High-strength spinel carrier and preparation method thereof

Abstract

The invention provides a high-strength spinel carrier and a preparation method thereof, and relates to the field of petrochemical industry. The spinel carrier has a porous structure, the chemical general formula of the spinel carrier is MxNyAl2O4, and the element M is one or more of Zn, Co, Ni and Fe; the N element is one or more of Na, K, Ca, Mg and Ba, and x + y = 1, 0lt; xlt; 1, 0lt; yt; Yt; 1. The spinel carrier is prepared by one of a solid-phase grinding method, an alkoxide hydrolysis method and a precipitation method. As a carrier of a catalyst active component, the carrier has good stability and good processability, and a catalyst prepared from the carrier has the characteristics of high conversion rate, high product propylene selectivity, strong anti-sintering capability, good stability and the like in a propane dehydrogenation reaction.

Description

Technical Field

[0001] The invention relates to the field of petrochemical industry, and in particular to a high-strength spinel carrier and a preparation method thereof. Background Art

[0002] The dehydrogenation of low-carbon alkanes to corresponding olefins is the main way to utilize low-carbon alkanes. At present, there are three main methods for dehydrogenating alkanes: direct dehydrogenation, oxidative dehydrogenation, and membrane catalytic dehydrogenation. Direct dehydrogenation refers to the process in which alkanes directly remove two hydrogen atoms to generate olefins in the presence of a catalyst. The activity, selectivity, and stability of the catalyst directly affect the cost and efficiency of the dehydrogenation reaction.

[0003] There are many processes for direct dehydrogenation under the action of catalysts, among which Catofin and Oleflex processes are the most widely used. The Catofin process uses CrOx / Al2O3 as a catalyst and adopts an adiabatic fixed bed reactor. During the reaction process, one part of the reactor performs dehydrogenation reaction, and the other part of the reactor performs catalyst regeneration reaction, and the alternating cycle (a complete cycle takes 15-30 minutes) is carried out to ensure the continuous production of propylene. The Oleflex process uses Pt-Sn / Al2O3 catalyst. The entire device uses an adiabatic radial fluidized bed reactor. The intermediate series preheater provides heat for the reaction system, and the last reactor is connected to the catalyst regeneration device. The catalyst flows in the entire device, and the regenerated catalyst re-enters the first reactor (a complete cycle takes 5-10 days). The entire device is in continuous operation and the reaction product is obtained uninterruptedly. Compared with CrOx / Al2O3 catalysts, Pt-based catalysts have high reaction activity, high propylene selectivity and low toxicity. However, Pt particles are easy to sinter and grow under high temperature conditions, and are also easy to be deactivated by carbon deposition, and have poor stability, which greatly reduces the production capacity of the equipment.

[0004] For alkane dehydrogenation catalysts, alumina is often used as a carrier. The acidic sites on the surface of the alumina carrier are both the active centers of the catalytic reaction and the carbon deposition centers of the reaction. Hydrocarbons are easily cracked and condensed on the L acid centers on the surface of the carrier to produce carbon deposition, and the stronger the acidity of the acid center, the easier it is to produce carbon deposition. Therefore, the strength of the acidity of the alumina surface has a great influence on the dispersion of active metals on the carrier surface and the anti-carbon deposition performance of the catalyst. The Chinese patent (CN107303508A) contacts the alumina carrier with an inorganic acid aqueous solution and provides a method for modifying the alumina carrier. Although this method is not doped with metal elements and non-metallic elements, it retains the original components of the carrier and improves the selectivity of propylene, but after 24h evaluation, the catalyst activity shows a downward trend. The Chinese patent (CN105642264A) provides a dehydrogenation catalyst prepared by a sol-gel method on a magnesium aluminum spinel carrier. Although it improves the selectivity of propylene in the propane dehydrogenation reaction, its stability is not good. After 4h of reaction, the propane conversion rate decreases.

[0005] In the above-mentioned dehydrogenation catalyst in the prior art, the acidity and alkalinity of the carrier are not well improved, which causes the catalyst to deactivate linearly quickly, and the catalyst is not molded, making it difficult to achieve industrial application. Summary of the invention

[0006] The object of the present invention is to provide a high-strength spinel carrier, which, as a carrier of a catalyst active component, has good stability and good processability. The catalyst prepared from the carrier has the characteristics of high conversion rate, high product propylene selectivity, strong anti-sintering ability and good stability in the propane dehydrogenation reaction.

[0007] Another object of the present invention is to provide a method for preparing a high-strength spinel carrier, which has simple preparation steps, low requirements on equipment, and can be industrially produced.

[0008] The present invention solves the technical problem by adopting the following technical solutions.

[0009] On the one hand, the embodiment of the present invention provides a high-strength spinel carrier, wherein the spinel carrier has a porous structure and its chemical formula is: x N y Al2O4, wherein the M element is one or more of Zn, Co, Ni, and Fe; the N element is one or more of Na, K, Ca, Mg, and Ba, and x+y=1,0 <x<1,0<y<1。

[0010] In some embodiments of the present invention, the precursor of the M element is one or more of its nitrate, hydrochloride, acetate, and oxide.

[0011] In some embodiments of the present invention, the precursor of the N element is one or more of its nitrate, hydrochloride, acetate, and oxide.

[0012] In some embodiments of the present invention, the precursor of the Al element is one or more of aluminum chloride, aluminum nitrate, aluminum acetate, aluminum oxide, aluminum ore, and organic alcohol aluminum salt.

[0013] In some embodiments of the present invention, the spinel carrier has a specific surface area of ​​10-100m 2 / g, pore size range is 3nm-30nm, pore volume range is 0.1-0.7g / mL, and carrier mechanical strength is 100-200N / cm.

[0014] On the other hand, an embodiment of the present invention provides a method for preparing a high-strength spinel carrier, which comprises: preparing the spinel carrier by adopting one of a solid phase grinding method, an alcohol salt hydrolysis method, and a precipitation method.

[0015] In some embodiments of the present invention, the solid phase grinding method comprises the following steps:

[0016] Weigh the precursors of M, N and Al elements into a grinding jar; grind the precursors in the grinding jar by dry grinding or wet grinding; the grinding time is 5 min to 60 min.

[0017] In some embodiments of the present invention, the above-mentioned alkoxide hydrolysis method comprises the following steps:

[0018] Weigh the aluminum salt of the organic alcohol of element Al into a beaker; then add a solvent to hydrolyze; then add the precursors of elements M and N to continue hydrolyzing; after the hydrolysis is completed, place in an oven and dry;

[0019] The solvent is one or more of ethanol, water, acetone, ethylene glycol, and isopropanol.

[0020] In some embodiments of the present invention, the above precipitation method comprises the following steps:

[0021] Weigh the soluble salt precursors of the M element, the N element, and the Al element into a beaker, add a solvent to dissolve them; then add a precipitant to precipitate them; after aging for a certain period of time, filter them by suction;

[0022] Wherein, the precipitant is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and urea.

[0023] In some embodiments of the present invention, a molding step is further included: placing the prepared spinel carrier in a kneader, adding a binder, kneading, and extruding in an extruder to form.

[0024] Compared with the prior art, the embodiments of the present invention have at least the following advantages or beneficial effects:

[0025] The high-strength spinel carrier provided by the present invention has a general chemical formula of M x N y Al2O4 has low surface acidity and a porous structure, which can improve the stability of the carrier. At the same time, the special molding process is used to improve the strength of the carrier, so that it can remain stable under high temperature and high pressure conditions.

[0026] The high-strength spinel provided by the present invention is used as a carrier, and noble metals are loaded as active components. Through the action of the Sn element additive, the active center in the catalyst can be adjusted, the existence state of the noble metal elements can be changed, and its highly dispersed spatial structure can be maintained. The dehydrogenation catalyst has good comprehensive performance, high conversion rate of low-carbon alkanes, can inhibit deep dehydrogenation, acidic cracking, and carbon deposition reactions of alkanes, and has potential industrial application prospects. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0028] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to specific embodiments.

[0029] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0030] Example 1

[0031] The preparation method of high-strength spinel carrier is:

[0032] Weigh 1020g of aluminum isopropoxide into a beaker, add 3L of deionized water, hydrolyze for 2h, add 610g of zinc acetate, continue stirring for 2h, heat to 100℃, evaporate the solvent, dry in an oven, and calcine at 600℃.

[0033] The calcined sample was placed in a kneader, and 30 g of nitric acid, 6 g of cyclodextrin, and 60 g of deionized water were added and kneaded for 30 minutes, followed by extrusion molding, drying, and calcination.

[0034] The preparation method of the light alkane dehydrogenation catalyst is as follows:

[0035] Weigh 10g of the above carrier and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.01g of Pt precursor solution chloroplatinic acid and add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h to obtain the catalyst Pt / ZnAl2O4.

[0036] The carrier has a specific surface area of ​​136 g / ㎡, a pore volume of 0.18 cc / g, and a pore diameter of 10.78 nm.

[0037] Example 2

[0038] The preparation method of high-strength spinel carrier is:

[0039] Weigh 1020g of aluminum isopropoxide into a beaker, add 3L of a mixed solution of deionized water and isopropanol, hydrolyze for 2h, add 442.5g of cobalt acetate, continue stirring for 2h, heat to 100℃, evaporate the solvent, put it in an oven to dry, and calcine at 600℃.

[0040] The calcined sample was placed in a kneader, and 36 g of nitric acid, 4.5 g of starch, and 70 g of deionized water were added and kneaded for 30 minutes, followed by extrusion molding, drying, and calcining.

[0041] The preparation method of the light alkane dehydrogenation catalyst is as follows:

[0042] Weigh 10g of the above carrier and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.01g of Pt precursor solution chloroplatinic acid and add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h to obtain the catalyst Pt / CoAl2O4.

[0043] The carrier has a specific surface area of ​​129 g / ㎡, a pore volume of 0.11 cc / g, and a pore diameter of 9.83 nm.

[0044] Example 3

[0045] The preparation method of high-strength spinel carrier is:

[0046] Weigh 540 g of aluminum ore, 400 g of zinc acetate, and 50 g of calcium acetate into a grinding jar, dry grind for 15 minutes, and then take out the sample.

[0047] The ground sample was placed in a kneader, and 45 g of nitric acid, 12 g of glacial acetic acid, and 80 g of deionized water were added and kneaded for 30 minutes, and then extruded, dried, and calcined.

[0048] The preparation method of the light alkane dehydrogenation catalyst is as follows:

[0049] Weigh 10g of the above carrier and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.01g of Pt precursor solution chloroplatinic acid and 0.02g of Sn precursor solution, add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h to obtain the catalyst PtSn / Zn 0.9 Ca 0.1 Al2O4.

[0050] The carrier has a specific surface area of ​​132 g / ㎡, a pore volume of 0.24 cc / g, and a pore diameter of 8.02 nm.

[0051] Example 4

[0052] The preparation method of high-strength spinel carrier is:

[0053] Weigh 673 g of aluminum ore (aluminum content 75%), 867 g of nickel nitrate, and 52.05 g of barium chloride into a grinding jar, add a mixed solution of water and ethanol, wet grind for 15 minutes, and then take out the sample.

[0054] The ground sample was placed in a kneader, and 45 g of nitric acid, 12 g of glacial acetic acid, and 80 g of deionized water were added and kneaded for 30 minutes, and then extruded, dried, and calcined.

[0055] The preparation method of the light alkane dehydrogenation catalyst is as follows:

[0056] Weigh 10g of the above carrier and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.01g of Pt precursor solution chloroplatinic acid and 0.02g of Sn precursor solution, add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h to obtain the catalyst PtSn / Ni 0.95 Ba 0.05 Al2O4.

[0057] The carrier has a specific surface area of ​​118 g / ㎡, a pore volume of 0.15 cc / g, and a pore diameter of 8.74 nm.

[0058] Example 5

[0059] The preparation method of high-strength spinel carrier is:

[0060] Weigh 1508g of aluminum nitrate, 366g of zinc acetate, and 0.8g of sodium chloride and dissolve them in 2L of deionized water, and dissolve them by ultrasonic. Under high-speed stirring, add ammonia water dropwise, adjust the pH to 5-8, stir the mixture at high speed to make it precipitate completely, and then let it stand for aging. The aged product is filtered and washed, and the filter cake is dried in an oven at 80°C to obtain Zn 0.99 Na 0.01 Al2O4 precursor.

[0061] The obtained Zn 0.99 Na 0.01 The Al2O4 precursor was placed in a kneader, and 7.32 g of methyl cellulose, 36.6 g of nitric acid solution and 58 g of deionized water were weighed and poured into the kneader. After kneading for 15-20 minutes, the extrusion molding was performed. The extruded carrier was placed in an oven for drying at 100°C and calcined at 800°C for 4 hours to obtain Zn 0.99 Na 0.01 Al2O4 carrier.

[0062] The preparation method of the light alkane dehydrogenation catalyst is as follows:

[0063] Weigh 10g of the above carrier and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.01g of Pt precursor solution chloroplatinic acid and 0.02g of Sn precursor solution, add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h to obtain the catalyst Pt-Sn / Zn 0.99 Na 0.01 Al2O4.

[0064] The carrier has a specific surface area of ​​127 g / ㎡, a pore volume of 0.19 cc / g, and a pore diameter of 10.58 nm.

[0065] Example 6

[0066] The preparation method of high-strength spinel carrier is:

[0067] Weigh 950g magnesium chloride, 18.3g zinc acetate, and 754g aluminum nitrate and dissolve them in 1L deionized water. Perform ultrasonic dissolution. Weigh a certain amount of urea and pour it into the above mixture. Stir at high speed for 2h. Then heat the water bath to 80℃ to decompose the urea and precipitate it completely. Then let it stand for aging. Filter and wash the aged product. Dry the filter cake in an oven at 80℃ and calcine it in a muffle furnace at 1000℃ to obtain Zn 0.02 Mg 0.98 Al2O=support.

[0068] The obtained Zn 0.02 Mg 0.98 The Al2O4 precursor was placed in a kneader, and 7.32 g of sesbania powder, 36.6 g of nitric acid solution and 60 g of deionized water were weighed and poured into the kneader. After kneading for 15-20 minutes, the extrusion molding was performed. The extruded carrier was placed in an oven for drying at 100°C and calcined at 800°C for 4 hours to obtain Zn 0.02 Mg 0.98 Al2O4 carrier.

[0069] The preparation method of the light alkane dehydrogenation catalyst is as follows:

[0070] Weigh 10g of the above carrier and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.01g of Pt precursor solution chloroplatinic acid and 0.02g of Sn precursor solution, add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h to obtain the catalyst Pt-Sn / Zn 0.02 Mg 0.98 Al2O4.

[0071] The carrier has a specific surface area of ​​133 g / ㎡, a pore volume of 0.25 cc / g, and a pore diameter of 9.24 nm.

[0072] Comparative Example 1

[0073] Weigh 10g of commercially formed carrier α-alumina and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.1g of Pt precursor solution chloroplatinic acid and add 20ml of deionized water for ultrasonic dissolution to obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent to dryness by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and calcined at 600℃ for 4h.

[0074] The carrier has a specific surface area of ​​131 g / ㎡, a pore volume of 0.19 cc / g, and a pore diameter of 11.26 nm.

[0075] Comparative Example 2

[0076] Weigh 373g of aluminum nitrate and dissolve it in 1L of deionized water, and dissolve it by ultrasonic. Under high-speed stirring, add ammonia water dropwise, adjust the pH to 5-8, stir the mixture at high speed to make it precipitate completely, and then let it stand for aging. The aged product is filtered and washed, and the obtained filter cake is dried in an oven at 80℃ and calcined in a muffle furnace at 1000℃ to obtain an Al2O3 carrier.

[0077] Weigh 10g of the above-mentioned carrier powder and disperse it in 50ml of deionized water, stir at high speed for 30min to obtain mixed solution A. Weigh 0.1g of Pt precursor solution platinum nitrate in a beaker, add 20ml of deionized water for ultrasonic dissolution, and obtain solution B. Under the condition of high-speed stirring of mixed solution A, add solution B dropwise, mix evenly, stir at room temperature for 2h, and evaporate the solvent to dryness by rotary evaporation. The obtained dry product is placed in an oven at 80℃ for drying and roasted at 600℃ for 4h.

[0078] The carrier has a specific surface area of ​​138 g / ㎡, a pore volume of 0.22 cc / g, and a pore diameter of 10.97 nm.

[0079] Comparative Example 3

[0080] Weigh 102 g of aluminum oxide and 81 g of zinc oxide sample and put them into a kneader, add 30 g of nitric acid, 6 g of cyclodextrin, and 60 g of deionized water, knead for 30 minutes, extrude and shape, dry, and calcine.

[0081] The calcined sample was added with 500g of deionized water and stirred for dispersion. The mixture was stirred at high speed for 30min to obtain a mixed solution A. Platinum nitrate, a precursor solution containing 0.1g of Pt, was weighed into a beaker and 20ml of deionized water was added for ultrasonic dissolution to obtain a solution B. While stirring the mixed solution A at high speed, the solution B was added dropwise and mixed evenly. After stirring at room temperature for 2h, the solvent was evaporated to dryness by rotary evaporation. The obtained dry product was placed in an oven at 80℃ for drying and calcined at 600℃ for 4h.

[0082] The carrier has a specific surface area of ​​127 g / ㎡, a pore volume of 0.21 cc / g, and a pore diameter of 9.51 nm.

[0083] Experimental example

[0084] 1. Propane dehydrogenation test

[0085] The process flow adopted is the existing process flow, which will not be elaborated in detail in the embodiment. The control parameters in the process flow are as follows: propane space velocity is 1h -1, introduce an appropriate amount of hydrogen, maintain the propane partial pressure at 50 kPa, and the total pressure of the reaction system is atmospheric pressure; the bed temperature is 550-600° C. The carrier preparation and catalyst composition of each embodiment and comparative example are shown in Table 1, and the test results are shown in Table 2.

[0086] Table 1. Carrier preparation and catalyst composition of each embodiment and comparative example

[0087]

[0088]

[0089] It can be concluded from Table 1 that the spinel carriers of Examples 1-5 provided by the present invention have high strength, which can reach above 132 N / cm, which is significantly higher than the strength of the carriers of Comparative Examples 1-3.

[0090] Table 2. Catalytic performance evaluation of each catalyst

[0091] Catalyst composition Propane conversion rate % Propylene selectivity % Propylene yield% By-product % Example 1 <![CDATA[Pt / ZnAl2O4]]> 36.28 88.67 32.17 4.11 Example 2 <![CDATA[Pt / CoAl2O4]]> 30.53 87.76 26.79 3.74 Example 3 <![CDATA[Pt-Sn / Zn 0.9 That 0.1 Al2O4]]> 40.46 88.48 35.80 4.66 Example 4 <![CDATA[PtSn / Ni 0.95 Not 0.05 Al2O4。]]> 31.76 88.31 28.05 3.71 Example 5 <![CDATA[Pt-Sn / Zn 0.99 Na 0.01 Al2O4]]> 39.15 84.70 33.16 5.99 Example 6 <![CDATA[Pt-Sn / Zn 0.02 Mg 0.98 Al2O4]]> 35.16 89.88 31.60 3.56 Comparative Example 1 <![CDATA[Pt / Al2O3]]> 21.05 80.76 17.00 4.05 Comparative Example 2 <![CDATA[Pt / Al2O3]]> 24.36 84.73 20.64 3.72 Comparative Example 3 <![CDATA[Pt / ZnAl2O4]]> 27.53 85.91 23.65 3.88

[0092] It can be concluded from Table 2 that the catalysts obtained by loading the Pt active component on the carriers of Examples 1-5 have a higher conversion rate of propane and a higher yield of propylene in the propane dehydrogenation reaction, that is, the activity of the catalyst is high. At the same time, the selectivity of propylene and the yield of by-products are not much different.

[0093] In summary, the spinel carrier provided in the embodiment of the present invention has a porous structure, and the active sites on the carrier surface have low acidity. After loading the Pt active component, it is not easy to generate carbon deposits on the carrier surface, and thus during the reaction, the catalyst can maintain a high activity.

[0094] The embodiments described above are part of the embodiments of the present invention, rather than all of the embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Claims

1. A high-strength spinel carrier, characterized in that: The spinel carrier has a porous structure and its general chemical formula is: x N y Al2O4, wherein the M element is one or more of Zn, Co, Ni, and Fe; the N element is one or more of Na, K, Ca, Mg, and Ba, and x+y=1,0 <x<1,0<y<1。 2. The high-strength spinel carrier according to claim 1, characterized in that: The precursor of the M element is one or more of its nitrate, hydrochloride, acetate, and oxide.

3. The high-strength spinel carrier according to claim 1, characterized in that: The precursor of the N element is one or more of its nitrate, hydrochloride, acetate, and oxide.

4. The high-strength spinel carrier according to claim 1, characterized in that: The precursor of the Al element is one or more of aluminum chloride, aluminum nitrate, aluminum acetate, aluminum oxide, aluminum stone, and organic alcohol aluminum salt.

5. The high-strength spinel carrier according to claim 1, characterized in that: The spinel carrier has a specific surface area of ​​10-100m 2 / g, pore size range is 3nm-30nm, pore volume range is 0.1-0.7g / mL, and carrier mechanical strength is 100-200N / cm.

6. A method for preparing a high-strength spinel carrier according to any one of claims 1 to 5, characterized in that: The spinel carrier is prepared by using one of a solid phase grinding method, an alcohol salt hydrolysis method and a precipitation method.

7. The method for preparing a high-strength spinel carrier according to claim 6, characterized in that: The solid phase grinding method comprises the following steps: Weigh the precursors of M, N and Al elements into a grinding jar; grind the precursors in the grinding jar by dry grinding or wet grinding; the grinding time is 5 min to 60 min.

8. The method for preparing a high-strength spinel carrier according to claim 6, characterized in that: The alkoxide hydrolysis method comprises the following steps: Weigh the Al element organic alcohol aluminum salt into a beaker; then add the solvent to hydrolyze; then add the precursors of the M and N elements to continue hydrolyzing; after the hydrolysis is completed, put it into an oven for drying; The solvent is one or more of ethanol, water, acetone, ethylene glycol, and isopropanol.

9. The method for preparing a high-strength spinel carrier according to claim 6, characterized in that: The precipitation method comprises the following steps: Weigh the soluble salt precursors of the M element, the N element, and the Al element into a beaker, add a solvent to dissolve them; then add a precipitant to precipitate them; after aging for a certain period of time, filter them by suction; Wherein, the precipitant is one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and urea.

10. The method for preparing a high-strength spinel carrier according to claim 6, characterized in that: The method also includes a molding step: placing the prepared spinel carrier in a kneader, adding a binder, kneading, and extruding the spinel carrier in an extruder.

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