Preparation method of catalyst for hydrogen peroxide production by anthraquinone fluidized bed method and product

Abstract

The application discloses a preparation method of a catalyst for hydrogen peroxide production by an anthraquinone method in a fluidized bed and a product, the carrier prepared by the method has high wear resistance, the bulk density of the carrier and the catalyst is 0.650-1.050 g / ml, and the wear index is 2.400-6.000%. Active alumina powder is reacted with acid to prepare a colloid; nitric acid solution or oxalic acid solution is used as a base liquid, stirring is started, the active alumina powder and alumina colloid are added, an appropriate amount of auxiliary raw materials is added, a dispersing agent is added, the suspension subjected to high-speed shearing stirring is granulated by using a centrifugal and a spray dryer to obtain microspheres of the fluidized bed carrier, and the fluidized bed carrier is obtained through calcination. The carrier is loaded with active components and adjuvants, and the fluidized bed catalyst for hydrogen peroxide production by the anthraquinone method in the fluidized bed is obtained through drying and calcination. The customized catalyst evaluation device for hydrogen peroxide production by the anthraquinone method in the fluidized bed is used to evaluate the catalyst under the condition of a working liquid system, and the activity of the catalyst is investigated.

Description

TECHNICAL FIELD

[0001] The catalyst prepared by the present application includes the field of fluidized bed (or suspended bed) catalyst carrier preparation, catalyst preparation. Specifically relates to the preparation of catalyst for anthraquinone method fluidized bed hydrogen peroxide production, which is prepared by adding related auxiliary materials, etc. through the related steps of beating, spraying, centrifugal drying, etc. based on alumina as the basic raw material. Anthraquinone method for preparing hydrogen peroxide working fluid system. BACKGROUND

[0002] Catalysts have various uses and types, which can be used in fixed bed, fluidized bed (suspended bed). The structure of the device determines the type of catalyst required. The fluidized bed reaction device has a unique reaction mode, which can effectively improve the catalytic efficiency of the catalyst. As the carrier of the fluidized bed catalyst, it must have strong wear resistance. The wear resistance of the catalyst is directly related to the service life of the catalyst. Therefore, this is the key to the performance of the fluidized bed catalyst. SUMMARY

[0003] The present application provides a preparation method and product of a catalyst for anthraquinone method fluidized bed hydrogen peroxide production. The creativity of the present application lies in: 1. In the preparation process, the prepared carrier performance has a large range of adjustability by using specific alumina powder; 2. By adjusting the colloidal acidity and the ratio of alumina powder, the bulk density, wear index and pore structure of the fluidized bed carrier are adjusted; 3. Based on the kinematic viscosity of the suspension, the flowability of the suspension and the particle size range of the carrier are ensured; 4. According to the adsorption capacity of the carrier, equal volume spraying impregnation is adopted to avoid the loss of active components; 5. The catalyst after loading is a catalyst preparation process integrating drying, calcination and reduction.

[0004] Based on the above creativity, the bulk density, wear index, specific surface area, pore size and pore volume of the catalyst change within a certain range, thereby meeting the performance and use requirements of the fluidized bed catalyst for anthraquinone method hydrogen peroxide production.

[0005] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows.

[0006] A preparation method of a catalyst for anthraquinone method fluidized bed hydrogen peroxide production, the steps of carrier preparation include:

[0007] Step one, active alumina powder is reacted with an acid solution to prepare alumina gel;

[0008] Step two, alumina gel and alumina powder are added to the acid solution under stirring to obtain slurry;

[0009] Step three, auxiliary materials are added to the slurry of step two;

[0010] Step four, add suspension agent to the mixture of step three;

[0011] Step five, the mixture obtained in step four is stirred by high speed shearing to form a suspension, and the suspension is aged for 3-25 hours in a sealed state, and then granulated and calcined to obtain the fluidized bed catalyst carrier;

[0012] Step six, the fluidized bed catalyst carrier is loaded with active components and auxiliary agents, and then calcined to obtain the fluidized bed catalyst.

[0013] The active alumina powder used as the main raw material has a dry bulk density of 0.25-0.35 g / ml, a specific surface area of 180.0000-350.0000 m 2 / g, a pore volume of 0.6000-1.2000 cm 2 / g, and a pore size of 8.0000-15.0000 nm.

[0014] The acid solution in steps one and two is selected from any one or a combination of multiple of nitric acid, acetic acid and oxalic acid;

[0015] The mass concentration of the nitric acid, acetic acid and oxalic acid is 3-25%.

[0016] In step one, the mass ratio of the active alumina powder to the acid solution is 1:(5-10), and the active alumina powder and the acid solution are gelled in a water bath at 60-90°C for 1-5 hours, and then taken out for standby use. In the scheme of the present application, the purpose of gelling first is to provide a certain basis for the bulk density of the carrier after molding. If the gelling is not performed first, the bulk density of the carrier is low, the attrition index is high, and the attrition index of the catalyst and the service life of the catalyst are affected.

[0017] In step two, the feeding ratio of the alumina gel to the alumina powder is (3-10):1. Using this ratio range can ensure that the bulk density of the carrier after molding is within the control range. Higher or lower than this range will affect the pore structure of the catalyst carrier, which is not conducive to the performance of the catalyst.

[0018] The auxiliary raw material in step three is added in an amount of 0.03%-15% of the amount of the alumina gel, and the auxiliary raw material is selected from two or more of silica sol, kaolin, water glass, molecular sieve and silicon-aluminum dry gel powder. The auxiliary raw material in the present application provides a silicon source for the fluidized bed carrier, and the presence of silicon plays a certain protective role for the attrition of the carrier.

[0019] In step four, the suspension agent is selected from two or more of polyethylene glycol 200, sodium tripolyphosphate, sodium hexametaphosphate, methyl amyl alcohol and polyacrylamide, and is added in an amount of 0.010-0.500% of the amount of the alumina gel. The suspension agent in the present application ensures that the raw and auxiliary materials are uniformly suspended in the solution, and also plays a certain role in the viscosity of the mixture.

[0020] The high-speed shearing stirring in step five is at a speed of 500-1000 rpm, and after shearing, the uniform suspension is formed by keeping in a water bath at 60-98℃ for 20-300 minutes; the kinematic viscosity of the suspension is controlled at 6000-18000 cp, preferably 10000-15000 cp. The shearing speed can ensure the uniform mixing of the raw materials, and the kinematic viscosity can be controlled by such shearing conditions. The viscosity can reflect the viscosity and solid content of the suspension. The viscosity will directly affect the size, uniformity and yield of the carrier particles during the granulation process.

[0021] The granulation is spray granulation, and the spray granulation of the high-speed sheared suspension is carried out at an inlet temperature of 180-280℃, preferably 210-250℃, and a pressure of 0.05-0.12 Mpa, preferably 0.06-0.10 Mpa, to obtain the fluidized bed catalyst carrier. The fluidized bed catalyst carrier obtained by spray granulation is calcined at 800-1000℃ for 2-10 hours to obtain the microspherical carrier.

[0022] The granulation can also be centrifugal granulation, and the spray granulation of the high-speed sheared suspension is carried out at an inlet temperature of 180-250 degrees, preferably 200-230 degrees, a centrifugal frequency of 120-180 Hz, preferably 140-160 Hz, and a feeding frequency of 25-60 Hz, preferably 30-50 Hz, to obtain the fluidized bed catalyst carrier. The fluidized bed catalyst carrier obtained by centrifugal granulation is calcined at 800-1000℃ for 2-10 hours to obtain the microspherical carrier.

[0023] The noble metal solution is added to the transition metal salt solution, and then the spray loading is carried out to the microspherical carrier by an equal volume adsorption amount to obtain the catalyst precursor.

[0024] The catalyst precursor is transferred to a rotary furnace, the rotation speed is controlled at 5-20 r / min, and the temperature is baked at 80-120℃ for 2-5 hours, then the temperature of the rotary furnace is controlled to 450℃-500℃, and hydrogen gas is passed at a flow rate of 20-200 ml / min for 2-8 hours to obtain the catalyst product.

[0025] The noble metal in the application includes any one of pd, pt and Rh, and the loading amount is 1.5-2.5 wt%;

[0026] The transition metal salt solution is selected from the nitrate or hydrochloride of Mn, Ni, Fe, Zr, Co, Ir, Os and Re, and the amount is 0.05-10.0 wt% of the amount of noble metal, the pH is adjusted to 1.5-4.0, preferably 2.0-3.5, and the spray loading is carried out by an equal volume adsorption amount.

[0027] Another technical solution of the present application is the anthraquinone fluidized bed hydrogen peroxide catalyst prepared by the method.

[0028] The hydrogenation efficiency of the catalyst reaches 12 parts per liter or more under the condition that the total amount of heavy aromatic hydrocarbon and one or two of the four solvents of diisobutyl methyl alcohol, tricaprylyl phosphate, methylcyclohexyl acetate, and tetrabutyl urea is 180-220 parts per liter.

[0029] The hydrogenation efficiency of the catalyst reaches 12 parts per liter or more under the condition that the total amount of heavy aromatic hydrocarbon and one or two of the four solvents of diisobutyl methyl alcohol, tricaprylyl phosphate, methylcyclohexyl acetate, and tetrabutyl urea is 180-220 parts per liter. DETAILED DESCRIPTION

[0030] The prepared alumina gel: 10wt% nitric acid solution 1000 parts, add 190 parts of active alumina powder, stirring reaction, in a hot water bath at 80°C for 2 hours, to obtain alumina gel.

[0031] Example 1

[0032] In the container, add water 100 parts, 10% nitric acid solution 280 parts, placed in a constant temperature water bath at 80°C, open the stirring, add the prepared alumina gel 210 parts, alumina powder 30 parts, water glass 16 parts, molecular sieve 0.5 parts, dispersant 0.02 parts of polyethylene glycol 200. Adjust the stirring speed to 1000 revolutions per minute, under the condition of 80°C temperature, high speed shearing dispersion for 1 hour. The prepared suspension is centrifuged and granulated to obtain microspheres. Under the condition of high temperature at 950°C, calcine for 2 hours to obtain the corresponding carrier 1 of the fluidized bed catalyst.

[0033] Example 2

[0034] In the container, add water 100 parts, 10wt% nitric acid solution 260 parts, placed in a constant temperature water bath at 80°C, open the stirring, add the prepared alumina gel 200 parts, alumina powder 40 parts, silica sol 0.2 parts, water glass 8 parts, dispersant sodium tripolyphosphate 0.03 parts, adjust the stirring speed to 1000 revolutions per minute, under the condition of 60°C temperature, high speed shearing dispersion for 1 hour. The prepared suspension is spray granulated to obtain microspheres. Under the condition of high temperature at 800-1000°C, calcine for 2.5 hours to obtain the corresponding carrier 2 of the fluidized bed catalyst.

[0035] Example 3

[0036] In a container, add 220 parts of water, 250 parts of 10wt% nitric acid solution, place in a constant temperature water bath at 80°C, start stirring, add 200 parts of previously prepared alumina sol, 45 parts of alumina powder, 4 parts of water glass, 0.2 parts of molecular sieve, 0.03 parts of dispersant sodium tripolyphosphate, adjust the stirring speed to 1000 rpm, carry out high speed shearing dispersion at 60°C for 2 hours. The prepared suspension is spray granulated to obtain microspheres. The microspheres are calcined at a high temperature of 900°C for 2.5 hours to obtain the corresponding carrier 3 of the fluidized bed catalyst.

[0037] Example 4

[0038] In a container, add 100 parts of water, 300 parts of 8wt% oxalic acid solution, place in a constant temperature water bath at 80°C, start stirring, add 200 parts of previously prepared alumina sol, 50 parts of alumina powder, 7.5 parts of water glass, 8 parts of kaolin, 0.3 parts of silica sol, 0.04 parts of dispersant polyethylene glycol 200, adjust the stirring speed to 1000 rpm, carry out high speed shearing dispersion at 80°C for 1 hour. The prepared suspension is centrifugally granulated to obtain microspheres. The microspheres are calcined at a high temperature of 850°C for 2 hours to obtain the corresponding carrier 4 of the fluidized bed catalyst.

[0039] Example 5

[0040] In a container, add 100 parts of water, 220 parts of 8wt% oxalic acid solution, 20 parts of 20% nitric acid solution, place in a constant temperature water bath at 80°C, start stirring, add 200 parts of previously prepared alumina sol, 40 parts of alumina powder, 8 parts of kaolin, 3.2 parts of water glass, 0.05 parts of dispersant polyethylene glycol 200, adjust the stirring speed to 1000 rpm, carry out high speed shearing dispersion at 80°C for 1 hour. The prepared suspension is spray granulated to obtain microspheres. The microspheres are calcined at a high temperature of 800°C for 2 hours to obtain the corresponding carrier 5 of the fluidized bed catalyst.

[0041] Carrier preparation example results

[0042]

[0043] Example 6

[0044] Catalyst preparation.

[0045] Take 1300 parts of carrier 4 (prepared in Example 4), treat with 0.3 wt% aqueous alkali metal solution for 30 minutes, and dry at 120°C. Prepare a solution containing active component palladium and 0.05 wt% Mn, 3 wt% Ni promoter at a loading of 1.80 wt%, adjust the pH to 2.8, and perform isovolume adsorption loading by spray. Transfer the loaded catalyst to a rotary furnace, rotate at 10 r / min, and dry at 120°C for 2 hours, then program the temperature to rise to 450°C, and calcine for 3 hours. Remove the catalyst, reduce with 3% aqueous ammonium bicarbonate solution and a small amount of hydrazine hydrate added dropwise for 30 minutes, then wash with pure water 5 times, transfer to a rotary furnace, rotate at 10 r / min, dry at 120°C, then program the temperature to rise to 450°C, and reduce with hydrogen at a flow rate of 300 ml / min for 4 hours to obtain catalyst 1.

[0046] Example 7

[0047] Catalyst preparation

[0048] Take 1300 parts of carrier 5 (prepared in Example 5), treat with 0.3 wt% aqueous alkali metal solution for 30 minutes, and dry at 120°C. Prepare a solution containing active component palladium and 0.05 wt% Mn, 1.0 wt% Co promoter at a loading of 2.0 wt%, adjust the pH to 2.6, and perform isovolume adsorption loading by spray. Transfer the loaded catalyst to a rotary furnace, rotate at 10 r / min, and dry at 120°C for 2 hours, then program the temperature to rise to 450°C, and calcine for 3 hours. Remove the catalyst, reduce with 3 wt% aqueous ammonium bicarbonate solution and a small amount of hydrazine hydrate added dropwise for 30 minutes, then wash with pure water 5 times, transfer to a rotary furnace, rotate at 10 r / min, dry at 120°C, then program the temperature to rise to 450°C, and reduce with hydrogen at a flow rate of 300 ml / min for 4 hours at 450°C to obtain catalyst 2.

[0049] Example 8

[0050] Catalyst preparation

[0051] Take 1300 parts of carrier 5 (prepared in Example 5), and perform isovolume adsorption loading by spray with a solution of active component Rh at a loading of 1.5 wt%, 1.5 wt% Ni promoter, and 1.0 wt% Mn nitrate. Transfer the loaded catalyst to a rotary furnace, rotate at 10 r / min, and dry at 100°C for 2 hours. Program the temperature to rise to 350°C, and hold for 2 hours until the nitric acid is completely decomposed. Program the temperature to rise to 450°C, then reduce with hydrogen at a flow rate of 300 ml / min for 8 hours to obtain catalyst 3.

[0052] Catalyst evaluation results

[0053] The above catalysts 1, 2, and 3 were tested for efficiency using the process of Example 1 in the patent "Fluidized Bed Hydrogen Peroxide Process, CN111732083A", at a temperature of 40-60℃, a bed pressure of 0.1-0.3Mpa, and under the following working liquid conditions, the hydrogenation efficiency was as follows:

[0054]

[0055] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

[0056] In addition, it should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A method for preparing a catalyst for preparing hydrogen peroxide in an anthraquinone process fluidized bed, characterized in that: The steps of vector preparation include: Step 1: The activated alumina powder reacts with the acid solution to prepare alumina gel. The activated alumina powder used has a dry bulk density of 0.25-0.35 g / ml and a specific surface area of ​​180-350 m 2 / g, pore volume 0.6-1.2cm 2 / g, pore size 8-15nm, the mass ratio of activated alumina powder to acid solution is 1: (5-10), the activated alumina powder and acid solution are gelled in a water bath at 60-90°C for 1-5 hours, and then taken out and set aside; Step 2: adding alumina gel and alumina powder to the acid solution under stirring to obtain a slurry; In step 2, the ratio of alumina glue to alumina powder is (3-10):1; Step 3, adding auxiliary raw materials to the slurry of step 2, wherein the auxiliary raw materials are selected from two or more of silica sol, kaolin, water glass, molecular sieve, and silica-alumina dry glue powder; Step 4: adding a suspending agent to the mixed solution of step 3, wherein the suspending agent is selected from two or more of polyethylene glycol 200, sodium tripolyphosphate, sodium hexametaphosphate, methylpentanol, and polyacrylamide; Step 5: The mixture obtained in step 4 is subjected to high-speed shear stirring to form a suspension. After the suspension is sealed and aged for 3-25 hours, it is granulated and calcined to obtain a fluidized bed catalyst support. The kinematic viscosity of the suspension is controlled to be 6000-18000cp; Step six, adding the precious metal solution to the transition metal salt solution and spraying it onto the microsphere carrier by equal volume adsorption amount to obtain a catalyst precursor, which is then calcined to obtain a fluidized bed catalyst; the precious metal includes any one of Pd, Pt, and Rh, and the transition metal salt solution is selected from the nitrate or hydrochloride of Mn, Ni, Fe, Zr, and Co.

2. The method for preparing a catalyst for preparing hydrogen peroxide in anthraquinone fluidized bed according to claim 1, wherein: The acid solution in steps 1 and 2 is selected from any one or more combinations of nitric acid, acetic acid, and oxalic acid; the mass concentration of nitric acid, acetic acid, and oxalic acid is 3-25%.

3. The method for preparing a catalyst for preparing hydrogen peroxide in anthraquinone fluidized bed according to claim 2, wherein: Add 0.03%-15% of the amount of alumina glue to the auxiliary raw materials in step three.

4. The method for preparing a catalyst for preparing hydrogen peroxide in anthraquinone fluidized bed according to claim 1, wherein: In step 4, the suspending agent is added at 0.010-0.500% of the amount of alumina gel.

5. The method for preparing a catalyst for preparing hydrogen peroxide in anthraquinone fluidized bed according to claim 1, wherein: In step 5, high-speed shear stirring is performed at a speed of 500-1000 rpm, and after shearing, the mixture is kept in a water bath at 60-98° C. for 20-300 minutes to form a uniform suspension; the kinematic viscosity of the suspension is controlled at 10,000-15,000 cp.

6. The method for preparing a catalyst for preparing hydrogen peroxide by anthraquinone process fluidized bed according to claim 1, characterized in that: The granulation is spray granulation, and the spray granulation is carried out by spraying granulation on a suspension with high-speed shearing at an inlet temperature of 180-280° C. and a pressure of 0.05-0.12 MPa to obtain a fluidized bed catalyst carrier.

7. The method for preparing a catalyst for preparing hydrogen peroxide in anthraquinone fluidized bed according to claim 6, wherein: The granulation is spray granulation, and the spray granulation is to spray granulate the suspension with high-speed shearing at an inlet temperature of 210-250° C. and a pressure of 0.06-0.10 MPa to obtain a fluidized bed catalyst carrier.

8. The method for preparing a catalyst for preparing hydrogen peroxide by anthraquinone process fluidized bed according to claim 1, characterized in that: The fluidized bed catalyst carrier obtained by spray granulation is calcined at 800-1000° C. for 2-10 hours to obtain a microsphere carrier.

9. The method for preparing a catalyst for preparing hydrogen peroxide in anthraquinone fluidized bed according to claim 1, wherein: The catalyst precursor is transferred to a rotary kiln, the speed is controlled at 5-20r / min, and the temperature is 80-120℃ for 2-5 hours. Then the temperature is programmed to control the temperature of the rotary kiln to 450℃-500℃, and hydrogen is passed through at a flow rate of 20-200ml / min for 2-8 hours to obtain the finished catalyst.

10. The method for preparing a catalyst for preparing hydrogen peroxide by anthraquinone process in a fluidized bed according to claim 9, characterized in that: The loading of precious metals is 1.5-2.5wt%; The amount of transition metal used is 0.05-10.0 wt % of the amount of noble metal used, and the pH is adjusted to 1.5-4.0 for spray loading with equal volume adsorption amount.

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