CN103691283A - Method for fixing carbon dioxide in industrial smoke - Google Patents
Method for fixing carbon dioxide in industrial smoke Download PDFInfo
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- CN103691283A CN103691283A CN201310719929.5A CN201310719929A CN103691283A CN 103691283 A CN103691283 A CN 103691283A CN 201310719929 A CN201310719929 A CN 201310719929A CN 103691283 A CN103691283 A CN 103691283A
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- carbon dioxide
- reaction
- solid waste
- sulfur acid
- acid calcium
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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 relates to a method for fixing carbon dioxide in industrial smoke, and particularly relates to a method for fixing carbon dioxide in industrial smoke through carbonation by solid wastes containing calcium sulfate. The method provided by the invention comprises the following steps: at first, adding water into the solid wastes containing the calcium sulfate to obtain a solid powder water solution; adding ammonia water into the solid powder water solution and simultaneously introducing the industrial smoke; and filtering, washing and drying after stirring for reaction is finished under a constant pressure and at 20-40 DEG C, thus obtaining a product. According to the method provided by the invention, the solid wastes containing the calcium sulfate are reused; the method provides a good thought for large-scale emission reduction of carbon dioxide.
Description
Technical field
The present invention relates to a kind of method of fixing industrial carbon dioxide in flue gas, be specifically related to a kind of method of using the fixing industrial carbon dioxide in flue gas of the direct carbonating of sulfur acid calcium solid waste.
Background technology
SO
2be one of major pollutants of atmosphere, when serious, can cause the disasters such as acid rain, bring great harm to ecological environment and human social economy.Along with country is to SO
2emission control, flue gas desulfurization technique is more and more paid attention to.Desuifurized is that employing dry method, the semidry methods such as coal-burning power plant, sintering plant utilize desulfurizing agent to carry out to flue gas the solid waste that desulfurization produces, and is the partially yellow dry powder-shaped mixture of white that desulfurization reaction product, unreacted desulfurizing agent and fume duct fly ash form.According to the middle Electricity Federation statistics of 2009, estimation China approximately produces desuifurized 2,000 ten thousand tons the whole year.Desuifurizedly not only take a large amount of soils, cause a large amount of land resource to be occupied, if deal with improperly, its objectionable impurities more can cause serious secondary pollution to environment.It is to abandon that current desuifurized method of disposal is mainly one; The 2nd, for building material industry, soil improvement, administers waste liquid and metallurgy industry etc.
Summary of the invention
The main component of sulfur acid calcium solid waste comprises calcium sulfate, calcium sulfite and calcium hydroxide etc., has higher calcium content and reactivity; And the generation of these sulfur acid calcium solid waste ground is generally all attended by the discharge of large-scale industry flue gas, for this feature, the present invention is by reasonably design, a kind of method of solid waste as the fixing industrial carbon dioxide in flue gas of the direct carbonating of raw material of take is provided, the method not only can realize the recycling of sulfur acid calcium solid waste, simultaneously also for extensive carbon dioxide discharge-reduction provides a kind of better thinking.
Concrete technical scheme
A method for fixing industrial carbon dioxide in flue gas first adds water in sulfur acid calcium solid waste, obtains the pressed powder aqueous solution, add again ammonia spirit, and pass into industrial smoke simultaneously, reaction, after reacting completely, filter, wash, be dried, obtain product;
Wherein, described industrial smoke is the mist of carbon dioxide, oxygen and nitrogen, and the content of carbon dioxide by volume percentage is counted 5%-30%;
In every gram of sulfur acid calcium solid waste, pass into 0.5-3L industrial smoke, the speed that passes into of industrial smoke is 300-800mL/min;
Too fast Ventilation Rate can reduce the curing efficiency of carbon dioxide in flue gas, and too low Ventilation Rate can extend the carbonation reaction time;
The molar concentration of described ammoniacal liquor is preferably 1-4moL/L, in every gram of sulfur acid calcium solid waste, preferably adds 3-8mL ammoniacal liquor.
Described sulfur acid calcium solid waste is preferably desulfurization slag or desulfurated plaster.
Sulfur acid calcium solid waste of the present invention can derive from coal-burning power plant or sintering plant desuifurized etc.
In every gram of sulfur acid calcium solid waste, the content of calcium sulfate is preferably more than 75%.
The particle diameter of described desulfurization slag or desulfurated plaster is preferably 80-250 order.
Described particle diameter is that 80-250 object desulfurization slag Deng Shi steel plant or sintering plant carry out the alkali solid discarded object producing after sulfur removal technology, and the pressed powder source place of sulfur acid calcium is generally all attended by the discharge of large-scale industry flue gas.
During reaction, temperature is 20-40 ℃.
Reaction pressure is normal pressure.
The speed stirring in course of reaction is preferably 200-500 rev/min.
The time of reaction is preferably 60-240min.
After filtration, gained filtrate is ammonium sulfate, is a kind of important nitrogenous fertilizer; Gained filter cake washs and is dried by deionized water, obtains carbonate product, and wherein the quality percentage composition of calcium carbonate is greater than 95%.
Inventive principle and advantage
In the present invention, using ammoniacal liquor as auxiliary agent, first carbon dioxide in carbonation in industrial smoke reacts with ammoniacal liquor and generates ammonium carbonate, and then utilize calcium sulfate to be dissolved in this feature of ammonium salt solution, the ammonium carbonate generating is reacted with the calcium sulfate that is slightly soluble in water, generate calcium carbonate, thereby realized the carbon dioxide in efficient fixedly flue gas under low temperature, condition of normal pressure, in the present invention, the conversion ratio of calcium ion reaches more than 90%, has overcome that in prior art, the leaching rate of calcium ion is low, reaction temperature is high, the problems such as carbonate treatment rate is low under normal pressure.
In addition, in prior art during carbonating stabilizing carbon dioxide, required carbon dioxide is for purifying, high-purity carbon dioxide after removal of impurities, and deposit at normal temperatures and pressures the problems such as carbonate treatment rate is low, the present invention is by reasonably utilizing the abundant sulfur acid calcium solid waste of reserves directly to absorb the flue gas discharging in industrial process, make carbon dioxide and the calcium binding in raw material in flue gas form stable calcium carbonate, thereby greenhouse gases carbon dioxide conversion is stored for more stable carbonate, the present invention not only can realize the utilization of sulfur acid calcium solid waste, and realized directly extensive reduction of discharging of carbon dioxide in industrial smoke.
Although the present invention's reaction principle is comparatively simple, someone does not attempt this method at present, and also someone attempts using sulfur acid calcium solid waste directly to absorb the flue gas discharging in industrial process in industrial process.And the present inventor finds afterwards by countless experiments, the method is not only efficiently feasible, and can turn waste into wealth, and alleviates to a certain extent environmental pressure.
In addition, experiment shows, the industrial smoke that the present invention is applied in power plant and smeltery etc. is processed upper, can make one ton of sulfur acid calcium solid waste absorb 2000-3000kg industrial smoke, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of gained carbonate product in embodiment 1;
As can be seen from Figure 1, the desulfurization of raw material slag in embodiment 1 all changes calcium carbonate into after carbonation reaction, does not detect the second thing phase in solid product.
Fig. 2 is the stereoscan photograph of gained carbonate product in embodiment 1.
In embodiment 1, the pattern of carbonate product calcium carbonate is cube and spherical as can be seen from Figure 2, is of a size of 5-15 μ m.
Specific embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
Sulfur acid calcium solid waste in the present embodiment is selected desulfurization slag, and the main chemical compositions of desulfurization slag is, by weight percentage: SO
333%, CaO47%, Fe
2o
32%, other are 18% years old; The main chemical compositions of simulated flue gas is, in percent by volume: O
220%, CO
215%, N
265%, specific embodiment is as follows:
1) getting above-mentioned desulfurization slag powder 20g pours in 400mL beaker, then in beaker, add 200mL deionized water, above-mentioned beaker is put into 30 ℃ of water-baths of magnetic agitation, to the ammonia spirit 100mL that slowly splashes into 3moL/L in beaker, in solution, pass into simulated flue gas simultaneously, passing into speed is 600mL/min, stirring reaction 60min, in course of reaction, in solution, continue to pass into simulated flue gas, after question response completes, stop stirring, heating, stop passing into simulated flue gas;
2) pour out reacted mixture in described beaker, through suction filtration, obtain filtrate and solid product;
3) by above-mentioned steps 2) filtrate that obtains of suction filtration dries, and obtains ammonium sulfate powder;
4) by above-mentioned steps 2) the solid matter with deionized water washing that obtains of suction filtration three times, then at 105 ℃, be dried 12 hours, obtain 16.08 grams of carbonation reaction products, solid product is calcined 2 hours at 600 ℃, weigh calcining after quality be 15.93 grams, and then 900 ℃ of calcinings 2 hours, claiming to such an extent that the quality after calcining is 9.21 grams, the difference by two quality calculates the CO that 20g desulfurization slag carbonating has absorbed 6.72 grams
2.
5) by formula η=40M
2/ (44c
1m
1) to calculate carbonate treatment rate be 91%.M in formula
1for the quality of desulfurization slag, c
1for the percentage composition of calcium in desulfurization slag, M
2for the CO absorbing
2quality.
6) by formula n=100M
2/ (44M
3) percentage composition that calculates calcium carbonate in carbonate product is 95.2%.M in formula
2for the CO absorbing
2quality, M
3quality for carbonate product.
Embodiment 2
The solid waste of the sulfur acid calcium in the present embodiment is selected desulfurization slag, and the main chemical compositions of desulfurization slag is, by weight percentage: SO
333%, CaO47%, Fe
2o
32%, other are 18% years old; The main chemical compositions of simulated flue gas is, in percent by volume: O
210%, CO
225%, N
265%, specific embodiment is as follows:
1) get above-mentioned desulfurization slag powder 20g, then add wherein 200mL deionized water, above-mentioned beaker is put into 25 ℃ of water-baths of magnetic agitation, to the ammonia spirit 80mL that slowly splashes into 2moL/L in reaction solution, in solution, pass into simulation industrial smoke simultaneously, passing into speed is 400mL/min, stirring reaction 100min, in course of reaction, in solution, continue to pass into simulated flue gas, after question response completes, stop stirring, heating, stop passing into gas;
2) pour out reacted mixture in described beaker, through suction filtration, obtain filtrate and solid product;
3) by above-mentioned steps 2) filtrate that obtains of suction filtration dries, and obtains ammonium sulfate powder;
4) by above-mentioned steps 2) the solid matter with deionized water washing that obtains of suction filtration three times, then at 110 ℃ dry 12 hours, obtain 18.26 grams of carbonation reaction products;
5) by step 2) solid product that obtains is respectively 600 ℃ and 900 ℃ of calcinings 2 hours, calcines the quality of front and back by weighings, and calculating desulfurization slag carbonate treatment rate is 94%, in product, the percentage composition of calcium carbonate is that 96.6%(method is with embodiment 1).
Embodiment 3
Sulfur acid calcium solid waste in the present embodiment is selected desulfurated plaster, and the main chemical compositions of desulfurated plaster is, by weight percentage: SO
345%, CaO32%, other are 23% years old; The main chemical compositions of simulated flue gas is, in percent by volume: O
214%, CO
220%, N
266%, specific embodiment is as follows:
1) get above-mentioned desulfurated plaster powder 30g, then add wherein 100mL deionized water, above-mentioned beaker is put into 25 ℃ of water-baths of magnetic agitation, to the ammonia spirit 120mL that slowly splashes into 4moL/L in reaction solution, in solution, pass into simulated flue gas simultaneously, passing into speed is 500mL/min, stirring reaction 180min, in course of reaction, in solution, continue to pass into simulated flue gas, after question response completes, stop stirring, heating, stop passing into simulated flue gas;
2) pour out reacted mixture in described beaker, through suction filtration, obtain filtrate and solid product;
3) by above-mentioned steps 2) filtrate that obtains of suction filtration dries, and obtains ammonium sulfate powder;
4) by above-mentioned steps 2) the solid matter with deionized water washing that obtains of suction filtration three times, then at 80 ℃ dry 24 hours, obtain 20.07 grams of carbonation reaction products;
5) by step 2) solid product that obtains is respectively 600 ℃ and 900 ℃ of calcinings 2 hours, calcines the quality of front and back by weighings, and the carbonate treatment rate that calculates desulfurated plaster is 98%, in product, the percentage composition of calcium carbonate is that 98.6%(method is with embodiment 1).
Embodiment 4
The alkali solid discarded object of the sulfur acid calcium in the present embodiment is selected desulfurated plaster, and the main chemical compositions of desulfurated plaster is, by weight percentage: SO
345%, CaO32%, other are 23% years old; The main chemical compositions of simulated flue gas is, in percent by volume: O
25%, CO
215%, N
280%, specific embodiment is as follows:
1) get above-mentioned desulfurated plaster powder 30g, then add wherein 100mL deionized water, above-mentioned beaker is put into 35 ℃ of water-baths of magnetic agitation, to the ammonia spirit 200mL that slowly splashes into 1moL/L in reaction solution, in solution, pass into simulation industrial smoke simultaneously, passing into speed is 300mL/min, stirring reaction 240min, in course of reaction, in solution, continue to pass into simulated flue gas, after question response completes, stop stirring, heating, stop passing into gas;
2) pour out reacted mixture in described beaker, through suction filtration, obtain filtrate and solid product;
3) by above-mentioned steps 2) filtrate that obtains of suction filtration dries, and obtains ammonium sulfate powder;
4) by above-mentioned steps 2) the solid matter with deionized water washing that obtains of suction filtration three times, then at 80 ℃ dry 24 hours, obtain 21.49 grams of carbonation reaction products;
5) by step 2) solid product that obtains is respectively 600 ℃ and 900 ℃ of calcinings 2 hours, calcines the quality of front and back by weighings, and the carbonate treatment rate that calculates desulfurated plaster is 95%, in product, the percentage composition of calcium carbonate is that 97.4%(method is with embodiment 1).
Table 1
As shown in table 1, the raw material that the present invention uses is sulfur acid calcium solid waste and industrial smoke, and reaction condition is normal temperature, normal pressure, and finally the carbon dioxide conversion of acquisition is up to 98%, and in product, the content of calcium carbonate is up to 98.6%.
Claims (7)
1. a method for fixing industrial carbon dioxide in flue gas first adds water in sulfur acid calcium solid waste, obtains the pressed powder aqueous solution, add again ammonia spirit, and pass into industrial smoke reaction simultaneously, after reacting completely, filter, wash, be dried, obtain product;
Wherein, described industrial smoke is the mist of carbon dioxide, oxygen and nitrogen, and the content of carbon dioxide by volume percentage is counted 5%-30%;
In every gram of sulfur acid calcium solid waste, pass into 0.5-3L industrial smoke, the speed that passes into of industrial smoke is 300-800mL/min;
The molar concentration of described ammoniacal liquor is 1-4moL/L, in every gram of sulfur acid calcium solid waste, adds 3-8mL ammoniacal liquor.
2. method according to claim 1, is characterized in that, described sulfur acid calcium solid waste is desulfurization slag or desulfurated plaster.
3. method according to claim 1 and 2, is characterized in that, in every gram of sulfur acid calcium solid waste, the mass content of calcium sulfate is more than 75%.
4. method according to claim 1, is characterized in that, in the described pressed powder aqueous solution, the solid-to-liquid ratio of sulfur acid calcium solid waste and water is 2-10g/mL.
5. method according to claim 1 and 2, is characterized in that, the particle diameter of described desulfurization slag or desulfurated plaster is 80-250 order.
6. method according to claim 1, is characterized in that, during reaction, is reaction while stirring, and reaction temperature is 20-40 ℃.
7. according to the method described in claim 1 or 6, it is characterized in that,, during stirring reaction, the speed of stirring is 200-500 rev/min, the time of reaction is 60-240min.
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|---|---|---|---|
| CN201310719929.5A CN103691283A (en) | 2013-12-24 | 2013-12-24 | Method for fixing carbon dioxide in industrial smoke |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985251A (en) * | 2015-02-04 | 2016-10-05 | 北京紫光英力化工技术有限公司 | Clean production process for amino acids such as iminodiacetic acid |
| CN111298616A (en) * | 2019-12-17 | 2020-06-19 | 四川大学 | Desulfurized slag regenerated CO2Method for trapping solvent |
| CN112090252A (en) * | 2020-09-15 | 2020-12-18 | 中国矿业大学 | Modified desulfurized fly ash for fixing carbon dioxide and preparation method thereof |
| CN113769564A (en) * | 2021-09-22 | 2021-12-10 | 中南大学 | Semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and recycling method thereof |
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Cited By (6)
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| CN105985251A (en) * | 2015-02-04 | 2016-10-05 | 北京紫光英力化工技术有限公司 | Clean production process for amino acids such as iminodiacetic acid |
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| CN113769564A (en) * | 2021-09-22 | 2021-12-10 | 中南大学 | Semi-dry desulfurization ash solidified industrial flue gas carbon dioxide and recycling method thereof |
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Application publication date: 20140402 |