CN102240497A - Method and device for preparing methanoic acid from carbon dioxide recovered from flue gas by utilizing electric power at night - Google Patents
Method and device for preparing methanoic acid from carbon dioxide recovered from flue gas by utilizing electric power at night Download PDFInfo
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- CN102240497A CN102240497A CN2011101765238A CN201110176523A CN102240497A CN 102240497 A CN102240497 A CN 102240497A CN 2011101765238 A CN2011101765238 A CN 2011101765238A CN 201110176523 A CN201110176523 A CN 201110176523A CN 102240497 A CN102240497 A CN 102240497A
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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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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Abstract
The invention relates to a method and a device for preparing methanoic acid from carbon dioxide recovered from flue gas by utilizing electric power at night. The method comprises the following steps of: recovering the carbon dioxide, namely separating and recovering the carbon dioxide from the flue gas obtained by combusting a fuel; preparing the methanoic acid by electrochemical reduction, namely conveying the carbon dioxide obtained by separation to a membrane electrolysis device for reducing by direct current, and reducing the carbon dioxide to form the methanoic acid; and refining the methanoic acid, namely refining methanoic acid dilute solution obtained by membrane electrolysis to prepare a methanoic acid product, wherein the membrane electrolysis device is divided into a cathode chamber, a concentration chamber and an anode chamber or is divided into the cathode chamber and the anode chamber; and membrane electrolysis units are combined in a mode of series connection or parallel connection or combination of the series connection and the parallel connection. In the method and the device, the efficient membrane electrolysis device, a gas-liquid mixed feeding mode and a process for refining the methanoic acid recovered from the carbon dioxide are adopted, the efficiency of the electrochemical process is high, and the carbon dioxide is collected and recovered and subjected to electrolytic reduction to form high-concentration methanoic acid liquid, so that the carbon dioxide is recovered and converted effectively, and the electric power at night in electric power plants also can be utilized effectively.
Description
Technical field
The present invention relates to a kind of method and apparatus that carbon dioxide utilizes night electricity system formic acid that from flue gas, reclaims, belong to effective utilization of CO 2 waste gas recycling technology and night electricity.
Background technology
Along with the quick growth of World Economics and energy consumption, the human annual carbon dioxide that discharges in atmosphere causes Atmospheric Carbon Dioxide concentration to increase year by year, causes global warming, and natural calamity takes place frequently.Discharge of carbon dioxide greenhouse gas has become the key factor of restriction economy, social sustainable development, adds that carbon dioxide is potential carbon resource, therefore develops corresponding carbon dioxide recovery and utilizes technology to have the important strategic meaning.
The recovery of carbon dioxide and the key of utilization are the selection of way of recycling, and the selection that utilizes mode of suitable industrial condition, but the application of all methods all needs to realize on the basis of the balance of recovery value and input cost.The recovery of carbon dioxide at present transforms and mainly concentrates on synthetic organic-fuel of catalytic activation or industrial chemicals, as CH
4, CO+H
2, methyl alcohol etc.But these reaction needed just can be carried out under HTHP and the condition that has catalyst to exist, course of reaction need consume lot of energy and power, the performance of catalyst is lower in addition, therefore utilizes the extensive trans-utilization carbon dioxide of this high pressure catalytic hydrogenation method to also have a lot of difficulties.Electrochemistry hydrogenation reducing process is another important channel with the carbon dioxide trans-utilization, it mainly concentrates in the preparation of synthesis gas at present, promptly utilizing carbon dioxide to be electrochemically reduced to carbon monoxide utilizes the hydrogen that produces in the electrolytic process to form the different admixture of gas of C/Hratio simultaneously, but the hydrogen in this process route is inconvenient energy-accumulating medium, because it has volatility and easily blasts, so relatively difficulty and cost are very high aspect processing, storage, transportation and dispensing.If can anthropogenics such as formic acid etc., then can solve storage problem preferably.Formic acid is widely used in industries such as chemical industry, medicine, agricultural chemicals, leather, weaving, printing and dyeing, rubber, plastics and feed as important basic Organic Chemicals.Because formic acid is the antibiotic optimum substituent of feed OTC, little to ambient influnence, thereby market demand is in continuous increase, price also raises up always, becomes the focus product of C-1 chemistry.In addition, can also be synthetic other chemical products of raw material with formic acid.
The power consumption of electrochemical Reduction of Carbon Dioxide process need, daytime, higher power cost caused this method to be difficult to industrial applications; And the night electricity of power plant is abundant, and is difficult to store, easily cause waste, it if can be used, and then can significantly reduce the cost that its carbon dioxide recovery is utilized.Utilizing night electricity is that raw material is made the effective way that utility just becomes minimizing carbon emission, effective use of energy sources with the carbon dioxide.
Electrochemical Reduction of Carbon Dioxide equipment needed thereby investment is big, therefore, develops film electrolysis cells structure and combined system efficiently, and each link accomplishes that coupling is good, is to obtain the higher formic acid solution of purity, the basis that improve current efficiency, reduces cost.In addition, in the film electroreduction of carbon dioxide, catholyte and concentrate not only are related to electrochemical reaction direction, efficient and speed, the difficulty or ease and the cost that also are related to the purifying engineering of product, therefore, catholyte is formed, and the setting of concentration and condition just becomes one of key problem in technology of titanium dioxide carbon film electroreduction system formic acid.Also have, the contact condition of carbon dioxide and negative electrode is directly determining the efficient of electrochemical reduction, and therefore, the lead-in mode of carbon dioxide also just becomes another key technology.With carbon dioxide system formic acid is a system engineering that relates to processes such as carbon dioxide recovery, electrochemical reduction, formic acid be concentrated and purified, therefore, all need to accomplish efficiently in each link, low cost, stable operation could realize from carbon dioxide finishing to the formic acid product.But the technology exploration of this respect also lacks very much at present.
Extensity and the potential resource of carbon dioxide based on formic acid market are worth, develop a kind of low cost, can resource, operational administrative is simple, formic acid production method and formic acid process units just seem extremely important in the hope of better economy, society and environmental benefit efficiently.Comprising electrochemical reactor, method and technology that the recovery conversion of carbon dioxide and formic acid are refining.
Summary of the invention
The object of the present invention is to provide a kind of method that carbon dioxide utilizes night electricity system formic acid that reclaims from flue gas, this method has the characteristics of high efficiency, low cost, resource, stable operation.
The present invention is realized by following technical proposals.
From flue gas, reclaim the method for carbon dioxide system formic acid, comprise following process at least:
(1) from the flue gas that fuel combustion obtains, separate the carbon dioxide recovery process that reclaims carbon dioxide,
(2) above-mentioned (1) is separated the carbon dioxide obtain and sends into the membrane electrolyser that reduces with direct current, make its reduction obtain the electrochemical reduction system formic acid process of formic acid,
(3) the formic acid weak solution that obtains of film electrolysis makes the formic acid subtractive process of formic acid product through refining step.Subtractive process comprises concentrated and purifying, can save the purge process of decontamination under the very high situation of formic acid weak solution purity, and have only concentration process.
Described membrane electrolyser is divided into cathode chamber, enriched chamber and anode chamber, between cathode chamber and enriched chamber, isolate with anion-exchange membrane, isolate with cation-exchange membrane between enriched chamber and the anode chamber, carbon dioxide enters cathode chamber, obtain the formic acid weak solution from enriched chamber's outlet, do not add any acid outside any inorganic salts and the formic acid in the catholyte, or adding the combination of sodium formate or potassium formate or formic acid and NaOH or formic acid and potassium hydroxide or these materials in the catholyte, anolyte is an acid solution; Or device is divided into cathode chamber and anode chamber, isolate with cation-exchange membrane between cathode chamber and anode chamber, carbon dioxide enters cathode chamber, obtains the formic acid weak solution from the cathode chamber outlet, do not add any acid outside any inorganic salts and the formic acid in the catholyte, anolyte is an acid solution.The formic acid liquid that three Room membrane electrolysers obtain can be purer and suitable high concentration, the structure that two cell structures have been simplified membrane electrolyser has reduced equipment investment.Described catholyte, anolyte and concentrate are all wanted each self-loopa, and promptly liquid is being sent it into separately import from outlet with pump, and liquid circulates in the chamber of separately membrane electrolyser, and is stable to promote material Transfer and to keep liquid to form.Carbon dioxide of the present invention enters cathode chamber and comprises that carbon dioxide directly enters and is dissolved into and enter dual mode in the solution.Membrane electrolyser is used in multiple industrial practice, but each uses the concrete condition have again separately, has only concrete condition specifically is provided with just and can obtain good effect.The membrane electrolyser of the present invention's exploitation flows through along cathode plane by catholyte, makes carbon dioxide and dissolved matter thereof be reduced at negative electrode, and the contact-making surface of liquid and negative electrode is upgraded fast, has greatly improved the electrochemical reaction effect and the efficient of electrode surface.The cathode chamber of three Room membrane electrolysers and the anion-exchange membrane between the enriched chamber make the formate ion of generation see through amberplex and arrive the enriched chamber, the cation-exchange membrane that hydrogen ion in the anolyte of acid solution sees through between anode chamber and the enriched chamber enters the enriched chamber, and not only purity is protected but also concentration is improved to make the formic acid of enriched chamber.Do not add any acid in addition of any inorganic salts and formic acid in the catholyte, guaranteed to have only formate anion in the catholyte, make that the anion that penetrates into the enriched chamber is a formate, guaranteed the purity and the current efficiency of concentrate.Add sodium formate or formic acid and NaOH in the catholyte and can freely regulate pH value and formate ion concentration simultaneously, reach and when improving electroreduction efficient, improve the speed that formate ion passes anion-exchange membrane, to improve the efficient of system.Hydrogen ion in the anolyte of two Room membrane electrolysers sees through cation-exchange membrane and enters cathode chamber under electric field action, make the film electrolysis carry out smoothly.Catholyte can also can accumulate formic acid initially just adding formic acid in circulation, make formic acid concn reach certain value, becomes to have certain density formic acid solution, lays the foundation for the efficient of follow-up concentrated subtractive process improves.The acid of anolyte can be sulfuric acid, and nitric acid, or other inorganic acids or organic acid also can be these sour mixed liquor, wherein preferably sulfuric acids.
Described film electrolysis cells can make up with the any-mode that combines in parallel with serial or parallel connection or series connection.The aforementioned films electrolysis cells is as most basic unit, and three-chamber type film electrolysis cells and two cell-type film electrolysis cells can make up arbitrarily in actual device, promptly not only can in parallelly use, and the use of can also connecting can improve the formic acid concn in the outlet liquid like this.
The used minus plate of aforesaid membrane electrolyser is stereotype, or plumbous alloy sheets, or zine plate or kirsite plate, or sheet tin or ashbury metal plate.These minus plates have guaranteed to have prevented the generation of other reactions in the reaction of the carbon dioxide reduction formic acid of negative electrode.
Aforesaid membrane electrolyser is provided with air and liquid mixer before the cathode chamber inlet, carbon dioxide in this blender with after catholyte mixes, enter cathode chamber together, be provided with gas-liquid separator in the cathode chamber outlet, gained gas is sent it into aforementioned carbon dioxide mix device with adding press, and catholyte recycles; Or before the cathode chamber inlet, be provided with air and liquid mixer, and the liquid in the blender is sent into cathode chamber as catholyte, and the liquid of cathode chamber outlet is back to aforementioned blender and recycles.
The operating condition of aforesaid membrane electrolyser be pH value at the porch of cathode chamber catholyte between 2-6, at the pressure of cathode chamber exit catholyte between gauge pressure 0-1.0MPa.Under this conditional parameter, operate, both can guarantee hydrogen ion concentration, can guarantee the dissolving in catholyte of carbon dioxide again, can reach taking into account of carbon dioxide reduction and equipment investment efficiently.Described gauge pressure is with respect to atmospheric pressure.
Parting material in the retracting device of aforesaid carbon dioxide is made organic film of organic compound or the membrane separator formed with the made ceramic membrane of inorganic material, and is provided with flue gas cleaner before this separator.Membrane separator divides the equipment investment of the carbon dioxide in the separable flue gas low, and operation is also convenient.Flue gas cleaner is set before membrane separator can removes dust etc., prevent that the film of membrane separator from stopping up.
The aforesaid method that reclaims carbon dioxide from flue gas is to adopt Na
2CO
3Or K
2CO
3, or alkanolamine solution, or the mixed liquor of these materials absorbs heats the carbon dioxide desorb that absorption rich solution behind the described absorbing carbon dioxide makes its absorption, carbon dioxide is made the raw material of film electrolysis, the liquid absorption that circulates.Can obtain highly purified carbon dioxide by these absorption process, help follow-up film electrolytic process.
The used raw material of aforesaid membrane electrolyser can also be to derive from chemical industry, the carbon dioxide that fermentation industry produces.The normal highly purified carbon dioxide of by-product such as some process such as sweat can be made formic acid equally by film electroreduction carbon dioxide in chemical industry and the fermentation industry, obtains and simplifies the purifying carbon dioxide process but also can save carbon dioxide.
The process for purification of the formic acid that aforesaid carbon dioxide makes is to adopt the combined method of counter-infiltration or rectifying or these methods to obtain the formic acid product.The formic acid concn that the film electrolysis obtains is lower, need make with extra care and improve concentration.Process for purification can adopt a kind of of described method, also can adopt diverse ways in the variable concentrations section according to the different requirements of product, as the counter-infiltration of low concentration section, and high concentration section rectificating method.
Described film electrolysis station service power is the night electricity of power plant, can be that the carbon dioxide that reclaims night reduces with night electricity, also can right and wrong night the carbon dioxide that reclaims night with night electricity reduction system formic acid, also can be aforementioned both combination.The film electrolytic process is a high power consumption process, so its process can be carried out at night, power plant particularly, not only has abundant night electricity, and abundant in addition carbon dioxide, utilize the night electricity reducing carbon dioxide to produce formic acid, for effective utilization of power plant's night electricity provides an approach.
Above-mentioned carbon dioxide reduction is produced device and other devices of formic acid can make formic acid with the carbon dioxide that produces in flue gas and the Industrial Engineering efficiently, and in the design of actual device, the supporting of peripheral equipment can get final product according to the industrial general knowledge of routine.
The invention has the advantages that, this process adopts the feeding manner and the carbon dioxide recovery formic acid process for refining of membrane electrolyser and gas-liquid mixed efficiently, electrochemical process efficient height, collect and reclaim carbon dioxide and obtain concentration formic acid and high liquid by electroreduction, realize the recovery and the conversion of carbon dioxide effectively, can also effectively utilize the night electricity of power plant.
Description of drawings
The process flow diagram of Fig. 1: embodiment 1;
The process flow diagram of Fig. 2: embodiment 2;
The process flow diagram of Fig. 3: embodiment 3;
The process flow diagram of Fig. 4: embodiment 4;
The process flow diagram of Fig. 5: embodiment 5;
The process flow diagram of Fig. 6: embodiment 6.
Reference numeral
1. power-plant flue gas; 2. absorption tower; 3. the absorption tower flue gas of discharging; 4. the rich solution behind the absorbing carbon dioxide; 5. desorber; 6. the absorption liquid after regenerating; 7. noncorrosive pump; 8. the carbon dioxide after the desorb; 9. carbon dioxide storage tank; 10. air and liquid mixer; 11. cathode chamber import liquid; 12. two Room membrane electrolysers; 13. negative electrode stereotype; 14. positive plate; 15. cation-exchange membrane; 16. the cathode outlet liquid of two Room membrane electrolysers; 17. gas-liquid separator; 18. gas-liquid separator exit gas; 19. blower fan; 20. gas-liquid separator outlet liquid; 21. be back to the outlet liquid of the gas-liquid separator of air and liquid mixer; 22. enter the outlet liquid of the gas-liquid separator of formic acid storage tank; 23. formic acid storage tank; 24. formic acid storage tank liquid; 25. reverse osmosis unit; 26. reverse osmosis membrane; 27. the formic acid of reverse osmosis unit outlet; 28. rectifying column; 29. high-purity formic acid product; 30. anolyte storage tank; 31. anolyte; 32. the anode chamber of two Room membrane electrolysers outlet liquid; 33. anode chamber's gas; 34. three Room membrane electrolysers; 35. anion-exchange membrane; 36. three Room membrane electrolyser cathode chamber outlet liquid; 37. membrane electrolyser enriched chamber, three Room outlet liquid; 38. membrane electrolyser anode chamber, three Room outlet liquid; 39. return the formic acid liquid storage of three Room membrane electrolyser medial compartments (enriched chamber); 40. the carbon dioxide that beer fermentation industry produces; 41. flue gas cleaner; 42. the flue gas of flue gas cleaner outlet; 43. dust; 44. membrane separator
The specific embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments:
As shown in Figure 1, the power-plant flue gas 1 of this technological process import adopts the way of contact of adverse current to enter absorption tower 2 with absorption liquid to carry out carbon dioxide absorption.It is 112 sodium carbonate liquor that absorption liquid adopts pH, and the pH value of absorption liquid constantly descends in the absorption process, absorbs rich solution 4 and enter desorption apparatus 5 and carry out the carbon dioxide thermal desorption when pH drops to 8.4, and while flue gas after being purified 3 enters atmosphere.Absorption liquid obtains regeneration when the pH value that absorbs rich solution rises to 10.5 in the thermal desorption process, and the absorption liquid 6 after the regeneration is returned absorption tower 2 by pump 7, proceeds to absorb in the form inflow tower of absorption liquid with spray; Carbon dioxide 8 after the desorb enters carbon dioxide storage tank 9, the carbon dioxide that comes out from storage tank enter contain 0.1mol/L formic acid liquid air and liquid mixer 10 to saturated, and the gauge pressure of carbon dioxide is 1.0MPa in the blender, and at this moment pH is the cathode chamber 12a that contains negative electrode stereotype 13 that 2.3 gas-liquid mixture 11 enters the two Room membrane electrolysers of being made up of single cation-exchange membrane 15 12.The anolyte that contains 0.1mol/L sulfuric acid 31 that comes from anode storage tank 30 is squeezed into the 12c of anode chamber that contains positive plate 14 of two Room membrane electrolysers 12 by pump, hydrogen ion in the electrolytic process enters cathode chamber 12a by cation-exchange membrane 15, thus, the continuous enrichment method of formic acid mixed liquor of cathode chamber electrolysis generation.The mixture 16 of cathode chamber outlet enters gas-liquid separator 17 and carries out gas-liquid separation, it is recycling that effluent air 18 is sent into air and liquid mixer 10 through blower fan 19 suctions, the liquid 20 that flows out a wherein part 21 enters air and liquid mixer 10 and recycles, and another part 22 enters formic acid storage tank 23 as the formic acid product.Formic acid storage tank liquid 24 is sent to the reverse osmosis unit 25 that contains reverse osmosis membrane 26 and carries out formic acid separation purification, and the formic acid product of separating 27 enters rectifying column 28 again and carries out the secondary rectification and purification, obtains the higher formic acid liquid 29 of purity.The gas-liquid mixture 32 of membrane electrolyser anode chamber, two Room outlet enters anolyte storage tank 30, and anolyte sulfuric acid 31 is returned the anode chamber by pump 7 and continued to recycle, and effluent air 33 is connected with oxygen storage tank by pipeline.Wherein, used electric power is power plant's night electricity in the film electrolytic process.When the carbon dioxide that reclaims night when night electric power reduction was not enough, it was additional to carry out raw material with the carbon dioxide that reclaims non-night (be stored in jar 9).
As shown in Figure 2, the gas 8 that comes out via carbon dioxide storage tank 9 shown in Figure 1 enters the air and liquid mixer 10 of the mixed solution that contains 0.6mol/L sodium formate and 0.3mol/L formic acid to saturated, and the gauge pressure of carbon dioxide is 0.8MPa in the blender, at this moment pH is the cathode chamber 34a that 3.4 gas-liquid mixture 11 enters the three Room membrane electrolysers 34 that the negative and positive film forms, the formate ion that produces in the electrolytic process is medial compartment 34b by the enriched chamber that anion-exchange membrane 35 enters between anion-exchange membrane and the cation-exchange membrane 15, the hydrogen ion of anode chamber's anolyte enters the enriched chamber by cation-exchange membrane, and the liquid 37 of enriched chamber's outlet enters formic acid storage tank 23.The mixture 36 of cathode chamber outlet enters gas-liquid separator 17, and it is recycling that effluent air 18 is sent into air and liquid mixer 10 through blower fan 19 suctions, and the liquid 20 of outflow enters air and liquid mixer 10 and recycles.The liquid 38 of anode chamber's outlet loops back anolyte storage tank 30.According to technological requirement a part of formic acid liquid storage 39 is proceeded to concentrate as the medial compartment 34b that circulation fluid returns membrane electrolyser 34, another part is delivered to follow-up separation purification process as formic acid product 24.Other parts are identical with embodiment 1.
The embodiment that reclaims carbon dioxide system formic acid from power-plant flue gas is substantially the same manner as Example 1, and as shown in Figure 3, different is that membrane electrolyser is to be in series by two two Room membrane electrolysers.Promptly the pH that obtains via air and liquid mixer shown in Figure 1 is the cathode chamber 12a that 2.3 gas-liquid mixture 11 enters the two Room membrane electrolysers 12 that single anode membrane forms, the mixed liquor of cathode chamber outlet enters the cathode chamber of next stage two Room membrane electrolysers behind the electrochemical reduction, the mixed liquor 16 of cathode chamber outlet enters gas-liquid separator 17 after the electrolysis, and other parts are identical with embodiment 1.
The embodiment that reclaims carbon dioxide system formic acid from power-plant flue gas is substantially the same manner as Example 2, and as shown in Figure 4, different is that membrane electrolyser is to be in series by two three Room membrane electrolysers.Promptly enter the air and liquid mixer 10 of the mixed liquor that initially contains 1.2mol/L sodium formate and 1.5mol/L formic acid via carbon dioxide shown in Figure 18, and the gauge pressure of carbon dioxide is 0.5MPa in the blender, pH is the cathode chamber 34a that about 3.8 gas-liquid mixture 11 enters the first order three Room membrane electrolysers 34 that the negative and positive film forms, the mixture of cathode chamber outlet enters the cathode chamber of next stage three Room membrane electrolysers after the electrolysis, and the mixture 36 of cathode chamber outlet afterwards enters gas-liquid separator 17; The liquid of first order medial compartment outlet enters next stage three Room membrane electrolyser medial compartments and carries out enrichment method, the liquid 37 of medial compartment outlet enters formic acid storage tank 23, wherein the part of formic acid liquid storage is delivered to follow-up separation purification process as product 24, another part formic acid liquid storage 39 is back to the medial compartment enrichment method of the first order three Room membrane electrolysers by pump 7, and other parts are identical with embodiment 2.
As shown in Figure 5, come from carbon dioxide 40 (not shown)s that produce in the Beer Brewage sweat and be stored in carbon dioxide storage tank 9 via carbon dioxide absorption shown in Figure 1, desorption process, simultaneously a part of carbon dioxide in the storage tank also comes from carbon dioxide in the power-plant flue gas through the absorption desorption process of example 1.The carbon dioxide 8 that comes out from storage tank enters the air and liquid mixer 10 that contains the 0.1mol/L formic acid solution, the gauge pressure of carbon dioxide is 0.2MPa in the blender, the pH that comes out from air and liquid mixer is the cathode chamber 12a that 2.3 gas-liquid mixture 11 enters the two Room membrane electrolysers of being made up of single cation-exchange membrane 12, cathode mix 16 after the electrolysis enters the cathode chamber 34a of next stage three Room membrane electrolysers, and the mixture 36 of its outlet enters gas-liquid separator 17; The mixture 32 of the 12c of the anode chamber outlet of two Room membrane electrolysers 12 enters the 34c of anode chamber of next stage three Room membrane electrolysers; The formate ion that electrolysis produces in three Room membrane electrolysers 34 passes anion-exchange membrane by cathode chamber and enters medial compartment 34b, and the hydrogen ion of anolyte passes cation-exchange membrane by the anode chamber and enters medial compartment simultaneously.Thus, the formic acid of medial compartment mixes weak solution and constantly obtains enrichment method, and formic acid storage tank 23 is discharged and imported to formic acid concentrate 37 from the medial compartment 34b of three Room membrane electrolysers.A part of formic acid liquid storage can be separated purification as formic acid product 24 according to technological requirement, another part is proceeded to concentrate through the medial compartment 34b that pump 7 enters three Room membrane electrolysers as circulation fluid 39, and other parts are identical with embodiment 1.
As shown in Figure 6, power-plant flue gas 1 enters flue gas cleaner 41, and the dust of removing 43 reclaims; Flue gas after being purified 42 enters membrane separator 44 and isolates carbon dioxide 8, and is stored in carbon dioxide storage tank 9.Thereafter the operation of carbon dioxide system formic acid is undertaken by the mode of embodiment 1 or embodiment 2 or embodiment 3 or embodiment 4 or embodiment 5.
Present embodiment is substantially the same manner as Example 4, different is membrane electrolyser by the three-chamber type electrolysis cells after series connection two cell-type electrolysis cells.Promptly the catholyte of three Room film electrolysis cells circulates separately; Concentrate enters the cathode chamber of two Room membrane electrolysers, is sent to formic acid storage tank 23 in the part of the liquid of its cathode chamber outlet, and a part is returned the medial compartment inlet of three Room membrane electrolysers; The anolyte series circulation of three Room electrolysis units and two Room electrolysis units.The part of carbon dioxide reclaims the carbon dioxide that the back stores daytime from power plant.The cathode chamber porch initial pH of catholyte of three Room membrane electrolysers is that the cathode chamber outlet pressure of 6.0, two Room membrane electrolysers is gauge pressure 0MPa.
Claims (10)
1. method that reclaims carbon dioxide system formic acid from flue gas is characterized in that comprising at least following process:
(1) from the flue gas that fuel combustion obtains, separates the carbon dioxide recovery process that reclaims carbon dioxide;
(2) above-mentioned (1) is separated the carbon dioxide that obtains and send into the membrane electrolyser that reduces with direct current, make its reduction obtain the electrochemical reduction system formic acid process of formic acid;
(3) the formic acid weak solution that obtains of film electrolysis makes the formic acid subtractive process of formic acid product through refining step.
2. the carbon dioxide system that from flue gas, the reclaims formic acid membrane electrolyser of claim 1, it is characterized in that device is divided into cathode chamber, enriched chamber and anode chamber, between cathode chamber and enriched chamber, isolate with anion-exchange membrane, isolate with cation-exchange membrane between enriched chamber and the anode chamber, carbon dioxide enters cathode chamber, obtain the formic acid weak solution from enriched chamber's outlet, do not add any acid outside any inorganic salts and the formic acid in the catholyte, or adding the combination of sodium formate or potassium formate or formic acid and NaOH or formic acid and potassium hydroxide or these materials in the catholyte, anolyte is an acid solution.
3. device as claimed in claim 2, it is characterized in that device is divided into cathode chamber and anode chamber, between cathode chamber and anode chamber, isolate with cation-exchange membrane, carbon dioxide enters cathode chamber, obtain the formic acid weak solution from the cathode chamber outlet, do not add any acid outside any inorganic salts and the formic acid in the catholyte, anolyte is an acid solution.
4. as claim 2 or 3 described devices, it is characterized in that described film electrolysis cells makes up with the mode that combines in parallel with serial or parallel connection or series connection.
5. as claim 2 or 3 described devices, it is characterized in that used minus plate is alloy sheets, zine plate, kirsite plate, sheet tin or the ashbury metal plate of stereotype, lead.
6. as claim 2 or 3 described devices, it is characterized in that before the cathode chamber inlet, being provided with air and liquid mixer, carbon dioxide in this blender with after catholyte mixes, enter cathode chamber together, be provided with gas-liquid separator in the cathode chamber outlet, gained gas is sent it into aforementioned carbon dioxide mix device with adding press, and catholyte recycles; Or before the cathode chamber inlet, be provided with air and liquid mixer, and the liquid in the blender is sent into cathode chamber as catholyte, and the liquid of cathode chamber outlet is back to aforementioned blender and recycles.
7. as the method for operating of claim 2 or 3 described devices, it is characterized in that pH value at the porch of cathode chamber catholyte between 2-6, at the pressure of cathode chamber exit catholyte between gauge pressure 0-1.0MPa.
8. the method for claim 1, it is characterized in that separating in described step (1) flue gas carbon dioxide recovery process that reclaims carbon dioxide is, the membrane separator that adopts the made organic film of organic compound or form with the made ceramic membrane of inorganic material, and before this separator, be provided with flue gas cleaner.
9. the method that reclaims carbon dioxide from flue gas as claimed in claim 1 is characterized in that adopting Na in the method that reclaims carbon dioxide from flue gas
2CO
3Or K
2CO
3, or alkanolamine solution, or the mixed liquor of these materials absorbs heats the carbon dioxide desorb that absorption rich solution behind the described absorbing carbon dioxide makes its absorption, carbon dioxide is made the raw material of film electrolysis, the liquid absorption that circulates.
10. claim 1,2 or 3 described membrane electrolysis methods, it is characterized in that station service power is the night electricity of power plant, be that the carbon dioxide that reclaims night reduces with night electricity, or the carbon dioxide that reclaims non-night night with night electricity reduction system formic acid, or aforementioned both combination.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966625A (en) * | 2014-05-19 | 2014-08-06 | 同济大学 | Preparation method of novel photoelectric cathode used for efficiently reducing and converting CO2 to hydrocarbon fuels |
| CN104204301A (en) * | 2012-03-06 | 2014-12-10 | 液体光有限公司 | Reducing carbon dioxide to products |
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| CN103668311B (en) * | 2013-12-09 | 2016-09-07 | 华中师范大学 | For electro-catalysis reduction CO2to the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid |
| CN107002259A (en) * | 2014-12-05 | 2017-08-01 | 西门子公司 | Power plant |
| CN107614090A (en) * | 2015-05-19 | 2018-01-19 | 信实工业公司 | A kind of technique for being used to trap carbon dioxide from air-flow |
| CN108385129A (en) * | 2018-03-29 | 2018-08-10 | 碳能科技（北京）有限公司 | A kind of preparation method of formic acid |
| WO2019011577A1 (en) * | 2017-07-12 | 2019-01-17 | Siemens Aktiengesellschaft | Membrane-coupled cathode for the reduction of carbon dioxide in acid-based electrolytes without mobile cations |
| CN109790632A (en) * | 2016-09-27 | 2019-05-21 | 西门子股份公司 | The method and apparatus for utilizing carbon dioxide for electrochemistry |
| CN110983357A (en) * | 2019-12-04 | 2020-04-10 | 昆明理工大学 | Three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts |
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| US20210047743A1 (en) * | 2018-03-05 | 2021-02-18 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for electrochemically reducing carbon dioxide |
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| WO2024114838A3 (en) * | 2022-12-01 | 2024-07-25 | 清华大学 | Carbon dioxide electrolysis device and carbon dioxide electrolysis method |
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| CN104204301A (en) * | 2012-03-06 | 2014-12-10 | 液体光有限公司 | Reducing carbon dioxide to products |
| CN103668311B (en) * | 2013-12-09 | 2016-09-07 | 华中师范大学 | For electro-catalysis reduction CO2to the catalysis electrode of formic acid, application and electro-catalysis reduction carbon dioxide to the method for formic acid |
| CN103966625A (en) * | 2014-05-19 | 2014-08-06 | 同济大学 | Preparation method of novel photoelectric cathode used for efficiently reducing and converting CO2 to hydrocarbon fuels |
| CN103966625B (en) * | 2014-05-19 | 2016-06-29 | 同济大学 | A kind of for efficiently reducing CO2The preparation method being converted into the novel photoelectric negative electrode of hydrocarbon fuel |
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| JP2021516290A (en) * | 2018-03-05 | 2021-07-01 | ネーデルランセ オルハニサチエ フォール トゥーヘパスト−ナツールウェーテンシャッペルック オンデルズク テーエヌオーＮｅｄｅｒｌａｎｄｓｅ Ｏｒｇａｎｉｓａｔｉｅ ｖｏｏｒ ｔｏｅｇｅｐａｓｔ−ｎａｔｕｕｒｗｅｔｅｎｓｃｈａｐｐｅｌｉｊｋ ｏｎｄｅｒｚｏｅｋ ＴＮＯ | How to electrochemically reduce carbon dioxide |
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| US20210047743A1 (en) * | 2018-03-05 | 2021-02-18 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method for electrochemically reducing carbon dioxide |
| CN108385129A (en) * | 2018-03-29 | 2018-08-10 | 碳能科技（北京）有限公司 | A kind of preparation method of formic acid |
| CN110983357A (en) * | 2019-12-04 | 2020-04-10 | 昆明理工大学 | Three-chamber diaphragm electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide and simultaneously producing chlorine and bicarbonate as byproducts |
| CN111690946B (en) * | 2020-05-20 | 2023-12-19 | 西安交通大学 | Intermittent carbon dioxide capturing and converting coupling device and operation method thereof |
| CN111690946A (en) * | 2020-05-20 | 2020-09-22 | 西安交通大学 | Intermittent carbon dioxide capture and conversion coupling device and operation method thereof |
| JP2022139003A (en) * | 2021-03-11 | 2022-09-26 | 本田技研工業株式会社 | Carbon dioxide treatment device and method for producing carbon compound |
| JP7176027B2 (en) | 2021-03-11 | 2022-11-21 | 本田技研工業株式会社 | Carbon dioxide treatment device and method for producing carbon compound |
| US11840768B2 (en) | 2021-03-11 | 2023-12-12 | Honda Motor Co., Ltd. | Carbon dioxide treatment device and method of producing carbon compound |
| CN114645290A (en) * | 2022-02-25 | 2022-06-21 | 东南大学 | CO (carbon monoxide)2Trapping and electric regeneration synchronous conversion system and method |
| US12031222B2 (en) | 2022-02-25 | 2024-07-09 | Southeast University | System and method for CO2 capture and electroregeneration and synchronous conversion |
| CN114887471A (en) * | 2022-04-28 | 2022-08-12 | 昆明理工大学 | Method and system for recycling pharmaceutical waste gas |
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