CN113385165A - Yttria composite metal oxide catalyst and preparation method and application thereof - Google Patents

Yttria composite metal oxide catalyst and preparation method and application thereof Download PDF

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CN113385165A
CN113385165A CN202110796707.8A CN202110796707A CN113385165A CN 113385165 A CN113385165 A CN 113385165A CN 202110796707 A CN202110796707 A CN 202110796707A CN 113385165 A CN113385165 A CN 113385165A
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composite metal
metal oxide
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yttrium
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王芬芬
董文迪
曲冬雪
陈宇辉
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Nanjing Tech University
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Abstract

The invention discloses an yttrium oxide composite metal oxide catalyst and a preparation method and application thereof, wherein the yttrium oxide composite metal oxide catalyst comprises a carrier and an active component loaded on the carrier; the carrier is selected from Al2O3、ZrO2、ZnO、Nb2O5Any one of the above; the active component is Y2O3. Prepared by a wet impregnation method, and a series of novel supported Y obtained by high-temperature calcination2O3A composite oxide catalyst. The method can accurately adjust the acid position of the catalyst by regulating and controlling the acid strength and the ratio of the Bronsted acid to the Lewis acid position in the catalyst, improve the catalytic effect of the catalyst, and realize the preparation of the lactic acid by catalyzing the hydrolysis of cellulose efficiently, highly productively and stably under hydrothermal conditions.

Description

Yttria composite metal oxide catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of composite metal oxides, and particularly relates to an yttrium oxide composite metal oxide catalyst as well as a preparation method and application thereof.
Background
With the development of society, people increasingly consume natural resources, and with the exhaustion of resources and environmental pollution, especially the excessive consumption of non-renewable resources such as petroleum and coal, and environmental problems are also prominent, which become a problem of particular attention in the present society. Therefore, the search for renewable natural resources is a problem to be solved urgently. As a renewable natural resource, biomass is known as the fourth major energy source inferior to coal, petroleum and natural gas due to its characteristics of renewability, low cost, low pollution and the like. The main components of biomass include cellulose, hemicellulose and lignin. Lactic acid, one of three major organic acids recognized in the world, has many applications in the directions of food, medicine, pesticide, cosmetics and the like, and is also a main raw material for producing novel biodegradable material polylactic acid. Therefore, the cellulose is catalyzed and hydrolyzed by a chemical method to produce the lactic acid under certain reaction conditions, so that the method has great development potential.
Cellulose is the main component of lignocellulosic biomass and is a biopolymer composed of glucose units linked by beta-1, 4 glycosidic bonds. Chain molecules of glucose units connected by intermolecular and intramolecular hydrogen bonds are packaged into microfibers, and the interaction force between molecular chains is strong. Cellulose is therefore difficult to depolymerize into chemicals and fuels under mild conditions in conventional solvents. Some of the cellulose depolymerization methods commonly used at present are enzymolysis,Liquid inorganic acid hydrolysis, or hydrolysis in unconventional solvents such as ionic liquids and supercritical media. In the Bioresource Technology Reports 5(2019) 66-73, Ning Shi et Al prepared solid catalyst Al by coprecipitation2(WO4)3And for catalyzing the conversion of cellulose to lactic acid. Under the optimal conditions of 220 ℃ and 3h, the cellulose is in Al2(WO4)3Under the catalytic conditions of (3), 46% of lactic acid was produced. In the literature Catalysis Letters (2019)149: 2078-2088, Xiaoiia He and the like prepared Co/H-ZSM-5 catalyst for the catalytic conversion of cellulose in an aqueous medium, and the highest yield of 4H at 240 ℃ is 27.81%. In Green Chem,2019,21,6161, asitina a. marianou et al studied bifunctional catalysts composed of heteropolyacids and oxides, and proved through studies that the acidity type plays a key role in the reaction pathway and product distribution. TSA/SiO in the catalysis of cellulose to lactic acid2～Al2O3Has high ratio of Lewis acid to Bronsted acid, and can react at 175 deg.c for 60min to reach cellulose conversion rate of 61.2% and lactic acid yield of 23.5%. However, these methods have low conversion rate and yield of lactic acid, and long reaction time, and cannot be applied to industrial production, and are not suitable for large-scale production of lactic acid.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention provides a supported Y for preparing lactic acid in cellulose hydrolysis reaction2O3A composite oxide catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a yttrium oxide composite metal oxide catalyst comprises a carrier and an active component loaded on the carrier; the carrier is selected from Al2O3、ZrO2、ZnO、Nb2O5Any one of the above; the active component is Y2O3. The catalyst is prepared by a wet impregnation method, and the specific surface area of the catalyst is 4.40-66.44 m2Between/g.
Further, the catalystAnd the loading amount of Y is 2-20 wt%. Prepared by a wet impregnation method, and a series of novel supported Y obtained by high-temperature calcination2O3A composite oxide catalyst. The method can accurately adjust the acid position of the catalyst by regulating and controlling the acid strength and the ratio of the Bronsted acid to the Lewis acid position in the catalyst, thereby improving the catalytic effect of the catalyst.
Further, the present invention also provides the above Y2O3The preparation method of the composite metal oxide catalyst comprises the following steps:
(1) dissolving yttrium nitrate hexahydrate in deionized water, and performing ultrasonic treatment and oscillation to obtain an yttrium nitrate hexahydrate aqueous solution;
(2) slowly dripping the yttrium nitrate hexahydrate aqueous solution obtained in the step (1) into carrier powder, continuously stirring and dipping for 12-24 h, and then drying moisture to obtain a solid product;
(3) and (3) grinding the solid product obtained in the step (2), calcining the powder at a constant temperature of 500-700 ℃ for 3-8 h, and naturally cooling to room temperature to obtain the catalyst.
Wherein in the step (1), the mass-to-volume ratio of the yttrium nitrate hexahydrate to the deionized water is (0.1815-3.498 g) to (3-4) ml; controlling the ultrasonic time to be more than 10min, and continuously oscillating the ultrasonic time until the solid is completely dissolved.
In the step (2), the carrier powder is Al2O3、ZrO2、ZnO、Nb2O5Any one of them.
Preferably, in the step (2), the mass ratio of the carrier powder to the yttrium nitrate hexahydrate in the step (1) is 2.0g (0.1815-3.498 g).
In the step (3), the temperature is increased to 500-700 ℃ at a temperature increase rate of 2-5 ℃/min.
Further, the present invention also claims the above Y2O3The composite metal oxide catalyst is used for catalyzing the hydrolysis reaction of cellulose to prepare lactic acid.
Specifically, the application method is that Y is mixed2O3Composite metal oxide catalyst, cellulose, and deionizationMixing the water with the water, and reacting at the constant temperature of 240-260 ℃ for more than 0.5h in the inert gas atmosphere to obtain the product lactic acid.
Preferably, said Y is2O3The addition amount of the composite metal oxide catalyst is 3-5% of the mass of the cellulose.
Has the advantages that:
the invention adopts low-cost Al2O3、ZrO2、ZnO、Nb2O5Is a carrier and is loaded with Y2O3A metal oxide. Mainly because the rare earth elements in China have rich reserves, the yttrium-rich heavy rare earth mineral resources are unique in the world. In the route, the catalyst regulates and controls the ratio of the Bronsted acid to the Lewis acid in the catalyst, and the acid position promotes the conversion of carbon-carbon bond breakage in glucose to lactic acid, so that the catalytic effect of the catalyst is improved. The method realizes that the lactic acid can be prepared by efficiently, highly productively and stably catalyzing cellulose hydrolysis under hydrothermal conditions, the catalyst and reactants are heterogeneous, the binding capacity between the active components of the catalyst and the carrier is strong, the active components of the catalyst are not easy to lose in the reaction process, the obtained product is easy to separate from the catalyst, and the recovered catalyst can be recycled and has high recycling activity, so that the method is suitable for industrial production.
Drawings
The foregoing and other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 shows a load type Y in example 32O3XRD spectrum of the composite oxide catalyst.
FIG. 2 shows a load type Y in example 32O3/Al2O3NH of composite catalyst3-TPD-ms spectrum. Detailed Description
The invention will be better understood from the following examples.
Example 1
Aluminum hydroxide powder (supplied by Meclin reagent company) was placed in a muffle furnace, raised to 800 ℃ at a temperature rise rate of 5 ℃/min and held for 6 hours,then naturally cooling to room temperature in a muffle furnace to obtain Al2O3。
0.1815g of yttrium nitrate hexahydrate is dissolved in 3-4 mL of deionized water, and the deionized water is placed in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and is continuously vibrated during the ultrasonic treatment until the solid is completely dissolved. Accurately weighing 2.0g of Al2O3The carrier is placed in a 100mL round-bottom flask, the solution is slowly dripped into the flask under the stirring condition, after stirring for 24 hours at normal temperature, the solution is placed in a 110 ℃ oven for 12 hours, and the water is thoroughly dried. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 5 hours to obtain Y with the Y loading capacity of 2 wt%2O3/Al2O3A catalyst.
Example 2
Dissolving 0.49g of yttrium nitrate hexahydrate in 3-4 mL of deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and continuously oscillating the mixture until the solid is completely dissolved. Accurately weighing 2.0g of Al2O3The carrier (the preparation method is the same as that of example 1) is placed in a 100mL round-bottom flask, the solution is slowly dripped into the flask under the stirring condition, after stirring for 24 hours at normal temperature, the solution is transferred into a 110 ℃ oven for 12 hours, and the water is thoroughly dried. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 5 hours to obtain Y with the Y loading of 5 wt%2O3/Al2O3A catalyst.
Example 3
Dissolving 1.15g of yttrium nitrate hexahydrate in 3-4 mL of deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and continuously shaking the ultrasonic cleaning machine until the solid is completely dissolved. Accurately weighing 2.0g of Al2O3The carrier (the preparation method is the same as that of example 1) is placed in a 100mL round-bottom flask, the solution is slowly dripped into the flask under the stirring condition, after stirring for 24 hours at normal temperature, the solution is transferred into a 110 ℃ oven for 12 hours, and the water is thoroughly dried. Taking out, grinding the solid sufficiently, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 3 DEGh, obtaining Y with Y loading of 10 wt%2O3/Al2O3A catalyst. Al (Al)2O3XRD before and after the carrier loading is shown in FIG. 1. It can be seen that: load Y2O3Then, Al2O3Has no change in structure and no occurrence of Y2O3The surface yttrium oxide is amorphous or highly dispersed in Al2O3Of (2) is provided. FIG. 2 shows a load type Y in example 32O3/Al2O3NH of composite catalyst3TPD-ms spectrum using NH3The TPD and pyridine adsorption infrared characterization means are used for measuring the acid content and acid sites of the catalyst, and as can be seen from the figure, the surface of the catalyst has weak acid sites.
Example 4
Dissolving 3.498g of yttrium nitrate hexahydrate in 3-4 mL of deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and continuously oscillating the mixture until the solid is completely dissolved. Accurately weighing 2.0g of Al2O3The carrier (the preparation method is the same as that of example 1) is placed in a 100mL round-bottom flask, the solution is slowly dripped into the flask under the stirring condition, after stirring for 24h at normal temperature, the solution is transferred to a 110 ℃ oven for 12h, and the water is thoroughly dried. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 3 hours to obtain Y with the Y loading of 20 wt%2O3/Al2O3A catalyst.
Example 5
Adding 20g of 25-27% ammonia water by mass into 100mL of distilled water, dissolving 8.2g of zirconium oxychloride octahydrate in 100mL of deionized water, slowly dropwise adding the two solutions to form a white precipitate, continuously stirring, controlling the pH value of the solution to be about 9.5, aging for 0.5h after dropwise adding, centrifugally filtering and thoroughly washing the precipitate, transferring the obtained solid into a 110 ℃ oven for 12h, and thoroughly drying the water. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 6 hours to obtain ZrO2And (3) a carrier.
Dissolving 1.15g of yttrium nitrate hexahydrate in 3-4 mL of deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and continuously shaking the ultrasonic cleaning machine until the solid is completely dissolved. Accurately weighing 2.0g of ZrO2And placing the carrier into a 100mL round-bottom flask, slowly dripping the solution into the flask under the stirring condition, stirring at normal temperature for 24 hours, transferring into a 110 ℃ oven for 12 hours, and completely drying the water. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 3 hours to obtain Y with the Y loading of 10 wt%2O3/ZrO2A catalyst.
Example 6
Dissolving 1.15g of yttrium nitrate hexahydrate in 3-4 mL of deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and continuously shaking the ultrasonic cleaning machine until the solid is completely dissolved. 2.0g of ZnO carrier (supplied by Aladdin reagent company) was accurately weighed, placed in a 100mL round-bottomed flask, and the solution was slowly dropped into the flask with stirring, stirred at room temperature for 24 hours, then transferred to a 110 ℃ oven for 12 hours, and the water was thoroughly dried. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 3 hours to obtain Y with the Y loading of 10 wt%2O3a/ZnO catalyst.
Example 7
Dissolving 1.15g of yttrium nitrate hexahydrate in 3-4 mL of deionized water, placing the deionized water in an ultrasonic cleaning machine for ultrasonic treatment for 10min, and continuously shaking the ultrasonic cleaning machine until the solid is completely dissolved. Accurately weighing 2.0g of Nb2O5The carrier (provided by Annagi chemical company) was placed in a 100mL round-bottomed flask, the solution was slowly dropped into the flask with stirring, and after stirring at room temperature for 24 hours, the solution was transferred to a 110 ℃ oven for 12 hours, and the water was thoroughly dried. Taking out, fully grinding the solid, placing the ground powder in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the constant temperature for 3 hours to obtain Al with the Y loading of 10 wt%2O3/Nb2O5A catalyst.
The specific surface areas of the catalysts obtained in example 3, example 5, example 6, and example 7 were measured, and the results are shown in table 1.
TABLE 1
Sample (I) Pore volume (cm)3/g) Specific surface area (m)2/g) Pore size (nm)
Y2O3 0.024 11.38 8.52
Al2O3 0.242 98.19 9.85
Y2O3/Al2O3 0.160 66.44 9.64
Y2O3/ZrO2 0.116 24.54 18.98
Y2O3/ZnO 0.031 8.35 14.80
Y2O3/Nb2O5 0.013 4.40 12.05
Example 8
Examples 1-7 Supported Y2O3The application of the composite oxide catalyst in preparing lactic acid in cellulose hydrolysis reaction is as follows:
0.01g of load type Y2O3Catalyst, 0.2g cellulose and 12mL deionized water are added into a 25mL high-temperature high-pressure reaction kettle, and high-purity N is used2Charging and discharging the air in the reaction kettle for three times, and then charging 2MPa N2Heating to 240 ℃ at the heating rate of 5 ℃/min, keeping the temperature constant for 30min, placing the reaction kettle into an ice water bath for rapid cooling, centrifugally filtering the product, injecting the filtrate into a high performance liquid chromatography, and performing qualitative and quantitative analysis on the product. The results are shown in Table 2 below.
The calculation formulas of the conversion rate and the product yield of the cellulose are respectively as follows:
conversion (%) of cellulose (mass of starting cellulose-mass of cellulose remaining after reaction)/mass of starting cellulose ] × 100%.
The yield (%) of lactic acid was ═ 100% (number of moles of C contained in the product lactic acid/number of moles of C contained in the starting cellulose).
TABLE 2
Figure BDA0003163068270000071
Table 3 shows the supported forms Y prepared in examples 3, 5, 6 and 72O3The catalyst is used for catalyzing and hydrolyzing cellulose to prepare the lactic acid. After the reaction is finished, the catalyst is filtered, washed and dried, and then raw materials with the same mass are added to carry out the next circulation experiment under the same reaction conditions.
TABLE 3
Figure BDA0003163068270000072
As can be seen from the experimental results in tables 2 and 3, the catalyst of the present invention shows excellent catalytic activity in the preparation of lactic acid by hydrolysis of cellulose, the conversion rate of cellulose is as high as 100%, wherein the loading amount of the active component Y in the catalyst is 2% -20%, and the catalyst carrier is Al2O3、ZrO2、ZnO、Nb2O5. The yield of the lactic acid can reach more than 50 percent, the obtained product is easy to separate from the catalyst, the recovered catalyst can be recycled, and the recycling activity is high, so that the method is suitable for industrial production.
Y loading of 10 wt% prepared in example 32O3/Al2O3The influence of the catalyst dosage on the cellulose conversion rate and the lactic acid yield was respectively examined, and the results are shown in table 4.
TABLE 4
Amount of catalyst used (g) Cellulose conversion (%) Lactic acid yield (%)
0.006 100 57.7
0.008 100 62.6
0.01 100 72.8
0.03 100 52.6
0.05 100 50.0
Note: in the table, the amount of cellulose used is 0.2g, the reaction temperature is 240 ℃, the catalytic reaction time is 0.5h, N2The initial pressure was 2 MPa.
Further, Y loading of 5 wt% prepared in example 3 was used2O3/Al2O3The influence of different reaction temperatures on the cellulose conversion rate and the lactic acid yield was examined respectively by catalyzing the hydrolysis of cellulose to prepare lactic acid, and the results are shown in Table 5.
TABLE 5
Temperature of catalytic reaction (. degree.C.) Cellulose conversion (%) Lactic acid yield (%)
180 6.7 1.3
200 15.6 3.7
220 57.5 35.6
240 100 72.8
260 100 70.2
Note: in the table, the amount of cellulose used was 0.2g, the amount of catalyst used was 0.01g, the catalytic reaction time was 0.5h, and N was2The initial pressure was 2 MPa.
As can be seen from tables 4 and 5, when the dosage of the cellulose is 0.2g and the dosage of the catalyst is 0.01g, namely the dosage of the catalyst is 5 percent of the mass of the cellulose, the catalytic reaction temperature is 240 ℃, and the N is2The best catalytic effect is achieved when the initial pressure is 2 MPa.
The present invention provides a yttria composite metal oxide catalyst, a preparation method thereof, and ideas and methods for applying the same, and a plurality of methods and ways for specifically implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the present invention, and the improvements and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.

Claims (10)

1. The yttrium oxide composite metal oxide catalyst is characterized by comprising a carrier and an active component loaded on the carrier; the carrier is selected from Al2O3、ZrO2、ZnO、Nb2O5Any one of the above; the active component is Y2O3。
2. The yttria composite metal oxide catalyst of claim 1, wherein a loading amount of Y in the catalyst is 2 to 20 wt%.
3. The method for producing an yttria composite metal oxide catalyst according to claim 1, comprising the steps of:
(1) dissolving yttrium nitrate hexahydrate in deionized water, and performing ultrasonic treatment and oscillation to obtain an yttrium nitrate hexahydrate aqueous solution;
(2) slowly dripping the yttrium nitrate hexahydrate aqueous solution obtained in the step (1) into carrier powder, continuously stirring and dipping for 12-24 h, and then drying moisture to obtain a solid product;
(3) and (3) grinding the solid product obtained in the step (2), calcining the powder at a constant temperature of 500-700 ℃ for 3-8 h, and naturally cooling to room temperature to obtain the catalyst.
4. The preparation method of the yttrium oxide composite metal oxide catalyst according to claim 3, wherein in the step (1), the mass-to-volume ratio of yttrium nitrate hexahydrate to deionized water is (0.1815-3.498) g (3-4) ml; controlling the ultrasonic time to be more than 10min, and continuously oscillating the ultrasonic time until the solid is completely dissolved.
5. The process for producing a catalyst of yttrium oxide composite metal oxide according to claim 3The method is characterized in that in the step (2), the carrier powder is Al2O3、ZrO2、ZnO、Nb2O5Any one of them.
6. The method for preparing an yttrium oxide composite metal oxide catalyst according to claim 3, wherein in the step (2), the mass ratio of the carrier powder to the yttrium nitrate hexahydrate in the step (1) is 2.0g (0.1815-3.498 g).
7. The method for preparing a catalyst comprising yttrium oxide composite metal oxide according to claim 3, wherein in the step (3), the temperature is raised to 500-700 ℃ at a temperature raising rate of 2-5 ℃/min.
8. The use of the yttria composite metal oxide catalyst of claim 1 for catalyzing hydrolysis of cellulose to produce lactic acid.
9. The application of the lactic acid as claimed in claim 8, wherein the yttrium oxide composite metal oxide catalyst, cellulose and deionized water are mixed and reacted at a constant temperature of 240-260 ℃ for more than 0.5h in an inert gas atmosphere to obtain the product lactic acid.
10. The use according to claim 8, wherein the yttrium oxide composite metal oxide catalyst is added in an amount of 3-5% by mass of cellulose.
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CN115121248A (en) * 2022-07-13 2022-09-30 南京工业大学 Ruthenium-loaded metal oxide catalyst and preparation method and application thereof
CN115141174A (en) * 2022-07-19 2022-10-04 珠海市昊岭环保科技有限公司 Method for one-step synthesis of lactide by catalysis of rare earth molecular sieve catalyst
CN115888687A (en) * 2023-02-01 2023-04-04 安徽师范大学 Oxidation catalyst, preparation method and application thereof, and method for preparing lactic acid by glucose cracking

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CN115121248A (en) * 2022-07-13 2022-09-30 南京工业大学 Ruthenium-loaded metal oxide catalyst and preparation method and application thereof
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