CN103071373B - Method for preparing high-activity CO2 absorbent with carbide slag - Google Patents
Method for preparing high-activity CO2 absorbent with carbide slag Download PDFInfo
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- CN103071373B CN103071373B CN201310039273.2A CN201310039273A CN103071373B CN 103071373 B CN103071373 B CN 103071373B CN 201310039273 A CN201310039273 A CN 201310039273A CN 103071373 B CN103071373 B CN 103071373B
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- carbide slag
- absorbent
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- water
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Abstract
The invention relates to a method for preparing a high-activity CO2 absorbent with carbide slag, and belongs to the technical field of environmental pollution prevention and clean combustion. The method comprises the steps that water and glycerol are uniformly mixed according to an isopyknic fraction as a solvent; the carbide slag and aluminium nitrate are dissolved in the solvent according to a certain Ca/Al molar ratio, and fully stirred; a homogeneous solution is generated; calcination is conducted at 750-900 DEG C for 1-4h; screening is conducted; and a solid, namely the high-activity CO2 absorbent is obtained. A research indicates that the high-activity CO2 absorbent prepared by the method presents a better CO2 trapping property compared with the carbide slag. With the adoption of the method, large-scale resource utilization of the carbide slag can be achieved; the reactivity and cycling stability of the absorbent are improved; and the absorbent is an ideal absorbent for trapping CO2 in flue gas of a coal-fired boiler.
Description
Technical field
The present invention relates to utilize calcium carbide slag to prepare high activity CO
2the method of absorbent, belongs to environmental pollution prevention and control and clean burning technical field.
Background technology
Combustion of fossil fuel discharges a large amount of CO
2, cause serious greenhouse effects, environment for human survival has been formed to very large threat.China, taking coal as main primary energy, controls coal fired power plant CO
2instant stage has been arrived in discharge.At present, CO
2trapping most possibly realizes with Plugging Technology Applied (CCS) thereby be considered to the method that extensive carbon emission reduction suppresses global warming.At numerous CO
2in trapping technique, calcium round-robin method, namely calcium-base absorbing agent Cyclic Calcination/carbonation reaction trapping CO
2technology has been subject to the extensive concern of Chinese scholars.This technology utilizes widely distributed lime stone and dolomite etc. as absorbent, has good economy.And now very ripe recirculating fluidized bed of this technology utilization, without redesigning special reactor.Calcium round-robin method mainly comprises two reactors: calcining furnace and carbonating stove.First calcium-base absorbing agent enters calcining furnace, generates CaO and CO 850-1000 DEG C of high-temperature calcination
2(shown in (1)), the CaO that calcining generates enters the CO in carbonating stove and flue gas
2there is carbonation reaction at 550-750 DEG C and generate CaCO
3(shown in (2)), reach trapping CO
2object, the CaCO of generation
3reenter calcining furnace high-temperature calcination, reach the object that absorbent recycles.Calcining furnace inner absorbent calcining institute energy requirement is provided by fuel pure oxygen burning, so CO in calcining furnace outlet flue gas
2concentration, up to more than 95%, can be sealed up for safekeeping or be utilized through overcompression.
Carbide slag is calcium carbide (CaC
2) be hydrolyzed and produce acetylene (C
2h
2) waste residue that the main component that produces after gas is calcium hydroxide, its reaction equation is suc as formula shown in (3).Acetylene gas is the main raw material(s) of producing polyvinyl chloride (PVC).In China, approximately 70% acetylene is to be made by calcium carbide hydrolysis, and 1 ton of PVC of every production approximately generates 1.5-1.9 ton carbide slag.At present, most of white clay cannot effectively utilize, and generally piles up as industrial refuse, has taken a large amount of soils and has caused a lot of environmental problems simultaneously.
CaC
2+2H
2O→C
2H
2+Ca(OH)
2 (3)
Trial utilizes carbide slag as the CO in high temperature sorbent circularly trapping coal-burning boiler tail flue gas in calcium round-robin method
2, realize recycling and the CO of carbide slag
2remove the process route combining.Experimental result shows, carbide slag has embodied good CO
2trapping performance.But identical with the calcium-base absorbing agent such as lime stone, increase carbide slag circularly trapping CO with cycle-index
2performance reduces rapidly.After 20 circulations, carbide slag carbonate treatment rate only has 35% left and right.In order to keep high CO
2arresting efficiency, need to be to the addition that increases carbide slag in reactor, and this has not only increased operating cost, and causes reactor wear aggravation, threatens equipment safety operation.Therefore, how research improves the CO in carbide slag circular response process
2trapping performance, slows down with the decay of cycle-index increase carbide slag Cyclic Carbonation conversion ratio and has great importance.Research shows, in calcium-base absorbing agent, adds inert carrier, and these inert carriers can slow down the sintering of absorbent in Cyclic Calcination/carbonation, thereby improves absorbent trapping CO
2the stability of ability.For example, in calcium-base absorbing agent, add a certain amount of alundum (Al2O3) or aluminum nitrate, the absorbent obtaining after high-temperature calcination, anti-sintering property is better, shows good trapping CO in circular response process
2performance.Study and also show, if calcium-base absorbing agent and inert carrier can jointly dissolve in solvent, calcium-base absorbing agent will be attached to inert carrier surface uniformly, and the absorbent of preparation shows better CO like this
2trapping performance.Carbide slag main component is calcium hydroxide, is slightly soluble in water, is insoluble to alcohol, thus carbide slag and aluminum nitrate cannot common solvent as water and ethanol in realize simultaneously dissolve.Therefore prepare a kind of solvent, can realize carbide slag and aluminum nitrate and dissolve therein simultaneously, further after high-temperature calcination, likely prepare high activity CO
2absorbent.
Summary of the invention
For above-mentioned prior art, the invention provides and utilize calcium carbide slag to prepare high activity CO
2the method of absorbent.The method is mixed carbide slag, glycerine, aluminum nitrate and water according to a certain percentage, and after fully stirring, high-temperature calcination obtains high activity CO
2absorbent.Research is found, high activity CO prepared by the method
2absorbent shows compared with the better CO of carbide slag in Cyclic Calcination/carbonation
2trapping ability.
The present invention is achieved by the following technical solutions:
One is utilized calcium carbide slag to prepare high activity CO
2the method of absorbent, its step is as follows:
(1) measure water and the glycerine of certain volume, the volume ratio of water and glycerine is 0.7～1.2:1, in container, evenly mixes, and obtains solvent; Because G & W can be miscible with arbitrary proportion, and calcium hydroxide dissolves in glycerine, and aluminum nitrate water soluble, so the mixed liquor being made up of water and glycerine can be used as solvent, realizes the common dissolving of carbide slag and aluminum nitrate;
(2) take carbide slag and the nine water aluminum nitrates of certain mass, these two kinds of solids are added in the solvent of water prepared by above-mentioned steps (1) and glycerine composition, under room temperature condition, stir 1～2 hour, obtain homogeneous phase solution; After abundant stirring, carbide slag, glycerine, aluminum nitrate and water can form homogeneous phase solution; The usage ratio of described carbide slag and solvent is every 10g carbide slag 25～100mL solvent; Described carbide slag and nine water aluminum nitrates with magnitude relation be: Ca/Al mol ratio is 8～16:1;
(3) homogeneous phase solution step (2) being obtained is contained in ceramic crucible, puts into Muffle furnace, under 750～900 DEG C of conditions, calcines 1～4 hour, and the sample obtaining after calcining, is high activity CO
2absorbent.
Preferably, in described step (1), the volume ratio of water and glycerine is 1:1.
Preferably, in described step (2), the best proportioning of carbide slag and solvent is 10g carbide slag: 50mL solvent.
Preferably, in described step (2), the optimum amount of carbide slag and nine water aluminum nitrates closes and is: Ca/Al mol ratio is 9:1.
Preferably, in described step (3), homogeneous phase solution optimum calcinating temperature in Muffle furnace is 800 DEG C.
The calcium carbide slag to prepare high activity CO that utilizes of the present invention
2the principle of absorbent is: in high-temperature calcination process, calcium hydroxide and aluminum nitrate are decomposed into calcium oxide and alundum (Al2O3), partial oxidation calcium and alundum (Al2O3) reaction, generate calcium aluminium compound, and these calcium aluminium compounds are in circular response process, as inert carrier, well support absorbent internal void structure, improve the anti-sintering property of absorbent, thereby the high activity CO of preparation
2absorbent has embodied very high CO in circular response process
2absorbability and cyclical stability are CO in trapping fire coal boiler fume
2desirable absorbent.
The calcium carbide slag to prepare high activity CO that utilizes of the present invention
2the method of absorbent, has the following advantages:
1. obviously improved CO in carbide slag circularly trapping fire coal boiler fume
2reactivity, has reduced carbide slag input amount, CO
2trapping system operating cost is corresponding reduction also.
2. reduce carbide slag input amount, the wearing and tearing of calcining furnace and carbonating stove are weakened, improved the security of system.
3. technological process is simple to operate, and equipment needed thereby is few, invests little.
Brief description of the drawings
Fig. 1 is that the present invention utilizes calcium carbide slag to prepare high activity CO
2the schematic diagram of absorbent.
Fig. 2 is high activity CO prepared by embodiment 1
2absorbent and carbide slag circularly trapping CO
2ability comparison diagram, wherein, high activity CO
2absorbent preparation condition: 10g carbide slag+5.24g nine water aluminum nitrate+25mL water+25mL glycerine (Ca/Al=9:1), mixing time is 2 hours, and calcining heat is 800 DEG C, and calcination time is 2 hours; Cyclic Calcination/carbonating experiment condition is: 30 minutes carbonating time, carbonating atmosphere 15%CO
2-85%N
2(volume fraction), calcination time 10 minutes, calcination atmosphere N
2, 700 DEG C of carbonating temperature, 850 DEG C of calcining heats, calcination/carbonation is double-fixed bed.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further illustrated.
Highly active absorbent preparation principle figure of the present invention as shown in Figure 1.Carbide slag and nine water aluminum nitrates dissolve in the solvent that water and glycerine equal-volume mark are mixed with, and form homogeneous phase solution.Like this, aluminum nitrate mixes more even with the calcium hydroxide in carbide slag, and after high-temperature calcination, calcium aluminium compound is evenly distributed in absorbent inside more.And the formation of these inert carriers has slowed down the sintering of absorbent in Cyclic Calcination/carbonation, so absorbent activity is higher, CO after repeatedly circulating
2trapping ability fall is little.
Embodiment 1
Utilize calcium carbide slag to prepare high activity CO
2absorbent, step is as follows:
(1) measure respectively 25mL glycerine and 25mL distilled water with graduated cylinder, after evenly mixing in beaker, for subsequent use as solvent.
(2) carbide slag is taken from Shandong acetylene factory, take 10g carbide slag with electronic balance, taking 5.24g analyzes pure nine water aluminum nitrates and (prepares absorbent taking Ca/Al mol ratio as 9:1, nine water aluminum nitrates add quality and convert and draw thus), load weighted 2 kinds of solids are added in the solvent of being prepared by step (1) being contained in beaker, under room temperature condition, stir 2 hours, obtain homogeneous phase solution.
(3) homogeneous phase solution step (2) being obtained is poured in resistant to elevated temperatures ceramic crucible, puts into Muffle furnace and calcines 2 hours under 800 DEG C of conditions.Cooled sample is ground to screening, obtain high activity CO
2absorbent.
High activity CO prepared by EXPERIMENTAL EXAMPLE 1
2absorbent and carbide slag circularly trapping CO
2ability contrast
On the double-fixed bed reactor of calcination/carbonation, study high activity CO prepared by embodiment 1
2absorbent and untreated carbide slag circularly trapping CO
2ability.Every kind of absorbent has all carried out circular response 20 times.First high-temperature calcination in calcination reactor of absorbent, calcination atmosphere is pure N
2, calcining heat is 850 DEG C, calcination time is 10min; Then the CaO that calcining obtains enters carbonation reactor and CO
2carry out carbonation reaction, carbonating atmosphere is 15%CO
2-85%N
2(volume fraction), carbonating temperature is 700 DEG C, the carbonating time is 30min.After calcining and carbonating, sample is accurately weighed on high-precision electronic balance, calculates the CO of absorbent by mass change before and after carbonation reaction
2trapping ability.CO
2the CO that trapping ability absorbs to calcine rear unit mass absorbent
2quality represents, shown in (4).
Y in formula
nthe CO absorbing for calcining rear unit mass absorbent
2quality; N is circular response number of times; m
nit is absorbent quality after the N time circular response; m
calfor calcining the quality of rear absorbent.
Experimental result shows, the high activity CO preparing by the method for the invention
2absorbent shows than the better circularly trapping CO of carbide slag
2performance, as shown in Figure 2.The 1st circulation, highly active absorbent CO after unit mass calcining
2uptake is more smaller than carbide slag, and this is mainly due to the adding of inert carrier, due in absorbent, CaO content reduces.Increase with cycle-index, highly active absorbent cyclical stability is better, CO
2absorbability decay is slower, since the 3rd circulation, and highly active absorbent CO after unit mass calcining
2uptake is greater than the rear carbide slag of unit mass calcining.Through 20 circulations, highly active absorbent CO after unit calcining
2uptake is higher by 81.3% than the rear carbide slag of unit mass calcining.
Claims (5)
1. one kind is utilized calcium carbide slag to prepare high activity CO
2the method of absorbent, is characterized in that: step is as follows:
(1) measure water and glycerine, the volume ratio of water and glycerine is 0.7～1.2:1, in container, evenly mixes, and obtains solvent;
(2) take carbide slag and nine water aluminum nitrates, these two kinds of solids are added in the solvent of water prepared by above-mentioned steps (1) and glycerine composition, under room temperature condition, stir 1～2 hour, obtain homogeneous phase solution; The usage ratio of described carbide slag and solvent is every 10g carbide slag 25～100mL solvent; Described carbide slag and nine water aluminum nitrates with magnitude relation be: Ca/Al mol ratio is 8～16:1;
(3) homogeneous phase solution step (2) being obtained is contained in ceramic crucible, puts into Muffle furnace, under 750～900 DEG C of conditions, calcines 1～4 hour, and the sample obtaining after calcining, is high activity CO
2absorbent.
2. the calcium carbide slag to prepare high activity CO that utilizes according to claim 1
2the method of absorbent, is characterized in that: in described step (1), the volume ratio of water and glycerine is 1:1.
3. the calcium carbide slag to prepare high activity CO that utilizes according to claim 1
2the method of absorbent, is characterized in that: in described step (2), the proportioning of carbide slag and solvent is 10g carbide slag: 50mL solvent.
4. the calcium carbide slag to prepare high activity CO that utilizes according to claim 1
2the method of absorbent, is characterized in that: in described step (2), carbide slag and nine water aluminum nitrates with magnitude relation be: Ca/Al mol ratio is 9:1.
5. the calcium carbide slag to prepare high activity CO that utilizes according to claim 1
2the method of absorbent, is characterized in that: in described step (3), homogeneous phase solution calcining heat in Muffle furnace is 800 DEG C.
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|---|---|---|---|
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|---|---|---|---|
| CN201310039273.2A CN103071373B (en) | 2013-02-01 | 2013-02-01 | Method for preparing high-activity CO2 absorbent with carbide slag |
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| CN103936543B (en) * | 2014-04-08 | 2015-09-16 | 昆明理工大学 | A kind of method with acetylene synchronization gain carbon-dioxide absorbent |
| CN107744716B (en) * | 2017-11-15 | 2019-09-06 | 山东大学 | The hollow compound CO of shell-type carbide slag2Absorbent and its synthetic method and application |
| CN109927968A (en) * | 2019-03-12 | 2019-06-25 | 福建省亚热带植物研究所 | A kind of packing method of flatulence remover and agricultural product |
| CN111485063B (en) * | 2020-06-06 | 2021-09-17 | 内蒙古铧钰环保材料有限公司 | High-efficiency utilization process of aluminum ash in electrolytic aluminum plant |
| 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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| CN1317065C (en) * | 2005-01-21 | 2007-05-23 | 清华大学 | High active calcium-base CO2 absorbent and its preparing method |
| CN102527225B (en) * | 2010-12-17 | 2016-04-06 | 中国科学院过程工程研究所 | A kind of method using reproducible carbide slag collecting carbon dioxide from fuel gas |
| CN102836635A (en) * | 2012-08-17 | 2012-12-26 | 东南大学 | Preparation method of modified carbon dioxide calcium-based absorbent |
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