CN109759058B - Preparation method of Pd/C catalyst for one-step synthesis of alkylcyclohexylcyclohexanone liquid crystal intermediates - Google Patents
Preparation method of Pd/C catalyst for one-step synthesis of alkylcyclohexylcyclohexanone liquid crystal intermediates Download PDFInfo
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Abstract
The invention discloses a preparation method of a Pd/C catalyst for synthesizing an alkylcyclohexyl cyclohexanone liquid crystal intermediate by a one-step method, wherein the catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, and the auxiliary agent is Zn and Sn; the preparation method comprises the following steps: firstly, preparing Ti-doped modified activated carbon; secondly, preparing a Pd active component precursor; adding a stabilizer, a precipitator and a reducing agent into the Ti-doped modified activated carbon, pulping by pure water, uniformly stirring, dripping a Pd active component precursor, and uniformly stirring to obtain mixed slurry; fourthly, the mixed slurry is heated, then is subjected to heat preservation and reduction, and is added with ZnCl after being cooled2Solution and SnCl2And stirring and filtering the solution to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method. The catalyst prepared by the invention has good selectivity to alkyl cyclohexyl cyclohexanone, and Na does not need to be added in a reaction system2CO3And the method can obtain good yield, simplify the operation and reduce the cost.
Description
Technical Field
The invention belongs to the technical field of industrial catalyst preparation, and particularly relates to a preparation method of a Pd/C catalyst for synthesizing an alkyl cyclohexyl cyclohexanone liquid crystal intermediate by a one-step method.
Background
The liquid crystal material synthesized by taking the alkyl cyclohexyl cyclohexanone as the intermediate has low viscosity, moderate refractive index and wider liquid crystal phase temperatureInterval and other excellent comprehensive performance and excellent market foreground. The traditional preparation method of the compound is to take Raney Ni as a catalyst to catalyze alkyl cyclohexyl phenol to generate alkyl cyclohexyl cyclohexanol, and then take chromium oxide as a catalyst to catalyze and oxidize the alkyl cyclohexyl cyclohexanol to generate the alkyl cyclohexyl cyclohexanone, namely a two-step reaction. The method needs to be carried out under the harsh conditions of high temperature and high pressure, has the defects of long production period, low product yield, high operation risk and the like, and has great harm to the environment and human bodies. Researches show that the palladium catalyst is adopted under proper reaction conditions, the alkyl cyclohexyl phenol can be hydrogenated to generate the alkyl cyclohexyl cyclohexanone in one step, and the method is simple to operate, mild in reaction conditions and free of pollution, and is a green and environment-friendly synthesis method. Since Pd/C can catalyze the further hydrogenation of the alkylcyclohexyl cyclohexanone to produce the alkylcyclohexyl cyclohexanol, the reaction kinetic conditions need to be changed to avoid the further hydrogenation of the alkylcyclohexyl cyclohexanone to produce the alkylcyclohexyl cyclohexanol, and the temperature, the pressure, the solvent and the catalyst are important influencing factors, wherein the catalyst is the key. Patent US6015927 takes nontoxic and easily-recycled cyclohexane as a solvent, Pd/C as a catalyst, and a small amount of borax as an auxiliary agent to perform a hydrogenation reaction, thereby obtaining an alkylcyclohexanone yield of more than 80%; patent US3076810 finds that Pd/C catalyst is treated with alkali metal Na+、K+The modification can improve the yield of the alkyl cyclohexanone.
At present, the problems of low yield of target products, easy inactivation of catalysts and the like still exist in the synthesis of alkyl cyclohexyl cyclohexanone by one-step method of Pd/C catalytic alkyl cyclohexyl phenol. How to prepare the liquid crystal intermediate suitable for synthesizing the alkyl cyclohexyl cyclohexanone by the one-step method is always a hotspot and difficulty of the research of the Pd/C catalyst.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a Pd/C catalyst for one-step synthesis of alkyl cyclohexyl cyclohexanone liquid crystal intermediates, aiming at the defects in the prior art. The method is characterized in that after the activated carbon is modified by Ti doping at high temperature, a Ti oxide layer is formed on the surface of the activated carbon, so that the interface effect of the activated carbon is changed, and the method has the advantages ofThe desorption of the cyclohexanone molecules from the activated carbon is facilitated, so that the contact between the cyclohexanone compounds and the active Pd for further hydrogenation is reduced, and the selectivity of the alkyl cyclohexanone can be improved; active component H2PdCl4Complexing with trisodium nitrilotriacetate in disodium hydrogen phosphate-sodium dihydrogen phosphate buffer to form Pd2+The prepared catalyst has good Pd dispersibility and high activity, and the complexation capability of nitrilotriacetic acid and Pd is strong, after reduction, part of Pd is in an electron-deficient state which is not completely reduced, and the Pd is cooperatively catalyzed with the completely reduced Pd to greatly improve the selectivity of the alkyl cyclohexanone; zn and Sn are used as auxiliary agents and cooperate with a Pd/C catalyst to form a Pd/C-Lewis acid catalyst, and the selectivity of substituted cyclohexanone can be further improved under the combined action. The catalyst prepared by the method has strong surface alkalinity, good selectivity to alkyl cyclohexyl cyclohexanone, and no need of adding Na in a reaction system2CO3And the method can obtain good yield, simplify the operation and reduce the cost.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a Pd/C catalyst for synthesizing an alkylcyclohexyl cyclohexanone liquid crystal intermediate by a one-step method is characterized in that the catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 3-7%, the mass percent of Zn is 0.3-1.0%, and the mass percent of Sn is 0.05-0.5%;
the preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: uniformly mixing activated carbon and a butyl titanate solution, evaporating the solvent to dryness, and then sequentially carrying out room-temperature aging and high-temperature nitrogen treatment to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: mixing disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with H2PdCl4Mixing the solutions, adding trisodium nitrilotriacetate, heating and stirring to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding a stabilizer and a precipitator into the Ti-doped modified activated carbon obtained in the step oneAdding pure water, pulping, uniformly stirring, dripping the Pd active component precursor in the step two, and uniformly stirring to obtain mixed slurry; the stabilizer is glucose, PVP or PEG, and the precipitator is NaHCO3、Na2CO3、CH3COONa or NaOH, wherein the reducing agent is paraformaldehyde, formaldehyde, hydrazine hydrate, sodium formate, sodium hypophosphite or ascorbic acid;
step four, reduction: heating the mixed slurry in the third step, preserving heat, reducing, cooling, and adding ZnCl2Solution and SnCl2And stirring and filtering the solution to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that the mass of Ti in the butyl titanate solution in the step one is 4-6% of that of the activated carbon.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that the room temperature aging time in the step one is 12-24 h; the temperature of the high-temperature nitrogen treatment in the first step is 500-800 ℃, and the time is 0.5-2 h.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that in the second step, the concentration of the disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is 0.2mol/L, the pH value is 6-8, and the volume of the disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is H2PdCl4The mass of Pd in the solution is 20-40 times, wherein the unit of volume is mL, and the unit of mass is g.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that the H in the step two2PdCl4The mass concentration of Pd in the solution is 0.03-0.07 g/mL, the mass of the trisodium nitrilotriacetate is 0.8-3.0 times of that of Pd, and the temperature for heating and stirring is 60-80 ℃.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that in the third step, the mass of the stabilizer is 0.5-2 times that of Pd, the mass of the precipitator is 2-6 times that of Pd, the mass of the reducing agent is 5-15 times that of Pd, the volume of the pure water is 10-30 times that of Ti-doped modified activated carbon, wherein the unit of the volume is mL, and the unit of the mass is g.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that the temperature for heat preservation and reduction in the step four is 60-90 ℃, and the time for heat preservation and reduction is 0.5-2 h.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that ZnCl is added in the step four when the temperature is reduced to below 50 DEG C2Solution and SnCl2And (3) solution.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that the ZnCl is used in the step four2The mass concentration of Zn in the solution is 0.05 g/mL-0.2 g/mL, SnCl2The mass concentration of Sn in the solution is 0.02 g/mL-0.1 g/mL.
The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediate by the one-step method is characterized in that the stirring time in the step four is 20-60 min.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, after the activated carbon is modified by Ti doping at high temperature, a Ti oxide layer is formed on the surface of the activated carbon, so that the interface effect of the activated carbon is changed, and the cyclohexanone molecules are favorably desorbed from the activated carbon, thereby reducing the contact between the cyclohexanone compounds and the active Pd for further hydrogenation, and improving the selectivity of the alkyl cyclohexanone.
2. Active ingredient H in the invention2PdCl4Complexing with trisodium nitrilotriacetate in disodium hydrogen phosphate-sodium dihydrogen phosphate buffer to form Pd2+Macromolecular precursor, the prepared catalyst has good Pd dispersibility and high activity, and nitrilotriacetic acid is complexed with PdThe synthetic ability is strong, after reduction, part of Pd is in an electron-deficient state which is not completely reduced, and the Pd is synergistically catalyzed with the completely reduced Pd to greatly improve the selectivity of the alkyl cyclohexanone.
3. The invention adopts Zn and Sn as auxiliary agents, and the Zn and the Sn cooperate with the Pd/C catalyst to form the Pd/C-Lewis acid catalyst, and the selectivity of substituted cyclohexanone can be further improved under the combined action.
4. It is generally believed that the Pd/C catalyst needs to be pretreated by alkali or added with borax and Na2CO3The invention has the advantages that the palladium active component is always in strong alkaline environment in the adsorption and reduction processes, the surface alkalinity of the prepared catalyst is strong, the selectivity to the alkyl cyclohexyl cyclohexanone is good, and Na does not need to be added into a reaction system2CO3And the method can obtain good yield, simplify the operation and reduce the cost.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
Example 1
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 1.0%, and the mass percent of Sn is 0.5%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 24h at room temperature, and aging at 800 ℃ under N2Performing protection treatment for 30min to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 6 into 100mL of the solution, then adding 15g of trisodium nitrilotriacetate, and stirring at 80 ℃ for 30min to obtain a Pd active component precursor;
step three,Pd precursor adsorption: adding 10g of PVP and 30g of Na into 93.5g of the Ti-doped modified activated carbon obtained in the step one2CO3And 75g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 90 ℃, preserving heat, reducing for 30min, then cooling to below 50 ℃, adding ZnCl with the Zn mass concentration of 0.1g/mL210mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL2And stirring the solution for 30min by 10mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 2
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 0.3%, and the mass percent of Sn is 0.05%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 12h at room temperature, and aging at 500 ℃ under N2Performing protection treatment for 2 hours to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 6.4 into 100mL of the solution, then adding 4g of trisodium nitrilotriacetate, and stirring for 30min at the temperature of 60 ℃ to obtain a Pd active component precursor;
step three, Pd precursor adsorption: 94.65g of Ti-doped modified activated carbon obtained in the step one, 2.5g of PVP and 10g of Na are added2CO3And 25g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 60 ℃, preserving heat and reducing for 2h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.05g/mL26mL of solution and SnCl with the mass concentration of Sn of 0.02g/mL2And stirring the solution for 30min by 2.5mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 3
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 0.8%, and the mass percent of Sn is 0.4%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 20h at room temperature, and aging at 700 ℃ under N2Performing protection treatment for 30min to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 6 into 100mL of the solution, then adding 6g of trisodium nitrilotriacetate, and stirring at 75 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 8g of PVP and 20g of Na into 93.8g of the Ti-doped modified activated carbon obtained in the step one2CO3And 60g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 80 ℃, preserving heat, reducing for 30min, then cooling to below 50 ℃, adding ZnCl with the Zn mass concentration of 0.2g/mL24mL of solution and SnCl with the mass concentration of Sn of 0.1g/mL24mL of the solution is stirred for 20min and then filtered to obtain P for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step methodd/C catalyst.
Example 4
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 1.0%, and the mass percent of Sn is 0.25%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 15h at room temperature, and aging at 650 ℃ under N2Performing protection treatment for 1.5h to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 7.0 into 100mL of the solution, then adding 10g of trisodium nitrilotriacetate, and stirring at 70 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 5g of PVP and 15g of Na into 93.75g of the Ti-doped modified activated carbon obtained in the step one2CO3And 35g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 70 ℃, preserving heat, reducing for 1.5h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.1g/mL210mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL25mL of the solution is stirred for 60min and then filtered to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 5
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 0.5%, and the mass percent of Sn is 0.4%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ and room temperature for 18h, and aging at 600 ℃ under N2Performing protection treatment for 2 hours to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 7.4 into 100mL of the solution, then adding 12g of trisodium nitrilotriacetate, and stirring at 80 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 6g of PVP and 18g of Na into 94.1g of the Ti-doped modified activated carbon obtained in the step one2CO3And 30g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 65 ℃, preserving heat, reducing for 2 hours, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.1g/mL25mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL2Stirring the solution for 30min by 8mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 6
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 0.8%, and the mass percent of Sn is 0.2%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent, aging at 25 ℃ for 24h at room temperature, and performing 800 DEG CLower N2Performing protection treatment for 2 hours to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 7.6 into 100mL of the solution, then adding 9g of trisodium nitrilotriacetate, and stirring at 80 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 4g of PVP and 25g of Na into 94g of the Ti-doped modified activated carbon obtained in the step one2CO3And 45g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 80 ℃, preserving heat, reducing for 1.5h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.1g/mL2Solution 8mL and SnCl with Sn mass concentration of 0.05g/mL24mL of the solution is stirred for 30min and then filtered to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 7
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 5%, the mass percent of Zn is 0.3%, and the mass percent of Sn is 0.5%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 12h at room temperature, and aging at 700 ℃ under N2Performing protection treatment for 2 hours to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.05g/mL2PdCl4100mL of the solution was added 200mL of a disodium hydrogenphosphate-sodium dihydrogenphosphate buffer solution at a concentration of 0.2mol/L and pH 8.0, followed by 5g of trisodium nitrilotriacetateStirring the mixture for 30min at 65 ℃ to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 6g of PVP and 30g of Na into 94.2g of the Ti-doped modified activated carbon obtained in the step one2CO3And 65g of paraformaldehyde, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 85 ℃, preserving heat, reducing for 1h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.1g/mL23mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL2And stirring the solution for 40min by 10mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 8
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 3%, the mass percent of Zn is 1.0%, and the mass percent of Sn is 0.5%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: 28.44g of butyl titanate is dissolved in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, 96g of activated carbon is added, the mixture is stirred for 30min, the solvent is evaporated to dryness, the mixture is aged at room temperature of 25 ℃ for 24h and N at 800 DEG C2Performing protection treatment for 30min to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.03g/mL2PdCl4Adding 60mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 6 into 100mL of the solution, then adding 9g of trisodium nitrilotriacetate, and stirring at 80 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 6g of glucose and 18g of NaHCO into 95.5g of the Ti-doped modified activated carbon in the step one3And 45g of hydrazine hydrate, pulping with 2000mL of pure water, stirring for 30min, and then dropwise adding the mixture obtained in the second step at the speed of 5mL/minUniformly stirring a Pd active component precursor to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 90 ℃, preserving heat, reducing for 30min, then cooling to below 50 ℃, adding ZnCl with the Zn mass concentration of 0.1g/mL210mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL2And stirring the solution for 30min by 10mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 9
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 3%, the mass percent of Zn is 0.3%, and the mass percent of Sn is 0.05%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: 40.28g of butyl titanate is dissolved in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, 94g of activated carbon is added, the mixture is stirred for 30min, the solvent is evaporated to dryness, the mixture is aged at 25 ℃ for 12h at room temperature and N at 500 DEG2Performing protection treatment for 2 hours to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.03g/mL2PdCl4Adding 120mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 6.4 into 100mL of the solution, then adding 2.4g of trisodium nitrilotriacetate, and stirring for 30min at the temperature of 60 ℃ to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 1.5g of PVP and 6g of Na into 96.65g of the Ti-doped modified activated carbon obtained in the step one2CO3And 15g of ascorbic acid, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 60 ℃, preserving heat and reducing for 2h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.05g/mL26mL of solution and SnCl with the mass concentration of Sn of 0.02g/mL2And stirring the solution for 30min by 2.5mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 10
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 3%, the mass percent of Zn is 0.8%, and the mass percent of Sn is 0.4%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 20h at room temperature, and aging at 700 ℃ under N2Performing protection treatment for 30min to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.03g/mL2PdCl4Adding 100mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 8 into 100mL of the solution, then adding 3.6g of trisodium nitrilotriacetate, and stirring at 75 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 4.8g of PEG, 12g of NaOH and 36g of formaldehyde into 95.8g of the Ti-doped modified activated carbon obtained in the step one, pulping with 1200mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor obtained in the step two at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 80 ℃, preserving heat, reducing for 30min, then cooling to below 50 ℃, adding ZnCl with the Zn mass concentration of 0.2g/mL24mL of solution and SnCl with the mass concentration of Sn of 0.1g/mL24mL of the solution is stirred for 20min and then filtered to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 11
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 3%, the mass percent of Zn is 1.0%, and the mass percent of Sn is 0.25%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 100g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 15h at room temperature, and aging at 650 ℃ under N2Performing protection treatment for 1.5h to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.03g/mL2PdCl4Adding 120mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 7.0 into 100mL of the solution, then adding 6g of trisodium nitrilotriacetate, and stirring at 70 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 3g of PVP and 9gCH to 95.75g of the Ti-doped modified activated carbon obtained in the step one3Pulping COONa and 21g sodium hypophosphite by 1915mL pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the step two at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 70 ℃, preserving heat, reducing for 1.5h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.1g/mL210mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL25mL of the solution is stirred for 60min and then filtered to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 12
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 7%, the mass percent of Zn is 0.5%, and the mass percent of Sn is 0.4%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: 35.55g of butyl titanate was dissolved in a mixed solution of 365mL of absolute ethanol, 80mL of acetylacetone and 20mL of nitric acid, and 124g of active carbon was addedStirring for 30min, evaporating solvent, aging at 25 deg.C for 18 hr and 500 deg.C under N2Performing protection treatment for 2 hours to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.07g/mL2PdCl4Adding 200mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 6 into 100mL of the solution, then adding 21g of trisodium nitrilotriacetate, and stirring at 80 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 14g of PVP and 14g of Na into 92.1g of the Ti-doped modified activated carbon obtained in the step one2CO3And 35g of paraformaldehyde, pulping with 921mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the second step at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 60 ℃, preserving heat and reducing for 2h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.1g/mL25mL of solution and SnCl with the mass concentration of Sn of 0.05g/mL2Stirring the solution for 30min by 8mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 13
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 7%, the mass percent of Zn is 1.0%, and the mass percent of Sn is 0.05%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: 40.28g of butyl titanate is dissolved in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, 94g of activated carbon is added, the mixture is stirred for 30min, the solvent is evaporated to dryness, the mixture is aged at 25 ℃ for 24h at room temperature and N at 800 DEG C2Performing protection treatment for 0.5h to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.07g/mL2PdCl4100mL of the solution was added with phosphoric acid at a concentration of 0.2mol/L and pH 7.6280mL of disodium hydrogen-sodium dihydrogen phosphate buffer solution, then adding 9g of trisodium nitrilotriacetate, and stirring at 60 ℃ for 40min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: 91.95g of the Ti-doped modified activated carbon obtained in the step one, 3.5g of PVP and 35g of Na are added2CO3And 63g of sodium formate, pulping with 2750mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the step two at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 90 ℃, preserving heat and reducing for 0.5h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.2g/mL25mL of solution and SnCl with the mass concentration of Sn of 0.02g/mL2And stirring the solution for 30min by 2.5mL, and filtering to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
Example 14
The catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 7%, the mass percent of Zn is 0.3%, and the mass percent of Sn is 0.5%.
The preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: dissolving 35.55g of butyl titanate in a mixed solution of 365mL of absolute ethyl alcohol, 80mL of acetylacetone and 20mL of nitric acid, adding 95g of activated carbon, stirring for 30min, evaporating the solvent to dryness, aging at 25 ℃ for 12h at room temperature, and aging at 700 ℃ under N2Performing protection treatment for 1h to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: measuring H with Pd mass concentration of 0.07g/mL2PdCl4Adding 140mL of disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with the concentration of 0.2mol/L and the pH value of 8.0 into 100mL of the solution, then adding 5.6g of trisodium nitrilotriacetate, and stirring at 65 ℃ for 30min to obtain a Pd active component precursor;
step three, Pd precursor adsorption: adding 8.4g of PVP and 42g of Na into 92.2g of the Ti-doped modified activated carbon obtained in the step one2CO3And 105g of sodium formatePulping with 1000mL of pure water, stirring for 30min, then dropwise adding the Pd active component precursor in the step two at the speed of 5mL/min, and uniformly stirring to obtain mixed slurry;
step four, reduction: heating the mixed slurry in the third step to 85 ℃, preserving heat, reducing for 1h, then cooling to below 50 ℃, and adding ZnCl with the Zn mass concentration of 0.05g/mL26mL of solution and SnCl with the mass concentration of Sn of 0.1g/mL25mL of the solution is stirred for 40min and then filtered to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
The Pd/C catalysts prepared in inventive examples 1 to 14 were subjected to the following performance tests:
reaction system: preparing trans-4-propylcyclohexyl cyclohexanone by one-step hydrogenation of trans-4-propylcyclohexyl phenol;
the operation process is as follows: adding 100g of trans-4-propylcyclohexylphenol, 400mL of cyclohexane and 2g of the Pd/C catalyst in a 1L high-pressure reaction kettle in sequence; sealing the high-pressure reaction kettle, firstly using N2Replacing the air in the kettle for 3 times and then using H2Substitution of N2Thirdly, heating to 100 ℃, and charging H2When the hydrogen pressure in the kettle is 0.2MPa, the stirring is started for 200r/min, and the reaction solution is detected by Agilent 7890A gas chromatography, and the results are shown in Table 1.
TABLE 1 Pd/C catalyst performance results prepared in examples 1-14
The catalyst prepared in example 3 of the invention was used for the set-up experiment: after the reaction, the catalyst was centrifuged, 400mL of cyclohexane was used to back flush the catalyst into the reactor, and the above operation was repeated, with the application properties shown in table 2.
TABLE 2 Performance results for Pd/C catalyst application prepared in example 3
As can be seen from tables 1 and 2, the one-step catalytic synthesis of the liquid crystal intermediate of the alkylcyclohexylcyclohexanone by using the catalyst of the invention has the advantages of conversion rate of 100%, selectivity of more than 94.86%, stable performance of the catalyst, and no obvious reduction of conversion rate and selectivity after repeated application.
The catalyst of the other embodiments of the present invention is mechanically applied according to the above-mentioned method, and the results show that the catalyst has stable performance, and the conversion rate and selectivity are not significantly reduced after being mechanically applied for many times.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalent changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a Pd/C catalyst for synthesizing an alkylcyclohexyl cyclohexanone liquid crystal intermediate by a one-step method is characterized in that the catalyst comprises Ti-doped modified activated carbon, an active component Pd and an auxiliary agent, wherein the auxiliary agent is Zn and Sn; in the catalyst, the mass percent of Pd is 3-7%, the mass percent of Zn is 0.3-1.0%, and the mass percent of Sn is 0.05-0.5%;
the preparation method of the catalyst comprises the following steps:
step one, active carbon pretreatment: uniformly mixing activated carbon and a butyl titanate solution, evaporating the solvent to dryness, and then sequentially carrying out room-temperature aging and high-temperature nitrogen treatment to obtain Ti-doped modified activated carbon;
step two, Pd precursor preparation: mixing disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution with H2PdCl4Mixing the solutions, adding trisodium nitrilotriacetate, heating and stirring to obtain a Pd active component precursor; the concentration of the disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is 0.2mol/L, the pH value is 6-8, and the volume of the disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution is H2PdCl4The mass of Pd in the solution is 20-40 times, wherein the unit of volume is mL, and the unit of mass is g; h2PdCl4The mass concentration of Pd in the solution is 0.03 g/mL-0.07 g/mL, the mass of the trisodium nitrilotriacetate is 0.8-3.0 times of that of Pd, and the temperature for heating and stirring is 60-80 ℃;
step three, Pd precursor adsorption: adding a stabilizer, a precipitator and a reducing agent into the Ti-doped modified activated carbon obtained in the step one, then adding pure water, pulping, uniformly stirring, then dripping the Pd active component precursor obtained in the step two, and uniformly stirring to obtain mixed slurry; the stabilizer is glucose, PVP or PEG, and the precipitator is NaHCO3、Na2CO3、CH3COONa or NaOH, wherein the reducing agent is paraformaldehyde, formaldehyde, hydrazine hydrate, sodium formate, sodium hypophosphite or ascorbic acid;
step four, reduction: heating the mixed slurry in the third step, preserving heat and reducing, reducing to ensure that part of Pd is in an electron-deficient state which is not completely reduced, catalyzing with the completely reduced Pd in a synergetic way, cooling, and adding ZnCl2Solution and SnCl2And stirring and filtering the solution to obtain the Pd/C catalyst for synthesizing the alkylcyclohexyl cyclohexanone liquid crystal intermediate by the one-step method.
2. The preparation method of the Pd/C catalyst for the one-step synthesis of the alkylcyclohexylcyclohexanone liquid crystal intermediates according to claim 1, wherein the mass of Ti in the butyl titanate solution in the first step is 4-6% of the mass of the activated carbon.
3. The preparation method of the Pd/C catalyst for the one-step synthesis of the alkylcyclohexylcyclohexanone liquid crystal intermediates according to claim 1, wherein the room temperature aging time in the step one is 12-24 h; the temperature of the high-temperature nitrogen treatment in the first step is 500-800 ℃, and the time is 0.5-2 h.
4. The method for preparing the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediates by the one-step method according to claim 1, wherein the mass of the stabilizer is 0.5-2 times of the mass of Pd, the mass of the precipitator is 2-6 times of the mass of Pd, the mass of the reducing agent is 5-15 times of the mass of Pd, and the volume of the pure water is 10-30 times of the mass of the Ti-doped modified activated carbon, wherein the unit of the volume is mL, and the unit of the mass is g.
5. The preparation method of the Pd/C catalyst for synthesizing the alkylcyclohexylcyclohexanone liquid crystal intermediates by the one-step method according to claim 1, wherein the temperature for the heat preservation reduction in the fourth step is 60 ℃ to 90 ℃, and the time for the heat preservation reduction is 0.5h to 2 h.
6. The method for preparing Pd/C catalyst for synthesizing alkylcyclohexylcyclohexanone liquid crystal intermediates by one-step process according to claim 5, wherein ZnCl is added in the fourth step after the temperature is reduced to below 50 ℃2Solution and SnCl2And (3) solution.
7. The method for preparing Pd/C catalyst for one-step synthesis of alkylcyclohexylcyclohexanone liquid crystal intermediates according to claim 1, wherein the ZnCl is used in the fourth step2The mass concentration of Zn in the solution is 0.05 g/mL-0.2 g/mL, and SnCl2The mass concentration of Sn in the solution is 0.02 g/mL-0.1 g/mL.
8. The method for preparing the Pd/C catalyst for the one-step synthesis of the alkylcyclohexylcyclohexanone liquid crystal intermediates according to claim 1, wherein the stirring time in the fourth step is 20min to 60 min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1471854A (en) * | 1975-02-20 | 1977-04-27 | Inventa Ag | Process for preparing cyclohexanone |
| CN1698952A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Method for preparing supported palladium/carbon catalyst |
| CN101709027A (en) * | 2009-11-27 | 2010-05-19 | 中国科学院化学研究所 | Method and special catalyst for preparing cyclohexanone in one step by phenol hydrogenation |
| CN103691431A (en) * | 2013-12-24 | 2014-04-02 | 湘潭大学 | Palladium carbon catalyst as well as preparation method and application thereof |
| CN104610030A (en) * | 2015-01-16 | 2015-05-13 | 浙江大学 | Method for preparing cyclohexanone compounds through catalytic action and vapor phase hydrogenation of phenolic compounds |
-
2019
- 2019-02-27 CN CN201910146633.6A patent/CN109759058B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1471854A (en) * | 1975-02-20 | 1977-04-27 | Inventa Ag | Process for preparing cyclohexanone |
| CN1698952A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Method for preparing supported palladium/carbon catalyst |
| CN101709027A (en) * | 2009-11-27 | 2010-05-19 | 中国科学院化学研究所 | Method and special catalyst for preparing cyclohexanone in one step by phenol hydrogenation |
| CN103691431A (en) * | 2013-12-24 | 2014-04-02 | 湘潭大学 | Palladium carbon catalyst as well as preparation method and application thereof |
| CN104610030A (en) * | 2015-01-16 | 2015-05-13 | 浙江大学 | Method for preparing cyclohexanone compounds through catalytic action and vapor phase hydrogenation of phenolic compounds |
Non-Patent Citations (3)
| Title |
|---|
| Effect of Preparation Conditions on the Hydrogenation Activity and Metal Dispersion of Pt/C and Pd/C Catalysts;Sung Hwa Jhung,et al.;《Bull. Korean Chem. Soc.》;20051231;第26卷(第4期);563-568 * |
| Selective Phenol Hydrogenation to Cyclohexanone Over a Dual Supported Pd -Lewis Acid Catalyst;Huizhen Liu et al.;《Science》;20091231;第326卷;1250-1252 * |
| 用于一步法合成丙基环己基环己酮的Pd/C催化剂;宋有永等;《石油化工》;20061231;第35卷(第10期);937-942 * |
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