CN107626349B - Catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid and method for preparing benzyl alcohol, benzaldehyde and benzoic acid - Google Patents
Catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid and method for preparing benzyl alcohol, benzaldehyde and benzoic acid Download PDFInfo
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Abstract
The invention relates to a production process for preparing benzyl alcohol, benzaldehyde and benzoic acid by direct liquid-phase oxidation of toluene. Specifically, under the synergistic catalytic action of supported ionic liquid and metal-organic framework Materials (MOFs), methylbenzene is used as a raw material, hydrogen peroxide is used as an oxidant, and in a mild reaction system, the high-selectivity liquid phase controlled oxidation reaction is carried out to prepare benzyl alcohol, benzaldehyde and benzoic acid. The catalyst disclosed by the invention is easy to prepare, can be well recycled and reused, has high chemical selectivity, mild reaction conditions, simple operation and high hydrogen peroxide utilization rate, and is an efficient and environment-friendly method.
Description
Technical Field
The invention relates to a novel method for preparing benzyl alcohol, benzaldehyde and benzoic acid by liquid-phase selective controlled oxidation of supported ionic liquid and metal-organic framework Materials (MOFs) catalytic toluene, and belongs to the technical field of chemical industry.
Technical Field
Benzyl alcohol, benzaldehyde and benzoic acid are very important chemical products, have wide industrial application range and are widely applied to synthesis of compounds such as dyes, medical intermediates, pesticides and the like. Meanwhile, the toluene is used as a main product in petroleum processing and coal chemical industry, and the toluene is deeply processed to generate high value-added products such as benzyl alcohol, benzaldehyde, benzoic acid and the like, so that the method has important significance. At present, the main methods for producing benzyl alcohol, benzaldehyde and benzoic acid by using toluene include a toluene chlorination hydrolysis method, a toluene gas phase oxidation method and a toluene liquid phase oxidation method. Among the three methods, the chlorination and hydrolysis method of toluene is the most widely used method for producing byproduct benzyl alcohol and benzaldehyde of benzoic acid in industry at present. However, this method has many disadvantages: long process flow, difficult product separation, low atom utilization rate, and serious environmental pollution caused by the discharge of acid gas and organic waste. The toluene gas-phase oxidation method partially overcomes the defects of a toluene chlorination hydrolysis method, but the main defects of the method are as follows: the conversion rate of toluene is low, the toluene in the tail gas is difficult to recycle, the product yield is low, the selectivity is low, excessive oxides are generated, and the production cost is high.
In recent years, the liquid-phase selective oxidation of toluene to prepare benzyl alcohol, benzaldehyde and benzoic acid is widely concerned by chemical workers at home and abroad, and is a new hotspot for the research and development of a toluene selective oxidation process. The molecular oxygen and the hydrogen peroxide are used as the oxidant, so that the method has the characteristics of small harm to the environment and clean and environment-friendly performance. The air (oxygen) toluene liquid phase oxidation method (CN101613269A, JP2003286210A, US6495726B1) has the advantages of mild reaction conditions, high requirements on reaction equipment, low reaction conversion rate and expensive catalyst. The method for preparing benzyl alcohol, benzaldehyde and benzoic acid (Z.Guo, B.Liu, Q.Zhang, W.Deng, Y.Wang, Y.Yang, chem.Soc.Rev.,2014,43, 3480; X.Wang, J.Wu, M.ZHao, Y.Lv, G.Li, C.Hu, J.Phys.chem.C,2009,113,14270) by liquid-phase selective oxidation of hydrogen peroxide and toluene has the advantages of high conversion rate, short process route, high atom economy and the like, and is considered to be a clean production method with wide application prospect.
The heterogeneous catalysis has easy separation and catalystGood stability and reusability, etc., therefore, some chemists apply the heterogeneous catalyst to the liquid-phase selective oxidation of toluene by hydrogen peroxide. For example: CN101972646A utilizes the prepared transition metal vanadate Co-V-O catalyst and hydrogen peroxide as oxidant to oxidize toluene at 60 ℃ through liquid phase, and as a result, the conversion rate of toluene is close to 50%, the selectivity of benzaldehyde is about 70%, and the selectivity of benzyl alcohol is about 13%. Liu et al (applied. Catal. A: Gen.,2012,425-426,191) found that when HZSM-5-0.20 molecular sieve was used as the catalyst, hydrogen peroxide was used as the oxidant, water was used as the solvent, and the reaction was carried out at 90-95 ℃ for 5 hours, the conversion of toluene was only 32%, while the selectivities of benzaldehyde, benzyl alcohol and benzoic acid were only 25%, 20.8% and 27.5%, respectively, and 22.3% by-product phenolic compound was also produced. Xia et al (Catal. Commun.,2016,86,72) use prepared V-Mo-Fe-O as catalyst, hydrogen peroxide as oxidant, and carry out liquid phase oxidation reaction at 80 deg.C, with toluene conversion rate of only 40.3% and benzaldehyde selectivity of 84.5%. Silva et al as complexes [ Fe (BMPA) Cl3]Is a catalyst (J.mol.Catal.A: chem.,2017,426,564), hydrogen peroxide is an oxidant, acetonitrile is a solvent, the maximum yield of benzaldehyde is only 10.5%, the selectivity is only 36%, the yield of benzyl alcohol is only less than 4%, the selectivity is 13%, and a large amount of byproducts such as phenol quinone peroxide are generated.
In a word, the existing toluene selective oxidation method has the defects of low catalyst activity, low reaction selectivity, complex process and the like.
Disclosure of Invention
The invention aims to develop a green method for preparing benzyl alcohol, benzaldehyde and benzoic acid by directly oxidizing toluene with high conversion rate and high selectivity.
In order to achieve the purpose, the invention provides a novel method for preparing benzyl alcohol, benzaldehyde and benzoic acid by liquid-phase selective oxidation of hydrogen peroxide and toluene, namely, toluene is used as a raw material, 30% hydrogen peroxide is used as an oxidant, metal modified ZSM-5 molecular sieve supported ionic liquid and metal-organic framework Materials (MOFs) are used as catalysts, and the selective control oxidation reaction of the toluene is realized under the solvent-free condition.
The promoter metal-organic framework Material (MOFs) is one of MIL-53(Fe), MIL-53(Cr), MIL-53(Al), Ce-MIL-101(Fe) and Ce-MIL-101 (Cr). And Mn, Cu, Co and Fe transition metal modified ZSM-5 molecular sieve supported imidazole ionic liquid is used as a main catalyst.
The chemical reaction principle and the structure of the preparation of the Mn, Cu, Co and Fe transition metal modified ZSM-5 molecular sieve supported imidazole ionic liquid used by the invention are as follows:
the anion of the ionic liquid in the general formula can be chlorine, FeCl4,CuCl3,CuClBr,SnCl3And (4) negative ions. The transition metal M can be Mn, Cu, Co, Fe. The general formula M-ZSM-5@ IL [ anion]The reaction principle of the catalyst comprises the following steps:
(1) imidazole and 3-chloropropyltriethoxysilane are subjected to reflux reaction in a toluene solvent at 90-110 ℃ for 20-25 hours, then the reaction is continued for 2 hours after triethylamine is added, the solvent is recovered and dried to obtain an intermediate 1,
(2) reflux reaction of the intermediate 1 and 1-chlorohexane in toluene at 90-110 deg.c for 10-15 hr, recovering solvent, drying to obtain intermediate 2,
(3) the intermediate 2 and the metal modified molecular sieve M-ZSM-5 are refluxed and reacted for 20 to 25 hours in toluene at the temperature of between 90 and 110 ℃, filtered and dried to obtain ionic liquid 3,
(4) and continuously carrying out reflux reaction on the ionic liquid 3 and ferric chloride, cupric chloride, cuprous bromide or stannous chloride in an acetonitrile solvent for 24 hours, filtering, washing acetonitrile, and drying to obtain the supported imidazole ionic liquid catalyst.
In the step (1), the molar ratio of imidazole, 3-chloropropyltriethoxysilane and triethylamine is 1: 0.5-5: 0.5 to 5;
more preferably, the molar ratio of imidazole, 3-chloropropyltriethoxysilane and triethylamine is 1: 1: 1.
in the step (2), the molar ratio of the intermediate 1 to the 1-chlorohexane is 1: 0.5 to 2;
more preferably, the molar ratio of the intermediate 1 to the 1-chlorohexane is 1: 1.
in the step (3), the mass ratio of the intermediate 2 to the metal modified molecular sieve M-ZSM-5 is 1-3: 1
More preferably, the mass ratio of the intermediate 2 to the metal modified molecular sieve M-ZSM-5 is 1.5: 1
In the above reaction process, the toluene solvent was added in excess.
The molar ratio of the materials used in the invention is toluene: the catalyst comprises 30% of hydrogen peroxide (1: 1-6), a main catalyst in an amount of 1-10% of the mass of toluene, and a cocatalyst in an amount of 0.01-1.0 g, wherein the materials, MOFs and a supported ionic liquid catalyst are fed in proportion, mixed and stirred for reaction.
The reaction temperature is 25-70 ℃.
The reaction time is 0.5-8 hours.
The main catalyst is one of M-ZSM-5 molecular sieve supported imidazole ferric chloride salt ionic liquid, M-ZSM-5 molecular sieve supported imidazole cupric chloride salt ionic liquid, M-ZSM-5 molecular sieve supported imidazole chlorocuprous bromide salt ionic liquid and M-ZSM-5 molecular sieve supported imidazole stannous chloride salt ionic liquid.
The invention relates to a method for preparing benzyl alcohol, benzaldehyde and benzoic acid by phase-controlled oxidation of transition metal modified ZSM-5 molecular sieve supported imidazole ionic liquid and MOFs (metal-organic frameworks) in a manner of cooperatively catalyzing toluene hydrogen peroxide solution, wherein after the reaction is finished, the reaction product is cooled and kept stand, catalyst particles are deposited at the bottom of a flask, and the catalyst can be recovered and reused without treatment, and the method comprises the following steps: and feeding 30% hydrogen peroxide in a ratio of 1: 1-6 to perform the next catalytic oxidation reaction.
The catalytic oxidation reaction principle of the invention is as follows:
according to the method for preparing the benzyl alcohol, the benzaldehyde and the benzoic acid, the key technology is that the prepared modified M-ZSM-5 molecular sieve supported imidazole ionic liquid and MOFs are adopted to cooperatively catalyze toluene hydrogen peroxide to perform liquid-phase controlled oxidation reaction to obtain the benzyl alcohol, the benzaldehyde and the benzoic acid.
The invention adopts transition metal modified ZSM-5 molecular sieve supported imidazole ionic liquid main catalyst and catalyst promoter MOFs as heterogeneous catalyst systems to catalyze toluene hydrogen peroxide solution phase-controlled oxidation to prepare benzyl alcohol, benzaldehyde and benzoic acid under mild conditions, and experimental results show that the conversion rate of toluene and the selectivity and yield of the benzyl alcohol, the benzaldehyde and the benzoic acid can be obviously improved.
Compared with the prior art, the invention has the advantages that: (1) the M-ZSM-5 molecular sieve supported imidazole ionic liquid and the MOFs catalyst are adopted, so that the preparation is easy, the catalytic activity is high, the stability is good, and the catalyst can be recycled. (2) The reaction is heterogeneous synergistic catalytic oxidation, the product and the catalyst are simple to separate, and the catalyst can be conveniently recycled and reused. (3) The whole reaction system is green and efficient, the reaction conditions are mild, the product selectivity is high, the hydrogen peroxide utilization rate is high, and the solvent-free environment-friendly effect is achieved.
Detailed Description
The following embodiments are merely descriptions of the best mode of the present invention and do not limit the scope of the present invention in any way, and the spirit of the present invention is further explained by the following examples.
Preparation of the catalyst:
(1) imidazole (1mol) and 3-chloropropyltriethoxysilane (1mol) are put into a toluene (800mL) solvent to carry out reflux reaction for 22 hours at 105 ℃, then triethylamine (1mol) is added to continue the reaction for 2 hours, the solvent is recovered and dried to obtain an intermediate 1,
(2) then 1(0.5mol) and 1-chlorohexane (0.5mol) are refluxed in toluene (350mL) at 105 ℃ for 12 hours, the solvent is recovered and dried to obtain an intermediate 2,
(3) refluxing and reacting the intermediate 2(0.05mol) and metal modified molecular sieve M-ZSM-5(15g) toluene (300mL) at 105 ℃ for 24 hours, filtering, drying the ionic liquid 3,
(4) the ionic liquid 3(10g) is continuously refluxed and reacted with ferric chloride (0.02mol), cupric chloride (0.02mol), cuprous bromide (0.02mol) or stannous chloride (0.02mol) in acetonitrile (100mL) solvent for 24 hours,
(5) filtering, washing with acetonitrile, and drying to obtain the supported imidazole ionic liquid main catalyst 4. Sequentially comprises the following steps: M-ZSM-5 molecular sieve supported imidazole ferric chloride salt ionic liquid, M-ZSM-5 molecular sieve supported imidazole cupric chloride salt ionic liquid, M-ZSM-5 molecular sieve supported imidazole chlorocuprous bromide ionic liquid and M-ZSM-5 molecular sieve supported imidazole stannous chloride salt ionic liquid.
Example 1
In a reaction flask, toluene (1mol) and supported ionic liquid Mn-ZSM-5@ IL [ CuCl ] are added3](5.5g) and MIL-53(Fe) (0.15g), and 30% hydrogen peroxide (1.1mol) was slowly added with stirring, followed by further stirring at 50 ℃ to react for 3.5 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 87 percent, the selectivity of the benzaldehyde is 74 percent, the selectivity of the benzoic acid is 24 percent, and the selectivity of the benzyl alcohol and other products is 2 percent.
Example 2
In a reaction flask, toluene (1mol) and supported ionic liquid Cu-ZSM-5@ IL [ CuCl ] are added3](6.0g) and MIL-53(Fe) (0.2g), and 30% hydrogen peroxide (1mol) was slowly added with stirring, followed by further stirring at 55 ℃ to react for 3 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of toluene is 78%, the selectivity of benzaldehyde is 82%, the selectivity of benzyl alcohol is 10%, and the selectivity of benzoic acid and other products is 8%.
Example 3
In a reaction flask, toluene (1mol) and supported ionic liquid Co-ZSM-5@ IL [ CuCl ] are added3](5.5g) and MIL-53(Fe) (0.3g), and 30% hydrogen peroxide (1.1mol) was slowly added with stirring, followed by further stirring at 55 ℃ to react for 2.5 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 84%, the selectivity of the benzaldehyde is 87%, the selectivity of the benzyl alcohol is 5%, and the selectivity of the benzoic acid and other products is 8%.
Example 4
In a reaction flask, toluene (1mol) and supported ionic liquid Fe-ZSM-5@ IL [ CuCl ] are added3](6.0g) and MIL-53(Fe) (0.25g), and 30% hydrogen peroxide (1.2mol) was slowly added with stirring, followed by further stirring at 50 ℃ to react for 2 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows thatThe conversion rate of toluene is 90%, the selectivity of benzaldehyde is 80%, the selectivity of benzyl alcohol is 2%, and the selectivity of benzoic acid and other products is 18%.
Example 5
In a reaction flask, toluene (1mol) and supported ionic liquid Co-ZSM-5@ IL [ CuCl ] are added3](5.5g) and MIL-53(Cr) (0.35g), 30% hydrogen peroxide (1.1mol) was slowly added with stirring, and then the reaction was continued at 45 ℃ with stirring for 2 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 86 percent, the selectivity of the benzaldehyde is 85 percent, the selectivity of the benzyl alcohol is 10 percent, and the selectivity of the benzoic acid and other products is 5 percent.
Example 6
In a reaction flask, toluene (1mol) and supported ionic liquid Co-ZSM-5@ IL [ CuCl ] are added3](6.0g) and Ce-MIL-101(Fe) (0.5g), and 30% hydrogen peroxide (1mol) was slowly added with stirring, and then the reaction was continued at 50 ℃ with stirring for 3 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 92 percent, the selectivity of the benzaldehyde is 75 percent, the selectivity of the benzyl alcohol is 23 percent, and the selectivity of the benzoic acid and other products is 2 percent.
Example 7
In a reaction flask, toluene (1mol) and supported ionic liquid Co-ZSM-5@ IL [ CuCl ] are added3](8.0g) and MIL-53(Al) (0.8g), and 30% hydrogen peroxide (1.2mol) was slowly added with stirring, followed by further reaction with stirring at 65 ℃ for 5 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 62 percent, the selectivity of the benzaldehyde is 79 percent, the selectivity of the benzyl alcohol is 8 percent, and the selectivity of the benzoic acid and other products is 13 percent.
Example 8
In a reaction flask, toluene (1mol) and supported ionic liquid Cu-ZSM-5@ IL [ CuCl ] are added3](5.0g) and Ce-MIL-101(Cr) (1.0g), and 30% hydrogen peroxide (1.1mol) was slowly added with stirring, and then the reaction was continued at 40 ℃ with stirring for 6 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 83 percent, the selectivity of the benzyl alcohol is 47 percent, the selectivity of the benzaldehyde is 45 percent, and the selectivity of the benzoic acid and other products is 8 percent.
Example 9
In a reaction flask, toluene (1mol) and supported ionic liquid Cu-ZSM-5@ IL [ CuCl ] are added3](8.0g) and Ce-MIL-101(Cr) (0.7g), and 30% hydrogen peroxide (1.1mol) was slowly added with stirring, and then the reaction was continued at 40 ℃ with stirring for 8 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 85 percent, the selectivity of the benzyl alcohol is 59 percent, the selectivity of the benzaldehyde is 38 percent, and the selectivity of the benzoic acid and other products is 3 percent.
Example 10
In a reaction flask, toluene (1mol) and supported ionic liquid Co-ZSM-5@ IL [ SnCl ] are added3](7.0g) and Ce-MIL-101(Cr) (0.8g), and 30% hydrogen peroxide (1.1mol) was slowly added with stirring, and then the reaction was continued at 60 ℃ with stirring for 4 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 85 percent, the selectivity of the benzaldehyde is 83 percent, the selectivity of the benzyl alcohol is 8 percent, and the selectivity of the benzoic acid and other products is 9 percent.
Example 11
In a reaction flask, toluene (1mol) and supported ionic liquid Co-ZSM-5@ IL [ SnCl ] are added3](6.0g) and Ce-MIL-101(Cr) (0.9g), and 30% hydrogen peroxide (1.3mol) was slowly added with stirring, and then the reaction was continued at 55 ℃ with stirring for 5 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 92 percent, the selectivity of the benzaldehyde is 90 percent, the selectivity of the benzoic acid is 8 percent, and the selectivity of the benzyl alcohol and other products is 2 percent.
Example 12
Toluene (1mol) and supported ionic liquid Fe-ZSM-5@ IL [ FeCl ] are added into a reaction flask4](8.0g) and Ce-MIL-101(Fe) (0.6g), and 30% hydrogen peroxide (3mol) was slowly added with stirring, followed by further reaction with stirring at 605 ℃ for 7 hours. Cooling and filtering to recover the catalyst. The GC-MS analysis result shows that the conversion rate of the toluene is 90 percent, the selectivity of the benzoic acid is 91 percent, and the selectivity of the benzaldehyde and other products is 9 percent.
Example 13
Toluene (1mol) and supported ionic liquid Mn-ZSM-5@ IL [ FeCl ] are added into a reaction flask4](9.0g) and Ce-MIL-101(Fe) (0.8g), and 30% hydrogen peroxide (4mol) was slowly added with stirring, and then the reaction was continued at 60 ℃ with stirring for 5 hours. ColdThe catalyst was recovered by filtration. The GC-MS analysis results show that the conversion rate of toluene is 94%, the selectivity of benzoic acid is 93%, and the selectivity of benzaldehyde and other products is 7%.
Example 14
The catalyst in the embodiment 3 is recovered, the catalytic reaction is carried out according to the conditions in the embodiment 3, the recovered catalyst is repeatedly used for 3 times, and the experimental result shows that the activity of the catalyst is not reduced, the conversion rate of toluene is 76-84%, and the selectivity of benzaldehyde is 82-87%.
Example 15
The catalyst in the embodiment 11 is recovered, the catalytic reaction is carried out according to the conditions in the embodiment 11, the recovered catalyst is repeatedly used for 4 times, and the experimental result shows that the activity of the catalyst does not reduce the conversion rate of toluene by 86-92% and the selectivity of benzaldehyde by 85-90%.
Example 16
The catalyst in the embodiment 13 is recovered, the catalytic reaction is carried out according to the conditions in the embodiment 13, the recovered catalyst is repeatedly used for 4 times, and the experimental result shows that the activity of the catalyst is not reduced, the conversion rate of toluene is 90-94%, and the selectivity of benzoic acid is 90-93%.
Claims (9)
1. A catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid is characterized by specifically being a transition metal modified ZSM-5 molecular sieve supported imidazole ion liquid, and having the following specific structure:
2. The catalyst for preparing benzyl alcohol, benzaldehyde and benzoic acid as claimed in claim 1, wherein the chloride ion compound is SnCl3The transition metal M is Co.
3. The method for preparing a catalyst according to claim 1 or 2, comprising the steps of: (1) imidazole and 3-chloropropyltriethoxysilane are subjected to reflux reaction in a toluene solvent at 90-110 ℃ for 20-25 hours, then triethylamine is added, the reaction is continued for 2 hours, the solvent is recovered and dried to obtain an intermediate 1, 2, the intermediate 1 and 1-chlorohexane are subjected to reflux reaction in toluene at 90-110 ℃ for 10-15 hours, the solvent is recovered and dried to obtain an intermediate 2,
(3) the intermediate 2 and the metal modified molecular sieve M-ZSM-5 are refluxed and reacted for 20 to 25 hours in toluene at the temperature of 90 to 110 ℃, and then filtered to obtain dry ionic liquid 3,
(4) and continuously carrying out reflux reaction on the ionic liquid 3 and ferric chloride, cupric chloride, cuprous bromide or stannous chloride in an acetonitrile solvent for 24 hours, filtering, washing acetonitrile, and drying to obtain the supported imidazole ionic liquid catalyst.
4. The method of claim 3,
in the step (1), the molar ratio of imidazole, 3-chloropropyltriethoxysilane and triethylamine is 1: 0.5-5: 0.5 to 5;
in the step (2), the molar ratio of the intermediate 1 to the 1-chlorohexane is 1: 0.5 to 2;
in the step (3), the mass ratio of the intermediate 2 to the metal modified molecular sieve M-ZSM-5 is 1-3: 1;
in the above reaction process, the toluene solvent was added in excess.
5. The method of claim 3,
in the step (1), the molar ratio of imidazole, 3-chloropropyltriethoxysilane and triethylamine is 1: 1: 1;
in the step (2), the molar ratio of the intermediate 1 to the 1-chlorohexane is 1: 1;
in the step (3), the mass ratio of the intermediate 2 to the metal modified molecular sieve M-ZSM-5 is 1.5: 1.
6. the method for preparing benzyl alcohol, benzaldehyde and benzoic acid by using the catalyst of claim 1 or 2, characterized in that toluene is used as a raw material, 30% hydrogen peroxide is used as an oxidant, a transition metal modified ZSM-5 molecular sieve supported imidazole ionic liquid main catalyst and a cocatalyst MOFs are added, the mixture is stirred and reacted for 0.5-8 hours at the temperature of 25-70 ℃ under the solvent-free condition, the mixture is filtered, and the product benzyl alcohol, benzaldehyde and benzoic acid are sequentially obtained after separation, wherein the cocatalyst is a metal-organic framework Material (MOFs), and specifically comprises any one of MIL-53(Fe), MIL-53(Cr), MIL-53(Al), Ce-MIL-101(Fe), and Ce-MIL-101 (Cr).
7. The process according to claim 6, characterized in that the molar ratio of the materials used is toluene: 30% of hydrogen peroxide = 1: 1-6, the dosage of a main catalyst of the transition metal modified ZSM-5 molecular sieve supported imidazole ionic liquid is 1-10% of the mass of the toluene, and the dosage of a cocatalyst MOFs is 0.01-1.0% of the mass of the toluene.
8. The method of claim 6, wherein the temperature is controlled to be 55-60 ℃ when the main catalyst is Co-ZSM-5@ IL [ SnCl3] and the cocatalyst is Ce-MIL-101 (Cr).
9. The method of claim 6, wherein the reaction time is controlled to be 4-5 hours when the main catalyst is Co-ZSM-5@ IL [ SnCl3] and the cocatalyst is Ce-MIL-101 (Cr).
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