CN113813962A - Preparation method of high-activity foamed nickel catalyst - Google Patents
Preparation method of high-activity foamed nickel catalyst Download PDFInfo
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- CN113813962A CN113813962A CN202111038763.1A CN202111038763A CN113813962A CN 113813962 A CN113813962 A CN 113813962A CN 202111038763 A CN202111038763 A CN 202111038763A CN 113813962 A CN113813962 A CN 113813962A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 238000005260 corrosion Methods 0.000 claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 6
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 45
- 230000007797 corrosion Effects 0.000 claims description 26
- 238000009713 electroplating Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007832 Na2SO4 Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000000866 electrolytic etching Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 229910000564 Raney nickel Inorganic materials 0.000 abstract description 19
- 239000006260 foam Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000007868 Raney catalyst Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 16
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000012855 volatile organic compound 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
- B01J23/70—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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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 process. Firstly, uniformly depositing copper with a certain thickness on the surface of the foamed nickel by adopting an electrodeposition method, then calcining at high temperature to form a nickel-copper alloy, and then removing the copper in the alloy by adopting an electroerosion method to form a rough porous structure, thereby obtaining the high-activity foamed nickel catalyst. In the electro-corrosion, copper is deposited on a cathode, and can be used as a raw material solution for electro-deposition after being dissolved by acid, 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 industrial amplification, and the prepared catalyst has high activity and good repeatability.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a preparation method of a high-activity foamed nickel catalyst.
Background
The raney nickel catalyst is an important industrial catalyst, and has been widely applied to various organic reactions such as hydrogenation, dehydrogenation, dehalogenation, desulfurization and the like due to low price and strong process controllability. According to statistics, the global capacity in 2017 is close to 2.8 ten thousand tons. According to the application and the form of the Raney nickel catalyst, the Raney nickel catalyst can be divided into slurry Raney nickel, powder Raney nickel and fixed bed Raney nickel catalyst, wherein the fixed bed Raney nickel catalyst is a new generation catalyst specially used for the fixed bed continuous hydrogenation process development, and accounts for larger proportion in the Raney nickel catalyst.
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 alkali extraction method is generally adopted, and the preparation process is the same as that of the powder Raney nickel. However, there are various methods for forming, for example, a method for crushing a bulk alloy material (US6262307B1, US6284703, CN96121302.7, US9586879), crushing a melted bulk alloy material into a material having a certain size, and extracting with an alkali to obtain a raney nickel catalyst, but the catalyst obtained by the method has a low utilization rate, only a surface layer forms a porous structure, the center is still an alloy material, and the catalyst is not fully utilized. For another example, methods for bonding and molding alloy powder by using a binder (Industrial Catalysis,2013,21(7):59-63, US20030120116, US20150231612a1, US4895994) mainly include pseudo-boehmite, metal powder or polymer, but the method causes the problems of difficult leaching and activation of the catalyst, small specific surface area, low catalytic activity and the like. For another example, a thermal spray coating method (US20060224027a1) is adopted, the alloy material is melted and sprayed on a metal foil, and after folding and forming, alkali extraction is carried out to obtain the fixed bed raney nickel catalyst, but the performance of the catalyst obtained by the method is weaker. Therefore, the development of a new method for preparing the fixed bed Raney nickel catalyst or the replacement of the fixed bed Raney nickel catalyst by the novel high-efficiency porous nickel fixed bed catalyst has very important significance.
The foamed nickel material has the characteristics of small density, communicated pore channels, large void degree, 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 CN110142046A), is modified with other active components on the surface, and is applied to catalytic oxidation of volatile organic compounds and the like. However, the development of the self-catalytic performance of the foamed nickel is relatively less, the foamed nickel is modified into a catalyst with certain catalytic performance, and the self-porosity, the excellent mass transfer characteristic and the excellent mechanical performance are utilized, so that the foamed nickel has important significance for replacing the traditional fixed bed Raney nickel catalyst.
The currently known preparation method of the fixed bed Raney nickel catalyst has reference significance for modifying a foamed nickel material, aluminum is covered on the foamed nickel by adopting different methods such as melt impregnation, electroplating/chemical plating, spraying and the like, and the fixed bed Raney nickel catalyst can be obtained after alkaline leaching. However, these modification methods all use high-concentration alkali liquor, which is corrosive to equipment and generates a large amount of waste liquid. In addition, in the processes of melt impregnation and spraying, the content of aluminum in the foam nickel and on the surface of the foam nickel 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 flammable strong reducing agents and the like in the using process. Based on the above problems, it is necessary to develop a method for preparing high-activity foamed nickel with more environmental protection, safety and low cost.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a preparation method of a high-activity foamed nickel catalyst, which adopts an electro-corrosion technology to realize green, safe and low-cost preparation of the high-activity foamed nickel catalyst.
The technical scheme of the invention is as follows:
a preparation method of a high-activity foamed nickel catalyst comprises the following steps:
the invention adopts the electrodeposition technology to uniformly deposit copper on the surface of the foamed 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 electro-corrosion to form the high-activity foamed nickel catalyst.
The method utilizes the characteristic that nickel and copper are easy to dissolve mutually, firstly utilizes the electrodeposition to realize the uniform deposition on the porous surface of the foamed nickel, then utilizes calcination to promote the mutual dissolution of nickel and copper so as to form an alloy layer on the surface of the porous nickel, the alloy layer is integrally formed on the porous surface of the original foamed nickel in situ, then utilizes the electrocorrosion selectivity to remove the copper in the alloy, and forms a microporous structure in situ on the porous surface structure of the original foamed nickel, so that the surface structure is roughened, thereby obtaining good catalytic performance, and simultaneously, the in-situ rough micropores are uniform and are not easy to fall off, and have very high catalytic performance stability.
In the electrodeposition technology, foamed nickel is used as a working electrode, and a graphite plate is used as a counter electrode; the electroplating solution is CuSO4、Cu(NO3)2Or CuCl2One or more of aqueous solutions; the concentration of the electroplating solution is 0.01M-1M; the electrodeposition voltage is-0.1V to-0.8V; the electrodeposition amount is 3C/cm2-100C/cm2. And (3) calcining at high temperature to form the alloy, wherein the calcining temperature is 600-1000 ℃, and the calcining time is 1-8 h. Then carrying out electric corrosion on the alloy, wherein the electrolytic corrosion solution is H3BO4、H2SO4、Na2SO4One or more of the aqueous solutions are mixed; the concentration of the electrolytic corrosion solution is 0.01M-1M; the voltage of the electric corrosion is 0.1V-1V; the electro-corrosion time is 5min-300 min; the counter electrode is a graphite plate.
Preferably, in the electrodeposition technology, the foamed nickel is used as a working electrode, and the graphite plate is used as a counter electrodeA pole; the electroplating solution is CuSO4、Cu(NO3)2Or CuCl2One of aqueous solutions; the concentration of the electroplating solution is 0.4M-1M; the electrodeposition voltage is-0.3V to-0.8V; the electrodeposition amount is 20C/cm2-80C/cm2. And (3) calcining at high temperature to form the alloy, wherein the calcining temperature is 600-800 ℃, and the calcining time is 3-8 h. Then carrying out electric corrosion on the alloy, wherein the electrolytic corrosion solution is H3BO4、H2SO4、Na2SO4One or more of the aqueous solutions are mixed, and H is more preferable3BO4Or it and H2SO4And/or Na2SO4Mixing; the concentration of the electrolytic corrosion solution is 0.01M-0.6M; the voltage of the electric corrosion is 0.3V-1V; the electro-corrosion time is 60min-300 min; the counter electrode is a graphite plate.
The invention explores and optimizes the process conditions of electrodeposition, calcination and electroerosion operation, so that the foam nickel is roughened on the in-situ surface, the conversion rate is obtained, and the catalytic conversion performance level is further improved. Although the pore structure of the foamed nickel is loose, improper process conditions can also cause structural damage or performance reduction, and the problems of hole blocking, hole collapse, layer falling and the like which are possibly generated in the process of modifying the surface of the foamed nickel are effectively avoided through the matching and optimization of the process conditions, so that the foamed nickel product with high catalytic activity is successfully obtained. The nickel foam feedstock of the present invention is directly commercially available.
In the electro-corrosion process, Cu dissolved in a corrosive liquid is deposited on a cathode, and can be cleaned by using an acid solution after electroplating, such as sulfuric acid, nitric acid, boric acid, hydrochloric acid and the like, and can be reused as an electroplating solution in the electro-deposition step.
The invention has the advantages and beneficial effects that:
the prepared high-activity foamed nickel catalyst can be used as a fixed bed catalyst, and the problems of low catalyst utilization efficiency, low catalytic activity caused by a forming agent and the like in the traditional preparation process are solved. 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, deposition of the electro-corrosion copper on the carbon plate, easy recovery, low production cost, simple preparation process, easy control, easy industrial scale-up production, high activity of the prepared catalyst and good repeatability, and can be used as an electroplating solution after dissolution.
Drawings
FIG. 1 is a XRD and color change of the foamed nickel catalyst.
Detailed Description
Example 1
Different copper salts are used as raw materials of the electroplating solution, under different concentrations of the electroplating solution, copper is electrodeposited (the deposition voltage is-0.3V, and the deposition amount is 60C/cm2) Then in Ar/H2Calcining at 800 deg.C for 4 hr in mixed gas to form alloy, and electroetching to remove copper (corrosion voltage of 0.5V, solution of 0.5M H)3BO4The corrosion time of the solution is 3h), the catalyst obtained after drying is subjected to phenylacetylene normal-temperature normal-pressure hydrogenation performance evaluation (the phenylacetylene concentration is 0.3M, ethanol is used as a solvent, the reaction is carried out for 2h), under the same condition, the conversion rate of the phenylacetylene is 11.2 percent by using the industrial liquid-sealed powder Raney nickel catalyst, and the original foam nickel has no catalytic activity. In addition, the selectivity of styrene is around 90%, and no obvious change exists, and other analysis results are shown in the following table 1. Therefore, different copper salt electroplating solutions can enable the foamed nickel to obtain certain catalytic conversion activity under proper concentrations, and the final catalyst roughness can be influenced by adjusting the concentrations, so that the conversion efficiency is optimized.
TABLE 1
Example 2
With CuSO4Different amounts of copper are deposited for electroplating solution raw materials under different electrodeposition voltages, and then Ar/H2In the mixed gas, the mixed gas is mixed,roasting at 800 deg.C for 4h to form alloy, and electroerosion to remove copper (corrosion voltage 0.5V, solution 0.5M H)3BO4Solution, corrosion time is 3h), the catalyst obtained after drying is subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, and the analysis result is shown in the following table 2. Therefore, certain deposition voltage and deposition amount can enable the foamed nickel to obtain certain catalytic conversion activity, and the final roughness of the catalyst can be comprehensively adjusted by optimizing the deposition voltage and the deposition amount, so that the conversion efficiency is influenced.
TABLE 2
Example 3
With CuSO4The electrodeposition voltage is selected to be-0.3V and the electrodeposition amount is selected to be 30C/cm for electroplating solution raw materials2In Ar/H2Different calcination conditions are selected under the condition of mixed gas to explore the optimal calcination conditions. Then, the copper is removed by electro-etching (the etching voltage is 0.5V, the solution is 0.5M H)3BO4Solution, corrosion time is 3h), the catalyst obtained after drying is subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, and the analysis result is shown in the following table 3. The calcination temperature and time will affect the formation of the nickel-copper alloy and thus the catalyst roughness.
TABLE 3
Example 4
With CuSO4The electrodeposition voltage is selected to be-0.3V and the calcination condition is Ar/H for electroplating solution raw materials2Roasting in mixed gas at 600 deg.C for 4 hr to form alloy, and removing copper by electrolytic corrosion (solution 0.5M H)3BO4Solution, etching time is 3h)The influence of different corrosion voltages and different electrodeposition amounts on the catalytic performance is investigated. The catalyst obtained after drying was subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, and the analysis results are shown in table 4 below. The corrosion voltage also affects the catalyst roughness and conversion, and is related to the amount of electrodeposition, which is seen to be a combination of factors previously involved in the electrodeposition, calcination, and electroerosion processes.
TABLE 4
Example 5
With CuSO4The electrodeposition voltage is selected to be-0.3V and the electrodeposition amount is selected to be 30C/cm for electroplating solution raw materials2The calcining condition is Ar/H2And roasting the mixture for 4 hours at the temperature of 600 ℃ in the mixed gas to form the alloy. Electrolytic etching to remove copper (etching voltage 0.85V, solution 0.5M H)3BO4Solution, 0.01M H2SO4、0.01M Na2SO4One or two of the aqueous solutions are mixed, and the corrosion time is 3 h). The catalyst obtained after drying was subjected to phenylacetylene normal temperature and normal pressure hydrogenation performance evaluation, and the analysis results are shown in table 5 below. From the results, H can be seen3BO4Or the composite solution thereof has advantages over other etching solutions.
TABLE 5
Example 6
Electroplating copper on cathode graphite plate in electroerosion process with 2M H2Soaking in SO4, and diluting to 0.5M CuSO4The 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 selected30C/cm2The calcining condition is Ar/H2And roasting the mixture for 4 hours at the temperature of 600 ℃ in the mixed gas to form the alloy. After calcination, the copper is removed by electroerosion (the corrosion voltage is 0.85V, the solution is 0.5M H)3BO4The corrosion time of the solution is 3h), the conversion rate of the catalyst obtained after drying can reach 32.1 percent when the catalyst is subjected to phenylacetylene normal-temperature normal-pressure hydrogenation performance evaluation, compared with commercial CuSO4The catalyst prepared by the raw material of the electroplating solution has equivalent performance. Therefore, the Cu element can be recycled in the electrodeposition-electroerosion process, so that a large amount of waste liquid is avoided, and the production cost is saved.
Example 7
FIG. 1 shows the reaction with CuSO4Is used as electroplating solution raw material, and is carried out at an electrodeposition voltage of-0.3V and at a concentration of 30C/cm2Electrodeposition, Ar/H2Roasting in mixed gas at 600 deg.C for 4H, and then under 0.5V voltage, adopting H3BO4And (3) performing electro-corrosion on the solution for 3 hours to finally obtain an XRD (X-ray diffraction) and a material object diagram of the high-activity foamed nickel in the whole process. As can be seen from the figure, the original nickel Foam XRD contains only the characteristic peaks of nickel, a silvery porous appearance (Foam Ni); after electrodeposition, XRD respectively detects characteristic peaks of nickel and copper, and the foamed nickel is displayed as red due to surface copper plating (Cu position); after calcination (calcination), the XRD phase still only shows a single characteristic peak which is the characteristic peak of the alloy due to the fact that copper atoms penetrate into the surface of the porous nickel framework to form the alloy, and meanwhile, the red-red color is weakened and is recovered to the silver color due to the formation of the alloy; after electroerosion (electroerosion), Cu on the surface of the alloy is stripped, and the characteristic peak position in the XRD pattern is basically unchanged but the color of the material shows a shift to depth change, which may be the color change caused by the increase of surface roughness due to Cu stripping, because a small amount of alloy phase mainly containing nickel still remains on the surface.
Claims (7)
1. A preparation method of a high-activity foamed nickel catalyst is characterized by comprising the following steps: the method comprises the steps of uniformly depositing copper on the surface of the foamed nickel by adopting electrodeposition, then calcining at high temperature to promote the surface to form nickel-copper alloy, and selectively removing the copper in the nickel-copper alloy by virtue of electro-corrosion to form the high-activity foamed nickel catalyst.
2. The method for preparing a high-activity foamed nickel catalyst according to claim 1, wherein: in the electrodeposition process, the foamed nickel is used as a working electrode, and the graphite plate is used as a counter electrode; the electroplating solution is CuSO4、Cu(NO3)2Or CuCl2One or more of aqueous solutions; the concentration of the electroplating solution is 0.01M-1M; the electrodeposition voltage is-0.1V to-0.8V; the electrodeposition amount is 3C/cm2-100C/cm2。
3. The method for preparing a high-activity foamed nickel catalyst according to claim 1, wherein: the high-temperature calcination process is carried out in Ar/H calcination atmosphere2The mixed atmosphere, the calcining temperature is 600-1000 ℃, and the calcining time is 1-8 h.
4. The method for preparing a high-activity foamed nickel catalyst according to claim 1, wherein: the electrolytic corrosion solution is H3BO4、H2SO4、Na2SO4One or more of aqueous solutions; the concentration of the electrolytic corrosion solution is 0.01M-1M; the voltage of the electric corrosion is 0.1V-1V; the electro-corrosion time is 5min-300 min; the counter electrode is a graphite plate.
5. The method for preparing a high-activity foamed nickel catalyst according to claim 1, wherein: in the electrodeposition, the foamed nickel is used as a working electrode, and the graphite plate is used as a counter electrode; the electroplating solution is CuSO4、Cu(NO3)2Or CuCl2One or more of aqueous solutions; the concentration of the electroplating solution is 0.4M-1M; the electrodeposition voltage is-0.3V to-0.8V; the electrodeposition amount is 20C/cm2-80C/cm2. And (3) calcining at high temperature to form the alloy, wherein the calcining temperature is 600-800 ℃, and the calcining time is 3-8 h. Then carrying out electric corrosion on the alloy, wherein the electrolytic corrosion solution is H3BO4、H2SO4、Na2SO4One or more of the aqueous solutions are mixed, and H is more preferable3BO4Or it and H2SO4And/or Na2SO4Mixing; the concentration of the electrolytic corrosion solution is 0.01M-0.6M; the voltage of the electric corrosion is 0.3V-1V; the electro-corrosion time is 60min-300 min; the counter electrode is a graphite plate.
6. The method for preparing a high-activity foamed nickel catalyst according to any one of claims 1 to 5, wherein: copper deposited on the graphite plate in the electroetching is dissolved by acid and then used as an electrolyte solution raw material for the electrodeposition.
7. Use of the catalyst obtained according to any one of claims 1 to 5 in catalytic hydrogenation reactions.
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