CN113813962B - Preparation method of high-activity foam nickel catalyst - Google Patents

Preparation method of high-activity foam nickel catalyst Download PDF

Info

Publication number
CN113813962B
CN113813962B CN202111038763.1A CN202111038763A CN113813962B CN 113813962 B CN113813962 B CN 113813962B CN 202111038763 A CN202111038763 A CN 202111038763A CN 113813962 B CN113813962 B CN 113813962B
Authority
CN
China
Prior art keywords
catalyst
copper
foam nickel
activity
nickel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202111038763.1A
Other languages
Chinese (zh)
Other versions
CN113813962A (en
Inventor
肖子辉
杨振颢
姜子崴
印会鸣
丁轶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University of Technology
Original Assignee
Tianjin University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin University of Technology filed Critical Tianjin University of Technology
Priority to CN202111038763.1A priority Critical patent/CN113813962B/en
Publication of CN113813962A publication Critical patent/CN113813962A/en
Application granted granted Critical
Publication of CN113813962B publication Critical patent/CN113813962B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • B01J35/56—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated

Abstract

The invention discloses a preparation method of a high-activity foam nickel catalyst, which mainly solves the problems of low catalyst use efficiency, low activity, large amount of waste liquid generation and the like caused in the traditional Raney nickel fixed bed catalyst forming and pore forming. Firstly, uniformly depositing copper with a certain thickness on the surface of foam nickel by adopting an electrodeposition method, then calcining at a high temperature to form nickel-copper alloy, and then removing copper in the alloy by adopting an electroerosion method, thereby forming a rough porous structure and obtaining the high-activity foam nickel catalyst. Copper is deposited on the cathode in the electrolytic corrosion, and after acid dissolution, the copper can be used as raw material liquid for the electrolytic deposition, so that the cost is saved. Compared with the traditional method, the method does not use strong acid and strong alkali with high concentration, has safe process, simple preparation process, easy control and easy industrial amplification, and the prepared catalyst has high activity and good repeatability.

Description

Preparation method of high-activity foam nickel catalyst
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a preparation method of a high-activity foam nickel catalyst.
Background
Raney nickel catalyst is an important industrial catalyst, and has been widely used in hydrogenation, dehydrogenation, dehalogenation, desulfurization and other organic reactions due to its low cost and strong process controllability. The global capacity in 2017 was statistically close to 2.8 ten thousand tons. The Raney nickel catalyst can be classified into slurry Raney nickel, powder Raney nickel and fixed bed Raney nickel catalyst according to the application and form of the Raney nickel catalyst, wherein the fixed bed Raney nickel catalyst is a new generation catalyst specially used for the development of fixed bed continuous hydrogenation process, and has a larger specific gravity.
The traditional preparation process of the fixed bed Raney nickel catalyst mainly comprises two steps of forming and pore-forming. For the pore-forming step, an alkaline extraction method is generally adopted, which is the same as the preparation process of the powder Raney nickel. However, various shaping methods are available, such as a method for crushing bulk alloy materials (US 6262307B1, US6284703, CN96121302.7, US 9586879), crushing the melted bulk alloy materials into materials with a certain size, and performing alkali extraction to obtain the raney nickel catalyst. In another example, the method (Industrial Catalysis,2013,21 (7)) of bonding and molding alloy powder by using an adhesive agent is 59-63, US20030120116, US20150231612A1, US4895994, mainly comprises pseudo-boehmite, metal powder or polymer, but the method causes the problems of difficult leaching and activation, small specific surface area, low catalytic activity and the like of the catalyst. And then, if a thermal spraying coating method (US 20060224027A 1) is adopted, the alloy material is sprayed on the metal foil after being melted, and after folding and forming, the fixed bed Raney nickel catalyst is obtained by alkali extraction, but the catalyst obtained by the method has weaker performance. Therefore, the development of a novel method for preparing the fixed bed Raney nickel catalyst or the novel high-efficiency porous nickel fixed bed catalyst for replacing the fixed bed Raney nickel catalyst has very important significance.
The foam nickel material has the characteristics of small density, communicated pore channels, large void volume, high specific surface area and the like, and is widely used as a catalyst carrier and a catalytic electrode material in industry. In the traditional catalysis, the catalyst has no catalytic activity, is only used as a catalyst carrier to improve the performance (such as CN200610085775.9 and CN 110142046A), and is used for catalytically oxidizing volatile organic compounds and the like by modifying other active components on the surface of the catalyst. However, the development of the self-catalytic performance of the foam nickel is relatively less, the foam nickel is modified into a catalyst with certain catalytic performance, and the foam nickel has important significance for replacing the traditional fixed bed Raney nickel catalyst by utilizing the self-porosity and excellent mass transfer characteristic and mechanical performance.
The currently known preparation method of the fixed bed Raney nickel catalyst has reference significance for modifying the foam nickel material, and different methods such as melt impregnation, electroplating/electroless plating, spraying and the like are adopted to cover aluminum on the foam nickel, and the fixed bed Raney nickel catalyst can be obtained after alkaline leaching. However, these modification methods all use alkali liquor with high concentration, which has certain corrosiveness to equipment and generates a large amount of waste liquid. In addition, in the process of melting, dipping and spraying, the content of aluminum in the foam nickel and on the surface is obviously uneven, and although the problem of uneven aluminum plating can be solved by adopting electroplating and chemical plating, the cost and the potential safety hazard are increased by adopting high-temperature electroplating or using inflammable strong reducing agents and the like in the use process. Based on the problems, the development of a more green, safer and low-cost preparation method of the high-activity foam nickel is necessary.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of a high-activity foam nickel catalyst, which adopts an electroerosion technology to realize the green, safe and low-cost preparation of the high-activity foam nickel catalyst.
The technical scheme of the invention is as follows:
a preparation method of a high-activity foam nickel catalyst, which comprises the following steps:
the invention adopts the electrodeposition technology to uniformly deposit copper on the surface of the foam nickel, then high-temperature calcination is carried out to promote the surface to form nickel-copper alloy, and then the copper in the nickel-copper alloy is selectively removed through electric corrosion to form the high-activity foam nickel catalyst.
According to the invention, by utilizing the characteristic that nickel and copper are easy to dissolve mutually, uniform deposition on the porous surface of the foam nickel is realized firstly by utilizing electrodeposition, then the mutual dissolution of nickel and copper is promoted by calcination to form an alloy layer on the surface of the porous nickel, the alloy layer is formed on the porous form surface of the original foam nickel in situ integrally, copper in the alloy is selectively removed by utilizing electroerosion, a microporous structure is formed on the porous surface structure of the original foam nickel in situ, and the surface structure is roughened, so that good catalytic performance is obtained, and meanwhile, in-situ rough micropores are uniform and are not easy to fall off, and the catalyst has high catalytic performance stability.
In the electrodeposition technology, foam nickel is used as a working electrode, and a graphite plate is used as a counter electrode; the electroplating solution is CuSO 4 、Cu(NO 3 ) 2 Or CuCl 2 One or more of the aqueous solutions; the concentration of the electroplating solution is 0.01M-1M; electrodepositing voltage-0.1V-0.8V; the electrodeposition amount was 3C/cm 2 -100C/cm 2 . High-temperature calcination is carried out to form an alloy, wherein the calcination temperature is 600-1000 ℃ and the calcination time is 1-8h. Then carrying out electric corrosion on the steel plate, wherein the electrolytic corrosion liquid is H 3 BO 4 、H 2 SO 4 、Na 2 SO 4 Mixing one or more of the aqueous solutions; the concentration of the electrolytic corrosive liquid is 0.01M-1M; the voltage of the electric corrosion is 0.1V-1V; the electric corrosion time is 5min-300min; the counter electrode is a graphite plate.
Preferably, in the electrodeposition technology, the foam nickel is used as a working electrode, and the graphite plate is used as a counter electrode; the electroplating solution is CuSO 4 、Cu(NO 3 ) 2 Or CuCl 2 One of the aqueous solutions; the concentration of the electroplating solution is 0.4M-1M; electrodepositing voltage-0.3V-0.8V; the electrodeposition amount was 20C/cm 2 -80C/cm 2 . High-temperature calcination is carried out to form an alloy, wherein the calcination temperature is 600-800 ℃ and the calcination time is 3-8h. Then carrying out electric corrosion on the steel plate, wherein the electrolytic corrosion liquid is H 3 BO 4 、H 2 SO 4 、Na 2 SO 4 One or more of the aqueous solutions, more preferably H 3 BO 4 Or it is with H 2 SO 4 And/or Na 2 SO 4 Is a mixture of (a) and (b); electrolytic corrosion solution concentrationThe degree is 0.01M-0.6M; the voltage of the electric corrosion is 0.3V-1V; the electric corrosion time is 60min-300min; the counter electrode is a graphite plate.
The invention explores and optimizes the technological conditions of electrodeposition, calcination and electric corrosion operation, so that the catalytic conversion performance level is further improved while the foam nickel is roughened on the surface in situ and the conversion rate is obtained. Although the foam nickel pore canal structure is loose, improper process conditions can also cause structural damage or performance reduction, and through matching and optimization of the process conditions, the problems of pore blocking, pore collapse, layer falling and the like possibly generated in the foam nickel surface modification process are effectively avoided, and the foam nickel product with high catalytic activity is successfully obtained. The foam nickel raw material of the invention can be directly obtained in a commercial way.
In the electro-corrosion process, cu dissolved in the corrosive liquid is deposited on the cathode, and can be cleaned by adopting acid liquor such as sulfuric acid, nitric acid, boric acid, hydrochloric acid and the like after electroplating is finished, and can be reused as electroplating liquid in the electro-deposition step.
The invention has the advantages and beneficial effects that:
the prepared high-activity foam nickel catalyst can be used as a fixed bed catalyst, so that the problems of low catalyst utilization efficiency, low catalytic activity and the like caused by a forming process in the traditional preparation process are avoided. In addition, the problems that the catalyst structure can not be accurately controlled, high-concentration alkali is used, a large amount of waste liquid is generated and the like in the traditional alkali extraction pore-forming process are avoided. The method has the advantages of safe process, electrodeposition of copper on the carbon plate, easy recovery, low production cost, simple and easily controlled preparation process, easy industrial mass production, high activity of the prepared catalyst and good repeatability, and can be used as an electroplating solution after being dissolved.
Drawings
Figure 1 is an XRD and physical color change pattern of a foam nickel catalyst.
Detailed Description
Example 1
Different copper salts are used as electroplating liquid raw materials, copper is electrodeposited under different electroplating liquid concentrations (deposition voltage is-0.3V,deposition amount was 60C/cm 2 ) Then in Ar/H 2 In the mixed gas, roasting for 4 hours at 800 ℃ to form alloy, and removing copper by electric corrosion after roasting (corrosion voltage is 0.5V, solution is 0.5M H) 3 BO 4 Solution, corrosion time is 3 h), the catalyst obtained after drying is subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation (phenylacetylene concentration is 0.3M, ethanol is used as a solvent, reaction is carried out for 2 h), under the same condition, the industrial liquid seal powder Raney nickel catalyst has the phenylacetylene conversion rate of 11.2%, and the original foam nickel has no catalytic activity. In addition, the selectivity of styrene was about 90%, and the other analysis results were as shown in Table 1 below. Therefore, different copper salt electroplating solutions can enable foam nickel to obtain certain catalytic conversion activity under proper concentration, and meanwhile, the final catalyst roughness can be influenced through concentration adjustment, so that the conversion efficiency is optimized.
TABLE 1
Example 2
In CuSO 4 For electroplating solution raw material, different amounts of copper are deposited under different electrodeposition voltages, and then Ar/H is used for the electroplating 2 In the mixed gas, roasting for 4 hours at 800 ℃ to form alloy, and removing copper by electric corrosion after roasting (corrosion voltage is 0.5V, solution is 0.5M H) 3 BO 4 Solution, corrosion time is 3 h), and the catalyst obtained after drying is subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, and analysis results are shown in the following table 2. It can be seen that a certain deposition voltage and deposition amount can enable the foam nickel to obtain a certain catalytic conversion activity, and the final roughness of the catalyst can be comprehensively adjusted by optimizing the deposition voltage and deposition amount, so that the conversion efficiency is affected.
TABLE 2
Example 3
In CuSO 4 For the electroplating solution raw material, the electrodeposition voltage is selected to be-0.3V, and the electrodeposition amount is selected to be 30C/cm 2 In Ar/H 2 Different calcining conditions are selected under the condition of the mixed gas to explore the optimal calcining conditions. Then removing copper by electrolytic etching (etching voltage of 0.5V, solution of 0.5M H) 3 BO 4 Solution, corrosion time is 3 h), and the catalyst obtained after drying is subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, and the analysis results are shown in the following table 3. The calcination temperature and time can affect the formation of nickel-copper alloy and thus the roughness of the catalyst.
TABLE 3 Table 3
Example 4
In CuSO 4 For the electroplating solution raw material, the electrodeposition voltage is selected to be-0.3V, and the calcination condition is Ar/H 2 In the mixed gas, roasting for 4 hours at 600 ℃ to form alloy, and then removing copper by electric corrosion (solution is 0.5M H 3 BO 4 The solution, the corrosion time is 3 h), different corrosion voltages and the influence of different electrodeposit amounts on the catalytic performance are examined. The catalyst obtained after drying was subjected to evaluation of phenylacetylene hydrogenation performance at normal temperature and normal pressure, and the analysis results are shown in Table 4 below. The corrosion voltage also affects the roughness and conversion of the catalyst, and is also related to the amount of electrodeposition, it being seen that the roughness and conversion are affected by a combination of factors from the previous electrodeposition, calcination, and electroerosion processes.
TABLE 4 Table 4
Example 5
In CuSO 4 For the electroplating solution raw material, the electrodeposition voltage is selected to be-0.3V, and the electrodeposition amount is selected to be 30C/cm 2 The calcination condition is Ar/H 2 And (3) roasting in the mixed gas at 600 ℃ for 4 hours to form an alloy. Electrolytic copper removal (etching voltage of 0.85V, solution of 0.5. 0.5M H) 3 BO 4 Solution, 0.01. 0.01M H 2 SO 4 、0.01M Na 2 SO 4 One of the aqueous solutions, or two by two, is mixed, and the corrosion time is 3 h). The catalyst obtained after drying was subjected to evaluation of phenylacetylene hydrogenation performance at normal temperature and normal pressure, and the analysis results are shown in Table 5 below. From the results, it can be seen that H 3 BO 4 Or a composite solution thereof may be advantageous over other corrosive solutions.
TABLE 5
Example 6
Copper electroplated on cathode graphite plate in electro-corrosion process is used for 2M H 2 Soaking in SO4, and finally diluting to 0.5M CuSO 4 The solution is used as the raw material of the electroplating solution, the electrodeposition voltage is selected to be-0.3V, and the electrodeposition amount is selected to be 30C/cm 2 The calcination condition is Ar/H 2 And (3) roasting in the mixed gas at 600 ℃ for 4 hours to form an alloy. Electrolytic corrosion to remove copper after calcination (corrosion voltage of 0.85V, solution of 0.5. 0.5M H 3 BO 4 Solution, corrosion time is 3 h), the catalyst obtained after drying is subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, the conversion rate can reach 32.1%, compared with commercial CuSO 4 The catalyst prepared by the electroplating solution raw material has equivalent performance. The Cu element can be recycled in the electrodeposition-electric corrosion process, so that a large amount of waste liquid is avoided, and the production cost is saved.
Example 7
FIG. 1 shows the process of CuSO 4 Is used as a raw material of the electroplating solution, and is carried out at the voltage of minus 0.3V electrodeposition for 30C/cm 2 Electrodeposition, ar/H 2 Roasting for 4 hours at 600 ℃ in the mixed gas, and then adopting H under the voltage of 0.5V 3 BO 4 And (3) carrying out electrolytic corrosion on the solution for 3 hours, and finally obtaining XRD and a physical pattern of the high-activity foam nickel in the whole process. As can be seen from the figure, the original Foam nickel XRD contains only characteristic peaks of nickel, silver porous appearance (Foam Ni); after electrodeposition, XRD detects characteristic peaks of nickel and copper, respectively, and nickel foam exhibits reddish color (Cu position) due to surface copper plating; after calcination (calculation), as copper atoms go deep into the surface of the porous nickel skeleton to form an alloy, the XRD phase still only shows a single characteristic peak which is the characteristic peak of the alloy, and simultaneously, the reddish color is weakened and restored to silver color due to the formation of the alloy; after electro corrosion (Electrocorrosion), cu on the surface of the alloy is stripped, and the characteristic peak position in the XRD pattern is basically unchanged due to a small amount of alloy phase mainly containing nickel remaining on the surface, but the object shows color bias depth change, which is probably due to color change caused by surface roughness increase caused by Cu stripping.

Claims (2)

1. The application of the high-activity foam nickel catalyst in evaluating the normal-temperature and normal-pressure hydrogenation performance of phenylacetylene is characterized in that the preparation method of the high-activity foam nickel catalyst comprises the following steps: uniformly depositing copper on the surface of the foam nickel by adopting electrodeposition, then calcining at high temperature to promote the surface to form nickel-copper alloy, and then carrying out electrolytic corrosion to selectively remove copper in the nickel-copper alloy to form a high-activity foam nickel catalyst;
in the electrodeposition process, foam nickel is used as a working electrode, a graphite plate is used as a counter electrode, and an electroplating solution is CuSO 4 、Cu(NO 3 ) 2 Or CuCl 2 One or more of the aqueous solutions, the concentration of the electroplating solution is 0.01M-1M, the electrodeposition voltage is 0.1V-0.8V, and the electrodeposition amount is 3C/cm 2 -100C/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The high-temperature calcination process is carried out in Ar/H atmosphere 2 Mixing the gases, wherein the calcination temperature is 600-1000 ℃ and the calcination time is 1-8h;
in the process of electrolytic corrosion,the electrolytic corrosion liquid is H 3 BO 4 、H 2 SO 4 、Na 2 SO 4 One or more of the aqueous solutions, the concentration of the electrolytic corrosion solution is 0.01M-1M, the electrolytic corrosion voltage is 0.1V-1V, the electrolytic corrosion time is 5min-300min, and the counter electrode is a graphite plate.
2. The application of the high-activity foam nickel catalyst in evaluating the normal-temperature and normal-pressure hydrogenation performance of phenylacetylene, according to claim 1, is characterized in that copper deposited on a graphite plate in the electroerosion can be reused as an electrolyte solution raw material for electrodepositing after being dissolved by acid.
CN202111038763.1A 2021-09-06 2021-09-06 Preparation method of high-activity foam nickel catalyst Active CN113813962B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111038763.1A CN113813962B (en) 2021-09-06 2021-09-06 Preparation method of high-activity foam nickel catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111038763.1A CN113813962B (en) 2021-09-06 2021-09-06 Preparation method of high-activity foam nickel catalyst

Publications (2)

Publication Number Publication Date
CN113813962A CN113813962A (en) 2021-12-21
CN113813962B true CN113813962B (en) 2024-02-02

Family

ID=78921783

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111038763.1A Active CN113813962B (en) 2021-09-06 2021-09-06 Preparation method of high-activity foam nickel catalyst

Country Status (1)

Country Link
CN (1) CN113813962B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101537360A (en) * 2008-03-17 2009-09-23 汉能科技有限公司 Preparation method of fixed-bed Raney nickel catalyst
CN105810443A (en) * 2016-04-11 2016-07-27 中国工程物理研究院材料研究所 Alloy/nickel-cobalt sulpho-spinel composite electrode for supercapacitor and preparation method for composite electrode
CN107673332A (en) * 2017-09-18 2018-02-09 山东大学 A kind of method that large area 3D graphenes are prepared using composition metal template
CN113042055A (en) * 2021-03-23 2021-06-29 天津理工大学 Safety porous nickel catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101537360A (en) * 2008-03-17 2009-09-23 汉能科技有限公司 Preparation method of fixed-bed Raney nickel catalyst
CN105810443A (en) * 2016-04-11 2016-07-27 中国工程物理研究院材料研究所 Alloy/nickel-cobalt sulpho-spinel composite electrode for supercapacitor and preparation method for composite electrode
CN107673332A (en) * 2017-09-18 2018-02-09 山东大学 A kind of method that large area 3D graphenes are prepared using composition metal template
CN113042055A (en) * 2021-03-23 2021-06-29 天津理工大学 Safety porous nickel catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Electrocatalytic hydrogenation of furfural using non-noble-metal electrocatalysts in alkaline medium";Ram Ji Dixit等;Green Chem;第23卷;第4201-4212页 *
"Kirkendall Effect in Creating Three-Dimensional Metal Catalysts for Hierarchically Porous Ultrathin Graphite with Unique Properties";Jianhe Guo等;Chem. Mater.;第29卷;第4991−4998页 *

Also Published As

Publication number Publication date
CN113813962A (en) 2021-12-21

Similar Documents

Publication Publication Date Title
US3150011A (en) Shaped metal parts having a superficial double skeleton catalyst structure
Cai et al. Fabrication of three-dimensional nanoporous nickel films with tunable nanoporosity and their excellent electrocatalytic activities for hydrogen evolution reaction
Ott et al. Direct electrodeposition of porous platinum honeycomb structures
CN103205780B (en) Grate type titanium-based PbO2 electrode for nonferrous metal electrodeposition and preparation method of grate type titanium-based PbO2 electrode
CN100529193C (en) Jet electroform method and equipment for manufacturing foamed metal
KR20130061123A (en) Method for producing aluminum structure and aluminum structure
CN102051634A (en) Titanium electrode material with porous titanium as substrate and preparation method of titanium electrode material
JP5648588B2 (en) Aluminum structure manufacturing method and aluminum structure
CN109778250A (en) A method of magnetic metal nanotube is prepared by controlling electrodeposition condition
JP2003534459A (en) Cathode for electrochemical regeneration of permanganate etching solution
CN113813962B (en) Preparation method of high-activity foam nickel catalyst
CN108160683A (en) A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes
WO2024027108A1 (en) Electrode having integrated composite structure of matrix and catalyst layer and preparation method therefor
CN102268714A (en) Electrochemical pretreatment method of cathode for electrolytic extraction of metal gallium
Jiang et al. Dynamic self-optimization of hierarchical NiAl architecture catalysing oxygen evolution reaction in alkaline water electrolysis
JP5692233B2 (en) Aluminum structure manufacturing method and aluminum structure
Fow et al. Highly active gauze-supported skeletal nickel catalysts
JP3245837B2 (en) Method for producing porous metal foil
CN113149141A (en) Graphite-phase carbon nitride modified lead dioxide electrode and preparation method and application thereof
CN113695568B (en) Preparation method of metal framework capable of designing nano holes and preparation method of catalyst
CN113584533B (en) Preparation method of carbon fiber titanium-based lead dioxide electrode
CN110085429A (en) A kind of method of aluminium electrolutic capacitor mesohigh anode aluminium foil pulsed deposition nanometer tin point
CN113151868B (en) Porous nickel-tungsten alloy material and preparation method thereof
CN102974352B (en) Nickel-aluminum oxide catalysis complex membrane, preparation method thereof and application thereof
Skibińska et al. Study on SyntheSiS and Modification of conical ni StructureS by one-Step Method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant