CN101549297A - Preparation method of fixed bed raney nickel catalyst - Google Patents
Preparation method of fixed bed raney nickel catalyst Download PDFInfo
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- CN101549297A CN101549297A CNA2008103007882A CN200810300788A CN101549297A CN 101549297 A CN101549297 A CN 101549297A CN A2008103007882 A CNA2008103007882 A CN A2008103007882A CN 200810300788 A CN200810300788 A CN 200810300788A CN 101549297 A CN101549297 A CN 101549297A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a preparation method of fixed bed raney nickel catalyst, comprising the following steps of: putting foamed nickel into an organic solvent for soaking for 10 to 120 minutes, then cleaning the foamed nickel by a diluted acid solution, and then washing and drying; heating metallic aluminium to 660 to 800 DEG C under inert atmosphere so as to be completely melt, then immerging the obtained foamed nickel in the melted metallic aluminium, with the temperature of being kept to be 660 to 800 DEG C, and taking out the foamed nickel after being immerged for 0.5 to 6 hours, and naturally cooling to room temperature, namely obtaining aluminium-plated foamed nickel; and immerging the obtained alumunium-plated foamed nickel in a sodium hydroxide or potassium hydroxide solution, thus obtaining the catalyst. The fixed bed raney nickel catalyst prepared by the method has the advantages of high strength, good catalytic activity, uniform activity of the catalyst and good repetitiveness. The invention belongs to the field of catalyst preparation.
Description
Technical field
The present invention relates to a kind of preparation method of fixed bed raney catalyst, relate to a kind of preparation method of raney catalyst of high activity specifically.
Background technology
Hydrogen Energy is that human society is a kind of future source of energy developing direction that alleviation resource and environmental problem propose, and the core content of this development is exactly to replace the fuel of existing fossil fuel (coal, oil and natural gas) as cleaning, green, the conveying that is easy to carry with hydrogen.The fuel cell that with hydrogen is fuel then is a kind of TRT efficient, cleaning, and becomes the desirable supporting power supply of portable type electronic product and electric automobile gradually.At present, fuel cell development and the subject matter of using are the storages of hydrogen, and the storage hydrogen mode that extensively adopts now, hydrogen storage content is all lower, as gas cylinder storage hydrogen, hydrogen-storage alloy Chu Qing etc.And boron hydride is a kind of material of high storage hydrogen content, is 21.2% as the hydrogen storage content of sodium borohydride.These compounds react as a kind of strong reductant and water, can discharge highly purified hydrogen, do not need to purify directly can supply with fuel cell power generation.And hydrogen feedstock can solid transportation and storage, reduces cost greatly.Reaction equation is as follows:
NaBH
4+2H
2O→4H
2+NaBO
2
At present, the catalyst of borohydride hydrolytic hydrogen production mainly contains metal halide (CoCl
2), load on noble metal (as Pt, Pd, Ru etc.), thunder damping alloy (thunder Buddhist nun Ni) of ion exchange resin etc.But all there are some problems, as problems such as catalyst loss problem, the uncontrollable and cost of reaction or the like.
Bin Hong Liu etc. reported catalysis sodium borohydride hydrolysis generation hydrogen such as adopting Raney's nickel, thunder Buddhist nun cobalt and Raney's nickel cobalt method (Journal of Alloys and Compounds, 415,2006,288-293).In this report, utilize catalysis sodium borohydride decomposing hydrogen-productions such as powder Raney's nickel, powder thunder Buddhist nun cobalt.Powdered Reni catalyst runs off in actual applications easily, has increased to generate the difficulty of hydrogen and catalyst separation, thereby has made its application be restricted.At Chinese publication number be CN1774390A patent disclosure a kind of method of utilizing the raney ni catalysis producing hydrogen by decomposing sodium borohydride, adopt two kinds of methods to solve the losing issue of powder Raney's nickels in the patent.First method is, Raney's nickel is attached on the magnet of catalyst fixed cell, is immersed in the water.Second method is with polyurethane foam Raney's nickel to be fixed on the nickel screen, is stored in the distilled water then.These two kinds of methods all make reaction unit more complicated, and the catalyst strength for preparing is lower, active component comes off easily.
Japanese publication number be JP2005205265 patent report prepare the method for fixed-bed Raney nickel catalyst for preparing hydrogen, concrete steps are that aluminium powder and binding agent mixing are coated on the nickel foam, through high-temperature roasting, the nickel foam of preparation surface alloying, through the alkali lye activation, be fixed a Raney's nickel catalyst for preparing hydrogen again, solved some common problems at present, as the catalyst loss problem, effectively overcome the limitation of powder Reni catalyst.But the catalyst activity of this patent preparation is on the low side, and the catalytic activity heterogeneity of each several part has also limited practical application.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of intensity height, catalytic activity is good, activity of such catalysts is even and the preparation method of the Raney's nickel catalyst of good reproducibility.
For solving the problems of the technologies described above, the present inventor has carried out a large amount of research and performing creative labour on the basis of existing technology, developed the preparation method of a kind of high activity, high-intensity Raney's nickel catalyst, its concrete steps are as follows: after 1. nickel foam being put into organic solvent and soaking 10～120min, clean with dilute acid soln, washing then, drying;
2. metallic aluminium is heated to 660～800 ℃ under inert atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 660～800 ℃, takes out behind dipping 0.5～6h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in is 2. leached in alkaline solution, promptly.
The organic solvent of described step in 1. is a kind of in acetone, ethanol, ether, benzene, toluene, benzinum and the chloroform.
The dilute acid soln of described step in 1. is watery hydrochloric acid, dilute sulfuric acid or phosphoric acid,diluted.
The drying of described step in 1. is that temperature is at 60～100 ℃ of following vacuum drying 10～120min.
The alkaline solution of described step in 3. is NaOH or the potassium hydroxide solution of 10～30wt%, and described leaching is in temperature being 60～85 ℃ of leaching 1～12h down.
The inert gas of described step in 2. is a kind of in nitrogen, helium, neon and the argon gas.
Described metallic aluminium can be aluminium powder, aluminium wire, aluminium ingot, aluminum strip, aluminium sheet etc.
The consumption of described metallic aluminium is the nickel foam submergence can be advisable after the metallic aluminium fusion.
The present invention adopts melt impregnation metallic aluminium to be carried on uniformly on the hole wall of nickel foam, the Raney's nickel catalyst that obtains after the aqueous slkali leaching then has catalytic activity and is evenly distributed, the characteristics that catalytic activity is good, the conversion ratio of the Raney's nickel catalyst catalysis boron hydride of the present invention's preparation reaches as high as more than 90%.Adopt melt impregnation can control the nickel foam of aluminizing of the load capacity that dip time, dipping temperature obtain expecting by strictness, after thereby aqueous slkali leaches under the same terms, can prepare performance homogeneous catalyst, preparation method of the present invention has good repeatability, is suitable for the batch process of industrialization.The nickel foam that the present invention adopts as the nickel source of nickel alumin(i)um alloy, had been again a carrier simultaneously both, so the catalyst of the present invention's preparation has higher mechanical strength.Before the preparation catalyst, can nickel foam be made the shape and the size of actual needs according to actual needs, and then carry out melt impregnation preparation, can save the operation of the follow-up moulding of catalyst, make the preparation technology of Raney's nickel catalyst of fixed bed simplify, and can reduce production costs.
The specific embodiment
The present invention is further detailed explanation below in conjunction with the specific embodiment.
The Raney's nickel catalyst of fixed bed for preparing among the embodiment carries out activity rating through following steps: the NaBH that consists of 5wt% of reactant liquor
4, the NaOH of 10wt%, the deionized water of 85wt%.The reactor that fills the 100mL reactant liquor is positioned in 30 ℃ of waters bath with thermostatic control, take by weighing Raney's nickel catalyst 5g, put it into reactant liquor, in the course of reaction, with mass-flow gas meter record unit time hydrogen output, be the catalytic conversion of sodium borohydride catalyzing hydrolyzation hydrogen production reaction with the ratio of theoretical hydrogen output.
Embodiment 1
1. after nickel foam being put into acetone immersion 10min, clean with dilute hydrochloric acid solution, then after the washing, in 60 ℃ of following vacuum drying 120min;
2. metallic aluminium powder is heated to 660 ℃ under nitrogen atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 660 ℃, takes out behind the dipping 0.5h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. aluminizing nickel foam in 10wt% NaOH with what step obtained in 2., is under 60 ℃ the condition in temperature, leaching 12h, promptly.
Preparing resulting Raney's nickel catalyst of fixed bed can get its catalytic conversion through activity rating and be: 82%.
Embodiment 2
1. after nickel foam being put into ethanol immersion 60min, clean with dilution heat of sulfuric acid, then after the washing, in 80 ℃ of following vacuum drying 10min;
2. metal aluminum filament is heated to 700 ℃ under helium atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 700 ℃, takes out behind the dipping 1h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. aluminizing nickel foam in 20wt% NaOH with what step obtained in 2., is under 65 ℃ the condition in temperature, leaching 12h, promptly.
Preparing resulting Raney's nickel catalyst of fixed bed can get its catalytic conversion through activity rating and be: 85%.
Embodiment 3
1. after nickel foam being put into benzene immersion 100min, clean with dilute phosphoric acid solution, then after the washing, in 100 ℃ of following vacuum drying 60min;
2. the metal aluminium strip is heated to 750 ℃ under neon atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 750 ℃, takes out behind the dipping 2h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. aluminizing nickel foam in 30wt% NaOH with what step obtained in 2., is under 85 ℃ the condition in temperature, leaching 4h, promptly.
Preparing resulting Raney's nickel catalyst of fixed bed can get its catalytic conversion through activity rating and be: 90%.
Embodiment 4
1. after nickel foam being put into toluene immersion 120min, clean with dilute hydrochloric acid solution, then after the washing, in 70 ℃ of following vacuum drying 20min;
2. the metal aluminum strip is heated to 800 ℃ under argon gas atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 800 ℃, takes out behind the dipping 3h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. aluminizing nickel foam in 25wt% potassium hydroxide with what step obtained in 2., is under 70 ℃ the condition in temperature, leaching 6h, promptly.
Preparing resulting Raney's nickel catalyst of fixed bed can get its catalytic conversion through activity rating and be: 88%.
Embodiment 5
1. after nickel foam being put into benzinum immersion 80min, clean with dilute hydrochloric acid solution, then after the washing, in 75 ℃ of following vacuum drying 40min;
2. metal aluminum sheet is heated to 720 ℃ under nitrogen atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 720 ℃, takes out behind the dipping 5h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. aluminizing nickel foam in 18wt% potassium hydroxide with what step obtained in 2., is under 75 ℃ the condition in temperature, leaching 8h, promptly.
Preparing resulting Raney's nickel catalyst of fixed bed can get its catalytic conversion through activity rating and be: 91%.
Embodiment 6
1. after nickel foam being put into chloroform immersion 40min, clean with dilution heat of sulfuric acid, then after the washing, in 80 ℃ of following vacuum drying 90min;
2. metal aluminum sheet is heated to 780 ℃ under nitrogen atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 780 ℃, takes out behind the dipping 6h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. aluminizing nickel foam in 20wt% potassium hydroxide with what step obtained in 2., is under 80 ℃ the condition in temperature, leaching 10h, promptly.
Preparing resulting Raney's nickel catalyst of fixed bed can get its catalytic conversion through activity rating and be: 92%.
Claims (6)
1. the preparation method of a Raney's nickel catalyst of fixed bed is characterized in that described preparation method's concrete steps are as follows:
1. after nickel foam being put into organic solvent and soaking 10～120min, clean washing then, drying with dilute acid soln;
2. metallic aluminium is heated to 660～800 ℃ under inert atmosphere, makes its whole fusions, the nickel foam that then 1. step is obtained immerses wherein, maintains the temperature at 660～800 ℃, takes out behind dipping 0.5～6h, naturally cools to room temperature, promptly gets the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in is 2. leached in alkaline solution, promptly.
2. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1 is characterized in that organic solvent during described step 1. is a kind of in acetone, ethanol, ether, benzene, toluene, benzinum and the chloroform.
3. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1 is characterized in that the dilute acid soln during described step 1. is watery hydrochloric acid, dilute sulfuric acid or phosphoric acid,diluted.
4. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1 is characterized in that the drying during described step 1. is that temperature is at 60～100 ℃ of following vacuum drying 10～120min.
5. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1, it is characterized in that the alkaline solution during described step 3. is NaOH or the potassium hydroxide solution of 10～30wt%, described leaching is to be 60～85 ℃ in temperature to leach 1～12h down.
6. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1 is characterized in that inert gas during described step 2. is a kind of in nitrogen, helium, neon and the argon gas.
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| CN200810300788A CN101549297B (en) | 2008-03-31 | 2008-03-31 | Preparation method of fixed bed raney nickel catalyst |
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|---|---|---|---|
| CN200810300788A CN101549297B (en) | 2008-03-31 | 2008-03-31 | Preparation method of fixed bed raney nickel catalyst |
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| CN101549297B CN101549297B (en) | 2012-09-05 |
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Cited By (6)
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| CN103966473A (en) * | 2013-02-06 | 2014-08-06 | 艾蓝腾欧洲有限公司 | Surface Modified Metallic Foam Body, Process For Its Production And Use Thereof |
| US20200016579A1 (en) * | 2016-09-23 | 2020-01-16 | Basf Se | Method for activating a fixed catalyst bed which contains monolithic shaped catalyst bodies or consists of monolithic shaped catalyst bodies |
| WO2021058704A1 (en) * | 2019-09-25 | 2021-04-01 | Evonik Operations Gmbh | Metal-foam body and method for the production thereof and the use thereof as a catalyst |
| CN114531855A (en) * | 2019-09-25 | 2022-05-24 | 赢创运营有限公司 | Cobalt-containing metal foam element and method for the production thereof |
| CN115354184A (en) * | 2022-09-05 | 2022-11-18 | 常德力元新材料有限责任公司 | Preparation method of aluminum-nickel foam alloy |
| CN115818568A (en) * | 2022-11-25 | 2023-03-21 | 王凯 | Cracking agent for cracking water vapor to produce hydrogen, preparation, use and reactivation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049580A (en) * | 1976-07-23 | 1977-09-20 | The United States Of America As Represented By The Secretary Of The Interior | Method for producing supported Raney nickel catalyst |
| CN1260008C (en) * | 2003-06-13 | 2006-06-21 | 上海师范大学 | Method for preparing novel Raney Ni catalyzer and its application |
| CN1283359C (en) * | 2004-02-13 | 2006-11-08 | 中国石油天然气集团公司 | Skeletal metal catalyst for hydrogenation in fixed bed and its preparing process |
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2008
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| CN103966473A (en) * | 2013-02-06 | 2014-08-06 | 艾蓝腾欧洲有限公司 | Surface Modified Metallic Foam Body, Process For Its Production And Use Thereof |
| EP2764916A1 (en) * | 2013-02-06 | 2014-08-13 | Alantum Europe GmbH | Surface modified metallic foam body, process for its production and use thereof |
| WO2014122194A1 (en) | 2013-02-06 | 2014-08-14 | Alantum Europe Gmbh | Surface modified metallic foam body, process for its production and use thereof |
| EP3216522A1 (en) * | 2013-02-06 | 2017-09-13 | Alantum Europe GmbH | Surface modified metallic foam body, process for its production and use thereof |
| US10596556B2 (en) | 2013-02-06 | 2020-03-24 | Alantum Europe Gmbh | Surface modified metallic foam body, process for its production and use thereof |
| US20200016579A1 (en) * | 2016-09-23 | 2020-01-16 | Basf Se | Method for activating a fixed catalyst bed which contains monolithic shaped catalyst bodies or consists of monolithic shaped catalyst bodies |
| WO2021058704A1 (en) * | 2019-09-25 | 2021-04-01 | Evonik Operations Gmbh | Metal-foam body and method for the production thereof and the use thereof as a catalyst |
| CN114514070A (en) * | 2019-09-25 | 2022-05-17 | 赢创运营有限公司 | Metal foam body, method for the production thereof and use thereof as catalyst |
| CN114531855A (en) * | 2019-09-25 | 2022-05-24 | 赢创运营有限公司 | Cobalt-containing metal foam element and method for the production thereof |
| CN115354184A (en) * | 2022-09-05 | 2022-11-18 | 常德力元新材料有限责任公司 | Preparation method of aluminum-nickel foam alloy |
| CN115818568A (en) * | 2022-11-25 | 2023-03-21 | 王凯 | Cracking agent for cracking water vapor to produce hydrogen, preparation, use and reactivation method thereof |
| CN115818568B (en) * | 2022-11-25 | 2024-04-09 | 王凯 | Cracking agent for hydrogen production by cracking water vapor, preparation, use and reviving method thereof |
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| CN101549297B (en) | 2012-09-05 |
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