Hydroisomerization catalyst as well as preparation method and application thereof

Abstract

The invention discloses a hydroisomerization catalyst and a preparation method and application thereof, and relates to the technical field of catalysts, the hydroisomerization catalyst comprises the following components by weight: 80-90 parts of an MOF-molecular sieve composite carrier, 1.0-2.5 parts of a Ni-Pt-Pd-rare earth multi-metal active component, and 0.2-1.0 part of a composite additive; the molar ratio of Ge to Sn to Ta in the compound additive is 1: (0.8-1.2): (0.1-0.3); the molar ratio of Ni to Pt to Pd to rare earth in the Ni-Pt-Pd-rare earth multi-metal active component is (3-5): 1: 1: (0.1-0.2). The hydroisomerization catalyst is high in catalytic performance, excellent in stability and simple in preparation process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, in particular to a hydroisomerization catalyst and a preparation method and application thereof. BACKGROUND

[0002] Isomerized alkanes have the advantages of low pour point, high VI, good oxidation stability, etc., and are the core component of high-quality lubricating oil base oil. They are usually made by hydroisomerization of long-chain n-alkanes. With the increasing demand for high-quality oil products, higher requirements are placed on the performance of hydroisomerization catalysts.

[0003] Currently, hydroisomerization catalysts mostly use molecular sieves as carriers and load noble metals such as Pt and Pd as active components. However, due to the unreasonable distribution of acid sites of traditional molecular sieves, excessive cracking and other side reactions are easily triggered during the reaction process, reducing the selectivity of the target product. The pore diameter of traditional microporous molecular sieves is close to that of long-chain alkanes, resulting in large diffusion resistance of alkanes in the pores and easy occurrence of secondary cracking. Although such traditional hydroisomerization catalysts have a large loading amount of active components, they have poor dispersibility and are prone to sintering (metal particle growth at high temperatures), resulting in a shortened catalyst life. In addition, the hydroisomerization catalysts on the market also have the problem of poor stability to varying degrees. When processing raw materials containing impurities such as sulfur, nitrogen, and oxygen, the active metals are prone to poisoning or agglomeration. In particular, when there is a small amount of water in the raw material, the hydrolysis of the molecular sieve framework is intensified, leading to the collapse of its pore structure.

[0004] In order to solve the above problems, a hydroisomerization catalyst and a preparation method and application thereof are disclosed in a Chinese patent with the authorization publication number CN115672392B. The hydroisomerization catalyst uses aluminum phosphate molecular sieves as carriers and Group VIII noble metals as active components. The micropores of the hydroisomerization catalyst are filled with carbon deposits, and the carbon deposit content is 0.5-4wt% of the catalyst weight. The medium-strong acid amount of the hydroisomerization catalyst is greater than 0.6mmol / g. The preparation method of the hydroisomerization catalyst is as follows: first, dry the aluminum phosphate molecular sieves containing a template to remove the adsorbed free water; then, perform partial oxidation template removal treatment under an ozone atmosphere and at 80-200℃ to carbonize the template and form carbon deposits filled in part of the micropore channels of the molecular sieves; then, load metal active components on the obtained molecular sieve carrier, and obtain the target catalyst through drying and low-temperature reduction. By controlling the atmosphere and temperature of the molecular sieve carrier oxidation template removal, as well as the reduction temperature and reduction gas flow rate, the effective regulation of the molecular sieve channel depth and acidity is achieved. However, this catalyst has the contradiction between micropore plugging and acidity regulation and selectivity, and in addition, the noble metal stability is poor and the preparation process is complex.

[0005] It can be seen that the hydrogenation isomerization catalyst with high catalytic performance, excellent stability and simple preparation process, the preparation method and application thereof meet the market demand, have wide market value and application prospect, and have very important significance for promoting the development of the field of hydrogenation isomerization catalysts. SUMMARY

[0006] The main purpose of the present application is to provide a hydrogenation isomerization catalyst with high catalytic performance, excellent stability and simple preparation process, and a preparation method and application thereof.

[0007] To achieve the above purpose, the present application provides a hydrogenation isomerization catalyst, which comprises the following components in parts by weight: MOF-molecular sieve composite carrier 80-90 parts, Ni-Pt-Pd-rare earth multi-metal active ingredient 1.0-2.5 parts, and composite additive 0.2-1.0 parts; the molar ratio of Ge, Sn and Ta in the composite additive is 1:(0.8-1.2):(0.1-0.3); the molar ratio of Ni, Pt, Pd and rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is (3-5):1:1:(0.1-0.2).

[0008] Preferably, the rare earth is at least one of La, Ce and Pr.

[0009] Another purpose of the present application is to provide a preparation method of the hydrogenation isomerization catalyst, comprising the following steps: Step S1, synthesis of the composite carrier: phosphoric acid, pseudo-boehmite and silica sol are added to deionized water, and magnetic stirring is performed for 30-60 minutes to obtain a SAPO-11 precursor; ZrCl4·8H2O and terephthalic acid are uniformly mixed to obtain a mixture; the SAPO-11 precursor is mixed with the mixture, and a microwave reactor is added, and microwave irradiation is performed at 158-162℃ for 28-32 minutes, and after cooling, filtration, washing and drying at 100℃ for 5-7 hours, a Zr-MOF / SAPO-11 composite carrier is obtained; Step S2, metal loading: an equal volume impregnation method is used, the composite carrier is immersed in a mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, rare earth nitrate, GeCl4, Sn(NO3)4 and ethanol tantalum, stirring is performed at 78-82℃ for 2-4 hours, then drying is performed at 118-125℃ for 4-6 hours, then it is placed in a muffle furnace and heated to 480-520℃ at a heating rate of 4-6℃ / min, and heat preservation is performed for 3-4 hours under anaerobic roasting, and finally hydrogen reduction is performed at 330-370℃ for 2-4 hours to obtain the hydrogenation isomerization catalyst.

[0010] Preferably, the molar ratio of the orthophosphoric acid, pseudo-boehmite, silica sol and deionized water in step S1 is 1:0.8:0.15:(6-8).

[0011] Preferably, the molar ratio of the ZrCl4·8H2O and terephthalic acid in step S1 is 1:1.

[0012] Preferably, the mass ratio of the SAPO-11 precursor and the mixture in step S1 is 3:1.

[0013] Preferably, the power of the microwave radiation in step S1 is 600-800W, and the pH value is controlled to be 4.5-5.0.

[0014] Preferably, the concentration of Ni(NO3)2·6H2O in the mixed solution in step S2 is 0.1mol / L, and the concentration of GeCl4 is 0.01mol / L.

[0015] Preferably, the oxygen-free roasting in step S2 is roasting under an inert gas atmosphere, and the inert gas is selected from any one of nitrogen, argon and helium.

[0016] Still another object of the present application is to provide an application of the hydrogenation isomerization catalyst in the n-alkane hydrogenation isomerization reaction, and the reaction conditions of the reaction are as follows: the temperature is 300-350℃, the pressure is 3-6MPa, the hydrogen / oil ratio is (500-1200):1, the liquid hourly space velocity is 0.5-2h-1, and the reaction time is 1-3h. 10 -C 20 n-alkane hydrogenation isomerization reaction, and the reaction conditions of the reaction are as follows: the temperature is 300-350℃, the pressure is 3-6MPa, the hydrogen / oil ratio is (500-1200):1, the liquid hourly space velocity is 0.5-2h -1 .

[0017] Due to the use of the above technical solutions, the present application has the following beneficial effects: (1) The preparation method of the hydrogenation isomerization catalyst disclosed by the present application has simple preparation process, convenient operation control, low dependence on equipment, high preparation efficiency and product qualification rate, is suitable for continuous large-scale production, and has high popularization and application value.

[0018] (2) The hydrogenation isomerization catalyst disclosed in the application comprises the following components in parts by weight: MOF-molecular sieve composite carrier 80-90 parts, Ni-Pt-Pd-rare earth multi-metal active ingredient 1.0-2.5 parts, and composite additive 0.2-1.0 part. The molar ratio of Ge, Sn and Ta in the composite additive is 1:(0.8-1.2):(0.1-0.3). The molar ratio of Ni, Pt, Pd and rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is (3-5):1:1:(0.1-0.2). Through mutual cooperation between the components, the catalyst has high catalytic performance and excellent stability. The MOF material has high specific surface area and open framework structure, which is complementary to the acid sites of the molecular sieve. The mesoporous network of the MOF can shorten the mass transfer path and reduce the diffusion resistance of long-chain alkanes in the micropores, while the micropores of the molecular sieve provide high-concentration acid sites to promote isomerization. The unsaturated metal nodes of the MOF can anchor noble metal nanoparticles to inhibit sintering and improve the stability of the active ingredient.

[0019] (3) The hydrogenation isomerization catalyst disclosed in the application, Ni as the main hydrogenation active site, can quickly activate H2 molecules to provide hydrogen source for isomerization. The difference in the d-band electronic structure of Pt and Pd can optimize the adsorption energy of intermediates and promote the isomerization path. The rare earth stabilizes the metal particles through electrostatic interaction and adjusts the carrier acidity. The redox ability of the rare earth element can promote the oxidation and elimination of carbon deposition precursors. In addition, the electronic synergistic effect of the Ni-Pt-Pd alloy can weaken the adsorption strength of strong adsorption species such as aromatics and reduce carbon deposition. Ge and Sn as electronic additives can change the d-band electronic structure of noble metals through alloying, enhance the activation ability of H2, and inhibit cracking reactions. The addition of Ta further optimizes the isomerization path by introducing strong Lewis acid sites. The synergistic effect of Sn and Ge can form an "electronic buffer layer" to reduce the adsorption of carbon deposition precursors on the metal surface. The high melting and oxidation resistance of Ta can enhance the stability of the catalyst at high temperatures and inhibit metal particle coarsening.

[0020] (4) The hydrogenation isomerization catalyst disclosed in the application has higher catalytic performance and more excellent stability through reasonable selection of preparation process parameters. DETAILED DESCRIPTION

[0021] The following description is used to disclose the application so that those skilled in the art can implement the application. The preferred embodiments in the following description are only as examples, and other obvious modifications can be conceived by those skilled in the art. Example 1

[0022] A hydroisomerization catalyst, comprising the following components in parts by weight: 90 parts of MOF-molecular sieve composite carrier, 1.0 parts of Ni-Pt-Pd-rare earth multi-metal active ingredient, and 0.2 parts of composite additive; the molar ratio of Ge, Sn, and Ta in the composite additive is 1:0.8:0.1; the molar ratio of Ni, Pt, Pd, and rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is 3:1:1:0.1; and the rare earth is La.

[0023] A preparation method of the hydroisomerization catalyst, comprising the following steps: Step S1, synthesis of the composite carrier: phosphoric acid, pseudo-boehmite, and silica sol are added to deionized water, and magnetic stirring is performed for 30 minutes to obtain a SAPO-11 precursor; ZrCl4·8H2O and terephthalic acid are uniformly mixed to obtain a mixture; the SAPO-11 precursor and the mixture are mixed, and a microwave reactor is used for microwave irradiation at 158℃ for 28 minutes; after cooling, filtration, washing, and drying at 100℃ for 5 hours, a Zr-MOF / SAPO-11 composite carrier is obtained; Step S2, metal loading: an equal-volume impregnation method is used, the composite carrier is immersed in a mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, a rare earth nitrate, GeCl4, Sn(NO3)4, and ethanol tantalum, stirring is performed at 78℃ for 2 hours, then drying is performed at 118℃ for 4 hours, then heating is performed in a muffle furnace at a heating rate of 4℃ / min to 480℃, and then the temperature is maintained for 3 hours of anaerobic calcination, and finally hydrogen reduction is performed at 330℃ for 2 hours, to obtain the hydroisomerization catalyst.

[0024] In step S1, the molar ratio of the phosphoric acid, pseudo-boehmite, silica sol, and deionized water is 1:0.8:0.15:6; in step S1, the molar ratio of the ZrCl4·8H2O and terephthalic acid is 1:1; in step S1, the mass ratio of the SAPO-11 precursor and the mixture is 3:1; and in step S1, the power of the microwave irradiation is 600W, and the pH value is controlled to be 4.5.

[0025] In step S2, the concentration of Ni(NO3)2·6H2O in the mixed solution is 0.1mol / L; the concentration of GeCl4 is 0.01mol / L; in step S2, the anaerobic calcination is calcination in an inert gas atmosphere; and the inert gas is nitrogen. Example 2

[0026] A kind of hydroisomerization catalyst, by weight parts, including the following components: MOF-molecular sieve composite carrier 88 parts, Ni-Pt-Pd-rare earth multi-metal active ingredient 1.5 parts, composite adjuvant 0.4 parts;The molar ratio of Ge, Sn, Ta in the composite adjuvant is 1:0.9:0.15;The molar ratio of Ni, Pt, Pd, rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is 3.5:1:1:0.13;The rare earth is Ce.

[0027] A kind of preparation method of the hydroisomerization catalyst, comprising the following steps: Step S1, the synthesis of composite carrier: orthophosphoric acid, pseudoboehmite, silica sol are added to deionized water, magnetic stirring for 40 minutes, to obtain SAPO-11 precursor;ZrCl4·8H2O, terephthalic acid are mixed uniformly, to obtain a mixture;SAPO-11 precursor and the mixture are mixed, added to microwave reactor, microwave irradiation at 159 ℃ for 29 minutes, after cooling, filtration, washing, drying at 100 ℃ for 5.5 hours, to obtain Zr-MOF / SAPO-11 composite carrier; Step S2, metal loading: using equal volume impregnation method, the composite carrier is immersed in mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, rare earth nitrate, GeCl4, Sn(NO3)4, ethanol tantalum, stirring at 79 ℃ for 2.5 hours, then drying at 120 ℃ for 4.5 hours, then placed in muffle furnace with a heating rate of 4.5 ℃ / min to 490 ℃, and then kept at 490 ℃ for 3.2 hours without oxygen roasting, finally hydrogen reduction at 340 ℃ for 2.5 hours, to obtain the hydroisomerization catalyst.

[0028] The molar ratio of orthophosphoric acid, pseudoboehmite, silica sol and deionized water in step S1 is 1:0.8:0.15:6.5;The molar ratio of ZrCl4·8H2O and terephthalic acid in step S1 is 1:1;The mass ratio of SAPO-11 precursor and the mixture in step S1 is 3:1;The power of microwave irradiation in step S1 is 650 W, and the pH value is controlled at 4.7.

[0029] The concentration of Ni(NO3)2·6H2O in the mixed solution in step S2 is 0.1 mol / L;The concentration of GeCl4 is 0.01 mol / L;The oxygen-free roasting in step S2 is roasting in inert gas atmosphere;The inert gas is argon. Example 3

[0030] A hydroisomerization catalyst, comprising the following components in parts by weight: 85 parts of MOF-molecular sieve composite carrier, 1.8 parts of Ni-Pt-Pd-rare earth multi-metal active ingredient, and 0.6 parts of composite additive; the molar ratio of Ge, Sn, and Ta in the composite additive is 1:1:0.2; the molar ratio of Ni, Pt, Pd, and rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is 4:1:1:0.15; and the rare earth is Pr.

[0031] A preparation method of the hydroisomerization catalyst, comprising the following steps: Step S1, synthesis of the composite carrier: phosphoric acid, pseudo-boehmite, and silica sol are added to deionized water, and magnetic stirring is performed for 45 minutes to obtain a SAPO-11 precursor; ZrCl4·8H2O and terephthalic acid are uniformly mixed to obtain a mixture; the SAPO-11 precursor and the mixture are mixed, and a microwave reactor is used for microwave irradiation at 160℃ for 30 minutes; after cooling, filtration, washing, and drying at 100℃ for 6 hours, a Zr-MOF / SAPO-11 composite carrier is obtained; Step S2, metal loading: an equal-volume impregnation method is used, the composite carrier is immersed in a mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, a rare earth nitrate, GeCl4, Sn(NO3)4, and ethanol tantalum, stirring is performed at 80℃ for 3 hours, followed by drying at 121℃ for 5 hours, then heating to 500℃ at a heating rate of 5℃ / min in a muffle furnace, and keeping the temperature for 3.5 hours of oxygen-free calcination, and finally hydrogen reduction at 350℃ for 3 hours to obtain the hydroisomerization catalyst.

[0032] In step S1, the molar ratio of the phosphoric acid, pseudo-boehmite, silica sol, and deionized water is 1:0.8:0.15:7; in step S1, the molar ratio of the ZrCl4·8H2O and terephthalic acid is 1:1; in step S1, the mass ratio of the SAPO-11 precursor and the mixture is 3:1; and in step S1, the power of the microwave irradiation is 700W, and the pH value is controlled to be 4.8.

[0033] In step S2, the concentration of Ni(NO3)2·6H2O in the mixed solution is 0.1mol / L; the concentration of GeCl4 is 0.01mol / L; the oxygen-free calcination in step S2 is calcination in an inert gas atmosphere; and the inert gas is helium. Example 4

[0034] A hydroisomerization catalyst, comprising the following components in parts by weight: 83 parts of MOF-molecular sieve composite carrier, 2.3 parts of Ni-Pt-Pd-rare earth multi-metal active ingredient, and 0.9 parts of composite additive; the molar ratio of Ge, Sn, and Ta in the composite additive is 1:1.1:0.25; the molar ratio of Ni, Pt, Pd, and rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is 4.5:1:1:0.18; and the rare earth is La.

[0035] A preparation method of the hydroisomerization catalyst, comprising the following steps: Step S1, synthesis of the composite carrier: orthophosphoric acid, pseudoboehmite, and silica sol are added to deionized water, and magnetic stirring is performed for 50 minutes to obtain a SAPO-11 precursor; ZrCl4·8H2O and terephthalic acid are uniformly mixed to obtain a mixture; the SAPO-11 precursor and the mixture are mixed, and a microwave reactor is used for microwave irradiation at 161℃ for 31 minutes; after cooling, filtration, washing, and drying at 100℃ for 6.5 hours, a Zr-MOF / SAPO-11 composite carrier is obtained; Step S2, metal loading: an equal-volume impregnation method is used, the composite carrier is immersed in a mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, a rare earth nitrate, GeCl4, Sn(NO3)4, and ethanol tantalum, stirring is performed at 81℃ for 3.5 hours, followed by drying at 123℃ for 5.5 hours, then heating to 510℃ at a heating rate of 5.5℃ / min in a muffle furnace, and then annealing under an oxygen-free atmosphere for 3.8 hours, and finally hydrogen reduction at 365℃ for 3.5 hours to obtain the hydroisomerization catalyst.

[0036] In step S1, the molar ratio of the orthophosphoric acid, pseudoboehmite, silica sol, and deionized water is 1:0.8:0.15:7.5; in step S1, the molar ratio of the ZrCl4·8H2O and terephthalic acid is 1:1; in step S1, the mass ratio of the SAPO-11 precursor and the mixture is 3:1; and in step S1, the power of the microwave irradiation is 750W, and the pH value is controlled to be 4.9.

[0037] In step S2, the concentration of Ni(NO3)2·6H2O in the mixed solution is 0.1mol / L; the concentration of GeCl4 is 0.01mol / L; in step S2, the oxygen-free annealing is annealing under an inert gas atmosphere; and the inert gas is nitrogen. Example 5

[0038] A hydroisomerization catalyst, comprising the following components in parts by weight: 80 parts of MOF-molecular sieve composite carrier, 2.5 parts of Ni-Pt-Pd-rare earth multi-metal active ingredient, and 1.0 part of composite additive; the molar ratio of Ge, Sn and Ta in the composite additive is 1:1.2:0.3; the molar ratio of Ni, Pt, Pd and rare earth in the Ni-Pt-Pd-rare earth multi-metal active ingredient is 5:1:1:0.2; and the rare earth is Ce.

[0039] A preparation method of the hydroisomerization catalyst, comprising the following steps: Step S1, synthesis of the composite carrier: phosphoric acid, pseudo-boehmite and silica sol are added to deionized water, and magnetic stirring is performed for 60 minutes to obtain a SAPO-11 precursor; ZrCl4·8H2O and terephthalic acid are uniformly mixed to obtain a mixture; the SAPO-11 precursor and the mixture are mixed, and a microwave reactor is used for microwave irradiation at 162℃ for 32 minutes, and then filtration, washing and drying at 100℃ for 7 hours are performed to obtain a Zr-MOF / SAPO-11 composite carrier; Step S2, metal loading: an equal-volume impregnation method is used to immerse the composite carrier in a mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, rare earth nitrate, GeCl4, Sn(NO3)4 and ethanol tantalum, stirring is performed at 82℃ for 4 hours, followed by drying at 125℃ for 6 hours, then heating to 520℃ at a heating rate of 6℃ / min in a muffle furnace, and then annealing for 4 hours under oxygen-free roasting, and finally hydrogen reduction at 370℃ for 4 hours to obtain the hydroisomerization catalyst.

[0040] In step S1, the molar ratio of the phosphoric acid, pseudo-boehmite, silica sol and deionized water is 1:0.8:0.15:8; in step S1, the molar ratio of the ZrCl4·8H2O and terephthalic acid is 1:1; in step S1, the mass ratio of the SAPO-11 precursor and the mixture is 3:1; and in step S1, the power of the microwave irradiation is 800W, and the pH value is controlled to be 5.0.

[0041] In step S2, the concentration of Ni(NO3)2·6H2O in the mixed solution is 0.1mol / L; the concentration of GeCl4 is 0.01mol / L; the oxygen-free roasting in step S2 is roasting under an inert gas atmosphere; and the inert gas is nitrogen.

[0042] Comparative Example 1 A hydroisomerization catalyst and a preparation method thereof, which are basically the same as those of Example 1, except that an equal amount of SAPO-11 molecular sieve is used to replace the MOF-molecular sieve composite carrier, and an equal amount of Sn is used to replace Ta.

[0043] Comparative Example 2 A hydroisomerization catalyst and a preparation method thereof, which are substantially the same as those of Example 1, except that an equal amount of Ta is used to replace Sn; and an equal amount of Pd is used to replace the rare earth.

[0044] To further illustrate the beneficial technical effects of the hydroisomerization catalysts involved in the embodiments of the present application, the hydroisomerization catalysts involved in Examples 1-5 and Comparative Examples 1-2 are subjected to relevant performance tests, and the test results are shown in Table 1, and the test methods are as follows: n-dodecane (purity ≥ 99%, National Pharmaceutical Group) is used as a raw material, and the reaction conditions are: a fixed bed reactor, 320℃, 4MPa, hydrogen / oil ratio 800:1, liquid hourly space velocity 1.5h-1. -1 The conversion rate, isomerization selectivity, cracking rate and stability are counted and calculated; the conversion rate (%) = (n-dodecane content in the raw material - n-dodecane content in the product) / n-dodecane content in the raw material × 100%; the isomerization selectivity (%) = (isomeric alkanes content in the product) / (n-dodecane content in the raw material - n-dodecane content in the product) × 100%; the cracking rate (%) = (C 11 and the following hydrocarbons content in the product) / (n-dodecane content in the raw material - n-dodecane content in the product) × 100%; the stability: after continuous reaction for 100 hours, sample analysis is performed every 20 hours, and the activity retention rate (final conversion rate / initial conversion rate × 100%) is calculated.

[0045] As can be seen from Table 1, the hydroisomerization catalysts disclosed in the embodiments of the present application have more excellent catalytic performance than the products of the comparative examples; the combination of the MOF-molecular sieve composite carrier, Sn, Ta, Pd and the rare earth is beneficial to improving the above-mentioned performance.

[0046] Table 1 Item Conversion Isomerization selectivity Cracking rate Stability Unit % % % % Example 1 94.5 88.3 2.5 98.1 Example 2 95.2 88.7 2.2 98.5 Example 3 95.7 90.0 2.0 99.1 Example 4 96.0 90.8 1.7 99.3 Example 5 96.6 91.3 1.2 99.5 Comparative Example 1 88.7 79.1 7.8 77.6 Comparative Example 2 91.3 81.0 6.0 80.9 The above shows and describes the basic principles, main features and advantages of the present application. It should be understood by those skilled in the art that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection claimed by the present application is defined by the appended claims and their equivalents.

Claims

1. A hydroisomerization catalyst, characterized in that, The product comprises the following components by weight: 80-90 parts of MOF-molecular sieve composite carrier, 1.0-2.5 parts of Ni-Pt-Pd-rare earth polymetallic active ingredient, and 0.2-1.0 parts of composite additive; the molar ratio of Ge, Sn, and Ta in the composite additive is 1:(0.8-1.2):(0.1-0.3); the molar ratio of Ni, Pt, Pd, and rare earth in the Ni-Pt-Pd-rare earth polymetallic active ingredient is (3-5):1:1:(0.1-0.2).

2. The hydroisomerization catalyst according to claim 1, characterized in that, The rare earth element is at least one of La, Ce, and Pr.

3. A method for preparing a hydroisomerization catalyst according to any one of claims 1-2, characterized in that, Includes the following steps: Step S1, Synthesis of the composite support: Phosphoric acid, boehmite, and silica sol were added to deionized water and magnetically stirred for 30-60 minutes to obtain the SAPO-11 precursor; ZrCl4·8H2O and terephthalic acid were mixed evenly to obtain a mixture; the SAPO-11 precursor was mixed with the mixture and added to a microwave reactor, and microwave irradiated at 158-162℃ for 28-32 minutes. After cooling, the mixture was filtered, washed, and dried at 100℃ for 5-7 hours to obtain the Zr-MOF / SAPO-11 composite support. Step S2, Metal Support: Using the equal-volume impregnation method, the composite support is immersed in a mixed solution containing Ni(NO3)2·6H2O, H2PtCl6·6H2O, Pd(NO3)2·2H2O, rare earth nitrates, GeCl4, Sn(NO3)4, and tantalum ethoxide. The mixture is stirred at 78-82℃ for 2-4 hours, then dried at 118-125℃ for 4-6 hours. Subsequently, it is placed in a muffle furnace and heated to 480-520℃ at a heating rate of 4-6℃ / min, and calcined in an oxygen-free environment for 3-4 hours. Finally, it is reduced with hydrogen at 330-370℃ for 2-4 hours to obtain the hydroisomerization catalyst.

4. The method for preparing the hydroisomerization catalyst according to claim 3, characterized in that, The molar ratio of orthophosphoric acid, boehmite, silica sol, and deionized water in step S1 is 1:0.8:0.15:(6-8).

5. The method for preparing the hydroisomerization catalyst according to claim 3, characterized in that, The molar ratio of ZrCl4·8H2O and terephthalic acid in step S1 is 1:

1.

6. The method for preparing the hydroisomerization catalyst according to claim 3, characterized in that, The mass ratio of SAPO-11 precursor to mixture in step S1 is 3:

1.

7. The method for preparing the hydroisomerization catalyst according to claim 3, characterized in that, The power of the microwave radiation in step S1 is 600-800W, and the pH value is controlled at 4.5-5.

0.

8. The method for preparing the hydroisomerization catalyst according to claim 3, characterized in that, In step S2, the concentration of Ni(NO3)2·6H2O in the mixed solution is 0.1 mol / L; the concentration of GeCl4 is 0.01 mol / L.

9. The method for preparing the hydroisomerization catalyst according to claim 3, characterized in that, The oxygen-free calcination in step S2 is calcination under an inert gas atmosphere; the inert gas is selected from any one of nitrogen, argon, and helium.

10. A hydroisomerization catalyst according to any one of claims 1-2 at C 10 -C 20 Its application in the hydroisomerization reaction of n-alkanes is characterized by, The reaction conditions are: temperature 300-350℃, pressure 3-6 MPa, hydrogen-to-oil ratio (500-1200):1, and liquid hourly space velocity (LHSV) 0.5-2 h⁻¹. -1 .