CN104001518B - A kind of preparation method of nickel alloy/porous material catalyst - Google Patents
A kind of preparation method of nickel alloy/porous material catalyst Download PDFInfo
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- CN104001518B CN104001518B CN201410263865.7A CN201410263865A CN104001518B CN 104001518 B CN104001518 B CN 104001518B CN 201410263865 A CN201410263865 A CN 201410263865A CN 104001518 B CN104001518 B CN 104001518B
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- catalyst
- nickel alloy
- porous material
- silicon oxide
- mesoporous carbon
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Abstract
The present invention relates to the preparation method of a kind of nickel alloy/porous material catalyst.Nickel alloy/porous material catalyst is by Ni3Sn or Ni3Fe is supported on porous material surfaces externally and internally；Condensed, break into pieces, mill, it is thus achieved that nickel alloy/porous material catalyst；This catalyst has the advantages such as reactivity height, good stability；To methanol, the Hydrocarbon cracking such as ethylene glycol has well catalysis activity and H2Selectivity.The features such as the nickel-base catalyst preparation technology of the present invention is simple, low cost, beneficially industrialized production, have good application prospect.
Description
Technical field
The invention belongs to technical field of hydrogen preparation, particularly relate to the preparation method of a kind of nickel alloy/porous material catalyst.
Background technology
Nickel alloy is the catalyst that hydrogen preparation field is conventional in recent years, and nickel alloy has and is well catalyzed activity and selectivity, is widely used in
Methanol, hydrocarbon reformation or the cracking hydrogen production such as ethylene glycol.The catalysis activity of nickel alloy is main next to two aspects；1) nickel alloy is made
For catalyst precursor, course of reaction generates catalyst, such as Ni3Al, Ni3(SiTi).Ni3Al at hydrocarbon reformation or
Cracking process generates catalyst n i/Al2O3；Ni/Al2O3Particle size is little, and catalyst activity is high, but Ni catalyst exists carbon distribution
Problem；2) nickel alloy is originally as catalyst, such as Ni3Sn, Ni3Fe；Ni3Sn, Ni3Fe alloy has good selectivity. but high-purity
Phase Ni3Sn and Ni3The catalysis activity of Fe alloy is often affected by particle size, and activity has much room for improvement.
Fan uses smelting process to be prepared for Ni3Sn, cleaved, break into pieces, mill acquisition alloyed powder granule, this Ni3Sn powder is at methanol
Cracking process has good hydrogen selective；600 DEG C, the methanol decomposition of 45h, the selectivity of hydrogen, close to 100%, there is no
At all decay.Ni3Sn powder particle size is big, and initial reaction stage catalysis activity is relatively low, extends with the response time, alloy powder
Catalysis activity be gradually increased, shown by Micro-Structure Analysis: Ni3Sn has good stability, but alloy powder particle chi
Very little with the response time extend and reduce.(Mei Qiang Fan, Ya Xu, Junya Sakurai, et al.Catalytic
performance of Ni3Sn and Ni3Sn2for hydrogen production from methanol
Decomposition.Catal.Lett., 2014,33:843-849.)
Y Xu is prepared for single-phase Ni3Fe alloy, and have studied its catalysis activity.Ni3Fe alloy is anti-at hydrocarbon reformation or cracking
There is in Ying good stability, but form Ni3The nanostructured of Fe/C, thus improve catalysis activity (Ya Xu, Junya
Sakurai, et al.Catalytic properties of Ni3Fe foil for hydrogen production from
Methanol.Material Science Forum, 2011,706-709:1052-1057).
At present, lot of documents uses chemical method at carrier such as SiO2, Al2O3, the surface such as Carbon deposition Ni3Sn and Ni3Fe.Such
Catalyst has and is well catalyzed activity.But pure phase Ni cannot be obtained at carrier surface3Sn and Ni3Fe, other impurity effect is to catalysis
The selectivity of agent.
Summary of the invention
Present invention aim at providing the preparation method of a kind of nickel alloy/porous material catalyst, overcome the defect of existing technology of preparing,
Improve catalysis activity and the hydrogen selective of nickel alloy.For achieving the above object, the technical scheme is that, with Ni3Fe
Or Ni3Sn is that nickel-base catalyst prepares presoma；Nickel alloy mixes porous material through high-temperature fusion, slowly condenses, and breaks into pieces, mills
Deng, it is thus achieved that nickel alloy/porous material catalyst；The mol ratio of nickel alloy/porous material is 0.2～5；Nickel alloy/porous material is urged
The preparation method of agent comprises the steps:
1), smelting process is used to prepare Ni3Fe or Ni3Sn alloy；
2), the nickel alloy high temperature of step (1) is mixed into porous material；Mixing temperature 1000～1500 DEG C, shelve the time 2～10h；
3), the condensed product that step (2) obtains is broken into pieces, mill, it is thus achieved that nickel alloy/porous material catalyst；
Described porous material is the one of meso-porous carbon material and mesoporous silicon material；
Described meso-porous carbon material is CMK-1, the one of CMK-2, CMK-3；
Described mesoporous silicon material is the one of MCM-41, MCM-48 and SBA-15.
The preparation method of a kind of nickel alloy/porous material catalyst that the present invention provides, with other nickel-base catalyst preparation method phase
Ratio, has the advantage that
1) present invention process is simple and convenient to operate, beneficially industrialized production.
2) nickel alloy prepared by/porous material catalyst, composition mix homogeneously, nickel alloy purity are high, and particle size is little, reaction
Activity height and H2The advantages such as selectivity；Hydrocarbon cracking or reformation had well catalysis activity and H2Selectivity.0.2
G catalyst, methanol flow 50ul/min；Reaction temperature is 360～520 DEG C；Methanol decomposition conversion ratio ＞ 80%, H2Selectivity ＞ 95%.
3) this catalyst can be applicable to the reformation hydrogen productions such as Hydrocarbon such as ethylene glycol, glucose, sorbitol, ethanol, has at hydrogen preparation field
Have wide practical use.
Accompanying drawing illustrates:
Fig. 1 is the schematic diagram of nickel alloy prepared by the embodiment of the present invention 1/porous material catalyst.
Fig. 2 is the XRD of nickel alloy prepared by the embodiment of the present invention 1/porous material catalyst.
Nickel alloy prepared by Fig. 3 embodiment of the present invention 1/porous material catalyst is at the methanol conversion of 320～520 DEG C and gas
Selectivity of product curve.
Nickel alloy prepared by Fig. 4 embodiment of the present invention 1/porous material catalyst selects at methanol conversion and the gaseous product of 400 DEG C
Select linearity curve.
Embodiment one,
Detailed description of the invention
For the summary of the invention of the present invention, feature and effect can be further appreciated that, hereby lift following example, and coordinate accompanying drawing specifically
Bright as follows:
Embodiment 1
A kind of preparation method of nickel alloy/porous material catalyst, composition is designed as:
System 1:Ni3Sn, 1mol；CMK-3,0.2mol；
It concretely comprises the following steps: 1), use smelting process to prepare single-phase Ni3Sn alloy；2), by the 1mol Ni of step (1)3Sn
Alloy is mixed into 0.2molCMK-3；1200 DEG C, argon shield, constant temperature 5h；3), the condensed product that step (2) obtains is broken into pieces,
Mill, it is thus achieved that nickel alloy/porous material catalyst.
Catalyst schematic diagram is shown in that Fig. 1, nickel alloy are dispersed in inner surface and the outer surface of porous material, and alloying pellet is in nanoscale；
Ni3Sn is mixed into CMK-3, and system microcosmic construction structure is shown in Fig. 2. and catalyst activity is tested；Weigh 0.2g catalyst and put into reactor
In, methanol flow 25ul/min；Reaction temperature is 320～520 DEG C；See Fig. 3；Ni3Sn/CMK-3 has and is well catalyzed work
Property and gas-selectively；Methanol conversion is more than 60%；Hydrogen and carbon monoxide selection rate are more than 95%, substantially without methane, and titanium dioxide
Carbon and water vapour generate. at 400 DEG C；Catalyst extended and then the most incremental trend of first successively decreasing with the response time, and the former is probably
Catalyst granules contacts suddenly methanol, and specific surface area is big and causes methanol conversion high；It is stable with methanol contact area with catalyst,
The conversion ratio of methanol has faint successively decreasing；But extending with the response time, catalyst activity is incremented by, and methanol conversion is slowly increased. 62
Hour reaction in, the activity of catalyst and gas-selectively keep stable, and methanol conversion is more than 60%, hydrogen and carbon monoxide
Selectivity is more than 95%.
Embodiment 2
A kind of preparation method of nickel alloy/porous material catalyst, catalyst formulations is:
System 2:Ni3Sn, 1mol；CMK-3,0.3mol；
System 3:Ni3Sn, 1mol；CMK-3,0.5mol；
System 4:Ni3Sn, 1mol；CMK-3,0.7mol；
System 5:Ni3Sn, 1mol；CMK-3,0.9mol；
It concretely comprises the following steps: 1), use smelting process to prepare single-phase Ni3Sn alloy；2), by the 1mol Ni of step (1)3Sn
Alloy is mixed into the CMK-3 of different moles；1500 DEG C, argon shield, constant temperature 10h；3), the condensed product that step (2) is obtained
Break into pieces, mill, it is thus achieved that nickel alloy/porous material catalyst.
Catalyst activity is tested；Weighing 0.2g catalyst is put in reactor, methanol flow 25ul/min；Reaction temperature be 320～
520℃；Catalyst 2,3,4,5 have well catalysis activity and gas-selectively.Methanol conversion is more than 60%；Hydrogen and an oxygen
Changing carbon selection rate and be more than 95%, substantially without methane, carbon dioxide and water vapour generate.
Embodiment 3
Operating with embodiment 1, catalyst formulations is:
System 6:Ni3Sn, 1mol；CMK-1,0.3mol；
System 7:Ni3Sn, 1mol；CMK-2,0.3mol；
System 8:Ni3Sn, 1mol；MCM-41,0.3mol；
System 9:Ni3Sn, 1mol；MCM-48,0.3mol；
System 10:Ni3Sn, 1mol；SBA-15,0.3mol；
Catalyst activity is tested；Weighing 0.2g catalyst is put in reactor, methanol flow 25ul/min；Reaction temperature be 320～
520℃；Catalyst 6,7,8,9,10 have well catalysis activity and gas-selectively.Methanol conversion is more than 60%；Hydrogen and
Carbon monoxide selection rate is more than 95%, and substantially without methane, carbon dioxide and water vapour generate.
Embodiment 4
Operating with embodiment 2, catalyst formulations is:
System 11:Ni3Fe, 1mol；CMK-1,0.4mol；
System 12:Ni3Fe, 1mol；CMK-2,0.4mol；
System 13:Ni3Fe, 1mol；CMK-3,0.4mol；
System 14:Ni3Fe, 1mol；MCM-41,0.3mol；
System 15:Ni3Fe, 1mol；MCM-48,0.3mol；
System 16:Ni3Fe, 1mol；SBA-15,0.3mol；
Catalyst activity is tested；Weighing 0.2g catalyst is put in reactor, methanol flow 25ul/min；Reaction temperature be 320～
520℃；Catalyst 11,12,13,14,15,16 have well catalysis activity and gas-selectively.Methanol conversion is more than 60%；
Hydrogen and carbon monoxide selection rate are more than 95%, and substantially without methane, carbon dioxide and water vapour generate.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, Ke Yili
Solution can carry out multiple change without departing from the principles and spirit of the present invention, revise, replaces these embodiments
And modification, the scope of the present invention be defined by the appended.
Claims (3)
1. nickel alloy/mesoporous carbon or mesopore silicon oxide are the method for preparing catalyst of carrier, it is characterised in that: prepared by nickel-base catalyst
Presoma is Ni3Fe, Ni3The one of Sn；Nickel alloy, through high-temperature fusion mixing mesoporous carbon or mesopore silicon oxide, slowly condenses, breaks into pieces,
Mill, it is thus achieved that nickel alloy/mesoporous carbon or mesopore silicon oxide are the catalyst of carrier；Rubbing of nickel alloy/mesoporous carbon or mesopore silicon oxide
Your ratio is 0.2～5；A kind of nickel alloy/mesoporous carbon or the method for preparing catalyst that mesopore silicon oxide is carrier comprise the steps:
1), smelting process is used to prepare Ni3Fe or Ni3Sn；
2), by step 1) nickel alloy high temperature be mixed into mesoporous carbon or mesopore silicon oxide；Mixing temperature 1000～1500 DEG C, shelve the time 2～
10h:
3), by step 2) condensed product that obtains breaks into pieces, mills, it is thus achieved that nickel alloy/mesoporous carbon or mesopore silicon oxide are the catalyst of carrier.
Nickel alloy/mesoporous carbon the most according to claim 1 or mesopore silicon oxide are the method for preparing catalyst of carrier, it is characterised in that:
Described meso-porous carbon material is CMK-1, the one of CMK-2, CMK-3.
Nickel alloy/mesoporous carbon the most according to claim 1 or mesopore silicon oxide are the method for preparing catalyst of carrier, it is characterised in that:
Described meso pore silicon oxide material is the one of MCM-41, MCM-48 and SBA-15.
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| 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 |
| 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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