Bagasse-derived carbon-based loaded bimetallic catalyst, preparation method thereof and application of bagasse-derived carbon-based loaded bimetallic catalyst in synthesis of combined cumquat

Abstract

The invention discloses a bagasse-derived carbon-based loaded bimetallic catalyst, a preparation method thereof and an application of the bagasse-derived carbon-based loaded bimetallic catalyst in synthesis of combined cumquat. A preparation method of a bagasse-derived carbon-based loaded bimetallic catalyst comprises the following steps: crushing bagasse, sieving, drying, activating with an acid solution to obtain acid-activated bagasse, adding a salt solution containing bimetallic into the acid-activated bagasse, and sequentially carrying out hydrothermal treatment and pyrolysis to obtain the bagasse-derived carbon-based loaded bimetallic catalyst. The bagasse derived carbon-based loaded bimetallic catalyst is obtained. According to the preparation method, cheap bagasse non-noble metal rich in content is used as a raw material, successful preparation of the bagasse loaded bimetallic catalyst is achieved, the preparation cost is low, the operation process is simple, and the prepared catalyst is good in stability and environmentally friendly.

Description

Technical field:

[0001] The invention relates to the technical field of catalysts, and in particular to a bagasse-derived carbon-based supported bimetallic catalyst, a preparation method thereof, and an application thereof in synthesizing oligomeric carbon. Background technology:

[0002] Lianku, or 2,3-dimethyl-2,3-diphenylbutane, is a new type of additive. Lianku can be used as a synergistic agent for polymer fire retardancy. Its addition can significantly increase the oxygen index of the material and shorten the flame extinguishing time. Lianku can also be used as a catalyst and initiator for polymer cross-linking graft copolymerization under high temperature conditions. It is widely used in the modification of various polymer materials such as polyolefins, polyacrylates, polycarbonates, polyethers, etc.

[0003] At present, there are two main methods for synthesizing dimethoxybenzene: one is to use α-methylstyrene as raw material, first convert it into a halide intermediate, and then prepare it into a Grignard reagent for coupling. This method has a long process, and the generated halide Grignard reagent has poor stability, is easy to decompose, and is dangerous, so it is not suitable for industrial production. The second method uses isopropylbenzene as raw material, and uses peroxide to decompose into free radicals under heat or light to further induce the generation of isopropylbenzene free radicals, and the isopropylbenzene free radicals are self-coupled to obtain dimethoxybenzene. This method has few by-products, the products are easy to separate, and the operability is strong. The most commonly used peroxide is di-tert-butyl peroxide, which is heated to 120°C to induce free radical coupling, with few side reactions and high economic benefits. However, as the reaction proceeds, the tert-butyl free radicals in the reaction system generate tert-butyl alcohol, and the boiling point of tert-butyl alcohol (82.3°C) is low. Lowering the temperature of the reaction system causes the decomposition efficiency of di-tert-butyl peroxide to decrease, and the yield of dimethoxybenzene is not high. Patent CN 107827693A mentions a Pd@Pt / RGO PNs catalyst and its preparation method, which loads palladium / platinum nanospheres on a reduced graphene oxide carrier to catalyze the synthesis of cumene from isopropylbenzene, which can effectively improve the synthesis yield of cumene. However, palladium and platinum are both precious metals, and the pretreatment process of graphene is complicated and costly, which greatly reduces the economic efficiency of the reaction.

[0004] my country is the third largest sugarcane producer, with production second only to Brazil and India, and produces 20 million tons of bagasse every year. The reuse of bagasse can reduce the accumulation of agricultural and forestry waste and environmental pollution, improve the economic benefits of sugar-making enterprises, and promote the development of circular economy in enterprises. Carbon-based materials prepared from bagasse have developed pore structures and are widely used as catalyst carriers. They are often used to load acidic or alkaline catalysts for catalytic or adsorption reactions, but there are few studies on the direct loading of metals for catalytic synthesis reactions. Loading single metals is prone to aggregation, which reduces the catalytic efficiency. In order to further improve the catalytic performance of the catalyst, provide more abundant active sites for free radical reactions, and enhance the electrocatalytic activity, we designed and introduced bimetallic loading on bagasse-derived carbon-based materials.

[0005] In summary, it is of great significance to prepare a type of sugarcane bagasse-derived carbon-based supported non-precious metal catalyst with high catalytic activity, low preparation cost, simple preparation method and easy recovery, and use it in the synthesis of cumene. Summary of the invention:

[0006] The present invention solves the problems existing in the prior art, provides a bagasse-derived carbon-based supported bimetallic catalyst, a preparation method thereof, and an application thereof in the synthesis of sintered carbon. The preparation method proposed in the present invention utilizes abundant and inexpensive non-precious metals in bagasse as raw materials to achieve the successful preparation of the bagasse-supported bimetallic catalyst, with low preparation cost, simple operation process, good stability of the prepared catalyst, and green environmental protection. The present invention also provides the application of the catalyst in the synthesis of sintered carbon, with high catalytic activity, easy recovery, and multiple recycling, which can meet the needs of industrial production applications.

[0007] The first object of the present invention is to provide a method for preparing a bagasse-derived carbon-based supported bimetallic catalyst, comprising the following steps: crushing and screening the bagasse and then drying it, activating it with an acid solution to obtain acid-activated bagasse, adding a bimetallic salt solution to the acid-activated bagasse, and sequentially subjecting it to hydrothermal treatment and pyrolysis to obtain a bagasse-derived carbon-based supported bimetallic catalyst.

[0008] Preferably, the preparation method is prepared by the following steps:

[0009] (1) Using bagasse as raw material, crushing and sieving in a pulverizer, placing in an oven to dry, and setting aside;

[0010] (2) taking an appropriate amount of the sugarcane bagasse treated in step (1), adding an acid solution, and soaking it at room temperature overnight; filtering, taking the filter residue, and washing it with deionized water until it is neutral; finally, placing the washed sample in an oven and drying it to a constant weight;

[0011] (3) preparing a metal solution, mixing and stirring the metal solution with the bagasse treated in step (2), and then placing the mixture in a hydrothermal reaction vessel. After heating for several hours, filtering, washing with deionized water, and then washing with an alcohol solution until the filtrate is colorless and transparent, and transferring the filter residue to an oven for drying to obtain a black solid.

[0012] (4) The solid obtained above is placed in a reaction container, heated to the target temperature under a nitrogen atmosphere for a certain period of time for pyrolysis and cooled to room temperature, and finally the solid is ground into a powder with uniform particles to obtain a bagasse-derived carbon-based supported bimetallic catalyst.

[0013] Preferably, the acid solution is one of nitric acid, phosphoric acid and sulfuric acid, and the concentration of the acid solution is 0.05-0.5 mol / L.

[0014] Preferably, the bimetal is a mixture of copper and other transition metals, and the transition metal is selected from one of nickel, manganese, cobalt and iron. Nickel, manganese, cobalt and iron salts are taken from any one of nickel chloride, nickel sulfate hexahydrate, nickel acetate tetrahydrate, manganese chloride monohydrate, manganese sulfate, cobalt chloride hexahydrate, cobalt sulfate and ferric chloride; copper salt is taken from any one of copper chloride, copper sulfate pentahydrate and copper nitrate trihydrate.

[0015] Further preferably, the bimetallic acid accounts for 5% to 10% of the weight of the bagasse; and the molar ratio of copper ions to other transition metal ions in the bimetallic acid is 1:5 to 10.

[0016] Preferably, the hydrothermal treatment conditions are: hydrothermal reaction temperature 150°C to 240°C, and hydrothermal reaction time 8 to 16 hours.

[0017] Preferably, the pyrolysis conditions are: heating to 300°C to 500°C at a heating rate of 8 to 12°C / min in a nitrogen atmosphere of 180 to 220 mL / min, and a reaction time of 2 to 4 hours.

[0018] Preferably, the bagasse is crushed and sieved to a mesh size of 100 to 200 meshes.

[0019] The second object of the present invention is to provide a bagasse-derived carbon-based supported bimetallic catalyst obtained by the preparation method.

[0020] The third object of the present invention is to provide an application of the bagasse-derived carbon-based supported bimetallic catalyst in the synthesis of dimethicone, wherein the dimethicone is synthesized by the following steps: adding isopropylbenzene and di-tert-butyl peroxide to a reaction container, adding the catalyst, heating the reaction system to reflux for several hours, adding a sodium sulfite solution to quench the peroxide after the reaction is completed, filtering the reaction system to remove the catalyst, distilling under reduced pressure, and obtaining the target product dimethicone through silica gel column chromatography.

[0021] The reaction equation for the synthesis of cumene by using bagasse-derived carbon-based supported bimetallic catalyst is as follows:

[0022]

[0023] Preferably, the molar ratio of cumene to di-tert-butyl peroxide is 1:0.5-4; the amount of catalyst added is 5%-15% of the weight of cumene; and the catalytic reaction conditions are 120°C-140°C for 8-24h.

[0024] Further preferably, the molar ratio of cumene to di-tert-butyl peroxide is 1:2; the amount of catalyst added is 10% of the weight of cumene; and the catalytic reaction conditions are 120° C. for 10 hours.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] (1) The preparation method of the bagasse-derived carbon-based supported bimetallic catalyst proposed in the present invention is simple. The bagasse is converted into a carbon material by a one-step hydrothermal synthesis method, and two active metal components are supported on the carbon material. The bagasse is then pyrolyzed to ensure complete carbonization and to form a more catalytically active phase for the supported metals. The cost is low and the preparation conditions are mild, which is conducive to large-scale industrial production.

[0027] (2) The present invention uses sugarcane bagasse, an agricultural and forestry waste, as a carrier, which has low cost and wide source, can also solve the pollution problem and realize the recycling of agricultural and forestry biomass.

[0028] (3) Using isopropylbenzene and di-tert-butyl peroxide as raw materials and the catalyst proposed by the present invention to prepare the dimethicone, the reaction operation is simple, the catalytic effect is good, and the yield is high.

[0029] (4) The catalyst is easy to separate after the reaction, has strong stability, and can be recycled many times. After the catalyst is reused 5 times, the efficiency of the catalyst remains basically unchanged, but there is a certain loss of catalyst during the recycling process. Description of the drawings:

[0030] Figure 1 is a SEM image of the bagasse-derived carbon-based supported bimetallic catalyst in Example 1 of the present invention;

[0031] Figure 2 This is the XPS graph of the bagasse-derived carbon-based supported bimetallic catalyst in Example 1 of the present invention. Specific implementation method:

[0032] The following examples are provided to further illustrate the present invention, rather than to limit the present invention.

[0033] Unless otherwise defined, all professional terms used hereinafter have the same meaning as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specified, the experimental materials and reagents herein are conventional commercial products in the art.

[0034] Example 1

[0035] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0036] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0037] (2) Weigh 0.4416 g nickel chloride (3.4 mmol, nickel content accounts for 10% of the weight of bagasse) and 0.0653 g copper chloride (copper ion to nickel ion molar ratio = 1:7), dissolve in 30 mL deionized water, mix with 2 g treated bagasse, stir and put into a 100 mL reactor, and react in a 190 ° C oven for 10 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105 ° C to constant weight to obtain a black solid.

[0038] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h, and then the temperature was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.78 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0039] The morphology of the bagasse-derived carbon-based supported bimetallic catalyst was observed by SEM test. Figure 1 It can be seen that the bagasse-derived carbon-based supported bimetallic catalyst presents an uneven surface and porous structure, and the supported metals are dispersed on the surface of the material. The elemental composition and content of the catalyst surface of the bagasse-derived carbon-based supported bimetallic catalyst were observed by XPS testing. Figure 2 It can be seen that two metals, Ni and Cu, are successfully loaded in the catalyst, with the Ni content being 0.17% and the Cu content being 0.12%.

[0040] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0041] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the above-prepared catalyst (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8682 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 80.99%.

[0042] The catalyst separated by filtration was washed with water and ethanol and dried to recover 102 mg of catalyst, which was used for the second synthesis of coke in proportion with a yield of 79.32%.

[0043] The catalyst separated by filtration for the second time was washed with water and ethanol and dried to recover 94.3 mg of catalyst, which was used for the third synthesis of coke in proportion with a yield of 76.5%.

[0044] The catalyst separated by filtration for the third time was washed with water and ethanol and dried to recover 87.2 mg of catalyst, which was used for the fourth synthesis of coke in proportion with a yield of 75.3%.

[0045] The catalyst separated by filtration for the fourth time was washed with water and ethanol and dried to recover 82.6 mg of catalyst, which was used for the fifth time to synthesize the distillate in proportion, with a yield of 72%.

[0046] Comparative Example 1

[0047] Without using a catalyst, distilled water was prepared from cumene in the same manner as in Example 1, the steps being as follows:

[0048] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.056 g of white solid dimethicone was obtained by silica gel column chromatography, and the yield was 5.23%.

[0049] Comparative Example 2

[0050] For comparison, activated carbon prepared from bagasse without metal loading was used as catalyst to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were the same as those in Example 1.

[0051] The preparation method of bagasse catalyst comprises the following steps:

[0052] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0053] (2) Take 2 g of the treated bagasse, add 30 mL of deionized water, put it into a 100 mL reactor, and react in a 190°C oven for 10 h. After the reactor cools to room temperature, filter the sample in the autoclave reactor, wash it with deionized water, and then wash it with anhydrous ethanol. Finally, dry the washed sample in an oven at 105°C to constant weight to obtain a black solid.

[0054] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h. The solid was cooled to room temperature and finally ground into a powder with uniform particles to obtain 0.74 g of bagasse catalyst.

[0055] The steps of synthesizing co-drying using bagasse catalyst are as follows:

[0056] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the prepared catalyst (108 mg, 10% wt isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.0546 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 5.09%.

[0057] Comparative Example 3

[0058] For comparison, a bagasse-derived carbon-based supported single metal catalyst was prepared to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were the same as in Example 1.

[0059] The preparation method of the bagasse-derived carbon-based supported single metal nickel catalyst comprises the following steps:

[0060] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0061] (2) Weigh 0.5069 g of nickel chloride, dissolve it in 30 mL of deionized water, mix it with 2 g of treated bagasse, stir it, put it into a 100 mL reactor, and react it in an oven at 190°C for 10 h. After the reactor cools to room temperature, filter the sample in the autoclave reactor, wash it with deionized water, and then wash it with anhydrous ethanol. Finally, dry the washed sample in an oven at 105°C to constant weight to obtain a black solid.

[0062] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h. The solid was cooled to room temperature and finally ground into a powder with uniform particles to obtain 0.73 g of a bagasse-derived carbon-based supported monometallic catalyst.

[0063] The steps of synthesizing the co-reduction of sugarcane bagasse-derived carbon-based supported monometallic catalyst are as follows:

[0064] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the prepared catalyst (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.3487 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 32.53%.

[0065] Comparative Example 4

[0066] For comparison, a bagasse-derived carbon-based supported single metal catalyst was prepared to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were the same as in Example 1.

[0067] The preparation method of bagasse-derived carbon-based supported single metal copper catalyst comprises the following steps:

[0068] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0069] (2) Weigh 0.5069 g of copper chloride, dissolve it in 30 mL of deionized water, mix it with 2 g of treated bagasse, stir it, put it into a 100 mL reactor, and react it in a 190°C oven for 10 h. After the reactor cools to room temperature, filter the sample in the autoclave reactor, wash it with deionized water, and then wash it with anhydrous ethanol. Finally, dry the washed sample in an oven at 105°C to constant weight to obtain a black solid.

[0070] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h, and then cooled to room temperature. Finally, the solid was ground into a powder with uniform particles, namely 0.71 g of sugarcane bagasse-derived carbon-based supported monometallic catalyst.

[0071] The steps of synthesizing the co-reduction of sugarcane bagasse-derived carbon-based supported monometallic catalyst are as follows:

[0072] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the prepared catalyst (108 mg, 10 wt% isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.1560 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 14.56%.

[0073] Comparative Example 5

[0074] For comparison, a bagasse-derived carbon-based supported single metal catalyst was prepared to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were the same as in Example 1.

[0075] The preparation method of bagasse-derived carbon-based supported single metal manganese catalyst comprises the following steps:

[0076] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0077] (2) Weigh 0.5069 g of manganese sulfate, dissolve it in 30 mL of deionized water, mix it with 2 g of treated bagasse, stir it, put it into a 100 mL reactor, and react it in an oven at 190°C for 10 h. After the reactor cools to room temperature, filter the sample in the autoclave reactor, wash it with deionized water, and then wash it with anhydrous ethanol. Finally, dry the washed sample in an oven at 105°C to constant weight to obtain a black solid.

[0078] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h. The solid was cooled to room temperature and finally ground into a powder with uniform particles to obtain 0.73 g of a bagasse-derived carbon-based supported monometallic catalyst.

[0079] The steps of synthesizing the co-reduction of sugarcane bagasse-derived carbon-based supported monometallic catalyst are as follows:

[0080] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the prepared catalyst (108 mg, 10% wt isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.3061 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 28.56%.

[0081] Comparative Example 6

[0082] For comparison, a bagasse-derived carbon-based supported single metal catalyst was prepared to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were the same as in Example 1.

[0083] The preparation method of bagasse-derived carbon-based supported single metal cobalt catalyst comprises the following steps:

[0084] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0085] (2) Weigh 0.5069 g of cobalt chloride hexahydrate, dissolve it in 30 mL of deionized water, mix it with 2 g of treated bagasse, stir it, put it into a 100 mL reactor, and react it in an oven at 190°C for 10 h. After the reactor cools to room temperature, filter the sample in the autoclave reactor, wash it with deionized water, and then wash it with anhydrous ethanol. Finally, dry the washed sample in an oven at 105°C to constant weight to obtain a black solid.

[0086] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h. The solid was cooled to room temperature and finally ground into a powder with uniform particles to obtain 0.75 g of a bagasse-derived carbon-based supported monometallic catalyst.

[0087] The steps of synthesizing the co-reduction of sugarcane bagasse-derived carbon-based supported monometallic catalyst are as follows:

[0088] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the prepared catalyst (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.3234 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 30.17%.

[0089] Comparative Example 7

[0090] For comparison, a bagasse-derived carbon-based supported single metal catalyst was prepared to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were the same as in Example 1.

[0091] The preparation method of bagasse-derived carbon-based supported monometallic iron catalyst comprises the following steps:

[0092] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.72 g.

[0093] (2) Weigh 0.5069 g of ferric chloride, dissolve it in 30 mL of deionized water, mix it with 2 g of treated bagasse, stir it, put it into a 100 mL reactor, and react it in a 190°C oven for 10 h. After the reactor cools to room temperature, filter the sample in the autoclave reactor, wash it with deionized water, and then wash it with anhydrous ethanol. Finally, dry the washed sample in an oven at 105°C to constant weight to obtain a black solid.

[0094] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h. The solid was cooled to room temperature and finally ground into a powder with uniform particles to obtain 0.73 g of a bagasse-derived carbon-based supported monometallic catalyst.

[0095] The steps of synthesizing the co-reduction of sugarcane bagasse-derived carbon-based supported monometallic catalyst are as follows:

[0096] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the prepared catalyst (108 mg, 10 wt% isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.3081 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 28.74%.

[0097] Comparative Example 8

[0098] For comparison, commercially available palladium chloride was used as a catalyst to catalyze the synthesis of cumene from isopropylbenzene, and the other conditions were consistent with those in Example 1.

[0099] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and palladium chloride (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.4887 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 45.59%.

[0100] Example 2

[0101] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0102] (1) Sugarcane bagasse was crushed and sieved to obtain a product of 200 mesh, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.5 mol / L phosphoric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.45 g.

[0103] (2) Weigh 0.4468 g of nickel sulfate hexahydrate (1.7 mmol, nickel content accounts for 5% of the weight of sugarcane bagasse) and 0.0424 g of copper sulfate pentahydrate (copper ion concentration to nickel ion concentration molar ratio = 1:10), dissolve in 30 mL of deionized water, mix and stir with 2 g of treated sugarcane bagasse, put into a 100 mL reactor, and react in an oven at 240°C for 8 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105°C to constant weight to obtain a black solid.

[0104] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 4 h, and then the temperature was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.74 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0105] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0106] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the above-prepared catalyst (108 mg, 10 wt% isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8431 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 78.65%.

[0107] Example 3

[0108] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0109] (1) Sugarcane bagasse was crushed and sieved to obtain a product of 200 mesh, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.2 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.62 g.

[0110] (2) Weigh 0.6784 g of nickel acetate tetrahydrate (2.7 mmol, nickel content accounts for 8% of the weight of sugarcane bagasse) and 0.0454 g of copper chloride (molar ratio of copper ion concentration to nickel ion concentration = 1:8), dissolve in 30 mL of deionized water, mix and stir with 2 g of treated sugarcane bagasse, put into a 100 mL reactor, and react in an oven at 200°C for 10 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105°C to constant weight to obtain a black solid.

[0111] (3) The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 400°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 3 h, and then the temperature was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.74 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0112] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0113] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the catalyst prepared above (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8582 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 80.06%.

[0114] Example 4

[0115] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0116] (1) Sugarcane bagasse was crushed and sieved to obtain a product of 200 mesh, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.05 mol / L sulfuric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.74 g.

[0117] (2) Weigh 0.4891 g of manganese chloride monohydrate (3.4 mmol, manganese content accounts for 10% of the weight of sugarcane bagasse) and 0.08214 g of copper nitrate trihydrate (molar ratio of copper ion concentration to manganese ion concentration = 1:5), dissolve in 30 mL of deionized water, mix and stir with 2 g of treated sugarcane bagasse, put into a 100 mL reactor, and react in an oven at 150°C for 16 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105°C to constant weight to obtain a black solid.

[0118] The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h, and then the mixture was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.75 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0119] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0120] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the above-prepared catalyst (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8532 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 79.59%.

[0121] Example 5

[0122] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0123] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was dried in an oven at 105°C. 10 g of the dried sugarcane bagasse was soaked in a 0.3 mol / L phosphoric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was dried in an oven at 105°C to constant weight, and the mass of the obtained product was 9.47 g.

[0124] (2) Weigh 0.4077 g of manganese sulfate (2.7 mmol, manganese content accounts for 8% of the weight of sugarcane bagasse) and 0.1348 g of copper sulfate pentahydrate (molar ratio of copper ion concentration to manganese ion concentration = 1:5), dissolve in 30 mL of deionized water, mix and stir with 2 g of treated sugarcane bagasse, put into a 100 mL reactor, and react in a 200°C oven for 12 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105°C to constant weight to obtain a black solid.

[0125] The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 400°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 4 h, and then the temperature was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.73 g of bagasse-derived carbon-based supported bimetallic catalyst.

[0126] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0127] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the catalyst prepared above (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8381 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 78.18%.

[0128] Example 6

[0129] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0130] (1) Sugarcane bagasse was crushed and sieved to obtain a product of 200 mesh, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.4 mol / L nitric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.48 g.

[0131] (2) Weigh 0.6424 g of cobalt chloride hexahydrate (2.7 mmol, cobalt content accounts for 8% of the weight of bagasse) and 0.1348 g of copper sulfate pentahydrate (copper ion concentration to cobalt ion concentration molar ratio = 1:5), dissolve in 30 mL of deionized water, mix with 2 g of treated bagasse, stir, put into a 100 mL reactor, and react in a 200°C oven for 12 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105°C to constant weight to obtain a black solid.

[0132] The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 400°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 4 hours, then the temperature was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.75 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0133] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0134] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the above-prepared catalyst (108 mg, 10 wt% isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8431 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 78.65%.

[0135] Example 7

[0136] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0137] (1) Sugarcane bagasse was crushed and sieved to obtain a 100-mesh product, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L sulfuric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.67 g.

[0138] (2) Weigh 0.527 g of cobalt sulfate (3.4 mmol, cobalt content is 10% by mass compared to bagasse) and 0.1173 g of copper nitrate trihydrate (copper ion concentration to cobalt ion concentration molar ratio = 1:7), dissolve in 30 mL of deionized water, mix with 2 g of treated bagasse, stir, put into a 100 mL reactor, and react in a 220 ° C oven for 10 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105 ° C to constant weight to obtain a black solid.

[0139] The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 4 h, and then the temperature was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.72 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0140] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0141] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the above-prepared catalyst (108 mg, 10 wt% propylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8331 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 77.71%.

[0142] Example 8

[0143] The preparation method of bagasse-derived carbon-based supported bimetallic catalyst comprises the following steps:

[0144] (1) Sugarcane bagasse was crushed and sieved to obtain a product of 200 mesh, which was placed in an oven at 105°C for drying. 10 g of the dried sugarcane bagasse was soaked in a 0.1 mol / L phosphoric acid solution at room temperature overnight, and then washed with deionized water until the pH of the supernatant was ≈ 7. Finally, the sugarcane bagasse was placed in an oven at 105°C for drying to constant weight, and the mass of the obtained product was weighed to be 9.62 g.

[0145] (2) Weigh 0.5515 g of ferric chloride (3.4 mmol, iron content is 10% by mass compared to bagasse) and 0.1173 g of copper nitrate trihydrate (copper ion concentration to cobalt ion concentration molar ratio = 1:7), dissolve in 30 mL of deionized water, mix with 2 g of treated bagasse, stir, put into a 100 mL reactor, and react in an oven at 230 ° C for 10 h. After the reactor is cooled to room temperature, the sample in the autoclave reactor is filtered, washed with deionized water, and then washed with anhydrous ethanol. Finally, the washed sample is dried in an oven at 105 ° C to constant weight to obtain a black solid.

[0146] The black solid was placed in a crucible, which was opened and placed in a tubular furnace. The temperature was raised to 500°C at a heating rate of 10°C / min under a nitrogen atmosphere of 200 mL / min for pyrolysis for 2 h, and the mixture was cooled to room temperature. Finally, the solid was ground into a powder with uniform particles to obtain 0.71 g of a bagasse-derived carbon-based supported bimetallic catalyst.

[0147] The steps of synthesizing the disulfide using bagasse-derived carbon-based supported bimetallic catalyst are as follows:

[0148] Isopropylbenzene (1.08 g, 9 mmol) and di-tert-butyl peroxide (2.63 g, 18 mmol) were added to a 50 mL three-necked flask equipped with a reflux device and a stirring device, and the above-prepared catalyst (108 mg, 10 wt% isopropylbenzene) was added, and the reaction system was heated to 120° C. and refluxed for 10 h. After the reaction was completed, sodium sulfite solution was added to quench the peroxide, the reaction system was filtered to remove the catalyst, and the reaction was distilled under reduced pressure. 0.8130 g of white solid distilled was obtained by silica gel column chromatography, and the yield was 75.84%.

[0149] Example 9

[0150] The same as Example 1, except that the molar ratio of cumene to di-tert-butyl peroxide is 1:0.5, the amount of catalyst added is 5% of the weight of cumene, the catalytic reaction conditions are 120° C. for 24 hours, and the co-reaction yield is 77.35%.

[0151] Example 10

[0152] The same as Example 1, except that: the molar ratio of isopropylbenzene to di-tert-butyl peroxide is 1:4; the amount of catalyst added is 15% of the weight of isopropylbenzene; the catalytic reaction conditions are 140° C. for 8 hours, and the co-reaction yield is 78.29%.

[0153] The description of the above embodiments is only used to help understand the technical solution and core ideas of the present invention. It should be pointed out that for technicians in this technical field, several improvements and modifications can be made to the present invention without departing from the principles of the present invention. These improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a bagasse-derived carbon-based supported bimetallic catalyst, characterized in that: The method comprises the following steps: crushing and sieving bagasse and then drying it, activating it with an acid solution to obtain acid-activated bagasse, adding a bimetallic salt solution into the acid-activated bagasse, and sequentially subjecting it to hydrothermal treatment and pyrolysis to obtain a bagasse-derived carbon-based loaded bimetallic catalyst.

2. The preparation method according to claim 1, characterized in that: The acid solution is one of nitric acid, phosphoric acid and sulfuric acid, and the concentration of the acid solution is 0.05-0.5 mol / L.

3. The preparation method according to claim 1 or 2, characterized in that: The bimetal is a mixture of copper and other transition metals, and the transition metal is selected from one of nickel, manganese, cobalt and iron.

4. The preparation method according to claim 3, characterized in that: The bimetallic acid accounts for 5% to 10% of the weight of bagasse; the molar ratio of copper ions to other transition metal ions in the bimetallic acid is 1:5 to 10.

5. The preparation method according to claim 1 or 2, characterized in that: The hydrothermal treatment conditions are: hydrothermal reaction temperature 150°C to 240°C, and hydrothermal reaction time 8 to 16 hours.

6. The preparation method according to claim 1 or 2, characterized in that: The pyrolysis conditions are: heating to 300°C-500°C at a heating rate of 8-12°C / min in a nitrogen atmosphere of 180-220 mL / min, and a reaction time of 2-4 hours.

7. The preparation method according to claim 1 or 2, characterized in that: The bagasse is crushed and sieved to a mesh number of 100 to 200 meshes.

8. The bagasse-derived carbon-based supported bimetallic catalyst obtained by the preparation method according to any one of claims 1 to 7.

9. The use of the bagasse-derived carbon-based supported bimetallic catalyst in the synthesis of polysulfide according to claim 8, characterized in that: The following steps are adopted to synthesize the di-butyl peroxide: isopropylbenzene and di-tert-butyl peroxide are added into a reaction container, the bagasse-derived carbon-based supported bimetallic catalyst is added, the reaction system is heated to reflux for several hours, after the reaction is completed, a sodium sulfite solution is added to quench the peroxide, the reaction system is filtered to remove the catalyst, and the target product di-butyl peroxide is obtained by reduced pressure distillation and silica gel column chromatography.

10. The use according to claim 9, characterized in that: The molar ratio of isopropylbenzene to di-tert-butyl peroxide is 1:0.5-4; the amount of catalyst added is 5%-15% of the weight of isopropylbenzene; and the catalytic reaction conditions are 120-140°C for 8-24h.

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