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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- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000003756 stirring Methods 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 28
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 25
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 18
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000003223 protective agent Substances 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000005470 impregnation Methods 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic nitro compound Chemical class 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000219503 Casuarina equisetifolia Species 0.000 description 1
- 229910020674 Co—B Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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Abstract
The Ru nano catalyst is prepared by the following method: 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; mixing Al2O3Soaking in the obtained Ru nano sol, stirring for adsorption, standing, drying, and performing N treatment at 500 deg.C2Calcining for 2 hours under the atmosphere condition to prepare the Ru nano catalyst; the invention can obtain the Ru nano catalyst with high dispersity, does not need a stable protective agent in the preparation process, can still keep higher activity and stability under the condition of lower noble metal loading capacity, has simple preparation method, cheap and easily obtained carrier, greatly reduces the cost of the Ru nano catalyst,the industrialization is convenient; 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.
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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| CN115445609A (en) * | 2022-09-30 | 2022-12-09 | 浙江工业大学 | Active carbon-loaded ruthenium catalyst and preparation method and application thereof |
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