Normal olefin isomerization catalyst based on ZMQ-1 molecular sieve and preparation method thereof

Abstract

The invention discloses a ZMQ-1 molecular sieve-based normal olefin isomerization catalyst and a preparation method thereof, and belongs to the technical field of normal olefin isomerization catalysts, the ZMQ-1 molecular sieve-based normal olefin isomerization catalyst comprises a ZMQ-1 molecular sieve, a KIT-6 molecular sieve, a beta-ketoamide rhodium complex and a nano thin layer; the preparation method comprises the following steps: preparing a composite molecular sieve from a ZMQ-1 molecular sieve and a KIT-6 molecular sieve according to a weight ratio of 1: (0.2-0.4), and modifying the composite molecular sieve by using a beta-ketoamide rhodium complex; and then forming a potassium niobate nano thin layer of 1-3 nanometers on the surface of the composite molecular sieve by adopting a physical vapor deposition method. The method is beneficial to reducing the possibility of olefin polymerization, inhibiting the formation of carbon deposition, avoiding the loss of active components and the damage of a carrier structure, and is beneficial to improving the reaction efficiency. And after the catalyst is regenerated for five times, the reduction amounts of the n-amylene conversion rate and the isoamylene yield of the catalyst are lower than 10%.

Description

Technical Field

[0001] The present invention relates to the technical field of normal olefin isomerization catalysts, and in particular to a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve and a preparation method thereof. Background Art

[0002] Normal olefin isomerization is the reaction process of converting normal olefins into isomerized olefins, which is of great significance in the field of petrochemicals, such as improving the octane number of gasoline.

[0003] Various types of n-olefin isomerization catalysts are available in the prior art. For example, Patent Application No. 201210276105.0 discloses a catalyst for n-olefin isomerization and its preparation method. The catalyst comprises a support and a modifying compound selected from phenol, a monosaccharide or disaccharide, a polyol, or an organic acid ammonium. The catalyst comprises a mixed molecular sieve comprising a medium-pore molecular sieve and a large-pore molecular sieve. Both isopentene yield and isopentene selectivity are significantly improved.

[0004] However, the performance of most catalysts will decline after a period of time during one loading and use, and they need to be regenerated. However, after multiple regeneration treatments, the catalyst performance is significantly reduced. The reasons are generally carbon deposition, loss of active components and damage to the carrier structure.

[0005] Based on this, the present invention designs a ZMQ-1 molecular sieve-based normal olefin isomerization catalyst and a preparation method thereof to solve the above problems. Summary of the Invention

[0006] In view of the above-mentioned shortcomings of the prior art, the present invention provides a ZMQ-1 molecular sieve-based normal olefin isomerization catalyst and a preparation method thereof.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0008] A ZMQ-1 molecular sieve-based normal olefin isomerization catalyst comprises a ZMQ-1 molecular sieve, a KIT-6 molecular sieve, a β-ketoamide rhodium complex, and a nano-thin layer. A composite molecular sieve is prepared by using the ZMQ-1 molecular sieve and the KIT-6 molecular sieve in a weight ratio of 1:0.2-0.4. The composite molecular sieve is then modified with the β-ketoamide rhodium complex, wherein the weight ratio of the ZMQ-1 molecular sieve to the β-ketoamide rhodium complex is 100:5.1-8.3. A 1-3 nanometer potassium niobate nano-thin layer is then formed on the surface of the composite molecular sieve by physical vapor deposition.

[0009] The beta-ketoamide rhodium complex is formed by complexing a rhodium compound and a beta-ketoamide ligand, and the molar ratio of the beta-ketoamide ligand to the rhodium compound is 2 to 3:1.

[0010] Furthermore, the rhodium compound is selected from one of dicarbonyl acetylacetonate rhodium, tetracarbonyl dirhodium dichloride, and tris(triphenylphosphine)rhodium chloride.

[0011] Furthermore, the β-ketoamide ligand is selected from one of N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, and N-cyclohexyl-3-oxobutyramide.

[0012] Furthermore, the preparation method of the β-ketoamide rhodium complex is: in an inert gas atmosphere, a rhodium compound and a β-ketoamide ligand are added to an organic solvent, and the complexation is stirred at room temperature for 30 to 50 minutes. After the reaction is completed, the product is separated and purified to obtain a β-ketoamide rhodium complex.

[0013] Furthermore, the organic solvent is toluene or dichloromethane.

[0014] In order to better achieve the purpose of the present invention, the present invention also provides a method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve, comprising the following steps:

[0015] Step 1, preparing a composite molecular sieve: ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate are added to water and slurried. The total mass concentration of the molecular sieve in the slurry is controlled at 13-22%, and the mass concentration of ammonium acetate is controlled at 0.3-1%. Then, the mixture is placed in an autoclave and crystallized at 200-220° C. for 24-50 hours to obtain a composite molecular sieve;

[0016] Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: dissolve the β-ketoamide rhodium complex in an organic solvent, add the composite molecular sieve into the solution of the β-ketoamide rhodium complex, and perform equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 5 to 10 hours to allow the β-ketoamide rhodium complex to fully diffuse and adsorb in the molecular sieve pores; and then dry.

[0017] Step 3: Forming a potassium niobate nano-thin layer on the surface of the composite molecular sieve by physical vapor deposition: placing the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nano-thin layer on the surface of the composite molecular sieve.

[0018] Furthermore, in step 2, the drying process is carried out at 105-125° C. for 30-45 minutes.

[0019] Furthermore, in step 3, the parameter control is:

[0020] Vacuum degree: 10 -4 ~10 -6 Pa;

[0021] Working gas pressure: 0.05~0.1Pa;

[0022] Laser energy density: 2~4J / cm 2 ;

[0023] Pulse frequency 4-8 Hz;

[0024] Composite molecular sieve substrate temperature: 300~500℃;

[0025] The distance between potassium niobate target and composite molecular sieve substrate: 4-6 cm;

[0026] Sedimentation time: 5 to 15 minutes.

[0027] In order to better achieve the purpose of the present invention, the present invention also provides a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve obtained according to the preparation method.

[0028] In order to better achieve the purpose of the present invention, the present invention also provides an application of a ZMQ-1 molecular sieve-based normal olefin isomerization catalyst in a normal olefin isomerization catalytic reaction.

[0029] Compared with the prior art, the present invention has the following beneficial effects: after the composite molecular sieve is modified with a β-ketoamide rhodium complex, the number of strong acid centers is reduced, which helps reduce the possibility of olefin polymerization and inhibits the formation of carbon deposits. At the same time, the β-ketoamide rhodium complex can be uniformly and stably loaded on the surface of the composite molecular sieve, avoiding the loss of active components and damage to the carrier structure. A nanometer-thick potassium niobate nanolayer is formed on the surface of the composite molecular sieve using physical vapor deposition. The potassium niobate nanolayer is coated on the surface of the composite molecular sieve to form a core-shell structure. The intercrystalline mesoporous structure of the core-shell structure can remain relatively stable after multiple regeneration treatments. At the same time, reactant molecules can quickly reach the active sites of the catalyst through the intercrystalline mesopores, which helps improve the reaction efficiency. After five regenerations, the catalyst's n-pentene conversion rate and isopentene yield decreased by less than 10%. DETAILED DESCRIPTION

[0030] To make the purpose, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0031] Example 1: In some embodiments, a method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve comprises the following steps:

[0032] Step 1. Preparation of a composite molecular sieve: ZMQ-1 molecular sieve (prepared by the method disclosed in patent application number 202410606237.8), KIT-6 molecular sieve and ammonium acetate are added to water and slurried. The total mass concentration of the molecular sieve in the slurry is controlled at 13%, the weight ratio of ZMQ-1 molecular sieve to KIT-6 molecular sieve is 1:0.4, and the mass concentration of ammonium acetate is controlled at 0.3%. Then, the mixture is placed in an autoclave and crystallized at 220°C for 24 hours to obtain a composite molecular sieve;

[0033] Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: In an inert gas atmosphere, β-ketoamide ligands (N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, N-cyclohexyl-3-oxobutyramide) and rhodium compounds (dicarbonyl acetylacetonato rhodium, tetracarbonyl dichlororhodium, tris(triphenylphosphine) rhodium chloride) were added to an organic solvent (toluene or dichloromethane) in a molar ratio of 2:1, and the complexation was stirred at room temperature for 50 minutes. After the reaction is completed, the product is separated and purified to obtain a β-ketoamide rhodium complex; ZMQ-1 molecular sieve and β-ketoamide rhodium complex are weighed according to a weight ratio of 100:5.1, the β-ketoamide rhodium complex is dissolved in an organic solvent, and the composite molecular sieve is added to the solution of the β-ketoamide rhodium complex for equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 10 hours to allow the β-ketoamide rhodium complex to be fully diffused and adsorbed in the molecular sieve pores; and then dried at 105° C. for 45 minutes.

[0034] Step 3: Form a nanometer-thick potassium niobate nanolayer on the surface of the composite molecular sieve by physical vapor deposition: Place the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nanolayer on the surface of the composite molecular sieve. The parameters are controlled as follows: vacuum degree: 10 -4 a; Working gas pressure: 0.1Pa; Laser energy density: 2J / cm 2 ; Pulse frequency 8 Hz; Composite molecular sieve substrate temperature: 300 ° C; Distance between potassium niobate target and composite molecular sieve substrate: 6 cm; Deposition time: 5 min.

[0035] Example 2: In some embodiments, a method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve comprises the following steps:

[0036] Step 1, preparing a composite molecular sieve: taking ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate, adding them to water, beating, the total mass concentration of the molecular sieve in the slurry is controlled at 22%, the weight ratio of ZMQ-1 molecular sieve to KIT-6 molecular sieve is 1:0.2, and the mass concentration of ammonium acetate is controlled at 1%. Then, placing it in an autoclave, crystallization treatment at 200°C for 50h, to obtain a composite molecular sieve;

[0037] Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: In an inert gas atmosphere, add a β-ketoamide ligand (N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, N-cyclohexyl-3-oxobutyramide) and a rhodium compound (dicarbonyl acetylacetonato rhodium, tetracarbonyl dichlororhodium, tris(triphenylphosphine) rhodium chloride) in a molar ratio of 3:1 to an organic solvent (toluene or dichloromethane), and stir the complexation at room temperature for 30 minutes. After the reaction is completed, the product is separated and purified to obtain a β-ketoamide rhodium complex; ZMQ-1 molecular sieve and β-ketoamide rhodium complex are weighed according to a weight ratio of 100:8.3, the β-ketoamide rhodium complex is dissolved in an organic solvent, and the composite molecular sieve is added to the solution of the β-ketoamide rhodium complex for equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 5 hours so that the β-ketoamide rhodium complex can be fully diffused and adsorbed in the molecular sieve pores; and then dried at 125°C for 30 minutes.

[0038] Step 3: Form a nanometer-thick potassium niobate nanolayer on the surface of the composite molecular sieve by physical vapor deposition: Place the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nanolayer on the surface of the composite molecular sieve. The parameters are controlled as follows: vacuum degree: 10 -6 Pa; working gas pressure: 0.05Pa; laser energy density: 4J / cm 2 ; Pulse frequency 4 Hz; Composite molecular sieve substrate temperature: 500 ° C; Distance between potassium niobate target and composite molecular sieve substrate: 4 cm; Deposition time: 15 min.

[0039] Example 3: In some embodiments, a method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve comprises the following steps:

[0040] Step 1, preparing a composite molecular sieve: taking ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate, adding them to water, beating, the total mass concentration of the molecular sieve in the slurry is controlled at 15%, the weight ratio of ZMQ-1 molecular sieve to KIT-6 molecular sieve is 1:0.3, the mass concentration of ammonium acetate is controlled at 0.5%, and then placing it in an autoclave and crystallizing it at 210°C for 40 hours to obtain a composite molecular sieve;

[0041] Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: In an inert gas atmosphere, β-ketoamide ligands (N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, N-cyclohexyl-3-oxobutyramide) and rhodium compounds (dicarbonyl acetylacetonato rhodium, tetracarbonyl dichlororhodium, tris(triphenylphosphine) rhodium chloride) were added to an organic solvent (toluene or dichloromethane) at a molar ratio of 2.5:1, and the complexation was stirred at room temperature for 40 minutes. n. After the reaction is completed, the product is separated and purified to obtain a β-ketoamide rhodium complex; ZMQ-1 molecular sieve and β-ketoamide rhodium complex are weighed according to a weight ratio of 100:7, the β-ketoamide rhodium complex is dissolved in an organic solvent, and the composite molecular sieve is added to the solution of the β-ketoamide rhodium complex for equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 7 hours to allow the β-ketoamide rhodium complex to be fully diffused and adsorbed in the molecular sieve pores; and then dried at 115° C. for 35 minutes.

[0042] Step 3: Form a nanometer-thick potassium niobate nanolayer on the surface of the composite molecular sieve by physical vapor deposition: Place the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nanolayer on the surface of the composite molecular sieve. The parameters are controlled as follows: vacuum degree: 10 -5 Pa; working gas pressure: 0.08Pa; laser energy density: 3J / cm 2 ; Pulse frequency 6 Hz; Composite molecular sieve substrate temperature: 400 ° C; Distance between potassium niobate target and composite molecular sieve substrate: 5 cm; Deposition time: 10 min.

[0043] Example 4: In some embodiments, a method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve comprises the following steps:

[0044] Step 1, preparing a composite molecular sieve: taking ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate, adding them to water, beating, the total mass concentration of the molecular sieve in the slurry is controlled at 20%, the weight ratio of ZMQ-1 molecular sieve to KIT-6 molecular sieve is 1:0.25, and the mass concentration of ammonium acetate is controlled at 0.7%. Then, placing it in an autoclave, crystallizing it at 205°C for 45h to obtain a composite molecular sieve;

[0045] Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: In an inert gas atmosphere, add a β-ketoamide ligand (N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, N-cyclohexyl-3-oxobutyramide) and a rhodium compound (dicarbonyl acetylacetonato rhodium, tetracarbonyl dichlororhodium, tris(triphenylphosphine) rhodium chloride) in a molar ratio of 2.8:1 to an organic solvent (toluene or dichloromethane), and stir the complex at room temperature for 35 minutes. After the reaction is completed, the product is separated and purified to obtain a β-ketoamide rhodium complex; ZMQ-1 molecular sieve and β-ketoamide rhodium complex are weighed according to a weight ratio of 100:8, the β-ketoamide rhodium complex is dissolved in an organic solvent, and the composite molecular sieve is added to the solution of the β-ketoamide rhodium complex for equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 8.5 hours to allow the β-ketoamide rhodium complex to fully diffuse and adsorb in the molecular sieve pores; and then dried at 108°C for 40 minutes.

[0046] Step 3: Form a nanometer-thick potassium niobate nanolayer on the surface of the composite molecular sieve by physical vapor deposition: Place the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nanolayer on the surface of the composite molecular sieve. The parameters are controlled as follows: vacuum degree: 10 -4 Pa; working gas pressure: 0.07Pa; laser energy density: 2.5J / cm 2 ; Pulse frequency 6 Hz; Composite molecular sieve substrate temperature: 420 ℃; Distance between potassium niobate target and composite molecular sieve substrate: 4.5 cm; Deposition time: 8 min.

[0047] Comparative Example 1: A method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve, comprising the following steps:

[0048] Step 1, preparing a composite molecular sieve: taking ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate, adding them to water, beating, the total mass concentration of the molecular sieve in the slurry is controlled at 15%, the weight ratio of ZMQ-1 molecular sieve to KIT-6 molecular sieve is 1:0.3, the mass concentration of ammonium acetate is controlled at 0.5%, and then placing it in an autoclave and crystallizing it at 210°C for 40 hours to obtain a composite molecular sieve;

[0049] Step 2: Use physical vapor deposition to form a nanometer-thick potassium niobate nanolayer on the surface of the composite molecular sieve: Place the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nanolayer on the surface of the composite molecular sieve. The parameters are controlled as follows: vacuum degree: 10 -5 Pa; working gas pressure: 0.08Pa; laser energy density: 3J / cm 2; Pulse frequency 6 Hz; Composite molecular sieve substrate temperature: 400 ° C; Distance between potassium niobate target and composite molecular sieve substrate: 5 cm; Deposition time: 10 min.

[0050] Comparative Example 2: A method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve, comprising the following steps:

[0051] Step 1, preparing a composite molecular sieve: taking ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate, adding them to water, beating, the total mass concentration of the molecular sieve in the slurry is controlled at 15%, the weight ratio of ZMQ-1 molecular sieve to KIT-6 molecular sieve is 1:0.3, the mass concentration of ammonium acetate is controlled at 0.5%, and then placing it in an autoclave and crystallizing it at 210°C for 40 hours to obtain a composite molecular sieve;

[0052] Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: In an inert gas atmosphere, β-ketoamide ligands (N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, N-cyclohexyl-3-oxobutyramide) and rhodium compounds (dicarbonyl acetylacetonato rhodium, tetracarbonyl dichlororhodium, tris(triphenylphosphine) rhodium chloride) were added to an organic solvent (toluene or dichloromethane) at a molar ratio of 2.5:1, and the complexation was stirred at room temperature for 40 minutes. n. After the reaction is completed, the product is separated and purified to obtain a β-ketoamide rhodium complex; ZMQ-1 molecular sieve and β-ketoamide rhodium complex are weighed according to a weight ratio of 100:7, the β-ketoamide rhodium complex is dissolved in an organic solvent, and the composite molecular sieve is added to the solution of the β-ketoamide rhodium complex for equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 7 hours to allow the β-ketoamide rhodium complex to be fully diffused and adsorbed in the molecular sieve pores; and then dried at 115° C. for 35 minutes.

[0053] Experimental Example 1: The catalysts prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 2 were evaluated: the fixed bed reactor had an inner diameter of 12 mm, a catalyst loading volume of 10 mL, and an n-pentene space velocity of 2 h -1 The reaction temperature was 300°C and the reaction temperature was 400°C. After 12 hours of reaction, the conversion rate of n-pentene and the yield of isopentene were analyzed. The results are shown in Table 1.

[0054] Table 1 Catalyst evaluation results

[0055] project n-pentene conversion rate % Isoamylene yield % Example 1 99.3 85.3 Example 2 99.1 82.1 Example 3 99.5 86.7 Comparative Example 1 96.4 78.3 Comparative Example 2 95.8 80.4

[0056] Experimental Example 2: After the catalyst was operated once (800 hours), it was burned and regenerated. After the catalyst was operated and regenerated by burning for 5 times, it was evaluated using the method of Experimental Example 1. The results are shown in Table 2.

[0057] Table 2 Evaluation results of regenerated catalyst

[0058]

[0059]

[0060] The present invention uses a β-ketoamide rhodium complex to modify a composite molecular sieve. By reducing the number of strong acid centers, the possibility of olefin polymerization is reduced and the formation of carbon deposits is suppressed. At the same time, the β-ketoamide rhodium complex can be uniformly and stably loaded on the surface of the composite molecular sieve, avoiding the loss of active components and damage to the carrier structure. A nanometer-thick potassium niobate nanolayer is formed on the surface of the composite molecular sieve using a physical vapor deposition method. The potassium niobate nanolayer is coated on the surface of the composite molecular sieve to form a core-shell structure. The intercrystalline mesoporous structure in the core-shell structure can remain relatively stable after multiple regeneration treatments. At the same time, reactant molecules can quickly reach the active sites of the catalyst through the intercrystalline mesopores, which is conducive to improving reaction efficiency. After five regenerations, the reduction in the n-pentene conversion rate and isopentene yield of the catalyst is less than 10%.

[0061] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A catalyst for the isomerization of normal olefins based on ZMQ-1 molecular sieve, characterized in that: The method comprises a ZMQ-1 molecular sieve, a KIT-6 molecular sieve, a β-ketoamide rhodium complex and a nano-thin layer; a composite molecular sieve is prepared by using the ZMQ-1 molecular sieve and the KIT-6 molecular sieve in a weight ratio of 1:0.2-0.4; the composite molecular sieve is then modified with the β-ketoamide rhodium complex, wherein the weight ratio of the ZMQ-1 molecular sieve to the β-ketoamide rhodium complex is 100:5.1-8.3; and a 1-3 nanometer potassium niobate nano-thin layer is formed on the surface of the composite molecular sieve by a physical vapor deposition method; The beta-ketoamide rhodium complex is formed by complexing a rhodium compound and a beta-ketoamide ligand, and the molar ratio of the beta-ketoamide ligand to the rhodium compound is 2 to 3:

1.

2. The normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 1, characterized in that: The rhodium compound is selected from one of dicarbonyl acetylacetonate rhodium, tetracarbonyl dirhodium dichloride, and tris(triphenylphosphine)rhodium chloride.

3. The normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 2, characterized in that: The β-ketoamide ligand is selected from one of N,N-dimethyl-3-oxobutyramide, N,N-diisopropyl-3-oxohexanamide, and N-cyclohexyl-3-oxobutyramide.

4. The normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 3, characterized in that: The preparation method of the β-ketoamide rhodium complex comprises the following steps: adding a rhodium compound and a β-ketoamide ligand to an organic solvent in an inert gas atmosphere, stirring and complexing at room temperature for 30 to 50 minutes, and separating and purifying the product after the reaction to obtain the β-ketoamide rhodium complex.

5. The normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 4, characterized in that: The organic solvent is toluene or dichloromethane.

6. A method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 5, characterized in that: The following steps are involved: Step 1, preparing a composite molecular sieve: ZMQ-1 molecular sieve, KIT-6 molecular sieve and ammonium acetate are added to water and slurried. The total mass concentration of the molecular sieve in the slurry is controlled at 13-22%, and the mass concentration of ammonium acetate is controlled at 0.3-1%. Then, the mixture is placed in an autoclave and crystallized at 200-220° C. for 24-50 hours to obtain a composite molecular sieve; Step 2: Modify the composite molecular sieve using a β-ketoamide rhodium complex: dissolve the β-ketoamide rhodium complex in an organic solvent, add the composite molecular sieve into the solution of the β-ketoamide rhodium complex, and perform equal volume impregnation; the impregnated composite molecular sieve is placed at room temperature for aging for 5 to 10 hours to allow the β-ketoamide rhodium complex to fully diffuse and adsorb in the molecular sieve pores; and then dry. Step 3: Forming a potassium niobate nano-thin layer on the surface of the composite molecular sieve by physical vapor deposition: placing the composite molecular sieve in a pulsed laser deposition device to deposit a potassium niobate nano-thin layer on the surface of the composite molecular sieve.

7. The method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 6, characterized in that: In step 2, the product is dried at 105-125° C. for 30-45 minutes.

8. The method for preparing a normal olefin isomerization catalyst based on ZMQ-1 molecular sieve according to claim 7, characterized in that: In step 3, the parameter control is: Vacuum degree: 10 -4 ~10 -6 Pa; Working gas pressure: 0.05~0.1Pa; Laser energy density: 2~4J / cm 2 ; Pulse frequency 4-8 Hz; Composite molecular sieve substrate temperature: 300~500℃; The distance between potassium niobate target and composite molecular sieve substrate: 4-6 cm; Sedimentation time: 5 to 15 minutes.

9. A normal olefin isomerization catalyst based on ZMQ-1 molecular sieve obtained according to the preparation method of claim 8.

10. Use of the ZMQ-1 molecular sieve-based normal olefin isomerization catalyst according to claim 9 in a normal olefin isomerization catalytic reaction.

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