CN104707626A - Raney nickel catalyst and preparation method thereof - Google Patents
Raney nickel catalyst and preparation method thereof Download PDFInfo
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- CN104707626A CN104707626A CN201510136402.9A CN201510136402A CN104707626A CN 104707626 A CN104707626 A CN 104707626A CN 201510136402 A CN201510136402 A CN 201510136402A CN 104707626 A CN104707626 A CN 104707626A
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Abstract
The invention provides a Raney nickel catalyst. The Raney nickel catalyst takes Ni as an active component, and is prepared from the following components by mass percent: 87wt%-92wt% of Ni, 5wt%-10wt% of Al and 2wt%-7wt% of an auxiliary agent metal. The Raney nickel catalyst has the advantages of simple preparation process, uniform catalyst grain diameter and size, and relatively high activity.
Description
Technical field
The invention belongs to a kind of Catalysts and its preparation method, relate to a kind of Raney's nickel catalyst and preparation method thereof concretely.
Background technology
Raney's nickel is a kind of solid-state different-phase catalyst be made up of the nickel alumin(i)um alloy small grains of band loose structure, and have stronger adsorptivity to hydrogen, its high catalytic activity and heat endurance make Raney's nickel catalyst be widely used in a lot of organic synthesis.
Tradition Raney's nickel catalyst is by by finely divided mixed-metal feedstock heat fused in high-temperature smelting pot, by the melt cooling obtained, again by pulverizing, grinding, suspend gradation, then the alloy catalyst presoma of selected required grain diameter size, adopts alkali or acid the process of alloy catalyst presoma to be prepared.The method of conventional high-temperature heating and melting often can not obtain high degree of dispersion and the Raney's nickel catalyst of even particle size, usually adopts increase alloy catalyst presoma grinding step or other preparation methods to obtain evengranular Raney's nickel catalyst.
Patent CN104058974A, the preparation method of Raney's nickel catalyst disclosed in CN104045569A and CN103977818, all in different atmosphere, adopt heating using microwave feed metal simple substance to make it fuse form alloy molten thing, then diverse ways is adopted to be atomized the alloyed powder forming different meshes, but this kind of method is comparatively loaded down with trivial details and considerably increase the catalyst preparing cycle, simultaneously also higher to the requirement of equipment.
A kind of preparation method of Raney's nickel catalyst disclosed in Japan Patent JP2005205265, be characterised in that and be coated in nickel foam by aluminium powder and binding agent mixing, the nickel foam of surface alloying is prepared in high-temperature roasting, then activates through alkali lye and obtain Raney's nickel catalyst.A kind of preparation method of Raney's nickel catalyst disclosed in patent CN101537361B, the nickel foam first preparing alloying equally, difference is first to adopt hot coating method to be sprayed in nickel foam by metallic aluminium, then in different atmosphere, carries out high-temperature roasting obtain nickel foam.Above two patents are all adopt nickel foam as the presoma preparing Raney's nickel catalyst, although all decrease the operations such as pulverizing, grinding, suspension and atomization, but need the operation increasing preparation nickel foam early stage, and the expression activitiy of the catalyst prepared is low, catalytic activity heterogeneity.
Summary of the invention
The object of this invention is to provide a kind of preparation process simple, catalyst particle size size evenly and Raney's nickel catalyst with greater activity and preparation method thereof.。
Raney's nickel catalyst of the present invention, it is characterized in that catalyst is take Ni as active component, and its quality group becomes: Ni 87-92wt%, Al 5-10wt%, promoter metal 2-7wt%.
Promoter metal as described above is one or more in Fe, Cr, Mo, Pt.
The preparation method of Raney's nickel catalyst of the present invention, concrete steps are as follows:
(1) by granularity be 3-9 μm of nickel powder, 4-10 μm of aluminium powder and 4-10 μm of promoter metal powder mix, and obtain mixed metal powder, and its content respectively formed is: Ni 45-58wt%, Al 40-54wt% metal promoter 1-5wt%;
(2) CO of 100 ~ 200W is adopted
2laser instrument carries out ablation 80 ~ 200s by its melting to step (1) mixed metal powder, and then cooling obtains alloy powder caltalyst presoma;
(3) be that the sodium hydroxide solution of 4 ~ 6mol/L dropwise adds in step (2) alloy powder caltalyst presoma by concentration, to remain in ice-water bath and with 80 ~ 100r/min magnetic agitation, what control NaOH adds 0.9 ~ 1.3 times that mole is the mole of metal A l;
(4), after dropping terminates, be repeatedly washed to neutrality by deionized water, obtain Raney's nickel catalyst, and be kept in water for subsequent use.
Accompanying drawing explanation
Fig. 1 is the SEM figure of comparative example Raney's nickel catalyst presoma.
Fig. 2 is the SEM figure of Raney's nickel catalyst presoma prepared by the embodiment of the present invention 1.
Technical advantage of the present invention is:
(1) the present invention adopts free of contamination high energy laser beam as thermal source, the metal simple-substance powder mixed is carried out the presoma that Raney's nickel catalyst is prepared in melting, compared with employing high-temperature heating motlten metal simple substance powder, laser ablation method can reduce labour intensity, shorten the preparation time of catalyst precursor alloyed powder, the manufacturing cycle of catalyst is shortened by a relatively large margin.
(2) the present invention adopts laser ablation method to prepare Raney's nickel catalyst presoma alloy, and compared with traditional handicraft, its cooling velocity quickly, greatly reduces due to cooling procedure, the gathering caking phenomenon that long-lasting catalytic is in hot environment and causes.
(3) the present invention adopts laser ablation method to prepare the presoma alloy of Raney's nickel catalyst, can by controlling the parameter of laser, to the rise time of particle, the scope of uniformity and yardstick can have good control, prepare the catalyst of corresponding particle size, catalysis can be carried out for various reaction, decrease loss that is less because of granularity or the uneven catalyst caused.
(4) the present invention adopts laser ablation synthetic catalyst presoma alloy, compared with other synthesis techniques, Laser synthesizing is reactor heating wall and other materials not, make use of energy efficiently, ensure that the pure property of catalyst precursor alloy to a certain extent, the finished product Raney's nickel catalyst making it prepare has higher purity.
Detailed description of the invention
Following content is only several typical embodiment of the present invention, and object is the preparation method and application describing this patent catalyst in detail, can not limit scope of the present invention with this.Namely the equalization change generally done according to the present patent application the scope of the claims with modify, all should still belong in scope that patent of the present invention contains.The performance probe of the Raney's nickel catalyst now adopting dinitrotoluene (DNT) (DNT) hydrogenation synthesis toluenediamine (TDA) to prepare for this patent.
Embodiment 1
Be 3-5 μm of nickel powder 5.8g by granularity, 8-10 μm of aluminium powder 4.1g and 4-8 μm of iron powder 0.1g mixes; Adopt the CO of 100W
2its melting, then cooling are obtained alloy powder caltalyst presoma by laser ablation 180s; Be that the sodium hydroxide solution 34mL of 4mol/L dropwise adds in above-mentioned alloy powder caltalyst presoma by concentration, remain in ice-water bath and with 80r/min magnetic agitation; After dropping terminates, become neutral with deionized water cyclic washing, obtain Raney's nickel catalyst, be kept in water for subsequent use.Detect through ICP, the quality group of product catalyst becomes Ni 88.4%, Al 9.2%, Fe 2.4%.
The reaction utilizing DNT catalytic hydrogenation to produce TDA is evaluated finished catalyst.Evaluation detailed process is: will add in reactor after 5g DNT, 0.5g finished catalyst and the mixing of 100mL methanol solvate, and with nitrogen and hydrogen air purge 3 times, subsequently Hydrogen Vapor Pressure will be charged to 2.0MPa, under 110 DEG C of conditions, carry out hydrogenation reaction.Utilize GC-9160 type gas-chromatography to carry out quantitative analysis to product after reaction terminates, catalyst preparation conditions and evaluation result see attached list 1.
Embodiment 2
Be 3-5 μm of nickel powder 5.6g by granularity, 8-10 μm of aluminium powder 4.3g and 4-8 μm of molybdenum powder 0.1g mixes; Adopt the CO of 120W
2its melting, then cooling are obtained alloy powder caltalyst presoma by laser ablation 150s; Be that the sodium hydroxide solution 38mL of 5mol/L dropwise adds in above-mentioned alloy powder caltalyst presoma by concentration, remain in ice-water bath and with 90r/min magnetic agitation; After dropping terminates, become neutral with deionized water cyclic washing, obtain Raney's nickel catalyst, be kept in water for subsequent use.Detect through ICP, the quality group of product catalyst becomes Ni 90.3%, Al 6.7%, Mo 3.0%.
Evaluation procedure is with embodiment 1, and catalyst preparation conditions and evaluation result see attached list 1.
Embodiment 3
Be 4-8 μm of nickel powder 5.4g by granularity, 4-9 μm of aluminium powder 4.3g and 4-8 μm of platinum powder 0.3g mixes; Adopt the CO of 140W
2laser ablation 120s is by its melting, and then cooling obtains alloy powder caltalyst presoma; Be that the sodium hydroxide solution 35mL of 6mol/L dropwise adds in above-mentioned alloy powder caltalyst presoma by concentration, remain in ice-water bath and with 100r/min magnetic agitation; After dropping terminates, become neutral with deionized water cyclic washing, obtain Raney's nickel catalyst, be kept in water for subsequent use.Detect through ICP, the quality group of product catalyst becomes Ni 91.6%, Al 5.3%, Pt 3.1%.
Evaluation procedure is with embodiment 1, and catalyst preparation conditions and evaluation result see attached list 1.
Embodiment 4
Be that 5-9 μm of nickel powder 5.0g, 4-6 μm of aluminium powder 4.5g, 8-10 μm of chromium 0.3g and ferrous metal powder 0.2g mix by granularity; Adopt the CO of 100W
2laser ablation 180s is by its melting, and then cooling obtains alloy powder caltalyst presoma; Be that the sodium hydroxide solution 46mL of 4mol/L dropwise adds in above-mentioned alloy powder caltalyst presoma by concentration, remain in ice-water bath and with 90r/min magnetic agitation; After dropping terminates, become neutral with deionized water cyclic washing, obtain Raney's nickel catalyst, be kept in water for subsequent use.Detect through ICP, the quality group of product catalyst becomes Ni 88.7%, Al 6.0%, Fe 2.1wt%, Cr 3.2wt%.。
Evaluation procedure is with embodiment 1, and catalyst preparation conditions and evaluation result see attached list 1.
Embodiment 5
Be 3-5 μm of nickel powder 4.8g, 8-10 μm of aluminium powder 5.1g by granularity, 4-8 μm of iron and each 0.05g of platinum powder mix; Adopt the CO of 100W
2laser ablation 180s is by its melting, and then cooling obtains alloy powder caltalyst presoma; Be that the sodium hydroxide solution 38mL of 5mol/L dropwise adds in above-mentioned alloy powder caltalyst presoma by concentration, remain in ice-water bath and with 100r/min magnetic agitation; After dropping terminates, become neutral with deionized water cyclic washing, obtain Raney's nickel catalyst, be kept in water for subsequent use.Detect through ICP, the quality group of product catalyst becomes Ni 90.6%, Al 7.9%, Fe 0.7wt%, Pt 0.8wt%.
Evaluation procedure is with embodiment 1, and catalyst preparation conditions and evaluation result see attached list 1.
Embodiment 6
Be 3-5 μm of nickel powder 4.5g, 6-8 μm of aluminium powder 5.3g by granularity, 4-8 μm of iron 0.05g, molybdenum 0.05g and platinum 0.1g mix; Adopt the CO of 100W
2laser ablation 180s is by its melting, and then cooling obtains alloy powder caltalyst presoma; Be that the sodium hydroxide solution 36mL of 6mol/L dropwise adds in above-mentioned alloy powder caltalyst presoma by concentration, remain in ice-water bath and with 80r/min magnetic agitation; After dropping terminates, become neutral with deionized water cyclic washing, obtain Raney's nickel catalyst, be kept in water for subsequent use.Detect through ICP, the quality group of product catalyst becomes Ni 89.3%, Al 7.6%, Fe 0.7wt%, Mo 0.8wt%, Pt 1.6wt%.
Evaluation procedure is with embodiment 1, and catalyst preparation conditions and evaluation result see attached list 1.
Comparative example
Directly using the Ni-Al alloyed powder (Shandong Jia Hong Chemical Co., Ltd.) bought as alloy skeletal nickel catalyst presoma, 10g alloyed powder and 10mL deionized water are put into beaker, the NaOH solution of 50mL16wt% is added while stirring in 40 DEG C of water-baths, react to bubble-free generates, become neutral with deionized water cyclic washing and be kept in water for subsequent use.
Raney's nickel catalyst prepared by this comparative example is probe by the reaction of hydrogenation of dinitro toluene preparing methylbenzene diamines, and reaction condition and step are with embodiment 1, and evaluation result sees attached list 1..
Subordinate list 1 is Raney's nickel catalyst catalysis hydrogenation of dinitro toluene synthesis toluenediamine Evaluation results prepared by embodiment and comparative example.As can be seen from subordinate list 1, in the reaction of catalysis dinitrotoluene (DNT) synthesis toluenediamine, the catalytic activity of embodiment 1 ~ 6 is all higher than comparative example.
As can be seen from accompanying drawing, comparative example Raney's nickel catalyst presoma size distribution is uneven, and easily reunites, this mother bright embodiment 1 Raney's nickel catalyst presoma alloy not easily reunite and also particle size distribution even.
Subordinate list 1
Claims (3)
1. a Raney's nickel catalyst, it is characterized in that catalyst is take Ni as active component, and its quality group becomes: Ni 87-92wt%, Al 5-10wt%, promoter metal 2-7wt%.
2. a kind of Raney's nickel catalyst as claimed in claim 1, is characterized in that described promoter metal is one or more in Fe, Cr, Mo, Pt.
3. the preparation method of a kind of Raney's nickel catalyst as claimed in claim 1 or 2, is characterized in that comprising step as follows:
(1) by granularity be 3-9 μm of nickel powder, 4-10 μm of aluminium powder and 4-10 μm of promoter metal powder mix, and obtain mixed metal powder, and its content respectively formed is: Ni 45-58wt%, Al 40-54wt% metal promoter 1-5wt%;
(2) CO of 100 ~ 200W is adopted
2laser instrument carries out ablation 80 ~ 200s by its melting to step (1) mixed metal powder, and then cooling obtains alloy powder caltalyst presoma;
(3) be that the sodium hydroxide solution of 4 ~ 6mol/L dropwise adds in step (2) alloy powder caltalyst presoma by concentration, to remain in ice-water bath and magnetic force with 80 ~ 100r/min magnetic agitation, what control NaOH adds 0.9 ~ 1.3 times that mole is the mole of metal A l;
(4), after dropping terminates, be repeatedly washed to neutrality by deionized water, obtain Raney's nickel catalyst, and be kept in water for subsequent use.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537577A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Iron-molybdic catalyst presoma, iron-molybdic catalyst and its application |
| CN109718779A (en) * | 2018-12-26 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of ball-type skeleton Ni hydrogenation catalyst and its preparation method and application |
| CN114618525A (en) * | 2020-12-11 | 2022-06-14 | 万华化学集团股份有限公司 | Preparation method and application of porous Raney nickel catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977818A (en) * | 2014-05-15 | 2014-08-13 | 太原理工大学 | Raney nickel catalyst used for low-pressure hydrogenation of dinitrotoluenem, preparation method and application thereof |
| CN104014800A (en) * | 2014-06-09 | 2014-09-03 | 天津大学 | Preparing method for controllably synthesizing monodisperse active metal nanoparticles through lasers |
| CN104069872A (en) * | 2014-07-08 | 2014-10-01 | 赛鼎工程有限公司 | Preparation method and application of catalyst applicable to methanation of slurry reactor |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977818A (en) * | 2014-05-15 | 2014-08-13 | 太原理工大学 | Raney nickel catalyst used for low-pressure hydrogenation of dinitrotoluenem, preparation method and application thereof |
| CN104014800A (en) * | 2014-06-09 | 2014-09-03 | 天津大学 | Preparing method for controllably synthesizing monodisperse active metal nanoparticles through lasers |
| CN104069872A (en) * | 2014-07-08 | 2014-10-01 | 赛鼎工程有限公司 | Preparation method and application of catalyst applicable to methanation of slurry reactor |
Non-Patent Citations (1)
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| 程广萍: "激光反应合成Ni-Al金属间化合物涂层", 《材料热处理学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537577A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Iron-molybdic catalyst presoma, iron-molybdic catalyst and its application |
| CN107537577B (en) * | 2016-06-23 | 2019-11-15 | 中国石油化工股份有限公司 | Iron-molybdic catalyst presoma, iron-molybdic catalyst and its application |
| CN109718779A (en) * | 2018-12-26 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of ball-type skeleton Ni hydrogenation catalyst and its preparation method and application |
| CN114618525A (en) * | 2020-12-11 | 2022-06-14 | 万华化学集团股份有限公司 | Preparation method and application of porous Raney nickel catalyst |
| CN114618525B (en) * | 2020-12-11 | 2024-03-01 | 万华化学集团股份有限公司 | Preparation method and application of porous Raney nickel catalyst |
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