CN102029199A - Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method - Google Patents
Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method Download PDFInfo
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Abstract
The invention discloses a method for preparing a load-type noble metal nanometer catalyst by a solvent-free microwave-assisted pyrolysis method and application thereof, belonging to the technical field of catalysis. The method comprises the following steps of: fully grinding and mixing a noble metal coordination compound and a vector, and forming the stable load-type noble metal catalyst by the microwave-assisted pyrolysis in an inert atmosphere. The invention has the advantages of simple process, no solvent, low energy consumption in the process, and the like. In the prepared catalyst, Ru, Rh, Re, Pd, Pt, and other particles are evenly distributed on the outer surface of the vector, therefore, the utilization ratio of noble metal particles is improved, the cost of the catalyst is effectively reduced, and the method has potential industrial application value. The load-type noble metal catalyst has favorable catalysis performance in a plurality field of hydrogenation, hydrogenolysis, ammonia synthesis, ammonia decomposition, hydrocarbon synthesis, hydrogenation formylation, and the like, shows the characteristics of high activity, good stability, reduced reaction energy consumption, and the like and has wide application prospect.
Description
Technical field
The invention belongs to the heterogeneous catalysis technology field, the preparation method who relates to a kind of carried noble metal nano catalytic material, specially refer to the auxiliary method for pyrolysis of a kind of employing solvent-free microwave and make precious metals complex be decomposed into noble metal, and the catalyst of preparation is used for catalytic reactions such as olefine aldehydr selection hydrogenation, synthetic ammonia and ammonia decomposition.
Background technology
Many fields such as loaded noble metal catalyst synthesizes at hydrogenation, hydrogenolysis, ammonia synthesis, hydro carbons, hydroformylation have good catalytic performance, show characteristics such as active height, good stability, reduction energy consumption of reaction, have broad application prospects.The use of carrier helps improving metal dispersity, especially can reduce the consumption of noble metal, improves its activity, reduces the catalyst cost, and has improved its heat endurance to a certain extent, has prolonged the service life of catalyst.
Traditional preparation loaded noble metal catalyst method has: infusion process, the precipitation method and ion-exchange etc.Infusion process is to prepare the most frequently used method of loaded catalyst.As people such as Galvagno (Journal of Molecular Catalysis, 1991,237-246) reported that the aqueous solution with active carbon and ruthenium trichloride prepares the Ru/AC catalyst by infusion process.Adopt traditional infusion process, influenced by several factors, comprising: the concentration of metal ion, solution viscosity, carrier character, dip time, dipping method (dry method or wet method) and dry run etc. in pH value, the maceration extract.The precipitation method also are the effective ways of preparation noble metal load CNT, CNT must play the effect of precipitation nucleation through pre-treatment, pH value by control solution can make metal directly load on the CNT, and the catalyst metal particles that this method obtains is less.The method is one of industrial preparation technology of present comparative maturity, it should be noted that in precipitation process, if condition control is improper, the agglomeration of noble metal can take place.Ion-exchange can better improve the homogeneity of granular size, and the catalyst metals load capacity depends mainly on the number of the ion that carrier surface can exchange, rather than is decided by pore structure and surface area.People such as Gallezot (Journal of Catalysis, 1998,180:51-55) reported with ion-exchange and prepared the Ru/AC catalyst, the activated carbon of handling with clorox be impregnated in the water, under the nitrogen atmosphere protection, Ru (NH
3)
6Cl
3Solution slowly adds in the solution that is suspended with activated carbon, at room temperature stirs 24h and carries out ion-exchange, filters, and is washed to neutrality, the oven dry reduction, and catalyst gets product.The method technical process weak point is complex steps, and solvent cost is worth high, is unfavorable for industrialization.
The noble ruthenium catalyst is very high to the synthetic ammonia reactivity under low temperature, low pressure, under the normal pressure than the active high 10-20 of the ammonia synthesis of iron catalyst doubly, to water, CO and CO
2Insensitive, be described as the second generation ammonia synthesis catalyst after iron catalyst.The converted products of ammonia and ammonia has important effect in industry such as plastics, medicine, explosive, metallurgy, environmental protection.It still is the main source of nitrogen manure in the agricultural in addition, can increase the output of grain significantly, is related to the stable and development of society.The continuous growth of and population growing along with society, the demand of ammonia is also with increasing, and the status of ammonia synthesizing industry in national economy highlights day by day.Loaded noble metal catalyst also has good catalytic activity at α in the selective hydrogenation of beta-unsaturated aldehyde.Many fine chemicals synthetic, especially flavor chemistry and pharmaceutical field all relate to this committed step of selective hydrogenation of unsaturated aldehyde compounds intermediate.
Summary of the invention
The invention provides a kind of solvent-free microwave auxiliary heat solution and prepare carried noble metal nano-catalytic agent method, is with precious metals complex and carrier ground and mixed, by the auxiliary pyrolysis of microwave in the inert atmosphere, forms stable carried noble metal nanocatalyst.The auxiliary heating of solvent-free microwave changes reaction mechanism, has reduced reaction activity, has improved solid-phase reaction velocity.The key for preparing equal dispersible granule is to make reaction system to produce crystal seed explosively, and makes all crystal seeds grow into homogeneous granules synchronously.Heating using microwave makes in the system temperature basically identical everywhere, helps the formation of dispersed system.
Technical scheme of the present invention is as follows:
With precious metals complex and the abundant ground and mixed of carrier, the percentage by weight of noble metal load is 0.1%-15%, and the mixture after grinding is packed in fixed bed or the fluidized-bed reactor.Fixed bed reactors are as for the bottom, with inertia/reducing gas purging and maintenance inertia/reducing atmosphere with reactant; Fluidized-bed reactor is that the uniform sample of ground and mixed is placed on the sieve plate, purges from bottom to top with inertia/reducing gas, makes mix powder fluidisation in pipe.Under inert atmosphere, adopt microwave-heating, drop to room temperature in inertia or reducing atmosphere then, promptly be carried on the precious metal catalyst material on the carrier accordingly.
Described precious metals complex comprises that metal carbonyl, bunch shape complex, organo-metallic compound, halogen close complex or acetylacetonate compound etc., and described noble metal comprises Ru, Rh, Re, Pd or Pt etc.;
Described carrier is raw material of wood-charcoal material, oxide or molecular sieve, and wherein the raw material of wood-charcoal material package is drawn together active carbon, carbon black, CNT or charcoal nanofiber; Oxide carrier comprises aluminium oxide, silica, titanium oxide or their binary mixed oxide; Described molecular sieve carrier is MCM series, ZSM series, SBA series or faujasite etc.;
Described inert atmosphere can be adopted as argon gas, nitrogen or helium etc., also can adopt the reductive hydrogen atmosphere, and flow is the 10-1000 ml/min;
Prepared noble metal nano catalyst is applied to the cinnamic acid selective hydrogenation.In autoclave, add the noble metal nano catalyst, cinnamic acid is with the cyclohexane give solvent.Catalyst needs reduction before reaction: at H
2Under the atmosphere, with 5 ℃ of min
-1Heating rate to 300 ℃ and keep 2h to remove surface passivation layer, obtain the catalyst of fresh attitude.With the air in the hydrogen exchange still three times, in still, fill hydrogen then to certain pressure and test leakage.The cinnamic acid selective hydrogenation is to carry out under uniform temperature and constant agitation speed.Gas-chromatography is adopted in the analysis of product, measures the conversion ratio of cinnamic acid, the productive rate and the selectivity of product.
Prepared according to the methods of the invention carried noble metal nano catalytic material can be applicable to many fields such as hydrogenation, hydrogenolysis, ammonia synthesis, ammonia decompose, hydro carbons is synthetic, hydroformylation and has good catalytic performance; show characteristics such as active height, good stability, reduction energy consumption of reaction, have broad application prospects.
Effect of the present invention and benefit have provided that a kind of method is solvent-free, easy fast, the method for preparing the noble metal nano catalysis material of environmental friendliness, energy efficient, particles such as Ru, Rh, Re, Pd, Pt are evenly distributed on carrier surface in the nanocatalyst of preparation, reduced the consumption of noble metal, effectively reduce the catalyst cost, have favorable industrial application prospect.This loaded noble metal catalyst can be used for reactions such as catalytic hydrogenation, synthetic ammonia and ammonia decomposition.
Description of drawings
Fig. 1 is the transmission electron microscope photo of 5 minutes Ru/CNTs of 5% reaction for loading.
Fig. 2 is the transmission electron microscope photo of 5 minutes Ru/CNTs of 10% reaction for loading.
Fig. 3 is the transmission electron microscope photo of 5 minutes Ru/CNTs of 15% reaction for loading.
The specific embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Take by weighing 0.0316g ten dicarbapentaborane, three rutheniums (Ru:15wt.%) and the undressed CNT of 0.1g, mix, in the fluidisation formula reaction tube of in agate mortar, packing into behind the grinding 20min, argon purge 2h, microwave 800W heats 1min, 3min, 5min respectively, 7min, 15min, the argon gas flow velocity is in the reaction: 100mL/min is cooled to room temperature in the argon gas atmosphere, about 12h can obtain carbon nanotube loaded ruthenium catalyst (Ru/CNTs).
| Sample number into spectrum | The microwave-heating time | Content of metal |
| 1 | 1min | 15wt.％ |
| 2 | 3min | 15wt.％ |
| 3 | 5min | 15wt.％ |
| 4 | 7min | 15wt.％ |
| 5 | 15min | 15wt.％ |
Embodiment 2
Take by weighing 0.0316g (15wt.%) respectively, 0.0210g (10wt.%), 0.0105g (5wt.%) ten dicarbapentaborane, three rutheniums and the undressed CNT of 0.1g mix, in the fluidisation formula reaction tube of packing into behind the grinding 20min in agate mortar, argon purge 2h, microwave 800W heats 5min, and the argon gas flow velocity is in the reaction: 100mL/min is cooled to room temperature in the argon gas atmosphere, about 12h can obtain carbon nanotube loaded ruthenium catalyst (Ru/CNTs).The XRD spectra of the Ru/CNTs that obtains as shown in Figure 2.Be accredited as metal Ru through X-ray powder diffraction.The transmission electron microscope photo of gained sample is seen Fig. 1,2,3.
| Sample number into spectrum | The microwave-heating time | Content of metal |
| 6 | 5min | 5wt.％ |
| 7 | 5min | 10wt.％ |
Embodiment 3
Measure the 60mL deionized water, measure the 60mL red fuming nitric acid (RFNA) again, with the red fuming nitric acid (RFNA) stirring that is added to the water.Measure the 180mL concentrated sulfuric acid, making the volume ratio of the concentrated sulfuric acid, red fuming nitric acid (RFNA) and water is 3: 1: 1, and the three is mixed.Take by weighing the CNT of 3g, and join in the nitration mixture, behind the ultrasonic 5min, at 120 ℃, reflow treatment, constant temperature 4h.Be cooled to room temperature, filtration washing is to pH=6, and 120 ℃ of dry 3h seal up for safekeeping standby.
Embodiment 4
Take by weighing 0.0316g (15wt.%) respectively, 0.0210g (10wt.%), 0.0105g (5wt.%) CNT of ten dicarbapentaborane, three rutheniums and 0.1g nitration mixture oxidation processes mixes, in the fluidisation formula reaction tube of packing into behind the grinding 20min in agate mortar, argon purge 2h, microwave 800W heats 5min, and the argon gas flow velocity is in the reaction: 100mL/min is cooled to room temperature in the argon gas atmosphere, about 12h can obtain carbon nanotube loaded ruthenium catalyst (Ru/o-CNTs).
| Sample number into spectrum | The microwave-heating time | Content of metal |
| 8 | 5min | 5wt.％ |
| 9 | 5min | 10wt.％ |
| 10 | 5min | 15wt.％ |
Embodiment 5
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add sample 6 (5wt.%Ru/CNTs catalyst) 0.1g of embodiment 2 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reaction is 3 hours in the atmosphere, and product carries out gas chromatographic analysis, obtains cinnamic acid conversion ratio 18%, to the selectivity 17% of cinnamyl alcohol, to the selectivity 77% of benzenpropanal, to the selectivity 6% of phenylpropanol.
| Experimental result | The cinnamic acid conversion ratio | The cinnamyl alcohol selectivity | The benzenpropanal selectivity | The phenylpropanol selectivity |
| ％ | 18 | 17 | 77 | 6 |
Embodiment 6
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add sample 7 (10wt.%Ru/CNTs catalyst) 0.1g of embodiment 2 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reaction is 3 hours in the atmosphere, and product carries out gas chromatographic analysis, obtains cinnamic acid conversion ratio 43%, to the selectivity 22% of cinnamyl alcohol, to the selectivity 60% of benzenpropanal, to the selectivity 18% of phenylpropanol.
| Experimental result | The cinnamic acid conversion ratio | The cinnamyl alcohol selectivity | The benzenpropanal selectivity | The phenylpropanol selectivity |
| ％ | 43 | 22 | 60 | 18 |
Embodiment 7
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add sample 3 (15wt.%Ru/CNTs catalyst) 0.1g of embodiment 2 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reaction is 3 hours in the atmosphere, and product carries out gas chromatographic analysis, obtains cinnamic acid conversion ratio 67%, to the selectivity 24% of cinnamyl alcohol, to the selectivity 64% of benzenpropanal, to the selectivity 12% of phenylpropanol.
| Experimental result | The cinnamic acid conversion ratio | The cinnamyl alcohol selectivity | The benzenpropanal selectivity | The phenylpropanol selectivity |
| ％ | 67 | 24 | 64 | 12 |
Embodiment 8
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add sample 8 (5wt.%Ru/o-CNTs catalyst) 0.1g of embodiment 4 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reaction is 3 hours in the atmosphere, and product carries out gas chromatographic analysis, obtains cinnamic acid conversion ratio 5%, to the selectivity 26% of cinnamyl alcohol, to the selectivity 69% of benzenpropanal, to the selectivity 4% of phenylpropanol.
| Experimental result | The cinnamic acid conversion ratio | The cinnamyl alcohol selectivity | The benzenpropanal selectivity | The phenylpropanol selectivity |
| ％ | 5 | 26 | 69 | 4 |
Embodiment 9
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add sample 9 (10wt.%Ru/o-CNTs catalyst) 0.1g of embodiment 4 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reaction is 3 hours in the atmosphere, and product carries out gas chromatographic analysis, obtains cinnamic acid conversion ratio 9%, to the selectivity 16% of cinnamyl alcohol, to the selectivity 80% of benzenpropanal, to the selectivity 4% of phenylpropanol.
| Experimental result | The cinnamic acid conversion ratio | The cinnamyl alcohol selectivity | The benzenpropanal selectivity | The phenylpropanol selectivity |
| ％ | 9 | 16 | 80 | 4 |
Embodiment 10
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add sample 10 (15wt.%Ru/o-CNTs catalyst) 0.1g of embodiment 4 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reaction is 3 hours in the atmosphere, and product carries out gas chromatographic analysis, obtains cinnamic acid conversion ratio 10%, to the selectivity 21% of cinnamyl alcohol, to the selectivity 75% of benzenpropanal, to the selectivity 4% of phenylpropanol.
| Experimental result | The cinnamic acid conversion ratio | Cinnamyl alcohol is selected | The benzenpropanal selectivity | The phenylpropanol selectivity |
| ％ | 10 | 21 | 75 | 4 |
Embodiment 11
Take by weighing cinnamic acid 0.01mol, be dissolved in the 13.0mL cyclohexane, put into the 50mL autoclave, add the 10wt.%Ru/CNTs catalyst 0.1g of embodiment 2 gained again,, stir under the 3.0MPa condition, feed H 80 ℃ (water-baths)
2, remain on H
2Reacted in the atmosphere 1,3,5,7 hour, product carries out gas chromatographic analysis.
Claims (4)
1. a solvent-free microwave auxiliary heat solution prepares the method for carried noble metal nanocatalyst, it is characterized in that following steps:
With precious metals complex and the abundant ground and mixed of carrier, the percentage by weight of noble metal load is 0.1%-15%, and the mixture after grinding is packed in fixed bed or the fluidized-bed reactor; Fixed bed reactors are as for the bottom, with inertia/reducing gas purging and maintenance inertia/reducing atmosphere with reactant; Fluidized-bed reactor is that the uniform sample of ground and mixed is placed on the sieve plate, purges from bottom to top with inertia/reducing gas, makes mix powder fluidisation in pipe; Under inert atmosphere, adopt microwave-heating, drop to room temperature in inertia or reducing atmosphere then, promptly be carried on the precious metal catalyst material on the carrier accordingly.
2. method according to claim 1 is characterized in that described precious metals complex comprises that metal carbonyl, bunch shape complex, organo-metallic compound, halogen close complex or acetylacetonate compound; Described noble metal comprises Ru, Rh, Re, Pd or Pt.
3. method according to claim 1 is characterized in that described carrier is raw material of wood-charcoal material, oxide or molecular sieve, and wherein the raw material of wood-charcoal material package is drawn together active carbon, carbon black, CNT or charcoal nanofiber; Oxide carrier comprises aluminium oxide, silica, titanium oxide or their binary mixed oxide; Described molecular sieve carrier is MCM series, ZSM series, SBA series or faujasite.
4. according to claim 1,2 or 3 described methods, it is characterized in that described inert atmosphere is adopted as argon gas, nitrogen, helium or reductive hydrogen atmosphere, flow is the 10-1000 ml/min.
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| CN102641733A (en) * | 2012-04-17 | 2012-08-22 | 上海大学 | Method for preparing Pt/CNTs material with high catalytic activity |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456491A (en) * | 2003-06-09 | 2003-11-19 | 清华大学 | Cartalyst for preparing hydrogen without COx by ammonia decompsition reaction and preparing method thereof |
| CN1475472A (en) * | 2003-06-30 | 2004-02-18 | 华东理工大学 | Preparation method of 1,3-poly propylene glycol |
| CN1481933A (en) * | 2002-09-12 | 2004-03-17 | 厦门大学 | Ammonia synthetic catalyst and method for making the same |
| CN1736597A (en) * | 2005-06-11 | 2006-02-22 | 太原理工大学 | Solid phase supported catalyst and preparation process |
| US20070101824A1 (en) * | 2005-06-10 | 2007-05-10 | Board Of Trustees Of Michigan State University | Method for producing compositions of nanoparticles on solid surfaces |
-
2010
- 2010-11-15 CN CN 201010543066 patent/CN102029199A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1481933A (en) * | 2002-09-12 | 2004-03-17 | 厦门大学 | Ammonia synthetic catalyst and method for making the same |
| CN1456491A (en) * | 2003-06-09 | 2003-11-19 | 清华大学 | Cartalyst for preparing hydrogen without COx by ammonia decompsition reaction and preparing method thereof |
| CN1475472A (en) * | 2003-06-30 | 2004-02-18 | 华东理工大学 | Preparation method of 1,3-poly propylene glycol |
| US20070101824A1 (en) * | 2005-06-10 | 2007-05-10 | Board Of Trustees Of Michigan State University | Method for producing compositions of nanoparticles on solid surfaces |
| CN1736597A (en) * | 2005-06-11 | 2006-02-22 | 太原理工大学 | Solid phase supported catalyst and preparation process |
Non-Patent Citations (1)
| Title |
|---|
| 《Ind. Eng. Chem. Res.》 20100326 Min Pang et al. Microwave-Assisted Preparation of Mo2C/CNTs Nanocomposites as Efficient Electrocatalyst Supports for Oxygen Reduction Reaction 第4169-4174页 1-4 第49卷, 第9期 2 * |
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| CN108671908A (en) * | 2011-06-21 | 2018-10-19 | 优美科股份公司及两合公司 | Method for the deposited metal in support oxide |
| CN102641733A (en) * | 2012-04-17 | 2012-08-22 | 上海大学 | Method for preparing Pt/CNTs material with high catalytic activity |
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| CN103920525A (en) * | 2013-01-14 | 2014-07-16 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst for alkylation of dimethyl ether and benzene |
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| CN110586153A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in ammonia decomposition reaction |
| CN113181957A (en) * | 2021-02-09 | 2021-07-30 | 厦门大学 | Low-temperature activation high-efficiency ammonia decomposition catalyst |
| CN113181909A (en) * | 2021-04-29 | 2021-07-30 | 上海大学 | Preparation method of noble metal composite catalyst and noble metal composite catalyst |
| CN113694954A (en) * | 2021-08-31 | 2021-11-26 | 安徽大学 | Preparation method and application of microwave in-situ rapid synthesis heteroatom functionalized supported metal catalyst |
| CN117732465A (en) * | 2024-02-20 | 2024-03-22 | 山西安仑化工有限公司 | Continuous preparation method and preparation device of palladium/carbon black catalyst |
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Application publication date: 20110427 |