CN102413901B - Apparatus and method for compressing co2, system and method for separating and recovering co2 - Google Patents

Apparatus and method for compressing co2, system and method for separating and recovering co2 Download PDF

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CN102413901B
CN102413901B CN201080018322.9A CN201080018322A CN102413901B CN 102413901 B CN102413901 B CN 102413901B CN 201080018322 A CN201080018322 A CN 201080018322A CN 102413901 B CN102413901 B CN 102413901B
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carbon dioxide
absorption
heat pump
solution
reactor
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CN102413901A (en
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苏庆泉
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Beijing Lianliyuan Technology Co Ltd
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Beijing Lianliyuan Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/65—Employing advanced heat integration, e.g. Pinch technology
    • 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
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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

Abstract

Disclosed are an apparatus and a method for compressing CO2, a system and a method for separating and recovering CO2. The apparatus for compressing CO2 comprises an absorption reactor (101), a regeneration reactor (102), a supercharge pump (103) and a throttling valve (104). The CO2 gas is absorbed in the absorption reactor (101), and the absorbent having absorbed CO2 gas is regenerated in the regeneration reactor (102) and desorbed CO2 gas. A heat exchanger (105) in the absorption reactor (101) is used for transferring the absorption heat out of the CO2 absorbent solution, and a heat exchanger (106) in the regeneration reactor (102) is used for supplying the regeneration heat for the CO2 absorbent solution. The apparatus for compressing CO2 can utilize waste heat to compress CO2.

Description

Carbon dioxide compression set and method, carbon dioxide separation recovery system and method
The application advocates that the applying date in China's application is on February 26th, 2009, the priority of the patent application that application number is 200910078363.6.
Technical field
The present invention relates to the carbon dioxide separation recovery technology of a kind of chemical industry and field of environment engineering, particularly a kind of carbon dioxide compression set and method, and separation and recovery system and the method that can effectively remove carbon dioxide in flue gas.
Background technology
CO 2a large amount of discharges of isothermal chamber gas are major reasons that causes global warming.Therefore, CO 2emission problem caused the very big concern of international community.Reduce the CO of combustion of fossil fuel 2discharge mainly contains two approach: the one, improve efficiency of energy utilization, the 2nd, separation of C O from combustion product gases 2, and be used, store or seal up for safekeeping.
At CO 2remove in technology, with ammonia spray thermal power station boiler discharging flue gas, absorb CO 2, not only can reach CO 2the object reducing discharging, can also obtain high-quality chemical fertilizer.But, because carbonic hydroammonium under the environment temperature higher than 60 ℃ can be decomposed into ammonia, water and CO 2, cause CO 2return to atmosphere, therefore this CO 2the application of discharge-reducing method also needs further research.CO 2the technology that removes also have the CO of CaO carbonating-calcination cycle 2separated (CCR) technology, polymeric membrane remove CO 2, O 2/ CO 2circulating combustion technology and burning chemistry chains (CLC) technology etc.But often industrializing implementation cost is higher for above-mentioned technology.
At CO 2remove in technology, a kind of very important method is to adopt solution absorption method to remove CO 2.According to the difference of absorbent properties, can be divided into two large classes.One class is Physical Absorption method, as WATER-WASHING METHOD, low-temperature rectisol method (Rectisol), polyglycol dimethyl ether process (Selexol), propene carbonate method.Another kind of is chemical absorption method, as hot potash method, and low hear rate Benfield method, activatedMDEAmethod, MEA process etc.Above-mentioned CO 2remove technology all very ripe, at chemical field, realized already industrialization.
Someone proposed to utilize chemical absorption method from the burnt gas in thermal power plant the separated scheme that reclaims carbon dioxide (please refer to: clear former positive height, from generating with reclaiming CO boiler exhaust 2test, the energy. resource, the energy. resource science meeting, 1993, the 14th volume, the 1st its, 91-97 page).According to this scheme, although different with the difference of condition, the separated rate of recovery of carbon dioxide can reach more than 80%.Yet, adopt the required energy consumption of traditional chemical absorption method separated recovery carbon dioxide from combustion product gases up to 750～900kcal/kg-CO 2, therefore the separated operating cost reclaiming is very high.And the liquefaction of gaseous carbon dioxide adopts the technique of secondary or three grades of compressions condensations afterwards conventionally.Because the compression of carbon dioxide in this technique is undertaken by compressor, thereby power consumption is very large.
Summary of the invention
The object of the invention is to, a kind of carbon dioxide compression set and method are provided, the technical problem solving is to adopt waste heat to compress carbon dioxide, thereby can effectively utilize waste heat, improves the utilization ratio of the energy.
Another object of the present invention is to; a kind of carbon dioxide separation recovery system and separation and recovery method of low energy consumption are provided; technical problem to be solved is that it can remove the carbon dioxide in flue gas; reduce and be discharged into the amount of carbon dioxide in atmosphere; can separated carbon dioxide be compressed simultaneously; obtain the carbon dioxide of high pressure, be conducive to storage and the transportation of carbon dioxide, thereby be conducive to protection of the environment.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of carbon dioxide compression set that the present invention proposes, comprising: absorption reactor thermally, regeneration reactor, booster pump and choke valve, be filled with carbon dioxide absorption solution, for absorbing carbon dioxide gas in described absorption reactor thermally; Described regeneration reactor is for making from the gas that splits the carbon dioxide off of the carbon dioxide absorption solution in absorption reactor thermally; Described booster pump is used for the carbon dioxide absorption solution supercharging in absorption reactor thermally and is transported in regeneration reactor; Choke valve is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor; In absorption reactor thermally, be also provided with heat exchanger, for exporting the absorption heat of absorption reaction; In regeneration reactor, be provided with heat exchanger, for the regenerated heat of regenerative response is provided.
The present invention also proposes a kind of carbon dioxide compression systems, and this system comprises the above-mentioned carbon dioxide compression set of plural serial stage, and wherein, the absorption reactor thermally of rear one-level compression set is connected in the regeneration reactor of previous stage compression set.Preferably, this system also comprises a condenser, is connected in the regeneration reactor of afterbody carbon dioxide compression set, the carbon dioxide for condensation from this regeneration reactor.
The invention allows for a kind of carbon dioxide compression systems, it comprises compression subsystem and heat pump subsystem: described compression subsystem comprises the compression set of one-level or plural serial stage, every grade of compression set comprises: absorption reactor thermally, for absorbing carbon dioxide gas; Regeneration reactor, for making absorbent solution from the absorption reactor thermally gas that splits the carbon dioxide off; Booster pump, for being transported to the carbon dioxide absorption solution of absorption reactor thermally in regeneration reactor; Choke valve, is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor; In compression subsystem, the carbon dioxide absorption reactor of rear one-level compression set is connected in the regeneration reactor of previous stage compression set; The regeneration reactor of afterbody compression set is connected in a condenser; Described heat pump subsystem comprises: heat pump generator, in it, be filled with the first heat pump absorbent solution, and in this heat pump generator, be provided with and heat exchanger occur for receiving the absorption heat from above-mentioned absorption reactor thermally; Heat pump absorber, is filled with the second heat pump absorbent solution in it, be provided with absorption heat-exchange device for the regeneration reactor heat supply to above-mentioned in this heat pump absorber; Steam channel, is communicated with described heat pump generator and described heat pump absorber; Described the first heat pump absorbent solution and the second heat pump absorbent solution are comprised of working medium and absorbent, and the concentration of absorbing of the first heat pump absorbent solution can be infinitesimal, and the first heat pump absorbent solution can only be comprised of working medium; The first heat pump absorbent solution and the second heat pump absorbent solution can adopt identical absorbent, also can adopt different absorbents, when the first heat pump absorbent solution and the second heat pump absorbent solution adopt same absorbent, the concentration of absorbing of the second heat pump absorbent solution is higher than the concentration of absorbing of the first heat pump absorbent solution; Described working medium is the mixture of water, ammonia, methyl alcohol and ethanol one of them or several materials; Described absorbent is LiBr, NaBr, KBr, NH 4br, MgBr 2, CaBr 2, LiI, NaI, KI, NH 4i, MgI 2, CaI 2, LiCl, NaCl, KCl, NH 4cl, MgCl 2, CaCl 2, LiNO 3, NaNO 3, KNO 3, NH 4nO 3, Mg(NO 3) 2and Ca(NO 3) 2the mixture of one of them or several materials; Described generation heat exchanger is connected in the heat exchanger in above-mentioned absorption reactor thermally at different levels, and described absorption heat-exchange device is connected in the heat exchanger in above-mentioned regeneration reactor at different levels.
Preferably, the carbon dioxide compression systems that the embodiment of the present invention proposes, also comprise absorbent crystallizer, reception is from the heat pump absorbent solution of heat pump absorber and/or heat pump generator and carry out cooling, heat pump absorbent solution after formation absorbent crystallization and crystallization, after described crystallization, heat pump absorbent solution is delivered to heat pump generator as the first heat pump absorbent solution, and the absorbent solution that contains described absorbent crystallization is delivered to heat pump absorber as the second heat pump absorbent solution.
Preferably, the carbon dioxide compression systems that the embodiment of the present invention proposes, also comprise that heat pump absorbent solution is from heat exchanger, for the described heat pump absorbent solution from heat pump generator and/or from the heat pump absorbent solution of heat pump absorber, with absorbent solution after crystallization and/or absorbent crystallization or carry out heat exchange containing the absorbent solution of absorbent crystallization.
Preferably, the carbon dioxide compression systems that the embodiment of the present invention proposes, is also provided with generation heater in described heat pump generator, for heating the first heat pump absorbent solution in heat pump generator.
The present invention also proposes a kind of carbon dioxide separation recovery system, comprises isolated subsystem, compression subsystem and heat pump subsystem: described isolated subsystem comprises: absorption tower, for from carbon dioxide containing gas absorbing carbon dioxide; Regenerator, for regenerating carbon dioxide absorption solution; Described compression subsystem comprises the compression set of one-level or plural serial stage, and every grade of compression set comprises: absorption reactor thermally, for absorbing the carbon dioxide from isolated subsystem; Regeneration reactor, for making absorbent solution from the absorption reactor thermally gas that splits the carbon dioxide off; Booster pump, for being transported to the carbon dioxide absorption solution of absorption reactor thermally in regeneration reactor; Choke valve, is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor; In compression subsystem, the carbon dioxide absorption reactor of rear one-level compression set is connected in the regeneration reactor of previous stage compression set; The carbon dioxide absorption reactor of first order compression set is connected in isolated subsystem, for receiving carbon dioxide; The regeneration reactor of afterbody compression set is connected in a condenser; Described heat pump subsystem comprises: heat pump generator, in it, be filled with the first heat pump absorbent solution, and in this heat pump generator, be provided with the first generation heat exchanger and second heat exchanger occurs, for receiving the absorption heat from above-mentioned absorption tower and absorption reactor thermally; Heat pump absorber, is filled with the second heat pump absorbent solution in it, in this heat pump absorber, be provided with absorption heat-exchange device, for the regenerator to above-mentioned and regeneration reactor heat supply; Steam channel, is communicated with described heat pump generator and described heat pump absorber; Described first heat exchanger occurs is connected in the heat exchanger in absorption reactor thermallies at different levels in absorbent solution heat exchanger in above-mentioned isolated subsystem and above-mentioned compression subsystem; The described second entrance that heat exchanger occurs is connected in the gas vent at regenerator top in above-mentioned isolated subsystem; Described absorption heat-exchange device is connected in the heat exchanger in regeneration reactors at different levels in the reboiler of regenerator in above-mentioned isolated subsystem and compression subsystem.Preferably, also comprise gas-liquid separator, its entrance is connected in the outlet of above-mentioned the second generation heat exchanger; Its top outlet is connected in the absorption reactor thermally of described first order compression set.
Aforesaid carbon dioxide compression systems adopts potash, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD in described absorption reactor thermally or wherein two kinds or two or more mixtures carry out absorbing carbon dioxide.
The object of the invention to solve the technical problems can also realize by the following technical solutions.The present invention also proposes a kind of carbon dioxide compression method, comprises the following steps: in absorption reactor thermally, and carbon dioxide and carbon dioxide absorption solution reaction Formed acid compound; By above-mentioned carbonate compound supercharging and be transported in regeneration reactor; In regeneration reactor, from the carbonate compound of absorption reactor thermally, be heated decomposition, generate carbon dioxide and carbon dioxide absorption solution; And by the carbon dioxide absorption solution decompression generating in regeneration reactor and be transported in absorption reactor thermally.
The object of the invention to solve the technical problems can also realize by the following technical solutions.The present invention also proposes a kind of carbon dioxide compression method, comprises the compression process of plural serial stage, and every grade of compression process comprises: in absorption reactor thermally, carbon dioxide is absorbed by carbon dioxide absorption solution; By the carbon dioxide absorption solution supercharging after above-mentioned absorbing carbon dioxide and be transported in regeneration reactor; In regeneration reactor, from the carbon dioxide absorption solution of absorption reactor thermally, be heated, generate carbon dioxide and carbon dioxide absorption solution; And by the carbon dioxide absorption solution decompression generating in regeneration reactor and be transported in absorption reactor thermally; Except the first compression process, in other compression process, enter carbon dioxide in absorption reactor thermally and be the carbon dioxide that the regeneration reactor of previous stage compression process produces.Preferably, also comprise the carbon dioxide producing in regeneration reactor of one-level compression process is in the end carried out to condensation, form carbon dioxide liquid.
The object of the invention to solve the technical problems can also realize by the following technical solutions.The present invention also proposes a kind of carbon dioxide compression method and comprises the following steps: in absorption reactor thermally, carbon dioxide is absorbed by carbon dioxide absorption solution; Carbon dioxide absorption solution after above-mentioned absorbing carbon dioxide gas is transported in regeneration reactor; In regeneration reactor, from the carbon dioxide absorption solution of absorption reactor thermally, be heated, generate carbon dioxide and regenerating carbon dioxide absorption solution; And the regenerating carbon dioxide absorption solution generating in regeneration reactor is transported in absorption reactor thermally.
The present invention also proposes a kind of carbon dioxide compression method, comprises the compression process of plural serial stage, and every grade of compression process comprises: in absorption reactor thermally, carbon dioxide is absorbed by carbon dioxide absorption solution; By the carbon dioxide absorption solution supercharging after above-mentioned absorbing carbon dioxide and be transported in regeneration reactor; In regeneration reactor, from the carbon dioxide absorption solution of absorption reactor thermally, be heated, generate carbon dioxide and regenerating carbon dioxide absorption solution; And the regenerating carbon dioxide absorption solution generating in regeneration reactor is reduced pressure and be transported in absorption reactor thermally; Except first order compression process, in other compression process, enter carbon dioxide in absorption reactor thermally and be the carbon dioxide that the regeneration reactor of previous stage compression process produces.
Preferably, aforesaid carbon dioxide compression method, carries out condensation to the carbon dioxide producing in the regeneration reactor of one-level compression process in the end, forms carbon dioxide liquid.
Preferably, front described carbon dioxide compression method, also comprise: heat pump cycle process, this heat pump cycle process comprises: in described absorption reactor thermally, carbon dioxide is absorbed to the absorption heat that discharges by carbon dioxide absorption solution for heating the first heat pump absorbent solution, produce working substance steam; And described working substance steam is transported in heat pump absorber, and absorbed by the second heat pump absorbent solution in heat pump absorber, discharge and absorb heat, this absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution of thermal regeneration reactor.
The present invention also proposes a kind of carbon dioxide separation recovery method, and for reclaiming carbon dioxide from carbonated unstripped gas separation, the method comprises carbon dioxide separation process and carbon dioxide compression process; Described carbon dioxide separation process comprises: in absorption tower, with carbon dioxide absorption solution, contact with unstripped gas, make carbon dioxide absorption solution absorb the carbon dioxide in unstripped gas; Carbon dioxide absorption solution after absorbing carbon dioxide outputs in regenerator and is heated intensification, and the carbon dioxide absorbent solution of absorbing carbon dioxide is decomposed, and forms carbon dioxide and absorbent solution two-phase; Described carbon dioxide compression process is aforesaid carbon dioxide compression method, and the carbon dioxide forming in above-mentioned regenerator is compressed.
Preferably, before carrying out carbon dioxide compression process, the carbon dioxide forming and absorbent solution are first transported to respectively in heat pump generator, for heating the heat pump absorbent solution in heat pump generator in regenerator.In heat pump cycle process, a part for the absorption heat producing in heat pump absorber is transported in regenerator for the carbon dioxide absorption solution in thermal regeneration tower.
Preferably, the part heat pump absorbent solution in heat pump generator and/or the part heat pump absorbent solution in heat pump absorber are carried out cooling, form heat pump absorbent solution after absorbent crystallization and crystallization; Using described absorbent crystallization or containing the absorbent solution of absorbent crystallization, as the second heat pump absorbent solution, be transported in heat pump absorber, heat pump absorbent solution after described crystallization is transported in heat pump generator as the first heat pump absorbent solution.
Preferably, in the rear one-level absorption reactor thermally that the compression process of described plural serial stage is adjacent, the conversion degree of the absorbent of carbon dioxide absorption solution is larger more than 0.1 than the conversion degree of the absorbent of the carbon dioxide absorption solution in previous stage absorption reactor thermally.The conversion degree of absorbent has referred in the absorbent solution reaction bonded molar concentration of absorbent and the ratio of absorbent total mol concentration of carbon dioxide, under and condition that absorbent kind is identical with total mol concentration certain in regeneration temperature, the equalizing pressure of the carbon dioxide that regenerative response generates raises along with the increase of absorbent conversion degree.Carbon dioxide of the present invention compression is to improve regenerative response temperature when reducing absorption reaction temperature, and then improves step by step that the absorbent conversion degree of absorbent solution in regeneration reactor realizes.
The present invention compared with prior art has obvious advantage and beneficial effect.The absorption reaction of carbon dioxide is strong exothermal reaction, and the regenerative response of carbon dioxide absorption solution is the back reaction of carbon dioxide absorption reaction, is strong endothermic reaction.Existing carbon dioxide chemistry absorption techniques as shown in Figure 7, in order to improve the CO of absorption liquid 2absorbability, conventionally adopt external refrigeration water to carry out cooling to entering the carbon dioxide absorption solution on absorption tower, to guarantee absorption tower, at lower temperature, work, simultaneously in order to make the regeneration of absorption liquid more thorough, conventionally adopt external heat source, as regenerated heat, the absorption liquid in regenerator is heated to guarantee that regenerator works at the temperature higher than absorption tower operating temperature.Visible, existing carbon dioxide chemistry absorption techniques on the one hand need to be by external refrigeration water to a large amount of more low-grade heat of environmental emission, and need on the other hand to drop into more high-grade a large amount of external drive thermal source, because of but one not only consumed energy but also the process of water consumption.From above technical scheme, the carbon dioxide separation recovery system that the present invention proposes is actually carbon dioxide chemistry absorption techniques and absorption heat pump cycle technology is organically combined, the more low-grade absorption heat of carbon dioxide absorption process being emitted by the effect of absorption heat pump cycle is promoted to the more high-grade regenerated heat that can be used for carbon dioxide absorption regeneration of waste liquor, thereby realize, significantly reduces or without external refrigeration water and external drive thermal source.The present invention simultaneously adopts absorption compression process, and the carbon dioxide that separation is obtained compresses, and this compression process is by adopting waste heat to carry out, and has significantly saved electric power or other driving force.Therefore, compare with existing carbon dioxide separation recovery system, the carbon dioxide separation recovery system that the present invention proposes has advantages of low energy consumption, low operating cost.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of description, below with preferred embodiment of the present invention and coordinate accompanying drawing to be described in detail as follows.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the carbon dioxide compression set of the embodiment of the present invention 1.
Fig. 2 is the schematic diagram of the carbon dioxide compression systems of the embodiment of the present invention 2.
Fig. 3 is the schematic diagram of the carbon dioxide compression systems of the embodiment of the present invention 3.
Fig. 4 is the schematic diagram of the carbon dioxide compression systems of the embodiment of the present invention 4.
Fig. 5 is the schematic diagram of the carbon dioxide separation recovery system of the embodiment of the present invention 5.
Fig. 6 is the schematic diagram of the carbon dioxide separation recovery system of the embodiment of the present invention 6.
Fig. 7 is the schematic diagram of existing carbon dioxide separation recovery system.
realize the best mode of invention
For further setting forth the present invention, reach technological means and the effect that predetermined goal of the invention is taked, below in conjunction with accompanying drawing and preferred embodiment, its specific embodiment of carbon dioxide separation recovery system, structure, feature and effect thereof to proposing according to the present invention, be described in detail as follows.
Referring to shown in Fig. 1, is the carbon dioxide compression set that the embodiment of the present invention 1 proposes, and this device comprises absorption reactor thermally 101, regeneration reactor 102, booster pump 103 and choke valve 104.Described absorption reactor thermally 101 and regeneration reactor 102 are pressure vessel, accommodate respectively carbon dioxide absorption solution.In absorption reactor thermally 101, be provided with heat exchanger 105, for by the heat output producing in absorption reactor thermally, in regeneration reactor 102, be provided with heat exchanger 106, for provide heat in regeneration reactor.Between described absorption reactor thermally 101 and regeneration reactor 102, by pipeline, be connected, thereby carbon dioxide absorption solution is circulated between absorption reactor thermally 101 and regeneration reactor 102.Described booster pump 103 is for by the carbon dioxide absorption solution supercharging in absorption reactor thermally 101 and be transported in regeneration reactor 103, choke valve 104 is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor.The solute of the carbon dioxide absorption solution in absorption reactor thermally and regeneration reactor is: potash, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or wherein two kinds or two or more mixtures.The effect of carbon dioxide absorption solution is, in absorption reactor thermally, carbon dioxide and carbon dioxide absorption solution adsorb, dissolve or carries out chemical combination under lower temperature and pressure, thereby carbon dioxide is absorbed; Carbon dioxide absorption solution after absorbing carbon dioxide in regeneration reactor by high-temperature heating, occur and inverse process contrary in absorption reactor thermally, as desorption, separate out or decompose, thereby produce carbon dioxide and carbon dioxide absorption solution, the carbon dioxide at high temperature obtaining has higher pressure, thereby has realized the compression of carbon dioxide.
Refer to shown in Fig. 2, it is a kind of carbon dioxide compression systems that the embodiment of the present invention 2 proposes, this system comprises the multistage compression set of carbon dioxide as described in Example 1, compression set 100, compression set 200 and compression set 300 are connected successively, booster pump 103,203,303 is for by the carbon dioxide absorption solution supercharging of absorption reactor thermally and be transported in regeneration reactor, and choke valve 104,204,304 is poor for controlled pressure.Wherein, the absorption reactor thermally of a rear compression set is connected in the regeneration reactor of last compression set, as absorption reactor thermally 201 is connected in regeneration reactor 102, receives the carbon dioxide from regeneration reactor 102; Absorption reactor thermally 301 is connected in regeneration reactor 202, for receiving the carbon dioxide from regeneration reactor 202.Through compression set 100, compression set 200 and compression set 300 multi-stage compressions, can obtain at regeneration reactor 302 carbon dioxide of high pressure.Preferably, absorption reactor thermallies at different levels are worked at same lower temperature, and regeneration reactor at different levels is worked at the same temperature higher than absorption reactor thermally operating temperature.
Referring to shown in Fig. 3, is the carbon dioxide compression systems that the embodiment of the present invention 3 proposes, and it has increased a condenser 400 than embodiment 2, is connected in the regeneration reactor 302 of compression set 300, the carbon dioxide producing for receiving regeneration reactor 302.The carbon dioxide entering is carried out cooling condenser 400 is interior, make carbon dioxide condensation form carbon dioxide liquid.
Referring to shown in Fig. 4, is a kind of carbon dioxide compression systems that the embodiment of the present invention 4 proposes, and this system comprises the carbon dioxide compression set described in heat pump subsystem and previous embodiment 1.Described heat pump subsystem comprises: heat pump generator 21, in it, be filled with the first heat pump absorbent solution, and in this heat pump generator 21, be provided with and heat exchanger 32 occur for receiving the absorption heat from described absorption reactor thermally 101; Heat pump absorber 22, is filled with the second heat pump absorbent solution in it, be provided with absorption heat-exchange device 26 for regeneration reactor 102 heat supplies to above-mentioned in this heat pump absorber 22; Steam channel 23, is communicated with described heat pump generator 21 and described heat pump absorber 22; The concentration of absorbing of the first heat pump absorbent solution described in described heat pump generator 21 is lower than the concentration of absorbing of the second heat pump absorbent solution described in heat pump absorber 22; Described generation heat exchanger 32 is connected in the heat exchanger 105 in above-mentioned absorption reactor thermally 101, and described absorption heat-exchange device 26 is connected in the heat exchanger 106 in above-mentioned regeneration reactor 102.So the absorption heat producing during due to carbon dioxide absorption solution absorbing carbon dioxide in absorption reactor thermally 101 can be transported in heat pump generator 21, for heating the first heat pump absorbent solution in heat pump generator 21 to produce working substance steam.Described working substance steam enters in heat pump absorber by steam channel 23, the second heat pump absorbent solution in heat pump absorber 22 absorbs described working substance steam and produces absorption heat, this absorption heat is transported in regeneration reactor 102 for heating carbon dioxide absorption solution, thereby split the carbon dioxide off gas, and carbon dioxide absorption solution is regenerated.Described the first heat pump absorbent solution and the second heat pump absorbent solution are comprised of working medium and absorbent, and the concentration of absorbing of the first heat pump absorbent solution can be infinitesimal, and the first heat pump absorbent solution can only be comprised of working medium.The first heat pump absorbent solution and the second heat pump absorbent solution can adopt identical absorbent, also can adopt different absorbents.When the first heat pump absorbent solution and the second heat pump absorbent solution adopt same absorbent, the concentration of absorbing of the second heat pump absorbent solution is higher than the concentration of absorbing of the first heat pump absorbent solution.Described working medium is the mixture of water, ammonia, methyl alcohol and ethanol one of them or several materials; Described absorbent is LiBr, NaBr, KBr, NH 4br, MgBr 2, CaBr 2, LiI, NaI, KI, NH 4i, MgI 2, CaI 2, LiCl, NaCl, KCl, NH 4cl, MgCl 2, CaCl 2, LiNO 3, NaNO 3, KNO 3, NH 4nO 3, Mg(NO 3) 2and Ca(NO 3) 2the mixture of one of them or several materials.The carbon dioxide compression systems of the present embodiment, the absorption heat that can effectively utilize each absorption process to produce, thus heat economizing consumption improves efficiency of energy utilization.
In addition, can also be by the heat pump subsystem application of the present embodiment in the carbon dioxide compression systems of embodiment 2 or embodiment 3, adopt the identical connected mode with embodiment 4, described generation heat exchanger is connected in to the heat exchanger in described absorption reactor thermally at different levels, and described absorption heat-exchange device is connected in the heat exchanger in described regeneration reactor at different levels.Thereby can make the carbon dioxide compression systems with multi-stage compression device there is good efficiency of energy utilization.
Referring to shown in Fig. 5, is the schematic diagram of the carbon dioxide separation recovery system of the embodiment of the present invention 5 propositions.This carbon dioxide separation recovery system mainly comprises: isolated subsystem, heat pump subsystem and compression subsystem, isolated subsystem is for isolating carbon dioxide from carbonated unstripped gas such as combustion product gases, described compression subsystem is for the carbon dioxide being obtained by isolated subsystem is compressed to carbon dioxide or the carbon dioxide liquid that obtains high pressure, and described heat pump subsystem is for providing heat to isolated subsystem and compression subsystem.
Described isolated subsystem comprises: absorption tower 10 and regenerator 40.Described absorption tower 10, for absorbing the carbon dioxide of the unstrpped gas of carbon dioxide containing gas.Described absorption tower 10 comprises: at the bottom of tower 11, for holding carbon dioxide absorption solution; Packing layer 12, is arranged on the medium position in this absorption tower 10, its role is to make carbon dioxide absorption solution and the gas entering in tower to have larger contact interface; Air supply opening 16, is arranged under above-mentioned packing layer 12, for carbonated unstrpped gas is provided in absorption tower; Exhaust outlet 15, is arranged on the top on absorption tower 10, for discharging the gas after carbon dioxide separation; Sprinkling equipment 13, is arranged on above-mentioned packing layer 12, for evenly spraying carbon dioxide absorption solution.In this absorption tower, under carbon dioxide absorption solution drenches from top to bottom in absorption tower, gas flows from bottom to top, and carbon dioxide absorption solution contacts with the carbon dioxide containing gas (as flue gas) in entering absorption tower, and the acid gas component such as carbon dioxide wherein of absorption and SOx, NOx.The absorbent of the carbon dioxide absorption solution of described isolated subsystem can adopt potash, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or wherein two kinds or two or more mixtures.
Described heat pump subsystem comprises: heat pump generator 21 and heat pump absorber 22.Described heat pump generator 21, is provided with the first generation heat exchanger 31 and second heat exchanger 25 occurs in it, be filled with the first heat pump absorbent solution of low concentration in this heat pump generator 21, and this first heat pump absorbent solution is comprised of working medium and absorbent.The effect of this heat pump generator is, the first heat pump absorbent solution of the low concentration in this heat pump generator is heated, thereby produces working substance steam.Described heat pump generator 21, is also provided with in it heater 32 occurs, for heating the first heat pump absorbent solution in heat pump generator, and the shortage of heat causing with radiation loss and the crystallizer cooling loss compensating due to system.
Described heat pump absorber 22, in it, be filled with the second heat pump absorbent solution, the kind of its working medium and absorbent is identical or different from the first absorbent solution in heat pump generator 21, and preferably, its concentration of absorbing is higher than the concentration of absorbing of the first absorbent solution in heat pump generator 21; Preferably, the second heat pump absorbent solution in heat pump absorber 22 is saturated solution (or supersaturated solution, or the absorbent crystallization that coexisted).Between described heat pump generator 21 and described heat pump absorber 22, be provided with working substance steam passage 23, for the working substance steam of heat pump generator 21 interior generations is entered in heat pump absorber 22.In this heat pump absorber 22, be provided with absorption heat-exchange device 26, be connected in the reboiler 46 of described regenerator 40, for the heat delivery of heat pump absorber 22 interior generations is arrived to reboiler 46.
Described regenerator 40, is connected with reboiler 46, and its top is provided with sprinkling equipment 43, is connected in the carbon dioxide absorption taphole of 10 bottoms, described absorption tower.At the middle part of regenerator 40, be provided with packing layer 42, for carbon dioxide absorption solution can fully be regenerated, the bottom of regenerator be at the bottom of tower 41 for holding carbon dioxide absorption solution, regenerator 40 tops are provided with exhaust outlet 45.By pipeline, the carbon dioxide absorption solution of 10 bottoms, absorption tower is delivered to the regeneration that regenerator carries out absorption liquid, forms gas and liquid two-phase.The main component of this gas is carbon dioxide and steam, and the main component of described liquid is carbon dioxide absorption solution, still, and because the gas concentration lwevel through containing in this liquid of regeneration reduces greatly.The described first entrance that heat exchanger 31 occurs is connected in the absorption liquid outlet of above-mentioned regenerator 40 bottoms, the described first outlet that heat exchanger 31 occurs connects the sprinkling equipment 13 on above-mentioned absorption tower 10, and the carbon dioxide absorption solution after heat exchange cooling in the first generation heat exchanger 31 is entered in absorption tower again.The described second entrance that heat exchanger 25 occurs is connected in the top vent 45 of above-mentioned regenerator 40.The exhaust of regenerator gas temperature after heat exchange reduces, and part steam generation condensation.Then, from the outlet of the second generation heat exchanger 25, obtain the carbon dioxide of high concentration.Preferably, in the second above-mentioned outlet that heat exchanger 25 occurs, be connected with gas-liquid separator 30 to obtain the carbon dioxide that purity is higher.
Described compression subsystem, compresses for the carbon dioxide of high concentration that described isolated subsystem is obtained.This compression subsystem comprises the compression set of plural serial stage, the quantity of compression set can be according to concrete operating mode setting, in general the compression set number of series connection manyly will obtain the carbon dioxide that pressure is higher, and the present embodiment be take 3 grades of compression sets series connection and described as example.This enforcement comprises that the structure of 100,200 and 300, three grades of compression sets of three grades of compression sets is identical, below take compression set 100 and describes as example.This compression set 100 comprises absorption reactor thermally 101, regeneration reactor 102, booster pump 103 and choke valve 104.It is connected in described isolated subsystem absorption reactor thermally 101, receives carbon dioxide.In described absorption reactor thermally 101, be provided with carbon dioxide absorption solution, the carbon dioxide entering in it is absorbed by carbon dioxide absorption solution.Described regeneration reactor 102 heats for the carbon dioxide absorption solution in self-absorption in future reactor 101, makes its gas that splits the carbon dioxide off, thereby carbon dioxide absorption solution is regenerated.Described booster pump 103 is for by the carbon dioxide absorption solution supercharging in absorption reactor thermally 101 and be transported in regeneration reactor 103.The internal pressure of described regeneration reactor is higher than the internal pressure of absorption reactor thermally.Carbon dioxide absorption solution after regeneration is transferred back in absorption reactor thermally again, and choke valve 104 is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally for controlling the pressure differential between absorption reactor thermally 101 and regeneration reactor 103.In absorption reactor thermally 101, be also provided with heat exchanger, for exporting, absorb heat; In regeneration reactor 103, be provided with heat exchanger, for providing carbon dioxide absorption regeneration of waste liquor required heat.
Compression set 200 comprises absorption reactor thermally 201, regeneration reactor 202, booster pump 203 and choke valve 204; Its absorption reactor thermally 201 is connected in the regeneration reactor 102 of compression set 100; Compression set 300 comprises absorption reactor thermally 301, regeneration reactor 302, booster pump 303 and choke valve 304; Its absorption reactor thermally 301 is connected in the regeneration reactor 202 of compression set 200.Condenser 400 is connected in regeneration reactor 302, receives carbon dioxide, and carbon dioxide is condensed into liquid state.
Heat exchanger in each absorption reactor thermally in compression subsystem is connected in the generation heat exchanger 32(of heat pump subsystem because annexation is identical with Fig. 4, for succinct drawing, in Fig. 5, do not draw annexation), for carbon dioxide being absorbed to the hot number of produced absorption, delivering to heat pump generator and produce working substance steam with heating heat pump absorbent solution, thereby can save the consumption of external heat source.Absorption heat-exchange device 26 in described heat pump subsystem can also be connected with the heat exchanger in each regeneration reactor, be used for the carbon dioxide absorption solution of thermal regeneration reactor (because annexation is identical with Fig. 4, for succinct drawing, in Fig. 5, do not draw annexation).
Referring to shown in Fig. 6, is the schematic diagram of the carbon dioxide separation recovery system of the embodiment of the present invention 6 propositions.Compare with the separation and recovery system of the above embodiments 5, the present embodiment has increased liquid-feeding pump 24, carbon dioxide absorption solution from heat exchanger 27 and absorbent crystallizer 28, and effect is to make the concentration difference of the carbon dioxide absorption solution in heat pump generator 21 and heat pump absorber 22 to maintain a relatively stable state.In addition, the present embodiment has also increased carbon dioxide absorption solution from heat exchanger 44, and effect is to make the regeneration efficiency of absorption liquid to be further improved.
Described liquid-feeding pump 24 is connected in described heat pump generator 21 and heat pump absorber 22 by pipeline, for the partial CO 2 absorbent solution in heat pump generator 21 and heat pump absorber 22 is transported to absorbent crystallizer 28.This absorbent crystallizer 28, comprising: crystallizer carbon dioxide absorption solution entrance, is connected in the carbon dioxide absorption taphole of liquid-feeding pump 24 by pipeline; Crystallizer weak solution exports, and is connected in the carbon dioxide absorption solution entrance of heat pump generator 21 by pipeline; And containing crystallization solution delivery outlet, by pipeline, be connected in the carbon dioxide absorption solution entrance of heat pump absorber 22.This absorbent crystallizer 28 also has refrigerant circulation equipment, for the carbon dioxide absorption solution in absorbent crystallizer 28, provide cold, carbon dioxide absorption solution temperature in absorbent crystallizer 28 is reduced, when reaching the crystallization temperature of absorbent when following, separate out absorbent crystallization.After Separation of Solid and Liquid, absorbent crystallization is from outputing to heat pump absorber 22 containing crystallization solution delivery outlet, and the weak solution that concentration of absorbing has reduced is transported in heat pump generator 21 from the outlet of crystallizer weak solution.
On the pipeline that carbon dioxide absorption solution is connected with liquid-feeding pump 24 from the absorbent crystallizer 28 described in heat exchanger 27 is arranged at, for the crystallization solution that contains that enters the carbon dioxide absorption solution of absorbent crystallizer 28, the weak solution of exporting from absorbent crystallizer and export from absorbent crystallizer is carried out to heat exchange.Carbon dioxide absorption solution is from the beneficial effect of heat exchanger 27, through after heat exchange, enters the carbon dioxide absorption solution temperature reduction of absorbent crystallizer 28, is conducive to the formation of crystallization, thereby has saved the required cold of crystallization; The temperature that outputs to the weak solution of heat pump generator 21 is improved, and is conducive to the evaporation of absorption cycle working medium; The temperature containing absorbent crystallization solution of output is also improved, thereby is conducive to keep heat pump absorber 22 to be worked at higher temperature.
Described carbon dioxide absorption solution from heat exchanger can also for by the carbon dioxide absorption solution from heat pump absorber with from the crystallization of absorbent crystallizer after carbon dioxide absorption solution carry out heat exchange, for by the carbon dioxide absorption solution from heat pump absorber with from the absorbent crystallization of absorbent crystallizer or containing the carbon dioxide absorption solution of absorbent crystallization, carry out heat exchange and for by the carbon dioxide absorption solution from heat pump absorber with from the crystallization of absorbent crystallizer after carbon dioxide absorption solution and absorbent crystallization or carry out heat exchange containing the carbon dioxide absorption solution of absorbent crystallization.
Described carbon dioxide absorption solution is from heat exchanger 44, be arranged on the pipeline that connects the absorption liquid outlet of 10 bottoms, absorption tower and the absorption liquid entrance on regenerator 40 tops, for to the 41 carbon dioxide absorption solution that are delivered to the first generation heat exchanger 31 at the bottom of the tower from regenerator 40 with at the bottom of absorbing tower, 11 between the carbon dioxide absorption solution of regenerator conveying, carry out heat exchange, to improve the temperature of the carbon dioxide absorption solution that enters regenerator 40, thereby further improve the carbon dioxide absorption regeneration of waste liquor efficiency of regenerator 40.
In above-mentioned each embodiment, the basic procedure that completes technical solution of the present invention has only been described, for other parts or the equipment of realizing this flow process, omit, for example, guarantee pump or valve that each flow of matter direction is required.For needed other equipment of power circulation system or the part realized described in above-mentioned each embodiment, those skilled in the art all can find corresponding technological means in the prior art, and the inventor does not repeat them here.
Embodiments of the invention 7 have also proposed a kind of carbon dioxide compression method, and it adopts the compression set described in embodiment 1 to realize.This method comprises the following steps:
Absorption reactor thermally receives carbon dioxide, the carbon dioxide absorption solution absorbing carbon dioxide gas in absorption reactor thermally, and carbon dioxide and carbon dioxide absorption solution adsorb, dissolve or carries out combination reaction.The absorbent of described carbon dioxide absorption solution is: potash, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or wherein two kinds or two or more mixtures.For example, when absorbent is potash, carbon dioxide and the potash production saleratus that reacts in absorption reactor thermally.
By the absorption in above-mentioned absorption reactor thermally carbon dioxide the supercharging of carbon dioxide absorption solution and be transported in regeneration reactor;
In regeneration reactor, from the carbon dioxide absorption solution of absorption reactor thermally, be heated, generate carbon dioxide and carbon dioxide absorption solution; And
The carbon dioxide absorption solution generating in regeneration reactor is transported in absorption reactor thermally.
The carbon dioxide compression method that embodiments of the invention 8 propose, adopts the compressibility described in embodiment 2 to realize.The method comprises the compression process of plural serial stage, every grade of compression process is identical with the process of embodiment 6, except the first compression process, in other compression process, enter carbon dioxide in absorption reactor thermally and be the carbon dioxide that the regeneration reactor of last compression process produces.Preferably, the carbon dioxide producing of one-level compression process is in the end carried out to condensation in regeneration reactor, form carbon dioxide liquid.
Embodiments of the invention 9 also propose a kind of carbon dioxide compression method, and it comprises outside the carbon dioxide compression method described in previous embodiment 7 or embodiment 8, also comprises heat pump cycle process.With reference to the carbon dioxide compression systems shown in Fig. 4, described heat pump cycle process comprises: in described absorption reactor thermally, carbon dioxide is absorbed to the absorption heat that discharges by carbon dioxide absorption solution for heating the first heat pump absorbent solution, produce working substance steam; And described working substance steam is transported in heat pump absorber, and absorbed by the second heat pump absorbent solution in heat pump absorber, discharge and absorb heat, this absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution of thermal regeneration reactor.For the heat of system loss, be to provide by external heat source, but adopt above-mentioned heat pump cycle process can reduce the consumption of external heat source, thereby can effectively utilize heat, improve efficiency of energy utilization.For the multi-stage compression described in embodiment 8, in compression processes at different levels, carbon dioxide is absorbed produced heat all can be used to heat the generating process in heat pump cyclic process, for concentrating heat pump absorbent solution and producing working substance steam; And in heat pump cycle, the absorption heat producing when working substance steam is absorbed also can be used to the regenerative process in regeneration reactors at different levels.
The embodiment of the present invention 10 has also proposed a kind of carbon dioxide separation recovery method, and it adopts the carbon dioxide separation recovery system described in embodiment 5.This carbon dioxide separation recovery method comprises carbon dioxide separation process, carbon dioxide compression process and heat pump cycle process.
Carbon dioxide separation process comprises: in absorption tower, with carbon dioxide absorption solution, contacts with combustion product gases, makes carbon dioxide absorption solution absorb the carbon dioxide in flue gas, and at the bottom of dropping to the tower on absorption tower; Carbon dioxide absorption solution after absorbing carbon dioxide at the bottom of tower is outputed in regenerator and is heated intensification, the absorption liquid of absorbing carbon dioxide is decomposed, form gas and liquid two-phase, this gas is mainly carbon dioxide, and because a large amount of carbon dioxide has formed gaseous state, the carbon dioxide content in the liquid that regeneration forms reduces.
The compression process of carbon dioxide comprises multi-stage compression, and every grade of compression step comprises: the carbon dioxide absorption solution absorbing carbon dioxide of absorption reactor thermally; Then this carbon dioxide absorption solution is transported in regeneration reactor, is heated the carbon dioxide absorption solution decompositing out after gaseous carbon dioxide and regeneration, and the pressure of regeneration reactor is higher than the pressure of absorption reactor thermally; Carbon dioxide absorption solution after regeneration is transferred back in absorption reactor thermally.The carbon dioxide producing in regeneration reactor is transported to next stage compression process and compresses; Through multistage compression, can in compression step subsequently, obtain the carbon dioxide of high pressure; The carbon dioxide of high pressure is carried out to condensation, can obtain the carbon dioxide liquid of high pressure, thereby can more be conducive to recovery, storage and the transportation of carbon dioxide.
Described heat pump cycle process comprises: in described absorption reactor thermally, carbon dioxide is absorbed to the absorption heat that discharges by carbon dioxide absorption solution for heating the first heat pump absorbent solution, produce working substance steam; And described working substance steam is transported in heat pump absorber, and absorbed by the second heat pump absorbent solution in heat pump absorber, discharge and absorb heat, this absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution of thermal regeneration reactor.For described multi-stage compression, in compression processes at different levels, carbon dioxide is absorbed produced heat all can be used to heat the generating process in heat pump cyclic process, for concentrating hot the first pump absorbent solution and producing working substance steam; And in heat pump cycle, the absorption heat producing when working substance steam is absorbed also can be used to the regenerative process in regeneration reactors at different levels.
In addition, the carbon dioxide that the regeneration in above-mentioned carbon dioxide separation process can also be formed afterwards passes into second of heat pump generator heat exchanger occurs, and the liquid that forms after regeneration is passed into the first generation heat exchanger of heat pump generator, for heating the carbon dioxide absorption solution of heat pump generator, make its formation working substance steam; Above-mentioned working substance steam enters into heat pump absorber by steam channel, is absorbed to discharge to absorb heat by the second heat pump absorbent solution in heat pump absorber, and this absorption heat is used for heating the carbon dioxide absorption solution in reboiler by heat exchange mode.
The difference of the absorbent molar fraction of the first heat pump absorbent solution in the second heat pump absorbent solution in wherein said heat pump absorber and described heat pump generator is greater than 0.1, concentration difference is more conducive to improve the temperature in heat pump absorber more greatly, thereby is conducive to the regeneration of carbon dioxide absorption solution; From the liquid of the first generation heat exchanger output, turn back to top, absorption tower again for absorbing the carbon dioxide of flue gas; The second above-mentioned gas that heat exchanger output occurs is carried out to gas-liquid separation and can obtain highly purified carbon dioxide.
The carbon dioxide separation recovery method of the present embodiment 10 can remove more than 80% carbon dioxide in flue gas, the purity of the carbon dioxide that separation obtains (being dry gas content) under the condition of disregarding steam composition can reach more than 99%, and after three grades of compressions and condensation, can obtain 2.7MPa, the carbon dioxide liquid of-10 ℃.
The embodiment of the present invention 11 has also proposed a kind of carbon dioxide separation recovery method, is with the separation and recovery method difference of embodiment 10, and it adopts the piece-rate system described in embodiment 6.The present embodiment has increased the circulation step of heat pump absorbent solution in heat pump generator and heat pump absorber than embodiment 10, it comprises: part the first heat pump absorbent solution in the second heat pump absorbent solution of the part in heat pump absorber and heat pump generator is passed in absorbent crystallizer jointly, and carry out cooling to the mixing heat pump absorbent solution in crystallizer, thereby can form absorbent crystallization, then carry out Separation of Solid and Liquid; After the crystallization obtaining after Separation of Solid and Liquid, heat pump absorbent solution imports in heat pump generator, absorbent crystallization after Separation of Solid and Liquid to be to import in heat pump absorber containing the mode of crystallization solution, thereby can make the poor maintenance of solution concentration in heat pump absorber and heat pump generator within the specific limits.The present invention can realize the continuity of carbon dioxide separation process.In above-mentioned absorbent crystallizer, can pass into external source carries out cooling to the mixing heat pump absorbent solution in crystallizer.
Preferably, before after described crystallization, heat pump absorbent solution is transported to heat pump generator, and the heat pump absorbent solution of heat pump absorber output carry out cooling before, after the heat pump absorbent solution of described heat pump absorber output and described crystallization, heat pump absorbent solution is carried out heat exchange.
Preferably, before described absorbent crystallization is transported to heat pump absorber, and the heat pump absorbent solution of heat pump absorber output carry out cooling before, described absorbent crystallization is carried out heat exchange with the heat pump absorbent solution that described heat pump absorber is exported.
Preferably, before after described crystallization, heat pump absorbent solution is transported to heat pump generator, before absorbent crystallization is transported to heat pump absorber, and the heat pump absorbent solution of described heat pump absorber output carry out cooling before, after the heat pump absorbent solution of described heat pump absorber output and described absorbent crystallization and crystallization, heat pump absorbent solution is carried out heat exchange.
Preferably, before after described crystallization, heat pump absorbent solution is transported to heat pump generator, before absorbent crystallization is transported to heat pump absorber, the heat pump absorbent solution of heat pump absorber output carry out cooling before, and before the heat pump absorbent solution of described heat pump generator output is transported to heat pump absorber, the heat pump absorbent solution that the absorbent solution of this heat pump generator output is exported with described heat pump absorber is mixed to form mixes heat pump absorbent solution, and after this mixes two heat pump absorbent solutions and described absorbent crystallization and crystallization, heat pump absorbent solution is carried out heat exchange.
Through this heat exchange steps, thereby the temperature that can improve the heat pump absorbent solution in importing heat pump absorber and heat pump generator can keep the operating temperature of heat pump absorbent solution in heat pump absorber and heat pump generator, can be lowered into the temperature of the heat pump absorbent solution in absorbent crystallizer, thereby can save the consumption of low-temperature receiver simultaneously.Preferably, at the bottom of the tower of regenerator, be delivered to the carbon dioxide absorption solution of the first generation heat exchanger and between the absorption liquid of regenerator conveying, carry out heat exchange at the bottom of adsorption tower tower, to improve the temperature of the carbon dioxide absorption solution that enters regenerator, thereby further improve the regeneration efficiency of the carbon dioxide absorption solution of regenerator.
For realizing the necessary other technologies means of technique scheme, all can adopt technology of the prior art to realize.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations, in every case be the content that does not depart from technical solution of the present invention, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
industrial applicability
The carbon dioxide separation recovery system that the present invention proposes is actually carbon dioxide chemistry absorption techniques and absorption heat pump cycle technology is organically combined, the more low-grade absorption heat of carbon dioxide absorption process being emitted by the effect of absorption heat pump cycle is promoted to the more high-grade regenerated heat that can be used for carbon dioxide absorption regeneration of waste liquor, thereby realize, significantly reduces or without external refrigeration water and external drive thermal source.The present invention simultaneously adopts absorption compression process, and the carbon dioxide that separation is obtained compresses, and this compression process is by adopting waste heat to carry out, and has significantly saved electric power or other driving force.

Claims (20)

1. a carbon dioxide compression set, is characterized in that this device comprises: absorption reactor thermally, regeneration reactor, booster pump and choke valve,
In described absorption reactor thermally, be filled with carbon dioxide absorption solution, for absorbing carbon dioxide gas;
Described regeneration reactor is for making carbon dioxide absorption solution from the absorption reactor thermally gas that splits the carbon dioxide off;
Described booster pump is for being transported to the carbon dioxide absorption solution of absorption reactor thermally in regeneration reactor;
Choke valve is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor;
In absorption reactor thermally, be also provided with heat exchanger, for exporting the absorption heat of absorption reaction; In regeneration reactor, be provided with heat exchanger, for the regenerated heat of regenerative response is provided.
2. a carbon dioxide compression systems, is characterized in that, this system comprises the carbon dioxide compression set as claimed in claim 1 of plural serial stage, and wherein, the absorption reactor thermally of rear one-level compression set is connected in the regeneration reactor of previous stage compression set.
3. carbon dioxide compression systems according to claim 2, characterized by further comprising a condenser, is connected in the regeneration reactor of afterbody carbon dioxide compression set, the carbon dioxide for condensation from this regeneration reactor.
4. according to the carbon dioxide compression systems described in claim 2 or 3, it is characterized in that adopting potash, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or wherein two kinds or two or more mixtures carry out absorbing carbon dioxide in described absorption reactor thermally.
5. a carbon dioxide compression systems, is characterized in that it comprises compression subsystem and heat pump subsystem:
Described compression subsystem comprises the compression set of one-level or plural serial stage, and every grade of compression set comprises:
Absorption reactor thermally, for absorbing carbon dioxide gas;
Regeneration reactor, for making absorbent solution from the absorption reactor thermally gas that splits the carbon dioxide off;
Booster pump, for being transported to the carbon dioxide absorption solution of absorption reactor thermally in regeneration reactor;
Choke valve, is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor;
In compression subsystem, the carbon dioxide absorption reactor of rear one-level compression set is connected in the regeneration reactor of previous stage compression set; The regeneration reactor of afterbody compression set is connected in a condenser;
Described heat pump subsystem comprises:
Heat pump generator, is filled with the first heat pump absorbent solution in it, be provided with and heat exchanger occur for receiving the absorption heat from above-mentioned absorption reactor thermally in this heat pump generator;
Heat pump absorber, is filled with the second heat pump absorbent solution in it, be provided with absorption heat-exchange device for the regeneration reactor heat supply to above-mentioned in this heat pump absorber;
Steam channel, is communicated with described heat pump generator and described heat pump absorber;
Described generation heat exchanger is connected in the heat exchanger in above-mentioned absorption reactor thermally at different levels, and described absorption heat-exchange device is connected in the heat exchanger in above-mentioned regeneration reactor at different levels;
Described heat pump absorbent solution is comprised of working medium and absorbent, and described working medium is the mixture of water, ammonia, methyl alcohol and ethanol one of them or several materials; Described absorbent is LiBr, NaBr, KBr, NH 4br, MgBr 2, CaBr 2, LiI, NaI, KI, NH 4i, MgI 2, CaI 2, LiCl, NaCl, KCl, NH 4cl, MgCl 2, CaCl 2, LiNO 3, NaNO 3, KNO 3, NH 4nO 3, Mg (NO 3) 2and Ca (NO 3) 2the mixture of one of them or several materials.
6. carbon dioxide compression systems according to claim 5, it is characterized in that it also comprises absorbent crystallizer, reception is from the heat pump absorbent solution of heat pump absorber and/or heat pump generator and carry out cooling, heat pump absorbent solution after formation absorbent crystallization and crystallization, after described crystallization, heat pump absorbent solution is delivered to heat pump generator as the first heat pump absorbent solution, and the absorbent solution that contains described absorbent crystallization is delivered to heat pump absorber as the second heat pump absorbent solution.
7. according to the carbon dioxide compression systems described in claim 5 or 6, it is characterized in that it also comprises that heat pump absorbent solution is from heat exchanger, for the described heat pump absorbent solution from heat pump generator and/or from the heat pump absorbent solution of heat pump absorber, with absorbent solution after crystallization and/or absorbent crystallization or carry out heat exchange containing the absorbent solution of absorbent crystallization.
8. according to the carbon dioxide compression systems described in claim 5 or 6, it is characterized in that being also provided with generation heater in described heat pump generator, for heating the first heat pump absorbent solution in heat pump generator.
9. carbon dioxide compression systems according to claim 7, is characterized in that being also provided with generation heater in described heat pump generator, for heating the first heat pump absorbent solution in heat pump generator.
10. a carbon dioxide separation recovery system, is characterized in that it comprises isolated subsystem, compression subsystem and heat pump subsystem:
Described isolated subsystem comprises:
Absorption tower, for from carbon dioxide containing gas absorbing carbon dioxide;
Regenerator, for regenerating carbon dioxide absorption solution;
Described compression subsystem comprises the compression set of one-level or plural serial stage, and every grade of compression set comprises:
Absorption reactor thermally, for absorbing the carbon dioxide from isolated subsystem;
Regeneration reactor, for making absorbent solution from the absorption reactor thermally gas that splits the carbon dioxide off;
Booster pump, for being transported to the carbon dioxide absorption solution of absorption reactor thermally in regeneration reactor;
Choke valve, is arranged on from regeneration reactor and flows to the pipeline of absorption reactor thermally, for controlling the pressure differential between absorption reactor thermally and regeneration reactor;
In compression subsystem, the carbon dioxide absorption reactor of rear one-level compression set is connected in the regeneration reactor of previous stage compression set; The carbon dioxide absorption reactor of first order compression set is connected in isolated subsystem, for receiving carbon dioxide; The regeneration reactor of afterbody compression set is connected in a condenser;
Described heat pump subsystem comprises:
Heat pump generator, is filled with the first heat pump absorbent solution in it, be provided with the first generation heat exchanger and second heat exchanger occurs, for receiving the absorption heat from above-mentioned absorption tower and absorption reactor thermally in this heat pump generator;
Heat pump absorber, is filled with the second heat pump absorbent solution in it, in this heat pump absorber, be provided with absorption heat-exchange device, for the regenerator to above-mentioned and regeneration reactor heat supply;
Steam channel, is communicated with described heat pump generator and described heat pump absorber;
Described first heat exchanger occurs is connected in the heat exchanger in absorption reactor thermallies at different levels in absorbent solution heat exchanger in above-mentioned isolated subsystem and above-mentioned compression subsystem; The described second entrance that heat exchanger occurs is connected in the gas vent at regenerator top in above-mentioned isolated subsystem;
Described absorption heat-exchange device is connected in the heat exchanger in regeneration reactors at different levels in the reboiler of regenerator in above-mentioned isolated subsystem and compression subsystem.
11. carbon dioxide separation recovery systems according to claim 10, is characterized in that it also comprises gas-liquid separator, and its entrance is connected in the outlet of above-mentioned the second generation heat exchanger; Its top outlet is connected in the absorption reactor thermally of described first order compression set.
The carbon dioxide compression method of 12. 1 kinds of carbon dioxide compression sets as claimed in claim 1, is characterized in that comprising the following steps:
In absorption reactor thermally, carbon dioxide is absorbed by carbon dioxide absorption solution;
By the carbon dioxide absorption solution supercharging after above-mentioned absorbing carbon dioxide gas and be transported in regeneration reactor;
In regeneration reactor, from the carbon dioxide absorption solution of absorption reactor thermally, be heated, generate carbon dioxide and regenerating carbon dioxide absorption solution; And
The regenerating carbon dioxide absorption solution generating in regeneration reactor is reduced pressure and is transported in absorption reactor thermally.
The carbon dioxide compression method of 13. 1 kinds of carbon dioxide compression systems as described in any one in claim 2 to 9, is characterized in that comprising the compression process of plural serial stage, and every grade of compression process comprises:
In absorption reactor thermally, carbon dioxide is absorbed by carbon dioxide absorption solution;
By the carbon dioxide absorption solution supercharging after above-mentioned absorbing carbon dioxide and be transported in regeneration reactor;
In regeneration reactor, from the carbon dioxide absorption solution of absorption reactor thermally, be heated, generate carbon dioxide and regenerating carbon dioxide absorption solution; And
The regenerating carbon dioxide absorption solution generating in regeneration reactor is reduced pressure and be transported in absorption reactor thermally;
Except first order compression process, in other compression process, enter carbon dioxide in absorption reactor thermally and be the carbon dioxide that the regeneration reactor of previous stage compression process produces.
14. carbon dioxide compression methods according to claim 13, is characterized in that, the carbon dioxide producing in the regeneration reactor of one-level compression process is in the end carried out to condensation, form carbon dioxide liquid.
15. according to the carbon dioxide compression method described in claim 12-14 any one, characterized by further comprising: heat pump cycle process, and this heat pump cycle process comprises:
In described absorption reactor thermally, carbon dioxide is absorbed to the absorption heat that discharges by carbon dioxide absorption solution for heating the first heat pump absorbent solution, produce working substance steam; And
Described working substance steam is transported in heat pump absorber, and absorbed by the second heat pump absorbent solution in heat pump absorber, discharge and absorb heat, this absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution of thermal regeneration reactor.
16. 1 kinds of carbon dioxide separation recovery methods, for from the separated carbon dioxide that reclaims of carbonated unstripped gas, is characterized in that the method comprises carbon dioxide separation process and carbon dioxide compression process;
Described carbon dioxide separation process comprises:
In absorption tower, with carbon dioxide absorption solution, contact with unstripped gas, make carbon dioxide absorption solution absorb the carbon dioxide in unstripped gas;
Carbon dioxide absorption solution after absorbing carbon dioxide outputs in regenerator and is heated intensification, and the carbon dioxide absorbent solution of absorbing carbon dioxide is decomposed, and forms carbon dioxide and absorbent solution two-phase;
Described carbon dioxide compression process is the carbon dioxide compression method described in claim 14, and the carbon dioxide forming in above-mentioned regenerator is compressed.
17. carbon dioxide separation recovery methods according to claim 16, it is characterized in that: before carrying out carbon dioxide compression process, the carbon dioxide forming in regenerator and absorbent solution are first transported to respectively in heat pump generator, for heating the heat pump absorbent solution in heat pump generator.
18. carbon dioxide separation recovery methods according to claim 17, is characterized in that, in heat pump cycle process, a part for the absorption heat producing in heat pump absorber is transported in regenerator for the carbon dioxide absorption solution in thermal regeneration tower.
19. carbon dioxide separation recovery methods according to claim 16, it is characterized in that, part heat pump absorbent solution in heat pump generator and/or the part heat pump absorbent solution in heat pump absorber are carried out cooling, form heat pump absorbent solution after absorbent crystallization and crystallization; Using described absorbent crystallization or containing the absorbent solution of absorbent crystallization, as the second heat pump absorbent solution, be transported in heat pump absorber, heat pump absorbent solution after described crystallization is transported in heat pump generator as the first heat pump absorbent solution.
20. carbon dioxide separation recovery methods according to claim 16, is characterized in that the conversion degree of the absorbent of carbon dioxide absorption solution in rear one-level absorption reactor thermally that the compression process of wherein said plural serial stage is adjacent is larger more than 0.1 than the conversion degree of the absorbent of the carbon dioxide absorption solution in previous stage absorption reactor thermally.
CN201080018322.9A 2009-02-26 2010-02-25 Apparatus and method for compressing co2, system and method for separating and recovering co2 Expired - Fee Related CN102413901B (en)

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