CN111298797A - Copper-aluminum catalyst and preparation method thereof, and preparation method of 3-campholenyl-2-butanol - Google Patents

Copper-aluminum catalyst and preparation method thereof, and preparation method of 3-campholenyl-2-butanol Download PDF

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CN111298797A
CN111298797A CN202010244007.3A CN202010244007A CN111298797A CN 111298797 A CN111298797 A CN 111298797A CN 202010244007 A CN202010244007 A CN 202010244007A CN 111298797 A CN111298797 A CN 111298797A
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copper
aluminum
aluminum catalyst
salt
roasting
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CN111298797B (en
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应登宇
应思斌
胡成明
陈伟
罗功禹
吴敬恒
林熙阳
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Jiangsu Xinrui Spice Co ltd
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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
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/70—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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • C07C29/132—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
    • C07C29/136—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
    • C07C29/143—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 ketones
    • C07C29/145—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 ketones with hydrogen or hydrogen-containing gases
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • 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 copper-aluminum catalyst, which comprises the following steps: s100, dissolving copper salt, aluminum salt and rare metal salt in water to prepare a mixed solution; s200, reacting the mixed solution with alkali liquor to obtain slurry; s300, carrying out suction filtration and drying on the slurry, and roasting the dried solid for the first time to obtain powder; s400, carrying out secondary roasting on the powder, wherein the temperature of the secondary roasting is higher than that of the primary roasting. The invention also discloses a copper-aluminum catalyst for synthesizing 3-campholenyl-2-butanol by hydrogenation. The invention also discloses a preparation method of the 3-campholenyl-2-butanol.

Description

Copper-aluminum catalyst and preparation method thereof, and preparation method of 3-campholenyl-2-butanol
Technical Field
The invention relates to the field of chemical synthesis, in particular to a copper-aluminum catalyst for synthesizing 3-campholenyl-2-butanol by hydrogenation and a preparation method thereof, and a preparation method of the 3-campholenyl-2-butanol.
Background
3-Campholenyl-2-butanol (3-Campholenyl-2-butanol) is called sandalwood 210 in China, also called 5- (2, 2, 3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol, has strong costustoot fragrance, is similar to natural sandalwood fragrance, is an important perfume tested in fine chemical engineering, and is widely applied to cosmetic essence, soap essence, detergent essence and household essence.
The 3-campholenyl-2-butanol is prepared by taking campholenic aldehyde as a raw material, performing aldol condensation on the campholenic aldehyde and butanone, and then performing catalytic hydrogenation on the condensation product.
Figure BDA0002433478520000011
In the conventional preparation method, hydrogen reduction is mostly adopted, a Cu/Cr catalyst is adopted as a hydrogenation catalyst, a large amount of intermediate products (shown as I and II) are generated in the incomplete reaction, and a large amount of by-products (shown as III and IV) are generated in the transitional hydrogenation.
Figure BDA0002433478520000012
Patent CN101125798A provides a method of hydrogenation using a copper-chromium catalyst and then continuing the reduction by chemical reduction, which requires two steps. The conversion rate of the reaction substrate of the copper-chromium catalyst is low, the selectivity of the product 3-campholenyl-2-butanol is low, and the content of byproducts is high.
Disclosure of Invention
Based on the above, there is a need for a copper-aluminum catalyst with high conversion rate and low byproduct content for the hydro-synthesis of 3-campholenyl-2-butanol, a preparation method thereof, and a preparation method of 3-campholenyl-2-butanol.
A preparation method of a copper-aluminum catalyst comprises the following steps:
s100, dissolving copper salt, aluminum salt and rare metal salt in water to prepare a mixed solution, wherein the copper salt accounts for 30-59 percent, the aluminum salt accounts for 40-69 percent and the rare metal salt accounts for 1-5 percent in terms of molar percentage of metal elements;
s200, reacting the mixed solution with alkali liquor to obtain slurry;
s300, carrying out solid-liquid separation on the slurry, drying the obtained solid component, and roasting the dried solid for the first time to obtain a powdery substance;
s400, carrying out secondary roasting on the powder, wherein the temperature of the secondary roasting is higher than that of the primary roasting.
In one embodiment, the copper salt is selected from one or more of copper nitrate, copper sulfate, copper chloride and copper acetate;
and/or the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum acetate;
and/or the rare metal salt is selected from one or more of nitrate, sulfate, chloride and acetate of rare metal.
In one embodiment, in step S300, the drying temperature is 80 ℃ to 150 ℃.
In one embodiment, in step S300, the drying time is 8 to 20 hours.
In one embodiment, the temperature of the first roasting is 150-300 ℃.
In one embodiment, the temperature rise rate of the first roasting is 2-8 ℃/min.
In one embodiment, the time for the first roasting is 1-4 h.
In one embodiment, the method further comprises the step of washing the powder in an acidic solution and an aqueous solution sequentially before the step of roasting the powder twice.
In one embodiment, the temperature of the secondary roasting is 300-600 ℃.
In one embodiment, the temperature rise rate of the secondary roasting is 4-12 ℃/min.
In one embodiment, the secondary roasting time is 2-8 h.
A copper-aluminum catalyst for hydrogenation synthesis of 3-campholenyl-2-butanol is prepared by the preparation method of the copper-aluminum catalyst.
In one embodiment, the copper-aluminum catalyst comprises the following components in mole percentage of metal elements:
30 to 59 percent of copper oxide;
40 to 69 percent of alumina;
1-5% of rare metal oxide.
In one embodiment, the rare metal oxide is selected from one or more of manganese oxide, zirconium oxide, and cerium oxide.
In one embodiment, the mole percent of the copper oxide is 40% to 50%;
and/or, the mole percentage of the alumina is 50-60%;
and/or the mole percentage of the rare metal oxide is 1.5-3%.
A preparation method of 3-campholenyl-2-butanol comprises the following steps:
and heating the copper-aluminum catalyst, the 3-campholenic-2-butanone and the solid alkali to react in a hydrogen atmosphere.
In one embodiment, the heating temperature is 160 ℃ to 180 ℃.
The invention provides a copper-aluminum catalyst which is used for synthesizing 3-campholenyl-2-butanol by catalytic hydrogenation. The copper-aluminum catalyst is prepared from copper salt, aluminum salt and rare metal salt through a series of reactions. The copper-aluminum catalyst is a mixture of copper oxide, aluminum oxide and rare metal oxide. Compared with the traditional catalyst, the copper-aluminum catalyst can realize the catalytic hydrogenation process through one-step reaction to obtain the 3-campholenyl-2-butanol, thereby reducing the intermediate reaction steps and improving the production efficiency. In addition, the catalytic reaction of the copper-aluminum catalyst can realize high conversion rate and selectivity, and has stability and environmental friendliness.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment of the invention provides a preparation method of a copper-aluminum catalyst, which comprises the following steps:
s100, dissolving copper salt, aluminum salt and rare metal salt in water to prepare a mixed solution;
s200, reacting the mixed solution with alkali liquor to obtain slurry;
s300, carrying out solid-liquid separation on the slurry, drying the obtained solid component, and roasting the dried solid for the first time to obtain a powdery substance;
s400, carrying out secondary roasting on the powder, wherein the temperature of the secondary roasting is higher than that of the primary roasting.
The embodiment of the invention provides a copper-aluminum catalyst which is used for synthesizing 3-campholenyl-2-butanol by catalytic hydrogenation. The copper-aluminum catalyst is prepared from copper salt, aluminum salt and rare metal salt through a series of reactions. The copper-aluminum catalyst is a mixture of copper oxide, aluminum oxide and rare metal oxide. Compared with the traditional catalyst, the copper-aluminum catalyst can realize the catalytic hydrogenation process through one-step reaction to obtain the 3-campholenyl-2-butanol, thereby reducing the intermediate reaction steps and improving the production efficiency. In addition, the catalytic reaction of the copper-aluminum catalyst can realize high conversion rate and selectivity, and has stability and environmental friendliness.
In this embodiment, the preparation principle of the copper-aluminum catalyst is as follows: the copper salt, the aluminum salt and the rare metal salt react with alkali liquor to obtain metal hydroxide precipitate, the metal hydroxide is roasted for the first time to obtain metal oxide, the metal oxide is roasted for the second time to optimize the structure and form to form optimized metal oxide, and the optimized metal oxide has higher catalytic activity and stronger selectivity, is favorable for catalytic hydrogenation reaction to be carried out towards the direction of generating 3-campholenyl-2-butanol, so that the formation of byproducts can be reduced, and the generation rate of the 3-campholenyl-2-butanol is improved.
In step S100, the mixing ratio of the copper salt, the aluminum salt and the rare metal salt is determined in accordance with the molar ratio of each metal oxide in the copper-aluminum catalyst to be actually produced. Basically, the mixing ratio of the copper salt, the aluminum salt and the rare metal salt is in accordance with the molar ratio of copper oxide, aluminum oxide and rare metal oxide in the copper-aluminum catalyst.
In one embodiment, the mole percentage of the copper salt is 30% to 59%. Preferably, the mole percentage of the copper salt is 40% to 50%, respectively. In one embodiment, the mole percentage of aluminum salt is 40% to 69%. Preferably, the molar percentage of the aluminum salt is 50% to 60%. In one embodiment, the mole percent of rare metal salt is 1% to 5%. Preferably, the mole percentage of the rare metal salt is 1.5% to 3%.
In one embodiment, the copper salt may be selected from one or more of copper nitrate, copper sulfate, copper chloride and copper acetate. Preferably, the copper salt is selected from copper nitrate.
In one embodiment, the aluminium salt is selected from one or more of aluminium nitrate, aluminium sulphate, aluminium chloride and aluminium acetate. Preferably, the copper salt is selected from aluminum nitrate.
In one embodiment, the rare metal salt is selected from one or more of the nitrates, sulfates, chlorides, and acetates of rare metals. In one embodiment, the rare metal may be selected from one or more of manganese, zirconium, cerium. The rare metal salt may be selected from one or more of rare metal salts of manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, zirconium nitrate, zirconium sulfate, zirconium chloride, zirconium acetate, cerium nitrate, cerium sulfate, cerium chloride and cerium acetate. Preferably, the rare metal salt is selected from the group consisting of nitrates of rare metals.
In step S200, the copper salt, the aluminum salt and the rare metal salt are reacted with an alkali solution to obtain copper hydroxide, aluminum hydroxide and rare metal hydroxide precipitates, respectively.
In one embodiment, the alkali solution may be at least one selected from ammonia, potassium hydroxide and sodium hydroxide. Preferably, the amount of the alkali solution is such that the copper salt, the aluminum salt and the rare metal salt react sufficiently to give the hydroxide. In one embodiment, the mass concentration of the alkali liquor can be 25-35%.
In one embodiment, the reaction time of the copper salt, the aluminum salt and the rare metal salt with the alkali solution may be 10min to 120min, preferably 30min to 50 min.
In step S300, the solvent in the slurry is removed through the preliminary heat treatment in the drying process, so that the product in the subsequent baking process is more stable, and the formation of the byproduct of the baking reaction is reduced.
In one embodiment, the drying temperature may be 80 ℃ to 150 ℃. Specifically, the drying temperature may be 80-90 deg.C, 90-100 deg.C, 100-110 deg.C, 110-120 deg.C, 120-130 deg.C, 130-140 deg.C or 140-150 deg.C. Preferably, the drying temperature may be 100 ℃ to 130 ℃. In one embodiment, the drying time may be 8 to 20 hours. Specifically, the drying time can be 8-12 h, 12-16 h or 16-20 h.
The first roasting is carried out at a lower temperature, so that the reaction of the hydroxide is not carried out explosively, the formation of the oxide can be carried out under a mild condition, the form of the oxide is more stable, and the purity of the oxide is higher. The temperature of the first roasting can be higher than the drying temperature.
In one embodiment, the temperature for the first firing is 150 ℃ to 300 ℃. Specifically, the first roasting temperature may be 150-180 deg.c, 180-200 deg.c, 200-220 deg.c, 220-250 deg.c, 250-270 deg.c or 270-300 deg.c. Preferably, the temperature for the first calcination may be 200 to 250 ℃.
In one embodiment, the temperature of the first firing is gradually increased. In one embodiment, the first calcination temperature rise rate can be 2-8 deg.C/min. Preferably, the temperature rise rate of the first roasting can be 4-6 ℃/min. Preferably, the rate of temperature rise of the first firing is a constant rate.
In one embodiment, the first calcination time may be 1 to 4 hours. Preferably, the time for the first roasting is 2 to 3 hours.
In one embodiment, the method further comprises the step of washing the powder in an acidic solution and an aqueous solution in sequence before the step of roasting the powder twice. Residual unreacted alkali liquor is removed through washing of the acid solution and water, the purity of the secondary roasting environment is improved, impurity interference is reduced, and the secondary roasting can obtain an oxidation product with a more optimized structure. In one embodiment, the acidic solution may be selected from at least one of acetic acid, formic acid, and propionic acid.
In step S400, the temperature of the secondary firing is greater than the temperature of the primary firing.
The purpose of sectional roasting is as follows: (1) can dispose the ineffective components, and leads the catalyst to have more stable performance and better shape. (2) The catalyst is formed into smaller particles. (3) The catalyst has concentrated pore size distribution and less abrasion. The difficulty that other catalysts are mechanically shaped is overcome, and meanwhile, the waste of the catalysts caused by shaping is reduced.
In one embodiment, the temperature of the secondary roasting is 300-600 ℃. Specifically, the secondary roasting temperature can be 300-350 ℃, 350-400 ℃, 400-450 ℃, 450-500 ℃, 500-550 ℃ or 550-600 ℃. Preferably, the temperature of the secondary roasting may be 400 to 500 ℃.
In one embodiment, the temperature of the second calcination is gradually increased. In one embodiment, the temperature rise rate of the secondary roasting is 4-12 ℃/min. Preferably, the temperature rise rate of the secondary roasting is 6-8 ℃/min. Preferably, the rate of temperature rise of the secondary calcination is a constant rate.
In one embodiment, the second roasting time may be 2 to 8 hours. Preferably, the time for the secondary roasting is 4 to 6 hours.
The embodiment of the invention also provides a copper-aluminum catalyst for synthesizing 3-campholenyl-2-butanol by hydrogenation, which is prepared by adopting the preparation method of the copper-aluminum catalyst in any embodiment.
In one embodiment, the copper-aluminum catalyst comprises the following components in mole percentage of metal elements:
30 to 59 percent of copper oxide;
40 to 69 percent of alumina;
1-5% of rare metal oxide.
In one embodiment, the rare metal oxide may be selected from one or more of manganese oxide, zirconium oxide, and cerium oxide.
Preferably, the mole percentage of the copper oxide is 40 to 50 percent;
preferably, the mole percentage of the alumina is 50 to 60 percent;
preferably, the mole percentage of the rare metal oxide is 1.5% to 3%.
In one embodiment, the copper aluminum catalyst is black particles. In one embodiment, the average particle size of the copper aluminum catalyst may be 10nm to 15 nm. In one embodiment, the copper aluminum catalyst has a porous structure. In one embodiment, the pore size of the porous structure may be 2nm to 4 nm.
The embodiment of the invention also provides a preparation method of the 3-campholenyl-2-butanol, which comprises the following steps:
the copper-aluminum catalyst prepared by the preparation method of the copper-aluminum catalyst of any embodiment or the copper-aluminum catalyst, the 3-campholenyl-2-butanone and the solid alkali of any embodiment are heated and reacted in a hydrogen atmosphere.
In one embodiment, the heating temperature may be 160 ℃ to 180 ℃. Specifically, the temperature can be 160-65 ℃, 165-170 ℃, 170-175 ℃ or 175-180 ℃.
In one embodiment, the solid base may be selected from one or more of potassium hydroxide, sodium hydroxide and potassium carbonate.
In one embodiment, an alcohol, which may be selected from one or more of ethanol, isopropanol, isobutanol, and sec-butanol, may be added to the reaction vessel.
The following are specific examples.
Example 1
Weighing 9.66g of copper nitrate trihydrate, 21.95g of aluminum nitrate nonahydrate and 0.65g of cerous nitrate hexahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the cerous nitrate hexahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring for reaction for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at the heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower layer precipitate with distilled water, raising the temperature to 500 ℃ at the heating rate of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst A.
Example 2
Weighing 10.87g of copper nitrate trihydrate, 20.07g of aluminum nitrate nonahydrate and 0.65g of cerous nitrate hexahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the cerous nitrate hexahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring for reaction for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at the heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower layer precipitate with distilled water, raising the temperature to 500 ℃ at the heating rate of 6 ℃/min after carrying out suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst B.
Example 3
Weighing 12.08g of copper nitrate trihydrate, 18.19g of aluminum nitrate nonahydrate and 0.65g of cerous nitrate hexahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the cerous nitrate hexahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring for reaction for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at the heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower layer precipitate with distilled water, raising the temperature to 500 ℃ at the heating rate of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst C.
Example 4
Weighing 9.66g of copper nitrate trihydrate, 21.95g of aluminum nitrate nonahydrate and 0.64g of zirconium nitrate pentahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the zirconium nitrate pentahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring and reacting for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at the heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower layer precipitate with distilled water, raising the temperature to 500 ℃ at the heating rate of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst D.
Example 5
Weighing 9.66g of copper nitrate trihydrate, 21.95g of aluminum nitrate nonahydrate and 0.43g of manganese nitrate hexahydrate, dissolving the copper nitrate trihydrate, dripping excessive 28% wt% of ammonia water solution under a stirring state, stirring and reacting for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at the heating rate of 4 ℃/min, roasting for 2 hours to obtain powdery solid, washing the powdery solid with acetic acid solution, centrifuging, washing the lower-layer precipitate with distilled water, raising the temperature to 500 ℃ at the heating rate of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst E.
Comparative example 1
Weighing 4.83g of copper nitrate trihydrate, 29.44g of aluminum nitrate nonahydrate and 0.65g of cerous nitrate hexahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the cerous nitrate hexahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring for reaction for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at the heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower layer precipitate with distilled water, raising the temperature to 500 ℃ at the heating rate of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst F.
Comparative example 2
Weighing 16.55G of copper nitrate trihydrate, 11.2G of aluminum nitrate nonahydrate and 0.65G of cerium nitrate hexahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the cerium nitrate hexahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring and reacting for 30min, then carrying out suction filtration, placing the precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at a heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower layer precipitate with distilled water, raising the temperature to 500 ℃ at a heating rate of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst G.
Comparative example 3
Weighing 10.87g of copper nitrate trihydrate, 20.07g of aluminum nitrate nonahydrate and 0.65g of cerous nitrate hexahydrate, dissolving the copper nitrate trihydrate, the aluminum nitrate nonahydrate and the cerous nitrate hexahydrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring for reaction for 30min, then carrying out suction filtration, placing a precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature to 300 ℃ at a heating rate of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, and grinding the powdery solid to obtain a catalyst H.
Comparative example 4
Weighing 10.87g of copper nitrate trihydrate and 20.63g of aluminum nitrate, dissolving the copper nitrate trihydrate and the aluminum nitrate in 200ml of deionized water, dropwise adding an excessive 28 wt% ammonia water solution under a stirring state, stirring and reacting for 30min, then carrying out suction filtration, placing a precipitate in a 120 ℃ oven for drying for 6 hours, placing the precipitate in a muffle furnace, raising the temperature rate to 300 ℃ at a speed of 4 ℃/min, roasting for 2 hours to obtain a powdery solid, washing the powdery solid with an acetic acid solution, centrifuging, washing a lower-layer precipitate with distilled water, raising the temperature rate to 500 ℃ at a speed of 6 ℃/min after suction filtration, roasting for 5 hours, and grinding to obtain a black catalyst I.
Comparative example 5
The catalyst was a commercially available common powder mixture of copper oxide, aluminum oxide and cerium oxide with mole fractions of 40%, 58.5%, 1.5%, respectively.
Comparative example 6
The catalyst is a copper-chromium catalyst, wherein the mole percentages of copper and chromium are 60% and 40%, respectively.
Evaluation of all catalysts the reaction was carried out in a 200ml autoclave, to which 200g (0.97mol) of 3-campholenyl-2-butanone, 0.06g of KOH and 10g of the catalyst of the comparative example of the above example were added. Hydrogen was then fed to the reaction vessel to an initial pressure of 30bar and heated with stirring to a temperature of 170 ℃ before the reaction was started for 1 hour. The reaction was then stopped. The evaluation results are shown in table 1.
The conversion rate is equal to the consumption of 3-campholenic-2-butanone/the feeding amount of 3-campholenic-2-butanone multiplied by 100 percent;
the selectivity of 3-campholenyl-2-butanol was ═ amount of 3-campholenyl-2-butanol produced/total amount produced × 100%.
TABLE 1
Figure BDA0002433478520000101
Figure BDA0002433478520000111
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (17)

1. The preparation method of the copper-aluminum catalyst is characterized by comprising the following steps:
s100, dissolving copper salt, aluminum salt and rare metal salt in water to prepare a mixed solution, wherein the copper salt accounts for 30-59 percent, the aluminum salt accounts for 40-69 percent and the rare metal salt accounts for 1-5 percent in terms of molar percentage of metal elements;
s200, reacting the mixed solution with alkali liquor to obtain slurry;
s300, carrying out solid-liquid separation on the slurry, drying the obtained solid component, and roasting the dried solid for the first time to obtain a powdery substance;
s400, carrying out secondary roasting on the powder, wherein the temperature of the secondary roasting is higher than that of the primary roasting.
2. The method for preparing the copper-aluminum catalyst according to claim 1, wherein the copper salt is selected from one or more of copper nitrate, copper sulfate, copper chloride and copper acetate;
and/or the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum chloride and aluminum acetate;
and/or the rare metal salt is selected from one or more of nitrate, sulfate, chloride and acetate of rare metal.
3. The method for preparing the copper-aluminum catalyst according to claim 1 or 2, wherein in the step S300, the drying temperature is 80 ℃ to 150 ℃.
4. The method for preparing the copper-aluminum catalyst according to claim 3, wherein in the step S300, the drying time is 8-20 h.
5. The process for preparing a copper-aluminum catalyst according to claim 1 or 2, wherein the temperature of the first calcination is 150 ℃ to 300 ℃.
6. The method for preparing the copper-aluminum catalyst according to claim 5, wherein the temperature rise rate of the first calcination is 2-8 ℃/min.
7. The method for preparing the copper-aluminum catalyst according to claim 6, wherein the time for the first calcination is 1-4 h.
8. The method for preparing a copper-aluminum catalyst according to claim 1 or 2, further comprising a step of washing the powder in an acidic solution and an aqueous solution in this order before subjecting the powder to secondary calcination.
9. The method for preparing the copper-aluminum catalyst according to claim 1 or 2, wherein the temperature of the secondary calcination is 300 ℃ to 600 ℃.
10. The method for preparing the copper-aluminum catalyst according to claim 9, wherein the temperature rise rate of the secondary calcination is 4 to 12 ℃/min.
11. The method for preparing the copper-aluminum catalyst according to claim 10, wherein the time for the secondary calcination is 2 to 8 hours.
12. A copper-aluminum catalyst for the hydrogenation synthesis of 3-campholenyl-2-butanol, characterized in that it is prepared by the method of any one of claims 1-11.
13. The copper aluminum catalyst of claim 12, wherein the copper aluminum catalyst is comprised of, in mole percent of metallic elements:
30 to 59 percent of copper oxide;
40 to 69 percent of alumina;
1-5% of rare metal oxide.
14. The copper aluminum catalyst in accordance with claim 13, wherein the rare metal oxide is selected from one or more of manganese oxide, zirconium oxide, and cerium oxide.
15. The copper aluminum catalyst of claim 13 or 14, wherein the mole percent of copper oxide is 40% to 50%;
and/or, the mole percentage of the alumina is 50-60%;
and/or the mole percentage of the rare metal oxide is 1.5-3%.
16. A preparation method of 3-campholenyl-2-butanol is characterized by comprising the following steps:
heating the copper-aluminum catalyst of any one of claims 12 to 15, 3-campholenyl-2-butanone and solid base in a hydrogen atmosphere for reaction.
17. The method of claim 16, wherein the heating is at a temperature of 160 ℃ to 180 ℃.
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