CN106391029A - Preparation method and application of carbon nanofiber-bimetal composite catalyst - Google Patents
Preparation method and application of carbon nanofiber-bimetal composite catalyst Download PDFInfo
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- CN106391029A CN106391029A CN201610920829.2A CN201610920829A CN106391029A CN 106391029 A CN106391029 A CN 106391029A CN 201610920829 A CN201610920829 A CN 201610920829A CN 106391029 A CN106391029 A CN 106391029A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000002407 reforming Methods 0.000 claims abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 239000002905 metal composite material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 150000001447 alkali salts Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 238000006057 reforming reaction Methods 0.000 claims description 6
- 230000003993 interaction Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical class [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 6
- -1 alkaline earth metal salt Chemical class 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 238000005502 peroxidation Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000010041 electrostatic spinning Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 4
- 229940068984 polyvinyl alcohol Drugs 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a preparation method and an application of a carbon nanofiber-bimetal composite catalyst. Specifically, alkaline earth metal salt is mixed in a spinning solution for spinning, proto-filaments are mixed with nitric acid, and transition metal salt is impregnated. Obtained bimetal composite proto-fibers are subjected to peroxidation and carbonization, and the carbon nanofiber-bimetal composite catalyst is prepared. Active components are fixed under the mutual action of alkaline earth metal and transition metal embedded in the fibers at the high temperature during spinning, high dispersion and high-temperature sintering resistance of active components on the carrier surface are guaranteed, and meanwhile, the conversion rate is ensured to be about 95% at 800 DEG C by using the characteristic that alkaline earth metal adsorbs activated CO2 in the CH4/CO2 reforming process.
Description
Technical field
The invention belongs to composite catalyst preparation and gasification reforming art, it is related to a kind of carbon nano-fiber/bimetallic and is combined
The preparation method of catalyst and its in CH4/CO2Application in reforming process.
Background technology
Remain high and rugged environment pollution further with petroleum resources increasingly depleted, oil price, exploitation cleaning,
Cheap fuel source become one need badly faced by problem.Fuel the cleanest at present is natural gas, and its pollution is little (about
The 1/800 of coal, the 1/40 of oil), it is also preferable industrial chemicals, and methane is the main component (90%) of natural gas.Its
Stable chemical nature, has environmental friendliness, inexpensively, the advantage such as resource abundance.It rationally utilizes and has been subject to various countries' research work
The extensive concern of person.Meanwhile, the global extreme climate problem that the discharge of great amount of carbon dioxide is brought also has caused section
The strong interest of educational circles, national governments and the public.For this reason, how rationally to utilize CH4, reduce CO2Emission problem be increasingly becoming
The top-priority problem in countries in the world.Synthesizing gas by reforming methane with co 2 is economical and environmentally friendly worth because it is potential and forms
Emphasis for research both at home and abroad in recent ten years.This process is by CH4And CO2Two kinds of abundant greenhouse gases are converted into important change
Work material synthesis gas, on the one hand decrease CO2Discharge, improves the utilization rate of methane resource simultaneously.By this reaction gained
Synthesis gas hydrogen charcoal is relatively low frequently, more suitable for F-T synthesis, alleviation industrial chemicals and energy crisis is significant.
In recent decades, Chinese scholars have been carried out the research work of detailed system to methane reforming with carbon dioxide
Make, mainly in terms of the carrier of catalyst, active component, auxiliary agent, carbon distribution and reaction mechanism etc., carry out extensive and deep grinding
Study carefully and inquire into.Because noble metal has higher carbon dissolution than common metal, show preferably activity and anti-carbon performance, state
Outer more to noble metal catalyst research.And domestic from economic benefit consideration, research is then concentrated mainly on non-precious metal catalyst
On, the research to non-precious metal catalyst shows, their active orders Ni to reforming reaction>Co>Cu>Fe.Because Ni has
Relatively high activity and low price, thus cause the attention of numerous researcheres.But supported nickel catalyst have one very big
Shortcoming：Carbon distribution makes catalyst activity reduce.And during the course of the reaction, due to the rising of temperature, easily sinter.Therefore,
Developing new anti-carbon deposit reforming catalyst and improve operating condition reducing carbon deposit is highly important research direction.
Because Carbon Materials have many excellent properties, researcher starts with Carbon Materials (activated carbon, CNT, semicoke)
Do study on the carrier methane reforming reaction by using carbon dioxide.The higher mechanical strength of carbon fiber, thermally-stabilised and larger specific surface area makes
It starts to be taken seriously as catalyst carrier.Metal can be made very using the fibril that method of electrostatic spinning prepares alkaline including earth metal
Good fixation, is dispersed in carrier surface, can effectively suppress its sintering in hot stage.But, CH4/CO2Reforming reaction one
As occur during carrier surface, electrostatic spinning, metallic is dispersed on fibre structure so that surface metal levels
Relatively low.By infusion process, active metal component is supported on the fibril containing alkaline-earth metal, both can be contained using surface height
The active center of amount ensures the high efficiency of reaction, again can be using the interaction between bimetallic and alkaline-earth metal to CH4, CO2
Surface adsorption effect, be capable of significantly more efficient improve the service life of catalyst and activity, reduce sintering of catalyst.
Content of the invention
Technical problem：The invention aims to solving existing catalyst in CH4/CO2Easy-sintering in reforming process, makes
With the life-span is low and infusion process preparation process in easily cause carrier duct and block the shortcomings of, a kind of carbon nano-fiber/bimetallic is provided
The preparation method of composite catalyst, prepares the nanofiber precursor of alkaline including earth metal by method of electrostatic spinning, by precursor mixing nitre
Acid, transition metal salt carries out impregnating, washs to neutral, drying.Gained bimetallic is combined fibril and obtains final product after pre-oxidation, carbonization
Carbon nano-fiber/double-metal composite catalyst.Gained catalyst maintains the flourishing pore structure in carbon fiber composite surface and height
The advantage of surface area, make use of alkaline-earth metal to CH in application process4, CO2Preferably absorption property, the height in active center
Effect catalytic action and the interphase interaction anti-carbon of bimetallic, the advantage of anti-sintering.
Technical scheme：A kind of preparation method of carbon nano-fiber-double-metal composite catalyst of the present invention is using being embedded in fibre
The interaction when alkaline-earth metal in dimension and transition metal high temperature fixing active component is it is ensured that carrier surfactant component
High degree of dispersion and anti-agglutinatting property, utilize alkaline-earth metal adsorption activation CO simultaneously2Improve reforming efficiency, specifically include following steps：
1). by alkali salt, lignin, organic solvent, 5～15wt% polyvinyl alcohol, at 60 DEG C～90 DEG C
Lower stirring 0.5～3h is configured to the spinning liquid of alkaline including earth metal；
2). it is 18～22KV in operating voltage, the flow velocity of spinning liquid is 0.4～1.5ml/h, accepts the spinning for 15cm for the distance
It is spun into the composite nano fiber precursor of alkaline including earth metal salt under the conditions of silk；
3). more above-mentioned composite fiber precursor mixed nitrate, transition metal salt solution are carried out impregnating 6～24h, be evaporated rear institute
Obtain complex and be 150～270 DEG C in temperature, pre-oxidation treatment 3～10h under air conditionses, it is 600～900 DEG C in temperature, nitrogen
Carbon nano-fiber-double-metal composite catalyst is obtained after carbonization 1～2h under atmosphere.
Wherein:
Described alkali salt is Ba, one of Mg, Ca.
Described organic solvent includes acetic acid, one of ethanol or DMF solution.
Described by alkali salt, lignin, organic solvent, 5～15wt% polyvinyl alcohol, its mixed proportion
For alkali salt：Lignin：Organic solvent：5～15wt% polyvinyl alcohol=0.01～2wt%：5g：15ml：5ml.
Step 3) in transition metal include in Cu, Fe, Mn, Ni, In or Co any one.
The present invention also resides in carbon nano-fiber-double-metal composite catalyst in CH4/CO2Application in reforming process, specifically
Comprise the following steps：
1.) take 0.2～1g composite catalyst in fixed bed reactors, nitrogen atmosphere be warming up to 500～600 DEG C,
It is passed through hydrogen reducing 0.5～1.5h；
2., after) reduction terminates, it is passed through CH4：CO2：N2=1：1：1, total flow is the gaseous mixture of 150～300ml/min,
Carry out reforming reaction at 800 DEG C, gas collection its catalytic effect of gas chromatographic analysiss.The present invention by alkaline-earth metal, transition metal with
Lignin-base nano carbon fibre passes through fabricated in situ and follow-up dipping forms carbon nano-fiber/bimetallic complex, composite fibre
Prepare the catalyst of high-specific surface area and catalytic performance by pre-oxidation, carbonization and activation.Described organic solvent is as spinning
The solvent of silk liquid, can substantially increase the electric conductivity of spinning liquid.In dipping process, added nitric acid enables transition metal to bear well
Being loaded on carrier, the pore structure of fiber surface being effectively increased so that generating in fiber surface in follow-up carbonisation simultaneously
Flourishing pore structure and high-specific surface area.
The present invention is to CH4/CO2Reforming reaction has good catalytic effect, and this invention needed raw material is cheap and easy to get, preparation
Method is simple to operation, and this invention provides preferable thinking to metal-based catalyst high temperature easy-sintering.
Beneficial effect：
(1) adopt lignin as raw material, it is possible to achieve Liginon Resourceization utilizes, and reduces being prepared into of carbon nano-fiber
This, remarkable in economical benefits；
(2) using first electrostatic spinning, the method impregnating afterwards prepares the catalyst of bimetallic load, more general infusion process metal
Using less, more rationally.And the homodisperse metallic in surface being formed in spinning process can be used as impregnating below
In journey, the load centre of transition metal, so that required active component also can be dispersed in carrier surface, reduces duct and blocks up
Plug, modifies the bimetallic in material surface, not only maintains the flourishing pore structure in carbon fiber composite surface and high-specific surface area
Feature, and highlight its good catalysis activity, embody difunctional feature.
(3) gained carbon nano-fiber/double-metal composite catalyst of the present invention in fixed-bed catalytic device to CH4/CO2Instead
Catalytic reforming reaction should be carried out, the presence of alkaline-earth metal on carbon fiber has beneficial to CH4, CO2Surface adsorption, the depositing of transition metal
Significantly improve in the conversion ratio making reactant.The fixation of the interaction between bimetallic and carbon fiber makes high temperature
Stage still keeps good catalytic effect and anti-agglutinatting property.
Brief description
Fig. 1 show the N2 adsorption curve that the present invention prepares carbon nano-fiber/bimetallic complex.
Specific embodiment
Described below is the preferred embodiment of the present invention it is noted that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Case study on implementation 1
(1) first weigh a certain amount of magnesium sulfate to be dissolved in acetic acid solution, then weigh the mixing of 3～5g lignin, will be above-mentioned mixed
Close solution heated and stirred, setting outlet temperature is 60～80 DEG C, adds the 10wt%'s of 3～5mL in whipping process with needle tubing
Poly-vinyl alcohol solution.Close heater after continuing stirring a period of time afterwards, be naturally cooling to room temperature and be transferred in syringe；
(2) above-mentioned spinning liquid is carried out on electrostatic spinning machine spinning operation, by the nanofiber and the Ni (NO that are obtained3)2Mixed
Close steeped overnight, be evaporated.Then it is washed to neutrality, dry.
(3) complex after the drying of above-mentioned gained is placed in horizontal pipe stove, is 150mL/min in air velocity, rise
Warm speed is constant temperature pre-oxidation a period of time after being warming up to 200～250 DEG C under 0.3～1 DEG C/min, after being down to room temperature, in nitrogen
Atmosphere encloses middle intensification carbonization；
(4) go above-mentioned prepared carbon nano-fiber/bimetallic catalyst to take to be placed in right amount in fixed-bed catalytic device,
Carry out CH in the case of 800 DEG C4/CO2Reform and test.
Claims (7)
1. a kind of preparation method of carbon nano-fiber-double-metal composite catalyst is it is characterised in that using the alkali being embedded on fiber
The fixing active component of interaction when earth metal and transition metal high temperature is it is ensured that the high degree of dispersion of carrier surfactant component
And anti-agglutinatting property, utilize alkaline-earth metal adsorption activation CO simultaneously2Improve reforming efficiency, specifically include following steps：
1）. by alkali salt, lignin, organic solvent, 5 ~ 15wt% polyvinyl alcohol, at 60 DEG C ~ 90 DEG C stir
0.5 ~ 3h is configured to the spinning liquid of alkaline including earth metal；
2）. it is 18 ~ 22KV in operating voltage, the flow velocity of spinning liquid is 0.4 ~ 1.5ml/h, accepts the spinning bar for 15cm for the distance
It is spun into the composite nano fiber precursor of alkaline including earth metal salt under part；
3）. more above-mentioned composite fiber precursor mixed nitrate, transition metal salt solution are carried out impregnating 6 ~ 24h, be evaporated rear gained multiple
Compound is 150 ~ 270 DEG C in temperature, pre-oxidation treatment 3 ~ 10h under air conditionses, is 600 ~ 900 DEG C in temperature, under nitrogen atmosphere
Carbon nano-fiber-double-metal composite catalyst is obtained after carbonization 1 ~ 2h.
2. a kind of carbon nano-fiber-double-metal composite catalyst according to claim 1 preparation method it is characterised in that
Described alkali salt is Ba, one of Mg, Ca.
3. a kind of carbon nano-fiber-double-metal composite catalyst according to claim 1 preparation method it is characterised in that
Described organic solvent includes acetic acid, one of ethanol or DMF solution.
4. a kind of carbon nano-fiber-double-metal composite catalyst according to claim 1 preparation method it is characterised in that
Described by alkali salt, lignin, organic solvent, 5 ~ 15wt% polyvinyl alcohol, its mixed proportion is, alkaline earth gold
Belong to salt：Lignin：Organic solvent：5 ~ 15wt% polyvinyl alcohol=0.01 ~ 2wt%：5g：15ml：5ml.
5. a kind of carbon nano-fiber-double-metal composite catalyst according to claim 1 preparation method it is characterised in that
Step 3）In transition metal include in Cu, Fe, Mn, Ni, In or Co any one.
6. a kind of a kind of carbon nano-fiber-double-metal composite catalyst of employing claim 1 methods described preparation is in CH4/CO2
Application in reforming process.
7. a kind of carbon nano-fiber-double-metal composite catalyst according to claim 6 is in CH4/CO2In reforming process
Application is it is characterised in that specifically include following steps：
1.）Take 0.2 ~ 1g composite catalyst in fixed bed reactors, nitrogen atmosphere is warming up to 500 ~ 600 DEG C, is passed through hydrogen
Gas reduces 0.5 ~ 1.5h；
2.）After reduction terminates, it is passed through CH4：CO2：N2=1：1：1, total flow is the gaseous mixture of 150 ~ 300ml/min, at 800 DEG C
Carry out reforming reaction, gas collection its catalytic effect of gas chromatographic analysiss.
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| CN109364876A (en) * | 2018-11-20 | 2019-02-22 | 东南大学 | A kind of preparation method of biomass carbon-houghite compound |
| CN109652976A (en) * | 2018-12-26 | 2019-04-19 | 宜兴市中碳科技有限公司 | A kind of carbon fibre material for antibacterial |
| CN112624783A (en) * | 2020-12-17 | 2021-04-09 | 西南交通大学 | Preparation method of preoxidized fiber reinforced pantograph slide plate for growing carbon nano tube |
| CN113058603A (en) * | 2021-03-18 | 2021-07-02 | 内蒙古工业大学 | Two-dimensional fully-hydrolyzed carbon nanofiber material and preparation method thereof |
| CN116078441A (en) * | 2023-02-01 | 2023-05-09 | 内蒙古工业大学 | Carbon fiber-based CH 4 -CO 2 Reforming catalyst and method for preparing the same |
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| CN109364876A (en) * | 2018-11-20 | 2019-02-22 | 东南大学 | A kind of preparation method of biomass carbon-houghite compound |
| CN109652976A (en) * | 2018-12-26 | 2019-04-19 | 宜兴市中碳科技有限公司 | A kind of carbon fibre material for antibacterial |
| CN112624783A (en) * | 2020-12-17 | 2021-04-09 | 西南交通大学 | Preparation method of preoxidized fiber reinforced pantograph slide plate for growing carbon nano tube |
| CN112624783B (en) * | 2020-12-17 | 2022-03-25 | 西南交通大学 | Preparation method of preoxidized fiber reinforced pantograph slide plate for growing carbon nano tube |
| CN113058603A (en) * | 2021-03-18 | 2021-07-02 | 内蒙古工业大学 | Two-dimensional fully-hydrolyzed carbon nanofiber material and preparation method thereof |
| CN113058603B (en) * | 2021-03-18 | 2023-01-10 | 内蒙古工业大学 | Two-dimensional fully-hydrolyzed carbon nanofiber material and preparation method thereof |
| CN116078441A (en) * | 2023-02-01 | 2023-05-09 | 内蒙古工业大学 | Carbon fiber-based CH 4 -CO 2 Reforming catalyst and method for preparing the same |
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