CN112871159A - Ru nano catalyst and preparation method and application thereof - Google Patents
Ru nano catalyst and preparation method and application thereof Download PDFInfo
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Abstract
一种Ru纳米催化剂，按如下方法制备得到：将RuCl3·3H2O与三乙胺溶于碳酸丙烯酯，体系抽真空后，在80～130℃下搅拌反应1～6h，制得Ru纳米溶胶；将Al2O3浸渍于所得Ru纳米溶胶中，搅拌吸附，静置，干燥后于500℃、N2氛围条件下煅烧2h，制得所述Ru纳米催化剂；本发明可以得到分散度高的Ru纳米催化剂，制备过程中不需要稳定保护剂，在贵金属负载量较低的情况下仍然能保持较高活性与稳定性，制备方法简单，载体廉价易得，Ru纳米催化剂的成本大幅降低，便于工业化；将本发明Ru纳米催化剂应用于邻氯硝基苯选择性加氢反应中，能够降低合成邻氯苯胺的成本并提高其转化率、选择性。A Ru nano-catalyst is prepared as follows: RuCl 3 ·3H 2 O and triethylamine are dissolved in propylene carbonate, and after the system is evacuated, the reaction is stirred at 80-130° C. for 1-6 hours to prepare Ru nano-catalysts. sol; Al 2 O 3 is immersed in the obtained Ru nano-sol, stirred and adsorbed, allowed to stand, dried and then calcined at 500° C. and N 2 atmosphere for 2 hours to obtain the Ru nano-catalyst; the present invention can obtain a high degree of dispersion. The Ru nanocatalyst does not require a stable protective agent during the preparation process, and can still maintain high activity and stability under the condition of low noble metal loading. The preparation method is simple, the support is cheap and easy to obtain, and the cost of Ru nanocatalyst is greatly reduced. Industrialization is convenient; the Ru nano-catalyst of the present invention is applied to the selective hydrogenation reaction of o-chloronitrobenzene, which can reduce the cost of synthesizing o-chloroaniline and improve its conversion rate and selectivity.
Description
Technical Field
The invention belongs to the technical field of nano-catalysts, and particularly relates to a Ru nano-catalyst, a preparation method thereof and application thereof in preparation of o-chloroaniline by selective catalytic hydrogenation of o-chloronitrobenzene.
Background
Ru (ruthenium) catalysts have high catalytic activity and are widely used as catalysts for hydrogenation reactions. Therefore, the development and research of the Ru catalyst with higher catalytic activity have important theoretical significance and industrial application prospect. The preparation method of the common Ru catalyst mainly comprises the following steps: impregnation, coprecipitation, ion exchange, and the like. The impregnation process is a common method for preparing supported catalysts. However, the impregnation method has certain disadvantages, and factors affecting the impregnation method include the impregnation method, the impregnation time, chemical changes occurring during drying and baking, and the adsorption strength. The influence factors are difficult to control, so that the metal distribution is difficult to control according to the preset distribution, and the metal loading capacity is possibly low. The coprecipitation method is a method for preparing the catalyst by carrying out double decomposition reaction on a solution containing metal salts and a precipitator, so as to generate insoluble salts, metal oxides or gel, precipitating the insoluble salts, the metal oxides or the gel from the solution, and carrying out processes such as filtering, washing, drying, forming, roasting and the like. The precipitation process of the precipitation method needs complex chemical reaction, the generated precipitation crystal is easy to agglomerate, so that the final metal particles are uneven in size distribution, and meanwhile, the precipitation method is easy to hide impurities and introduce other impurities. The ion exchange method is to exchange active components with ions existing on the surface of a carrier, load the active components on the carrier, and then prepare the catalyst through washing, drying, roasting and the like. The Ru loading of the ion exchange method depends mainly on the number of groups exchangeable on the surface of the support, and the larger the number of exchangeable groups, the higher the Ru loading; however, the alumina surface tends to lack exchangeable ions, so that the process is generally only suitable for low loadings of Ru/Al2O3And (3) preparing a catalyst. In the meantime, the defects of the prior methods are overcome, and a Ru/Al catalyst with simple preparation process, high catalytic activity and good stability is found2O3The catalyst is a relatively hot problem at present.
Arylamine, a reduction product of an aromatic nitro compound, is a very important organic intermediate, and is widely applied to the fields of medicines, dyes, pesticides, auxiliaries and the like. With the improvement of environmental awareness and scientific and technical development, the catalytic hydrogenation method has better application prospect due to the advantages of high yield, high atom economy, environmental friendliness, recyclable catalyst and the like, and is an important field of current research.
The patent: CN2012103303921 provides a method for preparing o-chloroaniline from o-chloronitrobenzene by solvent-free catalytic hydrogenation, wherein a vanadium-added platinum-carbon catalyst is used for catalytic hydrogenation to inhibit dechlorination side reactions. But the preparation conditions in the method are harsh, the used reagent is not friendly to the environment, the dispersibility of the active component is not good, and the particle size is larger.
The patent: CN1660774A takes o-chloronitrobenzene as raw material and ethanol solvent as solvent, hydrogen is produced by cracking, and Ru/C, amorphous NiB and N1-Fe-B, N1-Co-B catalyst are used to obtain o-chloroaniline at 150-250 ℃. But the dosage of the catalyst of the method is 10 to 20 percent of the mass of the raw materials, the dosage of the catalyst is large, and the production cost is increased.
Disclosure of Invention
The invention aims to provide a Ru nano catalyst, a preparation method and application thereof, and RuCl is used in the invention3·3H2The Ru nano catalyst with uniform granularity is prepared by a liquid phase reduction method by taking O as a precursor and triethylamine as a reducing agent, and is applied to the O-chloronitrobenzene selective hydrogenation reaction, so that the cost for synthesizing the O-chloroaniline is reduced, and the yield and the selectivity of the O-chloroaniline are improved.
The technical scheme of the invention is as follows:
the Ru nano catalyst is prepared by the following method:
(1) adding RuCl3·3H2Dissolving O and triethylamine in propylene carbonate, vacuumizing the system, and stirring and reacting for 1-6 h (preferably 3h) at 80-130 ℃ (preferably 120 ℃) to prepare Ru nano sol;
the RuCl3·3H2The mass ratio of O to triethylamine was 1: 5-20, preferably 1: 10;
the volume dosage of the propylene carbonate is 1-10 mL/mg, preferably 1.66mL/mg, based on the mass of Ru;
(2) mixing Al2O3Dipping into the Ru nano sol obtained in the step (1), stirring and adsorbing (12h), standing (30min), drying (60 ℃) and then500℃、N2Calcining for 2 hours under the atmosphere condition to prepare the Ru nano catalyst;
the Al is2O3The mass ratio of Ru to Ru is 100: 1-10, preferably 100: 5.
the Ru nano catalyst can be applied to o-chloronitrobenzene selective hydrogenation reaction. The invention utilizes a continuous reaction device to measure the catalytic activity of the Ru nano catalyst on the selective hydrogenation of o-chloronitrobenzene. The result shows that the Ru nano catalyst has high-efficiency catalytic hydrogenation performance, realizes the selective hydrogenation of o-chloronitrobenzene at lower temperature and has better stability.
Compared with the prior art, the invention has the beneficial effects that:
according to the Ru nano catalyst and the preparation method thereof provided by the invention, the Ru nano catalyst with high dispersity can be obtained, a stable protective agent is not needed in the preparation process, high activity and stability can be still kept under the condition of low noble metal loading, the preparation method is simple, the carrier is cheap and easy to obtain, the cost of the Ru nano catalyst is greatly reduced, and the method is convenient for industrialization. The Ru nano catalyst provided by the invention is applied to the o-chloronitrobenzene selective hydrogenation reaction, so that the cost for synthesizing o-chloroaniline can be reduced, and the conversion rate and selectivity of the o-chloroaniline can be improved.
Drawings
Fig. 1 is an electron micrograph of the Ru nanocatalyst prepared in example 4.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
The invention utilizes a continuous reaction device to measure the catalytic activity of the Ru nano catalyst on the selective hydrogenation of o-chloronitrobenzene, and the method mainly comprises the following steps:
placing 1g of Ru nano catalyst in the middle of a reaction tube of a continuous hydrogenation device, inputting a reaction raw material solution into the reaction tube at a flow rate of 1ml/min by an infusion pump, adjusting a back pressure valve to a pressure 4MPa required by the reaction, setting a temperature control instrument to indicate a temperature required by the reaction to be 200 ℃, sampling a product every 1h after a system is stable (the flow rate, the pressure and the temperature reach set values), and analyzing the conversion rate of o-chloronitrobenzene and the selectivity of o-chloroaniline under different conditions by adopting a Flame Ionization Detector (FID);
the reaction raw material solution is 5% o-chloronitrobenzene-ethanol water solution, wherein the alcohol-water ratio is 8/2.
Example 1
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at the temperature of 80 ℃, and stirring for reacting for 3 hours to obtain the Ru nano sol of 0.6 mg/mL. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 2
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 100 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 3
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at the temperature of 110 ℃, and stirring for reacting for 3 hours to obtain the Ru nano sol of 0.6 mg/mL. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 4
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 5
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 130 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
The Ru nano catalyst prepared by the method of the embodiment 1-embodiment 5 is used for the reaction of preparing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, and the catalytic performance is as follows:
| examples | 1 | 2 | 3 | 4 | 5 |
| Conversion rate% | 76.4％ | 91.2％ | 96.7 | 99.5％ | 89.1％ |
| Selectivity% | 100％ | 98.4％ | 96.6％ | 97.6％ | 97.3％ |
From the analysis results of the above examples, it can be seen that in RuCl3·3H2The mass ratio of O to triethylamine is 1:10, the concentration of Ru nano sol is 0.6mg/mL, the reduction time is 3h, the loading amount is 5 wt%, and the reaction temperature is 120 ℃, and then the Ru/Al2O3The catalytic effect of (3) is optimal.
Example 6
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system in an oil bath kettle at 120 ℃, and stirring for reacting for 1h to obtain the Ru nano sol of 0.6 mg/mL. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 7
134mg (0.6mmol) of RuCl3·3H2O and 606mg (6mmol) of triethylamine is added into 100mL of solvent propylene carbonate together, stirred and dissolved, then the mixture is transferred into a Schlenk bottle, the system is vacuumized, and then the mixture is placed into an oil bath kettle at 120 ℃ to be stirred and reacted for 3 hours, so that the Ru nano sol of 0.6mg/mL is obtained. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 8
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 120 ℃, and stirring for reacting for 4 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 9
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system in an oil bath kettle at 120 ℃, and stirring for reacting for 6 hours to obtain the Ru nano sol of 0.6 mg/mL. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
The Ru nano-catalyst prepared by the method of example 4 and examples 6 to 9 is used for the reaction of preparing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, and has the following catalytic properties:
| examples | 4 | 6 | 7 | 8 | 9 |
| Conversion rate% | 99.5％ | 80.4％ | 93.1％ | 95.7 | 93.5％ |
| Selectivity% | 97.6％ | 99.6％ | 98.6％ | 98.3％ | 97.9％ |
From the analysis results of the above examples, it can be seen that in RuCl3·3H2The mass ratio of O to triethylamine is 1:10, the concentration of Ru nano sol is 0.6mg/mL, the reduction time is 3h, the loading amount is 5 wt%, and the reaction temperature is 120 ℃, and then the Ru/Al2O3The catalytic effect of (3) is optimal.
Example 10
23mg (0.1mmol) of RuCl3·3H2O and 101mg (1mmol) of triethylamine are added together to 100mL of propylene carbonate as a solvent, dissolved with stirring, and thenTransferring the sol into a Schlenk bottle, vacuumizing the system, then placing the system in an oil bath kettle at the temperature of 120 ℃, and stirring for reaction for 3 hours to obtain Ru nano sol of 0.1 mg/mL. Mixing 1g of Al2O3Adding the carrier into 500ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and carrying out N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 11
69mg (0.3mmol) of RuCl3·3H2Adding O and 303mg (3mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system in an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.3mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 166.6ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 12
230mg (1mmol) of RuCl3·3H2Adding O and 1010mg (10mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system in an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 1mg/mL Ru nano sol. Mixing 1g of Al2O3Adding the carrier into 50ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and carrying out N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
The Ru nano-catalyst prepared by the method of example 4, example 10 to example 12 is used in the reaction of preparing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, and the catalytic performance is as follows:
| examples | 4 | 10 | 11 | 12 |
| Conversion rate% | 99.5％ | 85.4％ | 93.1％ | 89.6％ |
| Selectivity% | 97.6％ | 99.1％ | 98.5％ | 98.9％ |
From the analysis results of the above examples, it can be seen that in RuCl3·3H2The mass ratio of O to triethylamine is 1:10, the concentration of Ru nano sol is 0.6mg/mL, the reduction time is 3h, the loading amount is 5 wt%, and the reaction temperature is 120 ℃, and then the Ru/Al2O3The catalytic effect of (3) is optimal.
Example 13
134mg (0.6mmol) of RuCl3·3H2Adding O and 303mg (3mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system in an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcination under atmospheric conditions 2h, obtaining the Ru nano catalyst with the load of 5 wt%.
Example 14
134mg (0.6mmol) of RuCl3·3H2Adding O and 909mg (9mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, then transferring the mixture into a Schlenk bottle, vacuumizing the system, then placing the system into an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
Example 15
134mg (0.6mmol) of RuCl3·3H2Adding O and 1212mg (12mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system in an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 83.3ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 5 wt%.
The Ru nano-catalyst prepared by the method of example 4, example 13 to example 15 is used in the reaction of preparing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, and the catalytic performance is as follows:
| examples | 4 | 13 | 14 | 15 |
| Conversion rate% | 99.5％ | 84.9％ | 91.1％ | 87.4 |
| Selectivity% | 97.6％ | 99.0％ | 98.2％ | 98.5％ |
From the analysis results of the above examples, it can be seen that in RuCl3·3H2The mass ratio of O to triethylamine is 1:10, the concentration of Ru nano sol is 0.6mg/mL, the reduction time is 3h, the loading amount is 5 wt%, and the reaction temperature is 120 ℃, and then the Ru/Al2O3The catalytic effect of (3) is optimal.
Example 16
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 16.6ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 1 wt%.
Example 17
134mg (0.6mmol) of RuCl3·3H2O and 606mg (6mmol) of triethylamine are added together to 100mL of propylene carbonate solvent, dissolved by stirring and then transferred into a Schlenk bottleAnd vacuumizing the system, then placing the system in an oil bath kettle at the temperature of 120 ℃, and stirring for reacting for 3 hours to obtain the Ru nano sol of 0.6 mg/mL. Mixing 1g of Al2O3Adding the carrier into 41.6ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and carrying out N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 2.5 wt%.
Example 18
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 125ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 7.5 wt%.
Example 19
134mg (0.6mmol) of RuCl3·3H2Adding O and 606mg (6mmol) of triethylamine into 100mL of propylene carbonate solvent, stirring for dissolving, transferring the mixture into a Schlenk bottle, vacuumizing the system, placing the system into an oil bath kettle at 120 ℃, and stirring for reacting for 3 hours to obtain 0.6mg/mL Ru nano sol. Mixing 1g of Al2O3Adding carrier into 166.6ml of the Ru nano sol, stirring for adsorption, standing for 30min, drying, and performing N reaction at 500 DEG C2Calcining for 2h under the atmosphere condition to obtain the Ru nano catalyst with the load of 10 wt%.
The Ru nano-catalyst prepared by the method of example 4 and examples 16 to 19 is used for the reaction of preparing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, and has the following catalytic properties:
| examples | 4 | 16 | 17 | 18 | 19 |
| Conversion rate% | 99.5％ | 84.9％ | 91.1％ | 100％ | 100％ |
| Selectivity% | 97.9％ | 99.0％ | 98.2％ | 92.5％ | 87.9％ |
From the analysis results of the above examples, it can be seen that in RuCl3·3H2The mass ratio of O to triethylamine is 1:10, the concentration of Ru nano sol is 0.6mg/mL, the reduction time is 3h, the loading amount is 5 wt%, and the reaction temperature is 120 ℃, and then the Ru/Al2O3The catalytic effect of (3) is optimal.
The results show that the Ru nano catalyst is used for the reaction of preparing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, has high activity, simple preparation method and cheap and easily-obtained carrier, greatly reduces the cost of the Ru nano catalyst, and is convenient for industrialization.
Claims (7)
1. The Ru nano catalyst is characterized by being prepared by the following method:
(1) adding RuCl3·3H2Dissolving O and triethylamine in propylene carbonate, vacuumizing the system, and stirring and reacting for 1-6 h at 80-130 ℃ to prepare Ru nano sol;
the RuCl3·3H2The mass ratio of O to triethylamine was 1: 5-20;
the volume dosage of the propylene carbonate is 1-10 mL/mg in terms of the mass of Ru;
(2) mixing Al2O3Dipping into the Ru nano sol obtained in the step (1), stirring, adsorbing, standing, drying, and then carrying out N reaction at 500 DEG C2Calcining for 2 hours under the atmosphere condition to prepare the Ru nano catalyst;
the Al is2O3The mass ratio of Ru to Ru is 100: 1 to 10.
2. The Ru nanocatalyst of claim 1, wherein in step (1), the reaction is carried out with stirring at 120 ℃ for 3 hours.
3. The Ru nanocatalyst of claim 1, wherein in step (1), the RuCl is present3·3H2The mass ratio of O to triethylamine was 1: 10.
4. the Ru nanocatalyst of claim 1, wherein the volume usage of the propylene carbonate in step (1) is 1.66mL/mg based on the mass of Ru.
5. The Ru nanocatalyst of claim 1, wherein in step (2), the stirring adsorption time is 12 hours.
6. The Ru nanocatalyst of claim 1, wherein in step (2), the Al is present in2O3The mass ratio of Ru to Ru is 100: 5.
7. the use of the Ru nano-catalyst of claim 1 in the reaction of o-chloroaniline preparation by selective hydrogenation of o-chloronitrobenzene.
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