Superacid carrier and preparation method therefor, and isomerization catalyst and preparation method therefor

Abstract

The present invention relates to the technical field of catalysts, and relates to a superacid carrier and a preparation method therefor, and an isomerization catalyst and a preparation method therefor. On the basis of the total dry weight of the superacid carrier, the superacid carrier comprises the following components in percentage by weight: 45%-88% of a main component, 5%-20% of a first additive component, 1%-10% of a second additive component, 1%-10% of a third additive component, and 5%-15% of a fourth additive component. The main component is ZrO2-SO4 2-; the first additive component is AlPO4; the second additive component is SAPO-34 molecular sieve; the third additive component is phosphotungstomolybdic acid; and the fourth additive component is pseudoboehmite. The superacid carrier provided by the present invention has high stability, strong acidity, and large specific surface area, thereby improving the activity and selectivity of the catalyst, and increasing the yield of isomerization products.

Description

A superacid support and its preparation method, and an isomerization catalyst and its preparation method. Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a superacid support and its preparation method, and an isomerization catalyst and its preparation method. Background Technology

[0002] The current global trend towards cleaner fuels is towards lower sulfur, olefin, aromatic, and benzene content in gasoline, and lower sulfur, olefin, and aromatic content (mainly polycyclic aromatic hydrocarbons), lower density, and higher cetane number in diesel. Currently, gasoline in my country is primarily composed of FCC (Fluid Catalytic Cracking) gasoline, followed by reformed gasoline, and finally MTBE (methyl tert-butyl ether) and alkylated oils. Due to the high olefin and sulfur content and uneven octane number distribution in gasoline components, it is necessary to adjust the gasoline composition. Isomerized oil components, due to their absence of olefins, aromatics, and sulfur, high octane number, and low vapor pressure, are ideal blending components for clean gasoline. In conclusion, the catalytic isomerization process for light alkanes has broad application prospects in the future.

[0003] Isomerization is an exothermic reaction, and low temperatures favor the forward reaction. Under low-temperature conditions, it is necessary to improve the isomerization performance of the catalyst, i.e., the acidity of the catalyst. Current isomerization processes use bifunctional catalysts of metal and acid, under hydrogen-containing conditions, to improve isomerization efficiency while suppressing side reactions. Currently, there are three main types of catalysts used industrially. The first type is the Pt-Al₂O₃-Cl low-temperature catalyst. This catalyst has strong acidity and a low isomerization reaction temperature, resulting in a high yield of isomeric alkanes. However, this type of catalyst requires continuous chlorination to maintain its catalytic activity. The chlorination process causes corrosion of the equipment and environmental pollution. Furthermore, this type of catalyst is very sensitive to the content of water and sulfur, requiring strict control over the water and sulfur content of the feedstock, essentially requiring the feedstock to be free of water and sulfur. The second type is a modified medium-temperature catalyst supported on zeolite. Due to the low acidity of zeolite materials, the isomerization reaction needs to be carried out at a higher temperature. Due to thermodynamic limitations, isomerization catalytic activity is relatively low. However, these catalysts have the advantage of being somewhat tolerant of sulfur and water in the feedstock and not corroding reaction equipment. The third type is sulfur-resistant catalysts supported by solid superacids. These catalysts have advantages such as strong acidity, no need for chlorine injection during the reaction process, safe operation, low equipment requirements, and low pollution, and have been widely used.

[0004] A Japanese energy company filed a US patent application, US6326328, disclosing a type of SO4. 2-The preparation method of ZrO2 solid acid catalyst showed that the catalyst had low activity and isomerism.

[0005] US Patent 5157199 describes the catalyst as SO4. 2- / ZrO2 is used in the hydroisomerization reaction of C4-C6 straight-chain alkanes.

[0006] US Patent 3032599 and European Patent 0174836 also describe the use of SO4 2- / ZrO2 is used as a catalyst for the hydroisomerization of C4-C6 straight-chain alkanes.

[0007] US Patent 6080904 describes a method for the hydroisomerization of straight-chain alkanes. The catalyst used is Pt-WO3 / ZrO2.

[0008] In summary, the emergence of solid superacid isomerization catalysts, with their wide range of applications and advantages such as water and sulfur resistance, has gradually replaced low-temperature Pt-Al₂O₃-Cl catalysts and modified medium-temperature catalysts supported on zeolites. However, the low isomerization performance of solid superacid catalysts still requires further improvement.

[0009] Summary of the Invention

[0010] To address the above problems, this invention provides a superacid support and its preparation method, as well as an isomerization catalyst and its preparation method.

[0011] In a first aspect, the present invention provides a superacid carrier, wherein, based on the total dry weight of the superacid carrier, the superacid carrier comprises the following components in weight fractions: main component: 45% to 88%, first additive component: 5% to 20%, second additive component: 1% to 10%, third additive component: 1% to 10%, and fourth additive component: 5% to 15%.

[0012] The main components are: ZrO2-SO4 2- ;

[0013] First added component: AlPO4;

[0014] The second added component: SAPO-34 molecular sieve;

[0015] The third additive component: phosphotungstic molybdenum heteropoly acid;

[0016] The fourth additive component: pseudoboehmite.

[0017] Furthermore, the specific surface area of ​​the superacid carrier is 5 m². 2 / g~300m 2 / g.

[0018] Furthermore, the pore size range of the superacid carrier is 5 nm to 40 nm.

[0019] In a second aspect, the present invention provides a method for preparing the superacid support according to any one of the first aspects, the preparation method comprising the following steps:

[0020] The main component, the first additive component, the second additive component, the third additive component, and the fourth additive component are added to a kneader in proportion for the first kneading to obtain a mixture.

[0021] A second kneading process is performed by adding an aqueous nitric acid solution to the mixture to obtain a clinker.

[0022] The clinker is added to an extruder for extrusion molding, and then dried and calcined to obtain the super acid carrier.

[0023] Further, the weight ratio of the mixture to the nitric acid aqueous solution is (90-92):(10-8); the weight percentage of nitric acid in the nitric acid aqueous solution is 35-40%; the working parameters for the first kneading include: kneading time 20-50 min; the working parameters for the second kneading include: kneading time 20-40 min; the working parameters for the drying include: drying at 80-120℃ for 6-12 hours; the working parameters for the calcination include: calcination treatment at 400-800℃ for 4-16 hours.

[0024] Thirdly, the present invention provides an isomerization catalyst, wherein, based on the total dry weight of the isomerization catalyst, the isomerization catalyst comprises the following components in weight percentage: core component 0.01% to 5%, first auxiliary agent 0.1% to 10%, second auxiliary agent 0.1% to 10%, third auxiliary agent 0.1% to 10%, and the balance being the superacid support as described in either the first or second aspect;

[0025] The core component is one or a mixture of several of the elements Pd, Pt, Ir, and Rh.

[0026] The first additive is one or a mixture of rare earth metal elements.

[0027] The second additive is one or a mixture of several alkaline earth elements.

[0028] The third auxiliary agent is one or a mixture of several elements from Group VIII.

[0029] Furthermore, the isomerization catalyst contains the metal elements Pd, Pt, Y, Ba, and Co.

[0030] Furthermore, the Pd and Pt are derived from one of the following: metal powders, oxides, halides, sulfates, nitrates, acetates, and oxalates of Pd and Pt elements; the Y is derived from one of the following: yttrium-containing oxides, halides, sulfates, nitrates, acetates, and oxalates; the Ba is derived from one of the following: barium-containing nitrates and barium-containing soluble compounds; and the Co is derived from one of the following: cobalt nitrate, cobalt acetate, cobalt chloride, and soluble compounds.

[0031] Fourthly, the present invention provides a method for preparing the isomerization catalyst according to any one of the third aspects, the preparation method comprising the following steps:

[0032] The superacid carrier was obtained;

[0033] Prepare an aqueous solution containing the core component, the first auxiliary agent, the second auxiliary agent, and the third auxiliary agent;

[0034] The aqueous solution was impregnated onto the superacid support by impregnation, then dried at 80–120°C for 6–12 hours, and then calcined at 450–800°C for 4–16 hours to obtain the isomerization catalyst.

[0035] Fifthly, the present invention provides a method for alkane isomerization, wherein the method uses the isomerization catalyst described in any one of the third and fourth aspects as the catalyst for alkane isomerization, and the operating parameters of the method include: a fixed-bed reactor, a reaction pressure of 1.0–4.0 MPa, a temperature of 160°C–260°C, and a mass hourly space velocity of 1 h⁻¹. -1 ~3h -1 Hydrogen-to-oil molar ratio: 1.0–3.0; by weight percentage, raw material composition: n-butane: 1%, isopentane: 24%, n-pentane: 26%, n-hexane: 9%, isohexane: 40%.

[0036] The technical solutions provided in the embodiments of the present invention have at least the following advantages compared with the prior art:

[0037] This invention provides a superacid support and its preparation method, as well as an isomerization catalyst and its preparation method. The superacid support provided by this invention has the characteristics of support stability, strong acidity, and large specific surface area, which can improve the activity and selectivity of the catalyst and increase the yield of isomerization products. Specifically:

[0038] 1. The composite metal catalyst prepared based on the modified superacid support of the present invention is suitable for fixed-bed process. By using the modified support, the activity and selectivity of the catalyst are improved, and the yield of isomerization products is increased.

[0039] 2. The present invention uses a carrier of a mixture of various materials. The carrier is stable, has strong acidity, and has a large specific surface area, which is conducive to the main reaction of the catalyst and improves the isomerization yield.

[0040] 3. In this invention, rare earth metals are used for modification. The rare earth metal elements are combined with the support to inhibit the aggregation of noble metals and improve the isomerization performance of the catalyst. Attached Figure Description

[0041] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0042] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0043] Figure 1 is a flowchart of the preparation method of the superacid carrier provided in the embodiment of the present invention. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.

[0046] In a first aspect, the present invention provides a superacid carrier, wherein, based on the total dry weight of the superacid carrier, the superacid carrier comprises the following components in weight fractions: main component: 45% to 88%, first additive component: 5% to 20%, second additive component: 1% to 10%, third additive component: 1% to 10%, and fourth additive component: 5% to 15%.

[0047] The main components are: ZrO2-SO4 2- ;

[0048] First added component: AlPO4;

[0049] The second added component: SAPO-34 molecular sieve;

[0050] The third additive component: phosphotungstic molybdenum heteropoly acid;

[0051] The fourth additive component: pseudoboehmite.

[0052] This invention provides a superacid support and its preparation method, as well as an isomerization catalyst and its preparation method. The superacid support provided by this invention has the characteristics of support stability, strong acidity, and large specific surface area, which can improve the activity and selectivity of the catalyst and increase the yield of isomerization products. Specifically:

[0053] 1. The composite metal catalyst prepared based on the modified superacid support of the present invention is suitable for fixed-bed process. By using the modified support, the activity and selectivity of the catalyst are improved, and the yield of isomerization products is increased.

[0054] 2. The present invention uses a carrier of a mixture of various materials. The carrier is stable, has strong acidity, and has a large specific surface area, which is conducive to the main reaction of the catalyst and improves the isomerization yield.

[0055] 3. In this invention, rare earth metals are used for modification. The rare earth metal elements are combined with the support to inhibit the aggregation of noble metals and improve the isomerization performance of the catalyst.

[0056] In some specific embodiments, the specific surface area of ​​the superacid carrier is 5 m². 2 / g~300m 2 / g, preferably 100-200m 2 / g; pore size range is 5nm to 40nm, preferably 8 to 15nm.

[0057] It should be noted that, unless otherwise specified or indicated, all raw materials used in the superacid carriers provided in the embodiments of the present invention can be commercially available products.

[0058] Secondly, based on a general inventive concept, the present invention provides a method for preparing the superacid support according to any one of the first aspects, as shown in Figure 1, the preparation method comprising the following steps:

[0059] The main component, the first additive component, the second additive component, the third additive component, and the fourth additive component are added to a kneader in proportion for the first kneading to obtain a mixture.

[0060] A second kneading process is performed by adding an aqueous nitric acid solution to the mixture to obtain a clinker.

[0061] The clinker is added to an extruder for extrusion molding, and then dried and calcined to obtain the super acid carrier.

[0062] In some specific embodiments, the weight ratio of the mixture to the nitric acid aqueous solution is (90-92):(10-8); the weight percentage of nitric acid in the nitric acid aqueous solution is 35-40%; the working parameters for the first kneading include: kneading time 20-50 min; the working parameters for the second kneading include: kneading time 20-40 min; the working parameters for the drying include: drying at 80-120℃ for 6-12 hours; the working parameters for the calcination include: calcination treatment at 400-800℃ for 4-16 hours.

[0063] Thirdly, the present invention provides an isomerization catalyst, wherein, based on the total dry weight of the isomerization catalyst, the isomerization catalyst comprises the following components in weight percentage: core component 0.01% to 5%, first auxiliary agent 0.1% to 10%, second auxiliary agent 0.1% to 10%, third auxiliary agent 0.1% to 10%, and the balance being the superacid support as described in either the first or second aspect;

[0064] The core component is one or a mixture of several of the elements Pd, Pt, Ir, and Rh.

[0065] The first additive is one or a mixture of rare earth metal elements.

[0066] The second additive is one or a mixture of several alkaline earth elements.

[0067] The third auxiliary agent is one or a mixture of several elements from Group VIII.

[0068] In some specific embodiments, the isomerization catalyst contains the metal elements Pd, Pt, Y, Ba, and Co.

[0069] In some specific embodiments, the Pd and Pt are derived from one of the following: metal powders, oxides, halides, sulfates, nitrates, acetates, and oxalates of Pd and Pt elements; the Y is derived from one of the following: yttrium-containing oxides, halides, sulfates, nitrates, acetates, and oxalates; the Ba is derived from one of the following: barium-containing nitrates and barium-containing soluble compounds; and the Co is derived from one of the following: cobalt nitrate, cobalt acetate, cobalt chloride, and soluble compounds.

[0070] Fourthly, the present invention provides a method for preparing the isomerization catalyst according to any one of the third aspects, the preparation method comprising the following steps:

[0071] The superacid carrier was obtained;

[0072] Prepare an aqueous solution containing the core component, the first auxiliary agent, the second auxiliary agent, and the third auxiliary agent;

[0073] The aqueous solution was impregnated onto the superacid support by impregnation, then dried at 80–120°C for 6–12 hours, and then calcined at 450–800°C for 4–16 hours to obtain the isomerization catalyst.

[0074] Fifthly, the present invention provides a method for alkane isomerization, wherein the method uses the isomerization catalyst described in any one of the third and fourth aspects as the catalyst for alkane isomerization, and the operating parameters of the method include: a fixed-bed reactor, a reaction pressure of 1.0–4.0 MPa, a temperature of 160°C–260°C, and a mass hourly space velocity of 1 h⁻¹. -1 ~3h -1 Hydrogen-to-oil molar ratio: 1.0–3.0; by weight percentage, raw material composition: n-butane: 1%, isopentane: 24%, n-pentane: 26%, n-hexane: 9%, isohexane: 40%.

[0075] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Experimental methods in the following embodiments, unless otherwise specified, are generally performed according to national standards. If no corresponding national standard exists, then generally accepted international standards, conventional conditions, or conditions recommended by the manufacturer are followed.

[0076] Example 1

[0077] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0078] Carrier preparation:

[0079] 700g of ZrO2-SO4 2- The following ingredients were added sequentially to a kneader: 100g AlPO4, 50g SAPO-34, 50g phosphotungstic heteropoly acid, and 100g pseudoboehmite. The kneading time was 20–50 min. Then, 200g of a 35% nitric acid aqueous solution was added, and kneading continued for 20–40 min. The kneaded material was then extruded using an extruder. The extruded strip support was dried at 100℃ for 8 hours, and then calcined at 550℃ for 8 hours to obtain catalyst support 1 with a specific surface area of ​​260 m². 2 / g, strength 128N / cm.

[0080] Catalyst preparation:

[0081] 96.4g of support 1 was placed in a rotary evaporator and evacuated for 2 hours. 0.42g of chloroplatinic acid, 0.17g of palladium dichloride, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the support and evaporated at 2 r / min for 30 min. Excess water was evaporated under vacuum. After the support surface was dry, it was removed and dried at 80℃ for 6 hours, followed by calcination at 600℃ for 8 hours to obtain catalyst A.

[0082] Example 2

[0083] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0084] 96.4g of support 1 was placed in a rotary evaporator and evacuated for 2 hours. 0.63g of chloroplatinic acid, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the support and evaporated at 2 r / min for 30 min. Excess water was evaporated under vacuum. After the surface of the support was dried, it was removed and dried at 80℃ for 6 hours, followed by calcination at 600℃ for 8 hours to obtain catalyst B.

[0085] Example 3

[0086] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0087] Carrier preparation:

[0088] 750g of ZrO2-SO4 2- The following ingredients were added sequentially to a kneader: 50g AlPO4, 50g SAPO-34, 50g phosphotungstic heteropoly acid, and 100g pseudoboehmite. The kneading time was 20–50 min. Then, 180g of a 35% nitric acid aqueous solution was added, and kneading continued for 20–40 min. The kneaded material was then extruded using an extruder. The extruded strip support was dried at 100℃ for 8 hours, and then calcined at 550℃ for 8 hours to obtain catalyst support 2 with a specific surface area of ​​230 m². 2 / g, strength 115N / cm.

[0089] Catalyst preparation:

[0090] 96.4g of support 2 was placed in a rotary evaporator and evacuated for 2 hours. 0.42g of chloroplatinic acid, 0.17g of palladium dichloride, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the support and evaporated at 2 r / min for 30 min. Excess water was evaporated under vacuum. After the support surface was dry, it was removed and dried at 80℃ for 6 hours, followed by calcination at 600℃ for 8 hours to obtain catalyst C.

[0091] Example 4

[0092] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0093] Carrier preparation:

[0094] 96.4g of support 2 was placed in a rotary evaporator and evacuated for 2 hours. 0.63g of chloroplatinic acid, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the support and rotated at 2r / min for 30min. Excess water was evaporated under vacuum. After the surface of the support was dried, it was removed and dried at 80℃ for 6 hours, and then calcined at 600℃ for 8 hours to obtain catalyst D.

[0095] Example 5

[0096] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0097] Carrier preparation:

[0098] 650g of ZrO2-SO4 2- The following ingredients were added sequentially to a kneader: 100g AlPO4, 50g SAPO-34, 50g phosphotungstic heteropoly acid, and 150g pseudoboehmite. The kneading time was 20–50 min. Then, 220g of a 35% nitric acid aqueous solution was added, and kneading continued for 20–40 min. The kneaded material was then extruded using an extruder. The extruded strip support was dried at 100℃ for 8 hours, and then calcined at 550℃ for 8 hours to obtain catalyst support 3 with a specific surface area of ​​300 m². 2 / g, strength 135N / cm.

[0099] Catalyst preparation:

[0100] 96.4g of support 3 was placed in a rotary evaporator and evacuated for 2 hours. 0.42g of chloroplatinic acid, 0.17g of palladium dichloride, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the support and evaporated at 2 r / min for 30 min. Excess water was evaporated under vacuum. After the support surface was dry, it was removed and dried at 80℃ for 6 hours, followed by calcination at 600℃ for 8 hours to obtain catalyst E.

[0101] Example 6

[0102] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0103] Take 96.4g of support 3 and place it in a rotary evaporator flask. Vacuum for 2 hours. Dissolve 0.63g of chloroplatinic acid, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate in 60g of water to prepare a solution. Pour the solution into the rotary evaporator flask containing the support and rotate at 2r / min for 30min. Vacuum evaporate excess water. After the surface of the support is dry, take it out and dry it at 80℃ for 6 hours. Then calcine it at 600℃ for 8 hours to obtain catalyst F.

[0104] Example 7

[0105] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0106] Carrier preparation:

[0107] 550g of ZrO2-SO4 2- The following ingredients were added sequentially to a kneader: 100g AlPO4, 100g SAPO-34, 50g phosphotungstic heteropoly acid, and 150g pseudoboehmite. The kneading time was 20–50 min. Then, 220g of a 35% nitric acid aqueous solution was added, and kneading continued for 20–40 min. The kneaded material was then extruded using an extruder. The extruded strip support was dried at 100℃ for 8 hours, and then calcined at 550℃ for 8 hours to obtain catalyst support 4 with a specific surface area of ​​350 m². 2 / g, strength 150N / cm.

[0108] Catalyst preparation:

[0109] 96.4g of support 4 was placed in a rotary evaporator and evacuated for 2 hours. 0.42g of chloroplatinic acid, 0.17g of palladium dichloride, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the support and evaporated at 2 r / min for 30 min. Excess water was evaporated under vacuum. After the support surface was dry, it was removed and dried at 80℃ for 6 hours, followed by calcination at 600℃ for 8 hours to obtain catalyst G.

[0110] Example 8

[0111] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0112] Take 96.4g of support 4 and place it in a rotary evaporator flask. Vacuum for 2 hours. Dissolve 0.63g of chloroplatinic acid, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate in 60g of water to prepare a solution. Pour the solution into the rotary evaporator flask containing the support and rotate at 2r / min for 30min. Vacuum evaporate excess water. After the surface of the support is dry, take it out and dry it at 80℃ for 6 hours. Then calcine it at 600℃ for 8 hours to obtain catalyst H.

[0113] Comparative Example 1

[0114] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0115] Carrier preparation:

[0116] 700g of ZrO2-SO4 2- The powder and 300g of pseudoboehmite were added sequentially to a kneader for 20-50 minutes. Then, 200g of a 35% nitric acid aqueous solution was added, and kneading continued for 20-40 minutes. The kneaded material was then extruded through an extruder. The extruded strip-shaped carrier was dried at 100℃ for 8 hours, and then calcined at 550℃ for 8 hours to obtain catalyst carrier 5 with a specific surface area of ​​200m². 2 / g, strength 100N / cm.

[0117] Catalyst preparation:

[0118] Take 96.4g of carrier 5 and place it in a rotary evaporator flask. Vacuum for 2 hours. Dissolve 0.42g of chloroplatinic acid, 0.17g of palladium dichloride, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate in 60g of water to prepare a solution. Immerse the solution into the rotary evaporator flask containing the carrier. Rotate at 2r / min for 30min. Vacuum evaporate excess water. After the surface of the carrier is dry, remove it and dry it at 80℃ for 6 hours. Then calcine it at 600℃ for 8 hours to obtain catalyst contrast agent 1.

[0119] Comparative Example 2

[0120] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0121] Carrier preparation:

[0122] 1000g of pseudoboehmite was added sequentially to a kneader for 20-50 minutes. Then, 400g of a 35% nitric acid aqueous solution was added, and kneading continued for 20-40 minutes. The kneaded material was then extruded using an extruder. The extruded strip-shaped support was dried at 100℃ for 8 hours, and then calcined at 550℃ for 8 hours to obtain catalyst support 6 with a specific surface area of ​​180m². 2 / g, strength 80N / cm.

[0123] Catalyst preparation:

[0124] 96.4g of carrier 1 was placed in a rotary evaporator and evacuated for 2 hours. 0.42g of chloroplatinic acid, 0.17g of palladium dichloride, 0.57g of barium nitrate, 3.09g of yttrium nitrate, and 6.31g of cobalt nitrate were dissolved in 60g of water to prepare a solution. The solution was then added to the rotary evaporator containing the carrier and evaporated at 2 r / min for 30 min. Excess water was evaporated under vacuum. After the surface of the carrier was dry, it was removed and dried at 80℃ for 6 hours, followed by calcination at 600℃ for 8 hours to obtain catalyst contrast agent 2.

[0125] Comparative Example 3

[0126] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0127] Take 99.7g of carrier 3 and place it in a rotary evaporator flask. Vacuum for 2 hours. Dissolve 0.42g of chloroplatinic acid and 0.17g of palladium dichloride in 60g of water to prepare a solution. Add the solution to the rotary evaporator flask containing the carrier. Rotate at 2r / min for 30min. Vacuum evaporate excess water. After the surface of the carrier is dry, take it out and dry it at 80℃ for 6 hours. Then calcine it at 600℃ for 8 hours to obtain catalyst contrast agent 3.

[0128] Comparative Example 4

[0129] This example provides an isomerization catalyst, the preparation method of which includes the following steps:

[0130] Take 99.7g of carrier 3 and place it in a rotary evaporation flask. Vacuum for 2 hours. Dissolve 0.63g of chloroplatinic acid in 60g of water to prepare a solution. Add the solution to the rotary evaporation flask containing the carrier. Rotate at 2r / min for 30min. Vacuum evaporate excess water. After the surface of the carrier is dry, take it out and dry it at 80℃ for 6 hours. Then calcine it at 600℃ for 8 hours to obtain catalyst contrast agent 4.

[0131] Test case

[0132] The isomerization catalysts obtained in the examples and comparative examples were used in a fixed-bed reactor at a reaction pressure of 2.5 MPa, a temperature of 180 °C, and a mass hourly space velocity of 1.5 h⁻¹. -1 Hydrogen-to-oil molar ratio: 2.0. Raw material composition: n-Butane: 1%, Isopentane: 24%, n-Pentane: 26%, n-Hexane: 9%, Isopentane: 40%.

[0133] The physicochemical properties of the catalyst are shown in Table 1, and the test data of the isomerization properties of the catalyst are shown in Table 2.

[0134] Table 1

[0135] Table 2

[0136] As shown in Tables 1 and 2 above, the composite metal catalyst prepared using a modified superacid support can improve the catalyst's activity and selectivity, and increase the yield of isomerization products. Using a support composed of multiple mixtures results in a stable support with strong acidity and a large specific surface area, which is beneficial for the main reaction of the catalyst and improves the isomerization yield. In this invention, rare earth elements and transition metals are used for modification. The rare earth metal elements combine with the support, inhibiting the aggregation of noble metals and improving the isomerization performance of the catalyst.

[0137] Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible subranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the range referred to.

[0138] In this invention, unless otherwise stated, directional terms such as "upper" and "lower" specifically refer to the drawing directions in the accompanying drawings. Furthermore, in the description of this invention, terms such as "comprising" and "including" mean "including but not limited to." In this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this document, "and / or" describes the relationship between related objects, indicating that three relationships may exist; for example, A and / or B can represent: A alone, A and B simultaneously, or B alone. A and B can be singular or plural. In this document, "at least one" means one or more, and "more than one" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be a single or multiple.

[0139] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A superacid carrier, characterized in that, Based on the total dry weight of the superacid carrier, the superacid carrier comprises the following components in weight fractions: main component: 45% to 88%, first additive component: 5% to 20%, second additive component: 1% to 10%, third additive component: 1% to 10%, fourth additive component: 5% to 15%. The main components are: ZrO2-SO4 2- ; First added component: AlPO4; The second added component: SAPO-34 molecular sieve; The third additive component: phosphotungstic molybdenum heteropoly acid; The fourth additive component: pseudoboehmite.

2. The superacid carrier according to claim 1, characterized in that, The specific surface area of ​​the superacid carrier is 5m². 2 / g~300m 2 / g.

3. The superacid carrier according to claim 1, characterized in that, The pore size range of the superacid carrier is 5 nm to 40 nm.

4. A method for preparing a superacid carrier according to any one of claims 1 to 3, characterized in that, The preparation method includes the following steps: The main component, the first additive component, the second additive component, the third additive component, and the fourth additive component are added to a kneader in proportion for the first kneading to obtain a mixture. A second kneading process is performed by adding an aqueous nitric acid solution to the mixture to obtain a clinker. The clinker is added to an extruder for extrusion molding, and then dried and calcined to obtain the super acid carrier.

5. The method for preparing the superacid carrier according to claim 4, characterized in that, The weight ratio of the mixture to the nitric acid aqueous solution is (90-92):(10-8); the weight percentage of nitric acid in the nitric acid aqueous solution is 35-40%. The working parameters for the first kneading include: kneading time 20-50 min; the working parameters for the second kneading include: kneading time 20-40 min; the working parameters for the drying include: drying at 80-120℃ for 6-12 hours; and the working parameters for the calcination include: calcination at 400-800℃ for 4-16 hours.

6. An isomerization catalyst, characterized in that, Based on the total dry weight of the isomerization catalyst, the isomerization catalyst comprises the following components in weight percentage: core component 0.01% to 5%, first auxiliary agent 0.1% to 10%, second auxiliary agent 0.1% to 10%, third auxiliary agent 0.1% to 10%, and the balance being the superacid support as described in any one of claims 1 to 5; The core component is one or a mixture of several of the elements Pd, Pt, Ir, and Rh. The first additive is one or a mixture of rare earth metal elements; The second additive is one or a mixture of several alkaline earth elements; The third auxiliary agent is one or a mixture of several elements from Group VIII.

7. The isomerization catalyst according to claim 6, characterized in that, The isomerization catalyst contains the metal elements Pd, Pt, Y, Ba, and Co.

8. The isomerization catalyst according to claim 7, characterized in that, The Pd and Pt are derived from one of the following: metal powders, oxides, halides, sulfates, nitrates, acetates, and oxalates of Pd and Pt elements; the Y is derived from one of the following: yttrium-containing oxides, halides, sulfates, nitrates, acetates, and oxalates; the Ba is derived from one of the following: barium-containing nitrates and barium-containing soluble compounds; and the Co is derived from one of the following: cobalt nitrate, cobalt acetate, cobalt chloride, and soluble compounds.

9. A method for preparing the isomerization catalyst according to any one of claims 6 to 8, characterized in that, The preparation method includes the following steps: The superacid carrier was obtained; Prepare an aqueous solution containing the core component, the first auxiliary agent, the second auxiliary agent, and the third auxiliary agent; The aqueous solution was impregnated onto the superacid support by impregnation, then dried at 80–120°C for 6–12 hours, and then calcined at 450–800°C for 4–16 hours to obtain the isomerization catalyst.

10. A method for alkane isomerization, characterized in that, The method uses the isomerization catalyst according to any one of claims 6 to 9 as the catalyst for alkane isomerization. The operating parameters of the alkane isomerization method include: a fixed-bed reactor, a reaction pressure of 1.0–4.0 MPa, a temperature of 160°C–260°C, and a mass hourly space velocity of 1 h⁻¹. -1 ~3h -1 Hydrogen-to-oil molar ratio: 1.0–3.0; by weight percentage, raw material composition: n-butane: 1%, isopentane: 24%, n-pentane: 26%, n-hexane: 9%, isohexane: 40%.

Images