CN102413901A - 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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CN102413901A
CN102413901A CN2010800183229A CN201080018322A CN102413901A CN 102413901 A CN102413901 A CN 102413901A CN 2010800183229 A CN2010800183229 A CN 2010800183229A CN 201080018322 A CN201080018322 A CN 201080018322A CN 102413901 A CN102413901 A CN 102413901A
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carbon dioxide
heat pump
solution
heat
compression
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CN102413901B (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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)

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

Apparatus and method for compressing co2, system and method for separating and recovering co2
Carbon dioxide compression device and method, carbon dioxide separation recovery system and method the application advocate that in the applying date of China's application be 26 days 2 months, the priority of the patent application of Application No. 200910078363. 6 in 2009.Technical field
The present invention relates to a kind of chemical industry and the carbon dioxide separation recovery technology of field of environment engineering, more particularly to a kind of carbon dioxide compression device and method, and it can effectively remove the separation and recovery system and method for carbon dioxide in flue gas.Background technology
C02A large amount of discharges of isothermal chamber gas are a major reasons for causing global climate to become dim.Therefore, C02Emission problem caused the very big concern of international community.Reduce the C0 of combustion of fossil fuel2Discharge mainly has two approach：One be improve efficiency of energy utilization, two be that co is separated from combustion product gases2, and be used, store or seal up for safekeeping.
0)2Removing sulfuldioxide in, absorb C0 with ammonia spray thermal power station boiler discharging flue gas2, can not only reach C02The purpose of emission reduction, can also obtain high-quality chemical fertilizer.But, because ammonium hydrogen carbonate can be decomposed into ammonia gas and water and co under the environment temperature higher than 60 °C2, cause C02Return to air, therefore this C02The application of discharge-reducing method also needs further research. C02Removing sulfuldioxide also have the C0 of CaO carbonatings-calcination cycle2(CCR) technology of separation, polymeric membrane removing C02、 02/C02Circulating combustion technology and burning chemistry chains (CLC) technology etc..But often industrializing implementation cost is higher for above-mentioned technology.
In C02Removing sulfuldioxide in, it is important that a kind of method be using solution absorption method remove C02.According to the difference of absorbent properties, two major classes can be divided into.One class is Physical Absorption method, and such as WATER-WASHING METHOD, low-temp methanol wash method (Rectisol), polyglycol dimethyl ether process（), Selexol propylene carbonate ester process.Another kind of is chemical absorption method, such as hot potash method, low heat dissipation Benfield method, activatedMDEAmethod, MEA methods etc..Above-mentioned C02Removing sulfuldioxide is all very ripe, and industrialization is early had been achieved with chemical field.
It is proposed that the scheme of carbon dioxide is separated and recovered from the burning waste gas in thermal power plant using chemical absorption method（It refer to：It is clear former positive high, reclaim C0 from boiler for power generation exhaust2Experiment, energy resources, energy resource science meetings, 1993, volume 14, the 1st its, 91-97 pages）.According to This scheme, although with the different and different of condition, the separation and recovery rate of carbon dioxide can reach
More than 80%.However, high energy consumption needed for carbon dioxide is separated and recovered from combustion product gases using traditional chemical absorption method is up to 750 900kcal/kg-C02, therefore the operating cost of separation and recovery is very high.And the liquefaction of gaseous carbon dioxide is generally using the technique condensed after two grades or three stage compression.Compression due to carbon dioxide in the technique is carried out by compressor, thus power consumption is very big.The content of the invention
It is an object of the present invention to provide a kind of carbon dioxide compression device and method, the technical problem solved is that carbon dioxide is compressed using waste heat, so as to effectively utilize waste heat, the utilization ratio of the energy is improved.
Another object of the present invention is to; the carbon dioxide separation recovery system and separation and recovery method of a kind of low energy consumption are provided; technical problem to be solved is that it can remove the carbon dioxide in flue gas; reduce the amount of carbon dioxide being discharged into air; the carbon dioxide of separation can be compressed simultaneously; the carbon dioxide of high pressure is obtained, is conducive to the storage and transport of carbon dioxide, so as to be conducive to environmental protection.
The object of the invention to solve the technical problems is realized using following technical scheme.A kind of pressurized carbon dioxide compression apparatus proposed by the present invention, including：Filled with carbon dioxide absorption solution in absorbing reaction device, regeneration reactor, booster pump and choke valve, described absorbing reaction device, for absorbing carbon dioxide gas；Described regeneration reactor is used to make the carbon dioxide absorption solution in absorbing reaction device split the carbon dioxide off gas；Described booster pump is used to the carbon dioxide absorption solution in absorbing reaction device is pressurized and is transported in regeneration reactor；Choke valve is arranged on the pipeline for flowing to absorbing reaction device from regeneration reactor, for controlling the pressure differential between absorbing reaction device and regeneration reactor；Heat exchanger is additionally provided with absorbing reaction device, the absorption heat for exporting absorbing reaction；Heat exchanger, the regenerated heat for providing regenerative response are provided with regeneration reactor.
The present invention also proposes a kind of carbon dioxide compression systems, and the system includes the above-mentioned pressurized carbon dioxide compression apparatus of plural serial stage, wherein, the absorbing reaction device of rear stage compression set is connected to the regeneration reactor of previous stage compression set.Preferably, the system also includes a condenser, the regeneration reactor of afterbody pressurized carbon dioxide compression apparatus is connected to, for condensing the carbon dioxide from the regeneration reactor.
The invention also provides a kind of carbon dioxide compression systems, it includes compression subsystem and heat pump subsystem：The compression subsystem includes the compression set of one-level or plural serial stage, every grade of compression set Including：Absorbing reaction device, for absorbing carbon dioxide gas；Regeneration reactor, for making the absorbent solution from absorbing reaction device split the carbon dioxide off gas；In compression subsystem, the carbon dioxide absorption reactor of rear stage compression set is connected to the regeneration reactor of previous stage compression set；The regeneration reactor of afterbody compression set is connected to a condenser；The heat pump subsystem includes：Heat pump generator, it is interior filled with the first heat pump absorbent solution, hot for absorption of the reception from above-mentioned absorbing reaction device provided with occurring heat exchanger in the heat pump generator；Heat pump absorber, it is interior filled with the second heat pump absorbent solution, is used in the heat pump absorber provided with absorption heat-exchange device to above-mentioned regeneration reactor heat supply；Steam channel, connection described heat pump generator and described heat pump absorber；Described the first heat pump absorbent solution and the second heat pump absorbent solution is made up of working medium and absorbent, and the concentration of absorbing of the first heat pump absorbent solution can be infinitesimal, i.e. the first heat pump absorbent solution only can be made up of working medium；First heat pump absorbent solution and the second heat pump absorbent solution can use identical absorbent, different absorbents can also be used, when the first heat pump absorbent solution and the second heat pump absorbent solution use 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 one of water, ammonia, methanol and ethanol or several materials；Described absorbent is LiBr, NaBr, KBr, beautiful4Br、 MgBr2、 CaBr2、 Lil、 Nal、 KI、 NHJ、 Mgl2、 Cal2、 LiCl、 NaCl、 KC1、 NH4C1、 MgCl2、 CaCl2、 LiN03、 NaN03、 KN03、 NH4N03、 Mg (N03) ^P Ca (N03) 2The mixture of one of them or several materials；Described to occur the heat exchanger that heat exchanger is connected in above-mentioned absorbing reaction device at different levels, the absorption heat-exchange device is connected to the heat exchanger in above-mentioned regeneration reactor at different levels.
It is preferred that, the carbon dioxide compression systems that the embodiment of the present invention is proposed, also include absorbent crystallizer, receive the heat pump absorbent solution from heat pump absorber and/or heat pump generator and cooled down, form heat pump absorbent solution after absorbent crystallization and crystallization, heat pump absorbent solution is delivered to heat pump generator as the first heat pump absorbent solution after described crystallization, and the absorbent solution containing described absorbent crystallization is delivered to heat pump absorber as the second heat pump absorbent solution.
It is preferred that, the carbon dioxide compression systems that the embodiment of the present invention is proposed, also include heat pump absorbent solution from heat exchanger, for the heat pump absorbent solution from heat pump generator and/or the heat pump absorbent solution from heat pump absorber, exchanged heat with absorbent solution after crystallization and/or absorbent crystallization or containing the absorbent solution that absorbent is crystallized.
It is preferred that, the carbon dioxide compression systems that the embodiment of the present invention is proposed are additionally provided with generation heater in the 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, including isolated subsystem, compression System and heat pump subsystem：The isolated subsystem includes：Absorption tower, for the absorbing carbon dioxide from carbon dioxide containing gas；Regenerator, for regenerating carbon dioxide absorption solution；The compression subsystem includes the compression set of one-level or plural serial stage, and every grade of compression set includes：Absorbing reaction device, for absorbing the carbon dioxide from isolated subsystem；Regeneration reactor, for making the absorbent solution from absorbing reaction device split the carbon dioxide off gas；In compression subsystem, the carbon dioxide absorption reactor of rear stage compression set is connected to the regeneration reactor of previous stage compression set；The carbon dioxide absorption reactor of first order compression set is connected to isolated subsystem, for receiving carbon dioxide;The regeneration reactor of afterbody compression set is connected to a condenser；The heat pump subsystem includes:Heat pump generator, it is interior filled with the first heat pump absorbent solution, and occurring heat exchanger and second provided with first in the heat pump generator occurs heat exchanger, hot for receiving the absorption from above-mentioned absorption tower and absorbing reaction device；Heat pump absorber, the second heat pump absorbent solution is filled with it, and absorption heat-exchange device is provided with the heat pump absorber, for above-mentioned regenerator and regeneration reactor heat supply；Steam channel, connection described heat pump generator and described heat pump absorber；The first generation heat exchanger is connected to the heat exchanger in the absorbent solution heat exchanger in above-mentioned isolated subsystem and above-mentioned compression subsystem in absorbing reaction devices at different levels；The entrance of the second generation heat exchanger is connected to the gas vent in above-mentioned isolated subsystem at the top of regenerator；The absorption heat-exchange device is connected to the heat exchanger in the reboiler and compression subsystem of regenerator in regeneration reactors at different levels in above-mentioned isolated subsystem.Preferably, also including gas-liquid separator, its entrance is connected to the above-mentioned second outlet for occurring heat exchanger；Its upper outlet is connected to the absorbing reaction device of described first order compression set.
Foregoing carbon dioxide compression systems, using potassium carbonate, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or two of which or two or more mixtures come absorbing carbon dioxide in described absorbing reaction device.
The object of the invention to solve the technical problems can also be realized using following technical scheme.The present invention also proposes a kind of pressurized carbon dioxide compression method, comprises the following steps：In absorbing reaction device, carbon dioxide generates carbonate compound with carbon dioxide absorption solution reaction；Above-mentioned carbonate compound is pressurized and is transported in regeneration reactor；In regeneration reactor, the carbonate compound from absorbing reaction device, which is heated, to be decomposed, generation carbon dioxide and carbon dioxide absorption solution；And by the carbon dioxide absorption solution decompression generated in regeneration reactor and be transported in absorbing reaction device.
The object of the invention to solve the technical problems can also be realized using following technical scheme.The present invention also proposes a kind of pressurized carbon dioxide compression method, includes the compression process of plural serial stage, every grade of compression process includes：In absorbing reaction device, carbon dioxide is absorbed by carbon dioxide absorption solution；Will Carbon dioxide absorption solution after above-mentioned absorbing carbon dioxide is pressurized and is transported in regeneration reactor；In regeneration reactor, the carbon dioxide absorption solution from absorbing reaction device is heated, generation carbon dioxide and carbon dioxide absorption solution；And by the carbon dioxide absorption solution decompression generated in regeneration reactor and be transported in absorbing reaction device；It is the carbon dioxide produced by the regeneration reactor of previous stage compression process into the carbon dioxide in absorbing reaction device in other compression processes in addition to the first compression process.Preferably, also including condensing the carbon dioxide produced in regeneration reactor in afterbody compression process, carbon dioxide liquid is formed.
The object of the invention to solve the technical problems can also be realized using following technical scheme.The present invention also proposes that a kind of pressurized carbon dioxide compression method comprises the following steps：In absorbing reaction device, 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, the carbon dioxide absorption solution from absorbing reaction device is heated, generation carbon dioxide and regenerating carbon dioxide absorption solution;And the regenerating carbon dioxide absorption solution generated in regeneration reactor is transported in absorbing reaction device.
The present invention also proposes a kind of pressurized carbon dioxide compression method, includes the compression process of plural serial stage, every grade of compression process includes：In absorbing reaction device, carbon dioxide is absorbed by carbon dioxide absorption solution；Carbon dioxide absorption solution after above-mentioned absorbing carbon dioxide is pressurized and is transported in regeneration reactor；In regeneration reactor, the carbon dioxide absorption solution from absorbing reaction device is heated, generation carbon dioxide and regenerating carbon dioxide absorption solution；And the regenerating carbon dioxide absorption solution generated in regeneration reactor is depressurized and is transported in absorbing reaction device；It is the carbon dioxide produced by the regeneration reactor of previous stage compression process into the carbon dioxide in absorbing reaction device in other compression processes in addition to first order compression process.
It is preferred that, foregoing pressurized carbon dioxide compression method is condensed to the carbon dioxide produced in the regeneration reactor of afterbody compression process, forms carbon dioxide liquid.
It is preferred that, preceding described pressurized carbon dioxide compression method, in addition to：Heat pump cycle process, the heat pump cycle process includes：In described absorbing reaction device, carbon dioxide is absorbed to the absorption heat discharged by carbon dioxide absorption solution to be used to heat the first heat pump absorbent solution, produces 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, absorption heat is discharged, the absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution in thermal regeneration reactor.
The present invention also proposes a kind of carbon dioxide separation recovery method, and for separating and recovering carbon dioxide from carbonated unstripped gas, this method includes carbon dioxide separation process and carbon dioxide compression mistake Journey；Described carbon dioxide separation process includes：Carbon dioxide absorption solution and feed gas are used in absorption tower, carbon dioxide absorption solution is absorbed the carbon dioxide in unstripped gas；Carbon dioxide absorption solution after absorbing carbon dioxide is output in regenerator and is heated up, and decomposes the carbon dioxide absorbent solution of absorbing carbon dioxide, forms carbon dioxide and absorbent solution two-phase；Described pressurized carbon dioxide compression process is foregoing pressurized carbon dioxide compression method, and the carbon dioxide formed in above-mentioned regenerator is compressed.
Preferably, before to progress pressurized carbon dioxide compression process, the carbon dioxide formed in regenerator and absorbent solution are first respectively delivered in heat pump generator, for heating the heat pump absorbent solution in heat pump generator.During heat pump cycle, a part for the absorption heat produced in heat pump absorber is transported to the carbon dioxide absorption solution being used in regenerator in thermal regeneration tower.
It is preferred that, the part heat pump absorbent solution in the part heat pump absorbent solution and/or heat pump absorber in heat pump generator is cooled down, heat pump absorbent solution after absorbent crystallization and crystallization is formed；It is transported in heat pump absorber, is transported to heat pump absorbent solution after described crystallization as the first heat pump absorbent solution in heat pump generator as the second heat pump absorbent solution using described absorbent crystallization or containing the absorbent solution that absorbent is crystallized.
It is preferred that, the conversion degree of absorbent of the conversion degree than the carbon dioxide absorption solution in previous stage absorbing reaction device of the absorbent of carbon dioxide absorption solution is big by more than 0. 1 in described rear stage absorbing reaction device.The conversion degree of absorbent refers to the ratio between the molar concentration of the absorbent of carbon dioxide of reaction bonded in absorbent solution and absorbent total mol concentration, regeneration temperature is certain and absorbent species and total mol concentration under the same conditions, the balance pressure of the carbon dioxide of regenerative response generation is raised with the increase of absorbent conversion degree.The carbon dioxide compression of the present invention is, by reducing while absorbing reaction temperature raising regenerative response temperature, and then to improve the absorbent conversion degree of absorbent solution in regeneration reactor step by step to realize.
The present invention has clear advantage and beneficial effect compared with prior art.The absorbing 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 C0 of absorbing liquid2Absorbability, generally the carbon dioxide absorption solution for entering absorption tower is cooled down using outside cooling water, to ensure that absorption tower works at a lower temperature, simultaneously in order that the regeneration of absorbing liquid is more thorough, generally use external heat source to heat the absorbing liquid in regenerator as regenerated heat to ensure that regenerator works at a temperature of higher than absorption tower operating temperature.It can be seen that, existing carbon dioxide chemistry absorption techniques on the one hand need by outside cooling water to environmental emission it is substantial amounts of compared with Low-grade heat, and need the more high-grade substantial amounts of external drive thermal source of input on the other hand, thus be one and not only consumed energy but also the process of water consumption.From above technical scheme, carbon dioxide separation recovery system proposed by the present invention is actually organically to combine carbon dioxide chemistry absorption techniques with absorption heat pump cycle technology, more low-grade absorption heat that carbon dioxide absorption process is released is promoted to by the more high-grade regenerated heat regenerated available for carbon dioxide absorption solution by the effect of absorption heat pump cycle, is greatly reduced or without outside cooling water and external drive thermal source so as to realize.The present invention uses absorption compression process simultaneously, and isolated carbon dioxide is compressed, and the compression process can be carried out by using waste heat, significantly eliminates electric power or other driving forces.Therefore, compared with existing carbon dioxide separation recovery system, carbon dioxide separation recovery system proposed by the present invention has the advantages that low energy consumption, low operating cost.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, and can be practiced according to the content of specification, with presently preferred embodiments of the present invention and coordinates accompanying drawing to describe in detail as after below.Brief description of the drawings
Fig. 1 is two ^ of the embodiment of the present invention 1：Change the schematic diagram of carbon pressure compression apparatus.
Fig. 2 is two ^ of the embodiment of the present invention 2：Change the schematic diagram of carbon pressure compression system.
Fig. 3 is two ^ of the embodiment of the present invention 3：Change the schematic diagram of carbon pressure compression system.
Fig. 4 is two ^ of the embodiment of the present invention 4：Change the schematic diagram of carbon pressure compression system.
Fig. 5 is two ^ of the embodiment of the present invention 5：Change the schematic diagram of carbon separation and recovery system
Fig. 6 is two ^ of the embodiment of the present invention 6：Change the schematic diagram of carbon separation and recovery system
Realize the best mode of invention
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with accompanying drawing and preferred embodiment, to according to its embodiment of carbon dioxide separation recovery system proposed by the present invention, structure, feature and its effect, describing in detail as after.
Refer to shown in Fig. 1, be the pressurized carbon dioxide compression apparatus that the embodiment of the present invention 1 is proposed, the device includes absorbing reaction device 101, regeneration reactor 102, booster pump 103 and choke valve 104.Described absorbing reaction device 101 and regeneration reactor 102 are pressure vessel, and carbon dioxide absorption solution is accommodated respectively.Heat exchanger 105 is provided with the absorbing reaction device 101, for will be produced in absorbing reaction device Heat is exported, and heat exchanger 106 is provided with regeneration reactor 102, for providing heat into regeneration reactor.It is connected between described absorbing reaction device 101 and regeneration reactor 102 by pipeline, so that carbon dioxide absorption solution is circulated between absorbing reaction device 101 and regeneration reactor 102.Described booster pump 103 is used to the carbon dioxide absorption solution in absorbing reaction device 101 is pressurized and is transported in regeneration reactor 103, choke valve 104 is arranged on the pipeline for flowing to absorbing reaction device from regeneration reactor, for controlling the pressure differential between absorbing reaction device and regeneration reactor.The solute of carbon dioxide absorption solution in absorbing reaction device and regeneration reactor is：Potassium carbonate, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or two of which or two or more mixtures.The effect of carbon dioxide absorption solution is that carbon dioxide adsorbs, dissolves or carried out chemical combination at relatively low temperatures and pressures with carbon dioxide absorption solution in absorbing reaction device, so that carbon dioxide is absorbed；Carbon dioxide absorption solution after absorbing carbon dioxide is heated at high temperature in regeneration reactor, then occur the inverse process opposite with absorbing reaction device, such as desorption, precipitation are decomposed, so as to produce carbon dioxide and carbon dioxide absorption solution, the carbon dioxide obtained at high temperature has higher pressure, it is achieved thereby that 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 is proposed, the system includes multistage pressurized carbon dioxide compression apparatus as described in Example 1, compression set 100, compression set 200 and compression set 300 are sequentially connected in series, booster pump 103,203,303 is used to the carbon dioxide absorption solution of absorbing reaction device is pressurized and is transported in regeneration reactor, and it is poor that choke valve 104,204,304 is used for control pressure.Wherein, the absorbing reaction device of latter compression set is connected to the regeneration reactor of previous compression set, and such as absorbing reaction device 201 is connected to regeneration reactor 102, receives the carbon dioxide from regeneration reactor 102；Absorbing reaction device 301 is connected to regeneration reactor 202, for receiving the carbon dioxide from regeneration reactor 202.By compression set 100, compression set 200 and the multi-stage compression of compression set 300, the carbon dioxide of high pressure can be obtained in regeneration reactor 302.Preferably, absorbing reaction devices at different levels work at same relatively low temperature, and regeneration reactor at different levels works under the same temperature higher than absorbing reaction device operating temperature.
Refer to shown in Fig. 3, it is the carbon dioxide compression systems that the embodiment of the present invention 3 is proposed, it adds a condenser 400 than embodiment 2, is connected to the regeneration reactor 302 of compression set 300, the carbon dioxide for receiving the generation of regeneration reactor 302.The carbon dioxide of entrance is cooled down in condenser 400, makes carbon dioxide condense to form carbon dioxide liquid.
Refer to shown in Fig. 4, be a kind of carbon dioxide compression systems that the embodiment of the present invention 4 is proposed, The system includes the pressurized carbon dioxide compression apparatus described in heat pump subsystem and previous embodiment 1.The heat pump subsystem includes：Heat pump generator 21, it is interior filled with the first heat pump absorbent solution, provided with generation heat exchanger 32 for absorption heat of the reception from described absorbing reaction device 101 in the heat pump generator 21；Heat pump absorber 22, it is interior filled with the second heat pump absorbent solution, is used in the heat pump absorber 22 provided with absorption heat-exchange device 26 to the above-mentioned heat supply of regeneration reactor 102；Steam channel 23, connection described heat pump generator 21 and described heat pump absorber 22;Concentration of absorbing of the concentration of absorbing of the first heat pump absorbent solution described in the heat pump generator 21 less than the second heat pump absorbent solution described in heat pump absorber 22；Described to occur the heat exchanger 105 that heat exchanger 32 is connected in above-mentioned absorbing reaction device 101, the absorption heat-exchange device 26 is connected to the heat exchanger 106 in above-mentioned regeneration reactor 102.The absorption heated conveying produced when so can be by absorbing reaction device 101 due to carbon dioxide absorption solution absorbing carbon dioxide is into 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 is entered in heat pump absorber by steam channel 23, the second heat pump absorbent solution in heat pump absorber 22, which absorbs described working substance steam and produced, absorbs heat, the absorption heat, which is transported in regeneration reactor 102, to be used to heat carbon dioxide absorption solution, so as to the gas that splits the carbon dioxide off, and carbon dioxide absorption solution is regenerated.Described the first heat pump absorbent solution and the second heat pump absorbent solution is made up of working medium and absorbent, and the concentration of absorbing of the first heat pump absorbent solution can be infinitesimal, i.e. the first heat pump absorbent solution only can be made up of working medium.First heat pump absorbent solution and the second heat pump absorbent solution can use identical absorbent, it would however also be possible to employ different absorbents.When the first heat pump absorbent solution and the second heat pump absorbent solution use 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 one of water, ammonia, methanol and ethanol or several materials；Described absorbent is LiBr, NaBr, KBr, NH4Br、 MgBr2、 CaBr2、 Lil、 Nal、 KI、 NH4I、 Mgl2、 Cal2、 LiCl、 NaCl、 KC1、 NH4C1、 MgCl2、 CaCl2、 LiN03、 NaN03, jump, NH4N03、 Mg (N03) 2With Ca (N03) 2The mixture of one of them or several materials.The carbon dioxide compression systems of the present embodiment, the absorption heat that effectively can be produced using each absorption process, so that heat economizing consumption, improves efficiency of energy utilization.
In addition, the heat pump subsystem of the present embodiment can also be applied to the carbon dioxide compression systems of embodiment 2 or embodiment 3, using connected mode identical with embodiment 4, the generation heat exchanger is connected to the heat exchanger in the absorbing reaction device at different levels, the absorption heat-exchange device is connected to the heat exchanger in the regeneration reactor at different levels.So as to so that the carbon dioxide compression with multistage compressing device Refer to shown in Fig. 5, be the schematic diagram for the carbon dioxide separation recovery system that the embodiment of the present invention 5 is proposed.The carbon dioxide separation recovery system mainly includes：Isolated subsystem, heat pump subsystem and compression subsystem, isolated subsystem is used to isolate carbon dioxide from the carbonated unstripped gas such as combustion product gases, described compression subsystem is used to the carbon dioxide obtained being compressed the carbon dioxide or carbon dioxide liquid for obtaining high pressure by isolated subsystem, and described heat pump subsystem is used to provide heat to isolated subsystem and compression subsystem.
Described isolated subsystem includes：Absorption tower 10 and regenerator 40.Described absorption tower 10, the carbon dioxide in unstrpped gas for absorbing carbon dioxide containing gas.Described absorption tower 10 includes:Bottom of towe 11, for accommodating carbon dioxide absorption solution；Packing layer 12, is arranged on the medium position in the absorption tower 10, and its role is to make carbon dioxide absorption solution with having bigger contact interface into the gas in tower；Air supply opening 16, is arranged under above-mentioned packing layer 12, for providing carbonated unstrpped gas into 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 uniformly spraying carbon dioxide absorption solution.In the 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 is with entering the carbon dioxide containing gas in absorption tower（Such as flue gas）Contact, and absorb the acid gas components such as carbon dioxide therein and S0x, NOx.The absorbent of the carbon dioxide absorption solution of the isolated subsystem can use potassium carbonate, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or two of which or two or more mixtures.
Described heat pump subsystem includes：Heat pump generator 21 and heat pump absorber 22.Described heat pump generator 21, occurs heat exchanger 31 and second provided with first in it and occurs the first heat pump absorbent solution that low concentration is filled with heat exchanger 25, the heat pump generator 21, the first heat pump absorbent solution is made up of working medium and absorbent.The effect of the heat pump generator is that the first heat pump absorbent solution of the low concentration in the heat pump generator is heated, so as to produce working substance steam.Described heat pump generator 21, generation heater 32 is additionally provided with it, for heating the first heat pump absorbent solution in heat pump generator, to compensate shortage of heat caused by radiation loss and the crystallizer cooling loss due to system.
Described heat pump absorber 22, the second heat pump absorbent solution is filled with it, its working medium and species of absorbent is identical with the first absorbent solution in heat pump generator 21 or difference, 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 absorbent crystallization has coexisted）.Work is provided between described heat pump generator 21 and described heat pump absorber 22 Matter steam channel 23, the working substance steam for making to produce in heat pump generator 21 enters in heat pump absorber 22.Absorption heat-exchange device 26 is provided with the heat pump absorber 22, the reboiler 46 of the regenerator 40 is connected to, for the heat produced in heat pump absorber 22 to be transported into reboiler 46.
Described regenerator 40, is connected with reboiler 46, and its top is provided with sprinkling equipment 43, is connected to the carbon dioxide absorption taphole of the bottom of absorption tower 10.Packing layer 42 is provided with the middle part of regenerator 40, for alloing carbon dioxide absorption solution fully to regenerate, the bottom of regenerator is used to accommodate carbon dioxide absorption solution for bottom of towe 41, and the top of regenerator 40 is provided with exhaust outlet 45.The carbon dioxide absorption solution of the bottom of absorption tower 10 is delivered to by the regeneration that regenerator carries out absorbing liquid by pipeline, gas and liquid two-phase is formed.The main component of the gas is carbon dioxide and vapor, and the main component of the liquid is carbon dioxide absorption solution, still, due to being substantially reduced by regenerating the gas concentration lwevel contained in the liquid.The entrance of the first generation heat exchanger 31 is connected to the absorbing liquid outlet of the above-mentioned bottom of regenerator 40, described first occurs the sprinkling equipment 13 on the outlet above-mentioned absorption tower 10 of connection of heat exchanger 31, the carbon dioxide absorption solution in the first generation heat exchanger 31 after heat exchange cooling is re-introduced into absorption tower.The entrance of the second generation heat exchanger 25 is connected to the top vent 45 of above-mentioned regenerator 40.The exhaust of regenerator gas temperature after heat exchange is reduced, and part vapor is condensed.Then, the carbon dioxide of high concentration is obtained from the outlet of the second generation heat exchanger 25.Preferably, being connected with gas-liquid separator 30 to obtain the carbon dioxide that purity is higher in the outlet of the second above-mentioned generation heat exchanger 25.
Described compression subsystem, the carbon dioxide of the high concentration for the isolated subsystem to be obtained is compressed.The compression subsystem includes the compression set of plural serial stage, the quantity of compression set can be set according to specific operating mode, in general the compression set number connected is more will to obtain the higher carbon dioxide of pressure, and the present embodiment is illustrated by taking 3 grades of compression sets series connection as an example.This implementation includes three stage compression device 100,200 and 300, and the structure of three stage compression device is identical, is illustrated below by taking compression set 100 as an example.The compression set 100 includes absorbing reaction device 101, regeneration reactor 102, booster pump 103 and choke valve 104.It is connected to the isolated subsystem with absorbing reaction device 101, receives carbon dioxide.Carbon dioxide absorption solution is provided with described absorbing reaction device 101, into it in carbon dioxide absorbed by carbon dioxide absorption solution.The carbon dioxide absorption solution that described regeneration reactor 102 is used in self-absorption in future reactor 101 is heated, and makes its gas that splits the carbon dioxide off, so that carbon dioxide absorption solution is regenerated.Described booster pump 103 is used to the carbon dioxide absorption solution in absorbing reaction device 101 is pressurized and is transported in regeneration reactor 103.The internal pressure of described regeneration reactor is higher than the internal pressure of absorbing reaction device.By regeneration Carbon dioxide absorption solution afterwards is transmitted back in absorbing reaction device again, and choke valve 104, which is arranged on the pipeline that absorbing reaction device is flowed to from regeneration reactor, to be used to control the pressure differential between absorbing reaction device 101 and regeneration reactor 103.Heat exchanger is additionally provided with absorbing reaction device 101, heat is absorbed for exporting；Heat exchanger is provided with regeneration reactor 103, for providing the regeneration of carbon dioxide absorption solution required heat.
Compression set 200 includes absorbing reaction device 201, regeneration reactor 202, booster pump 203 and choke valve 204;Its absorbing reaction device 201 is connected to the regeneration reactor 102 of compression set 100;Compression set 300 includes absorbing reaction device 301, regeneration reactor 302, booster pump 303 and choke valve 304;Its absorbing reaction device 301 is connected to the regeneration reactor 202 of compression set 200.Condenser 400 is connected to regeneration reactor 302, receives carbon dioxide, and carbon dioxide is condensed into liquid.
The generation heat exchanger 32 that the heat exchanger in each absorbing reaction device in compression subsystem is connected to heat pump subsystem (because annexation is identical with Fig. 4, is succinct drawing, annexation is not drawn in Figure 5）, working substance steam is produced to heat heat pump absorbent solution for carbon dioxide to be sent in heat pump generator by the hot number of absorption produced by absorbing, so as to 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, for the carbon dioxide absorption solution in thermal regeneration reactor（Because annexation is identical with Fig. 4, it is succinct drawing, annexation is not drawn in Figure 5）.
Refer to shown in Fig. 6, be the schematic diagram for the carbon dioxide separation recovery system that the embodiment of the present invention 6 is proposed.Compared with the separation and recovery system of the above embodiments 5, embodiment adds liquid-feeding pump 24, carbon dioxide absorption solution from heat exchanger 27 and absorbent crystallizer 28, 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 also add carbon dioxide absorption solution from heat exchanger 44, effect is the regeneration efficiency of absorbing liquid can be made to be further improved.
Described liquid-feeding pump 24 is connected to 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 to be transported into absorbent crystallizer 28.The absorbent crystallizer 28, including：Crystallizer carbon dioxide absorption solution inlet, the carbon dioxide absorption taphole of liquid-feeding pump 24 is connected to by pipeline；Crystallizer weak solution is exported, and the carbon dioxide absorption solution inlet of heat pump generator 21 is connected to by pipeline；And delivery outlet containing crystallization solution, the carbon dioxide absorption solution inlet of heat pump absorber 22 is connected to by pipeline.The absorbent crystallizer 28 also has refrigerant circulation equipment, provides cold for the carbon dioxide absorption solution into absorbent crystallizer 28, makes the carbon dioxide absorption solution temperature in absorbent crystallizer 28 Reduction, when below the crystallization temperature for reaching absorbent, separates out absorbent crystallization.After separation of solid and liquid, absorbent crystallization is output in heat pump absorber 22 from delivery outlet containing crystallization solution, and the weak solution that concentration of absorbing is reduced is transported in heat pump generator 21 from the outlet of crystallizer weak solution.
Carbon dioxide absorption solution is arranged on the pipeline that described absorbent crystallizer 28 is connected with liquid-feeding pump 24 from heat exchanger 27, and the weak solution exported for the carbon dioxide absorption solution to entering absorbent crystallizer 28, from absorbent crystallizer and the crystallization solution that contains exported from absorbent crystallizer carry out heat exchange.The beneficial effect of carbon dioxide absorption solution from heat exchanger 27 is, after heat exchange, and the carbon dioxide absorption solution temperature into absorbent crystallizer 28 is reduced, and is conducive to the formation of crystallization, so as to save the cold needed for crystallization；The temperature for being output to the weak solution of heat pump generator 21 is improved, and is conducive to the evaporation of absorption cycle working medium；The temperature of the crystallization solution containing absorbent of output is also improved, so as to be conducive to keeping heat pump absorber 22 to work at a higher temperature.
Described carbon dioxide absorption solution from heat exchanger can be also used for the carbon dioxide absorption solution of self-heating pump absorber in future with after the crystallization of absorbent crystallizer carbon dioxide absorption solution exchanged heat, the carbon dioxide absorption solution for self-heating pump absorber in future and the crystallization of the absorbent from absorbent crystallizer or exchanged heat containing the carbon dioxide absorption solution that absorbent is crystallized and carbon dioxide absorption solution for self-heating pump absorber in future is crystallized with the carbon dioxide absorption solution after the crystallization of absorbent crystallizer and absorbent or the carbon dioxide absorption solution of the crystallization containing absorbent is exchanged heat.
Described carbon dioxide absorption solution is from heat exchanger 44, on the pipeline for being arranged on the absorbing liquid outlet of the connection bottom of absorption tower 10 and the absorbing liquid entrance on the top of regenerator 40, for carrying out heat exchange between the carbon dioxide absorption solution to being delivered to the carbon dioxide absorption solution of the first generation heat exchanger 31 from the bottom of towe 41 of regenerator 40 and being conveyed from absorbing tower bottom 11 to regenerator, to improve the temperature for the carbon dioxide absorption solution for entering regenerator 40, so as to further improve the carbon dioxide absorption solution regeneration efficiency of regenerator 40.
In each above-mentioned embodiment, the basic procedure for completing technical solution of the present invention is only described, for realizing that the other parts or equipment of the flow are omitted, for example, it is ensured that pump or valve needed for each material flow direction.For realizing other equipment or part required for the power circulation system described in each above-mentioned embodiment, those skilled in the art can all find corresponding technological means in the prior art, and the present inventor will not be repeated here.
Embodiments of the invention 7 also proposed a kind of pressurized carbon dioxide compression method, and it uses the compression set described in embodiment 1 to realize.This method comprises the following steps：
Absorbing reaction device receives carbon dioxide, the carbon dioxide absorption solution in absorbing reaction device Absorbing carbon dioxide gas, carbon dioxide occurs absorption, dissolving with carbon dioxide absorption solution or carries out combination reaction.The absorbent of described carbon dioxide absorption solution is：Potassium carbonate, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or two of which or two or more mixtures.For example, when absorbent is potassium carbonate, carbon dioxide and potassium carbonate react production saleratus in absorbing reaction device.
The carbon dioxide absorption solution for absorbing carbon dioxide in above-mentioned absorbing reaction device is pressurized and is transported in regeneration reactor；
In regeneration reactor, the carbon dioxide absorption solution from absorbing reaction device is heated, generation carbon dioxide and carbon dioxide absorption solution；And
The carbon dioxide absorption solution generated in regeneration reactor is transported in absorbing reaction device.
The pressurized carbon dioxide compression method that embodiments of the invention 8 are proposed, is realized using the compressibility described in embodiment 2.This method includes the compression process of plural serial stage, every grade of compression process is identical with the process of embodiment 6, it is the carbon dioxide produced by the regeneration reactor of previous compression process into the carbon dioxide in absorbing reaction device in other compression processes in addition to the first compression process.Preferably, being condensed to the carbon dioxide produced in regeneration reactor in afterbody compression process, carbon dioxide liquid is formed.
Embodiments of the invention 9 also propose a kind of pressurized carbon dioxide compression method, and it is included outside previous embodiment 7 or pressurized carbon dioxide compression method described in embodiment 8, in addition to heat pump cycle process.Carbon dioxide compression systems shown in reference picture 4, described heat pump cycle process includes：In described absorbing reaction device, carbon dioxide is absorbed to the absorption heat discharged by carbon dioxide absorption solution to be used to heat the first heat pump absorbent solution, produces 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, absorption heat is discharged, the absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution in thermal regeneration reactor.For the heat of system loss, provided by external heat source, but the consumption of external heat source can be reduced using above-mentioned heat pump cycle process, so as to 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 all can be used for the generating process during heating heat pump cycle by the heat produced by absorbing, for concentrating heat pump absorbent solution and producing working substance steam；And in heat pump cycle, working substance steam absorption heat produced when being absorbed may be alternatively used for the regenerative process in regeneration reactors at different levels.
The embodiment of the present invention 10 also proposed a kind of carbon dioxide separation recovery method, and it uses the carbon dioxide separation recovery system described in embodiment 5.The carbon dioxide separation recovery method includes carbon dioxide point From process, pressurized carbon dioxide compression process and heat pump cycle process.
Carbon dioxide separation process includes：Contacted in absorption tower with carbon dioxide absorption solution with combustion product gases, carbon dioxide absorption solution is absorbed the carbon dioxide in flue gas, and drop to the bottom of towe on absorption tower；Carbon dioxide absorption solution after the absorbing carbon dioxide of bottom of towe is output in regenerator and is heated up, decompose the absorbing liquid of absorbing carbon dioxide, form gas and liquid two-phase, the gas is mainly carbon dioxide, and because substantial amounts of carbon dioxide forms gaseous state, regenerate the carbon dioxide content reduction in the liquid formed.
The compression process of carbon dioxide includes multi-stage compression, and every grade of compression step includes：The carbon dioxide absorption solution absorbing carbon dioxide of absorbing reaction device；Then the carbon dioxide absorption solution is transported in regeneration reactor, is heated the carbon dioxide absorption solution decomposited out after gaseous carbon dioxide and regeneration, and the pressure of regeneration reactor is higher than the pressure of absorbing reaction device；Carbon dioxide absorption solution after regeneration is transmitted back in absorbing reaction device.From the carbon dioxide produced in regeneration reactor be transported to next stage compression process in be compressed；The carbon dioxide of high pressure can be obtained in subsequent compression step by multistage compression；The carbon dioxide of high pressure is condensed, you can obtain the carbon dioxide liquid of high pressure, so as to be more beneficial for the recovery, storage and transport of carbon dioxide.
Described heat pump cycle process includes：In described absorbing reaction device, carbon dioxide is absorbed to the absorption heat discharged by carbon dioxide absorption solution to be used to heat the first heat pump absorbent solution, produces 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, absorption heat is discharged, the absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution in thermal regeneration reactor.For described multi-stage compression, in compression processes at different levels, carbon dioxide all can be used for the generating process during heating heat pump cycle by the heat produced by absorbing, for concentrating hot first pump absorbent solution and producing working substance steam；And in heat pump cycle, working substance steam absorption heat produced when being absorbed may be alternatively used for the regenerative process in regeneration reactors at different levels.
In addition, heat exchanger occurs for second that the carbon dioxide formed after the regeneration during above-mentioned carbon dioxide separation can also be passed through to heat pump generator, and the liquid formed after regeneration is passed through to the first generation heat exchanger of heat pump generator, the carbon dioxide absorption solution for heating in heat pump generator forms it into working substance steam；Above-mentioned working substance steam is entered in heat pump absorber by steam channel, and absorbing release by the second heat pump absorbent solution in heat pump absorber absorbs heat, the carbon dioxide absorption solution that absorption heat is used in heated reboiler by heat exchange mode.
The second heat pump absorbent solution in wherein described heat pump absorber with described heat pump generator The first heat pump absorbent solution absorbent molar fraction difference be more than 0. 1, concentration difference it is more big be conducive to improve heat pump absorber in temperature, so as to be conducive to the regeneration of carbon dioxide absorption solution；The carbon dioxide returned to from the liquid of the first generation heat exchanger output in being re-used for absorbing flue gas at the top of absorption tower；It is the carbon dioxide that can obtain high-purity that gas-liquid separation is carried out to the gas that the second above-mentioned generation heat exchanger is exported.
The carbon dioxide separation recovery method of the present embodiment 10 can remove in flue gas more than 80% carbon dioxide, and the purity of isolated carbon dioxide is under conditions of water vapor component is disregarded（That is dry gas content）Up to more than 99%, and 2. 7MPa, _ 10 °C of carbon dioxide liquid can be obtained after three stage compression and condensation.
The embodiment of the present invention 11 also proposed a kind of carbon dioxide separation recovery method, be that it uses the piece-rate system described in embodiment 6 with the separation and recovery method difference of embodiment 10.The present embodiment adds the circulation step of heat pump absorbent solution in heat pump generator and heat pump absorber than embodiment 10, and it includes：Part the first heat pump absorbent solution in part the second heat pump absorbent solution and heat pump generator in heat pump absorber is passed through in absorbent crystallizer jointly, and the heat of mixing pump absorbent solution in crystallizer is cooled down, so as to form absorbent crystallization, separation of solid and liquid is then carried out；Heat pump absorbent solution is imported in heat pump generator after the crystallization obtained after separation of solid and liquid, absorbent crystallization after separation of solid and liquid is imported in the way of containing crystallization solution in heat pump absorber, so as to so that the solution concentration difference in heat pump absorber and heat pump generator is kept within the specific limits.The present invention can realize the continuity of carbon dioxide separation process.External source can be passed through in above-mentioned absorbent crystallizer to being cooled down to the heat of mixing pump absorbent solution in crystallizer.
Preferably, heat pump absorbent solution is transported to before heat pump generator after described crystallization, and before the heat pump absorbent solution of heat pump absorber output is cooled down, the heat pump absorbent solution of described heat pump absorber output is exchanged heat with heat pump absorbent solution after described crystallization.
Preferably, before described absorbent crystallization is transported to heat pump absorber, and the output of heat pump absorber heat pump absorbent solution cooled down before, the heat pump absorbent solution of described absorbent crystallization and described heat pump absorber output is exchanged heat.
Preferably, heat pump absorbent solution is transported to before heat pump generator after described crystallization, absorbent crystallization is transported to before heat pump absorber, and before the heat pump absorbent solution of the heat pump absorber output is cooled down, heat pump absorbent solution and the heat pump absorbent solution after described absorbent crystallization and crystallization of the heat pump absorber output are exchanged heat.
Preferably, heat pump absorbent solution is transported to before heat pump generator after described crystallization, absorb Agent crystallization is transported to before heat pump absorber, before the heat pump absorbent solution of heat pump absorber output is cooled down, and the heat pump absorbent solution of the heat pump generator output is transported to before heat pump absorber, the heat pump absorbent solution that the absorbent solution of heat pump generator output is exported with the heat pump absorber is mixed to form heat of mixing pump absorbent solution, and the heat pump absorbent solution of mixing two is exchanged heat with heat pump absorbent solution after described absorbent crystallization and crystallization.
By the heat exchange steps, it can improve and import the temperature of heat pump absorber and the heat pump absorbent solution in heat pump generator to keep the operating temperature of heat pump absorbent solution in heat pump absorber and heat pump generator, the temperature for the heat pump absorbent solution that can be lowered into simultaneously in absorbent crystallizer, so as to save the consumption of low-temperature receiver.Preferably, the carbon dioxide absorption solution of the first generation heat exchanger is delivered to from the bottom of towe of regenerator and from adsorption tower bottom of towe to carrying out heat exchange between the absorbing liquid that regenerator is conveyed, to improve the temperature for the carbon dioxide absorption solution for entering regenerator, so as to further improve the regeneration efficiency of the carbon dioxide absorption solution of regenerator.
Other technologies means can all be realized using technology of the prior art necessary to realizing above-mentioned technical proposal.
It is described above, only it is presently preferred embodiments of the present invention, any formal limitation not is made to the present invention, although the present invention is disclosed above with preferred embodiment, but it is not limited to the present invention, any those skilled in the art, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or are modified to the equivalent embodiment of equivalent variations, in every case it is the content without departing from technical solution of the present invention, any simple modification that technical spirit according to the present invention is made to above example, equivalent variations and modification, in the range of still falling within technical solution of the present invention.Industrial applicability
Carbon dioxide separation recovery system proposed by the present invention is actually organically to combine carbon dioxide chemistry absorption techniques with absorption heat pump cycle technology, more low-grade absorption heat that carbon dioxide absorption process is released is promoted to by the more high-grade regenerated heat regenerated available for carbon dioxide absorption solution by the effect of absorption heat pump cycle, is greatly reduced or without outside cooling water and external drive thermal source so as to realize.The present invention uses absorption compression process simultaneously, and isolated carbon dioxide is compressed, and the compression process can be carried out by using waste heat, significantly eliminates electric power or other driving forces.

Claims (1)

  1. Claim
    1st, a kind of pressurized carbon dioxide compression apparatus, it is characterised in that the device includes：Absorbing reaction device, regeneration reactor, booster pump and choke valve,
    Filled with carbon dioxide absorption solution in described absorbing reaction device, for absorbing carbon dioxide gas；Described regeneration reactor is used to make the carbon dioxide absorption solution from absorbing reaction device split the carbon dioxide off gas；
    Described booster pump is used to the carbon dioxide absorption solution of absorbing reaction device being transported in regeneration reactor；
    Choke valve is arranged on the pipeline for flowing to absorbing reaction device from regeneration reactor, for controlling the pressure differential between absorbing reaction device and regeneration reactor；
    Heat exchanger is additionally provided with absorbing reaction device, the absorption heat for exporting absorbing reaction；Heat exchanger, the regenerated heat for providing regenerative response are provided with regeneration reactor.
    2nd, a kind of carbon dioxide compression systems, it is characterized in that, the system includes the pressurized carbon dioxide compression apparatus as described in claim 1 of plural serial stage, wherein, the absorbing reaction device of rear stage compression set is connected to the regeneration reactor of previous stage compression set.
    3rd, carbon dioxide compression systems according to claim 2, it is characterised in that also including a condenser, the regeneration reactor of afterbody pressurized carbon dioxide compression apparatus is connected to, for condensing the carbon dioxide from the regeneration reactor.
    4th, the carbon dioxide compression systems according to Claims 2 or 3, it is characterised in that using potassium carbonate, monoethanolamine, diethanol amine, methyl diethanolamine, amion acetic acid, propene carbonate, NHD or two of which or two or more mixtures come absorbing carbon dioxide in described absorbing reaction device.
    5th, a kind of carbon dioxide compression systems, it is characterised in that it includes compression subsystem and heat pump subsystem：
    The compression subsystem includes the compression set of one-level or plural serial stage, and every grade of compression set includes：
    Absorbing reaction device, for absorbing carbon dioxide gas；
    Regeneration reactor, for making the absorbent solution from absorbing reaction device split the carbon dioxide off gas； In compression subsystem, the carbon dioxide absorption reactor of rear stage compression set is connected to the regeneration reactor of previous stage compression set；The regeneration reactor of afterbody compression set is connected to a condenser；
    The heat pump subsystem includes：
    Heat pump generator, it is interior filled with the first heat pump absorbent solution, hot for absorption of the reception from above-mentioned absorbing reaction device provided with occurring heat exchanger in the heat pump generator；
    Heat pump absorber, it is interior filled with the second heat pump absorbent solution, is used in the heat pump absorber provided with absorption heat-exchange device to above-mentioned regeneration reactor heat supply；
    Steam channel, connection described heat pump generator and described heat pump absorber；
    Described to occur the heat exchanger that heat exchanger is connected in above-mentioned absorbing reaction device at different levels, the absorption heat-exchange device is connected to the heat exchanger in above-mentioned regeneration reactor at different levels；
    Described heat pump absorbent solution is made up of working medium and absorbent, and described working medium is one of water, ammonia, methanol and ethanol or the mixture of several materials；Described absorbent is LiBr, NaBr, KBr, NH4Br、 MgBr2、 CaBr2、 Lil、 Nal、 KI、 NHJ、 Mgl2、 Cal2、 LiCl、 NaCl、 KC1、 NH4C1、 MgCl2、 CaCl2、 LiN03、 NaN03、 KN03、 NH4N03、 § 03) 2With.& (3) 2The mixture of one of them or several materials.
    6th, carbon dioxide compression systems according to claim 5, it is characterized in that it also includes absorbent crystallizer, receive the heat pump absorbent solution from heat pump absorber and/or heat pump generator and cooled down, form heat pump absorbent solution after absorbent crystallization and crystallization, heat pump absorbent solution is delivered to heat pump generator as the first heat pump absorbent solution after described crystallization, and the absorbent solution crystallized containing the absorbent as the second heat pump absorbent solution is delivered to heat pump absorber.
    7th, the carbon dioxide compression systems according to claim 5 or 6, it is characterized in that it also includes heat pump absorbent solution from heat exchanger, for the heat pump absorbent solution from heat pump generator and/or the heat pump absorbent solution from heat pump absorber, exchanged heat with absorbent solution after crystallization and/or absorbent crystallization or containing the absorbent solution that absorbent is crystallized.
    8th, the carbon dioxide compression systems according to claim any one of 5-7, it is characterised in that be additionally provided with generation heater in the heat pump generator, for heating the first heat pump absorbent solution in heat pump generator.
    9th, a kind of carbon dioxide separation recovery system, it is characterised in that it includes isolated subsystem, compression subsystem and heat pump subsystem：
    The isolated subsystem includes： Absorption tower, for the absorbing carbon dioxide from carbon dioxide containing gas；
    Regenerator, for regenerating carbon dioxide absorption solution；
    The compression subsystem includes the compression set of one-level or plural serial stage, and every grade of compression set includes：
    Absorbing reaction device, for absorbing the carbon dioxide from isolated subsystem；Regeneration reactor, for making the absorbent solution from absorbing reaction device split the carbon dioxide off gas；
    In compression subsystem, the carbon dioxide absorption reactor of rear stage compression set is connected to the regeneration reactor of previous stage compression set；The carbon dioxide absorption reactor of first order compression set is connected to isolated subsystem, for receiving carbon dioxide；The regeneration reactor of afterbody compression set is connected to a condenser；
    The heat pump subsystem includes：
    Heat pump generator, it is interior filled with the first heat pump absorbent solution, and occurring heat exchanger and second provided with first in the heat pump generator occurs heat exchanger, hot for receiving the absorption from above-mentioned absorption tower and absorbing reaction device；
    Heat pump absorber, the second heat pump absorbent solution is filled with it, and absorption heat-exchange device is provided with the heat pump absorber, for above-mentioned regenerator and regeneration reactor heat supply；
    Steam channel, connection described heat pump generator and described heat pump absorber；
    The first generation heat exchanger is connected to the heat exchanger in the absorbent solution heat exchanger in above-mentioned isolated subsystem and above-mentioned compression subsystem in absorbing reaction devices at different levels；The entrance of the second generation heat exchanger is connected to the gas vent in above-mentioned isolated subsystem at the top of regenerator；
    The absorption heat-exchange device is connected to the heat exchanger in the reboiler and compression subsystem of regenerator in regeneration reactors at different levels in above-mentioned isolated subsystem.
    10th, carbon dioxide separation recovery system according to claim 9, it is characterised in that it also includes gas-liquid separator, its entrance is connected to the above-mentioned second outlet for occurring heat exchanger；Its upper outlet is connected to the absorbing reaction device of described first order compression set.
    11st, a kind of pressurized carbon dioxide compression method, it is characterised in that comprise the following steps：
    In absorbing reaction device, carbon dioxide is absorbed by carbon dioxide absorption solution；Carbon dioxide absorption solution after above-mentioned absorbing carbon dioxide gas is pressurized and is transported in regeneration reactor；
    In regeneration reactor, the carbon dioxide absorption solution from absorbing reaction device is heated, generation Carbon dioxide and regenerating carbon dioxide absorption solution；And
    The regenerating carbon dioxide absorption solution generated in regeneration reactor is depressurized and is transported in absorbing reaction device.
    12nd, a kind of pressurized carbon dioxide compression method, it is characterised in that the compression process including plural serial stage, every grade of compression process includes：
    In absorbing reaction device, carbon dioxide is absorbed by carbon dioxide absorption solution；
    Carbon dioxide absorption solution after above-mentioned absorbing carbon dioxide is pressurized and is transported in regeneration reactor；
    In regeneration reactor, the carbon dioxide absorption solution from absorbing reaction device is heated, generation carbon dioxide and regenerating carbon dioxide absorption solution；And
    The regenerating carbon dioxide absorption solution generated in regeneration reactor is depressurized and is transported in absorbing reaction device；
    It is the carbon dioxide produced by the regeneration reactor of previous stage compression process into the carbon dioxide in absorbing reaction device in other compression processes in addition to first order compression process.
    13rd, pressurized carbon dioxide compression method according to claim 11, it is characterised in that condensed to the carbon dioxide produced in the regeneration reactor of afterbody compression process, forms carbon dioxide liquid.
    14th, the pressurized carbon dioxide compression method according to claim any one of 11-13, it is characterised in that also include：Heat pump cycle process, the heat pump cycle process includes：
    In described absorbing reaction device, carbon dioxide is absorbed to the absorption heat discharged by carbon dioxide absorption solution to be used to heat the first heat pump absorbent solution, produces 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, absorption heat is discharged, the absorption heat is transported in described regeneration reactor, for the carbon dioxide absorption solution in thermal regeneration reactor.
    15th, a kind of carbon dioxide separation recovery method, for separating and recovering carbon dioxide from carbonated unstripped gas, it is characterised in that this method includes carbon dioxide separation process and pressurized carbon dioxide compression process；
    Described carbon dioxide separation process includes：
    Carbon dioxide absorption solution and feed gas are used in absorption tower, carbon dioxide absorption solution is absorbed the carbon dioxide in unstripped gas；
    Carbon dioxide absorption solution after absorbing carbon dioxide is output in regenerator and is heated up, The carbon dioxide absorbent solution of absorbing carbon dioxide is decomposed, carbon dioxide and absorbent solution two-phase is formed；
    Described pressurized carbon dioxide compression process is the pressurized carbon dioxide compression method described in claim 14, and the carbon dioxide formed in above-mentioned regenerator is compressed.
    16th, carbon dioxide separation recovery method according to claim 15, it is characterised in that：Before pressurized carbon dioxide compression process is carried out, the carbon dioxide formed in regenerator and absorbent solution are first respectively delivered in heat pump generator, for heating the heat pump absorbent solution in heat pump generator.
    17th, carbon dioxide separation recovery method according to claim 16, it is characterized in that, during heat pump cycle, a part for the absorption heat produced in heat pump absorber is transported to the carbon dioxide absorption solution being used in regenerator in thermal regeneration tower.
    18th, carbon dioxide separation recovery method according to claim 15, it is characterized in that, part heat pump absorbent solution in part heat pump absorbent solution and/or heat pump absorber in heat pump generator is cooled down, heat pump absorbent solution after absorbent crystallization and crystallization is formed；It is transported in heat pump absorber, is transported to heat pump absorbent solution after described crystallization as the first heat pump absorbent solution in heat pump generator as the second heat pump absorbent solution using described absorbent crystallization or containing the absorbent solution that absorbent is crystallized.
    19th, carbon dioxide separation recovery method according to claim 15, it is characterised in that the conversion degree of absorbent of the conversion degree than the carbon dioxide absorption solution in previous stage absorbing reaction device of the absorbent of carbon dioxide absorption solution is big by more than 0. 1 in wherein described rear stage absorbing reaction device.
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