CN109364973B - Application of nitrogen-doped activated carbon-loaded Cu catalyst in catalytic hydrogenation of cinnamaldehyde - Google Patents
Application of nitrogen-doped activated carbon-loaded Cu catalyst in catalytic hydrogenation of cinnamaldehyde Download PDFInfo
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- CN109364973B CN109364973B CN201811301068.8A CN201811301068A CN109364973B CN 109364973 B CN109364973 B CN 109364973B CN 201811301068 A CN201811301068 A CN 201811301068A CN 109364973 B CN109364973 B CN 109364973B
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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- 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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
Abstract
The invention discloses an application of a nitrogen-doped activated carbon-loaded Cu catalyst in catalyzing cinnamaldehyde hydrogenation. The invention indirectly controls the size of copper particles by utilizing the adsorption effect of the active carbon on the glycine and the complexing effect of the glycine on copper ions, and completes the anchoring of copper on a carrier. And then roasting the precursor at high temperature, decomposing glycine to form nitrogen-doped activated carbon, reducing copper into cuprous and copper simple substances by the nitrogen-doped activated carbon, wherein the doping of nitrogen not only enables the copper to be more easily reduced, but also can reduce the dissociation energy of hydrogen in the hydrogenation reaction, so that the reaction is easier to carry out, and the conversion rate of cinnamaldehyde is obviously improved. The complexation and nitrogen doping of glycine enable the conversion rate and selectivity of cinnamaldehyde hydrogenation to reach a high level. The catalyst avoids the use of noble metals and heavy metals, is more economical and environment-friendly, and has simple preparation process, high efficiency and easy popularization.
Description
Technical Field
The invention relates to the field of material preparation, in particular to application of a nitrogen-doped activated carbon loaded Cu catalyst in catalyzing cinnamaldehyde hydrogenation.
Background
Alpha, beta-unsaturated alcohols are important raw materials and intermediates for medicines, perfumes, and the like. Cinnamaldehyde is a typical representative of α, β -unsaturated aldehydes. At present, the industrial production methods of cinnamyl alcohol mainly comprise a cinnamic aldehyde catalytic hydrogenation method, a cinnamic aldehyde reduction method, a styrene chloromethyl esterification hydrolysis method, a storax saponification method and an improved industrial preparation method, and the methods have high production cost and pollute the environment. The method for preparing cinnamyl alcohol by liquid-phase selective hydrogenation of cinnamyl aldehyde can overcome the defects and better meet the requirements of green chemistry. Therefore, the liquid-phase selective hydrogenation of the cinnamaldehyde has important theoretical significance and industrial application prospect.
At present, researches on hydrogenation of cinnamaldehyde mainly focus on supported metal catalysts, which are mainly divided into two types, one is a noble metal catalyst, such as Pt, Au and the like; the other is non-noble metal, such as Cu, Co, Ni, etc. Typical supports include acidic Al2O3，SiO2，TiO2And alkaline MgO, CNT, activated carbon.
The prunus red et al tried to use Pt/SiC for the hydrogenation of cinnamaldehyde, resulting in higher conversion and selectivity of cinnamyl alcohol, but use of noble metal increased production cost and complicated catalyst preparation process.
Zhangxin et al used 16% Cu/ZSM-5, with a cinnamaldehyde conversion of 48% and a cinnamyl alcohol selectivity of 42.3%. Huangpeng, et Al attempted to prepare Co-Ni/Al2O3The bimetallic catalyst is used for the selective hydrogenation reaction of the cinnamaldehyde, the conversion rate of the obtained cinnamaldehyde is 30%, and the selectivity of the cinnamyl alcohol is 68.5%. It is found that when a non-metal catalyst such as Cu or Co is used, although the catalyst cost can be reduced, the conversion and selectivity cannot be improved at the same time.
C = C and C = O in cinnamaldehyde form a conjugated system, and selective hydrogenation thereof is a difficult process, and high conversion and high selectivity of obtaining cinnamyl alcohol are difficult regardless of the catalyst used. Therefore, it is of great importance if a new non-noble metal catalyst is developed that promotes conversion and selectivity.
Disclosure of Invention
Aiming at the technical problems, the invention provides an application of a nitrogen-doped activated carbon-loaded Cu catalyst in catalyzing cinnamaldehyde hydrogenation.
The technical scheme of the invention is as follows:
the application of the nitrogen-doped activated carbon loaded Cu catalyst in catalyzing cinnamaldehyde hydrogenation comprises the following steps:
(1) adding cinnamaldehyde, isopropanol serving as a solvent and a nitrogen-doped activated carbon loaded Cu catalyst accounting for 1-8% of the mass of the cinnamaldehyde into a high-pressure reaction kettle;
(2) sealing the kettle, closing an outlet valve, introducing hydrogen, and heating to raise the temperature to 120-170 ℃;
(3) when the temperature in the kettle reaches the reaction temperature, opening a main valve of a hydrogen cylinder and an air inlet valve, adding the pressure to the reaction pressure of 0.5-2 MPa, and reacting for 4-8 hours;
(4) and (4) closing the oil bath pot and the hydrogen cylinder main valve after the reaction is finished, cooling and centrifuging the reaction liquid, and analyzing.
Further, the preparation method of the nitrogen-doped activated carbon-supported Cu catalyst comprises the following steps:
(1) adding concentrated nitric acid into activated carbon according to a solid-to-liquid ratio of 5-10: 100-180 g/ml, and refluxing for 6-20 hours at 90-140 ℃;
(2) after the reflux is finished, cooling, washing to be neutral, and drying to obtain oxidized activated carbon which is marked as OAC;
(3) dissolving copper sulfate and glycine in deionized water, and stirring at 40-70 ℃ for 20-60 min to prepare a copper glycine solution with excessive glycine;
(4) adding the oxidized activated carbon obtained in the step (2) into the copper glycine solution with excessive glycine obtained in the step (3), stirring for 2-6 hours at 40-70 ℃ until deionized water is evaporated to dryness, and then drying and grinding;
(5) and roasting in a nitrogen atmosphere to obtain the nitrogen-doped copper oxidation activated carbon catalyst which is recorded as Cu @ N-OAC.
Further, the mass fraction of the concentrated nitric acid is 65-68%.
Further, glycine is in excess relative to copper sulfate, and the mass ratio of copper sulfate to glycine is more preferably 1: 10 to 20.
Further, the mass ratio of oxidized activated carbon to copper glycinate is preferably 1: 5 to 20.
Further, the drying in the step (2) and the step (4) is carried out at the temperature of 50-80 ℃ for 10-30 hours.
Further, the roasting in the step (5) is carried out at the temperature of 700-900 ℃ for 1-4 hours.
The invention has the beneficial effects that:
(1) according to the invention, the adsorption effect of the activated carbon on glycine and the complexing effect of the glycine on copper ions are utilized to successfully anchor copper on the oxidized activated carbon, so that the dispersity of the copper is improved, the nitrogen element is doped in the preparation process of the catalyst, and the obtained nitrogen-doped activated carbon loaded copper catalyst has excellent performance.
(2) According to the invention, the reduction effect of carbon-reduced copper can be improved by nitrogen doping, and most of copper is reduced into cuprous oxide and copper simple substance under high-temperature roasting; the nitrogen-doped activated carbon loaded copper is used as a cinnamaldehyde hydrogenation catalyst, so that the dissociation energy of hydrogen can be effectively reduced, and the reaction is easier to carry out; compared with the catalyst for industrial application, the anchored copper particles are not easy to lose, not only can not cause environmental pollution, but also have excellent recovery performance.
Drawings
FIG. 1 is a block diagram of a process flow for the preparation of a catalyst according to the present invention.
FIG. 2 is a TEM representation of the Cu/N-OAC-700 catalyst obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
Cu @ N-OAC for hydrogenation reaction of cinnamaldehyde
(1) Taking 10g of activated carbon, putting the activated carbon into a 250ml round-bottom flask, adding 135ml of concentrated nitric acid (65-68%), and refluxing for 12 hours at 120 ℃;
(2) after the reflux is finished, cooling to room temperature, filtering and washing with deionized water for multiple times until the solution is neutral;
(3) drying the solid obtained in step (2) at 60 ℃ for 12h to obtain Oxidized Activated Carbon (OAC);
(4) dissolving 0.135g of copper nitrate and 0.2g of glycine in 20ml of water, and stirring at 50 ℃ for 30min to prepare a copper glycine solution with excessive glycine;
(5) 0.5g of OAC from (3) was taken in a small beaker (4) and stirring was continued at 50 ℃ for 3h until the deionised water had evaporated to dryness
(6) Drying at 60 deg.C for 12 h;
(7) grinding the solid obtained in step (6), and roasting at 600 ℃, 700 ℃ and 800 ℃ for 2h in a nitrogen atmosphere to obtain the nitrogen-doped copper oxide activated carbon catalyst (respectively marked as Cu @ N-OAC-600, Cu @ N-OAC-700, Cu @ N-OAC-800, 600, 700 and 800 respectively represent the calcination temperature)
(8) Adding 2.5g of cinnamaldehyde and 15ml of isopropanol serving as solvents into a high-pressure reaction kettle with a 50ml lining, and then adding 3mg of the catalyst prepared in the step (7);
(9) sealing the kettle, closing the outlet valve, introducing hydrogen with certain pressure, and heating to the reaction temperature of 180 ℃;
(10) when the temperature in the kettle reaches the designated reaction temperature, opening a main valve of a hydrogen cylinder and an air inlet valve, adding the pressure to 4MPa of reaction pressure, and recording the start time of the reaction;
(11) after the reaction is finished after 6 hours, closing the oil bath pot and the total valve of the hydrogen cylinder, and placing the reaction kettle in a cold water bath to be cooled to room temperature;
(12) taking out the reaction solution cooled in the step (11), putting the reaction solution into a centrifuge tube, washing the inner liner with isopropanol, quantifying, centrifuging at the rotating speed of 9000r/min for 3 hours, and then replacing one centrifuge tube to repeat the operation;
(13) and (4) taking a proper amount of the reaction liquid centrifuged in the step (12), and determining the amount of the reaction product by using a gas chromatography and a chemical titration method.
The catalyst obtained by different roasting temperatures is used for reacting for 6 hours at 180 ℃ and 4MPa, the conversion rate of the cinnamaldehyde is 54.5 percent, and the selectivity of the product cinnamyl alcohol is more than 80 percent.
| Catalyst and process for preparing same | Time/h | Conversion rate/% | Selectivity/%) |
| Cu@N-OAC-600 | 6 | 18.7 | 75.8 |
| Cu@N-OAC-700 | 6 | 54.5 | 80.3 |
| Cu@N-OAC-800 | 6 | 60.9 | 63.0 |
Example 2
Preparation of catalyst for hydrogenation of cinnamaldehyde by changing use amount of glycine
(1) Taking 10g of activated carbon, putting the activated carbon into a 250ml round-bottom flask, adding 135ml of concentrated nitric acid (65-68%), and refluxing for 12 hours at 120 ℃;
(2) after the reflux is finished, cooling to room temperature, filtering and washing with deionized water for multiple times until the solution is neutral;
(3) drying the solid obtained in step (2) at 60 ℃ for 12h to obtain Oxidized Activated Carbon (OAC);
(4) dissolving 0.135g of copper nitrate and 0g, 0.1g and 0.2g of glycine in 20ml of water (numbers 1, 2 and 3), and stirring at 50 ℃ for 30min to prepare a copper glycine solution with excessive glycine;
(5) taking 0.5g of the OACs obtained in (4) into a small beaker, and continuing stirring for 3 hours at 50 ℃ until deionized water is evaporated to dryness;
(6) drying at 60 deg.C for 12 h;
(7) grinding the solid obtained in the step (6), and roasting for 2h at 700 ℃ in a nitrogen atmosphere to obtain a nitrogen-doped copper oxidation activated carbon catalyst marked as 1, 2, 3 (Cu @ N-OAC);
(8) adding 2.5g of cinnamaldehyde and 15g of isopropanol serving as solvents into a high-pressure reaction kettle with a 50ml lining, and then adding 3mg of the catalyst prepared in the step (7);
(9) sealing the kettle, closing the outlet valve, introducing hydrogen with certain pressure, and heating to the reaction temperature of 150 ℃;
(10) when the temperature in the kettle reaches the designated reaction temperature, opening a main valve of a hydrogen cylinder and an air inlet valve, adding the pressure to the reaction pressure of 2MPa, and recording the reaction starting time;
(11) after the reaction is finished after 6 hours, closing the oil bath pot and the total valve of the hydrogen cylinder, and placing the reaction kettle in a cold water bath to be cooled to room temperature;
(12) taking out the reaction solution cooled in the step (11), putting the reaction solution into a centrifuge tube, washing the inner liner with isopropanol, quantifying, centrifuging at the rotating speed of 9000r/min for 3 hours, and then replacing one centrifuge tube to repeat the operation;
(13) and (4) taking a proper amount of the reaction liquid centrifuged in the step (12), and determining the amount of the reaction product by using a gas chromatography and a chemical titration method.
The reaction is carried out for 6 hours at 180 ℃ and under the condition of 6MPa, the conversion rate of the cinnamaldehyde is 54.5 percent, and the selectivity of the product cinnamyl alcohol is more than 80 percent.
| Glycine dosage/g | Temperature/. degree.C | pressure/MPa | Time/h | Transformation ofRate/%) | Selectivity/%) |
| 0g | 180 | 4 | 6 | 8.6 | 76.5 |
| 0.1 | 180 | 4 | 6 | 30.7 | 77.9 |
| 0.2 | 180 | 4 | 6 | 54.5 | 80.3 |
In a word, the invention indirectly controls the size of copper particles by utilizing the adsorption effect of the activated carbon on the glycine and the complexing effect of the glycine on copper ions, and completes the anchoring of copper on a carrier. And then roasting the precursor at high temperature, decomposing glycine to form nitrogen-doped activated carbon, reducing copper into cuprous and copper simple substances by the nitrogen-doped activated carbon, wherein the doping of nitrogen not only enables the copper to be more easily reduced, but also can reduce the dissociation energy of hydrogen in the hydrogenation reaction, so that the reaction is easier to carry out, and the conversion rate of cinnamaldehyde is obviously improved. The complexation and nitrogen doping effects of the glycine enable the conversion rate and selectivity of cinnamaldehyde hydrogenation to reach a very high level, and the catalyst avoids the use of noble metals and heavy metals, is more economical and environment-friendly, and is simple in preparation process, high in efficiency and easy to popularize.
Claims (7)
1. The application of the nitrogen-doped activated carbon-loaded Cu catalyst in catalyzing cinnamaldehyde hydrogenation is characterized by comprising the following steps:
(1) adding cinnamaldehyde, isopropanol serving as a solvent and a nitrogen-doped activated carbon loaded Cu catalyst accounting for 1-8% of the mass of the cinnamaldehyde into a high-pressure reaction kettle;
(2) sealing the kettle, closing an outlet valve, introducing hydrogen, and heating to raise the temperature to 120-170 ℃;
(3) when the temperature in the kettle reaches the reaction temperature, opening a main valve of a hydrogen cylinder and an air inlet valve, adding the pressure to the reaction pressure of 0.5-2 MPa, and reacting for 4-8 hours;
(4) after the reaction is finished, closing the oil bath pot and the hydrogen cylinder main valve, cooling and centrifuging the reaction liquid, and then analyzing;
the preparation method of the nitrogen-doped activated carbon loaded Cu catalyst comprises the following steps:
(1) adding concentrated nitric acid into activated carbon according to a solid-to-liquid ratio of 5-10: 100-180 g/ml, and refluxing for 6-20 hours at 90-140 ℃;
(2) after the reflux is finished, cooling, washing to be neutral, and drying to obtain oxidized activated carbon which is marked as OAC;
(3) dissolving copper sulfate and glycine in deionized water, and stirring at 40-70 ℃ for 20-60 min to prepare a copper glycine solution with excessive glycine;
(4) adding the oxidized activated carbon obtained in the step (2) into the copper glycine solution with excessive glycine obtained in the step (3), stirring for 2-6 hours at 40-70 ℃ until deionized water is evaporated to dryness, and then drying and grinding;
(5) and roasting at 700-900 ℃ in a nitrogen atmosphere to obtain the nitrogen-doped copper oxidation activated carbon catalyst which is marked as Cu @ N-OAC.
2. The application of the nitrogen-doped activated carbon-supported Cu catalyst in catalytic cinnamaldehyde hydrogenation is characterized in that the mass fraction of concentrated nitric acid is 65-68%.
3. The use of a nitrogen-doped activated carbon-supported Cu catalyst in the catalytic hydrogenation of cinnamaldehyde according to claim 1, wherein glycine is in excess to copper sulfate.
4. The application of the nitrogen-doped activated carbon-supported Cu catalyst in catalytic hydrogenation of cinnamaldehyde according to claim 1, wherein the mass ratio of copper sulfate to glycine is 1: 10 to 20.
5. The application of the nitrogen-doped activated carbon-supported Cu catalyst in catalytic hydrogenation of cinnamaldehyde according to claim 1, wherein the mass ratio of oxidized activated carbon to copper glycinate is 1: 5 to 20.
6. The application of the nitrogen-doped activated carbon-supported Cu catalyst in catalytic hydrogenation of cinnamaldehyde according to claim 1, wherein the drying in the step (2) and the step (4) is performed at 50-80 ℃ for 10-30 hours.
7. The application of the nitrogen-doped activated carbon-supported Cu catalyst in catalytic hydrogenation of cinnamaldehyde according to claim 1, wherein the roasting in the step (5) is carried out for 1-4 hours.
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| CN101348419A (en) * | 2007-07-19 | 2009-01-21 | 浙江工业大学 | Method for preparing cinnamic alcohol by hydrogen transfer reaction of benzalacet aldehyde |
| KR20110038324A (en) * | 2009-10-08 | 2011-04-14 | 주식회사 엘지화학 | Method for the hydrogenation of aldehydes and apparatus using the same |
| CN106390930A (en) * | 2016-12-18 | 2017-02-15 | 中南大学 | Method for preparing silver-loaded activated carbon through glycine and silver nitrate complexation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348419A (en) * | 2007-07-19 | 2009-01-21 | 浙江工业大学 | Method for preparing cinnamic alcohol by hydrogen transfer reaction of benzalacet aldehyde |
| KR20110038324A (en) * | 2009-10-08 | 2011-04-14 | 주식회사 엘지화학 | Method for the hydrogenation of aldehydes and apparatus using the same |
| CN106390930A (en) * | 2016-12-18 | 2017-02-15 | 中南大学 | Method for preparing silver-loaded activated carbon through glycine and silver nitrate complexation |
Non-Patent Citations (1)
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| Highly selective copper nanoparticles for the hydrogenation of α,β-unsaturated aldehydes in liquid phase;Victoria Gutiérrez等;《Applied Catalysis A:General》;20130602(第464-465期);第109-115页 * |
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