CN113304750A - Preparation method and application of petal-shaped catalyst - Google Patents
Preparation method and application of petal-shaped catalyst Download PDFInfo
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- CN113304750A CN113304750A CN202110593402.7A CN202110593402A CN113304750A CN 113304750 A CN113304750 A CN 113304750A CN 202110593402 A CN202110593402 A CN 202110593402A CN 113304750 A CN113304750 A CN 113304750A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
Abstract
The invention relates to a preparation method of a catalyst, in particular to a preparation method and application of a petal-shaped catalyst, wherein the preparation method of the catalyst comprises the following steps: firstly, respectively dissolving aluminum oxide, nickel nitrate hexahydrate, zinc nitrate hexahydrate and ammonium nitrate in deionized water, stirring and dissolving, then reacting for 40-60 h at the temperature of 80-100 ℃ and the stirring speed of 100-150 r/min, centrifuging the precipitate after the reaction is finished, washing for 3-5 times by using the deionized water, drying for 20-24 h at the temperature of 65-75 ℃ to obtain a NiZnAl-LDHs precursor, placing the obtained NiZnAl-LDHs precursor in a hydrogen atmosphere for reduction reaction, and then passivating for 3-5 h in a nitrogen atmosphere to obtain a petal-shaped catalyst NiZn-MMO loaded on Ni-Zn oxide, wherein the catalyst is used for catalytic conversion reaction of cellulose, and the conversion rate is 94.5-99.9%; the method has the advantages of simple operation, low raw material price, less by-products, wide industrial application of the main product and good industrial application prospect.
Description
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of a petal-shaped catalyst loaded on Ni-Zn oxide for catalyzing and converting cellulose and application thereof.
Background
In the face of the decreasing of non-renewable energy sources such as petroleum, biomass energy is a clean energy source with large reserve and renewable energy is receiving more and more attention. In the wood fiber, cellulose accounts for about 40% of the total energy proportion, is macromolecular polysaccharide consisting of glucose, and is a polysaccharide which is widely distributed and has the largest content in nature. The effective utilization of the cellulose can relieve the problem of energy shortage in the world and promote the sustainable development of energy, so that the method has important significance in the research of high-added-value catalytic conversion on the cellulose.
At present, catalysts commonly used for the hydrodeoxygenation reaction of cellulose are mainly divided into catalysts taking noble metals as catalytic active components and catalysts taking non-noble metals as catalytic active components. However, noble metal catalysts have been difficult to apply industrially on a large scale due to their high cost and low reserves. As for the non-noble metal catalysts, nickel-based catalysts exhibit excellent C — O bond cleavage activity and have been studied in large numbers. However, the traditional nickel-based supported catalyst has poor stability due to weak interaction force between metal and a carrier, and nickel nanoparticles are easy to agglomerate, sinter and lose, so that the effective utilization of metal active components is reduced.
At present, a non-noble metal catalyst does not exist, the problems that the dispersity of metal active centers is not high, the metal active centers are easy to agglomerate, and the interaction between metal and a carrier is weak can be solved, the catalyst has good catalytic activity when being applied to the hydrodeoxygenation reaction of cellulose, and main products of ethylene glycol and 1, 2-propylene glycol have high yield.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a petal-shaped catalyst, which is simple and unique in preparation, has excellent catalytic performance and low processing cost, and can solve the problems of low dispersity and easy agglomeration of metal active centers and weak interaction between metal and a carrier.
It is another object of the present invention to use petal catalysts for the catalytic conversion of cellulose.
The invention is realized by the following modes:
a preparation method of a petal-shaped catalyst is characterized by comprising the following steps: firstly, respectively dissolving aluminum oxide, nickel nitrate hexahydrate, zinc nitrate hexahydrate and ammonium nitrate in deionized water, stirring and dissolving, then reacting for 40-60 h at the temperature of 80-100 ℃ and the stirring speed of 100-150 r/min, centrifuging the precipitate after the reaction is finished, washing for 3-5 times by using the deionized water, drying for 20-24 h at the temperature of 65-75 ℃ to obtain a NiZnAl-LDHs precursor, placing the obtained NiZnAl-LDHs precursor in a hydrogen atmosphere for reduction reaction, and then passivating for 3-5 h in a nitrogen atmosphere to obtain a petal-shaped catalyst NiZn-MMO loaded on a Ni-Zn oxide;
the molar volume concentration ratio of the aluminum oxide to the ammonium nitrate to the nickel nitrate hexahydrate to the zinc nitrate hexahydrate is 1.96-2.94: 144-196: 5.97-8.95: 11.68-17.52;
the reduction reaction conditions are as follows: heating to 400-500 ℃ at the heating rate of 5 ℃ per minute in the hydrogen atmosphere, stopping heating, and keeping the temperature for 1.5-3 h;
the NiZnAl-LDHs precursor is a light green solid;
the prepared petal-shaped catalyst is used for catalyzing and converting cellulose, and is characterized in that: the method specifically comprises the following steps: adding 0.1-0.2 g of cellulose into 20-40 ml of deionized water, and carrying out catalytic reaction with hydrogen under an anaerobic condition, wherein the addition amount of the petal-shaped catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 200-240 ℃, the stirring revolution is 800-1000 r/min, the hydrogen pressure is 3-4 MPa, and the reaction time is 0.5-2.5 h.
The invention has the following effects:
1) the method is simple and unique: the preparation method of the catalyst provided by the invention comprises the steps of firstly, respectively adding aluminum oxide, nickel nitrate hexahydrate, zinc nitrate hexahydrate and ammonium nitrate into deionized water, stirring and fully dissolving, and then adjusting the pH value to 6-7 by using ammonia water. Preparing a NiZnAl-LDHs precursor by adopting an in-situ growth method, and calcining the dried precursor in a hydrogen atmosphere at 400-500 ℃ to obtain a petal-shaped catalyst loaded on a Ni-Zn oxide; the catalyst provided by the invention adopts an in-situ growth method to prepare a NiZnAl-LDHs precursor, and then the dried precursor is calcined at high temperature in a hydrogen atmosphere to obtain the petal-shaped catalyst loaded on the Ni-Zn oxide.
2) High conversion rate, few byproducts, high yields of ethylene glycol and 1, 2-propylene glycol: the catalyst provided by the invention is used for the catalytic conversion reaction of cellulose, the conversion rate is 94.5-99.9%, the main products are ethylene glycol and 1, 2-propylene glycol, the yield of the ethylene glycol and the 1, 2-propylene glycol is 70.2-81.5%, and the main product is widely applied in industry and has good industrial application prospect;
3) has excellent catalytic performance: the nickel-based non-noble metal catalyst prepared by using the layered double hydroxide as the precursor template solves the problems of low dispersity and easy agglomeration of metal active centers and weak interaction between metal and a carrier, and has good catalytic activity when being applied to the hydrodeoxygenation reaction of cellulose.
4) The processing cost is low: the catalyst prepared by the invention takes metal Ni as an active center, the price of the used raw materials is low, and the reaction condition of the preparation method is convenient to regulate and control, so the preparation cost is low.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to better understand the present invention.
Example 1: a preparation method of a petal-shaped catalyst loaded on Ni-Zn oxide comprises the following steps: firstly, 0.25g of aluminum oxide, 2.17g of nickel nitrate hexahydrate, 6.55g of zinc nitrate hexahydrate and 14.4g of ammonium nitrate are weighed and added into 250ml of deionized water to be fully mixed and dissolved, the mixture reacts for 48 hours at the temperature of 90 ℃, after the reaction is finished, the temperature is reduced to room temperature, the mixture is centrifuged, precipitates are washed for 5 times by the deionized water, and the precipitates are dried for 24 hours at the temperature of 70 ℃ to obtain light green solid NiZnAl-LDHs. And putting the light green solid NiZnAl-LDHs into a reactor, stopping heating when the temperature rises to 500 ℃ at the rate of 5 ℃ per minute in hydrogen atmosphere, preserving the temperature for 2 hours, introducing nitrogen for passivation, and then cooling to room temperature to obtain the black powder NiZn-MMO catalyst.
The prepared NiZn-MMO petal-shaped catalyst is used for the catalytic conversion reaction of cellulose. Adding 0.15g of cellulose into 30ml of deionized water, and carrying out catalytic reaction with hydrogen under the anaerobic condition, wherein the adding amount of a catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 240 ℃, the stirring revolution is 900r/min, the hydrogen pressure is 3MPa, and the reaction time is 2 hours. The conversion rate of the cellulose is 97.0 percent and the yield of the ethylene glycol and the 1, 2-propylene glycol is 81.5 percent by using a high performance liquid chromatography-mass spectrometer for detection.
Example 2: a preparation method of a petal-shaped catalyst loaded on Ni-Zn oxide comprises the following steps: firstly, 0.20g of aluminum oxide, 1.74g of nickel nitrate hexahydrate, 4.34g of zinc nitrate hexahydrate and 11.52g of ammonium nitrate are weighed and added into 250ml of deionized water to be fully mixed and dissolved, the mixture reacts for 44 hours at the temperature of 80 ℃, after the reaction is finished, the temperature is reduced to room temperature, the mixture is centrifuged, precipitates are washed for 5 times by the deionized water, and the precipitates are dried for 20 hours at the temperature of 75 ℃ to obtain light green solid NiZnAl-LDHs. And putting the light green solid NiZnAl-LDHs into a reactor, stopping heating when the temperature rises to 480 ℃ at the rate of 5 ℃ per minute in a hydrogen atmosphere, preserving the temperature for 1.9h, introducing nitrogen for passivation, and then cooling to room temperature to obtain the black powder NiZn-MMO catalyst.
The prepared NiZn-MMO petal-shaped catalyst is used for the catalytic conversion reaction of cellulose. Adding 0.15g of cellulose into 30ml of deionized water, and carrying out catalytic reaction with hydrogen under the anaerobic condition, wherein the adding amount of a catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 230 ℃, the stirring revolution is 900r/min, the hydrogen pressure is 3.5MPa, and the reaction time is 150 min. The conversion rate of the cellulose is 95.5 percent and the yield of the ethylene glycol and the 1, 2-propylene glycol is 79.2 percent by using a high performance liquid chromatography-mass spectrometer.
Example 3: a preparation method of a petal-shaped catalyst loaded on Ni-Zn oxide comprises the following steps: firstly, 0.29g of aluminum oxide, 2.60g of nickel nitrate hexahydrate, 6.55g of zinc nitrate hexahydrate and 15.68g of ammonium nitrate are weighed and added into 250ml of deionized water to be fully mixed and dissolved, the mixture reacts for 48 hours at 90 ℃, after the reaction is finished, the temperature is reduced to room temperature, the mixture is centrifuged, precipitates are washed for 5 times by the deionized water, and the precipitates are dried for 24 hours at 70 ℃ to obtain light green solid NiZnAl-LDHs. And putting the light green solid NiZnAl-LDHs into a reactor, stopping heating when the temperature rises to 470 ℃ at the temperature rise rate of 5 ℃ per minute in the hydrogen atmosphere, preserving the temperature for 2.4 hours, introducing nitrogen for passivation, and then cooling to the room temperature to obtain the black powder NiZn-MMO catalyst.
The prepared NiZn-MMO petal-shaped catalyst is used for the catalytic conversion reaction of cellulose. Adding 0.15g of cellulose into 30ml of deionized water, and carrying out catalytic reaction with hydrogen under the anaerobic condition, wherein the adding amount of a catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 240 ℃, the stirring revolution is 900r/min, the hydrogen pressure is 4MPa, and the reaction time is 150 min. The conversion rate of the cellulose is 99.9 percent and the yield of the ethylene glycol and the 1, 2-propylene glycol is 80.1 percent by using a high performance liquid chromatography-mass spectrometer for detection.
Example 4: a preparation method of a petal-shaped catalyst loaded on Ni-Zn oxide comprises the following steps: firstly, 0.23g of aluminum oxide, 2.41g of nickel nitrate hexahydrate, 2.19g of zinc nitrate hexahydrate and 14.07g of ammonium nitrate are weighed and added into 250ml of deionized water to be fully mixed and dissolved, the mixture reacts for 40 hours at 70 ℃, after the reaction is finished, the temperature is reduced to room temperature, the mixture is centrifuged, precipitates are washed for 5 times by the deionized water, and the precipitates are dried for 18 hours at 65 ℃ to obtain light green solid NiZnAl-LDHs. And putting the light green solid NiZnAl-LDHs into a reactor, heating to 400 ℃ at a heating rate of 5 ℃ per minute in a hydrogen atmosphere, stopping heating, keeping the temperature for 3 hours, introducing nitrogen for passivation, and cooling to room temperature to obtain the black powder NiZn-MMO catalyst.
The prepared NiZn-MMO petal-shaped catalyst is used for the catalytic conversion reaction of cellulose. Adding 0.15g of cellulose into 30ml of deionized water, and carrying out catalytic reaction with hydrogen under the anaerobic condition, wherein the adding amount of a catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 220 ℃, the stirring revolution is 900r/min, the hydrogen pressure is 3.5MPa, and the reaction time is 100 min. The conversion rate of the cellulose is 94.5 percent and the yield of the ethylene glycol and the 1, 2-propylene glycol is 70.2 percent by using a high performance liquid chromatography-mass spectrometer.
Example 5: a preparation method of a petal-shaped catalyst loaded on Ni-Zn oxide comprises the following steps: firstly, 0.28g of aluminum oxide, 1.84g of nickel nitrate hexahydrate, 3.25g of zinc nitrate hexahydrate and 12.17g of ammonium nitrate are weighed and added into 250ml of deionized water to be fully mixed and dissolved, the mixture reacts for 42 hours at the temperature of 100 ℃, after the reaction is finished, the temperature is reduced to room temperature, the mixture is centrifuged, precipitates are washed for 5 times by the deionized water, and the precipitates are dried for 22 hours at the temperature of 75 ℃ to obtain light green solid NiZnAl-LDHs. And putting the light green solid NiZnAl-LDHs into a reactor, stopping heating when the temperature rises to 450 ℃ at the rate of 5 ℃ per minute in the hydrogen atmosphere, preserving the temperature for 2.5 hours, introducing nitrogen for passivation, and then cooling to room temperature to obtain the black powder NiZn-MMO catalyst.
The prepared NiZn-MMO petal-shaped catalyst is used for the catalytic conversion reaction of cellulose. Adding 0.15g of cellulose into 30ml of deionized water, and carrying out catalytic reaction with hydrogen under the anaerobic condition, wherein the adding amount of a catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 200 ℃, the stirring revolution is 900r/min, the hydrogen pressure is 3.2MPa, and the reaction time is 90 min. The conversion rate of the cellulose is 95.7 percent and the yield of the ethylene glycol and the 1, 2-propylene glycol is 74.5 percent by using a high performance liquid chromatography-mass spectrometer.
The foregoing is only a preferred embodiment of the invention and it should be noted that modifications and scaling could be made by those skilled in the art without departing from the principle of the invention and that such modifications and scaling should also be considered as within the scope of the invention.
Claims (5)
1. A preparation method of a petal-shaped catalyst is characterized by comprising the following steps: the preparation method comprises the steps of firstly respectively dissolving aluminum oxide, nickel nitrate hexahydrate, zinc nitrate hexahydrate and ammonium nitrate in deionized water, stirring and dissolving, then reacting for 40-60 hours at the temperature of 80-100 ℃ and the stirring speed of 100-150 r/min, centrifuging precipitates after the reaction is finished, washing for 3-5 times by using the deionized water, drying for 20-24 hours at the temperature of 65-75 ℃ to obtain a NiZnAl-LDHs precursor, placing the obtained NiZnAl-LDHs precursor in a hydrogen atmosphere for reduction reaction, and then passivating for 3-5 hours in a nitrogen atmosphere to obtain the petal-shaped catalyst NiZn-MMO loaded on the Ni-Zn oxide.
2. The method of claim 1, wherein the method comprises the steps of: the molar volume concentration ratio of the aluminum oxide to the ammonium nitrate to the nickel nitrate hexahydrate to the zinc nitrate hexahydrate is 1.96-2.94: 144-196: 5.97-8.95: 11.68-17.52.
3. The method of claim 1, wherein the method comprises the steps of: the reduction reaction conditions are as follows: heating to 400-500 ℃ at the heating rate of 5 ℃ per minute in the hydrogen atmosphere, stopping heating, and keeping the temperature for 1.5-3 h.
4. The method of claim 1, wherein the method comprises the steps of: the NiZnAl-LDHs precursor is a light green solid.
5. Use of the petal catalyst prepared according to claim 1 for the catalytic conversion of cellulose, characterized in that: the method specifically comprises the following steps: adding 0.1-0.2 g of cellulose into 20-40 ml of deionized water, and carrying out catalytic reaction with hydrogen under an anaerobic condition, wherein the addition amount of the petal-shaped catalyst is 0.3 time of the mass ratio of the cellulose, the reaction temperature is controlled to be 200-240 ℃, the stirring revolution is 800-1000 r/min, the hydrogen pressure is 3-4 MPa, and the reaction time is 0.5-2.5 h.
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Cited By (2)
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| CN115041175A (en) * | 2022-07-21 | 2022-09-13 | 合肥学院 | Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound with multi-metal oxide supported nickel catalyst |
| CN115041175B (en) * | 2022-07-21 | 2024-05-10 | 合肥学院 | Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound by using multi-metal oxide supported nickel catalyst |
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Cited By (2)
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| CN115041175A (en) * | 2022-07-21 | 2022-09-13 | 合肥学院 | Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound with multi-metal oxide supported nickel catalyst |
| CN115041175B (en) * | 2022-07-21 | 2024-05-10 | 合肥学院 | Multi-metal oxide supported nickel catalyst, preparation method and method for preparing primary amine by catalytic hydrogenation of nitrile compound by using multi-metal oxide supported nickel catalyst |
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