CN114029095B - Cu/SiO for preparing cyclohexanone by efficiently catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 Preparation method and application of catalyst - Google Patents
Cu/SiO for preparing cyclohexanone by efficiently catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 Preparation method and application of catalyst Download PDFInfo
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- CN114029095B CN114029095B CN202111542616.8A CN202111542616A CN114029095B CN 114029095 B CN114029095 B CN 114029095B CN 202111542616 A CN202111542616 A CN 202111542616A CN 114029095 B CN114029095 B CN 114029095B
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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
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J23/72—Copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the field of catalysts, and in particular relates to Cu/SiO for preparing cyclohexanone by efficiently catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 Preparation method and application of catalyst, and chemical precipitation method is adopted to synthesize Cu/SiO under specific conditions 2 Catalyst, obtain the Cu/SiO 2 The color of (2) is black, and under certain reaction conditions, a fixed bed device is adopted to catalyze alcohol to prepare aldehyde through non-oxidative dehydrogenation. Cu/SiO of the present invention 2 The catalyst can efficiently prepare the cyclohexanone by catalytic dehydrogenation of cyclohexanol under a proper temperature condition, has very excellent yield and stability, has the yield of 81% at 280 ℃ and basically unchanged activity after 48 hours of operation. The preparation method has the characteristics of easily controlled preparation conditions, environment friendliness, simple process, good operability, high catalytic efficiency, low energy consumption, high stability, no secondary pollution and the like.
Description
Technical Field
The invention belongs to the field of catalysts, and in particular relates to an oxygen vacancy Cu/SiO applied to catalyzing cyclohexanol to prepare cyclohexanone by non-oxidative dehydrogenation 2 A catalyst and a method for preparing the same.
Background
Cyclohexanone, a colorless transparent liquid with a clay smell, is a saturated cyclic ketone having carbonyl carbon atoms included in a six-membered ring. Is an important intermediate for preparing nylon-66 and nylon-6, is widely applied to the fields of pesticides, medicines, synthetic fibers, organic solvents and the like, and has important industrial value and economic value.
Common methods for preparing cyclohexanone are cyclohexane oxidation, cyclohexene hydration and phenol hydrogenation, respectively. Cyclohexane oxidation can be classified into catalytic oxidation and non-catalytic oxidation, the former generates a series of byproducts, and the sintering of the catalyst occurs during the reaction, which reduces economic efficiency.
Although the cyclohexene hydration method avoids the problems of coking and waste lye generation in the synthesis process, the cyclohexene hydration method has high reaction temperature in the production process and can generate great energy consumption.
Since phenol is the most toxic phenol compound in the phenol hydrogenation process, the physical health of operators is inevitably damaged in the production process.
The reaction for preparing cyclohexanone by adopting cyclohexanol non-oxidative dehydrogenation only needs to directly remove hydrogen atoms on cyclohexanol through the interaction of the catalyst and cyclohexanol under the protection of a dehydrogenation catalyst and argon under the condition of not introducing an oxidant, so that cyclohexanone is generated, and the reaction for preparing hydrogen is also realized. The process is relatively simple, low in production cost and sufficient in raw materials. Basically no side reaction is generated in the production process, and the method accords with the green environment-friendly pollution-free index.
Copper is one of the earliest metals used by humans, which is characterized by low cost and large stock compared with other metals, and copper-based catalysts are widely used in various redox reactions, and there is a current preparation of Cu-SiO 2 Catalytic gas phase dehydrogenation of cyclohexanol to prepare cyclohexanone. But Cu-SiO prepared at present 2 The catalyst is poor in reaction stability, and the copper-based catalyst is easily sintered at high temperature and high pressure to lose activity. Wherein 280 ℃ is a critical temperature point for the reaction of the copper catalyst, and the higher reaction temperature (more than or equal to 280 ℃) can lead the copper catalyst to grow up in the long-time reaction process, thereby leading to rapid deactivation of the catalyst. In order to improve its stability. Usually, other metals or metal oxides are doped or the activity is prevented from being reduced, the reaction is generally carried out at a lower temperature, the reaction temperature of most copper catalysts is controlled below 260 ℃ at most, and the conversion rate is sacrificed to ensure the catalysisThe activity of the catalyst can be maintained for a long time because the catalyst high-temperature crystal is easy to grow up and easy to coke. Therefore, how to prepare Cu-SiO with high stability 2 The catalyst is applied to the conversion of cyclohexanol into cyclohexanone, can ensure the long-term stability of the catalyst even at a higher temperature, and solves the problem that a copper-based catalyst is easy to deactivate.
Disclosure of Invention
The invention aims to provide a method for loading copper on silicon dioxide to synthesize oxygen vacancies Cu/SiO 2 A method for preparing the catalyst. The catalyst is used for catalyzing cyclohexanol into cyclohexanone and removing hydrogen atoms to form hydrogen under the combined action of copper and silicon dioxide in a non-oxidizing environment, and the reaction process is green and pollution-free and has high atom utilization rate.
Synthesizing a catalyst precursor by adopting a chemical precipitation method, and introducing argon to protect gas, wherein a certain mass of CuO (NO 3 ) 2 ·3H 2 O is dissolved in deionized water, and a certain amount of sodium borohydride solution and aerosol silica sol are sequentially added thereto. And adjusting the PH by sodium borohydride, stirring for one hour, filtering, washing to be neutral by deionized water, and drying in a vacuum drying oven at 60 ℃ to obtain the catalyst precursor. Then adopting a calcination and reduction method to obtain Cu/SiO 2 The catalyst is prepared by calcining a proper amount of dried catalyst precursor in a muffle furnace at 400 ℃ for 4 hours to obtain copper oxide powder, and reducing the copper oxide powder with hydrogen at a certain temperature for 3 hours to obtain Cu/SiO 2 A catalyst.
Wherein Cu (NO) 3 ) 2 ·3H 2 The mass ratio of O to sodium borohydride is as follows: 3-4:1. Too little sodium borohydride results in Cu in the solution 2+ The ions cannot be fully reduced to solid particles. The pH adjustment by sodium borohydride is a key operation of the invention, and the traditional alkaline substances such as sodium hydroxide can only adjust the pH and can not carry out reduction reaction with copper salt, while the invention adopts Cu/SiO prepared by sodium borohydride 2 Compared with the traditional process, the catalyst can remarkably improve the thermal stability of the catalyst.
Cu(NO 3 ) 2 ·3H 2 O and gas phase IIThe mass ratio of the silicon oxide is as follows: 5:0.5-3.
The compounds that regulate the pH are: the pH of the sodium borohydride solution was adjusted to a range of 5-8, thereby making the adjusted copper black, which has oxygen vacancies. Whereas Cu/SiO prepared by the prior art 2 The copper of the catalyst was red. Further preferably ph=7.5.
The temperature of the reduction is: the temperature rises to 350 ℃ for one hour and then to 400 ℃ for two hours, and the temperature rising rates in the temperature rising process are as follows: 2 ℃/min.
The catalyst prepared by the method is used for catalyzing cyclohexanol to be subjected to non-oxidative dehydrogenation to prepare cyclohexanone, and the method comprises the following steps: weighing 0.5g of catalyst, and carrying out catalytic cyclohexanol non-oxidative dehydrogenation in a fixed bed under the protection of 10ml/min argon to generate cyclohexanone, wherein the reaction temperature range is as follows: the reaction pressure is normal pressure at 200-340 ℃.
The invention has the following advantages:
(1) The active component of the catalyst is copper, the copper is used as a common metal element, the source is wide, the price is low, a large number of oxygen vacancies are generated through black copper, and the problem that the copper-based catalyst is unstable and easy to deactivate is solved.
(2) Compared with the common traditional oxidants, molecular sieve catalysts, active carbon supported catalysts and oxide supported catalysts, the catalyst converts cyclohexanol into cyclohexanone through kettle type long-time reaction, so that the reaction time is greatly shortened.
(3) The catalyst directly removes hydrogen in hydroxyl in cyclohexanol to generate cyclohexanone and generates hydrogen, no other oxidant such as oxygen is introduced in the reaction process, the reaction is clean, coking of the catalyst is not easy to occur, the activity of the catalyst is reduced, side reaction is low, the yield is high, the atomic utilization rate is high, and the catalyst accords with the idea of green chemistry.
Description of the drawings:
fig. 1 is an XRD pattern of the synthetic catalyst of example 1 and comparative example 1.
Fig. 2 is an SEM image of the synthetic catalyst of example 1.
Fig. 3 is an SEM image of the synthetic catalyst of comparative example 1.
Fig. 4 is a graph of cyclohexanone yields at a temperature of 280 c for the synthesis catalysts of example 1, example 4, example 5 and example 6.
Fig. 5 is a graph of cyclohexanone yields at a temperature of 280 c for the synthesis catalysts of example 1, example 2, example 3 and comparative examples 1 and 2.
FIG. 6 is a graph showing the stability of the synthetic catalysts of example 1, example 2, example 3 and comparative examples 1 and 2 at 280℃for 6 h.
FIG. 7 is a 48h stability profile of the synthetic catalysts of example 2 and example 3 at a temperature of 280 ℃.
FIG. 8 is a diagram of Cu/SiO obtained by different reduction methods 2 Stability comparison at 280 ℃.
FIG. 9 is a graph showing the crystalline Cu/SiO obtained at different pH 2 SEM and EDS images at 280 ℃.
Detailed Description
Example 1
Weighing Cu (NO) 3 ) 2 ·3H 2 O5 g, dissolving in 50mL deionized water, dissolving 1.6g of sodium borohydride in 50mL deionized water, dissolving 1g of fumed silica in 20mL deionized water, stirring copper nitrate solution under the protection of argon, adding sodium borohydride solution and fumed silica solution respectively during stirring, and regulating the pH to 7.5 by using the sodium borohydride solution. Stirring for one hour, filtering, washing, drying after the reaction is finished, and calcining for 4 hours at 400 ℃ in a muffle furnace after drying. Cooling to room temperature, putting into a fixed bed, introducing hydrogen for reduction, firstly reducing for 1h at 350 ℃, and reducing for 2h at 400 ℃. Taking out the obtained black powder after reduction as a catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 280 ℃ for reaction, and the reaction yield is: 81%.
Example 2
The pH of the solution was adjusted to 7.2, and the procedure was followed in example 1 to obtainThe black powder is catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 280 ℃ for reaction, and the reaction yield is: 63%.
Example 3
The pH of the solution was adjusted to 5.1, the procedure was otherwise as in example 1, and the black powder obtained finally was used as catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 280 ℃ for reaction, and the reaction yield is: 77%.
Example 4
The procedure is as in example 1, the black powder obtained finally being the catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 260 ℃ for reaction, and the reaction yield is: 65%.
Example 5
The procedure is as in example 1, the black powder obtained finally being the catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 300 ℃ for reaction, and the reaction yield is: 78%.
Example 6
The procedure is as in example 1, the black powder obtained finally being the catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 320 ℃ for reaction, and the reaction yield is: 72%.
Stability experiment:
the black powder obtained in examples 1-3 was used as catalyst Cu/SiO 2 0.5g of catalyst is weighed and put into a fixed bed, cyclohexanol solution is introduced under the protection of 10ml/min argon, the temperature is raised to 280 ℃ for reaction, and the reaction is carried out for six hours for stability test.
Then pH of example 1 to 7.5,EXAMPLE 2 Cu/SiO with pH adjusted to 7.2 2 0.5g of the mixture is weighed and placed in a fixed bed, a cyclohexanol solution is introduced under the protection of 10ml/min of nitrogen, the temperature is raised to 280 ℃ for reaction, and the reaction is carried out for 48 hours for stability test.
FIG. 6 shows conversion efficiency at different pH values, the best stability of example 1 was determined, and FIG. 7 shows 48h stability test of the catalysts of example 1 and example 2. The stability was optimal at pH 7.2.
FIG. 9 is a graph showing the crystalline Cu/SiO obtained at different pH 2 SEM and EDS images at 280 ℃. The content of specific elements can be known more through EDS, and the catalyst elements consist of Cu, si and O.
Comparative example 1
The pH of the solution was adjusted to 2.4, the procedure was otherwise as in example 1, and the red powder obtained finally was used as catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 280 ℃ for reaction, and the reaction yield is: 18%.
Comparative example 2
The pH of the solution was adjusted to 3.0, and the red powder obtained in the same manner as in example 1 was used as a catalyst Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 280 ℃ for reaction, and the reaction yield is: 21%.
Stability experiment:
the catalysts obtained in comparative example 1 and comparative example 2 were Cu/SiO 2 0.5g of catalyst is weighed and placed in a fixed bed, cyclohexanol solution is introduced under the protection of 10ml/min argon, the temperature is raised to 280 ℃ for reaction, and the reaction is carried out for six hours for stability test. It can be seen that the stability of the catalysts of comparative examples 1 and 2 was poor.
Comparative example 3
Compared to example 1, the catalyst reduction method was changed:
weighing Cu (NO) 3 ) 2 ·3H 2 O5 g, dissolved in 50In mL of deionized water, 1.6g of sodium borohydride is weighed and dissolved in 50mL of deionized water, 1g of fumed silica is weighed and dissolved in 20mL of deionized water, the copper nitrate solution is stirred under the protection of argon, the sodium borohydride solution and the fumed silica solution are respectively added in the stirring process, and the pH is adjusted to 7.5 by the sodium borohydride solution. Stirring for one hour, filtering, washing, drying after the reaction is finished, and calcining for 4 hours at 400 ℃ in a muffle furnace after drying. Cooling to room temperature, putting into a fixed bed, introducing hydrogen for reduction, and directly heating to 400 ℃ for reduction for 3 hours. Taking out the obtained black powder after reduction to obtain catalytic Cu/SiO 2 。
0.5g of catalyst is weighed and put into a fixed bed, and cyclohexanol solution is introduced under the protection of 10ml/min argon, and the temperature is raised to 280 ℃ for reaction, and the reaction yield is: 58.5%. And the stability of the obtained catalyst is poor.
Claims (5)
1. Cu/SiO for preparing cyclohexanone by efficiently catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 The preparation method of the catalyst is characterized in that: the preparation method of the catalyst comprises the following steps:
(1) Cu (NO) was introduced under argon shield gas 3 ) 2 ·3H 2 O is dissolved in deionized water, sodium borohydride solution and aerosol silica sol are sequentially added into the deionized water, the pH value of the solution is regulated to 5-8 by sodium borohydride, after stirring, the solution is filtered, deionized water is used for washing to be neutral, and the solution is dried in a vacuum drying oven to obtain a catalyst precursor; cu (NO) 3 ) 2 ·3H 2 The mass ratio of O to sodium borohydride is as follows: 3-4:1;
(2) Placing the dried catalyst precursor in a muffle furnace, and calcining at 400 ℃ to obtain CuO/SiO 2 Grinding the catalyst to obtain catalyst powder;
(3) Taking a proper amount of CuO/SiO calcined by a muffle furnace 2 Reducing with hydrogen, and keeping at 40 ℃ to 350 ℃ for 1h, and keeping at 400 ℃ for 2h, wherein the heating rate is as follows: 2 ℃/min to obtain Cu/SiO 2 A catalyst.
2. For high efficiency according to claim 1Cu/SiO for preparing cyclohexanone by catalyzing cyclohexanol to perform anaerobic dehydrogenation 2 A process for producing a catalyst, characterized in that in the step (1), cu (NO 3 ) 2 ·3H 2 The mass ratio of O to the gas phase silicon dioxide is as follows: 5-6:1.
3. Cu/SiO for the efficient catalytic anaerobic dehydrogenation of cyclohexanol to cyclohexanone according to claim 1 2 A process for preparing the catalyst, characterized in that the pH of the solution is adjusted to 7.5 with sodium borohydride.
4. A Cu/SiO prepared according to the method of any one of claims 1-3 2 The application of the catalyst is characterized in that the catalyst is used for catalyzing cyclohexanol to be subjected to non-oxidative dehydrogenation to prepare cyclohexanone.
5. The Cu/SiO according to claim 4 2 The application of the catalyst is characterized in that the application method comprises the following steps: weighing a catalyst, and carrying out catalytic cyclohexanol non-oxidative dehydrogenation in a fixed bed under the protection of 10mL/min argon to generate cyclohexanone, wherein the reaction temperature range is as follows: 260-320 ℃.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4918239A (en) * | 1988-12-27 | 1990-04-17 | National Science Council | Method of producing cyclohexanone from cyclohexanol through oxidative dehydrogenation |
| CN1236668A (en) * | 1998-05-22 | 1999-12-01 | 中国科学院山西煤炭化学研究所 | Non-crystal Cu/SiO2 catalyst and its preparing process and usage |
| CN1868988A (en) * | 2006-07-03 | 2006-11-29 | 浙江工业大学 | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol |
| CN102060656A (en) * | 2010-12-21 | 2011-05-18 | 湘潭大学 | Method for preparing cyclohexanone |
| CN102247854A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing cyclohexanone by virtue of cyclohexanol dehydrogenation as well as preparation method thereof |
| CN102921420A (en) * | 2012-11-09 | 2013-02-13 | 上海应用技术学院 | Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent |
| CN112452326A (en) * | 2020-11-25 | 2021-03-09 | 常州大学 | Preparation method of copper black titanium catalyst and application of copper black titanium catalyst in selective catalytic oxidation denitration |
-
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- 2021-12-16 CN CN202111542616.8A patent/CN114029095B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4918239A (en) * | 1988-12-27 | 1990-04-17 | National Science Council | Method of producing cyclohexanone from cyclohexanol through oxidative dehydrogenation |
| CN1236668A (en) * | 1998-05-22 | 1999-12-01 | 中国科学院山西煤炭化学研究所 | Non-crystal Cu/SiO2 catalyst and its preparing process and usage |
| CN1868988A (en) * | 2006-07-03 | 2006-11-29 | 浙江工业大学 | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol |
| CN102060656A (en) * | 2010-12-21 | 2011-05-18 | 湘潭大学 | Method for preparing cyclohexanone |
| CN102247854A (en) * | 2011-07-26 | 2011-11-23 | 烟台大学 | Catalyst for preparing cyclohexanone by virtue of cyclohexanol dehydrogenation as well as preparation method thereof |
| CN102921420A (en) * | 2012-11-09 | 2013-02-13 | 上海应用技术学院 | Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent |
| CN112452326A (en) * | 2020-11-25 | 2021-03-09 | 常州大学 | Preparation method of copper black titanium catalyst and application of copper black titanium catalyst in selective catalytic oxidation denitration |
Non-Patent Citations (1)
| Title |
|---|
| "Catalytic Dehydrogenation Reaction Activity of Cyclohexanol Over Cu2O/Mg(OH)2 Catalysts";WANG Yuan Qiang等;《Advanced Materials Research》;第652-654卷;711-716 * |
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