CN104162341A - Device and method for removing CO2 from smoke by using solid amine adsorbent - Google Patents
Device and method for removing CO2 from smoke by using solid amine adsorbent Download PDFInfo
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- CN104162341A CN104162341A CN201410400478.3A CN201410400478A CN104162341A CN 104162341 A CN104162341 A CN 104162341A CN 201410400478 A CN201410400478 A CN 201410400478A CN 104162341 A CN104162341 A CN 104162341A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
The invention belongs to the technical field of CO2 removal, and in particular relates to a device and a method for removing CO2 from smoke by using a solid amine adsorbent. The device consists of a reactor, a material discharging valve, a heating machine, a cooling machine, a material supplying machine, a lifting pipe, a roots fan, a pressurization fan, a circulating fan, an induced draft fan, gas-solid separation equipment and a heat exchanger. According to the method, the smoke containing CO2 is introduced into the reactor, so that the CO2 gas is in full contact with the adsorbent from top to bottom; the decarburized smoke is discharged through the gas-solid separation equipment and induced draft fan; the adsorbent enters the heating machine for heating regeneration to obtain the CO2 gas and the desorbed adsorbent; the desorbed adsorbent is introduced into the cooling machine for cooling to obtain the adsorbent with a proper temperature; and the cooled solid adsorbent is reintroduced into the reactor. The device is high in adaptability to source gas, and a system is high in running stability; the energy utilization efficiency in a regeneration process can be improved, the heat loss is reduced, and an optimized scheme for realizing relatively low investment and relatively low energy consumption is achieved.
Description
Technical field
The invention belongs to and belong to CO
2remove technical field, particularly a kind of solid amine absorption agent removes CO in flue gas
2device and method.
Background technology
A large amount of uses of fossil fuel and the greenhouse gas emissions that cause increase day by day, have caused many climate disasters to the whole world.The current CO of China
2discharge capacity occupies second place of the world, and still at rapid growth, and China must become the focus of the whole world in honouring an agreement, and the international pressure bearing can be increasing.Current industrial sour gas remove the solution absorption methods such as main employing MEA, MEDA, NHD and low-temperature rectisol, but maximum problem is to need heating water to overcome sensible heat and the latent heat of vaporization of water in the regenerative process of these solution, energy consumption is huge.This makes CO
2separation costs is too high, in the future, even along with technological improvement, can further reduce CO
2separation costs, but potentiality and space are very limited.For such developing country of China, must adopt the CO that is applicable to China's national situation
2isolation technics route.Existing CO
2no matter isolation technics, be before burning, after burning, or O
2/ CO
2burning, all can make electricity generation system performance relatively decline more than 1/4 (～10%), means that technical merit fell back nearly half a century, also can seriously aggravate the consumption of fossil energy simultaneously.
For overcoming above shortcoming, liquid organic amine is flooded by physics in consideration or chemical grafting loads on porous media carrier, thereby is prepared into amine solid adsorbent (referred to as solid amine).The specific heat capacity of the solid carrier that adopts is less than liquid specific heat of water, has reduced the sensible heat power consumption of regenerative process adsorbent.In addition, solid amine regenerative process has been avoided the latent heat of vaporization of liquid water, thereby can significantly reduce regeneration energy consumption.And solid amine can be avoided the corrosion to equipment.From economic considerations, when the effective absorptive capacity of solid absorbent reaches 2mol-CO
2when/kg, energy consumption is lower than MEA solwution method; Reach 3mol-CO
2when/kg is above, comparable existing MEA solwution method is saved more than 50% energy consumption.
The research origin of amine solid absorbent is CO in the closed in space such as submarine, space station
2remove, some scholars started amine solid absorbent to be incorporated into CO in flue gas and natural gas in recent years
2separation.As patent CN 101804332A, relate to one and utilize gangue for development of raw materials amine solid absorbent is for catching CO
2; Patent CN 101500704A, relates to and is deposited on for example amine on silica of nano-structured carrier or the support type absorbent of amine/glycol composition.And at solid amine separation of C O
2technical matters aspect, patent US2012160098A1, relates to and utilizes two static bed solid amine systems to remove the CO in closed in space
2, two beds carry out respectively " absorption-desorption " and " desorb-absorption " process, and bed temperature switches between adsorption temp (10～65 DEG C) and desorption temperature (55～80 DEG C), and desorption process adopts vavuum pump to reduce CO
2dividing potential drop improves bed temperature to realize solid amine regeneration simultaneously; Patent WO2011013332A1 relates to and utilizes two filling tank systems that contain solid amine absorption material to carry out CO
2absorption and desorption process, and utilize amine retracting device, support means and avoid again the decline of sorbing material performance, solid amine is inactive state in filling groove, the gas passing into by switching completes absorption and desorption process, adsorption process passes into containing CO
2processing gas, after having adsorbed, pass into heated air stream and complete and remove, pass into again afterwards cooling blast, adsorb.Aspect the paper of having published, absorption and regeneration course of reaction is all to adopt double-fluidized-bed reactor assembly substantially, realize Matter Transfer as U.S. ADAEnvironmental Solutions adopts double-fluidized-bed system, absorption reactor thermally reactor is fast fluidized bed (Pilot test results of post-combustion CO
2capture using solid sorbents) or multilayer bubbling bed reactor (Post-Combustion CO
2capture using solid sorbents:1MWe pilot evaluation) etc.Thermal Power Engineering system of Tsing-Hua University had also carried out correlative study for this technology in recent years, and patent CN201110138501.2 and CN201210042863.6 relate to double-fluidized-bed system and realize flue gas or synthesis gas CO
2remove.And adopt solid amine to carry out CO to low temperature (0～80 DEG C) source of the gas (conventionally containing a certain amount of steam)
2remove, adopt double-fluidized-bed system in process of the test, to find to have some problems: 1) solid amine can absorb the steam in source of the gas, become wet and be bonded to piece and cannot fluidisation; 2) fluctuation of source gas flow can cause the unstability of Matter Transfer; 3) regenerative process fluidized gas cognition is taken away a large amount of sensible heats, causes the waste of energy.In order effectively to avoid steam in source of the gas and the impact of flowed fluctuation, reduce the waste of regenerative process energy simultaneously, thereby be more suitable for that industry is amplified and application from now on, the choose reasonable of absorption and regeneration type of reactor is very important.
Summary of the invention
For prior art deficiency, the invention provides a kind of solid amine absorption agent and remove CO in flue gas
2device and method, apparatus of the present invention to source gas have good adaptability, system has good operation stability, can improve regenerative process energy utilization efficiency, reduce thermal loss, be investment and the lower a kind of prioritization scheme of energy consumption.
A kind of solid amine absorption agent removes CO in flue gas
2device, described device is made up of reactor, discharge valve, heater, cooler, batcher, riser, roots blower, booster fan, circulating fan, air-introduced machine, gas-solid separation equipment, heat exchanger; Wherein, the bottom of reactor is connected with the charging aperture of heater by the first discharge valve, and the discharging opening of heater is connected with the charging aperture of cooler by the second discharge valve, and the discharging opening of cooler is connected with the charging aperture of batcher; The discharging opening of batcher connects gas transmission pipeline, and gas transmission pipeline communicates with the bottom of riser, and the discharging opening of riser is positioned at reactor internal upper part center; The top of reactor is connected with gas-solid separation equipment, and gas-solid separation equipment is connected with air-introduced machine; Booster fan is connected with the bottom of reactor; Heater is connected with the first circulating fan, forms closed circuit, and keeping regeneration atmosphere is CO
2; Cooler is connected with the second circulating fan, forms closed circuit, realizes cooling under atmosphere of inert gases or under air atmosphere; Roots blower communicates with gas transmission pipeline; Heat exchanger is connected with reactor.
Described the first discharge valve and the second discharge valve are respectively two-stage discharge valve.
Described reactor is gas-solid adverse current descending-bed reactor; Described heater is hollow pair of blade heater; Described cooler is hollow pair of blade cooler; Described batcher is screw(-type) feeder.
Solid amine absorption agent is removed CO in flue gas by one
2method, its concrete steps are as follows:
A, will contain CO
2flue gas introduce reactor, make the CO in flue gas
2gas fully contacts with top-down solid amine absorption agent particle, CO
2gas is adsorbed by solid amine absorption agent particle, and the flue gas after decarburization is discharged through gas-solid separation equipment and air-introduced machine, and solid amine absorption agent particle enters heater by the first discharge valve;
B, will absorb CO
2solid amine absorption agent particle introduce in heater, carry out thermal regeneration processing, obtain CO
2the solid amine absorption agent particle of gas and desorb;
C, by the solid amine absorption agent particle of the desorb of gained by second discharge valve introduce cooler, processings that cool, acquisition proper temperature solid amine absorption agent particle;
D, by cooled solid amine absorption agent particle through batcher, the gas being produced by roots blower is incorporated in reactor again by riser.
Described reactor is gas-solid adverse current descending-bed reactor, and solid material flows from top to bottom, and gas flows from bottom to up, the CO in gas-solid counter-current process in the adsorbed gas of solid amine particle
2.
Described heater is hollow pair of blade heater, and blade, axle and the inner surface of blade are heat-transfer surface, and solid contacts by heat conducting form and carries out heat exchange with heat-transfer surface, realizes intensification and the regeneration of particle.
Described cooler is hollow pair of blade cooler, the solid amine absorption agent particle after regeneration cool process heat exchange mode be hot conductive form.
Described gas-solid adverse current down-flow fluidized bed using ECT absorption reactor thermally removes by heat exchanger the heat that reaction discharges, the temperature of reactor maintains 0～80 DEG C, pressure is 0.5atm～20atm, the temperature of heater is 80 DEG C～300 DEG C, pressure is 0～20atm, the temperature of cooler is 0～50 DEG C, and pressure is 0.5atm～20atm.
The heat medium of described heater is conduction oil, steam or hot water.
The cooling medium of described cooler is cooling water.
Described reactor outlet gas is realized gas solid separation through gas-solid separation equipment, and the gas after separation enters atmosphere by air-introduced machine after cleaner further purifies.
Described cleaner is sack cleaner.
Described the first discharge valve and the second discharge valve are respectively two-stage discharge valve, between each self-corresponding two valves of the first discharge valve and the second discharge valve, there is respectively straight-run of pipe section, in running, can fill respectively solid amine absorption agent particle, to realize the sealing of gas.
Solid circulating rate regulates by batcher.
Described solid amine absorption agent particle is the solid particle that contains amido functional group (can flood or chemical grafting preparation obtains by physics), or the sorbing material that contains amido functional group.
The described solid particle that contains amido functional group is made up of organic amine and porous solid carrier, and wherein organic amine is attracted in the hole of porous solid carrier; Organic amine account for the solid particle that contains amido functional group gross mass 10%～80%.
Described porous solid carrier is one or more in silica gel, zeolite molecular sieve, active carbon, resin, aluminium oxide and metal organic frame.
Described organic amine is one or more in MEA, diethanol amine, methyl diethanolamine, TEPA and polymine.
The described sorbing material that contains amido functional group is amido ion exchange resin.
Beneficial effect of the present invention is:
Solid amine of the present invention carrier used has less specific heat capacity, required heat can significantly reduce adsorbent and be increased to regeneration temperature by adsorption temp time; The carrier of solid amine is solid, in regenerative process, has avoided the heat loss of being brought by evaporation of water in traditional liquid amine technique; Solid amine is nutty structure, for absorption reactor thermally and regeneration reactor, does not have the etching problem in traditional liquid amine technique.Processes and apparatus global design of the present invention is simple compact, investment and operating cost is cheap, stable and reliable operation, can adapt to fluctuation and the humidity of incoming flow gas, improving regenerative process energy utilization efficiency, reduce thermal loss, is investment and the lower a kind of prioritization scheme of energy consumption.
Brief description of the drawings
Fig. 1 is that solid amine absorption agent of the present invention removes CO in flue gas
2apparatus structure schematic diagram;
Number in the figure: 1-reactor, 2-a-the first discharge valve, 2-b-the second discharge valve, 3-heater, 4-cooler, 5-batcher, 6-riser, 7-roots blower, 8-booster fan, 9-a-the first circulating fan, 9-b-the second circulating fan, 10-air-introduced machine, 11-gas-solid separation equipment, 12-heat exchanger; The pending flue gas of A-, B-remove CO
2after flue gas, conduction oil, the D-that C-returns to heat-conducting oil furnace draw conduction oil, the E-CO from heat-conducting oil furnace
2source of the gas body, F-separate the CO obtaining
2water on gas, G-inert gas or air, H-cooling water backwater, K-cooling water.
Detailed description of the invention
The invention provides a kind of solid amine absorption agent and remove CO in flue gas
2device and method, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
A kind of solid amine absorption agent removes CO in flue gas
2device, described device is made up of reactor 1, discharge valve 2-a and 2-b, heater 3, cooler 4, batcher 5, riser 6, roots blower 7, booster fan 8, circulating fan 9-a and 9-b, air-introduced machine 10, gas-solid separation equipment 11, heat exchanger 12; Wherein, the bottom of reactor 1 is connected with the charging aperture of heater 3 by the first discharge valve 2-a, and the discharging opening of heater 3 is connected with the charging aperture of cooler 4 by the second discharge valve 2-b, and the discharging opening of cooler 4 is connected with the charging aperture of batcher 5; The discharging opening of batcher 5 connects gas transmission pipeline, and gas transmission pipeline communicates with the bottom of riser 6, and the discharging opening of riser 6 is positioned at reactor 1 internal upper part center; The top of reactor 1 is connected with gas-solid separation equipment 11, and gas-solid separation equipment 11 is connected with air-introduced machine 10; Booster fan 8 is connected with the bottom of reactor 1; Heater 3 is connected with the first circulating fan 9-a, forms closed circuit, and keeping regeneration atmosphere is CO
2; Cooler 4 is connected with the second circulating fan 9-b, forms closed circuit, realizes cooling under atmosphere of inert gases or under air atmosphere; Roots blower 7 communicates with gas transmission pipeline; Heat exchanger 12 is connected with reactor 1.
Described the first discharge valve 2-a and the second discharge valve 2-b are respectively two-stage discharge valve.
Described reactor 1 is gas-solid adverse current descending-bed reactor; Described heater 3 is hollow pair of blade heater; Described cooler 4 is hollow pair of blade cooler; Described batcher 5 is screw(-type) feeder.
Embodiment 1
A kind of solid amine absorption agent removes CO in flue gas
2apparatus and method, carry out in accordance with the following steps:
First the flue gas after desulphurization denitration is introduced in gas-solid adverse current descending-bed reactor 1 through booster fan 8, and gas radially flows equably from bottom to top through a conical distributor, with the solid amine absorption agent particle haptoreaction falling from top to bottom, CO
2constantly adsorbed by solid amine absorption agent particle along journey, remove reaction liberated heat by heat exchanger 12, make temperature of reactor maintain 30 DEG C of left and right; By controlling the height of solid circulating rate and gas-solid adverse current descending-bed reactor 1, make flue gas at gas-solid adverse current descending-bed reactor 1 CO of top exit place
2removal efficiency reaches more than 99%, removes CO
2flue gas drawn discharge through cyclone separator 11 by air-introduced machine 10; CO absorption
2after solid amine particle introduce in hollow pair of blade heater 3 at gas-solid adverse current descending-bed reactor 1 bottom the first star discharge valve 2-a, between two star discharge valves of chess, keep certain material high to prevent gas blowby, hollow pair of blade heater 3 passes into the conduction oil of 180 DEG C, solid amine absorption agent particle is heated to 140 DEG C of effects by heat-transfer surface, discharges the CO of absorption
2, the CO of desorb
2drawn and carry out subsequent recovery processing by the first circulating fan 9-a; Solid amine absorption agent particle after regeneration is introduced hollow pair of blade cooler 4 through the second star discharge valve 2-b, cooling medium is that temperature is the cooling water of 5 DEG C of left and right, by adjusting the time of staying of blade rotating speed control solid amine absorption agent particle in blade, ensure that the temperature of outlet solid amine absorption agent particle is below 30 DEG C; Cooled solid amine absorption agent particle enters screw(-type) feeder 5, by adjusting the solid circulating rate that screw(-type) feeder 5 rotating speeds can control system, the wind that solid amine absorption agent particle is produced by roots blower 7 out from screw(-type) feeder 5 is transported to gas-solid adverse current descending-bed reactor 1 top by riser 6, material is by dispersed opening of conical distributor, fall from top to bottom along down-flow fluidized bed using ECT, so realize operation continuously.
The solid amine absorption agent particle that the present embodiment adopts comprises organic amine and porous solid carrier, and organic amine is attracted in the hole of porous solid carrier, works as CO
2when gas molecule diffuses into the duct of porous solid carrier, adsorbed and react by amine molecule therebetween.Porous solid carrier is unordered mesoporous silica gel, and organic amine is polymine (PEI).In solid amine absorption agent particle, organic amine accounts for 50% of solid amine absorption agent particle gross mass.
Claims (19)
1. a solid amine absorption agent removes CO in flue gas
2device, it is characterized in that: described device is by reactor (1), discharge valve (2-a, 2-b), heater (3), cooler (4), batcher (5), riser (6), roots blower (7), booster fan (8), circulating fan (9-a, 9-b), air-introduced machine (10), gas-solid separation equipment (11), heat exchanger (12) composition; Wherein, the bottom of reactor (1) is connected with the charging aperture of heater (3) by the first discharge valve (2-a), the discharging opening of heater (3) is connected with the charging aperture of cooler (4) by the second discharge valve (2-b), and the discharging opening of cooler (4) is connected with the charging aperture of batcher (5); The discharging opening of batcher (5) connects gas transmission pipeline, and gas transmission pipeline communicates with the bottom of riser (6), and the discharging opening of riser (6) is positioned at reactor (1) internal upper part center; The top of reactor (1) is connected with gas-solid separation equipment (11), and gas-solid separation equipment (11) is connected with air-introduced machine (10); Booster fan (8) is connected with the bottom of reactor (1); Heater (3) is connected with the first circulating fan (9-a), forms closed circuit, and keeping regeneration atmosphere is CO
2; Cooler (4) is connected with the second circulating fan (9-b), forms closed circuit, realizes cooling under atmosphere of inert gases or under air atmosphere; Roots blower (7) communicates with gas transmission pipeline; Heat exchanger (12) is connected with reactor (1).
2. a kind of solid amine absorption agent according to claim 1 removes CO in flue gas
2device, it is characterized in that: described the first discharge valve (2-a) and the second discharge valve (2-b) are respectively two-stage discharge valve.
3. a kind of solid amine absorption agent according to claim 1 removes CO in flue gas
2device, it is characterized in that: described reactor (1) is gas-solid adverse current descending-bed reactor; Described heater (3) is hollow pair of blade heater; Described cooler (4) is hollow pair of blade cooler; Described batcher (5) is screw(-type) feeder.
4. one kind is utilized the device described in claim 1 that solid amine absorption agent is removed to CO in flue gas
2method, it is characterized in that, concrete steps are as follows:
A, will contain CO
2flue gas introduce reactor (1), make the CO in flue gas
2gas fully contacts with top-down solid amine absorption agent particle, CO
2gas is adsorbed by solid amine absorption agent particle, flue gas after decarburization is discharged through gas-solid separation equipment (11) and air-introduced machine (10), and solid amine absorption agent particle enters heater (3) by the first discharge valve (2-a);
B, will absorb CO
2solid amine absorption agent particle introduce in heater (3), carry out thermal regeneration processing, obtain CO
2the solid amine absorption agent particle of gas and desorb;
C, by the solid amine absorption agent particle of the desorb of gained by the second discharge valve (2-b) introduce cooler (4), processings that cool, acquisition proper temperature solid amine absorption agent particle;
D, by cooled solid amine absorption agent particle through batcher (5), the gas being produced by roots blower (7) is incorporated in reactor (1) again by riser.
5. method according to claim 4, is characterized in that: described reactor (1) is gas-solid adverse current descending-bed reactor, and solid material flows from top to bottom, and gas flows from bottom to up, the CO in gas-solid counter-current process in the adsorbed gas of solid amine particle
2.
6. method according to claim 4, it is characterized in that: described heater (3) is hollow pair of blade heater, blade, axle and the inner surface of blade are heat-transfer surface, and solid contacts by heat conducting form and carries out heat exchange with heat-transfer surface, realize intensification and the regeneration of particle.
7. method according to claim 4, is characterized in that: described cooler (4) is hollow pair of blade cooler, the solid amine absorption agent particle after regeneration cool process heat exchange mode be hot conductive form.
8. method according to claim 4, it is characterized in that: described gas-solid adverse current down-flow fluidized bed using ECT absorption reactor thermally (1) removes by heat exchanger (12) heat that reaction discharges, the temperature of reactor (1) maintains 0～80 DEG C, pressure is 0.5atm～20atm, the temperature of heater (3) is 80 DEG C～300 DEG C, pressure is 0～20atm, and the temperature of cooler (4) is 0～50 DEG C, and pressure is 0.5atm～20atm.
9. method according to claim 4, is characterized in that: the heat medium of described heater (3) is conduction oil, steam or hot water.
10. method according to claim 4, is characterized in that: the cooling medium of described cooler (4) is cooling water.
11. methods according to claim 4, it is characterized in that: described reactor (1) exit gas is realized gas solid separation through gas-solid separation equipment (11), the gas after separation enters atmosphere by air-introduced machine (10) after cleaner further purifies.
12. methods according to claim 11, is characterized in that: described cleaner is sack cleaner.
13. methods according to claim 4, it is characterized in that: described the first discharge valve (2-a) is respectively two-stage discharge valve with the second discharge valve (2-b), between each self-corresponding two valves of the first discharge valve (2-a) and the second discharge valve (2-b), there is respectively straight-run of pipe section, in running, can fill respectively solid amine absorption agent particle, to realize the sealing of gas.
14. methods according to claim 4, is characterized in that: solid circulating rate regulates by batcher (5).
15. methods according to claim 4, is characterized in that: described solid amine absorption agent particle is the solid particle that contains amido functional group, or the sorbing material that contains amido functional group.
16. methods according to claim 15, is characterized in that: described in contain amido functional group solid particle formed by organic amine and porous solid carrier, wherein organic amine is attracted in the hole of porous solid carrier; Organic amine account for the solid particle that contains amido functional group gross mass 10%～80%.
17. methods according to claim 16, is characterized in that: described porous solid carrier is one or more in silica gel, zeolite molecular sieve, active carbon, resin, aluminium oxide and metal organic frame.
18. methods according to claim 16, is characterized in that: described organic amine is one or more in MEA, diethanol amine, methyl diethanolamine, TEPA and polymine.
19. methods according to claim 15, is characterized in that: described in contain amido functional group sorbing material be amido ion exchange resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410400478.3A CN104162341A (en) | 2014-08-14 | 2014-08-14 | Device and method for removing CO2 from smoke by using solid amine adsorbent |
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|---|---|---|---|
| CN201410400478.3A CN104162341A (en) | 2014-08-14 | 2014-08-14 | Device and method for removing CO2 from smoke by using solid amine adsorbent |
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| CN104826610A (en) * | 2015-04-02 | 2015-08-12 | 华南理工大学 | Metallic organic skeletal material PEI@UiO-66, preparation method thereof, and application thereof in adsorptive separation of CO2 |
| CN106824094A (en) * | 2017-02-28 | 2017-06-13 | 南京师范大学 | One kind is using modified gangue removing power-plant flue gas CO2System and its implementation |
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| CN107485960A (en) * | 2016-06-13 | 2017-12-19 | 中国石油化工股份有限公司 | CO in a kind of amine solid adsorbent removing flue gas2Device and removal methods |
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| CN116688714A (en) * | 2023-06-07 | 2023-09-05 | 贵州绿色产业技术研究院 | System and method for continuous capture of solid amine carbon |
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