CN116120966A - Hydrogenation conversion method of wide-distillation-range Fischer-Tropsch synthetic wax - Google Patents
Hydrogenation conversion method of wide-distillation-range Fischer-Tropsch synthetic wax Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 90
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 191
- 239000003921 oil Substances 0.000 claims abstract description 97
- 239000000047 product Substances 0.000 claims abstract description 59
- 239000002199 base oil Substances 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 238000005336 cracking Methods 0.000 claims abstract description 32
- 239000010687 lubricating oil Substances 0.000 claims abstract description 14
- 239000012043 crude product Substances 0.000 claims abstract description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 239000002283 diesel fuel Substances 0.000 claims abstract description 8
- 239000003502 gasoline Substances 0.000 claims abstract description 8
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 6
- 239000002808 molecular sieve Substances 0.000 claims description 87
- 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 87
- 239000002253 acid Substances 0.000 claims description 70
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 47
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 41
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 claims description 37
- 229910052763 palladium Inorganic materials 0.000 claims description 37
- 229910052697 platinum Inorganic materials 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 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
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 17
- 238000005194 fractionation Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000001993 wax Substances 0.000 description 35
- 238000011049 filling Methods 0.000 description 27
- 239000000306 component Substances 0.000 description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 7
- 239000000523 sample Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RXAFXHRAUBYNMP-UHFFFAOYSA-N C(C)(C)(C)C1=NC(=CC=C1)C(C)(C)C.C(C)(C)(C)C1=NC(=CC=C1)C(C)(C)C Chemical compound C(C)(C)(C)C1=NC(=CC=C1)C(C)(C)C.C(C)(C)(C)C1=NC(=CC=C1)C(C)(C)C RXAFXHRAUBYNMP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 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
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 1
- 238000002215 pyrolysis infrared spectroscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of lubricating oil base oil preparation, in particular to a wide-boiling-range Fischer-Tropsch synthetic wax hydro-conversion method with normal alkane content not less than 90wt%, which comprises the following steps: the wide-distillation-range Fischer-Tropsch synthetic wax firstly enters a hydrogenation pretreatment reaction zone to finish the hydrogenation saturation and hydrodeoxygenation of non-alkane components in the raw materials; the obtained hydrogenation pretreatment oil enters a hydrogenation isomerization-cracking reaction zone, and hydrogenation isomerization and hydrocracking of the hydrogenation pretreatment oil are completed on a combined catalyst with a specific grain size; the obtained hydroisomerized and cracked oil enters a hydrofining reaction zone for further treatment to obtain a crude product; fractionating the crude product by an atmospheric/vacuum tower to obtain lubricating oil base oil, diesel oil, gasoline and other products. Compared with the prior art, the method can obtain the low pour point and high viscosity index lubricating oil base oil with higher yield.
Description
Technical Field
The invention relates to a hydrogenation conversion method of Fischer-Tropsch synthesis products, in particular to a method for producing a main product of base oil by taking wide-distillation-range Fischer-Tropsch synthesis wax as a raw material and carrying out hydrogenation conversion.
Background
Fischer-Tropsch waxes are synthesis gas (CO and H) 2 ) The main product is produced by Fischer-Tropsch synthesis reaction. The method takes long-chain alkane as a main material, and can be used for further hydro-upgrading to produce liquid fuel and chemicals. The Fischer-Tropsch wax has the main component of straight-chain alkane, almost no sulfur, nitrogen and aromatic hydrocarbon, and is a high-quality high-grade lubricating oil base oil raw material. The technical key point of the Fischer-Tropsch synthetic wax product is that 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 conversion of the Fischer-Tropsch synthetic wax product into high-grade lubricating oil base oil can be realized through hydrocracking and hydroisomerization reaction.
In the field of preparing lubricating oil base oil by hydro-upgrading Fischer-Tropsch wax, a number of related patents have been published at home and abroad, for example, US5834522 discloses a method for producing lubricating oil base oil by taking Fischer-Tropsch synthesis products as raw materials, hydroisomerizing the Fischer-Tropsch synthesis products in a hydroisomerization reaction zone, distilling and separating generated oil, and dewaxing a distillation bottom product 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 full or wide cut Fischer-Tropsch waxes are used as a feed, it is difficult to have both the light and heavy base components meet the pour point and viscosity index requirements. 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 III light lubricating oil base oil product with a viscosity index of > 120; while when the viscosity index of the light base oil component is acceptable, the heavy component cannot be used as a lubricant base oil product with acceptable pour points. When the traditional hydrocracking catalyst is adopted, the full-fraction or wide-fraction Fischer-Tropsch wax 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 generated in the process, the yield of the light and heavy base oil is too low, and the process economy is seriously influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation conversion method of wide-distillation-range Fischer-Tropsch synthetic wax, which can prepare low pour point and high viscosity index lubricating oil base oil with high yield through hydrogenation pretreatment, hydroisomerization, hydrofining and fractionation processes. The technical core is that based on the combined molecular sieve catalyst hydroisomerization cracking process with specific grain size, both light and medium components in the wide-boiling-range raw material can be converted into an isomerism product with high selectivity, and heavy components can be continuously hydrocracked to generate light and medium base oil components after high-selectivity isomerisation, so that full-fraction simultaneous excessive cracking is avoided, the generation of gas hydrocarbon and gasoline and diesel fraction byproducts is reduced, and the yield and performance of the base oil product are improved.
The wide distillation range Fischer-Tropsch wax hydroconversion method mainly comprises the following steps: the wide-distillation-range Fischer-Tropsch synthetic wax firstly enters a hydrogenation pretreatment reaction zone to finish the hydrogenation saturation and hydrodeoxygenation of non-alkane components in the raw materials; the obtained hydrogenation pretreatment oil enters a hydrogenation isomerization reaction zone, and the hydrogenation isomerization-cracking of the hydrogenation pretreatment oil is completed on a combined molecular sieve catalyst with specific grain size; the obtained hydroisomerized and cracked oil enters a hydrofining reaction zone for further treatment to obtain a crude product; fractionating the crude product by an atmospheric/vacuum tower to obtain base oil, diesel oil, gasoline and other products.
The technical scheme of the invention comprises the following implementation steps:
1) Mixing Fischer-Tropsch synthesis wax wide distillation range fraction raw material and hydrogen gas, and feeding the mixture into hydrogenation pretreatmentThe reaction zone is arranged on a bed layer filled with a hydrogenation pretreatment catalyst, the temperature is 150-450 ℃, the hydrogen partial pressure is 3-18MPa, and the volume space velocity of raw oil is 0.3-5h -1 Completing the hydrogenation saturation and hydrodeoxygenation of non-alkane components in the raw materials under the condition that the hydrogen-oil ratio is 200:1-2000:1, so as to obtain hydrogenation pretreatment oil;
2) Feeding the hydrotreated oil obtained in the step 1) into a hydroisomerization-cracking reaction zone, and on a combined catalyst with specific grain size, the reaction temperature is 250-400 ℃, the hydrogen partial pressure is 2-20MPa, and the volume space velocity of the raw oil is 0.3-5h -1 Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 200:1-2000:1, and completing hydroisomerization and hydrocracking reactions of the hydrotreated oil to obtain hydroisomerized cracked oil;
3) The hydroisomerization cracking oil obtained in the step 2) enters a hydrofining reaction zone, and the reaction temperature is 180-320 ℃ and the hydrogen partial pressure is 2-20MPa on a hydrofining catalyst, and the volume space velocity of the raw oil is 0.3-5h -1 Under the condition that the hydrogen-oil ratio is 200:1-2000:1, further hydrogenation saturation of the hydroisomerization cracking oil is completed, and a crude product is obtained;
4) Feeding the crude product obtained in the step 3) into an atmospheric/vacuum tower, and fractionating to obtain products such as gasoline, diesel oil, base oil and the like;
wherein, the combined catalyst with specific grain size in the step 2) is as follows: the catalyst A is prepared by taking a molecular sieve with a grain size of 10-500 nm and an AEL structure as a carrier and carrying platinum, palladium and/or iridium, and the catalyst B is prepared by taking a molecular sieve with a grain size of 500-10 mu m and a TON structure as a carrier and carrying platinum, palladium and/or iridium according to a certain proportion.
The method, wherein the Fischer-Tropsch wax wide distillation range distillate raw material in the step 1) refers to a Fischer-Tropsch wax distillate with an initial distillation point not higher than 240 ℃ and not lower than 180 ℃ and a final distillation point not lower than 700 ℃ and not higher than 730 ℃.
The method comprises the step 1) that the normal alkane content in the Fischer-Tropsch synthesis wax wide distillation range fraction raw material is not less than 90wt%.
The method comprises the step 1) of preparing a hydrogenation pretreatment catalyst by taking a heat-resistant inorganic oxide as a carrier and loading the heat-resistant inorganic oxide on a transition metal and a non-metal auxiliary agent.
The method comprises the step 1) of hydrogenating the heat-resistant inorganic oxide in the pretreatment catalyst, wherein the heat-resistant inorganic oxide is alumina, silica and/or an amorphous compound of the alumina and the silica.
The method comprises the step 1) of carrying out hydrogenation pretreatment on a catalyst, wherein a transition metal loading component in the catalyst is composed of one or more metals of cobalt, nickel, molybdenum and tungsten and one or more non-metal auxiliary agents selected from nitrogen, phosphorus, sulfur or boron.
The method comprises the step 1) of carrying out hydrogenation pretreatment on one or more transition metals selected from cobalt, nickel, molybdenum and tungsten, wherein the mass content of the transition metals is 10-28wt%.
The method comprises the step 1) of carrying out hydrogenation pretreatment on a catalyst, wherein the nonmetal auxiliary agent loaded by the catalyst is one or more of nitrogen, phosphorus, sulfur and boron, and the mass content of the nonmetal auxiliary agent is 2-8wt%.
The method, wherein the reaction conditions of the hydrogenation pretreatment in the step 1) are as follows: the temperature is 180-320 ℃, the hydrogen partial pressure is 5-12MPa, and the volume space velocity of the raw oil is 0.5-3h -1 The hydrogen-oil ratio is 200:1-1600:1.
The method, wherein the hydrotreated oil obtained in the step 1) is directly fed into a subsequent hydroisomerization-cracking reaction zone for continuous reaction without atmospheric and vacuum distillation.
The method comprises the step 2), wherein catalysts A and B are catalysts which adopt ten-membered ring molecular sieve carriers and load platinum, palladium and/or iridium metal components.
In the method, the catalyst A in the step 2) is a catalyst which takes a molecular sieve with an AEL structure as a carrier and loads platinum, palladium and/or iridium metal components.
The method comprises the step 2), wherein the mass content of active metal on the catalyst A is 0.3-0.6wt%.
In the method, the catalyst B in the step 2) is a catalyst which takes a molecular sieve with TON structure as a carrier and loads platinum, palladium and/or iridium metal components.
The method comprises the step 2), wherein the mass content of active metal on the catalyst B is 0.4-0.8wt%.
The method comprises the step 2), wherein the grain size of the AEL structure molecular sieve carrier adopted by the catalyst A is 20-200 nm.
The method comprises the step 2), wherein the grain size of the TON structure molecular sieve carrier adopted by the catalyst B is 800 nm-5 mu m.
The method comprises the step of preparing a molecular sieve with an AEL structure, wherein the molecular sieve is one or more of SAPO-11 and MeAPO-11 (one or more of Me= Zn, mg, mn, co, cr, cu, cd or Ni).
In the method, in the molecular sieve MeAPO-11 (one or more than two of Me= Zn, mg, mn, co, cr, cu, cd or Ni) with the AEL structure, the mass percentage of Me is 0.5-1.5 wt%.
The method comprises the step of preparing a molecular sieve with TON structure, wherein the molecular sieve with TON structure is one or more of ZSM-22, me-ZSM-22 (one or more of Me= Zn, mg, mn, co, cr, cu, fe, cd or Ni, etc.), theta-1, KZ-2, ISI-1, NU-10, etc.
In the method, the molecular sieve with TON structure is Me-ZSM-22 (one or more than two of Me= Zn, mg, mn, co, cr, cu, fe, cd or Ni and the like), and the mass percentage of Me is 0.2-2.0wt%.
The method comprises the step of carrying out a Pyridine adsorption infrared spectrum test and calculation to obtain the total acid amount of 200-800 mu mol (Pyridine)/g of the molecular sieve carrier with the AEL structure.
The method comprises the step of carrying out an adsorption infrared spectrum test on the external surface acid of the molecular sieve carrier with the AEL structure by using 2,6-Di-tert-butylpyridine, wherein the external surface acid amount is 100-300 mu mol (2, 6-Di-tert-butyl pyridine)/g.
The method comprises the step of carrying out a Pyridine adsorption infrared spectrum test and calculation, wherein the total acid amount of the molecular sieve carrier with the TON structure is 100-600 mu mol (Pyridine)/g.
The method comprises the steps of carrying out an adsorption infrared spectrum test on the external surface acid amount of the molecular sieve carrier with the TON structure by adopting 2,6-Di-tert-butylpyridine, wherein the external surface acid amount is 0-100 mu mol (2, 6-Di-tert-butyl pyridine)/g.
The method comprises the steps of A, B and a catalyst in the step 2), wherein the combination mode of the catalyst A and the catalyst B is that the volume ratio of the catalyst A to the catalyst B is 1:10-10:1.
The method comprises the step 2), wherein the volume ratio of the catalyst A to the catalyst B is 1:6-6:1.
The method comprises the step 2), wherein the volume ratio of the catalyst A to the catalyst B is 1:3-3:1.
The method, wherein the hydroisomerization reaction conditions in the step 2) are as follows: the temperature is 250-400 ℃, the hydrogen partial pressure is 2-15MPa, and the volume space velocity of the raw oil is 0.5-3h -1 The hydrogen-oil ratio is 200:1-1600:1.
The method, wherein the preferable hydroisomerization reaction conditions in the step 2) are: the temperature is 280-380 ℃, the hydrogen partial pressure is 2.5-8MPa, and the volume space velocity of the raw oil is 0.5-1.5h -1 The hydrogen-oil ratio is 200:1-800:1.
The method comprises the step 3) of adding hydrogen to refine the catalyst, wherein the catalyst consists of a heat-resistant inorganic oxide serving as a carrier and a metal component loaded on the carrier.
The method, wherein the refractory inorganic oxide in the hydrofining catalyst in the step 3) is alumina, silica and/or an amorphous compound of the alumina and the silica.
The method comprises the step 3) of hydrofining the metal component of the catalyst, wherein the metal component is one or more metals of platinum, palladium and iridium, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten.
The method comprises the steps of 3) carrying out hydrofining on the catalyst, wherein the mass content of active metals of platinum, palladium and iridium in the hydrofining catalyst is 0.2-0.5wt% and the mass content of auxiliary agent is 0.5-3wt%.
The method, wherein the reaction conditions of the hydrofining in the step 3) are as follows: the temperature is 180-320 ℃, and the hydrogen content isThe pressure is 2-15MPa, the volume space velocity of the raw oil is 0.5-3h -1 The hydrogen-oil ratio is 200:1-1600:1.
The crude product obtained in the step 3) sequentially enters a normal pressure tower and a vacuum tower for fractionation to obtain products such as gasoline, kerosene, diesel oil and base oil.
The method, wherein the fractionation of the atmospheric distillation tower and the vacuum distillation tower in the step 4) is a well-known operation in the field, and generally comprises one or more operation units of flash evaporation, atmospheric distillation and vacuum distillation towers to realize separation of products with different distillation ranges.
Compared with the prior art, the Fischer-Tropsch wax hydroconversion method provided by the invention has the following advantages: the wide-boiling-range Fischer-Tropsch wax can be converted into a lubricating oil base oil product with high selectivity; the process condition is simple, the hydroisomerization-cracking product is not required to be circularly treated, and the target product can be obtained through one-time passing; the base oil product prepared by the method has high yield and excellent performance.
Compared with the prior art, the method can obtain the base oil with high yield and low pour point and high viscosity index.
Drawings
FIG. 1 is a simplified process flow diagram
Detailed Description
The present invention will be further described with reference to specific examples, but it should be noted that the present invention is not limited thereto.
The information of the pre-hydrogenation catalyst, the hydroisomerization catalyst and the hydrofining catalyst used in the embodiment of the invention and the preparation method are as follows:
1. hydrogenation pretreatment catalyst T1
The hydrogenation pretreatment catalyst T1 is prepared by a conventional impregnation method. The catalyst is composed of heat-resistant inorganic oxide alumina and/or silica as a 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 catalyst comprises 25wt% of cobalt, nickel, molybdenum and tungsten, 5wt% of nitrogen, phosphorus, sulfur and boron, and the balance of aluminum oxide and/or silicon oxide.
2. Hydroisomerization-cracking catalysts A and B, etc
The hydroisomerization-cracking catalyst A is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The catalyst adopts molecular sieve carrier with AEL structure, which is one or more of SAPO-11 and MeAPO-11 (Me= Zn, mg, mn, co, cr, cu, cd or one or more than two of Ni), the grain size of the molecular sieve is 20 nm-200 nm, the total acid amount is 200-800 mu mol (Pyridine)/g, and the acid amount at the outer surface is 100-300 mu mol (2, 6-Di-tert-butyl Pyridine)/g. The content of platinum, palladium and/or iridium is 0.5wt% based on the weight percentage of the catalyst, and the balance is the molecular sieve with the AEL structure.
The hydroisomerization-cracking catalyst B is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The catalyst adopts a molecular sieve carrier with TON structure, which is one or more of ZSM-22, me-ZSM-22 (one or more than two of Me= Zn, mg, mn, co, cr, cu, fe, cd or Ni, etc.), theta-1, KZ-2, ISI-1, NU-10, etc., the grain size of the molecular sieve is 800 nm-5 mu m, the total acid amount is 100-600 mu mol (Pyridine)/g, and the acid amount of the outer surface is 0-100 mu mol (2, 6-Di-tert-butyl Pyridine)/g. The content of platinum, palladium and/or iridium is 0.5wt% based on the weight percentage of the catalyst, and the balance is the molecular sieve with the TON structure.
The hydroisomerization-cracking catalyst C is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The catalyst adopts a molecular sieve carrier with TON structure, which is one or more of ZSM-22, me-ZSM-22 (one or more than two of Me= Zn, mg, mn, co, cr, cu, fe, cd or Ni, etc.), theta-1, KZ-2, ISI-1, NU-10, etc., the grain size of the molecular sieve is 20 nm-200 nm, the total acid amount is 300-800 mu mol (Pyridine)/g, and the acid amount of the outer surface is 100-300 mu mol (2, 6-Di-tert-butyl Pyridine)/g. The content of platinum, palladium and/or iridium is 0.5wt% based on the weight percentage of the catalyst, and the balance is the molecular sieve with the TON structure.
The industrial catalyst D, the carrier is SAPO-11 molecular sieve, belonging to AEL structure, the grain size of the molecular sieve is 600nm, the total acid amount is 850 mu mol (Pyridine)/g, and the acid amount at the outer surface is 330 mu mol (2, 6-Di-tert-butyl Pyridine)/g. The content of platinum, palladium and/or iridium is 0.5wt% based on the weight percentage of the catalyst, and the balance is the SAPO-11 molecular sieve.
The industrial catalyst E is a ZSM-22 molecular sieve with a grain size of 600nm, a total acid content of 700 mu mol (Pyridine)/g and an external acid content of 240 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and belongs to TON structures. The content of platinum, palladium and/or iridium is 0.5wt% based on the weight percentage of the catalyst, and the balance is the ZSM-22 molecular sieve.
Other catalyst characteristics are described in detail in the comparative examples.
3. Hydrofining catalyst T2
The hydrofining catalyst T2 is prepared by adopting a conventional impregnation method. The catalyst is composed of 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 content of platinum, palladium and/or iridium is 0.25wt%, the content of cobalt, nickel, molybdenum and tungsten is 1.5wt% based on the weight percentage of the catalyst, and the balance is alumina and/or silica.
Test of total acid amount of sample (pyridine adsorption infrared (Py-IR) test): weighing 10-20mg of sample, pressing into circular self-supporting piece with diameter of 13mm, and placing into an in-situ infrared cell. Firstly, vacuumizing and preprocessing for 30min at 350 ℃, cooling to room temperature, and recording a blank sample spectrogram. After Pyridine (Pyridine) is adsorbed, the temperature is raised to 150 ℃, the vacuum treatment is carried out for 30min, the Pyridine is cooled to room temperature, and a Pyridine adsorption spectrogram is recorded. And calculating the total acid amount of the sample according to the characteristic peak area.
Sample external surface acid test (2, 6-di-tert-butylpyridine adsorption infrared (DTBPy-IR) test): weighing 10-20mg of sample, pressing into circular self-supporting piece with diameter of 13mm, and placing into an in-situ infrared cell. Firstly, vacuumizing and preprocessing for 30min at 350 ℃, cooling to 150 ℃, and recording a blank sample spectrogram. After adsorbing 2,6-Di-tert-butylpyridine (2, 6-Di-tert-butyl pyridine), vacuum was applied for 30min, and a spectrum of 2,6-Di-tert-butylpyridine adsorption was recorded. Then heating to 300 ℃, vacuumizing for 30min, cooling to 150 ℃ and recording a spectrogram of 2,6-di-tert-butylpyridine adsorption. And calculating the total acid amount of the sample according to the characteristic peak area.
In the examples of the present invention, a Fischer-Tropsch wax having a wide distillation range was used as a raw material, and the properties thereof are shown in Table 1.
A simplified process flow diagram of the present invention is shown in fig. 1.
1) Mixing a Fischer-Tropsch synthesis wax wide-boiling-range distillate raw material with hydrogen, entering a hydrogenation pretreatment reaction zone, and reacting on a bed layer filled with a hydrogenation pretreatment catalyst to finish hydrogenation saturation and hydrodeoxygenation of non-alkane components in the raw material to obtain hydrogenation pretreatment oil;
2) The hydrotreated oil obtained in the step 1) enters a hydroisomerization-cracking reaction zone, hydroisomerization reaction is carried out on a combined catalyst with a specific grain size, hydroisomerization and hydrocracking reaction of the hydrotreated oil are completed, and hydroisomerization cracked oil is obtained;
3) The hydroisomerization cracking oil obtained in the step 2) enters a hydrofining reaction zone, and further hydrogenation saturation of the hydroisomerization cracking oil is completed on a hydrofining catalyst to obtain a crude product;
4) Feeding the crude product obtained in the step 3) into an atmospheric tower and/or a vacuum tower, and fractionating to obtain gasoline, diesel oil and lubricating oil base oil;
example 1
The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 15wt percent of Ni-6wt percent of Mo-4wt percent of W-5wt percent of P/Al 2 O 3 The reaction condition is 220 ℃,6MPa (hydrogen pressure, same below) and airspeed of 1.5h -1 (raw oil volume space velocity, hereinafter the same) hydrogen-to-oil ratio 700;
hydroisomerization-cracking reactor adopts hydroisomerization catalysts A and B, wherein the catalyst A adopts SAPO-11 molecular sieve as carrier, the grain size of the molecular sieve is 120nm, the total acid amount is 650 mu mol (Pyridine)/g, the acid amount at the outer surface is 230 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and 0.5wt% Pd, namely 0.5wt% Pd/SAPO-11 is loaded on the catalyst A; the catalyst B adopts ZSM-22 molecular sieve as a carrier, the grain size of the molecular sieve is 2.3 mu m, the total acid amount is 300 mu mol (Pyridine)/g, the acid amount of the outer surface is 20 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst B is loaded0.5wt% Pt, i.e., 0.5wt% Pt/ZSM-22. The filling modes are that the filling volume ratio is 1:1 under the condition that the filling mode is that the raw materials flow through B from A during reaction, the reaction condition is 336 ℃, the pressure of hydrogen is 8MPa (the same as the lower pressure), and the airspeed is 0.7h -1 (raw oil volume space velocity, hereinafter the same) hydrogen-to-oil ratio 600;
the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% Co/SiO 2 The reaction condition is 230 ℃,8MPa (hydrogen pressure, same below) and airspeed of 1.5h -1 (raw oil volume space velocity, hereinafter the same applies) hydrogen-oil ratio 600. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Example 2
The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 14wt percent of Ni-7wt percent of Mo-4wt percent of W-4wt percent of P-1wt percent of B/Al 2 O 3 The reaction condition is 250 ℃,5MPa and airspeed of 3.0h -1 Hydrogen-to-oil ratio 800; hydroisomerization-cracking reactor adopts hydroisomerization catalysts A and B, wherein the catalyst A adopts SAPO-11 molecular sieve as carrier, the grain size of the molecular sieve is 100nm, the total acid amount is 600 mu mol (Pyridine)/g, the acid amount at the outer surface is 260 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and 0.5wt% Pt, namely 0.5wt% Pt/SAPO-11 is loaded on the catalyst A; the catalyst B adopts a ZSM-22 molecular sieve as a carrier, the grain size of the molecular sieve is 2.5 mu m, the total acid amount is 260 mu mol (Pyridine)/g, the acid amount of the outer surface is 30 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and 0.5wt% Pd, namely 0.5wt% Pd/ZSM-22 is loaded on the catalyst B. The filling modes are that the filling volume ratio is 3:1 under the condition that the filling mode is that the filling volume ratio is 3:1, the raw materials flow through B from A during reaction, the reaction condition is 357 ℃, the reaction condition is 10MPa, and the space velocity is 0.8h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 210 ℃,10MPa and airspeed of 1.0h -1 Hydrogen to oil ratio 800. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Example 3
The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 16wt percent of Ni-4wt percentMo-5wt％W-5wt％B/Al 2 O 3 The reaction condition is 260 ℃,7MPa and airspeed of 3.0h -1 Hydrogen to oil ratio 600; hydroisomerization-cracking reactor adopts hydroisomerization catalysts A and B, wherein the catalyst A adopts SAPO-11 molecular sieve as carrier, the grain size of the molecular sieve is 80nm, the total acid amount is 580 mu mol (Pyridine)/g, the acid amount at the outer surface is 240 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst A is loaded with 0.4wt% Pt-0.1wt% Pd, namely 0.4wt% Pt-0.1wt% Pd/SAPO-11; the catalyst B adopts a ZSM-22 molecular sieve as a carrier, the grain size of the molecular sieve is 3.5 mu m, the total acid amount is 360 mu mol (Pyridine)/g, the acid amount of the outer surface is 40 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and 0.25wt% Pd-0.25wt% Pt, namely 0.25wt% Pd-0.25wt% Pt/ZSM-22 is loaded on the catalyst B. The filling modes are that the filling volume ratio is 1:3 under the condition that the filling mode is that the filling volume ratio is 1:3, the raw materials flow through B from A during reaction, the reaction condition is 325 ℃, the reaction pressure is 9MPa, and the space velocity is 1.0h -1 Hydrogen-to-oil ratio 700; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% Co/SiO 2 The reaction condition is 220 ℃,9MPa and airspeed of 1.2h -1 Hydrogen to oil ratio 700. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Example 4
The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 13wt percent Ni-5wt percent Mo-7wt percent W-5wt percent N/Al 2 O 3 The reaction condition is 270 ℃,8MPa and the space velocity is 3.0h -1 Hydrogen to oil ratio 500; hydroisomerization-cracking reactor adopts hydroisomerization catalysts A and B, wherein the catalyst A adopts SAPO-11 molecular sieve as carrier, the grain size of the molecular sieve is 60nm, the total acid amount is 700 mu mol (Pyridine)/g, the acid amount at the outer surface is 280 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst A is loaded with 0.3wt% Pt-0.2wt% Pd, namely 0.3wt% Pt-0.2wt% Pd/SAPO-11; the catalyst B adopts ZSM-22 molecular sieve as a carrier, the grain size of the molecular sieve is 5.0 mu m, the total acid amount is 380 mu mol (Pyridine)/g, the acid amount of the outer surface is 50 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and 0.3wt% Pd-0.2wt% Pt, namely 0.3wt% Pd-0.2wt% Pt/ZSM-22 is loaded on the catalyst B. The filling modes are A upper part and B lower part, the filling volume ratio is 1:5, and the raw materials flow through from A during reactionB, the reaction condition is 320 ℃,6MPa and the space velocity is 0.9h -1 Hydrogen to oil ratio 550; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 260 ℃,12MPa and the space velocity is 2.5h -1 Hydrogen to oil ratio 500. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow 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 embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 15wt percent of Ni-6wt percent of Mo-4wt percent of W-5wt percent of P/Al 2 O 3 The reaction condition is 220 ℃,6MPa and airspeed of 1.5h -1 Hydrogen-to-oil ratio 700; the hydroisomerization-cracking reactor adopts a hydroisomerization catalyst A, wherein the catalyst A adopts a SAPO-11 molecular sieve as a carrier, the grain size of the molecular sieve is 120nm, the total acid amount is 650 mu mol (Pyridine)/g, the acid amount on the outer surface is 230 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and 0.5wt% Pd, namely 0.5wt% Pd/SAPO-11 is loaded on the catalyst A; the reaction condition is 356 ℃,8MPa and the space velocity is 0.7h -1 Hydrogen to oil ratio 600; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% Co/SiO 2 The reaction condition is 230 ℃,8MPa and airspeed of 1.5h -1 Hydrogen to oil ratio 600. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow 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 embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 14wt percent of Ni-7wt percent of Mo-4wt percent of W-4wt percent of P-1wt percent of B/Al 2 O 3 The reaction condition is 250 ℃,5MPa and airspeed of 3.0h -1 Hydrogen-to-oil ratio 800; hydroisomerization-cracking reactor adopts hydroisomerization catalysts B and A, catalyst A adopts SAPO-11 molecular sieve as carrier, the grain size of molecular sieve is 100nm, the total acid amount is 600 mu mol (Pyridine)/g, the acid amount at the outer surface is 260 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and catalyst A is loaded with 0.5wt% Pt, namely 0.5wt% Pt/SAPO-11; the catalyst B adopts ZSM-22 molecular sieve as a carrier, and the grain size of the molecular sieve is 2.5 mum, total acid amount 260. Mu. Mol (Pyridine)/g, external acid amount 30. Mu. Mol (2, 6-Di-tert-butyl Pyridine)/g, 0.5wt% Pd, i.e., 0.5wt% Pd/ZSM-22, was supported on the B catalyst. The filling modes are B upper and A lower, the filling volume ratio is 3:1, the raw materials flow through A from B during the reaction, the reaction condition is 357 ℃,10MPa and the airspeed is 0.8h -1 Hydrogen to oil ratio 500; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 210 ℃,10MPa and airspeed of 1.0h -1 Hydrogen to oil ratio 800. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow 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 embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 16wt percent of Ni-4wt percent of Mo-5wt percent of W-5wt percent of B/Al 2 O 3 The reaction condition is 260 ℃,7MPa and airspeed of 3.5h -1 Hydrogen to oil ratio 600; hydroisomerization-cracking reactor adopts hydroisomerization catalysts D and C, the carrier adopted by the catalyst D is SAPO-11 molecular sieve, the grain size of the molecular sieve is 600nm, the total acid amount is 850 mu mol (Pyridine)/g, the acid amount at the outer surface is 330 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst D is loaded with 0.5wt% Pd, namely 0.5wt% Pd/SAPO-11-D; the carrier adopted by the catalyst C is ZSM-22 molecular sieve, the grain size of the molecular sieve is 100nm, the total acid amount is 500 mu mol (Pyridine)/g, the acid amount at the outer surface is 200 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst C is loaded with 0.5wt% Pt, namely 0.5wt% Pt/ZSM-22-C. The filling modes are D, C and C, the filling volume ratio is 1:3, the raw materials flow through C from D during the reaction, the reaction condition is 325 ℃,9MPa and the airspeed is 1.0h -1 Hydrogen-to-oil ratio 700; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% Co/SiO 2 The reaction condition is 220 ℃,9MPa and airspeed of 1.2h -1 Hydrogen to oil ratio 700. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow 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 embodiment was employed. The hydrogenation pretreatment reactor adoptsThe hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 13wt percent Ni-5wt percent Mo-7wt percent W-5wt percent N/Al 2 O 3 The reaction condition is 270 ℃,8MPa and the space velocity is 4.0h -1 Hydrogen to oil ratio 500; hydroisomerization-cracking reactor adopts hydroisomerization catalysts D and E, the carrier adopted by the catalyst D is SAPO-11 molecular sieve, the grain size of the molecular sieve is 600nm, the total acid amount is 850 mu mol (Pyridine)/g, the acid amount at the outer surface is 330 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst D is loaded with 0.5wt% Pd, namely 0.5wt% Pd/SAPO-11-D; the carrier adopted by the catalyst E is ZSM-22 molecular sieve, the grain size of the molecular sieve is 600nm, the total acid amount is 700 mu mol (Pyridine)/g, the acid amount at the outer surface is 240 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the catalyst E is loaded with 0.5wt% Pt, namely 0.5wt% Pt/ZSM-22-E. The filling modes are D, E and E, the filling volume ratio is 1:5, the raw materials flow through E from D during the reaction, the reaction condition is 320 ℃,6MPa and the airspeed is 0.9h -1 Hydrogen to oil ratio 550; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 260 ℃,12MPa and the space velocity is 2.5h -1 Hydrogen to oil ratio 500. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Comparative example 5
A process flow similar to the present embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 13wt percent Ni-5wt percent Mo-7wt percent W-5wt percent N/Al 2 O 3 The reaction condition is 270 ℃,8MPa and the space velocity is 4.0h -1 Hydrogen to oil ratio 500; hydroisomerization-cracking reactor adopts hydroisomerization catalysts F and G, catalyst F adopts molecular sieve carrier with ATO structure, which is CoAPO-31 (hetero atom Co content is 1.5 wt%), the grain size of the molecular sieve is 100nm, the total acid amount is 420 mu mol (Pyridine)/G, the acid amount of the outer surface is 180 mu mol (2, 6-Di-tert-butyl Pyridine)/G, and the total content of supported metal is 0.4wt% Pt; the catalyst G adopts a molecular sieve carrier with FER structure, which is Fe-ZSM-35 (the content of hetero atom Fe is 2.0 wt%), the grain size of the molecular sieve is 2.0 mu m, the total acid amount is 280 mu mol (Pyridine)/G, the acid amount of the outer surface is 50 mu mol (2, 6-Di-tert-butyl Pyridine)/G, and the content of the supported metal is0.4wt% Pd. The filling modes are F and G, the filling volume ratio is 1:5, the raw materials flow through G from F during the reaction, the reaction condition is 320 ℃,6MPa and the airspeed is 0.9h -1 Hydrogen to oil ratio 550; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 260 ℃,12MPa and the space velocity is 2.5h -1 Hydrogen to oil ratio 500. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Comparative example 6
A process flow similar to the present embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 13wt percent Ni-5wt percent Mo-7wt percent W-5wt percent N/Al 2 O 3 The reaction condition is 270 ℃,8MPa and the space velocity is 4.0h -1 Hydrogen to oil ratio 500; the hydroisomerization-cracking reactor adopts hydroisomerization catalysts H and I, the catalyst H adopts a heteroatom aluminum phosphate molecular sieve carrier with an AEL structure, the heteroatom aluminum phosphate molecular sieve carrier is ZnAPO-11 (the heteroatom Zn content is 1.0 wt%), the grain size of the molecular sieve is 80nm, the total acid amount is 500 mu mol (Pyridine)/g, the acid amount of the outer surface is 150 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the metal loading amount is 0.5wt% Pt; the catalyst I adopts a heteroatom aluminum silicate molecular sieve carrier with an MTT structure, namely Ni-ZSM-23 (the heteroatom Ni content is 1.5 wt%) and has a grain size of 1 mu m, a total acid amount of 300 mu mol (Pyridine)/g, an external surface acid amount of 60 mu mol (2, 6-Di-tert-butyl Pyridine)/g and a metal loading amount of 0.4wt% Pd. The filling mode of the two is H, the filling volume ratio is 1:5, the raw materials flow through I from H during the reaction, the reaction condition is 320 ℃, the pressure is 6MPa, and the space velocity is 0.9H -1 Hydrogen to oil ratio 550; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 260 ℃,12MPa and the space velocity is 2.5h -1 Hydrogen to oil ratio 500. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Comparative example 7
A process flow similar to the present embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, and the catalyst T1 is13wt％Ni-5wt％Mo-7wt％W-5wt％N/Al 2 O 3 The reaction condition is 270 ℃,8MPa and the space velocity is 4.0h -1 Hydrogen to oil ratio 500; hydroisomerization-cracking reactor adopts hydroisomerization catalysts J and K, catalyst J adopts molecular sieve carrier with AFI structure, which is SAPO-5, the grain size of the molecular sieve is 50nm, the total acid amount is 780 mu mol (Pyridine)/g, the acid amount at the outer surface is 280 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the noble metal content is 0.4wt% Pd; the catalyst K adopts a molecular sieve carrier with an MRE structure, namely ZSM-48, the grain size of the molecular sieve is 4.5 mu m, the total acid amount is 560 mu mol (Pyridine)/g, the acid amount of the outer surface is 80 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the noble metal content is 0.3wt% Pt. The filling modes are J, the filling volume ratio is 1:5, the raw materials flow through K from J during the reaction, the reaction condition is 320 ℃, the pressure is 6MPa, and the space velocity is 0.9h -1 Hydrogen to oil ratio 550; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 260 ℃,12MPa and the space velocity is 2.5h -1 Hydrogen to oil ratio 500. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow is shown in table 2, and the properties of the base oil product are shown in table 3.
Comparative example 8
A process flow similar to the present embodiment was employed. The hydrogenation pretreatment reactor adopts a hydrogenation pretreatment catalyst T1, wherein the catalyst T1 is 13wt percent Ni-5wt percent Mo-7wt percent W-5wt percent N/Al 2 O 3 The reaction condition is 270 ℃,8MPa and the space velocity is 4.0h -1 Hydrogen to oil ratio 500; hydroisomerization-cracking reactor adopts hydroisomerization catalysts L and M, catalyst L adopts molecular sieve carrier with AFO structure, which is SAPO-41, the grain size of the molecular sieve is 350nm, the total acid amount is 600 mu mol (Pyridine)/g, the acid amount at the outer surface is 260 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the metal loading amount is 0.5wt% Pt; the catalyst M adopts a molecular sieve carrier with an MTW structure, namely ZSM-12, the grain size of the molecular sieve is 4.5 mu M, the total acid amount is 450 mu mol (Pyridine)/g, the acid amount at the outer surface is 120 mu mol (2, 6-Di-tert-butyl Pyridine)/g, and the metal loading amount is 0.5wt% Pd. The filling modes are L, M and 5 in the filling volume ratio, the raw materials flow through M from L during reaction, the reaction condition is 320 ℃, and the reaction condition is 6%MPa, airspeed 0.9h -1 Hydrogen to oil ratio 550; the hydrofining reactor adopts hydrofining catalyst T2, and the catalyst T2 is 0.25wt% Pt-1.5wt% W/SiO 2 The reaction condition is 260 ℃,12MPa and the space velocity is 2.5h -1 Hydrogen to oil ratio 500. The yield of the product obtained by the conversion and fractionation of the raw materials in the reaction flow 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, compared with the comparative example, the method of the present invention has the advantages of significantly improved yield of base oil, significantly reduced yields of light hydrocarbon and diesel oil, which are byproducts with lower value, less heavy wax remained in the product, and completely and efficiently converted Fischer-Tropsch wax components with wide distillation ranges. Meanwhile, as can be seen from Table 3, the base oil obtained by the method of the present invention has a higher viscosity index and a lower pour point than those obtained by the comparative example.
TABLE 1 oil Properties of Fischer-Tropsch wax feedstock with broad distillation ranges
TABLE 2 product yields
Table 3 base oil product properties
Claims (10)
1. The wide distillation range Fischer-Tropsch wax hydroconversion method is characterized by comprising the following steps of:
1) Mixing Fischer-Tropsch synthetic wax wide distillation range fraction material with hydrogen, and introducing into a hydrogenation pretreatment reaction zone, and loading with hydrogenationOn the bed layer of the pretreatment catalyst, the temperature is 150-450 ℃, the hydrogen partial pressure is 3-18MPa, and the volume space velocity of the raw oil is 0.3-5h -1 Completing the hydrogenation saturation and hydrodeoxygenation of non-alkane components in the raw materials under the condition that the hydrogen-oil ratio is 200:1-2000:1, so as to obtain hydrogenation pretreatment oil;
2) Feeding the hydrotreated oil obtained in the step 1) into a hydroisomerization-cracking reaction zone, and on a combined catalyst with specific grain size, the reaction temperature is 250-400 ℃, the hydrogen partial pressure is 2-20MPa, and the volume space velocity of the raw oil is 0.3-5h -1 Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 200:1-2000:1, and completing hydroisomerization and hydrocracking reactions of the hydrotreated oil to obtain hydroisomerized cracked oil;
3) The hydroisomerization cracking oil obtained in the step 2) enters a hydrofining reaction zone, and the reaction temperature is 180-320 ℃ and the hydrogen partial pressure is 2-20MPa on a hydrofining catalyst, and the volume space velocity of the raw oil is 0.3-5h -1 Under the condition that the hydrogen-oil ratio is 200:1-2000:1, further hydrogenation saturation of the hydroisomerization cracking oil is completed, and a crude product is obtained;
4) Feeding the crude product obtained in the step 3) into an atmospheric tower and/or a vacuum tower, and fractionating to obtain gasoline, diesel oil and lubricating oil base oil;
wherein, the combined catalyst with specific grain size in the step 2) is as follows: the catalyst A is prepared by taking a molecular sieve with a grain size of 10-500 nm and an AEL structure as a carrier and loading one or more than two of active metals of platinum, palladium or iridium, and the catalyst B is prepared by taking a molecular sieve with a grain size of 500-10 mu m and a TON structure as a carrier and loading one or more than two of active metals of platinum, palladium or iridium.
2. The method according to claim 1, wherein the molecular sieve with AEL structure is one or more of SAPO-11, meAPO-11 (one or more of me= Zn, mg, mn, co, cr, cu, cd or Ni, me mass content is 0.5-1.5 wt%); the molecular sieve with TON structure is one or more of ZSM-22, me-ZSM-22 (Me= Zn, mg, mn, co, cr, cu, fe, cd or Ni, etc.), me mass content is 0.2-2.0%), theta-1, KZ-2, ISI-1, NU-10, etc.;
the mass content of the supported active metal in the catalyst A is 0.3-0.6wt%, and the mass content of the supported active metal in the catalyst B is 0.4-0.7wt%.
3. The method according to claim 1 or 2, wherein in the combined catalyst having a specific grain size, the grain size of the AEL structured molecular sieve carrier used for catalyst a is 20nm to 200nm; the grain size of the TON structure molecular sieve carrier used in the catalyst B is 800 nm-5 mu m.
4. A process according to claim 1, 2 or 3, wherein in the combination catalyst having a specific crystallite size, catalyst a uses an AEL structured molecular sieve support having a total acid content of 200 to 800 μmol (pyredine)/g and an external surface acid content of 100 to 300 μmol (2, 6-Di-tert-butyl Pyridine)/g; the total acid amount of the TON structure molecular sieve carrier used in the catalyst B is 100-600 mu mol (Pyridine)/g, and the acid amount of the outer surface is 0-100 mu mol (2, 6-Di-tert-butyl Pyridine)/g.
5. The method according to claim 1, wherein the combination of catalysts a and B in step 2) is a combination of catalyst a and catalyst B in a volume ratio of 1:10 to 10:1, preferably a volume ratio of 1:6 to 6:1, wherein the feedstock flows through a and B sequentially for hydroisomerization-cracking reactions.
6. The method according to claim 1, wherein the reaction conditions for the hydrotreatment in step 1) are: the temperature is 180-320 ℃, the hydrogen partial pressure is 5-12MPa, and the volume space velocity of the raw oil is 0.5-3h -1 The hydrogen-oil ratio is 200:1-1600:1;
the hydrogenation pretreatment catalyst consists of one or more of alumina and/or silicon oxide loaded active metals cobalt, nickel, molybdenum and tungsten and one or more non-metal auxiliary agents selected from nitrogen, phosphorus, sulfur or boron, wherein the mass content of the active metals in the catalyst is 10-28wt%, and the mass content of the auxiliary agents is 2-8wt%.
7. The process according to claim 1, wherein the hydroisomerization reaction conditions in step 2) are: the temperature is 250-400 ℃, the hydrogen partial pressure is 2-15MPa, and the volume space velocity of the raw oil is 0.5-3h -1 The hydrogen-oil ratio is 200:1-1600:1.
8. The method according to claim 1, wherein the hydrofinishing reaction conditions in step 3) are: the temperature is 180-320 ℃, the hydrogen partial pressure is 2-15MPa, and the volume space velocity of the raw oil is 0.5-3h -1 The hydrogen-oil ratio is 200:1-1600:1;
the hydrofining catalyst consists of one or more metals of platinum, palladium and iridium which are alumina and/or silica supported active metals, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten, wherein the mass content of the active metals in the catalyst is 0.2-0.5wt% and the mass content of the auxiliary agents is 0.5-3wt%.
9. The method according to claim 1, wherein the crude product obtained in the step 3) is sequentially subjected to fractionation in a normal pressure tower and a reduced pressure tower to obtain products such as gasoline, diesel oil and lubricating oil base oil.
10. The process according to claim 1, wherein the Fischer-Tropsch wax wide distillation range fraction feed is a Fischer-Tropsch wax fraction having an initial distillation point of not higher than 240 ℃ and not lower than 180 ℃ and an end distillation point of not lower than 700 ℃ and not higher than 730 ℃, and the Fischer-Tropsch wax fraction has an n-alkane content of not lower than 90wt%.
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| US20170335208A1 (en) * | 2015-02-11 | 2017-11-23 | Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. | Method of hydrotreatment of fischer-tropsch synthesis products |
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