CN107376936A - A kind of platinum cobalt/attapulgite catalyst and its preparation method and application - Google Patents
A kind of platinum cobalt/attapulgite catalyst and its preparation method and application Download PDFInfo
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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Abstract
The invention discloses a kind of platinum cobalt/attapulgite catalyst, including Concave-convex clay rod as carrier and the platinum and cobalt that are supported on Concave-convex clay rod.When platinum cobalt/attapulgite catalyst of the present invention is applied in catalytic reforming bio oil and its model thing hydrogen manufacturing, reaction temperature can be effectively reduced, conversion ratio >=98% of raw material can be realized, hydrogen yield >=95%, hydrogen selective >=96%, and service life >=200h, the advantages of active high, selectivity height, long lifespan, good, cheap stability, meet the industrial requirement of catalyzing and reforming biologic oil hydrogen manufacturing.
Description
Technical field
The present invention relates to catalyst field, relates in particular to a kind of platinum-cobalt/attapulgite catalyst and preparation method thereof
And application.
Background technology
Bio oil refers to the polyphosphazene polymer for making composition biomass under conditions of starvation by way of quickly heating
Compound is cracked into low molecule organic matter steam, and using the method for quenching, the liquid condensed into, it have raw material sources extensively,
It is renewable, be readily transported, the features such as energy density is higher, be a kind of potential liquid fuel and industrial chemicals.
The main Land use systems to bio oil are to prepare synthesis gas or hydrogen for catalytic reforming at present, so not only can be with
The utilization rate of biomass is improved, and alleviates the consumption of the energy.Bio oil (CxHyOz) reformation hydrogen production mainly includes following reaction：
Main reaction：CnHmOp+(2n-p)H2O→nCO2+(2n-p+m/2)H2；
Side reaction：CnHmOp→CxHyOz+CO+CO2+CH4+H2+…..+coke(x<n；y<m；z<p)；
CO+H2O→CO2+H2；……；
To improve the efficiency of biological oil reforming hydrogen production, must just be fixed against to contained carbon-carbon bond, carbon-oxygen bond in bio oil
With carbon-hydrogen link with stronger fracture energy and to catalyst of the water gas shift reation with facilitation.Currently, to reforming
The active component of bio oil catalyst is concentrated mainly on noble metal (Pt, Pd, Ru and Rh etc.) and transition metal (Ni, Co, Fe and Cu
Deng), the selection to carrier is concentrated mainly on metal oxide (Al2O3, ZrO2, MgO, CeO2And SiO2Deng).These catalyst exist
Excellent reactivity and hydrogen selective are shown during catalytic reforming bio oil.However, the sintering of active metal
It is still the principal element for influenceing catalyst life with the formation of catalyst surface carbon deposit.
Therefore selection is born with bigger serface and pore volume, with hydrothermal stability, material cheap and easy to get as carrier
Carrying under lower temperature has strong fracture energy to carbon-carbon bond, carbon-oxygen bond and carbon-hydrogen link, has strong selectivity to water gas shift reation
Active metal compound, increase the anti-caking power and anti-carbon deposition ability of catalyst, be that the inactivation for solving reforming catalyst is asked
The key factor of topic.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of high activity, selectivity height, long lifespan, preparation method letter
Single, cheap platinum-cobalt/attapulgite catalyst.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：A kind of platinum-cobalt/attapulgite catalyst,
Including the Concave-convex clay rod as carrier and the platinum and cobalt that are supported on Concave-convex clay rod.
Noble metal platinum, not only there is high activity of conversion to bio oil and its model thing, and can significantly drop
Temperature required for low reforming reaction.As the transition metals cobalt of auxiliary agent, then easily metal is formed in calcination process and is dissolved with platinum
Body and alloy, increase the anti-caking power of catalyst, strengthen the reproducibility of catalyst, there is provided more reaction active sites, may be used also
To promote water gas shift reation, hydrogen yield is improved.
Concave-convex clay rod is a kind of clay mineral of zeopan containing Shuifu County with chain layer structure, and its structure belongs to 2:
1 type clay mineral.Each 2:In 1 unit structure layer, tetrahedron chip angle top overturns in direction at a certain distance, forming layer chain
Shape.The passage parallel with chain is formed in tetrahedron bar interband.Therefore higher specific surface area and larger pore volume are made it have, made
The decentralization of active metal can be promoted for catalyst carrier use.And Concave-convex clay rod have certain heat endurance,
Amount of storage is big, cheap and easy to get, therefore is preferable native catalytic agent carrier.
Further, the content of platinum is 5~15wt.%, and cobalt content is 10~20wt.%.
The present invention also provides above-mentioned platinum-cobalt/attapulgite catalyst in catalytic reforming bio oil and its model thing hydrogen manufacturing
Application.
Further, catalytic reforming bio oil and its reaction condition of model thing hydrogen manufacturing are：Catalyst amount 1g~5g, it is former
Feeding coal 1g/h~15g/h of material, raw water carbon mol ratio 1~20, reaction temperature are 300 DEG C~500 DEG C.Implementing the present invention
During, inventor has found, under this reaction condition, it is possible to achieve conversion ratio >=98% of raw material, hydrogen yield >=95%, hydrogen
Gas selectivity >=96%.
The present invention also provides the preparation method of above-mentioned platinum-cobalt/attapulgite catalyst, comprises the following steps：Before taking platinum
The precursor salt of body salt and cobalt is driven, platinum and cobalt are then supported on by Concave-convex clay rod using synchronous infusion process or step impregnation method
On, the platinum-cobalt/attapulgite catalyst is made.
Further, the precursor salt of the platinum is ammonium chloroplatinate, and the precursor salt of the cobalt is cabaltous nitrate hexahydrate
Or cobalt chloride hexahydrate.
Further, synchronous infusion process concretely comprises the following steps：Concave-convex clay rod is added to the precursor salt and cobalt of platinum
Precursor salt ethanol solution in, then stir, through ultrasonic disperse, aging, standing, evaporation, washing and filtering, dry
After dry, grinding screening process, then calcined successively under nitrogen atmosphere and reducing atmosphere.
Further, step impregnation method concretely comprises the following steps：Concave-convex clay rod is added to the nothing of the precursor salt of platinum
Hydrous ethanol solution, the precursor salt of cobalt ethanol solution in one of which in, then stir, through ultrasonic disperse,
After aging, standing, evaporation, washing and filtering, drying, grinding screening process, solid powder is made, then solid powder is added to platinum
The ethanol solution of precursor salt, cobalt precursor salt ethanol solution in another in, then stirring is equal
It is even, after ultrasonic disperse, aging, standing, evaporation, washing and filtering, drying, grinding screening process, then successively in nitrogen atmosphere and
Calcined under reducing atmosphere.
Further, burin-in process be in autoclave, be passed through nitrogen protection gas, 4~6MPa, 100~150 DEG C
Under the conditions of, 4~6h is first stirred, then stand 12~18h.
Further, calcination processing is to rise to 400~600 DEG C from room temperature with 1~3 DEG C/min heating rate, Ran Houheng
2~4h of temperature.
Further, it is stirred for 4~6h of magnetic agitation under 40~60 DEG C of water bath conditions.
Further, ultrasonic disperse processing for be stirred continuously under conditions of ultrasonic wave, 40~60 DEG C 3~5h formed it is suspended
Liquid.
Further, stewing process is under room temperature condition of normal pressure, places 16~18.
Further, evaporation process is under the conditions of 60~80 DEG C, and ethanol evaporation is removed.
Further, washing and filtering processing is that filtering 5~10 times is washed with deionized.
Further, drying process is that 12~16h is dried under the conditions of normal pressure, 80~100 DEG C.
Further, grind screening process dried solid to be ground with mortar, and screen out a diameter of 0.18~
0.25mm particle.
Further, the reducing atmosphere be hydrogen volume fraction be 5~10% hydrogen and argon gas mixed gas.
Beneficial effects of the present invention are embodied in：
, can 1. platinum-cobalt/attapulgite catalyst of the present invention is applied in catalytic reforming bio oil and its model thing hydrogen manufacturing
Reaction temperature is effectively reduced, can realize conversion ratio >=98% of raw material, hydrogen yield >=95%, hydrogen selective >=
96%, and service life >=200h, the advantages of active high, selectivity height, long lifespan, good, cheap stability, expire
The industrial requirement of sufficient catalyzing and reforming biologic oil hydrogen manufacturing.
2. platinum-cobalt/attapulgite catalyst of the present invention using cobalt as auxiliary component and platinum carry out it is multiple and, calcining and and also
Cobalt can form metal alloy with platinum, improve the interaction of active metal and carrier during original, and strengthen catalyst uses the longevity
Life.Other cobalt can promote Pt as auxiliary agent4+Reduction under reducing atmosphere, improve the content of active catalyst sites, enter
And improve the conversion frequency of reactant and product.
3. in the preparation method of platinum-cobalt/attapulgite catalyst of the present invention, high-temperature pressurizing is entered in selection autoclave
Row burin-in process, relative under traditional normal pressure, aged at room temperature, can significantly improve active metal load efficiency and be uniformly dispersed
Property, and can make active metal and carrier that strong interaction occur, and then improve the service life of catalyst；Other anhydrous second
Alcohol has good meeting hair property, as organic dispersing agent, can not only promote active metal in the equal of Attapulgite carrier surface
It is even scattered, evaporation time can also be shortened, preparation method when being a kind of green, pollution-free, easy to operate, low consumption.
4. the present invention using natural, rich reserves, has high-specific surface area relative to other noble metal-based catalysts
Cheap attapulgite reduces the preparation cost of catalyst as carrier.
5. the present invention is applied in bio oil and its reaction of model thing catalytically reforming hydrogen producing, reaction temperature can be significantly reduced
Degree, catalyst anti-carbon and anti-sintering, increase catalyst service life are improved, there is the prospect promoted the use of.
Embodiment
With reference to embodiment, the invention will be further described：
Various raw materials, are such as not specifically noted used in following examples, are commercially available prod well known in the art.
Embodiment 1
Active component platinum (Pt) content in platinum-cobalt/attapulgite catalyst manufactured in the present embodiment is 5wt.%, auxiliary agent
The content of cobalt (Co) is 10wt.%, and composition is Concave-convex clay rod more than institute, and preparation method is as follows：
Weigh 0.67g ammonium chloroplatinate ((NH4)2PtCl6) it is dissolved completely in 50mL absolute ethyl alcohol formation solution A 1；
Weigh 2.90g cabaltous nitrate hexahydrate (Co (NO3)2·6H2O the absolute ethyl alcohol for) being dissolved completely in 50mL forms solution A 2；Weigh
5.00g Concave-convex clay rod, is added in A1, the magnetic agitation 4h under 40 DEG C of water bath conditions, then is placed in supersonic cleaning machine
3h is stirred continuously under the conditions of 40 DEG C, forms uniform suspension B1；B1 is transferred in autoclave, is filled with 4MPa nitrogen
Gas is protected, after being stirred continuously 4h under the conditions of 100 DEG C, then stands 12h under the same conditions, obtains solidliquid mixture B2；Then
B2 is moved in beaker, after placing 16h under room temperature normal pressure, excess acetic acid is evaporated under the conditions of 60 DEG C in Rotary Evaporators
Solution, obtain solid C1；C1 is washed with deionized after filtering 5 times, dries 12h under the conditions of 80 DEG C in baking oven, obtain
Solid C2；C2 is ground with mortar, then is sieved with the sieve of 70 mesh, 80 mesh to obtain the particle that particle diameter is 0.18mm~0.21mm,
Obtain solid powder C3；C3 is added in A2, the magnetic agitation 4h under 40 DEG C of water bath conditions, then is placed in supersonic cleaning machine in 40 DEG C
Under the conditions of be stirred continuously 3h, form uniform suspension D1；D1 is transferred in autoclave, is filled with 4MPa nitrogen protection
Gas, after being stirred continuously 4h under the conditions of 100 DEG C, then 12h is stood under the same conditions, obtain solidliquid mixture D2；Then by D2
Move in beaker, after placing 16h under room temperature normal pressure, it is molten in Rotary Evaporators at a temperature of 60 DEG C to evaporate excess acetic acid
Liquid, obtain solid E1；E1 is washed with deionized after filtering 5 times, dries 12h under the conditions of 80 DEG C in baking oven, consolidate
Body E2；E2 is ground with mortar, then is sieved with the sieve of 70 mesh, 80 mesh to obtain the particle that particle diameter is 0.18mm~0.21mm, is obtained
Solid powder E3；E3 is placed in tube furnace, is passed through nitrogen atmosphere, 400 DEG C are risen to from room temperature with 1 DEG C/min heating rate,
Room temperature is cooled to after calcining at constant temperature 2h, then be passed through hydrogen volume fraction be 5% hydrogen and argon gas mixed gas, from room temperature
400 DEG C are risen to 1 DEG C/min heating rate, room temperature is cooled to after calcining at constant temperature 2h, the platinum-cobalt/attapulgite is obtained and urges
Agent, numbering 1#.
Embodiment 2
Active component platinum (Pt) content in platinum-cobalt/attapulgite catalyst manufactured in the present embodiment is 15wt.%；Help
The content of agent cobalt (Co) is 20wt.%；Composition is Concave-convex clay rod more than institute.
Weigh 2.62g ammonium chloroplatinate ((NH4)2PtCl6) it is dissolved completely in 50mL absolute ethyl alcohol formation solution A 1；
Weigh 6.22g cobalt chloride hexahydrate (CoCl2·6H2O the absolute ethyl alcohol for) being dissolved completely in 50mL forms solution A 2；Weigh
5.00g Concave-convex clay rod, be added in A2, the magnetic agitation 6h under 60 DEG C of water bath conditions, then be placed in supersonic cleaning machine
5h is stirred continuously under the conditions of 60 DEG C, forms uniform suspension B1；B1 is transferred in autoclave, is filled with 6MPa nitrogen
Gas is protected, after being stirred continuously 6h under the conditions of 150 DEG C, then stands 18h under the same conditions, obtains solidliquid mixture B2；Then
B2 is moved in beaker, after placing 18h under room temperature normal pressure, excess acetic acid is evaporated under the conditions of 80 DEG C in Rotary Evaporators
Solution, obtain solid C1；C1 is washed with deionized after filtering 10 times, dries 16h under the conditions of 100 DEG C in baking oven, obtain
To solid C2；C2 is ground with mortar, then is sieved with the sieve of 60 mesh, 70 mesh to obtain that particle diameter is 0.21mm~0.25mm
Grain, obtains solid powder C3；C3 is added in A1, the magnetic agitation 6h under 60 DEG C of water bath conditions, then be placed in supersonic cleaning machine
5h is stirred continuously under the conditions of 60 DEG C, forms uniform suspension D1；D1 is transferred in autoclave, is filled with 6MPa nitrogen
Gas is protected, after being stirred continuously 6h under the conditions of 150 DEG C, then stands 18h under the same conditions, obtains solidliquid mixture D2；Then
D2 is moved in beaker, after placing 18h under room temperature normal pressure, excess acetic acid is evaporated under the conditions of 80 DEG C in Rotary Evaporators
Solution, obtain solid E1；E1 is washed with deionized after filtering 10 times, dries 16h under the conditions of 100 DEG C in baking oven, obtain
To solid E2；E2 is ground with mortar, then is sieved with the sieve of 60 mesh, 70 mesh to obtain that particle diameter is 0.21mm~0.25mm
Grain, obtains solid powder E3；E3 is placed in tube furnace, is passed through nitrogen atmosphere, is risen to from room temperature with 3 DEG C/min heating rate
600 DEG C, room temperature is cooled to after calcining at constant temperature 4h, then it is 10% hydrogen and the gaseous mixture of argon gas to be passed through the volume fraction of hydrogen
Body, rise to 600 DEG C from room temperature with 3 DEG C/min heating rate, room temperature be cooled to after calcining at constant temperature 4h, obtain described platinum-cobalt/
Attapulgite catalyst, numbering 2#.
Embodiment 3
Active component platinum (Pt) content in platinum-cobalt/attapulgite catalyst manufactured in the present embodiment is 10wt.%；Help
The content of agent cobalt (Co) is 10wt.%；Composition is Concave-convex clay rod more than institute.
Weigh 1.44g ammonium chloroplatinate ((NH4)2PtCl6) it is dissolved completely in 50mL absolute ethyl alcohol formation solution A 1；
Weigh 3.09g cabaltous nitrate hexahydrate (Co (NO3)2·6H2O the absolute ethyl alcohol for) being dissolved completely in 50mL forms solution A 2；By A1
It is sufficiently mixed with A2 and is formed uniformly solution A 3；5.00g Concave-convex clay rod is weighed, is added in A3, in 50 DEG C of water bath conditions
Lower magnetic agitation 5h, then be placed in supersonic cleaning machine and be stirred continuously 4h under the conditions of 50 DEG C, form uniform suspension B1；B1 is turned
Move in autoclave, 5MPa nitrogen protection gas is filled with, after being stirred continuously 5h under the conditions of 120 DEG C, then in the same terms
Lower standing 16h, obtain solidliquid mixture B2；Then B2 is moved in beaker, after placing 17h under room temperature normal pressure, steamed in rotation
Excess acetic acid solution is evaporated under the conditions of 70 DEG C in hair instrument, obtains solid C1；C1 is washed with deionized after filtering 7 times,
14h is dried under the conditions of 90 DEG C in baking oven, obtains solid C2；C2 is ground with mortar, then sieved with the sieve of 70 mesh, 80 mesh
To the particle that particle diameter is 0.18mm~0.21mm, solid powder C3 is obtained；C3 is placed in tube furnace, is first passed through nitrogen atmosphere, from
Room temperature rises to 500 DEG C with 2 DEG C/min heating rate, and room temperature is cooled to after calcining at constant temperature 3h, then is passed through the volume fraction of hydrogen
The mixed gas of hydrogen and argon gas for 8%, 500 DEG C are risen to from room temperature with 2 DEG C/min heating rate, it is cold after calcining at constant temperature 3h
But to room temperature, described platinum-cobalt/attapulgite catalyst, numbering 3# are obtained.
Embodiment 4
Active component platinum (Pt) content in platinum-cobalt/attapulgite catalyst manufactured in the present embodiment is 15wt.%；Help
The content of agent cobalt (Co) is 15wt.%；Composition is Concave-convex clay rod more than institute.
Weigh 2.43g ammonium chloroplatinate ((NH4)2PtCl6) it is dissolved completely in 50mL absolute ethyl alcohol formation solution A 1；
Weigh 3.09g cabaltous nitrate hexahydrate (Co (NO3)2·6H2O the absolute ethyl alcohol for) being dissolved completely in 50mL forms solution A 2；By A1
It is sufficiently mixed with A2 and is formed uniformly solution A 3；5.00g Concave-convex clay rod is weighed, is added in A3, in 45 DEG C of water bath conditions
Lower magnetic agitation 5h, then be placed in supersonic cleaning machine and be stirred continuously 4h under the conditions of 55 DEG C, form uniform suspension B1；B1 is shifted
Into autoclave, 5MPa nitrogen protection gas is filled with, after being stirred continuously 5h under the conditions of 130 DEG C, then under the same conditions
14h is stood, obtains solidliquid mixture B2；Then B2 is moved in beaker, after placing 17h under room temperature normal pressure, in rotary evaporation
Excess acetic acid solution is evaporated in instrument under the conditions of 75 DEG C, obtains solid C1；C1 is washed with deionized after filtering 8 times, in
15h is dried in baking oven under the conditions of 95 DEG C, obtains solid C2；C2 is ground with mortar, then sieves to obtain with the sieve of 70 mesh, 80 mesh
Particle diameter is 0.18mm~0.21mm particle, obtains solid powder C3；C3 is placed in tube furnace, is first passed through nitrogen atmosphere, from room
Temperature rises to 550 DEG C with 2.5 DEG C/min heating rate, room temperature is cooled to after calcining at constant temperature 3h, then be passed through the volume fraction of hydrogen
The mixed gas of hydrogen and argon gas for 8%, 550 DEG C are risen to from room temperature with 2.5 DEG C/min heating rate, after calcining at constant temperature 3h
Room temperature is cooled to, obtains described platinum-cobalt/attapulgite catalyst, numbering 4#.
Embodiment 5
The catalytic reforming bio oil of platinum-cobalt/attapulgite catalyst and its model thing hydrogen manufacturing test
Above-mentioned 1#~4# catalyst 1g~3g is taken to be placed in fixed bed reactors, the feeding coal 10g/h of reactant feed~
15g/h, raw water carbon mol ratio (S/C) 6~20, reaction temperature are 300 DEG C~500 DEG C.Specific reaction condition and result are shown in
Table 1.
Table 1
Can be drawn from result above, platinum-cobalt/attapulgite catalyst of the present invention can realize the conversion ratio of raw material >=
98%, hydrogen yield >=95%, hydrogen selective >=96%, service life >=200h.
It should be understood that example as described herein and embodiment are not intended to limit the invention, this area only for explanation
Technical staff can make various modifications or change according to it, within the spirit and principles of the invention, any modification for being made,
Equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
- A kind of 1. platinum-cobalt/attapulgite catalyst, it is characterised in that：Including the Concave-convex clay rod as carrier and load Platinum and cobalt on Concave-convex clay rod.
- 2. platinum-cobalt/attapulgite catalyst as claimed in claim 1, it is characterised in that：The content of platinum is 5~15wt.%, Cobalt content is 10~20wt.%.
- 3. platinum-cobalt/attapulgite catalyst as claimed in claim 1 or 2 is in catalytic reforming bio oil and its model thing hydrogen manufacturing In application.
- 4. platinum-cobalt/attapulgite catalyst as claimed in claim 3 is in catalytic reforming bio oil and its model thing hydrogen manufacturing Using, it is characterised in that：Catalytic reforming bio oil and its reaction condition of model thing hydrogen manufacturing are：Catalyst amount 1g~5g, it is former Feeding coal 1g/h~15g/h of material, raw water carbon mol ratio 1~20, reaction temperature are 300 DEG C~500 DEG C.
- 5. the preparation method of platinum-cobalt/attapulgite catalyst as claimed in claim 1 or 2, it is characterised in that：Including following Step：The precursor salt of platinum and the precursor salt of cobalt are taken, is then loaded platinum and cobalt using synchronous infusion process or step impregnation method On Concave-convex clay rod, the platinum-cobalt/attapulgite catalyst is made.
- 6. the preparation method of platinum-cobalt/attapulgite catalyst as claimed in claim 5, it is characterised in that：The forerunner of the platinum Body salt is ammonium chloroplatinate, and the precursor salt of the cobalt is cabaltous nitrate hexahydrate or cobalt chloride hexahydrate.
- 7. the preparation method of platinum-cobalt/attapulgite catalyst as claimed in claim 5, it is characterised in that：Synchronous infusion process Concretely comprise the following steps：Concave-convex clay rod is added in the ethanol solution of the precursor salt of platinum and the precursor salt of cobalt, so After stir, after ultrasonic disperse, aging, standing, evaporation, washing and filtering, drying, grinding screening process, then successively in nitrogen Calcined under gas atmosphere and reducing atmosphere.
- 8. the preparation method of platinum-cobalt/attapulgite catalyst as claimed in claim 5, it is characterised in that：Step impregnation method Concretely comprise the following steps：Concave-convex clay rod is added to the ethanol solution of the precursor salt of platinum, cobalt precursor salt it is anhydrous In one of which in ethanol solution, then stir, through ultrasonic disperse, aging, standing, evaporation, washing and filtering, drying, After grinding screening process, solid powder is made, then solid powder is added to the ethanol solution of the precursor salt of platinum, cobalt In another in the ethanol solution of precursor salt, then stir, through ultrasonic disperse, aging, standing, evaporation, After washing and filtering, drying, grinding screening process, then calcined successively under nitrogen atmosphere and reducing atmosphere.
- 9. the preparation method of platinum-cobalt/attapulgite catalyst as claimed in claim 7 or 8, it is characterised in that：Burin-in process Gas is protected in autoclave, to be passed through nitrogen, under the conditions of 4~6MPa, 100~150 DEG C, first stirs 4~6h, then stand 12~18h.
- 10. the preparation method of platinum-cobalt/attapulgite catalyst as claimed in claim 7 or 8, it is characterised in that：Calcination processing To rise to 400~600 DEG C from room temperature with 1~3 DEG C/min heating rate, then 2~4h of constant temperature.
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|---|---|---|---|---|
| CN110787810A (en) * | 2019-11-16 | 2020-02-14 | 许昌学院 | Preparation method and application of ruthenium-cobalt binary catalyst |
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| CN114212777A (en) * | 2021-12-15 | 2022-03-22 | 广东省科学院化工研究所 | Graphene nanosphere and preparation method and application thereof |
| CN115518652A (en) * | 2022-06-13 | 2022-12-27 | 安徽理工大学 | Silicon-cerium composite microporous material packaged metal catalyst and preparation method and application thereof |
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| CN107376936B (en) | 2020-05-26 |
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