Catalyst particles suitable for fluidized bed production, and methods of making and using the same

Abstract

The present application relates to a kind of catalyst particles suitable for fluidized bed production and its preparation method and application, belong to catalytic material preparation field.A kind of catalyst particles suitable for fluidized bed production, it is composed of following components: the catalyst particles are used to catalytically prepare perfluorohexanone;The catalyst particles are bonded into aggregate particles using binder with 5-20 parts of catalyst active component, 90-150 parts of molecular sieve carrier and 9-20 parts of wear-resistant agent;The catalyst active component is alkali metal fluoride salt.The catalyst particles of the present application are suitable for fluidized bed production, catalyst loss is slow, durable, and the yield of the product prepared is high.The specific surface area of the molecular sieve is larger, which can make the loaded active component fully spread out, and the molecular sieve channel is multiple, so that the active component inside the particle can also participate in the reaction, and the catalytic activity is improved.

Description

Technical Field

[0001] This invention relates to a catalyst particle suitable for fluidized bed production, its preparation method and application, belonging to the field of catalytic material preparation. Background Technology

[0002] Perfluorohexanone is an important component of fire extinguishing agents. The commonly used catalysts in its preparation are metal fluorides, typically one or a mixture of two or more of NaF, KF, CsF, and RbF. The chemical reaction occurs in two forms: one in an aprotic solvent, and the other in a gas-phase reaction in a fluidized bed. In the gas-phase reaction, if the metal fluoride is directly used as a catalyst in the fluidized bed, the metal fluoride particles are not strong enough. During mutual friction, the particle size decreases and becomes finer, and the particles are carried away by the gas flow. This results in significant catalyst loss and difficulty in removing impurities from the product, ultimately leading to a low product yield and insufficient catalyst utilization in fluidized bed preparation. Summary of the Invention

[0003] The purpose of this invention is to provide a catalyst particle suitable for fluidized bed production, which solves the problems of low yield, insufficient catalyst utilization and large loss in the preparation of products from metal fluorides in fluidized beds in the prior art.

[0004] The second objective of this invention is to provide a method for preparing catalyst particles suitable for fluidized bed production, which is simple to operate and easy to implement.

[0005] A third objective of this invention is to provide an application of catalyst particles, as described above, suitable for fluidized bed production in the preparation of perfluorohexanone, wherein the catalyst particles in this application exhibit high catalytic activity and high product yield.

[0006] To achieve the above objectives, the technical solution of the present invention for catalyst particles applicable to fluidized bed production is as follows:

[0007] A catalyst particle suitable for fluidized bed production is composed of the following components: the catalyst particle is used for the catalytic preparation of perfluorohexanone; the catalyst particle is formed by bonding 5-20 parts of catalyst active component, 90-150 parts of molecular sieve support and 9-20 parts of wear-resistant agent into aggregate particles using a binder; the catalyst active component is an alkali metal fluoride salt.

[0008] The catalyst particles of this invention are suitable for fluidized bed production, exhibiting slow catalyst depletion, durability, and high product yield. The component combination of this invention enhances the catalytic activity of the catalyst. The molecular sieve has a large specific surface area, allowing the supported active components to spread sufficiently, and its numerous pores enable the active components within the particles to participate in the reaction, thereby improving catalytic activity.

[0009] Preferably, the catalyst particles are aggregated particles formed by bonding 6-19 parts of the catalyst active component, 95-150 parts of the molecular sieve support, and 9-16 parts of the wear-resistant agent into aggregate particles using a binder.

[0010] The catalyst particles are microspheres, which are spherical or nearly spherical.

[0011] Preferably, the active component of the catalyst is one or more selected from NaF, KF, and CsF. These active components are conventional alkali metal fluoride salts and have excellent catalytic effects.

[0012] To better load the active components of the catalyst, the molecular sieve support is preferably one or more of SAPO-5, SAPO-34, SAPO-44, SAPO-47, and SAPO-56.

[0013] To improve the wear resistance of the catalyst, preferably, the wear-resistant agent is one or more of montmorillonite, kaolinite, alumina, and silicon dioxide.

[0014] In order to better bond the catalyst active component, molecular sieve support and wear-resistant agent together, the binder is preferably a cured product of inorganic oxide sol.

[0015] To improve bonding performance, preferably, the amount of inorganic oxide sol added is 36 to 160 parts.

[0016] More preferably, the inorganic oxide sol is one or more of polysilicon sol, aluminum sol, and boehmite sol.

[0017] To reduce the loss of catalyst particles during fluidized bed production, preferably, the catalyst particles are microspheres with a diameter of 20–300 μm.

[0018] The technical solution of the method for preparing catalyst particles applicable to fluidized bed production according to the present invention is as follows:

[0019] A method for preparing catalyst particles suitable for fluidized bed production includes the following steps: mixing the catalyst active component, molecular sieve support, wear-resistant agent, and binder in water, spray drying, and calcining to obtain catalyst particles. This preparation method is simple to operate and easy to implement.

[0020] To facilitate the solidification and shaping of the catalyst particles, preferably, the spray drying temperature is 150–200°C; and the calcination temperature is 400–600°C.

[0021] More preferably, in order to increase the particle size of the catalyst and improve the catalytic effect, the spray drying can be repeated more than twice.

[0022] The technical solution of this invention for the application of catalyst particles in fluidized bed production is as follows:

[0023] Application of catalyst particles suitable for fluidized bed production in the catalytic preparation of perfluorohexanone. When the catalyst particles of this invention are used in the catalytic fluidized bed production of perfluorohexanone, the yield of perfluorohexanone is high. Detailed Implementation

[0024] This invention utilizes a binder to bond alkali metal fluoride salts, molecular sieve supports, and wear-resistant agents into aggregated particles, which can be used for the fluidized bed production of perfluorohexanone. Because this invention loads alkali metal fluoride salts onto molecular sieves, the active components inside the catalyst particles can also participate in the reaction, thus improving catalytic activity.

[0025] The method for preparing catalyst particles according to the present invention includes the following steps: mixing alkali metal fluoride salt and binder in water to obtain a mixture; then mixing molecular sieve support, wear-resistant agent and the mixture to obtain a slurry mixture, spray drying and calcining to obtain catalyst particles.

[0026] Preferably, the adhesive is one or more of polysilicon sol, aluminum sol, and boehmite sol.

[0027] Preferably, the content of the effective components of polysilicon sol, alumina sol, and boehmite sol is 10–35 wt%.

[0028] More preferably, the effective component of the polysilicon sol is SiO2, and the effective component of the aluminum sol and the pseudoboehmite sol is Al2O3.

[0029] Preferably, the content of the effective component of the polysilicon sol is 25-35 wt%; the effective component of the aluminum sol and the pseudoboehmite sol is 10-20 wt%.

[0030] Preferably, the solid content of the slurry mixture is 30-40%.

[0031] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0032] I. Specific embodiments of the catalyst particles and their preparation method applicable to fluidized bed production of the present invention are as follows:

[0033] Example 1

[0034] The catalyst particles suitable for fluidized bed production in this embodiment are made from the following components by weight: 6.5 kg NaF, 95 kg molecular sieve SAPO-5, 12 kg kaolin and binder, the binder being a solidified product of 36 kg silica sol; the particle size of the catalyst particles is 20-260 μm.

[0035] The method for preparing catalyst particles suitable for fluidized bed production in this embodiment adopts the following steps:

[0036] (1) Add 200kg of pure water to the mixing tank, then add 6.5kg of NaF and 36kg of silica sol (solute SiO2 content 33.6wt%), and stir for 120min;

[0037] (2) Add 95 kg of molecular sieve SAPO-5 and 12 kg of kaolin to the solution in step (1), with a shear line velocity of 21 m / s and stirring for 150 min to obtain a slurry mixture with a solid content of 35.94%.

[0038] (3) The product obtained in step (2) is spray-dried at a feed temperature of 150°C, a spray wheel speed of 10000 r / min, and a feed rate of 0.8 L / min to obtain micro spherical particles.

[0039] (4) The microspheres obtained in step (3) are redispersed in pure water, with a shear line velocity of 15 m / s and stirring for 60 min. The mixture is sprayed again. This process is repeated 3 times to obtain microspheres with a particle size distribution of 20-260 μm.

[0040] (5) The microspheres obtained in step (4) are calcined at 400°C for 3 hours to obtain catalyst particles suitable for fluidized bed production.

[0041] Example 2

[0042] The catalyst particles suitable for fluidized bed production in this embodiment are made from the following components by weight: 15 kg KF, 140 kg molecular sieve SAPO-56, 16 kg alumina and binder, wherein the binder is a solidified product of 160 kg alumina sol; the particle size of the catalyst particles is 25-275 μm.

[0043] The method for preparing catalyst particles suitable for fluidized bed production in this embodiment adopts the following steps:

[0044] (1) Add 200kg of pure water to the mixing tank, then add 15kg of KF and 160kg of aluminum sol (solute Al2O3 content 10wt%), and stir for 120min;

[0045] (2) Add 140 kg of molecular sieve SAPO-56 and 16 kg of alumina to the solution in step (1), with a shear line speed of 21 m / s and stirring for 150 min to obtain a slurry mixture with a solid content of 35.22%.

[0046] (3) The product obtained in step (2) is spray-dried at a feed temperature of 150°C, a spray wheel speed of 10000 r / min, and a feed rate of 0.8 L / min to obtain micro spherical particles.

[0047] (4) The microspheres obtained in step (3) are redispersed in pure water, with a shear line velocity of 15 m / s and stirring for 60 min. The mixture is sprayed again. This process is repeated 3 times to obtain microspheres with a particle size distribution of 25-275 μm.

[0048] (5) The microspheres obtained in step (4) are calcined at 600°C for 2 hours to obtain catalyst particles suitable for fluidized bed production.

[0049] Example 3

[0050] The catalyst particles suitable for fluidized bed production in this embodiment are made from the following components by weight: 18.6 kg CsF, 149 kg molecular sieve SAPO-44, 9.5 kg silica and binder, wherein the binder is a solidified product of 160 kg pseudoboehmite sol; the particle size of the catalyst particles is 40-290 μm.

[0051] The method for preparing catalyst particles suitable for fluidized bed production in this embodiment adopts the following steps:

[0052] (1) Add 200kg of pure water to the mixing tank, then add 18.6kg of CsF and 150kg of pseudoboehmite sol (solute Al2O3 content 10wt%), and stir for 120min;

[0053] (2) Add 149 kg of molecular sieve SAPO-44 and 9.5 kg of silicon dioxide to the solution in step (1), and stir for 150 min at a shear line speed of 21 m / s to obtain a slurry mixture with a solid content of 36.44%.

[0054] (3) The product obtained in step (2) is spray-dried at a feed temperature of 200°C, a spray wheel speed of 10000 r / min, and a feed rate of 0.8 L / min to obtain micro spherical particles.

[0055] (4) The microspheres obtained in step (3) are redispersed in pure water, with a shear line velocity of 15 m / s and stirring for 60 min. The mixture is sprayed again. This process is repeated 3 times to obtain microspheres with a particle size distribution of 40-290 μm.

[0056] (5) The microspheres obtained in step (4) are calcined at 550°C for 3 hours to obtain catalyst particles suitable for fluidized bed production.

[0057] II. Specific embodiments of the application of the catalyst particles of the present invention in fluidized bed production are as follows:

[0058] Example 4

[0059] The application of catalyst particles suitable for fluidized bed production in the catalytic preparation of perfluorohexanone in this embodiment:

[0060] 10 kg of catalyst particles suitable for fluidized bed production obtained in Example 1 were loaded into a fluidized bed reactor and preheated to 150°C. Perfluoro-2-methyl-2-pentene was preheated to 150°C, and the resulting steam, along with oxygen and nitrogen, was introduced into the reactor from the bottom to fluidize the catalyst using the gas flow. The gas discharged from the top of the reactor was then reintroduced into the reactor for circulation. When the perfluorohexanone content reached more than 95%, the material was collected. The final reaction lasted 1.5 hours, and samples were taken to test the perfluorohexanone content in the product.

[0061] Example 5

[0062] The application of catalyst particles suitable for fluidized bed production in the catalytic preparation of perfluorohexanone in this embodiment:

[0063] 10 kg of the catalyst obtained in Example 2 was loaded into a fluidized bed reactor and preheated to 250 °C. Perfluoro-2-methyl-2-pentene was preheated to 250 °C, and the resulting steam, along with oxygen and nitrogen, was introduced into the reactor from the bottom to fluidize the catalyst. The gas discharged from the top of the reactor was then reintroduced into the reactor for circulation. When the perfluorohexanone content reached more than 95%, the material was collected. The reaction was carried out for 1 hour, and samples were taken to test the perfluorohexanone content in the product.

[0064] Example 6

[0065] The application of catalyst particles suitable for fluidized bed production in the catalytic preparation of perfluorohexanone in this embodiment:

[0066] 10 kg of the catalyst obtained in Example 3 was loaded into a fluidized bed reactor and preheated to 200°C. Perfluoro-2-methyl-2-pentene was preheated to 200°C, and the resulting steam, along with oxygen and nitrogen, was introduced into the reactor from the bottom to fluidize the catalyst. The gas discharged from the top of the reactor was then reintroduced into the reactor for circulation. When the perfluorohexanone content reached more than 95%, the material was collected, and the final reaction lasted 1.5 hours. Samples were taken to test the perfluorohexanone content in the product.

[0067] II. Comparative Example

[0068] Comparative Example 1

[0069] The catalyst particles in this comparative example consist of the following components by weight: 6.5 kg NaF, 107 kg kaolin, and 12.1 kg binder; the particle size of the catalyst particles is 20-260 μm.

[0070] The preparation method of the catalyst in this comparative example is basically the same as that in Example 1, except that the molecular sieve component is removed. Specifically, the following steps are used:

[0071] (1) Add 200kg of pure water, 6.5kg of NaF and 36kg of silica sol to the mixing tank and stir for 120min;

[0072] (2) Add 107 kg of kaolin to the solution in step (1), shear line speed 21 m / s, stir for 150 min, and obtain a slurry mixture with a solid content of 35.94%.

[0073] (3) The product obtained in step (2) is spray-dried at a feed temperature of 150°C, a spray wheel speed of 10000 r / min, and a feed rate of 0.8 L / min to obtain micro spherical particles.

[0074] (4) The microspheres obtained in step (3) are redispersed in pure water, with a shear line velocity of 15 m / s and stirring for 60 min. The mixture is sprayed again. This process is repeated 3 times to obtain microspheres with a particle size distribution of 20-260 μm.

[0075] (5) The microspheres obtained in step (4) are calcined at 400°C for 3 hours to obtain catalyst particles suitable for fluidized bed production.

[0076] Application of these catalyst particles in the catalytic preparation of perfluorohexanone:

[0077] 10 kg of catalyst particles obtained in this comparative example were loaded into a fluidized bed reactor and preheated to 150 °C. Perfluoro-2-methyl-2-pentene was preheated to 150 °C. The resulting steam, along with oxygen and nitrogen, was introduced into the reactor from the bottom to fluidize the catalyst using the gas flow. The gas discharged from the top of the reactor was then reintroduced into the reactor for circulation. The reaction was carried out for 1.5 hours, and samples were taken to test the perfluorohexanone content in the product.

[0078] Comparative Example 2

[0079] The catalyst used in this comparative example is NaF powder.

[0080] The application of this catalyst particle in the catalytic preparation of perfluorohexanone is the same as that in Comparative Example 1.

[0081] III. Experimental Examples

[0082] This experiment measured the particle size distribution parameters of the catalysts in Examples 5-6 and Comparative Examples 1 and 2, as well as the yield of perfluorohexanone prepared by catalysis and the catalyst recovery rate. The results are shown in Table 1.

[0083] Table 1 Catalyst particle size distribution parameters, perfluorohexanone yield, and catalyst recovery rate

[0084]

[0085] As shown in Table 1, the perfluorohexanone yield prepared by the catalysts in Examples 4-6 reached over 95.6%, and the catalyst recovery rate was over 97.9%. Comparative Example 1 had a higher catalyst recovery rate of 99.1%, but a lower perfluorohexanone yield of only 78.7%. This is because the active components inside the catalyst particles could not participate in the reaction, and only the surface active components participated. Comparative Example 2 achieved a higher perfluorohexanone yield of 98.4% using NaF powder in a fluidized bed catalysis, but suffered significant catalyst loss, recovering only 60.8%. This was due to the collision and abrasion of the sodium fluoride powder particles, with fine powder being carried away by the airflow.

Claims

1. A catalyst particle suitable for fluidized bed production, characterized in that, The catalyst particles are used to catalyze the preparation of perfluorohexanone. The catalyst particles are aggregated by binding 5-20 parts of the catalyst active component, 90-150 parts of the molecular sieve support, and 9-20 parts of the wear-resistant agent into aggregate particles using a binder. The catalyst active component is an alkali metal fluoride salt. The wear-resistant agent is one or more of montmorillonite, kaolin, alumina, and silica. The catalyst active component is one or more of NaF, KF, and CsF. The molecular sieve support is one or more of SAPO-5, SAPO-34, SAPO-44, SAPO-47, and SAPO-56. The preparation method of the catalyst particles includes the following steps: mixing the catalyst active component, molecular sieve support, wear-resistant agent and binder in water, spray drying and calcining to obtain catalyst particles; the calcination temperature is 400~600℃.

2. The catalyst particles suitable for fluidized bed production according to claim 1, characterized in that, The catalyst particles are aggregated by binding 6-19 parts of the catalyst active component, 95-150 parts of the molecular sieve support and 9-16 parts of the wear-resistant agent into aggregate particles using a binder.

3. The catalyst particles suitable for fluidized bed production according to claim 1, characterized in that, The binder is silica sol, alumina sol, or pseudoboehmite sol.

4. The catalyst particles suitable for fluidized bed production according to claim 3, characterized in that, The amount of adhesive added is 36 to 160 parts.

5. The catalyst particles suitable for fluidized bed production according to any one of claims 1-4, characterized in that, The catalyst particles have a diameter of 20~300μm.

6. A method for preparing catalyst particles suitable for fluidized bed production as described in any one of claims 1-5, characterized in that, The process includes the following steps: mixing the catalyst active component, molecular sieve support, wear-resistant agent and binder in water, spray drying and calcining to obtain catalyst particles; the calcination temperature is 400~600℃.

7. The method for preparing catalyst particles suitable for fluidized bed production according to claim 6, characterized in that, The spray drying temperature is 150~200℃.

8. The application of the catalyst particles as described in claim 1, suitable for fluidized bed production, in the catalytic preparation of perfluorohexanone.

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