CN101249377A - Modification method of calcium-based ascarite - Google Patents

Modification method of calcium-based ascarite Download PDF

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Publication number
CN101249377A
CN101249377A CNA2008100232338A CN200810023233A CN101249377A CN 101249377 A CN101249377 A CN 101249377A CN A2008100232338 A CNA2008100232338 A CN A2008100232338A CN 200810023233 A CN200810023233 A CN 200810023233A CN 101249377 A CN101249377 A CN 101249377A
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ethanol
calcium
ascarite
absorbent
kmno
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CN101249377B (en
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赵长遂
李英杰
梁财
陈晓平
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Southeast University
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Southeast University
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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
    • 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
    • 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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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

A method to modify calcium based carbon-dioxide absorbent is that the prepared water solution of ethanol/KMnO4 is arranged in a container under the condition of normal temperature and normal pressure. The calcium based absorbent is calcined for one to two hours, and CaO particles generated are gradually added into the water solution of ethanol/KMnO4, and are stirred all along. After the mixture is stirred for one hour, the reaction product is dried, thus getting the high performance calcium based carbon-dioxide absorbent. The method can be applied in the process of removal of carbon dioxide in large scale by circulated calcination/carbonation during combustion or gasification of fossil fuel, and ethanol can be reclaimed and recycled according to the theory that the boiling points of ethanol and water are different. According to research, the modification method improves the caking resistance and the carbonation capacity of the calcium based absorbent during long circulated calcination/carbonation. With simple and convenient operation, the modification method needs low investment and cost, and is prospective in industrial application.

Description

The method of modifying of calcium-based ascarite
Technical field
The present invention relates to improve the method for calcium-based ascarite cyclic carbon acidifying performance, belong to environmental pollution prevention and control and clean coal combustion technology field.
Background technology
World energy sources mechanism once asserted, to the earth environment that is fit to human living produce the most direct influence no more than the CO in the atmosphere 2Content.The reality of global warming is just constantly sounded the alarm to the countries in the world people.Climate warming over nearly 50 years mainly is CO 2The warming effect of isothermal chamber gas causes.The negative effect that global warming brought comprises: sea level rise floods with land, the aggravation of the moving of climate zone, hurricane, vegetation migrate that variation and EI Nino with species extinction, ocean current takes place frequently, the change of rainfall pattern and pestilence popular etc.
At present, China CO 2Discharge capacity has occupied the second place of the world, expects 2025 and will occupy the No. 1 in the world.In the period of quite growing future, China can not change based on the energy general layout of coal, and the coal consumption amount is with sustainable growth.China's capacity of installed generator moderate heat Denso machine capacity accounts for more than 74%, and fired power generating unit is again based on coal-fired unit, and power industry is coal-fired rich and influential family, and the CO that causes thus 2Emission problem is serious day by day.
Countries in the world all remove and control CO on a large scale in research 2Technology and method, as membrane separation technique, amine absorption process, O 2/ CO 2Recycle combustion, burning chemistry chains method, rare-earth oxide absorption process, solid absorbent absorption process etc., economy will be the key factors that these methods are considered when using.In recent years, utilize the circulation calcination/carbonation Reaction Separation CO of the cheap calcium-base absorbing agents such as lime stone that enrich 2Method has caused countries in the world scholars' extensive concern.This method flow as shown in Figure 1, lime stone is O in calcining furnace 2/ CO 2CO in the flue gas is discharged in calcining (＞900 ℃) under the atmosphere 2Concentration height (＞95%) can reclaim, and the CaO of formation enters carbonation reactor and absorbs CO 2Pressurize (850-950 ℃) or normal pressure carbonation reaction (650-750 ℃), CO in the flue gas of discharge 2Concentration low (＜5%), the CaCO that reaction generates 3Enter the calcining furnace circular response again.Yet studies show that CO such as lime stone 2There is the problem of the serious decay of a performance in absorbent, and promptly along with the increase of circulation calcination/carbonation reaction times, absorbent descends rapidly because of sintering causes the carbonating conversion ratio, approximately reduces to below 30% through carbonating conversion ratio behind 10 circular responses.In order to keep high CO 2Removal efficiency, the addition of the fresh absorbent of having to additionally increase, this has not only increased cost, and the reactor wear that a large amount of absorbent causes threatens device security and economical operation.Therefore improve calcium base CO 2The long-term cyclic carbon souring ability of absorbent has great importance and is worth.
Summary of the invention
Technical problem: the method for modifying that the purpose of this invention is to provide a kind of calcium-based ascarite, this method can effectively suppress to increase with the circular response number of times the serious decay of calcium-base absorbing agent carbonating conversion ratio, increase the anti-agglutinatting property energy of absorbent in the circular response process, reduce the addition of fresh absorbent, alleviate the wearing and tearing and the corrosion of consersion unit, keep the safety and the economical operation of carbon dioxide circularly removing equipment.
Technical scheme: calcium-base absorbing agent method of modifying of the present invention is: under normal temperature and pressure conditions, ethanol being added distilled water in container, to be mixed with volumetric concentration be 50～90% ethanol water.The KMnO of weighing certain mass 4Particle adds it in ethanolic solution, and stirring is mixed with ethanol/KMnO 4The aqueous solution.Calcium-based ascarite was calcined 1～2 hour under 850 ℃ of conditions in Muffle furnace, and the CaO particle that calcining is formed adds ethanol/KMnO gradually 4(KMnO in the aqueous solution 4Be about 0.5～1% with the CaO mass ratio), the limit edged stirs, and stirs after 1 hour, the product in the container is carried out heat drying be calcium-based ascarite efficiently.This method of modifying can be applicable to that the circulation calcination/carbonation removes in the technology of carbon dioxide on a large scale in combustion of fossil fuel or the gasification, the principle different with water boiling point according to ethanol, and ethanol can reclaim and is recycling.
Experimental result shows, the CaO particle with ethanol/KMnO 4When hydration reaction took place in the solution, ethanol can strengthen the adhesion of CaO molecule and hydrone on the one hand, thereby bigger when making specific area after the hydrated product calcining of formation and pore volume ratio not have ethanol participation hydration, the pore size distribution characteristic is also more superior.On the other hand, the particle diameter of CaO and ethanolic solution hydrated product is significantly less than the particle diameter of the hydrated product that does not have the ethanol participation, so more helps absorbent and carries out carbonation reaction.KMnO as additive 4At CaO and H 2Can evenly penetrate in the particle hole of hydrated product KMnO in the circular response process in the hydration reaction of O 4(＞800 ℃) can be decomposed into MnO after calcining 2/ Mn 2O 3/ Mn 3O 4And K xMn yO zThe isoreactivity material, they not only can strengthen CO 2With the reaction of CaO, promote CO 2By the diffusion of carbonate product layer, and the pore structure of CaO played certain supporting role in long-term circular response process, improved the anti-agglutinatting property energy of CaO in circulation calcination/carbonation process, strengthened the carbonating ability.
Beneficial effect:
With unmodified calcium base CO 2Absorbent is compared, and the method for modifying that the present invention relates to has the following advantages:
1. calcium-base absorbing agent anti-agglutinatting property energy and cyclic carbon acidifying conversion ratio in long-term circulation calcination/carbonation process have obviously been improved.
2. adopt the calcium base CO of modification 2Absorbent can reduce operating cost, can alleviate carbonating to a certain extent
In the process calcium-base absorbing agent to the wearing and tearing of equipment.
4. this technological process is simple to operate, and equipment needed thereby is few, and floor space is little.
Description of drawings
Fig. 1 removes CO for the reaction of lime stone circulation calcination/carbonation 2Double-fluidized-bed coal combustion systems,
Fig. 2 is calcium base CO 2Absorbent carries out modification in circulation calcination/carbonation process process chart;
Fig. 3 is calcium base CO 2Absorbent modifying process simplified schematic diagram;
Fig. 4 is for measuring modification and unmodified calcium base CO 2The double-fixed bed pilot system of absorbent carbonating conversion ratio.
The specific embodiment
The present invention will be described below in conjunction with accompanying drawing:
Fig. 2 is calcium base CO 2Carry out the technological process of modification in the absorbent circulation calcination/carbonation process.Calcium base CO 2Absorbent such as lime stone, dolomite etc. enter and carry out pyrolytic in the calcining furnace, produce CaO.CaO enters hydration reactor again, with ethanol/KMnO 4Solution generation hydration reaction is carried out modification.The calcium base CO after the modification 2Absorbent is transported to distillation reactor, and dry box also reclaims ethanol.Absorbent after the modification enters carbonation reactor again, absorbs the CO that is produced by burning or gasification 2Replenish a small amount of fresh calcium-base absorbing agent simultaneously, enter behind the calcining furnace again by ethanol/KMnO 4Solution carries out modification to be handled, like this repeatable operation.
Fig. 3 is calcium base CO 2Absorbent modifying process schematic diagram.Concrete modification method of operating is as described below: under normal temperature and pressure conditions, with ethanol (volumetric concentration is 50～the 90%)/KMrO for preparing 4The aqueous solution places in the container, and the CaO particle that is generated by calcium-base absorbing agent calcining back is added ethanol/KMnO gradually 4In the aqueous solution, stir while adding.KMnO 4Quality and CaO mass ratio are about 0.5～1%, if add KMnO 4Very little, if DeGrain is but addition too big (for example＞2%) then can play opposite effect.After fully stirring 1 hour, under 120 ℃ of temperature to container in the modification absorbent carry out drying, this just obtains the calcium base CO of modification 2Absorbent.
The double-fixed bed test system of process modification and unmodified calcium-base absorbing agent carbonic acid conversion ratio in circulation calcination/carbonation process as shown in Figure 4.With the calcium-base absorbing agent in the porcelain boat in calcining furnace fully calcined after, enter the carbonating stove again and carry out carbonation reaction, weigh by the high-precision electronic balance behind the sufficient reacting.Calculate modification and unmodified calcium base CO according to formula (1) 2The cyclic carbon acidifying conversion ratio of absorbent.Calcining heat is 920 ℃, and the carbonating temperature is 650-700 ℃, and calcination atmosphere is N 2, carbonating atmosphere is 15%CO 2/ 85%N 2
X N = m N - m 1 m 0 · A · W CaO W CO 2 - - - ( 1 )
Wherein, X NBe the carbonating conversion ratio, N is a circulation calcination/carbonation reaction times, m NBe the quality of absorbent behind the N time circular response, m 1Be the 1st calcining back sample quality, m 0Be the initial sample quality, A is the content of CaO in the initial sample, W CaCO3And W CaOBe respectively CaCO 3Molal weight with CaO.
Adopt lime stone as CO 2Calcium-base absorbing agent.Experimental result shows, the carbonating conversion ratio of unmodified CaO is along with the increase of circular response number of times, and decling phase is when serious, less than 15%, and passes through ethanolic solution/KMnO through 20 circulation back conversion ratios 4CaO conversion ratio after the modification is along with the increase of cycle-index decay is comparatively slow, and the carbonating conversion ratio behind 20 circular responses is still up to more than 55%.

Claims (4)

1. the method for modifying of a calcium-based ascarite, it is characterized in that: the method for modifying of this calcium-based ascarite is:
Under normal temperature and pressure conditions, in container, ethanol is added distilled water preparation ethanol water, with KMnO 4Particle adds in the ethanol water, and stirring is mixed with ethanol/KMnO 4The aqueous solution; With calcium base CO 2Absorbent was calcined in Muffle furnace 1～2 hour, and the CaO particle that calcining is formed adds ethanol/KMnO gradually 4In the aqueous solution, the limit edged stirs, and stirs after 1 hour, the product in the container is carried out heat drying be calcium-based ascarite efficiently, and ethanol can reclaim and is recycling in dry run.
2. the method for modifying of calcium-based ascarite according to claim 1, the raw material that it is characterized in that calcium-based ascarite can be lime stone, dolomite.
3. according to the method for modifying of right 1 described calcium-based ascarite, it is characterized in that the ethanol water volumetric concentration of ethanol and distilled water preparation is 50～90%.
4. according to the method for modifying of right 1 described calcium-based ascarite, it is characterized in that the KMnO that adds 4Be about 0.5～1% with the CaO mass ratio.
CN2008100232338A 2008-04-03 2008-04-03 Modification method of calcium-based ascarite Expired - Fee Related CN101249377B (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844038A (en) * 2010-06-13 2010-09-29 东南大学 Method for preparing modified calcium-base absorbent for removing carbon dioxide in flue gas
CN102001657A (en) * 2010-10-28 2011-04-06 绍兴文理学院 Calcium-based CO2 regeneration furnace
CN102482596A (en) * 2009-03-31 2012-05-30 阿尔斯通技术有限公司 A hot solids process selectively operable based on a type of application that is involved
CN101732979B (en) * 2010-01-22 2012-08-15 东南大学 Preparation method of composite absorber for removing carbon dioxide from flue gas
CN102658010A (en) * 2012-05-17 2012-09-12 东南大学 Preparation method of carbon dioxide composite calcium-base absorbent
CN104168983A (en) * 2011-06-24 2014-11-26 西班牙高等科研理事会 Device and method for the capture of C02 by CaO carbonation and for maintaining sorbent activity
CN105126599A (en) * 2014-06-02 2015-12-09 阿尔斯通技术有限公司 Carbon capture system and method for capturing carbon dioxide
CN106194283A (en) * 2016-09-14 2016-12-07 东南大学 A kind of low energy consumption realizes the method for Gas Generator Set heating-cooling-power cogeneration zero carbon emission
CN106215682A (en) * 2016-08-05 2016-12-14 东南大学 A kind of CO towards Gas Generator Set heating-cooling-power cogeneration system2method for catching
CN110124644A (en) * 2019-04-12 2019-08-16 华中科技大学 A kind of multicomponent collaboration enhanced Ca-base adsorbent and preparation method thereof
CN111603902A (en) * 2020-05-18 2020-09-01 武汉理工大学 Magnesium chloride-based adsorbent and preparation method thereof
CN113041833A (en) * 2021-03-26 2021-06-29 沈阳工业大学 High-activity calcium-based absorbent containing ion transmission channel and preparation method thereof
CN113318699A (en) * 2021-01-28 2021-08-31 华中科技大学 Method for reducing composite molten salt in adsorbent by adding high-activity ions
CN113648826A (en) * 2021-08-20 2021-11-16 山东大学 Synergistic CO removal based on calcium circulation2And NO process
CN114904481A (en) * 2022-04-25 2022-08-16 沈阳工业大学 Tubular porous high-activity calcium-based absorbent and preparation method thereof

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102482596A (en) * 2009-03-31 2012-05-30 阿尔斯通技术有限公司 A hot solids process selectively operable based on a type of application that is involved
CN101732979B (en) * 2010-01-22 2012-08-15 东南大学 Preparation method of composite absorber for removing carbon dioxide from flue gas
CN101844038A (en) * 2010-06-13 2010-09-29 东南大学 Method for preparing modified calcium-base absorbent for removing carbon dioxide in flue gas
CN102001657A (en) * 2010-10-28 2011-04-06 绍兴文理学院 Calcium-based CO2 regeneration furnace
CN102001657B (en) * 2010-10-28 2012-07-25 绍兴文理学院 Calcium-based CO2 regeneration furnace
CN104168983A (en) * 2011-06-24 2014-11-26 西班牙高等科研理事会 Device and method for the capture of C02 by CaO carbonation and for maintaining sorbent activity
CN102658010A (en) * 2012-05-17 2012-09-12 东南大学 Preparation method of carbon dioxide composite calcium-base absorbent
CN105126599A (en) * 2014-06-02 2015-12-09 阿尔斯通技术有限公司 Carbon capture system and method for capturing carbon dioxide
CN106215682B (en) * 2016-08-05 2019-03-12 东南大学 A kind of CO towards Gas Generator Set heating-cooling-power cogeneration system2Method for catching
CN106215682A (en) * 2016-08-05 2016-12-14 东南大学 A kind of CO towards Gas Generator Set heating-cooling-power cogeneration system2method for catching
CN106194283B (en) * 2016-09-14 2017-07-21 东南大学 A kind of method that the carbon emission of Gas Generator Set heating-cooling-power cogeneration zero is realized in low energy consumption
CN106194283A (en) * 2016-09-14 2016-12-07 东南大学 A kind of low energy consumption realizes the method for Gas Generator Set heating-cooling-power cogeneration zero carbon emission
CN110124644A (en) * 2019-04-12 2019-08-16 华中科技大学 A kind of multicomponent collaboration enhanced Ca-base adsorbent and preparation method thereof
CN111603902A (en) * 2020-05-18 2020-09-01 武汉理工大学 Magnesium chloride-based adsorbent and preparation method thereof
CN113318699A (en) * 2021-01-28 2021-08-31 华中科技大学 Method for reducing composite molten salt in adsorbent by adding high-activity ions
CN113318699B (en) * 2021-01-28 2023-04-25 华中科技大学 Method for reducing composite molten salt in adsorbent by adding high-activity ions
CN113041833A (en) * 2021-03-26 2021-06-29 沈阳工业大学 High-activity calcium-based absorbent containing ion transmission channel and preparation method thereof
CN113648826A (en) * 2021-08-20 2021-11-16 山东大学 Synergistic CO removal based on calcium circulation2And NO process
CN113648826B (en) * 2021-08-20 2022-08-26 山东大学 Synergistic CO removal based on calcium circulation 2 And NO method
CN114904481A (en) * 2022-04-25 2022-08-16 沈阳工业大学 Tubular porous high-activity calcium-based absorbent and preparation method thereof
CN114904481B (en) * 2022-04-25 2024-05-31 沈阳工业大学 Tubular porous high-activity calcium-based absorbent and preparation method thereof

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