CN117839379A - High-pressure chemical chain coupling calcium circulation carbon dioxide capturing system and application thereof - Google Patents
High-pressure chemical chain coupling calcium circulation carbon dioxide capturing system and application thereof Download PDFInfo
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- CN117839379A CN117839379A CN202311839869.0A CN202311839869A CN117839379A CN 117839379 A CN117839379 A CN 117839379A CN 202311839869 A CN202311839869 A CN 202311839869A CN 117839379 A CN117839379 A CN 117839379A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 72
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 71
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 55
- 239000011575 calcium Substances 0.000 title claims abstract description 55
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 230000008878 coupling Effects 0.000 title abstract description 21
- 238000010168 coupling process Methods 0.000 title abstract description 21
- 238000005859 coupling reaction Methods 0.000 title abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003546 flue gas Substances 0.000 claims abstract description 116
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 81
- 239000001301 oxygen Substances 0.000 claims abstract description 81
- 239000002918 waste heat Substances 0.000 claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000010248 power generation Methods 0.000 claims abstract description 56
- 239000007789 gas Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000003345 natural gas Substances 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000002485 combustion reaction Methods 0.000 claims description 29
- 239000003463 adsorbent Substances 0.000 claims description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims description 18
- 150000004706 metal oxides Chemical class 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- 230000002950 deficient Effects 0.000 claims description 10
- 230000001351 cycling effect Effects 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 3
- 238000005261 decarburization Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010586 diagram Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
- F22B1/1892—Systems therefor not provided for in F22B1/1807 - F22B1/1861
-
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
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Abstract
The present invention relates to CO 2 The technical field of trapping, in particular to a high-pressure chemical chain coupling calcium cycle carbon dioxide trapping system and application thereof, wherein the trapping system comprises: gas power generation unit, first waste heat power generation unit and CO 2 A separation unit; CO 2 The separation unit includes: the device comprises a first compressor, an air reactor, a first turbine, a carbonating tower and a calciner. The method adopts a coupling mode of calcium circulation and a chemical-looping air reactor, utilizes oxygen with higher concentration in the tail flue gas of natural gas to oxidize a metal oxygen carrier in the air reactor, provides an oxygen source for a calciner, replaces the originally required air, drives combined circulation to do work, solves the problem of flue gas preheating in the natural gas flue gas calcium circulation trapping technology, fully utilizes the residual oxygen in the flue gas, and improves the flue gas entering a carbonatorCO in the gas 2 Concentration, reduce and trap the energy consumption; and because a part of energy is used for driving the combined cycle, the heat exchange loss can be effectively reduced, and the work output of the trapping system is improved.
Description
Technical Field
The present invention relates to CO 2 The technical field of trapping, in particular to a high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system and application thereof.
Background
High amounts of CO produced by combustion of fossil fuels in the power and industry sectors 2 The emission forms a threat to the environment, and carbon dioxide trapping and sequestration is expected to be the alleviation of CO 2 Emissions and reduced environmental impact; at different COs 2 In the trapping technology, CO after combustion 2 Trapping technology is the only end trapping mode that can reduce carbon emissions from stationary sources without changing the industrial plant.
CO after combustion 2 In the trapping technology, the calcium circulating process is a promising low-energy-consumption CO 2 The trapping technology has the advantages of wide raw material sources, high reaction activity, low cost and the like. The calcium circulation process mainly comprises two processes of carbonation and calcination, but the two processes have larger waste heat at higher reaction temperature, wherein the waste heat comprises reaction waste heat released by carbonation reaction at 600-650 ℃, and waste heat released by decarbonizing flue gas products and calciner products at 850-850 ℃. The prior research mainly adopts steam circulation to absorb the residual heat of the calcium circulation, but has larger temperature difference between the high-temperature residual heat and the temperature of the main steam, thereby causing a larger temperature differenceLarge heat exchange losses; at the same time, to avoid N in the air 2 For enrichment of CO 2 The calcium circulating process usually adopts an oxygen-enriched combustion mode, and the high-purity oxygen required by the oxygen-enriched combustion needs to consume huge space-division energy consumption, which leads to the rise of the cost and the reduction of the efficiency of the technology in practical application, and restricts the wide application of the technology. In addition, when the calcium cycling process is used for tail flue gas capture of a natural gas combined cycle, the carbonator will require additional heat supply without flue gas preheating, which also presents challenges for the application of the calcium cycling technology in natural gas power plants.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a high-pressure chemical chain coupled calcium circulating carbon dioxide capturing system and application thereof, which aims to solve the existing CO 2 The trapping system has the problems of larger heat loss, higher energy consumption and the like.
The technical scheme of the invention is as follows:
a high pressure chemical chain coupled calcium cycle carbon dioxide capture system comprising: the gas power generation unit, the first waste heat power generation unit for generating power by utilizing the flue gas exhausted by the gas power generation unit, and the method for performing CO on the flue gas exhausted by the first waste heat power generation unit 2 Separated CO 2 A separation unit;
the CO 2 The separation unit includes:
the first compressor is used for pressurizing the flue gas exhausted by the first waste heat power generation unit to form compressed flue gas;
the air reactor is connected with the first air compressor and is used for transmitting oxygen in the compressed flue gas to a metal oxygen carrier to form metal oxide; the air reactor is filled with a metal oxygen carrier and a carbon dioxide adsorbent;
the first turbine is connected with the air reactor, and oxygen-deficient flue gas at the outlet of the air reactor is used for driving the first turbine to do work;
a carbonation tower coupled to the air reactor and the first turbine; transferring the carbon dioxide adsorbent and the metal oxide in the air reactor into the carbonator to capture carbon dioxide in the oxygen-depleted flue gas at the outlet of the first turbine;
a calciner connected to the carbonation tower and the air reactor; the product in the carbonation tower is transferred to the calciner for reduction to form a reduced product, which is returned to the air reactor.
The high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system comprises a metal oxygen carrier and a high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system, wherein the metal oxygen carrier comprises one or more of Fe, cu, co, mn and a composite metal oxygen carrier; and/or, the carbon dioxide adsorbent is calcium oxide.
The high-pressure chemical chain is coupled with a calcium circulation carbon dioxide trapping system, wherein, the first compressor pressurizes the flue gas exhausted by the first waste heat power generation unit to 1-15bar to form compressed flue gas; the compressed flue gas enters the air reactor through a pipeline.
The high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system is characterized in that the reaction pressure in the air reactor is 1-15bar, and the reaction temperature in the air reactor is 950-1100 ℃.
The high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system is characterized in that the reaction temperature in the carbonator is 600-650 ℃.
The high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system is characterized in that the reaction temperature in the calciner is 900-950 ℃.
The high-pressure chemical chain coupling calcium circulating carbon dioxide capturing system, wherein the gas power generation unit comprises:
the second compressor is used for pressurizing air to form compressed air;
the combustion chamber is connected with the second air compressor and is used for mixing and combusting natural gas and the compressed air;
and the second turbine is connected with the combustion chamber, and the flue gas at the outlet of the combustion chamber is used for driving the second turbine to do work.
The high-pressure chemical chain coupling calcium cycle carbon dioxide trapping system, wherein the first waste heat power generation unit comprises: the system comprises a first waste heat boiler, a third turbine, a first condenser and a first pump;
the first waste heat boiler is connected with the second turbine; the first waste heat boiler is connected with the third turbine, the first condenser and the first pump in a closed loop manner; and the flue gas exhausted by the first waste heat boiler enters the first air compressor.
The high-pressure chemical chain coupling calcium circulating carbon dioxide capturing system further comprises a second waste heat power generation unit; the second waste heat power generation unit includes: the second waste heat boiler, the fourth turbine, the second condenser and the second pump;
the second waste heat boiler is connected with the carbonator tower and the calciner; the second waste heat boiler is connected with the fourth turbine, the second condenser and the second pump in a closed loop manner; the second waste heat boiler discharges decarburization flue gas and is rich in CO 2 And (3) gas.
An application of a high-pressure chemical chain coupled calcium circulating carbon dioxide trapping system in natural gas power plant tail gas trapping.
The beneficial effects are that: the invention provides a high-pressure chemical chain coupling calcium circulating carbon dioxide capturing system and application thereof, wherein the high-pressure chemical chain coupling calcium circulating carbon dioxide capturing system comprises: the gas power generation unit, the first waste heat power generation unit for generating power by utilizing the flue gas exhausted by the gas power generation unit, and the method for performing CO on the flue gas exhausted by the first waste heat power generation unit 2 Separated CO 2 A separation unit; the CO 2 The separation unit includes: the first compressor is used for pressurizing the flue gas exhausted by the first waste heat power generation unit to form compressed flue gas; the air reactor is connected with the first air compressor and is used for transmitting oxygen in the compressed flue gas to a metal oxygen carrier to form metal oxide; the air reactor is filled with a metal oxygen carrier and carbon dioxide adsorptionAn agent; the first turbine is connected with the air reactor, and oxygen-deficient flue gas at the outlet of the air reactor is used for driving the first turbine to do work; a carbonation tower coupled to the air reactor and the first turbine; transferring the carbon dioxide adsorbent and the metal oxide in the air reactor into the carbonator to capture carbon dioxide in the oxygen-depleted flue gas at the outlet of the first turbine; a calciner connected to the carbonation tower and the air reactor; the product in the carbonation tower is transferred to the calciner for reduction to form a reduced product, which is returned to the air reactor. The invention adopts a coupling mode of calcium circulation and a chemical-looping air reactor, utilizes the high-concentration flue gas in the tail flue gas of the natural gas to oxidize the metal oxygen carrier in the air reactor, provides an oxygen source for a calciner, replaces the air originally required and drives the combined circulation to do work, not only can solve the problem of flue gas preheating in the natural gas flue gas calcium circulation trapping technology, but also can fully utilize the residual oxygen in the flue gas and improve the CO in the flue gas entering the carbonator 2 Concentration, reduce and trap the energy consumption; meanwhile, the power consumption of the space division unit is avoided. And because a part of energy is used for driving the combined cycle, the traditional steam cycle is replaced, the heat exchange loss can be effectively reduced, and the work output of the trapping system is improved.
Drawings
FIG. 1 is a schematic diagram of a high pressure chemical chain coupled calcium cycle carbon dioxide capture system according to the present invention;
FIG. 2 is a process flow diagram of the application of the high pressure chemical chain coupled calcium cycle carbon dioxide capture system of example 1 in natural gas power plant tail gas capture;
FIG. 3 is a process flow diagram of the natural gas calcium looping oxygen-enriched combustion capture system of comparative example 1;
FIG. 4 is a process flow diagram of a non-captured natural gas combined cycle power generation system of comparative example 2;
reference numerals illustrate: the gas power generation unit 100, the second compressor 101, the combustion chamber 102, the second turbine 103, the first waste heat power generation unit 200, the first waste heat boiler 201, the third turbine 202, the first condenser 203, the first pump 204, the CO2 separation unit 300, the first compressor 301, the air reactor 302, the first turbine 303, the carbonator 304, the calciner 305, the second waste heat power generation unit 400, the second waste heat boiler 401, the fourth turbine 402, the second condenser 403, and the second pump 404.
Detailed Description
The invention provides a high-pressure chemical chain coupling calcium circulating carbon dioxide capturing system and application thereof, and the invention is further described in detail below for making the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As shown in fig. 1, the present invention provides a high pressure chemical chain coupled calcium cycle carbon dioxide capture system comprising: the gas power generation unit 100, the first waste heat power generation unit 200 for generating power by using the flue gas discharged from the gas power generation unit 100, and the method for generating CO from the flue gas discharged from the first waste heat power generation unit 200 2 Separated CO 2 A separation unit 300;
the CO 2 The separation unit 300 includes:
a first compressor 301, configured to compress the flue gas exhausted from the first cogeneration unit 200 to form compressed flue gas;
an air reactor 302, wherein the air reactor 302 is connected with the first compressor 301 and is used for transferring oxygen in the compressed flue gas to a metal oxygen carrier to form metal oxide; the air reactor 302 is loaded with a metal oxygen carrier and a carbon dioxide adsorbent;
the first turbine 303 is connected with the air reactor 302, and the oxygen-deficient flue gas at the outlet of the air reactor is used for driving the first turbine to do work;
a carbonation tower 304 coupled to said air reactor 302 and said first turbine 303; the carbon dioxide adsorbent and the metal oxide in the air reactor 302 are transferred to the carbonator 304 to capture carbon dioxide in the oxygen-depleted flue gas at the outlet of the first turbine 303;
a calciner 305 connected to the carbonation tower 304 and the air reactor 302; the product in the carbonation tower 304 is transferred to the calciner 305 for reduction to form a reduced product, which is returned to the air reactor 302.
In this embodiment, a coupling mode of calcium circulation and a chemical-looping air reactor is adopted, the first compressor 301 is utilized to pressurize the flue gas discharged from the first waste heat power generation unit 200 to form compressed air, the compressed air is then delivered into the air reactor 302, and the metal oxygen carrier in the air reactor 302 is utilized to react with oxygen in the compressed flue gas to form metal oxide and oxygen-depleted flue gas; the oxygen-deficient flue gas is conveyed to the first turbine 303 to do work, and the oxygen-deficient flue gas after doing work is conveyed to the carbonic acid flower tower to do CO 2 While the metal oxide and carbon dioxide adsorbent in the air reactor are fed into the carbonation tower to utilize the carbon dioxide adsorbent therein for the capture of CO in the oxygen-depleted flue gas 2 Capturing; and then the products (including metal oxide) in the carbonation tower are conveyed into the calciner 305, natural gas and the metal oxide are introduced to generate oxidation reaction heat release and waste heat released by the air reactor 302 are utilized to provide heat for the calcination reaction together, so as to obtain a carbon dioxide adsorbent and a metal oxygen carrier, and finally the carbon dioxide adsorbent and the metal oxygen carrier obtained by reduction are conveyed into the air reactor 302 to wait for the next circulation.
Specifically, the invention oxidizes the metal oxygen carrier in the air reactor by utilizing the tail flue gas of the natural gas to replace the air originally required and drive the combined cycle to do work, thereby not only solving the problem of flue gas preheating in the natural gas flue gas calcium loop trapping technology, but also fully utilizing the residual oxygen in the flue gas, improving the concentration of carbon dioxide in the flue gas entering the carbonator tower and reducing the trapping energy consumption. In addition, compared with the traditional oxygen-enriched combustion calcium circulation process, the method has the advantages that as the metal oxide is adopted to provide oxygen for fuel in the calciner, the air separation unit power consumption caused by directly separating oxygen from air is avoided; further, as a part of energy is used for driving the combined cycle, the traditional steam cycle is replaced, the heat exchange loss can be effectively reduced, and the work output of the trapping system is improved.
In some embodiments, the metal oxygen carrier comprises one or more of Fe, cu, co, mn, a composite metal oxygen carrier; and/or, the carbon dioxide adsorbent is calcium oxide. When the compressed flue gas enters the air reactor 302, the Me reacts with oxygen in the compressed flue gas to form metal oxide, and the main chemical reaction is that
CaO+CO 2 →CaCO 3 Thereby realizing the CO in the flue gas 2 Collecting to obtain decarbonized flue gas.
In some embodiments, the first compressor 301 pressurizes the flue gas discharged from the first cogeneration unit 200 to 1-15bar to form compressed flue gas; the compressed flue gas enters the air reactor 302 through a conduit.
In particular, the CO 2 In the separation unit 300, the metal oxygen carrier Me and the carbon dioxide adsorbent together serve as CO 2 Separating the circulating medium of the unit; the flue gas discharged from the first cogeneration unit 200 is pressurized to 1-15bar by the first compressor 301 and then enters the air reactor 302. In the air reactor 302, the compressed flue gas reacts with the metal oxygen carrier Me, and oxygen in the compressed flue gas is transferred to the metal oxygen carrier to generate metal oxide MeO; the oxygen-depleted flue gas then enters the first turbine 303 to perform workThe oxygen-depleted flue gas after doing work enters the carbonator 304 again; in the carbonation tower 304, the carbon dioxide adsorbent separates CO from the flue gas 2 And the resulting product is fed to the calciner 305 for regeneration to regenerate carbon dioxide adsorbent and CO-rich 2 And (3) gas.
In some embodiments, the reaction pressure in the air reactor is 1-15bar and the reaction temperature in the air reactor is 950-1100 ℃. The medium entering the air reactor 302 is calcium oxide and a metal oxygen carrier, wherein under this condition only the metal oxygen carrier Me participates in the reaction, and the main chemical reaction occurring is Me+O 2 →MeO。
In some embodiments, the reaction in the carbonation tower is carried out at atmospheric pressure, the reaction temperature in the carbonation tower being 600 to 650 ℃; the medium entering the carbonator column is calcium oxide and MeO, wherein only CaO participates in the reaction, and the main reaction is CaO+CO 2 →CaCO 3 。
In some embodiments, the reaction in the calciner is carried out at atmospheric pressure, the reaction temperature in the calciner being 900-950 ℃; the medium entering the calciner 305 is CaCO 3 And MeO, caCO in the calciner 3 And MeO participate in the reaction at the same time, and the main chemical reaction is CaCO 3 →CaO+CO 2 And CH (CH) 4 +MeO→Me+CO 2 +H 2 O。
Specifically, the oxygen required in the calciner is provided by MeO, i.e. MeO acts to transfer oxygen and reacts with fuel fed to the calciner to form CaCO in the calciner 3 Providing energy for the regeneration reaction of (a); the energy required by the calciner is obtained from fuel (natural gas CH 4 ) Combustion and the air reactor 302 release heat.
In some embodiments, the CO 2 The separation unit 300 needs to be timely supplemented with new carbon dioxide adsorbent and oxygen carrier in order to maintain the activities of the carbon dioxide adsorbent and the metal oxygen carrier, which is performed in the calciner; simultaneously removing excess metal oxygen carrier and carbon dioxide adsorbent from the reactorAnd (5) cleaning in the calciner.
In some embodiments, the gas power generation unit 100 includes:
a second compressor 101 for pressurizing air to form compressed air;
a combustion chamber 102 connected to the second compressor for mixing and combusting natural gas with the compressed air;
and the second turbine 103 is connected with the combustion chamber, and the flue gas discharged from the combustion chamber is used for driving the second turbine to do work.
Specifically, in the gas power generation unit 100, natural gas enters the combustion chamber 102 and is mixed with compressed air pressurized by the second compressor 101, and is combusted in the combustion chamber 102; the high-temperature and high-pressure flue gas discharged from the combustion chamber 102 drives the second turbine 103 to do work, and the high-temperature and high-pressure flue gas in the outlet of the second turbine 103 continuously enters the first waste heat power generation unit 200.
In some embodiments, the first cogeneration unit 200 includes: a first waste heat boiler 201, a third turbine 202, a first condenser 203 and a first pump 204;
the first waste heat boiler 201 is connected with the second turbine 103; the first waste heat boiler 201 is in closed loop connection with the third turbine 202, the first condenser 203 and the first pump 204; the flue gas discharged from the first exhaust-heat boiler 201 enters the first compressor 301.
Specifically, in the first cogeneration unit 200, the flue gas discharged from the second turbine 103 enters the first exhaust-heat boiler 201, heats the water in the first exhaust-heat boiler, heats the water into steam, enters the third turbine 202 to apply work, the low-temperature steam at the outlet of the third turbine 202 enters the first condenser 203 to condense into water, is pressurized, and is sent back to the first exhaust-heat boiler 201 through the first pump 204 to absorb heat, so as to start the next cycle.
In some embodiments, the high pressure chemical chain coupled calcium cycle carbon dioxide capture system further comprises a second cogeneration unit 400; the second cogeneration unit 400 includes: a second waste heat boiler 401, a fourth turbine 402, a second condenser 403 and a second pump 404;
the second waste heat boiler 401 is connected to the carbonator column 304 and the calciner 305; the second waste heat boiler 401 is in closed loop connection with the fourth turbine 402, the second condenser 403 and the second pump 404; the second waste heat boiler 401 discharges decarburized flue gas and is rich in CO 2 And (3) gas.
In particular, the calciner generates CO-rich 2 The gas, the decarbonized flue gas generated by the carbonating tower and the waste heat released by the carbonating tower are sent into the second waste heat boiler 401, water in the second waste heat boiler is heated, the heated water enters the fourth turbine 402 to do work after being heated into steam, low-temperature steam at the outlet of the fourth turbine 402 enters the second condenser 403 to be condensed into water, and then the water is pressurized and then sent back to the second waste heat boiler 401 through the second pump 404 to absorb heat, and the next cycle is started; while the decarbonized flue gas, the heat of which is absorbed by the second waste heat boiler 401, is discharged into the atmosphere, and is rich in CO 2 The gas can be pressurized and then sent to underground sealing and can also be used as raw materials for producing other products.
In some embodiments, the first turbine 303 is a gas turbine; the second turbine 103 is a gas turbine; the third turbine 202 is a steam turbine; the fourth turbine 404 is a steam turbine.
In addition, the invention also provides application of the high-pressure chemical chain coupled calcium circulating carbon dioxide trapping system in natural gas power plant tail gas trapping.
In the embodiment, the high-pressure chemical chain coupled calcium circulating carbon dioxide capturing system is applied to the tail gas capturing of a natural gas power plant, so that heat exchange loss can be reduced, the work output of the capturing system is improved, and the energy consumption required for capturing carbon dioxide is reduced.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
The embodiment provides an application of a high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system in natural gas power plant tail gas trapping, a process flow chart of which is shown in figure 2, wherein the high-pressure chemical chain coupling calcium circulating carbon dioxide trapping system comprises a gas power generation unit, a waste heat power generation unit and CO 2 A separation unit; the gas power generation unit comprises a gas compressor, a combustion chamber and a gas turbine; the waste heat power generation unit comprises a waste heat boiler, a steam turbine, a condenser and a pump; CO 2 The separation unit comprises a gas compressor, an air reactor, a gas turbine, a carbonator tower and a calciner.
In the gas power generation unit, natural gas enters a combustion chamber and is mixed with air pressurized by a gas compressor, and the natural gas is combusted in the combustion chamber. The high-temperature and high-pressure flue gas at the outlet of the combustion chamber drives the gas turbine to do work, and the high-temperature flue gas in the outlet of the gas turbine continuously enters the waste heat boiler to heat the water supply to generate steam to drive the turbine to do work. In the waste heat power generation unit, flue gas at the outlet of the gas turbine enters the waste heat boiler to heat water, the water is heated into steam and then enters the turbine to do work, low-temperature steam at the outlet of the turbine enters the condenser to be condensed into water, and then the water is pressurized and then is sent back to the waste heat boiler to absorb heat, and the next cycle is started. CO 2 In the separation unit, the metal oxygen carrier Me and the carbon dioxide adsorbent CaO are used together as a circulating medium of the separation unit. The trapped flue gas is first pressurized to 1-15bar by a compressor and then enters an air reactor. In the air reactor, the pressurized flue gas reacts with a metal oxygen carrier Me, and oxygen in the flue gas is transferred to the metal oxygen carrier to generate metal oxide MeO. And then, the oxygen-deficient flue gas enters a turbine to do work, and the oxygen-deficient flue gas after doing work enters a carbonator. In the carbonator, the CaO separates CO from the flue gas 2 CaO and CO 2 Reacting to generate CaCO 3 . Generated CaCO 3 Then is sent into a calciner for regeneration to generate CaO and rich CO 2 And (3) gas. Decarbonizing flue gas and heat obtained by carbonating tower and CO-rich generated by calciner 2 The gas enters the waste heat boiler together to heat the water supplyThe steam is heated to steam and then enters a turbine to do work, low-temperature steam at the outlet of the turbine enters a condenser to be condensed into water, then the water is pressurized and then is sent back to the waste heat boiler to absorb heat, the next cycle is started, and decarbonized flue gas with heat absorbed by the waste heat boiler is discharged into the atmosphere and is rich in CO 2 The gas is pressurized and then sent to underground sealing.
Comparative example 1
The comparative example provides a natural gas calcium loop oxygen-enriched combustion trapping system, the process flow chart of which is shown in figure 3, comprising a gas power generation unit, a waste heat boiler power generation unit and CO 2 And a separation unit. In comparison with example 1, comparative example 1 uses an air separation unit to provide pure oxygen to the calciner, without an air reactor. And meanwhile, the flue gas of the power plant is heated by the material flow at the outlet of the carbonating tower and then is sent into the carbonating tower for decarburization, and the rest processes are similar.
Comparative example 2
The comparative example provides a non-trapped natural gas combined cycle power generation system, the process flow diagram of which is shown in fig. 4, comprising a gas power generation unit and a waste heat boiler power generation unit. After the combustion of the fuel gas and the air, the flue gas drives the fuel gas turbine to do work, and after the work is done, the flue gas releases heat in the waste heat boiler to heat water, so that steam is generated to drive the turbine to do work, and the low-temperature flue gas is directly discharged to amplify the air.
In example 1 and comparative examples 1-2, the gas turbine model had PG9171E, a gas turbine pressure ratio of 11.8, a natural gas input mass flow of 7.4kg/s, an air input mass flow of 403.7kg/s, a compressor pressure ratio of 11.8, and a gas turbine inlet temperature of 1100deg.C; the waste heat boiler power generation unit is of double pressure, the high pressure is 61bar, the low pressure is 6bar, and the main steam temperature is 527 ℃. The operating conditions for the carbonation reaction were: the temperature is 650 ℃, and the pressure is normal pressure; the operating conditions of the calcination reaction are: the temperature is 900 ℃ and the pressure is normal pressure; the operating conditions of the air reactor were: the temperature was 950℃and the pressure 7bar. CO in flue gas 2 The concentration is 3-5%, CO 2 The trapping rate is 90%, and the volume fractions of the components in the input natural gas are as follows: CH (CH) 4 -79.75％，C 2 H 6 -9.68％，C 3 H 8 -4.45％，C 4 H 10 -2.37％，CO 2 -2.92％，N 2 -0.83% lower heating value 49.44MJ/kg.
The performance of the systems of example 1 and comparative examples 1-2 were counted and the data are shown in Table 1:
table 1 comparison of system performance data for example 1 and comparative examples 1-2
* Energy efficiency= (power output-power input)/natural gas input
The results show that the high-pressure chemical-looping coupled calcium-cycling carbon dioxide capture system of example 1 is greatly improved compared with the natural gas calcium-looping oxygen-enriched combustion capture system of comparative example 2. In the system provided in example 1, the air reactor outlet gas was used to drive combined cycle work, increasing the gas unit output compared to the system of comparative example 1. And because of avoiding the space separation unit, the space separation power consumption is saved, and compared with an oxygen-enriched combustion system, the output of the steam power generation unit is increased. The efficiency penalty of example 1 was reduced from 9.1 percent for comparative example 1 to 5.2 percent. Therefore, the high-pressure chemical-looping coupled calcium-cycling carbon dioxide capturing system provided in the embodiment 1 can provide an efficient CO for the flue gas capturing of the natural gas power plant 2 Trapping scheme.
In summary, the high-pressure chemical chain coupled calcium cycle carbon dioxide capturing system and the application thereof provided by the invention comprise: the gas power generation unit, the first waste heat power generation unit for generating power by utilizing the flue gas exhausted by the gas power generation unit, and the method for performing CO on the flue gas exhausted by the first waste heat power generation unit 2 Separated CO 2 A separation unit; the CO 2 The separation unit includes: the first compressor is used for pressurizing the flue gas exhausted by the first waste heat power generation unit to form compressed flue gas; the air reactor is connected with the first air compressor and is used for capturing oxygen in the compressed flue gas to form metal oxides; the air isThe reactor is filled with a metal oxygen carrier and a carbon dioxide adsorbent; the first turbine is connected with the air reactor and is used for doing work on the oxygen-deficient flue gas exhausted by the air reactor; a carbonation tower coupled to the air reactor and the first turbine; carbon dioxide adsorbent and the metal oxide in the air reactor are transferred to the carbonation tower, and oxygen-deficient flue gas which is acted by the first turbine enters the carbonation tower; a calciner connected to the carbonation tower and the air reactor; the product in the carbonation tower is transferred to the calciner for reduction to form a reduced product, which is returned to the air reactor. The invention adopts a coupling mode of calcium circulation and a chemical-looping air reactor, utilizes the high-concentration flue gas in the tail flue gas of the natural gas to oxidize the metal oxygen carrier in the air reactor, provides an oxygen source for a calciner, replaces the air originally required and drives the combined circulation to do work, not only can solve the problem of flue gas preheating in the natural gas flue gas calcium circulation trapping technology, but also can fully utilize the residual oxygen in the flue gas and improve the CO in the flue gas entering the carbonator 2 Concentration, reduce and trap the energy consumption; meanwhile, the power consumption of the space division unit is avoided. And because a part of energy is used for driving the combined cycle, the traditional steam cycle is replaced, the heat exchange loss can be effectively reduced, and the work output of the trapping system is improved.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A high pressure chemical looping coupled calcium cycling carbon dioxide capture system, comprising: the gas power generation unit, the first waste heat power generation unit for generating power by utilizing the flue gas exhausted by the gas power generation unit, and the method for performing CO on the flue gas exhausted by the first waste heat power generation unit 2 Separated CO 2 A separation unit;
the CO 2 The separation unit includes:
the first compressor is used for pressurizing the flue gas exhausted by the first waste heat power generation unit to form compressed flue gas;
the air reactor is connected with the first air compressor and is used for transmitting oxygen in the compressed flue gas to a metal oxygen carrier to form metal oxide; the air reactor is filled with a metal oxygen carrier and a carbon dioxide adsorbent;
the first turbine is connected with the air reactor, and oxygen-deficient flue gas at the outlet of the air reactor is used for driving the first turbine to do work;
a carbonation tower coupled to the air reactor and the first turbine; transferring the carbon dioxide adsorbent and the metal oxide in the air reactor into the carbonator to capture carbon dioxide in the oxygen-depleted flue gas at the outlet of the first turbine;
a calciner connected to the carbonation tower and the air reactor; the product in the carbonation tower is transferred to the calciner for reduction to form a reduced product, which is returned to the air reactor.
2. The high pressure chemical looping coupled calcium cycling carbon dioxide capturing system according to claim 1, wherein the metal oxygen carrier comprises one or more of Fe, cu, co, mn, composite metal oxygen carrier; and/or, the carbon dioxide adsorbent is calcium oxide.
3. The high pressure chemical looping coupled calcium cycling carbon dioxide capturing system according to claim 1, wherein the first compressor pressurizes the flue gas exhausted from the first waste heat power generation unit to 1-15bar to form compressed flue gas; the compressed flue gas enters the air reactor through a pipeline.
4. The high pressure chemical looping coupled calcium looping carbon dioxide capture system according to claim 1, wherein the reaction pressure in said air reactor is 1-15bar and the reaction temperature in said air reactor is 950-1100 ℃.
5. The high pressure chemical looping coupled calcium looping carbon dioxide capture system according to claim 1, wherein a reaction temperature in the carbonation tower is 600 ℃ to 650 ℃.
6. The high pressure chemical looping coupled calcium looping carbon dioxide capture system according to claim 1, wherein the reaction temperature in the calciner is 900-950 ℃.
7. The high pressure chemical looping coupled calcium cycling carbon dioxide capturing system according to claim 1, wherein the gas power generation unit comprises:
the second compressor is used for pressurizing air to form compressed air;
the combustion chamber is connected with the second air compressor and is used for mixing and combusting natural gas and the compressed air;
and the second turbine is connected with the combustion chamber, and the flue gas at the outlet of the combustion chamber is used for driving the second turbine to do work.
8. The high pressure chemical looping coupled calcium looping carbon dioxide capture system according to claim 7, wherein said first cogeneration unit comprises: the system comprises a first waste heat boiler, a third turbine, a first condenser and a first pump;
the first waste heat boiler is connected with the second turbine; the first waste heat boiler is connected with the third turbine, the first condenser and the first pump in a closed loop manner; and the flue gas exhausted by the first waste heat boiler enters the first air compressor.
9. The high pressure chemical looping coupled calcium cycling carbon dioxide capturing system according to claim 1, further comprising a second waste heat power generation unit; the second waste heat power generation unit includes: the second waste heat boiler, the fourth turbine, the second condenser and the second pump;
the second waste heat boiler is connected with the carbonator tower and the calciner; the second waste heat boiler is connected with the fourth turbine, the second condenser and the second pump in a closed loop manner; the second waste heat boiler discharges decarburization flue gas and is rich in CO 2 And (3) gas.
10. Use of a high pressure chemical looping coupled calcium cycling carbon dioxide capture system according to any of claims 1-9 in natural gas power plant tail gas capture.
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