Process for producing a hydroisomerization cracking combined catalyst and a lubricating base oil

Abstract

The present application relates to the technical field of lubricating oil base oil preparation, in particular to a hydrogenation isomerization-cracking combined catalyst suitable for preparing base oil from Fischer-Tropsch synthesis wax hydrocracking tail oil raw material with a normal alkane content of not more than 30wt%, and application thereof.The catalyst composition is composed of a hydrogenation isomerization-cracking catalyst with specific particle size AEL structure heteroatom aluminum phosphate molecular sieve and specific particle size MTT structure heteroatom aluminum silicate molecular sieve loaded with noble metal.The catalyst composition provided by the present application is applied to the hydrogenation isomerization / cracking process in the hydrogenation isomerization / cracking-supplement refining of Fischer-Tropsch synthesis wax hydrocracking tail oil conversion, which can significantly improve the yield of lubricating oil base oil, and obtain higher yield of low pour point, high viscosity index base oil.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating oil base oil preparation, and particularly relates to a hydroisomerization-cracking combined catalyst suitable for preparing base oil from Fischer-Tropsch synthesis wax hydrocracking tail oil raw material and application thereof. BACKGROUND

[0002] Lubricating oil is known as the blood of industry, and plays an irreplaceable role in energy saving and emission reduction and environmental protection. Base oil accounts for about 90% of the composition of lubricating oil, and the quality of base oil plays a decisive role in the performance of lubricating oil. As the core of the composition of lubricating oil, the most important performance of base oil is the viscosity-temperature characteristic, including the viscosity change of different temperature application scenarios and the flow performance when used in low temperature environment, and the corresponding performance parameters include viscosity index and pour point. At present, the main means of producing base oil is to prepare base oil from mineral oil fractions including petroleum and coal chemical products. Its technical route has experienced the evolution from solvent dewaxing method to hydrodewaxing method. The main purpose of dewaxing is to greatly reduce the pour point while maintaining the viscosity index of oil, so as to obtain qualified viscosity-temperature characteristics. In recent years, the coal chemical industry in China has developed rapidly, and 10-400 million tons / year industrial demonstration and industrial production devices have been built, and the Fischer-Tropsch synthesis wax produced thereby is an excellent lubricating oil base oil raw material.

[0003] At present, domestic coal-to-oil enterprises mainly further hydrocrack the Fischer-Tropsch synthesis generated wax to produce clean fuel and α-olefin and other chemical products. However, the Fischer-Tropsch synthesis wax has a wide distillation range, and in the production of the above products, a large amount of Fischer-Tropsch synthesis wax hydrocracking tail oil is also produced, which has a high pour point and cannot meet the product standard of base oil and needs to be further converted to reduce the pour point. In the field of Fischer-Tropsch synthesis wax hydro-upgrading to produce lubricating oil base oil, many related patents have been disclosed at home and abroad. For example, US5834522 discloses a method for producing lubricating oil base oil from Fischer-Tropsch synthesis products. The Fischer-Tropsch synthesis products are hydro-isomerized in a hydro-isomerization reaction zone to generate oil, which is separated by distillation, and the distillation column bottom product is dewaxed to obtain oil and non-oil fractions. US5882505 discloses a method for producing lubricating oil base oil from Fischer-Tropsch synthesis wax with a boiling point greater than 370°C by using a countercurrent reactor. The raw material is contacted with a hydro-isomerization catalyst in a fixed bed reactor, and the reacted product is contacted with a hydro-dewaxing catalyst in at least one fixed bed reactor to produce a target product, wherein the hydro-isomerization reaction product and the hydrogen-containing gas flow in the opposite direction. CN1688674 discloses a multi-step method for preparing heavy lubricating oil base oil from Fischer-Tropsch wax, which includes hydro-dewaxing the wax in a first hydro-dewaxing step to produce an isomerization product of a partially dewaxed heavy base oil fraction, and then hydro-dewaxing the heavy lubricating oil fraction in one or more subsequent hydro-dewaxing steps to remove the heavy lubricating oil fraction below the hydrocarbon, thereby obtaining the heavy lubricating oil base oil. CN1703488 discloses a method for preparing fuel and lubricating oil base oil from Fischer-Tropsch wax, which includes (1) hydro-dewaxing the Fischer-Tropsch wax to produce an isomerization product containing fuel and a partially hydro-dewaxed base oil fraction, (2) separating the two fractions, (3) separating the partially hydro-dewaxed base oil fraction into a heavy fraction and a lower boiling point fraction, and (4) further hydro-dewaxing the lower boiling point fraction and the heavy fraction, respectively, to produce lubricating oil base oil including heavy lubricating oil base stock. CN101230290 discloses a method for producing solvent oil, lubricating oil base oil and heavy wax from Fischer-Tropsch synthesis wax. The full distillation product obtained by converting the wax in a hydrofining zone is fractionated to obtain a solvent oil light fraction, and the base oil fraction product is separated and then subjected to hydro-isomerization conversion, and the remaining heavy fraction is directly subjected to hydrofining to obtain a decolorized wax. US7198710 discloses a method for producing high viscosity index lubricating oil base oil from Fischer-Tropsch wax, which first fractionates the Fischer-Tropsch wax to obtain light components and heavy components, and then separately performs hydro-isomerization dewaxing to reduce the pour point of the raw material, so as to obtain light lubricating oil base oil with a qualified pour point. The heavy component is subjected to hydro-isomerization dewaxing, and due to the unqualified pour point, solvent dewaxing is used to further reduce the pour point of the heavy component, and finally heavy lubricating oil base oil products with a qualified pour point are obtained.

[0004] The above process has the following disadvantages when using a conventional hydroisomerization dewaxing catalyst in the hydrodewaxing operation unit: it is difficult to simultaneously meet the requirements of the light and heavy components for pour point and viscosity index. When the pour point of the heavy base oil component is qualified, the viscosity index of the light base oil component is greatly lost, and it is difficult to produce API III light lubricating oil base oil products with a viscosity index > 120; and when the viscosity index of the light base oil component is qualified, the heavy component cannot be used as a lubricating oil base oil product with a qualified pour point. When using a conventional hydrocracking catalyst, a large amount of cracking products is produced in the process, and the yield of light and heavy base oils is too low, which seriously affects the economic efficiency of the process.

[0005] Since the hydrocracking tail oil of Fischer-Tropsch synthesis wax is the tail oil of clean fuel produced by hydrocracking of Fischer-Tropsch synthesis wax, the hydrocracking process has already undergone a high degree of isomerization-cracking, and the content of branched hydrocarbons is relatively high, and the content of n-alkanes is relatively low. However, when the above technology is directly used for the conversion of the hydrocracking tail oil of Fischer-Tropsch synthesis wax, the multi-branched hydrocarbons in the raw material are prone to over-cracking, and the n-alkanes in the raw material that have not been converted cannot be completely converted due to competition for pore adsorption with the multi-branched hydrocarbons, resulting in low yield of lubricating oil base oil and high content of unconverted residual wax, thereby causing high pour point or cloud point. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a hydroisomerization-cracking combined catalyst for preparing base oil from a hydrocracking tail oil of catalytic Fischer-Tropsch synthesis wax and an application method thereof, which overcomes the deficiencies of the prior art. The hydroisomerization-cracking combined catalyst is composed of a hydroisomerization-cracking catalyst with a specific particle size of AEL heteroatom aluminophosphate molecular sieve and MTT heteroatom aluminosilicate molecular sieve loaded with noble metals. The catalyst composition provided by the present application is applied to the hydroisomerization-cracking section in the hydroisomerization-cracking-supplement refining used in the conversion of the hydrocracking tail oil of Fischer-Tropsch synthesis wax, which can convert the hydrocracking tail oil of Fischer-Tropsch synthesis wax into base oil fraction isomerization products with high selectivity, reduce the generation of gaseous hydrocarbons, gasoline and diesel oil fraction by-products, and obtain base oil with low pour point and high viscosity index, and significantly improve the yield of lubricating oil base oil, thereby achieving simultaneous improvement of the yield and performance of base oil products.

[0007] One of the technical solutions of the present application is achieved by the following measures: a hydroisomerization-cracking combined catalyst is composed of catalyst A and catalyst B in a volume ratio of 1:8 to 8:1, catalyst A is composed of a carrier selected from a heteroatom aluminophosphate molecular sieve with an AEL structure and a crystal grain size of 20 nm to 400 nm, and loaded with active metals platinum and / or palladium, and catalyst B is composed of a carrier selected from a heteroatom aluminosilicate molecular sieve with an MTT structure and a crystal grain size of 700 nm to 4 μm, and loaded with active metals platinum and / or palladium.

[0008] The hydrogen isomerization-cracking combined catalyst, wherein the AEL is a structure type of molecular sieve, has one-dimensional ten-membered ring straight pore structure characteristics, and the molecular sieve has a pore size of

[0009] The hydrogen isomerization-cracking combined catalyst, wherein the MTT is a structure type of molecular sieve, has one-dimensional ten-membered ring straight pore structure characteristics, and the molecular sieve has a pore size of

[0010] The hydrogen isomerization-cracking combined catalyst, wherein the heteroatom aluminophosphate molecular sieve with the AEL structure has a crystal grain size of 50 nm to 200 nm.

[0011] The hydrogen isomerization-cracking combined catalyst, wherein the heteroatom aluminosilicate molecular sieve with the MTT structure has a crystal grain size of 800 nm to 2 μm.

[0012] The hydrogen isomerization-cracking combined catalyst, wherein the heteroatom aluminophosphate molecular sieve with the AEL structure has a total acid amount of 300 to 800 μmol (pyridine) / g, which is obtained by pyridine adsorption infrared spectrum test and calculation.

[0013] The hydrogen isomerization-cracking combined catalyst, wherein the heteroatom aluminosilicate molecular sieve with the MTT structure has a total acid amount of 200 to 500 μmol (pyridine) / g, which is obtained by pyridine adsorption infrared spectrum test and calculation.

[0014] The hydrogen isomerization-cracking combined catalyst, wherein the heteroatom aluminophosphate molecular sieve with the AEL structure is MeAPO-11 (Me is one of Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni).

[0015] The hydrogen isomerization-cracking combined catalyst, wherein in the MeAPO-11 (Me is one of Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni) with the AEL structure, the mass content of Me is 1.0-3.0 wt%.

[0016] The hydrogen isomerization-cracking combined catalyst, wherein the heteroatom aluminosilicate molecular sieve with the MTT structure is Me-ZSM-23 (Me is one of Cr, Cu, Fe, Cd or Ni).

[0017] The hydrogen isomerization-cracking combined catalyst, wherein in the Me-ZSM-23 (Me is one of Cr, Cu, Fe, Cd or Ni) with the MTT structure, the mass content of Me is 2.0-5.0 wt%.

[0018] The hydrogen isomerization-cracking combined catalyst, wherein the mass loading of the active metal in catalyst A is 0.3wt% to 1.0wt%.

[0019] The hydrogen isomerization-cracking combined catalyst, wherein the mass loading of the active metal in catalyst B is 0.2wt% to 0.8wt%.

[0020] The hydrogen isomerization-cracking combined catalyst, wherein catalyst A and catalyst B are in a volume ratio of 1:5 to 5:1, and the combined mode is A on B.

[0021] The hydrogen isomerization-cracking combined catalyst, wherein when the catalyst is used, the reactant first contacts catalyst A, and then contacts catalyst B.

[0022] The second technical solution of the present application is realized by the following measures: a method for preparing base oil from Fischer-Tropsch synthesis wax hydrocracking tail oil by using the hydrogen isomerization-cracking combined catalyst according to the first technical solution, which is carried out according to the following steps: 1) Fischer-Tropsch synthesis wax hydrocracking tail oil and hydrogen are reacted on the hydrogen isomerization-cracking combined catalyst, the reaction temperature is 270°C to 360°C, the hydrogen partial pressure is 6MPa to 12MPa, the volume space velocity of the raw material oil is 0.5h -1 to 5h -1 , the hydrogen to oil ratio is 400:1 to 1000:1, the hydrogen isomerization-cracking reaction is carried out, the hydrogen isomerization and moderate hydrocracking of the Fischer-Tropsch synthesis wax hydrocracking tail oil are completed, and hydrogen isomerization-cracking oil is obtained; 2) the hydrogen isomerization-cracking oil obtained in step 1) is reacted on the hydrogenation refining catalyst, the reaction temperature is 150°C to 300°C, the hydrogen partial pressure is 10MPa to 20MPa, the volume space velocity of the raw material oil is 0.5h -1 to 5h -1 , the hydrogen to oil ratio is 500:1 to 1500:1, the further hydrogen saturation of the hydrogen isomerization-cracking oil is completed, and a crude product is obtained; 3) the crude product obtained in step 2) is fed into an atmospheric tower or a vacuum tower, and is fractionated to obtain gasoline, diesel and base oil.

[0023] The method for preparing base oil from Fischer-Tropsch synthesis wax hydrocracking tail oil by using the hydrogen isomerization-cracking combined catalyst, wherein the hydrogen isomerization-cracking reaction conditions are: the temperature is 280°C to 350°C, the hydrogen partial pressure is 6MPa to 10MPa, the volume space velocity of the raw material oil is 0.5-3h -1 , and the hydrogen to oil ratio is 400:1 to 800:1.

[0024] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the hydrogenation refining reaction conditions are: the temperature is 180-300 DEG C, the hydrogen partial pressure is 12-15 MPa, the raw oil volume space velocity is 0.5-3 h -1 , and the hydrogen oil ratio is 500:1-1000:1.

[0025] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the crude product obtained in step 3) is subjected to fractionation in sequence in an atmospheric column and a vacuum column to obtain gasoline, kerosene, diesel and base oil.

[0026] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the normal alkane content of the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material is not higher than 30 wt%.

[0027] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the distillation range of the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material is that the initial boiling point is not lower than 320 DEG C, not higher than 380 DEG C, and the final boiling point is not higher than 690 DEG C, not lower than 580 DEG C.

[0028] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the sulfur content in the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material is not higher than 4 mu g / g.

[0029] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the nitrogen content in the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material is not higher than 2 mu g / g.

[0030] The method for preparing base oil from the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material catalyzed by the hydrogenation isomerization-cracking combined catalyst, wherein the oxygen content in the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material is not higher than 5 mu g / g.

[0031] The method can prepare the low pour point and high viscosity index lubricating base oil in high yield by subjecting the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material to the hydrogenation isomerization-cracking, hydrogenation refining and fractionation processes, and the technical core lies in the hydrogenation isomerization-cracking process based on the combined specific particle size AEL heteroatom aluminum phosphate molecular sieve and specific particle size MTT heteroatom aluminum silicate molecular sieve supported noble metal catalyst, so that the Fischer-Tropsch synthesis wax hydrocracking tail oil is converted into base oil fraction segment isomerization products with high selectivity, thereby realizing the simultaneous improvement of product yield and performance. DETAILED DESCRIPTION

[0032] The application will be further described in connection with specific embodiments. It should be pointed out that the application is not limited to the following content.

[0033] The information and preparation method of the hydroisomerization cracking combined catalyst and the hydrofining catalyst used in the embodiments of the application are as follows:

[0034] 1. Hydroisomerization cracking catalysts A and B

[0035] The hydroisomerization cracking catalyst A is prepared by impregnation, electrostatic adsorption or ion exchange. The catalyst uses a heteroatomic aluminophosphate molecular sieve carrier with AEL structure, which is MeAPO-11 (Me = one of Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni), and the grain size of the molecular sieve is 50 nm to 200 nm, and the total acid amount is 300 to 800 μmol (pyridine) / g. The content of platinum and palladium is 0.5% by weight based on the weight percentage of the catalyst, and the rest is the above-mentioned heteroatomic aluminophosphate molecular sieve with AEL structure.

[0036] The hydroisomerization cracking catalyst B is prepared by impregnation, electrostatic adsorption or ion exchange. The catalyst uses a heteroatomic aluminosilicate molecular sieve carrier with MTT structure, which is Me-ZSM-23 (Me = one of Cr, Cu, Fe, Cd or Ni, etc.), and the grain size of the molecular sieve is 800 nm to 2 μm, and the total acid amount is 200 to 500 μmol (pyridine) / g. The content of platinum and palladium is 0.4% by weight based on the weight percentage of the catalyst, and the rest is the above-mentioned heteroatomic aluminosilicate molecular sieve with MTT structure.

[0037] 2. Comparative hydroisomerization cracking catalysts C and D

[0038] The comparative hydroisomerization cracking catalyst C is prepared by impregnation, electrostatic adsorption or ion exchange. The catalyst carrier is a SAPO-11 molecular sieve, which belongs to AEL structure, and the grain size of the molecular sieve is 600 nm, and the total acid amount is 900 μmol (pyridine) / g. The content of platinum, palladium and / or iridium is 0.5% by weight based on the weight percentage of the catalyst, and the rest is the above-mentioned SAPO-11 molecular sieve.

[0039] The comparative hydroisomerization cracking catalyst D is prepared by impregnation, electrostatic adsorption or ion exchange. The catalyst carrier is a ZSM-23 molecular sieve, which belongs to MTT structure, and the grain size of the molecular sieve is 400 nm, and the total acid amount is 800 μmol (pyridine) / g. The content of platinum, palladium and / or iridium is 0.4% by weight based on the weight percentage of the catalyst, and the rest is the above-mentioned ZSM-23 molecular sieve.

[0040] Further catalyst characteristics are described in the context of the comparative examples.

[0041] 3. Hydrofining catalyst H0

[0042] The hydrofining catalyst H0 is a commercially available hydrofining catalyst. The catalyst consists of amorphous silica-alumina supported platinum. The platinum content is 0.4 wt% based on the weight of the catalyst.

[0043] Total acid amount of the sample (Pyridine adsorption infrared (Py-IR) test): 10-20 mg of sample is pressed into a self-supporting disc with a diameter of 13 mm and placed in an in-situ infrared cell. First, a vacuum pretreatment at 350°C for 30 min is performed and the blank sample spectrum is recorded after cooling to room temperature. After adsorption of pyridine, a vacuum treatment at 150°C for 30 min is performed and the spectrum of the pyridine adsorption is recorded after cooling to room temperature. The total acid amount of the sample is calculated from the characteristic peak areas.

[0044] In the present application, the Fischer-Tropsch synthesis wax hydrocracking tail oil is used as the raw material, and its properties are shown in Table 1.

[0045] 1) The Fischer-Tropsch synthesis wax hydrocracking tail oil raw material and hydrogen are subjected to hydroisomerization-cracking reaction on the hydroisomerization-cracking combined catalyst to complete the hydroisomerization and moderate hydrocracking of the Fischer-Tropsch synthesis wax hydrocracking tail oil, and obtain a hydroisomerization-cracking oil;

[0046] 2) The hydroisomerization-cracking oil obtained in step 1) is further reacted on the hydrofining catalyst to complete the further hydrogenation saturation of the hydroisomerization-cracking oil, and obtain a crude product;

[0047] 3) The crude product obtained in step 2) is subjected to fractionation in an atmospheric column and / or a vacuum column to obtain gasoline, diesel and lubricating oil base oil.

[0048] Example 1

[0049] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts A and B. Catalyst A uses a heteroatomic aluminophosphate molecular sieve support with AEL structure, which is MgAPO-11 (heteroatomic Mg content of 1.5 wt%), the grain size of the molecular sieve is 60 nm, the total acid amount is 400 μmol (pyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst B uses a heteroatomic aluminosilicate molecular sieve support with MTT structure, which is Fe-ZSM-23 (heteroatomic Fe content of 2.5 wt%), the grain size of the molecular sieve is 900 nm, the total acid amount is 250 μmol (pyridine) / g, and the metal loading is 0.4 wt% Pd. The two are loaded in the manner of A on top and B on the bottom, with a loading volume ratio of 5:1. The feedstock flows through B from A during the reaction, and the reaction conditions are 347°C, 6.5 MPa (hydrogen pressure, same below), a space velocity of 1.2 h -1 (Feedstock oil volume space velocity, same below), and a hydrogen to oil ratio of 600. The hydrofining reactor uses hydrofining catalyst H0, which is composed of amorphous silica-alumina (ASA, SiO2 / Al2O3 = 40 / 60) loaded with platinum, with a metal loading of 0.4 wt% Pt. The reaction conditions are 225°C, 13 MPa (hydrogen pressure, same below), a space velocity of 1.0 h -1 (Feedstock oil volume space velocity, same below), and a hydrogen to oil ratio of 600. The product yield after conversion and fractionation of the feedstock through the reaction process is shown in Table 2, and the properties of the base oil product are shown in Table 3.

[0050] Example 2

[0051] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts A and B. Catalyst A uses a heteroatomic aluminophosphate molecular sieve support with AEL structure, which is ZnAPO-11 (heteroatomic Zn content of 1.5 wt%), the grain size of the molecular sieve is 80 nm, the total acid amount is 500 μmol (pyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst B uses a heteroatomic aluminosilicate molecular sieve support with MTT structure, which is Ni-ZSM-23 (heteroatomic Ni content of 2.5 wt%), the grain size of the molecular sieve is 1 μm, the total acid amount is 300 μmol (pyridine) / g, and the metal loading is 0.4 wt% Pd. The two are loaded in the manner of A on top and B on the bottom, with a loading volume ratio of 3:1. The feedstock flows through B from A during the reaction, and the reaction conditions are 345°C, 7.2 MPa, a space velocity of 0.8 h -1, hydrogen to oil ratio 700; the hydrofining reactor used hydrofining catalyst H0, which was composed of amorphous silica-alumina (ASA, SiO2 / Al2O3=40 / 60) supported platinum, with a metal loading of 0.4wt% Pt, and the reaction conditions were 235°C, 12 MPa, space velocity 1.8h -1 , hydrogen to oil ratio 700. The product yield after the raw material was converted and fractionated by the reaction process is shown in Table 2, and the base oil product properties are shown in Table 3.

[0052] Example 3

[0053] The hydroisomerization-cracking reactor used a combination of hydroisomerization-cracking catalysts A and B, catalyst A used a heteroatomic aluminophosphate molecular sieve carrier with AEL structure, which was CoAPO-11 (heteroatomic Co content was 1.5wt%), the molecular sieve crystal grain size was 120nmnm, the total acid amount was 600μmol(Pyridine) / g, and the metal loading was 0.5wt% Pt; catalyst B used a heteroatomic aluminosilicate molecular sieve carrier with MTT structure, which was Ni-ZSM-23 (heteroatomic Ni content was 3.5wt%), the molecular sieve crystal grain size was 1.2μm, the total acid amount was 400μmol(Pyridine) / g, and the metal loading was 0.4wt% Pd. The loading mode was A on top and B on bottom, and the loading volume ratio was 1:1. The raw material flowed through B from A during the reaction, and the reaction conditions were 333°C, 8.5 MPa, space velocity 1.0h -1 , hydrogen to oil ratio 800; the hydrofining reactor used hydrofining catalyst H0, which was composed of amorphous silica-alumina (ASA, SiO2 / Al2O3=40 / 60) supported platinum, with a metal loading of 0.4wt% Pt, and the reaction conditions were 220°C, 12 MPa, space velocity 1.2h -1 , hydrogen to oil ratio 800. The product yield after the raw material was converted and fractionated by the reaction process is shown in Table 2, and the base oil product properties are shown in Table 3.

[0054] Example 4

[0055] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts A and B. Catalyst A uses a heteroatom aluminophosphate molecular sieve support with AEL structure, CuAPO-11 (heteroatom Cu content of 1.5 wt%), the molecular sieve crystal grain size is 180 nm, the total acid amount is 700 μmol (pyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst B uses a heteroatom aluminosilicate molecular sieve support with MTT structure, Cd-ZSM-23 (heteroatom Cd content of 4.0 wt%), the molecular sieve crystal grain size is 1.8 μm, the total acid amount is 480 μmol (pyridine) / g, and the metal loading is 0.4 wt% Pd. The loading mode is A on top and B on bottom, and the loading volume ratio is 1:3. The feedstock flows through B from A during the reaction, and the reaction conditions are 312°C, 6.5 MPa, space velocity 1.5 h -1 , and hydrogen to oil ratio 600. The hydrofining reactor uses hydrofining catalyst H0, which is composed of amorphous silica-alumina (Amorphous Silica-Alumina, abbreviated as ASA, SiO2 / Al2O3=40 / 60) loaded with platinum, and the metal loading is 0.4 wt% Pt. The reaction conditions are 238°C, 13 MPa, space velocity 2.5 h -1 , and hydrogen to oil ratio 600. The product yield after conversion and fractionation of the feedstock through the reaction process is shown in Table 2, and the properties of the base oil product are shown in Table 3.

[0056] Comparative Example 1

[0057] A process similar to the present example is used. The hydroisomerization-cracking reactor uses hydroisomerization-cracking catalyst A, which uses a heteroatom aluminophosphate molecular sieve support with AEL structure, MgAPO-11 (heteroatom Mg content of 1.5 wt%), the molecular sieve crystal grain size is 60 nm, the total acid amount is 400 μmol (pyridine) / g, and the metal loading is 0.5 wt% Pt. The reaction conditions are 348°C, 6.5 MPa, space velocity 1.2 h -1 , and hydrogen to oil ratio 600. The hydrofining reactor uses hydrofining catalyst H0, which is composed of amorphous silica-alumina (Amorphous Silica-Alumina, abbreviated as ASA, SiO2 / Al2O3=40 / 60) loaded with platinum, and the metal loading is 0.4 wt% Pt. The reaction conditions are 225°C, 13 MPa, space velocity 1.0 h -1 , and hydrogen to oil ratio 600. The product yield after conversion and fractionation of the feedstock through the reaction process is shown in Table 2, and the properties of the base oil product are shown in Table 3.

[0058] Comparative Example 2

[0059] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts B and A. Catalyst A uses a heteroatomic aluminophosphate molecular sieve support with AEL structure, which is ZnAPO-11 (heteroatomic Zn content of 1.5 wt%), the molecular sieve crystal grain size is 80 nm, the total acid amount is 500 μmol (pyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst B uses a heteroatomic aluminosilicate molecular sieve support with MTT structure, which is Ni-ZSM-23 (heteroatomic Ni content of 2.5 wt%), the molecular sieve crystal grain size is 1 μm, the total acid amount is 300 μmol (pyridine) / g, and the metal loading is 0.4 wt% Pd. The loading mode is B on top and A on bottom, and the loading volume ratio is 3:1. The raw material flows through A during the reaction, and the reaction conditions are 345°C, 6.2 MPa, space velocity 0.8 h -1 , and hydrogen to oil ratio 700. The hydrofining reactor uses hydrofining catalyst H0, which is composed of amorphous silica-alumina (Amorphous Silica-Alumina, abbreviated as ASA, SiO2 / Al2O3=40 / 60) loaded with platinum, and the metal loading is 0.4 wt% Pt. The reaction conditions are 235°C, 12 MPa, space velocity 1.8 h -1 , and hydrogen to oil ratio 700. The product yield after the raw material is converted and fractionated through the reaction process is shown in Table 2, and the base oil product properties are shown in Table 3.

[0060] Comparative Example 3

[0061] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts C and D. Catalyst C uses a SAPO-11 molecular sieve support, which belongs to AEL structure, and the molecular sieve crystal grain size is 600 nm, the total acid amount is 900 μmol (pyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst D uses a ZSM-23 molecular sieve support, which belongs to MTT structure, and the molecular sieve crystal grain size is 400 nm, the total acid amount is 800 μmol (pyridine) / g, and the metal loading is 0.4 wt% Pd. The loading mode is C on top and D on bottom, and the loading volume ratio is 1:1. The raw material flows through D during the reaction, and the reaction conditions are 333°C, 8.5 MPa, space velocity 1.0 h -1 , and hydrogen to oil ratio 800. The hydrofining reactor uses hydrofining catalyst H0, which is composed of amorphous silica-alumina (Amorphous Silica-Alumina, abbreviated as ASA, SiO2 / Al2O3=40 / 60) loaded with platinum, and the metal loading is 0.4 wt% Pt. The reaction conditions are 220°C, 12 MPa, space velocity 1.2 h -1 , and hydrogen to oil ratio 800. The product yield after the raw material is converted and fractionated through the reaction process is shown in Table 2, and the base oil product properties are shown in Table 3.

[0062] Comparative Example 4

[0063] The hydroisomerization-cracking reactor used a combination of hydroisomerization-cracking catalysts C and D. Catalyst C used a SAPO-11 molecular sieve support with an AEL structure, a crystal grain size of 600 nm, a total acid amount of 900 μmol (Pyridine) / g, and a metal loading of 0.5 wt% Pt. Catalyst D used a ZSM-23 molecular sieve support with an MTT structure, a crystal grain size of 400 nm, a total acid amount of 800 μmol (Pyridine) / g, and a metal loading of 0.4 wt% Pd. The two were loaded in a C-on-top and D-on-bottom manner with a loading volume ratio of 1:3. The feedstock flowed through D during the reaction, and the reaction conditions were 312°C, 6.5 MPa, a space velocity of 1.5 h -1 , and a hydrogen to oil ratio of 600. The hydrofining reactor used a hydrofining catalyst H0 composed of amorphous silica-alumina (Amorphous Silica-Alumina, abbreviated as ASA, SiO2 / Al2O3 = 40 / 60) loaded with platinum, with a metal loading of 0.4 wt% Pt. The reaction conditions were 238°C, 13 MPa, a space velocity of 2.5 h -1 , and a hydrogen to oil ratio of 600. The product yield after the feedstock was converted and fractionated by the reaction process is shown in Table 2, and the base oil product properties are shown in Table 3.

[0064] Comparative Example 5

[0065] The hydroisomerization-cracking reactor used a combination of hydroisomerization-cracking catalysts E and F. Catalyst E used a SAPO-11 molecular sieve support with a crystal grain size of 120 nm, a total acid amount of 650 μmol (Pyridine) / g, an external surface acid amount of 230 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 0.5 wt% Pd. Catalyst F used a ZSM-22 molecular sieve support with a crystal grain size of 2.3 μm, a total acid amount of 300 μmol (Pyridine) / g, an external surface acid amount of 20 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 0.5 wt% Pt. The two were loaded in an E-on-top and F-on-bottom manner with a loading volume ratio of 1:3. The feedstock flowed through F during the reaction, and the reaction conditions were 312°C, 6.5 MPa, a space velocity of 1.5 h -1 , and a hydrogen to oil ratio of 600. The hydrofining reactor used a hydrofining catalyst H0 composed of amorphous silica-alumina (Amorphous Silica-Alumina, abbreviated as ASA, SiO2 / Al2O3 = 40 / 60) loaded with platinum, with a metal loading of 0.4 wt% Pt. The reaction conditions were 238°C, 13 MPa, a space velocity of 2.5 h-1 The product yield of the raw material after conversion and fractionation by this reaction process is shown in Table 2, and the properties of the base oil product are shown in Table 3.

[0066] Comparative Example 6

[0067] The hydrogen isomerization-cracking reactor used a combination of hydrogen isomerization-cracking catalysts G and H. Catalyst G used a molecular sieve carrier with ATO structure, CoAPO-31 (heteroatom Co content of 1.2 wt%), the molecular sieve crystal grain size was 100 nm, the total acid content was 420 μmol (pyridine) / g, the external surface acid content was 180 μmol (2,6-di-tert-butylpyridine) / g, and the platinum content was 0.4 wt%. Catalyst H used a molecular sieve carrier with FER structure, Fe-ZSM-35 (heteroatom Fe content of 3.5 wt%), the molecular sieve crystal grain size was 2.0 μm, the total acid content was 280 μmol (pyridine) / g, the external surface acid content was 50 μmol (2,6-di-tert-butylpyridine) / g, and the palladium content was 0.4 wt%. The two were loaded in a G-on-H-down manner, with a loading volume ratio of 1:3. The raw material flowed through H from G during the reaction, and the reaction conditions were 312°C, 6.5 MPa, and a space velocity of 1.5 h -1 The hydrogen isomerization-cracking reactor used a combination of hydrogen isomerization-cracking catalysts G and H. Catalyst G used a molecular sieve carrier with ATO structure, CoAPO-31 (heteroatom Co content of 1.2 wt%), the molecular sieve crystal grain size was 100 nm, the total acid content was 420 μmol (pyridine) / g, the external surface acid content was 180 μmol (2,6-di-tert-butylpyridine) / g, and the platinum content was 0.4 wt%. Catalyst H used a molecular sieve carrier with FER structure, Fe-ZSM-35 (heteroatom Fe content of 3.5 wt%), the molecular sieve crystal grain size was 2.0 μm, the total acid content was 280 μmol (pyridine) / g, the external surface acid content was 50 μmol (2,6-di-tert-butylpyridine) / g, and the palladium content was 0.4 wt%. The two were loaded in a G-on-H-down manner, with a loading volume ratio of 1:3. The raw material flowed through H from G during the reaction, and the reaction conditions were 312°C, 6.5 MPa, and a space velocity of 1.5 h -1 The product yield of the raw material after conversion and fractionation by this reaction process is shown in Table 2, and the properties of the base oil product are shown in Table 3.

[0068] Comparative Example 7

[0069] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts I and J. Catalyst I uses a molecular sieve carrier with AFI structure, which is SAPO-5, and has a crystal grain size of 50 nm, a total acid amount of 780 μmol (pyridine) / g, an external surface acid amount of 280 μmol (2,6-di-tert-butylpyridine) / g, and a noble metal content of 0.4 wt% Pd. Catalyst J uses a molecular sieve carrier with *MRE structure, which is ZSM-48, and has a crystal grain size of 4.5 μm, a total acid amount of 560 μmol (pyridine) / g, an external surface acid amount of 80 μmol (2,6-di-tert-butylpyridine) / g, and a noble metal content of 0.3 wt% Pt. Both are loaded in a manner of I on top and J on bottom, with a loading volume ratio of 1:3. The raw material flows through J during reaction, and the reaction conditions are 312°C, 6.5 MPa, a space velocity of 1.5 h -1 , and a hydrogen to oil ratio of 600. The hydrofining reactor uses hydrofining catalyst H0, which is composed of amorphous silica-alumina (ASA, SiO2 / Al2O3=40 / 60) loaded with platinum, and has a metal loading amount of 0.4 wt% Pt. The reaction conditions are 238°C, 13 MPa, a space velocity of 2.5 h -1 , and a hydrogen to oil ratio of 600. The product yield obtained after conversion and fractionation of the raw material through the reaction process is shown in Table 2, and the properties of the base oil product are shown in Table 3.

[0070] Comparative Example 8

[0071] The hydroisomerization-cracking reactor uses a combination of hydroisomerization-cracking catalysts K and L. Catalyst K uses a molecular sieve carrier with AFO structure, which is SAPO-41, and has a crystal grain size of 350 nm, a total acid amount of 600 μmol (pyridine) / g, an external surface acid amount of 260 μmol (2,6-di-tert-butylpyridine) / g, and a metal loading amount of 0.5 wt% Pt. Catalyst L uses a molecular sieve carrier with MTW structure, which is ZSM-12, and has a crystal grain size of 4.5 μm, a total acid amount of 450 μmol (pyridine) / g, an external surface acid amount of 120 μmol (2,6-di-tert-butylpyridine) / g, and a metal loading amount of 0.5 wt% Pd. Both are loaded in a manner of K on top and L on bottom, with a loading volume ratio of 1:3. The raw material flows through L during reaction, and the reaction conditions are 312°C, 6.5 MPa, a space velocity of 1.5 h -1, hydrogen to oil ratio 600; the hydrofining reactor used hydrofining catalyst H0, which was composed of amorphous silica-alumina (ASA, SiO2 / Al2O3=40 / 60) supported platinum, the metal loading was 0.4wt% Pt, the reaction conditions were 238℃, 13MPa, space velocity 2.5h -1 , hydrogen to oil ratio 600. The product yield after the raw material was converted and fractionated by the reaction process was shown in Table 2, and the base oil product properties were shown in Table 3.

[0072] From Table 2, it could be seen that, compared with the comparative example, the base oil yield was significantly improved by using the method of the present application, the yield of low-value by-products light hydrocarbon and diesel was significantly reduced, and there was no unconverted residual wax, and the Fischer-Tropsch synthesis wax hydrocracking tail oil raw material was efficiently converted. At the same time, from Table 3, it could be seen that, compared with the comparative example, the viscosity index of the base oil prepared by using the method of the present application was higher, and the pour point was lower.

[0073] Table 1 Fischer-Tropsch synthesis wax hydrocracking tail oil raw material properties

[0074] Item Feedstock Density (25°C), kg / m 3 ]] 838 Kinematic viscosity (100°C), mm 2 / s]]> 8.9 Sulfur content, pg / g <1.0 Nitrogen content, pg / g <1.0 Oxygen content, pg / g <1.0 Distillation range, °C Initial boiling point 322 10％ 376 30％ 408 50％ 437 70％ 502 90％ 603 95％ 642 Final boiling point 685 n-alkanes content, wt% Item Feedstock Sulfur content, pg / g Nitrogen content, pg / g Oxygen content, pg / g Distillation range, °C Initial boiling point Final boiling point n-alkanes content, wt% Item Feedstock Sulfur content, pg / g Nitrogen content, pg / g 26.8

[0075] Table 2 product yield

[0076]

[0077] Table 3 base oil product properties

[0078]

Claims

1. A process for hydroisomerization cracking combination catalyst processing of hydrocracking tail oil of Fischer-Tropsch synthesis waxes to lubricating oil base oil, characterized by, The method is carried out in the following steps: 1) the Fischer-Tropsch synthesis wax hydrocracking tail oil feedstock and hydrogen are reacted over a hydroisomerization-cracking combined catalyst at a reaction temperature of 270-360°C, a hydrogen partial pressure of 6-12 MPa, a feedstock oil volume space velocity of 0.5-5 h -1 , and a hydrogen / oil ratio of 400:1-1000:1 to perform hydroisomerization-cracking reactions, complete the hydroisomerization and moderate hydrocracking reactions of the Fischer-Tropsch synthesis wax hydrocracking tail oil, and obtain a hydroisomerization-cracking oil; 2) The hydroisomerization-cracking oil obtained in step 1) is further reacted on a hydrofining catalyst to complete the further hydrogenation saturation of the hydroisomerization-cracking oil, to obtain a crude product; 3) The crude product obtained in step 2) enters an atmospheric column and / or a vacuum column to be fractionated to obtain gasoline, diesel and lubricating oil base oil; The hydroisomerization-cracking combined catalyst is composed of catalyst A and catalyst B in a volume ratio of 1:8 to 8:1, and the combination mode is A on B, and when the catalyst is used, the reactant flows through catalyst B from catalyst A, Catalyst A is composed of a support selected from a heteroatomic aluminum phosphate molecular sieve with AEL structure with a crystal grain size of 20 nm to 400 nm, and loaded active metals platinum and / or palladium, and the heteroatomic aluminum phosphate molecular sieve with AEL structure is MeAPO-11, wherein Me = one or two or more of Zn, Mg, Mn, Co, Cr, Cu, Cd or Ni, and the mass content of Me is 1.0-3.0wt%; Catalyst B is composed of a support selected from a heteroatomic aluminum silicate molecular sieve with MTT structure with a crystal grain size of 700 nm to 4 μm, and loaded active metals platinum and / or palladium, and the heteroatomic aluminum silicate molecular sieve with MTT structure is Me-ZSM-23, wherein Me = one or two or more of Cr, Cu, Fe, Cd or Ni, and the mass content of Me is 2.0-5.0wt%.

2. The method for processing Fischer-Tropsch synthesis wax hydrocracking tail oil into lubricating oil base oil by using the hydroisomerization-cracking combined catalyst according to claim 1, characterized in that, The crystal grain size of the heteroatomic aluminum phosphate molecular sieve with AEL structure is 50 nm to 200 nm, and the crystal grain size of the heteroatomic aluminum silicate molecular sieve with MTT structure is 800 nm to 2 μm.

3. The method for processing Fischer-Tropsch synthesis wax hydrocracking tail oil into lubricating oil base oil by using the hydroisomerization-cracking combined catalyst according to claim 1 or 2, characterized in that, The total acid amount of the heteroatomic aluminum phosphate molecular sieve with AEL structure is 300-800 μmol pyridine / g, and the total acid amount of the heteroatomic aluminum silicate molecular sieve with MTT structure is 200-500 μmol pyridine / g.

4. The method for processing Fischer-Tropsch synthesis wax hydrocracking tail oil into lubricating oil base oil by using the hydroisomerization-cracking combined catalyst according to claim 1 or 2, characterized in that, The AEL is a structure type of molecular sieve, with one-dimensional ten-membered ring elliptical straight pore structure characteristics, and the molecular sieve pore size is 4.0*6.5 Å, The MTT is a structure type of molecular sieve, with one-dimensional ten-membered ring straight pore structure characteristics, and the molecular sieve pore size is 4.5*5.2 Å.

5. The process for hydroisomerocracking combo catalyst processing Fischer-Tropsch synthesis wax hydrocracking tail oil to lube base oil according to claim 1, characterized in that, The mass loading amount of active metals in catalyst A is 0.3wt% to 1.0wt%, and the mass loading amount of active metals in catalyst B is 0.2wt% to 0.8wt%.

6. The process for hydroisomerocracking combo catalyst processing Fischer-Tropsch synthesis wax hydrocracking tail oil to lube base oil of claim 1, characterized in that, Catalyst A and catalyst B are composed in a volume ratio of 1:5 to 5:

1.

7. The method of claim 1, wherein, The Fischer-Tropsch synthesis wax hydrocracking tail oil feedstock has a normal alkane content of not higher than 30wt%.

8. The method of claim 1, wherein, The feedstock of the hydrocracking tail oil of the Fischer-Tropsch synthesis wax has a initial boiling point of not less than 320 DEG C and not more than 380 DEG C, a final boiling point of not more than 690 DEG C and not less than 580 DEG C, a sulfur content of not more than 4 ug / g, a nitrogen content of not more than 2 ug / g and an oxygen content of not more than 5 ug / g.

9. The method of claim 1, wherein, The reaction conditions of the step 2) are 150-300°C, hydrogen partial pressure is 10-20 MPa, raw oil volume space velocity is 0.5-5 h -1 , and hydrogen / oil ratio is 500:1-1500:1.

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