Hydroisomerization catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalysis, and particularly discloses a hydroisomerization catalyst as well as a preparation method and application thereof. The hydroisomerization catalyst is prepared from the following components in parts by weight: 97.5 to 99.4 parts of molecular sieve carrier and 0.5 to 1.5 parts of oxide containing active metal, 0.1 to 1.0 part of an oxide of a metal containing an auxiliary agent; the molecular sieve carrier is synthesized by adopting a double-template agent; in the oxide containing the active metal, the active metal is selected from one or more of a platinum-palladium combination, a molybdenum-tungsten combination and a nickel-cobalt combination; in the oxide containing the additive metal, the additive metal is cerium; the preparation method comprises the following steps: co-impregnating the molecular sieve carrier with a salt solution containing the active metal and the additive metal, drying, and performing hydrogen reduction to obtain the hydroisomerization catalyst. When the hydroisomerization catalysis is applied, the conversion rate, the selectivity and the water-oxygen tolerance are synergistically considered and improved, and the overall application effect and the service life are remarkably improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalysis technology, more particularly, it relates to a hydroisomerization catalyst and a preparation method and application thereof. BACKGROUND

[0002] The hydroisomerization catalyst refers to a catalyst capable of catalyzing the hydroisomerization reaction of petroleum hydrocarbon molecules. It acts on the carbon-carbon double bond and carbon-carbon triple bond in the petroleum hydrocarbon raw material under high temperature and high pressure together with a hydrogenation agent (such as hydrogen) to break and recombine, forming relatively symmetrical and shorter chain isomerized hydrocarbons, thereby improving the octane rating of the fuel. At the same time, the hydroisomerization catalyst can also degrade toxic and harmful substances such as benzene, alcohol and ether in the reaction, reducing harmful substance emissions in vehicle exhaust.

[0003] The hydroisomerization catalyst is usually composed of a metal active component (such as platinum group metal) and an acidic carrier (such as molecular sieve), which realizes the conversion of straight-chain alkanes to branched-chain alkanes through synergistic effect; wherein, in the application process, the metal active site adsorbs hydrogen molecules and dissociates into hydrogen atoms to participate in the hydrogenation reaction, while the acidic carrier (such as molecular sieve) provides acid catalytic sites to promote carbon chain breaking and branch generation, and optimize the performance of the oil product.

[0004] At present, biodiesel is a long-chain fatty acid monoalkyl ester renewable fuel prepared by transesterification reaction with plant oil, animal fat or waste oil as raw material; biojet fuel is a clean aviation fuel prepared by hydrogenation deoxidization, isomerization and other processes with renewable resources such as catering waste oil and animal and plant oil; both have excellent environmental performance, fuel performance close to petrochemical diesel, and wide raw material sources and renewable, so they are widely used, and the hydroisomerization catalyst is also applied to biodiesel and biojet fuel.

[0005] The existing hydroisomerization catalysts generally have the problem of insufficient selectivity of active sites, which leads to high amount of by-product generation, affects the hydrogen partial pressure stability and catalyst activity, and the water and oxygen tolerance is also not good, which easily causes the activity retention rate to decrease when the raw material contains water, so it is difficult to realize the conversion rate, selectivity and water and oxygen tolerance of biodiesel and biojet fuel, and at present, a scheme is urgently needed to solve the above technical problems. SUMMARY

[0006] In order to realize the conversion rate, selectivity and water and oxygen tolerance of the hydroisomerization catalyst, the present application provides a hydroisomerization catalyst.

[0007] In the first aspect, the present application provides a hydroisomerization catalyst, which adopts the following technical scheme: A hydroisomerization catalyst, comprising the following components by weight: Molecular sieve carrier 97.5-99.4 parts; active metal-containing oxide 0.5-1.5 parts; auxiliary metal-containing oxide 0.1-1.0 parts; The molecular sieve carrier is synthesized by using double templates; In the active metal-containing oxide, the active metal is selected from one or a combination of platinum-palladium combination, molybdenum-tungsten combination and nickel-cobalt combination. In the auxiliary metal-containing oxide, the auxiliary metal is cerium.

[0008] By using the above technical solution, the synthesis of the molecular sieve carrier by using double templates can accurately control the pore topological structure of the molecular sieve, forming a hierarchical meso-microporous system, in which the mesopore accelerates the diffusion of long-chain alkanes, the micropore provides isomerization active sites, and can promote the catalytic effect of the pore mouth and inhibit the cracking side reaction. In the active metal-containing oxide, the active metal is selected from platinum-palladium combination, which can enhance the dehydrogenation / hydrogenation ability and has high electron transfer efficiency; the active metal is selected from molybdenum-tungsten combination, which can form a sulfide active phase and has strong anti-carbon deposition ability; the active metal is selected from nickel-cobalt combination, which is a low-cost scheme of non-noble metal but can synergize with the acid center of the molecular sieve. In the auxiliary metal-containing oxide, the auxiliary metal is cerium, which can capture active metal electrons by using the oxygen vacancies of its oxide, improve the intrinsic hydrogenation activity of the metal site, buffer oxygen impact and reduce acid center hydrolysis, and maintain the stability of the catalyst. In this way, the hydrogen isomerization catalyst containing the above components achieves a synergistic improvement in conversion rate, selectivity and water-oxygen resistance when applied, and significantly enhances the overall application effect and service life.

[0009] Preferably, the active metal is composed of the following components by weight: platinum-palladium combination 0.4-0.8 parts; molybdenum-tungsten combination 0.3-0.6 parts; nickel-cobalt combination 0.1-0.4 parts.

[0010] By using the above technical solution, platinum-palladium combination, molybdenum-tungsten combination and nickel-cobalt combination are used as active metals according to the above weight parts. In the process, platinum and palladium form a rich electron structure to promote hydrogen molecule dissociation and adsorption; molybdenum and tungsten provide strong hydrogenation active sites and are bonded to the molecular sieve framework oxygen to bring about framework anchoring; nickel and cobalt reduce the isomerization activation energy and accelerate the hydrogenation stability of carbonium ions to reduce cracking byproducts; through the ternary synergy of platinum-palladium combination, molybdenum-tungsten combination and nickel-cobalt combination, a complex system of "platinum-palladium activation-molybdenum-tungsten sulfur resistance-nickel-cobalt diffusion optimization" is formed, bringing about a comprehensive improvement in conversion rate, selectivity and water-oxygen resistance, and a hydrogen isomerization catalyst with better quality can be obtained.

[0011] Preferably, the platinum-palladium combination is composed of platinum and palladium in a weight ratio of (0.9-1.1):1. The molybdenum-tungsten combination is composed of molybdenum and tungsten in a weight ratio of (2.8-3.2):1. The nickel-cobalt combination is composed of nickel and cobalt in a weight ratio of (1.8-2.2):1.

[0012] By adopting the above technical solution, the platinum-palladium combination mainly drives rapid dehydrogenation, the molybdenum-tungsten combination mainly ensures sulfur stability, and the nickel-cobalt combination mainly inhibits cracking side reactions. In addition to the above excellent effects, the platinum-palladium combination, the molybdenum-tungsten combination and the nickel-cobalt combination composed of the above raw materials can achieve conversion-selectivity balance, inhibit oxygen adsorption, capture free oxygen and reduce active site oxidation, thereby exhibiting better water-oxygen tolerance mechanism, so that the hydroisomerization catalyst performs better in conversion, selectivity and water-oxygen tolerance.

[0013] Preferably, the molecular sieve carrier is prepared by the following steps: The silicon source, the aluminum source and the double template agent are dissolved in water, the pH is adjusted to 10-11, and then hydrothermal crystallization treatment is performed, followed by washing, drying and calcination to obtain the molecular sieve carrier.

[0014] By adopting the above technical solution, the double template agent generates mesopores or micropores in the crystallization process in the above preparation process, constructs the pore structure, and provides isomerization active sites; and adjusting the pH to 10-11 can promote the polycondensation of silicate and aluminate, and stabilize the silicate-aluminate colloid. In the subsequent hydrothermal crystallization treatment process, the double template agent is bonded with the framework to form a network of through mesopores or micropores, realizing precise design of the carrier pore structure and acid sites, and thus obtaining a molecular sieve carrier with better quality.

[0015] Preferably, the temperature of the hydrothermal crystallization treatment is 160-180℃, and the time is 68-76h; the calcination temperature is 540-560℃, and the calcination time is 5-6h.

[0016] By adopting the above technical solution, the silicate-aluminate polycondensation rate can be significantly slowed down at 160-180℃, avoiding the generation of sodalite and other impurities, and the time of 68-76h allows the double template agent to fully penetrate the gel network and form intercrystalline pores with concentrated pore size distribution; finally, using a calcination temperature of 540-560℃ and a calcination time of 5-6h can completely carbonize and remove the double template agent, and avoid pore collapse, thereby obtaining a stable molecular sieve carrier with excellent quality.

[0017] Preferably, the double template agent is composed of C6H 14 Br2 and TEAOH in a molar ratio of 1:(2-4).

[0018] By adopting the above technical solution, the above ratio can make TEAOH fully neutralize C6H 14 H+ , maintain the basic environment of pH = 10-11, guarantee the condensation rate of silicon and aluminum and the purity of crystals, and inhibit excessive expansion of the pore, maintain the mechanical strength of the skeleton, and make the pore connectivity optimal, thereby precisely regulating the pore structure and acid site distribution of the molecular sieve carrier through synergistic effect, and obtaining a molecular sieve carrier with better reference quality.

[0019] Preferably, after the hydrothermal crystallization treatment is completed, the NH4Cl ion exchange is used to convert it into H type; wherein the concentration of the NH4Cl solution used is 0.4-0.6 mol / L, the temperature is 55-65℃, and the time is 1.8-2.2h.

[0020] By using the above technical solution, NH4 + By ion exchange, Na + in the molecular sieve skeleton is replaced by NH4 + , which is decomposed into H 2 after calcination, forming B acid sites and directly improving the catalytic activity, and can inhibit the dealumination of the skeleton; and the concentration of the above NH4Cl solution and the selection of temperature and time can realize the synergistic optimization of kinetics and stability, guarantee the exchange depth and acid stability control, and be beneficial to precisely regulating the proton replacement efficiency and skeleton stability, realizing the efficient construction of molecular sieve acid sites and the protection of structural integrity.

[0021] Preferably, the molecular sieve carrier has three-dimensional ten-membered ring cross-pore, which is 0.54*0.56 nm straight channel and 0.52*0.58 nm Z-shaped channel, the specific surface area is 150-230 m 2 / g, and the total acid amount is 0.9-2.8 mmol / g.

[0022] By using the above technical solution, the straight channel reduces the diffusion resistance of linear molecules, improves the mass transfer efficiency of reactants, the Z-shaped channel separates isomer molecules through curved pore, enhances the selectivity of products, and the local enlarged cavity is formed at the cross of the pore, which concentrates strong acid sites and becomes the key catalytic active center; at the same time, through the control of the specific surface area and the total acid amount, the acid site exposure density can be increased, the acid strength and distribution can be optimized, and the excellent catalytic performance can be guaranteed.

[0023] In the second aspect, the application provides a preparation method of a hydroisomerization catalyst, which adopts the following technical solution: A preparation method of a hydroisomerization catalyst, comprising the following steps: (1) preparing raw materials including a molecular sieve carrier and a salt solution containing active metal and auxiliary metal according to the preparation requirements; (2) co-impregnating the salt solution containing active metal and auxiliary metal in the molecular sieve carrier, drying, and hydrogen reduction to obtain a hydroisomerization catalyst.

[0024] In a third aspect, the application provides a use of the hydroisomerization catalyst in production of biodiesel and biojet fuel.

[0025] In summary, the application has the following beneficial effects: The application uses a specially prepared molecular sieve carrier, platinum-palladium combination, molybdenum-tungsten combination and nickel-cobalt combination as active metals, and cooperates with the auxiliary metal, so that the obtained hydroisomerization catalyst can realize the synergistic consideration and improvement of conversion rate, selectivity and water oxygen resistance in application, and significantly enhances the overall application effect and service life. DETAILED DESCRIPTION

[0026] The application will be further described in detail below in combination with preparation examples, examples and comparative examples.

[0027] The raw materials used in the preparation examples, examples and comparative examples of the application are commercially available, except for special instructions.

[0028] The silicon source is silica sol, in which the content of SiO2 is 40 wt%; The aluminum source is sodium aluminate; The salt solution containing platinum metal is H2PtCl6 solution; The salt solution containing palladium metal is Pd(NO3)2 solution; The salt solution containing molybdenum metal is (NH4)2MoO4 solution; The salt solution containing tungsten metal is ammonium metatungstate solution; The salt solution containing nickel metal is Ni(NO3)2 solution; The salt solution containing cobalt metal is Co(NO3)2 solution; The salt solution containing cerium metal is Ce(NO3)3 solution.

[0029] Preparation examples of raw materials and / or intermediates Preparation example 1 A molecular sieve carrier is prepared by the following steps: The silicon source, aluminum source and double template are dissolved in water, and the pH is adjusted to 10-11 with ammonia water, and then hydrothermal crystallization treatment is performed, and then the molecular sieve carrier is obtained after washing, drying and calcination.

[0030] Note: The molar ratio of SiO2 and Al2O3 in the molecular sieve carrier is 40. The amount of double template is 12% of the total weight of silicon source and aluminum source. The temperature of hydrothermal crystallization treatment is 170℃, and the time is 72h; the calcination temperature is 550℃, and the calcination time is 5.5h. The double template is C6H 14Br2and TEAOH were composed in a molar ratio of 1:3. The molecular sieve carrier had three-dimensional ten-membered ring cross-pore channels, 0.54*0.56 nm straight channels and 0.52*0.58 nm Z-shaped channels, and a specific surface area of 190 m 2 / g, and a total acid amount of 1.85 mmol / g.

[0031] Preparation Example 2 A molecular sieve carrier, which was different from that of Preparation Example 1 in that the temperature of the hydrothermal crystallization treatment was 160℃, and the time was 76h; the calcination temperature was 540℃, and the calcination time was 6h.

[0032] Preparation Example 3 A molecular sieve carrier, which was different from that of Preparation Example 1 in that the temperature of the hydrothermal crystallization treatment was 180℃, and the time was 68h; the calcination temperature was 560℃, and the calcination time was 5h.

[0033] Preparation Example 4 A molecular sieve carrier, which was different from that of Preparation Example 1 in that the double template agent was composed of C6H 14 Br2and TEAOH were composed in a molar ratio of 1:2.

[0034] Preparation Example 5 A molecular sieve carrier, which was different from that of Preparation Example 1 in that the double template agent was composed of C6H 14 Br2and TEAOH were composed in a molar ratio of 1:4.

[0035] Preparation Example 6 A molecular sieve carrier, which was different from that of Preparation Example 1 in that the molecular sieve carrier had three-dimensional ten-membered ring cross-pore channels, 0.54*0.56 nm straight channels and 0.52*0.58 nm Z-shaped channels, and a specific surface area of 150 m 2 / g, and a total acid amount of 0.9 mmol / g.

[0036] Preparation Example 7 A molecular sieve carrier, which was different from that of Preparation Example 1 in that the molecular sieve carrier had three-dimensional ten-membered ring cross-pore channels, 0.54*0.56 nm straight channels and 0.52*0.58 nm Z-shaped channels, and a specific surface area of 230 m 2 / g, and a total acid amount of 2.8 mmol / g.

[0037] Preparation Example 8 A molecular sieve carrier, which was different from that of Preparation Example 1 in that, after the hydrothermal crystallization treatment was completed, ion exchange with NH4Cl was performed to convert it into an H type; wherein the concentration of the NH4Cl solution used was 0.5 mol / L, the temperature was 60℃, and the time was 2h.

[0038] Preparation Example 9 A molecular sieve carrier, which is different from Preparation Example 1 in that, after the hydrothermal crystallization treatment is completed, it is converted into H type through NH4Cl ion exchange; wherein the concentration of the NH4Cl solution used is 0.4 mol / L, the temperature is 55℃, and the time is 2.2h.

[0039] Preparation Example 10 A molecular sieve carrier, which is different from Preparation Example 1 in that, after the hydrothermal crystallization treatment is completed, it is converted into H type through NH4Cl ion exchange; wherein the concentration of the NH4Cl solution used is 0.6 mol / L, the temperature is 65℃, and the time is 1.8h.

[0040] Example 1 A hydroisomerization catalyst, the components contained therein and their corresponding weight parts are shown in Table 1, and is prepared by the following steps: (1) preparing raw materials containing a molecular sieve carrier, a salt solution containing active metal and auxiliary metal agent according to the preparation needs; (2) equal volume impregnation, co-impregnating the salt solution containing active metal and auxiliary metal agent in the molecular sieve carrier, single salt solution impregnation for 50 min, vacuum degassing treatment (-0.08 MPa, 30 min) is carried out between the steps of impregnation, followed by drying at 120℃ for 6h and hydrogen reduction at 400℃ for 4h to obtain a hydroisomerization catalyst.

[0041] Note: the molecular sieve carrier is obtained in Preparation Example 1; in the oxide containing active metal, the raw materials used and their corresponding weight parts are shown in Table 2, wherein the platinum-palladium combination is composed of platinum and palladium in a weight ratio of 1:1, the molybdenum-tungsten combination is composed of molybdenum and tungsten in a weight ratio of 3:1, and the nickel-cobalt combination is composed of nickel and cobalt in a weight ratio of 2:1. In the oxide containing auxiliary metal, the auxiliary metal is cerium.

[0042] Examples 2-3 A hydroisomerization catalyst, which is different from Example 1 in that the components contained therein and their corresponding weight parts are shown in Table 1.

[0043] Table 1 Components contained in Examples 1-3 and their corresponding weight parts (parts / kg)

[0044] Examples 4-5 A hydroisomerization catalyst, which is different from Example 1 in that the raw materials used for active metal composition and their corresponding weight parts are shown in Table 2.

[0045] Table 2 Raw materials used for active metal composition in Examples 1, 4-5 and their corresponding weight parts (parts / kg)

[0046] Example 6 A hydroisomerization catalyst, differing from Example 1 in that the platinum-palladium combination consists of platinum and palladium in a weight ratio of 0.9:1, the molybdenum-tungsten combination consists of molybdenum and tungsten in a weight ratio of 2.8:1, and the nickel-cobalt combination consists of nickel and cobalt in a weight ratio of 2.2:1.

[0047] Example 7 A hydroisomerization catalyst, differing from Example 1 in that the platinum-palladium combination consists of platinum and palladium in a weight ratio of 1.1:1, the molybdenum-tungsten combination consists of molybdenum and tungsten in a weight ratio of 3.2:1, and the nickel-cobalt combination consists of nickel and cobalt in a weight ratio of 2.2:1.

[0048] Example 8 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 2.

[0049] Example 9 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 3.

[0050] Example 10 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 4.

[0051] Example 11 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 5.

[0052] Example 12 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 6.

[0053] Example 13 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 7.

[0054] Example 14 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 8.

[0055] Example 15 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 9.

[0056] Example 16 A hydroisomerization catalyst, differing from Example 1 in that the molecular sieve support is obtained in Preparatory Example 10.

[0057] Example 17 A hydroisomerization catalyst, different from Example 1, is that the combination of platinum and palladium is not used in the active metal.

[0058] Example 18 A hydroisomerization catalyst, different from Example 1, is that the combination of molybdenum and tungsten is not used in the active metal.

[0059] Example 19 A hydroisomerization catalyst, different from Example 1, is that the combination of nickel and cobalt is not used in the active metal.

[0060] Example 20 A hydroisomerization catalyst, different from Example 1, is that the combination of platinum and palladium, the combination of nickel and cobalt is not used in the active metal.

[0061] Example 21 A hydroisomerization catalyst, different from Example 1, is that the combination of platinum and palladium, the combination of molybdenum and tungsten is not used in the active metal.

[0062] Example 22 A hydroisomerization catalyst, different from Example 1, is that the combination of molybdenum and tungsten, the combination of nickel and cobalt is not used in the active metal.

[0063] Comparative Example 1 A hydroisomerization catalyst, different from Example 1, is that the component does not contain an oxide containing a promoter metal.

[0064] Comparative Example 2 A hydroisomerization catalyst, different from Example 1, is that the molecular sieve carrier uses ZSM-5 as the carrier.

[0065] Comparative Example 3 A hydroisomerization catalyst, different from Example 1, is that a commercial Ni / Al2O3 catalyst is selected, which is purchased from Shandong Dengzhuo Chemical Co., Ltd., with the product number DC-2.

[0066] Performance detection test Test sample: The hydroisomerization catalysts obtained in Examples 1-22 are selected as test samples 1-22, and the hydroisomerization catalysts obtained in Comparative Examples 1-3 are selected as control samples 1-3.

[0067] Test method: The hydroisomerization catalysts are tested for application, and the reaction conditions are as follows: The raw oil is waste catering oil (acid value 5.6 mgKOH / g, water content 2000 ppm, oxygen content 8.5 wt%); The mass ratio of catalyst to raw oil is 1:120; The reaction conditions were a temperature of 320°C, a pressure of 4.5 MPa, a hydrogen to oil ratio of 800:1, and a space velocity of 2 h⁻¹.

[0068] (1) Conversion test / selectivity test: GC-MS analysis (ASTM D7798); (2) Water-oxygen resistance test: activity retention rate (%) after cyclic injection of water (5000 ppm) / oxygen (5 vol%); (3) Life test: deactivation rate (%) for 1000 h of continuous operation at 340°C; After the above tests were performed on the test samples 1-22 and the control sample 1-3, the test results were correspondingly recorded in Table 3.

[0069] Table 3 Test results of test samples 1-22 and control sample 1-3

[0070] In combination with Example 1 and Comparative Examples 1-3 and in combination with Table 3, it can be seen that, by using the specially prepared molecular sieve carrier, the platinum-palladium combination, the molybdenum-tungsten combination and the nickel-cobalt combination as the active metal, and in combination with the auxiliary metal, the obtained hydrogen isomerization catalyst can realize the synergistic consideration and promotion of conversion rate, selectivity and water-oxygen resistance in application, and brings significant enhancement in overall application effect and service life. If the auxiliary metal is not used or the molecular sieve carrier is replaced by ZSM-5 as the carrier, it is found that the conversion rate (%), selectivity (%), activity retention rate (%) and 1000 h deactivation rate (%) obtained by the above tests are all greatly lost. It is also found that the hydrogen isomerization catalyst obtained in the present application has greater improvement in the above product performance compared with the commercially available catalyst.

[0071] In combination with Example 1 and Examples 14-16 and in combination with Table 3, it can be seen that, after the hydrothermal crystallization treatment is completed, the H-type is converted by NH4Cl ion exchange in the preparation of the molecular sieve carrier, which can precisely control the proton replacement efficiency and the skeleton stability, realize the efficient construction of the molecular sieve acid site and the protection of the structural integrity, and thus the hydrogen isomerization catalyst prepared has improved performance in conversion rate (%), selectivity (%), activity retention rate (%) and 1000 h deactivation rate (%).

[0072] It can be seen from the combination of Embodiment 1 and Embodiments 17-22 and Table 3 that the platinum-palladium combination, the molybdenum-tungsten combination and the nickel-cobalt combination are applied as active metals in the above weight parts, can form a complex action system of "platinum-palladium activation-molybdenum-tungsten sulfur resistance-nickel-cobalt diffusion optimization", and can obtain a hydrogen isomerization catalyst with better quality; if any one or two of the platinum-palladium combination, the molybdenum-tungsten combination and the nickel-cobalt combination is applied as active metals, it is found that the corresponding effect brought by them is far inferior to the corresponding effect brought by the synergy of the three; it can be seen that the ternary synergy of the platinum-palladium combination, the molybdenum-tungsten combination and the nickel-cobalt combination can ensure that the hydrogen isomerization catalyst finally obtained can realize the synergistic consideration and improvement of conversion rate, selectivity and water oxygen resistance when applied, and can bring significant enhancement in service life.

[0073] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A hydroisomerization catalyst, characterized in that Contains the following components in parts by weight: Molecular sieve carrier 97.5-99.4 parts; Containing 0.5-1.5 parts of active metal oxide; Contains 0.1-1.0 parts of oxide of auxiliary metal; The molecular sieve carrier is synthesized using a dual template agent; The active metal in the active metal oxide is selected from one or more of a platinum-palladium combination, a molybdenum-tungsten combination, and a nickel-cobalt combination; In the oxide containing a promoter metal, the promoter metal is cerium.

2. The hydroisomerization catalyst according to claim 1, characterized in that: The active metal is composed of the following components in parts by weight: 0.4-0.8 parts of platinum-palladium combination; ‌Molybdenum-tungsten combination 0.3-0.6 parts; Nickel-cobalt combination 0.1-0.4 parts.

3. The hydroisomerization catalyst according to claim 1, characterized in that: The platinum-palladium combination consists of platinum and palladium in a weight ratio of (0.9-1.1):1; The molybdenum-tungsten combination consists of molybdenum and tungsten in a weight ratio of (2.8-3.2):1; The nickel-cobalt combination consists of nickel and cobalt in a weight ratio of (1.8-2.2):

1.

4. The hydroisomerization catalyst according to claim 1, characterized in that: The molecular sieve carrier is prepared by the following steps: The silicon source, the aluminum source and the dual template agent are dissolved in water, the pH is adjusted to 10-11, and then a hydrothermal crystallization treatment is performed. The molecular sieve carrier is obtained after washing, drying and calcining.

5. The hydroisomerization catalyst according to claim 4, characterized in that: The temperature of the hydrothermal crystallization treatment is 160-180° C., and the time is 68-76 hours; the calcination temperature is 540-560° C., and the calcination time is 5-6 hours.

6. The hydroisomerization catalyst according to claim 4, characterized in that: The dual template agent is composed of C6H 14 Br2 and TEAOH are composed in a molar ratio of 1:(2-4).

7. The hydroisomerization catalyst according to claim 4, characterized in that: After the hydrothermal crystallization treatment is completed, it is converted into the H-type through NH4Cl ion exchange; wherein the concentration of the NH4Cl solution used is 0.4-0.6 mol / L‌, the temperature is 55-65°C, and the time is 1.8-2.2h.

8. The hydroisomerization catalyst according to claim 1, characterized in that: The molecular sieve carrier has a three-dimensional ten-membered ring cross channel, which is a 0.54×0.56 nm straight channel and a 0.52×0.58 nm zigzag channel, with a specific surface area of ​​150-230 m 2 / g, and the total acid content is 0.9-2.8 mmol / g.

9. The method for preparing the hydroisomerization catalyst according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) preparing raw materials including a molecular sieve support, a salt solution containing an active metal and a promoter metal as required; (2) The salt solution containing the active metal and the auxiliary metal is co-impregnated into the molecular sieve carrier, and then reduced with hydrogen after drying to obtain a hydrogenation isomerization catalyst.

10. Use of the hydroisomerization catalyst according to any one of claims 1 to 8 in the production of biodiesel and bio-jet fuel.

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