CN103331096B - Preparation method of modified carbon dioxide calcium-based absorbent - Google Patents
Preparation method of modified carbon dioxide calcium-based absorbent Download PDFInfo
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- CN103331096B CN103331096B CN201310242184.8A CN201310242184A CN103331096B CN 103331096 B CN103331096 B CN 103331096B CN 201310242184 A CN201310242184 A CN 201310242184A CN 103331096 B CN103331096 B CN 103331096B
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Abstract
The invention relates to a preparation method of a modified carbon dioxide calcium-based absorbent. The method comprises the steps of dissolving calcium nitrate, magnesium nitrate and citric acid in deionized water at the temperature of 20-50 DEG C to form a mixed solution, adding ethylene glycol into the mixed solution, carrying out evaporating dehydration in water bath at the temperature of 80-85 DEG C to form gel, drying the gel in a drying oven at the temperature of 120-130 DEG C, grinding the dried gel to obtain solid powder, calcining the solid powder at the temperature of 800-900 DEG C for 2-5 hours and obtaining the modified carbon dioxide calcium-based absorbent. The carbon dioxide calcium-based absorbent prepared through two modifications (the magnesium nitrate is the primary modifier and the ethylene glycol is the secondary modifier) has the advantages of high carbon dioxide cyclic absorption efficiency, strong sintering resistance and good pore structure distribution at the same time, so that the carbon dioxide calcium-based absorbent still has high carbon dioxide collecting efficiency in the multiple cyclic calcination/carbonation reaction processes and the defects of the existing carbon dioxide calcium-based absorbents, that the superficial area is decreased and the porosity is reduced after multiple cyclic calcinations, are overcome.
Description
Technical field
The invention belongs to environmental emission and administer field, particularly relate to a kind of preparation method of modified carbon dioxide calcium-base absorbing agent, this calcium-base absorbing agent can be used for the trapping of the carbon dioxide in the flue gas of the fuel combustion such as fossil fuel and living beings generation.
Background technology
Greenhouse gases and climate change are one of key problems of studying of Present Global various countries.CO
2be one of predominant gas causing greenhouse effects, be also a kind of potential carbon resource simultaneously.In recent years, increasing researcher thinks by CO
2the global warming that the greenhouse effects of taking the factor as the leading factor cause just is threaten the existence of the mankind with sea level rise, the CO in air
2mainly from the product of fossil fuel, biomass fire and animal metabolism.
Along with China's rapid economic development, CO2 emissions also have and increase largely, are increased to 73.6 hundred million tons in 2009 from 1980 15.1 hundred million tons.It should be noted that China's CO2 emissions in 2007 reach 6,300,000,000 tons, exceeding the U.S. becomes the first in the world." 12 " planning clearly proposes the target call of unit GDP CO2 emission in 2015 than decline 17% in 2010, and the work of visible enforcement carbon dioxide discharge-reduction is very urgent.
Carbon dioxide discharge-reduction technology can be divided into three kinds: decarburization technique, the front decarburization technique of burning and oxygen-enriched combustion technology after burning.After burning, decarburization technique can be divided into according to the mechanism difference be separated: Physical Absorption technology, chemical absorbing technology, pressure swing adsorption method, chemical-looping combustion technology, cryogenic separation technology, membrane separation technique and microbial technique.Main employing is absorption techniques and adsorption technology at present.
Chemical absorbing technology is the collecting carbonic anhydride technology of current development comparative maturity.The technological principle of this technology is carbon dioxide in flue gas and absorbent generation chemical reaction.Conventional absorbent has: alkanolamine solution (MEA, MDEA etc.), carbonate solution alkali lye (ammoniacal liquor) and alkali and alkaline earth metal ions oxide etc.
Calcium-base absorbing agent has abundant raw material source, cheap, environmentally safe and can the feature such as repetitive cycling utilization, is just more and more used in the trapping technique of carbon dioxide.The application essence of Ca-base adsorbent is carbonating and the regeneration of CaO, and namely under certain condition, CaO absorbs CO
2generate CaCO
3, the CaCO will generated afterwards
3transfer in calcining furnace and calcine, regenerate CaO.Reaction equation is as follows:
CaO+CO
2→CaCO
3
CaCO
3→CaO+CO
2
But, common calcium-base absorbing agent along with the increase of absorption/desorption cycle-index, its CO
2uptake reduces rapidly.Natural dolomite is after 20 circulations, and its carbonate treatment rate drops to 20%.This is because in calcination process, absorbent surface sintering causes the reduction of its surface area and the reduction of porosity.
As Chinese invention patent application (application publication number CN102658010A, Shen Qing Publication day 2012.09.12) discloses a kind of preparation method of carbon dioxide composite calcium-base absorbent, although have higher carbon dioxide absorption ability, but repeatedly after Cyclic Calcination, its carbonate treatment rate declines.
Summary of the invention
Object of the present invention is exactly for above-mentioned defect, a kind of preparation method of modified carbon dioxide calcium-base absorbing agent is provided, through the carbon dioxide calcium-base absorbing agent of twice-modified preparation, both there is higher carbon dioxide recycle absorption efficiency, also there is stronger anti-sintering property.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method providing a kind of modified carbon dioxide calcium-base absorbing agent, calcium nitrate, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 20 ~ 50 DEG C and form mixed solution, ethylene glycol is added and dehydration by evaporation forms gel after stir into pasty state in 80 ~ 85 DEG C of constant temperature water baths in mixed solution, and dry in the baking oven of 120 ~ 130 DEG C, gel is dried after grinding obtains pressed powder and is calcined 2 ~ 5 hours at 800 ~ 900 DEG C, obtained modified carbon dioxide calcium-base absorbing agent.
In described mixed solution, calcium magnesium metal ion and be 0.8:1 ~ 1:1 with the mol ratio of citric acid.
In described mixed solution, the mol ratio of calcium metal ion and magnesium metal ion is 10:0.5 ~ 10:2.0.
The mol ratio of described citric acid and ethylene glycol is 1:1.5 ~ 1:2.
The present invention compared with prior art, beneficial effect is: (magnesium nitrate is a modifier by twice-modified, ethylene glycol is twice-modified dose) the carbon dioxide calcium-base absorbing agent prepared of method, not only there is higher carbon dioxide recycle absorption efficiency, carbon dioxide calcium-base absorbing agent has stronger anti-sintering property simultaneously, good pore structure distribution, thus maintain carbon dioxide calcium-base absorbing agent still have higher collecting carbonic anhydride efficiency in repeatedly Cyclic Calcination/carbonation reaction process, overcome existing carbon dioxide calcium-base absorbing agent repeatedly after Cyclic Calcination, the defect that its surface area reduces and porosity reduces.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the process chart that the present invention prepares modified carbon dioxide calcium-base absorbing agent;
Fig. 2, Fig. 3 and Fig. 4 are respectively the carbon dioxide calcium-base absorbing agent sample a of modification, the XRD image of sample b and sample c;
Fig. 5, Fig. 6 are CaO (analyzing pure) the SEM comparison diagram before and after circulation experiment;
Fig. 7, Fig. 8 are the SEM comparison diagram of sample b before and after circulation experiment;
Fig. 9 is that CaO(analysis is pure) and the specific area comparison diagram of sample b before and after circulation experiment;
Figure 10 is that CaO(analysis is pure) and the pore volume comparison diagram of sample b before and after circulation experiment;
Figure 11 is CaO (AR) and the pore-size distribution comparison diagram of sample b before and after circulating;
Figure 12 is the modified carbon dioxide calcium-base absorbing agent prepared of the present invention and CaO (AR) carbonation efficiencies comparison diagram.
Detailed description of the invention
Embodiment 1
Be that 10:0.5 takes appropriate calcium nitrate and magnesium nitrate (is converted to corresponding CaO and MgO quality according to calcium ions and magnesium ions mol ratio by calcium metal ion and magnesium metal ion mol ratio, and then be converted to the content of MgO, the calcium magnesium mol ratio of such as, 10:0.5 in this example, the MgO of CaO and 20g into 560g can be converted, then in this example, the content of MgO is 20/ (560+20)=3.5%), by calcium magnesium metal ion, the mol ratio of citric acid and ethylene glycol is that 0.8:1:1.5 takes appropriate citric acid and ethylene glycol, by the calcium nitrate after taking, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 20 DEG C and form mixed solution, the ethylene glycol taken is joined in mixed solution, and dehydration by evaporation forms gel be stirred to pasty state in 80 DEG C of waters bath with thermostatic control after, the baking oven that the gel of formation puts into 130 DEG C is dried, dry after grinding obtains pressed powder and calcine 5 hours at 900 DEG C, obtained content of MgO is the twice-modified carbon dioxide calcium-base absorbing agent of 3.5%.
Embodiment 2
Be that 10:0.7 takes appropriate calcium nitrate and magnesium nitrate by calcium metal ion and magnesium metal ion mol ratio, by calcium magnesium metal ion, the mol ratio of citric acid and ethylene glycol is that 0.9:1:1.5 takes appropriate citric acid and ethylene glycol, by the calcium nitrate after taking, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 30 DEG C and form mixed solution, the ethylene glycol taken is joined in mixed solution, and dehydration by evaporation forms gel be stirred to pasty state in 80 DEG C of waters bath with thermostatic control after, the baking oven that the gel of formation puts into 120 DEG C is dried, dry after grinding obtains pressed powder and calcine 4 hours at 850 DEG C, obtained through twice-modified carbon dioxide calcium-base absorbing agent.
Embodiment 3
Be that 10:1.6 takes appropriate calcium nitrate and magnesium nitrate by calcium metal ion and magnesium metal ion mol ratio, by calcium magnesium metal ion, the mol ratio of citric acid and ethylene glycol is that 0.8:1:1.8 takes appropriate citric acid and ethylene glycol, by the calcium nitrate after taking, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 50 DEG C and form mixed solution, the ethylene glycol taken is joined in mixed solution, and dehydration by evaporation forms gel be stirred to pasty state in 80 DEG C of waters bath with thermostatic control after, the baking oven that the gel of formation puts into 125 DEG C is dried, dry after grinding obtains pressed powder and calcine 5 hours at 900 DEG C, obtained through twice-modified carbon dioxide calcium-base absorbing agent.
Embodiment 4
Be that 10:2.0 takes appropriate calcium nitrate and magnesium nitrate by calcium metal ion and magnesium metal ion mol ratio, by calcium magnesium metal ion, the mol ratio of citric acid and ethylene glycol is that 0.8:1:2 takes appropriate citric acid and ethylene glycol, by the calcium nitrate after taking, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 35 DEG C and form mixed solution, the ethylene glycol taken is joined in mixed solution, and dehydration by evaporation forms gel be stirred to pasty state in 80 DEG C of waters bath with thermostatic control after, the baking oven that the gel of formation puts into 130 DEG C is dried, dry after grinding obtains pressed powder and calcine 5 hours at 800 DEG C, obtained through twice-modified carbon dioxide calcium-base absorbing agent.
Embodiment 5
Be that 10:1.5 takes appropriate calcium nitrate and magnesium nitrate by calcium metal ion and magnesium metal ion mol ratio, by calcium magnesium metal ion, the mol ratio of citric acid and ethylene glycol is that 1:1:1.5 takes appropriate citric acid and ethylene glycol, by the calcium nitrate after taking, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 25 DEG C and form mixed solution, the ethylene glycol taken is joined in mixed solution, and dehydration by evaporation forms gel be stirred to pasty state in 80 DEG C of waters bath with thermostatic control after, the baking oven that the gel of formation puts into 130 DEG C is dried, dry after grinding obtains pressed powder and calcine 5 hours at 800 DEG C, obtained through twice-modified carbon dioxide calcium-base absorbing agent.
Embodiment 6
Be that 10:2.0 takes appropriate calcium nitrate and magnesium nitrate by calcium metal ion and magnesium metal ion mol ratio, by calcium magnesium metal ion, the mol ratio of citric acid and ethylene glycol is that 1:1:2 takes appropriate citric acid and ethylene glycol, by the calcium nitrate after taking, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 45 DEG C and form mixed solution, the ethylene glycol taken is joined in mixed solution, and dehydration by evaporation forms gel be stirred to pasty state in 80 DEG C of waters bath with thermostatic control after, the baking oven that the gel of formation puts into 130 DEG C is dried, dry after grinding obtains pressed powder and calcine 5 hours at 900 DEG C, obtained through twice-modified carbon dioxide calcium-base absorbing agent.
Test analysis
1. XRD analysis
Fig. 2, Fig. 3 and Fig. 4 are respectively the carbon dioxide calcium-base absorbing agent sample a of modification, the XRD image of sample b and sample c.As can be seen from Figure, three samples are all have MgO and CaO two phase composition.
2. sem analysis
Fig. 5,6,7,8 for CaO(analyze pure) with the surface topography comparison diagram of sample b before and after circulation experiment.Comparison diagram 5 and Fig. 6 can find out, before and after 10 circulation experiments, CaO(analyzes pure) surface there occurs and obviously change, and the sintering of surperficial occurrence of large-area, grain diameter obviously increases.Comparison diagram 7 and Fig. 8 can find out, before and after 10 circulation experiments, significantly change does not occur the configuration of surface of sample b, and surface particles distributes very evenly, and particle also exists abundant pore structure.
3. the Pore Characteristics of sample and carbonation efficiencies analysis are as Fig. 9,10,11,12.
By reference to the accompanying drawings embodiments of the invention are described above; but the present invention is not limited to above-mentioned detailed description of the invention; above-mentioned detailed description of the invention is only schematic; instead of it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; do not departing under the ambit that present inventive concept and claim protect, also can make a lot of form, these all belong within protection scope of the present invention.
Claims (4)
1. the preparation method of a modified carbon dioxide calcium-base absorbing agent, it is characterized in that: calcium nitrate, magnesium nitrate and citric acid are dissolved in deionized water, be stirred to dissolve completely at 20 ~ 50 DEG C and form mixed solution, ethylene glycol is added and dehydration by evaporation forms gel after stir into pasty state in 80 ~ 85 DEG C of constant temperature water baths in mixed solution, and dry in the baking oven of 120 ~ 130 DEG C, gel is dried after grinding obtains pressed powder and is calcined 2 ~ 5 hours at 800 ~ 900 DEG C, obtained modified carbon dioxide calcium-base absorbing agent.
2. the preparation method of modified carbon dioxide calcium-base absorbing agent according to claim 1, is characterized in that: in described mixed solution, calcium magnesium metal ion and be 0.8:1 ~ 1:1 with the mol ratio of citric acid.
3. the preparation method of modified carbon dioxide calcium-base absorbing agent according to claim 1, is characterized in that: in described mixed solution, and the mol ratio of calcium metal ion and magnesium metal ion is 10:0.5 ~ 10:2.0.
4. the preparation method of modified carbon dioxide calcium-base absorbing agent according to claim 1, is characterized in that: the mol ratio of described citric acid and ethylene glycol is 1:1.5 ~ 1:2.
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| 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 |
| 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 |
| CN107262018B (en) * | 2017-07-31 | 2018-04-24 | 华中科技大学 | A kind of porous calcium-base absorbing agent of high-performance and preparation method thereof |
| CN108159843B (en) * | 2018-01-19 | 2019-09-27 | 清华大学 | A kind of calcium base CO using zirconic acid calcium stable2Absorbent and preparation method thereof |
| CN108525637B (en) * | 2018-03-21 | 2020-10-30 | 中国矿业大学 | Carbon template method modified calcium-based carbon dioxide adsorbent and preparation method thereof |
| CN110624381A (en) * | 2018-06-25 | 2019-12-31 | 沈阳三聚凯特催化剂有限公司 | Gas-phase dechlorinating 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 |
| CN111632476A (en) * | 2020-05-29 | 2020-09-08 | 武汉理工大学 | Carbon dioxide 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 |
| CN113856617A (en) * | 2021-10-08 | 2021-12-31 | 山西大学 | Preparation method of calcium-based carbon dioxide adsorbent |
| 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 |
| CN115555016A (en) * | 2022-09-27 | 2023-01-03 | 上海交通大学 | Carbon dioxide capturing and converting integrated implementation method based on adsorption/catalysis dual-function material |
| CN115636613B (en) * | 2022-10-20 | 2023-07-28 | 江苏中建商品混凝土有限公司 | Additive for improving carbonization resistance of concrete and application thereof |
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