CN102225760A - Coal combustion CO2 capturing method and device based on metal oxide-CaCO3 absorbent - Google Patents
Coal combustion CO2 capturing method and device based on metal oxide-CaCO3 absorbent Download PDFInfo
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- CN102225760A CN102225760A CN2011100694127A CN201110069412A CN102225760A CN 102225760 A CN102225760 A CN 102225760A CN 2011100694127 A CN2011100694127 A CN 2011100694127A CN 201110069412 A CN201110069412 A CN 201110069412A CN 102225760 A CN102225760 A CN 102225760A
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- metal oxide
- cao
- coal
- caco
- reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention provides a coal combustion CO2 capturing method and a device based on a metal oxide-CaCO3 absorbent. The method provided by the invention is performed by firstly reacting a metal oxide and coal powder to generate high-concentration CO2 and using CaCO3 calcination product namely CaO as the CO2 absorbent. The method not only promotes the sufficient conversion of coal, but also realizes online activation of CaO by the reaction of CaO and steam, and maintains the stable absorption capacity of CaO to CO2 during multi-time circular reactions.
Description
Technical field
The present invention relates to CO in the coal combustion field, particularly coal combustion process
2Catching method and device.
Background technology
Control and minimizing coal combustion process CO
2Discharging, have important effect for reply Global warming and Greenhouse effect.Particularly for China, in view of the characteristics of its energy structure based on coal, CO
2Emission level sharply increases and has occupy the present situation of No. 1 in the world, the current CO that faces of China
2Reducing discharging pressure increases day by day, develops coal-fired efficiently CO
2Isolation technique realizes CO
2The reduction of discharging target, have important social meaning and economic worth.
Coal-fired CO
2The core that reduces discharging is to reclaim the CO that obtains high density
2At all kinds of coal-fired CO
2In the emission-reduction technology, with Wingdale as CO
2The absorption process of absorption agent, its major advantage are to have certain technology handiness, can be directly used in CO in the coal-fired tail flue gas
2Catch separation; Absorptive capacity is big, even the CaO transformation efficiency has only 50%, every Kg CaO is to CO
2Absorptive capacity also can reach 393g; Simultaneously, CaCO
3After the calcination and regeneration, can obtain high-purity CO near 100%
2Gas.But, when coal and air directly burn, produce a large amount of coal combustion tail flue gas, because inertia N in the air
2Doping dilution, CO in the tail flue gas
2Volume share is lower, is no more than 20%, low excessively CO
2The gas share causes the transforming degree of CaO greatly to reduce; And in repeatedly limestone calcination and CaO carbonation reaction process, along with the circulating reaction number of times increases, the reactive decay fast of CaO, CO
2Absorptive capacity constantly reduces.Therefore, improve CO in the coal combustion reaction end gas
2Concentration, promote CaO and CO
2The carbonating transforming degree, and suppress repeatedly the reactive decay of CaO in the circulating reaction process, for coal combustion CO
2Catch, extremely important.
Summary of the invention
The invention provides a kind of coal dust firing CO
2Catching method and device at first utilize the reaction of metal oxide and coal dust to produce high concentration CO
2, utilize Wingdale again as CO
2Absorption agent, not only promote the abundant conversion of coal, and by the online activation of the reaction of CaO and water vapour CaO, in circulating reaction repeatedly, make CaO to CO
2It is stable that absorptive capacity keeps.
Based on metal oxide-CaCO
3The coal combustion CO of absorption agent
2Catching method is specially:
(1) carry out coal dust gasification and metal oxide simultaneously and decompose, gasification product and metal oxide and this metal oxide decompose the more lower valency reactive metal oxide that is produced, and generate CO
2, water vapour, CO, H
2And metal, metal oxide decomposes the O that produces
2With the CO, the H that generate
2Carry out oxidizing reaction, generate CO
2And water vapour;
(2) CO of CaO absorption step (1) generation
2Generate CaCO with water vapour
3And Ca (OH)
2, Ca (OH)
2Further absorb CO
2Generate CaCO
3
(3) CaCO
3Decompose and produce pure CO
2Gas.
Further, metal and the atmospheric oxidation that also described step (1) is generated is regenerated as metal oxide.
Further, the CaO in the described step (2) derives from step (3) CaCO
3Calcining and decomposing.
Further, described metal oxide is CuO, CuFe
2O
4, MnFe
2O
4, CoFe
2O
4In any one.
Realize the device of aforesaid method, comprise the two-part bubbling fluidized bed 1, grit separator 2, the CaCO that join successively
3Separator 3, fast fluidized bed 4, first cyclonic separator 5, first seal valve 6, fast fluidized bed 7, second cyclonic separator 8, second seal valve 9 and two-part bubbling fluidized bed 1, bubbling fluidized bed 1 also is connected with coal fly ash trap 11 with the 3rd cyclonic separator 10 respectively.
Technique effect of the present invention is embodied in:
1. be fuel with coal or other carbonaceous fuel (comprising biomass, mud etc.), Wingdale is as the main ingredient of carrier, and reserves are big, the source is wide, price is low;
With metal oxide-Wingdale as complex carrier, be used for the coal combustion high concentration CO
2Catch the aspect, its reactivity is fully utilized.Theoretical foundation is as follows:
The molecular formula of supposing carbonaceous fuels such as coal is reduced to C, and Wingdale is with main ingredient CaCO wherein
3Expression, metal oxide is chosen CuO, in fuel reaction device 1, carbonaceous fuel and CuO-Wingdale complex carrier generation complex series of reactions such as coal, specific as follows:
At first, in the lower end of fuel reaction device 1, at water vapour or CO
2Under the atmosphere, carbonaceous fuels such as coal absorb a certain amount of water vapour (perhaps CO
2) and heat, carry out gasification reaction, produce CO and H
2, shown in following (1), (2) formula.
C+H
2O (gas) → H
2(gas)+CO (gas) (1)
C+CO
2(gas) → 2CO (gas) (2)
Simultaneously, in the lower end of fuel reaction device 1, gasification product (H
2CO) with CuO and Cu
2The O reaction produces CO
2And water vapour, and discharge certain heat; In addition, CaO and CO
2Carry out carbonation reaction, specific as follows shown in:
H
2/ CO (gas)+CuO → Cu+H
2O/CO
2(gas) (3)
H
2/ CO (gas)+Cu
2O → 2Cu+H
2O/CO
2(gas) (4)
CaO+CO
2(gas) → CaCO
3(5)
And in the upper end of fuel reaction device 1, the CuO decomposition discharges O
2, and with coal fully a small amount of incondensable gas of being produced of reaction (comprise CO and H
2) directly burning, produce CO
2And water vapour; Simultaneously, CaO finishes and the reaction of water vapour activation and CO
2Absorption, specifically react as follows:
4CuO → 2Cu
2O+O
2(gas) (6)
2CO/H
2(gas)+O
2(gas) → 2CO
2/ H
2O (gas) (7)
CaO+H
2O (gas) → Ca (OH)
2(8)
Ca(OH)
2+CO
2→CaCO
3+H
2O (9)
Secondly, in air reactor 4, finish Cu and air (O
2+ 3.76N
2) oxidation regeneration, and discharge a large amount of heats, specifically react as follows:
2Cu+ (O
2+ 3.76N
2) (gas) → 2CuO+3.76N
2(gas) (10)
At last, in calcinatory 7, utilize the entrained heat of CuO, finish the calcination and regeneration of Wingdale, produce the CO of CaO and high density
2Gas, concrete reaction formula is as follows:
CaCO
3/CuO→CaO/CuO+CO
2 (11)
By above-mentioned analysis, as can be seen, not only realized abundant conversion, the high concentration CO of coal dust
2Generation, but also finished the reducing/regenerating of CuO, the calcining and decomposing of Wingdale, online activation and the CO of CaO
2Absorption.
(3) this process has promoted the abundant conversion of coal dust, can obtain the CO of high density
2
(4) by the online activation of CaO and water vapour, avoided CaO to CO
2Absorptive capacity helps the reactive maintenance of CaO along with the reduction of circulating reaction number of times;
(5) simultaneously, by CaO to CO in the fuel reaction device tail flue gas
2And H
2The absorption of O steam has reduced the quantity discharged of fuel reaction device tail flue gas and the cost that condensation process expends greatly;
(6), realized the system capacity balance by the utilization of heat absorption between the differential responses and thermal discharge.
Description of drawings
Fig. 1. with CuO-CaCO
3Coal combustion CO for complex carrier
2Acquisition equipment figure.
Fig. 2. with CuO-CaCO
3Coal combustion CO for complex carrier
2Catch schema.
Embodiment
Coal dust firing CO proposed by the invention
2Acquisition equipment, as shown in Figure 1, by two-part bubbling fluidized bed 1, grit separator 2, CaCO
3Separator 3, the 3rd cyclonic separator 10 and coal fly ash trap 11 are formed the fuel reaction device A of system; Form the B of air reactor system by fast fluidized bed 4, first cyclonic separator 5, first seal valve 6 again; At last, link to each other successively, form the calcinatory C of system by fast fluidized bed 7, second cyclonic separator 8, second seal valve 9.
The present invention is a raw material with carbonaceous fuels such as coal and CuO-Wingdale complex carrier, carries out a series of reaction, finishes the abundant burning and the high concentration CO of coal
2Capture, flow process as shown in Figure 2, embodiment is as follows:
1. at first, at the lower semisection of fuel reaction device 1, the water vapour or the CO of 850 ℃ of left and right sides temperature of reaction and high density
2Under the atmosphere, finish coal gasification, gasification product and CuO/Cu
2The oxidizing reaction of O, the carbonation reaction of CaO (specifically suc as formula shown in (1)-(5));
2. at the upper semisection of fuel reaction device 1, under the temperature of reaction about 550 ℃, finish the decomposition thermo-negative reaction of CuO respectively, the O that discharges
2With coal at the fuel reaction device 1 lower semisection incondensable gas of complete reaction (CO and H not
2) carry out oxidizing reaction; Simultaneously, CaO absorbs water vapour and activates, and absorbs a large amount of CO that the coal combustion reaction produces
2, specifically suc as formula shown in (6)-(9).
3. the solid remnants of fuel reaction device 1 hypomere comprise coal ash, Cu and CaCO
3, by grit separator 2, separate coal ash, remaining Cu and CaCO
3Deliver into separator 3 again, finish CaCO
3Separation, then Cu is delivered into air reactor 4; And the residual gas of fuel reaction device 1 epimere and coal fly ash particle then by the 3rd cyclonic separator 10 and coal ash trap 11, are finished the processing of fly ash particle and residual gas.
4. in air reactor 4, under 850 ℃ the temperature of reaction, finish the oxidation of Cu and air, regeneration forms CuO and discharges a large amount of heats, and specifically as reacting shown in (10) formula, the residual air that is produced separates emptying by first cyclonic separator 5; The CuO that produces is then by first cyclonic separator 5 and first seal valve 6, and transmission enters calcination reactor 7;
5. in calcination reactor 7, temperature of reaction about 900 ℃ and CO
2Under the atmosphere, the heat that utilizes CuO to carry is finished CaCO
3Calcining, concrete as reaction produces CaO, and takes with CuO and pass through second cyclonic separator 8 and second seal valve 9 together as (11) formula shown in, circulating enters the epimere of fuel reaction device 1.Said process constantly repeats, thereby realizes the coal combustion high concentration CO
2Capture, obtain highly purified CO
2Gas.
The present invention is also with CuFe
2O
4, MnFe
2O
4, CoFe
2O
4With the Wingdale complex carrier be that raw material is tested, specific implementation process is as follows:
1. at the lower semisection of fuel reaction device 1, the water vapour or the CO of 850 ℃ of left and right sides temperature of reaction and high density
2Under the atmosphere, finish coal gasification, gasification product and MeFe
2O
4(Me=Cu, Mn and Co) and vacant wustite MeFe thereof
2O
4-xThe oxidizing reaction of (0≤x≤2), the carbonation reaction of CaO (concrete and step (1)-(5) formula is similar);
2. at the upper semisection of fuel reaction device 1, under the temperature of reaction about 900 ℃, finish MeFe respectively
2O
4The decomposition thermo-negative reaction of (Me=Cu, Mn and Co), the O that discharges
2With coal at the fuel reaction device 1 lower semisection incondensable gas of complete reaction (CO and H not
2) carry out oxidizing reaction; Simultaneously, CaO absorbs water vapour and activates, and absorbs a large amount of CO that the coal combustion reaction produces
2, concrete similar with (6)-(9) formula.
3. the solid remnants of fuel reaction device 1 hypomere comprise coal ash, Me (Me=Cu, Mn and Co), Fe
3O
4And CaCO
3, by grit separator 2, separate coal ash, remaining Me (Me=Cu, Mn and Co), Fe
3O
4And CaCO
3Deliver into separator 3 again, finish CaCO
3Separation, then Me (Me=Cu, Mn and Co) and Fe
3O
4Deliver into air reactor 4; And the residual gas of fuel reaction device 1 epimere and coal fly ash particle then by the 3rd cyclonic separator 10 and coal ash trap 11, are finished the processing of fly ash particle and residual gas.
4. in air reactor 4, under 850 ℃ the temperature of reaction, finish Me (Me=Cu, Mn and Co), Fe
3O
4With the oxidation of air, regeneration forms MeFe
2O
4(Me=Cu, Mn and Co) also discharges a large amount of heats, and concrete similar as reaction and (10) formula, the residual air that is produced separates emptying by first cyclonic separator 5; And the MeFe that produces
2O
4(Me=Cu, Mn and Co) then by first cyclonic separator 5 and first seal valve 6, transmission enters calcination reactor 7;
5. in calcination reactor 7, temperature of reaction about 900 ℃ and CO
2Under the atmosphere, utilize MeFe
2O
4The heat that (Me=Cu, Mn and Co) carries is finished CaCO
3Calcining, concrete as reaction is similar with (11), produce CaO, and take same MeFe
2O
4(Me=Cu, Mn and Co) together by second cyclonic separator 8 and second seal valve 9, circulation enters the epimere of fuel reaction device 1.Said process constantly repeats, thereby realizes the coal combustion high concentration CO
2Capture, obtain highly purified CO
2Gas.
Claims (5)
1. based on metal oxide-CaCO
3The coal combustion CO of absorption agent
2Catching method is specially:
(1) carry out coal dust gasification and metal oxide simultaneously and decompose, coal dust gasification product and metal oxide and this metal oxide decompose the more lower valency reactive metal oxide that is produced, and generate CO
2, water vapour, CO, H
2And metal, and metal oxide decomposes the O that produces
2With the CO and the H that generate
2Carry out oxidizing reaction, generate CO
2And water vapour;
(2) CO of CaO absorption step (1) generation
2And water vapour, generate CaCO
3And Ca (OH)
2, Ca (OH)
2Further absorb CO
2Generate CaCO
3
(3) CaCO that step (2) is generated
3Calcining and decomposing produces pure CO
2Gas and CaO.
2. coal dust firing CO according to claim 1
2Catching method is characterized in that, metal and atmospheric oxidation with described step (1) generates are regenerated as metal oxide.
3. coal dust firing CO according to claim 1
2Catching method is characterized in that, the CaO in the described step (2) derives from step (3) CaCO
3Decomposition.
4. coal dust firing CO according to claim 1
2Catching method is characterized in that, described metal oxide is CuO, CuFe
2O
4, MnFe
2O
4, CoFe
2O
4In any one.
5. realize the device of one of claim 1 to 4 described method, comprise the two-part bubbling fluidized bed, grit separator, the CaCO that join successively
3Separator, fast fluidized bed, first cyclonic separator, first seal valve, fast fluidized bed, second cyclonic separator, second seal valve and two-part bubbling fluidized bed, bubbling fluidized bed also are connected with the coal fly ash trap with the 3rd cyclonic separator respectively.
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CN2011100694127A CN102225760A (en) | 2011-03-22 | 2011-03-22 | Coal combustion CO2 capturing method and device based on metal oxide-CaCO3 absorbent |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115715984A (en) * | 2022-09-28 | 2023-02-28 | 山东大学 | Copper-cerium modified CaO for synergistically removing carbon dioxide and NO based on calcium circulation, and preparation method and application thereof |
CN116964002A (en) * | 2020-12-22 | 2023-10-27 | 石灰网社会效益有限责任公司 | Facility and method for producing decarbonized oxides or hydroxides using carbonates and electricity |
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CN101666546A (en) * | 2009-09-30 | 2010-03-10 | 华中科技大学 | Pulverized coal combustion method and device with function of capturing CO2 |
CN101878059A (en) * | 2007-11-27 | 2010-11-03 | 韦斯特克环境方案有限责任公司 | Method and means for capture and long-term sequestration of carbon dioxide |
-
2011
- 2011-03-22 CN CN2011100694127A patent/CN102225760A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101878059A (en) * | 2007-11-27 | 2010-11-03 | 韦斯特克环境方案有限责任公司 | Method and means for capture and long-term sequestration of carbon dioxide |
CN101666546A (en) * | 2009-09-30 | 2010-03-10 | 华中科技大学 | Pulverized coal combustion method and device with function of capturing CO2 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116964002A (en) * | 2020-12-22 | 2023-10-27 | 石灰网社会效益有限责任公司 | Facility and method for producing decarbonized oxides or hydroxides using carbonates and electricity |
CN116964002B (en) * | 2020-12-22 | 2024-09-20 | 石灰网社会效益有限责任公司 | Facility and method for producing decarbonized oxides or hydroxides using carbonates and electricity |
CN115715984A (en) * | 2022-09-28 | 2023-02-28 | 山东大学 | Copper-cerium modified CaO for synergistically removing carbon dioxide and NO based on calcium circulation, and preparation method and application thereof |
CN115715984B (en) * | 2022-09-28 | 2024-03-08 | 山东大学 | Copper-cerium modified CaO for cooperatively removing carbon dioxide and NO based on calcium circulation, and preparation method and application thereof |
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Application publication date: 20111026 |