CN109225281B - Catalyst containing multivalent copper active component, preparation method and application - Google Patents
Catalyst containing multivalent copper active component, preparation method and application Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B01J27/122—Halides of copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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Abstract
The invention provides a catalyst containing a multi-valence copper active component, which consists of Cuh 0‑Cum nXaYbZcThe copper-base alloy material comprises a component containing 0-valence copper and n-valence copper, wherein n is more than 0, and the value ranges of h and m are 1-10; a. the value ranges of b and c are 0-30; x, Y, Z are inorganic acid radical and/or organic acid radical respectively; s is one or more oxide carriers. According to the invention, the copper-containing active component solution and the precipitator solution are precipitated on the oxide carrier, and the precipitation temperature and the precipitation pH value are accurately controlled, so that after the prepared catalyst is subjected to reduction treatment in a reducing atmosphere, the obtained multi-valence copper catalyst has higher cyclohexanol conversion rate and cyclohexene selectivity, and the production efficiency is improved.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst containing a multivalent copper active component, and a preparation method and application thereof.
Background
Cyclohexene as an important organic synthetic raw material has wide application. Can be used as a petroleum extractant in petroleum exploitation; can be used as a stabilizer of high-octane gasoline in the oil refining industry; can be used for synthesizing L-lazine, adipic acid, butadiene, cyclohexene oxide, cyclohexyl formic acid and the like in the pharmaceutical industry; it can also be used as intermediate of synthetic pesticide and reaction solvent. Concentrated sulfuric acid or concentrated phosphoric acid is generally adopted as a catalyst in the current industrial production, and the cyclohexene is produced by dehydrating cyclohexanol in a liquid phase. The cyclohexene yield of the production process is only 46-56% generally; and the sulfuric acid phosphoric acid has serious corrosion to equipment, serious carbonization in the reaction process, more byproducts, complicated subsequent treatment process and environmental pollution. Therefore, there is a need to develop a new solid catalyst for replacing the concentrated acid catalyst, and improve the process for producing cyclohexene by dehydrating cyclohexanol.
Disclosure of Invention
In view of the above, the invention aims to provide a catalyst containing a multivalent copper active component, a preparation method and an application thereof, wherein the preparation method is simple and feasible, and the prepared catalyst has metal-acid dual-function activity, high catalyst selection conversion rate and good selectivity.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a catalyst containing multi-valence copper active component is composed of Cuh 0-Cum nXaYbZcThe copper-base alloy material comprises a component containing 0-valence copper and n-valence copper, wherein n is more than 0, and the value ranges of h and m are 1-10; a. the value ranges of b and c are 0-30; x, Y, Z are inorganic acid radical and/or organic acid radical respectively; s is one or more oxide carriers.
Further, inorganic acid groups include, but are not limited to, phosphate, phosphite, nitrate, sulfate, bisulfate, sulfite, hydrochloride, borate.
Further, organic acid groups include, but are not limited to, formate, acetate, oxalate, propionate, citrate.
The invention also provides a method for preparing the catalyst containing the multivalent copper active component, which comprises the following steps:
the method comprises the following steps: mixing at least one copper source with water to obtain a solution A, wherein the copper source is calculated by Cu, the ratio of copper source: the molar ratio of water is 1: 1-500, and more preferably 1: 2-50; mixing a precipitator and water to obtain a solution B, wherein the molar ratio of the precipitator to the water is 1: 1-500, more preferably 1: 10-100, the preferable precipitation temperature is 10-100 ℃, more preferably 20-70 ℃, the pH of the precipitation solution is 5.0-13.0, more preferably 6.0-11.0, and the precipitation aging time is 2-12 hours, more preferably 2-6 hours;
step two: precipitating copper in the solution A in the solution B, coating the copper on an oxide carrier, separating, drying, and then roasting at 250-850 ℃ to obtain a solid, wherein the preferable drying temperature is 30-150 ℃, the more preferable drying temperature is 60-120 ℃, the drying atmosphere is air, inert gas or vacuum, the drying time is 6-48 h, the more preferable drying time is 10-24h, the preferable roasting temperature is 200-900 ℃, the more preferable baking temperature is 400-; the roasting time is 2-12 h, and more preferably 4-10 h; the sediment is precipitated by adopting a single-drop method or a double-drop method;
step three: reducing the solid obtained in the second step in a reducing atmosphere to obtain the catalyst containing the multivalent copper active component, wherein the preferable reducing temperature is 180-300 ℃, the more preferable reducing temperature is 200-280 ℃, the reducing pressure is 0.1-5.0 MPa, the more preferable reducing pressure is 0.5-3.0 MPa, and the volume space velocity is 100-100000 h-1More preferably 200 to 5000 hours-1The reduction time is 1-10 hours, more preferably 2-6 hours, and the reduction atmosphere is hydrogen, carbon monoxide, or a mixed gas of hydrogen, carbon monoxide and inert gas in any proportion, more preferably a mixed gas of hydrogen and/or nitrogen; hydrogen gas: the molar ratio of the nitrogen gas mixture is 1:0 to 1000, and more preferably 1:0 to 50.
Further, the solid obtained in the second step is returned to the second step by an equal-volume impregnation method or an excess impregnation method, or the solid obtained in the third step is returned to the second step by an equal-volume impregnation method or an excess impregnation method.
Further, the coating mass fraction of copper is from 0.1 to 50%, more preferably from 10 to 40%, based on the total mass of the catalyst.
Further, the copper source is an organic copper source including, but not limited to, copper citrate, copper formate, copper acetate and/or an inorganic copper source including, but not limited to, one or more of copper chloride, copper phosphate, copper nitrate, copper sulfate.
Further, the precipitant is alkali and/or alkaline salt, the alkali includes but is not limited to potassium hydroxide, sodium hydroxide, ammonia water, the alkaline salt includes but is not limited to potassium carbonate, sodium carbonate, ammonium carbonate, potassium bicarbonate, sodium sulfide, urea.
Further, the oxide carrier is selected from one or more of alumina, silica, titania, zirconia, calcia and magnesia in a solid state and/or a sol state.
The invention also provides an application of the catalyst containing the multivalent copper active component in preparing cyclohexene through dehydration of cyclohexanol, wherein the reaction is carried out in a fixed bed, a fluidized bed or a slurry bed, the reaction temperature is 150-400 ℃, the preferable temperature is 200-300 ℃, the reaction pressure is 0.1-5.0 MPa, the preferable pressure is 0.1-2.0 MPa, and the volume space velocity is 0.1-10 h-1Preferably 0.5 to 2.5 hours-1。
Compared with the prior art, the catalyst containing the multivalent copper active component, the preparation method and the application have the following advantages:
in the current industrial production, concentrated sulfuric acid or concentrated phosphoric acid is generally used as a catalyst in the production of cyclohexene by the liquid phase dehydration of cyclohexanol. The cyclohexene yield is lower, and is generally only 46-56%; intermittent reaction is mostly adopted, so that the production efficiency is low; the sulfuric acid phosphoric acid or the phosphoric acid has serious corrosion to equipment and higher requirements on production equipment; the waste acid amount is large, the treatment is complex and the cost is high; the carbonization in the reaction process is serious, the number of byproducts is large, the subsequent treatment process is complicated and the environment is polluted.
According to the invention, the copper-containing active component solution and the precipitator solution are precipitated on the oxide carrier, and the precipitation temperature and the precipitation pH value are accurately controlled, so that the prepared multivalent copper catalyst has higher cyclohexanol conversion rate and cyclohexene selectivity after the reduction treatment in the reducing atmosphere; the catalyst is in a solid form, can be suitable for continuous production operations of fixed beds, fluidized beds, slurry beds and the like, and has less amount of generated waste catalyst, and the waste catalyst is simple and easy to recycle; compared with the concentrated sulfuric acid process used in the existing industry, the invention improves the production efficiency and reduces the production cost and the environmental pollution.
Drawings
FIG. 1 is an X-ray diffraction pattern of a catalyst containing a multi-valence copper active component according to example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of a catalyst containing a multi-valence copper active component according to example 2 of the present invention;
fig. 3 is an X-ray diffraction pattern of a catalyst containing a multi-valence copper active component according to example 3 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
According to the weight percentage of copper chloride: copper chloride and water were sufficiently stirred and dissolved at a molar ratio of 1:50 to obtain a solution a. Urea: the solution B was obtained by dissolving water in a molar ratio of 1:50 with stirring. According to the weight ratio of copper: deionized water was prepared at a mass ratio of 1:10, copper: silicon oxide was prepared in a mass ratio of 1:10, and deionized water was mixed with the silicon oxide and stirred to obtain solution C.
Solution A and solution B were added dropwise to solution C simultaneously at a precipitation temperature of 50 ℃ and pH controlled at 7.0. After the dropwise addition, the mixture is crystallized for 6 hours at the temperature of 50 ℃, centrifugally separated, and the obtained solid product is dried for 12 hours at the temperature of 50 ℃ under the vacuum condition, and the dried solid is roasted for 5 hours at the temperature of 450 ℃. Reducing for 5h at 250 ℃ and 1.0MPa in a pure hydrogen atmosphere at the airspeed of 5000h-1Obtaining the catalyst 0.3Cu-1.0CuCl containing the multivalent copper active component2/SiO2. The X-ray diffraction pattern is shown in FIG. 1.
The prepared catalyst containing the multivalent copper active component is used in the reaction of dehydrating cyclohexanol serving as a raw material to prepare cyclohexene, the reaction temperature is 220 ℃, the pressure is 0.1MPa, and the airspeed is 1.0h-1The reaction results are shown in Table 1.
Example 2
According to the weight percentage of copper nitrate: the solution a was obtained by dissolving water in a molar ratio of 1:30 with stirring. Sodium carbonate: the solution B was obtained by dissolving water in a molar ratio of 1:50 with stirring. According to the weight ratio of copper: deionized water is prepared according to the mass ratio of 1:25, and the weight ratio of copper: silicon oxide was prepared in a mass ratio of 1:20, and deionized water and alumina were mixed and stirred to obtain solution C.
Solution A and solution B were added dropwise to solution C simultaneously at a precipitation temperature of 70 ℃ and pH controlled at 7.0. After the dropwise addition, crystallizing at 70 ℃ for 6h, performing centrifugal separation, drying the obtained solid product in air at 50 ℃ for 12h, and roasting the dried solid at 450 ℃ for 5h to obtain a solid D, wherein the weight ratio of copper: preparing a certain amount of copper sulfate according to the mass ratio of silicon oxide to silicon oxide of 1:20, wherein the weight ratio of copper sulfate: fully stirring and dissolving water in a mass ratio of 1:1.5 to obtain a solution E, impregnating the solid D with the solution E in an equal volume, aging for 12h, drying the obtained solid product in air at 50 ℃ for 12h, and roasting the dried solid at 450 ℃ for 5 h. Reducing for 5h at 250 ℃ and 1.0MPa in a pure hydrogen atmosphere at the airspeed of 5000h-1Obtaining the catalyst containing the multi-valence copper active component, namely 0.1Cu-0.3Cu (NO)3)2-1.0CuSO4/SiO2. The X-ray diffraction pattern is shown in FIG. 2.
Cyclohexanol is used as a raw material, the reaction is carried out at 220 ℃, the pressure is 0.1MPa, and the space velocity is 1.0h-1The reaction results are shown in Table 1.
Example 3
According to the weight percentage of the copper citrate: the solution a was obtained by dissolving water in a molar ratio of 1:60 with stirring. Urea: the solution B was obtained by dissolving water in a molar ratio of 1:30 with stirring. According to the weight ratio of copper: preparing a certain amount of deionized water according to the mass ratio of 1:10, wherein the mass ratio of copper: a certain amount of silicon oxide was prepared in a mass ratio of 1:15, and deionized water was mixed with the silicon oxide and stirred to obtain solution C.
Solution A and solution B were added dropwise to solution C simultaneously at a precipitation temperature of 80 ℃ and pH controlled at 7.0. After the dropwise addition, the mixture is crystallized for 6 hours at the temperature of 80 ℃, centrifugally separated, and the obtained solid product is dried for 12 hours at the temperature of 50 ℃ under vacuum condition, and the dried solid is roasted for 5 hours at the temperature of 150 ℃. Reducing for 5h at 250 ℃ and 1.0MPa in a pure hydrogen atmosphere at the airspeed of 5000h-1Obtaining the catalyst 0.15Cu-1.0C containing the multi-valence copper active component6H4Cu2O7/SiO2. The X-ray diffraction pattern is shown in FIG. 3.
Cyclohexanol is used as a raw material, the reaction is carried out at 220 ℃, the pressure is 0.1MPa, and the space velocity is 1.0h-1The reaction results are shown in Table 1.
As shown in fig. 1, 2, and 3, the X-ray diffraction patterns of the catalysts obtained in example 1, example 2, and example 3 revealed that the catalyst containing the multivalent copper active component contained 0-valent copper, oxidized copper, and an acid group. The 0-valence copper and the oxidation-state copper in the catalyst provide metal catalytic activity to promote and activate hydrogen on a six-membered ring in cyclohexanol, and meanwhile, acid radicals provide acid catalytic activity to promote dehydration reaction of hydroxyl in cyclohexanol. The multivalent copper and the acid radical act synergistically to promote the dehydration of cyclohexanol to produce cyclohexene.
TABLE 1 results of examples 1-3 in catalytic cyclohexene preparation by dehydration of cyclohexanol
From table 1, it is known that the catalyst of the present invention can realize the dehydration of cyclohexanol to prepare cyclohexene at a low temperature of 220 ℃ with a high selectivity of > 97% and a high conversion rate of > 87% or even > 99%. The catalyst has better catalytic action on the preparation of cyclohexene by cyclohexanol dehydration.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A catalyst containing a multivalent copper active component, characterized in that: the catalyst has a composition of Cuh 0-Cum nXaYbZcThe copper-base alloy material comprises a component containing 0-valence copper and n-valence copper, wherein n is more than 0, and the value ranges of h and m are 1-10; a. the value ranges of b and c are 0-30; x, Y, Z are eachAn inorganic acid group and/or an organic acid group; s is one or more oxide carriers;
the catalyst is applied to preparing cyclohexene by cyclohexanol dehydration.
2. The catalyst containing a multivalent copper active component according to claim 1, characterized in that: inorganic acid groups include, but are not limited to, phosphate, phosphite, nitrate, sulfate, bisulfate, sulfite, hydrochloride, borate.
3. The catalyst containing a multivalent copper active component according to claim 1, characterized in that: organic acid groups include, but are not limited to, formate, acetate, oxalate, propionate, citrate.
4. A process for preparing a catalyst comprising a multivalent copper active component according to any of claims 1 to 3, wherein: the method comprises the following steps:
the method comprises the following steps: mixing at least one copper source with water to obtain a solution A; mixing a precipitator and water to obtain a solution B, wherein the precipitation temperature is 10-100 ℃, the pH of the precipitation solution is 5.0-13.0, and the precipitation aging time is 2-12 h;
step two: precipitating copper in the solution A in the solution B, coating the copper on an oxide carrier, separating, drying, and roasting at 250-850 ℃ to obtain a solid, wherein the drying temperature is 30-150 ℃, the drying atmosphere is air, inert gas or vacuum, the drying time is 6-48 h, the roasting condition is air atmosphere, inert gas atmosphere or vacuum, and the roasting time is 2-12 h;
step three: reducing the solid obtained in the step two in a reducing atmosphere to obtain the catalyst containing the multivalent copper active component, wherein the reducing temperature is 180-300 ℃, the reducing pressure is 0.1-5.0 MPa, and the volume space velocity is 100-100000 h-1The reduction time is 1-10 hours, and the reduction atmosphere is hydrogen, carbon monoxide or a mixed gas of hydrogen, carbon monoxide and inert gas in any proportion.
5. The method of claim 4, wherein the method comprises the steps of: and (4) returning the solid obtained in the step two to the step two through an equal-volume impregnation method or an excess impregnation method, or returning the solid obtained in the step three to the step two through an equal-volume impregnation method or an excess impregnation method.
6. The method of claim 4, wherein the method comprises the steps of: the coating mass fraction of copper on the oxide carrier is 0.1-50% based on the total mass of the catalyst.
7. The method of claim 4, wherein the method comprises the steps of: the copper source is an organic copper source including but not limited to copper citrate, copper formate, copper acetate and/or an inorganic copper source including but not limited to one or more of copper chloride, copper phosphate, copper nitrate, copper sulfate.
8. The method of claim 4, wherein the method comprises the steps of: the precipitant is alkali and/or alkaline salt, the alkali includes but is not limited to potassium hydroxide, sodium hydroxide, ammonia water, the alkaline salt includes but is not limited to potassium carbonate, sodium carbonate, ammonium carbonate, potassium bicarbonate, sodium sulfide, urea.
9. The method of claim 4, wherein the method comprises the steps of: the oxide carrier is selected from one or more of alumina, silica, titania, zirconia, calcia and magnesia in a solid state and/or a sol state.
10. The application of a catalyst containing a multivalent copper active component in preparing cyclohexene by cyclohexanol dehydration is characterized in that: the reaction is carried out in a fixed bed, a fluidized bed or a slurry bed, and the reaction conditions are as follows: the reaction temperature is 150-400 ℃, the reaction pressure is 0.1-5.0 MPa, and the volume airspeed is 0.1-10 h-1。
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