CN104001518A - Preparing method for nickel alloy/porous material catalyst - Google Patents
Preparing method for nickel alloy/porous material catalyst Download PDFInfo
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- CN104001518A CN104001518A CN201410263865.7A CN201410263865A CN104001518A CN 104001518 A CN104001518 A CN 104001518A CN 201410263865 A CN201410263865 A CN 201410263865A CN 104001518 A CN104001518 A CN 104001518A
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- porous material
- nickel alloy
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Abstract
The invention relates to a preparing method for a nickel alloy/porous material catalyst. The preparing method includes the steps that Ni3Sn or Ni3Fe is carried on the inner surface and the outer surface of a porous material, and the nickel alloy/porous material catalyst is obtained through condensing, breaking into pieces, grinding and the like. The nickel alloy/porous material catalyst has the advantages of being high in reaction activity and stability and the like, and has excellent catalytic activity and H2 selectivity for splitting decomposition of hydrocarbons such as methyl alcohol and ethylene glycol. The nickel alloy/porous material catalyst has the advantages of being low in cost, the preparing method is beneficial to industrialized production and has excellent application prospects, and the preparing technology is simple.
Description
Technical field
The invention belongs to technical field of hydrogen preparation, particularly relate to a kind of preparation method of nickel alloy/porous material catalyst.
Background technology
Nickel alloy is the conventional catalyst of hydrogen preparation field in recent years, and nickel alloy has good catalytic activity and selective, is widely used in methyl alcohol, and the hydrocarbons such as ethylene glycol are reformed or cracking hydrogen production.The catalytic activity of nickel alloy is mainly come to two aspects; 1) nickel alloy, as catalyst precursor, generates catalyst, as Ni in course of reaction
3al, Ni
3(SiTi) .Ni
3al generates catalyst n i/Al in hydrocarbon reformation or cracking process
2o
3; Ni/Al
2o
3particle size is little, and catalyst activity is high, but Ni catalyst exists carbon distribution problem; 2) nickel alloy is originally as catalyst, as Ni
3sn, Ni
3fe; Ni
3sn, Ni
3fe alloy has well selective. but high pure phase Ni
3sn and Ni
3the catalytic activity of Fe alloy is affected by particle size often, and activity has much room for improvement.
Fan adopts smelting process to prepare Ni
3sn, through cutting, break into pieces, mill acquisition alloyed powder particle, this Ni
3sn powder has good hydrogen selective in methanol decomposition process; 600 ℃, the methanol decomposition of 45h, hydrogen selectively approach 100%, there is no a bit decay.Ni
3sn powder particle size is large, and initial reaction stage catalytic activity is lower, and with reaction time prolongation, the catalytic activity of alloy powder increases gradually, by Micro-Structure Analysis, shows: Ni
3sn has good stability, but alloy powder particle size extended and reduces with the reaction time.(Mei?Qiang?Fan，Ya?Xu，Junya?Sakurai，et?al.Catalytic?performance?of?Ni
3Sn?and?Ni
3Sn
2for?hydrogen?production?from?methanol?decomposition.Catal.Lett.，2014，33：843-849.)
Y Xu has prepared single-phase Ni
3fe alloy, and studied its catalytic activity.Ni
3fe alloy has good stability in hydrocarbon reformation or cracking reaction, but forms Ni
3the nanostructured of Fe/C, thus catalytic activity (Ya Xu, Junya Sakurai, et al.Catalytic properties of Ni improved
3fe foil for hydrogen production from methanol.Material Science Forum, 2011,706-709:1052-1057).
At present, lot of documents adopt chemical method at carrier as SiO
2, Al
2o
3, the surface deposition Ni such as Carbon
3sn and Ni
3fe.Such catalyst has good catalytic activity.But cannot obtain pure phase Ni at carrier surface
3sn and Ni
3fe, other impurity effect is selective to catalyst.
Summary of the invention
The object of the invention is to provide a kind of preparation method of nickel alloy/porous material catalyst, overcomes the defect of existing technology of preparing, improves catalytic activity and the hydrogen selective of nickel alloy.For achieving the above object, technical scheme of the present invention is, with Ni
3fe or Ni
3sn is that nickel-base catalyst is prepared presoma; Nickel alloy mixes porous material through high-temperature fusion, and slowly condensation, breaks into pieces, mills etc., obtains nickel alloy/porous material catalyst; The mol ratio of nickel alloy/porous material is 0.2～5; The preparation method of nickel alloy/porous material catalyst comprises the steps:
1), adopt smelting process to prepare Ni
3fe or Ni
3sn alloy;
2), the nickel alloy high temperature of step (1) is sneaked into porous material; 1000～1500 ℃ of mixing temperatures, shelve time 2～10h;
3), condensed product that step (2) is obtained breaks into pieces, mills, and obtains nickel alloy/porous material catalyst;
Described porous material is a kind of of meso-porous carbon material and mesoporous silicon material;
Described meso-porous carbon material is CMK-1, CMK-2, and CMK-3's is a kind of;
Described mesoporous silicon material is MCM-41, and MCM-48 and SBA-15's is a kind of.
The preparation method of a kind of nickel alloy/porous material catalyst provided by the invention, preparation method compares with other nickel-base catalyst, and tool has the following advantages:
1) technique of the present invention is simple, easy to operate, is conducive to suitability for industrialized production.
2) prepared nickel alloy/porous material catalyst, composition mixes, nickel alloy purity is high, and particle size is little, the high and H of reactivity
2the advantage such as selective; Hydrocarbon cracking or reformation are had to good catalytic activity and H
2selectively.0.2g catalyst, methyl alcohol flow 50ul/min; Reaction temperature is 360～520 ℃; Methanol decomposition conversion ratio > 80%, H
2selective > 95%.
3) this catalyst can be applicable to hydrocarbon as ethylene glycol, glucose, and sorbierite, the reformation hydrogen productions such as ethanol, are with a wide range of applications at hydrogen preparation field.
Accompanying drawing explanation:
Fig. 1 is the schematic diagram of the prepared nickel alloy/porous material of the embodiment of the present invention 1 catalyst.
Fig. 2 is the XRD of the prepared nickel alloy/porous material of the embodiment of the present invention 1 catalyst.
Prepared nickel alloy/the porous material of Fig. 3 embodiment of the present invention 1 catalyst is at methanol conversion and the gas selectivity of product curve of 320～520 ℃.
Prepared nickel alloy/the porous material of Fig. 4 embodiment of the present invention 1 catalyst is at methanol conversion and the gas selectivity of product curve of 400 ℃.
Embodiment mono-,
The specific embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby lift following examples, and coordinate accompanying drawing to be described in detail as follows:
Embodiment 1
A preparation method for nickel alloy/porous material catalyst, Composition Design is:
System 1:Ni
3sn, 1mol; CMK-3,0.2mol;
1), adopt smelting process to prepare single-phase Ni its concrete steps are:
3sn alloy; 2), by the 1mol Ni of step (1)
3sn alloy is sneaked into 0.2molCMK-3; 1200 ℃, argon shield, constant temperature 5h; 3), condensed product that step (2) is obtained breaks into pieces, mills, and obtains nickel alloy/porous material catalyst.
Fig. 1 is shown in by catalyst schematic diagram, and nickel alloy is dispersed in inner surface and the outer surface of porous material, and alloying pellet is in nanoscale; Ni
3sn sneaks into CMK-3, and system microcosmic construction structure is shown in Fig. 2. catalyst activity test; Weigh 0.2g catalyst and put into reactor, methyl alcohol flow 25ul/min; Reaction temperature is 320～520 ℃; See Fig. 3; Ni
3sn/CMK-3 has good catalytic activity and gas-selectively; Methanol conversion is greater than 60%; Hydrogen and carbon monoxide selection rate are greater than 95%, and substantially without methane, carbon dioxide and water vapour generate. at 400 ℃; The trend that catalyst first successively decreases and then slowly increases progressively with reaction time prolongation, the former may be that catalyst granules contacts suddenly methyl alcohol, specific area causes methanol conversion high greatly; Stable with catalyst and methyl alcohol contact area, the conversion ratio of methyl alcohol has faint successively decreasing; But extend with the reaction time, catalyst activity increases progressively, and methanol conversion slowly increases. in the reaction of 62 hours, it is stable that the activity of catalyst and gas-selectively keep, and methanol conversion is greater than 60%, hydrogen and carbon monoxide be selectively greater than 95%.
Embodiment 2
A preparation method for nickel alloy/porous material catalyst, catalyst component is designed to:
System 2:Ni
3sn, 1mol; CMK-3,0.3mol;
System 3:Ni
3sn, 1mol; CMK-3,0.5mol;
System 4:Ni
3sn, 1mol; CMK-3,0.7mol;
System 5:Ni
3sn, 1mol; CMK-3,0.9mol;
1), adopt smelting process to prepare single-phase Ni its concrete steps are:
3sn alloy; 2), by the 1mol Ni of step (1)
3sn alloy is sneaked into the CMK-3 of different moles; 1500 ℃, argon shield, constant temperature 10h; 3), condensed product that step (2) is obtained breaks into pieces, mills, and obtains nickel alloy/porous material catalyst.
Catalyst activity test; Weigh 0.2g catalyst and put into reactor, methyl alcohol flow 25ul/min; Reaction temperature is 320～520 ℃; Catalyst 2,3,4,5 have good catalytic activity and gas-selectively.Methanol conversion is greater than 60%; Hydrogen and carbon monoxide selection rate are greater than 95%, and substantially without methane, carbon dioxide and water vapour generate.
Embodiment 3
With embodiment 1 operation, catalyst component is designed to:
System 6:Ni
3sn, 1mol; CMK-1,0.3mol;
System 7:Ni
3sn, 1mol; CMK-2,0.3mol;
System 8:Ni
3sn, 1mol; MCM-41,0.3mol;
System 9:Ni
3sn, 1mol; MCM-48,0.3mol;
System 10:Ni
3sn, 1mol; SBA-15,0.3mol;
Catalyst activity test; Weigh 0.2g catalyst and put into reactor, methyl alcohol flow 25ul/min; Reaction temperature is 320～520 ℃; Catalyst 6,7,8,9,10 have good catalytic activity and gas-selectively.Methanol conversion is greater than 60%; Hydrogen and carbon monoxide selection rate are greater than 95%, and substantially without methane, carbon dioxide and water vapour generate.
Embodiment 4
With embodiment 2 operations, catalyst component is designed to:
System 11:Ni
3fe, 1mol; CMK-1,0.4mol;
System 12:Ni
3fe, 1mol; CMK-2,0.4mol;
System 13:Ni
3fe, 1mol; CMK-3,0.4mol;
System 14:Ni
3fe, 1mol; MCM-41,0.3mol;
System 15:Ni
3fe, 1mol; MCM-48,0.3mol;
System 16:Ni
3fe, 1mol; SBA-15,0.3mol;
Catalyst activity test; Weigh 0.2g catalyst and put into reactor, methyl alcohol flow 25ul/min; Reaction temperature is 320～520 ℃; Catalyst 11,12,13,14,15,16 have good catalytic activity and gas-selectively.Methanol conversion is greater than 60%; Hydrogen and carbon monoxide selection rate are greater than 95%, and substantially without methane, carbon dioxide and water vapour generate.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (4)
1. a preparation method for nickel alloy/porous material catalyst, is characterized in that: it is Ni that nickel-base catalyst is prepared presoma
3fe, Ni
3sn's is a kind of; Nickel alloy mixes porous material through high-temperature fusion, and slowly condensation, breaks into pieces, mills etc., obtains nickel alloy/porous material catalyst; The mol ratio of nickel alloy/porous material is 0.2～5; The preparation method of nickel alloy/porous material catalyst comprises the steps:
1), adopt smelting process to prepare Ni
3fe or Ni
3sn;
2), the nickel alloy high temperature of step (1) is sneaked into porous material; 1000～1500 ℃ of mixing temperatures, shelve time 2～10h;
3), condensed product that step (2) is obtained breaks into pieces, mills, and obtains nickel alloy/porous material catalyst.
2. nickel alloy/porous material method for preparing catalyst according to claim 1, is characterized in that: described porous material is a kind of of meso-porous carbon material and mesoporous silicon material.
3. nickel alloy/porous material method for preparing catalyst according to claim 2, is characterized in that: described meso-porous carbon material is CMK-1, CMK-2, and CMK-3's is a kind of.
4. nickel alloy/porous material method for preparing catalyst according to claim 2, is characterized in that: described mesoporous silicon material is MCM-41, and MCM-48 and SBA-15's is a kind of.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383935A (en) * | 2014-10-23 | 2015-03-04 | 中国计量学院 | Preparation method of nickel-based catalyst for hydrogen production by methanol decomposition |
| CN109248703A (en) * | 2018-09-12 | 2019-01-22 | 南京师范大学 | A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application |
| CN113562694A (en) * | 2021-08-13 | 2021-10-29 | 江苏乾景新能源产业技术研究院有限公司 | Hydrolysis hydrogen production method based on magnesium-based composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426503A (en) * | 1990-05-23 | 1992-01-29 | Mitsubishi Heavy Ind Ltd | Method for reforming methanol |
| CN102225761A (en) * | 2011-04-11 | 2011-10-26 | 武汉科技大学 | TiC material with Ti-Si-Fe alloy as raw material and preparation method thereof |
-
2014
- 2014-06-10 CN CN201410263865.7A patent/CN104001518B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0426503A (en) * | 1990-05-23 | 1992-01-29 | Mitsubishi Heavy Ind Ltd | Method for reforming methanol |
| CN102225761A (en) * | 2011-04-11 | 2011-10-26 | 武汉科技大学 | TiC material with Ti-Si-Fe alloy as raw material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A. PENKOVAA等: ""Hydrogen production by methanol steam reforming on NiSn/MgO-Al2O3 catalysts: The role of MgO addition"", 《APPLIED CATALYSIS A: GENERAL》 * |
| MEIQIANG FAN等: ""Catalytic Performance of Ni3Sn and Ni3Sn2 for Hydrogen Production from Methanol Decomposition"", 《CATALYSIS LETTERS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383935A (en) * | 2014-10-23 | 2015-03-04 | 中国计量学院 | Preparation method of nickel-based catalyst for hydrogen production by methanol decomposition |
| CN109248703A (en) * | 2018-09-12 | 2019-01-22 | 南京师范大学 | A kind of load Ni3The preparation method and its resulting materials of the nitrogen-doped carbon nanocomposite of Fe and application |
| CN109248703B (en) * | 2018-09-12 | 2021-07-27 | 南京师范大学 | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof |
| CN113562694A (en) * | 2021-08-13 | 2021-10-29 | 江苏乾景新能源产业技术研究院有限公司 | Hydrolysis hydrogen production method based on magnesium-based composite material |
| CN113562694B (en) * | 2021-08-13 | 2023-01-10 | 江苏乾景新能源产业技术研究院有限公司 | Hydrolysis hydrogen production method based on magnesium-based composite material |
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| CN104001518B (en) | 2016-11-09 |
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