A hydrogenation catalyst composition and its application in Fischer-Tropsch wax-based oil

Abstract

The present invention relates to the technical field of lubricating oil base oil made from Fischer-Tropsch wax, and specifically to a hydrogenation catalyst composition and its application in the hydrogenation of Fischer-Tropsch wax with a narrow distillation range and a normal alkane content of not less than 90wt% to make lubricating oil base oil. The present invention can produce a low pour point and high viscosity index lubricating oil base oil with high yield by subjecting a narrow distillation range Fischer-Tropsch wax raw material to hydrogenation isomerization on a hydrogenation isomerization combination catalyst, hydrogenation refining on a hydrogenation refining catalyst, and fraction separation in a fractionation system.

Description

Technical Field

[0001] The invention relates to the technical field of lubricating oil base oil prepared from Fischer-Tropsch wax, and in particular to a hydrogenation catalyst composition and application thereof in preparing lubricating oil base oil by hydrogenating Fischer-Tropsch wax. Background Art

[0002] Fischer-Tropsch wax is the main product of the Fischer-Tropsch synthesis reaction of synthesis gas (CO and H2). It is mainly composed of long-chain alkanes, which can be further hydrogenated to produce liquid fuels and chemicals. The main components of Fischer-Tropsch wax are straight-chain alkanes, which contain almost no sulfur, nitrogen and aromatics. It is a high-quality raw material for high-grade lubricant base oil. The technical key to converting Fischer-Tropsch wax products into high-grade lubricant base oil is to improve the low-temperature flow properties of the oil while maintaining a high viscosity index, that is, to lower the freezing point, which can be achieved through hydrocracking and hydroisomerization reactions.

[0003] In the field of lubricating base oil produced by hydrogenation and reforming of Fischer-Tropsch wax, many relevant patents have been published at home and abroad. For example, US5834522 discloses a method for producing lubricating base oil using Fischer-Tropsch synthesis products as raw materials, wherein the Fischer-Tropsch synthesis products are hydrogenated and isomerized in a hydrogenation and isomerization reaction zone, and the generated oil is separated by distillation, and then the distillation bottoms are dewaxed to obtain oil and non-oil fractions. US5882505 discloses a method for producing lubricating base oil by converting Fischer-Tropsch synthesis wax with a boiling point greater than 370°C using a countercurrent reactor, wherein the raw material is contacted with a hydrogenation and isomerization catalyst in a fixed bed reactor, and the product after the reaction is contacted with a hydrogenation and dewaxing catalyst in at least one fixed bed reactor to obtain the target product, wherein the hydrogenation and isomerization reaction products flow in the opposite direction to the hydrogen-containing gas. CN1688674 discloses a multi-step method for preparing a heavy lubricating oil base from Fischer-Tropsch wax, which comprises hydrodewaxing the wax in a first hydrodewaxing step to obtain an isomerization product of a partially dewaxed heavy base oil fraction, and then hydrodewaxing the heavy lubricating oil fraction in one or more successive hydrodewaxing steps to remove hydrocarbons below the heavy lubricating oil fraction to obtain a heavy lubricating oil base. CN1703488 discloses a method for preparing fuel and lubricating oil base from Fischer-Tropsch wax, which comprises (1) hydrodewaxing the Fischer-Tropsch wax to prepare an isomerization product comprising a fuel and a partially hydrodewaxed base oil fraction, (2) separating the two fractions, (3) separating the partially hydrodewaxed base oil fraction into a heavy fraction and a lower boiling point fraction, and (4) further hydrodewaxing the lower boiling point fraction and the heavy fraction to prepare a lubricating oil base including a heavy lubricating oil base. CN101230290 discloses a method for producing solvent oil, lubricating oil base oil and heavy wax from Fischer-Tropsch wax, wherein the whole fraction product obtained by converting the wax in the hydrorefining zone is fractionated to obtain a light fraction of solvent oil, and then the base oil fraction segment product is separated and then subjected to hydroisomerization conversion, and the remaining heavy fraction is directly subjected to hydrorefining to obtain decolorized wax. US7198710 discloses a method for producing a high viscosity index lubricating oil base oil from Fischer-Tropsch wax, wherein the Fischer-Tropsch wax is first fractionated to obtain a light component and a heavy component, and then hydroisomerization dewaxing is performed to reduce the pour point of the raw material, and a light lubricating oil base oil with a pour point that meets the requirements can be obtained. When the heavy component is hydroisomerized dewaxed, since the pour point is unqualified, the solvent dewaxing method is used to further reduce the pour point of the heavy component, and finally a heavy lubricating oil base oil product with a pour point that meets the requirements is obtained.

[0004] In the above process, the disadvantage of using the traditional hydroisomerization dewaxing catalyst in the hydrodewaxing operation unit is that when the full-fraction or wide-fraction Fischer-Tropsch wax is used as the feed, it is difficult to make the light and heavy base components meet the requirements of pour point and viscosity index at the same time. When the heavy base oil component has a qualified pour point, the viscosity index loss of the light base oil component is large, and it is difficult to produce API III light lubricating base oil products with a viscosity index>120; and when the light base oil component has a qualified viscosity index, the heavy component cannot be used as a lubricating base oil product with a qualified pour point. When the traditional hydrocracking catalyst is used, whether the full-fraction or wide-fraction Fischer-Tropsch wax is used as the feed, the light and heavy base oil products can mostly meet the requirements of pour point and viscosity index at the same time, but the process produces a large amount of cracking products, and the yield of light and heavy base oils is too low, which seriously affects the process economy.

[0005] Since the yield of lubricating oil base oil produced directly from Fischer-Tropsch wax is low, domestic coal-to-liquid enterprises currently mainly use the wax generated by Fischer-Tropsch synthesis for further hydrocracking to produce gasoline, diesel, α-olefins and other products. However, the distillation range of Fischer-Tropsch wax is too wide. While producing the above products, a large amount of Fischer-Tropsch wax hydrocracking tail oil is also produced. This tail oil is mainly branched long-chain alkanes. Compared with the initial raw material, its low-temperature performance has been greatly improved, but it still cannot meet the product standards of base oil, and further conversion is required to reduce its pour point.

[0006] The Fischer-Tropsch wax is subjected to vacuum distillation to cut out the fraction (320-580°C) suitable for the production of commonly used lubricating base oils, and then hydrogenated to obtain lubricating base oils with a high viscosity index. When this narrow fraction is used as a raw material, due to its high wax content and high freezing point, a hydroisomerization catalyst with extremely high shape selectivity is required to highly isomerize the wax component. At the same time, a small amount of long carbon chain straight-chain hydrocarbons and single-branched hydrocarbon molecules that have not been highly isomerized can also use the shape selectivity of the pores to further shape-selectively transform, and finally complete the deep hydrogenation saturation of the product on the hydrorefining catalyst to improve the photothermal stability of the product, thereby obtaining a lubricating base oil product with a low pour point and a high viscosity index at a high yield. However, the aforementioned existing processes cannot yet meet this technical requirement. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present invention provides a hydrogenation catalyst composition and an application method thereof in the production of lubricating base oil by hydrogenation of narrow-range Fischer-Tropsch wax, which overcomes the above-mentioned deficiencies in the prior art. The Fischer-Tropsch wax raw material can be used to produce a low pour point, high viscosity index lubricating base oil in high yield through a hydrogenation isomerization-hydrorefining-fractionation process. The technical core is a one-dimensional ten-membered ring elliptical pore SAPO-41 molecular sieve and a one-dimensional twelve-membered ring elliptical pore ZSM-12 molecular sieve catalyst based on specific crystals and acid distribution of non-precious metals, which enable the normal alkanes in the narrow-range Fischer-Tropsch wax raw material to be highly selectively converted into isomerized products to generate base oil components, reduce the generation of gaseous hydrocarbons and gasoline and diesel fraction by-products, and achieve simultaneous improvement in the yield and performance of base oil products.

[0008] One of the technical solutions of the present invention is achieved through the following measures: a hydrogenation catalyst composition, characterized in that it includes a hydrogenation isomerization catalyst composition and a hydrogenation refining catalyst; the hydrogenation isomerization combined catalyst is composed of catalyst A and catalyst B in a volume ratio of 1:10 to 10:1, catalyst A is composed of a one-dimensional ten-membered ring elliptical pore SAPO-41 molecular sieve carrier and loaded Ni and / or W metal, and catalyst B is composed of a one-dimensional twelve-membered ring elliptical pore ZSM-12 molecular sieve carrier and loaded Ni and / or Co and / or W metal; the hydrogenation refining catalyst is composed of an amorphous silicon aluminum carrier and one or more of loaded Ni, Co, Mo, and W.

[0009] The hydroisomerization catalyst composition, wherein the SAPO-41 has an AFO structure, a one-dimensional ten-membered ring elliptical channel, and the channel opening size is

[0010] The hydroisomerization catalyst composition, wherein the ZSM-12 has an MTW structure, a one-dimensional twelve-membered ring elliptical channel, and the channel opening size is

[0011] The hydroisomerization catalyst composition, wherein the SAPO-41 molecular sieve is a nano molecular sieve, and its crystal particle size is 80 to 300 nm.

[0012] The hydroisomerization catalyst composition, wherein the ZSM-12 molecular sieve is a micron molecular sieve, and its grain size is 4 to 8 μm.

[0013] The hydroisomerization catalyst composition, wherein the total acid content of the SAPO-41 is 300-700 μmol (Pyridine) / g, and the total acid content is measured and calculated using pyridine adsorption infrared spectroscopy.

[0014] The hydroisomerization catalyst composition, wherein the external surface acid amount of the SAPO-41 is 150-300 μmol (2,6-Di-tert-butylpyridine) / g, and the external surface acid amount is measured and calculated using 2,6-di-tert-butylpyridine adsorption infrared spectrum.

[0015] The hydroisomerization catalyst composition, wherein the total acid content of the ZSM-12 is 200-500 μmol (Pyridine) / g, and the total acid content is measured and calculated using pyridine adsorption infrared spectroscopy.

[0016] The hydroisomerization catalyst composition, wherein the external surface acid amount of the ZSM-12 is 0-150 μmol (2,6-Di-tert-butylpyridine) / g, and the external surface acid amount is measured and calculated using 2,6-di-tert-butylpyridine adsorption infrared spectrum.

[0017] The hydroisomerization catalyst composition, wherein the mass loading amount of Ni and / or W metal in catalyst A is 3wt% to 10wt%.

[0018] In the hydroisomerization catalyst composition, the mass loading amount of Ni and / or Co and / or W metal in catalyst B is 10wt% to 20wt%.

[0019] The hydroisomerization catalyst composition, wherein catalyst A and catalyst B are composed in a volume ratio of 1:5 to 5:1, and the combination is A on top and B on the bottom.

[0020] The hydroisomerization catalyst composition, wherein when the catalyst is used, the reactants first contact the catalyst A and then contact the catalyst B.

[0021] The hydrogenation catalyst composition, wherein the carrier in the hydrogenation refining catalyst is amorphous silicon-aluminum.

[0022] The hydrogenation catalyst composition, wherein the mass loading of Ni, Co, Mo and W in the hydrogenation refining catalyst is 12wt% to 25wt%.

[0023] The second technical solution of the present invention is achieved by the following measures: a method for converting a narrow-range Fischer-Tropsch wax feedstock into a base oil by using the hydrogenation catalyst composition described in one of the technical solutions, which is carried out according to the following steps: 1) the narrow-range Fischer-Tropsch wax feedstock oil and hydrogen are mixed into a hydroisomerization zone, and a hydroisomerization reaction is carried out on the hydroisomerization catalyst composition to complete the hydroisomerization of the Fischer-Tropsch wax feedstock oil and obtain a hydroisomerized oil;

[0024] 2) The hydroisomerized oil obtained in step 1) enters the hydrorefining zone, and further hydrogenation saturation of the hydroisomerized oil is completed on the hydrorefining catalyst to obtain a crude product;

[0025] 3) The crude product obtained in step 2) enters an atmospheric pressure tower or a vacuum tower for fractionation to obtain gasoline, diesel and base oil.

[0026] The method for converting a narrow-range Fischer-Tropsch wax raw material into a base oil by using a hydrogenation catalyst composition, wherein the conditions for the hydrogenation isomerization reaction are: a reaction temperature of 300° C. to 420° C., a hydrogen partial pressure of 1.0 MPa to 5.0 MPa, and a raw oil volume space velocity of 0.5 h -1 Until 3h -1 , the hydrogen-to-oil ratio is 200:1 to 1000:1.

[0027] The method for converting a narrow-range Fischer-Tropsch wax raw material into a base oil by using a hydrogenation catalyst composition, wherein the hydrofining reaction conditions are: a reaction temperature of 200°C to 320°C, a hydrogen partial pressure of 5.0MPa to 12MPa, and a raw oil volume space velocity of 0.5h -1 Until 3h -1 , the hydrogen-to-oil ratio is 500:1 to 2000:1.

[0028] The method for converting a narrow-range Fischer-Tropsch wax raw material into a base oil using a hydrogenation catalyst composition, wherein the crude product obtained in step 3) enters a normal pressure tower and a vacuum tower in sequence for fractionation to obtain gasoline, diesel and base oil.

[0029] The method for converting a narrow-range Fischer-Tropsch wax raw material into a base oil using a hydrogenation catalyst composition, wherein the Fischer-Tropsch wax raw material is a Fischer-Tropsch wax prepared by Fischer-Tropsch synthesis of synthesis gas.

[0030] The method for converting a narrow-distillation range Fischer-Tropsch wax raw material into a base oil using a hydrogenation catalyst composition, wherein the Fischer-Tropsch wax raw material is a Fischer-Tropsch wax prepared by Fischer-Tropsch synthesis of synthesis gas, and the distillation range is an initial distillation point of not less than 320°C and not more than 380°C, and a final distillation point of not more than 580°C and not less than 480°C.

[0031] The method for converting a narrow-range Fischer-Tropsch wax raw material into a base oil using a hydrogenation catalyst composition, wherein the Fischer-Tropsch wax raw material is a Fischer-Tropsch wax prepared by Fischer-Tropsch synthesis of synthesis gas, and the normal alkane content is not less than 90wt%.

[0032] The method for converting a narrow-range Fischer-Tropsch wax raw material into a base oil using a hydrogenation catalyst composition, wherein the sulfur content of the Fischer-Tropsch wax raw material is not higher than 5 μg / g, the nitrogen content is not higher than 5 μg / g, and the oxygen content is not higher than 10 μg / g.

[0033] The method of the present invention can obtain a lubricating base oil with a low pour point and a high viscosity index in high yield by placing a narrow-range Fischer-Tropsch wax raw material on a hydrogenation catalyst composition, and undergoing hydrogenation isomerization, hydrorefining and fractionation processes. The technical core of the method is a hydrogenation isomerization process based on a one-dimensional ten-membered ring elliptical channel SAPO-41 molecular sieve with specific crystals and acid distribution of non-precious metals and a one-dimensional twelve-membered ring elliptical channel ZSM-12 molecular sieve catalyst, so that the narrow-range Fischer-Tropsch wax raw material is highly selectively converted into a base oil fraction isomerization product, thereby achieving simultaneous improvement in product yield and performance. In addition, compared with precious metal catalysts, the non-precious metal catalyst provided by the present invention can also significantly reduce catalyst costs. DETAILED DESCRIPTION

[0034] The present invention is further described below in conjunction with specific embodiments, but it should be pointed out that the present invention is not limited thereto.

[0035] The information and preparation methods of the hydroisomerization catalyst and hydrotreating catalyst used in the examples of the present invention are as follows:

[0036] 1. Hydroisomerization catalysts A and B

[0037] Hydroisomerization catalyst A is prepared by impregnation. The catalyst uses a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a particle size of 80nm to 300nm, a total acid content of 300 to 700μmol (Pyridine) / g, and an external surface acid content of 150 to 300μmol (2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the content of Ni and / or W is 3wt% to 10wt%, and the rest is the above-mentioned SAPO-41 molecular sieve.

[0038] Hydroisomerization catalyst B is prepared by impregnation. The catalyst uses a molecular sieve carrier with an MTW structure, which is ZSM-12. The molecular sieve has a particle size of 4μm to 8μm, a total acid content of 200 to 500μmol (Pyridine) / g, and an external surface acid content of 0 to 150μmol (2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the content of Ni and / or Co and / or W metal is 10wt% to 20wt%, and the rest is the above-mentioned ZSM-12 molecular sieve.

[0039] 2. Comparison of Hydroisomerization Catalysts C and D

[0040] Comparative hydroisomerization catalyst C was prepared by impregnation. The catalyst used SAPO-41 molecular sieve, the particle size of the molecular sieve was 600nm, the total acid content was 800μmol (Pyridine) / g, and the external surface acid content was 140μmol (2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the content of platinum, palladium and / or iridium was 0.35wt%, and the rest was the above-mentioned SAPO-41 molecular sieve.

[0041] Comparative hydroisomerization catalyst D is prepared by impregnation. Hydroisomerization catalyst D is prepared by impregnation, electrostatic adsorption or ion exchange. The carrier is ZSM-12 molecular sieve, the molecular sieve has a particle size of 400nm, a total acid content of 600μmol (Pyridine) / g, and an external surface acid content of 200μmol (2,6-Di-tert-butylpyridine) / g. Based on the weight percentage of the catalyst, the content of platinum, palladium and / or iridium is 0.45wt%, and the rest is the above-mentioned ZSM-12 molecular sieve.

[0042] 3. Hydrorefining catalyst T

[0043] The hydrorefining catalyst T is prepared by an impregnation method. The catalyst is composed of amorphous silica-alumina (ASA, SiO2 / Al2O3=40 / 60) as a carrier and one or more metals of Ni, Co, Mo, and W loaded on the carrier. Based on the weight percentage of the catalyst, the mass loading of Ni, Co, Mo, and W is 12wt% to 25wt%, and the rest is amorphous silica-alumina.

[0044] Test of total acidity of samples (pyridine adsorption infrared (Py-IR) test): Weigh 10-20 mg of sample and press it into a circular self-supporting sheet with a diameter of 13 mm, and put it into the in-situ infrared cell. Pre-treat it at 350℃ for 30 minutes, cool it to room temperature and record the blank sample spectrum. After pyridine is adsorbed, heat it to 150℃ and vacuum it for 30 minutes, cool it to room temperature and record the spectrum of pyridine adsorption. Calculate the total acidity of the sample based on the characteristic peak area.

[0045] Sample external surface acidity test (2,6-di-tert-butylpyridine adsorption infrared (DTBPy-IR) test): Weigh 10-20 mg of sample and press it into a circular self-supporting sheet with a diameter of 13 mm, and place it in an in-situ infrared cell. First, vacuum pre-treat at 350°C for 30 minutes, cool to 150°C and record the blank sample spectrum. After adsorbing 2,6-di-tert-butylpyridine (2,6-Di-tert-butylpyridine), vacuum for 30 minutes and record the spectrum of 2,6-di-tert-butylpyridine adsorption. After that, heat to 300°C and vacuum for 30 minutes, cool to 150°C and record the spectrum of 2,6-di-tert-butylpyridine adsorption. Calculate the total acidity of the sample based on the characteristic peak area.

[0046] The embodiments of the present invention use a narrow distillation range Fischer-Tropsch wax as a raw material, and its properties are shown in Table 1.

[0047] 1) The narrow-range Fischer-Tropsch wax feedstock oil and hydrogen are mixed into a hydroisomerization zone, and a hydroisomerization reaction is carried out on a hydroisomerization catalyst composition to complete the hydroisomerization of the Fischer-Tropsch wax feedstock oil and obtain a hydroisomerized oil;

[0048] 2) The hydroisomerized oil obtained in step 1) enters the hydrorefining zone, and further hydrogenation saturation of the hydroisomerized oil is completed on the hydrorefining catalyst to obtain a crude product;

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

[0050] Example 1

[0051] The hydroisomerization reactor adopts a composition of hydroisomerization catalysts A and B. Catalyst A adopts a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a grain size of 300nm, a total acid content of 600μmol (Pyridine) / g, an external surface acid content of 260μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 5wt% Ni. Catalyst B adopts a molecular sieve carrier with an MTW structure, which is ZSM-12. The molecular sieve has a grain size of 4.5μm, a total acid content of 450μmol (Pyridine) / g, an external surface acid content of 120μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 10wt% Ni-5wt% W. The two were loaded in the following manner: A on top and B on the bottom, with a loading volume ratio of 1:1. During the reaction, the raw materials flowed from A to B. The reaction conditions were 342°C, 2.8 MPa (hydrogen pressure, the same below), and a space velocity of 0.8 h -1(raw oil volume space velocity, the same below), hydrogen-to-oil ratio 600; the hydrotreating reactor uses hydrotreating catalyst T, which is 15wt% Ni-2wt% W / ASA, and the reaction conditions are 230℃, 6MPa (hydrogen pressure, the same below), space velocity 1.5h -1 (Volume space velocity of raw oil, the same below), hydrogen to oil ratio is 600. The product yields obtained after the raw materials are converted and fractionated through the 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 reactor adopts a composition of hydroisomerization catalysts A and B. Catalyst A adopts a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a grain size of 200nm, a total acid content of 500μmol (Pyridine) / g, an external surface acid content of 210μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 4wt% Ni-4wt% W. Catalyst B adopts a molecular sieve carrier with an MTW structure, which is ZSM-12. The molecular sieve has a grain size of 5.0μm, a total acid content of 400μmol (Pyridine) / g, an external surface acid content of 100μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 14wt% Ni-4wt% Co. The two were loaded in the manner of A on top and B on the bottom, with a loading volume ratio of 3:1. During the reaction, the raw materials flowed from A to B. The reaction conditions were 363°C, 3.5 MPa, and a space velocity of 1.2 h -1 , hydrogen-to-oil ratio 500; the hydrotreating reactor uses a hydrotreating catalyst T, which is 14wt% Ni-3wt% Co / ASA, and the reaction conditions are 225℃, 12MPa, and a space velocity of 1.0h -1 , hydrogen to oil ratio 700. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor adopts a composition of hydroisomerization catalysts A and B. Catalyst A adopts a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a grain size of 150 nm, a total acid content of 400 μmol (Pyridine) / g, an external surface acid content of 180 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 4wt% Ni-5wt% W. Catalyst B adopts a molecular sieve carrier with an MTW structure, which is ZSM-12. The molecular sieve has a grain size of 5.5 μm, a total acid content of 300 μmol (Pyridine) / g, an external surface acid content of 80 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 8wt% Ni-10wt% Mo. The two were loaded in the manner of A on top and B on the bottom, with a loading volume ratio of 1:3. During the reaction, the raw materials flowed from A to B. The reaction conditions were 335°C, 4.5 MPa, and a space velocity of 1.5 h -1 , hydrogen-to-oil ratio 700; the hydrotreating reactor uses a hydrotreating catalyst T, which is 16wt% Ni-5wt% Mo / ASA, and the reaction conditions are 215℃, 12MPa, and a space velocity of 1.2h -1 , hydrogen to oil ratio 800. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor adopts a composition of hydroisomerization catalysts A and B. Catalyst A adopts a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a grain size of 100 nm, a total acid content of 350 μmol (Pyridine) / g, an external surface acid content of 160 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 3wt% Ni-6wt% W. Catalyst B adopts a molecular sieve carrier with an MTW structure, which is ZSM-12. The molecular sieve has a grain size of 7.0 μm, a total acid content of 240 μmol (Pyridine) / g, an external surface acid content of 50 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 8wt% Ni-3wt% Mo-3wt% W. The two were loaded in the manner of A on top and B on the bottom, with a loading volume ratio of 1:2. During the reaction, the raw materials flowed from A to B. The reaction conditions were 328°C, 3.6 MPa, and a space velocity of 1.2 h -1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 5wt% Ni-4wt% W / ASA, and the reaction conditions are 232°C, 10MPa, and a space velocity of 2.1h -1, hydrogen to oil ratio 500. The product yields obtained after the raw materials were converted and fractionated through the 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] The hydroisomerization reactor uses a hydroisomerization catalyst A. Catalyst A uses a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a particle size of 350nm, a total acid content of 600μmol (Pyridine) / g, an external surface acid content of 260μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 0.5wt% Pt. The reaction conditions are 365°C, 2.8MPa, and a space velocity of 0.8h -1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 15wt% Ni-2wt% W / ASA, and the reaction conditions are 230°C, 6MPa, and a space velocity of 1.5h -1 , hydrogen to oil ratio 600. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts B and A. Catalyst A uses a molecular sieve carrier with an AFO structure, which is SAPO-41. The molecular sieve has a grain size of 200 nm, a total acid content of 500 μmol (Pyridine) / g, an external surface acid content of 210 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 4wt% Ni-4wt% W. Catalyst B uses a molecular sieve carrier with an MTW structure, which is ZSM-12. The molecular sieve has a grain size of 5.0 μm, a total acid content of 400 μmol (Pyridine) / g, an external surface acid content of 100 μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 14wt% Ni-4wt% Co. The two were loaded in the manner of B on top and A on the bottom, with a loading volume ratio of 3:1. During the reaction, the raw materials flowed from B to A. The reaction conditions were 363°C, 3.5 MPa, and a space velocity of 1.2 h -1 , hydrogen-to-oil ratio 500; the hydrotreating reactor uses a hydrotreating catalyst T, which is 14wt% Ni-3wt% Co / ASA, and the reaction conditions are 225℃, 12MPa, and a space velocity of 1.0h -1 , hydrogen to oil ratio 700. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts C and D. Catalyst C uses SAPO-41 molecular sieve carrier, the molecular sieve crystal particle size is 600nm, the total acid content is 800μmol (Pyridine) / g, the external surface acid content is 140μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5wt% Pt; catalyst D uses ZSM-12 molecular sieve carrier, the molecular sieve crystal particle size is 400nm, the total acid content is 600μmol (Pyridine) / g, the external surface acid content is 200μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5wt% Pd. The two are loaded in the manner of C on top and D on the bottom, with a loading volume ratio of 1:3. During the reaction, the raw material flows from C to D, and the reaction conditions are 335℃, 4.5MPa, and an air velocity of 1.5h -1 , hydrogen-to-oil ratio 700; the hydrotreating reactor uses a hydrotreating catalyst T, which is 16wt% Ni-5wt% Mo / ASA, and the reaction conditions are 215℃, 12MPa, and a space velocity of 1.2h -1 , hydrogen to oil ratio 800. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts C and D. Catalyst C uses SAPO-41 molecular sieve carrier, the molecular sieve crystal particle size is 600nm, the total acid content is 800μmol (Pyridine) / g, the external surface acid content is 140μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5wt% Pt; catalyst D uses ZSM-12 molecular sieve carrier, the molecular sieve crystal particle size is 400nm, the total acid content is 600μmol (Pyridine) / g, the external surface acid content is 200μmol (2,6-Di-tert-butylpyridine) / g, and the metal loading is 0.5wt% Pd. The two are loaded in the manner of C on top and D on the bottom, with a loading volume ratio of 1:2. During the reaction, the raw material flows from C to D, and the reaction conditions are 328°C, 3.6MPa, and an air velocity of 1.2h -1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 5wt% Ni-4wt% W / ASA, and the reaction conditions are 232°C, 10MPa, and a space velocity of 2.1h -1 , hydrogen to oil ratio 500. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts E and F. The E catalyst uses SAPO-11 molecular sieve as a carrier, the molecular sieve crystal particle size is 120nm, the total acid content is 650μmol (Pyridine) / g, the external surface acid content is 230μmol (2,6-Di-tert-butylpyridine) / g, and the catalyst is loaded with 0.5wt% Pd; the F catalyst uses ZSM-22 molecular sieve as a carrier, the molecular sieve crystal particle size is 2.3μm, the total acid content is 300μmol (Pyridine) / g, the external surface acid content is 20μmol (2,6-Di-tert-butylpyridine) / g, and the catalyst is loaded with 0.5wt% Pt. The two are loaded in the manner of E on top and F on the bottom, with a loading volume ratio of 1:2. During the reaction, the raw materials flow from E to F, and the reaction conditions are 328℃, 3.6MPa, and an air velocity of 1.2h -1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 5wt% Ni-4wt% W / ASA, and the reaction conditions are 232°C, 10MPa, and a space velocity of 2.1h -1 , hydrogen to oil ratio 500. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts G and H. Catalyst G uses CoAPO-31 (heteroatom Co content is 1.5wt%) molecular sieve as a carrier. The molecular sieve has a grain size of 100nm, a total acid amount of 420μmol (Pyridine) / g, an external surface acid amount of 180μmol (2,6-Di-tert-butylpyridine) / g, and a precious metal content of 0.4wt% Pt. Catalyst H uses Fe-ZSM-35 (heteroatom Fe content is 2.5wt%) molecular sieve with a FER structure as a carrier. The molecular sieve has a grain size of 2.0μm, a total acid amount of 280μmol (Pyridine) / g, an external surface acid amount of 50μmol (2,6-Di-tert-butylpyridine) / g, and a precious metal content of 0.4wt% Pd. The filling method of the two is G on top and H on bottom, with a filling volume ratio of 1:2. During the reaction, the raw materials flow from G to H. The reaction conditions are 328℃, 3.6MPa, and a space velocity of 1.2h -1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 5wt% Ni-4wt% W / ASA, and the reaction conditions are 232°C, 10MPa, and a space velocity of 2.1h -1, hydrogen to oil ratio 500. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts I and J. Catalyst I uses a heteroatom aluminum phosphate molecular sieve carrier with an AEL structure, which is ZnAPO-11 (the heteroatom Zn content is 1.0wt%), the molecular sieve has a grain size of 80nm, a total acid amount of 500μmol (Pyridine) / g, an external surface acid amount of 150μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 0.5wt% Pt; Catalyst J uses a heteroatom aluminum silicate molecular sieve carrier with an MTT structure, which is Ni-ZSM-23 (the heteroatom Ni content is 2.0wt%), the molecular sieve has a grain size of 1μm, a total acid amount of 300μmol (Pyridine) / g, an external surface acid amount of 60μmol (2,6-Di-tert-butylpyridine) / g, and a metal loading of 0.4wt% Pd. The two were loaded in the manner of I on top and J on the bottom, with a loading volume ratio of 1:2. During the reaction, the raw materials flowed from I to J. The reaction conditions were 328°C, 3.6 MPa, and a space velocity of 1.2 h -1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 5wt% Ni-4wt% W / ASA, and the reaction conditions are 232°C, 10MPa, and a space velocity of 2.1h -1 , hydrogen to oil ratio 500. The product yields obtained after the raw materials were converted and fractionated through the 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 reactor uses hydroisomerization catalysts K and L. Catalyst K uses a molecular sieve carrier with an AFI structure, which is SAPO-5. The molecular sieve has a particle size of 50nm, a total acid content of 780μmol (Pyridine) / g, an external surface acid content of 280μmol (2,6-Di-tert-butylpyridine) / g, and a precious metal content of 0.4wt% Pd. Catalyst L uses a molecular sieve carrier with a *MRE structure, which is ZSM-48. The molecular sieve has a particle size of 4.5μm, a total acid content of 560μmol (Pyridine) / g, an external surface acid content of 80μmol (2,6-Di-tert-butylpyridine) / g, and a precious metal content of 0.3wt% Pt. The two are loaded in a manner of K on top and L on the bottom, with a loading volume ratio of 1:2. During the reaction, the raw material flows from K through L. The reaction conditions are 328°C, 3.6MPa, and an air velocity of 1.2h-1 , hydrogen-to-oil ratio 600; the hydrotreating reactor uses a hydrotreating catalyst T, which is 5wt% Ni-4wt% W / ASA, and the reaction conditions are 232°C, 10MPa, and a space velocity of 2.1h -1 , hydrogen to oil ratio 500. The product yields obtained after the raw materials were converted and fractionated through the reaction process are shown in Table 2, and the properties of the base oil products are shown in Table 3.

[0074] As shown in Table 2, compared with the comparative example, the base oil yield is significantly improved by the method of the present invention, the yield of light hydrocarbons and diesel of lower value byproducts is significantly reduced, and the unconverted Fischer-Tropsch wax remaining in the product is less, and the narrow-range Fischer-Tropsch wax component is completely and efficiently converted. At the same time, as shown in Table 3, compared with the comparative example, the base oil obtained by the method of the present invention has a higher viscosity index and a lower pour point.

[0075] Table 1 Properties of narrow distillation range Fischer-Tropsch wax feedstock oil

[0076] project raw material <![CDATA[Density (25 °C), kg / m 3 > 819 <![CDATA[Kinematic viscosity (100 °C), mm 2 / s]]> 5.3 Sulfur content, μg / g 1.8 Nitrogen content, μg / g <1.0 Oxygen content, μg / g <1.0 Distillation range, ℃ Initial distillation point 322 10％ 352 30％ 388 50％ 426 70％ 463 90％ 524 95％ 569 Final distillation point 575 Normal alkane content, wt% 96.7

[0077] Table 2 Product yield

[0078]

[0079] Table 3 Base oil product properties

[0080]

Claims

1. A method for processing a Fischer-Tropsch wax lubricating oil base oil having a narrow distillation range and a normal alkane content of not less than 90 wt % using a hydrogenation catalyst composition, characterized in that: The hydrogenation catalyst composition includes a hydroisomerization catalyst composition and a hydrorefining catalyst; the hydroisomerization catalyst composition is composed of catalyst A and catalyst B in a volume ratio of 1:10 to 10:1; Catalyst A is composed of a one-dimensional ten-membered ring elliptical pore SAPO-41 molecular sieve carrier and supported Ni and / or W metal; Catalyst B is composed of a one-dimensional twelve-membered ring elliptical pore ZSM-12 molecular sieve carrier and one or more metals of Ni, Co, and W loaded; The hydrotreating catalyst is composed of an amorphous silicon-aluminum carrier and one or more of Ni, Co, Mo, and W; The method is carried out according to the following steps: 1) The narrow-range Fischer-Tropsch wax feedstock oil and hydrogen are mixed into the hydroisomerization zone, and a hydroisomerization reaction is carried out on the hydroisomerization catalyst composition to complete the hydroisomerization of the Fischer-Tropsch wax feedstock oil and obtain hydroisomerized oil. The hydroisomerization catalyst composition is catalyst A on top and catalyst B on the bottom. When the catalyst is used, the reactant first contacts catalyst A and then contacts catalyst B. 2) The hydroisomerized oil obtained in step 1) enters the hydrorefining zone, and further hydrogenation saturation of the hydroisomerized oil is completed on the hydrorefining catalyst to obtain a crude product; 3) The crude product obtained in step 2) enters an atmospheric pressure tower or a vacuum tower for fractionation to obtain gasoline, diesel and base oil.

2. The method according to claim 1, characterized in that The SAPO-41 molecular sieve is a nano molecular sieve, and its crystal particle size is 80-300 nm; the ZSM-12 molecular sieve is a micron molecular sieve, and its crystal particle size is 4-8 μm.

3. The method according to claim 1, characterized in that The mass loading of Ni and / or W metal in Catalyst A is 3wt% to 10wt%, and the mass loading of one or more metals among Ni, Co, and W in Catalyst B is 10wt% to 20wt%.

4. The method according to claim 1 or 2, characterized in that: The total acid content of the SAPO-41 molecular sieve is 300-700 μmol pyridine / g, and the external surface acid content is 150-300 μmol 2,6-di-tert-butylpyridine / g.

5. The method according to claim 1 or 2, characterized in that: The total acid content of the ZSM-12 molecular sieve is 200-500 μmol pyridine / g, and the external surface acid content is 0-150 μmol 2,6-di-tert-butylpyridine / g.

6. The method according to claim 1, characterized in that In the hydrotreating catalyst, the mass loading of one or more of Ni, Co, Mo and W is 12wt% to 25wt%.

7. The method according to claim 1, characterized in that Catalyst A and catalyst B are composed in a volume ratio of 1:5 to 5:

1.

8. The method according to claim 1, characterized in that The narrow-range Fischer-Tropsch wax feedstock oil has an initial distillation point of not less than 320°C and not more than 380°C, a final distillation point of not more than 580°C and not less than 480°C, a normal alkane content of not less than 90wt%, a sulfur content of not more than 5μg / g, a nitrogen content of not more than 5μg / g, and an oxygen content of not more than 10μg / g.

9. The method according to claim 1, characterized in that: The reaction temperature of the hydroisomerization zone is 300°C to 420°C, the hydrogen partial pressure is 1.0MPa to 5.0MPa, and the volumetric space velocity of the feedstock is 0.5h -1 Until 3h -1 , the hydrogen-to-oil ratio is 200:1 to 1000:1; the reaction temperature of the hydrotreating zone is 200°C to 320°C, the hydrogen partial pressure is 5.0MPa to 12MPa, and the volume space velocity of the hydroisomerized oil is 0.5h -1 Until 3h -1 , the hydrogen-to-oil ratio is 500:1 to 2000:1.

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