CN111992231A - Bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, and preparation method and application thereof - Google Patents
Bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, and preparation method and application thereof Download PDFInfo
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- CN111992231A CN111992231A CN202010919763.1A CN202010919763A CN111992231A CN 111992231 A CN111992231 A CN 111992231A CN 202010919763 A CN202010919763 A CN 202010919763A CN 111992231 A CN111992231 A CN 111992231A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07H3/02—Monosaccharides
Abstract
The invention provides a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, and a preparation method and application thereof, and belongs to the technical field of catalysts. According to the invention, ruthenium phosphide is used as a hydrogenation active center, and a phosphorus atom can be inserted into a crystal lattice of ruthenium metal, so that the crystal structure of ruthenium metal is changed from a hexagonal crystal system to an orthorhombic crystal system of ruthenium phosphide, the hydrogenation activity of ruthenium can be improved, and the yield of sorbitol as a product in one-step hydrolysis hydrogenation of cellulose is improved. Before loading ruthenium, the invention mixes the ethanol dispersion liquid of the phosphine bromide ionic liquid with the ruthenium source aqueous solution, so that the phosphine bromide ionic liquid and ruthenium ions are complexed, the obtained ruthenium complex is easier to be reduced to generate ruthenium phosphide, and meanwhile, due to the physical barrier effect of the phosphine bromide ionic liquid, the ruthenium phosphide active center with smaller particle size can be obtained in the heat treatment process, the dispersion degree of the ruthenium phosphide is improved, the agglomeration of ruthenium phosphide particles is inhibited, and the high activity of the hydrogenation center is realized.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, and a preparation method and application thereof.
Background
Sorbitol is an important fine chemical and is widely applied to the fields of food, medicine, light industry, chemical industry and the like. At present, edible starch and glucose are mainly used as raw materials in China, sorbitol is prepared in a kettle type hydrogenation mode, and high-quality sorbitol prepared by cellulose conversion can not only avoid food consumption, but also bring great economic value.
The conversion of cellulose to sorbitol mainly involves two reactions: cellulose hydrolysis to make glucose and glucose hydrogenation to make sorbitol. Inorganic acid is generally adopted as a homogeneous catalyst for preparing glucose by cellulose hydrolysis, metal is generally adopted as a catalyst for preparing sorbitol by glucose hydrogenation, and if a bifunctional catalyst capable of catalyzing the preparation of glucose by cellulose hydrolysis and the preparation of sorbitol by glucose hydrogenation is provided, the production period is greatly shortened, and the production cost is reduced. Therefore, in recent years, attention is paid to the preparation of sorbitol by adopting the bifunctional catalyst and starting from cellulose through one-step (hydrolysis/hydrogenation) conversion, the research focus and difficulty of the reaction mainly focus on the design and preparation of the high-efficiency bifunctional catalyst, and the full play of the synergistic effect of two active sites under the same condition is the key of the bifunctional catalyst in realizing the one-step preparation of sorbitol from cellulose. The subject group of professor wanye researches the hydrolysis/hydrogenation performance of the phosphoric acid treated cellulose under the catalysis of Ru/CNT, and the yield of sorbitol can reach 73 percent (Catal. Lett.2009,133-167), but the large-scale use of the method is limited due to the high cost of the carbon nano tube.
Disclosure of Invention
In view of the above, the present invention aims to provide a bifunctional catalyst for preparing sorbitol by hydrolysis and hydrogenation of cellulose in one step, and a preparation method and an application thereof. The bifunctional catalyst obtained by the invention has a hydrolysis active center and a hydrogenation active center at the same time, is low in cost, and has a good catalytic effect when being used for catalyzing cellulose to prepare sorbitol through one-step hydrolysis hydrogenation.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, which comprises a first method or a second method, wherein the first method comprises the following steps:
(1) providing an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution;
(2) mixing the ethanol dispersion liquid of the phosphine bromide ionic liquid with a ruthenium source water solution at the temperature of 60-70 ℃ to obtain a complex solution of the phosphine bromide ionic liquid and ruthenium ions;
(3) placing a carbonaceous carrier in a complexing solution of phosphine bromide ionic liquid and ruthenium ions, and performing first impregnation to obtain a ruthenium-loaded carbonaceous carrier;
(4) placing the carbonaceous carrier loaded with ruthenium in a hypophosphorous acid compound aqueous solution, carrying out second impregnation, and then drying under the condition of ultrasonic water bath heating to obtain a carbonaceous carrier loaded with ruthenium and hypophosphite;
(5) carrying out heat treatment, washing and drying on the carbonaceous carrier loaded with ruthenium and hypophosphite in sequence to obtain a carbonaceous carrier with a hydrogenation active center;
(6) mixing the carbonaceous carrier with the hydrogenation active center with a sulfuric acid aqueous solution, and performing sulfonation treatment to obtain a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation;
the second method comprises the steps of:
(I) mixing a carbonaceous carrier with a sulfuric acid aqueous solution, and performing sulfonation treatment to obtain a carbonaceous carrier with a hydrolysis active center;
(II) providing an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution;
(III) mixing the ethanol dispersion liquid of the phosphine bromide ionic liquid with a ruthenium source water solution at the temperature of 60-70 ℃ to obtain a complex solution of the phosphine bromide ionic liquid and ruthenium ions;
(IV) placing the carbonaceous carrier with the hydrolysis active center in a complexing solution of phosphine bromide ionic liquid and ruthenium ions, and performing first impregnation to obtain an active carbonaceous carrier loaded with ruthenium;
(V) placing the carbonaceous carrier loaded with ruthenium in hypophosphorous acid compound aqueous solution, carrying out second impregnation, and then drying under the heating condition of ultrasonic water bath to obtain an active carbonaceous carrier loaded with ruthenium and hypophosphite;
(VI) sequentially carrying out heat treatment, washing and drying on the active carbonaceous carrier loaded with ruthenium and hypophosphite to obtain a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation;
the steps (I) and (II) to (III) are not limited in chronological order.
Preferably, in the first method and the second method, the phosphonium bromide ionic liquid is independently one or more of tetrabutylphosphonium bromide ionic liquid, 3-bromopropyltriphenylphosphonium bromide ionic liquid and tetraphenylphosphonium bromide ionic liquid;
the ruthenium source is ruthenium trichloride;
the hypophosphorous acid compound is one or more of sodium hypophosphite, ammonium hypophosphite and hypophosphorous acid independently;
the carbonaceous carrier is independently biochar or biochar solid sulfonic acid.
Preferably, in the first method and the second method, the molar ratio of the phosphine bromide ionic liquid to the ruthenium source in the complex solution of the phosphine bromide ionic liquid and the ruthenium source is 0.5-3: 1;
the molar concentration of a ruthenium source in the complexing liquid of the phosphine bromide ionic liquid and ruthenium ions is 0.027-0.27 mol/L;
the molar concentration of the hypophosphorous acid compound aqueous solution is 0.13-1.3 mol/L.
Preferably, in the first method, the loading amount of ruthenium in the ruthenium-loaded carbonaceous carrier is 0.5 to 5 wt.%; the molar ratio of hypophosphite to ruthenium in the carbonaceous carrier loaded with ruthenium and hypophosphite is 1-5: 1;
in the second method, the loading amount of ruthenium in the ruthenium-loaded activated carbonaceous carrier is 0.5 to 5 wt.%; the molar ratio of hypophosphite to ruthenium in the active carbonaceous carrier loaded with ruthenium and hypophosphite is 1-5: 1.
Preferably, in the first method and the second method, the time of the first impregnation and the second impregnation is independently more than or equal to 3 hours;
the temperature of ultrasonic water bath heating is independently 60-80 ℃.
Preferably, in the first method and the second method, the heat treatment is carried out under a sealed nitrogen atmosphere, the temperature of the heat treatment is 300-500 ℃ independently, and the time is 1-3 hours independently.
Preferably, in the first method and the second method, the mass concentration of the sulfuric acid aqueous solution is independently 2-10%;
the temperature of the sulfonation treatment is independently 150-200 ℃, and the time is independently 8-12 h.
The invention provides the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose, which is prepared by the preparation method.
The invention provides application of the bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation in preparing sorbitol by catalyzing cellulose one-step hydrolysis hydrogenation.
Preferably, the method of application comprises the steps of:
mixing cellulose, bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis and hydrogenation and sulfuric acid aqueous solution, and reacting in the presence of hydrogen peroxide2And carrying out one-step hydrolysis hydrogenation reaction under the atmosphere to obtain the sorbitol.
The invention provides a preparation method of a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, which comprises two methods, namely a first method, firstly, ruthenium and hypophosphite are sequentially loaded on a carbonaceous carrierCarrying out heat treatment to obtain a carbonaceous carrier with a hydrogenation active center, and then sulfonating the carbonaceous carrier with the hydrogenation active center to obtain the bifunctional catalyst for preparing the sorbitol by cellulose one-step hydrolysis hydrogenation; and secondly, firstly sulfonating the carbonaceous carrier to obtain the carbonaceous carrier with a hydrolysis active center, then sequentially loading ruthenium and hypophosphite on the carbonaceous carrier with the hydrolysis active center, and carrying out heat treatment to obtain the bifunctional catalyst for preparing the sorbitol by cellulose one-step hydrolysis hydrogenation. The invention can obtain the sulfonate (-SO) through sulfonation treatment3H) The active center is hydrolyzed, thereby catalyzing the hydrolysis of the cellulose to obtain the glucose. According to the invention, ruthenium phosphide is used as a hydrogenation active center, and a phosphorus atom can be inserted into a crystal lattice of ruthenium metal, so that the crystal structure of ruthenium metal is changed from a hexagonal crystal system to an orthorhombic crystal system of ruthenium phosphide, the hydrogenation activity of ruthenium can be improved, excessive hydrogenation of sorbitol by a ruthenium catalyst is avoided, and the yield of sorbitol product in hydrolysis hydrogenation of cellulose in one step is improved. Before loading ruthenium, the invention mixes the ethanol dispersion liquid of the phosphine bromide ionic liquid with the ruthenium source aqueous solution, so that the phosphine bromide ionic liquid and ruthenium ions are complexed, the obtained ruthenium complex is easier to be reduced to generate ruthenium phosphide, and meanwhile, due to the physical barrier effect of the phosphine bromide ionic liquid, the ruthenium phosphide active center with smaller particle size can be obtained in the heat treatment process, the dispersion degree of the ruthenium phosphide is improved, the agglomeration of ruthenium phosphide particles is inhibited, and the high activity of the hydrogenation center is realized. The invention uses hypophosphorous acid compounds as phosphorus sources, prepares ruthenium phosphide by a hypophosphite thermal decomposition method, can reduce the loss of active components to the maximum extent, and prevents the active center from agglomerating. Furthermore, ruthenium ions and hypophosphite are prevented from generating redox reaction in a solution by loading ruthenium and hypophosphite on the carbonaceous carrier step by step, so that the loading effect of ruthenium and hypophosphite is reduced; when the carbonaceous carrier of ruthenium and hypophosphite is prepared, the method adopts an ultrasonic water bath heating mode for drying, so that the ruthenium and hypophosphite are prevented from agglomerating in the carbonaceous carrier.
The bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose, which is obtained by the invention, has a hydrolysis active center and a hydrogenation active center at the same time, and has a good catalytic effect when being used for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose. The results of the examples show that the catalyst provided by the invention has good catalytic activity when catalyzing cellulose to prepare sorbitol through one-step hydrolysis hydrogenation, the cellulose conversion rate can reach 99.3%, and the yield of sorbitol can reach 71.5%.
Meanwhile, the preparation method provided by the invention is simple to operate, low in cost and suitable for industrial mass production.
Drawings
FIG. 1 is a mapping chart of the bifunctional catalyst obtained in example 3;
FIG. 2 is a TEM image of the bifunctional catalyst obtained in example 3;
FIG. 3 is a HRTEM image of the bifunctional catalyst obtained in example 3;
FIG. 4 is an XPS plot of the bifunctional catalyst obtained in example 3;
figure 5 is an XRD pattern of the bifunctional catalysts obtained in example 3 and example 6.
Detailed Description
The invention provides a preparation method of a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation, which comprises a first method or a second method, wherein the first method comprises the following steps:
(1) providing an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution;
(2) mixing the ethanol dispersion liquid of the phosphine bromide ionic liquid with a ruthenium source water solution at the temperature of 60-70 ℃ to obtain a complex solution of the phosphine bromide ionic liquid and ruthenium ions;
(3) placing a carbonaceous carrier in a complexing solution of phosphine bromide ionic liquid and ruthenium ions, and performing first impregnation to obtain a ruthenium-loaded carbonaceous carrier;
(4) placing the carbonaceous carrier loaded with ruthenium in a hypophosphorous acid compound aqueous solution, carrying out second impregnation, and then drying under the condition of ultrasonic water bath heating to obtain a carbonaceous carrier loaded with ruthenium and hypophosphite;
(5) carrying out heat treatment, washing and drying on the carbonaceous carrier loaded with ruthenium and hypophosphite in sequence to obtain a carbonaceous carrier with a hydrogenation active center;
(6) and mixing the carbonaceous carrier with the hydrogenation active center with a sulfuric acid aqueous solution, and performing sulfonation treatment to obtain the bifunctional catalyst for preparing the sorbitol by one-step hydrolysis hydrogenation of cellulose.
The invention firstly provides an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution. In the present invention, the method for preparing the ethanol dispersion of the phosphine bromide ionic liquid preferably comprises the following steps:
and mixing the phosphine bromide ionic liquid with ethanol, and stirring to obtain an ethanol dispersion liquid of the phosphine bromide ionic liquid.
In the invention, the phosphine bromide ionic liquid is preferably one or more of tetrabutyl phosphonium bromide ionic liquid, 3-bromopropyltriphenyl phosphonium bromide ionic liquid and tetraphenyl phosphonium bromide ionic liquid; the ethanol is preferably anhydrous ethanol. In the invention, the stirring speed is preferably 400-800 r/min, and more preferably 500-600 r/min; the stirring time is preferably equal to or more than 30min, and the temperature is preferably room temperature. In the invention, the mass concentration of the phosphine bromide ionic liquid in the ethanol dispersion liquid of the phosphine bromide ionic liquid is preferably 0.05-0.5 mol/L, and more preferably 0.15-0.4 mol/L.
In the present invention, the method for preparing the aqueous ruthenium source solution preferably includes the steps of:
and mixing the ruthenium source with deionized water, and stirring to obtain a ruthenium source aqueous solution.
In the present invention, the ruthenium source is preferably ruthenium trichloride. In the invention, the stirring speed is preferably 400-800 r/min, and more preferably 500-600 r/min; the stirring time is preferably equal to or more than 30min, and the temperature is preferably room temperature. In the invention, the mass concentration of the ruthenium source water solution is preferably 0.081-0.162 mol/L.
In the present invention, the method for preparing the hypophosphorous acid compound aqueous solution preferably comprises the steps of:
mixing hypophosphorous acid compounds with deionized water, and stirring to obtain hypophosphorous acid compound aqueous solution.
In the invention, the hypophosphorous acid compound is preferably one or more of sodium hypophosphite, ammonium hypophosphite and hypophosphorous acid. In the invention, the stirring speed is preferably 400-800 r/min, and more preferably 500-600 r/min; the stirring time is preferably equal to or more than 30min, and the temperature is preferably room temperature. In the invention, the mass concentration of the hypophosphorous acid compound aqueous solution is preferably 0.13-1.3 mol/L, and more preferably 0.5-1 mol/L.
According to the invention, the ethanol dispersion liquid of the phosphine bromide ionic liquid is mixed with the ruthenium source water solution at the temperature of 60-70 ℃ to obtain the complex solution of the phosphine bromide ionic liquid and ruthenium ions. In the present invention, the mixing method is preferably to drop the ruthenium source aqueous solution into the ethanol dispersion of the phosphine bromide ionic liquid, and to seal and stir. In the invention, the rotation speed of the closed stirring is preferably 400-800 r/min, and more preferably 500-600 r/min; the temperature of the closed stirring is 60-70 ℃, and preferably 64-68 ℃; according to the invention, the ionic liquid can be fully dissolved and has a better complexing effect with ruthenium ions by mixing at 60-70 ℃; in the invention, the mixing time is preferably not less than 3 hours, and more preferably 3-5 hours. According to the invention, through the closed stirring, the quality loss in the stirring process can be avoided.
In the invention, the mol ratio of the phosphine bromide ionic liquid to the ruthenium source in the complex solution of the phosphine bromide ionic liquid and the ruthenium source is preferably 0.5-3: 1, and more preferably 1-2: 1; the molar concentration of the ruthenium source in the complexing liquid is preferably 0.027-0.27 mol/L, and more preferably 0.05-0.2 mol/L.
The carbonaceous carrier is placed in a phosphine bromide ionic liquid and ruthenium ion complex solution for first impregnation, so that the ruthenium-loaded carbonaceous carrier is obtained. In the present invention, the carbonaceous carrier is preferably biochar or biochar solid sulfonic acid; the biochar is preferably one or more of charcoal, bamboo charcoal, straw biochar and coconut shell charcoal. In the present invention, the method for preparing the biochar solid sulfonic acid preferably comprises the following steps:
mixing the carbohydrate organic matter with p-toluenesulfonic acid, and sequentially grinding, thermally treating, washing and drying to obtain the biological carbon solid sulfonic acid.
In the invention, the saccharide organic matter is preferably one or more of sucrose, fructose, sucralose and xylose; the mass ratio of the sucrose to the p-toluenesulfonic acid is preferably 1-5: 1, and more preferably 3: 1. The grinding mode is not particularly required, and the grinding mode known to a person skilled in the art can be used; the grinding time is preferably 5-20 min, and more preferably 10 min.
In the invention, the temperature of the heat treatment is preferably 160-220 ℃, and more preferably 180 ℃; the time is preferably 12-48 h, and more preferably 24 h; the heat treatment is preferably carried out in a stainless steel reaction vessel with a polytetrafluoroethylene lining.
In the present invention, the washing detergent is preferably deionized water; the invention washes the product after heat treatment until the washing liquid is neutral. The invention has no special requirement on the drying mode, and the moisture can be completely removed by using the drying mode which is well known to the technical personnel in the field.
The method has no special requirement on the dosage ratio of the carbonaceous carrier to the phosphine bromide ionic liquid, and can ensure that the carbonaceous carrier is completely immersed. In the invention, the temperature of the first impregnation is preferably room temperature, and the time is preferably not less than 3h, and more preferably 3-5 h. After the impregnation, the impregnated carbonaceous carrier is preferably dried, wherein the drying temperature is preferably 80-100 ℃, and more preferably 90 ℃; the invention has no special requirement on the drying time, and the dried solid has constant weight. In the present invention, the amount of ruthenium supported on the ruthenium-supported carbonaceous carrier is preferably 0.5 to 5 wt.%, and more preferably 1 to 3 wt.%.
After the carbonaceous carrier loaded with ruthenium is obtained, the carbonaceous carrier loaded with ruthenium is placed in hypophosphorous acid compound aqueous solution for second impregnation, and then is dried under the condition of ultrasonic water bath heating, so that the carbonaceous carrier loaded with ruthenium and hypophosphite is obtained. The method has no special requirement on the dosage ratio of the carbonaceous carrier loaded with ruthenium to the phosphoric acid compound aqueous solution, and can ensure that the carbonaceous carrier loaded with ruthenium is completely immersed. In the invention, the temperature of the second impregnation is preferably room temperature, and the time is preferably not less than 3h, and more preferably 3-5 h. The temperature of the ultrasonic water bath heating is preferably 60-80 ℃, and the power is preferably 100W. The invention has no special requirement on the drying time, and the dried solid has constant weight. The invention adopts an ultrasonic water bath heating mode for drying, and prevents ruthenium and hypophosphite from agglomerating in a carbonaceous carrier. In the invention, the molar ratio of hypophosphite to ruthenium in the carbonaceous carrier loaded with ruthenium and hypophosphite is preferably 1-5: 1, and more preferably 2-4: 1.
The carbonaceous carrier loaded with ruthenium and hypophosphite is obtained, and the carbonaceous carrier loaded with ruthenium and hypophosphite is subjected to heat treatment, washing and drying in sequence to obtain the carbonaceous carrier with a hydrogenation active center. In the invention, the heat treatment is preferably carried out under the condition of closed nitrogen, and the temperature of the heat treatment is preferably 300-500 ℃, more preferably 350-450 ℃; the heating rate of the heating to the heat treatment temperature is preferably 5-10 ℃/min, and more preferably 6-8 ℃/min; in the invention, the time of the heat treatment is preferably 1-3 h, more preferably 2h, and the time of the heat treatment is calculated from the temperature reaching the heat treatment temperature. In the present invention, the heat treatment is preferably performed in a tube furnace; according to the invention, through the heat treatment, hypophosphite can be thermally decomposed and reacts with ruthenium ions to generate ruthenium phosphide, and a hydrogenation active center is formed.
The invention mixes the carbonaceous carrier with hydrogenation active center with sulfuric acid water solution, and carries out sulfonation treatment to obtain the bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation. In the present invention, the mass concentration of the sulfuric acid aqueous solution is preferably 2 to 10%, and more preferably 4 to 8%. The invention has no special requirement on the dosage ratio of the carbonaceous carrier with the hydrogenation active center and the sulfuric acid aqueous solution, and the carbonaceous carrier with the hydrogenation active center can be completely immersed. In the invention, the mixing mode is preferably stirring mixing, and the stirring speed is preferably 400-800 r/min, more preferably 500-600 r/min; the stirring time is preferably more than or equal to 30 min. In the invention, the temperature of the sulfonation treatment is preferably 150-200 ℃, more preferably 160-180 ℃, and the time is preferably 8-12 hours, more preferably 9-10 hours. In the present invention, the sulfonation treatment is preferably carried out in a hydrothermal reaction kettle with a polytetrafluoroethylene lining.
In the present invention, after the sulfonation treatment, it is also preferable to wash and dry the sulfonation-treated product. In the invention, the washing is preferably deionized water washing, no special requirement is required for the washing times, and the pH value of the washing liquid after washing is ensured to be between 5 and 7. The invention has no special requirements on the drying mode, and the constant weight of the dried solid is ensured.
In the present invention, the second method for preparing the bifunctional catalyst for preparing sorbitol by hydrolysis and hydrogenation of cellulose in one step comprises the following steps:
(I) mixing a carbonaceous carrier with a sulfuric acid aqueous solution, and performing sulfonation treatment to obtain a carbonaceous carrier with a hydrolysis active center;
(II) providing an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution;
(III) mixing the ethanol dispersion liquid of the phosphine bromide ionic liquid with a ruthenium source water solution at the temperature of 60-70 ℃ to obtain a complex solution of the phosphine bromide ionic liquid and ruthenium ions;
(IV) placing the carbonaceous carrier with the hydrolysis active center in a complexing solution of phosphine bromide ionic liquid and ruthenium ions, and performing first impregnation to obtain an active carbonaceous carrier loaded with ruthenium;
(V) placing the carbonaceous carrier loaded with ruthenium in hypophosphorous acid compound aqueous solution, carrying out second impregnation, and then drying under the heating condition of ultrasonic water bath to obtain an active carbonaceous carrier loaded with ruthenium and hypophosphite;
(VI) sequentially carrying out heat treatment, washing and drying on the active carbonaceous carrier loaded with ruthenium and hypophosphite to obtain a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation;
the steps (I) and (II) to (III) are not limited in chronological order.
The method mixes the carbonaceous carrier with a sulfuric acid aqueous solution, and carries out sulfonation treatment to obtain the carbonaceous carrier with a hydrolysis active center. In the present invention, the kind of the carbonaceous carrier and the concentration of the aqueous sulfuric acid solution are the same as those of the first method, and are not described herein again. In the present invention, the specific operating conditions of the sulfonation treatment are the same as those of the first method, and are not described herein again.
In the present invention, the steps (II) to (III) are the same as the steps (1) to (2), and are not described herein again.
The carbonaceous carrier with the hydrolysis active center is placed in a complexing solution of phosphine bromide ionic liquid and ruthenium ions for first impregnation, and the active carbonaceous carrier loaded with ruthenium is obtained. The invention has no special requirement on the dosage ratio of the carbonaceous carrier with the hydrolysis active center to the complexing solution, and can ensure that the carbonaceous carrier with the hydrolysis active center is completely immersed. In the present invention, the method of the first impregnation is the same as above, and is not described herein again. In the invention, the loading amount of ruthenium in the ruthenium-loaded activated carbonaceous carrier is preferably 0.5 to 5 wt.%, and more preferably 1 to 3 wt.%.
After the active carbon carrier loaded with ruthenium is obtained, the ruthenium-loaded carbon carrier is placed in hypophosphorous acid compound aqueous solution for second impregnation, and then is dried under the heating condition of ultrasonic water bath to obtain the active carbon carrier loaded with ruthenium and hypophosphite. The method has no special requirement on the dosage ratio of the carbonaceous carrier loaded with ruthenium to the hypophosphorous acid compound aqueous solution, and can completely immerse the carbonaceous carrier loaded with ruthenium. In the present invention, the specific operation manner of the second dipping and drying is the same as that of the first method, and is not described herein again. In the invention, the molar ratio of hypophosphite to ruthenium in the active carbonaceous carrier loaded with ruthenium and hypophosphite is preferably 1-5: 1, and more preferably 2-4: 1.
After the active carbon carrier loaded with ruthenium and hypophosphite is obtained, the active carbon carrier loaded with ruthenium and hypophosphite is sequentially subjected to heat treatment, washing and drying to obtain the bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation. In the present invention, the specific operation of the heat treatment, washing and drying is the same as that of the first method, and thus, the detailed description thereof is omitted.
The invention provides the bifunctional catalyst for preparing the sorbitol by the cellulose one-step hydrolysis hydrogenation, which is prepared by the preparation method. In the present invention, the bifunctional catalyst comprises a carbonaceous carrier and a hydrolysis active center and a hydrogenation active center supported in the carbonaceous carrier; the hydrolysis active center is a sulfonate; the hydrogenation active center is ruthenium phosphide, and the loading capacity of the hydrogenation active center is 0.5-5%.
The invention provides application of the bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation in preparing sorbitol by catalyzing cellulose one-step hydrolysis hydrogenation. In the present invention, the method of application preferably comprises the steps of:
mixing cellulose, bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis and hydrogenation and sulfuric acid aqueous solution, and reacting in the presence of hydrogen peroxide2And carrying out one-step hydrolysis hydrogenation reaction under the atmosphere to obtain the sorbitol.
In the present invention, the cellulose is preferably ball milled cellulose; the mass concentration of the sulfuric acid aqueous solution is preferably 0.02 to 0.1 wt%, and more preferably 0.04 to 0.08 wt%. In the invention, the mass ratio of the cellulose to the catalyst is preferably 1-5: 1, more preferably 2-4: 1; the mass ratio of the cellulose to the sulfuric acid aqueous solution is preferably 1: 10-50, and more preferably 1: 20-40.
In the invention, the one-step hydrolysis hydrogenation reaction is preferably carried out in a stainless steel needle valve reaction kettle; said H2The pressure of (A) is preferably 1 to 4MPa, more preferably 2 to 3 MPa. In the invention, the temperature of the one-step hydrolysis hydrogenation reaction is preferably 120-200 ℃, and more preferably 140-180 ℃; the time is preferably 1 to 15 hours, and more preferably 3 to 10 hours. The one-step hydrolysis isAfter the hydrogen reaction is finished, the stainless steel needle valve reaction kettle is preferably cooled, and the cooling mode is preferably natural cooling.
The following examples are provided to illustrate the bifunctional catalyst for preparing sorbitol by hydrolysis and hydrogenation of cellulose in one step, and the preparation method and application thereof, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Under the stirring state of 500r/min at room temperature, 0.17g of tetrabutyl phosphonium bromide ionic liquid is dissolved in 10mL of absolute ethanol, and stirring is carried out for 30min, so as to obtain ethanol dispersion liquid of the tetrabutyl phosphonium bromide ionic liquid;
(2) under the stirring state of 500r/min at room temperature, 0.11g of ruthenium trichloride is dissolved in 10mL of deionized water, and the mixture is stirred for 30min to obtain an aqueous solution of ruthenium trichloride;
(3) dropwise adding an aqueous solution of ruthenium trichloride into an ethanol dispersion of tetrabutyl phosphonium bromide ionic liquid under a stirring state at 60 ℃, and then stirring for 3 hours in a sealed manner to obtain a complex solution of tetrabutyl phosphonium bromide ionic liquid and ruthenium ions, wherein the molar ratio of tetrabutyl phosphonium bromide to ruthenium trichloride in the complex solution is 1: 1;
(4) soaking a charcoal carbonaceous carrier in a tetrabutyl phosphonium bromide ionic liquid and ruthenium ion complex solution for 3h, then taking out the carbonaceous carrier, and drying at 80 ℃ to obtain a ruthenium-loaded carbonaceous carrier, wherein the loading capacity of ruthenium in the carbonaceous carrier is 0.5%;
(5) under the condition of stirring at room temperature, 0.23g of sodium hypophosphite is dissolved in 10mL of deionized water to obtain a hypophosphite aqueous solution, the carbonaceous carrier loaded with ruthenium is placed in the hypophosphite aqueous solution for soaking for 3h, and then is dried in an ultrasonic water bath at 80 ℃ to obtain the carbonaceous carrier loaded with ruthenium and sodium hypophosphite, wherein the molar ratio of the sodium hypophosphite to the ruthenium in the carbonaceous carrier is 5: 1;
(6) loading a carbonaceous carrier loaded with ruthenium and sodium hypophosphite into a tubular furnace, driving away air in a tubular furnace system by using nitrogen, then closing the nitrogen, then heating the tubular furnace to 500 ℃ at a heating rate of 5 ℃/min, maintaining for 1h, then cooling to room temperature under a flowing nitrogen atmosphere, then washing the obtained product by using deionized water for at least 3 times, removing soluble impurities of the product, and then drying the product at 120 ℃ to obtain the carbonaceous carrier with a hydrogenation activity center;
(7) adding a carbonaceous carrier with a hydrogenation active center into a sulfuric acid aqueous solution with the mass fraction of 10% and the volume of 3 times of that of the carbonaceous carrier, stirring for 30min, putting the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, and sulfonating at 150 ℃ for 12 h; and fully washing the obtained product with deionized water until the pH value of the filtrate is between 5 and 7, and drying to obtain the bifunctional catalyst for preparing the sorbitol by one-step hydrolysis and hydrogenation of cellulose, which is marked as CAT-1.
Example 2
(1) Under the stirring state of 500r/min at room temperature, dissolving 1.70g of tetrabutyl phosphonium bromide ionic liquid in 10mL of absolute ethanol, and stirring for 30min to obtain ethanol dispersion of the tetrabutyl phosphonium bromide ionic liquid;
(2) under the stirring state of 500r/min at room temperature, 1.1g of ruthenium trichloride is dissolved in 10mL of deionized water, and the mixture is stirred for 30min to obtain an aqueous solution of ruthenium trichloride;
(3) dropwise adding an aqueous solution of ruthenium trichloride into an ethanol dispersion of tetrabutyl phosphonium bromide ionic liquid under a stirring state at 60 ℃, and then stirring for 3 hours in a sealed manner to obtain a complex solution of tetrabutyl phosphonium bromide ionic liquid and ruthenium ions, wherein the molar ratio of tetrabutyl phosphonium bromide to ruthenium trichloride in the complex solution is 1: 1;
(4) soaking 10g of charcoal carbonaceous carrier in a tetrabutyl phosphonium bromide ionic liquid and ruthenium ion complex solution for 3h, then taking out the carbonaceous carrier, and drying at 80 ℃ to obtain a ruthenium-loaded carbonaceous carrier, wherein the loading capacity of ruthenium in the carbonaceous carrier is 5%;
(5) under the condition of stirring at room temperature, 2.28g of sodium hypophosphite is dissolved in 10mL of deionized water to obtain a hypophosphite aqueous solution, the carbonaceous carrier loaded with ruthenium is placed in the hypophosphite aqueous solution for soaking for 3h, and then is dried in an ultrasonic water bath at 80 ℃ to obtain the carbonaceous carrier loaded with ruthenium and sodium hypophosphite, wherein the molar ratio of the sodium hypophosphite to the ruthenium in the carbonaceous carrier is 5: 1;
(6) loading a carbonaceous carrier loaded with ruthenium and sodium hypophosphite into a tubular furnace, driving away air in a tubular furnace system by using nitrogen, then closing the nitrogen, then heating the tubular furnace to 500 ℃ at a heating rate of 5 ℃/min, maintaining for 1h, then cooling to room temperature under a flowing nitrogen atmosphere, then washing the obtained product by using deionized water for at least 3 times, removing soluble impurities of the product, and then drying the product at 120 ℃ to obtain the carbonaceous carrier with a hydrogenation activity center;
(7) adding a carbonaceous carrier with a hydrogenation active center into a sulfuric acid aqueous solution with the mass fraction of 10% and the volume of 3 times of that of the carbonaceous carrier, stirring for 30min, putting the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, and sulfonating at 150 ℃ for 12 h; and fully washing the obtained product with deionized water until the pH value of the filtrate is between 5 and 7, and drying to obtain the bifunctional catalyst for preparing the sorbitol by one-step hydrolysis and hydrogenation of cellulose, which is marked as CAT-2.
Example 3
(1) Under the stirring state of 500r/min at room temperature, dissolving 1.02g of tetrabutyl phosphonium bromide ionic liquid in 10mL of absolute ethanol, and stirring for 30min to obtain ethanol dispersion of the tetrabutyl phosphonium bromide ionic liquid;
(2) under the stirring state of 500r/min at room temperature, 0.66g of ruthenium trichloride is dissolved in 10mL of deionized water, and the mixture is stirred for 30min to obtain an aqueous solution of ruthenium trichloride;
(3) dropwise adding an aqueous solution of ruthenium trichloride into an ethanol dispersion of tetrabutyl phosphonium bromide ionic liquid under a stirring state at 60 ℃, and then stirring for 3 hours in a sealed manner to obtain a complex solution of tetrabutyl phosphonium bromide ionic liquid and ruthenium ions, wherein the molar ratio of tetrabutyl phosphonium bromide to ruthenium trichloride in the complex solution is 1: 1;
(4) soaking 10g of charcoal carbonaceous carrier in a tetrabutyl phosphonium bromide ionic liquid and ruthenium ion complex solution for 3h, then taking out the carbonaceous carrier, and drying at 80 ℃ to obtain a ruthenium-loaded carbonaceous carrier, wherein the loading capacity of ruthenium in the carbonaceous carrier is 3%;
(5) under the condition of stirring at room temperature, dissolving 1.68g of sodium hypophosphite in 10mL of deionized water to obtain a hypophosphite aqueous solution, putting the carbonaceous carrier loaded with ruthenium into the hypophosphite aqueous solution, soaking for 3h, and drying in an ultrasonic water bath at 80 ℃ to obtain the carbonaceous carrier loaded with ruthenium and sodium hypophosphite, wherein the molar ratio of the sodium hypophosphite to the ruthenium in the carbonaceous carrier is 5: 1;
(6) loading a carbonaceous carrier loaded with ruthenium and sodium hypophosphite into a tubular furnace, driving away air in a tubular furnace system by using nitrogen, then closing the nitrogen, then heating the tubular furnace to 500 ℃ at a heating rate of 5 ℃/min, maintaining for 1h, then cooling to room temperature under a flowing nitrogen atmosphere, then washing the obtained product by using deionized water for at least 3 times, removing soluble impurities of the product, and then drying the product at 120 ℃ to obtain the carbonaceous carrier with a hydrogenation activity center;
(7) adding a carbonaceous carrier with a hydrogenation active center into a sulfuric acid aqueous solution with the mass fraction of 10% and the volume of 3 times of that of the carbonaceous carrier, stirring for 30min, putting the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, and sulfonating at 150 ℃ for 12 h; and fully washing the obtained product with deionized water until the pH value of the filtrate is between 5 and 7, and drying to obtain the bifunctional catalyst for preparing the sorbitol by one-step hydrolysis and hydrogenation of cellulose, which is marked as CAT-3.
The STEM and mapping patterns of the obtained bifunctional catalyst are shown in FIG. 1, (a) is a dark field projection electron microscope (STEM) pattern of the bifunctional catalyst, (b) is a scan pattern of Ru element, (c) is a scan pattern of P element, and (d) is a scan pattern of S element. As can be seen from FIG. 1, the Ru, P, and S elements have been uniformly distributed on the carbon support.
The TEM image of the resulting bifunctional catalyst is shown in FIG. 2, and it can be seen from FIG. 2 that Ru2The P particles are uniformly distributed on the carbonaceous carrier, and the particle size is 1.5-5 nm.
The HRTEM image of the obtained bifunctional catalyst is shown in FIG. 3, and it can be seen from FIG. 3 that Ru corresponds to the spacing of crystal stripes2(013) crystal face of P particle, Ru corresponding to XRD2The P PDF #65-2832 results are consistent.
The XPS map of the resulting catalyst is shown in FIG. 4, in FIG. 4 a) is an XPS survey, b) is a 3P orbital binding energy map of Ru element, c) is a 3d orbital binding energy map of Ru element, d) is a 2P orbital binding energy map of P element; e) 2p orbital junction of S elementResultant energy diagram, f) is Ru2P/C， Ru2P/C-SO3XRD pattern of H. As can be seen from FIG. 4, the hydrogenation active center produced was Ru2P。
Example 4
The preparation process is basically the same as that of the preparation process in the example 3, except that 1.02g of tetrabutyl phosphonium bromide ionic liquid is replaced by 0.51g of tetrabutyl phosphonium bromide ionic liquid, so that the molar ratio of the tetrabutyl phosphonium bromide ionic liquid to ruthenium is 0.5:1, and the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose is obtained and is marked as CAT-4.
Example 5
The preparation process is basically the same as that of the preparation process in the example 3, except that 1.02g of tetrabutyl phosphonium bromide ionic liquid is replaced by 3.06g of tetrabutyl phosphonium bromide ionic liquid, so that the molar ratio of the tetrabutyl phosphonium bromide ionic liquid to ruthenium is 3:1, and the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose is obtained and is marked as CAT-5.
Example 6
Essentially identical to the procedure used in example 3, except that 1.68g of sodium hypophosphite was replaced with 0.336g of sodium hypophosphite such that the molar ratio of sodium hypophosphite to ruthenium was 1:1, a bifunctional catalyst for the one-step hydrolytic hydrogenation of cellulose to sorbitol was obtained, designated CAT-6.
The XRD patterns of the original charcoal carbonaceous carriers of example 6 and example 3 are shown in FIG. 5. from FIG. 5, it can be seen that the XRD patterns of the bifunctional catalysts prepared in example 6 and example 3 and the Ru of PDF card 65-23822P corresponds to, but is absent from RuP and Ru.
Example 7
The preparation process is basically the same as that of the preparation process in the example 3, except that 1.02g of tetrabutyl phosphonium bromide ionic liquid is replaced by 1.39g of 3-bromopropyltriphenyl phosphonium bromide to obtain the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose, which is marked as CAT-7.
Example 8
The procedure was essentially the same as that used in example 3 except that 1.02g of tetrabutylphosphonium bromide ionic liquid was replaced with 1.26g of tetraphenylphosphonium bromide to give a bifunctional catalyst for the one-step hydrolysis hydrogenation of cellulose to sorbitol, designated CAT-8.
Example 9
Essentially identical to the procedure used in example 3, except that 1.68g of sodium hypophosphite was replaced by 1.58g of ammonium hypophosphite, a bifunctional catalyst for the one-stage hydrolytic hydrogenation of cellulose to sorbitol was obtained and designated CAT-9.
Example 10
The procedure was essentially the same as that used in example 3 except that 1.68g of sodium hypophosphite was replaced with 1.26g of hypophosphorous acid to provide the bifunctional catalyst for the one-step hydrolysis hydrogenation of cellulose to sorbitol, designated CAT-10.
Example 11
The preparation process is basically the same as that of the preparation process in the example 3, except that the temperature of the tubular furnace is increased to 500 ℃ at the heating rate of 5 ℃/min and is replaced by 300 ℃, and the bifunctional catalyst for preparing the sorbitol by the cellulose one-step hydrolysis hydrogenation is obtained and is marked as CAT-11.
Example 12
(1) Adding 10g of charcoal carbon carrier into 3 times volume of 10% sulfuric acid aqueous solution, stirring for 30min, placing into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing, and sulfonating at 200 deg.C for 12 h; fully washing the obtained product with deionized water until the pH value of the filtrate is between 5 and 7, and drying to obtain a carbonaceous carrier with a hydrolysis active center;
(2) under the stirring state at the room temperature of 600r/min, dissolving 0.17g of tetrabutyl phosphonium bromide ionic liquid in 10mL of absolute ethanol, and stirring for 30min to obtain ethanol dispersion liquid of the tetrabutyl phosphonium bromide ionic liquid;
(3) under the stirring state at the room temperature of 600r/min, 0.11g of ruthenium trichloride is dissolved in 10mL of deionized water, and the mixture is stirred for 30min to obtain an aqueous solution of ruthenium trichloride;
(4) dropwise adding an aqueous solution of ruthenium trichloride into an ethanol dispersion of tetrabutyl phosphonium bromide ionic liquid under the stirring state of 600r/min at the temperature of 60 ℃, and then stirring for 3 hours in a sealed manner to obtain a complex solution of the tetrabutyl phosphonium bromide ionic liquid and ruthenium ions, wherein the molar ratio of the phosphonium bromide ionic liquid to ruthenium in the complex solution is 1: 1;
(5) mixing a tetrabutyl phosphonium bromide ionic liquid and a complexing solution of ruthenium ions with a carbonaceous carrier with a hydrolysis active center, soaking for 3h, and drying at 80 ℃ to obtain an active carbonaceous carrier loaded with ruthenium, wherein the loading amount of ruthenium in the active carbonaceous carrier is 0.5%;
(6) under the stirring state of 600r/min at room temperature, 0.23g of sodium hypophosphite is dissolved in 10mL of deionized water to obtain an aqueous solution of the sodium hypophosphite, then the aqueous solution is loaded into an active carbon carrier of ruthenium, the obtained sample is dried in an ultrasonic water bath at 80 ℃, the active carbon carrier of ruthenium and sodium hypophosphite is obtained, and the molar ratio of the sodium hypophosphite to the ruthenium in the active carbon carrier is 5: 1;
(7) loading an active carbonaceous carrier loaded with ruthenium and sodium hypophosphite into a tubular furnace, driving away air in a tubular furnace system by using nitrogen, then closing the nitrogen, then heating the tubular furnace to 500 ℃ at a heating rate of 10 ℃/min, maintaining for 1h, and then cooling to room temperature under a flowing nitrogen atmosphere; and then washing the obtained sample with deionized water for at least 3 times to remove soluble impurities of the product species, and then drying the sample at 120 ℃ to obtain the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose, which is marked as CAT-12.
Example 13
The preparation process is basically the same as that of example 12, except that 0.17g of tetrabutyl phosphonium bromide ionic liquid is replaced by 1.70g of tetrabutyl phosphonium bromide ionic liquid, 0.11g of ruthenium trichloride is replaced by 1.10g of ruthenium trichloride, so that the loading amount of ruthenium in the active carbonaceous carrier is 5%, and the bifunctional catalyst for preparing sorbitol by one-step hydrolysis and hydrogenation of cellulose, which is recorded as CAT-13, is obtained.
Example 14
The preparation process is basically the same as that of the preparation process in the example 12, except that 0.17g of tetrabutyl phosphonium bromide ionic liquid is replaced by 0.54g of tetrabutyl phosphonium bromide ionic liquid, so that the molar ratio of the phosphine bromide ionic liquid to ruthenium in the complexing solution is 3:1, and the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose, which is marked as CAT-14, is obtained.
Example 15
The procedure was essentially the same as in example 12 except that 0.23g of sodium hypophosphite was replaced with 0.14g of sodium hypophosphite such that the molar ratio of sodium hypophosphite to ruthenium in the activated carbonaceous support was 3:1, yielding a bifunctional catalyst for the one-step hydrolysis hydrogenation of cellulose to sorbitol, designated as CAT-15.
Example 16
The preparation process is basically the same as that of the preparation process in the example 1, except that the carbonaceous carrier is replaced by biological carbonaceous solid sulfonic acid, and the bifunctional catalyst for preparing the sorbitol by the one-step hydrolysis and hydrogenation of the cellulose is obtained and is marked as CAT-16.
The preparation method of the biological carbon solid sulfonic acid comprises the following steps:
(1) mixing 6.0g of sucrose and 2.0g of p-toluenesulfonic acid, and fully grinding in a mortar for 10min to obtain a solid mixture A;
(2) transferring the solid mixture A into a 100mL stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven at 180 ℃, continuously heating for 24h, taking out, cooling and placing at room temperature;
(3) and fully washing the solid mixture in the reaction kettle by using a large amount of deionized water until the washing liquid is neutral, and drying the washed mixture to obtain the biological carbon solid sulfonic acid.
Example 17
The preparation process is basically the same as that in example 16, except that 0.17g of tetrabutyl phosphonium bromide ionic liquid is replaced by 1.70g of tetrabutyl phosphonium bromide ionic liquid, and 0.11g of ruthenium trichloride is replaced by 1.10g of ruthenium trichloride, so that the loading amount of ruthenium in the carbonaceous carrier is 5%, and the bifunctional catalyst for preparing sorbitol by one-step hydrolysis and hydrogenation of cellulose, which is recorded as CAT-17, is obtained.
Example 18
The procedure was essentially the same as in example 16 except that 0.23g of sodium hypophosphite was replaced with 0.14g of sodium hypophosphite such that the molar ratio of sodium hypophosphite to ruthenium in the carbonaceous support was 3:1, giving a bifunctional catalyst for the one-step hydrolysis hydrogenation of cellulose to sorbitol, designated CAT-18.
Comparative example 1
The purpose of comparative example 1 is to illustrate the effect of ruthenium phosphide as an active site on the catalyst, in comparison with example 3.
Comparative example 1 is different from example 3 in that the loading of sodium hypophosphite in step (5) is omitted and the ruthenium-loaded carbonaceous support is directly subjected to heat treatment and sulfonation, which are the same operations as in steps (6) and (7), respectively, to obtain comparative CAT-1.
Comparative example 2
The purpose of comparative example 2 is to illustrate the effect of the phosphonium bromide ionic liquid in comparison with example 3.
Comparative example 2 is different from example 3 in that the addition of tetrabutyl phosphonium bromide ionic liquid is omitted, the carbonaceous carrier is directly put into ruthenium trichloride solution for impregnation, and the rest operations are the same, thus obtaining comparative CAT-2.
Comparative example 3
The purpose of comparative example 3 is to illustrate the effect of the mole ratio of hypophosphite to ruthenium on the catalyst, compared to example 3.
Comparative example 3 differs from example 3 in that sodium hypophosphite was used in an amount of 3.36g such that the molar ratio of sodium hypophosphite to ruthenium in the carbonaceous support was 10:1, and the remaining operations were the same, yielding comparative CAT-3.
Comparative example 4
The purpose of comparative example 4 is to illustrate the effect of the complexation temperature of the phosphonium bromide ionic liquid with metallic ruthenium on the catalyst, in comparison with example 3.
Comparative example 4 differs from example 3 in that the temperature of stirring in step (3) was room temperature and the rest of the operation was the same, giving comparative CAT-4.
Comparative example 5
The purpose of comparative example 5 is to illustrate the effect of the complexation temperature of the phosphonium bromide ionic liquid with metallic ruthenium on the catalyst, in comparison with example 3.
Comparative example 5 differs from example 3 in that the stirring temperature in step (3) was 100 ℃ and the rest of the operation was the same, giving comparative CAT-5.
Comparative example 6
Comparative example 6 is intended to be compared with example 3 and to illustrate the effect of stepwise loading of ruthenium and hypophosphite on the carbonaceous support on the catalyst.
The difference between the comparative example 6 and the example 3 is that ruthenium trichloride and sodium hypophosphite are mixed with deionized water and stirred for 30min to obtain a mixed aqueous solution of ruthenium trichloride and sodium hypophosphite; then, dripping mixed aqueous solution of ruthenium trichloride and sodium hypophosphite into tetrabutyl phosphonium bromide ionic liquid to obtain mixed solution; and then, dipping the mixed solution on a carbonaceous carrier to obtain the carbonaceous carrier loaded with ruthenium and sodium hypophosphite, wherein the rest operations are the same, and obtaining the comparative CAT-6.
Performance testing
The catalytic performance of the catalysts obtained in examples 1 to 18 and comparative examples 1 to 6 was tested by the following method:
(1) adding 0.1g of ball-milled cellulose and 0.05g of catalyst into a stainless steel needle valve reaction kettle filled with 10mL of 0.02 wt% dilute sulfuric acid aqueous solution, putting magnetons into the kettle, and filling 3MPa of H2Sealing, and then heating the reaction kettle to 200 ℃ under the stirring state and maintaining for 3 hours;
(2) after the reaction is finished, the reaction kettle is immediately cooled to obtain sorbitol, and then the cellulose conversion rate and the sorbitol yield are tested by using a liquid chromatography, wherein the obtained results are shown in table 1:
TABLE 1 catalytic Properties of catalysts obtained in examples 1 to 18 and comparative examples 1 to 6
As can be seen from Table 1, the bifunctional catalyst obtained by the present invention has a good catalytic effect when used for catalyzing the hydrolysis hydrogenation of cellulose to prepare sorbitol in one step.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a dual-function catalyst for preparing sorbitol by hydrolyzing and hydrogenating cellulose in one step comprises a first method or a second method, wherein the first method comprises the following steps:
(1) providing an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution;
(2) mixing the ethanol dispersion liquid of the phosphine bromide ionic liquid with a ruthenium source water solution at the temperature of 60-70 ℃ to obtain a complex solution of the phosphine bromide ionic liquid and ruthenium ions;
(3) placing a carbonaceous carrier in a complexing solution of phosphine bromide ionic liquid and ruthenium ions, and performing first impregnation to obtain a ruthenium-loaded carbonaceous carrier;
(4) placing the carbonaceous carrier loaded with ruthenium in a hypophosphorous acid compound aqueous solution, carrying out second impregnation, and then drying under the condition of ultrasonic water bath heating to obtain a carbonaceous carrier loaded with ruthenium and hypophosphite;
(5) carrying out heat treatment, washing and drying on the carbonaceous carrier loaded with ruthenium and hypophosphite in sequence to obtain a carbonaceous carrier with a hydrogenation active center;
(6) mixing the carbonaceous carrier with the hydrogenation active center with a sulfuric acid aqueous solution, and performing sulfonation treatment to obtain a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation;
the second method comprises the steps of:
(I) mixing a carbonaceous carrier with a sulfuric acid aqueous solution, and performing sulfonation treatment to obtain a carbonaceous carrier with a hydrolysis active center;
(II) providing an ethanol dispersion liquid of phosphine bromide ionic liquid, a ruthenium source water solution and a hypophosphorous acid compound water solution;
(III) mixing the ethanol dispersion liquid of the phosphine bromide ionic liquid with a ruthenium source water solution at the temperature of 60-70 ℃ to obtain a complex solution of the phosphine bromide ionic liquid and ruthenium ions;
(IV) placing the carbonaceous carrier with the hydrolysis active center in a complexing solution of phosphine bromide ionic liquid and ruthenium ions, and performing first impregnation to obtain an active carbonaceous carrier loaded with ruthenium;
(V) placing the carbonaceous carrier loaded with ruthenium in hypophosphorous acid compound aqueous solution, carrying out second impregnation, and then drying under the heating condition of ultrasonic water bath to obtain an active carbonaceous carrier loaded with ruthenium and hypophosphite;
(VI) sequentially carrying out heat treatment, washing and drying on the active carbonaceous carrier loaded with ruthenium and hypophosphite to obtain a bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis hydrogenation;
the steps (I) and (II) to (III) are not limited in chronological order.
2. The preparation method according to claim 1, wherein in the first method and the second method, the phosphonium bromide ionic liquid is independently one or more of tetrabutylphosphonium bromide ionic liquid, 3-bromopropyltriphenylphosphonium bromide ionic liquid and tetraphenylphosphonium bromide ionic liquid;
the ruthenium source is ruthenium trichloride;
the hypophosphorous acid compound is one or more of sodium hypophosphite, ammonium hypophosphite and hypophosphorous acid independently;
the carbonaceous carrier is independently biochar or biochar solid sulfonic acid.
3. The production method according to claim 1, wherein in the first method and the second method, the molar ratio of the phosphine bromide ionic liquid to the ruthenium source in the complex solution of the phosphine bromide ionic liquid and the ruthenium source is 0.5 to 3: 1;
the molar concentration of a ruthenium source in the complexing liquid of the phosphine bromide ionic liquid and ruthenium ions is 0.027-0.27 mol/L;
the molar concentration of the hypophosphorous acid compound aqueous solution is 0.13-1.3 mol/L.
4. The production method according to claim 1, wherein in the first method, the loading amount of ruthenium in the ruthenium-supporting carbonaceous carrier is 0.5 to 5 wt.%; the molar ratio of hypophosphite to ruthenium in the carbonaceous carrier loaded with ruthenium and hypophosphite is 1-5: 1;
in the second method, the loading amount of ruthenium in the ruthenium-loaded activated carbonaceous carrier is 0.5 to 5 wt.%; the molar ratio of hypophosphite to ruthenium in the active carbonaceous carrier loaded with ruthenium and hypophosphite is 1-5: 1.
5. The method of claim 1, wherein in the first and second methods, the time of the first and second impregnations is independently ≥ 3 h;
the temperature of ultrasonic water bath heating is independently 60-80 ℃.
6. The method according to claim 1, wherein the heat treatment is performed under a closed nitrogen atmosphere in the first and second methods, and the heat treatment is performed at a temperature of 300 to 500 ℃ for 1 to 3 hours.
7. The method according to claim 1, wherein in the first method and the second method, the mass concentration of the aqueous sulfuric acid solution is independently 2 to 10%;
the temperature of the sulfonation treatment is independently 150-200 ℃, and the time is independently 8-12 h.
8. The bifunctional catalyst for preparing sorbitol by cellulose one-step hydrolysis and hydrogenation, which is prepared by the preparation method of any one of claims 1 to 7.
9. The use of the bifunctional catalyst for preparing sorbitol by one-step hydrolysis and hydrogenation of cellulose according to claim 8 in catalyzing the preparation of sorbitol by one-step hydrolysis and hydrogenation of cellulose.
10. The application according to claim 9, characterized in that the method of application comprises the steps of:
mixing cellulose withMixing the bifunctional catalyst for preparing sorbitol by one-step hydrolysis and hydrogenation of cellulose with sulfuric acid aqueous solution in H2And carrying out one-step hydrolysis hydrogenation reaction under the atmosphere to obtain the sorbitol.
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| CN113410472A (en) * | 2021-06-03 | 2021-09-17 | 扬州大学 | Alcohol fuel cell anode catalyst and preparation method thereof |
| CN115350721A (en) * | 2022-10-21 | 2022-11-18 | 农业农村部环境保护科研监测所 | Nickel-based double-active-domain catalyst and preparation method and application thereof |
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| CN113410472B (en) * | 2021-06-03 | 2024-05-07 | 扬州大学 | Anode catalyst of alcohol fuel cell and preparation method thereof |
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