CN109364973A - A kind of nitrogen-dopped activated carbon loaded Cu catalyst adds the application in hydrogen in spirit catalytic of cinnamaldehyde - Google Patents
A kind of nitrogen-dopped activated carbon loaded Cu catalyst adds the application in hydrogen in spirit catalytic of cinnamaldehyde Download PDFInfo
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- CN109364973A CN109364973A CN201811301068.8A CN201811301068A CN109364973A CN 109364973 A CN109364973 A CN 109364973A CN 201811301068 A CN201811301068 A CN 201811301068A CN 109364973 A CN109364973 A CN 109364973A
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- hydrogen
- nitrogen
- activated carbon
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- glycine
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- 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
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C29/14—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 present invention discloses a kind of nitrogen-dopped activated carbon loaded Cu catalyst and adds application in hydrogen in spirit catalytic of cinnamaldehyde.The present invention utilizes active carbon, to the complexing of copper ion, to indirectly control the size of copper particle to the suction-operated of glycine and glycine, completed anchoring of the copper on carrier.Then roast presoma at high temperature, glycine is decomposed to form the active carbon of N doping, copper is reduced into cuprous and copper simple substance by nitrating active carbon, the doping of nitrogen not only makes copper be easier to restore, and the dissociation energy of hydrogen can be also reduced in hydrogenation reaction, make reaction be easier to carry out, significantly improves the conversion ratio of cinnamic acid.The complexing of glycine and N doping effect make the conversion ratio of hydrogenation on cinnamic aldehyde and selectivity all reach a high level.The catalyst avoids the use of noble metal, heavy metal, more economical environmental protection, and catalyst preparation process is simple, efficiently, easy to spread.
Description
Technical field
The present invention relates to field of material preparation, in particular to nitrogen-dopped activated carbon loaded Cu catalyst adds in spirit catalytic of cinnamaldehyde
Application in hydrogen.
Background technique
Alpha, beta unsaturated alcohol is the important source material and intermediate of medicine, fragrance etc..Cinnamic acid is the allusion quotation of alpha, beta-unsaturated aldehyde
Type represents.Currently, industrially the method for production cinnamyl alcohol mainly has cinnamic aldehyde catalytic hydrogenation, cinnamic aldehyde reduction method, styrene chloromethane
Base is at ester hydrolysis method, storax saponification method and improvement industrial making method, these methods not only high production cost, but also pollution ring
Border.And using cinnamic acid liquid phase selective add hydrogen prepare cinnamyl alcohol can overcome more than drawback, be more in line with Green Chemistry
It is required that.Therefore, the liquid phase selective of cinnamic acid adds hydrogen to have important theory significance and prospects for commercial application.
Currently, the research about hydrogenation on cinnamic aldehyde is concentrated mainly on load type metal catalyst, it is broadly divided into two classes, one
Class is noble metal catalyst, such as Pt, Au etc.；Another kind is base metal, such as Cu, Co, Ni etc..Typical carrier includes acidity
Al2O3, SiO2, TiO2With alkaline MgO and CNT, active carbon.
The trials such as Li Xiaohong use Pt/SiC, are used for hydrogenation on cinnamic aldehyde, have obtained higher conversion ratio and target product meat
The selectivity of cinnamic alcohol, but production cost is improved using noble metal, and catalyst preparation process is complicated.
Zhang Xinbo etc. uses 16%Cu/ZSM-5, and cinnamic acid conversion ratio is 48%, and cinnamyl alcohol is selectively 42.3%.Huang Pengmian
Equal trials are prepared for Co-Ni/Al2O3Bimetallic catalyst is used for the selective hydrogenation of cinnamic acid, obtains cinnamic acid conversion ratio
It is 30%, cinnamyl alcohol is selectively 68.5%.As it can be seen that using Cu, when the non-metallic catalysts such as Co, although can reduce catalyst at
This, but conversion ratio and selectivity can not improve simultaneously.
C=C and C=O in cinnamic acid form conjugated system, and selective hydrogenation is a more difficult process, no matter make
With which kind of catalyst, high conversion obtains cinnamyl alcohol with high selectivity and all there is certain difficulty.Therefore, if exploitation one
The new non-precious metal catalyst for promoting conversion ratio and selectivity of kind, then have very important significance.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of nitrogen-dopped activated carbon loaded Cu catalyst and adds in spirit catalytic of cinnamaldehyde
Application in hydrogen.
The technical solution of the present invention is as follows:
A kind of nitrogen-dopped activated carbon loaded Cu catalyst adds the application in hydrogen in spirit catalytic of cinnamaldehyde, includes the following steps:
(1) high pressure is added in the nitrogen-dopped activated carbon loaded Cu catalyst of cinnamic acid, solvent isopropanol and cinnamic acid quality 1 ~ 8%
In reaction kettle；
(2) outlet valve is closed after kettle being sealed, is passed through hydrogen, is begun to warm up and is warming up to 120 ~ 170 DEG C of reaction temperature；
(3) when temperature in the kettle reaches reaction temperature, hydrogen cylinder main valve and intake valve are opened, by pressure add to reaction pressure 0.5 ~
2MPa reacts 4 ~ 8 hours；
(4) oil bath pan and hydrogen cylinder main valve are closed after reaction, are analyzed after reaction solution is cooling, centrifugation.
Further, the preparation method of the nitrogen-dopped activated carbon loaded Cu catalyst, includes the following steps:
(1) press 5 ~ 10:100 ~ 180g/ml solid-to-liquid ratio, concentrated nitric acid is added in active carbon, then at 90 ~ 140 DEG C reflux 6 ~
20 hours；
(2) cooling, wash to neutrality after flowing back, the active carbon of dry oxidation is denoted as OAC；
(3) copper sulphate and glycine are dissolved in deionized water, in 40 ~ 70 DEG C of 20 ~ 60min of stirring, it is excessive is prepared into glycine
Cupric glycinate solution；
(4) active carbon aoxidized obtained by addition step (2) in the excessive cupric glycinate solution of glycine obtained by step (3), 40 ~
70 DEG C are stirred 2 ~ 6 hours, until deionized water is evaporated, is then dried and are ground；
(5) it is roasted under nitrogen atmosphere, obtains the copper oxidation activity Pd/carbon catalyst of nitrating, be denoted as Cu N-OAC.
Further, the mass fraction of concentrated nitric acid is 65 ~ 68%.
Further, glycine is excessive with respect to copper sulphate, and the mass ratio of copper sulphate and glycine is more preferably 1:10 ~ 20.
Further, the active carbon of oxidation and preferred 1:5 ~ 20 of the mass ratio of cupric glycinate.
Further, the drying of step (2) and step (4), temperature are 50 ~ 80 DEG C, and the time is 10 ~ 30 hours.
Further, the roasting of step (5), temperature are 700 ~ 900 DEG C, and the time is 1 ~ 4 hour.
The beneficial effects of the present invention are:
(1) present invention using active carbon to the suction-operated of glycine and glycine to the complexing of copper ion, successfully by copper
It is anchored on magnesium oxide/absorbent charcoal, not only increases the dispersion degree of copper, and be doped with nitrogen in the preparation process of catalyst,
Gained nitrogen-dopped activated carbon copper-loading catalyst function admirable.
(2) present invention can be improved the reduction effect of carbon also native copper by N doping, and under high-temperature roasting, copper is largely gone back
Original is at cuprous oxide and copper simple substance；The activated carbon supported copper of nitrating can be effectively reduced hydrogen as hydrogenation on cinnamic aldehyde catalyst
Dissociation energy, make reaction be easier to carry out；Compared with industrial application catalyst, the copper particle after anchoring is not easily runed off, and not only will not
Environmental pollution is caused, and recyclability is excellent.
Detailed description of the invention
Fig. 1 is the process flow diagram of catalyst preparation of the present invention.
Fig. 2 is the TEM phenogram of 1 gained Cu/N-OAC-700 catalyst of embodiment.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, but the present invention is not limited thereto.
Embodiment 1
Cu@N-OAC is reacted for hydrogenation on cinnamic aldehyde
(1) it takes 10g active carbon in the round-bottomed flask of 250ml, is added 135ml concentrated nitric acid (65% ~ 68%), flows back at 120 DEG C
12h；
(2) reflux finishes, and is cooled to room temperature, and filters and is repeatedly washed with deionized water to neutrality；
(3) solid that (2) obtain is dried into the active carbon (OAC) that 12h is aoxidized at 60 DEG C；
(4) 0.135g copper nitrate and 0.2g glycine are dissolved in 20ml water, stir 30min under 50 °, it is excessive to be made into glycine
Cupric glycinate solution；
(5) take 0.5g(3) obtained in OAC in the small beaker of (4), continue to stir 3h under 50 °, until deionized water is evaporated
Dry 12h at (6) 60 DEG C；
(7) solid that grinding (6) obtains, and in a nitrogen atmosphere, respectively in 600 DEG C, 700 DEG C, 800 DEG C of roasting 2h, obtain
To nitrating copper oxidation activity Pd/carbon catalyst (be denoted as Cu N-OAC-600, Cu N-OAC-700, Cu N-OAC-800 respectively,
600,700 and 800 calcination temperature is respectively indicated)
(8) in the autoclave with 50ml liner, 2.5g cinnamic acid is added and 15ml isopropanol makees solvent, adds
Catalyst obtained by 3mg step (7)；
(9) outlet valve is closed after kettle being sealed, is passed through the hydrogen of certain pressure, is begun to warm up and is warming up to 180 DEG C of reaction temperature；
(10) when temperature in the kettle reaches specified reaction temperature, hydrogen cylinder main valve and intake valve is opened, pressure is added into reaction pressure
Power 4MPa, and write down the reaction time started；
Reacting after (11) 6 hours terminates, and closes oil bath pan and hydrogen cylinder main valve, and reaction kettle is placed in cold bath and is down to room
Temperature；
(12) it takes out the reaction solution cooled down in step (11) to be placed in centrifuge tube, wash liner with isopropanol and quantifies,
A centrifuge tube, which is changed, after being centrifuged 3 hours under the revolving speed of 9000r/min repeats this operation；
(13) the appropriate reaction solution being centrifuged in step (12) is taken, determines reaction product using gas-chromatography and chemical titration
Amount.
The catalyst obtained using different maturing temperatures is reacted 6 hours, cinnamic acid conversion ratio at 180 DEG C under the conditions of 4MPa
54.5%, the selectivity of product cinnamyl alcohol is greater than 80%.
| Catalyst | Time/h | Conversion ratio/% | 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 |
Embodiment 2
The dosage for changing glycine prepares catalyst for hydrogenation on cinnamic aldehyde
(1) it takes 10g active carbon in the round-bottomed flask of 250ml, is added 135ml concentrated nitric acid (65% ~ 68%), flows back at 120 DEG C
12h；
(2) reflux finishes, and is cooled to room temperature, and filters and is repeatedly washed with deionized water to neutrality；
(3) solid that (2) obtain is dried into the active carbon (OAC) that 12h is aoxidized at 60 DEG C；
(4) 0.135g copper nitrate respectively with and 0g, 0.1g, 0.2g glycine be dissolved in 20ml water (number 1,2,3), under 50 °
30min is stirred, the excessive cupric glycinate solution of glycine is made into；
(5) take 0.5g(4) obtained in OACs in small beaker, continue to stir 3h under 50 °C, until deionized water is evaporated；
Dry 12h at (6) 60 DEG C；
(7) solid that grinding (6) obtains, and in a nitrogen atmosphere, 700 DEG C of roasting 2h, the copper magnesium oxide/absorbent charcoal for obtaining nitrating is urged
Agent is labeled as 1,2,3(Cu@N-OAC)；
(8) in the autoclave with 50ml liner, 2.5g cinnamic acid aldehyde is added and 15g isopropanol makees solvent, adds
Catalyst obtained by 3mg step (7)；
(9) outlet valve is closed after kettle being sealed, is passed through the hydrogen of certain pressure, is begun to warm up and is warming up to 150 DEG C of reaction temperature；
(10) when temperature in the kettle reaches specified reaction temperature, hydrogen cylinder main valve and intake valve is opened, pressure is added into reaction pressure
Power 2MPa, and write down the reaction time started；
Reacting after (11) 6 hours terminates, and closes oil bath pan and hydrogen cylinder main valve, and reaction kettle is placed in cold bath and is down to room
Temperature；
(12) it takes out the reaction solution cooled down in step (11) to be placed in centrifuge tube, wash liner with isopropanol and quantifies,
A centrifuge tube, which is changed, after being centrifuged 3 hours under the revolving speed of 9000r/min repeats this operation；
(13) the appropriate reaction solution being centrifuged in step (12) is taken, determines reaction product using gas-chromatography and chemical titration
Amount.
At 180 DEG C, reacted 6 hours under the conditions of 6MPa, the selectivity of cinnamic acid conversion ratio 54.5%, product cinnamyl alcohol is greater than
80%。
| Glycine dosage/g | Temperature/DEG C | Pressure/MPa | Time/h | Conversion ratio/% | 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 short, complexing of the present invention using active carbon to the suction-operated and glycine of glycine to copper ion, indirect control
The size for having made copper particle completes anchoring of the copper on carrier.Then roast presoma at high temperature, glycine decomposing shape
At the active carbon of N doping, copper is reduced into cuprous and copper simple substance by nitrating active carbon, and the doping of nitrogen not only makes copper be easier to restore, and
And the dissociation energy of hydrogen can be also reduced in hydrogenation reaction, make reaction be easier to carry out, significantly improves the conversion ratio of cinnamic acid.It is sweet
The complexing of propylhomoserin and N doping effect can make the conversion ratio of hydrogenation on cinnamic aldehyde and selectivity all reach a high level,
And the catalyst avoids the use of noble metal, heavy metal, more economical environmental protection, and catalyst preparation process is simple, efficiently,
It is easy to spread.
Claims (8)
1. a kind of nitrogen-dopped activated carbon loaded Cu catalyst adds the application in hydrogen in spirit catalytic of cinnamaldehyde, which is characterized in that including such as
Lower step:
(1) high pressure is added in the nitrogen-dopped activated carbon loaded Cu catalyst of cinnamic acid, solvent isopropanol and cinnamic acid quality 1 ~ 8%
In reaction kettle；
(2) outlet valve is closed after kettle being sealed, is passed through hydrogen, is begun to warm up and is warming up to 120 ~ 170 DEG C of reaction temperature；
(3) when temperature in the kettle reaches reaction temperature, hydrogen cylinder main valve and intake valve are opened, by pressure add to reaction pressure 0.5 ~
2MPa reacts 4 ~ 8 hours；
(4) oil bath pan and hydrogen cylinder main valve are closed after reaction, are analyzed after reaction solution is cooling, centrifugation.
2. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 1 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, the nitrogen-dopped activated carbon loaded Cu catalyst, preparation method includes the following steps:
(1) press 5 ~ 10:100 ~ 180g/ml solid-to-liquid ratio, concentrated nitric acid is added in active carbon, then at 90 ~ 140 DEG C reflux 6 ~
20 hours；
(2) cooling, wash to neutrality after flowing back, the active carbon of dry oxidation is denoted as OAC；
(3) copper sulphate and glycine are dissolved in deionized water, in 40 ~ 70 DEG C of 20 ~ 60min of stirring, it is excessive is prepared into glycine
Cupric glycinate solution；
(4) active carbon aoxidized obtained by addition step (2) in the excessive cupric glycinate solution of glycine obtained by step (3), 40 ~
70 DEG C are stirred 2 ~ 6 hours, until deionized water is evaporated, is then dried and are ground；
(5) it is roasted under nitrogen atmosphere, obtains the copper oxidation activity Pd/carbon catalyst of nitrating, be denoted as Cu N-OAC.
3. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 2 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, the mass fraction of concentrated nitric acid is 65 ~ 68%.
4. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 2 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, glycine is with respect to copper sulphate excess.
5. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 2 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, the mass ratio of copper sulphate and glycine is 1:10 ~ 20.
6. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 2 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, the active carbon of oxidation and the mass ratio of cupric glycinate are 1:5 ~ 20.
7. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 2 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, the drying of step (2) and step (4), temperature is 50 ~ 80 DEG C, and the time is 10 ~ 30 hours.
8. nitrogen-dopped activated carbon loaded Cu catalyst according to claim 2 adds the application in hydrogen in spirit catalytic of cinnamaldehyde,
It is characterized in that, the roasting of step (5), temperature is 700 ~ 900 DEG C, and the time is 1 ~ 4 hour.
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| CN201811301068.8A CN109364973B (en) | 2018-11-02 | 2018-11-02 | Application of nitrogen-doped activated carbon-loaded Cu catalyst in catalytic hydrogenation of cinnamaldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112340830A (en) * | 2020-11-13 | 2021-02-09 | 山东大学 | Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in persulfate activation treatment of high-salt organic wastewater |
| CN114471661A (en) * | 2022-02-18 | 2022-05-13 | 天津天科同创科技有限公司 | Preparation and application of normal-temperature catalyst for catalytic oxidation of ethyl acetate VOCs (volatile organic compounds) molding catalyst |
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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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2018
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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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112340830A (en) * | 2020-11-13 | 2021-02-09 | 山东大学 | Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in persulfate activation treatment of high-salt organic wastewater |
| CN114471661A (en) * | 2022-02-18 | 2022-05-13 | 天津天科同创科技有限公司 | Preparation and application of normal-temperature catalyst for catalytic oxidation of ethyl acetate VOCs (volatile organic compounds) molding catalyst |
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