CN102836635A - Preparation method of modified carbon dioxide calcium-based absorbent - Google Patents

Preparation method of modified carbon dioxide calcium-based absorbent Download PDF

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Publication number
CN102836635A
CN102836635A CN2012102955662A CN201210295566A CN102836635A CN 102836635 A CN102836635 A CN 102836635A CN 2012102955662 A CN2012102955662 A CN 2012102955662A CN 201210295566 A CN201210295566 A CN 201210295566A CN 102836635 A CN102836635 A CN 102836635A
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calcium
carbon dioxide
nitrate
preparation
absorbing agent
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段钰锋
张平平
陈惠超
赵长遂
陈晓平
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Southeast University
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Southeast University
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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
    • 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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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a preparation method of a modified carbon dioxide calcium-based absorbent. The method adopts tartaric acid and nitrate as raw materials to prepare a compound calcium-based absorbent doped with other metal oxides by a sol-gel method. The method comprises the following steps: performing liquid mixing to calcium nitrate serving as a main raw material, other metals nitrate serving as a modifying agent and tartaric acid serving as a complexing agent; distilling and dehydrating to obtain gel; drying and heating the gel; and calcining for 2 hours in the air atmosphere at a temperature between 500 and 600 DEG C to obtain the modified carbon dioxide calcium-based absorbent. The modified carbon dioxide calcium-based absorbent prepared by utilizing the method is high in carbon dioxide absorption capability and stable in reaction activity, maintains high CO2 capture efficiency in multiple cyclic calcining/carbonation reaction processes; and the absorbent indicates excellent performance in CO2 capture efficiency, mechanical strength, calcination resistance and the like in the cyclic calcining/carbonation process.

Description

A kind of preparation method of modification carbon dioxide calcium-base absorbing agent
Technical field
The present invention relates to a kind of preparation method of modification carbon dioxide calcium-base absorbing agent, be used for removing flue gas CO 2Technology.Belong to environmental pollution prevention and control and clean coal combustion technology field.
Background technology
Climate change is one of global problem of current international community common concern, and has become the key factor that influences various countries' future economy and social sustainable development.In December, 2009, in the climate change conference of Copenhagen, most countries is all recognized the seriousness of the caused environmental problem of climate change, indicates on reply climate change problem, to bear responsibility separately.Reaching of " Copenhagen agreement " is that international community is devoted to whole world reduction of discharging CO 2New milestone.
Carbon dioxide is the main greenhouse gases that cause climate change, global warming.Chinese Government promises to undertake that the CO2 emissions that arrive the year two thousand twenty China unit GDP will reduce 40%-45% than 2005.The completion of this target is to CO 2The reduction that reaches cost of constantly improving of emission-reduction technology has proposed more urgent and difficult task.
At present, catch or remove CO 2Technology, method numerous, like membrane separation technique, amine absorption process, O 2/ CO 2CFBC, burning chemistry chains, rare-earth oxide absorption process, solid absorbent method etc.Can the economic and practical of every kind of technical method will be to determine it obtain the prerequisite of wide range of industrial applications.Utilize the circulation calcination/carbonation Reaction Separation CO of the cheap calcium-base absorbing agents such as lime stone that enrich 2Technical method caused countries in the world scholar's extensive concern.The technological process of this method is as shown in Figure 2, and lime stone is O in calcining furnace 2/ CO 2Calcining (> under the atmosphere; 900 ℃), discharge flue gas and contain high concentration CO 2(>95%) can reclaim.The CaO that generates gets into the carbonating stove and under normal pressure (650-750 ℃) or pressurization (650-850 ℃) condition, carries out the CO in the carbonation reaction absorption flue gas 2CO in the flue gas that the carbonating fire grate goes out 2Content low (<5%) CaCO of reaction generation, 3The regeneration of entering calcining furnace; So circulation realizes CO 2Effectively catch.Yet research shows natural calcium base CO such as lime stone 2There is a serious problem in absorbent: along with the increase of circulation calcination/carbonation reaction times, agglomeration makes the carbonating conversion ratio of absorbent descend rapidly.Normal pressure cyclic carbon acidification reaction 10 times, the carbonating conversion ratio is reduced to below 30%.In order to keep higher CO 2Removal efficiency, needs increase the input amount of fresh absorbent, and the wearing and tearing that this will increase cost, aggravation stove internal heating surface threaten device security, influence economical operation.Therefore, improve calcium base CO 2The long period cyclic carbon souring ability of absorbent and anti-caking power are to CO 2The long-term stability operation of absorption plant has important industrial application value.
Summary of the invention
Technical problem: the technical issues that need to address of the present invention provide a kind of coal-fired flue-gas CO that is used for removing 2The preparation method of high-efficiency composite calcium base absorbant, solve calcium-base absorbing agent and remove CO 2The problem that absorbent easy-sintering, cyclic carbon souring ability are decayed rapidly in the technology.
Technical scheme: conception of the present invention: limestone resource is abundant, cheap and easy to get, and its calcined product has circulation and catches CO 2Advantage; But its calcined product CaO intensity difference, frangible, anti-caking power is poor, cause service life short and pulverize after powder be prone to cause the equipment fouling of heating surface serious, influence problems such as system stability safe operation.The CO that passes through Prepared by Sol Gel Method that the inventor proposes 2Absorbent not only has good anti-sintering and antiwear property, has good pore structure simultaneously and distributes, and is very beneficial for circulation and absorbs CO in the flue gas 2, significantly improved the CO of common calcium-base absorbing agent 2Remove performance.
The present invention is the preparation method who is used for removing the composite calcium-base absorbent of coal-fired flue-gas carbon dioxide, and this method is that calcium nitrate and modifier are dissolved in the salpeter solution; 50-60 ℃ is stirred adding tartaric acid down and forms mixed solution; Above mixed solution is put into 80-85 ℃ of water-bath, dehydration by evaporation 6-8 hour formation gel sample; Put into oven for drying foaming 2-3 hour, porphyrize gets pale yellow powder; Grind the back and calcined 2-3 hour down, make modification carbon dioxide calcium-base absorbing agent at 500-600 ℃.
Described modifier is the nitrate of magnesium, manganese or aluminium; When modifier was magnesium nitrate, calcium was n with the ratio of the amount of substance of magnesium Ca: n Mg=10:0.75-10:1.5; When modifier was manganese nitrate, calcium was n with the ratio of the amount of substance of manganese Ca: n Mn=100:1-100:2.5: when modifier was aluminum nitrate, calcium was n with the ratio of the amount of substance of aluminium Ca: n Al=10:1-10:5.
The ratio of the amount of substance of the metal nitrate in tartaric acid and calcium nitrate and the modifier is n Tartaric acid: n Metal leaves Son=1.3:1-1.6:1.
The molar concentration of salpeter solution is 2M.The temperature of gel oven dry is 120-150 ℃.Calcining heat is 500-600 ℃.
Beneficial effect: the method for preparing carbon dioxide composite calcium-base absorbent provided by the present invention, its advantage is: the CO that adopts sol-gal process to obtain 2Absorbent, contained CaO and other metal oxides in the particle, it is more even to distribute, the distribution of pores excellent, anti-agglutinatting property can improve; Consequently not only significantly strengthen the carbonating ability of absorbent, and strengthened the mechanical strength and the wear resistance of absorbent, reduced the loss of absorbent in carbonation, thereby improved the cyclic utilization rate of absorbent.
The present invention has overcome natural calcium base CO such as lime stone 2Absorbent is caught CO in circulation 2In the process conversion ratio decay rapidly, problem such as anti-caking power difference and easy efflorescence, have that preparation technology is simple, easy to operate, the synthetic material formability is good, anti-sintering and antiwear property are strong, advantages such as good cycle.
Description of drawings
Fig. 1 is that modification carbon dioxide calcium-base absorbing agent of the present invention prepares process flow diagram flow chart.
Fig. 2 is calcium-base absorbing agent CO 2Catch process chart.
The specific embodiment
Case study on implementation 1
Take by weighing the Ca (NO of 23.615g 3) 24H 2Mg (the NO of O and 2.5641g 3) 26H 2O (n Ca: n Mg=10:1), be dissolved in the salpeter solution that 50ml concentration is 2M; Under 50-60 ℃, in magnetic stirring apparatus, stir the back and add 21.45g tartaric acid (n Tartaric acid: n Metal ion=1.3:1), add water to 100ml then, stirred 5-10 minute; Solution after stirring is put into 80-85 ℃ of water-bath, dehydration by evaporation 6-8 hour formation gel sample; And then putting it in 140 ℃ of baking ovens oven dry foaming 3 hours, porphyrize gets pale yellow powder; Move into again in the Muffle furnace in 550 ℃ of calcinings 3 hours, promptly make magnesium-modified carbon dioxide calcium-base absorbing agent.
Case study on implementation 2
Take by weighing the Ca (NO of 23.615g 3) 24H 250%Mn (the NO of O and 0.5495ml 3) 24H 2O solution (n Ca: n Mn=100:2), be dissolved in the salpeter solution that 50ml concentration is 2M; Under 50-60 ℃, in magnetic stirring apparatus, stir the back and add 22.95g tartaric acid (n Tartaric acid: n Metal ion=1.5:1), add water to 100ml then, stirred 5-10 minute; Solution after stirring is put into 80-85 ℃ of water-bath, dehydration by evaporation 6-8 hour formation gel sample; And then putting it in 130 ℃ of baking ovens oven dry foaming 3 hours, porphyrize gets pale yellow powder; Move into again in the Muffle furnace in 500 ℃ of calcinings 3 hours, promptly make manganese modification carbon dioxide calcium-base absorbing agent.
Case study on implementation 3
Take by weighing the Ca (NO of 23.615g 3) 24H 2Al (the NO of O and 9.37825g 3) 39H 2O (n Ca: n Al=10:2.5), be dissolved in the salpeter solution that 50ml concentration is 2M; Under 50-60 ℃, in magnetic stirring apparatus, stir the back and add 22.5g tartaric acid (n Tartaric acid: n Metal ion=1.2:1), add water to 100ml then, stirred 5-10 minute; Solution after stirring is put into 80-85 ℃ of water-bath, dehydration by evaporation 6-8 hour formation gel sample; And then putting it in 150 ℃ of baking ovens oven dry foaming 3 hours, porphyrize gets pale yellow powder; Move into again in the Muffle furnace in 600 ℃ of calcinings 3 hours, promptly make aluminium modification carbon dioxide calcium-base absorbing agent.

Claims (6)

1. the preparation method of a modification carbon dioxide calcium-base absorbing agent is characterized in that calcium nitrate and modifier are dissolved in the salpeter solution; 50-60 ℃ is stirred adding tartaric acid down and forms mixed solution; Above mixed solution is put into 80-85 ℃ of water-bath, dehydration by evaporation 6-8 hour formation gel sample; Put into oven for drying foaming 2-3 hour, porphyrize gets pale yellow powder; Grind the back and calcined 2-3 hour down, make modification carbon dioxide calcium-base absorbing agent at 500-600 ℃.
2. the preparation method of modification carbon dioxide calcium-base absorbing agent according to claim 1, the molar concentration that it is characterized in that salpeter solution is 2M.
3. the preparation method of modification carbon dioxide calcium-base absorbing agent according to claim 1 is characterized in that described modifier is the nitrate of magnesium, manganese or aluminium; When modifier was magnesium nitrate, calcium was n with the ratio of the amount of substance of magnesium Ca: n Mg=10:0.75-10:1.5; When modifier was manganese nitrate, calcium was n with the ratio of the amount of substance of manganese Ca: n Mn=100:1-100:2.5; When modifier was aluminum nitrate, calcium was n with the ratio of the amount of substance of aluminium Ca: n Al=10:1-10:5.
4. the preparation method of modification carbon dioxide calcium-base absorbing agent according to claim 1 is characterized in that the ratio of the amount of substance of the metal nitrate in tartaric acid and calcium nitrate and the modifier is n Tartaric acid: n Metal ion=1.3:1-1.6:1.
5. the preparation method of modification carbon dioxide calcium-base absorbing agent according to claim 1 is characterized in that the temperature of gel oven dry is 120-150 ℃.
6. the preparation method of modification carbon dioxide calcium-base absorbing agent according to claim 1 is characterized in that calcining heat is 500-600 ℃.
CN2012102955662A 2012-08-17 2012-08-17 Preparation method of modified carbon dioxide calcium-based absorbent Pending CN102836635A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103071373A (en) * 2013-02-01 2013-05-01 山东大学 Method for preparing high-activity CO2 absorbent with carbide slag
CN103349891A (en) * 2013-07-16 2013-10-16 中国科学院工程热物理研究所 Calcium magnesium double salt CO2 absorbent prepared from modified dolomite and preparation method thereof
CN104096472A (en) * 2014-06-27 2014-10-15 华中科技大学 Carbon dioxide/sulfur dioxide calcium-based sorbent and preparation method thereof
CN104772020A (en) * 2014-01-14 2015-07-15 中国科学院工程热物理研究所 Calcium magnesium compound salt CO2 absorbent and preparation method thereof
CN108525637A (en) * 2018-03-21 2018-09-14 中国矿业大学 A kind of carbon template modified calcium-base carbon dioxide absorber and preparation method thereof
CN108744945A (en) * 2018-06-28 2018-11-06 沈阳工业大学 A kind of high circulation stability calcium-base absorbing agent and preparation method thereof
CN115178075A (en) * 2022-07-20 2022-10-14 合肥中亚环保科技有限公司 Process system for removing carbon dioxide in flue gas of small kiln

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103071373A (en) * 2013-02-01 2013-05-01 山东大学 Method for preparing high-activity CO2 absorbent with carbide slag
CN103349891A (en) * 2013-07-16 2013-10-16 中国科学院工程热物理研究所 Calcium magnesium double salt CO2 absorbent prepared from modified dolomite and preparation method thereof
CN104772020A (en) * 2014-01-14 2015-07-15 中国科学院工程热物理研究所 Calcium magnesium compound salt CO2 absorbent and preparation method thereof
CN104096472A (en) * 2014-06-27 2014-10-15 华中科技大学 Carbon dioxide/sulfur dioxide calcium-based sorbent and preparation method thereof
CN104096472B (en) * 2014-06-27 2016-04-13 华中科技大学 A kind of carbon dioxide/sulfur dioxide calcium-base absorbing agent and preparation method thereof
CN108525637A (en) * 2018-03-21 2018-09-14 中国矿业大学 A kind of carbon template modified calcium-base carbon dioxide absorber and preparation method thereof
CN108744945A (en) * 2018-06-28 2018-11-06 沈阳工业大学 A kind of high circulation stability calcium-base absorbing agent and preparation method thereof
CN108744945B (en) * 2018-06-28 2021-01-22 沈阳工业大学 Calcium-based absorbent with high circulation stability and preparation method thereof
CN115178075A (en) * 2022-07-20 2022-10-14 合肥中亚环保科技有限公司 Process system for removing carbon dioxide in flue gas of small kiln

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Application publication date: 20121226