CN114405258A - Is suitable for low partial pressure CO2Capture purified absorbent system - Google Patents
Is suitable for low partial pressure CO2Capture purified absorbent system Download PDFInfo
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- CN114405258A CN114405258A CN202111628965.1A CN202111628965A CN114405258A CN 114405258 A CN114405258 A CN 114405258A CN 202111628965 A CN202111628965 A CN 202111628965A CN 114405258 A CN114405258 A CN 114405258A
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/79—Injecting reactants
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/343—Heat recovery
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B30/00—Heat pumps
- F25B30/06—Heat pumps characterised by the source of low potential heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
Abstract
The invention discloses a method suitable for low partial pressure CO2The absorption system for trapping and purifying is a phase-change nano fluid absorption system, the regenerated layered phase-change nano absorbent consists of base liquid, layering agent, activating agent, nano particles, corrosion inhibitor and antioxidant, the base liquid consists of hydroxyethyl ethylenediamine and tetraethylenepentamine, the layering agent consists of N-ethyl ethylenediamine and 1, 4-butanediamine, the activating agent consists of piperazine or diethanolamine, the nano particles consist of copper oxide or magnesium oxide, and the corrosion inhibitor consists of benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt or benzoic acid imidazoline-chloromethane quaternary ammonium saltSalt, and antioxidant consisting of carbohydrazide or pyrogallol. The regenerative layered phase change nano absorbent can reduce the regeneration energy consumption and the regeneration temperature and improve the regeneration rate through the phase change in the regeneration process, has the characteristics of large absorption load, high absorption and desorption rates and low regeneration energy consumption, and can effectively reduce CO2Energy consumption capture and CO reduction2And (4) trapping cost.
Description
Technical Field
The invention relates to CO2A capture system, in particular to a system suitable for low partial pressure CO2An absorption system for trapping and purifying, which belongs to the technical field of flue gas purification.
Background
The CCUS (Carbon Capture, Utilization and Storage) technology is a new development trend of the CCS (Carbon Capture and Storage) technology, namely, the CO discharged in the production process of emission sources such as large-scale power plants, steel plants, chemical plants and the like2Collected and purified and then put into a new production process for recycling, rather than simply sequestration, CCUS can sequester CO, as compared to CCS2The resource utilization generates economic benefits and has practical operability.
Coal is the most important energy type in China at present, and a coal-fired power plant is CO in China2The main emission source of the method can reach the CO in China2Over 50 percent of the total emission, and low partial pressure flue gas CO discharged by a coal-fired power plant2The key of carbon emission reduction in China is to carry out capture, recovery, utilization and sealing storage. CO22Capture technique is the determination of CO in CCUS2The most critical links of the purity and the cost of resource utilization are that the energy consumption of the process accounts for more than 60 percent of the total energy consumption of the CCUS project, so that the energy consumption is reduced for the CO in the flue gas2The trapping is very important, and the technical bottleneck problem of key link in large-scale CCUS popularization is solved.
As shown in the following table, the current low partial pressure flue gas captures CO2The method comprises the methods of chemical absorption, physical absorption, membrane separation and the like, wherein the chemical absorption method is the most commonly selected flue gas CO in the CCUS project at present due to the technical maturity and the application prospect2Collecting squareThe method is carried out.
The chemical absorption method is to selectively mix CO in the flue gas with the absorbent2Chemical reaction to realize CO2Separated from other gases and regenerated by means of the reverse reaction of this reaction, releasing high-purity CO2And (4) carrying out enrichment. The reaction principle is that weak base and weak acid react to form water soluble salt which absorbs or releases CO2Is controlled by the chemical reaction equilibrium. The most important bottleneck limiting the large-scale application of the chemical absorption method at present is that the energy consumption is large and the cost is high.
In order to reduce energy consumption, researchers in the industry have conducted research in two major areas: the development of a high-efficiency absorbent absorption system and the capture process optimization of the capture system. Aiming at the absorbent, at present, there are several main types of absorbent, such as amine solution, ammonia water, caustic potash solution, ionic liquid and amino acid salt solution, etc., caustic potash solution and ionic liquid have high cost and are not easy to be used in large scale, while ammonia water is easy to volatilize and forms crystals to block pipelines, so that the mixed absorbent of different amines (ammonia) and novel phase change absorbent are the research focus of researchers in the industry at present. Aiming at the process optimization of the trapping system, the research focuses on an absorption system (a first type of phase-change absorption system) which is layered after absorption and an absorption system (a second type of phase-change absorption system) which is layered after desorption, and the regeneration energy consumption is reduced by reducing the regeneration liquid amount.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a low partial pressure CO separating agent suitable for low partial pressure CO2An absorption system for capturing and purifying, which can effectively reduce CO2Energy consumption capture and CO reduction2And (4) trapping cost.
To achieve the above purpose, the method is suitable for low partial pressure CO2The absorption system for trapping and purifying is a phase-change nano-fluid absorption system, the regenerated layered phase-change nano-absorbent of the phase-change nano-fluid absorption system consists of base liquid, a layering agent, an activating agent, nano particles, a corrosion inhibitor and an antioxidant, the base liquid consists of hydroxyethyl ethylenediamine and tetraethylenepentamine, the layering agent consists of N-ethyl ethylenediamine and 1, 4-butanediamine, the activating agent consists of piperazine or diethanolamine, the nano particles consist of copper oxide or magnesium oxide, the corrosion inhibitor consists of imidazoline benzoate-dimethyl sulfate quaternary ammonium salt or imidazoline benzoate-chloromethane quaternary ammonium salt, and the antioxidant consists of carbohydrazide or pyrogallol;
the total mass fraction of the regenerative layered phase change nano absorbent is 30 wt%, and the proportions of the base liquid, the layering agent, the activating agent, the nano particles, the corrosion inhibitor and the antioxidant are as follows: 15% -20%: 5% -9%: 1% -5%: 0.01% -0.05%: 0.025-0.05%: 0.025 to 0.05 percent.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: copper oxide: benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt: carbohydrazide 15%: 9%: 5%: 3%: 3%: 0.01%: 0.05%: 0.05 percent.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: diethanolamine: copper oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: pyrogallol 20%: 5%: 1%: 5%: 5%: 0.05%: 0.05%: 0.05 percent.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt: carbohydrazide 17%: 7%: 5%: 1%: 1%: 0.03%: 0.035%: 0.035%.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: diethanolamine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: pyrogallol 15%: 9%: 3%: 2%: 3%: 0.035%: 0.035%: 0.035%.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: pyrogallol 17%: 7%: 4%: 2%: 3%: 0.03%: 0.025%: 0.025 percent.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt: pyrogallol 16%: 6%: 3%: 2%: 3%: 0.03%: 0.035%: 0.035%.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: carbohydrazide 18%: 5%: 4%: 2%: 3%: 0.05%: 0.04%: 0.04 percent.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: diethanolamine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: carbohydrazide 17%: 7%: 3%: 2%: 3%: 0.05%: 0.04%: 0.04 percent.
As an embodiment of the invention, the regenerative layered phase change nano-absorbent of the phase change nano-fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: copper oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: carbohydrazide 17%: 6%: 4%: 1%: 2%: 0.05%: 0.04%: 0.04 percent.
Compared with the prior art, the method is suitable for low partial pressure CO2The regenerative layered phase-change nano absorbent of the trapping and purifying absorption system can reduce the regeneration energy consumption and the regeneration temperature and improve the regeneration rate through phase change in the regeneration process, has the characteristics of large absorption load, high absorption and desorption rate and low regeneration energy consumption, and the self regeneration energy consumption of the absorbent is less than 2.7GJ/tCO2Can effectively reduce CO2Energy consumption capture and CO reduction2And (4) trapping cost.
Drawings
FIG. 1 is a diagram of a system for low partial pressure CO absorption using phase change nanofluid absorption2An energy-saving process flow chart of trapping and purification.
In the figure: 1. a water washing pump, 2, a water washing tower, 3, an alkaline pump, 4, a water washing liquid heat exchanger, 5, a draught fan, 6, an absorption tower, 7, an interstage cooler, 8, an interstage cooling pump, 9, a dry bed section, 10, a tail gas washing tower A, 11, a tail gas washing liquid cooler A, 12, a tail gas washing pump A, 13, a tail gas washing liquid storage tank A, 14, a tail gas washing tower B, 15, a tail gas washing liquid cooler B, 16, a tail gas washing pump B, 17, a tail gas washing liquid storage tank B, 18, a liquid distribution tank, 19, a rich liquid pump, 20, a regeneration tower, 21, a lean liquid heat exchanger, 22, a lean liquid cooler, 23, a condensed water heat exchanger, 24, a flash tank, 25, a flash pump, 26, a flash compressor, 27, a lean liquid pump, 28, a composite heat pump, 29, an evaporator A, 30, an evaporator B, 31, an absorber A, 32, an absorber B, 33 and a generator A, 34. generators B, 35, condensers A, 36, condensers B, 37, a regeneration gas compressor, 38, a regenerator condenser, 39, a throttle valve, 40, a solution boiler,
Detailed Description
The method is suitable for low partial pressure CO2The trapping and purifying absorption system is a phase-change nano-fluid absorption system, and the regenerative layered phase-change nano-absorbent of the phase-change nano-fluid absorption system consists of base liquid, a layering agent, an activating agent, nano-particles, a corrosion inhibitor and an antioxidant; the base liquid is a basic absorption liquid for ensuring the large load and high absorption rate of the absorbent and consists of hydroxyethyl ethylenediamine (AEEA) and tetraethylenepentamine (TETA); layering agent for realizing CO regeneration of absorption system2The subsequent layering realizes the autonomous self-extraction of the organic phase, ensures a large layering proportion and further reduces energy consumption, and consists of N-ethyl ethylenediamine (N-ELDE) and 1, 4-Butanediamine (BDA); the activator is used for improving the absorption of CO by the absorption system2Reaction rate and desorption of CO2The reaction rate of (a) is composed of Piperazine (PZ) or Diethanolamine (DEA); the nano particles are used for strengthening mass transfer, improving the absorption rate and increasing the mass transfer absorption load and consist of copper oxide (CuO) or magnesium oxide (MgO); the corrosion inhibitor is used for reducing the corrosivity of an absorption system to steel (a reactor, heat exchange equipment, various storage tanks, pipelines and the like), and consists of benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt (IBDSQAS) or benzoic acid imidazoline-chloromethane quaternary ammonium salt (ICQAB); the antioxidant is used for reducing thermal degradation and oxidative degradation of the effective components of the absorbent and ensuring the stability of an absorption system and is composed of Carbohydrazide (CD) or pyrogallol (OTP). The total mass fraction of the regenerative layered phase-change nano absorbent of the phase-change nano fluid absorption system is 30 wt%, and the proportions of the base liquid, the layering agent, the activating agent, the nano particles, the corrosion inhibitor and the antioxidant are as follows: 15% -20%: 5% -9%: 1% -5%: 0.01% -0.05%: 0.025-0.05%: 0.025 to 0.05 percent.
Phase-change nano-fluid absorption system-based low partial pressure CO absorption system2An energy-saving process for capturing and purifying adopts a coupling process of a graded flow system, an interstage cooling system, a combined heat pump system, an MVR flash evaporation heat pump system and a compression type heat pump system, as shown in figure 1, and is suitable for low-partial-pressure CO2Is of trapping purityThe chemical system assembly comprises a water washing tower 2, an absorption tower 6, a regeneration tower 20, a flash tank 24 and a composite heat pump 28, wherein an evaporator, an absorber, a generator and a condenser are arranged in the composite heat pump 28, the input end of the generator is connected with an external steam source, and the output end of the generator is connected with the input end of a condensed water deoxygenator. To ensure the efficacy of the compound heat pump 28, the evaporator, absorber, generator, condenser may be provided as evaporator a29 and evaporator B30 connected in series, absorber a31 and absorber B32 connected in series, generator a33 and generator B34 connected in series, condenser a35 and condenser B36 connected in series, respectively.
Suitable for low partial pressure CO2The energy-saving process for trapping and purifying specifically comprises the following parts:
a. washing with water: the washing tower 2 is provided with a washing liquid circulating device for circularly conveying washing liquid from bottom to top, the washing liquid circulating device comprises a washing pump 1 and a washing liquid heat exchanger 4, the washing liquid enters the washing liquid heat exchanger 4 for heat exchange through external circulating water after being pressurized by the washing pump 1, and enters the washing tower 2 for spraying after heat exchange (the temperature is reduced to 35-45 ℃); the alkali supplementing amount of the water washing liquid is controlled by a pH meter arranged on a circulating pipeline, the pH meter is interlocked with an alkali supplementing pump 3, the output end of the alkali supplementing pump 3 is communicated with the circulating pipeline, and the NaOH supplementing amount is adjusted by adjusting the rotating speed of the alkali supplementing pump 3 according to the feedback of the pH meter; flue gas discharged from a coal-fired power plant enters a washing tower 2 through a pipeline, is subjected to desulfurization, denitrification, dedusting and heat exchange by using washing liquid (the gas temperature is controlled to be 35-45 ℃), and is discharged from the top of the washing tower 2 to enter a draught fan 5.
b. Decarbonization: the flue gas enters an absorption tower 6 from bottom to top after being pressurized by a draught fan 5, a barren liquor absorbent (with the temperature of 35-45 ℃) discharged by a barren liquor cooler 22 is sprayed from top to bottom and enters the absorption tower 6, the barren liquor absorbent and the absorption tower are in countercurrent contact, and amine and CO are in countercurrent contact2The amino carbonate (with the temperature of 45-55 ℃) generated by the reaction enters an interstage cooler 7 for exchanging heat through external circulating water, the temperature is reduced to 35-45 ℃, the amino carbonate enters an absorption tower 6 again after being pressurized by an interstage cooling pump 8, and therefore the amine and CO content is improved2The decarburization reaction rate of (3).
c. Washing tail gas: a dry bed section 9 is arranged above the packing at the top of the absorption tower 6, the height of the packing of the dry bed section 9 is more than 2m, the main function is to provide a cooling and condensing space for the tail gas discharged by the absorption tower 6, the moisture and the organic amine in the tail gas discharged from the tail gas discharge port of the absorption tower 6 are in a supersaturated state, the tail gas is cooled and condensed to form a liquid film with low amine concentration in the dry bed section 9, the liquid film further generates gas-liquid equilibrium mass transfer with the flue gas, and most of the organic amine in the gas phase is recovered; the decarbonized gas passes through a dry bed section 9 at the top of an absorption tower 6 and is discharged into a tail gas washing system through a tail gas discharge port at the top of the absorption tower 6, the tail gas washing system comprises a two-stage tail gas washing tower, the two-stage tail gas washing tower comprises a tail gas washing tower A10 and a tail gas washing tower B14 which are sequentially connected in series, enough growth space is mainly provided for aerosol to grow to 3 mu m or above, a conventional demister is arranged at exhaust ports of the tail gas washing tower A10 and the tail gas washing tower B14 in a matching manner, organic amine in an aerosol form can be effectively removed, tail gas washing liquid circulating devices for circularly conveying tail gas washing liquid from the bottom to the top are respectively arranged on the tail gas washing tower A10 and the tail gas washing tower B14, the tail gas washing liquid circulating device for the tail gas washing liquid in the tail gas washing tower A10 comprises a tail gas washing liquid storage tank A13, a tail gas washing liquid pump A12 and a tail gas washing liquid cooler A11, and the tail gas washing liquid circulating device for the tail gas washing liquid in the tail gas washing tower B14 comprises a tail gas washing liquid storage tank B17, The tail gas washing liquid pump B16 and the tail gas washing liquid cooler B15, the aerosol recovered in the tail gas washing process enters the tail gas washing liquid storage tank A13 and the tail gas washing liquid storage tank B17 and flows back to the liquid preparation tank 18, the barren solution in the liquid preparation tank 18 is replenished to the absorption tower 6 again, and the system solution balance is maintained; the tail gas after being washed discharged from the tail gas washing tower B14 is discharged into a chimney.
d.CO2Desorbing: absorb CO2The rich liquid of the gas is discharged from the bottom of the absorption tower 6, and is pressurized by a rich liquid pump 19 and then is conveyed in a grading way, wherein the first-stage rich liquid (the temperature of the rich liquid is 50-55 ℃) directly enters a first-stage spraying pipeline at the top of the regeneration tower 20, the second-stage rich liquid (the temperature of the rich liquid is 40-45 ℃) enters a second-stage rich liquid heat exchanger 21 for heat exchange and temperature rise, and the second-stage rich liquid (the temperature of the rich liquid is 95-105 ℃) enters a second-stage spraying pipeline of the regeneration tower 20 below the first-stage spraying pipeline; the third-stage rich liquid (the temperature of the rich liquid is 50-55 ℃) enters into the third stage of heat exchange through external steam condensed waterThe rich liquid heat exchanger 23 performs heat exchange and temperature rise, and enters a secondary spraying pipeline of the regeneration tower 20 after heat exchange (the temperature of the rich liquid is 95-105 ℃), so that CO is realized2Desorption from the absorbent.
e. Flash evaporation heat supply: a liquid supplementing pipeline of the flash tank 24 is communicated with a pipeline from the secondary rich liquid heat exchanger 21 to the regeneration tower 20, so that a liquid supplementing process of the flash tank 24 is realized; the rich liquid (the temperature is 80-90 ℃) in the flash tank 24 is pressurized by a flash circulating pump 25 and then sequentially enters an absorber A31 and an absorber B32 of the combined heat pump 28 for heat exchange and temperature rise, and returns to the flash tank 24 for a flash process after the temperature rises to 90-100 ℃; the flash steam discharged from the top of the flash tank 24 enters a third-stage spraying pipeline of the regeneration tower 20 below the second-stage spraying pipeline after being pressurized by a flash compressor 26 (the temperature is 105-115 ℃) to provide heat for the solution regeneration process in the regeneration tower 20.
f. And (3) cyclic regeneration of the absorption solvent: the desorbed barren solution (with the temperature of 100-105 ℃) is pressurized by a barren solution pump 27 from a barren solution outlet at the bottom of the regeneration tower 20 and then is divided into two-stage processes, wherein the first stage enters a condenser A35 and a condenser B36 of the compound heat pump 28 in sequence for heat exchange and temperature rise, and enters a secondary spraying pipeline of the regeneration tower 20 again after the temperature rises to 105-115 ℃; and the other stage of the heat exchange working medium as the heat exchange working medium of the secondary rich liquid heat exchanger 21 enters the secondary rich liquid heat exchanger 21 for heat exchange and temperature reduction, the temperature is reduced to 55-65 ℃, then the heat exchange working medium sequentially enters an evaporator A29 and an evaporator B30 of the combined heat pump 28 for heat exchange and temperature reduction, the temperature is reduced to 40-50 ℃, then the heat exchange working medium enters the lean liquid cooler 22 for continuous temperature reduction to be below 40 ℃, and finally the heat exchange working medium enters a spray pipeline of the absorption tower 6 and starts a new absorption process, so that the cyclic regeneration of the absorption solvent is realized.
g. Treating regenerated gas: the regenerated gas (the temperature is more than 100 ℃) sucked out by rich liquor decomposition enters a regenerated gas compressor 37 from the outlet at the top of the regeneration tower 20 for pressurization (the temperature is raised to about 120-160 ℃), then enters a regenerator condenser 38 for condensation and cooling, and the condensation heat is transferred to the working medium of the heat pump; the cooled regeneration gas (the temperature is reduced to 80-90 ℃) enters a regeneration gas heat exchanger 42 for heat exchange and cooling through external circulating water, the temperature is reduced to 60-70 ℃, then enters an air cooler 43 for continuous cooling to below 40 ℃, and finally enters a gas-liquid separator 44Separation of qi and liquid, separated CO2The gas is used as product gas to enter a subsequent flow, and the separated dilute solution enters the tower kettle of the regeneration tower 20 after being pressurized by the reflux pump 45, so that the water balance of the system is maintained. In order to further realize energy conservation and consumption reduction, the input end of the external circulating water of the regenerated gas heat exchanger 42 is connected with the condensed water output end of the shaft seal heater of the generator set, and the output end of the external circulating water of the regenerated gas heat exchanger 42 is connected with the condensed water input end of the shaft seal heater of the generator set.
h. A compression heat pump cycle: the compression type heat pump system comprises a solution boiler 40, a heat pump working medium heating coil is arranged in the solution boiler 40, a barren solution input end at the lower part of the solution boiler 40 is connected with the tower kettle of the regeneration tower 20, and a gasification output end at the upper part of the solution boiler 40 is connected with a gasification input end at the lower part of the tower kettle of the regeneration tower 20; the heat pump working medium can adopt 141b, 123a, 507a and the like, the heat pump working medium in the regenerator condenser 38 absorbs the condensation heat of the regeneration gas, then is totally vaporized and overheated, then enters the heat pump working medium compressor 41 for heating and pressurizing, the high-temperature and high-pressure heat pump working medium enters the heat pump working medium heating coil in the solution boiler 40 to be used as a heat source to release the heat to the barren solution in the solution boiler 40, and the barren solution is gasified and then returns to the regeneration tower 20 through the gasification output end, the heat pump working medium is totally condensed into liquid, and then is cooled and depressurized through the throttle valve 39 to be returned to the regenerator condenser 38 for heating and next cycle. In order to realize better gasification effect and ensure that the heat pump working medium is completely condensed into liquid after flowing through the solution boiler 40 and further realize energy conservation and consumption reduction, a steam heating coil connected with an external steam source can be arranged inside the solution boiler 40, the output end of the steam heating coil is connected with the input end of external circulating water of the tertiary rich liquid heat exchanger 23, the external steam source can supply hot steam to realize better gasification effect, meanwhile, the hot steam in the steam heating coil is condensed into water after heat exchange, the condensed water can be used as a heat exchange warming working medium of the tertiary rich liquid heat exchanger 23, and the condensed water can be recycled after being further cooled by the tertiary rich liquid heat exchanger 23 and deoxidized by a condensate water deoxidizer.
The following steps are carried out to carry out CO treatment on the flue gas discharged by a certain coal-fired power plant2Example of Collection purification and examination of the inventionThe discussion is made.
The parameters of the absorption tower and the regeneration tower are shown in Table 1, the flue gas composition is shown in Table 2, and CO is2Trap purification experiment operating parameters are shown in table 3. The absorption tower and the regeneration tower are both made of stainless steel materials and are filled with stainless steel corrugated structured packing, the absorption tower, the regeneration tower and the pipeline are all wrapped with heat insulation materials, the regeneration heat comes from an electric heater at the bottom of the regeneration tower 20, and the regeneration temperature of a voltage control system is adjusted by adopting silicon controlled rectifiers.
TABLE 1 absorption column and regeneration column parameters
TABLE 2 Smoke composition
TABLE 3 CO2Trapping and purifying experiment operating parameters
Example 1:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：PZ：CuO：IBDSQAS：CD＝15％：9％：5％：3％：3％：0.01％：0.05％：0.05％。
the specific performance parameters of the conventional process and the energy-saving process are shown in tables 4(a) and 4 (b).
Table 4(a) table of performance parameters for example 1 using conventional process
Table 4(b) table of performance parameters for example 1 using energy saving process
Example 2:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：DEA：CuO：ICQAB：OTP＝20％：5％：1％：5％：5％：0.05％：0.05％：0.05％。
the specific performance parameters of the conventional process and the energy-saving process are shown in tables 5(a) and 5 (b).
TABLE 5(a) TABLE of Performance parameters for example 2 using conventional process
TABLE 5(b) TABLE of Performance parameters for example 2 with energy saving Process
Example 3:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：PZ：MgO：IBDSQAS：CD＝17％：7％：5％：1％：1％：0.03％：0.035％：0.035％。
the specific performance parameters of the conventional process and the energy-saving process are shown in tables 6(a) and 6 (b).
Table 6(a) table of performance parameters for example 3 using conventional process
TABLE 6(b) TABLE of Performance parameters for example 3 with energy saving Process
Example 4:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：DEA：MgO：ICQAB：OTP＝15％：9％：3％：2％：3％：0.035％：0.035％：0.035％。
the specific performance parameters of the conventional process and the energy-saving process are shown in tables 7(a) and 7 (b).
Table 7(a) table of performance parameters for example 4 using conventional process
TABLE 7(b) TABLE 4 TABLE of Performance parameters Using energy saving Process
Example 5:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：PZ：MgO：ICQAB：OTP＝17％：7％：4％：2％：3％：0.03％：0.025％：0.025％。
the performance parameters of the energy-saving process are shown in table 8.
Table 8 table of performance parameters for example 5 using energy saving process
Example 6:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：PZ：MgO：IBDSQAS：OTP＝16％：6％：3％：2％：3％：0.03％：0.035％：0.035％。
the performance parameters of the energy-saving process are shown in table 9.
Table 9 table of performance parameters of example 6 using energy saving process
Example 7:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：PZ：MgO：ICQAB：CD＝18％：5％：4％：2％：3％：0.05％：0.04％：0.04％。
the performance parameters of the energy-saving process are shown in table 10.
Table 10 table of performance parameters for example 7 using energy saving process
Example 8:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：DEA：MgO：ICQAB：CD＝17％：7％：3％：2％：3％：0.05％：0.04％：0.04％。
the performance parameters of the energy-saving process are shown in table 11.
Table 11 table of performance parameters for example 8 using energy saving process
Example 9:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：PZ：CuO：ICQAB：CD＝17％：6％：4％：1％：2％：0.05％：0.04％：0.04％。
the performance parameters of the energy-saving process are shown in table 12.
Table 12 table of performance parameters for example 9 using energy saving process
Example 10:
the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
AEEA：TETA：N-ELDE：BDA：DEA：CuO：ICQAB：CD＝18％：5％：3％：2％：2％：0.05％：0.04％：0.04％。
the performance parameters of the energy-saving process are shown in table 13.
TABLE 13 TABLE 10 TABLE of Performance parameters for example 10 with energy saving Process
The method is suitable for low partial pressure CO2The regenerative layered phase-change nano absorbent of the trapping and purifying absorption system can reduce the regeneration energy consumption and the regeneration temperature through phase change in the regeneration process, improve the regeneration rate, has the characteristics of large absorption load, high absorption and desorption rate and low regeneration energy consumption, and the self regeneration energy consumption of the absorbent is less than 2.7GJ/tCO2。
The low-partial-pressure CO coupling process adopting the coupling process of the graded flow system, the interstage cooling system, the combined heat pump system, the MVR flash evaporation heat pump system and the compression heat pump system is suitable for low-partial-pressure CO2The energy-saving process of trapping and purifying partially replaces the traditional regeneration process of 'a desorption tower and a boiler', can effectively reduce the volume of the boiler, greatly reduce the regeneration energy consumption, and can reduce the medicament loss and medicament consumptionThe degradation and deterioration of the catalyst can improve the recycling times of the chemical absorbent, save the investment cost, realize the purposes of resource recovery and reducing environmental pollution, and ensure that CO can be recycled2The regeneration energy consumption of the trapping system is lower than 2.3GJ/tCO 2. The 'composite absorption heat pump + MVR flash evaporation heat pump system' can effectively recover the waste heat of the barren solution and is used for heating the rich solution, and compared with the regeneration energy consumption of the traditional process, the regeneration energy consumption can be reduced by 0.2-0.3 GJ/tCO 2; the 'regeneration tower top compression heat pump system' can effectively recover regeneration tower top gas, and compared with the regeneration energy consumption of the traditional process, the regeneration energy consumption can be reduced by 0.25-0.35 GJ/tCO 2; by adopting the tail gas washing process of 'a dry bed and a two-stage tail gas washing tower', the dry bed can directly lead the organic amine to return to an absorption circulation system, the organic amine in the tail gas washing tower is slowly accumulated, the frequent water regulation and control can be effectively avoided, the three control links are favorable for the growth of aerosol, large particles can be effectively removed, the solvent loss is reduced, the emission of tail gas pollutants is reduced, and the absorption entrainment loss amount is less than 0.6kg/tCO2Compared with the traditional first-stage water washing process (about 1.0 kg/tCO)2) The reduction can be more than 40%.
Claims (10)
1. Is suitable for low partial pressure CO2The absorption system is characterized by being a phase-change nano fluid absorption system, wherein a regenerated layered phase-change nano absorbent of the phase-change nano fluid absorption system consists of base liquid, a layering agent, an activating agent, nano particles, a corrosion inhibitor and an antioxidant, the base liquid consists of hydroxyethyl ethylenediamine and tetraethylenepentamine, the layering agent consists of N-ethyl ethylenediamine and 1, 4-butanediamine, the activating agent consists of piperazine or diethanolamine, the nano particles consist of copper oxide or magnesium oxide, the corrosion inhibitor consists of imidazoline benzoate-dimethyl sulfate quaternary ammonium salt or imidazoline benzoate-chloromethane quaternary ammonium salt, and the antioxidant consists of carbohydrazide or pyrogallol;
the total mass fraction of the regenerative layered phase change nano absorbent is 30 wt%, and the proportions of the base liquid, the layering agent, the activating agent, the nano particles, the corrosion inhibitor and the antioxidant are as follows: 15% -20%: 5% -9%: 1% -5%: 0.01% -0.05%: 0.025-0.05%: 0.025 to 0.05 percent.
2. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: copper oxide: benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt: carbohydrazide 15%: 9%: 5%: 3%: 3%: 0.01%: 0.05%: 0.05 percent.
3. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: diethanolamine: copper oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: pyrogallol 20%: 5%: 1%: 5%: 5%: 0.05%: 0.05%: 0.05 percent.
4. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt: carbohydrazide 17%: 7%: 5%: 1%: 1%: 0.03%: 0.035%: 0.035%.
5. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: diethanolamine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: pyrogallol 15%: 9%: 3%: 2%: 3%: 0.035%: 0.035%: 0.035%.
6. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: pyrogallol 17%: 7%: 4%: 2%: 3%: 0.03%: 0.025%: 0.025 percent.
7. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-dimethyl sulfate quaternary ammonium salt: pyrogallol 16%: 6%: 3%: 2%: 3%: 0.03%: 0.035%: 0.035%.
8. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: carbohydrazide 18%: 5%: 4%: 2%: 3%: 0.05%: 0.04%: 0.04 percent.
9. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: diethanolamine: magnesium oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: carbohydrazide 17%: 7%: 3%: 2%: 3%: 0.05%: 0.04%: 0.04 percent.
10. The method of claim 1 for low partial pressure CO2The trapping and purifying absorption system is characterized in that the regenerative layered phase change nano absorbent of the phase change nano fluid absorption system comprises the following components in percentage by mass:
hydroxyethyl ethylenediamine: tetraethylenepentamine: N-Ethylethylenediamine: 1, 4-butanediamine: piperazine: copper oxide: benzoic acid imidazoline-methyl chloride quaternary ammonium salt: carbohydrazide 17%: 6%: 4%: 1%: 2%: 0.05%: 0.04%: 0.04 percent.
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