Preparation method of supported light olefin midwifery catalyst microspheres with high specific surface area

Abstract

The invention discloses a preparation method of supported light olefin midwifery catalyst microspheres with high specific surface area, which comprises the following steps: adsorbing carbon dioxide by modified MOF powder, mixing the modified MOF powder with SAPO-34 powder and silica sol, freeze-drying, and calcining to obtain the supported light olefin midwifery catalyst microspheres with high specific surface area, according to the preparation method disclosed by the invention, the catalyst microspheres are loaded with the metal oxide capable of improving the catalytic efficiency by loading the In2O3 and ZrO2 with porous structures in the catalyst microspheres, and the prepared In2O3 and ZrO2 have the porous structures of the metal organic frameworks by synthesizing the corresponding metal organic frameworks, so that the specific surface area of the metal oxide is increased, and the catalytic efficiency of the catalyst is improved. Therefore, the specific surface area of the catalyst microsphere is increased, and the supported light olefin midwifery catalyst microsphere with high specific surface area is obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalytic cracking of petroleum, and particularly relates to a preparation method of a high specific surface area supported light olefin co-production catalyst microsphere. BACKGROUND

[0002] Low carbon olefins are widely used in the fields of organic plastics, agriculture, solvents, medicines and the like as important basic chemical raw materials. Silicoaluminophosphate (SAPO) molecular sieves have been used as adsorbents and catalysts. The molecular sieves have high methanol conversion rate and light olefin selectivity as catalysts. However, the surface coking easily makes the molecular sieves quickly lose activity, and the effective catalytic area is greatly reduced.

[0003] A Chinese patent application with the publication number CN102740970A discloses a high-strength SAPO-34 microsphere catalyst, a preparation method thereof and a method for preparing light olefins using the same. The SAPO-34 microspheres are prepared by hydrothermal synthesis and the microspheres are fired. The catalyst microspheres with high strength, small crystal size and multi-level porosity are obtained by removing the template. In this scheme, the molecular sieve powder is bonded and then fired into microspheres as a light olefin catalyst. The molecular sieve is easy to agglomerate in the process of mixing and bonding. The volume contact overlap caused by the agglomeration of the molecular sieve makes the internal pores easy to be blocked by the external molecular sieve powder, greatly reducing the effective surface area and the catalytic efficiency and product selectivity.

[0004] The introduction of metal into the molecular sieve catalyst has a positive effect on the catalytic performance. The incorporation of Ce into the SAPO-34 cage can limit the generation of high carbon transition state intermediates and improve the ethylene selectivity. The incorporation of La into the SAPO-34 can prolong the service life of the catalyst and be beneficial to the generation of ethylene products. However, the synthesis process is relatively complex.

[0005] A Chinese patent application with the publication number CN101121145A discloses a microsphere catalyst for converting oxygen-containing compounds into olefins and a preparation method thereof. A silicoaluminophosphatic molecular sieve containing a transition metal is used as the active component of the catalyst, mixed with other raw materials, freeze-dried and high-temperature calcined to prepare a microsphere catalyst with suitable particle size distribution, attrition index and high catalytic performance. However, the volume of the metal oxide in this scheme can block the pores of the molecular sieve catalyst, resulting in a reduction in the specific surface area of the effective catalysis and a reduction in the catalytic efficiency. SUMMARY

[0006] The present application aims to solve the problem of how to improve the specific surface area of the molecular sieve catalyst after the introduction of metal oxides and improve the catalytic efficiency, and provides a preparation method of a high specific surface area supported light olefin co-production catalyst microsphere.

[0007] The application loads In2O3 and ZrO2 with a porous structure in the catalyst microspheres, loads the metal oxide on the catalyst microspheres, synthesizes the corresponding metal organic framework, makes the prepared In2O3 and ZrO2 have a porous structure, increases the specific surface area of the metal oxide, and thus increases the specific surface area of the catalyst microspheres.

[0008] The object of the application can be achieved by the following technical scheme.

[0009] The preparation method of the high-specific-surface-area supported light olefin co-production catalyst microspheres comprises the following steps.

[0010] Step one: In-MOF is prepared by hydrothermal synthesis of indium nitrate tetrahydrate, imidazole and 5-aminobenzimidazole; Zr-MOF is prepared by hydrothermal synthesis of zirconium tetrachloride, 2-amino terephthalic acid and sodium formate; and modified In-MOF is prepared by modification of In-MOF with n-octyl isocyanate.

[0011] Step two: the modified In-MOF is ultrasonically dispersed in chloroform in a reaction kettle, Zr-MOF is added to the reaction kettle, ultrasonic treatment is performed for 20-24 h, the precipitate is collected by vacuum filtration after standing for 10-12 h, and the precipitate is washed with chloroform to obtain composite MOF powder.

[0012] Step three: the ionic liquid powder, the composite MOF powder, acetic acid and DMF are stirred in the reaction kettle for 10-12 h, the precipitate is collected by centrifugal filtration, the precipitate is washed with deionized water and ethanol, and the modified MOF powder is obtained by vacuum drying at 70-80 DEG C for 10-12 h.

[0013] Step four: the modified MOF powder is placed in a tube furnace, carbon dioxide is introduced, and adsorption is performed for 20-30 min to obtain carbon dioxide adsorption powder; the carbon dioxide adsorption powder, SAPO-34 powder and 30-40 wt% silica sol are mixed, and then freeze-drying is performed to obtain composite microspheres; and the composite microspheres are calcined in air at 500-600 DEG C for 4-5 h to obtain the high-specific-surface-area supported light olefin co-production catalyst microspheres.

[0014] Further, in step two, the amount ratio of the modified In-MOF, chloroform and Zr-MOF is 3-4 g: 200-300 mL: 1-1.5 g.

[0015] Further, in step three, the amount ratio of the ionic liquid powder, the composite MOF powder, acetic acid and DMF is 0.8-1 g: 3-4 g: 5-6 mL: 80-100 mL.

[0016] Further, the ionic liquid powder is prepared by the following steps.

[0017] Mixing N-methyl imidazole and 2-bromoethanol in the reaction kettle, stirring at 70-80 DEG C for 40-48h, drying after cooling to obtain ionic liquid powder.

[0018] Further, the amount ratio of carbon dioxide adsorption powder, SAPO-34 powder and silica sol in step four is 3-4g:25-40g:120-150g.

[0019] Further, the modified In-MOF is prepared by the following steps:

[0020] Ultrasonic dispersion of In-MOF in chloroform in the reaction kettle, adding n-octyl isocyanate, ultrasonic dispersion for 30-40min, standing for 20-24h, vacuum filtration to collect the precipitate, washing the precipitate, vacuum drying to obtain modified In-MOF.

[0021] Further, the amount ratio of In-MOF, chloroform and n-octyl isocyanate is 3-4g:200-300mL:5-6mL.

[0022] Further, the In-MOF is prepared by the following steps:

[0023] Ultrasonic treatment of indium nitrate tetrahydrate, imidazole and 5-aminobenzimidazole and dimethylacetamide in the reaction kettle, adding nitric acid solution to the reaction kettle, sealing and heating to 120-130 DEG C for 30-35h, centrifugal collection of the precipitate after cooling, washing the precipitate and vacuum drying to obtain In-MOF.

[0024] Further, the amount ratio of indium nitrate tetrahydrate, imidazole, 5-aminobenzimidazole, dimethylacetamide and nitric acid solution is 3-4g:15-16g:1-1.5g:300-400mL:80-100mL.

[0025] The nitric acid solution is prepared by mixing concentrated nitric acid and dimethylacetamide in a volume ratio of 4-5:100-120.

[0026] Further, the Zr-MOF is prepared by the following steps:

[0027] Ultrasonic dispersion of zirconium tetrachloride, 2-amino terephthalic acid and sodium formate in DMF in the reaction kettle, heating to 120-130 DEG C for 20-24h, centrifugal collection of the precipitate after cooling, washing the precipitate and vacuum drying to obtain Zr-MOF.

[0028] Further, the amount ratio of zirconium tetrachloride, 2-amino terephthalic acid, sodium formate and DMF is 1.5-2g:1.8-2.2g:2-2.5g:100-150mL.

[0029] The beneficial effects of the present application:

[0030] (1) The preparation method of the present application loads In2O3 and ZrO2 with a porous structure in the catalyst microspheres, loads the catalyst microspheres with metal oxides that have an enhancing effect on catalytic efficiency, synthesizes the corresponding metal organic framework, makes the prepared In2O3 and ZrO2 have the porous structure of the metal organic framework, increases the specific surface area of the metal oxides, thereby increasing the specific surface area of the catalyst microspheres, and obtains the supported light olefin co-production catalyst microspheres with high specific surface area.

[0031] (2) The preparation method of the present application synthesizes In-MOF by designing a ligand containing an amino group, then grafts n-octyl isocyanate on the surface of In-MOF through grafting reaction of n-octyl isocyanate and the amino group, and designs Zr-MOF also containing an amino group, and composites Zr-MOF on the surface of the modified In-MOF containing n-octyl isocyanate; using sodium formate as an end-capping agent can prepare Zr-MOF with smaller particles, which is beneficial to the grafting of Zr-MOF on In-MOF under the grafting action of n-octyl isocyanate, and has more uniform dispersion and higher grafting rate; and n-octyl isocyanate has a hydrophobic modification effect on the composite MOF powder, so that the composite MOF powder and the SAPO-34 powder are combined under the hydrophobic force, and the uniformity and strength of the combination are improved.

[0032] (3) The present application synthesizes an ionic liquid having adsorption and fixation effects on carbon dioxide, uses the adsorption effect of the composite MOF powder to impregnate the ionic liquid in the pores of the composite MOF powder, adsorbs carbon dioxide in the composite MOF powder by passing in carbon dioxide, and finally mixes the carbon dioxide adsorption powder and the SAPO-34 powder in silica sol, improves the combination uniformity and combination strength of the carbon dioxide adsorption powder and the SAPO-34 powder under the hydrophobic force, and finally removes the solvent by high-temperature calcination, which not only improves the combination strength of the carbon dioxide adsorption powder and the SAPO-34 powder during high-temperature calcination, but also oxidizes the In metal and the Zr metal in the composite MOF powder into In2O3 and ZrO2, and has the porous structure of MOF, the gas adsorbed in the carbon dioxide adsorption powder escapes during high-temperature calcination, has the effect of pore making and maintaining the pores of the composite MOF powder, and makes the catalyst microspheres after calcination have high specific surface area, and the loading of In2O3 and ZrO2 also improves the catalytic effect of SAPO-34 on light olefins and improves the catalytic efficiency. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0034] Embodiment 1: a preparation method of a high specific surface area supported light olefin co-production catalyst microsphere, comprising the following steps:

[0035] S1, 3g of indium nitrate tetrahydrate, 15g of imidazole and 1g of 5-amino benzimidazole were dissolved in 300mL of dimethylacetamide in a reaction kettle, and ultrasonic treatment was performed for 30min. 4mL of concentrated nitric acid was dissolved in 100mL of dimethylacetamide to obtain a nitric acid solution, 80mL of the nitric acid solution was added to the reaction kettle, and the reaction was heated to 120℃ for 30h after sealing. After cooling, the precipitate was collected by centrifugation, the precipitate was washed with dimethylacetamide and ethanol, and vacuum drying was performed at 70℃ for 10h to obtain In-MOF.

[0036] S2, 1.5g of zirconium tetrachloride, 1.8g of 2-amino terephthalic acid and 2g of sodium formate were ultrasonically dispersed in 100mL of DMF in a reaction kettle, and the reaction was performed at 120℃ for 20h. After cooling and centrifugation, the precipitate was collected, the precipitate was washed with DMF and ethanol, and vacuum drying was performed at 70℃ for 10h to obtain Zr-MOF.

[0037] S3, 3g of In-MOF was ultrasonically dispersed in 200mL of chloroform in a reaction kettle, 5mL of n-octyl isocyanate was added, ultrasonic dispersion was performed for 30min, the precipitate was collected by vacuum filtration after standing for 20h, the precipitate was washed with chloroform, and vacuum drying was performed at 90℃ for 10h to obtain modified In-MOF.

[0038] S4, 3g of modified In-MOF was ultrasonically dispersed in 200mL of chloroform in a reaction kettle, 1g of Zr-MOF was added, ultrasonic treatment was performed for 20h, the precipitate was collected by vacuum filtration after standing for 10h, and the precipitate was washed with chloroform to obtain composite MOF powder.

[0039] S5, N-methyl imidazole and 2-bromoethanol were mixed in equal molar amounts, and the temperature was increased to 70℃ for stirring for 40h, and then drying after cooling to obtain ionic liquid powder. 0.8g of ionic liquid powder, 3g of composite MOF powder and 5mL of acetic acid were mixed in 80mL of DMF, stirring was performed for 10h, the precipitate was collected by centrifugal filtration, the precipitate was washed with deionized water and ethanol, and vacuum drying was performed at 70℃ for 10h to obtain modified MOF powder.

[0040] S6, the modified MOF powder was placed in a tube furnace, and carbon dioxide was introduced and adsorbed for 20 min to obtain carbon dioxide adsorption powder. 3 g of the carbon dioxide adsorption powder, 25 g of SAPO-34 powder, and 120 g of 30 wt% silica sol were mixed, and freeze-drying was performed to obtain composite microspheres. The composite microspheres were calcined in air at 500°C for 4 h to obtain high specific surface area supported light olefin co-product catalyst microspheres.

[0041] Example 2: A method for preparing high specific surface area supported light olefin co-product catalyst microspheres, comprising the following steps:

[0042] S1, 3.5 g of indium nitrate tetrahydrate, 15.5 g of imidazole, and 1.25 g of 5- aminobenzimidazole were dissolved in 350 mL of dimethylacetamide in a reaction kettle, and ultrasonic treatment was performed for 35 min. 4.5 mL of concentrated nitric acid was dissolved in 110 mL of dimethylacetamide to obtain a nitric acid solution, 90 mL of the nitric acid solution was added to the reaction kettle, and heating was performed to 125°C for 32.5 h. After cooling, the precipitate was collected by centrifugation, the precipitate was washed with dimethylacetamide and ethanol, and vacuum drying was performed at 75°C for 11 h to obtain In-MOF.

[0043] S2, 1.75 g of zirconium tetrachloride, 2 g of 2-amino terephthalic acid, and 2.25 g of sodium formate were ultrasonically dispersed in 125 mL of DMF in a reaction kettle, and heating was performed to 125°C for 22 h. After cooling and centrifugation, the precipitate was collected, the precipitate was washed with DMF and ethanol, and vacuum drying was performed at 75°C for 11 h to obtain Zr-MOF.

[0044] S3, 3.5 g of In-MOF was ultrasonically dispersed in 250 mL of chloroform in a reaction kettle, 5.5 mL of n-octyl isocyanate was added, ultrasonic dispersion was performed for 35 min, the precipitate was collected by vacuum filtration after standing for 22 h, the precipitate was washed with chloroform, and vacuum drying was performed at 95°C for 11 h to obtain modified In-MOF.

[0045] S4, 3.5 g of modified In-MOF was ultrasonically dispersed in 250 mL of chloroform in a reaction kettle, 1.25 g of Zr-MOF was added, ultrasonic treatment was performed for 22 h, the precipitate was collected by vacuum filtration after standing for 11 h, and the precipitate was washed with chloroform to obtain composite MOF powder.

[0046] S5, N-methyl imidazole and 2-bromoethanol were mixed in equal molar amounts, heating was performed to 75°C, and stirring was performed for 44 h. After cooling, drying was performed to obtain ionic liquid powder. 0.9 g of the ionic liquid powder, 3.5 g of the composite MOF powder, and 5.5 mL of acetic acid were mixed in 90 mL of DMF, stirring was performed for 11 h, the precipitate was collected by centrifugal filtration, the precipitate was washed with deionized water and ethanol, and vacuum drying was performed at 75°C for 11 h to obtain modified MOF powder.

[0047] S6, the modified MOF powder was placed in a tube furnace, and carbon dioxide was introduced and adsorbed for 25 min to obtain a carbon dioxide adsorption powder. The carbon dioxide adsorption powder, SAPO-34 powder and 35 wt% silica sol were mixed in a weight ratio of 3.5:32.5:135, and the mixture was freeze-dried to obtain composite microspheres. The composite microspheres were calcined in air at 550°C for 4.5 h to obtain high specific surface area supported light olefin co-product catalyst microspheres.

[0048] Example 3: A method for preparing high specific surface area supported light olefin co-product catalyst microspheres, comprising the following steps:

[0049] S1, 4g of indium nitrate tetrahydrate, 16g of imidazole and 1.5g of 5-aminobenzimidazole were dissolved in 400mL of dimethylacetamide in a reaction kettle, and ultrasonic treatment was performed for 40min. 5mL of concentrated nitric acid was dissolved in 120mL of dimethylacetamide to obtain a nitric acid solution, 100mL of the nitric acid solution was added to the reaction kettle, and the reaction was heated to 130°C for 35h. After cooling, the precipitate was collected by centrifugation, and the precipitate was washed with dimethylacetamide and ethanol, and vacuum dried at 80°C for 12h to obtain In-MOF.

[0050] S2, 2g of zirconium tetrachloride, 2.2g of 2-amino terephthalic acid and 2.5g of sodium formate were ultrasonically dispersed in 150mL of DMF in a reaction kettle, and the reaction was carried out at 130°C for 24h. After cooling and centrifugation, the precipitate was collected, washed with DMF and ethanol, and vacuum dried at 80°C for 12h to obtain Zr-MOF.

[0051] S3, 4g of In-MOF was ultrasonically dispersed in 300mL of chloroform in a reaction kettle, 6mL of n-octyl isocyanate was added, ultrasonic dispersion was performed for 40min, and the precipitate was collected by vacuum filtration after standing for 24h, washed with chloroform, and vacuum dried at 100°C for 12h to obtain modified In-MOF.

[0052] S4, 4g of modified In-MOF was ultrasonically dispersed in 300mL of chloroform in a reaction kettle, 1.5g of Zr-MOF was added, ultrasonic treatment was performed for 24h, and the precipitate was collected by vacuum filtration after standing for 12h, and the precipitate was washed with chloroform to obtain composite MOF powder.

[0053] S5, N-methyl imidazole and 2-bromoethanol were mixed in equal molar amounts, heated to 80°C and stirred for 48h, and then dried after cooling to obtain ionic liquid powder. 1g of ionic liquid powder, 4g of composite MOF powder and 6mL of acetic acid were mixed in 100mL of DMF, stirred for 12h, and the precipitate was collected by centrifugal filtration, washed with deionized water and ethanol, and vacuum dried at 80°C for 12h to obtain modified MOF powder.

[0054] S6, the modified MOF powder is placed in a tube furnace, carbon dioxide is introduced, and adsorption is performed for 30 min to obtain carbon dioxide adsorption powder; 4 g of the carbon dioxide adsorption powder, 40 g of SAPO-34 powder, and 150 g of 40 wt% silica sol are mixed, and freeze-drying is performed to obtain composite microspheres. The composite microspheres are calcined in air at 600 DEG C for 5 h to obtain high specific surface area supported light olefin co-product catalyst microspheres.

[0055] The SAPO-34 powder, i.e., SAPO-34 molecular sieve, is purchased from Wuhan Kamik Technology Co., Ltd., and the remaining raw materials in the examples are commercially available products.

[0056] Principle of the application:

[0057] The application synthesizes In-MOF and Zr-MOF with a porous structure, composites indium metal and zirconium metal elements in the form of MOF, improves the specific surface area of the composite MOF powder, synthesizes In-MOF containing an amino group, grafts n-octyl isocyanate on the surface of In-MOF through grafting reaction of n-octyl isocyanate and the amino group, and composites Zr-MOF containing an amino group on the surface of the modified In-MOF containing n-octyl isocyanate; sodium formate is used as an end-capping agent to prepare smaller Zr-MOF, which is beneficial to grafting of Zr-MOF on In-MOF under the grafting action of n-octyl isocyanate, more uniform dispersion, and higher grafting rate; n-octyl isocyanate has a hydrophobic modification effect on the composite MOF powder, so that the composite MOF powder is combined with SAPO-34 powder under hydrophobic force, improving the uniformity and strength of the combination; ionic liquid with carbon dioxide adsorption and fixation is synthesized, the ionic liquid is impregnated in the pores of the composite MOF powder by using the adsorption of the composite MOF powder, carbon dioxide is adsorbed in the composite MOF powder by introducing carbon dioxide, and finally the carbon dioxide adsorption powder and SAPO-34 powder are mixed in silica sol to improve the combination uniformity and combination strength of the carbon dioxide adsorption powder and SAPO-34 powder under hydrophobic force. Finally, the solvent is removed by high-temperature calcination, which not only improves the combination strength of the carbon dioxide adsorption powder and SAPO-34 powder, but also oxidizes the In metal and Zr metal in the composite MOF powder into In2O3 and ZrO2, and has a porous structure of MOF. The gas adsorbed in the carbon dioxide adsorption powder escapes during high-temperature calcination, has a pore-forming and pore-maintaining effect of the composite MOF powder, so that the catalyst microspheres after calcination have a high specific surface area, the loading of In2O3 and ZrO2 also improves the catalytic effect of SAPO-34 on light olefins, and improves the catalytic efficiency.

[0058] Comparative Example 1: The difference from Example 1 is that no n-octyl isocyanate is added in S3, and the remaining steps are unchanged to prepare the catalyst microspheres.

[0059] Comparative Example 2: The difference from Example 1 is that in S4, the modified In-MOF is replaced with an equal amount of In2O3 powder, and the Zr-MOF is replaced with an equal amount of ZrO2 powder, and the remaining steps are unchanged to prepare the catalyst microspheres.

[0060] Comparative Example 3: The difference from Example 1 is that in S5, the composite MOF powder is replaced with an equal amount of modified In-MOF, and the remaining steps are unchanged to prepare the catalyst microspheres.

[0061] Comparative Example 4: The difference from Example 1 is that in S6, the carbon dioxide adsorption powder is replaced with an equal amount of composite MOF powder, and the remaining steps are unchanged to prepare the catalyst microspheres.

[0062] The catalyst microspheres prepared in Examples 1-3 and Comparative Examples 1-3 are subjected to light olefin synthesis reaction, which is carried out in a fixed bed reactor under the reaction conditions of 400℃, atmospheric pressure and 1.6hr -1 The space velocity, the olefin composition obtained after 240min of testing reaction, the conversion rate and the selectivity of light olefin are calculated to obtain the results shown in Table 1.

[0063] Table 1: Catalyst microsphere performance test table

[0064]

[0065] As can be seen from Table 1, the high specific surface area supported light olefin co-production catalyst microspheres prepared by the present application have good catalytic effect on light olefin synthesis reaction, high conversion rate and high selectivity of light olefin, which is significantly higher than the catalytic efficiency of Comparative Examples 1-3, indicating that the catalyst microspheres prepared by the present application have more catalytically active sites and higher specific surface area.

[0066] Comparative Example 1 has lower uniformity of Zr-MOF and In-MOF combination and is prone to agglomeration due to the absence of n-octyl isocyanate, resulting in lower synergistic effect of ZrO2 and In2O3 and lower light olefin co-catalytic effect.

[0067] Comparative Example 2 replaces In-MOF and Zr-MOF with ZrO2 powder and In2O3 powder, losing the porous structure in the MOF structure and reducing the specific surface area of the prepared catalyst microspheres, thus reducing the catalytic efficiency.

[0068] Comparative Example 3 does not contain ZrO2 in the prepared catalyst microspheres, and the conversion rate and light hydrocarbon selectivity are significantly lower than Example 1, indicating that ZrO2 has a catalytic effect on the conversion of light hydrocarbons.

[0069] Comparative Example 4 did not promote the formation of pores and the maintenance of the porous structure due to the absence of the ionic liquid to adsorb carbon dioxide, and the surface area of the obtained catalyst microspheres was lower than that of Example 1 to Example 3, which indicates that the ionic liquid to adsorb carbon dioxide in the present application has an effect of improving the porous area of the catalyst microspheres.

[0070] Although embodiments of the present application have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, alternatives, and variations can be made thereto without departing from the principles and spirit of the application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A process for the preparation of supported light olefin co-product catalyst microspheres of high specific surface area, characterized in that, It comprises the following steps: Step one, hydrothermal synthesis of indium nitrate tetrahydrate, imidazole and 5-amino benzimidazole to prepare In-MOF, hydrothermal synthesis of zirconium tetrachloride, 2-amino terephthalic acid and sodium formate to prepare Zr-MOF, modification of In-MOF with n-octyl isocyanate to prepare modified In-MOF; Step two, ultrasonic dispersion of modified In-MOF in chloroform in a reaction kettle, addition of Zr-MOF to the reaction kettle, ultrasonic treatment for 20-24h, standing for 10-12h, vacuum filtration to collect the precipitate, washing of the precipitate with chloroform to obtain composite MOF powder; Step three, stirring of ionic liquid powder, composite MOF powder, acetic acid and DMF in a reaction kettle for 10-12h, centrifugal filtration to collect the precipitate, washing of the precipitate with deionized water and ethanol, vacuum drying at 70-80℃ for 10-12h to obtain modified MOF powder; Step four, placing of the modified MOF powder in a tube furnace, introduction of carbon dioxide, adsorption for 20-30min to obtain carbon dioxide adsorption powder, mixing of the carbon dioxide adsorption powder, SAPO-34 powder and 30-40wt% silica sol, then freeze-drying to obtain composite microspheres, calcination of the composite microspheres in air at 500-600℃ for 4-5h to obtain high specific surface area supported light olefin co-production catalyst microspheres.

2. The process for the preparation of high surface area supported light olefin co-product catalyst microspheres according to claim 1, characterized in that, The amount ratio of the modified In-MOF, chloroform and Zr-MOF in step two is 3-4g:200-300mL:1-1.5g.

3. The method of claim 1, wherein the method is characterized by, The amount ratio of the ionic liquid powder, composite MOF powder, acetic acid and DMF in step three is 0.8-1g:3-4g:5-6mL:80-100mL. The ionic liquid powder is prepared by the following steps: Mixing of N-methyl imidazole and 2-bromoethanol in equimolar amount in a reaction kettle, heating to 70-80℃, stirring for 40-48h, drying after cooling to obtain ionic liquid powder.

4. The method of claim 1, wherein the method is characterized by, The amount ratio of the carbon dioxide adsorption powder, SAPO-34 powder and silica sol in step four is 3-4g:25-40g:120-150g.

5. The method of claim 2, wherein the method is characterized by, The modified In-MOF is prepared by the following steps: Ultrasonic dispersion of In-MOF in chloroform in a reaction kettle, addition of n-octyl isocyanate, ultrasonic dispersion for 30-40min, vacuum filtration to collect the precipitate after standing for 20-24h, washing of the precipitate, vacuum drying to obtain modified In-MOF.

6. The method of claim 5, wherein the method is characterized by, The amount ratio of the In-MOF, chloroform and n-octyl isocyanate is 3-4g:200-300mL:5-6mL.

7. The process for the preparation of high surface area supported light olefin co-product catalyst microspheres according to claim 6, characterized in that, The In-MOF is prepared by the following steps: Mixing of indium nitrate tetrahydrate, imidazole and 5-amino benzimidazole and dimethylacetamide in a reaction kettle, ultrasonic treatment for 30-40min, addition of nitric acid solution to the reaction kettle, sealing and heating to 120-130℃ for 30-35h, centrifugal collection of the precipitate after cooling, washing of the precipitate, vacuum drying to obtain In-MOF.

8. The process for the preparation of high surface area supported light olefin co- producer catalyst microspheres according to claim 7, characterized in that, The amount ratio of the indium nitrate tetrahydrate, imidazole, 5-amino benzimidazole, dimethylacetamide and nitric acid solution is 3-4g:15-16g:1-1.5g:300-400mL:80-100mL; The nitric acid solution is prepared by mixing concentrated nitric acid and dimethylacetamide in a volume ratio of 4-5:100-120.

9. The method of claim 2, wherein the method is characterized by, The Zr-MOF is prepared by the following steps: Zirconium tetrachloride, 2-amino terephthalic acid and sodium formate are ultrasonically dispersed in DMF in a reaction kettle, heated to 120-130℃ for 20-24h, and the precipitate is collected after cooling and centrifugation, washed and vacuum dried to obtain Zr-MOF.

10. The method of claim 9, wherein the method is characterized by, The amount ratio of the zirconium tetrachloride, 2-amino terephthalic acid, sodium formate and DMF is 1.5-2g:1.8-2.2g:2-2.5g:100-150mL.

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