CN108579781B - Phenol hydrogenation catalyst and preparation method thereof - Google Patents
Phenol hydrogenation catalyst and preparation method thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention relates to a phenol hydrogenation catalyst and a preparation method thereof, belonging to the technical field of catalysis. The catalyst is ZIF-67-TiO2Taking the ZIF-67-TiO as a precursor, and heating the precursor by adopting a slow temperature programming method2Calcination to form Co/CN-TiO2The material is then prepared into CN-TiO by an acid washing method2The carrier is stirred and dipped by active component salt and H2Reducing to obtain the catalyst. The invention has the advantage that small amount of anatase TiO is used2The modified ZIF-67 can obviously increase the specific surface area of the carrier, enhance the electron transmission capability, obviously improve the catalytic performance of preparing cyclohexanone by phenol hydrogenation, and the prepared catalyst has good catalytic stability.
Description
Technical Field
The invention relates to a phenol hydrogenation catalyst and a preparation method thereof, belonging to the technical field of catalysis.
Background
Cyclohexanone is an important chemical raw material, is an important intermediate for producing nylon 6 and nylon 66, and the main preparation route in the industry at present is a cyclohexane oxidation method. However, the cyclohexane oxidation process at high temperature and high pressure generates many byproducts, which is an environmentally unfriendly production process. In recent years, a process for preparing cyclohexanone by directly hydrogenating phenol, which has low energy consumption and is environment-friendly, has attracted more and more attention.
In recent years, carbon and nitrogen materials have attracted extensive attention from researchers, N-elementThe introduction of the element can change the acid-base property, the conductivity and the hydrophilicity/hydrophobicity of the carbon material, and can also be used as an alkaline site to adsorb a specific substrate, for example, when phenol is hydrogenated to prepare cyclohexanone, phenol is chemically adsorbed on the surface of a carrier, and hydrogen activated by active components on the carrier is reacted to generate the cyclohexanone. N in the carbon and nitrogen material has the function of selective adsorption on phenol, but has weaker adsorption capacity on cyclohexanone, so that the selectivity of cyclohexanone in the product can be improved. E.g. Pd @ mpg-C3N4Very high selectivity (99%) was achieved in this reaction. However, mpg-C was synthesized3N4The process is complex and the conditions are difficult to control. Therefore, it is important to find a simple and effective synthesis method of carbon and nitrogen carriers.
Zeolite imidazole-like framework ester (ZIFs) is a widely studied Metal-Organic framework (MOFs) material, which is synthesized by Metal node zinc or cobalt and imidazole or imidazole ester in a self-assembly manner. The ZIFs material has an ordered pore structure, and imidazole derivatives contain a large amount of carbon and nitrogen elements, so that the CN carrier can be prepared by a one-step pyrolysis method.
Researches show that the direct heterojunction structure of the metal and the semiconductor can effectively enhance the phenol hydrogenation performance of the catalyst. Titanium dioxide (TiO)2) As an environmentally friendly semiconductor material for use in catalysts or catalyst supports, in particular, anatase TiO2The catalyst has strong interaction with metal under the reduction of hydrogen at lower temperature (lower than 300 ℃), and can improve the catalytic performance. Thus introducing TiO into the CN material2The interaction between the carrier and the active component can be improved, so that the phenol hydrogenation performance of the catalyst is improved.
Disclosure of Invention
The invention aims to provide a high-performance catalyst for preparing cyclohexanone by phenol hydrogenation; anatase TiO is added in the process of synthesizing ZIF-672Preparing CN-TiO by high-temperature calcination and acid washing2Preparation of Pd @ CN-TiO by using carrier and loaded Pd nano-particles2A catalyst.
The technical scheme of the invention is as follows:
a preparation method of a phenol hydrogenation catalyst comprises the following specific steps:
the method comprises the following steps: preparing a solution I by using 2-methylimidazole as a solute and methanol as a solvent; preparing a solution II by using cobalt nitrate hexahydrate as a solute and methanol as a solvent; respectively carrying out ultrasonic treatment on the two solutions until the two solutions are clear and transparent for later use;
step two: TiO anatase2Dispersing in methanol solution of polyvinylpyrrolidone, and stirring for a period of time to obtain TiO stabilized with polyvinylpyrrolidone2A colloidal suspension;
step three: adding the solution I prepared in the step one into the suspension, stirring for a period of time, adding the solution II, continuing stirring for a period of time, and standing; centrifuging the mixed solution after standing to separate out precipitate, washing with methanol or ethanol, and oven drying to obtain ZIF-67-TiO2；
Step four: ZIF-67-TiO obtained in the third step2Placing the mixture in a tubular furnace, roasting the mixture in the atmosphere of nitrogen or inert gas to obtain a sample named as Co/CN-TiO2；
Step five: the Co/CN-TiO obtained in the fourth step2Refluxing and washing in acid solution with certain concentration and under the condition of water bath for a period of time, then washing with deionized water, placing in an oven for drying, and recording the obtained sample as CN-TiO2；
Step six: immersing the sample obtained in the step five into a palladium chloride aqueous solution, stirring and immersing, centrifuging, and drying in an oven;
step seven: reducing the sample obtained in the sixth step in a hydrogen atmosphere, and naturally cooling to obtain Pd @ CN-TiO2。
Preferably, the concentration of the 2-methylimidazole solution prepared in the first step is 0.4-1.6 mol/L; the concentration of the cobalt nitrate hexahydrate solution is 0.05-0.2 mol/L respectively.
Preferably, the mass concentration of the polyvinylpyrrolidone methanol solution in the second step is 10-40 g/L, and the mass concentration of TiO is2The concentration of the cobalt nitrate hexahydrate solution is 0-1/4, and the stirring time isIs 10-30 min.
Preferably, the solutions I, II and TiO described in step three2The volume ratio of the colloidal suspension is 1:1:1, the stirring time is 10-30 min and 8-20 h respectively after the solution I and the solution II are added, and the standing time is 0-5 h; the washing times are 2-5 times; the drying temperature is 50-80%oC, drying for 6-24 hours.
Preferably, the inert gas in the fourth step is helium or argon; the calcination temperature is 550-800 deg.CoC, calcining for 4-8 hours at a temperature rise rate of 1-4oC /min。
Preferably, the acid solution in the step five is nitric acid or hydrochloric acid, and the mass concentration is 20-40%; the reflux time is 2-5 h; washing with deionized water for 3-6 times; the drying temperature of the oven is 80-120 DEG CoC, drying for 6-10 hours.
Preferably, in the sixth step, the concentration of the palladium chloride dipping solution is 0.45-1.2 g/L, and the dipping time is 4-12 h.
Preferably, in the seventh step, the reduction temperature of the hydrogen is 150-300 DEGoC, reducing for 3-6 h at a heating rate of 1-4oC/min。
The invention adopts the cyclohexanone prepared by selective hydrogenation of phenol as a model reaction to evaluate the catalytic performance of the prepared catalyst. The specific process is as follows:
the reaction apparatus used in this reaction was a 25 mL Schrand tube. Firstly, 0.10 g of Pd @ CN-TiO2The catalyst was added to the tube followed by 5 mL of a 1 wt% aqueous solution of phenol. The reaction temperature was controlled to 80 deg.CoAnd C, the reaction pressure is 1 bar. The reaction time was 70 min. And centrifuging and filtering the reaction product, analyzing by using gas chromatography, and calculating the conversion rate of the raw material and the selectivity of the product according to a standard curve.
Has the advantages that:
anatase TiO is added in the process of synthesizing ZIF-672The CN-TiO with high specific surface area can be prepared by calcining and acid washing2The electron transmission capability between the carrier and the metal active center Pd nano-particles is enhanced, and the phenol hydrogenation performance of the catalyst is improved.
Drawings
FIG. 1 shows CN-TiO in example 120.01 and no TiO2Prepared CN-TiO2-0 carrier N2Removing the attached figure by adsorption, wherein a is without TiO2Prepared CN-TiO20 adsorption section of the support, a' is CN-TiO2-0 desorption section of the support. b is CN-TiO in example 12-0.01 adsorption section of support, b' is CN-TiO2-0.01 desorption section of the support.
FIG. 2 shows Pd @ CN-TiO in example 120.01 and no TiO2Prepared Pd @ CN-TiO2N1 s XPS characterization of-0 catalyst, wherein (a) Pd @ CN-TiO2-0，(b) Pd@CN-TiO2-0.01。
Detailed Description
The method and the catalyst of the present invention will be described in detail by the following examples, which are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) ZIF-67-TiO2Preparation of
First, 50 mL of 0.8 mol/L methanol solution of 2-methylimidazole and 50 mL of 0.1 mol/L methanol solution of cobalt nitrate hexahydrate were prepared. 0.01 g of TiO2Dispersing in 50 mL 20 g/L polyvinylpyrrolidone methanol solution, stirring for 10 min, adding 2-methylimidazole solution, stirring for 10 min, adding Co (NO)3)2·6H2And O, mixing and stirring the solution in methanol for 10 hours, stopping stirring, and standing the mixture for 1 hour at room temperature. After the end of the standing, the product is separated by centrifugation and washed 3 times with methanol and finally 80 timesoC oven drying for 6 h, sample designated ZIF-67-TiO2-0.01。
(2) CN-TiO2Preparation of the support
Taking 0.5 g of prepared ZIF-67-TiO20.01 in a tube furnace, under argon atmosphere and at a temperature of 600 ℃ for calcinationoAnd C, calcining for 5 h. The temperature is increased from room temperature to the target temperature with the temperature increase rate of 1oAnd C/min. The calcined sample was noted as Co/CN-TiO2-0.01. Prepared Co/CN-TiO20.01 sample in 34% nitric acid solution at 60oC. Pickling for 5 h under continuous stirring, washing with deionized water for 4 times after pickling, and collecting sample at 80 deg.CoC, drying in an oven for 10 hours, and marking the obtained sample as CN-TiO2-0.01。
(3) Pd@CN-TiO2Preparation of the catalyst
0.2 g of CN-TiO was taken20.01 of the catalyst is dispersed in 15 mL of 0.89 g/L palladium chloride aqueous solution, stirred and immersed for 12 hours, centrifuged, and dried in an oven for 8 hours. Placing the dried sample in a tubular furnace, and heating at a temperature rising rate of 2 under a hydrogen atmosphereoHeating to 250 ℃ at the speed of C/minoReducing for 6 hours under C to obtain Pd @ CN-TiO2-0.01 catalyst.
With Pd @ CN-TiO20.01 preparation in the same manner without TiO2The catalyst obtained by the preparation is marked as Pd @ CN-TiO2-0. FIG. 1 shows CN-TiO20.01 with CN-TiO2N of-02The figure shows that under the condition of lower relative pressure, the adsorption quantity has a sudden increase process, and when the relative pressure is higher, a hysteresis loop appears, which explains CN-TiO20.01 with CN-TiO2-0 each have a micro-mesoporous structure; by the level of the adsorption amount, it can be found that TiO is added2CN-TiO of2The specific surface area is obviously increased by-0.01. FIG. 2 is Pd @ CN-TiO2-0.01 and Pd @ CN-TiO2N1 s XPS peak diagram in-0 catalyst, and can find that graphite nitrogen and pyridine nitrogen exist simultaneously in the prepared catalyst, and Pd @ CN-TiO2The nitrogen content of graphite of-0.01 is obviously increased, and the electron transmission capability of a carrier is enhanced.
Catalyst Pd @ CN-TiO2-0.01 is applied to an experiment for preparing cyclohexanone by phenol hydrogenation, the conversion rate is 98.0 percent and the selectivity is 98.0 percent after the reaction is carried out for 70 min. Without addition of TiO2Prepared catalyst Pd @ CN-TiO2-0 is applied to an experiment for preparing cyclohexanone by phenol hydrogenation, the conversion rate is 72.3 percent and the selectivity is 98.3 percent after 70 min of reaction.
Example 2
(1) ZIF-67-TiO2Preparation of
First, 50 mL of 1.6 mol/L2-methylimidazolyl methanol was preparedThe solution and 50 mL of 0.05 mol/L cobalt nitrate hexahydrate in methanol. 0.05 g of TiO2Dispersing in 50 mL 10 g/L polyvinylpyrrolidone methanol solution, stirring for 30 min, adding 2-methylimidazole solution, stirring for 10 min, adding Co (NO)3)2·6H2And O, mixing and stirring the methanol solution for 8 hours, stopping stirring, and standing the mixture for 5 hours at room temperature. After the end of the standing, the product is separated by centrifugation and washed 5 times with methanol and finally 50 timesoC oven drying for 24 h, sample designated ZIF-67-TiO2-0.05。
(2) CN-TiO2Preparation of the support
Taking 0.5 g of prepared ZIF-67-TiO20.05 in a tube furnace under helium at a calcination temperature of 550 ℃oAnd C, the calcining time is 8 h. The temperature is increased from room temperature to the target temperature at a rate of 2oAnd C/min. The calcined sample was noted as Co/CN-TiO2-0.05. Prepared Co/CN-TiO20.05 sample in 40% nitric acid solution at 60%oC. Pickling for 2 h under continuous stirring, washing with deionized water for 6 times after pickling, and collecting sample at 100 deg.CoC, drying in an oven for 8 hours, and marking the obtained sample as CN-TiO2-0.05。
(3) Pd@CN-TiO2Preparation of the catalyst
0.2 g of CN-TiO was taken2-0.05 is dispersed in 12 mL of 0.45 g/L palladium chloride aqueous solution, stirred and immersed for 8 h, centrifuged, and oven-dried for 8 h. Placing the dried sample in a tubular furnace, and heating in hydrogen atmosphere at a heating rate of 1oHeating to 300 deg.C/minoC is reduced for 4 hours to obtain Pd @ CN-TiO2-0.05 catalyst.
Catalyst Pd @ CN-TiO2-0.05 is applied to an experiment for preparing cyclohexanone by phenol hydrogenation, and the conversion rate is 42.3 percent and the selectivity is 99.4 percent after the reaction is carried out for 70 min.
Example 3
(1) ZIF-67-TiO2Preparation of
First, 50 mL of 0.4 mol/L methanol solution of 2-methylimidazole and 50 mL of 0.2 mol/L methanol solution of cobalt nitrate hexahydrate were prepared.0.1 g of TiO2Dispersing in 50 mL of 40 g/L polyvinylpyrrolidone methanol solution, stirring for 20 min, adding 2-methylimidazole solution, stirring for 30 min, adding Co (NO)3)2·6H2Mixing O methanol solution, stirring for 20 hr, centrifuging, washing with ethanol for 2 times, and washing at 70 deg.CoC oven drying for 12 h, sample designated ZIF-67-TiO2-0.1。
(2) CN-TiO2Preparation of the support
Taking 0.5 g of prepared ZIF-67-TiO20.1 in a tube furnace, with a nitrogen atmosphere and a calcination temperature of 800 deg.CoAnd C, the calcining time is 4 h. The temperature is increased from room temperature to the target temperature at a heating rate of 4oAnd C/min. The calcined sample was noted as Co/CN-TiO2-0.1. Prepared Co/CN-TiO20.1 sample in 20% hydrochloric acid solution at 60%oC. Pickling for 2 h under continuous stirring, washing with deionized water for 3 times after pickling, and collecting the sample at 120 deg.CoBaking for 6 hours in a baking oven C to obtain a sample which is marked as CN-TiO2-0.1。
(3) Pd@CN-TiO2Preparation of the catalyst
0.2 g of CN-TiO was taken2-0.1 is dispersed in 14 mL of 1.2 g/L palladium chloride aqueous solution, stirred and immersed for 4 h, centrifuged, and oven-dried for 8 h. Placing the dried sample in a tubular furnace, and heating at a temperature rising rate of 4 under a hydrogen atmosphereoHeating to 150 deg.C/minoReducing for 3 hours under C to obtain Pd @ CN-TiO2-0.1 catalyst.
Catalyst Pd @ CN-TiO2-0.1 is applied to an experiment for preparing cyclohexanone by phenol hydrogenation, the conversion rate is 50.7 percent after 70 min of reaction, and the selectivity is 99.2 percent.
Claims (8)
1. A preparation method of a phenol hydrogenation catalyst is characterized by comprising the following specific steps:
the method comprises the following steps: preparing a solution I by using 2-methylimidazole as a solute and methanol as a solvent; preparing a solution II by using cobalt nitrate hexahydrate as a solute and methanol as a solvent; respectively carrying out ultrasonic treatment on the two solutions until the two solutions are clear and transparent for later use;
step two: TiO anatase2Dispersing in methanol solution of polyvinylpyrrolidone, and stirring for a period of time to obtain TiO stabilized with polyvinylpyrrolidone2A colloidal suspension;
step three: adding the solution I prepared in the step one to the TiO prepared in the step two2Stirring the colloidal suspension for a period of time, adding the solution II, continuously stirring for a period of time, and standing; centrifuging the mixed solution after standing to separate out precipitate, washing with methanol or ethanol, and oven drying to obtain ZIF-67-TiO2；
Step four: ZIF-67-TiO obtained in the third step2Placing the mixture in a tubular furnace, roasting the mixture in the atmosphere of nitrogen or inert gas to obtain a sample named as Co/CN-TiO2；
Step five: the Co/CN-TiO obtained in the fourth step2Placing the sample in an acid solution with certain concentration, refluxing for a period of time under the condition of water bath, then washing with deionized water, placing the washed sample in an oven for drying, and recording the obtained sample as CN-TiO2；
Step six: dipping the sample obtained in the fifth step into a palladium chloride aqueous solution, stirring and dipping, centrifuging, and drying in an oven;
step seven: reducing the sample obtained in the sixth step in a hydrogen atmosphere, and naturally cooling to obtain Pd @ CN-TiO2。
2. The method for preparing the phenol hydrogenation catalyst according to claim 1, wherein the concentration of the 2-methylimidazole solution prepared in the first step is 0.4-1.6 mol/L; the concentration of the cobalt nitrate hexahydrate solution is 0.05-0.2 mol/L.
3. The method for preparing the phenol hydrogenation catalyst according to claim 1, wherein the mass concentration of the polyvinylpyrrolidone methanol solution in the second step is 10-40 g/L, and TiO is2The concentration of the cobalt nitrate hexahydrate solution is 0-1/4, and the stirring time is 10-30 min.
4. A process for preparing a phenol hydrogenation catalyst as claimed in claim 1, characterized in that the solutions I, II and TiO mentioned in step three are2The volume ratio of the colloidal suspension is 1:1:1, the stirring time is 10-30 min and 8-20 h respectively after the solution I and the solution II are added, and the standing time is 0-5 h; the washing times are 2-5 times; the drying temperature is 50-80 ℃, and the drying time is 6-24 h.
5. The method of claim 1, wherein the inert gas in step four is helium or argon; the calcination temperature is 550-800 ℃, the calcination time is 4-8 h, and the heating rate is 1-4 ℃/min.
6. The preparation method of the phenol hydrogenation catalyst according to claim 1, wherein the acid solution in the step five is nitric acid or hydrochloric acid, and the mass concentration is 20-40%; the reflux time is 2-5 h; washing with deionized water for 3-6 times; the drying temperature of the oven is 80-120 ℃, and the drying time is 6-10 h.
7. The preparation method of the phenol hydrogenation catalyst according to claim 1, wherein the concentration of the palladium chloride impregnation solution in the sixth step is 0.45-1.2 g/L, and the impregnation time is 4-12 h.
8. The preparation method of the phenol hydrogenation catalyst according to claim 1, wherein in the seventh step, the hydrogen reduction temperature is 150-300 ℃, the reduction time is 3-6 h, and the temperature rise rate is 1-4 ℃/min.
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| CN109647478B (en) * | 2018-12-20 | 2021-10-22 | 首都师范大学 | Preparation method of copper and cobalt doped nitrogen-containing carbon layer catalyst |
| CN109794245B (en) * | 2019-01-11 | 2021-08-24 | 江苏理工学院 | Honeycomb iron-based hydrogenation catalyst (Fe)3O4@ C)/C and preparation method and application thereof |
| CN109796305B (en) * | 2019-02-13 | 2021-08-20 | 北京林业大学 | Method for preparing cyclohexanol by adopting composite catalyst |
| CN109772416B (en) * | 2019-03-04 | 2021-11-19 | 南京工业大学 | Oxygen vacancy-containing phenol hydrogenation catalyst and preparation method thereof |
| CN114797927A (en) * | 2021-01-27 | 2022-07-29 | 中国科学院大连化学物理研究所 | Composite carrier material loaded cobalt-based catalyst, preparation and application thereof |
| CN115254115B (en) * | 2022-08-01 | 2023-08-29 | 长江生态环保集团有限公司 | Co/C-TiO 2 Preparation method of composite material and application of composite material in CO 2 Application in photocatalytic reduction |
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