CN108452799B - Preparation method of supported silver catalyst and application of supported silver catalyst in preparation of benzaldehyde by catalyzing anaerobic dehydrogenation of benzyl alcohol - Google Patents
Preparation method of supported silver catalyst and application of supported silver catalyst in preparation of benzaldehyde by catalyzing anaerobic dehydrogenation of benzyl alcohol Download PDFInfo
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- CN108452799B CN108452799B CN201810444762.9A CN201810444762A CN108452799B CN 108452799 B CN108452799 B CN 108452799B CN 201810444762 A CN201810444762 A CN 201810444762A CN 108452799 B CN108452799 B CN 108452799B
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of a supported silver catalyst and application of the supported silver catalyst in catalyzing anaerobic dehydrogenation of benzyl alcohol to prepare benzaldehyde. The preparation method comprises the following steps: magnesium-aluminum hydrotalcite precursor is roasted to complete topological transformation to generate magnesium-aluminum mixed metal oxide as a carrier, a silver-ammonia complex is used as impregnation liquid, a metal Ag is loaded by an impregnation method, and the supported silver catalyst is obtained after roasting and activation. The supported silver catalyst has the advantages of uniform silver particle size, uniform dispersion, high catalytic efficiency, mild catalytic reaction conditions, and good stability and recyclability. When the catalyst is used in the reaction of preparing benzaldehyde by anaerobic dehydrogenation of benzyl alcohol, the conversion rate of the benzyl alcohol and the selectivity of the product both reach over 90 percent.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method of a supported silver catalyst and application of the supported silver catalyst in catalyzing anaerobic dehydrogenation of benzyl alcohol to prepare benzaldehyde.
Background
Benzaldehyde is an important chemical intermediate and an important raw material in the fields of medicines, resins, pesticides and the like. The traditional process for preparing benzaldehyde mainly comprises a benzyl chloride hydrolysis method and a toluene chlorination re-hydrolysis method, but the two methods have the problems of long process, difficult product separation, organic waste discharge and the like, and particularly, the application of the products in the pharmaceutical and food industries is severely restricted by the produced benzaldehyde because of containing chloride. In order to meet the production requirements of green chemistry, the selective oxidation reaction of benzyl alcohol is widely concerned by people due to the advantages of high atom utilization rate, good safety, high economic performance, few byproducts and the like.
The benzyl alcohol selective oxidation method comprises gas phase oxidation and liquid phase oxidation, wherein oxygen is mostly used as an oxidant in the benzyl alcohol gas phase oxidation method, a fixed bed reactor is used as a reaction site, and benzyl alcohol is selectively catalytically oxidized in a gas-solid phase mode. However, the reaction temperature of the gas phase oxidation method is generally high, which is not favorable for the development of industrialization, so in recent years, the research on the p-benzyl alcohol liquid phase oxidation method is gradually hot. The benzyl alcohol liquid phase oxidation method is generally considered to mainly use oxygen or hydrogen peroxide as an oxidant, or directly perform dehydrogenation oxidation on alcohol under the conditions of no oxygen and no hydrogen acceptor. Compared with a gas phase oxidation method, the method does not need a special reactor and has the characteristics of simple process and mild reaction. However, in the presence of the oxidant, when the reaction is carried out at a certain temperature, the reactant alcohol or organic matters have the potential of burning explosion. Therefore, attempts have been made to carry out the liquid phase selective oxidation of alcohols in the absence of an oxidizing agent. Besides the potential safety hazard can be avoided, because the reaction products are aldehyde and hydrogen, the alcohol has the potential of becoming a hydrogen storage medium easy to transfer, and the utilization value of the alcohol is greatly improved.
At present, catalysts for the reaction of preparing benzaldehyde by anaerobic dehydrogenation of benzyl alcohol mainly take noble metal supported catalysts such as Au, Pt, Pd and the like as main materials. Has the defects of high price, poor cyclicity and the like, and limits the industrial application of the catalyst. And if the preparation means and the geometric structure of the supported silver catalyst are optimized, the catalytic performance of the noble metal catalysts such as Au, Pt, Pd and the like can be achieved, and the stability and the recyclability of the catalyst are improved, so that the research value and the use value of the catalyst can be greatly increased.
Disclosure of Invention
The invention aims to provide a preparation method of a supported silver catalyst and application of the supported silver catalyst in catalyzing anaerobic dehydrogenation of benzyl alcohol to prepare benzaldehyde.
A preparation method of a supported silver catalyst comprises the following steps: magnesium-aluminum hydrotalcite precursor is roasted to complete topological transformation to generate magnesium-aluminum mixed metal oxide as a carrier, a silver-ammonia complex is used as impregnation liquid, a metal Ag is loaded by an impregnation method, and the supported silver catalyst is obtained after roasting and activation.
Further, the preparation method of the silver-ammonia complex impregnation liquid comprises the following steps: 0.005g to 0.05g of silver nitrate is weighed and added into 3ml of anhydrous ethylenediamine, and the silver nitrate is completely dissolved through ultrasonic treatment to obtain the silver-ammonia complex impregnation liquid.
Further, the preparation method of the magnesium-aluminum mixed metal oxide carrier comprises the following steps: weighing 35-45g of magnesium nitrate, 25-25g of aluminum nitrate and 20-30g of urea at the temperature of 0-50 ℃, simultaneously dissolving in 100ml of deionized water, completely dissolving to form a mixed solution, and transferring to a vacuum hydrothermal kettle for crystallization nucleation; centrifuging and washing the generated precipitate until the pH value is neutral; and transferring the powder into a muffle furnace after being dried in an oven overnight, and roasting to obtain the magnesium-aluminum mixed metal oxide carrier.
Further, the silver-ammonia complex impregnation liquid is added into 0.5-1.5g of magnesium-aluminum mixed metal oxide carrier, and the silver-ammonia complex impregnation liquid is uniformly dispersed into the magnesium-aluminum mixed metal oxide carrier through ultrasonic treatment, then is dried, and is activated by silver in a muffle furnace to obtain the supported silver catalyst.
Furthermore, the temperature of crystallization nucleation is 150 ℃, the crystallization time is 6 hours, and the drying temperature of the precipitate is 60 ℃.
Further, the conditions for roasting the magnesium-aluminum hydrotalcite precursor are 400-600 ℃, the heating rate is 2-10 ℃/min, and the temperature is reduced after the temperature is raised to the target temperature and is preserved for 3-5 h.
Further, the ultrasonic treatment time for uniformly dispersing the silver-ammonia complex impregnation liquid into the magnesium-aluminum mixed metal oxide carrier is 30-40 min; the drying temperature was 60 ℃.
Further, the activation condition of the silver is 250-450 ℃, the heating rate is 2-5 ℃/min, the temperature is kept for 0.5-1.5h after reaching the target temperature, and then the temperature is reduced.
The invention also relates to the application of the uniformly dispersed supported silver catalyst. The uniformly dispersed silver-loaded catalyst can be used for the reaction of preparing benzaldehyde by anaerobic dehydrogenation of benzyl alcohol.
Further, the use method of the supported silver catalyst for the reaction of preparing benzaldehyde by anaerobic dehydrogenation of benzyl alcohol comprises the following steps:
dissolving 0.05-0.2g of benzyl alcohol in 5ml of p-xylene solvent, and adding 0.05-0.2g of the supported silver catalyst; adding a magnetic stirrer; vacuumizing a glass reaction tube, introducing inert gas argon, heating at 70-150 ℃ in an oxygen-free reaction system, keeping a continuous stirring state, stirring at the rotation speed of 300-700r/min, reacting at normal pressure for 4 hours, and then centrifugally separating the catalyst and the reaction liquid.
Further, after the reaction is finished, the catalyst is centrifugally separated, and is dried and recycled.
The invention has the advantages that: the preparation method has the advantages of universality and simplicity and easiness in operation for the prepared uniformly-dispersed supported silver catalyst. Because the silver and the amino are easy to complex, the amino can well separate silver ions in the generation process of the silver-ammonia complex, and then silver particles can keep a uniformly dispersed shape and have uniform particle size after the roasting and activating process of the silver. And the state of the silver-ammonia complex has strong bonding force with the carrier, and the metal active component is not easy to desorb from the carrier, so the catalyst also has good stability and cyclicity, and the conversion rate of the benzyl alcohol and the selectivity of the product both reach more than 90 percent. After five times of circulation, the conversion rate of the benzyl alcohol is reduced from 96 percent of the first reaction to 90 percent, and the catalytic activity is still high.
Drawings
Fig. 1 is an SEM image of a magnesium aluminum hydrotalcite precursor prepared in example 1 of the present invention.
Fig. 2 is an SEM image of magnesium aluminum mixed metal oxide produced by topological transformation of hydrotalcite precursor in example 1 of the present invention.
Fig. 3 is a TEM image of a uniformly dispersed supported silver catalyst prepared by the impregnation method of example 1 of the present invention.
Detailed Description
Example 1
Weighing 0.01g of silver nitrate at room temperature, adding the silver nitrate into 3ml of anhydrous ethylenediamine, carrying out ultrasonic treatment to completely dissolve the silver nitrate, completing the preparation of a silver-ammonia complex, and recording the silver-ammonia complex as a solution A; weighing 25.64g of magnesium nitrate, 18.76g of aluminum nitrate and 21g of urea at room temperature, and simultaneously dissolving the magnesium nitrate, the aluminum nitrate and the urea in 100ml of deionized water to completely dissolve the magnesium nitrate, the aluminum nitrate and the urea to form a mixed solution; then transferring the mixture into a vacuum hydrothermal kettle, and carrying out crystallization nucleation for 6h at the temperature of 150 ℃; centrifuging and washing the generated precipitate for many times until the pH value is neutral; transferring the powder into a 60 ℃ oven for drying overnight, transferring the powder into a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 4h, and then cooling to finish the preparation of the magnesium-aluminum mixed metal oxide, wherein 1g of the powder is weighed and recorded as solid B; adding the solution A into the solid B by using an impregnation method, and simultaneously carrying out ultrasonic treatment to uniformly disperse the solution A into the solid B; transferring to a 60 ℃ oven for drying after 35 min; and after complete drying, transferring the silver-loaded catalyst into a muffle furnace, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 1h, cooling and taking out to complete the preparation of the uniformly dispersed silver-loaded catalyst.
The uniformly dispersed supported silver catalyst prepared by the invention is used for catalyzing the reaction of preparing benzaldehyde by anaerobic dehydrogenation of benzyl alcohol, and the specific reaction conditions are as follows: (1) weighing 0.1g of catalyst, and adding the catalyst into a glass reaction tube; (2) weighing 0.097g of benzyl alcohol, dissolving the benzyl alcohol in 5ml of p-xylene solvent, and adding the solution into a glass reaction tube; (3) adding a magnetic stirrer; vacuumizing the glass reaction tube; then introducing inert gas argon to create an oxygen-free reaction system; (4) heating a glass reaction tube at 100 ℃, keeping a continuous stirring state, stirring at a rotating speed of 500r/min, reacting at normal pressure for 4 hours, and then centrifugally separating a catalyst and a reaction solution; (5) and (3) carrying out gas chromatography analysis on the reaction liquid, drying the catalyst, repeating the steps for 5 times again, and comparing the change of the reaction performance.
The reaction product is quantitatively analyzed by using gas chromatography of Shimadzu corporation, tests show that the reaction of the uniformly dispersed supported silver catalyst for preparing benzaldehyde by the anaerobic dehydrogenation of benzyl alcohol is basically complete after reacting for 4 hours at the temperature of 100 ℃, the conversion rate of the benzyl alcohol reaches 95.87%, the selectivity of the target product benzaldehyde reaches 93.28%, and the yield is 89.45%. After the catalyst is recycled for 5 times, the yield can still reach more than 80%.
Claims (6)
1. The application of the supported silver catalyst in catalyzing the anaerobic dehydrogenation of the benzyl alcohol to prepare the benzaldehyde is characterized in that the reaction of catalyzing the anaerobic dehydrogenation of the benzyl alcohol to prepare the benzaldehyde by the supported silver catalyst comprises the following steps:
dissolving 0.05-0.2g of benzyl alcohol in 5mL of p-xylene solvent, and adding 0.05-0.2g of the supported silver catalyst; adding a magnetic stirrer; vacuumizing a glass reaction tube, introducing an inert gas argon, heating at 70-150 ℃ in an oxygen-free reaction system, keeping a continuous stirring state, stirring at the rotation speed of 300-700r/min, reacting at normal pressure for 4 hours, and then centrifugally separating a catalyst and a reaction liquid;
the preparation method of the supported silver catalyst comprises the following steps: roasting the magnesium-aluminum hydrotalcite precursor to complete topological transformation to generate magnesium-aluminum mixed metal oxide as a carrier, taking a silver-ammonia complex as impregnation liquid, loading metal Ag by using an impregnation method, and roasting and activating to obtain a supported silver catalyst; the activation condition of the silver is 250-450 ℃, the heating rate is 2-5 ℃/min, the temperature is kept for 0.5-1.5h after reaching the target temperature, and then the temperature is reduced;
the preparation method of the silver-ammonia complex impregnation liquid comprises the following steps: weighing 0.005g-0.05g of silver nitrate, adding the silver nitrate into 3mL of anhydrous ethylenediamine, and performing ultrasonic treatment to completely dissolve the silver nitrate to obtain silver-ammonia complex impregnation liquid;
the preparation method of the magnesium-aluminum mixed metal oxide carrier comprises the following steps: weighing 35-45g of magnesium nitrate, 25-25g of aluminum nitrate and 20-30g of urea at the temperature of 0-50 ℃, simultaneously dissolving in 100mL of deionized water, completely dissolving to form a mixed solution, and transferring to a vacuum hydrothermal kettle for crystallization nucleation; centrifuging and washing the generated precipitate until the pH value is neutral; and transferring the powder into a muffle furnace after being dried in an oven overnight, and roasting to obtain the magnesium-aluminum mixed metal oxide carrier.
2. The use of claim 1, wherein the silver-ammonia complex impregnation solution is added to 0.5-1.5g of magnesium aluminum mixed metal oxide support, and the supported silver catalyst is obtained by uniformly dispersing the silver-ammonia complex impregnation solution into the magnesium aluminum mixed metal oxide support through ultrasonic treatment, drying, and activating silver in a muffle furnace.
3. Use according to claim 2, wherein the crystallization nucleation temperature is 150 ℃, the crystallization time is 6h and the drying temperature of the precipitate is 60 ℃.
4. The application of claim 3, wherein the roasting condition is 400-600 ℃, the heating rate is 2-10 ℃/min, and the temperature is reduced after the temperature is raised to the target temperature and is preserved for 3-5 h.
5. The use of claim 4, wherein the sonication time to uniformly disperse the silver-ammonia complex impregnation solution into the magnesium aluminum mixed metal oxide support is from 30 to 40 min; the drying temperature was 60 ℃.
6. The use of claim 1, wherein the catalyst is centrifuged after the reaction is complete and dried for reuse.
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| CN110548507B (en) * | 2019-08-01 | 2020-11-13 | 厦门大学 | Preparation method of carbon-supported nano-silver catalyst |
| CN110665502A (en) * | 2019-09-03 | 2020-01-10 | 北京氦舶科技有限责任公司 | Monoatomic Ag-based catalyst, preparation thereof and application thereof in catalytic oxidation of formaldehyde |
| CN111420659B (en) * | 2020-04-21 | 2022-08-09 | 湖北荟煌科技股份有限公司 | Noble metal catalyst |
| CN112495387B (en) * | 2020-10-15 | 2022-10-11 | 南开大学 | Carbon fiber-based silver/cobalt-manganese layered double hydroxide composite material and preparation method and application thereof |
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