CN106824200A - A kind of carbon load nickel metallic catalyst and preparation method thereof - Google Patents
A kind of carbon load nickel metallic catalyst and preparation method thereof Download PDFInfo
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- CN106824200A CN106824200A CN201611227543.2A CN201611227543A CN106824200A CN 106824200 A CN106824200 A CN 106824200A CN 201611227543 A CN201611227543 A CN 201611227543A CN 106824200 A CN106824200 A CN 106824200A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/34—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 by reaction of hydrocarbons with gasifying agents
- C01B3/38—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 by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—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 by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a kind of carbon load nickel metallic catalyst and preparation method thereof, carbon load nickel metallic catalyst is carbon source and the nitric acid of 0.1~1mol/L, sulfuric acid or phosphoric acid solution press 200~350g：The ratio mixing of 400~1000mL, filters after the 6~12h that flowed back at being 70~85 DEG C in temperature, and filter residue is cleaned with deionized water until washing lotion pH=7；Solid A is then obtained after 100~110 DEG C of 8~12h of drying, solid A is incubated 12~24h under the conditions of 150~180 DEG C, cleaned, solid B is obtained after 100~110 DEG C of 8~12h of drying；Then nickel compound containing is dissolved in deionized water, stirring obtains solution C to being completely dissolved, then adds with B isometric solution C solid B, after standing 12~24h at room temperature, in 100~110 DEG C of 8~12h of drying, obtain solid D；Solid D is placed in not oxygenous gas flow, and is incubated 1~5 hour after being heated to 700~1100 DEG C, be then naturally cooling to room temperature and be obtained.Catalyst activity obtained in the method is high, good stability, and at 850 DEG C, with pure methane or natural gas as reactant, its reforming reaction is at least stablized 1000 hours.
Description
Technical field
The present invention relates to a kind of carbon load nickel metallic catalyst and preparation method thereof.
Background technology
China as energy-consuming big country, the exploitation of new energy, especially regenerative resource to national economy can
Sustainable development has great importance.The wherein research and development of biogas and utilization are increasingly paid attention to.Biogas is referred to including excrement
Fertilizer, sewage, municipal solid waste and the degradable organic substance of other biological, in the environment of anoxic, fermented or anaerobic
Gas produced by digestion process, the gas mainly includes methane (55~65%) and carbon dioxide (30~45%), also few
The nitrogen of amount, oxygen and micro hydrogen sulfide etc..
Although China's Methane Resources enrich, utilization ratio is not high, is mainly used for burning heating and provides illumination.Mirror
In biogas main component particularity (methane and carbon dioxide is all typical greenhouse gases, and methane greenhouse effects equivalent
It is 25 times of carbon dioxide), many scholars propose another technical method, and the technology can efficiently can be produced again using biogas energy
Raw added value is high and product of cleaning, i.e., using catalytic reforming technology, also referred to as biogas reforming technique turns both greenhouse gases
Chemical conversion synthesis gas (hydrogen and carbon monoxide).In commercial Application, synthesis gas is a kind of very important industrial chemicals, can be applied
In kinds of processes production, such as fischer-tropsch synthesis process, Ammonia Process and alcohol technique processed etc..In a word, the process realizes resource profit
With the double benefit with environmental protection.
The core of biogas reforming technique is exactly the research to catalyst performance.Catalyst used by the reaction generally uses VIII
Group 4 transition metal is used as active component.Research shows that not only activity is high for nickel-base catalyst, high conversion rate, and compared with other transition
For metal, low cost.So it is most widely used for biogas reforming reaction.At present, almost all of nickel-base catalyst be with
Metal oxide is carrier, such as silica and alundum (Al2O3).Although by adding different types of metal promoter, such as oxygen
Change magnesium, strontium oxide strontia etc., catalyst performance increases and improves, but it is existing still to there is the inactivation of the catalyst caused by carbon distribution
As.Also, after catalyst use, the mixture of this metal oxide cannot recycling, waste limited treasured
Expensive resource.
The present invention proposes to be applied to biogas catalytic reforming preparing synthetic gas skill as the carrier of nickel-base catalyst with renewable carbon
Art.Renewable carbon wide material sources and cheap, by after special preprocess method, the specific surface area of carbon source is greatly improved,
This characteristic is highly suitable as catalyst carrier.Also, after catalyst use, can be by carbon source of burning with recycling
Nickel metal, had not only reduced technical costs but also can save limited precious resources.In a word, the invention is whether in the preparation of catalyst
Or all it is that renewable resource is made full use of in the reaction of biogas catalytic reforming, embodies the technology reason of environmental protection
Read.
The content of the invention
Based on above the deficiencies in the prior art, in order to improve catalyst activity and stability, the recovery of catalyst is realized again
Utilize, the present invention provides a kind of preparation method and application of carbon load nickel metallic catalyst for biogas reforming technique.This is urged
Agent activity is high, good stability, and it is possible to realize the recycling after catalyst use, realize reduces cost and
The double benefit for economizing on resources.
In order to solve the above-mentioned technical problem, the present invention provides a kind of carbon load nickel metallic catalyst and preparation method thereof.
A kind of preparation method of carbon load nickel metallic catalyst, comprises the following steps：
The pretreatment of step one, carbon source：By the nitric acid of carbon source and 0.1~1mol/L, sulfuric acid or phosphoric acid solution by 200~
350g：The ratio mixing of 400~1000mL, filters, filter residue deionized water after the 6~12h that flowed back at being 70~85 DEG C in temperature
Cleaning is until washing lotion pH=7；Solid A is then obtained after 100~110 DEG C of 8~12h of drying, solid A is under the conditions of 150~180 DEG C
12~24h of insulation, cleaning obtains solid B after 100~110 DEG C of 8~12h of drying；
After step one, the pretreatment of carbon source, other contained metal ions, such as calcium ion in the removing carbon source
Deng the specific surface area of the increase solid B.
The preparation of step 2, nickel-base catalyst presoma：Nickel compound containing is dissolved in deionized water, stirring to completely it is molten
Solution obtains nickeliferous 0.2~3.5mol/L solution Cs, and solid B or carbon source then are added into isometric with B or carbon source or equivalent solution
In C, after standing 12~24h at room temperature, in 100~110 DEG C of 8~12h of drying, solid D is obtained；
The preparation of step 3, carbon load nickel metallic catalyst：Using carbothermic method, solid D is placed in not oxygenous
1~5 hour is incubated in gas flow, and after being heated to 700~1100 DEG C, room temperature is then naturally cooling to, last gained sample
E, as carbon load nickel metallic catalyst.
The core that carbon wraps up nickel metal has been wrapped to form by the solid B through active component Ni in step 3, gained catalyst
Shell structure.
As the preferred embodiment of above-mentioned technical proposal, carbon load nickel metallic catalyst provided in an embodiment of the present invention and
Its preparation method further includes the part or all of of following technical characteristic：
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, in the step one, carbon source is grape
One kind in sugar, fructose, cellobiose, sucrose, starch, cellulose, activated carbon, carbon black.
As the improvement of above-mentioned technical proposal, in one embodiment of the invention, in the step one, the acid solution
It is the nitric acid of 0.1~1mol/L, hydrochloric acid, sulfuric acid or phosphorus aqueous acid.
As the improvement of above-mentioned technical proposal, in one embodiment of the invention, in the step 2, nickeliferousization
Compound is Nickelous nitrate hexahydrate, nickel sulfide, nickel sulfate, nickelous carbonate, nickel hydroxide, hydroxy acid nickel and nickel halogenide any one.
A kind of carbon load nickel metallic catalyst, is prepared using the preparation method of foregoing any carbon load nickel metallic catalyst
Form.
Used as the improvement of above-mentioned technical proposal, in one embodiment of the invention, the not oxygenous air-flow can be with
It is the one kind in pure nitrogen, helium, hydrogen, methane, ethene, acetylene.
Catalyst of the invention is that, with Ni as active component, carbon is carrier, and carbon load nickel metal is synthesized with carbothermic method
Catalyst.The characteristics of catalyst shows high catalytic efficiency to 750~850 DEG C of biogas catalytic reforming reactions, and have
Good stability.The present invention has following features：
In (1) 750~850 DEG C of biogas catalytic reforming reaction, up to 70~90%, carbon dioxide turns for the conversion ratio of methane
Rate is up to 60~80%；
In (2) 750~850 DEG C of biogas catalytic reforming reactions, its hydrogen product is with the molar ratio range of carbon monoxide
0.90~0.97.
In (3) 750~850 DEG C of methane dry reforming reactions, the conversion ratio of methane is up to 50~97%, the conversion of carbon dioxide
Rate is up to 70~98%.
In (4) 800 DEG C of biogas catalytic reforming reactions, the stability of catalyst at least 1000 hours.
At (5) 800 DEG C, the biogas catalytic reforming of 1000 hours is prepared in synthesis gas reaction, and methane and carbon dioxide turns
Rate can be stablized 85% and 75% respectively.
At (6) 850 DEG C, the natural gas catalytic reforming of 1000 hours is prepared in synthesis gas reaction, methane and carbon dioxide
Conversion ratio can be stablized 89% and 94% respectively.
(7) the catalyst carbon source carrier raw material is cheap and readily available, and the catalyst nickel for preparing is uniformly dispersed, and activity is high,
The recyclable recycling of catalyst after good stability, and use, not only reduces cost but also had economized on resources.
Described above is only the general introduction of technical solution of the present invention, in order to better understand technological means of the invention,
And can be practiced according to the content of specification, and in order to allow the above and other objects, features and advantages of the invention can
Become apparent, below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, will simply be situated between to the accompanying drawing of embodiment below
Continue.
Fig. 1 is the transmission electron microscope picture (TEM) of the gained carbon load nickel metallic catalyst of present example 12；
Fig. 2 is the XRD spectra of the gained carbon load nickel metallic catalyst of present example 12；
Stability curve of the gained catalyst of Fig. 3 present examples 12 in biogas catalytic reforming reaction.
Fig. 4 is stability curve of the gained catalyst of present example 13 in biogas catalytic reforming reaction.
Fig. 5 is stability curve of the gained catalyst of present example 14 in natural gas catalytic reforming reaction.
Fig. 6 is the transmission electron microscope picture (TEM) of the gained catalyst of present example 17；
Fig. 7 is the polycrystalline diffracting spectrum of the gained metallic catalyst of present example 17；
Fig. 8 is stability curve of the gained catalyst of present example 18 when with pure methane as reactant.
Fig. 9 is stability curve of the gained catalyst of present example 19 when with natural gas as reactant.
Specific embodiment
The following detailed description of specific embodiment of the invention, its as part of this specification, by embodiment come
Principle of the invention is illustrated, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
A kind of preparation method of carbon load nickel metallic catalyst, comprises the following steps：
The pretreatment of step one, carbon source：By the nitric acid of carbon source and 0.1~1mol/L, sulfuric acid or phosphoric acid solution by 200~
350g：The ratio mixing of 400~1000mL, filters, filter residue deionized water after the 6~12h that flowed back at being 70~85 DEG C in temperature
Cleaning is until washing lotion pH=7；Solid A is then obtained after 100~110 DEG C of 8~12h of drying, solid A is under the conditions of 150~180 DEG C
12~24h of insulation, cleaning obtains solid B after 100~110 DEG C of 8~12h of drying；
The preparation of step 2, nickel-base catalyst presoma：Nickel compound containing is dissolved in deionized water, stirring to completely it is molten
Solution obtains solution C, then adds solid B or carbon source and in equal volume or in the solution C of equivalent, 12 is stood at room temperature with B or carbon source
After~24h, in 100~110 DEG C of 8~12h of drying, solid D is obtained；
The preparation of step 3, carbon load nickel metallic catalyst：Using carbothermic method, solid D is placed in not oxygenous
1~5 hour is incubated in gas flow, and after being heated to 700~1100 DEG C, room temperature is then naturally cooling to, last gained sample
E, as carbon load nickel metallic catalyst.
In step one, carbon source comes from the disaccharides such as monose, cellobiose, the sucrose such as glucose, fructose, starch, cellulose etc.
The renewable carbons material such as the charcoals such as polysaccharide, charcoal.
In step one, the acid solution is nitric acid, hydrochloric acid, sulfuric acid or the phosphorus aqueous acid of 0.1~1mol/L.
In step 2, the nickel compound containing is Nickelous nitrate hexahydrate, nickel sulfide, nickel sulfate, nickelous carbonate, nickel hydroxide,
Any one of hydroxy acid nickel and nickel halogenide.
The not oxygenous air-flow can be the one kind in pure nitrogen, helium, hydrogen, methane, ethene, acetylene.
A kind of carbon load nickel metallic catalyst, is prepared using the preparation method of foregoing any carbon load nickel metallic catalyst
Form.
Embodiment 1.
The preparation of catalyst：
(1) 250g starch is taken to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L salpeter solutions, in temperature 70 C,
Flow back 10h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 180 DEG C of hydro-thermal process after 24 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 36g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 20g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 700 DEG C are heated in 50mL/min stream of nitrogen gas, and it is then natural to be incubated 3 hours
Room temperature is cooled to, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in 100mg steps (3), in 50mL/min nitrogen
700 DEG C of insulations are heated in gas air-flow carries out prereduction reaction in 1 hour, then stops being passed through nitrogen, and switching to flow velocity is
The biogas and flow velocity of 15.5mL/min are the carbon dioxide of 5mL/min, are investigated under this condition, and how is the activity of catalyst, comments
Valency result such as table 1.Its reaction condition：700 DEG C of temperature, pressure 5psi, methane is 1 with carbon dioxide ratio:1, reaction velocity
(GHSV)11000mL/(gh)。
Embodiment 2.
The preparation of catalyst：
(1) take 250g starch to be fitted into the round-bottomed flask for filling 800mL 0.5mol/L salpeter solutions, in 75 DEG C of temperature, turn
Flow back 8h under conditions of fast 800RPM, is then cleaned with deionized water to supernatant pH=7, is dried at 100 DEG C of temperature immediately
12h obtains solid A.A again after maintaining temperature to be 150 DEG C of hydro-thermal process after 24 hours, cleaning, after drying 12h at 100 DEG C
Obtain solid B.
(2) Nickelous nitrate hexahydrate for taking 42g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 20g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 950 DEG C, insulation are heated in stream of nitrogen gas of the 50mL/min containing 3.5% hydrogen
Then it is naturally cooling to room temperature within 2 hours, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 50mL/min
950 DEG C of insulations are heated in the stream of nitrogen gas of 3.5% hydrogen carries out prereduction reaction in 1 hour, is then cooled to 800 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 5mL/min to switch to biogas and flow velocity that flow velocity is 15.5mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 1.Its reaction condition：800 DEG C of temperature, pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity (GHSV) 11000mL/ (gh).
Embodiment 3.
The preparation of catalyst：
(1) take 250g starch to be fitted into the round-bottomed flask for filling 600mL 1mol/L salpeter solutions, in 80 DEG C of temperature, rotating speed
Flow back 6h under conditions of 700RPM, is then cleaned with deionized water to supernatant pH=7, dries 12h at 100 DEG C of temperature immediately
Obtain solid A.A again after maintaining temperature to be 160 DEG C of hydro-thermal process after 24 hours, cleaning, after drying 12h at 100 DEG C
Solid B.
(2) Nickelous nitrate hexahydrate for taking 51g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 20g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 1100 DEG C, insulation are heated in hydrogen gas streams of the 50mL/min containing 20% methane
Then it is naturally cooling to room temperature within 1 hour, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 50mL/min
1100 DEG C of insulations are heated in the hydrogen gas stream of 20% methane carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 5mL/min to switch to biogas and flow velocity that flow velocity is 15.5mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 1.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity (GHSV) 11000mL/ (gh).
Table 1
Embodiment 4.
The preparation of catalyst：
(1) take 350g glucose to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L sulfuric acid solutions, in temperature 85
DEG C, flow back 10h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, immediately in 100 DEG C of temperature
Under dry 12h and obtain solid A.A is again after maintaining temperature to be 180 DEG C of hydro-thermal process after 18 hours, and cleaning is dry at 100 DEG C
Solid B is obtained after dry 12h.
(2) Nickelous nitrate hexahydrate for taking 31g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 40g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 15 DEG C/min, and 850 DEG C are heated in 100mL/min helium gas jets, is incubated 3 hours then certainly
Room temperature so is cooled to, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in 100mg steps (3), in 100mL/min helium
850 DEG C of insulations are heated in gas air-flow carries out prereduction reaction in 1 hour, then stops being passed through helium, switches to flow velocity for 13mL/
The biogas and flow velocity of min are the carbon dioxide of 4.5mL/min, are investigated under this condition, and how is the activity of catalyst, evaluation result
Such as table 2.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane is 1 with carbon dioxide ratio:1, reaction velocity (GHSV)
9000mL/(gh)。
Embodiment 5.
The preparation of catalyst：
(1) take 350g glucose to be fitted into the round-bottomed flask for filling 1000mL 0.3mol/L sulfuric acid solutions, in temperature 80
DEG C, flow back 10h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, immediately in 100 DEG C of temperature
Under dry 12h and obtain solid A.A is again after maintaining temperature to be 150 DEG C of hydro-thermal process after 18 hours, and cleaning is dry at 100 DEG C
Solid B is obtained after dry 12h.
(2) Nickelous nitrate hexahydrate for taking 26g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 35g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 15 DEG C/min, and 950 DEG C are heated in helium gas jets of the 100mL/min containing 3.5% hydrogen, is protected
Temperature is then naturally cooling to room temperature in 3 hours, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 100mL/min
950 DEG C of insulations are heated in the helium gas jet of 3.5% hydrogen carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 5mL/min to switch to biogas and flow velocity that flow velocity is 15.5mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 2.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity (GHSV) 11000mL/ (gh).
Embodiment 6.
The preparation of catalyst：
(1) 350g glucose is taken to be fitted into the round-bottomed flask for filling 800mL 0.5mol/L sulfuric acid solutions, in 75 DEG C of temperature,
Flow back 8h under conditions of rotating speed 800RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 180 DEG C of hydro-thermal process after 18 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 21g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 33g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 15 DEG C/min, and 1050 DEG C are heated in hydrogen gas streams of the 100mL/min containing 50% acetylene, is protected
Temperature is then naturally cooling to room temperature in 2 hours, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 100mL/min
1050 DEG C of insulations are heated in the hydrogen gas stream of 50% acetylene carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 7.5mL/min to switch to biogas and flow velocity that flow velocity is 18mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 2.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity (GHSV) 13000mL/ (gh).
Embodiment 7.
The preparation of catalyst：
(1) take 350g glucose to be fitted into the round-bottomed flask for filling 600mL 1mol/L sulfuric acid solutions, in temperature 70 C, turn
Flow back 6h under conditions of fast 700RPM, is then cleaned with deionized water to supernatant pH=7, is dried at 100 DEG C of temperature immediately
12h obtains solid A.A again after maintaining temperature to be 160 DEG C of hydro-thermal process after 18 hours, cleaning, after drying 12h at 100 DEG C
Obtain solid B.
(2) Nickelous nitrate hexahydrate for taking 16g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 30g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 15 DEG C/min, and 1100 DEG C are heated in hydrogen gas streams of the 100mL/min containing 20% ethene, is protected
Temperature is then naturally cooling to room temperature in 1 hour, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 100mL/min
1100 DEG C of insulations are heated in the hydrogen gas stream of 20% ethene carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 9mL/min to switch to biogas and flow velocity that flow velocity is 20mL/min, is investigated in the condition
Under, the activity of catalyst is how, evaluation result such as table 2.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and titanium dioxide
Carbon ratio example is 1:1, reaction velocity (GHSV) 15000mL/ (gh).
Table 2
Embodiment 8.
The preparation of catalyst：
(1) 300g sucrose is taken to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L phosphoric acid solutions, in 85 DEG C of temperature,
Flow back 10h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 180 DEG C of hydro-thermal process after 12 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 36g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 32g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 20 DEG C/min, and 850 DEG C are heated in 150mL/min argon streams, is incubated 3 hours then certainly
Room temperature so is cooled to, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in 100mg steps (3), in 150mL/min argons
850 DEG C of insulations are heated in gas air-flow carries out prereduction reaction in 1 hour, then stops being passed through reducing gas, and switching to flow velocity is
The biogas and flow velocity of 18mL/min are the carbon dioxide of 2.5mL/min, are investigated under this condition, and how is the activity of catalyst, comments
Valency result such as table 3.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane is 1 with carbon dioxide ratio:3, reaction velocity
(GHSV)11000mL/(gh)。
Embodiment 9.
The preparation of catalyst：
(1) 300g sucrose is taken to be fitted into the round-bottomed flask for filling 1000mL 0.3mol/L phosphoric acid solutions, in 80 DEG C of temperature,
Flow back 10h under conditions of rotating speed 800RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 150 DEG C of hydro-thermal process after 12 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 31g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 28g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 20 DEG C/min, and 950 DEG C are heated in argon streams of the 150mL/min containing 3.5% hydrogen, is protected
Temperature is then naturally cooling to room temperature in 3 hours, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 150mL/min
950 DEG C of insulations are heated in the argon stream of 3.5% hydrogen carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 4mL/min to switch to biogas and flow velocity that flow velocity is 16.5mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 3.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:2, reaction velocity (GHSV) 11000mL/ (gh).
Embodiment 10.
The preparation of catalyst：
(1) take 300g sucrose to be fitted into the round-bottomed flask for filling 800mL 0.5mol/L phosphoric acid solutions, in 75 DEG C of temperature, turn
Flow back 8h under conditions of fast 700RPM, is then cleaned with deionized water to supernatant pH=7, is dried at 100 DEG C of temperature immediately
12h obtains solid A.A again after maintaining temperature to be 160 DEG C of hydro-thermal process after 12 hours, cleaning, after drying 12h at 100 DEG C
Obtain solid B.
(2) Nickelous nitrate hexahydrate for taking 26g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 24g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 20 DEG C/min, and 1050 DEG C are heated in argon streams of the 150mL/min containing 50% hydrogen, is protected
Temperature is then naturally cooling to room temperature in 2 hours, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 150mL/min
1050 DEG C of insulations are heated in the argon stream of 50% hydrogen carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 5mL/min to switch to biogas and flow velocity that flow velocity is 15.5mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 3.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity (GHSV) 11000mL/ (gh).
Embodiment 11.
The preparation of catalyst：
(1) take 300g sucrose to be fitted into the round-bottomed flask for filling 600mL 1mol/L phosphoric acid solutions, in temperature 70 C, rotating speed
Flow back 6h under conditions of 700RPM, is then cleaned with deionized water to supernatant pH=7, dries 12h at 100 DEG C of temperature immediately
Obtain solid A.A again after maintaining temperature to be 180 DEG C of hydro-thermal process after 12 hours, cleaning, after drying 12h at 100 DEG C
Solid B.
(2) Nickelous nitrate hexahydrate for taking 21g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 20g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 20 DEG C/min, and 1100 DEG C are heated in hydrogen gas streams of the 150mL/min containing 3.5% methane, is protected
Temperature is then naturally cooling to room temperature in 1 hour, last gained sample E, as carbon load nickel metallic catalyst.
The evaluation of catalyst：
Take in the quartz tube reactor of 1 inch of external diameter of catalyst feeding obtained in 100mg steps (3), contain in 150mL/min
1100 DEG C of insulations are heated in the hydrogen gas stream of 3.5% methane carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Reducing gas is passed through, it is the carbon dioxide of 9mL/min to switch to biogas and flow velocity that flow velocity is 11.5mL/min, is investigated at this
Under part, how is the activity of catalyst, evaluation result such as table 3.Its reaction condition：850 DEG C of temperature, pressure 5psi, methane and dioxy
It is 2 to change carbon ratio example:1, reaction velocity (GHSV) 11000mL/ (gh).
Table 3
Embodiment 12.
The preparation of catalyst：
(1) 200g charcoals are taken to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L salpeter solutions, in 85 DEG C of temperature,
Flow back 12h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 180 DEG C of hydro-thermal process after 24 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 42g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 23g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 950 DEG C are heated in the stream of nitrogen gas of 50mL/min, is incubated 3 hours then certainly
Room temperature so is cooled to, last gained sample E, as carbon load nickel metallic catalyst.
The sign of catalyst：
Tem analysis, acquired results are carried out to gained carbon load nickel metallic catalyst as shown in figure 1, result display carbon source
Graphitization, and carbon is wrapped in nickel metallic perimeter.
XRD analysis, acquired results are carried out as shown in Fig. 2 this result shows list to gained carbon load nickel metallic catalyst
The formation of matter nickel metal and the graphitization of carbon source.
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in 100mg steps (3), 50mL/min's
950 DEG C of insulations are heated in stream of nitrogen gas carries out prereduction reaction in 1 hour, is then cooled to 800 DEG C, and stopping is passed through nitrogen, cuts
Change into flow velocity be 15.5mL/min biogas and flow velocity for 5mL/min carbon dioxide, investigate under this condition, catalyst it is steady
It is qualitative how, evaluation result such as Fig. 3.Its reaction condition：800 DEG C of temperature, pressure 5psi, methane is 1 with carbon dioxide ratio:1,
Reaction velocity (GHSV) 11000mL/ (gh).
Embodiment 13.
The preparation of catalyst：
(1) 200g charcoals are taken to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L salpeter solutions, in 85 DEG C of temperature,
Flow back 12h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 180 DEG C of hydro-thermal process after 24 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 40g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 24g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 950 DEG C are heated in the stream of nitrogen gas of 50mL/min, is incubated 3 hours then certainly
Room temperature so is cooled to, last gained sample E, as carbon load nickel metallic catalyst.
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 100mg embodiments 13 (3),
950 DEG C of insulations are heated in the stream of nitrogen gas of 50mL/min carries out prereduction reaction in 1 hour, is then cooled to 800 DEG C, stops logical
Enter nitrogen, switch to flow velocity for 15.5mL/min biogas and flow velocity are the carbon dioxide of 5mL/min, investigate under this condition, urge
How is the activity of agent, evaluation result such as Fig. 4.Its reaction condition：800 DEG C of temperature, pressure 5psi, methane and carbon dioxide ratio
It is 1:1, reaction velocity (GHSV) 14000mL/ (gh).
Embodiment 14
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 100mg embodiments 13 (3),
950 DEG C of insulations are heated in the stream of nitrogen gas containing 3.5% hydrogen of 50mL/min carries out prereduction reaction in 1 hour, then cooling
To 850 DEG C, stopping is passed through the nitrogen containing 3.5% hydrogen, switches to flow velocity for 15.5mL/min natural gases and flow velocity are 5mL/min
Carbon dioxide, investigate under this condition, catalyst activity how, evaluation result such as Fig. 5.Its reaction condition：Temperature 850
DEG C, pressure 10psi, methane is 1 with carbon dioxide ratio:1, reaction velocity (GHSV) 6000mL/ (gh).
Embodiment 15
The preparation of catalyst：
(1) take 200g activated carbons to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L phosphoric acid solutions, in temperature 85
DEG C, flow back 12h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, immediately in 100 DEG C of temperature
Under dry 12h and obtain solid A.A is again after maintaining temperature to be 180 DEG C of hydro-thermal process after 24 hours, and cleaning is dry at 100 DEG C
Solid B is obtained after dry 12h.
(2) Nickelous nitrate hexahydrate for taking 30g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 28g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 950 DEG C are heated in the stream of nitrogen gas of 50mL/min, is incubated 3 hours then certainly
Room temperature so is cooled to, last gained sample E, as carbon load nickel metallic catalyst.
At a temperature of differential responses, estimation of stability of the catalyst in biogas catalytic reforming reaction：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in 100mg steps (3), 50mL/min's
950 DEG C of insulations are heated in hydrogen gas stream containing 3.5% ethene carries out prereduction reaction in 1 hour, be then cooled to 750 respectively,
800th, 850 DEG C, stopping is passed through the hydrogen containing 3.5% ethene, switches to 15.5mL/min natural gases and 5mL/min carbon dioxide,
Investigate under this condition, how is the activity of catalyst, evaluation result such as table 4.Its reaction condition：Pressure 5psi, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity (GHSV) 14000mL/ (gh).
Table 4
Embodiment 16
The preparation of catalyst：
(1) 200g carbon blacks are taken to be fitted into the round-bottomed flask for filling 1000mL 0.1mol/L hydrochloric acid solutions, in 85 DEG C of temperature,
Flow back 12h under conditions of rotating speed 900RPM, is then cleaned with deionized water to supernatant pH=7, is done at 100 DEG C of temperature immediately
Dry 12h obtains solid A.Again after maintaining temperature to be 180 DEG C of hydro-thermal process after 24 hours, cleaning dries 12h to A at 100 DEG C
Solid B is obtained afterwards.
(2) Nickelous nitrate hexahydrate for taking 50g is dissolved in the deionized water of 200mL, and stirring obtains solution C to being completely dissolved.
Then take in the solid B addition solution Cs obtained by 20g steps (1), after standing 24h at room temperature, 12h is dried at 100 DEG C, obtain solid
D。
(3) take the crystal reaction tube that gained solid D in 300mg steps (2) sends into 1 inch of external diameter, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 950 DEG C are heated in the hydrogen gas stream containing 3.5% acetylene of 50mL/min, is protected
Temperature is then naturally cooling to room temperature in 3 hours, last gained sample E, as carbon load nickel metallic catalyst.
Under different air speeds, estimation of stability of the catalyst in natural gas catalytic reforming reaction：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in 100mg steps (3), 50mL/min's
950 DEG C of insulations are heated in hydrogen gas stream containing 3.5% ethene carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Only be passed through the hydrogen of 3.5% ethene, switch to 15mL/min natural gases and 5mL/min carbon dioxide, investigate air speed be 4000,
6000th, under conditions of 8000 and 10000mL/ (gh), how is the activity of catalyst, evaluation result such as table 5.Its reaction condition：Temperature
850 DEG C of degree, pressure 10psi, methane is 1 with carbon dioxide ratio:1.
Table 5
Embodiment 17.
The preparation of catalyst：
(1) Nickelous nitrate hexahydrate for taking 281g is dissolved in the deionized water of 500mL, and stirring obtains solution C to being completely dissolved.
Then take in the activated carbon dress addition solution C of 500g steps (1), after stirring 30min, 24h is stood at room temperature, then at 100 DEG C
12h is dried, solid D is obtained.
(2) take in 100g steps (2) in the crystal reaction tube of gained solid D 1 inch of external diameters of feeding, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 900 DEG C are heated in 150mL/min stream of nitrogen gas, is incubated 3 hours then certainly
So cool to room temperature, last gained sample E, as carbon load nickel metallic catalyst.
The sign of catalyst：
Tem analysis, acquired results are carried out to gained carbon load nickel metallic catalyst as shown in fig. 6, result display carbon source
Graphitization, and carbon is wrapped in nickel metallic perimeter.
Polycrystalline diffraction is carried out to gained carbon load nickel metallic catalyst, acquired results are as shown in Figure 7, it is shown that nickel metal list
The formation of matter and carrier carbon.
Embodiment 18.
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 50g embodiments 17 (2),
900 DEG C of insulations are heated in the stream of nitrogen gas of 150mL/min carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Nitrogen is passed through, flow velocity is switched to for 15.5mL/min methane and flow velocity are the carbon dioxide of 5mL/min, investigated under this condition,
How is the activity of catalyst, evaluation result such as Fig. 8.Its reaction condition：850 DEG C of temperature, pressure 0.1Mpa, methane and carbon dioxide
Ratio is 1:1, reaction velocity 6000h-1。
Embodiment 19.
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 50g embodiments 17 (2),
900 DEG C of insulations are heated in the stream of nitrogen gas of 150mL/min carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, stops
Nitrogen is passed through, flow velocity is switched to for 15.5mL/min natural gases and flow velocity are the carbon dioxide of 5mL/min, investigated in the condition
Under, the activity of catalyst is how, evaluation result such as Fig. 9.Its reaction condition：850 DEG C of temperature, pressure 0.1Mpa, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity 6000h-1。
Embodiment 20.
The preparation of catalyst：
(1) Nickelous nitrate hexahydrate for taking 350g is dissolved in the deionized water of 600mL, and stirring obtains solution C to being completely dissolved.
Then take in the activated carbon dress addition solution C of 600g steps (1), after stirring 30min, 24h is stood at room temperature, then at 100 DEG C
12h is dried, solid D is obtained.
(2) take in 100g steps (2) in the crystal reaction tube of gained solid D 1 inch of external diameters of feeding, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 1100 DEG C are heated in 50mL/min helium gas jets, is incubated 1 hour then certainly
So cool to room temperature, last gained sample E, as carbon load nickel metallic catalyst.
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 50g embodiments 20 (2), in 50mL/
1100 DEG C of insulations are heated in the helium gas jet of min carries out prereduction reaction in 1 hour, is then cooled to 850 DEG C, and stopping is passed through helium
Gas, switches to flow velocity for 15.5mL/min methane and flow velocity are the carbon dioxide of 5mL/min, investigates under this condition, catalyst
Activity how, evaluation result such as table 6.Its reaction condition：850 DEG C of temperature, pressure 0.1Mpa, methane is with carbon dioxide ratio
1:1, reaction velocity 4000h-1。
Embodiment 21.
The preparation of catalyst：
(1) Nickelous nitrate hexahydrate for taking 180g is dissolved in the deionized water of 400mL, and stirring obtains solution C to being completely dissolved.
Then take in the activated carbon dress addition solution C of 400g steps (1), after stirring 30min, 24h is stood at room temperature, then at 100 DEG C
12h is dried, solid D is obtained.
(2) take in 100g steps (2) in the crystal reaction tube of gained solid D 1 inch of external diameters of feeding, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 900 DEG C, insulation 2 are heated in hydrogen gas streams of the 50mL/min containing 10% methane
Hour, then natural cooling was cooled to room temperature, last gained sample E, as carbon load nickel metallic catalyst.
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 50g embodiments 21 (2), in 50mL/
Min is heated to 900 DEG C of insulations and carries out prereduction reaction in 1 hour in the hydrogen gas stream containing 10% methane, is then cooled to 850 DEG C,
Stopping is passed through the hydrogen containing 10% methane, switches to flow velocity for 15.5mL/min methane and flow velocity are the carbon dioxide of 5mL/min,
Investigate under this condition, how is the activity of catalyst, evaluation result such as table 6.Its reaction condition：850 DEG C of temperature, pressure
0.1Mpa, methane is 1 with carbon dioxide ratio:1, reaction velocity 8000h-1。
Embodiment 22.
The preparation of catalyst：
(1) Nickelous nitrate hexahydrate for taking 500g is dissolved in the deionized water of 500mL, and stirring obtains solution C to being completely dissolved.
Then take in the activated carbon dress addition solution C of 500g steps (1), after stirring 30min, 24h is stood at room temperature, then at 100 DEG C
12h is dried, solid D is obtained.
(2) take in 100g steps (2) in the crystal reaction tube of gained solid D 1 inch of external diameters of feeding, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 900 DEG C, insulation 1 are heated in hydrogen gas streams of the 50mL/min containing 10% ethene
Hour, then natural cooling was cooled to room temperature, last gained sample E, as carbon load nickel metallic catalyst.
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 50g embodiments 22 (2), in 50mL/
Min is heated to 900 DEG C of insulations and carries out within 1 hour prereduction reaction in the hydrogen gas stream containing 10% ethene, stopping is passed through containing 10% second
The hydrogen of alkene, switches to flow velocity for 15.5mL/min methane and flow velocity are the carbon dioxide of 5mL/min, investigates under this condition,
How is the activity of catalyst, evaluation result such as table 6.Its reaction condition：900 DEG C of temperature, pressure 0.1Mpa, methane and carbon dioxide
Ratio is 1:1, reaction velocity 6000h-1。
Embodiment 23.
The preparation of catalyst：
(1) Nickelous nitrate hexahydrate for taking 500g is dissolved in the deionized water of 500mL, and stirring obtains solution C to being completely dissolved.
Then take in the activated carbon dress addition solution C of 500g steps (1), after stirring 30min, 24h is stood at room temperature, then at 100 DEG C
12h is dried, solid D is obtained.
(2) take in 100g steps (2) in the crystal reaction tube of gained solid D 1 inch of external diameters of feeding, using temperature programmed control plus
Pyrotube furnace, heating rate is 10 DEG C/min, and 1000 DEG C, insulation are heated in stream of nitrogen gas of the 50mL/min containing 20% acetylene
Subsequent natural cooling is cooled to room temperature within 2.5 hours, last gained sample E, as carbon load nickel metallic catalyst.
The estimation of stability of catalyst：
In taking the quartz tube reactor of 1 inch of the external diameter of feeding of catalyst obtained in the step of 50g embodiments 22 (2), in 50mL/
Min is heated to 1000 DEG C of insulations and carries out within 0.5 hour prereduction reaction in the stream of nitrogen gas containing 20% acetylene, stopping is passed through containing 20%
The nitrogen of acetylene, switches to flow velocity for 15.5mL/min methane and flow velocity are the carbon dioxide of 5mL/min, investigates in the condition
Under, the activity of catalyst is how, evaluation result such as table 6.Its reaction condition：850 DEG C of temperature, pressure 0.1Mpa, methane and dioxy
It is 1 to change carbon ratio example:1, reaction velocity 6000h-1。
Table 6
Catalyst of the invention is that, with Ni as active component, carbon is carrier, and carbon load nickel metal is synthesized with carbothermic method
Catalyst.The characteristics of catalyst shows high catalytic efficiency to 750~850 DEG C of biogas catalytic reforming reactions, and have
Good stability.The present invention has following features：
In (1) 750~850 DEG C of biogas catalytic reforming reaction, up to 70~90%, carbon dioxide turns for the conversion ratio of methane
Rate is up to 60~80%；
In (2) 750~850 DEG C of biogas catalytic reforming reactions, its hydrogen product is with the molar ratio range of carbon monoxide
0.90~0.97.
In (3) 750~850 DEG C of methane dry reforming reactions, the conversion ratio of methane is up to 50~97%, the conversion of carbon dioxide
Rate is up to 70~98%.
In (4) 800 DEG C of biogas catalytic reforming reactions, the stability of catalyst at least 1000 hours.
At (5) 800 DEG C, the biogas catalytic reforming of 1000 hours is prepared in synthesis gas reaction, and methane and carbon dioxide turns
Rate can be stablized 85% and 75% respectively.
At (6) 850 DEG C, the natural gas catalytic reforming of 1000 hours is prepared in synthesis gas reaction, methane and carbon dioxide
Conversion ratio can be stablized 89% and 94% respectively.
(7) the catalyst carbon source carrier raw material is cheap and readily available, and the catalyst nickel for preparing is uniformly dispersed, and activity is high,
The recyclable recycling of catalyst after good stability, and use, not only reduces cost but also had economized on resources.
The above is the preferred embodiment of the present invention, can not limit the right model of the present invention with this certainly
Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, may be used also
To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.
Claims (6)
1. a kind of preparation method of carbon load nickel metallic catalyst, it is characterised in that comprise the following steps：
The pretreatment of step one, carbon source：By the nitric acid of carbon source and 0.1~1mol/L, sulfuric acid or phosphoric acid solution by 200~
350g：The ratio mixing of 400~1000mL, filters, filter residue deionized water after the 6~12h that flowed back at being 70~85 DEG C in temperature
Cleaning is until washing lotion pH=7；Solid A is then obtained after 100~110 DEG C of 8~12h of drying, solid A is under the conditions of 150~180 DEG C
12~24h of insulation, cleaning obtains solid B after 100~110 DEG C of 8~12h of drying；
The preparation of step 2, nickel-base catalyst presoma：Nickel compound containing is dissolved in deionized water, stirring is to being completely dissolved
To nickeliferous 0.2~3.5mol/L solution Cs, then solid B or carbon source are added with B or carbon source in equal volume or in the solution C of equivalent,
After standing 12~24h at room temperature, in 100~110 DEG C of 8~12h of drying, solid D is obtained；
The preparation of step 3, carbon load nickel metallic catalyst：Using carbothermic method, solid D is placed in not oxygenous gas
1~5 hour is incubated in air-flow, and after being heated to 700~1100 DEG C, room temperature is then naturally cooling to, last gained sample E, i.e.,
It is carbon load nickel metallic catalyst.
2. the preparation method of carbon load nickel metallic catalyst as claimed in claim 1, it is characterised in that：In step one, carbon source
It is at least one in glucose, fructose, cellobiose, sucrose, starch, cellulose, activated carbon, carbon black.
3. the preparation method of carbon load nickel metallic catalyst as claimed in claim 1, it is characterised in that：It is described in step one
Acid solution is nitric acid, hydrochloric acid, sulfuric acid or the phosphorus aqueous acid of 0.1~1mol/L.
4. the preparation method of carbon load nickel metallic catalyst as claimed in claim 1, it is characterised in that：It is described in step 2
Nickel compound containing is Nickelous nitrate hexahydrate, nickel sulfide, nickel sulfate, nickelous carbonate, nickel hydroxide, hydroxy acid nickel and nickel halogenide it is any one
Kind.
5. the preparation method of carbon load nickel metallic catalyst as claimed in claim 1, it is characterised in that：It is described not oxygenous
Gas is the one kind in nitrogen, helium, hydrogen, methane, ethene, acetylene.
6. a kind of carbon load nickel metallic catalyst, it is characterised in that any described carbon load nickel gold of usage right requirement 1 to 5
The preparation method of metal catalyst is prepared from.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ATE192997T1 (en) * | 1994-07-13 | 2000-06-15 | Zhaolong Zhang | A STABLE AND ACTIVE NICKEL CATALYST FOR THE CARBON DIOXIDE REFORMATION OF METHANE TO SYNTHESIS GAS |
| US20040077496A1 (en) * | 2002-07-26 | 2004-04-22 | Shizhong Zhao | Catalyst |
| CN102745648A (en) * | 2011-04-22 | 2012-10-24 | 太原理工大学 | Preparation method of catalyst for producing synthetic gas by methane and carbon dioxide reformation |
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| CN104741115A (en) * | 2013-12-31 | 2015-07-01 | 西北大学 | Method for preparing palladium carbon catalyst |
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| CN106824200A (en) * | 2016-12-27 | 2017-06-13 | 武汉科技大学 | A kind of carbon load nickel metallic catalyst and preparation method thereof |
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2016
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| CN108097255A (en) * | 2016-12-27 | 2018-06-01 | 武汉科技大学 | It is a kind of for porous carbon frame nickel-base catalyst of CO 2 reforming reaction and preparation method thereof and application method |
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| CN110732328A (en) * | 2018-07-23 | 2020-01-31 | 武汉科技大学 | multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof |
| CN110732328B (en) * | 2018-07-23 | 2023-09-26 | 武汉科技大学 | Multi-core shell structure nickel-based catalyst for carbon dioxide reforming reaction and preparation method and application thereof |
| CN110071300A (en) * | 2019-04-28 | 2019-07-30 | 三峡大学 | A kind of preparation method of transition metal/nitrogen-doped carbon fiber elctro-catalyst |
| CN110071300B (en) * | 2019-04-28 | 2021-10-01 | 三峡大学 | Preparation method of transition metal/nitrogen-doped carbon fiber electrocatalyst |
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| CN108097255A (en) | 2018-06-01 |
| CN108097255B (en) | 2021-03-23 |
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