CN112143520B - Hydroconversion composition and method for hydroconversion of Fischer-Tropsch wax - Google Patents
Hydroconversion composition and method for hydroconversion of Fischer-Tropsch wax Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 164
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 239000002199 base oil Substances 0.000 claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 43
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 20
- 238000005194 fractionation Methods 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 106
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000011068 loading method Methods 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229910052741 iridium Inorganic materials 0.000 claims description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 17
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- 239000002283 diesel fuel Substances 0.000 claims description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000003502 gasoline Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000010687 lubricating oil Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 239000000314 lubricant Substances 0.000 description 12
- 238000005457 optimization Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of Fischer-Tropsch synthesis product hydroconversion, in particular to a hydroconversion composition and a Fischer-Tropsch synthesis wax hydroconversion method. The invention can prepare the lubricating oil base oil with low pour point and high viscosity index in high yield by simple hydrogenation pretreatment, fractionation, hydroisomerization, hydrofining and fractionation processes of the fraction of the Fischer-Tropsch wax at 280-660 ℃. The technical core is that each component in the wide-boiling-range raw material can be converted into an isomerism product with high selectivity based on a hydroisomerization process of combining AEL and ATO structure aluminum phosphate molecular sieve catalysts, so that the product yield and the performance are improved at the same time.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch synthesis product hydroconversion, in particular to a hydroconversion composition and application thereof in improving the yield of Fischer-Tropsch synthesis wax base oil with low pour point and high viscosity index, and also relates to a Fischer-Tropsch synthesis wax hydroconversion method.
Background
With the increasing trend of heavy crude oil and poor quality and the increasing market demands for high-quality oil products and chemical raw materials, the preparation of liquid fuels and chemicals from coal through synthetic gas becomes a focus of attention. Fischer-Tropsch synthesis (Fischer-Tropsch Tropsch synthesis), abbreviated as FT reaction, is carried out on synthesis gas (CO and H) 2 ) The process is to synthesize liquid fuel and chemical product with long chain alkane as main material in the presence of catalyst and proper reaction condition. In the low temperature Fischer-Tropsch product, the waxy component comprises a soft wax (C 20 -C 30 ) And hard wax>C 30 ) The main component of the lubricant is straight-chain alkane, almost does not contain sulfur, nitrogen and aromatic hydrocarbon, and is a high-quality high-grade lubricant base oil raw material. The technical key points of the Fischer-Tropsch synthetic wax product to be converted into high-grade lubricating oil base oil are as follows: the low-temperature flow property of the oil product is improved, namely the freezing point is reduced under the condition of keeping high viscosity index, and the low-temperature flow property can be realized through hydrocracking and hydroisomerization reaction.
A number of related patents have been published at home and abroad, for example US5834522 discloses a process for producing lube base oils from fischer-tropsch synthesis products which are hydroisomerized in a hydroisomerisation reaction zone, the resulting oil is separated by distillation and the bottoms of the distillation is dewaxed to obtain oil and non-oil fractions. US5882505 discloses a process for producing lube base oils by converting fischer-tropsch wax having a boiling point greater than 370 ℃ using a countercurrent reactor, the feedstock being contacted with a hydroisomerisation catalyst in a fixed bed reactor, and the reacted product being contacted with a hydrodewaxing catalyst in at least one fixed bed reactor to produce the desired product, wherein the hydroisomerisation reaction product is counter-current to the hydrogen-containing gas. CN1688674 discloses a multi-step process for the preparation of heavy lubricant base oils from fischer-tropsch wax comprising hydrodewaxing the wax in a first hydrodewaxing step to produce an isomerised product of a partially dewaxed heavy base oil fraction, followed by hydrodewaxing said heavy lubricant fraction in one or more successive hydrodewaxing steps to remove hydrocarbons below the heavy lubricant fraction to give a heavy lubricant base oil. CN1703488 discloses a process for producing fuel and lubricant base oils from fischer-tropsch wax comprising (1) hydrodewaxing the fischer-tropsch wax to produce an isomerised product comprising fuel and partially hydrodewaxed base oil fractions, (2) separating the two fractions, (3) separating the partially hydrodewaxed base oil fraction into a heavy fraction and a lower boiling fraction, (4) further hydrodewaxing the lower boiling fraction and the heavy fraction, respectively, to produce lubricant base oils including heavy lubricant base stocks. CN101230290 discloses a method for producing solvent oil, lubricating oil base oil and heavy wax from fischer-tropsch wax, fractionating the whole fraction product obtained by converting wax in hydrofining zone to obtain light fraction of solvent oil, separating the base oil fraction product, hydroisomerizing and converting, and directly hydrofining the remaining heavy fraction to obtain decolorized wax. US7198710 discloses a process for producing a high viscosity index lube base oil from a fischer-tropsch wax by first fractionating the fischer-tropsch wax to obtain light and heavy components, and then separately hydroisomerising the wax to reduce the pour point of the feedstock to obtain a light lube base oil having a pour point meeting the requirements. When the heavy component is hydrodewaxed, the pour point is unqualified, and the pour point of the heavy component is further reduced by adopting a solvent dewaxing method, so that a heavy lubricant base oil product with the pour point meeting the requirement is finally obtained.
In the above process, the disadvantages of using a conventional hydroisomerization dewaxing catalyst in its entirety are: when whole or wide range waxy oils are used as feed, it is difficult to have both light and heavy base components meet the pour point and viscosity index requirements. In general, when the pour point of the heavy base oil component is acceptable, the viscosity index loss of the light base oil component is large, and it is difficult to produce an API group III light lubricating oil base oil product having a viscosity index > 120; while when the viscosity index of the light base oil component is acceptable, the heavy component cannot be used as an acceptable lubricant base oil product. When the traditional hydrocracking catalyst is adopted, whether full-fraction or wide-fraction wax-containing oil is used as a feed, the light and heavy base oil products can meet the requirements of pour point and viscosity index at the same time, but a large amount of cracked products are produced in the process, the yield of the light and heavy base oil is too low, and the process economy is seriously affected.
Disclosure of Invention
The invention provides a hydroconversion composition and a hydroconversion method of Fischer-Tropsch synthetic wax, which overcome the defects of the prior art, and are based on a hydroisomerization process combining AEL and ATO structure aluminum phosphate molecular sieve catalysts, so that each component in a wide-boiling-range raw material can be converted into an isomerism product with high selectivity, thereby realizing the simultaneous improvement of the product yield and the performance.
One of the technical schemes of the invention is realized by the following measures: a hydroconversion composition comprising a hydroprocessing catalyst, a combination catalyst, and a hydrofinishing catalyst; the combined catalyst is formed by combining a catalyst A and a catalyst B according to the volume ratio of 1:10 to 10:1, wherein the catalyst A is formed by taking an aluminum phosphate molecular sieve with an AEL structure as a carrier and loading active metal platinum and/or palladium and/or iridium, and the catalyst B is formed by taking an aluminum phosphate molecular sieve with an ATO structure as a carrier and loading active metal platinum and/or palladium and/or iridium; the hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, phosphorus, sulfur or boron; the hydrofining catalyst is composed of heat-resistant inorganic oxide as carrier, one or more active metals of platinum, palladium and iridium loaded on the carrier, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
the aluminum phosphate molecular sieve with the AEL structure is one or two of a molecular sieve SAPO-11 and a molecular sieve MeAPO-11, and Me in the molecular sieve MeAPO-11 is one or more than two of Zn, mg, mn, co, cr, cu, cd and Ni.
The molecular sieve with the ATO structure is one or two of molecular sieve SAPO-31 and molecular sieve MeAPO-31, and Me in the molecular sieve MeAPO-31 is one or more than two of Zn, mg, mn, co, cr, cu, cd and Ni.
The acid content of the catalyst A was 2.1mmol (NH 3 ) /g to 2.5mmol (NH) 3 ) Per g, the acid content of catalyst B was 1.9mmol (NH 3 ) /g to 2.8mmol (NH) 3 ) And/g, the mass loading of the active metal in the catalyst A is 0.1 to 0.5wt% and the mass loading of the active metal in the catalyst B is 0.3 to 0.8wt%.
In the hydrotreating catalyst, the mass loading of the active metal is 20 to 55wt%, and the mass loading of the auxiliary agent is 1 to 15wt%.
In the hydrofining catalyst, the mass loading of the active metal is 0.2 to 1.0 weight percent, and the mass loading of the auxiliary agent is 0.3 to 1.5 weight percent; the volume ratio of the catalyst A to the catalyst B is 1:5 to 5:1.
The second technical scheme of the invention is realized by the following measures: use of a hydroconversion composition for increasing the yield of a Fischer-Tropsch wax base oil having a low pour point and a high viscosity index.
The third technical scheme of the invention is realized by the following measures: a method for hydroconversion of Fischer-Tropsch wax comprises the following steps:
1) Mixing the fraction raw oil of Fischer-Tropsch wax at 280-660 ℃ with hydrogenFeeding the mixture into a hydrogenation pretreatment reaction zone, wherein the temperature is 150-350 ℃ and the hydrogen partial pressure is 1.0-20 MPa on a hydrogenation pretreatment catalyst, and the volume space velocity of raw oil is 0.2h -1 For 5h -1 Completing the hydrogenation saturation, the hydrogenation desulfurization, the hydrogenation denitrification and the hydrogenation deoxidation of non-alkane components in the raw oil under the condition that the hydrogen-oil ratio is 100:1 to 3000:1 to obtain hydrogenation pretreatment oil;
2) Feeding the hydrotreated oil obtained in the step 1) into a vacuum fractionating tower, and separating out heavy wax fractions with the temperature of more than 550 ℃;
3) The fraction with the temperature less than 550 ℃ obtained in the step 2) enters a hydroisomerization reaction zone, and the reaction temperature is 200 ℃ to 450 ℃ and the hydrogen partial pressure is 1.0MPa to 20MPa on a combined catalyst, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100:1 to 3000:1, and completing hydroisomerization and hydrocracking reaction of the hydrotreated oil to obtain hydroisomerized oil;
4) The hydroisomerization oil obtained in the step 3) enters a hydrofining reaction zone, and on a hydrofining catalyst, the reaction temperature is 150 ℃ to 350 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Under the condition that the hydrogen-oil ratio is 100:1 to 3000:1, further hydrogenation saturation of hydroisomerized oil is completed, and a crude product is obtained;
5) And (3) feeding the crude product obtained in the step (4) into an atmospheric tower or a vacuum tower, and fractionating to obtain gasoline, diesel oil and base oil.
The following is a further optimization and/or improvement of the third aspect of the present invention:
the position of the combined catalyst in the step 3) in the catalyst bed layer is that under the catalyst B on the catalyst A, the raw oil sequentially flows through the catalyst A and the catalyst B.
The reaction conditions of the hydrogenation pretreatment in the step 1) are as follows: the temperature is 200 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
The hydroisomerization reaction conditions in the step 3) are as follows: at a temperature of 250 ℃ to 400 ℃ and hydrogen partial pressure5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
The reaction conditions for hydrofining in the step 4) are as follows: the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
And (3) sequentially feeding the crude product obtained in the step (4) into an atmospheric tower and a vacuum tower for fractionation to obtain gasoline, kerosene, diesel oil and base oil.
The invention can prepare the lubricating oil base oil with low pour point and high viscosity index with high yield by simple hydrogenation pretreatment, fractionation, hydroisomerization, hydrofining and fractionation processes of the fraction of the Fischer-Tropsch wax at 280 ℃ to 660 ℃; the technical core is that each component in the wide-boiling-range raw material can be converted into an isomerism product with high selectivity based on a hydroisomerization process of combining AEL and ATO structure aluminum phosphate molecular sieve catalysts, so that the product yield and the performance are improved at the same time.
Drawings
FIG. 1 is a schematic process flow diagram of a process for hydroconversion of Fischer-Tropsch wax in accordance with the present invention.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The various chemical reagents and chemical supplies mentioned in the invention are all commonly known and used in the prior art unless specified otherwise; the percentages in the invention are mass percentages unless specified otherwise; the solutions in the invention are aqueous solutions in which the solvent is water unless otherwise specified, for example, the hydrochloric acid solution is hydrochloric acid aqueous solution; the room temperature and the room temperature in the present invention generally refer to temperatures ranging from 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to examples:
example 1: the hydroconversion composition comprises a hydrogenation pretreatment catalyst, a combination catalyst and a hydrofining catalyst; the combined catalyst is formed by combining a catalyst A and a catalyst B according to the volume ratio of 1:10 to 10:1, wherein the catalyst A is formed by taking an aluminum phosphate molecular sieve with an AEL structure as a carrier and loading active metal platinum and/or palladium and/or iridium, and the catalyst B is formed by taking an aluminum phosphate molecular sieve with an ATO structure as a carrier and loading active metal platinum and/or palladium and/or iridium; the hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, phosphorus, sulfur or boron; the hydrofining catalyst is composed of heat-resistant inorganic oxide as carrier, one or more active metals of platinum, palladium and iridium loaded on the carrier, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten.
Example 2: the hydroconversion composition comprises a hydrogenation pretreatment catalyst, a combination catalyst and a hydrofining catalyst; the combined catalyst is formed by combining a catalyst A and a catalyst B according to the volume ratio of 1:10 or 10:1, wherein the catalyst A is formed by taking an aluminum phosphate molecular sieve with an AEL structure as a carrier and loading active metal platinum and/or palladium and/or iridium, and the catalyst B is formed by taking an aluminum phosphate molecular sieve with an ATO structure as a carrier and loading active metal platinum and/or palladium and/or iridium; the hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, phosphorus, sulfur or boron; the hydrofining catalyst is composed of heat-resistant inorganic oxide as carrier, one or more active metals of platinum, palladium and iridium loaded on the carrier, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten.
The invention is based on the hydroisomerization process of combining AEL and ATO structured aluminum phosphate molecular sieve catalysts, so that each component in the raw materials with wide distillation range can be converted into an isomerism product with high selectivity, thereby realizing the simultaneous improvement of the product yield and performance.
The refractory inorganic oxide in both the hydrotreating catalyst and the hydrofinishing catalyst may be alumina and/or silica.
Example 3: as the optimization of the embodiment, the aluminum phosphate molecular sieve with the AEL structure is one or two of the molecular sieve SAPO-11 and the molecular sieve MeAPO-11, and Me in the molecular sieve MeAPO-11 is one or more than two of Zn, mg, mn, co, cr, cu, cd and Ni. The molecular sieve with ATO structure is one or two of molecular sieve SAPO-31 and molecular sieve MeAPO-31, and Me in molecular sieve MeAPO-31 is one or more than two of Zn, mg, mn, co, cr, cu, cd and Ni. The acid amount of the catalyst A is 2.1mmol (NH 3)/g to 2.5mmol (NH 3)/g, the acid amount of the catalyst B is 1.9mmol (NH 3)/g to 2.8mmol (NH 3)/g, the mass loading of the active metal in the catalyst A is 0.1wt% to 0.5wt%, and the mass loading of the active metal in the catalyst B is 0.3wt% to 0.8wt%. In the hydrogenation pretreatment catalyst, the mass loading of the active metal is 20 to 55 weight percent, and the mass loading of the auxiliary agent is 1 to 15 weight percent. In the hydrofining catalyst, the mass loading of the active metal is 0.2 to 1.0 weight percent, and the mass loading of the auxiliary agent is 0.3 to 1.5 weight percent; the volume ratio of the catalyst A to the catalyst B is 1:5 to 5:1.
Preferably, catalyst A and catalyst B are present in a volume ratio of 1:5 to 2:1.
Example 4: use of the hydroconversion composition described in the above examples to increase the yield of a Fischer-Tropsch waxy base oil having a low pour point and a high viscosity index.
Example 5: the hydroconversion composition used in the method for hydroconversion of Fischer-Tropsch wax as described in the above examples is carried out according to the following steps:
1) Mixing the distillate raw oil with hydrogen at 280-660 ℃ of Fischer-Tropsch synthetic wax, and feeding the mixture into a hydrogenation pretreatment reaction zone, wherein the temperature is 150-350 ℃ and the hydrogen partial pressure is 1.0-20 MPa on a hydrogenation pretreatment catalyst, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Completing the hydrogenation saturation, the hydrogenation desulfurization, the hydrogenation denitrification and the hydrogenation deoxidation of non-alkane components in the raw oil under the condition that the hydrogen-oil ratio is 100:1 to 3000:1 to obtain hydrogenation pretreatment oil;
2) Feeding the hydrotreated oil obtained in the step 1) into a vacuum fractionating tower, and separating out heavy wax fractions with the temperature of more than 550 ℃;
3) The fraction obtained in step 2) is fed to a temperature of less than 550 DEG CFeeding the mixture into a hydroisomerization reaction zone, and on a combined catalyst, the reaction temperature is 200-450 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of raw oil is 0.2h -1 For 5h -1 Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100:1 to 3000:1, and completing hydroisomerization and hydrocracking reaction of the hydrotreated oil to obtain hydroisomerized oil;
4) The hydroisomerization oil obtained in the step 3) enters a hydrofining reaction zone, and on a hydrofining catalyst, the reaction temperature is 150 ℃ to 350 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Under the condition that the hydrogen-oil ratio is 100:1 to 3000:1, further hydrogenation saturation of hydroisomerized oil is completed, and a crude product is obtained;
5) And (3) feeding the crude product obtained in the step (4) into an atmospheric tower or a vacuum tower, and fractionating to obtain products such as gasoline, diesel oil and base oil.
From example 6, it is understood that the fraction of Fischer-Tropsch wax at 280 ℃ to 660 ℃ is first fed into a hydrotreating reaction zone to complete the hydrodesaturation, hydrodesulphurisation, hydrodenitrogenation and hydrodeoxygenation of the non-paraffinic components of the feedstock; the obtained hydrotreated oil enters a vacuum fractionating tower (such as fractionating tower 1 in figure 1) to separate heavy wax components with the temperature of more than 550 ℃; the fraction below 550 ℃ enters a hydroisomerization reaction zone, and hydroisomerization of the hydrotreated oil is completed on a combined catalyst; the obtained hydroisomerized oil enters a hydrofining reaction zone for further treatment to obtain a crude product; the crude product is fractionated by an atmospheric tower or a vacuum tower (such as fractionating tower 2 in figure 1) to obtain base oil, diesel oil, gasoline and other products.
Example 6: as an optimization of example 5, the position of the combined catalyst in step 3) in the catalyst bed is that under the catalyst B on the catalyst a, the raw oil sequentially flows through the catalyst a and the catalyst B.
Example 7: as an optimization of examples 5 to 6, the reaction conditions for the hydrotreatment in step 1) are: the temperature is 200 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
Example 8:as an optimization of examples 5 to 7, the hydroisomerization reaction conditions in step 3) are: the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
Example 9: as an optimization of examples 5 to 8, the hydrofinishing reaction conditions in step 4) are: the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
Example 10: as an optimization of examples 5 to 9, the crude product obtained in step 4) is sequentially sent to an atmospheric tower and a vacuum tower for fractionation to obtain products such as gasoline, kerosene, diesel oil and base oil.
The atmospheric and vacuum towers are well known in the art and generally comprise one or more operating units of flash distillation, atmospheric distillation and vacuum distillation towers to separate products of different distillation ranges.
(1) Hydrogenation pretreatment catalyst H1
The hydrotreatment catalyst (which can be replaced by H1) is prepared by a conventional impregnation method. H1 is composed of heat-resistant inorganic oxide alumina and/or silica as carrier, one or more metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, phosphorus, sulfur or boron. The total content of cobalt, nickel, molybdenum and tungsten (the four element ratios of the same mass are adopted in the following examples and comparative examples) was 40wt%, the total content of nitrogen, phosphorus, sulfur and boron (the four element ratios of the same mass are adopted in the following examples and comparative examples) was 5wt%, and the balance was alumina and/or silica (the alumina and silica of the mass ratio of 1:1 are adopted in the following examples and comparative examples), based on the weight percentage of H1.
(2) Hydroisomerization catalysts A and B
Hydroisomerization catalyst a (i.e., catalyst a of the present invention) is prepared using conventional impregnation methods. The catalyst A takes an aluminum phosphate molecular sieve with an AEL structure, such as a SAPO-11 molecular sieve, as a carrier, and one or more metal groups selected from platinum, palladium and/or iridiumAnd (3) forming the finished product. Based on the weight percentage of the catalyst A, the total content of platinum, palladium and iridium (the same mass ratio of the three elements is adopted in the following examples and comparative examples) is 0.3wt%, the balance being the aluminum phosphate molecular sieve SAPO-11 having an AEL structure, and the acid amount of the catalyst A is 2.2mmol (NH 3 )/g。
Hydroisomerization catalyst B (i.e., catalyst B of the present invention) is prepared using conventional impregnation methods. The catalyst B is composed of an aluminum phosphate molecular sieve SAPO-31 molecular sieve with an ATO structure as a carrier and one or more metals selected from platinum, palladium and iridium. Based on the weight percentage of the catalyst B, the total content of platinum, palladium and iridium (the three elements with the same mass ratio are adopted in the following examples and comparative examples) is 0.5wt percent, the balance is the aluminum phosphate molecular sieve SAPO-31 with ATO structure, and the acid amount of the catalyst A is 2.3mmol (NH) 3 )/g。
(3) Hydrofining catalyst H2
The hydrogenation pretreatment catalyst H2 (which can be replaced by H2) is prepared by adopting a conventional impregnation method. The H2 is composed of a heat-resistant inorganic oxide alumina and/or silica as a carrier, one or more metals of platinum, palladium and iridium loaded on the carrier, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten. The total content of platinum, palladium and iridium (the same mass ratio of these three elements is used in the following examples and comparative examples) was 0.3wt%, the total content of cobalt, nickel, molybdenum and tungsten (the same mass ratio of these four elements is used in the following examples and comparative examples) was 1wt%, and the balance was alumina and/or silica (the mass ratio of alumina and silica is 1:1 in the following examples and comparative examples), based on the weight percentage of H2.
The following examples use Fischer-Tropsch wax as a starting material to prepare a lubricant base oil according to the method of the invention described in the above examples, the properties of which are shown in Table 1. Comparative example A lubricating base oil was also prepared from Fischer-Tropsch wax.
Example 11: as shown in figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction condition is 310 ℃,4MPa, and the space velocity is 2.0H -1 Hydrogen to oil ratio 500; distillation tower1 (vacuum fractionation column, same follow) to separate a heavy wax fraction greater than 550 ℃; hydroisomerization reactor adopts hydroisomerization catalysts A and B, the loading mode of the hydroisomerization catalysts A and B is that under the condition of catalyst B on catalyst A, the loading volume ratio is 2:1, the reaction condition is 355 ℃,12MPa, and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 220 ℃,5MPa and airspeed is 1.0H -1 Hydrogen to oil ratio 500. The yields of the obtained products after the raw materials shown in Table 1 are converted and fractionated by the reaction flow of the reaction flow are shown in Table 2, and the properties of the lubricating oil base oil products are shown in Table 3.
Example 12: as shown in figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction condition is 300 ℃,4MPa, and the space velocity is 2.0H -1 Hydrogen to oil ratio 600; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and B is that the filling volume ratio of the catalyst A to the catalyst B is 1:1, the reaction condition is 351 ℃,13MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 240 ℃,6MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the lubricating oil base oil product are shown in Table 3.
Example 13: as shown in figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction condition is 320 ℃,5MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio 600; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; hydroisomerization reactor adopts hydroisomerization catalysts A and B, the loading mode of the hydroisomerization catalysts A and B is that under the condition of catalyst B on catalyst A, the loading volume ratio is 1:2, the reaction condition is 347 ℃,15MPa, and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 240 ℃,6MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the base oil product are shown in Table 3.
Example 14: as shown in figure 1, the hydrogenation pretreatment reactor adopts addingHydrogen pretreatment catalyst H1, reaction condition of 315 ℃,3MPa and space velocity of 2.0H -1 Hydrogen to oil ratio 500; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; hydroisomerization catalysts A and B are adopted in the hydroisomerization reactor, the filling mode of the hydroisomerization catalysts A and B is that the filling volume ratio of the catalyst A to the catalyst B is 1:5, the reaction condition is 341 ℃,15MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 270 ℃,5MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the base oil product are shown in Table 3.
Comparative example 1: a process flow similar to the present invention is employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst H1, the reaction condition is 310 ℃,4MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio 500; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; the hydroisomerization reactor adopts hydroisomerization catalyst A, the reaction condition is 355 ℃,12MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 220 ℃,5MPa and airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the base oil product are shown in Table 3.
Comparative example 2: a process flow similar to the present invention is employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst H1, the reaction condition is 300 ℃,4MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio 600; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; the hydroisomerization reactor adopts hydroisomerization catalyst A, the reaction condition is 351 ℃,13MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 240 ℃,6MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the base oil product are shown in Table 3.
Comparative example 3: a process flow similar to the present invention is employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst H1, and the reaction condition is 320 DEG C5MPa, airspeed 2.0h -1 Hydrogen to oil ratio 600; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; hydroisomerization catalyst B is adopted in the hydroisomerization reactor, the reaction condition is 347 ℃,15MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 240 ℃,6MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the base oil product are shown in Table 3.
Comparative example 4: a process flow similar to the present invention is employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst H1, the reaction condition is 315 ℃,3MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio 500; the distillation column 1 separates out a heavy wax fraction of more than 550 ℃; hydroisomerization catalyst B is adopted in the hydroisomerization reactor, the reaction condition is 341 ℃,15MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction condition is 270 ℃,5MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio 500. The raw materials shown in Table 1 are converted and fractionated by the reaction flow, the yield of the obtained product is shown in Table 2, and the properties of the base oil product are shown in Table 3.
As can be seen from table 2, the base oil yield is significantly improved and the light hydrocarbon and diesel oil yields, which are lower in value, are significantly reduced by the method of the present invention, compared to the comparative examples. Meanwhile, as shown in Table 3, the viscosity index of the base oil obtained by the method of the present invention was higher and the pour point was lower than that of the comparative example.
In summary, the invention can prepare the low pour point and high viscosity index lubricating oil base oil with high yield through simple hydrogenation pretreatment, fractionation, hydroisomerization, hydrofining and fractionation processes of the fraction of the Fischer-Tropsch wax at 280 ℃ to 660 ℃; the technical core is that each component in the wide-boiling-range raw material can be converted into an isomerism product with high selectivity based on a hydroisomerization process of combining AEL and ATO structure aluminum phosphate molecular sieve catalysts, so that the product yield and the performance are improved at the same time.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (14)
1. A hydroconversion composition comprising a hydroprocessing catalyst, a combination catalyst, and a hydrofinishing catalyst; the combined catalyst is formed by combining a catalyst A and a catalyst B according to the volume ratio of 1:10 to 10:1, wherein the catalyst A is formed by taking an aluminum phosphate molecular sieve with an AEL structure as a carrier and loading active metal platinum and/or palladium and/or iridium, and the catalyst B is formed by taking an aluminum phosphate molecular sieve with an ATO structure as a carrier and loading active metal platinum and/or palladium and/or iridium; the hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, phosphorus, sulfur or boron; the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, one or more active metals of platinum, palladium and iridium loaded on the carrier, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten;
the aluminum phosphate molecular sieve with the AEL structure is one or two of a molecular sieve SAPO-11 and a molecular sieve MeAPO-11, and Me in the molecular sieve MeAPO-11 is one or more than two of Zn, mg, mn, co, cr, cu, cd and Ni; the molecular sieve with the ATO structure is one or two of molecular sieve SAPO-31 and molecular sieve MeAPO-31, and Me in the molecular sieve MeAPO-31 is one or more than two of Zn, mg, mn, co, cr, cu, cd and Ni; the acid amount of catalyst A was 2.1mmol (NH 3 ) /g to 2.5mmol (NH) 3 ) Per g, the acid content of catalyst B was 1.9mmol (NH 3 ) /g to 2.8mmol (NH) 3 ) /g, active gold in catalyst AThe mass loading of the active metal in the catalyst B is 0.1 to 0.5wt% and the mass loading of the active metal in the catalyst B is 0.3 to 0.8wt%; in the hydrogenation pretreatment catalyst, the mass loading of active metal is 20 to 55wt%, and the mass loading of auxiliary agent is 1 to 15wt%; in the hydrofining catalyst, the mass loading of the active metal is 0.2 to 1.0 weight percent, and the mass loading of the auxiliary agent is 0.3 to 1.5 weight percent; the volume ratio of the catalyst A to the catalyst B is 1:5 to 5:1;
the position of the combined catalyst in the catalyst bed layer is under the catalyst B on the catalyst A, and the raw oil sequentially flows through the catalyst A and the catalyst B.
2. Use of the hydroconversion composition of claim 1 to increase the yield of a fischer-tropsch wax base oil with low pour point and high viscosity index.
3. A process for the hydroconversion of fischer-tropsch wax in accordance with claim 1, characterized by the following steps:
1) Mixing the distillate raw oil with hydrogen at 280-660 ℃ of Fischer-Tropsch synthetic wax, and feeding the mixture into a hydrogenation pretreatment reaction zone, wherein the temperature is 150-350 ℃ and the hydrogen partial pressure is 1.0-20 MPa on a hydrogenation pretreatment catalyst, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Completing the hydrogenation saturation, the hydrogenation desulfurization, the hydrogenation denitrification and the hydrogenation deoxidation of non-alkane components in the raw oil under the condition that the hydrogen-oil ratio is 100:1 to 3000:1 to obtain hydrogenation pretreatment oil;
2) Feeding the hydrotreated oil obtained in the step 1) into a vacuum fractionating tower, and separating out heavy wax fractions with the temperature of more than 550 ℃;
3) The fraction with the temperature less than 550 ℃ obtained in the step 2) enters a hydroisomerization reaction zone, and the reaction temperature is 200 ℃ to 450 ℃ and the hydrogen partial pressure is 1.0MPa to 20MPa on a combined catalyst, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100:1 to 3000:1, and completing hydroisomerization and hydrocracking reaction of the hydrotreated oil to obtain hydroisomerized oil;
4) Step by stepThe hydroisomerization oil obtained in the step 3) enters a hydrofining reaction zone, and on a hydrofining catalyst, the reaction temperature is 150 ℃ to 350 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h -1 For 5h -1 Under the condition that the hydrogen-oil ratio is 100:1 to 3000:1, further hydrogenation saturation of hydroisomerized oil is completed, and a crude product is obtained;
5) And (3) feeding the crude product obtained in the step (4) into an atmospheric tower or a vacuum tower, and fractionating to obtain gasoline, diesel oil and base oil.
4. A method for hydroconversion of a fischer-tropsch wax as defined in claim 3, wherein the combined catalyst in step 3) is arranged in the catalyst bed at a position above catalyst a and below catalyst B, and the feed oil is passed through catalyst a and catalyst B in sequence.
5. The method for hydroconversion of Fischer-Tropsch wax according to claim 3 or 4, wherein the reaction conditions for the hydrotreatment in step 1) are as follows: the temperature is 200 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
6. The method for hydroconversion of Fischer-Tropsch wax according to claim 3 or 4, wherein the hydroisomerization reaction conditions in step 3) are as follows: the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
7. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 5, wherein the hydroisomerization reaction conditions in step 3) are: the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
8. A process for the hydroconversion of Fischer-Tropsch wax as defined in claim 3, 4 or 7, whereinThe reaction conditions for hydrofining in the step 4) are as follows: the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
9. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 5, wherein the hydrofinishing reaction conditions in step 4) are: the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
10. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 6, wherein the hydrofinishing reaction conditions in step 4) are: the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h -1 For 2h -1 The hydrogen-oil ratio is 200:1 to 1000:1.
11. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 3, 4, 7, 9 or 10, wherein the crude product obtained in step 4) is fractionated sequentially in an atmospheric tower and a vacuum tower to obtain gasoline, kerosene, diesel oil and base oil.
12. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 5, wherein the crude product obtained in the step 4) is sequentially fed into an atmospheric tower and a vacuum tower for fractionation to obtain gasoline, kerosene, diesel oil and base oil.
13. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 6, wherein the crude product obtained in the step 4) is sequentially fed into an atmospheric tower and a vacuum tower for fractionation to obtain gasoline, kerosene, diesel oil and base oil.
14. The method for hydroconversion of Fischer-Tropsch wax as defined in claim 8, wherein the crude product obtained in the step 4) is sequentially fed into an atmospheric tower and a vacuum tower for fractionation to obtain gasoline, kerosene, diesel oil and base oil.
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