CN101537361A - Preparation method of Raney's nickel catalyst of fixed bed - Google Patents
Preparation method of Raney's nickel catalyst of fixed bed Download PDFInfo
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- CN101537361A CN101537361A CN200810300670A CN200810300670A CN101537361A CN 101537361 A CN101537361 A CN 101537361A CN 200810300670 A CN200810300670 A CN 200810300670A CN 200810300670 A CN200810300670 A CN 200810300670A CN 101537361 A CN101537361 A CN 101537361A
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- raney
- nickel
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- fixed bed
- catalyst
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910000564 Raney nickel Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 51
- 239000006260 foam Substances 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 27
- 239000007921 spray Substances 0.000 claims description 24
- 238000005269 aluminizing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000007750 plasma spraying Methods 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002386 leaching Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010285 flame spraying Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 239000000446 fuel Substances 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of Raney's nickel catalyst of a fixed bed, which includes the following steps: foam nickel is placed into an organic solution and immersed for 10-120 minutes, and washed by diluted acid solution and water and then dried; metal aluminum is sprayed on processed foam nickel by a hot spraying method, and aluminum-coated foam nickel is obtained after being sprayed for 1-6 times; the obtained aluminum-coated foam nickel is baked for 0.1-5 hours under the protection of inert gases and at the temperature from 660 DEG C to 1100 DEG C and immersed in a sodium hydroxide or potassium hydroxide solution to obtain the Raney's nickel catalyst. The Raney's nickel catalyst of a fixed bed prepared by the invention has the advantages of high strength, good catalyst activity and uniform catalyst activity. The invention belongs to the filed 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 patent application publication No. is that JP2005205265 has reported the method for preparing the 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 that a kind of intensity height, catalytic activity are good, the preparation method of the uniform Raney's nickel catalyst of activity of such catalysts.
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. with hot spray process metallic aluminium is sprayed on the nickel foam that 1. step obtain, sprays 1～6 time, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under inert gas shielding, temperature is 660～1100 ℃ of following roasting 0.1～5h, leaches in alkaline solution then, 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 to be 60～100 ℃ of following vacuum drying 10～120min in temperature.
The hot spray process of described step in 2. is flame spraying, arc spraying or plasma spraying method, is preferably plasma spraying method.
The alkaline solution of described step in 3. is NaOH or the potassium hydroxide solution of 10～30wt%, and described leaching is to be 60～90 ℃ of leaching 1～12h down in temperature.
The inert gas of described step in 3. is a kind of in nitrogen, helium, neon and the argon gas.
The present invention adopts hot spray process metallic aluminium to be sprayed on the hole wall of nickel foam, hot spray process can make the very uniform surface that is covered in nickel foam of metallic aluminium, if it is even inadequately once to spray the sprayed coating that obtains, can spray the aluminium lamination that covers even compact several times on the nickel foam surface repeatedly, its thickness can be controlled by the spraying number of times.The nickel foam of aluminizing that obtains has catalytic activity through the Raney's nickel catalyst that obtains after calcining, leaching and is evenly distributed, the characteristics that catalytic activity is good, and 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%.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 spray, 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.
Plasma spraying equipment among the embodiment 1 to embodiment 5 is the S6 type plasma spray system that German GTV Co., Ltd produces
Flame-spraying equipment among the embodiment 6 is the QT-PS-1 type low-temperature metal flame-spraying system that Shanghai Ruifa Spray Coating Machine Co., Ltd produces.
Electric arc spraying equipment among the embodiment 7 is the CMD-AS1620 type arc spraying system that Beijing new enlightening sufacing equipment Co., Ltd produces.
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. with plasma spraying equipment metallic aluminium is sprayed on the nickel foam that 1. step obtain, sprays 1 time, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under nitrogen protection, temperature is 700 ℃ of following roasting 1h, in 10wt% NaOH, temperature is under 60 ℃ then, leaching 12h, promptly.
The operating condition of described plasma spraying equipment is: use nitrogen as powder feeding gas; The mixed gas of nitrogen and hydrogen (hydrogen volume content is 20%) is as working gas; Spray distance is 100mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 84%.
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. with plasma spraying equipment metallic aluminium is sprayed on the nickel foam that 1. step obtain, sprays 3 times, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under the helium protection, temperature is 660 ℃ of following roasting 0.8h, in 20wt% NaOH, temperature is under 70 ℃ then, leaching 6h, promptly.
The operating condition of described plasma spraying equipment is: argon gas is as powder feeding gas, and the mixed gas of argon gas and hydrogen (hydrogen volume content is 10%) is as working gas; Spray distance is 120mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating 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. use plasma spraying equipment, metallic aluminium is sprayed on the nickel foam that 1. step obtain, spray 6 times, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under the neon protection, temperature is 800 ℃ of following roasting 2h, in 30wt% NaOH, temperature is under 80 ℃ then, leaching 8h, promptly.
The operating condition of described plasma spraying equipment is: nitrogen is as powder feeding gas; The mixed gas of nitrogen and hydrogen (hydrogen volume content is 30%) is as working gas; Spray distance is 150mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 87%.
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. with plasma spraying equipment metallic aluminium is sprayed on the nickel foam that 1. step obtain, sprays 2 times, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under argon shield, temperature is 1100 ℃ of following roasting 0.1h, in 20wt% potassium hydroxide, temperature is under 85 ℃ then, leaching 1h, promptly.
The operating condition of described plasma spraying equipment is: argon gas is as powder feeding gas; The mixed gas of argon gas and hydrogen (hydrogen volume content is 25%) is as working gas; Spray distance is 180mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 90%.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 90%.
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. with plasma spraying equipment metallic aluminium is sprayed on the nickel foam that 1. step obtain, sprays 4 times, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under nitrogen protection, temperature is 900 ℃ of following roasting 2h, in 25wt% potassium hydroxide, temperature is under 90 ℃ then, leaching 4h, promptly.
The operating condition of described plasma spraying equipment is: nitrogen is as powder feeding gas; The mixed gas of nitrogen and hydrogen (hydrogen volume content is 15%) is as working gas; Spray distance is 200mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 93%.
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. with flame-spraying equipment metallic aluminium is sprayed on the nickel foam that 1. step obtain, the spraying number of times is 2 times, promptly gets the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under nitrogen protection, temperature is 660 ℃ of following roasting 5h, in 20wt% NaOH, temperature is under 80 ℃ then, leaching 1h, promptly.
The operating condition of described flame-spraying equipment is: powder feeding gas is a nitrogen, and gas pressure is 1.2Mpa; Spray distance is 250mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 88%.
Embodiment 7
1. after nickel foam being put into acetone immersion 30min, clean with dilute hydrochloric acid solution, then after the washing, in 70 ℃ of following vacuum drying 100min;
2. with electric arc spraying equipment metallic aluminium is sprayed on the nickel foam that 1. step obtain, the spraying number of times is 3 times, promptly gets the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under nitrogen protection, temperature is 1000 ℃ of following roasting 3h, in 20wt% NaOH, temperature is under 70 ℃ then, leaching 7h, promptly.
The operating condition of described electric arc spraying equipment is: the composition high pure nitrogen of atomization gas; Gas pressure is 0.5Mpa; Spray distance is 200mm.
Preparing resulting Raney's nickel catalyst of fixed bed, can to get its catalytic conversion through activity rating be 85%.
Claims (7)
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. with hot spray process metallic aluminium is sprayed on the nickel foam that 1. step obtain, sprays 1～6 time, promptly get the nickel foam of aluminizing;
3. the nickel foam of aluminizing that step is obtained in 2., under inert gas shielding, temperature is 660～1100 ℃ of following roasting 0.1～5h, leaches in alkaline solution then, 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 drying during described step 1. is is 60～100 ℃ of following vacuum drying 10～120min in temperature.
5. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1 is characterized in that the hot spray process during described step 2. is flame spraying, arc spraying or plasma spraying method.
6. 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 60～90 ℃ in temperature to leach 1～12h down.
7. the preparation method of Raney's nickel catalyst of fixed bed according to claim 1 is characterized in that inert gas during described step 3. is a kind of in nitrogen, helium, neon and the argon gas.
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|---|---|---|---|
| CN200810300670A CN101537361B (en) | 2008-03-21 | 2008-03-21 | Preparation method of Raney's nickel catalyst of fixed bed |
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|---|---|---|---|
| CN200810300670A CN101537361B (en) | 2008-03-21 | 2008-03-21 | Preparation method of Raney's nickel catalyst of fixed bed |
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| CN1260008C (en) * | 2003-06-13 | 2006-06-21 | 上海师范大学 | Method for preparing novel Raney Ni catalyzer and its application |
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| US10596556B2 (en) | 2013-02-06 | 2020-03-24 | Alantum Europe Gmbh | 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 |
| 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 |
| CN104056640A (en) * | 2014-07-08 | 2014-09-24 | 赛鼎工程有限公司 | Preparation method of raney nickel catalyst suitable for slurry reactor methanation and application thereof |
| CN104056640B (en) * | 2014-07-08 | 2016-08-17 | 赛鼎工程有限公司 | A kind of preparation method and application being suitable for slurry bed system methanation Raney's nickel catalyst |
| CN110368952A (en) * | 2019-08-06 | 2019-10-25 | 东莞市三聚氢能科技有限公司 | A kind of preparation method of jet printing type production sodium borohydride catalyst for preparing hydrogen |
| CN110368952B (en) * | 2019-08-06 | 2023-06-27 | 东莞市吉玺电子有限公司 | Preparation method of spray-type catalyst for producing sodium borohydride hydrogen |
| 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 |
| CN114122420A (en) * | 2021-03-24 | 2022-03-01 | 包头稀土研究院 | Method for manufacturing anode of direct sodium borohydride fuel cell |
| CN114122420B (en) * | 2021-03-24 | 2023-12-12 | 包头稀土研究院 | Method for manufacturing anode of direct sodium borohydride fuel cell |
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