CN101269320A - Method for preparing calcium group carbonic anhydride adsorption agent - Google Patents
Method for preparing calcium group carbonic anhydride adsorption agent Download PDFInfo
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- CN101269320A CN101269320A CNA2008101007568A CN200810100756A CN101269320A CN 101269320 A CN101269320 A CN 101269320A CN A2008101007568 A CNA2008101007568 A CN A2008101007568A CN 200810100756 A CN200810100756 A CN 200810100756A CN 101269320 A CN101269320 A CN 101269320A
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- waste water
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- acetic acid
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Abstract
The invention relates to a preparation method of a calcium-based sorbent of carbon dioxide, taking acetic acid waste water and the calcium-based sorbent as raw materials. The preparation method is as follows: under a condition of normal temperature and pressure, the acetic acid waste water is added in to a container, the calcium-based sorbent is added into the acetic acid waste water while stirring, the mol ratio between the acetic acid in the acetic acid waste water and the calcium in the calcium-based sorbent is over 1.5:1; stirring is kept in the reaction to ensure uniform reaction between the calcium-based sorbent and the acetic acid waste water, a reaction product in the container is dehydrated by heating; acetone is released by reaction product obtained from the calcium-based sorbent conditioned by the acetic acid waste water; and the acetone is recycled in a method of carbonization; and the left solid product is the calcium-based sorbent of the carbon dioxide. The method can be applied in the technique of large-scale removal of carbon dioxide by cyclic calcination and carbonation in the combustion or gasification of fossil fuel and biomass, besides, the acetone which is an important chemical raw material can be recycled from the acetic acid waste water.
Description
Technical field
The present invention relates to strengthen the Ca-base adsorbent circulation and catch CO
2The method of performance belongs to environmental pollution prevention and control and clean coal combustion technology field.
Background technology
At present, with CO
2It is the common concern that the main caused global warming of greenhouse gases has been subjected to countries in the world.The data of U.S.'s announcement in 2004 show the global CO from 2000 to 2004
2Emission level is annual to increase by 3%---and this speed is nineteen ninety to 1999 year CO
2Gather way (1.1%) nearly 3 times of discharging.This will cause migrating of vegetation and species extinction, and climate zone moves, and sea level rise and land is flooded, and ocean current changes and phenomenons such as EI Nino takes place frequently.China is CO
2Discharging big country, especially coal fired power plant CO
2Emission control arrived instant stage.
CO
2Control method is numerous, has both comprised physical partition method in these methods, as membrane separation process, also comprises chemiadsorption, as amine absorption process, biosorption process and burning chemistry chains method etc.It is generally acknowledged that chemiadsorption has higher CO
2Removal efficiency, however Technological Economy also is to select CO
2The key factor of reduction of discharging mode reduces discharging CO on a large scale
2Mode is had higher requirement for Technological Economy.Select the CO of Cheap highly effective
2Adsorbent is effectively to control CO
2The key of discharging.In recent years, the calcination/carbonation Reaction Separation CO of Ca-base adsorbent
2Method caused various countries scholars' very big interest and extensive concern.This method adopts cheap, widely distributed lime stone and dolomite as CO
2Adsorbent.Ca-base adsorbent circulation calcination/carbonation reaction, both the direct hydrogen manufacturing with coal that can propose in U.S. Los Alamos National Laboratory be separation of C O in the near-zero release coal generation technology of core
2, also can in the double-fluidized-bed coal combustion systems that Canadian energy minerals center (CANMET) proposes, directly catch CO in the bed
2
Catch CO with Ca-base adsorbent in fossil fuel, biomass combustion or the gasification such as lime stone circulation calcination/carbonation
2System is that example describes.As shown in Figure 1, Ca-base adsorbent enters calcining furnace, adopts O in this stove
2/ CO
2Recycle combustion provides Ca-base adsorbent to decompose required heat, makes the CO of decomposition
2Be convenient to reclaim, the CaO of formation enters into the CO that carbonation reactor is caught burning or gasification reaction generation
2, the calcium carbonate of formation again in the calcining furnace disintegrating and regeneration be CaO, reaction cycle is carried out.The CaO of inactivation is discharged from, and adds fresh adsorbent simultaneously to replenish the adsorbent of inactivation.Yet there is a significantly deficiency in Ca-base adsorbent in the reaction of circulation calcination/carbonation: promptly along with the increase of circular response number of times, the carbonating performance is promptly caught CO
2Ability descend rapidly.In order to keep higher CO
2Removal efficiency, a large amount of fresh adsorbent of having to additionally replenish.A large amount of Ca-base adsorbents circulates in reactor operating cost is increased, and can also make wearing and tearing, pickup and the corrosion aggravation of reactor.Therefore improve Ca-base adsorbent circulation CO absorption
2Ability, obtain higher CO with less Ca-base adsorbent
2The circularly removing ability has crucial meaning and value for safety and economic operation.
Summary of the invention
Technical problem: the purpose of this invention is to provide and a kind ofly can improve Ca-base adsorbent circulation and catch CO
2Performance can be handled the preparation method of the calcium group carbonic anhydride adsorption agent of acetate waste water again.This method can not only effectively suppress to increase with the circular response number of times the serious decay of Ca-base adsorbent carbonating conversion ratio, increase the anti-agglutinatting property energy of adsorbent in the circular response process, reduce the addition of fresh adsorbent, alleviate the wearing and tearing and the corrosion of consersion unit, and can handle the acetate in the acetate waste water and reclaim acetone.
Technical scheme: under normal temperature and pressure conditions, acetate waste water is placed in the container, Ca-base adsorbent particles such as lime stone, dolomite and calcium oxide are added in the acetate waste water, stir while adding, in the acetate waste water in acetate and the Ca-base adsorbent mol ratio of Ca be higher than 1.5: 1, in course of reaction, keep to stir and make Ca-base adsorbent and acetate waste water reaction even, react after 5 hours, the product in the container is carried out heat drying dewater.The product that obtains behind the modified Ca-base adsorbent of acetate waste water can discharge acetone, adopts the recyclable acetone of method of destructive distillation, and the remaining solid product is as CO
2Adsorbent.Acetate waste water is the acetate waste water of food or light textile or medicine or dyestuff or spices or agricultural chemicals generation, and the raw material of Ca-base adsorbent is lime stone or dolomite or calcium oxide.
Testing result shows, the CaO crystallite dimension after the 1st calcining back of the Ca-base adsorbent after acetic acid solution is modified CaO crystallite dimension is calcined for the 1st time less than former Ca-base adsorbent.Along with the increase of circular response number of times, the crystallite dimension of former Ca-base adsorbent calcining back CaO becomes big rapidly, and intercrystalline hole reduces thereupon, thereby has increased CO
2Diffusional resistance in particle is disadvantageous to carbonation reaction; And the adsorbent after acetic acid solution is modified is calcined the increase of back with cycle-index, and the CaO crystallite dimension increases slowly, has shown stronger anti-agglutinatting property energy, has kept intercrystalline hole preferably, and this helps CO
2In intercrystalline diffusion.Pore structure parameter after adopting n2 absorption apparatus to the calcining of the modified front and back of acetic acid solution adsorbent is analyzed, the result shows, increase with cycle-index reduces rapidly to compare with specific pore volume with the specific area of former adsorbent, adsorbent calcining back specific area after acetic acid solution is modified and specific pore volume are all far above former adsorbent, and, more be better than former adsorbent in the calcining of the adsorbent after acetic acid solution after the same loop reaction times is modified back pore size distribution along with the increase specific area and the specific pore volume of circular response number of times descends slowly.Optimize microstructure after the Ca-base adsorbent calcining because acetic acid solution is modified, made Ca-base adsorbent have more good carbonating performance and anti-agglutinatting property energy.
Beneficial effect: adopt the modified Ca-base adsorbent of acetate waste water to improve its circulation and catch CO
2Performance has the following advantages:
1. obviously improved the anti-agglutinatting property of Ca-base adsorbent in long-term circulation calcination/carbonation process and can catch CO with circulation
2Ability.
2. can effectively handle the acetate in the acetate waste water, reduce the caused environmental pollution of acetate discharge of wastewater.
3. can from the Ca-base adsorbent after acetate waste water is modified, reclaim acetone, can make industrial chemicals, improve the economy of course of reaction.
4. adopt the calcium base CO of modification
2Adsorbent can reduce operating cost, can alleviate in the carbonation Ca-base adsorbent to a certain extent to the abrasion of equipment.
Description of drawings
Fig. 1 is that Ca-base adsorbent is caught CO with circulation calcination/carbonation reactive mode in burning or gasification
2Flow chart;
Fig. 2 is the process chart that adopts the modified Ca-base adsorbent of acetate waste water in circulation calcination/carbonation process.
The specific embodiment
Fig. 2 is the process chart that adopts the modified Ca-base adsorbent of acetate waste water in circulation calcination/carbonation process.Ca-base adsorbent enters modified reaction tower and acetate waste water generation acidification reaction, and the adsorbent after modified enters the dry distillation reactor tower again and carries out destructive distillation, reclaims the acetone that modified adsorbent discharges, and then carries out the calcination/carbonation reaction cycle and catch CO
2
Adopt the concrete method of operating of the modified Ca-base adsorbent of acetate waste water as described below: under normal temperature and pressure conditions, the acetate waste water solution is placed in the container, Ca-base adsorbent particles such as lime stone, dolomite and calcium oxide are added in the acetate waste water, stir while adding, in the acetate waste water in acetate and the Ca-base adsorbent mol ratio of Ca be higher than 1.5: 1, in course of reaction, stir and make Ca-base adsorbent and acetate waste water reaction even, react after 5 hours, the product in the container is carried out the heat drying dehydration.The product that obtains behind the modified Ca-base adsorbent of acetate waste water can discharge acetone about 380 ℃, adopt the recyclable acetone of method of destructive distillation, and the remaining solid product is as CO
2Adsorbent.
In circulation calcination/carbonation course of reaction,, as shown in table 1 to the cyclic carbon acidifying conversion ratio of lime stone after adopting acetic acid solution modified and the former lime stone mensuration that experimentizes; To the cyclic carbon acidifying conversion ratio of dolomite after adopting acetic acid solution modified and the former dolomite mensuration that experimentizes, the results are shown in Table 2.Experiment condition is: calcining heat is 920 ℃, and calcination atmosphere is 80%CO
2And 20%O
2, the carbonating temperature is 650～700 ℃, carbonating atmosphere is 15%CO
2And 85%N
2Be not difficult to find that the carbonating conversion ratio of Ca-base adsorbent in circulation calcination/carbonation process is significantly improved after acetic acid solution is modified.
The carbonating conversion ratio of lime stone after table 1 acetic acid solution is modified and former lime stone
The carbonating conversion ratio of dolomite after table 2 acetic acid solution is modified and former dolomite
Claims (3)
1. the preparation method of a calcium group carbonic anhydride adsorption agent, it is characterized in that: described method is a raw material with acetate waste water, Ca-base adsorbent, and its method is as follows:
Under normal temperature and pressure conditions, acetate waste water is placed in the container, the Ca-base adsorbent particle is added in the acetate waste water, the limit edged stirs, in the acetate waste water in acetate and the Ca-base adsorbent mol ratio of calcium be higher than 1.5: 1, in reaction, keep to stir and make Ca-base adsorbent and acetate waste water reaction even, the product in the container is carried out heat drying dewater; The product that obtains behind the modified Ca-base adsorbent of acetate waste water can discharge acetone, adopts the method for destructive distillation to reclaim acetone, and the remaining solid product is a calcium group carbonic anhydride adsorption agent.
2. the preparation method of calcium group carbonic anhydride adsorption agent according to claim 1 is characterized in that acetate waste water is the acetate waste water of food or light textile or medicine or dyestuff or spices or agricultural chemicals generation.
3. the preparation method of calcium group carbonic anhydride adsorption agent according to claim 1, the raw material that it is characterized in that Ca-base adsorbent is lime stone or dolomite or calcium oxide.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001657A (en) * | 2010-10-28 | 2011-04-06 | 绍兴文理学院 | Calcium-based CO2 regeneration furnace |
| CN102549119A (en) * | 2009-09-18 | 2012-07-04 | 沃姆瑟能源解决方案公司 | Systems, devices and methods for calcium looping |
| CN102836635A (en) * | 2012-08-17 | 2012-12-26 | 东南大学 | Preparation method of modified carbon dioxide calcium-based absorbent |
| CN103657582A (en) * | 2012-09-13 | 2014-03-26 | 华东理工大学 | Improved calcium-oxide-based CO2 adsorbent and preparation method thereof |
| CN104193633A (en) * | 2014-08-22 | 2014-12-10 | 南京信息工程大学 | Preparation method of modified calcium-based decarburization and desulfurization agent, and product and application of calcium-based decarburization and desulfurization agent |
| 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 |
| CN105498710A (en) * | 2015-12-20 | 2016-04-20 | 高大元 | Preparation method for preparing modified compound calcium-based carbon dioxide adsorbent through fishbone |
| CN108212073A (en) * | 2017-12-04 | 2018-06-29 | 但建明 | A kind of anti-crushing type carbon dioxide absorber and preparation method thereof |
| CN111790266A (en) * | 2020-07-27 | 2020-10-20 | 山东大学 | System and method for simultaneously removing carbon dioxide and nitrogen oxide |
| CN114832611A (en) * | 2022-05-08 | 2022-08-02 | 南京理工大学 | Mercury carbon desorption device based on calcium circulation |
| US11572518B2 (en) | 2019-11-25 | 2023-02-07 | Wormser Energy Solutions, Inc. | Char preparation system and gasifier for all-steam gasification with carbon capture |
-
2008
- 2008-05-16 CN CNA2008101007568A patent/CN101269320A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102549119A (en) * | 2009-09-18 | 2012-07-04 | 沃姆瑟能源解决方案公司 | Systems, devices and methods for calcium looping |
| 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 |
| CN102836635A (en) * | 2012-08-17 | 2012-12-26 | 东南大学 | Preparation method of modified carbon dioxide calcium-based absorbent |
| CN103657582A (en) * | 2012-09-13 | 2014-03-26 | 华东理工大学 | Improved calcium-oxide-based CO2 adsorbent and preparation method thereof |
| 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 |
| CN104193633A (en) * | 2014-08-22 | 2014-12-10 | 南京信息工程大学 | Preparation method of modified calcium-based decarburization and desulfurization agent, and product and application of calcium-based decarburization and desulfurization agent |
| CN104193633B (en) * | 2014-08-22 | 2016-06-29 | 南京信息工程大学 | Modified calcium-base decarbonization, desulfuration agent preparation method and products thereof and application |
| CN105498710A (en) * | 2015-12-20 | 2016-04-20 | 高大元 | Preparation method for preparing modified compound calcium-based carbon dioxide adsorbent through fishbone |
| CN108212073A (en) * | 2017-12-04 | 2018-06-29 | 但建明 | A kind of anti-crushing type carbon dioxide absorber and preparation method thereof |
| US11572518B2 (en) | 2019-11-25 | 2023-02-07 | Wormser Energy Solutions, Inc. | Char preparation system and gasifier for all-steam gasification with carbon capture |
| CN111790266A (en) * | 2020-07-27 | 2020-10-20 | 山东大学 | System and method for simultaneously removing carbon dioxide and nitrogen oxide |
| CN114832611A (en) * | 2022-05-08 | 2022-08-02 | 南京理工大学 | Mercury carbon desorption device based on calcium circulation |
| CN114832611B (en) * | 2022-05-08 | 2024-04-19 | 南京理工大学 | Method for removing mercury carbon by mercury carbon removing device based on calcium circulation |
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Open date: 20080924 |