CN101423214A - Method for catching carbon dioxide in generating plant flue gas by ammonia process and equipment thereof - Google Patents
Method for catching carbon dioxide in generating plant flue gas by ammonia process and equipment thereof Download PDFInfo
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- CN101423214A CN101423214A CNA200810197730XA CN200810197730A CN101423214A CN 101423214 A CN101423214 A CN 101423214A CN A200810197730X A CNA200810197730X A CN A200810197730XA CN 200810197730 A CN200810197730 A CN 200810197730A CN 101423214 A CN101423214 A CN 101423214A
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Abstract
The invention provides a method and equipment used for collecting CO2 in flue gas of a power plant by an ammonia method. The method firstly adopts ammonia water to circularly spray and absorb the CO2 in the flue gas, subsequently heats, analyses and regenerates the generated ammonium bicarbonate rich solution, and washes the analyzed high-concentration mixed gas of CO2 and ammonia; the gained ammonia water lean solution is continued to carry out absorption cycle; the high-concentration CO2 gas is cooled, gas/liquid separated, dried, compressed and condensed to prepare the high-purity industrial liquid CO2. The equipment consists essentially of an absorbing tower, a regeneration tower, a water washing tower, a gas/liquid separator, a drier, a compressor, a condenser and the like which are connected by pumps and pipelines. The method and the equipment can completely adapt for the characteristics that the tail flue gas of the boiler of the power plant has huge flue gas flux, complex composition and low CO2 concentration, can effectively improve the removal rate of the CO2 in the flue gas, can produce the high-purity liquid CO2, have simple process flow, simplify the system structure and have low investment and running cost.
Description
Technical field
The present invention relates to the reduction of discharging and the application technology as the second resource of carbonic acid gas in the flue gas in power station boiler, refer to that particularly a kind of ammonia process captures the method and the equipment thereof of carbonic acid gas in the generating plant flue gas.
Background technology
The atmosphere Greenhouse effect are one of main environmental problems of facing of the mankind.Carbonic acid gas is main greenhouse gases, and thermal power plant is the concentrated emission source of carbonic acid gas, and its CO2 emissions accounts for 30% of carbonic acid gas total release that mankind's activity causes.The amount of carbon dioxide that the thermal power plant of a 600MW per hour discharges can reach 500 tons.Therefore, in order to reduce Atmospheric Carbon Dioxide content, primary is to reduce the station boiler tail flue gas to the airborne release carbonic acid gas.Say from another point of view, carbonic acid gas has purposes widely as a kind of industrial chemicals, can be used for food fresh keeping, expanded pipe tobacco, produce methyl alcohol, urea, degradable plastics etc., especially petroleum industry utilizes the carbon dioxide flooding oil tech can improve tar productivity greatly, and present stage has mostly wasted with the carbonic acid gas that the station boiler tail flue gas discharges.
Traditional carbonic acid gas improvement or extracting method have multiple, roughly can be divided into physical method and chemical process two big classes.The more employing chemical process of industrial application, chemical process mainly refers to chemical absorption method, its principle is carbon dioxide and chemical solvents are reacted and to be absorbed, absorbing carbon dioxide reaches the equilibrated chemical solvents and becomes rich solution, rich solution enters the regenerator column thermal degradation and goes out carbon dioxide, thereby reaches the purpose of Separation and Recovery carbonic acid gas.More common chemical solvents is the aqueous solution of ethanolamines, adopts alkanolamine solution circular flow in absorption tower and regenerator column, can obtain the carbonic acid gas of high density.But hydramine is a kind of expensive Chemicals, and certain wastage rate are arranged in systemic circulation; Simultaneously, the speed of reaction of hydramine and carbonic acid gas is lower, and the reaction times that needs is longer, and the design height on absorption tower is higher; Above reason all causes the cost that adopts alkanolamine solution to reclaim carbonic acid gas very high.And this hydramine method only is suitable for the little occasion of flue gas flow, also has very big gap from the processing of actual power station boiler tail flue gas.
The singularity of station boiler tail flue gas is that its carbon dioxide content is on the low side, flue gas flow is huge.Various types of after testing station boiler tail flue gas, its CO
2Concentration is about 10～15%.Power station with a 600MW is an example, the about 2000000Nm of its boiler tail flue gas quantity discharged
3/ h.When adopting above-mentioned alkanolamine solution to remove carbonic acid gas, can cause the absorption tower bulky, construction, operation and overhaul of the equipments difficulty are difficult to reach carbonic acid gas in the effective elimination flue gas and with the purpose of its recycling.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of ammonia process to capture the method and the equipment thereof of carbonic acid gas in the generating plant flue gas.Adopt this method and equipment thereof can adapt to the characteristics that station boiler tail flue gas flow is huge, gas concentration lwevel is low fully, both can effectively improve the decreasing ratio of carbonic acid gas in the flue gas, can produce highly purified liquid carbon dioxide again, and its technical process is simple, device structure simplification, investment and running cost are cheap.
For achieving the above object, the designed ammonia process of the present invention captures the method for carbonic acid gas in the generating plant flue gas, is the process of reprocessing through the station boiler tail flue gas of conventional dedusting and desulfurization processing.This method comprises the steps:
1) with ammonia soln as CO
2Absorption agent evenly is ejected into it through in the flue gas after dedusting and the desulfurization processing, makes the flue gas that moves upward contact CO in flue gas with the ammonia soln full regression that sprays downwards
2Gas and ammonia soln generation gas-liquid two-phase chemical reaction and be absorbed obtain the bicarbonate of ammonia rich solution.Its chemical equation is:
CO
2+NH
3＝NH
2COONH
4
NH
2COONH
4+H
2O＝NH
4HCO
3+NH
3
NH
3+H
2O＝NH
4OH
NH
4HCO
3+NH
4OH＝(NH
4)
2CO
3+H
2O
(NH
4)
2CO
3+CO
2+H
2O＝2NH
4HCO
3
2) the bicarbonate of ammonia rich solution to the step 1) gained heats dissection process, and regeneration obtains high concentration CO
2With the mixed gas of ammonia, the bicarbonate of ammonia rich solution is reduced into has removed CO
2The ammoniacal liquor lean solution.Its chemical equation is:
NH
4HCO
3＝NH
3+CO
2+H
2O
3) to step 2) high concentration CO of gained
2Wash spray with the mixed gas of ammonia and handle, make ammonia wherein be absorbed the generation ammonia soln, isolate high concentration CO simultaneously by water
2Gas.
4) with step 2) ammonia soln that generated of institute reductive ammoniacal liquor lean solution, step 3) all returns in the step 1), as CO
2Absorption agent continues to recycle.
5) to the isolated high concentration CO of step 3)
2Gas carries out cooling process, the hot water and steam that wherein contains is produced condense.
6) to the high concentration CO of step 5) cooling process
2Gas carries out gas-liquid separation to be handled, and removes the moisture content that condenses wherein, obtains purity and is higher than 99% CO
2Gas.
7) with step 6) gained high-purity CO
2Gas is further dry, again through overdraft and condensation process, with its liquefy, promptly can be made into high-concentration industrial level liquid carbon dioxide finished product.
In above-mentioned steps 1) in, the volumetric molar concentration of preferred ammonia soln is 0.6～26mol/L, NH in the ammonia soln
3With CO in the flue gas
2Mol ratio be 1.0～2.0.Simultaneously, the CO in the control flue gas
2The temperature of reaction of gas and ammonia soln is 0～45 ℃, and reaction pressure is 1～10atm.Like this, ammonia soln can be under suitable temperature and pressure with flue gas in CO
2Reaction fully completely takes place, and the carbonic acid gas of the overwhelming majority is converted into bicarbonate of ammonia.
In above-mentioned steps 2) in, the bicarbonate of ammonia rich solution of gained is heated the temperature of dissection process preferably in 100～160 ℃ scope.Under this temperature condition, bicarbonate of ammonia can decompose rapidly fully, makes the CO of the overwhelming majority
2Therefrom parse, obtain the CO of high density
2Gas.
In above-mentioned steps 3) in, to the high concentration CO of gained
2Wash the working temperature of spray processing preferably in 50～90 ℃ scope with the mixed gas of ammonia.Like this, spray water can absorb ammonia effectively, the ammoniacal liquor that is obtained simultaneously also not can with CO
2Gas reacts.
In above-mentioned steps 5) in, with the isolated high concentration CO of institute
2Gas cooling is handled the optimum temperature range to 20～35 ℃.Like this, the wherein water recovery of the overwhelming majority is come out.
For realizing that the custom-designed ammonia process of aforesaid method captures the equipment of carbonic acid gas in the generating plant flue gas, comprises the absorption tower, regenerator column, water wash column, gas-liquid separator, moisture eliminator, compressor and the condenser that link to each other by pipeline.Be disposed with two to three groups of packing layers and at least one group of demister between the bottom gas approach on described absorption tower and the top exhanst gas outlet from bottom to top, the top correspondence of every group of packing layer is provided with one group of ammonia spray layer.The bottom bicarbonate of ammonia rich solution outlet on described absorption tower links to each other with the upper inlet of regenerator column by the rich solution pump, the upper gas outlet of regenerator column links to each other with the lower inlet of water wash column by first water cooler, the upper gas outlet of water wash column links to each other with the import of gas-liquid separator by second water cooler, the lower liquid outlet of regenerator column and water wash column links to each other with the input aperture of storage ammonia jar simultaneously, and the delivery port of storage ammonia jar links to each other with the ammonia spray layer with the 3rd water cooler by lean pump.The pneumatic outlet of described gas-liquid separator is connected with moisture eliminator, compressor, condenser and liquid carbon dioxide storage tanks successively.Thus, in removing flue gas in the carbonic acid gas, by aforesaid combination be one equipment to its regenerate, dewater, dry, compression and condensation etc. handle continuously, until obtaining high-purity technical level liquid carbon dioxide.
Further, the gas approach top, bottom on above-mentioned absorption tower is provided with impels the equally distributed porous plate of flue gas, and the ratio of the hole area of porous plate and plate area is 30～40%.Upwards by behind the porous plate, air-flow distributes more even flue gas, has effectively eliminated the flue gas flow dead angle, helps flue gas and fully contacts with ammonia soln like this, on the one hand; On the other hand under the jetting action of many group ammonia spray layers, organize ammonia soln in the packing layer more and distribute more evenly, make carbonic acid gas in the flue gas have the contact area of maximum with it, can fully fully chemical reaction take place and be absorbed.
Further, on the transfer line of above-mentioned rich solution pump and lean pump, also be provided with poor rich liquid heat exchanger, the bottom bicarbonate of ammonia rich solution outlet on absorption tower links to each other with the upper inlet of regenerator column by rich solution pump, poor rich liquid heat exchanger, and the delivery port of storage ammonia jar links to each other with the ammonia spray layer with the 3rd water cooler by poor rich liquid heat exchanger, lean pump.Like this, can make full use of, give the bicarbonate of ammonia rich solution preheating that enters regenerator column, with the cooling of ammoniacal liquor lean solution, realize the benign cycle of heat exchange simultaneously, save heat resource from the waste heat of regenerator column and water wash column gained ammoniacal liquor lean solution.
Further, the condensation water of above-mentioned gas-liquid separator outlet links to each other with process water import on the water wash column.Like this, the condensation water of separating can be turned back in the water wash column again and circulate, reduce the process water amount, reduce production costs.
Compare with the carbon dioxide process that traditional alkanolamine solution removes in the flue gas, the present invention has following outstanding effect:
One adopts ammonia soln as absorption agent, and the receptivity of ammonia soln is 2～3 times of Monoethanolamine MEA BASF MEA, but price only is 1/6 of MEA, and the regeneration energy consumption of the bicarbonate of ammonia that is generated is lower.Therefore, utilize ammonia soln can effectively capture carbonic acid gas in the flue gas, the removal efficiency of carbonic acid gas is reached more than 90%, significantly reduce the collecting carbonic anhydride cost, be particularly suitable for handling the coal-fired power station boiler tail flue gas that gas concentration lwevel is low, flue gas flow is big.
Its two, correspondence is provided with two to three groups of packing layers and ammonia spray layer in the absorption tower, under the crosswise jet effect of each group ammonia spray layer, each ammonia soln of organizing in the packing layer distributes more even.And the porous plate that is arranged on the gas approach top can be eliminated the air-flow dead angle, and it is more even that air-flow is distributed.Thus, can effectively increase the contact area of carbonic acid gas and ammonia soln in the flue gas, make reaction more fully fully, significantly improve the decreasing ratio of carbonic acid gas.
They are three years old, by various pumps and pipeline equipment such as absorption tower, regenerator column, water wash column, water cooler, gas-liquid separator, moisture eliminator, compressor and condenser organically are combined into a complete process system, both simplify technical process and system architecture, significantly reduced investment, the operation and maintenance cost of equipment again.
Its four, utilize the station boiler tail flue gas to turn waste into wealth, when effectively reducing the carbon dioxide greenhouse gas discharging, obtain liquid carbon dioxide, its product purity can reach more than 99%, meets International Industry grade carbon-dioxide standard fully.Like this, both helped the comprehensive regulation of air environmental pollution, helped the benign development of recycling economy again, can realize the innoxious and recycling of station boiler tail flue gas, be particularly suitable for the national conditions of China based on coal fired power generation.
Description of drawings
Accompanying drawing is the structural representation that a kind of ammonia process captures the equipment of carbonic acid gas in the generating plant flue gas.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments:
Ammonia process shown in the figure captures the equipment of carbonic acid gas in the generating plant flue gas, mainly is made up of absorption tower 1, regenerator column 8, water wash column 11, gas-liquid separator 16, moisture eliminator 15, compressor 14 and the condenser 13 etc. that link to each other by pipeline.Absorption tower 1, regenerator column 8 and water wash column 11 are packing tower.Between the bottom on absorption tower 1 gas approach 5 and top exhanst gas outlet 22, be disposed with porous plate 4, packing layer 3, ammonia spray layer 2 and demister 21 from bottom to top.The manhole area of porous plate 4 and the ratio of plate area are 35%, packing layer 3 and the ammonia spray layer 2 supporting with it are provided with two groups altogether, demister 21 is made of upper and lower two layers of demist filter screen and the cleaning sprinkler part between upper and lower two layers of demist filter screen, to remove the ammoniacal liquor drop in the flue gas fully.
The bottom bicarbonate of ammonia rich solution outlet on absorption tower 1 links to each other with the upper inlet of regenerator column 8 by the endothermic tube of rich solution pump 6, poor rich liquid heat exchanger 7 successively.The upper gas outlet of regenerator column 8 links to each other with the lower inlet of water wash column 11 by first water cooler 18, and the upper gas outlet of water wash column 11 links to each other with the import of gas-liquid separator 16 by second water cooler 17.The boiling device 9 supporting with regenerator column 8 is arranged on the tower bottom outside.The lower liquid outlet of regenerator column 8 and water wash column 11 links to each other with the input aperture of storage ammonia jar 10 simultaneously, and the delivery port of storage ammonia jar 10 then links to each other with ammonia spray layer 2 by heat release pipe, lean pump 19 and the 3rd water cooler 20 of poor rich liquid heat exchanger 7 successively.The pneumatic outlet of gas-liquid separator 16 is connected with moisture eliminator 15, compressor 14, condenser 13 and liquid carbon dioxide storage tanks 12 successively, and the outlet of the condensation water of gas-liquid separator 16 then links to each other with process water import on the water wash column 11.Above each several part equipment is the chemical field common equipment, and its concrete structure repeats no more.
The principle of work that above-mentioned ammonia process captures the equipment of carbonic acid gas in the generating plant flue gas is as follows:
After the station boiler tail flue gas is handled through conventional dedusting and desulfurization, in the gas approach 5 input towers by 1 bottom, absorption tower, pass through porous plate 4, packing layer 3 is up.Meanwhile, ammonia soln sprays downwards by ammonia spray layer 2.According to CO in the flue gas
2Content, the volumetric molar concentration of ammonia soln can be chosen in the scope of 0.6～26mol/L, CO in the flue gas
2With the temperature of reaction of ammonia soln can be preferably 25～45 ℃ scope, and NH in the control ammonia soln
3With CO in the flue gas
2Mol ratio be 1.5～1.8, reaction pressure is 1～10atm.At this moment, the CO in the flue gas
2Gas contacts with porous plate 4 place's full regressions at packing layer 3 with ammonia soln, fast chemical reaction takes place and is absorbed by ammonia soln.
Removed CO by the ammonia soln suction
2Flue gas continue upwards to flow, remove the absorption agent droplet through the demister 21 that is arranged in 1 top, absorption tower after, cleaning flue gases directly enters atmosphere.And absorption CO
2The bicarbonate of ammonia rich solution that the back generates falls into the bottom on absorption tower 1, is transported to by rich solution pump 6 in the endothermic tube of poor rich liquid heat exchanger 7, sends in the tower from the upper inlet of regenerator column 8 then.After the bicarbonate of ammonia rich solution was sprayed to the packing layer of regenerator column 8, the steam gas that is risen was carried, and was heated to 100～130 ℃ through boiling device 9 at the bottom of the tower, parsed high concentration CO
2Gas makes the bicarbonate of ammonia rich solution be reduced into simultaneously and has removed CO
2The ammoniacal liquor lean solution.
The ammoniacal liquor lean solution is drawn from the lower liquid outlet of regenerator column 8, sends in the storage ammonia jar 10.The CO that parses
2Gas is for containing NH
3Mixed gas, this mixed gas is flowed out by the upper gas outlet of regenerator column 8 in company with a large amount of water vapors, after first water cooler 18 is cooled to 50～80 ℃, in the lower inlet input tower of water wash column 11.Meanwhile, process water evenly is sprayed on the packing layer of water wash column 11, and the ammonia in the mixed gas is absorbed by process water and forms ammonia soln, also sends into the storage ammonia jar 10 from the lower liquid outlet of water wash column 11.The CO of high density
2Gas is then flowed out by the upper gas outlet of water wash column 11, enters in second water cooler 17, is cooled to 25～35 ℃ at this air-flow, and water vapor is wherein freeze-outed.
Comprise ammoniacal liquor lean solution in the storage ammonia jar 10 from regenerator column 8 inputs, from the ammonia soln of water wash column 11 inputs and the fresh ammoniacal liquor that replenishes input in addition, these ammoniacal liquor are transfused in the ammonia spray layer 2 by heat release pipe, lean pump 19 and the 3rd water cooler 20 of poor rich liquid heat exchanger 7 successively, continue as CO
2Absorption agent recycles.
Through the high concentration CO after 17 processing of second water cooler
2Gas enters in the gas-liquid separator 16, by centrifugation with CO
2The condensation water of carrying secretly in the gas is separated fully, obtains purity and is higher than 99% CO
2Gas.Isolated condensation water flow out from the outlet of the condensation water of gas-liquid separator 16, reenter in it from the process water import of water wash column 11, recycle.Isolated high-purity CO
2Gas is then sent into moisture eliminator 15, and drying is delivered to compressor 14 after handling, and after the compressed processing, enters condenser 13 again, is condensed into liquid state, makes high-concentration industrial class liquid CO 2 finished product, sends at last in the liquid carbon dioxide storage tanks 12 and preserves.
Claims (10)
1. an ammonia process captures the method for carbonic acid gas in the generating plant flue gas, is the process that the station boiler tail flue gas of handling through conventional dedusting and desulfurization is reprocessed, and it is characterized in that: this method comprises the steps:
1) with ammonia soln as CO
2Absorption agent evenly is ejected into it through in the flue gas after dedusting and the desulfurization processing, makes the flue gas that moves upward contact CO in flue gas with the ammonia soln full regression that sprays downwards
2Gas and ammonia soln generation gas-liquid two-phase chemical reaction and be absorbed obtain the bicarbonate of ammonia rich solution;
2) the bicarbonate of ammonia rich solution to the step 1) gained heats dissection process, and regeneration obtains high concentration CO
2With the mixed gas of ammonia, the bicarbonate of ammonia rich solution is reduced into has removed CO
2The ammoniacal liquor lean solution;
3) to step 2) high concentration CO of gained
2Wash spray with the mixed gas of ammonia and handle, make ammonia wherein be absorbed the generation ammonia soln, isolate high concentration CO simultaneously by water
2Gas;
4) with step 2) ammonia soln that generated of institute reductive ammoniacal liquor lean solution, step 3) all returns in the step 1), as CO
2Absorption agent continues to recycle;
5) to the isolated high concentration CO of step 3)
2Gas carries out cooling process, the hot water and steam that wherein contains is produced condense;
6) to the high concentration CO of step 5) cooling process
2Gas carries out gas-liquid separation to be handled, and removes the moisture content that condenses wherein, obtains purity and is higher than 99% CO
2Gas;
7) with step 6) gained high-purity CO
2Gas is further dry, again through overdraft and condensation process, with its liquefy, promptly can be made into high-concentration industrial level liquid carbon dioxide finished product.
2. ammonia process according to claim 1 captures the method for carbonic acid gas in the generating plant flue gas, and it is characterized in that: in the said step 1), the volumetric molar concentration of ammonia soln is 0.6～26mol/L, NH in the ammonia soln
3With CO in the flue gas
2Mol ratio be 1.0～2.0.
3. ammonia process according to claim 1 and 2 captures the method for carbonic acid gas in the generating plant flue gas, it is characterized in that: in the said step 1), and the CO in the flue gas
2The temperature of reaction of gas and ammonia soln is 0～45 ℃, and reaction pressure is 1～10atm.
4. ammonia process according to claim 1 and 2 captures the method for carbonic acid gas in the generating plant flue gas, it is characterized in that: said step 2), the temperature that the bicarbonate of ammonia rich solution of gained is heated dissection process is 100～160 ℃.
5. ammonia process according to claim 1 and 2 captures the method for carbonic acid gas in the generating plant flue gas, it is characterized in that: in the said step 3), to the high concentration CO of gained
2The working temperature of washing the spray processing with the mixed gas of ammonia is 50～90 ℃.
6. ammonia process according to claim 1 and 2 captures the method for carbonic acid gas in the generating plant flue gas, it is characterized in that: in the said step 5), with the isolated high concentration CO of institute
2Gas cooling is handled to 20～35 ℃.
7. one kind is used for realizing that the ammonia process of the described method of claim 1 captures the equipment of generating plant flue gas carbonic acid gas, comprise the absorption tower (1), regenerator column (8), water wash column (11), gas-liquid separator (16), moisture eliminator (15), compressor (14) and the condenser (13) that link to each other by pipeline, it is characterized in that:
Be disposed with two to three groups of packing layers (3) and at least one group of demister (21) between the bottom gas approach (5) on described absorption tower (1) and the top exhanst gas outlet (22) from bottom to top, the top correspondence of every group of packing layer (3) is provided with one group of ammonia spray layer (2);
The bottom bicarbonate of ammonia rich solution outlet on described absorption tower (1) links to each other with the upper inlet of regenerator column (8) by rich solution pump (6), the upper gas outlet of regenerator column (8) links to each other with the lower inlet of water wash column (11) by first water cooler (18), the upper gas outlet of water wash column (11) links to each other with the import of gas-liquid separator (16) by second water cooler (17), the lower liquid outlet of regenerator column (8) and water wash column (11) links to each other with the input aperture of storage ammonia jar (10) simultaneously, and the delivery port of storage ammonia jar (10) links to each other with ammonia spray layer (2) with the 3rd water cooler (20) by lean pump (19);
The pneumatic outlet of described gas-liquid separator (16) is connected with moisture eliminator (15), compressor (14), condenser (13) and liquid carbon dioxide storage tanks (12) successively.
8. ammonia process according to claim 7 captures the equipment of carbonic acid gas in the generating plant flue gas, it is characterized in that: bottom gas approach (5) top of said absorption tower (1) is provided with impels the equally distributed porous plate of flue gas (4), and the hole area of porous plate (4) and the ratio of plate area are 30～40%.
9. according to the equipment of carbonic acid gas in claim 7 or the 8 described ammonia process capture generating plant flue gas, it is characterized in that: the bottom bicarbonate of ammonia rich solution outlet of said absorption tower (1) links to each other with the upper inlet of regenerator column (8) by rich solution pump (6), poor rich liquid heat exchanger (7); The delivery port of said storage ammonia jar (10) links to each other with ammonia spray layer (2) with the 3rd water cooler (20) by poor rich liquid heat exchanger (7), lean pump (19).
10. ammonia process according to claim 9 captures the equipment of carbonic acid gas in the generating plant flue gas, it is characterized in that: the condensation water outlet of said gas-liquid separator (16) links to each other with the process water import on the water wash column (11).
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