CN104630812B - Method for preparing synthesis gas based on electrolysis CO2 and H2O of molten carbonate electrolytic tank - Google Patents
Method for preparing synthesis gas based on electrolysis CO2 and H2O of molten carbonate electrolytic tank Download PDFInfo
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- CN104630812B CN104630812B CN201510057357.8A CN201510057357A CN104630812B CN 104630812 B CN104630812 B CN 104630812B CN 201510057357 A CN201510057357 A CN 201510057357A CN 104630812 B CN104630812 B CN 104630812B
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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
The invention discloses a method for preparing synthesis gas based on electrolysis CO2 and H2O of a molten carbonate electrolytic tank. The method comprises the following steps: filling carbonate electrolyte in an electrolytic tank anode runner, orderly assembling an anode bipolar plate, an anode Ni electrode, a diaphragm, a cathode Ni electrode and a cathode bipolar plate from top to bottom to form a molten carbonate electrolytic tank monomer; placing the electrolytic tank monomer in a heating furnace to heat, melting the carbonate electrolyte as liquid from the solid and then infiltrating in the diaphragm; electrifying the electrolytic tank monomer so that the electrolytic tank monomer is worked under the working voltage; introducing mixed gas of the CO2 and H2O into the cathode runner, and introducing the air and/or N2 into the anode runner, finally collecting a synthesis gas composed of CO, H2, H2O and CO2 at a cathode runner outlet of the electrolytic tank monomer. The molten carbonate is used as the electrolyte, the CO2 and the H2O are used as feed gas, the carbon deposition at the Ni electrode can be avoided, the produced synthesis gas can be used for chemical materials or fuel to realize the efficient conversion and utilization of the CO2.
Description
Technical field
The invention belongs to fused carbonate electrolysis tech field, particularly to a kind of electricity based on fused carbonate electrolyzer
Solution co2And h2The method of o producing synthesis gas.
Background technology
At present, the Global Environmental Problems with climate change as core are increasingly serious, have become as threat mankind's sustainable development
One of principal element of exhibition, cut down greenhouse gas emission becomes the focus of current international community concern with mitigation of climate change.With
The whole world greenhouse gas emission is increasingly paid close attention to, Kyoto Protocol, the holding of " Bali's route map ", specify that further
Global co2Trapping and the timetable utilizing, have promoted the development of global low-carbon economy.Using regenerative resource (wind energy, solar energy
Deng), by electrochemical method by co2And h2O converting for the raw materials of industry such as synthesis gas, hydro carbons or fuel, can not only realize
co2Trans-utilization, and be capable of the conversion of regenerative resource, to reducing co2Discharge and raising renewable energy utilization rate
Significant.
In order to realize co2Conversion, general using the low-temperature electrolytic pond based on PEM electrolyte, using metal platinum
As catalyst, relatively costly, and difficulty is regulated and controled to the component of product.And then, in order to reduce catalyst cost, control
Product component, some scholars propose and convert co using the electrolytic tank of solid oxide based on ceramic material2But, solid oxidation
Thing electrolyzer cells area is difficult to amplify, up to 800 DEG C of operating temperature, increases the requirement to sealing, afflux etc..Using fused salt
As electrolyte build molten-salt electrolysis pond, its operating temperature larger up to 600 DEG C -700 DEG C, need not using noble metal as catalysis
Agent, and cell area is easy to amplify, and has broad application prospects in fields such as military affairs, Aero-Space.But existing grind
In studying carefully, adopt molten salt electrolyte Direct Electrolysis co more2It is easy to the problems such as carbon distribution occurs is so that electrolyzer hydraulic performance decline.Therefore,
Reduce electrode carbon distribution, improve cell life, co can be reduced2Conversion cost, further promote co2Trans-utilization.
Content of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of be electrolysed based on fused carbonate
The electrolysis co in pond (molten carbonate fuel cell, mcec)2And h2The method of o producing synthesis gas, can reduce electrolysis
Pool cathode carbon distribution, improves cell life.
To achieve these goals, the technical solution used in the present invention is:
A kind of electrolysis co based on fused carbonate electrolyzer2And h2The method of o producing synthesis gas, comprises the steps:
Carbonate electrolyte is filled in the runner of anode bipolar plate 1, then by anode bipolar plate 1, anode ni electrode
2nd, barrier film 3, negative electrode ni electrode 4 and cathode bipolar plate 5 constitute fused carbonate electrolyzer according to order assembling from top to bottom
Monomer；
Electrolyzer monomer is placed in heating furnace, is heated to 600 DEG C -700 DEG C, so that carbonate electrolyte is melted from solid
For liquid, and infiltrate in barrier film 3, on the one hand play the effect of conduction carbanion, on the other hand can also intercept gas
Penetrate；
By external circuit, electrolyzer monomer is energized, so that electrolyzer monomer is operated under running voltage；
By co2With h2The gaseous mixture of o is passed in electrolyzer monomer cathode flow channels, by air and/or n2It is passed into electrolyzer
In single block anode runner；
Its course of reaction is:
co2With h2The gaseous mixture of o occurs cell reaction to generate co and h under running voltage effect2, and generate carbonate from
Son, carbanion passes through electrolyte membrance 3, generates o at anode ni electrode 22And co2.Meanwhile, electrolyzer monomer sun
Air and/or n that pole runner is passed through2The o that will generate2And co2Carry out anode, thus realizing co2Conversion.
Last outlet in electrolyzer monomer cathode flow channels is collected by co, h2、h2O and co2The synthesis gas of composition.
Described carbonate electrolyte is by li2co3、na2co3And k2co3In two kinds or three kinds mixing constitute, mixed proportion
The eutectic point meeting gained mixture is less than 600 DEG C.
Described anode bipolar plate 1 and cathode bipolar plate 5 are made using stainless steel material, and both sides have gas flow, side
For anode flow channel, opposite side is used for cathode flow channels, as gas distribution and conduction.
Described anode ni electrode 2 and negative electrode ni electrode 4, are obtained using the tape casting, and through 900 DEG C of high temperature sintering.
Described barrier film 3 adopts α-lialo2Or γ-lialo2It is obtained, there is loose structure, porosity 50%～75%, thickness
Spend for 0.3～1.0mm, average pore size is 0.25～0.8 μm.
The running voltage of described electrolyzer monomer is 1.2v-5.0v.
By monomer series-connected for multiple electrolyzers composition electrolyzer heap.
The running voltage of described electrolyzer heap, according to the quantity of electrolyzer monomer, scales up.
Described co2With h2In the gaseous mixture of o, h2The molar ratio of o is not less than 5%.
Compared with prior art, the present invention adopts fused carbonate as electrolyte, co2And h2O as unstripped gas, a side
Face is it can be avoided that the carbon distribution of ni electrode, the method being on the other hand readily able to realize battery scale.Produced synthesis gas, can
For industrial chemicals or fuel, thus realizing co2Efficient Conversion and utilization.
Brief description
Fig. 1 is the structural representation of fused carbonate electrolyzer monomer of the present invention.
Fig. 2 is the structural representation of the electrolyzer heap being made up of multiple fused carbonate electrolyzer monomers.
Specific embodiment
Describe embodiments of the present invention with reference to the accompanying drawings and examples in detail.
Bipolar plates employed in the embodiment of the present invention, are processed by 304 rustless steels, and flow passage structure is using straight trip stream
Road.
Ni electrode employed in the embodiment of the present invention, is all prepared using the tape casting and sinters prepared at 900 DEG C.
Barrier film employed in the embodiment of the present invention, is all prepared using the tape casting.
Embodiment 1
As shown in figure 1, a kind of electrolysis co based on fused carbonate electrolyzer2And h2The method of o producing synthesis gas, first
Carbonate electrolyte is filled in the runner of anode bipolar plate 1, then by anode bipolar plate 1, anode ni electrode 2, barrier film 3,
Negative electrode ni electrode 4 and cathode bipolar plate 5 constitute fused carbonate electrolyzer monomer according to order assembling from top to bottom.
Wherein, anode ni electrode 2 thickness is 0.8mm, and area is 500cm2.Negative electrode ni electrode 4 thickness 0.6mm, area
500cm2.Carbonate electrolyte is by li2co3And k2co3Mixing composition, the molar ratio 62:38 of the two, gross mass is 120g.Every
Film 3 adopts α-li2alo2, membrane thicknesses are 0.6mm, and area is 500cm2.
Afterwards, electrolyzer monomer is placed in heating furnace, is heated to 600 DEG C, carbonate electrolyte melts from solid and is
Liquid, and infiltrate in barrier film 3.By external circuit to electrolyzer monomer making alive, running voltage is 2.0v.Meanwhile, cloudy
It is passed through the co that molar ratio is 1:1 in the runner of pole2And h2O mixed gas, are passed through air in anode flow channel.Export in cathode flow channels,
Co, h of generation can be collected2、h2O and co2Synthesis gas.
Embodiment 2
As shown in figure 1, a kind of electrolysis co based on fused carbonate electrolyzer2And h2The method of o producing synthesis gas, first
Carbonate electrolyte is filled in the runner of anode bipolar plate 1, then by anode bipolar plate 1, anode ni electrode 2, barrier film 3,
Negative electrode ni electrode 4 and cathode bipolar plate 5 constitute fused carbonate electrolyzer monomer according to order assembling from top to bottom.
Wherein, anode ni electrode 2 thickness is 0.8mm, and area is 1000cm2.Negative electrode ni electrode 4 thickness 0.8mm, area
1000cm2.Carbonate electrolyte is by li2co3And k2co3Mixing composition, the molar ratio 43:57 of the two, gross mass is 240g.Every
Film 3 adopts γ-li2alo2, membrane thicknesses are 0.8mm, and area is 1000cm2.
Afterwards, electrolyzer monomer is placed in heating furnace, is heated to 650 DEG C, carbonate electrolyte melts from solid and is
Liquid, and infiltrate in barrier film 3.By external circuit to electrolyzer monomer making alive, running voltage is 3.0v.Meanwhile, cloudy
It is passed through the co that molar ratio is 2:1 in the runner of pole2And h2O mixed gas, are passed through air in anode flow channel.Export in cathode flow channels,
Co, h of generation can be collected2、h2O and co2Synthesis gas.
Embodiment 3
As shown in figure 1, a kind of electrolysis co based on fused carbonate electrolyzer2And h2The method of o producing synthesis gas, first
Carbonate electrolyte is filled in the runner of anode bipolar plate 1, then by anode bipolar plate 1, anode ni electrode 2, barrier film 3,
Negative electrode ni electrode 4 and cathode bipolar plate 5 constitute fused carbonate electrolyzer monomer according to order assembling from top to bottom.
Again as shown in Fig. 2 50 gained electrolyzer monomers are assembled into electrolyzer heap.
Wherein, anode ni electrode 2 thickness is 1.0mm, and area is 10000cm2.Negative electrode ni electrode 4 thickness 1.0mm, area
10000cm2.Carbonate electrolyte is by li2co3、na2co3And k2co3Mixing composition, the molar ratio of three is 43:31:26, always
Quality is 2400g.Barrier film 3 adopts α-li2alo2, membrane thicknesses are 1.0mm, and area is 10000cm2.
Afterwards, electrolyzer heap is placed in heating furnace, is heated to 700 DEG C, carbonate electrolyte melts as liquid from solid
Body, and infiltrate in barrier film 3.By external circuit to electrolyzer heap making alive, running voltage is 150.0v.Meanwhile, negative electrode
It is passed through the co that molar ratio is 1:2 in runner2And h2O, is passed through n in anode flow channel2, in cathode flow channels outlet, you can collect life
Co, the h becoming2、h2O and co2Synthesis gas.
Embodiment 4
Difference from Example 3 is, is passed through air and n in anode flow channel2Mixed gas.
Claims (8)
1. a kind of electrolysis co based on fused carbonate electrolyzer2And h2The method of o producing synthesis gas it is characterised in that include as
Lower step:
Carbonate electrolyte is filled in the runner of anode bipolar plate (1), then by anode bipolar plate (1), anode ni electrode
(2), barrier film (3), negative electrode ni electrode (4) and cathode bipolar plate (5) constitute melting carbonic acid according to order assembling from top to bottom
Salt electrolyzer monomer；
Electrolyzer monomer is placed in heating furnace, is heated to 600 DEG C -700 DEG C, so that carbonate electrolyte is melted as liquid from solid
Body, and infiltrate in barrier film (3)；
By external circuit, electrolyzer monomer is energized, so that electrolyzer monomer is operated under running voltage；
By co2With h2The gaseous mixture of o is passed in electrolyzer monomer cathode flow channels, by air and/or n2It is passed into electrolyzer monomer
In anode flow channel；
Collect by co, h in the outlet of electrolyzer monomer cathode flow channels2、h2O and co2The synthesis gas of composition；
Wherein, described carbonate electrolyte is by li2co3、na2co3And k2co3In two kinds or three kinds mixing constitute, mixing ratio
The eutectic point that example meets gained mixture is less than 600 DEG C.
2. the electrolysis co based on fused carbonate electrolyzer according to claim 12And h2The method of o producing synthesis gas, it is special
Levy and be, described anode bipolar plate (1) and cathode bipolar plate (5) are made using stainless steel material, and both sides have gas flow, one
Side is used for anode flow channel, and opposite side is used for cathode flow channels, as gas distribution and conduction.
3. the electrolysis co based on fused carbonate electrolyzer according to claim 12And h2The method of o producing synthesis gas, it is special
Levy and be, described anode ni electrode (2) and negative electrode ni electrode (4), it is obtained using the tape casting, and through 900 DEG C of high temperature sintering.
4. the electrolysis co based on fused carbonate electrolyzer according to claim 12And h2The method of o producing synthesis gas, it is special
Levy and be, described barrier film (3) adopts α-lialo2Or γ-lialo2It is obtained, there is loose structure, porosity 50%～75%, thickness
Spend for 0.3～1.0mm, average pore size is 0.25～0.8 μm.
5. the electrolysis co based on fused carbonate electrolyzer according to claim 12And h2The method of o producing synthesis gas, it is special
Levy and be, the running voltage of described electrolyzer monomer is 1.2v-5.0v.
6. the electrolysis co based on fused carbonate electrolyzer according to claim 12And h2The method of o producing synthesis gas, it is special
Levy and be, by monomer series-connected for multiple electrolyzers composition electrolyzer heap.
7. the electrolysis co based on fused carbonate electrolyzer according to claim 62And h2The method of o producing synthesis gas, it is special
Levy and be, the running voltage of described electrolyzer heap, according to the quantity of electrolyzer monomer, scales up.
8. the electrolysis co based on fused carbonate electrolyzer according to claim 12And h2The method of o producing synthesis gas, it is special
Levy and be, described co2With h2In the gaseous mixture of o, h2The molar ratio of o is not less than 5%.
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| CN105322188A (en) * | 2015-10-28 | 2016-02-10 | 中国华能集团清洁能源技术研究院有限公司 | Method for preparing modified nickel electrode of molten carbonate fuel cell through aqueous tape casting |
| CN114921798A (en) * | 2016-11-16 | 2022-08-19 | C2Cnt有限责任公司 | Method and system for producing long carbon nanofibers |
| CN107868962B (en) * | 2016-12-27 | 2018-11-27 | 中国科学院上海应用物理研究所 | A kind of synthesis gas preparation system and its method |
| JP7247150B2 (en) * | 2020-09-02 | 2023-03-28 | 株式会社東芝 | Carbon dioxide electrolysis device and carbon dioxide electrolysis method |
| CN115490251B (en) * | 2022-10-28 | 2023-08-29 | 华能国际电力股份有限公司 | Lithium metaaluminate powder, preparation method and application thereof |
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| IT1393711B1 (en) * | 2009-04-29 | 2012-05-08 | Ansaldo Fuel Cells Spa | SYSTEM AND PROCESS FOR THE SEPARATION OF CO2 AND RECOVERY OF FUEL FROM GAS EXHAUSTED ANODES OF CELLS A FUEL TO CARBONATES FUSI |
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