CN106964384B - A kind of nickel-base catalyst and preparation method thereof of nanometer silicon carbide load - Google Patents
A kind of nickel-base catalyst and preparation method thereof of nanometer silicon carbide load Download PDFInfo
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Abstract
The present invention relates to catalysis and environment protection fields; more particularly to a kind of nickel-base catalyst and preparation method thereof of nanometer silicon carbide load; the present invention uses nanometer silicon carbide, acetylacetone copper, 1- hexadecanethiol, nickel ion, ammonium hydroxide, cerous sulfate as raw material and prepares catalyst; preparation method is simple; reaction condition is mild, easy large-scale production；In reaction process, acetylacetone copper reacts generation cuprous sulfide with 1- hexadecanethiol first and nanometer silicon carbide is compound, generates nanometer silicon carbide/cuprous sulfide compound, then nickel hydroxide is deposited on composite surface, a small amount of auxiliary agent cerium of final load.The nickel-base catalyst of nanometer silicon carbide that the present invention is prepared load using nanometer silicon carbide as carrier, nickel-copper is activating component, cerium is auxiliary agent, it can be used for biomass gasifying hydrogen making, catalytic activity is high, selectivity is good, catalytic reaction condition is relatively mild, production cost is low, has good application prospect in industrialized production.
Description
Technical field
The present invention relates to catalysis and environment protection fields, and in particular to a kind of nickel-base catalyst and its system of nanometer silicon carbide load
Preparation Method.
Background technique
Although Resources of Carbon Dioxide conversion has discovered that preferable catalyzed conversion path in more in laboratory stage,
It is limited by the insufficient limitation of cheap hydrogen source, high production cost constrains carbon dioxide synthesis of low-carbon alcohol and moves towards industry
Change.Biomass resource is abundant, be a kind of important renewable energy and also its own be the carrier of hydrogen, compared with fossil fuel,
With volatile matter height, the advantages such as sulphur, nitrogen content are low, either from energy angle still from environmental, biomass hydrogen preparation all has
Its standby unique advantage provides new opportunity for Resources of Carbon Dioxide conversion.
Biomass pyrolytic hydrogen manufacturing is needed by catalyst, and the catalyst currently used for biomass gasifying hydrogen making is broadly divided into two
Kind: one is noble metal platinum group, such catalytic gold catalytic activity is high, but with high costs, is not used to industrialization at this stage；It is another
Kind be nickel system, metallic nickel is cheap and easy to get, can reduce industrialization cost, but existing nickel catalyst that there is also catalytic activity is low,
Hydrogen selective is poor, is easy the defects of inactivation.
Summary of the invention
The present invention be solve nickel system biomass gasifying hydrogen making in the prior art catalyst activity is low, hydrogen selective
Difference is easy the technical issues of inactivation.
To solve the above problems, technical scheme is as follows:
A kind of nickel-base catalyst of nanometer silicon carbide load, the raw material including following weight ratio,
Nanometer silicon carbide: 10-12 parts；
Acetylacetone copper: 1 part；
1- hexadecanethiol: 2 parts；
Nickel ion: 2-8 parts；
Ammonium hydroxide: 6-12 parts；
Cerous sulfate: 1 part.
Preferably, the source of the nickel ion is one of nickel chloride, nickel sulfate or nickel nitrate；
Preferably, the nickel-base catalyst of the nanometer silicon carbide load includes the raw material of following weight ratio,
Nanometer silicon carbide: 11 parts；
Acetylacetone copper: 3 parts；
1- hexadecanethiol: 6 parts；
Nickel chloride: 6 parts；
Ammonium hydroxide: 10 parts；
Cerous sulfate: 1 part.
The carrier of the nickel-base catalyst of the nanometer silicon carbide load is nanometer silicon carbide；Activating component is nickel-copper, nickel matter
Amount score is 33-48%, Copper mass fraction 11-18%；Cerium is auxiliary agent, mass fraction 4%-9%.
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4 is vigorously stirred lower dropwise addition by solid made from step 3 again ultrasonic disperse in the nickel ion solution
Ammonium hydroxide, 80 DEG C reaction 4-5 hours, ageing, filter, washing.
Solid made from step 4 is added the cerous sulfate solution, under stirring condition, adjusts pH to 9-9.5 by step 5,
80 DEG C reaction 2-3 hours, ageing filters, washing, bakes 4-5 hours under the conditions of 300 DEG C.
Preferably, the ammonium hydroxide mass fraction is 28%-32%.
Preferably, the nickel ion concentration is 0.2-2g/L.
Preferably, the cerous sulfate solution is 0.2-2g/L.
Compared with the existing technology, advantages of the present invention is as follows,
The present invention uses nanometer silicon carbide, acetylacetone copper, 1- hexadecanethiol, nickel ion, ammonium hydroxide, cerous sulfate as original
Material prepares catalyst, and reaction raw materials are cheap and easy to get, lays the foundation for the cheap hydrogen of industrial production；
Preparation method of the present invention is simple, and reaction condition is mild, easy large-scale production；In reaction process, acetylacetone,2,4-pentanedione first
Copper reacts generation cuprous sulfide with 1- hexadecanethiol and nanometer silicon carbide is compound, and it is compound to generate nanometer silicon carbide/cuprous sulfide
Object, then nickel hydroxide is deposited on composite surface, a small amount of auxiliary agent cerium of final load.
The nickel-base catalyst of nanometer silicon carbide that the present invention is prepared load is by carrier, nickel-copper of nanometer silicon carbide
Activating component, cerium are auxiliary agent；The solid matter accumulation of Si-C diatomic layer is easy to cause stacking fault during growing silicon carbice crystals,
This stacking fault is the novel quantum well structure with desired contact interface, and nanometer silicon carbide has biggish specific surface
Product provides more active sites for catalysis reaction；Auxiliary agent cerium co-deposition plays stable activation in charing silicon face
The effect of component structure, while dispersion and cover effect are carried out to the activated centre of nickel-copper activating component, improve the choosing of catalyst
Selecting property.
The nickel-base catalyst for the nanometer silicon carbide load that the present invention is prepared is used for biomass gasifying hydrogen making, catalytic activity
Height, selectivity is good, and catalytic reaction condition is relatively mild, and production cost is low, has good application prospect in industrialized production.
Specific embodiment
Embodiment 1:
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 10 parts；Acetylacetone copper: 1 part；1- hexadecanethiol: 2 parts；Nickel chloride: 2 parts；Ammonium hydroxide: 6 parts；
Cerous sulfate: 1 part.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4, by solid made from step 3 again ultrasonic disperse in the concentration be 0.2/L nickel chloride solution, acutely
Stirring is lower, and mass fraction is added dropwise is 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, ageing, is washed suction filtration.
Solid made from step 4 is added the solution as 0.2/L cerous sulfate solution, under stirring condition, adjusted by step 5
Save pH to 9-9.5,80 DEG C reaction 2-3 hour, ageing, is washed suction filtration, is baked 4-5 hours under the conditions of 300 DEG C.
Embodiment 2:
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 11；Acetylacetone copper: 1 part；1- hexadecanethiol: 2 parts；Nickel sulfate: 4 parts；Ammonium hydroxide: 8 parts；Sulphur
Sour cerium: 1 part.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4, by solid made from step 3 again ultrasonic disperse in the concentration be 0.8g/L nickel sulfate solution, it is acute
Under strong stirring be added dropwise mass fraction be 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, ageing, suction filtration, wash.
Solid made from step 4 is added the solution as 0.8g/L cerous sulfate solution, under stirring condition, adjusted by step 5
Save pH to 9-9.5,80 DEG C reaction 2-3 hour, ageing, is washed suction filtration, is baked 4-5 hours under the conditions of 300 DEG C.
Embodiment 3:
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 11 parts；Acetylacetone copper: 3 parts；1- hexadecanethiol: 6 parts；Nickel chloride: 6 parts；Ammonium hydroxide: 10 parts；
Cerous sulfate: 1 part.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4, by solid made from step 3 again ultrasonic disperse in the concentration be 1.4g/L nickel chloride solution, it is acute
Under strong stirring be added dropwise mass fraction be 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, ageing, suction filtration, wash.
Solid made from step 4 is added the solution as 1.4g/L cerous sulfate solution, under stirring condition, adjusted by step 5
Save pH to 9-9.5,80 DEG C reaction 2-3 hour, ageing, is washed suction filtration, is baked 4-5 hours under the conditions of 300 DEG C.
Embodiment 4:
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 12 parts；Acetylacetone copper: 1 part；1- hexadecanethiol: 2 parts；Nickel nitrate: 8 parts；Ammonium hydroxide: 12 parts；
Cerous sulfate: 1 part.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4, by solid made from step 3 again ultrasonic disperse in the concentration be 2g/L nickel nitrate solution, acutely
Stirring is lower, and mass fraction is added dropwise is 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, ageing, is washed suction filtration.
Solid made from step 4 is added the solution as 2g/L cerous sulfate solution, under stirring condition, adjusted by step 5
PH to 9-9.5,80 DEG C reaction 2-3 hours, ageing filters, washing, bakes 4-5 hours under the conditions of 300 DEG C.
Comparative example 1
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 11 parts；Acetylacetone copper: 1 part；1- hexadecanethiol: 2 parts；Nickel chloride: 12 parts；Ammonium hydroxide: 16
Part；Cerous sulfate: 1 part.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4, by solid made from step 3 again ultrasonic disperse in the concentration be 1.4g/L nickel chloride solution, it is acute
Under strong stirring be added dropwise mass fraction be 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, ageing, suction filtration, wash.
Solid made from step 4 is added the solution as 1.4g/L cerous sulfate solution, under stirring condition, adjusted by step 5
Save pH to 9-9.5,80 DEG C reaction 2-3 hour, ageing, is washed suction filtration, is baked 4-5 hours under the conditions of 300 DEG C.
Comparative example 2
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Copper chloride: 2 parts；Nickel chloride: 6 parts；Ammonium hydroxide: 10 parts；Cerous sulfate: 1 part.
Step 1, configuration concentration are 1.4g/L nickel chloride solution, and the copper chloride is added, after completely dissolution, is vigorously stirred
Lower dropwise addition mass fraction be 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, ageing, suction filtration, wash.
Solid made from step 2 is added the solution as 1.4g/L cerous sulfate solution, under stirring condition, adjusted by step 2
Save pH to 9-9.5,80 DEG C reaction 2-3 hour, ageing, is washed suction filtration, is baked 4-5 hours under the conditions of 300 DEG C.
Comparative example 3
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 11 parts；Nickel chloride: 6 parts；Ammonium hydroxide: 10 parts；Cerous sulfate: 1 part.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, ultrasonic disperse, and concentration is added and is
1.4g/L nickel chloride solution, be vigorously stirred lower dropwise addition mass fraction be 30% ammonium hydroxide, 80 DEG C reaction 4-5 hour, be aged, suction filtration,
Washing.
Solid made from step 1 is added the solution as 1.4g/L cerous sulfate solution, under stirring condition, adjusted by step 2
Save pH to 9-9.5,80 DEG C reaction 2-3 hour, ageing, is washed suction filtration, is baked 4-5 hours under the conditions of 300 DEG C.
Comparative example 4
A kind of preparation method of the nickel-base catalyst of nanometer silicon carbide load, comprising the following steps:
Raw material forms (molar ratio)
Nanometer silicon carbide: 11 parts；Acetylacetone copper: 3 parts；1- hexadecanethiol: 6 parts；Nickel chloride: 6 parts；Ammonium hydroxide: 10 parts.
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- 16 is added in ultrasonic disperse
Alkanethiol, ultrasound 20 minutes；
The acetylacetone copper is added in step 2, step 1 gained mixed solution under nitrogen atmosphere, intense agitation,
80 DEG C reaction 3-4 hours；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 20-40 points
Clock；Centrifuge washing after cooling；
Step 4, by solid made from step 3 again ultrasonic disperse in the concentration be 1.4g/L nickel chloride solution, it is acute
It is 30% ammonium hydroxide that mass fraction is added dropwise under strong stirring, 80 DEG C reaction 4-5 hour, ageing, is washed suction filtration, is baked under the conditions of 300 DEG C
4-5 hours.
Embodiment 5:
Using nickel, copper and cerium content in the nickel-base catalyst of ICP detection nanometer silicon carbide load
Nickel mass fraction is 33-48%, Copper mass fraction 11-18%；Cerium is auxiliary agent, mass fraction 4%-9%.
Nickel, copper and cerium content in one gasification of biomass catalyst for preparing hydrogen of table
| Group | Nickel content % | Copper content % | Cerium content % |
| Embodiment 1 | 33.1 | 18.4 | 8.5 |
| Embodiment 2 | 35.5 | 15.7 | 4.6 |
| Embodiment 3 | 41.6 | 13.5 | 6.3 |
| Embodiment 4 | 48.1 | 11.2 | 6.1 |
| Comparative example 1 | 56.9 | 12.7 | 1.2 |
Embodiment 6:
Reactor is urged to carry out biogas continous way fixed bed is micro- nickel-base catalyst that above-mentioned nanometer silicon carbide loads
Change the evaluation of catalyst for preparing hydrogen reactivity, reaction condition are as follows: glucose concentration 10wt%, 270 DEG C of reaction temperature, pressure
2.0MPa, the reaction time 5 hours.Gaseous product gas chromatographic detection includes hydrogen, methane, an oxygen in the gaseous product
Change carbon and carbon dioxide.
Two catalyst of table is used for catalytic activity, the selectivity of biomass gasifying hydrogen making
From table two it is found that catalyst prepared by embodiment 1- embodiment 4 is in the reaction process of hydrogen production from glucose gasification,
Inversion rate of glucose is up to 99%, and hydrogen selective is up to 99%, illustrates that catalyst has higher catalytic activity and selectivity；
Wherein embodiment 3 is optimal.
Catalyst activity component raw material nickel content made from comparative example 1 is excessively high, and the nickel of carrier depositing SiC is excessive, covering
The solid matter accumulation of silicon carbide, Si-C diatomic layer generates the effect that stacking fault no longer generates increase active site；Comparative example 2
It is not introduced into carrier silicon carbide, catalytic activity and selectivity are decreased obviously；Comparative example 3 is not introduced into activating component cuprous sulfide, catalysis
Reaction does not occur, illustrates that simple nickel can not generate catalytic action, 4 introducing assistant activator ceriums of comparative example, and catalytic activity reduces,
And hydrogen selective substantially reduces.It can be seen that this high activity of catalyst and selectivity be due to its unique composition and structure,
It is carrier, activating component, the result of auxiliary agent synergistic effect.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (7)
1. a kind of nickel-base catalyst of nanometer silicon carbide load, which is characterized in that the raw material including following weight ratio,
Nanometer silicon carbide: 10-12 parts；
Acetylacetone copper: 1 part；
1- hexadecanethiol: 2 parts；
Nickel ion: 2-8 parts；
Ammonium hydroxide: 6-12 parts；
Cerous sulfate: 1 part；
The preparation method of the nickel-base catalyst of the nanometer silicon carbide load, comprising the following steps:
Step 1 the nanometer carborundum is added in the pure water of 1000 times of weight, and the 1- hexadecane sulphur is added in ultrasonic disperse
Alcohol, ultrasound 20 minutes；
Step 2, mixed solution obtained by step 1 are added the acetylacetone copper under nitrogen atmosphere, intense agitation, and 80 DEG C
Reaction 20-40 minutes；
Step 2 acquired solution is transferred to microwave hydrothermal kettle by step 3, under nitrogen atmosphere, 220-250 DEG C reaction 1-2 hours；It is cold
But centrifuge washing after；
Step 4 is vigorously stirred lower dropwise addition ammonium hydroxide by solid made from step 3 again ultrasonic disperse in the nickel ion solution,
80 DEG C reaction 4-5 hours, ageing, filter, washing；
The cerous sulfate solution is added in solid made from step 4 by step 5, under stirring condition, adjusts pH to 9-9.5, and 80 DEG C
Reaction 2-3 hours, ageing filter, washing, bake 4-5 hours under the conditions of 300 DEG C.
2. the nickel-base catalyst of nanometer silicon carbide load as described in claim 1, which is characterized in that the source of the nickel ion
For one of nickel chloride, nickel sulfate or nickel nitrate.
3. the nickel-base catalyst of nanometer silicon carbide load as claimed in claim 2, which is characterized in that including following weight ratio
Raw material,
Nanometer silicon carbide: 11 parts；
Acetylacetone copper: 3 parts；
1- hexadecanethiol: 6 parts；
Nickel chloride: 6 parts；
Ammonium hydroxide: 10 parts；
Cerous sulfate: 1 part.
4. the nickel-base catalyst of nanometer silicon carbide load as claimed in claim 3, which is characterized in that the carrier of the catalyst
For nanometer silicon carbide；Activating component is nickel-copper, and nickel mass fraction is 33-48%, Copper mass fraction 11-18%；Cerium is to help
Agent, mass fraction 4%-9%.
5. the nickel-base catalyst of nanometer silicon carbide load as described in claim 1, which is characterized in that the ammonium hydroxide mass fraction
For 28%-32%.
6. the nickel-base catalyst of nanometer silicon carbide as claimed in claim 5 load, which is characterized in that the nickel ion concentration is
0.2-2g/L。
7. the nickel-base catalyst of nanometer silicon carbide as claimed in claim 6 load, which is characterized in that the cerous sulfate solution is
0.2-2g/L。
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| CN103878006A (en) * | 2014-03-26 | 2014-06-25 | 华南农业大学 | Preparation method of silicon carbide/carbon nano material composite visible-light photocatalyst |
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| JP2006291116A (en) * | 2005-04-14 | 2006-10-26 | Ueda Holdings:Kk | Ship bottom coating |
| CN103447059A (en) * | 2013-09-22 | 2013-12-18 | 神华集团有限责任公司 | Preparation method of acetate hydrogenation catalyst |
| CN103878006A (en) * | 2014-03-26 | 2014-06-25 | 华南农业大学 | Preparation method of silicon carbide/carbon nano material composite visible-light photocatalyst |
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