CN107519881B - Preparation method of cyclohexyl acetate hydrogenation catalyst, prepared hydrogenation catalyst and cyclohexyl acetate hydrogenation method - Google Patents
Preparation method of cyclohexyl acetate hydrogenation catalyst, prepared hydrogenation catalyst and cyclohexyl acetate hydrogenation method Download PDFInfo
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- 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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- 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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a preparation method of a cyclohexyl acetate hydrogenation catalyst, the prepared hydrogenation catalyst and a hydrogenation method of cyclohexyl acetate, wherein the preparation method comprises the following steps: a. adding a first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt and a first alkaline solution into a buffer solution with the pH value of 6-10 in a concurrent flow manner, so that the aluminum salt and the zinc salt form a precipitate at the pH value of 6-10 to obtain a precipitate slurry; wherein the molar ratio of the aluminum element to the zinc element in the first aqueous solution is 1: (0.2-5); b. adding a second aqueous solution containing water-soluble copper salt and water-soluble zinc salt and a second alkaline solution into the precipitation slurry in a concurrent flow manner, so that the copper salt and the zinc salt form a precipitate at a pH value of 6-10, and obtaining a cyclohexyl acetate hydrogenation catalyst; wherein the molar ratio of the copper element to the zinc element in the second aqueous solution is (1.5-15): 1. the hydrogenation catalyst prepared by the method can reduce the content of byproducts in the cyclohexyl acetate hydrogenation product.
Description
Technical Field
The invention relates to a preparation method of a cyclohexyl acetate hydrogenation catalyst, the prepared hydrogenation catalyst and a hydrogenation method of cyclohexyl acetate.
Background
Cyclohexanol is an important solvent and an organic synthesis intermediate, and is widely used in the production processes of paint, pesticide, dye, aviation lubricating oil, grease, wax, stripping, decontamination, spot removal and the like as the solvent. Cyclohexanol can be dehydrogenated to produce cyclohexanone with high selectivity, and can be used for producing caprolactam monomer, adipic acid and other chemicals.
The cyclohexanol production process mainly comprises a phenol hydrogenation method, a cyclohexane oxidation method, a cyclohexene hydration method and the like, wherein the phenol hydrogenation method is used for directly preparing cyclohexanol by hydrogenating phenol, the selectivity and the conversion rate can exceed 99%, but the cyclohexanol production process has the defects of high phenol price and low economic benefit. The cyclohexane oxidation method uses benzene as a raw material, cyclohexane is obtained by hydrogenation, and then cyclohexanol and cyclohexanone are obtained by oxidation. The cyclohexene hydration method was first developed successfully by Asahi Kasei Corp, where benzene was first selectively hydrogenated to produce cyclohexene and a small amount of cyclohexane, and the separated cyclohexene was then subjected to hydration reaction under a molecular sieve catalyst to directly produce cyclohexanone. The product obtained by the method has good quality, less three-waste discharge and safer production device than the oxidation process. The disadvantages are that: the single-pass conversion rate of the cyclohexene hydration reaction is only about 10 percent, the cyclohexene needs a large amount of circulation, and the investment and energy consumption are large.
A brand-new method for producing cyclohexanol is provided by the institute of petrochemical engineering science and technology, and is characterized in that pure cyclohexene or a cyclohexene mixture obtained by selective hydrogenation of benzene and acetic acid are subjected to esterification reaction to obtain cyclohexyl acetate, and then the cyclohexyl acetate is hydrogenated to generate cyclohexanol and ethanol. In the method, the esterification reaction has good adaptability to raw materials, the esterification and hydrogenation steps have high conversion rate and selectivity, and simultaneously, the ethanol is co-produced, so the technical economy is good.
Because the method is innovative, the hydrogenation catalyst for the hydrogenation process of the intermediate product, namely the cyclohexyl acetate, is not reported in documents, and the specific reaction formula is as follows:
the prior literature is commonly provided with other ester hydrogenation catalysts such as dimethyl oxalate, dimethyl adipate, maleate and the like.
Chinese patent CN 101474561A discloses a catalyst for producing glycol by oxalate hydrogenation, the active components of the catalyst comprise copper, copper oxide and mixture thereof, the auxiliary agent is one of zinc, manganese, barium, nickel, chromium and iron, the carrier is alumina, the catalyst is prepared by one-step coprecipitation method, the precipitate is washed, dried and roasted, then graphite powder is added for tabletting and molding, and the catalyst is applied to oxalate hydrogenation process, and the catalyst has higher conversion rate but about 85% selectivity.
Chinese patent CN 101138726A discloses a copper catalyst for industrial production of hexanediol, which is prepared by a coprecipitation method, the preparation method of the catalyst comprises the steps of preparing aqueous solution from copper nitrate and zinc nitrate, dispersing aluminum hydroxide powder in water to form slurry, mixing the copper-zinc mixed aqueous solution and the slurry containing aluminum hydroxide, and neutralizing the mixture with alkali solution containing sodium hydroxide and sodium carbonate until the pH value is 7-8, wherein the obtained catalyst has high activity for preparing 1, 6-hexanediol by hydrogenation of dimethyl adipate.
Chinese patent CN102125843A discloses a method for preparing a catalyst with silicon as a carrier, which comprises using urea as an alkaline precipitant, preparing an aqueous solution from urea and copper nitrate, mixing the aqueous solution with silica sol to obtain a slurry, stirring and heating the slurry in a high-pressure kettle, and generating ammonia water by leaning against a line to obtain a relatively uniform copper oxide precipitate. However, the catalyst prepared by the preparation method has poor application effect in oxalate hydrogenation conversion, and the patent does not consider the problem of improving the reasonable distribution of copper elements on the surface and in the bulk phase of the catalyst.
When the cyclohexyl acetate hydrogenation catalyst is used for catalyzing the cyclohexyl acetate hydrogenation reaction, alumina is used as a carrier, a copper component is used as an active component and an auxiliary agent, the existing hydrogenation catalyst preparation method usually adopts a one-step precipitation method, and a part of the copper component and the alumina are positioned in the catalyst together and cannot contact with reactants to participate in the reaction.
Disclosure of Invention
The invention aims to provide a preparation method of a cyclohexyl acetate hydrogenation catalyst, the prepared hydrogenation catalyst and a cyclohexyl acetate hydrogenation method.
In order to achieve the above object, the present invention provides a preparation method of a cyclohexyl acetate hydrogenation catalyst, comprising: a. adding a first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt and a first alkaline solution into a buffer solution with the pH value of 6-10 in a concurrent flow manner, so that the aluminum salt and the zinc salt form a precipitate at the pH value of 6-10 to obtain a precipitate slurry; wherein the molar ratio of the aluminum element to the zinc element in the first aqueous solution is 1: (0.2-5); b. adding a second aqueous solution containing water-soluble copper salt and water-soluble zinc salt and a second alkaline solution into the precipitation slurry in a concurrent flow manner, so that the copper salt and the zinc salt form a precipitate at a pH value of 6-10, and obtaining a cyclohexyl acetate hydrogenation catalyst; wherein the molar ratio of the copper element to the zinc element in the second aqueous solution is (1.5-15): 1; wherein, based on the amount of elemental substances and the total amount of aluminum, copper and zinc, the content of copper in the cyclohexyl acetate hydrogenation catalyst is 10-70 mol%, the content of zinc is 10-60 mol%, and the content of aluminum is 10-50 mol%.
Preferably, the buffer solution is at least one selected from the group consisting of an alkali metal dibasic phosphate-strong base buffer solution, an alkali metal monobasic phosphate-strong base buffer solution, an acetic acid-aqueous ammonia buffer solution, a formic acid-aqueous ammonia buffer solution, and an alkali metal carbonate-aqueous ammonia buffer solution.
Preferably, the first and second alkaline solutions are each independently selected from at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, and ammonia.
Preferably, the mass concentration of the solute in the first and second alkaline solutions is each independently 0.1 to 2 moles/liter.
Preferably, in the first aqueous solution, the mass concentration of the aluminum salt is 10 to 30 mass%, and the mass concentration of the zinc salt is 5 to 25 mass%; in the second aqueous solution, the mass concentration of the copper salt is 5-25 mass%, and the mass concentration of the zinc salt is 5-25 mass%.
Preferably, the water-soluble aluminum salt is aluminum sulfate and/or aluminum nitrate, the water-soluble copper salt is copper sulfate and/or copper nitrate, and the water-soluble zinc salt is zinc sulfate and/or zinc nitrate.
Preferably, in step a, the aluminium salt and the zinc salt are caused to form a precipitate at a pH between 6 and 8; in step b, the copper and zinc salts are precipitated at a pH of between 6 and 8.
Preferably, the preparation method further comprises: and c, sequentially aging, filtering, washing, drying and roasting the mixed slurry obtained by precipitation in the step b to obtain the cyclohexyl acetate hydrogenation catalyst.
Preferably, the aging temperature is 40-60 ℃, and the aging time is 3-10 hours; the drying temperature is 60-150 ℃, and the drying time is 12-48 hours; the roasting temperature is 300-700 ℃, and the roasting time is 2-10 hours.
The invention also provides a hydrogenation catalyst prepared by the preparation method provided by the invention.
The invention also provides a hydrogenation method of cyclohexyl acetate, which comprises the following steps: the hydrogenation catalyst provided by the invention is adopted to carry out the hydrogenation reaction of the cyclohexyl acetate.
The invention adopts a step precipitation method to precipitate aluminum salt firstly and then precipitate copper salt later, so that the copper component in the obtained hydrogenation catalyst can be positioned on the outer layer of the catalyst, the conversion rate and the selectivity of the reaction are improved, and the production of byproducts is reduced.
Because copper ions are completely precipitated when the pH value is about 5, and zinc ions generally begin to precipitate when the pH value is more than 5, copper hydroxide is often precipitated firstly and then precipitated zinc hydroxide is coated on the surface of the copper hydroxide if alkali liquor is dripped without controlling the pH value, and a zinc component also migrates to the surface of the catalyst in the process of forming and roasting the catalyst. Therefore, the method adopts the buffer solution to control the copper ions and the zinc ions to generate precipitation between the pH value of 5-9, so that the copper component and the zinc component in the catalyst are mixed more uniformly, the conversion rate and the selectivity of the hydrogenation reaction are improved, in addition, part of the zinc ions and aluminum ions are precipitated firstly, so that part of the zinc component in the obtained precipitate is positioned in the copper component, the copper component on the surface of the catalyst is prevented from being coated by roasting the zinc component in the obtained hydrogenation catalyst, the conversion rate and the selectivity of the reaction are improved, and the production of byproducts is reduced.
The method adopts a buffer solution as a base solution, titrates a metal salt solution and an alkali liquor to be precipitated into the buffer solution, and can control the pH value of the precipitated slurry to fluctuate within +/-0.5 in the titration process, thereby enabling the components in the catalyst to be distributed more uniformly.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a cyclohexyl acetate hydrogenation catalyst, which comprises the following steps: a. adding a first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt and a first alkaline solution into a buffer solution with the pH value of 6-10 in a concurrent flow manner, so that the aluminum salt and the zinc salt form a precipitate at the pH value of 6-10 to obtain a precipitate slurry; wherein the molar ratio of the aluminum element to the zinc element in the first aqueous solution is 1: (0.2-5), preferably 1 (0.5-3.5); b. adding a second aqueous solution containing water-soluble copper salt and water-soluble zinc salt and a second alkaline solution into the precipitation slurry in a concurrent flow manner, so that the copper salt and the zinc salt form a precipitate at a pH value of 6-10, and obtaining a cyclohexyl acetate hydrogenation catalyst; wherein the molar ratio of the copper element to the zinc element in the second aqueous solution is (1.5-15): 1, preferably (2-8): 1; wherein, based on the amount of elemental substances and the total amount of aluminum, copper and zinc, the content of copper in the cyclohexyl acetate hydrogenation catalyst is 10-70 mol%, the content of zinc is 10-60 mol%, and the content of aluminum is 10-50 mol%.
According to the present invention, the buffer solution is well known to those skilled in the art, and may be, for example, at least one selected from the group consisting of an alkali metal dibasic phosphate-strong base buffer solution, an alkali metal monobasic phosphate-strong base buffer solution, an acetic acid-aqueous ammonia buffer solution, a formic acid-aqueous ammonia buffer solution, and an alkali metal carbonate-aqueous ammonia buffer solution.
The present invention uses a buffer solution to control the pH of the slurry during the precipitation process, and in one embodiment, the pH of the slurry can be controlled to be within X + -0.5, preferably within X + -0.3, wherein X is a value of 6-10, and X + -0.5 is also within a range of 6-10.
According to the present invention, the alkaline solution is well known to those skilled in the art, for example, the first alkaline solution and the second alkaline solution may each independently be selected from at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide and ammonia water, and the amount concentration of the solute substance in the first alkaline solution and the second alkaline solution may each independently be 0.1 to 2 moles/liter. In addition, the first basic solution and the second basic solution are generally used in amounts sufficient to completely precipitate the aluminum salt and the zinc salt in the first aqueous solution and the copper salt and the zinc salt in the second aqueous solution, and for example, 1 mole of copper salt is required for precipitation of 1 mole of carbonate, 2 moles of bicarbonate or 2 moles of hydroxide. In the specific experimental process, in the steps a and b, if the adding speed and the adding amount of the first aqueous solution and the second aqueous solution can control the pH value of the slurry, when the aqueous solution containing the water-soluble salts is added, the adding of the first aqueous solution and the second aqueous solution is stopped (if the adding is not stopped, the pH value of the precipitation slurry is increased), at this time, the water-soluble salts can be completely precipitated, and the yield of the catalyst is generally 95-98% when the precipitation is completed according to the preparation amount of 100 g of the catalyst in terms of the yield of the catalyst product.
According to the present invention, water-soluble aluminum salts, copper salts and zinc salts are well known to those skilled in the art, for example, the water-soluble aluminum salt may be aluminum sulfate and/or aluminum nitrate, the water-soluble copper salt may be copper sulfate and/or copper nitrate, the water-soluble zinc salt may be zinc sulfate and/or zinc nitrate, the mass concentration of the aluminum salt may be 10 to 30 mass%, and the mass concentration of the zinc salt may be 5 to 25 mass% in the first aqueous solution; in the second aqueous solution, the mass concentration of the copper salt may be 5 to 25 mass%, and the mass concentration of the zinc salt may be 5 to 25 mass%.
According to the present invention, in order to make the precipitation distribution of the aluminum salt and the zinc salt and the copper salt and the zinc salt more uniform, in step a, the aluminum salt and the zinc salt may be precipitated at a pH of 6 to 8; in step b, the copper and zinc salts may be precipitated at a pH between 6 and 8.
According to the invention, the mixed slurry obtained by precipitation generally needs to be subjected to subsequent treatment to become a really usable catalyst, and the preparation method of the invention can also comprise the following steps: and c, sequentially aging, filtering, washing, drying and roasting the mixed slurry obtained by precipitation in the step b to obtain the cyclohexyl acetate hydrogenation catalyst. In order to complete the reaction, the precipitation slurry is stabilized in a static state at a temperature, i.e., aging, which may be 40 to 60 ℃ for 3 to 10 hours, for a certain period of time. Filtration, washing, drying and calcination are well known to those skilled in the art, and the temperature for drying in the present invention may be 60 to 150 ℃, preferably 90 to 120 ℃, and the time for drying may be 12 to 48 hours; the roasting temperature can be 300-700 ℃, preferably 350-450 ℃, and the roasting time can be 2-10 hours.
The invention also provides a hydrogenation catalyst prepared by the preparation method. The hydrogenation catalyst can also be used for hydrogenation reaction of other monoacid ester or diacid ester.
The invention also provides a hydrogenation method of cyclohexyl acetate, which comprises the following steps: the hydrogenation catalyst provided by the invention is adopted to carry out the hydrogenation reaction of the cyclohexyl acetate. The conditions of the cyclohexyl acetate hydrogenation reaction comprise: the temperature is 150 ℃ and 400 ℃, the pressure is 1-20 MPa, and the mass space velocity of the cyclohexyl acetate is 0.1-20 hours-1The molar ratio of hydrogen to ester is 1-1000.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, the reagents used in the examples of the present invention and comparative examples were all analytical grade.
In the test examples and test comparative examples of the present invention:
the conversion rate of the cyclohexyl acetate is (1-the mole number of unreacted cyclohexyl acetate/(the mole number of unreacted cyclohexyl acetate + the mole number of cyclohexane + the mole number of cyclohexanol + the mole number of ethyl cyclohexyl ether + the mole number of methyl cyclopentanol) × 100%;
cyclohexanol selectivity is × 100% (moles cyclohexanol/(moles cyclohexane + moles cyclohexanol + moles ethylcyclohexyl ether + moles methylcyclopentanol);
the cyclohexane yield is × 100 percent (cyclohexane mole number/(unreacted cyclohexyl acetate mole number + cyclohexane mole number + cyclohexanol mole number + ethyl cyclohexyl ether mole number + methyl cyclopentanol mole number);
the yield of methylcyclopentanol is 100% (mol of methylcyclopentanol/(mol of unreacted cyclohexyl acetate + mol of cyclohexane + mol of cyclohexanol + mol of ethyl cyclohexyl ether + mol of methylcyclopentanol) × 100%.
Example 1
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:4: 2.
50 ml of 0.2 mol/l sodium dihydrogen phosphate aqueous solution was prepared, and the solution was titrated with 0.1 mol/l sodium hydroxide aqueous solution to pH 7.0, and 120 ml of water was added to obtain a buffer solution A. A0.5 mol/l aqueous solution E of sodium hydroxide was prepared. 64.80 grams of copper nitrate trihydrate was weighed and dissolved in 105.20 grams of deionized water to yield 170.00 grams of aqueous copper nitrate solution. 79.79 g of zinc nitrate hexahydrate is weighed into 100.21 g of deionized water to obtain 180.00 g of zinc nitrate aqueous solution. 50.31 grams of aluminum nitrate nonahydrate was weighed into 109.69 grams of deionized water to yield 160.00 grams of aqueous aluminum nitrate solution. The aqueous solution of zinc nitrate was divided into 90 g and 90 g, and the aqueous solution of aluminum nitrate and the aqueous solution of copper nitrate were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the aqueous solution E in a cocurrent manner under the condition of rapid stirring, controlling the pH of the slurry to be 7.0 +/-0.5 by controlling the dropping speed of the first aqueous solution B and the aqueous solution E, and stopping dropwise adding the sodium hydroxide aqueous solution E at the same time after the dropwise adding of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 7.5 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst # 1.
Example 2
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:2: 4.
25 g of formic acid was dissolved in 80 ml of water, titrated with 15 mass% aqueous ammonia to pH 6.5, and added to 150 ml of water to obtain a buffer solution A. 0.5 mol/l of aqueous sodium carbonate solution E was prepared. 70.55 grams of copper nitrate trihydrate were weighed and dissolved in 119.45 grams of deionized water to yield 190.00 grams of aqueous copper nitrate solution. 43.44 grams of zinc nitrate hexahydrate was weighed into 96.56 grams of deionized water to yield 140.00 grams of aqueous zinc nitrate solution. 109.54 g of aluminum nitrate nonahydrate was weighed into 100.46 g of deionized water to obtain 210.00 g of aqueous aluminum nitrate solution. The aqueous solution of zinc nitrate was divided into two parts of 90 g and 50 g, and the aqueous solution of aluminum nitrate and the aqueous solution of copper nitrate were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the aqueous solution E in a parallel flow manner under the condition of rapid stirring, controlling the pH of the slurry to be 6.5 +/-0.5 by controlling the dropwise adding speed of the first aqueous solution B and the aqueous solution E, and stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 7.5 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst 2 #.
Example 3
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:4: 2.
30 g of glacial acetic acid was dissolved in 100 ml of deionized water, and the solution was titrated with 15 mass% aqueous ammonia to pH 7.0, and water was added to 150 ml to obtain buffer solution A. A0.5 mol/l aqueous solution E of sodium hydroxide was prepared. 66.81 grams of copper sulfate pentahydrate were weighed out and dissolved in 113.19 grams of deionized water to yield 180.00 grams of aqueous copper nitrate solution. 79.79 g of zinc nitrate hexahydrate is weighed into 100.21 g of deionized water to obtain 180.00 g of zinc nitrate aqueous solution. 50.31 grams of aluminum nitrate nonahydrate was weighed into 109.69 grams of deionized water to yield 160.00 grams of aqueous aluminum nitrate solution. The aqueous solution of zinc nitrate was divided into 120 g and 60 g, and the aqueous solution of aluminum nitrate and the aqueous solution of copper nitrate were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the aqueous solution E in a cocurrent manner under the condition of rapid stirring, controlling the pH of the slurry to be 7.0 +/-0.5 by controlling the dropping speed of the first aqueous solution B and the aqueous solution E, and stopping dropwise adding the sodium hydroxide aqueous solution E at the same time after the dropwise adding of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 7.5 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst # 3.
Example 4
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:2: 4.
15 g of anhydrous sodium carbonate was dissolved in 150 ml of water, and the solution was titrated with a 15 mass% aqueous ammonia solution to a pH of 7.5 to obtain a buffer solution A. A0.5 mol/l aqueous solution E of sodium hydroxide was prepared. 70.55 grams of copper nitrate trihydrate were weighed and dissolved in 119.45 grams of deionized water to yield 190.00 grams of aqueous copper nitrate solution. 43.44 grams of zinc nitrate hexahydrate was weighed into 96.56 grams of deionized water to yield 140.00 grams of aqueous zinc nitrate solution. 58.28 g of aluminum sulfate was weighed and dissolved in 141.72 g of deionized water to obtain 200.00 g of an aqueous aluminum nitrate solution. The aqueous solution of zinc nitrate was divided into two parts of 70 g and 70 g, and the aqueous solution of aluminum nitrate and the aqueous solution of copper nitrate were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the sodium hydroxide aqueous solution E in a cocurrent manner under the condition of rapid stirring, controlling the pH of the slurry to be 7.5 +/-0.5 by controlling the dropping speed of the first aqueous solution B and the aqueous solution E, and stopping dropping the aqueous solution E at the same time after the dropping of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 8.0 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst # 4.
Example 5
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:4: 2.
50 ml of 0.2 mol/l dipotassium phosphate aqueous solution is prepared, the pH value is titrated to 8.0 by 0.1 mol/l sodium hydroxide aqueous solution, and 120 ml of water is added to obtain a buffer solution A. 0.2 mol/l of aqueous sodium carbonate solution E was prepared. 64.80 grams of copper nitrate trihydrate was weighed and dissolved in 105.20 grams of deionized water to yield 170.00 grams of aqueous copper nitrate solution. 79.79 g of zinc nitrate hexahydrate is weighed into 100.21 g of deionized water to obtain 180.00 g of zinc nitrate aqueous solution. 50.31 grams of aluminum nitrate nonahydrate was weighed into 109.69 grams of deionized water to yield 160.00 grams of aqueous aluminum nitrate solution. The aqueous solution of zinc nitrate was divided into 100 g and 80 g, and the aqueous solution of aluminum nitrate and the aqueous solution of copper nitrate were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the aqueous solution E in a parallel flow manner under the condition of rapid stirring, controlling the pH of the slurry to be 8.0 +/-0.5 by controlling the dropwise adding speed of the first aqueous solution B and the aqueous solution E, and stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 8.0 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst # 5.
Example 6
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:2: 4.
50 ml of 0.3 mol/l sodium dihydrogen phosphate aqueous solution was prepared, and the solution was titrated with 0.1 mol/l sodium hydroxide aqueous solution to pH 7.5, and 120 ml of water was added to obtain a buffer solution A. 0.5 mol/l of aqueous sodium carbonate solution E was prepared. 70.55 grams of copper nitrate trihydrate were weighed and dissolved in 119.45 grams of deionized water to yield 190.00 grams of aqueous copper nitrate solution. 43.44 grams of zinc nitrate hexahydrate was weighed into 96.56 grams of deionized water to yield 140.00 grams of aqueous zinc nitrate solution. 109.54 g of aluminum nitrate nonahydrate was weighed into 100.46 g of deionized water to obtain 210.00 g of aqueous aluminum nitrate solution. The aqueous zinc nitrate solution was divided into 100 g and 40 g, and the aqueous aluminum nitrate solution and the aqueous copper nitrate solution were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the aqueous solution E in a parallel flow manner under the condition of rapid stirring, controlling the pH of the slurry to be 7.5 +/-0.5 by controlling the dropwise adding speed of the first aqueous solution B and the aqueous solution E, and stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 8.0 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst 6 #.
Example 7
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:2: 4.
25 g of glacial acetic acid was dissolved in 100 ml of deionized water, and the solution was titrated with 20 mass% aqueous ammonia to pH 7.0, and water was added to 150 ml to obtain a buffer solution A. A0.5 mol/l aqueous solution E of sodium hydroxide was prepared. 70.55 grams of copper nitrate trihydrate were weighed and dissolved in 119.45 grams of deionized water to yield 190.00 grams of aqueous copper nitrate solution. 43.44 grams of zinc nitrate hexahydrate was weighed into 96.56 grams of deionized water to yield 140.00 grams of aqueous zinc nitrate solution. 109.54 g of aluminum nitrate nonahydrate was weighed into 100.46 g of deionized water to obtain 210.00 g of aqueous aluminum nitrate solution. The aqueous solution of zinc nitrate was divided into two parts of 70 g and 70 g, and the aqueous solution of aluminum nitrate and the aqueous solution of copper nitrate were added, respectively, to obtain a first aqueous solution B containing a water-soluble aluminum salt and a water-soluble zinc salt and a second aqueous solution C containing a water-soluble copper salt and a water-soluble zinc salt. And (3) putting the buffer solution A as a base solution into a 1-liter beaker, dropwise adding the first aqueous solution B and the aqueous solution E in a parallel flow manner under the condition of rapid stirring, controlling the pH of the slurry to be 7.0 +/-0.5 by controlling the dropwise adding speed of the first aqueous solution B and the aqueous solution E, and stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the first aqueous solution B is finished to obtain a precipitation slurry D. And (3) dropwise adding the second aqueous solution C and the aqueous solution E in a parallel flow manner under rapid stirring by using the precipitation slurry D as a base solution, controlling the pH value of the slurry to be 7.5 +/-0.5 by controlling the dropwise adding speed of the second aqueous solution C and the aqueous solution E, stopping dropwise adding the aqueous solution E at the same time after the dropwise adding of the second aqueous solution C is finished, continuously stirring for 1 hour, and aging for 3 hours at the temperature of 45 ℃. And (3) carrying out suction filtration and washing on the aged precipitation slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst No. 7.
Comparative example 1
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:4: 2.
A0.5 mol/l aqueous solution of sodium hydroxide was prepared. 64.80 grams of copper nitrate trihydrate was weighed and dissolved in 105.20 grams of deionized water to yield 170.00 grams of aqueous copper nitrate solution. 79.79 g of zinc nitrate hexahydrate is weighed into 100.21 g of deionized water to obtain 180.00 g of zinc nitrate aqueous solution. 50.31 grams of aluminum nitrate nonahydrate was weighed into 109.69 grams of deionized water to yield 160.00 grams of aqueous aluminum nitrate solution. Mixing the copper nitrate aqueous solution, the zinc nitrate aqueous solution and the aluminum nitrate aqueous solution to be used as a base solution, dropwise adding a sodium hydroxide aqueous solution under rapid stirring to form a precipitation slurry, and adding the sodium hydroxide aqueous solution until the pH value of the precipitation slurry is 7.5. After stirring was continued for 1 hour at the end of the cocurrent flow, the mixture was aged at 45 ℃ for 3 hours. And (3) carrying out suction filtration and washing on the aged precipitate slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst D1 #.
Comparative example 2
This example prepared a hydrogenation catalyst having a copper-zinc-aluminum molar ratio of 4:2: 4.
0.5 mol/l sodium carbonate aqueous solution was prepared. 70.55 grams of copper nitrate trihydrate were weighed and dissolved in 119.45 grams of deionized water to yield 190.00 grams of aqueous copper nitrate solution. 43.44 grams of zinc nitrate hexahydrate was weighed into 96.56 grams of deionized water to yield 140.00 grams of aqueous zinc nitrate solution. 109.54 g of aluminum nitrate nonahydrate was weighed into 100.46 g of deionized water to obtain 210.00 g of aqueous aluminum nitrate solution. Mixing the copper nitrate aqueous solution, the zinc nitrate aqueous solution and the aluminum nitrate aqueous solution to be used as a base solution, adding the sodium hydroxide aqueous solution under rapid stirring to form a precipitation slurry, and adding the sodium hydroxide aqueous solution until the pH value of the precipitation slurry is 7.5. After stirring was continued for 1 hour at the end of the cocurrent flow, the mixture was aged at 45 ℃ for 3 hours. And (3) carrying out suction filtration and washing on the aged precipitate slurry, drying the obtained solid at 120 ℃ overnight (12 hours), and then roasting at 420 ℃ for 4 hours to obtain the hydrogenation catalyst D2 #.
Test examples 1 to 7
The hydrogenation catalysts prepared in examples 1 to 7 were subjected to performance evaluation using a fixed bed reactor. The specific evaluation method is as follows: the catalyst was crushed into 20-40 mesh granules after tabletting, and the reactor loading was 10.0 g. The catalyst was reduced in a reactor before use at 260 c under a hydrogen flow rate of 50 ml/min for 15 hours. The cyclohexyl acetate is fed into a reactor by a metering pump and is contacted with a reduced hydrogenation catalyst to carry out cyclohexyl acetate hydrogenation reaction, one hydrogenation catalyst is selected for each test embodiment to carry out reaction under two different reaction conditions, and the specific evaluation result is shown in table 1.
Reaction conditions 1: the reaction temperature is 220 ℃, the reaction pressure is 4.0 MPa, and the mass space velocity of the cyclohexyl acetate is 0.4 h-1The hydrogen flow rate is 210 ml/min (the molar ratio of hydrogen and ester is controlled to be 20); reaction conditions 2: the reaction temperature is 240 ℃, the reaction pressure is 5.5 MPa, and the mass space velocity of the cyclohexyl acetate is 0.4 h-1The flow rate of hydrogen was 210 ml/min (molar ratio of hydrogen to ester was controlled to 20).
Testing of comparative examples 1-2
The hydrogenation catalysts prepared in comparative examples 1 to 2 were evaluated according to the evaluation methods of test examples 1 to 7, and the specific evaluation results are shown in table 1.
As can be seen from the data in Table 1, as the reaction temperature and reaction pressure increased, the conversion of cyclohexyl acetate increased significantly, but the selectivity decreased. The hydrogenation catalyst prepared by the method provided by the invention is superior to the hydrogenation catalyst prepared without using a buffer solution in terms of conversion rate and selectivity and byproduct yield. In addition, taking the cyclohexanone produced by cyclohexanol and used for producing high-purity polymer grade caprolactam as an example, the methyl cyclopentanol in the cyclohexanol pollutes the cyclohexanone, the boiling points and the polarities of the methyl cyclopentanol and the cyclohexanol which is a main product are close, the separation difficulty is high, and the continuous separation cost of the subsequent products is improved.
TABLE 1 hydrogenation catalysts of test examples 1-7 and comparative test examples 1-2
Claims (11)
1. A preparation method of a cyclohexyl acetate hydrogenation catalyst comprises the following steps:
a. adding a first aqueous solution containing water-soluble aluminum salt and water-soluble zinc salt and a first alkaline solution into a buffer solution with the pH value of 6-10 in a concurrent flow manner, so that the aluminum salt and the zinc salt form a precipitate at the pH value of 6-10 to obtain a precipitate slurry; wherein the molar ratio of the aluminum element to the zinc element in the first aqueous solution is 1: (0.2-5);
b. adding a second aqueous solution containing water-soluble copper salt and water-soluble zinc salt and a second alkaline solution into the precipitation slurry in a concurrent flow manner, so that the copper salt and the zinc salt form a precipitate at a pH value of 6-10, and obtaining a cyclohexyl acetate hydrogenation catalyst; wherein the molar ratio of the copper element to the zinc element in the second aqueous solution is (1.5-15): 1;
wherein, based on the amount of elemental substances and the total amount of aluminum, copper and zinc, the content of copper in the cyclohexyl acetate hydrogenation catalyst is 10-70 mol%, the content of zinc is 10-60 mol%, and the content of aluminum is 10-50 mol%.
2. The production method according to claim 1, wherein the buffer solution is at least one selected from the group consisting of an alkali metal dibasic phosphate-strong base buffer solution, an alkali metal monobasic phosphate-strong base buffer solution, an acetic acid-aqueous ammonia buffer solution, a formic acid-aqueous ammonia buffer solution, and an alkali metal carbonate-aqueous ammonia buffer solution.
3. The production method according to claim 1, wherein the first and second alkaline solutions are each independently selected from at least one of an aqueous sodium carbonate solution, an aqueous sodium bicarbonate solution, an aqueous sodium hydroxide solution, and aqueous ammonia.
4. The production method according to claim 1, wherein the mass concentration of the solute substance in the first and second alkaline solutions is each independently 0.1 to 2 moles/liter.
5. The production method according to claim 1, wherein the first aqueous solution has a mass concentration of the aluminum salt of 10 to 30 mass% and a mass concentration of the zinc salt of 5 to 25 mass%; in the second aqueous solution, the mass concentration of the copper salt is 5-25 mass%, and the mass concentration of the zinc salt is 5-25 mass%.
6. The production method according to claim 1, wherein the water-soluble aluminum salt is aluminum sulfate and/or aluminum nitrate, the water-soluble copper salt is copper sulfate and/or copper nitrate, and the water-soluble zinc salt is zinc sulfate and/or zinc nitrate.
7. The preparation method according to claim 1, wherein in step a, the aluminum salt and the zinc salt are precipitated at a pH value of 6-8; in step b, the copper and zinc salts are precipitated at a pH of between 6 and 8.
8. The method of claim 1, further comprising: and c, sequentially aging, filtering, washing, drying and roasting the mixed slurry obtained by precipitation in the step b to obtain the cyclohexyl acetate hydrogenation catalyst.
9. The method according to claim 8, wherein the aging temperature is 40-60 ℃ and the aging time is 3-10 hours; the drying temperature is 60-150 ℃, and the drying time is 12-48 hours; the roasting temperature is 300-700 ℃, and the roasting time is 2-10 hours.
10. A hydrogenation catalyst prepared by the method of any one of claims 1 to 9.
11. A hydrogenation method of cyclohexyl acetate, which comprises the following steps: the hydrogenation catalyst of claim 10 is used to perform a cyclohexyl acetate hydrogenation reaction.
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