CN102527225B - A kind of method using reproducible carbide slag collecting carbon dioxide from fuel gas - Google Patents
A kind of method using reproducible carbide slag collecting carbon dioxide from fuel gas Download PDFInfo
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- CN102527225B CN102527225B CN201010608692.XA CN201010608692A CN102527225B CN 102527225 B CN102527225 B CN 102527225B CN 201010608692 A CN201010608692 A CN 201010608692A CN 102527225 B CN102527225 B CN 102527225B
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- carbide slag
- carbon dioxide
- flue gas
- absorbent
- calcium oxide
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
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Abstract
本发明涉及电石渣的应用领域，具体地，本发明涉及一种使用可再生的电石渣捕集烟气中二氧化碳的方法。根据本发明的使用可再生的电石渣捕集烟气中二氧化碳的方法包括以下步骤：1)将电石渣煅烧，得到有效成分为氧化钙的吸收剂；2)将步骤1)中的吸收剂加入碳化反应器中吸收烟气中的二氧化碳，得到碳酸钙和干净的烟气；3)将步骤2)中的碳酸钙煅烧，实现吸收剂的再生；4)将步骤3)中再生的吸收剂中失活的部分去除，补入新的电石渣，返回到步骤2)中循环利用，重复步骤2)～4)。本发明的优点在于遵循以废治废的环保理念，降低了烟气中二氧化碳的排放，具有良好的实际应用前景。
The invention relates to the application field of calcium carbide slag, and in particular, the invention relates to a method for capturing carbon dioxide in flue gas by using renewable calcium carbide slag. According to the present invention, the method of using renewable calcium carbide slag to capture carbon dioxide in flue gas comprises the following steps: 1) calcining carbide slag to obtain an absorbent whose active ingredient is calcium oxide; 2) adding the absorbent in step 1) to Absorb carbon dioxide in the flue gas in the carbonization reactor to obtain calcium carbonate and clean flue gas; 3) calcinate the calcium carbonate in step 2) to realize the regeneration of the absorbent; 4) put the regenerated absorbent in step 3) into Remove the inactivated part, add new carbide slag, return to step 2) for recycling, and repeat steps 2) to 4). The invention has the advantages of following the environmental protection concept of treating waste with waste, reducing the emission of carbon dioxide in flue gas, and having good practical application prospect.
Description
Technical field
The present invention relates to the application of carbide slag, particularly, the present invention relates to a kind of method using reproducible carbide slag collecting carbon dioxide from fuel gas.
Background technology
The global warming trend that greenhouse gases cause has become the environmental problem of current international community common concern, wherein CO
2be topmost class greenhouse gases, its greenhouse effects account for about 77% of all greenhouse gases, thus control CO
2discharge most important for control greenhouse effects, mitigation of climate change trend.The Chinese country maximum as world population, and energy consumption structure is based on coal, be thus that statistic unit calculates total amount with country, current China is greenhouse gas emission big country of the world.As developing country, with the quickening of modernization, the discharge of Chinese greenhouse gases will continue to increase in a short time, the CO that China facing is huge
2emission reduction, thus needs to carry out CO
2the research and development of emission-reduction technology.From CO
2the profile of industries of emission source, current and long term from now on, the CO of China
2the capable source of primary discharge is energy industry, especially power industry.At present, the CO of China's Electric Power Industry
2discharge capacity occupies total release about 50%, thus the effective CO of exploiting economy
2trapping technique will have very high practical prospect and competitive advantage.
Adopt calcium-base absorbing agent Reaction Separation CO
2method is the CO most with application prospect
2one of trapping technique.Current research field is investigated maximum natural calcium base ores such as lime stone that mainly utilize and is trapped CO
2performance.As shown in Figure 1: first lime stone in calcination reactor, high-temperature decomposition reaction occurs, the calcium oxide (CaO) of decomposition enters the CO in carbonization reactor trapping flue gas
2and generate CaCO
3, the clean flue gas after decarburization is discharged in air.The CaCO generated in carbonization reactor
3enter again a calcination reactor generation new round to decompose.The pure CO discharged
2can be used for sealing up for safekeeping or recycling.Ore resource is limited and belong to non-renewable resources.The natural crystals such as a large amount of exploitation lime stone, dolomite or calcite, as the source of calcium-base absorbing agent, will bring many negative effects to ecological environment (earth's surface resource, geological environment, the hydrology and weather conditions); In addition, because absorbent regeneration carries out under the high temperature conditions, thus high temperature sintering behavior seriously will cause the CO of absorbent
2absorption efficiency increases with cycle-index and constantly decays, bibliographical information: utilize natural limestone through 1000 circularly trapping CO
2after reaction, its remaining conversion ratio is only 3.5%, and thus above-mentioned shortcoming significantly limit the natural calcium foundation stone lime stones such as lime stone and removing CO
2the practical application of aspect.Finally, the natural calcium base ores such as lime stone are utilized CaCO can to occur in calcination process first
3decomposition reaction thus extra produce a certain amount of CO
2gas (be 90% calculating with calcium carbonate content, average 1 ton of lime stone after calcining by generation 0.396 ton of CO
2), thus will weaken the trapping such as the calcium-base absorbing agent that utilizes lime stone CO to a certain extent
2the environmental benefit of technology.
In order to make up the deficiency of natural calcium base absorbant, a kind of environmental friendliness must be sought and reactivity is better than the substitute of the natural absorbent such as natural limestone.
Carbide slag is that acetylene (C produced by raw material with calcium carbide
2h
2) solid by-product, and main component is calcium hydroxide (Ca (OH)
2), with oxide or the hydroxide of silicon, iron, aluminium, magnesium, sulphur, phosphorus, it is mainly discharged by the Production of PVC producer of chlor-alkali industry and the neoprene manufacturer of synthetic material industry.Estimate that China's carbide slag total output reaches 1,800 ten thousand tons/year.Compare the trade wastes such as white clay, red mud and blast furnace slag, carbide slag the active calcium ion content is higher, at present, mainly comprises for the process of carbide slag and the method for disposal: (1) fills out sea, the regular stacking of field ditch; (2) sell after natural subsidence, replace lime cement made of stones, production quick lime as carbide raw material, produce light-weight brick, produce expoxy propane, potassium chlorate etc. as industrial chemicals.Mode (1) is mainly taked in process disposal at present for carbide slag, this processing mode will take a large amount of soil, pollute phreatic water and cause the salinization of soil, thus this trade waste of carbide slag can not carry out effectively utilizing and administering by which.Mainly comprise for carbide slag recycling: (1) patent No. is that the Chinese invention patent of ZL200810116928.0 describes the wet fuel gas desulfurizing technology utilizing carbide slag to make absorbent, (2) patent No. be 200810146495.3 Chinese invention describe one and utilize carbide slag to prepare high-purity CaCO
3the method of product; But still very low to the effective rate of utilization of carbide slag at present, more still bury and stack, bringing pollution to environment.
Therefore, along with the greenhouse gases of mankind's discharge cause global warming trend to strengthen, international community obviously heats up for the attention rate of reduction of greenhouse gas discharge subject under discussion and extensively carries out the research work of collecting carbonic anhydride technology in recent years, comprehensive above-mentioned trapping CO
2the problem that in method, environmental benefit is low, absorbent attenuation coefficient large and carbide slag brings pollution as trade waste to environment and can not effectively utilize, the present invention is from the comprehensive regulation, the object improving environmental benefit is set out, with carbide slag as CO in calcium-base absorbing agent circularly trapping flue gas
2.
Summary of the invention
Dry removal CO is carried out with natural calcium base ores such as lime stones in order to make up
2deficiency, the invention provides one and utilize Industrial Solid Waste carbide slag to remove CO in flue gas
2method.The method effectively controls CO in flue gas on the one hand
2discharge, trapping CO
2process in also can remove sulfur dioxide (SO in flue gas simultaneously
2); Provide process and the method for disposal of carbide slag on the one hand, achieve the recycling of carbide slag, reach the object of waste recycling.
The object of the present invention is to provide a kind of method using reproducible carbide slag collecting carbon dioxide from fuel gas.
The method of the reproducible carbide slag collecting carbon dioxide from fuel gas of use according to the present invention, the method comprises the following steps:
1) carbide slag is calcined, obtain the absorbent that active ingredient is calcium oxide;
2) by step 1) in active ingredient be that the absorbent of calcium oxide adds in carbonization reactor the carbon dioxide absorbed in flue gas, obtain calcium carbonate and clean flue gas;
3) by step 2) in calcination of calcium carbonate, obtain regenerate active ingredient be the absorbent of calcium oxide and the carbon dioxide of high concentration, by the Resources of Carbon Dioxide of high concentration utilize or compression seal up for safekeeping;
4) by step 3) in regeneration active ingredient be mainly inactivation in the absorbent of calcium oxide part remove, discharge the raw material as fertilizer or cement, add the carbide slag that part is new simultaneously, turn back to step 2) in recycle, repeat step 2) ~ 4).
The method of the reproducible carbide slag collecting carbon dioxide from fuel gas of use according to the present invention, described step 2): can also react with the sulfur dioxide in flue gas while active ingredient is mainly the absorbent collecting carbon dioxide from fuel gas of calcium oxide, generate calcium sulfate, there is the effect of simultaneous removing sulfur dioxide.
The method of the reproducible carbide slag collecting carbon dioxide from fuel gas of use according to the present invention, described step 1) in the calcining heat of carbide slag be 450 ~ 900 DEG C, calcination time is 5 ~ 20min.
The method of the reproducible carbide slag collecting carbon dioxide from fuel gas of use according to the present invention, described step 2) in carbonization reactor in reaction temperature be 550 ~ 700 DEG C.
The method of the reproducible carbide slag collecting carbon dioxide from fuel gas of use according to the present invention, described step 3) in the calcining heat of calcium carbonate be 800 ~ 1100 DEG C, calcination time is 5 ~ 20min.
The method of the reproducible carbide slag collecting carbon dioxide from fuel gas of use according to the present invention, its principle is:
Ca(OH)
2(s)＝CaO(s)+H
2O(g)
CaO(s)+CO
2(g)＝CaCO
3(s)
CaCO
3(s)＝CaO(s)+CO
2(g)
Use in the carbon dioxide process in carbide slag trapping flue gas can remove sulfur dioxide in flue gas simultaneously, its principle is mainly:
CaO(s)+SO
2(g)+1/2O
2(g)＝CaSO
4(s)
According to the method for collecting carbon dioxide from fuel gas of the present invention, because carbide slag main component is Ca (OH)
2, when thus calcining first, that mainly occur is Ca (OH)
2decomposition reaction, compares the calcining first utilizing the raw materials such as lime stone, calcite or dolomite, and calcining carbide slag avoids CO
2generation; Solid material (main component is CaO) first after calcining enters the CO in carbonization reactor and in flue gas
2react, be discharged in air after flue gas decarbonization.Carbide slag is at circularly removing CO
2in process, absorption efficiency can decay along with increasing of cycle-index, thus for whole set process, the CaO discharging a small amount of inactivation is needed, supplement new carbide slag to calcination reactor simultaneously, but, although utilize carbide slag to also exist equally and the problem of the natural crystals such as lime stone as the absorption efficiency exhaustion of absorbent, with Ca (OH)
2compare with lime stone, no matter be low temperature calcination or calcine under the high temperature conditions, the CO of carbide slag
2the attenuation degree of absorption efficiency will be significantly less than analytically pure Ca (OH)
2and lime stone, the simultaneously CO of carbide slag
2absorption efficiency also makes moderate progress, and thus above-mentioned key character will extend carbide slag service life cycle thus reduce its consumption.Absorbent for inactivation can as the raw material of cement industry.
The present invention utilizes the unique physicochemical property of carbide slag, and namely have higher specific area, good pore structure and heat endurance, the method adopting Reaction Separation to be aided with regeneration realizes carbide slag circularly trapping CO
2.The industrial waste carbide slag that the present invention utilizes acetylene industry to produce is raw material, first carbide slag is realized in calcination reactor the decomposition of carbide slag, the CO subsequently in carbonization reactor in Reaction Separation flue gas
2, flue gas is purified.Solid material in carbonization reactor enters again calcination reactor and carries out new calcining once, realizes the regeneration of absorbent, and the absorbent of discharge section inactivation also supplements a part of fresh carbide slag simultaneously.Compare commercially available Ca (OH)
2and lime stone, utilize carbide slag to have the low feature of rate of decay as absorbent, thus effectively compensate for and utilize the natural calcium base absorbant circularly trapping CO such as lime stone at present
2in process, absorption efficiency decay is not enough faster; Utilize carbide slag as CO simultaneously
2absorbent avoids the ecological disruption problem that exploitation natural calcium base ore causes, and avoids the extra CO that the absorbents such as lime stone produce in calcination process
2.The present invention utilizes Industrial Solid Waste to administer flue gas, acts on the Advanced Idea of the treatment of wastes with processes of wastes against one another, embodies distinct environmental benefit and economic benefit, thus has good actual application prospect.
The invention has the advantages that: with bibliographical information utilize the natural calcium base absorbants such as lime stone to carry out dry method to trap CO
2compare, the carbide slag that utilizes provided by the invention removes CO
2method, follow the environmental protection concept of the treatment of wastes with processes of wastes against one another, reduce CO in flue gas
2discharge; Secondly, provide the new utilization ways for Industrial Solid Waste carbide slag, finally, effectively compensate for the trapping such as the natural crystal that utilizes lime stone CO
2deficiency, thus for CO in flue gas
2remove or the recycling of carbide slag all has good actual application prospect.
Accompanying drawing explanation
Fig. 1 is the natural calcium base absorbant dry method capturing carbon dioxide schematic diagrames such as the renewable lime stone recycled;
Fig. 2 is the renewable carbide slag dry method capturing carbon dioxide that recycles of the present invention and sulfur dioxide schematic diagram.
Detailed description of the invention
Embodiment 1
Utilize fixed bed reactors compared for be collected in carbide slag and the commercially available Ca (OH) of certain coal plant
2cO under low temperature calcination condition
2absorption characteristic.Carbide slag particle diameter: 160 ~ 180 orders; Calcination reaction temperature: 840 DEG C; Calcination time 10min; Carbonation reaction temperature: 700 DEG C; Carbonization time: 20min; Altogether examine or check 40 circularly trapping CO
2absorption efficiency (note: utilize CaO conversion ratio in absorbent to characterize CO
2absorption efficiency).Result shows: (1) 40 circulation end, carbide slag and Ca (OH)
2cO
2absorption efficiency is respectively 35.18% and 32.57%; In (2) 40 circularly trapping processes, carbide slag and Ca (OH)
2cO
2absorption efficiency attenuation coefficient is respectively 0.16426 and 0.21140 (the attenuation coefficient larger sign rate of decay is faster), thus shows: at guarantee CO
2under the prerequisite of absorption efficiency, carbide slag is for CO
2the attenuation degree of absorption efficiency is less than commercially available Ca (OH)
2.
Embodiment 2
Utilize fixed bed reactors compared for be collected in carbide slag and the CO of commercially available lime stone under low temperature calcination condition of certain coal plant
2absorption characteristic.Carbide slag particle diameter: 160 ~ 180 orders; Calcination reaction temperature: 840 DEG C; Calcination time 10min; Carbonation reaction temperature: 700 DEG C; Carbonization time: 20min; Altogether examine or check 40 circularly trapping CO
2absorption efficiency.Result shows: (1) 40 circulation end, the CO of carbide slag and lime stone
2absorption efficiency is respectively 35.18% and 26.22%; In (2) 40 cyclic processes, the average CO of carbide slag and lime stone
2absorption efficiency is respectively 41.01% and 38.14%; (3) CO of carbide slag and lime stone
2absorption efficiency attenuation coefficient is respectively 0.16426 and 0.28030, thus shows: at guarantee CO
2under the prerequisite of absorption efficiency, carbide slag is for CO
2the attenuation degree of absorption efficiency is less than commercially available lime stone.
Embodiment 3
Utilize fixed bed reactors compared for be collected in carbide slag and the CO of commercially available lime stone under higher calcining heat of certain coal plant
2absorption characteristic.Carbide slag particle diameter: 160 ~ 180 orders; Calcination reaction temperature: 940 DEG C; Calcination time 10min; Carbonation reaction temperature: 700 DEG C; Carbonization time: 20min; Altogether examine or check 20 circularly trapping CO
2absorption efficiency.Result shows: the CO of (1) 20 circulate last carbide slag and lime stone
2absorption efficiency is respectively 28.30% and 22.53%; In (2) 20 circularly trapping processes, the CO of carbide slag and lime stone
2absorption efficiency attenuation coefficient is respectively 0.23958 and 0.39961, thus shows: for high-temperature calcination condition, carbide slag is for CO
2the attenuation degree of absorption efficiency is also less than commercially available lime stone.
Embodiment 4
Utilize fixed bed reactors to investigate to be collected in the CO of the carbide slag of certain coal plant
2and SO
2absorption characteristic.Carbide slag particle diameter: 160 ~ 180 orders; Calcination reaction temperature: 840 DEG C; Calcination time 10min; Carbonation reaction temperature: 700 DEG C; Carbonization time: 30min; Altogether examine or check 20 circulation carbide slag trapping CO
2and SO
2absorption efficiency.Result shows: in (1) 20 cyclic process, the SO of carbide slag
2removal efficiency can reach more than 99%; In (2) 20 circularly trapping processes, the average CO of carbide slag
2absorption efficiency is 41.48%.The above results shows: CO in renewable carbide slag trapping flue gas
2also can reach in process simultaneously and remove SO
2effect.
Claims (3)
1. use a method for reproducible carbide slag collecting carbon dioxide from fuel gas, it is characterized in that, described method comprises the following steps:
1) be that 160 ~ 180 object carbide slags calcine 10min reaction temperature 840 DEG C by the particle diameter deriving from coal plant, obtain the absorbent that active ingredient is calcium oxide;
2) by step 1) in active ingredient be that the absorbent of calcium oxide adds in carbonization reactor the carbon dioxide absorbed in flue gas, obtain calcium carbonate and clean flue gas, carbonation reaction temperature: 700 DEG C; Carbonization time: 20min;
3) by step 2) in calcination of calcium carbonate, obtain the calcium oxide that regenerates and the carbon dioxide of high concentration, the Resources of Carbon Dioxide of high concentration utilized or seals up for safekeeping after compression;
4) by step 3) in regeneration calcium oxide in inactivation part remove, fill into new carbide slag, turn back to step 2) in recycle, repeat step 2) ~ 4);
Above-mentionedly to recycle, 40 circularly trapping CO
2absorption efficiency be 35.18%; In 40 circularly trapping processes, the CO of carbide slag
2absorption efficiency attenuation coefficient is 0.16426.
2. use a method for reproducible carbide slag collecting carbon dioxide from fuel gas, it is characterized in that, described method comprises the following steps:
1) be that 160 ~ 180 object carbide slags calcine 10min reaction temperature 940 DEG C by the particle diameter deriving from coal plant, obtain the absorbent that active ingredient is calcium oxide;
2) by step 1) in active ingredient be that the absorbent of calcium oxide adds in carbonization reactor the carbon dioxide absorbed in flue gas, obtain calcium carbonate and clean flue gas, carbonation reaction temperature: 700 DEG C; Carbonization time: 20min;
3) by step 2) in calcination of calcium carbonate, obtain the calcium oxide that regenerates and the carbon dioxide of high concentration, the Resources of Carbon Dioxide of high concentration utilized or seals up for safekeeping after compression;
4) by step 3) in regeneration calcium oxide in inactivation part remove, fill into new carbide slag, turn back to step 2) in recycle, repeat step 2) ~ 4);
Above-mentionedly to recycle, the CO of the last carbide slag that circulates for 20 times
2absorption efficiency is 28.30%; In 20 circularly trapping processes, the CO of carbide slag
2absorption efficiency attenuation coefficient is 0.23958.
3. use a method for reproducible carbide slag collecting carbon dioxide from fuel gas, it is characterized in that, described method comprises the following steps:
1) be that 160 ~ 180 object carbide slags calcine 10min reaction temperature 840 DEG C by the particle diameter deriving from coal plant, obtain the absorbent that active ingredient is calcium oxide;
2) by step 1) in active ingredient be that the absorbent of calcium oxide adds in carbonization reactor the carbon dioxide absorbed in flue gas, obtain calcium carbonate and clean flue gas, carbonation reaction temperature: 700 DEG C; Carbonization time: 30min;
3) by step 2) in calcination of calcium carbonate, obtain the calcium oxide that regenerates and the carbon dioxide of high concentration, the Resources of Carbon Dioxide of high concentration utilized or seals up for safekeeping after compression;
4) by step 3) in regeneration calcium oxide in inactivation part remove, fill into new carbide slag, turn back to step 2) in recycle, repeat step 2) ~ 4);
In step 2) in absorbing carbon dioxide simultaneously stability flue gas in sulfur dioxide, generate calcium sulfate;
Above-mentionedly to recycle, in 20 cyclic processes, the SO of carbide slag
2removal efficiency can reach more than 99%; In 20 circularly trapping processes, the average CO of carbide slag
2absorption efficiency is 41.48%.
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| CN103071373B (en) * | 2013-02-01 | 2014-12-10 | 山东大学 | Method for preparing highly active CO2 absorbent by utilizing carbide slag |
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