CN106540699B - A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube - Google Patents
A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube Download PDFInfo
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- CN106540699B CN106540699B CN201610888832.0A CN201610888832A CN106540699B CN 106540699 B CN106540699 B CN 106540699B CN 201610888832 A CN201610888832 A CN 201610888832A CN 106540699 B CN106540699 B CN 106540699B
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- 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
- B01J23/755—Nickel
Abstract
The invention belongs to the preparation fields of high activity nickel-base catalyst, and in particular to a method of high activity nickel-base catalyst is prepared using from growth carbon nanotube.The preparation method includes the following steps: for conventional nickel-base catalyst to be put into reactor, after reduction treatment, it is passed through vapor and organic matter, the molar ratio of carbon is 2-4:1 in water vapour and organic matter, 60-100min is reacted at 600-800 DEG C, the top and tube wall that carbon nanotube grows on conventional nickel-base catalyst surface and has surface nickel particle migration to carbon nanotube during the growth process, after completion of the reaction up to high activity nickel-base catalyst.Compared with existing conventional nickel-base catalyst, the present invention has obtained active higher catalyst in conventional nickel-base catalyst surface self-grown carbon nanotube；Compared with through the Ni/CNTs of load preparation, the present invention, which is utilized from growth carbon nanotube preparation high activity nickel-base catalyst, has the advantages that easy to operate, preparation cost is low etc., may advantageously facilitate application of the carbon nanotube on conventional catalyst carrier.
Description
Technical field
The invention belongs to the preparation fields of high activity nickel-base catalyst, and in particular to a kind of to utilize growth carbon nanotube system certainly
The method of standby high activity nickel-base catalyst.
Background technique
Nickel-base catalyst is a kind of common metallic catalyst, is widely used in catalytic hydrogenation, catalytic pyrolysis, catalytic reforming
Etc. in industrial productions.The nickel-base catalyst generally used is loading type nickel-based catalyst, i.e., active component nickel is supported on carrier
On material.The performance of catalyst is improved using properties such as the high surface area of carrier material, high mechanical strengths.Carrier is available
High surface area and suitable pore structure can increase active component nickel dispersion degree on carrier.The nickel-base catalyst of high degree of dispersion is not
The sintering and clustering phenomena for only making active component substantially reduce, and under the conditions of identical load amount, catalytic activity obtains bright
It is aobvious to improve.
Carbon nanotube (CNTs) is formally found in 1991, as monodimension nanometer material, is led in physics, chemistry and material etc.
Domain attracts wide attention.In catalyzed side reaction face, the bigger serface and outstanding absorption property that carbon nanotube has make it
There is important application value in terms of catalytic carrier.Compared to Al2O3、SiO2Equal conventional catalyst carriers, carbon nanotube conduct
Carrier can increase the dispersion degree of active component, improve catalyst reaction activity and anti-sintering property.Reaching identical catalysis
In the case where effect, the purpose for reducing catalyst amount may be implemented.Therefore, carbon nanotube is answered extensively as catalyst carrier
For noble metal (such as platinum, rhodium) catalyst.It is some studies have shown that Ni load carbon nano-tube catalyst (Ni/CNTs) be catalyzed
The reaction aspect such as reformation shows very outstanding catalytic performance.But since the preparation cost of carbon nanotube is higher, in routine
It applies on catalyst (such as nickel-base catalyst) and still develops slowly.
Summary of the invention
It utilizes the purpose of the present invention is to provide a kind of from the method for growing carbon nanotube preparation high activity nickel-base catalyst,
Overcome in the prior art because carbon nanotube preparation cost it is high caused by Ni load carbon nano-tube catalyst preparation cost it is high, promote
The deficiencies of application difficult.
The present invention realizes above-mentioned purpose the technical solution adopted is as follows: a kind of prepare high activity using from growth carbon nanotube
The method of nickel-base catalyst comprising following steps: conventional nickel-base catalyst is put into reactor, after reduction treatment,
It is passed through vapor and organic matter, the molar ratio of carbon is 2-4:1 in water vapour and organic matter, reacts 60- at 600-800 DEG C
100min, carbon nanotube grow on conventional nickel-base catalyst surface and have surface nickel particle migration to carbon nanometer during the growth process
The top of pipe and tube wall, after completion of the reaction up to the high activity nickel-base catalyst.
Based on the above technical solution, the present invention can also have following further concrete scheme or preferred embodiment.
Specifically, the routine nickel-base catalyst is Ni/ α-Al2O3、Ni/SiO2、Ni-M/α-Al2O3Or Ni-M/SiO2,
Wherein M is Fe, Co or Cu.The routine nickel-base catalyst is by infusion process or deposition-precipitation method preparation and its nickel loading is 5-
40wt%.
Specifically, the method that the routine nickel-base catalyst carries out reduction treatment is by it in 600-800 DEG C and reproducibility
1-3h is handled under atmosphere.The reducing atmosphere is formed by hydrogen or CO gas.
Specifically, the organic matter is one of methane, acetylene, ethylene, ethyl alcohol, toluene, benzene and phenol or a variety of.
Preferably, the vapor and carbon molar ratio in organic matter are 3:1, react 60min at 700 DEG C, are obtained described high living
Property nickel-base catalyst.
Specifically, the content of carbon nanotube accounts for the 10-50% of catalyst quality in the high activity nickel-base catalyst.
Specifically, the carbon nanotube is multi-walled carbon nanotube and its caliber is 10-80nm.
Specifically, the vapor and organic matter are injected into reactor under stream of nitrogen gas carrying.
The beneficial effects of the present invention are: the present invention is in conventional nickel-base catalyst compared with existing conventional nickel-base catalyst
Surface self-grown carbon nanotube has obtained active higher catalyst；Compared with through the Ni/CNTs of load preparation, present invention benefit
Have the advantages that easy to operate, preparation cost is low etc. with from growth carbon nanotube preparation high activity nickel-base catalyst, may advantageously facilitate
Application of the carbon nanotube on conventional catalyst carrier.
Detailed description of the invention
Fig. 1 is the SEM scanning electron microscope (SEM) photograph for the carbon nanotube that catalyst surface generates in embodiment 1.
Fig. 2 is the TEM transmission electron microscope picture for the carbon nanotube that catalyst surface generates in embodiment 1.
Fig. 3 is the TEM transmission electron microscope picture of the top of supply line for the carbon nanotube that catalyst surface generates in embodiment 1.
Fig. 4 is routine Ni/ α-Al2O3The high activity nickel-base catalyst prepared in catalyst and embodiment 1 is catalyzed toluene respectively
Toluene conversion changes over time curve when steam reforming reaction.
Specific embodiment
Below in conjunction with attached drawing, the present invention is described in further detail, and the given examples are served only to explain the present invention, not
For limiting the scope of the invention.
Embodiment 1
A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube, the specific steps are as follows:
Infusion process prepares Ni/ α-Al2O3Catalyst, nickel loading 10wt% take 0.3g Ni/ α-Al2O3Catalyst
It is placed in fixed bed reactors, in 50%H2/N2The lower 700 DEG C of reduction treatment 1h of atmosphere, switch to nitrogen atmosphere, in reactor
Portion's temperature is stablized at 700 DEG C, vapor and toluene vapor is injected into reactor under stream of nitrogen gas carrying, wherein the water injected
It is 21:1, reaction temperature 700 that the molar ratio of carbon, which is the molar ratio of 3:1 namely hydrone and toluene molecule, in steam and toluene
DEG C, reaction time 60min, carbon nanotube is in Ni/ α-Al2O3Catalyst surface grows and has surface nickel during the growth process
Grain moves to top and the tube wall of carbon nanotube, after reaction up to high activity nickel-base catalyst.
Performance test: field emission scanning electron microscope is carried out to obtained high activity nickel-base catalyst and adds energy spectrum analysis (SEM-
EDX), TEM transmission electron microscope, the temperature programmed oxidation reaction characterization such as (TPO) and specific surface area.
The SEM scanning electron microscope (SEM) photograph of the carbon nanotube on the high activity nickel-base catalyst surface that the present embodiment obtains as shown in Figure 1,
From fig. 1, it can be seen that Ni/ α-Al2O3The a large amount of carbon nanotubes of Surface Creation detect that carbon nanotube yield has reached 280mg/ by TPO
(g-cata), i.e., the content of carbon nanotube is 28wt% in the catalyst.
The TEM characterization of the carbon nanotube on the high activity nickel-base catalyst surface that the present embodiment obtains is as shown in Figures 2 and 3,
Generation carbon nanotube is multi-walled carbon nanotube, and outer diameter is in 11nm or so, and discovery has nickel on the top of carbon nanotube and tube wall
Grain attachment, therefore the growth course of carbon nanotube meets the mechanism of apical growth, i.e. carbon nanotube is precipitated from the lower part of nickel particle, nickel
Particle is always positioned at the top of carbon nanotube, as the growth of carbon nanotube is constantly migrated to the direction far from carrier, while one
A little nickel particles can be adhered on carbon nanotube tube wall, during carbon nanotube is grown certainly and obtains high nickel-base catalyst living,
Nickel particle is from α-Al2O3Carrier surface is detached from, and moves to carbon nano tube surface.
To Ni/ α-Al in the present embodiment2O3Catalyst and high activity nickel-base catalyst row specific surface area obtained and power spectrum point
EDX detection is analysed, as a result as shown in the table:
It is known after reaction in 1 hour from upper table, the carbon nanotube of raised growth causes specific surface area of catalyst bright
It is aobvious to increase, while average pore size is reduced, hole, which holds, to be increased.Elemental analysis, discovery reaction rear surface activity are carried out to catalyst surface
Component nickel content dramatically increases, and increases 20.05wt% from 11.53wt%, is mainly attributed to a part of nickel and moves to carbon
Nanotube surface, improves the dispersion degree of nickel particle on a catalyst, and active component content dramatically increases to improve catalysis
The reactivity of agent.
Embodiment 2
A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube, the specific steps are as follows:
Infusion process prepares Ni/SiO2Catalyst, nickel loading 5wt% take 0.3g Ni/SiO2Catalyst is placed on solid
In fixed bed reactor, in 50%H2/N2The lower 700 DEG C of reduction treatment 2h of atmosphere, switch to nitrogen atmosphere, inside reactor temperature is steady
700 DEG C are scheduled on, vapor and phenol vapor are injected into reactor under stream of nitrogen gas carrying, wherein the vapor and first that inject
The molar ratio of carbon is the molar ratio 18:1 of 3:1 namely hydrone and phenol molecule in benzene, and reaction temperature is 700 DEG C, the reaction time
For 60min, carbon nanotube is in Ni/SiO2Catalyst surface grows and has surface nickel particle migration to carbon nanometer during the growth process
The top of pipe and tube wall, after reaction up to high activity nickel-base catalyst.
Obtained high activity nickel-base catalyst is tested for the property, it is known that the carbon nanotube of the catalyst surface is multi wall
Carbon nanotube, caliber are about 10nm, and the content of carbon nanotube is 20wt% in the catalyst.
Embodiment 3
A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube, the specific steps are as follows:
Deposition-precipitation method prepares Ni-Fe/SiO2Catalyst, nickel loading 20wt%, takes 0.3gNi-Fe/SiO2Catalysis
Agent is placed in fixed bed reactors, in 50%H2/N2The lower 700 DEG C of reduction treatment 2h of atmosphere, switch to nitrogen atmosphere, reactor
Internal temperature is stablized at 700 DEG C, vapor and acetylene is injected into reactor under stream of nitrogen gas carrying, wherein the water injected steams
The molar ratio of carbon is the molar ratio 6:1 of 3:1 namely hydrone and phenol molecule in gas and acetylene, and reaction temperature is 700 DEG C, instead
It is 60min between seasonable, carbon nanotube is in Ni-Fe/SiO2Catalyst surface grows and has surface nickel particle to move during the growth process
Top and the tube wall of carbon nanotube are moved on to, after reaction up to high activity nickel-base catalyst.
Obtained high activity nickel-base catalyst is tested for the property, it is known that the carbon nanotube of the catalyst surface is multi wall
Carbon nanotube, caliber are about 15nm, and the content of carbon nanotube is 25wt% in the catalyst.
Embodiment 4
A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube, the specific steps are as follows:
Deposition-precipitation method prepares Ni-Co/SiO2Catalyst, nickel loading 30wt%, takes 0.3gNi-Co/SiO2Catalysis
Agent is placed in fixed bed reactors, in 50%H2/N2The lower 600 DEG C of reduction treatment 3h of atmosphere, switch to nitrogen atmosphere, reactor
Internal temperature is stablized at 600 DEG C, vapor and ethyl alcohol is injected into reactor under stream of nitrogen gas carrying, wherein the water injected steams
The molar ratio of carbon is the molar ratio 4:1 of 2:1 namely hydrone and ethanol molecule in gas and ethyl alcohol, and reaction temperature is 600 DEG C, instead
It is 80min between seasonable, carbon nanotube is in Ni-Co/SiO2Catalyst surface grows and has surface nickel particle to move during the growth process
Top and the tube wall of carbon nanotube are moved on to, after reaction up to high activity nickel-base catalyst.
Obtained high activity nickel-base catalyst is tested for the property, it is known that the carbon nanotube of the catalyst surface is multi wall
Carbon nanotube, caliber are about 25nm, and the content of carbon nanotube is 40wt% in the catalyst.
Embodiment 5
A method of high activity nickel-base catalyst is prepared using from growth carbon nanotube, the specific steps are as follows:
Deposition-precipitation method prepares Ni-Cu/ α-Al2O3Catalyst, nickel loading 40wt% take 0.3g Ni-Cu/ α-
Al2O3Catalyst is placed in fixed bed reactors, in 50%H2/N2The lower 800 DEG C of reduction treatment 3h of atmosphere, switch to nitrogen gas
Atmosphere, inside reactor temperature are stablized at 800 DEG C, and vapor and methane are injected into reactor under stream of nitrogen gas carrying, wherein
The molar ratio of carbon is the molar ratio 4:1 of 4:1 namely hydrone and methane molecule, reaction temperature in the vapor and methane of injection
It is 800 DEG C, reaction time 100min, carbon nanotube is in Ni-Cu/ α-Al2O3Catalyst surface grows and has during the growth process
Top and tube wall of the surface nickel particle migration to carbon nanotube, after reaction up to high activity nickel-base catalyst.
Obtained high activity nickel-base catalyst is tested for the property, it is known that the carbon nanotube of the catalyst surface is multi wall
Carbon nanotube, caliber are about 30nm, and the content of carbon nanotube is 50wt% in the catalyst.
Comparative example 1
Substantially completely identical as the preparation step of embodiment 1, carbon rubs in the water vapour and toluene that difference is only injected
You are than being 1:1.
The catalyst obtained after reaction is tested for the property, the instrument and method and embodiment that performance test uses
1 is identical, carries out the catalyst surface that analysis finds that comparative example 1 obtains to test result and primarily forms amorphous carbon, amorphous carbon
Deposition cause active component nickel content and specific surface area to reduce, surface nickel content is reduced to 6.06wt%.
Comparative example 2
Respectively with the conventional Ni/ α-Al in embodiment 12O3The high activity obtained after end reaction in catalyst and embodiment 1
Nickel-base catalyst is catalyzed reacting for water vapour and toluene in 700 DEG C of reactor, and wherein water steams the molar ratio with carbon in toluene
1:1, test toluene conversion respectively and reflect the activity of catalyst with the situation of change in reaction time, toluene conversion is with anti-
Answer time changing curve as shown in Figure 4.As can be seen from Fig. 4, the high activity nickel-base catalyst that embodiment 1 is prepared obviously compares routine
Ni/α-Al2O3The catalytic activity of catalyst is high, and routine Ni/ α-Al2O3Extend the decline of its catalytic performance obviously with the reaction time,
The high activity nickel-base catalyst that embodiment 1 is prepared with the reaction time extends the decline of its catalytic performance less, i.e. high activity nickel
The catalytic activity of base catalyst is higher and more stable.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst, which is characterized in that including walking as follows
It is rapid: conventional nickel-base catalyst is put into reactor, after reduction treatment, is passed through vapor and organic matter, water vapour with have
The molar ratio of carbon is 2-4:1 in machine object, reacts 60-100min at 600-800 DEG C, carbon nanotube is on conventional nickel-base catalyst surface
It grows and has top and tube wall of the surface nickel particle migration to carbon nanotube during the growth process, after completion of the reaction up to the height
Active nickel based catalyst.
2. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst according to claim 1,
It is characterized in that, the routine nickel-base catalyst is Ni/ α-Al2O3、Ni/SiO2、Ni-M/α-Al2O3Or Ni-M/SiO2, wherein M be
Fe, Co or Cu.
3. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst according to claim 2,
It is characterized in that, the routine nickel-base catalyst is by infusion process or deposition-precipitation method preparation and its nickel loading is 5-40wt%.
4. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst according to claim 1,
Be characterized in that, it is described routine nickel-base catalyst carry out reduction treatment method be by it under 600-800 DEG C and reducing atmosphere
Handle 1-3h.
5. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst according to claim 4,
It is characterized in that, the reducing atmosphere is formed by hydrogen or CO gas.
6. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst according to claim 1,
It is characterized in that, the organic matter is one of methane, acetylene, ethylene, ethyl alcohol, toluene, benzene and phenol or a variety of.
7. a kind of method using from growth carbon nanotube preparation high activity nickel-base catalyst according to claim 1,
It is characterized in that, carbon molar ratio is 3:1 in the vapor and organic matter, reacts 60min at 700 DEG C, it is Ni-based to obtain the high activity
Catalyst.
8. a kind of utilize from growth carbon nanotube according to any one of claims 1 to 7 prepares high activity nickel-base catalyst
Method, which is characterized in that in the high activity nickel-base catalyst content of carbon nanotube be 10-50wt%.
9. a kind of utilize from growth carbon nanotube according to any one of claims 1 to 7 prepares high activity nickel-base catalyst
Method, which is characterized in that the carbon nanotube is multi-walled carbon nanotube and its caliber is 10-80nm.
10. a kind of utilize from growth carbon nanotube according to any one of claims 1 to 7 prepares high activity nickel-base catalyst
Method, which is characterized in that the vapor and organic matter are injected into reactor under stream of nitrogen gas carrying.
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| CN113376406A (en) * | 2021-04-28 | 2021-09-10 | 西安交通大学 | Preparation method of carbon nanotube probe |
| CN114733507B (en) * | 2022-04-25 | 2023-07-28 | 南开大学 | Carbon nano tube coated diamond nickel particle catalyst and preparation method and application thereof |
| CN115582126B (en) * | 2022-09-22 | 2023-08-04 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Efficient chlorine poisoning resistant flue gas ozone decomposition catalyst and preparation method and application thereof |
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