Anti-sintering methanol cracking catalyst and preparation method thereof

Abstract

The application discloses an anti-sintering methanol cracking catalyst and a preparation method thereof, and belongs to the field of hydrogen production by methanol cracking catalysis. The anti-sintering methanol cracking catalyst comprises the following raw materials in parts by weight: strontium nitrate 1.8-3 parts, titanium nitrate 6.3-10.5 parts, a Cu active carrier 58-70 parts and polyvinyl alcohol 2-5 parts. The Cu active carrier comprises the following raw materials in parts by weight: copper acetate 12-21 parts and a Zr-HAP-P2O7 carrier 51-60 parts. The Zr-HAP-P2O7 carrier comprises the following raw materials in mole fractions: calcium nitrate 19-22 parts, zirconium nitrate 1.8-2.5 parts, ammonium dihydrogen phosphate 18 parts and sodium pyrophosphate 1.4-1.7 parts. The methanol cracking catalyst provided by the application has strong anti-sintering capacity, can effectively prevent the generation of carbon deposition and prolong the service life of the catalyst.

Description

TECHNICAL FIELD

[0001] The application discloses a sintering-resistant methanol cracking catalyst and a preparation method thereof, and belongs to the field of methanol cracking catalytic hydrogen production. BACKGROUND

[0002] Under the background of global energy structure transformation, hydrogen energy, as a clean and efficient energy, has a broad application prospect in the fields of chemical industry, energy, transportation and the like due to its unique advantages. Due to the problems of easy leakage of hydrogen and low efficiency of long-distance transportation, the application of hydrogen energy has been a bottleneck. Methanol, as a liquid carrier of hydrogen, is convenient for transportation, storage and refueling, so that the methanol cracking hydrogen production technology provides a low-cost and high-efficiency solution for the production of hydrogen. Copper-based catalysts are widely studied and applied in the field of methanol cracking hydrogen production because of their excellent intrinsic activity in breaking C-O bonds and activating C-H bonds at a relatively low temperature, and the cost is much lower than that of noble metal catalysts. However, the low Tammann temperature of metal copper nanoparticles makes them have a very high surface energy and mobility at the reaction temperature, and they are easy to sinter through Ostwald ripening and particle migration effect, resulting in a decrease in active sites, particle growth and catalyst deactivation.

[0003] The prior art with the publication number CN102631920B discloses a copper-based methanol cracking catalyst and a preparation method and application thereof, adopts SiO2 as the carrier and adds graphite for pore making, and the preparation process is simple and does not need pre-reduction. However, the carrier composition is single, Cu is mainly dispersed through physical action, and under a long-term high-temperature or hydrothermal environment, Cu particles are still easy to migrate and agglomerate, and the anti-sintering capacity is limited. The prior art with the publication number CN115642263A discloses a methanol reforming hydrogen production catalyst containing a CuO and Cu2O film and a preparation method and application thereof, and the preparation process involves vacuum impregnation, vapor deposition, controlled reduction and the like, the technical threshold and production cost are high, and in order to obtain a film structure, the copper loading is low, and the overall activity of the catalyst per unit volume is limited. The prior art with the publication number CN110292924A discloses a methanol low-temperature cracking catalyst and a preparation method thereof, and the catalyst comprises Pd, an additive and a carrier, and good low-temperature activity is achieved, but the active component is the noble metal Pd, the cost is high, the demand of large-scale application cannot be met, the preparation conditions are harsh, and large-scale production is also not suitable.

[0004] It can be seen from the above that the methanol cracking catalyst produced by the prior art still has problems of easy sintering and deactivation, complex process and high production cost. SUMMARY

[0005] In order to solve the above problems existing in the prior art, the application provides an anti-sintering methanol cracking catalyst and a preparation method thereof, and achieves the following application purposes: the anti-sintering methanol cracking catalyst is prepared by using relatively conventional chemical raw materials, has low production cost, high activity and high anti-sintering performance.

[0006] In order to achieve the above-mentioned purposes, the technical scheme adopted is as follows:

[0007] An anti-sintering methanol cracking catalyst, raw materials of which include strontium nitrate (Sr(NO3)2) 1.8-3 parts, titanium nitrate (Ti(NO3)4) 6.3-10.5 parts, Cu active carrier 58-70 parts and polyvinyl alcohol 2-5 parts by weight.

[0008] The Cu active carrier includes copper acetate 12-21 parts and Zr-HAP-P2O7 carrier 51-60 parts by weight.

[0009] The Zr-HAP-P2O7 carrier is prepared from calcium nitrate (Ca(NO3)2), zirconium nitrate (Zr(NO3)4), ammonium dihydrogen phosphate ((NH4)2HPO4) and sodium pyrophosphate (Na4P2O7); the molar ratio of calcium nitrate, zirconium nitrate, ammonium dihydrogen phosphate and sodium pyrophosphate is (19-22):(1.8-2.5):18:(1.4-1.7).

[0010] A preparation method of the anti-sintering methanol cracking catalyst, comprising the following steps:

[0011] Step one, preparation of the Zr-HAP-P2O7 carrier

[0012] (1) Ca(NO3)2, Zr(NO3)4 and (NH4)2HPO4 are dissolved in deionized water and continuously stirred; the amount of deionized water is 7-10 times the total mass of Ca(NO3)2, Zr(NO3)4 and (NH4)2HPO4. The pH value of the solution is adjusted to 11-12 by using 10% ammonia water, and then the solution is stirred and incubated at 30-45°C for 1-2h to generate white precipitate. The precipitate is separated and washed with deionized water until the washing liquid is neutral to obtain zirconium-hydroxyapatite (Zr-HAP).

[0013] (2) Zirconium-hydroxyapatite, sodium pyrophosphate and deionized water are mixed, and the amount of deionized water is 5 times the mass of Zr-HAP; under the condition of 50-65℃, high-speed stirring and dispersion are carried out at a speed of 6000-9000r / min, 10% ammonia water is used to adjust the pH value of the mixed solution to 9-10, and after stirring and dispersion for 2-3h, the speed is switched to 700-1000r / min for low-speed stirring and dispersion for 3.5-6h. After low-speed stirring, the reaction liquid is filtered, and the filter cake is reserved. The filter cake is washed with deionized water until the washing liquid is neutral, and then dried at 80-100℃ until the water content is less than 1%, and then transferred to an electric furnace, nitrogen is introduced, heated to 750-800℃ at a rate of 15-20℃ / min, and heat treated for 0.5-1h to obtain Zr-HAP-P2O7 carrier.

[0014] In this step, Zr 4+ Partly replace Ca in HAP 2+ , which helps to inhibit the collapse of the carrier at high temperature. This way not only retains the skeleton structure of HAP, but also introduces new active sites through pyrophosphate, providing an ideal carrier environment for subsequent active ingredient loading and catalytic reaction.

[0015] Step two, load active ingredients

[0016] Copper acetate is dissolved in deionized water, and the amount of deionized water is 15-20 times the mass of copper acetate; then Zr-HAP-P2O7 carrier is added, stirred uniformly, and then transferred to a hydrothermal kettle, and hydrothermal reaction is carried out at 140-155℃ for 7-9h, then stop heating, and after the liquid is naturally cooled to room temperature, perform filtration operation, and reserve the solid to obtain Cu active carrier loaded with Cu active ingredients.

[0017] Compared with single CuO component, the active ingredient on the Cu active carrier of the application is Cu2O-CuO heterojunction, which has the effect of inhibiting particle migration and agglomeration.

[0018] Step three, load auxiliary agent and calcination

[0019] Sr(NO3)2, Ti(NO3)4, Cu active carrier and polyvinyl alcohol are put into deionized water, stirred for 1-2h, and then immersed at room temperature for 20-30h. Stir every 2h for 5min during the immersion process; the amount of deionized water is 6-8 times the total mass of Sr(NO3)2, Ti(NO3)4, Cu active carrier and polyvinyl alcohol. After the immersion is completed, the immersion liquid is filtered, and the solid is reserved. The obtained solid is a catalyst precursor. The catalyst precursor is placed in an electric furnace, heated to 700-750℃ at a rate of 10-20℃ / min, and calcined in an air atmosphere for 0.5-1h, and then cooled to room temperature to obtain the finished catalyst.

[0020] After calcination, Sr(NO3)2 and Ti (NO3)4 are decomposed into SrO-TiO2 composite oxides, which form a physical barrier on the surface of the carrier to prevent particle migration or growth and inhibit the generation of carbon deposition.

[0021] The beneficial effects of the present application are as follows:

[0022] The initial methanol conversion rate of the anti-sintering methanol cracking catalyst prepared by the method is 97.62~98.58%; after heat treatment at 400℃ for 24h, the methanol conversion rate is 96.98~98.02% when the catalyst is tested again, the attenuation amplitude of the catalytic conversion rate is small; after 300h of continuous use, the carbon deposition amount is 0.02~0.05wt%, which indicates that it has excellent anti-sintering ability and can effectively prevent carbon deposition, prolonging the service life of the catalyst. The preparation method provided by the present application does not require special equipment such as ultra-low temperature and vacuum, and the preparation cost is relatively low, which is suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0023] FIG. 1 is a physical map of the methanol cracking catalyst prepared in Example 1. Figure 1 FIG. 2 is a physical map of the methanol cracking catalyst prepared in Example 2.

[0024] FIG. 3 is a SEM map of the methanol cracking catalyst prepared in Example 1. Figure 2 FIG. 4 is a SEM map of the methanol cracking catalyst prepared in Example 2. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical scheme and advantages of the present application clearer, the embodiments of the present application will be further described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0026] Example 1: An anti-sintering methanol cracking catalyst

[0027] An anti-sintering methanol cracking catalyst, the preparation raw materials include strontium nitrate 3 parts, titanium nitrate 10.5 parts, Cu active carrier 70 parts, and polyvinyl alcohol 5 parts by weight.

[0028] The Cu active carrier, the preparation raw materials include copper acetate 15 parts and Zr-HAP-P2O7 carrier 55 parts by weight.

[0029] The Zr-HAP-P2O7 carrier, the preparation raw materials include calcium nitrate (Ca(NO3)2), zirconium nitrate (Zr(NO3)4), ammonium dihydrogen phosphate ((NH4)2HPO4), and sodium pyrophosphate (Na4P2O7); the molar ratio of calcium nitrate, zirconium nitrate, ammonium dihydrogen phosphate, and sodium pyrophosphate is 20:2.5:18:1.4.

[0030] A preparation method of a methanol cracking catalyst resistant to sintering, comprising the following steps:

[0031] Step one, preparation of Zr-HAP-P2O7 carrier

[0032] (1) Dissolve Ca(NO3)2, Zr(NO3)4 and (NH4)2HPO4 in deionized water and continuously stir; the amount of deionized water is 10 times the total mass of Ca(NO3)2, Zr(NO3)4 and (NH4)2HPO4. Adjust the pH value of the solution to 11 with 10% ammonia water by mass, then keep stirring at 45°C for 1h to generate white precipitate. Separate the precipitate, wash the precipitate with deionized water until the washing liquid is neutral, and obtain zirconium-hydroxyapatite (Zr-HAP).

[0033] (2) Mix Zr-HAP, sodium pyrophosphate and deionized water, and the amount of deionized water is 5 times the mass of Zr-HAP. Stir and disperse at a speed of 6000r / min at 50°C, adjust the pH value of the mixture to 10 with 10% ammonia water by mass, stir and disperse for 2h, then switch to a stirring speed of 700r / min and continue stirring for 6h. After low-speed stirring is completed, the liquid is suction filtered, the filter cake is retained, and the filter cake is washed with deionized water until the washing liquid is neutral. After washing, dry at 100°C until the water content is less than 1%, transfer to an electric furnace, introduce nitrogen, heat to 800°C at a rate of 20°C / min, and heat treat for 0.5h to obtain Zr-HAP-P2O7 carrier.

[0034] Step two, loading active ingredients

[0035] Dissolve copper acetate in deionized water, and the amount of deionized water is 20 times the mass of copper acetate; then add Zr-HAP-P2O7 carrier, stir uniformly, and then transfer the liquid to a hydrothermal kettle for hydrothermal reaction at 155°C for 7h. After stopping heating, the liquid is naturally cooled to room temperature, and then suction filtration is performed to retain the solid to obtain Cu active carrier loaded with Cu active ingredients.

[0036] Step three, loading adjuvants and calcining and molding

[0037] Put Sr(NO3)2, Ti(NO3)4, Cu active carrier and polyvinyl alcohol into deionized water, stir for 1h, then immerse at room temperature for 30h. Stir every 2h for 5min during the immersion process; the amount of deionized water is 6 times the total mass of Sr(NO3)2, Ti(NO3)4, Cu active carrier and polyvinyl alcohol. After the immersion is completed, filter the immersion liquid to retain the solid, and the obtained solid is a catalyst precursor. Put the catalyst precursor into an electric furnace, heat to 700°C at a rate of 10°C / min, heat for 1h at a constant temperature, naturally cool to room temperature, and obtain the finished catalyst.

[0038] Example 2 Anti-sintering methanol cracking catalyst

[0039] An anti-sintering methanol cracking catalyst, the raw materials for preparation include strontium nitrate 2 parts, titanium nitrate 7 parts, Cu active carrier 58 parts, polyvinyl alcohol 3 parts by weight.

[0040] The Cu active carrier, the raw materials for preparation include copper acetate 21 parts, Zr-HAP-P2O7 carrier 60 parts by weight.

[0041] The Zr-HAP-P2O7 carrier, the raw materials for preparation include calcium nitrate (Ca(NO3)2), zirconium nitrate (Zr(NO3)4), ammonium dihydrogen phosphate ((NH4)2HPO4), sodium pyrophosphate (Na4P2O7); the molar ratio of calcium nitrate, zirconium nitrate, ammonium dihydrogen phosphate, sodium pyrophosphate is 22:1.8:18:1.5.

[0042] A preparation method of an anti-sintering methanol cracking catalyst, comprising the following steps:

[0043] Step one, preparation of Zr-HAP-P2O7 carrier

[0044] (1) Dissolve Ca(NO3)2, Zr(NO3)4, (NH4)2HPO4 in deionized water and continuously stir; the amount of deionized water is 10 times the total mass of Ca(NO3)2, Zr(NO3)4, (NH4)2HPO4. Adjust the pH value of the solution to 11 with 10% ammonia water, then incubate at 30℃ for 2h, generate white precipitate. Separate the precipitate, wash the precipitate with deionized water until the washing liquid is neutral, and obtain zirconium-hydroxyapatite (Zr-HAP).

[0045] (2) Mix zirconium-hydroxyapatite, sodium pyrophosphate and deionized water, the amount of deionized water is 5 times the mass of Zr-HAP, stir and disperse at 9000r / min under the condition of 60℃, adjust the pH value of the mixture to 10 with 10% ammonia water, stir and disperse for 3h, then switch to 1000r / min and continue stirring for 4h. After low-speed stirring is completed, the liquid is filtered, the filter cake is reserved, and the filter cake is washed with deionized water until the washing liquid is neutral. After washing, dry at 80℃ until the water content is less than 1%, transfer to an electric furnace, introduce nitrogen, heat to 750℃, heat treatment for 1h to obtain Zr-HAP-P2O7 carrier; the heating rate of heat treatment is controlled at 15℃ / min.

[0046] Step two, loading active ingredients

[0047] Copper acetate was dissolved in deionized water, and the amount of deionized water was 15 times the mass of copper acetate; then the Zr-HAP-P2O7 carrier was added, and after stirring uniformly, the liquid was transferred to a hydrothermal kettle, and hydrothermal reaction was carried out at 140℃ for 9h; after stopping heating, the liquid was naturally cooled to room temperature, and then filtration was carried out, and the solid was retained to obtain a Cu active carrier loaded with a Cu active component.

[0048] Step three, loading of the auxiliary and calcination molding

[0049] Sr(NO3)2, Ti(NO3)4, Cu active carrier, and polyvinyl alcohol were put into deionized water, stirred for 2h, and then immersed at room temperature for 20h. During the immersion process, stirring was carried out every 2h for 5min; the amount of deionized water was 6 times the total mass of Sr(NO3)2, Ti(NO3)4, Cu active carrier, and polyvinyl alcohol. After the immersion was completed, the immersion liquid was filtered, and the solid was retained, and the obtained solid was a catalyst precursor. The catalyst precursor was placed in an electric furnace, and the temperature was increased to 750℃ at a rate of 20℃ / min, and then the temperature was kept constant for 0.5h, and then the temperature was naturally cooled to room temperature, and a catalyst product was obtained.

[0050] Example 3: A sintering-resistant methanol cracking catalyst

[0051] A sintering-resistant methanol cracking catalyst, the raw materials include, by weight, 1.8 parts of strontium nitrate, 6.3 parts of titanium nitrate, 60 parts of Cu active carrier, and 2 parts of polyvinyl alcohol.

[0052] The Cu active carrier, the raw materials include, by weight, 12 parts of copper acetate and 51 parts of Zr-HAP-P2O7 carrier.

[0053] The Zr-HAP-P2O7 carrier, the preparation raw materials include calcium nitrate (Ca(NO3)2), zirconium nitrate (Zr(NO3)4), ammonium dihydrogen phosphate ((NH4)2HPO4), and sodium pyrophosphate (Na4P2O7); the molar ratio of calcium nitrate, zirconium nitrate, ammonium dihydrogen phosphate, and sodium pyrophosphate is 19:2:18:1.7.

[0054] A preparation method of a sintering-resistant methanol cracking catalyst, including the following steps:

[0055] Step one, preparation of Zr-HAP-P2O7 carrier

[0056] (1) Ca(NO3)2, Zr(NO3)4, (NH4)2HPO4 were dissolved in deionized water and continuously stirred; the amount of deionized water was 7 times the total mass of Ca(NO3)2, Zr(NO3)4, (NH4)2HPO4. The pH value of the solution was adjusted to 12 with 10% ammonia water by mass, and then the solution was stirred at 30°C for 2h to generate white precipitate. The precipitate was separated and washed with deionized water until the washing liquid was neutral to obtain zirconium-hydroxyapatite (Zr-HAP).

[0057] (2) Zr-HAP, sodium pyrophosphate and deionized water were mixed, and the amount of deionized water was 5 times the mass of Zr-HAP. Stirring and dispersion were carried out at 8000r / min at 65°C, the pH value of the mixture was adjusted to 9 with 10% ammonia water by mass, and stirring and dispersion were carried out for 2h, then the stirring speed was switched to 1000r / min and stirring was continued for 3.5h. After low-speed stirring was completed, the liquid was suction filtered, the filter cake was retained, and the filter cake was washed with deionized water until the washing liquid was neutral. After washing, it was dried at 90°C until the water content was less than 1%, and then it was transferred to an electric furnace, nitrogen was introduced, the temperature was raised to 750°C at a rate of 15°C / min, and heat treatment was carried out for 1h to obtain Zr-HAP-P2O7 carrier.

[0058] Step two, loading active ingredients

[0059] Copper acetate was dissolved in deionized water, and the amount of deionized water was 15 times the mass of copper acetate; then the Zr-HAP-P2O7 carrier was added, and after stirring evenly, the solution was transferred to an autoclave for hydrothermal reaction at 145°C for 7h. After stopping heating, the solution was naturally cooled to room temperature, and then suction filtration was carried out to retain the solid to obtain a Cu active carrier loaded with Cu active ingredients.

[0060] Step three, loading adjuvants and calcination

[0061] Sr(NO3)2, Ti(NO3)4, Cu active carrier, and polyvinyl alcohol were added to deionized water and stirred for 1h, and then immersed at room temperature for 30h. During the immersion process, stirring was carried out every 2h for 5min; the amount of deionized water was 8 times the total mass of Sr(NO3)2, Ti(NO3)4, Cu active carrier, and polyvinyl alcohol. After the immersion was completed, the immersion solution was filtered to retain the solid, and the obtained solid was a catalyst precursor. The catalyst precursor was placed in an electric furnace and heated to 750°C at a rate of 20°C / min, and then calcined at a constant temperature for 0.5h, and then naturally cooled to room temperature to obtain a finished catalyst product.

[0062] Comparative Example 1

[0063] In Example 1, Zr(NO3)4 was not added in step one, and the remaining steps and operations were the same as those of Example 1.

[0064] Comparative Example 2

[0065] Based on step one of Example 1, sodium pyrophosphate was not added, and zircon-hydroxyapatite was directly heat-treated for later use; the remaining steps and operations were the same as in Example 1.

[0066] Comparative Example 3

[0067] Step 1: Same as Step 1 in Example 1.

[0068] Step 2: Weigh 17 parts Cu(NO3)2·3H2O and 8 parts Ni(NO3)2·6H2O by weight to prepare an aqueous solution. Using 55 parts Zr-HAP-P2O7 as a support, prepare the catalyst by equal volume impregnation method for 30 hours. After drying, calcine at 600℃ for 4 hours under nitrogen atmosphere to obtain the catalyst.

[0069] Performance testing

[0070] The catalyst products obtained in Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests, and the test results are shown in Table 1.

[0071] The finished catalyst product is processed or tested under the following conditions:

[0072] Initial methanol conversion: Catalyst performance was tested in a micro fixed-bed reactor with a catalyst loading of 10.0 g, a pressure of 0.3 MPa, and a mass hourly space velocity (WHSV) of 2.0 h⁻¹. -1 The reaction temperature was 240℃. After the reaction stabilized for 2 hours, the amount of hydrogen generated at the reactor outlet was measured. The initial methanol conversion rate was calculated by comparing it with the actual methanol consumption.

[0073] Catalyst heat treatment: Place the catalyst in a furnace, set the temperature to 400℃, and heat treat for 24 hours.

[0074] Methanol conversion rate of catalyst after heat treatment at 400℃: The performance of the catalyst was tested in a micro fixed-bed reactor with a catalyst loading of 10.0 g after heat treatment, a pressure of 0.3 MPa, and a mass hourly space velocity of 2.0 h⁻¹. -1 The reaction temperature was 240℃. After the reaction stabilized for 2 hours, the amount of hydrogen generated at the reactor outlet was measured. The methanol conversion rate was calculated by comparing the amount of hydrogen generated with the actual methanol consumption.

[0075] Carbon deposition in the catalyst was determined: the catalyst was taken out after reaction for 300h under the test conditions of initial methanol conversion rate, and the carbon deposition amount was determined by thermogravimetric analysis. Temperature control: first, heat to 150℃ at a rate of 10℃ / min, keep for 20min, and perform dehydration by blowing with nitrogen atmosphere; switch the atmosphere to air, heat to 800℃ at a rate of 10℃ / min, keep for 20min; switch the atmosphere back to nitrogen, cool to room temperature.

[0076] Table 1 Test results of catalyst product performance

[0077]

[0078] It can be seen from the data in Table 1 that the initial methanol conversion rate of the methanol cracking catalyst prepared in the application is 97.62~98.58%; after heat treatment at 400℃ for 24h, the methanol conversion rate is 96.98~98.02% again, and the catalytic capacity attenuation amplitude is small; after continuous use for 300h, the carbon deposition amount is 0.02~0.05wt%, which shows that the methanol cracking catalyst prepared in the application has excellent anti-sintering ability, can effectively prevent carbon deposition, and prolongs the service life of the catalyst. In Comparative Example 1, Zr(NO3)4 is not used, and in Comparative Example 2, sodium pyrophosphate is not used, and the methanol conversion rate decreases significantly, which shows that the Zr-HAP-P2O7 carrier formed by the synergistic doping of Zr 4+ and HAP in the application has strong anti-sintering ability, and since the carrier is used in Comparative Example 3, the methanol conversion rate of the catalyst in Comparative Example 3 decreases less after heat treatment than that in Comparative Examples 1 and 2, which also confirms this point; however, since the conventional equal-volume impregnation method is used in Comparative Example 3, the Sr-Ti composite promoter is not loaded and is directly calcined and formed, and the test results show that the carbon deposition amount is relatively high, while the carbon deposition amounts in Comparative Examples 1 and 2 are relatively low, which shows that the Sr-Ti composite promoter in the technical scheme of the application has the effect of inhibiting carbon deposition.

[0079] Obviously, there are many specific implementation methods that can be changed under the concept of the application, and here it should be declared that any change made under the inventive concept of the application will fall within the protection scope of the application.

Claims

1. A sintering-resistant methanol cracking catalyst, characterized by: The methanol cracking catalyst: the raw materials for preparation include strontium nitrate 1.8~3 parts, titanium nitrate 6.3~10.5 parts, Cu active carrier 58~70 parts, polyvinyl alcohol 2~5 parts by weight; The Cu active carrier: the raw materials for preparation include copper acetate 12~21 parts, Zr-HAP-P2O7 carrier 51~60 parts by weight; The Zr-HAP-P2O7 carrier: the raw materials for preparation include calcium nitrate, zirconium nitrate, ammonium dihydrogen phosphate, sodium pyrophosphate; the molar ratio of calcium nitrate, zirconium nitrate, ammonium dihydrogen phosphate, sodium pyrophosphate is (19~22): (1.8~2.5): 18: (1.4~1.7); The preparation method of the methanol cracking catalyst includes the steps of preparing Zr-HAP-P2O7 carrier, loading active ingredients, loading auxiliary agents and calcining and molding; the preparation of Zr-HAP-P2O7 carrier: Ca(NO3)2, Zr(NO3)4, (NH4)2HPO4 are dissolved in water, the pH value of the solution is adjusted to 11~12 with ammonia water, and the zirconium-hydroxyapatite is generated after 1~2h of heat preservation and stirring; the zirconium-hydroxyapatite, sodium pyrophosphate and water are mixed, the pH value of the mixed solution is adjusted to 9~10 with ammonia water at 50~65℃, and after high-speed stirring and low-speed stirring, the filter cake is reserved after the reaction solution is filtered, and the filter cake is heat treated to obtain the Zr-HAP-P2O7 carrier; The loading of active ingredients: copper acetate is dissolved in 15~20 times mass of deionized water, then the Zr-HAP-P2O7 carrier is added, and after uniform stirring, the material liquid is transferred to an autoclave for hydrothermal reaction for 7~9h, and after the material liquid is cooled, the solid is reserved after filtration to obtain the Cu active carrier loaded with Cu active ingredients; the reaction temperature of the hydrothermal reaction is 140~155℃; the active ingredient is Cu2O-CuO heterojunction; The loading of auxiliary agents and calcining and molding: Sr(NO3)2, Ti(NO3)4, Cu active carrier and polyvinyl alcohol are put into deionized water and stirred for 1~2h, and then immersed at room temperature for 20~30h, and the catalyst precursor is obtained after intermittent stirring during the immersion process; the catalyst precursor is placed in an electric furnace for heating, and the catalyst product is obtained after constant temperature calcination in an air atmosphere for 0.5~1h; the constant temperature calcination: the temperature of the constant temperature calcination is 700~750℃.

2. The sintering-resistant methanol cracking catalyst of claim 1, wherein: The high-speed stirring and dispersion: stirring and dispersion at a speed of 6000~9000r / min for 2~3h; the low-speed stirring and dispersion: stirring and dispersion at a speed of 700~1000r / min for 3.5~6h.

3. The sintering-resistant methanol cracking catalyst of claim 1, wherein: The heat treatment: the filter cake is washed with deionized water until the washing liquid is neutral, and then dried at 80~100℃ until the water content is less than 1%, and then transferred to an electric furnace, nitrogen is introduced, heated to 750~800℃, and heat treated for 0.5~1h to obtain the Zr-HAP-P2O7 carrier; the heating rate of the heat treatment is controlled at 15~20℃ / min.

4. The sintering-resistant methanol cracking catalyst of claim 1, wherein: The intermittent stirring: stirring for 5min every 2h during the immersion process.

5. The sintering-resistant methanol cracking catalyst of claim 1, wherein: The heating: the heating rate is 10~20℃ / min.

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