CN105862060B - A kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming - Google Patents
A kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming Download PDFInfo
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- CN105862060B CN105862060B CN201610304774.2A CN201610304774A CN105862060B CN 105862060 B CN105862060 B CN 105862060B CN 201610304774 A CN201610304774 A CN 201610304774A CN 105862060 B CN105862060 B CN 105862060B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Abstract
A kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming, the present invention relates to a kind of electrochemical reforming system of methane and carbon dioxide dry reforming and its construction method and application methods, the purpose of the present invention is to solve caused by the limitation of the hot conditions in existing reforming reaction and carbon distribution the problem of catalyst inactivation, present system includes that multiple electrolytic cell thin slices, reactor and external power supply, construction method are：One, electrolytic thin-membrane is prepared by the tape casting；Two, electrode is prepared using silk screen print method and porous electrode is obtained using pore creating material and high-temperature calcination；Three, confluence layer is prepared, electrolytic cell thin slice is obtained after high temperature sintering；Four, electrolytic cell thin slice is connected to power supply as in reactor.The system that the present invention is built has many characteristics, such as methane conversion efficiency high, synthesis gas high selectivity and not carbon distribution, and preparation process is simple, at low cost, easy to operate.The invention belongs to the electrochemical reforming fields of methane and carbon dioxide dry reforming.
Description
Technical field
The present invention relates to a kind of electrochemical reforming system of methane and carbon dioxide dry reforming and its construction method and users
Method.
Background technology
The carbon dioxide dry reforming of methane can produce chemical products with high added-value, be that research both domestic and external is hot in recent ten years
One of point, the process have important theoretical and practical significance.Natural gas proportion in world's energy resource structure increasingly increases.
It is well known that methane and carbon dioxide is two big main greenhouse gases, a certain amount of titanium dioxide is all contained in many natural gases
Carbon, it is respectively 28 that Ru Natu, which receives with the ratio of the methane and carbon dioxide in Allan natural gas,：71 and 75：15.First in natural gas
The utilization of alkane, which generally requires, first removes carbon dioxide, and carbon dioxide is a kind of highly stable compound, thus convert and
Removal certainly will will consume more energy, therefore directly prepare synthesis gas using the reformation of methane and carbon dioxide and receive extensive pass
Note.Synthesis gas is widely used on chemical industry as industrial chemicals, can such as pass through Fischer-Tropsch synthesis and carbonyl
Synthesis can prepare a series of important chemical products such as methanol.
Methane generally passes through three kinds of methods for it is synthesized at present：Steam reforming, methane portion oxidation and methane
Carbon dioxide dry reforming.The hydrogen and carbon monoxide ratio that three kinds of methods generate are respectively 3：1,2：1 and 1：1.It is steamed compared to water
Gas is reformed and the partial oxidation of methane, CO 2 reformation process have the following advantages that：Hydrogen and carbon monoxide ratio in synthesis gas
Example about 1, the raw material that can be synthesized directly as carbonylation synthesis and Fischer-Tropsch, can make up steam reforming and obtain
Synthesis gas in the higher problem of hydrogen-carbon ratio；The carbon dioxide dry reforming of methane can utilize two kinds of methane and carbon dioxide simultaneously
Threaten the greenhouse gases of earth environment；Methane and carbon dioxide dry reforming process has higher reaction heat, can be deposited as energy
Storage media.But due to the inertia of methane and carbon dioxide, it is therefore desirable to select suitable catalyst to activate its conversion process.
CH4With CO2Catalytic reforming reaction temperature is higher and is also easy to produce carbon distribution, this proposes the design of catalyst harsh
Requirement.Therefore, between past 20 years, to CH4With CO2The research of reforming reaction focuses primarily upon in the research to catalyst.
Three activity, selectivity and stability factors are taken into account to the selection needs of catalyst.So far, almost all of transition metal pair
CH4With CO2All oneself was investigated the catalytic effect of reforming reaction.Wherein, Ni, Co, Ru, Rh, Pd, Ir and Pt all can serve as
The catalyst of effect.The anti-carbon of noble metal catalyst is much better than Ni base catalyst, but because Ni base catalyst is cheap, so
The design anti-carbon Ni base catalyst high well with stability is the Main Topics of numerous researchers.Carrier pair
CH4With CO2Catalytic reforming reaction play an important role.Carrier can by its interaction between metallic catalyst of modulation come
The particle size of metallic catalyst is controlled, and then achievees the purpose that enhance catalyst anti-carbon, as MgO thermal stability is good and valence
Lattice are cheap and are widely used as carrier.Plasma also can be used as a kind of effective means of modified catalyst.Corona treatment
Ni base catalyst can be improved Ni in the dispersion degree of carrier surface and enhance the interaction between Ni and carrier, therefore catalyst has height
Catalytic activity and good carbon accumulation resisting ability.
Although researcher is with regard to CH4With CO2Reforming reaction proposes different reaction mechanisms, still, in some committed steps
Held viewpoint is but consistent：CH4With CO2The rate determining step of reforming reaction is really CH4Decomposition reaction, and this reaction is
One reversible reaction；Active O source of species in reforming reaction is in CO2Adsorption-decomposition function, and the generation of this process will be earlier than
CH4Decomposition reaction.If CH can be improved4The rate of this rate-determining steps of decomposition reaction, and generate enough active O objects
Kind, CH4With CO2Total rate of reforming reaction will be improved, thus solve problem above key be how priming reaction
Object.With regard to CH under the conditions of Catalytic processes4CO2For reformation, how to overcome the limitation of hot conditions and avoid urging caused by carbon distribution
Agent inactivation needs two problems solved.
Invention content
The purpose of the present invention is to solve urged caused by the limitation of the hot conditions in existing reforming reaction and carbon distribution
The problem of agent inactivates provides electrochemical reforming system and its construction method and the user of a kind of methane and carbon dioxide dry reforming
Method.
A kind of electrochemical reforming system of methane and carbon dioxide dry reforming of the present invention includes multiple electrolytic cell thin slices, reactor
And external power supply；Multiple electrolytic cell book pieces are parallel in reactor in the horizontal direction, wherein electrolytic cell book piece packet
Electrolytic thin-membrane and 2 porous electrodes are included, the upper and lower surface of electrolytic thin-membrane connects with 2 porous electrodes respectively, more
Pore electrod is connected to by conducting wire with external power supply.
A kind of construction method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present invention is：One, pass through curtain coating
Electrolyte is prepared into electrolytic thin-membrane by method, and then high temperature sintering is molded, and obtains fine and close electrolytic thin-membrane；Two, it uses
Silk screen print method prepares electrode in fine and close electrolytic thin-membrane both sides, then pore creating material and high-temperature calcination is used to obtain porous electricity
Pole；Three, confluence layer is prepared on porous electrode by silk screen print method, electrolytic cell thin slice is then obtained after high temperature sintering；Four, will
N electrolytic cell thin slice is as in reactor, then is connected to external power supply by porous electrode and conducting wire to get to methane titanium dioxide
The electrochemical reforming system of carbon dry reforming, wherein n >=1.
A kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present invention is：By methane and dioxy
Change carbon by volume 1：1 mixing, mixed gas is passed through into the electrochemical reforming system of methane and carbon dioxide dry reforming, i.e., complete
At wherein mixed air air speed ratio is 2000-20000h-1, reaction temperature is 600-900 DEG C, supply voltage 1.0-2.0V.
The electrolytic cell of present system is made of electrolyte, electrode, if power supply is direct current, dioxy occurs in the cathode
Change the dissociation of carbon, generates carbon monoxide and oxonium ion.It is anti-with methane that oxonium ion comes anode under potential effect across electrolyte
Carbon monoxide and hydrogen, while ejected electron should be generated.If power supply is AC power, the electrode of electrolyte both sides sends out interaction
The dry carbon dioxide reforming process of methane is realized in reaction more than life.The activity of oxygen is produced in the present invention in electrochemical reaction
Species are greatly improved the reaction rate of reformation.The Joule heat generated in electrolytic cell in reaction is equally beneficial for reforming process
The generation of reaction.In addition the use of alternating current can eliminate the carbon distribution in reforming reaction, improve the service life of reactor.Therefore
Above structure design solves the problems, such as existing carbon distribution and the work of low-temp reaction object during methane and carbon dioxide dry reforming simultaneously
Change two large problems.
The electrochemical reforming method proposed in the present invention can break through the limitation of the dynamics suffered by conventional catalyst technique, can be low
The reforming reaction that methane is realized under the conditions of temperature, can get higher conversion ratio, solve the problems, such as carbon distribution in reforming reaction and low
The two large problems of the lower activated reactant of temperature.The electrochemical reforming method and reforming system built in invention has methane conversion efficiency
High, synthesis gas high selectivity and the not features such as carbon distribution, and preparation method is simple for process, at low cost, easy to operate.
Description of the drawings
Fig. 1 is electrolytic cell thin slice schematic diagram in the electrochemical reforming system of methane and carbon dioxide dry reforming of the present invention；
Fig. 2 is the front view of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present invention.
Specific implementation mode
Technical solution of the present invention is not limited to the specific implementation mode of act set forth below, further include each specific implementation mode it
Between arbitrary combination.
Specific implementation mode one：A kind of electrochemical reforming system of methane and carbon dioxide dry reforming of present embodiment includes more
A electrolytic cell thin slice, reactor 1 and external power supply 2；Multiple electrolytic cell book pieces are parallel to reaction in the horizontal direction
In device 1, wherein electrolytic cell book piece includes electrolytic thin-membrane 3 and 2 porous electrodes 4, the upper and lower surface of electrolytic thin-membrane 3
Connect respectively with 2 porous electrodes 4, porous electrode 4 is connected to by conducting wire with external power supply 2.
External power supply in present embodiment is direct current or alternating current.
The electrolytic cell of present embodiment system is made of electrolyte, electrode, if power supply is direct current, is occurred in the cathode
The dissociation of carbon dioxide generates carbon monoxide and oxonium ion.Oxonium ion comes anode and first under potential effect across electrolyte
Alkane reaction generates carbon monoxide and hydrogen, while ejected electron.If power supply is AC power, the electrode of electrolyte both sides will be handed over
Reaction more than mutually occurring, realizes the dry carbon dioxide reforming process of methane.It is produced in electrochemical reaction in present embodiment
The active specy of oxygen is greatly improved the reaction rate of reformation.The Joule heat generated in electrolytic cell in reaction is equally beneficial for
The generation of reforming process reaction.In addition the use of alternating current can eliminate the carbon distribution in reforming reaction, improve the use of reactor
Service life.Therefore above structure design solves the problems, such as that there are carbon distribution and low temperature are anti-during methane and carbon dioxide dry reforming simultaneously
Object is answered to activate two large problems.
Specific implementation mode two：The present embodiment is different from the first embodiment in that：Reactor described in 2 is ceramics
Pipe or glass tube.It is other same as the specific embodiment one.
Specific implementation mode three：A kind of structure of the electrochemical reforming system of methane and carbon dioxide dry reforming of present embodiment
Method is：One, electrolyte is prepared by electrolytic thin-membrane by the tape casting, then high temperature sintering is molded, and obtains densification
Electrolytic thin-membrane 3；Two, electrode is prepared in fine and close 3 both sides of electrolytic thin-membrane using silk screen print method, then use pore creating material and
High-temperature calcination obtains porous electrode 4；Three, confluence layer is prepared on porous electrode 4 by silk screen print method, then after high temperature sintering
Obtain electrolytic cell thin slice；Four, by n electrolytic cell thin slice as in reactor 1, then pass through porous electrode 4 and conducting wire and external electricity
The connection of source 2 is to get to the electrochemical reforming system of methane and carbon dioxide dry reforming, wherein n >=1.
The electrochemical reforming method proposed in present embodiment can break through the limitation of the dynamics suffered by conventional catalyst technique, can
The reforming reaction for realizing methane under cryogenic, can get higher conversion ratio, solves the problems, such as the carbon distribution in reforming reaction
With the two large problems of activated reactant under low temperature.The electrochemical reforming method and reforming system built in invention is converted with methane
Efficient, synthesis gas high selectivity and the not features such as carbon distribution, and preparation method is simple for process, at low cost, easy to operate.
Specific implementation mode four：Present embodiment is unlike specific implementation mode three：Electrolytic cell described in step 1
Material is：The ZrO that Y stablizes2The CeO of electrolyte, Sm or Gd doping2, Sc stablize ZrO2Electrolyte, Sr, Mg stablize
LaGaO3Electrolyte, BaCeO3Base electrolyte or BaZrO3It is one or more by a mixture of arbitrary proportions in base electrolyte.
It is other to be the same as the specific implementation mode 3.
Specific implementation mode five：Present embodiment is unlike specific implementation mode three or four：Height described in step 1
The temperature of warm sinter molding is 1200~1600 DEG C.It is other identical as specific implementation mode three or four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode three to five：Described in step 2
Electrode be Ni/YSZ, Ni/ScSZ, Ni/Sm or Gd doping CeO2, Sr and Co doping LaFeO3, Ba and Co doping
SrFeO3, Fe doping SrTiO3, La doping SrMnO3The LaFeO that material, Sr are adulterated3The SrTiO of material, La and Fe doping3、
The SrTiO of Ni doping3, La and Fe doping SrMnO3Material or the SrMoO of Fe doping3It is one or more by arbitrary in material
Than the mixture of composition.It is other identical as one of specific implementation mode three to five.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode three to six：Described in step 2
Pore creating material be starch or graphite.It is other identical as one of specific implementation mode three to six.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode three to seven：Described in step 2
High-temperature calcination temperature be 850~1300 DEG C.It is other identical as one of specific implementation mode three to seven.
Specific implementation mode nine：Unlike one of present embodiment and specific implementation mode three to eight：Described in step 3
Confluence layer be conducting resinl, silver paste, gold paste or platinum slurry.It is other identical as one of specific implementation mode three to eight.
Specific implementation mode ten：Unlike one of present embodiment and specific implementation mode three to nine：Described in step 3
High temperature sintering temperature be 600~850 DEG C.It is other identical as one of specific implementation mode three to nine.
Specific implementation mode 11：Unlike one of present embodiment and specific implementation mode three to ten：Step 4 institute
The reactor stated is ceramic tube or glass tube.It is other identical as one of specific implementation mode three to ten.
Specific implementation mode 12：A kind of electrochemical reforming system of methane and carbon dioxide dry reforming of present embodiment makes
It is with method：By methane and carbon dioxide by volume 1：1 mixing, to the electrochemical reforming system of methane and carbon dioxide dry reforming
In be passed through mixed gas, that is, complete, wherein mixed air air speed ratio be 2000-20000h-1, reaction temperature is 600-900 DEG C, power supply
Voltage is 1.0-2.0V.
Specific implementation mode 13：Present embodiment is unlike specific implementation mode 12：The power supply is straight
Galvanic electricity or alternating current, if power supply is alternating current, frequency range 0.01Hz-1MHz.Other and ten two-phase of specific implementation mode
Together.
Beneficial effects of the present invention are verified by following embodiment：
Embodiment 1
A kind of construction method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present embodiment is：One, using stream
The method of prolonging prepares a diameter of 100 millimeters, the YSZ (Y that thickness is 60 microns2O3Stable ZrO2) electrolyte, it is burnt by 1400 DEG C of high temperature
Knot 4 hours obtains fine and close electrolytic thin-membrane 3；Two, Ni/ is prepared in fine and close 3 both sides of electrolytic thin-membrane using silk screen print method
Then YSZ electrodes use starch as pore creating material, electrode sintering temperature is 1300 DEG C, and sintering time is 4 hours, is obtained porous
Electrode 4；Three, confluence layer is prepared on porous electrode 4 by silk screen print method, electrolytic cell is obtained after being then sintered at 750 DEG C
Thin slice, wherein confluence layer material is silver paste；Four, by 10 electrolytic cell thin slices 3 as in ceramic tube 1, then by porous electrode 4 with
External power supply 2 is connected to, and obtains the electrochemical reforming system of methane and carbon dioxide dry reforming.By volume by methane and carbon dioxide
1：1 mixing, mixed gas is passed through into system, that is, is completed, and wherein mixed air air speed ratio is 3000h-1, reaction temperature is 850 DEG C,
Supply voltage is 1.2V, and methane conversion is 91% after operation 500 hours, and the selectivity of carbon monoxide is 90%, electrolytic cell
1% can be decayed, the polarization resistance of electrolytic cell is 0.60 Ω cm2, and electrode surface is without carbon deposition phenomenon.
Embodiment 2
A kind of construction method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present embodiment is：One, using stream
The method of prolonging prepares a diameter of 100 millimeters, the ScSZ (Sc that thickness is 50 microns2O3Stable ZrO2) electrolyte, by 1550 DEG C of high temperature
Sintering 6 hours obtains fine and close electrolytic thin-membrane 3；Two, it is prepared in fine and close 3 both sides of electrolytic thin-membrane using silk screen print method
(La0.8Sr0.2)0.98FeO3Then electrode uses starch as pore creating material, electrode sintering temperature is 950 DEG C, and sintering time is 4 small
When, obtain porous electrode 4；Three, confluence layer is prepared on porous electrode 4 by silk screen print method, after being then sintered at 750 DEG C
Electrolytic cell thin slice is obtained, wherein confluence layer material is silver paste；Four, by 8 electrolytic cell thin slices 3 as in ceramic tube 1, then by more
Pore electrod 4 is connected to external power supply 2, obtains the electrochemical reforming system of methane and carbon dioxide dry reforming.By methane and titanium dioxide
Carbon by volume 1：1 mixing, mixed gas is passed through into system, that is, is completed, and wherein mixed air air speed ratio is 4000h-1, reaction temperature
Degree is 850 DEG C, supply voltage 1.4V, and methane conversion is 98% after operation 1000 hours, and the selectivity of carbon monoxide is
94%, the polarization resistance of electrolytic cell performance degradation 2%, electrolytic cell is 0.8 Ω cm2, and electrode surface is without carbon deposition phenomenon.
Embodiment 3
A kind of construction method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present embodiment is：One, using stream
The method of prolonging prepares a diameter of 100 millimeters, the SDC (Sm that thickness is 60 microns0.1CeO2) electrolyte, by 1550 DEG C of high temperature sinterings 10
Hour, obtain fine and close electrolytic thin-membrane 3；Two, it is prepared in fine and close 3 both sides of electrolytic thin-membrane using silk screen print method
Sr2Fe1.5Mo0.5O6Then electrode uses starch as pore creating material, electrode sintering temperature is 1300 DEG C, and sintering time is 6 hours,
Obtain porous electrode 4；Three, confluence layer is prepared on porous electrode 4 by silk screen print method, after being then sintered at 750 DEG C
To electrolytic cell thin slice, wherein confluence layer material is silver paste；Four, by 10 electrolytic cell thin slices as in ceramic tube 1, then by porous
Electrode 4 is connected to external power supply 2, obtains the electrochemical reforming system of methane and carbon dioxide dry reforming.By methane and carbon dioxide
By volume 1：1 mixing, mixed gas is passed through into system, that is, is completed, and wherein mixed air air speed ratio is 10000h-1, reaction temperature
Degree is 800 DEG C, applies amplitude 1.2V, and the alternating voltage of 0.1MHz when frequency, methane conversion is 95% after operation 1000 hours,
The selectivity of carbon monoxide is 94%, electrolytic cell performance degradation 1.5%, and the polarization resistance of electrolytic cell is 0.45 Ω cm2, and electrode
Surface is without carbon deposition phenomenon.
Embodiment 4
A kind of construction method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present embodiment is：One, using stream
The method of prolonging prepares a diameter of 100 millimeters, the La that thickness is 200 microns0.9Sr0.1Ga0.8Mg0.2O3Electrolyte, by 1550 DEG C of high temperature
Sintering 6 hours obtains fine and close electrolytic thin-membrane 3；Two, it is prepared in fine and close 3 both sides of electrolytic thin-membrane using silk screen print method
La0.4Sr0.6Ti0.3Fe0.7O3Then electrode uses starch as pore creating material, electrode sintering temperature is 1150 DEG C, and sintering time is
4 hours, obtain porous electrode 4；Three, confluence layer is prepared on porous electrode 4 by silk screen print method, is then burnt at 750 DEG C
Electrolytic cell thin slice is obtained after knot, wherein confluence layer material is silver paste；Four, by 20 electrolytic cell thin slices as in ceramic tube 1, then lead to
It crosses porous electrode 4 to be connected to external power supply 2, obtains the electrochemical reforming system of methane and carbon dioxide dry reforming.By methane and two
Carbonoxide by volume 1：1 mixing, mixed gas is passed through into system, that is, is completed, and wherein mixed air air speed ratio is 15000h-1,
Reaction temperature is 700 DEG C, applies amplitude 1.6V, and the alternating voltage of 50Hz when frequency, methane conversion is after operation 1000 hours
85%, the selectivity of carbon monoxide is 84%, electrolytic cell performance degradation 0.5%, and the polarization resistance of electrolytic cell is 0.85 Ω cm2,
And electrode surface is without carbon deposition phenomenon.
Embodiment 5
A kind of construction method of the electrochemical reforming system of methane and carbon dioxide dry reforming of the present embodiment is：One, using stream
The method of prolonging prepares a diameter of 100 millimeters, the BaCe that thickness is 80 microns0.7Zr0.3O3Electrolyte is small by 1600 DEG C of high temperature sinterings 20
When, obtain fine and close electrolytic thin-membrane 3；Two, it is prepared in fine and close 3 both sides of electrolytic thin-membrane using silk screen print method
Ba0.6Sr0.4Co0.2Fe0.8O3Then electrode uses starch as pore creating material, electrode sintering temperature is 1100 DEG C, and sintering time is
4 hours, obtain porous electrode 4；Three, confluence layer is prepared on porous electrode 4 by silk screen print method, is then burnt at 750 DEG C
Electrolytic cell thin slice is obtained after knot, wherein confluence layer material is silver paste；Four, by 10 electrolytic cell thin slices as in ceramic tube 1, then lead to
It crosses porous electrode 4 to be connected to external power supply 2, obtains the electrochemical reforming system of methane and carbon dioxide dry reforming.By methane and two
Carbonoxide by volume 1：1 mixing, mixed gas is passed through into system, that is, is completed, and wherein mixed air air speed ratio is 8000h-1, instead
It is 800 DEG C to answer temperature, applies amplitude 1.2V, and the alternating voltage of 50Hz when frequency, methane conversion is after operation 2000 hours
95%, the selectivity of carbon monoxide is 90%, electrolytic cell performance degradation 2%, and the polarization resistance of electrolytic cell is 0.25 Ω cm2, and
Electrode surface is without carbon deposition phenomenon.
The electrochemical reforming system of methane and carbon dioxide dry reforming in Examples 1 to 5 is as shown in Fig. 2, wherein electrolytic cell
The schematic diagram of thin slice is as shown in Figure 1, the electrolytic cell of system is made of electrolyte, electrode in embodiment, if power supply is direct current,
The dissociation that carbon dioxide occurs in the cathode, generates carbon monoxide and oxonium ion.Oxonium ion passes through electrolyte under potential effect
It comes anode and generates carbon monoxide and hydrogen, while ejected electron with methane reaction.If power supply is AC power, electrolyte two
Reaction more than interaction generation is realized the dry carbon dioxide reforming process of methane by the electrode of side.Electrochemical reaction in embodiment
In produce oxygen active specy, be greatly improved the reaction rate of reformation.The Joule heat generated in electrolytic cell in reaction is same
Sample is conducive to the generation of reforming process reaction.In addition the use of alternating current can eliminate the carbon distribution in reforming reaction, improve reaction
The service life of device.Therefore above structure design solves the problems, such as that there are carbon distributions during methane and carbon dioxide dry reforming simultaneously
Two large problems are activated with low-temp reaction object.
From embodiment it is found that the electrochemical reforming method proposed in the present invention can break through the power suffered by conventional catalyst technique
Limitation is learned, can realize the reforming reaction of methane under cryogenic, higher conversion ratio is can get, solves in reforming reaction
The two large problems of activated reactant under carbon distribution problem and low temperature.The electrochemical reforming method and reforming system built in invention has
Methane conversion efficiency is high, synthesis gas high selectivity and not features such as carbon distribution, and preparation method is simple for process, at low cost, behaviour
Make easy.
Claims (8)
1. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming, it is characterised in that application method is：
By methane and carbon dioxide by volume 1：1 mixing, mixed gas is passed through into system, that is, is completed, wherein mixed air air speed ratio
For 2000-20000h-1, reaction temperature is 600-900 DEG C, and supply voltage 1.0-2.0V, power supply is alternating current, then frequency range
For 0.01-1MHz；
A kind of electrochemical reforming system of methane and carbon dioxide dry reforming includes multiple electrolytic cell thin slices, reactor (1)
With external power supply (2)；Multiple electrolytic cell thin slices are parallel in the horizontal direction in reactor (1), wherein electrolytic cell
Thin slice includes electrolytic thin-membrane (3) and 2 porous electrodes (4), the upper and lower surface of electrolytic thin-membrane (3) respectively with 2
Porous electrode (4) connects, and porous electrode (4) is connected to by conducting wire with external power supply (2)；Construction method is one, passes through the tape casting
Electrolyte is prepared into electrolytic thin-membrane, then high temperature sintering is molded, and obtains fine and close electrolytic thin-membrane (3)；Two, it uses
Silk screen print method prepares electrode in fine and close electrolytic thin-membrane (3) both sides, then uses pore creating material and high-temperature calcination to obtain porous
Electrode (4)；Three, confluence layer is prepared on porous electrode (4) by silk screen print method, it is thin then to obtain electrolytic cell after high temperature sintering
Piece；Four, n electrolytic cell thin slice is placed in reactor (1), then is connected with external power supply (2) by porous electrode (4) and conducting wire
It is logical to get to the electrochemical reforming system of methane and carbon dioxide dry reforming, wherein n >=1.
2. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1, special
Sign is that the reactor is ceramic tube or glass tube.
3. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1,
It is characterized in that the electrolyte described in step 1 is：The ZrO that Y stablizes2The CeO of electrolyte, Sm or Gd doping2, Sc stablize
ZrO2The LaGaO that electrolyte, Sr, Mg stablize3Electrolyte, BaCeO3Base electrolyte or BaZrO3One kind or more in base electrolyte
Kind presses a mixture of arbitrary proportions.
4. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1,
It is characterized in that the temperature of the high temperature sintering molding described in step 1 is 1200~1600 DEG C.
5. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1,
It is characterized in that the electrode described in step 2 is the CeO of Ni/YSZ, Ni/ScSZ, Ni/Sm or Gd doping2, Sr and Co doping
LaFeO3, Ba and Co doping SrFeO3, Fe doping SrTiO3, La doping SrMnO3The LaFeO that material, Sr are adulterated3Material,
The SrTiO of La and Fe doping3, Ni doping SrTiO3, La and Fe doping SrMnO3Material or the SrMoO of Fe doping3In material
It is one or more press a mixture of arbitrary proportions.
6. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1,
It is characterized in that the pore creating material described in step 2 is starch or graphite.
7. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1,
It is characterized in that the temperature of the high-temperature calcination described in step 2 is 850~1300 DEG C.
8. a kind of application method of the electrochemical reforming system of methane and carbon dioxide dry reforming according to claim 1,
It is characterized in that the confluence layer described in step 3 is conducting resinl, silver paste, gold paste or platinum slurry.
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