CN112221508B - Catalyst for preparing phenethyl alcohol by acetophenone hydrogenation and preparation and application methods thereof - Google Patents
Catalyst for preparing phenethyl alcohol by acetophenone hydrogenation and preparation and application methods thereof Download PDFInfo
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- CN112221508B CN112221508B CN202010905115.0A CN202010905115A CN112221508B CN 112221508 B CN112221508 B CN 112221508B CN 202010905115 A CN202010905115 A CN 202010905115A CN 112221508 B CN112221508 B CN 112221508B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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Abstract
Discloses heterogeneous forming SiO2The loaded CuZn @ C catalyst comprises carrier formed SiO2Copper compounds, zinc compounds and elemental carbon; cu SiO2The weight ratio of (A) to (B) is 2-20: 100; the mass ratio of Cu to Zn is 1: 1-5. In addition, the preparation method and the application method of the catalyst in the reaction of preparing alpha-phenethyl alcohol by hydrogenating acetophenone are also disclosed. The catalyst has the advantages of low Cu content, simple preparation method, easy operation, long service life and the like.
Description
Technical Field
The invention belongs to the technical field of production of phenethyl alcohol; relates to a catalyst for preparing phenethyl alcohol by acetophenone hydrogenation and a preparation and application method thereof; more particularly relates to heterogeneous forming SiO for catalyzing acetophenone hydrogenation to prepare alpha-phenethyl alcohol2A loaded CuZn @ C catalyst and a preparation method thereof.
Background
Alpha-phenethyl alcohol is an important chemical intermediate and has wide application in the fields of medicine synthesis, spice manufacture, food additives and the like. The alpha-phenethyl alcohol is synthesized by a microbial fermentation method and an organic synthesis method. The microbial fermentation method generally takes L-phenylalanine and fluorophenylalanine as raw materials, and prepares the alpha-phenethyl alcohol by microbial fermentation. The raw materials adopted by the method are expensive, the production cost is high, and the method is not suitable for large-scale production. At present, acetophenone is mainly used as a raw material in industry, and alpha-phenethyl alcohol is synthesized on a large scale through hydrogenation reaction.
A plurality of side reactions exist in the acetophenone hydrogenation reaction, and the research of developing a heterogeneous catalyst with high activity and high selectivity is the key point of research. The catalyst used for acetophenone hydrogenation mainly comprises noble metal catalysts such as Pt, Pd, Rh and the like, and non-noble metal catalysts such as Ni, Cu and the like. Wherein, the noble metal catalyst and the Ni catalyst respectively have the defects of high price, poor alpha-phenethyl alcohol selectivity and the like. Compared with the Cu catalyst, the Cu catalyst has the advantages of high activity and selectivity, low cost and the like when being used for acetophenone hydrogenation reaction.
Lin et al [ Appl Catal A,1994,113, 59-73]Examine Pt/SiO2、Pt/Al2O3And Pt/TiO2The catalytic performance of the acetophenone hydrogenation reaction is found to be Pt/TiO2The selectivity (95%) of the phenethyl alcohol on the catalyst is much higher than the other two catalysts. Raj et al [ Catal Sci Technol,2012,2, 1429-]Research into the carrier TiO2The influence of the phase state on the hydrogenation reaction of the supported Ni catalytic acetophenone is found, and Ni/TiO2Rutile has the highest activity (phenethyl alcohol yield-96%). Vikanova et al [ Russ J Phys Chem A,2019,93(2):231-]Preparing a Pt/C e2–ZrО2The catalyst is used for acetophenone hydrogenation reaction, and the reaction is carried out for 2h at room temperature and normal pressure, and the yield of the phenethyl alcohol can reach 99%. Xuchangqing, etc. [ molecular catalysis, 2004,18(4):281-]Examine Ni-B/SiO2The catalytic performance of the amorphous catalyst on the acetophenone hydrogenation reaction shows that the temperature has great influence on the distribution of the product. Under the same other conditions, the reaction is carried out at 80 ℃, and the selectivity of the phenethyl alcohol is 92.1 percent; while at 120 deg.C, the selectivity to ethylbenzene was 90.2%. Wang et al [ Appl organic Chem,2019,33: e5000]Preparing Cu/SiO by precipitation method2The catalyst is used for the reaction of preparing the phenethyl alcohol by the hydrogenation of the acetophenone. By adjusting Cu in the catalyst+/(Cu++Cu0) The ratio of (a) to (b) can improve the activity and life of the catalyst. The catalyst continuously reacts for 150 hours at 100 ℃, and the yield of the phenethyl alcohol is still maintained to be 99 percent.
CN109482192A adopts a coprecipitation method to prepare a CuZnBi catalyst, and the CuZnBi catalyst is molded and roasted twice. Used for catalyzing acetophenone hydrogenation reaction, the hydrogen-ketone molar ratio is 15:1 and the liquid hourly space velocity is 0.4h at the temperature of 70 ℃ and the pressure of 2.5MPa-1Under the condition, the conversion rate of the acetophenone can reach 98.8 percent at most, and the selectivity of the alpha-phenethyl alcohol is 99.1 percent. CN1557545A adopts an immersion method to prepare Ni-Sn-B/SiO2Catalyst, using KBH4Reducing for a reducing agent. When the catalyst is used for catalyzing the hydrogenation reaction of acetophenone, the selectivity of phenethyl alcohol can reach 97.5 percent. CN109529870A adopts a precipitation method to prepare the CuSiMnBiPbNa multi-component catalyst, and carries out extrusion molding. Used for catalyzing acetophenone hydrogenation reaction, hydrogen ketone at 80 deg.C and 2.5MPaThe molar ratio is 2:1 and the liquid hourly space velocity is 0.3h-1Under the condition, the conversion rate of the acetophenone can reach 99.3 percent at most, and the selectivity of the alpha-phenethyl alcohol is 99.3 percent.
At present, a Cu-based catalyst for the reaction of preparing alpha-phenethyl alcohol by acetophenone hydrogenation usually needs higher Cu content so as to improve the activity and increase the conversion rate of acetophenone; meanwhile, a plurality of auxiliary agents are required to be added to improve the selectivity of the alpha-phenethyl alcohol. Therefore, how to prepare the supported Cu catalyst with high dispersity, reduce the using amount (reduce the cost) of the supported Cu catalyst, reduce the use of a cocatalyst and obtain the acetophenone hydrogenation catalyst with high activity and high selectivity has great significance for the industrialization of the reaction for preparing the alpha-phenethyl alcohol by acetophenone hydrogenation.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a heterogeneous phase forming SiO2A preparation method of a supported CuZn @ C catalyst and application thereof in the reaction of catalyzing acetophenone hydrogenation to prepare alpha-phenethyl alcohol. The heterogeneous phase forming SiO of the invention2The preparation method of the supported CuZn @ C catalyst is simple, easy to operate and high in repeatability; the catalyst is a heterogeneous catalyst with high activity and selectivity, is used for catalyzing the reaction of preparing alpha-phenethyl alcohol by acetophenone hydrogenation, overcomes the defects of large using amount of Cu, large using amount of an auxiliary agent and the like of the conventional catalyst system, can obviously inhibit side reactions in the reaction process, and has high selectivity on the alpha-phenethyl alcohol. In addition, in the method, the catalyst always keeps higher activity in the reaction process and has good stability.
According to a first aspect of the present invention, there is provided a heterogeneously shaped SiO2The supported CuZn @ C catalyst is characterized by comprising carrier-formed SiO2Copper compounds, zinc compounds and elemental carbon; the copper compound is calculated as Cu, Cu is SiO2The weight ratio of (A) to (B) is 2-20: 100; the zinc compound is calculated by Zn, and the mass ratio of Cu to Zn is 1: 1-5.
According to a second aspect of the present invention, there is provided a method for preparing the aforementioned catalyst, comprising:
according to the formula, respectively preparing water solutions of soluble copper salt and zinc salt and an ethanol solution of trimesic acid, and mixing the two solutions to obtain a suspension;
will shape SiO2Adding the mixture into the suspension, transferring the obtained mixture into a crystallization kettle lined with polytetrafluoroethylene, and reacting for 4-25 hours at 80-200 ℃;
drying after centrifugal separation, and roasting for 1-10 hours at 200-600 ℃ in an inert atmosphere.
According to the preparation method, the copper salt is copper nitrate, copper sulfate, copper chloride or copper acetate, and is preferably copper nitrate.
The preparation method of the invention is characterized in that the concentration of the copper salt is 0.01-0.09 g/ml.
The preparation method of the invention is characterized in that the zinc salt is zinc nitrate, zinc sulfate, zinc chloride or zinc acetate, and zinc nitrate is preferred.
The preparation method of the invention, wherein the formed SiO2The particle size is 20 to 200 meshes, preferably 40 to 100 meshes.
According to the preparation method, the mass ratio of trimesic acid to Cu is 1: 1-5.
According to the preparation method, the concentration of the trimesic acid is 0.01-0.05 g/ml.
According to a third aspect of the present invention, there is provided a method for using the aforementioned catalyst, which is characterized by being used as a catalyst in the preparation of alpha-phenylethyl alcohol by hydrogenation of acetophenone.
According to the application method, the reaction raw material is an ethylbenzene solution of acetophenone, and the concentration of the acetophenone is 5-20 wt%; the reaction conditions were as follows: the molar ratio of hydrogen to ketone is 5-15: 1; liquid hourly space velocity of 0.1-0.8 g (acetophenone). g (catalyst)-1· h-1(ii) a The reaction temperature is 60-100 ℃; the reaction pressure is 1-5 MPa.
The invention has the beneficial effects that: compared with the original method for preparing alpha-phenethyl alcohol by catalytic hydrogenation of acetophenone, the heterogeneous formed SiO prepared by the invention2The supported CuZn @ C catalyst has the advantages of low Cu content, simple preparation method, easy operation,Long service life and the like. The concrete embodiment is as follows:
(1) CuZn @ C/SiO in the invention2The Cu content in the catalyst is low, and the production cost is reduced.
(2) CuZn @ C/SiO in the invention2The catalyst has self-reduction function in the preparation process, and does not need to be reduced in advance before use, thereby simplifying the operation steps.
(3) CuZn @ C/SiO in the invention2The catalyst has high activity and long service life in the reaction of preparing alpha-phenethyl alcohol by acetophenone hydrogenation, and the activity is not obviously reduced after the experiment for 300 h.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the invention. Unless otherwise indicated, percentages in the examples are uniformly percentages by mass.
Preparation of example 1
(1) 2.18g (9mmol, Cu 0.58g) Cu (NO) was weighed3)2· 3H2O and 5.35g (18mmol) Zn (NO)3)2· 6H2O, dissolving the two into 30mL of deionized water;
(2) weighing trimesic acid (H)3BTC) (5mmol, 1.1g) and dissolved in 30mL absolute ethanol;
(3) weighing 6g of 40-60 mesh formed SiO2；
(4) Mixing the solutions obtained in the steps (1) and (2) to obtain a suspension, and forming SiO2Adding into the suspension;
(5) transferring the mixture obtained in the step (4) into a crystallization kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at 150 ℃;
(6) taking out the reaction mixture from the crystallization kettle, centrifugally separating, washing the obtained solid with deionized water, and then drying at 80 ℃ for 12 hours;
(7) putting the solid obtained in the step (6) into a tube furnace, and reacting in N2Roasting at 400 deg.c for 5 hr in atmosphere to obtain formed SiO2Supported CuZn @ C catalyst, noted CuZn @ C/SiO2。
Application example 1
Will make intoCuZn @ C/SiO solid prepared in preparation example 12The catalyst is used for the reaction of preparing alpha-phenethyl alcohol by acetophenone hydrogenation.
20ml of catalyst is filled in a stainless steel tubular reactor with the inner diameter of 20mm, the reaction raw material is ethylbenzene solution of acetophenone, the concentration of the acetophenone is 10 wt%, and the reaction conditions are as follows: the molar ratio of hydrogen to ketone is 10:1, and the liquid hourly space velocity is 0.4g (acetophenone). g (catalyst)-1· h-1And the reaction temperature is 80 ℃, the reaction pressure is 2.5MPa, and the acetophenone hydrogenation reaction is carried out under the conditions to obtain the alpha-phenethyl alcohol. The reaction condensate is analyzed by gas chromatography, and when the reaction lasts for 10 hours, the conversion rate of the acetophenone is 99.5 percent, and the selectivity of the alpha-phenethyl alcohol is 99.3 percent. When the reaction lasts for 300 hours, the conversion rate of the acetophenone is 97.9 percent, and the selectivity of the alpha-phenethyl alcohol is 98.1 percent.
Preparation examples 2 to 4
The same procedure as in preparation example 1 was repeated except for changing the Cu precursor compound contained in step (1) and the amounts of copper sulfate 1.44g, copper chloride 1.21g and copper acetate monohydrate 1.80g to prepare CuZn @ C/SiO in accordance with the present invention each as required2A catalyst.
Application examples 2 to 4
CuZn @ C/SiO prepared in application examples 2-42The catalyst is used for the reaction of preparing the alpha-phenethyl alcohol by the hydrogenation of the acetophenone, and the dosage of other chemical reagents and the reaction steps are the same as those in the application example 1.
The reaction results are shown in Table 1.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (12)
1. Heterogeneous shaping SiO2The supported CuZn @ C catalyst is characterized by comprising carrier-formed SiO2Copper compounds, zinc compounds and elemental carbon; the copper compound is calculated as Cu, Cu is SiO2The weight ratio of (A) to (B) is 2-20: 100; the zinc compound is calculated by Zn, and the mass ratio of Cu to Zn is 1: 1-5; the catalyst is used for the reaction of preparing alpha-phenethyl alcohol by acetophenone hydrogenation;
the preparation method of the catalyst comprises the following steps:
according to the formula, respectively preparing water solutions of soluble copper salt and zinc salt and an ethanol solution of trimesic acid, and mixing the two solutions to obtain a suspension;
will shape SiO2Adding the mixture into the suspension, transferring the obtained mixture into a crystallization kettle lined with polytetrafluoroethylene, and reacting for 4-25 hours at 80-200 ℃;
drying after centrifugal separation, and roasting for 1-10 hours at 200-600 ℃ in an inert atmosphere.
2. The catalyst of claim 1, wherein the copper salt is copper nitrate, copper sulfate, copper chloride or copper acetate.
3. The catalyst of claim 2, wherein the copper salt is copper nitrate.
4. The catalyst according to claim 1, wherein the copper salt is present in a concentration of 0.01 to 0.09 g/ml.
5. The catalyst of claim 1, wherein the zinc salt is zinc nitrate, zinc sulfate, zinc chloride or zinc acetate.
6. The catalyst of claim 5 wherein the zinc salt is zinc nitrate.
7. The catalyst of claim 1, wherein the shaped SiO2The particle size is 20-200 meshes.
8. The catalyst of claim 7, wherein the shaped SiO2The particle size is 40-100 meshes.
9. The catalyst according to claim 1, wherein the mass ratio of trimesic acid to Cu is 1:1 to 5.
10. The catalyst according to claim 1, wherein the concentration of trimesic acid is 0.01 to 0.05 g/ml.
11. The application method of the catalyst of claim 1, which is used as the catalyst in the reaction for preparing alpha-phenethyl alcohol by hydrogenation of acetophenone.
12. The application method of the acetophenone compound as claimed in claim 11, wherein the reaction raw material is ethylbenzene solution of acetophenone, the acetophenone concentration is 5-20 wt%; the reaction conditions were as follows: the molar ratio of hydrogen to ketone is 5-15: 1; liquid hourly space velocity of 0.1-0.8 g (acetophenone). g (catalyst)-1· h-1(ii) a The reaction temperature is 60-100 ℃; the reaction pressure is 1-5 MPa.
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| CN105080552A (en) * | 2014-05-09 | 2015-11-25 | 中国石油化工股份有限公司 | Copper oxide supported catalyst and preparation method therefor |
| CN108404919A (en) * | 2018-03-20 | 2018-08-17 | 天津大学 | Copper C catalyst and preparation method thereof for esters liquid-phase hydrogenatin synthetic fatty alcohol |
| CN109482192A (en) * | 2018-11-30 | 2019-03-19 | 万华化学集团股份有限公司 | A kind of hydrogenation of acetophenone prepares the preparation method and application of the catalyst of alpha-phenyl ethyl alcohol |
| CN110368946A (en) * | 2019-08-05 | 2019-10-25 | 青岛科技大学 | The method that carried non-crystal alloy catalysis hydrogenation of acetophenone prepares alpha-phenyl ethyl alcohol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105080552A (en) * | 2014-05-09 | 2015-11-25 | 中国石油化工股份有限公司 | Copper oxide supported catalyst and preparation method therefor |
| CN108404919A (en) * | 2018-03-20 | 2018-08-17 | 天津大学 | Copper C catalyst and preparation method thereof for esters liquid-phase hydrogenatin synthetic fatty alcohol |
| CN109482192A (en) * | 2018-11-30 | 2019-03-19 | 万华化学集团股份有限公司 | A kind of hydrogenation of acetophenone prepares the preparation method and application of the catalyst of alpha-phenyl ethyl alcohol |
| CN110368946A (en) * | 2019-08-05 | 2019-10-25 | 青岛科技大学 | The method that carried non-crystal alloy catalysis hydrogenation of acetophenone prepares alpha-phenyl ethyl alcohol |
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| 高性能纳米Cu/SiO2催化剂制备及其催化芳酮加氢性能;王兵等;《青岛科技大学学报(自然科学版)》;20200630;第41卷(第03期);48-55 * |
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