A bimetallic oxide supported catalyst, its preparation method and application

Abstract

This invention relates to a bimetallic oxide supported catalyst, its preparation method, and its application. The preparation method of the bimetallic oxide supported catalyst includes the following steps: (1) uniformly mixing inorganic tin salt, tetraethyl silicate, inorganic acid, and solvent to obtain a mixed solution; the obtained mixed solution is spray-dried to obtain acidic tin oxide powder; (2) uniformly mixing molecular sieve support, titanium tetrachloride powder, and the acidic tin oxide powder obtained in step (1); the obtained mixture is then subjected to vacuum treatment, gasification treatment, and calcination treatment in sequence to obtain the bimetallic oxide supported catalyst. This invention synthesizes a bimetallic oxide supported catalyst through a one-step gasification method and recovers waste epoxy resin through catalytic cracking, which can selectively recover high-value phenolic substances, providing a new approach for the resource-based recycling of waste epoxy resin.

Description

Technical Field

[0001] This invention relates to the field of catalysis technology, specifically to a bimetallic oxide supported catalyst, its preparation method, and its application. Background Technology

[0002] With the gradual retirement of early fiberglass wind turbine blades, the resulting waste blades urgently need disposal. Currently, the recycling of waste fiberglass wind turbine blades mainly focuses on recovering materials such as fiberglass and epoxy resin. Among these, recovering epoxy resin is one of the main challenges in the fiberglass recycling process.

[0003] Epoxy resin can be recycled using chemical methods, pyrolysis, and catalytic cracking to recover high-value chemicals. However, pyrolysis and chemical methods suffer from long processing times and the need for secondary treatment. For example, CN116078420A discloses a catalyst and its preparation method, as well as a method for preparing aromatic compounds and their applications. The preparation method includes the following steps: calcining a molecular sieve for the first time, then dispersing it in a gallium nitrate aqueous solution, ultrasonically dispersing it at room temperature, drying it, and then calcining it a second time to obtain the catalyst; the molecular sieve is one of ZSM-5 zeolite, γ-zeolite, or β-zeolite. Furthermore, chemical and pyrolysis methods for disposing of waste epoxy resin often involve direct treatment, failing to achieve resource recovery.

[0004] Catalytic cracking is a rapid method for processing epoxy resins. By adding a catalyst at high temperatures, it can quickly decompose the complex organic molecules in epoxy resins into phenolic substances, thereby achieving resource utilization of waste and recovering large amounts of high-value compounds. However, the selection of catalysts is one of the main factors restricting the industrialization of catalytic cracking for epoxy resin recovery. Under high-temperature conditions, the stability and activity of the catalyst may be structurally damaged or deactivated. Furthermore, catalyst regeneration and recycling are also factors that need to be considered to reduce costs and environmental impact. In addition, when using catalytic cracking to rapidly recover high-value compounds from epoxy resins, multiple aspects such as the high thermosetting properties, high thermoplasticity, and corrosion resistance of epoxy resins must be considered.

[0005] CN 114634653A discloses a method for the directional depolymerization and recycling of decommissioned wind turbine blades. The method includes: (1) blade pretreatment: crushing and drying the decommissioned wind turbine blades; (2) catalytic depolymerization: sending the pretreated decommissioned wind turbine blades into a depolymerization device, then adding a degradation liquid with catalytic oxidation properties and a catalyst, heating in an oil bath under normal pressure, and separating the fiber material and degradation residue after depolymerization treatment; (3) falling film recovery: sending the degradation residue obtained in step (2) into a falling film evaporator for degradation liquid recovery, and simultaneously obtaining residual liquid sedimentation; (4) resin recovery: centrifuging the sedimentation of the residual liquid obtained in step (3) to obtain centrifuged solid and waste liquid, and drying the obtained centrifuged solid to obtain degradation resin. However, this method still needs improvement in achieving reasonable recycling of high-value compounds.

[0006] Currently, some studies have found that metal catalysts such as platinum and palladium can recover aromatic products by catalytically cracking epoxy resins at suitable temperatures; nanomaterials such as silica and nano-alumina can also be used in the catalytic cracking process of epoxy resins due to their high specific surface area. However, these catalysts have not been widely used due to issues with the preparation of finished products, catalyst stability, and activity.

[0007] Therefore, to address the shortcomings of existing technologies, there is a need to provide a catalyst that is low in cost, highly stable, and has good catalytic activity, thereby enabling the resource-based recycling of waste epoxy resin. Summary of the Invention

[0008] The purpose of this invention is to provide a bimetallic oxide supported catalyst, its preparation method, and its application. A highly active bimetallic oxide supported catalyst is prepared by loading tin and titanium ions through a high-temperature gasification reaction using a molecular sieve as a support. A catalytic cracking method is employed to convert waste epoxy resin into high-value compounds, exhibiting highly selective conversion characteristics for phenolic compounds, thus providing a new and feasible approach for the resource recovery of waste epoxy resin.

[0009] To achieve this objective, the present invention employs the following technical solution:

[0010] In a first aspect, the present invention provides a method for preparing a bimetallic oxide supported catalyst, the method comprising the following steps:

[0011] (1) Inorganic tin salt, tetraethyl silicate, inorganic acid and solvent are uniformly mixed to obtain a mixed solution; the obtained mixed solution is spray dried to obtain acidic tin oxide powder;

[0012] (2) The molecular sieve support, titanium tetrachloride powder and acidic tin oxide powder obtained in step (1) are uniformly mixed. The resulting mixture is subjected to vacuum treatment, gasification treatment and calcination treatment in sequence to obtain the bimetallic oxide supported catalyst.

[0013] The method for preparing a bimetallic oxide supported catalyst provided by this invention first prepares acidic tin oxide powder by spray drying, then uses a molecular sieve as a support to load tin and titanium ions on the topological structure of the nanomaterial, and rapidly synthesizes the bimetallic oxide supported catalyst by a one-step gasification method. Through the synergistic effect of the two different metals, it exhibits high catalytic activity and selectivity during the reaction process. Specifically, the interaction of the metal double bonds can optimize the arrangement of catalytic active sites and electronic structure, thereby increasing the catalyst's conversion efficiency of reactants and improving the selectivity of catalytic products.

[0014] Preferably, the inorganic tin salt in step (1) includes crystalline tin tetrachloride and / or tin nitrate.

[0015] Preferably, the inorganic acid in step (1) includes hydrochloric acid and / or nitric acid.

[0016] Preferably, the solvent in step (1) includes deionized water.

[0017] Preferably, the mixed solution in step (1) includes silicon dioxide, tin dioxide, inorganic acid and solvent.

[0018] Preferably, the molar ratio of silicon dioxide, tin dioxide, inorganic acid, and solvent is (0.5-2):(0.1-3):(0.075-3):(20-50), for example, it can be 0.5:0.1:0.075:20, 0.8:0.5:0.5:25, 1:1:1:30, 1.5:2:2:40, or 2:3:3:50, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0019] Preferably, the uniform mixing in step (1) is carried out at room temperature.

[0020] Preferably, the spray drying process in step (1) is carried out in an aerosol spray drying apparatus.

[0021] Preferably, the spray drying process described in step (1) is followed by a drying step.

[0022] Preferably, the drying temperature is 105-115℃ and the time is 2.5-3.5h.

[0023] The drying temperature is 105-115℃, for example, it can be 105℃, 108℃, 110℃, 112℃ or 115℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0024] The drying time is 2.5-3.5 hours, for example, it can be 2.5 hours, 2.8 hours, 3 hours, 3.2 hours or 3.5 hours, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0025] Preferably, the molecular sieve carrier in step (2) is a molecular sieve carrier obtained by dealumination of H-beta molecular sieve.

[0026] The H-beta molecular sieve is a high-silica H-beta molecular sieve, which is obtained as a high-silica molecular sieve carrier after dealumination treatment.

[0027] Preferably, the reagent used in the dealumination process includes nitric acid.

[0028] Preferably, the dealuminization treatment time is 11-13 hours, for example, 11 hours, 11.5 hours, 12 hours, 12.5 hours or 13 hours, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] Preferably, the aluminum removal process is followed by drying at 105-115°C, for example, 105°C, 108°C, 110°C, 112°C or 115°C, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0030] Preferably, the molar ratio of acidic tin oxide powder to titanium tetrachloride powder in step (2) is 1:(1-3), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0031] By controlling the molar ratio of acidic tin oxide powder to titanium tetrachloride powder within a reasonable range, the prepared bimetallic oxide supported catalyst can be guaranteed to have a good catalytic effect. If the molar ratio is too high or too low, the catalyst performance will be reduced.

[0032] Preferably, the vacuum treatment in step (2) is performed to a vacuum level of 0.1-0.9 bar, for example, 0.1 bar, 0.4 bar, 0.5 bar, 0.7 bar or 0.9 bar, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0033] The vacuum treatment specifically includes: placing the mixture on a flat-bottomed crucible in a glove box, covering the crucible with a lid, and ensuring that all the air in the crucible is exhausted to a vacuum state.

[0034] Preferably, the gasification process in step (2) is carried out in a tubular furnace with a nitrogen atmosphere.

[0035] Preferably, the flow rate of the nitrogen gas is 190-210 mL / min, for example, it can be 190 mL / min, 195 mL / min, 200 mL / min, 205 mL / min or 210 mL / min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0036] Preferably, the temperature of the gasification process in step (2) is 540-560℃, for example, it can be 540℃, 545℃, 550℃, 555℃ or 560℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0037] Preferably, the gasification treatment time in step (2) is 5.5-6.5h, for example, it can be 5.5h, 5.8h, 6h, 6.2h or 6.5h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0038] The gasification process can uniformly load tin and titanium ions into a high-silicon beta framework to obtain Sn / Ti-beta molecular sieves.

[0039] Preferably, the roasting process in step (2) is carried out in a muffle furnace with an oxygen-containing atmosphere.

[0040] Preferably, the oxygen-containing atmosphere includes an air atmosphere and / or an oxygen atmosphere.

[0041] Preferably, the calcination temperature in step (2) is 540-560℃, for example, it can be 540℃, 545℃, 550℃, 555℃ or 560℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0042] Preferably, the roasting time in step (2) is 5.5-6.5h, for example, it can be 5.5h, 5.8h, 6h, 6.2h or 6.5h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0043] The calcination step is used to remove organic components present in the mixture, and further stabilize the metal oxides in the molecular sieve support framework.

[0044] In a second aspect, the present invention provides a bimetallic oxide supported catalyst, which is prepared by the preparation method described in the first aspect;

[0045] The bimetallic oxide supported catalyst comprises a molecular sieve support and tin and titanium active components supported on the molecular sieve support; the molar ratio of the tin active component to the titanium active component is 1:(1-3), and the mass percentage of the molecular sieve support is 20-70 wt% of the mass percentage of the bimetallic oxide supported catalyst.

[0046] The molar ratio of the tin active component to the titanium active component is 1:(1-3), for example, it can be 1:1, 1:1.5, 1:2, 1:2.5 or 1:3, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0047] The mass percentage of the molecular sieve support is 20-70 wt% of the mass percentage of the bimetallic oxide supported catalyst, for example, it can be 20 wt%, 30 wt%, 40 wt%, 60 wt% or 70 wt%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0048] The metal used in the bimetallic oxide supported catalyst is a non-precious metal, replacing commonly used precious metals such as platinum and palladium, which significantly reduces costs. At the same time, it is simultaneously loaded into the molecular sieve framework of nanomaterials through a one-step gasification method. The resulting bimetallic oxide supported catalyst can optimize the arrangement of catalytic active sites and electronic structure through the interaction of metal double bonds, thereby increasing the catalyst's conversion efficiency for reactants and improving the selectivity of catalytic products.

[0049] Thirdly, the present invention provides an application of the bimetallic oxide supported catalyst as described in the second aspect, wherein the bimetallic oxide supported catalyst is used for catalytic cracking of waste epoxy resin.

[0050] This invention employs a one-step gasification method to synthesize a bimetallic oxide supported catalyst and uses a catalytic cracking method to recover waste epoxy resin, thereby reducing the cost of waste epoxy resin recovery while improving its safety. The bimetallic oxide supported catalyst has high selectivity in recovering phenolic substances, providing high economic utilization for the recycling of waste epoxy resin.

[0051] Preferably, the waste epoxy resin includes waste glass fiber leaf resin and / or thermosetting bisphenol A type epoxy resin from waste electronic waste.

[0052] Preferably, the mass ratio of the waste epoxy resin to the bimetallic oxide supported catalyst is 1:(0.5-6), for example, it can be 1:0.5, 1:2, 1:3, 1:4 or 1:6, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0053] Preferably, the temperature of the catalytic cracking is 540-560℃, for example, it can be 540℃, 545℃, 550℃, 555℃ or 560℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0054] Preferably, the catalytic cracking time is 0.4-0.6 h, for example, it can be 0.4 h, 0.45 h, 0.5 h, 0.55 h or 0.6 h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0055] The process of disposing of waste epoxy resin in this invention involves rapid pyrolysis of the epoxy resin, which takes a short time, allows for the selective recovery of high-value phenolic substances, and poses minimal harm to the environment and ecology during the disposal process.

[0056] Preferably, the catalytic cracking is carried out under a nitrogen atmosphere.

[0057] Compared with the prior art, the present invention has the following beneficial effects:

[0058] (1) The preparation method of bimetallic oxide supported catalyst provided by the present invention uses molecular sieve as support, loads tin and titanium ions on the topological structure of nanomaterials, and rapidly synthesizes bimetallic oxide supported catalyst by one-step gasification method. Through the synergistic effect of two different metals, it exhibits high catalytic activity and selectivity in the reaction process. The selectivity of high-value target product phenol can reach 49%, which provides high economic utilization for the resource recycling of waste epoxy resin.

[0059] (2) The present invention recycles waste epoxy resin by catalytic cracking, which reduces the cost of waste epoxy resin recycling and improves the safety of recycling. At the same time, the process of disposing of waste epoxy resin is to rapidly crack the epoxy resin, which takes a short time and can selectively recover high-value phenolic substances. Furthermore, the process of disposal has minimal harm to the environment and ecology. Detailed Implementation

[0060] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0061] Example 1

[0062] This embodiment provides a bimetallic oxide supported catalyst, which includes a molecular sieve support and tin and titanium active components supported on the molecular sieve support; the molar ratio of the tin active component to the titanium active component is 1:1.5, and the mass percentage of the molecular sieve support is 40 wt% of the mass percentage of the bimetallic oxide supported catalyst.

[0063] The preparation method of the bimetallic oxide supported catalyst includes the following steps:

[0064] (1) Crystalline tin tetrachloride, tetraethyl silicate, hydrochloric acid and deionized water are uniformly mixed at room temperature to obtain a mixed solution. The molar ratio of silicon dioxide, tin dioxide, hydrochloric acid and deionized water in the mixed solution is 0.5:0.1:0.075:20. The obtained mixed solution is spray-dried and then dried at 110°C for 3 hours to obtain acidic tin oxide powder.

[0065] (2) The H-beta molecular sieve was treated with nitric acid for 12 h and dried at 110 °C to obtain a molecular sieve support; the molecular sieve support, titanium tetrachloride powder and acidic tin oxide powder obtained in step (1) were uniformly mixed, and the molar ratio of acidic tin oxide powder to titanium tetrachloride powder was 1:1.5; the resulting mixture was subjected to vacuum treatment to a vacuum degree of 0.4 bar, vaporization treatment at 550 °C and 200 mL / min nitrogen atmosphere for 6 h, and calcination treatment at 550 °C and air atmosphere for 6 h to obtain the bimetallic oxide supported catalyst.

[0066] Waste glass fiber leaf resin with a mass ratio of 1:4 and bimetallic oxide supported catalyst were placed in a fixed bed pyrolysis furnace and catalytically pyrolyzed at 550℃ for 0.5h under a nitrogen atmosphere, and the liquid phase product was collected.

[0067] Example 2

[0068] This embodiment provides a bimetallic oxide supported catalyst, which includes a molecular sieve support and tin and titanium active components supported on the molecular sieve support; the molar ratio of the tin active component to the titanium active component is 1:3, and the mass percentage of the molecular sieve support is 70 wt% of the mass percentage of the bimetallic oxide supported catalyst.

[0069] The preparation method of the bimetallic oxide supported catalyst includes the following steps:

[0070] (1) Crystalline tin tetrachloride, tetraethyl silicate, hydrochloric acid and deionized water are uniformly mixed at room temperature to obtain a mixed solution. The molar ratio of silicon dioxide, tin dioxide, hydrochloric acid and deionized water in the mixed solution is 1:1:1:30. The obtained mixed solution is spray-dried and then dried at 105°C for 3.5 h to obtain acidic tin oxide powder.

[0071] (2) The H-beta molecular sieve was treated with nitric acid for 11 h and dried at 105 °C to obtain a molecular sieve support; the molecular sieve support, titanium tetrachloride powder and acidic tin oxide powder obtained in step (1) were uniformly mixed, and the molar ratio of acidic tin oxide powder to titanium tetrachloride powder was 1:3; the mixture was subjected to vacuum treatment to a vacuum degree of 0.1 bar, vaporization treatment at 540 °C and nitrogen atmosphere at 190 mL / min for 6.5 h, and calcination treatment at 540 °C and air atmosphere for 6.5 h to obtain the bimetallic oxide supported catalyst.

[0072] Waste glass fiber leaf resin and bimetallic oxide supported catalyst were placed in a fixed bed pyrolysis furnace at a mass ratio of 1:0.5 and catalytically pyrolyzed at 540℃ for 0.6 h under a nitrogen atmosphere, and the liquid phase products were collected.

[0073] Example 3

[0074] This embodiment provides a bimetallic oxide supported catalyst, which includes a molecular sieve support and tin and titanium active components supported on the molecular sieve support; the molar ratio of the tin active component to the titanium active component is 1:1, and the mass percentage of the molecular sieve support is 20 wt% of the mass percentage of the bimetallic oxide supported catalyst.

[0075] The preparation method of the bimetallic oxide supported catalyst includes the following steps:

[0076] (1) Crystalline tin tetrachloride, tetraethyl silicate, hydrochloric acid and deionized water are uniformly mixed at room temperature to obtain a mixed solution. The molar ratio of silicon dioxide, tin dioxide, hydrochloric acid and deionized water in the mixed solution is 2:3:3:50. The obtained mixed solution is spray-dried and then dried at 115°C for 2.5 h to obtain acidic tin oxide powder.

[0077] (2) The H-beta molecular sieve was treated with nitric acid for 13 h and dried at 115 °C to obtain a molecular sieve support; the molecular sieve support, titanium tetrachloride powder and acidic tin oxide powder obtained in step (1) were uniformly mixed, and the molar ratio of acidic tin oxide powder to titanium tetrachloride powder was 1:1; the resulting mixture was subjected to vacuum treatment to a vacuum degree of 0.9 bar, vaporization treatment at 560 °C and nitrogen atmosphere at 210 mL / min for 5.5 h, and calcination treatment at 560 °C and air atmosphere for 5.5 h to obtain the bimetallic oxide supported catalyst.

[0078] Waste glass fiber leaf resin with a mass ratio of 1:6 and bimetallic oxide supported catalyst were placed in a fixed bed pyrolysis furnace and catalytically pyrolyzed at 560℃ for 0.4h under a nitrogen atmosphere, and the liquid phase product was collected.

[0079] Example 4

[0080] This embodiment provides a bimetallic oxide supported catalyst. The preparation method of the bimetallic oxide supported catalyst differs from that of Example 1 in that the temperature of the gasification treatment in step (2) is adjusted to 530°C, while the rest is the same as in Example 1.

[0081] Example 5

[0082] This embodiment provides a bimetallic oxide supported catalyst. The preparation method of the bimetallic oxide supported catalyst differs from that of Example 1 in that the temperature of the gasification treatment in step (2) is adjusted to 570°C, while the rest is the same as that of Example 1.

[0083] Example 6

[0084] This embodiment provides a bimetallic oxide supported catalyst. The preparation method of the bimetallic oxide supported catalyst differs from that of Example 1 in that the calcination temperature in step (2) is adjusted to 530°C, while the rest is the same as in Example 1.

[0085] Example 7

[0086] This embodiment provides a bimetallic oxide supported catalyst. The preparation method of the bimetallic oxide supported catalyst differs from that of Example 1 in that the calcination temperature in step (2) is adjusted to 570°C, while the rest is the same as in Example 1.

[0087] Example 8

[0088] This embodiment provides a bimetallic oxide supported catalyst. The preparation method of the bimetallic oxide supported catalyst differs from that of Example 1 in that the molecular sieve support in step (2) is not subjected to dealumination treatment, while the rest is the same as that of Example 1.

[0089] Example 9

[0090] This embodiment provides a bimetallic oxide supported catalyst, which differs from Embodiment 1 in that the mass ratio of the waste glass fiber leaf resin to the bimetallic oxide supported catalyst is adjusted to 1:0.3, while the rest is the same as in Embodiment 1.

[0091] Example 10

[0092] This embodiment provides a bimetallic oxide supported catalyst, which differs from Embodiment 1 in that the mass ratio of the waste glass fiber leaf resin to the bimetallic oxide supported catalyst is adjusted to 1:6.5, while the rest is the same as in Embodiment 1.

[0093] Example 11

[0094] This embodiment provides a bimetallic oxide supported catalyst, which differs from Embodiment 1 in that the waste glass fiber leaf resin is replaced by thermosetting bisphenol A type epoxy resin from waste electronic waste, while the rest is the same as in Embodiment 1.

[0095] Example 12

[0096] This embodiment provides a bimetallic oxide supported catalyst, which differs from Example 1 in that the catalytic cracking temperature is adjusted to 530°C and the time is adjusted to 0.8h, while the rest is the same as Example 1.

[0097] Example 13

[0098] This embodiment provides a bimetallic oxide supported catalyst, which differs from Example 1 in that the catalytic cracking temperature is adjusted to 570°C and the time is adjusted to 0.2 h, while the rest is the same as Example 1.

[0099] Comparative Example 1

[0100] This comparative example provides a bimetallic oxide supported catalyst. The difference between the preparation method of the bimetallic oxide supported catalyst and that of Example 1 is that the molar ratio of acidic tin oxide powder to titanium tetrachloride powder in step (2) is adjusted to 1:0.8. The molar ratio of tin active component to titanium active component in the adaptively obtained bimetallic oxide supported catalyst is 1:0.8. All other aspects are the same as in Example 1.

[0101] Comparative Example 2

[0102] This comparative example provides a bimetallic oxide supported catalyst. The difference between the preparation method of the bimetallic oxide supported catalyst and that of Example 1 is that the molar ratio of acidic tin oxide powder to titanium tetrachloride powder in step (2) is adjusted to 1:3.2. The molar ratio of tin active component to titanium active component in the adapted bimetallic oxide supported catalyst is 1:3.2. All other aspects are the same as in Example 1.

[0103] Comparative Example 3

[0104] This comparative example provides a bimetallic oxide supported catalyst, which differs from Example 1 in that the mass percentage of the molecular sieve support is adjusted to 15 wt% of the mass percentage of the bimetallic oxide supported catalyst, while the rest is the same as in Example 1.

[0105] Comparative Example 4

[0106] This comparative example provides a bimetallic oxide supported catalyst, which differs from Example 1 in that the mass percentage of the molecular sieve support is adjusted to 75 wt% of the mass percentage of the bimetallic oxide supported catalyst, while the rest is the same as in Example 1.

[0107] The liquid phase products obtained in Examples 1-13 and Comparative Examples 1-4 were analyzed by GC-MS. The product components were identified by identification search in the NIST and MS profiles. The main liquid phase products were calculated using the internal standard method, and the selectivity of the target product phenolic substances was calculated. The results are shown in Table 1.

[0108] Table 1

[0109]

[0110]

[0111] As can be seen from Table 1, the preparation method of the bimetallic oxide supported catalyst provided by the present invention synthesizes the bimetallic oxide supported catalyst through a one-step gasification method. Through the synergistic effect of tin and titanium, it exhibits high catalytic activity and selectivity in the reaction process, and the selectivity of the high-value target product phenolic substances can reach 49%.

[0112] A comparison of Examples 1 with Examples 4 and 5 shows that excessively high or low gasification temperatures lead to an increase in side reactions. A comparison of Examples 1 with Examples 6 and 7 shows that excessively high or low calcination temperatures inhibit the formation of phenolic compounds. A comparison of Examples 1 with Example 8 shows that not performing dealumination on the molecular sieve reduces the material porosity, thus affecting catalytic performance. A comparison of Examples 1 with Examples 9 and 10 shows that a low mass ratio of waste glass fiber leaf resin to bimetallic oxide-supported catalyst results in insufficient catalytic effect and reduced selectivity; a high mass ratio does not further increase selectivity and wastes catalyst, increasing costs. A comparison of Examples 1 with Example 11 shows that catalytic cracking of thermosetting bisphenol A epoxy resin can still achieve relatively high selectivity. A comparison of Examples 1 with Examples 12 and 13 shows that exceeding the specified range for catalytic cracking temperature and time leads to a decrease in aromatization ability.

[0113] As can be seen from the comparison between Example 1 and Comparative Examples 1 and 2, if the molar ratio of tin to titanium exceeds the limit, the catalytic performance will be reduced. As can be seen from the comparison between Example 1 and Comparative Examples 3 and 4, if the content of molecular sieve support in the bimetallic oxide supported catalyst is too high or too low, the catalytic performance will be reduced.

[0114] In summary, the preparation method of the bimetallic oxide supported catalyst provided by this invention uses molecular sieve as a support, loads tin and titanium ions on the topological structure of nanomaterials, and rapidly synthesizes the bimetallic oxide supported catalyst through a one-step gasification method. Through the synergistic effect of the two different metals, it exhibits high catalytic activity and selectivity in the reaction process, and the selectivity of the high-value target product phenolic substances can reach 49%, providing high economic utilization for the resource recycling of waste epoxy resin.

[0115] This invention recycles waste epoxy resin using a catalytic cracking method, which reduces the cost of waste epoxy resin recycling while improving its safety. At the same time, the process of disposing of waste epoxy resin involves rapid cracking of the epoxy resin, which is relatively short and allows for the selective recovery of high-value phenolic substances. Furthermore, the process poses minimal harm to the environment and ecology.

[0116] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. Use of a double metal oxide supported catalyst in catalytic cracking of waste epoxy resins, characterized in that, The catalytic cracking is carried out in a nitrogen atmosphere. The bimetallic oxide supported catalyst comprises a molecular sieve carrier and tin active component and titanium active component supported on the molecular sieve carrier; the molar ratio of the tin active component and the titanium active component is 1:(1-3), and the mass percentage of the molecular sieve carrier is 20-70wt% of the mass percentage of the bimetallic oxide supported catalyst. The preparation method of the bimetallic oxide supported catalyst comprises the following steps: (1) uniformly mixing an inorganic tin salt, tetraethyl orthosilicate, an inorganic acid and a solvent to obtain a mixed solution; the obtained mixed solution is subjected to spray drying treatment to obtain an acidic tin oxide powder; (2) uniformly mixing a molecular sieve carrier, titanium tetrachloride powder and the acidic tin oxide powder obtained in step (1), and sequentially subjecting the obtained mixture to vacuum treatment, gasification treatment and calcination treatment to obtain the bimetallic oxide supported catalyst; The gasification treatment in step (2) is carried out in a nitrogen atmosphere.

2. Use according to claim 1, characterized in that, The inorganic tin salt in step (1) comprises crystalline tin tetrachloride and / or tin nitrate.

3. Use according to claim 1, characterized in that, The inorganic acid in step (1) comprises hydrochloric acid and / or nitric acid.

4. Use according to claim 1, characterized in that, The solvent in step (1) comprises deionized water.

5. The use according to claim 1, characterized in that, The spray drying treatment in step (1) is further followed by a drying step.

6. Use according to claim 5, characterized in that, The temperature of the drying is 105-115℃, and the time is 2.5-3.5h.

7. The use according to claim 1, characterized in that, The molecular sieve carrier in step (2) is a molecular sieve carrier obtained by dealumination treatment of H-beta molecular sieve.

8. Use according to claim 7, characterized in that, The reagent used in the dealumination treatment comprises nitric acid.

9. Use according to claim 7, characterized in that, The time of the dealumination treatment is 11-13h.

10. Use according to claim 7, characterized in that, The dealumination treatment is followed by drying at 105-115℃.

11. Use according to claim 1, characterized in that, The molar ratio of the acidic tin oxide powder and the titanium tetrachloride powder in step (2) is 1:(1-3).

12. The use according to claim 1, characterized in that, The vacuum degree of the vacuum treatment in step (2) is 0.1-0.9bar.

13. The use according to claim 1, characterized in that, The flow rate of nitrogen in the gasification treatment in step (2) is 190-210mL / min.

14. The use according to claim 1, characterized in that, The temperature of the gasification treatment in step (2) is 540-560℃.

15. The use according to claim 1, characterized in that, The time of the gasification treatment in step (2) is 5.5-6.5h.

16. The use according to claim 1, characterized in that, The calcination treatment in step (2) is carried out in an oxygen-containing atmosphere.

17. Use according to claim 16, characterized in that, The oxygen-containing atmosphere comprises an air atmosphere and / or an oxygen atmosphere.

18. The use according to claim 1, characterized in that, The temperature of the calcination treatment in step (2) is 540-560℃.

19. The use according to claim 1, characterized in that, The time of the calcination treatment in step (2) is 5.5-6.5h.

20. The use according to claim 1, characterized in that, The waste and old epoxy resin comprises waste and old glass fiber blade resin and / or thermosetting bisphenol A type epoxy resin in waste electronic materials.

21. The use according to claim 1, characterized in that, The mass ratio of the waste and old epoxy resin and the bimetallic oxide supported catalyst is 1:(0.5-6).

22. The use according to claim 1, characterized in that, The temperature of the catalytic cracking is 540-560℃.

23. The use according to claim 1, characterized in that, The time of the catalytic cracking is 0.4-0.6h.

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