at 20-300 ℃ for 1-48 h, and roasting at 400-800 ℃ for 0.5-10 h.
In the method, the first reaction zone in the step (1) adopts a mode of catalyst grading filling to improve the selectivity of paraffin dehydrocyclization reaction. And sequentially filling the bifunctional catalyst A, the bifunctional catalyst B and the bifunctional catalyst C according to the flow direction of the Fischer-Tropsch wax and the hydrogen. The content of the rare earth element-containing TON type molecular sieve in the bifunctional catalyst A is 42wt% -45 wt%, the content of the rare earth element-containing TON type molecular sieve in the bifunctional catalyst B is 60wt% -64 wt%, the content of the rare earth element-containing TON type molecular sieve in the bifunctional catalyst C is 72wt% -75 wt%, and the filling volume ratio of the bifunctional catalyst A, the bifunctional catalyst B and the bifunctional catalyst C in the first reaction zone is 40-50: 40-30: 30 to 20.
In the method of the present invention, the reaction conditions of the first reaction zone are: the temperature is 350-480 ℃, the preferable temperature is 420-480 ℃, the hydrogen partial pressure is 0.05-1.0 MPa, the preferable pressure is 0.05-0.30 MPa, and the volume space velocity is 0.1h-1～3.0h-1Preferably 0.5h-1～2.0h-1The volume ratio of hydrogen to oil is 50: 1-1500: 1, preferably 200: 1-800: 1.
In the method of the present invention, the hydrofining catalyst used in step (2) is a conventional reduction type hydrofining catalyst, and may be a noble metal catalyst or a reduced nickel catalyst, when the catalyst is a noble metal catalyst, the active metal is one or two of Pt and Pd, the weight content of the active metal in the catalyst is generally 0.05% to 1%, when the catalyst is a reduced nickel catalyst, the active metal is 30% to 80% by weight of an oxide, and the catalyst carrier is generally Al2O3Or Al2O3-SiO2The composition may contain an auxiliary such as P, Ti, B, Zr or the like. The catalyst is used for conventional reduction, so that the hydrogenation active metal is in a reduction state in the reaction process. Can be selected from common commercial catalysts in the field or prepared according to a common method in the field.
In the method of the present invention, the reaction conditions of the second hydrogenation reaction zone in step (2) are as follows: the temperature is 150-280 ℃, preferably 210-260 ℃, the hydrogen partial pressure is 6.0-18.0 MPa, preferably 10.0-15.0 MPa, and the volume space velocity is 0.3h-1～3.0h-1Preferably 0.6h-1～1.2h-1The volume ratio of hydrogen to oil is 400: 1-1500: 1, preferably 600: 1-800: 1.
In the method of the present invention, the distillation in step (3) may be reduced pressure distillation, and the conditions of the reduced pressure distillation are as follows: the pressure at the top of the distillation tower is 5-40 mm Hg, preferably 5-15 mm Hg; the bottom temperature of the distillation tower is 250-350 ℃, and preferably 280-320 ℃.
In the method, under the action of the bifunctional catalyst filled in the first reaction zone, the Fischer-Tropsch wax serving as the raw material is subjected to dehydrocyclization reaction to generate alkylbenzene, and the relationship analysis of the condensation point and the viscosity index of hydrocarbon and the molecular structure shows that the alkylbenzene with the same carbon number is much lower than the condensation point of normal alkane, and the requirement of the lubricating oil base oil on low-temperature fluidity can be met. The method of the invention can achieve the purpose of reducing the Fischer-Tropsch wax freezing point as the existing isomerization dewaxing or catalytic dewaxing process. The invention has the advantages that the long-chain monocyclic aromatic hydrocarbon compound with the same condensation point has higher viscosity index than isoparaffin, so the viscosity index of the lubricating oil base oil produced by the invention is higher than that of isodewaxing base oil. Because the method adopts the bifunctional catalyst and the TON type molecular sieve modified by rare earth elements, the acidity and the acid strength of the molecular sieve are greatly improved, the reaction temperature of the first reaction zone is reduced, and the formation of carbon deposit in the process is reduced. Moreover, the dehydrocyclization pour point depression process in the first reaction zone is carried out at low pressure, so that the investment of equipment can be greatly reduced. In addition, the first reaction zone adopts a catalyst grading filling mode, and the characteristics that the dehydrogenation reaction is a temperature reduction process are utilized, so that the dehydrogenation reaction temperature and the activity of the catalyst are reasonably matched, the selectivity of the dehydrocyclization process is improved, the content of a molecular sieve in the catalyst is integrally reduced, and the production cost of the catalyst is reduced.
Detailed Description
The following examples are provided to illustrate the details and effects of the method of the present invention. The following examples further illustrate the process provided by the present invention, but do not limit the scope of the invention. The properties of the Fischer-Tropsch wax used in the present invention are shown in Table 1, and the physicochemical properties of the hydrorefining catalyst used in step (2) are shown in Table 2.
TABLE 1 Properties of the raw materials
TABLE 2 hydrofinishing catalyst Properties
| Item | Data of |
| Chemical composition in wt% | |
| Pd | 0.20 |
| Pt | 0.30 |
| Support gamma-Al2O3 | Balance of |
| Physical Properties | |
| Pore volume, mL.g-1 | ≮0.5 |
| Specific surface area, m2.g-1 | ≮220 |
| Crush strength, N.cm-1 | ≮100 |
| Bulk density, g.cm-3 | 0.55～0.62 |
| Shape of | Cylindrical bar |
| Size, mm | Φ3×(3～8) |
| Item | Data of |
| Chemical composition, weight% | |
| Platinum (Pt) | 0.2-0.5 |
| Physical Properties | |
| Outside dimension (phi × L)/mm | (1.4-1.6)×(3～8) |
| Pore volume, mL.g-1 | ≥0.30 |
| Specific surface area,/m2.g-1 | ≥180 |
| Bulk density, g.cm-3 | 0.65～0.75 |
| Crush strength, N.cm-1 | ≥100 |
| Shape of | Cylindrical bar |
Example 1
The preparation method of the bifunctional catalyst comprises the following steps:
(1) the ZSM-22 molecular sieve prepared according to the method of example 1 of Chinese patent CN1565969A has the molar ratio of aluminum of 95 and the specific surface area of 220m2The pore volume is 0.23 mL/g.
(2) Will be (NH)4）2Ce(NO3)6(Beijing chemical plant production, analytical purification) and water to prepare Ce2O3Mixing 1500 g of the molecular sieve obtained in the step (1) with 2000 g of the aqueous solution containing cerium fully, drying at the constant temperature of 120 ℃ for 8 hours, and roasting at the constant temperature of 460 ℃ for 8 hours to obtain Ce2O315 percent of cerium-containing ZSM-22.
(3) Fully mixing 1000 g of the cerium-containing molecular sieve obtained in the step (2) with 500 g of SB alumina powder, then adding 100 g of dilute nitric acid with the weight concentration of 40% and a proper amount of water, kneading into a plastic paste, extruding into a cylindrical strip with the diameter of 1.2mm, keeping the temperature of the formed product at 120 ℃ for 8 hours, and keeping the temperature at 550 ℃ for 6 hours to obtain a catalyst carrier, wherein the catalyst carrier comprises the following components: 75wt% modified ZSM-23 and 25wt% alumina.
(4) With a gas containing H2PtCl6Loading platinum on the carrier obtained in the step (3) by adopting a saturated impregnation method, keeping the temperature constant at 150 ℃ for 6 hours, and keeping the temperature constant at 500 ℃ for 8 hours to obtain the bifunctional catalyst 1, wherein the composition and the physicochemical properties of the bifunctional catalyst are shown in a table 3, and the reaction conditions and the reaction results are shown in a table 6.
Example 2
The preparation method of the bifunctional catalyst is the same as that of example 1, except that the rare earth element compound used is La (NO)3)3·6H2O (pure analytical, produced in Beijing chemical plant) and La in the lanthanum-containing solution2O3The content is 2.5 wt%, the hydrogenation component is palladium, the used palladium-containing compound is palladium nitrate, wherein the concentration of the solution is 3.2wt% in terms of metal, the composition and the physicochemical properties of the bifunctional catalyst 2 are shown in Table 3, and the reaction conditions and the reaction results are shown in Table 6.
Example 3
By adopting the cerium-containing ZSM-22 molecular sieve and the catalyst preparation method prepared in the example 1, three bifunctional catalysts 4, 5 and 6 are prepared according to the content of the molecular sieve of 42%, 60% and 72%, the composition and the physicochemical properties of the bifunctional catalysts are shown in Table 4, the catalysts 4, 5 and 6 are graded and filled according to the volume ratio of 40:40:30, and the reaction conditions and the reaction results are shown in Table 6.
Example 4
By adopting the lanthanum-containing ZSM-22 molecular sieve and the catalyst preparation method prepared in the example 2, three bifunctional catalysts 7, 8 and 9 are prepared according to the content of the molecular sieve of 45%, 64% and 75%, the composition and the physicochemical properties of the catalysts are shown in Table 5, the catalysts 7, 8 and 9 are graded and filled according to the volume ratio of 50:30:20, and the reaction conditions and the reaction results are shown in Table 6.
Comparative example 1
The preparation method of the bifunctional catalyst is the same as that of example 1, except that the molecular sieve is not treated with a rare earth element-containing solution to obtain bifunctional catalyst 3, the composition and physicochemical properties of which are shown in table 3, and the reaction conditions and the reaction results of which are shown in table 6.
Comparative example 2
The conditions and reaction results of the isodewaxing reaction in step (1) using a conventional isodewaxing catalyst, trade name FIW-12 (manufactured by China petrochemical catalyst Co., Ltd.) are shown in Table 6.
TABLE 3 bifunctional catalysts 1, 2, 3 Properties
TABLE 4 bifunctional catalysts 4, 5, 6 Properties
TABLE 5 bifunctional catalysts 7, 8, 9 Properties
TABLE 6 reaction conditions and results
The results in Table 6 show that the method has better selectivity than the traditional isomerization dewaxing pour point depression process, namely, the yield of the base oil product of the lubricating oil is improved, and the viscosity index of the obtained base oil is higher. The rare earth element modified TON molecular sieve and the catalyst are graded, so that the reaction temperature of the first reaction zone is reduced, and the formation of carbon deposit in the process is reduced.
Claims (23)
1. A process for producing a lubricant base oil, the process comprising:
(1) mixing Fischer-Tropsch wax and hydrogen, then entering a first reaction zone, and carrying out dehydrocyclization reaction under the action of a bifunctional catalyst; the bifunctional catalyst comprises a TON type molecular sieve, a metal component and an inorganic refractory oxide; wherein the TON type molecular sieve is a TON type molecular sieve containing rare earth elements; the hydrogen partial pressure of the first reaction zone is 0.05 MPa-1.0 MPa;
(2) carrying out gas-liquid separation on the reaction effluent obtained in the step (1), mixing the liquid phase effluent obtained by separation with hydrogen, then entering a second hydrogenation reaction zone, and carrying out hydrofining reaction under the action of a hydrofining catalyst;
(3) and (3) carrying out gas-liquid separation on the hydrofining effluent obtained in the step (2), and distilling the liquid-phase product obtained by separation to obtain the lubricating oil base oil with different viscosity grades.
2. The method of claim 1, wherein: the Fischer-Tropsch wax refers to Fischer-Tropsch product full fraction or heavy components of a Fischer-Tropsch product, which are obtained by synthesis gas through a Fischer-Tropsch synthesis process, and the distillation range of the heavy components is 350-700 ℃.
3. The method of claim 1, wherein: in the step (1), the inorganic refractory oxide is one or more of aluminum oxide, titanium oxide, boron oxide, silicon oxide, zirconium oxide and magnesium oxide, and the metal component is noble metal.
4. A method according to claim 1 or 3, characterized by: the metal component is platinum and/or palladium.
5. The method of claim 1, wherein: in the TON type molecular sieve containing rare earth elements, the rare earth elements are calculated by oxides (RE)2O3) The composition in the catalyst is 1wt% -15 wt%.
6. The method of claim 5, wherein: in the TON type molecular sieve containing rare earth elements, the rare earth elements are calculated by oxides (RE)2O3) The composition in the catalyst is 3wt% -10 wt%.
7. The method of claim 1, wherein: the specific surface area of the bifunctional catalyst is 200-350 m2The pore volume is 0.3 to 0.5 mL/g.
8. The method of claim 1, wherein: the TON type molecular sieve is one or more of ZSM-22 molecular sieve, Nu-10 molecular sieve, KZ-2 molecular sieve and ISI-1 molecular sieve.
9. The method of claim 1, wherein: the TON type molecular sieve is a ZSM-22 molecular sieve.
10. The method of claim 1, wherein: the TON type molecular sieve has a Si/Al molar ratio of 50-200.
11. The method of claim 1, wherein: the TON type molecular sieve has a silica-alumina molar ratio of 80-160.
12. The method of claim 1, wherein: the rare earth element is one or more of lanthanum, cerium, praseodymium, promethium, samarium, europium, dysprosium, gadolinium, erbium, thulium, ytterbium and lutetium.
13. The method of claim 1, wherein: the rare earth element is lanthanum and/or cerium.
14. The method of claim 1, wherein: the rare earth element-containing TON type molecular sieve is prepared by directly mixing a rare earth element compound with the TON type molecular sieve, drying at 20-300 ℃ for 1-48 h, and roasting at 400-800 ℃ for 0.5-10 h.
15. The method of claim 1, wherein: and (2) sequentially filling a bifunctional catalyst A, a bifunctional catalyst B and a bifunctional catalyst C in the first reaction zone in the step (1) according to the flowing direction of the Fischer-Tropsch wax and the hydrogen, wherein the content of the rare earth element-containing TON type molecular sieve in the bifunctional catalyst A is 42wt% -45 wt%, the content of the rare earth element-containing TON type molecular sieve in the bifunctional catalyst B is 60wt% -64 wt%, and the content of the rare earth element-containing TON type molecular sieve in the bifunctional catalyst C is 72wt% -75 wt%.
16. The method of claim 15, wherein: the filling volume ratio of the bifunctional catalyst A, the bifunctional catalyst B and the bifunctional catalyst C in the first reaction zone is 40-50: 40-30: 30 to 20.
17. The method of claim 1, wherein: what is needed isThe reaction conditions of the first reaction zone are as follows: the temperature is 350-480 ℃, and the volume space velocity is 0.1h-1～3.0h-1The volume ratio of hydrogen to oil is 50: 1-1500: 1.
18. The method of claim 1, wherein: the reaction conditions of the first reaction zone are as follows: the temperature is 420-480 ℃, the hydrogen partial pressure is 0.05-0.30 MPa, and the volume space velocity is 0.5h-1～2.0h-1The volume ratio of hydrogen to oil is 200: 1-800: 1.
19. The method of claim 1, wherein: the reaction conditions of the second hydrogenation reaction zone in the step (2) are as follows: the temperature is 150-280 ℃, the hydrogen partial pressure is 6.0-18.0 MPa, and the volume space velocity is 0.3h-1～3.0h-1The volume ratio of hydrogen to oil is 400: 1-1500: 1.
20. The method of claim 1, wherein: the reaction conditions of the second hydrogenation reaction zone in the step (2) are as follows: the temperature is 210-260 ℃, the hydrogen partial pressure is 10.0-15.0 MPa, and the volume space velocity is 0.6h-1～1.2h-1The volume ratio of hydrogen to oil is 600: 1-800: 1.
21. The method of claim 1, wherein: and (3) distilling under reduced pressure.
22. The method of claim 21, wherein: the reduced pressure distillation conditions are as follows: the pressure at the top of the distillation tower is 5-40 mm Hg, and the temperature at the bottom of the distillation tower is 250-350 ℃.
23. The method of claim 22, wherein: the reduced pressure distillation conditions are as follows: the pressure at the top of the distillation tower is 5-15 mm Hg; the temperature of the bottom of the distillation tower is 280-320 ℃.
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| CN101942321A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for producing base oil of lubricating oil by isomerization dewaxing |
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN105316036A (en) * | 2014-06-16 | 2016-02-10 | 中国石油化工股份有限公司 | Method of producing ultrahigh-viscosity-index lubricant base oil |
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| CN101173193A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Paraffinic hydrocarbon shape selecting isomerization catalyst and method for producing the same |
| CN101942321A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method for producing base oil of lubricating oil by isomerization dewaxing |
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN105316036A (en) * | 2014-06-16 | 2016-02-10 | 中国石油化工股份有限公司 | Method of producing ultrahigh-viscosity-index lubricant base oil |
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