Hydroisomerization-cracking catalyst for producing base oil from high wax-containing feedstock and its application

Abstract

The present invention relates to the technical field of lubricating base oil preparation, and specifically relates to a hydroisomerization-cracking catalyst for preparing base oil from a high-wax feedstock with a catalytic wide distillation range and a normal paraffin content of not less than 50%, and its application. The catalyst is composed of an AFI-structured aluminophosphate molecular sieve with a specific acid distribution and particle size, and a hydroisomerization-cracking catalyst loaded with noble metals on an MRE-structured aluminosilicate molecular sieve. Applying the catalyst provided by the present invention to the hydroisomerization / cracking process in the current hydrotreating-hydroisomerization / cracking-supplementary refining commonly used for the conversion of high-wax feedstocks can significantly improve the yield of lubricating base oil and obtain a base oil with a lower pour point and a higher viscosity index at a higher yield.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating oil base oil preparation, and particularly relates to a hydroisomerization-cracking catalyst for catalytically preparing base oil from high-wax-containing raw materials and its application. Background Art

[0002] Lubricating oil is known as the blood of industry and plays an irreplaceable role in energy conservation, emission reduction and environmental protection. Base oil accounts for about 90% of the lubricating oil composition, and the quality of base oil plays a decisive role in the performance of lubricating oil. As the core of lubricating oil composition, the most important performance of base oil is its viscosity-temperature characteristics, including the viscosity change in different temperature application scenarios and the flow performance when used in low-temperature environments. The corresponding performance parameters include viscosity index and pour point. At present, producing base oil from mineral oil fractions is still the main means of producing base oil. Its technical route has evolved from solvent dewaxing to hydrodewaxing. The main purpose of dewaxing is to significantly reduce its pour point while maintaining the viscosity index of the oil, so as to obtain qualified viscosity-temperature characteristics.

[0003] The technical route of hydrodewaxing mainly includes three steps, namely hydrotreating - hydrodewaxing - finishing. The records of this technical route can be found in many literature reports. For example, CN1225662A discloses a method for preparing lubricating oil base oil. The wax oil raw material with a boiling range of 316 - 677 °C is subjected to hydrotreating, isodewaxing and hydrorefining to obtain the target product. Among them, the catalyst used in the hydrodewaxing section is a mesoporous molecular sieve supported catalyst. CN102311785A discloses a method for producing naphthenic base oil from naphthenic fraction oil, and a high-viscosity lubricating oil base oil product is obtained through similar three steps. Among them, the catalyst used in the hydrodewaxing section is a Ni-Co catalyst supported on ZSM-5 molecular sieve. CN101230290 discloses a method for producing solvent oil, lubricating oil base oil and heavy wax from Fischer-Tropsch wax. The whole fraction product obtained by converting the wax in the hydrorefining zone is fractionated to obtain the light fraction of solvent oil, and then the base oil fraction product is separated and subjected to hydroisomerization conversion to obtain the base oil product, and the remaining heavy fraction is directly subjected to hydrorefining to obtain decolorized wax. In addition to the above-mentioned literatures, there are also many patent reports on similar technologies in this field, such as CN1154711C, CN108611120A, CN1676585A, etc. In these technologies, the most core hydrodewaxing section mainly uses a single supported molecular sieve catalyst, and it is still a huge challenge to achieve high-selectivity conversion of wide-boiling-range wax oil and balance the performance and yield of base oil products. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the present invention provides a hydroisomerization-cracking catalyst for catalytically converting a wide-boiling-range and high-wax raw material into base oil and an application method thereof, overcoming the above-mentioned deficiencies of the prior art. The hydroisomerization-cracking catalyst is composed of an aluminophosphate molecular sieve with an AFI structure having a specific acidic distribution and particle size and a catalyst in which a noble metal is supported on a silicoaluminate molecular sieve with an *MRE structure. Applying the catalyst provided by the present invention to the hydroisomerization / cracking section in the currently commonly used hydrotreating-hydroisomerization / cracking-supplemental refining for the conversion of wide-boiling-range and high-wax raw materials can enable the wax in the wide-boiling-range and high-wax raw materials to be highly selectively converted into isomerized products in the base oil fraction, reduce the generation of gaseous hydrocarbon and gasoline / diesel fraction by-products, obtain base oil with a low pour point and a high viscosity index, and significantly increase the yield of lubricating base oil, achieving the simultaneous improvement of the yield and performance of base oil products.

[0005] One of the technical solutions of the present invention is achieved by the following measures: A hydroisomerization-cracking catalyst for catalytically converting a wide-boiling-range and high-wax raw material into base oil, including catalyst A and catalyst B. Catalyst A is composed of an aluminophosphate molecular sieve carrier with one-dimensional twelve-membered ring circular pores and Pt and / or Pd supported thereon. Catalyst B is composed of a silicoaluminate molecular sieve carrier with one-dimensional ten-membered ring circular pores and Pt and / or Pd supported thereon.

[0006] For the hydroisomerization-cracking catalyst described above, catalyst A and catalyst B are formed in a volume ratio of 1:5 to 5:1, and the combination method is A on top of B.

[0007] For the hydroisomerization-cracking catalyst described above, when the hydroisomerization-cracking catalyst is used, the reactants first contact catalyst A and then contact catalyst B.

[0008] For the hydroisomerization-cracking catalyst described above, the aluminophosphate molecular sieve with one-dimensional twelve-membered ring circular pores is an aluminophosphate molecular sieve with an AFI structure.

[0009] For the hydroisomerization-cracking catalyst described above, for the aluminophosphate molecular sieve with one-dimensional twelve-membered ring circular pores, the pore size of its one-dimensional circular pores is

[0010] For the hydroisomerization-cracking catalyst described above, the silicoaluminate molecular sieve with one-dimensional ten-membered ring circular pores is a silicoaluminate molecular sieve with an *MRE structure.

[0011] For the hydroisomerization-cracking catalyst described above, for the silicoaluminate molecular sieve with one-dimensional ten-membered ring circular pores, the pore size of its one-dimensional circular pores is

[0012] The hydroisomerization-cracking catalyst described above, wherein the aluminophosphate molecular sieve with AFI structure is one of SAPO-5, MgAPO-5, ZnAPO-5 or CoAPO-5.

[0013] The hydroisomerization-cracking catalyst described above, wherein the aluminosilicate molecular sieve with *MRE structure is one of ZSM-48, Fe-ZSM-48, Cu-ZSM-48 or Ni-ZSM-48.

[0014] The hydroisomerization-cracking catalyst described above, wherein the total acid amount of the aluminophosphate molecular sieve with AFI structure is 200 - 800 μmol(Pyridine) / g, and this total acid amount is obtained by testing and calculating with pyridine adsorption infrared spectroscopy.

[0015] The hydroisomerization-cracking catalyst described above, wherein the external surface acid amount of the aluminophosphate molecular sieve with AFI structure is 100 - 300 μmol(2,6-Di-tert-butylpyridine) / g, and this external surface acid amount is obtained by testing and calculating with 2,6-di-tert-butylpyridine adsorption infrared spectroscopy.

[0016] The hydroisomerization-cracking catalyst described above, wherein the total acid amount of the aluminosilicate molecular sieve with *MRE structure is 100 - 600 μmol(Pyridine) / g, and this total acid amount is obtained by testing and calculating with pyridine adsorption infrared spectroscopy.

[0017] The hydroisomerization-cracking catalyst described above, wherein the external surface acid amount of the aluminosilicate molecular sieve with *MRE structure is 0 - 100 μmol(2,6-Di-tert-butylpyridine) / g, and this external surface acid amount is obtained by testing and calculating with 2,6-di-tert-butylpyridine adsorption infrared spectroscopy.

[0018] The hydroisomerization-cracking catalyst described above, wherein the crystal grain size of the aluminophosphate molecular sieve with AFI structure is 20 nm - 200 nm.

[0019] The hydroisomerization-cracking catalyst described above, wherein the crystal grain size of the aluminosilicate molecular sieve with *MRE structure is 800 nm - 5 μm.

[0020] The hydroisomerization-cracking catalyst described above, wherein the mass loading of Pt and / or Pd in catalyst A is 0.1 wt% to 0.8 wt%.

[0021] The hydroisomerization-cracking catalyst described above, wherein the mass loading of Pt and / or Pd in catalyst B is 0.2 wt% to 1.0 wt%.

[0022] The second technical solution of the present invention is achieved by the following measures: A method for producing base oil by catalytically cracking a wide-boiling-range high-wax raw material with the hydroisomerization-cracking catalyst described in Technical Solution 1 is carried out according to the following steps: 1) The reaction temperature is 300°C to 450°C, the hydrogen partial pressure is 10 MPa to 16 MPa, and the volumetric hourly space velocity of the feedstock oil is 0.5 h -1 to 5 h -1 , under the conditions of a hydrogen-oil ratio of 500:1 to 2000:1, carry out hydroisomerization-cracking reaction to complete the hydroisomerization of the high-wax raw material oil and the moderate hydrocracking reaction to obtain hydroisomerization-cracked oil; 2) The hydroisomerization-cracked oil obtained in step 1) is on a hydrofining catalyst, the reaction temperature is 200°C to 330°C, the hydrogen partial pressure is 10 MPa to 16 MPa, and the volumetric hourly space velocity of the feedstock oil is 0.8 h -1 to 5 h -1 , under the conditions of a hydrogen-oil ratio of 500:1 to 2000:1, complete the further hydrogen saturation of the hydroisomerization-cracked oil to obtain a crude product; 3) The crude product obtained in step 2) enters an atmospheric tower or a vacuum tower, and is fractionated to obtain gasoline, diesel, and base oil.

[0023] For the method for producing base oil by catalytically cracking a wide-boiling-range high-wax raw material with the hydroisomerization-cracking catalyst, wherein, the hydroisomerization-cracking reaction conditions are: the temperature is 300°C to 400°C, the hydrogen partial pressure is 12 MPa to 16 MPa, and the volumetric hourly space velocity of the feedstock oil is 0.5 - 2 h -1 , and the hydrogen-oil ratio is 500:1 to 1000:1.

[0024] For the method for producing base oil by catalytically cracking a wide-boiling-range high-wax raw material with the hydroisomerization-cracking catalyst, wherein, the hydrofining reaction conditions are: the temperature is 210°C to 320°C, the hydrogen partial pressure is 12 MPa to 16 MPa, and the volumetric hourly space velocity of the feedstock oil is 0.5 - 2 h -1 , and the hydrogen-oil ratio is 500:1 to 1000:1.

[0025] For the method for producing base oil by catalytically cracking a wide-boiling-range high-wax raw material with the hydroisomerization-cracking catalyst, wherein, the crude product obtained in step 3) enters the atmospheric tower and the vacuum tower in sequence for fractionation to obtain gasoline, kerosene, diesel, and base oil.

[0026] For the method for producing base oil by catalytically cracking a wide-boiling-range high-wax raw material with the hydroisomerization-cracking catalyst, wherein, in the high-wax raw material with sulfur, nitrogen, and oxygen removed, its initial boiling point is not higher than 280°C, and the final boiling point is not lower than 700°C.

[0027] For the method for producing base oil by catalytically cracking a wide-boiling-range high-wax raw material with the hydroisomerization-cracking catalyst, wherein, in the high-wax raw material with sulfur, nitrogen, and oxygen removed, the content of n-alkanes is not less than 50 wt%.

[0028] The method for preparing base oil from a wide-boiling-range high-wax feedstock using the described hydroisomerization-cracking catalyst, wherein in the high-wax feedstock with sulfur, nitrogen, and oxygen removed, the sulfur content is not higher than 5 μg / g.

[0029] The method for preparing base oil from a wide-boiling-range high-wax feedstock using the described hydroisomerization-cracking catalyst, wherein in the high-wax feedstock with sulfur, nitrogen, and oxygen removed, the nitrogen content is not higher than 5 μg / g.

[0030] The method for preparing base oil from a wide-boiling-range high-wax feedstock using the described hydroisomerization-cracking catalyst, wherein in the high-wax feedstock with sulfur, nitrogen, and oxygen removed, the oxygen content is not higher than 10 μg / g.

[0031] The method for preparing base oil from a wide-boiling-range high-wax feedstock using the described hydroisomerization-cracking catalyst, wherein the high-wax feedstock is one or more of vacuum gas oil, wax paste, under-wax oil, light deasphalted oil, and heavy deasphalted oil.

[0032] In the method of the present invention, by subjecting the wide-boiling-range high-wax feedstock after removing sulfur, nitrogen, and oxygen to hydroisomerization-cracking, hydrorefining, and fractionation processes, a lubricating base oil with a low pour point and a high viscosity index can be prepared in high yield. The technical core lies in the hydroisomerization-cracking process of the AFI aluminophosphate molecular sieve and the *MRE aluminosilicate molecular sieve supported noble metal catalyst based on a specific acid distribution and particle size, enabling the high-selective conversion of wax components with different chain lengths in the high-wax feedstock into isomerization products in the base oil fraction range, thereby achieving simultaneous improvement in product yield and performance. Detailed Embodiments

[0033] The following further illustrates the present invention with specific examples, but it should be noted that the content of the present invention is not limited thereto.

[0034] The information and preparation methods of the hydroisomerization-cracking catalyst and hydrorefining catalyst used in the embodiments of the present invention are as follows: [[ID=…]]

[0035] 1. Catalyst A and Catalyst B in the hydroisomerization-cracking catalyst

[0036] The hydroisomerization-cracking catalyst A is prepared by an impregnation method, an electrostatic adsorption method, or an ion exchange method. The catalyst uses a molecular sieve support with an AFI structure, which is one of SAPO-5, MgAPO-5, ZnAPO-5, or CoAPO-5. The crystal grain size of this molecular sieve is 20 nm to 200 nm, the total acid amount is 200 to 800 μmol(Pyridine) / g, and the external surface acid amount is 100 to 300 μmol(2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the contents of platinum and palladium are 0.4 wt%, and the rest is the molecular sieve with the above AFI structure.

[0037] The hydroisomerization-cracking catalyst B is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The catalyst uses a molecular sieve support with an *MRE structure, which is one of ZSM-48, Fe-ZSM-48, Cu-ZSM-48 or Ni-ZSM-48. The crystal grain size of the molecular sieve is 800 nm to 5 μm, the total acid amount is 100 to 600 μmol(Pyridine) / g, and the external surface acid amount is 0 to 100 μmol(2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the contents of platinum and palladium are 0.3 wt%, and the rest is the above-mentioned *MRE structure molecular sieve.

[0038] 2. Compare the hydroisomerization-cracking catalysts C and D

[0039] The comparative hydroisomerization-cracking catalyst C is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The catalyst uses a SAPO-5 molecular sieve support, which belongs to the AFI structure. The crystal grain size of the molecular sieve is 600 nm, the total acid amount is 900 μmol(Pyridine) / g, and the external surface acid amount is 350 μmol(2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the contents of platinum and palladium are 0.4 wt%, and the rest is the above-mentioned SAPO-5 molecular sieve.

[0040] The comparative hydroisomerization-cracking catalyst D is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The hydroisomerization-cracking catalyst D is prepared by an impregnation method, an electrostatic adsorption method or an ion exchange method. The support is a ZSM-48 molecular sieve, which belongs to the *MRE structure. The crystal grain size of the molecular sieve is 400 nm, the total acid amount is 800 μmol(Pyridine) / g, and the external surface acid amount is 180 μmol(2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the contents of platinum and palladium are 0.3 wt%, and the rest is the above-mentioned ZSM-48 molecular sieve.

[0041] For other catalyst characteristics, please refer to the description in the comparative example.

[0042] 3. Hydrofining catalyst T0

[0043] The hydrofining catalyst T0 uses a commonly used hydrofining catalyst in industry. The catalyst is composed of platinum supported on amorphous silica-alumina (abbreviated as ASA, SiO2 / Al2O3 = 40 / 60). Based on the weight percentage of the catalyst, the content of platinum is 0.4 wt%.

[0044] Test of total acid amount of sample (Pyridine adsorption infrared (Py-IR) test): Weigh 10 - 20 mg of the sample and press it into a circular self-supporting wafer with a diameter of 13 mm, and place it in an in-situ infrared cell. First, perform vacuum pretreatment at 350 °C for 30 min, cool it to room temperature and record the spectrum of the blank sample. After adsorbing pyridine, heat it to 150 °C and perform vacuum treatment for 30 min, cool it to room temperature and record the spectrum of pyridine adsorption. Calculate the total acid amount of the sample according to the characteristic peak area.

[0045] Test of acid amount on the outer surface of the sample (2,6-Di-tert-butylpyridine adsorption infrared (DTBPy-IR) test): Weigh 10 - 20 mg of the sample and press it into a circular self-supporting wafer with a diameter of 13 mm, and place it in an in-situ infrared cell. First, perform vacuum pretreatment at 350 °C for 30 min, cool it to 150 °C and record the spectrum of the blank sample. After adsorbing 2,6-Di-tert-butylpyridine, perform vacuum for 30 min and record the spectrum of 2,6-Di-tert-butylpyridine adsorption. Then, heat it to 300 °C and perform vacuum treatment for 30 min, cool it to 150 °C and record the spectrum of 2,6-Di-tert-butylpyridine adsorption. Calculate the total acid amount of the sample according to the characteristic peak area.

[0046] In the examples of the present invention, a high-wax vacuum gas oil is used as the raw material, and its properties are shown in Table 1.

[0047] 1) The wide-boiling-range high-wax feedstock and hydrogen are subjected to hydroisomerization-cracking reaction on a hydroisomerization-cracking combined catalyst to complete the hydroisomerization of the high-wax feedstock and moderate hydrocracking reaction, and a hydroisomerization-cracking oil is obtained.

[0048] 2) The hydroisomerization-cracking oil obtained in step 1) is further hydrogenated and saturated on a hydrofining catalyst to obtain a crude product.

[0049] 3) The crude product obtained in step 2) enters an atmospheric column or a vacuum column for fractionation to obtain gasoline, diesel, and base oil.

[0050] Example 1

[0051] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalyst A and catalyst B. Catalyst A uses a molecular sieve support with an AFI structure, which is SAPO-5. The crystal grain size of this molecular sieve is 50 nm, the total acid amount is 780 μmol(Pyridine) / g, the external surface acid amount is 280 μmol(2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pd. Catalyst B uses a molecular sieve support with an *MRE structure, which is ZSM-48. The crystal grain size of this molecular sieve is 4.5 μm, the total acid amount is 560 μmol(Pyridine) / g, the external surface acid amount is 80 μmol(2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.3 wt% Pt. The filling method of the two is A on top and B at the bottom, and the filling volume ratio is 3:1. During the reaction, the raw material flows through B from A. The reaction conditions are 345 °C, 12 MPa (hydrogen pressure, the same below), and the space velocity is 0.8 h -1 (volume space velocity of the feedstock oil, the same below), and the hydrogen-oil ratio is 600. The hydrotreating reactor uses a hydrotreating catalyst T0, and catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 220 °C, 12 MPa (hydrogen pressure, the same below), and the space velocity is 1.0 h -1 (volume space velocity of the feedstock oil, the same below), and the hydrogen-oil ratio is 600. The product yields obtained after the raw material is converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3

[0052] Example 2

[0053] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalyst A and catalyst B. Catalyst A uses a molecular sieve support with an AFI structure, which is MgAPO-5 (the heteroatom Mg content is 1.5 wt%). The crystal grain size of this molecular sieve is 80 nm, the total acid amount is 650 μmol(Pyridine) / g, the external surface acid amount is 240 μmol(2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pt. Catalyst B uses a molecular sieve support with an *MRE structure, which is Fe-ZSM-48 (the heteroatom Fe content is 2.5 wt%). The crystal grain size of this molecular sieve is 3.9 μm, the total acid amount is 430 μmol(Pyridine) / g, the external surface acid amount is 60 μmol(2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.3 wt% Pt. The filling method of the two is A on top and B at the bottom, and the filling volume ratio is 1:1. During the reaction, the raw material flows through B from A. The reaction conditions are 338 °C, 13 MPa, and the space velocity is 0.7 h -1, hydrogen-oil ratio is 700; the hydrofining reactor uses the hydrofining catalyst T0, the catalyst T0 is 0.4 wt% Pt / ASA, and the reaction conditions are 230 °C, 13 MPa, and space velocity 1.5 h -1 , hydrogen-oil ratio is 700. The product yields obtained after the raw materials are transformed and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0054] Example 3

[0055] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalysts A and B. Catalyst A uses a molecular sieve support with an AFI structure, which is ZnAPO-5 (the heteroatom Zn content is 1.0 wt%). The crystal grain size of this molecular sieve is 100 nm, the total acid amount is 580 μmol(Pyridine) / g, the external surface acid amount is 190 μmol(2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pd; Catalyst B uses a molecular sieve support with an *MRE structure, which is Cu-ZSM-48 (the heteroatom Cu content is 2.5 wt%). The crystal grain size of this molecular sieve is 2.8 μm, the total acid amount is 310 μmol(Pyridine) / g, the external surface acid amount is 40 μmol(2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.3 wt% Pd. The filling method of the two is A on top and B at the bottom, and the filling volume ratio is 1:2. When reacting, the raw materials flow through B from A, and the reaction conditions are 323 °C, 14 MPa, and space velocity 1.0 h -1 , hydrogen-oil ratio is 800; the hydrofining reactor uses the hydrofining catalyst T0, the catalyst T0 is 0.4 wt% Pt / ASA, and the reaction conditions are 220 °C, 12 MPa, and space velocity 1.2 h -1 , hydrogen-oil ratio is 700. The product yields obtained after the raw materials are transformed and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0056] Example 4

[0057] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalysts A and B. Catalyst A uses a molecular sieve support with an AFI structure, which is CoAPO-5 (the heteroatom Co content is 1.5 wt%). The crystal grain size of this molecular sieve is 180 nm, the total acid amount is 400 μmol (Pyridine) / g, the external surface acid amount is 150 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pt; Catalyst B uses a molecular sieve support with an *MRE structure, which is Ni-ZSM-48 (the heteroatom Ni content is 2.0 wt%). The crystal grain size of this molecular sieve is 1.9 μm, the total acid amount is 260 μmol (Pyridine) / g, the external surface acid amount is 20 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.3 wt% Pd. The filling method of the two is A on top and B at the bottom, and the filling volume ratio is 1:3. During the reaction, the raw material flows through B from A. The reaction conditions are 325 °C, 15 MPa, and the space velocity is 1.5 h -1 , and the hydrogen-oil ratio is 800; The hydrofining reactor uses the hydrofining catalyst T0, and the catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 230 °C, 12 MPa, and the space velocity is 2.0 h -1 , and the hydrogen-oil ratio is 600. The product yields obtained after the raw material is converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0058] Comparative Example 1

[0059] A process flow similar to that of this example is adopted. The hydroisomerization-cracking reactor uses the hydroisomerization-cracking catalyst A. Catalyst A uses a molecular sieve support with an AFI structure, which is SAPO-5. The crystal grain size of this molecular sieve is 50 nm, the total acid amount is 780 μmol (Pyridine) / g, the external surface acid amount is 280 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pd; The reaction conditions are 358 °C, 12 MPa, and the space velocity is 0.8 h -1 , and the hydrogen-oil ratio is 600; The hydrofining reactor uses the hydrofining catalyst T0, and the catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 220 °C, 12 MPa, and the space velocity is 1.0 h -1 , and the hydrogen-oil ratio is 600. The product yields obtained after the raw material is converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0060] Comparative Example 2

[0061] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalyst B and A. Catalyst A uses a molecular sieve support with an AFI structure, which is MgAPO-5 (the heteroatom Mg content is 1.5 wt%). The crystal grain size of this molecular sieve is 80 nm, the total acid amount is 650 μmol (Pyridine) / g, the external surface acid amount is 240 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pt. Catalyst B uses a molecular sieve support with an *MRE structure, which is Fe-ZSM-48 (the heteroatom Fe content is 2.5 wt%). The crystal grain size of this molecular sieve is 3.9 μm, the total acid amount is 430 μmol (Pyridine) / g, the external surface acid amount is 60 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.3 wt% Pt. The filling method of the two is B on the bottom and A on the top, and the filling volume ratio is 1:1. During the reaction, the raw material flows through A from B. The reaction conditions are 338 °C, 13 MPa, and the space velocity is 0.7 h -1 , and the hydrogen-oil ratio is 700. The hydrofining reactor uses a hydrofining catalyst T0, and catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 230 °C, 13 MPa, and the space velocity is 1.5 h -1 , and the hydrogen-oil ratio is 700. The product yields obtained after the raw material is converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0062] Comparative Example 3

[0063] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalyst C and D. Catalyst C uses a SAPO-5 molecular sieve support, which belongs to the AFI structure. The crystal grain size of this molecular sieve is 600 nm, the total acid amount is 900 μmol (Pyridine) / g, the external surface acid amount is 350 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pt. Catalyst D uses a ZSM-48 molecular sieve support, which belongs to the *MRE structure. The crystal grain size of this molecular sieve is 400 nm, the total acid amount is 800 μmol (Pyridine) / g, the external surface acid amount is 180 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pd. The filling method of the two is C on the bottom and D on the top, and the filling volume ratio is 1:2. During the reaction, the raw material flows through D from C. The reaction conditions are 323 °C, 14 MPa, and the space velocity is 1.0 h -1 , and the hydrogen-oil ratio is 800. The hydrofining reactor uses a hydrofining catalyst T0, and catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 220 °C, 12 MPa, and the space velocity is 1.2 h -1, with a hydrogen-oil ratio of 700. The product yields obtained after the raw materials are converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0064] Comparative Example 4

[0065] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of Catalysts C and D. Catalyst C uses a SAPO-5 molecular sieve support, belonging to the AFI structure. The crystal grain size of this molecular sieve is 600 nm, the total acid amount is 900 μmol (Pyridine) / g, the external surface acid amount is 350 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pt; Catalyst D uses a ZSM-48 molecular sieve support, belonging to the *MRE structure. The crystal grain size of this molecular sieve is 400 nm, the total acid amount is 800 μmol (Pyridine) / g, the external surface acid amount is 180 μmol (2,6-Di-tert-butylpyridine) / g, and the noble metal content is 0.4 wt% Pd. The filling method of the two is C on top of D, and the filling volume ratio is 1:3. During the reaction, the raw materials flow from C through D. The reaction conditions are 325 °C, 15 MPa, and the space velocity is 1.5 h -1 , with a hydrogen-oil ratio of 800; the hydrofining reactor uses a hydrofining catalyst T0, and Catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 230 °C, 12 MPa, and the space velocity is 2.0 h -1 , with a hydrogen-oil ratio of 600. The product yields obtained after the raw materials are converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0066] Comparative Example 5

[0067] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of Catalysts E and F. Catalyst E uses a SAPO-11 molecular sieve as the support. The crystal grain size of the molecular sieve is 120 nm, the total acid amount is 650 μmol (Pyridine) / g, the external surface acid amount is 230 μmol (2,6-Di-tert-butylpyridine) / g, and 0.5 wt% Pd is loaded on the catalyst; Catalyst F uses a ZSM-22 molecular sieve as the support. The crystal grain size of the molecular sieve is 2.3 μm, the total acid amount is 300 μmol (Pyridine) / g, the external surface acid amount is 20 μmol (2,6-Di-tert-butylpyridine) / g, and 0.5 wt% Pt is loaded on the catalyst. The filling method of the two is E on top of F, and the filling volume ratio is 1:3. During the reaction, the raw materials flow from E through F. The reaction conditions are 325 °C, 15 MPa, and the space velocity is 1.5 h -1, hydrogen-oil ratio is 800; the hydrofining reactor uses hydrofining catalyst T0, catalyst T0 is 0.4 wt% Pt / ASA, the reaction conditions are 230 °C, 12 MPa, and the space velocity is 2.0 h -1 , hydrogen-oil ratio is 600. The product yields obtained after the raw materials are transformed and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0068] Comparative Example 6

[0069] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalysts G and H. Catalyst G uses CoAPO-31 (the heteroatom Co content is 1.5 wt%) molecular sieve as the carrier. The crystal grain size of this molecular sieve is 100 nm, the total acid amount is 420 μmol(Pyridine) / g, and the external surface acid amount is 180 μmol(2,6-Di-tert-butylpyridine) / g. The total content of platinum and palladium is 0.4 wt% Pt; Catalyst H uses Fe-ZSM-35 (the heteroatom Fe content is 2.5 wt%) molecular sieve with FER structure as the carrier. The crystal grain size of this molecular sieve is 2.0 μm, the total acid amount is 280 μmol(Pyridine) / g, and the external surface acid amount is 50 μmol(2,6-Di-tert-butylpyridine) / g. The content of noble metals is 0.4 wt% Pd. The filling method of the two is G on top and H at the bottom, and the filling volume ratio is 1:3. During the reaction, the raw materials flow through H from G. The reaction conditions are 325 °C, 15 MPa, and the space velocity is 1.5 h -1 , hydrogen-oil ratio is 800; the hydrofining reactor uses hydrofining catalyst T0, catalyst T0 is 0.4 wt% Pt / ASA, the reaction conditions are 230 °C, 12 MPa, and the space velocity is 2.0 h -1 , hydrogen-oil ratio is 600. The product yields obtained after the raw materials are transformed and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0070] Comparative Example 7

[0071] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalyst I and catalyst J. Catalyst I uses a heteroatom aluminophosphate molecular sieve support with an AEL structure, which is ZnAPO-11 (the heteroatom Zn content is 1.0 wt%). The crystal grain size of this molecular sieve is 80 nm, the total acid amount is 500 μmol (Pyridine) / g, the external surface acid amount is 150 μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst J uses a heteroatom silicoaluminate molecular sieve support with an MTT structure, which is Ni-ZSM-23 (the heteroatom Ni content is 2.0 wt%). The crystal grain size of this molecular sieve is 1 μm, the total acid amount is 300 μmol (Pyridine) / g, the external surface acid amount is 60 μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.4 wt% Pd. The filling method of the two is I below J, and the filling volume ratio is 1:3. During the reaction, the raw material flows through J from I. The reaction conditions are 325 °C, 15 MPa, and the space velocity is 1.5 h -1 , and the hydrogen-oil ratio is 800. The hydrofining reactor uses a hydrofining catalyst T0, and catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 230 °C, 12 MPa, and the space velocity is 2.0 h -1 , and the hydrogen-oil ratio is 600. The product yields obtained after the raw material is converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0072] Comparative Example 8

[0073] The hydroisomerization-cracking reactor uses a hydroisomerization-cracking catalyst composed of catalyst K and catalyst L. Catalyst K uses a molecular sieve support with an AFO structure, which is SAPO-41. The crystal grain size of this molecular sieve is 350 nm, the total acid amount is 600 μmol (Pyridine) / g, the external surface acid amount is 260 μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5 wt% Pt. Catalyst L uses a molecular sieve support with an MTW structure, which is ZSM-12. The crystal grain size of this molecular sieve is 4.5 μm, the total acid amount is 450 μmol (Pyridine) / g, the external surface acid amount is 120 μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5 wt% Pd. The filling method of the two is K above L, and the filling volume ratio is 1:3. During the reaction, the raw material flows through L from K. The reaction conditions are 325 °C, 15 MPa, and the space velocity is 1.5 h -1 , and the hydrogen-oil ratio is 800. The hydrofining reactor uses a hydrofining catalyst T0, and catalyst T0 is 0.4 wt% Pt / ASA. The reaction conditions are 230 °C, 12 MPa, and the space velocity is 2.0 h-1 , with a hydrogen-oil ratio of 600. The product yields obtained after the raw material is converted and fractionated through this reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0074] As can be seen from Table 2, compared with the comparative example, by using the method described in the present invention, the yield of the base oil is significantly increased, the yields of the light hydrocarbons and diesel, which are by-products with lower values, are significantly reduced, and the wide-boiling-range and high-wax-containing vacuum gas oil raw material is efficiently converted. At the same time, as can be seen from Table 3, compared with the comparative example, by using the method described in the present invention, the base oil prepared has a higher viscosity index and a lower pour point.

[0075] Table 1 Properties of the wide-boiling-range and high-wax-containing vacuum gas oil raw material

[0076] Project Raw material <![CDATA[Density (25 °C), kg / m 3 > 827 <![CDATA[Kinematic viscosity (100 °C), mm 2 / s]]> 8.6 Sulfur content, μg / g 2.1 Nitrogen content, μg / g 3.4 Oxygen content, μg / g <1.0 Distillation range, °C Initial boiling point 276 10％ 352 30％ 405 50％ 483 70％ 561 90％ 668 95％ 692 Final boiling point 713 Normal paraffin content, wt% 65.3

[0077] Table 2 Product yields

[0078]

[0079] Table 3 Properties of the base oil products

[0080]

Claims

1. A hydroisomerization-cracking catalyst, characterized in that, It includes catalyst A and catalyst B. Catalyst A is composed of an aluminophosphate molecular sieve support with one-dimensional dodecasil 10-ring pore channels and loaded Pt and / or Pd. Catalyst B is composed of an aluminosilicate molecular sieve support with one-dimensional decasil 10-ring pore channels and loaded Pt and / or Pd; The aluminophosphate molecular sieve with one-dimensional dodecasil 10-ring pore channels is one of SAPO-5, MgAPO-5, ZnAPO-5 or CoAPO-5 which has an AFI structure, and the pore mouth size of its one-dimensional circular pore channels is 7.3*7.3 Å; The aluminosilicate molecular sieve with one-dimensional decasil 10-ring pore channels is one of ZSM-48, Fe-ZSM-48, Cu-ZSM-48 or Ni-ZSM-48 which has a *MRE structure, and the pore mouth size of its one-dimensional circular pore channels is 5.6*5.6 Å; The crystal grain size of the SAPO-5, MgAPO-5, ZnAPO-5 or CoAPO-5 is 20 nm to 200 nm, and the crystal grain size of the ZSM-48, Fe-ZSM-48, Cu-ZSM-48 or Ni-ZSM-48 is 800 nm to 5 μm.

2. The hydroisomerization-cracking catalyst according to claim 1, characterized in that, The catalyst A and catalyst B are composed in a volume ratio of 1:5 to 5:

1. When the catalyst is used, the reaction material flows through catalyst A and then through catalyst B.

3. The hydroisomerization-cracking catalyst according to claim 1, wherein, The total acid amount of the SAPO-5, MgAPO-5, ZnAPO-5 or CoAPO-5 is 200 to 800 μmol pyridine / g, and the external surface acid amount is 100 to 300 μmol 2,6-di-tert-butylpyridine / g.

4. The hydroisomerization-cracking catalyst according to claim 1, wherein, The total acid amount of the ZSM-48, Fe-ZSM-48, Cu-ZSM-48 or Ni-ZSM-48 is 100 to 600 μmol pyridine / g, and the external surface acid amount is 0 to 100 μmol 2,6-di-tert-butylpyridine / g.

5. The hydroisomerization-cracking catalyst according to claim 1, characterized in that, The mass loading amount of Pt and / or Pd in catalyst A is 0.1 wt% to 0.8 wt%, and the mass loading amount of Pt and / or Pd in catalyst B is 0.2 wt% to 1.0 wt%.

6. A method for processing a waxy feedstock into a lubricating base oil by using the hydroisomerization-cracking catalyst according to claim 1, characterized in that It is carried out according to the following steps: 1) The waxy feedstock oil and hydrogen are subjected to a hydroisomerization-cracking reaction on a hydroisomerization-cracking catalyst at a reaction temperature of 300 °C to 450 °C, a hydrogen partial pressure of 10 MPa to 16 MPa, a feedstock oil volume hourly space velocity of 0.5 h -1 to 5 h -1 , and a hydrogen-oil ratio of 500:1 to 2000:1 to complete the hydroisomerization of the waxy feedstock oil and a moderate hydrocracking reaction to obtain hydroisomerization-cracked oil; 2) The hydroisomerized-cracked oil obtained in step 1) is on a hydrofining catalyst, with a reaction temperature of 200°C to 330°C, a hydrogen partial pressure of 10 MPa to 16 MPa, a feedstock oil volume hourly space velocity of 0.8 h -1 to 5 h -1 , and a hydrogen-oil ratio of 500:1 to 2000:1, to complete the further hydrogen saturation of the hydroisomerized-cracked oil and obtain a crude product; 3) The crude product obtained in step 2) enters an atmospheric tower or a vacuum tower, and is fractionated to obtain gasoline, diesel oil and base oil.

7. The method according to claim 6, wherein The waxy raw material is one or several of petroleum-derived raw materials such as vacuum gas oil, wax paste, under-wax oil, light deasphalted oil, and heavy deasphalted oil. Its initial boiling point is not higher than 280 °C and not lower than 240 °C, and its final boiling point is not lower than 700 °C and not higher than 730 °C.

8. The method according to claim 6, characterized in that, The content of n-alkanes in the waxy raw material is not less than 50 wt%, its sulfur content is not higher than 5 μg / g, its nitrogen content is not higher than 5 μg / g, and its oxygen content is not higher than 10 μg / g.

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