CN105032113B - Process for capturing carbon dioxide in flue gas based on wet reclamation technology - Google Patents
Process for capturing carbon dioxide in flue gas based on wet reclamation technology Download PDFInfo
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a process for capturing carbon dioxide in flue gas based on the wet reclamation technology. The process comprises pretreatment, adsorption treatment, washing displacement treatment, water spraying desorption treatment, product air purging treatment, displacement air purging treatment and drying reclamation treatment. A method for efficient and low-cost adsorption separation of high-purity carbon dioxide based on the wet reclamation technology by adopting a functional ion exchange resin membrane material through organic integration with a thermodynamic system of a power plant is provided by the invention.
Description
Technical field
The present invention relates to the technical field of carbon dioxide discharge-reduction, more particularly to a kind of to trap flue gas based on wet reclamation technology
The method of middle carbon dioxide.
Background technology
With the aggravation of greenhouse effect, the discharge for how controlling the greenhouse gases based on carbon dioxide causes global
Extensive concern.The data display that world energy sources tissue (IEA) is announced, global carbon dioxide adds up discharge up to 36,000,000,000 tons within 2013,
Wherein account for 60% by the CO2 emission of the power system based on combustion of fossil fuel.And collecting carbonic anhydride with seal up for safekeeping
Technology (CCS) is considered as one of most effective mode of control power system CO2 emission, wherein, the trapping of carbon dioxide
It is the important step of CCS technologies.
For the environmental condition of power-plant flue gas, the capture method commonly used at present has：Absorption and separation method, adsorption method of separation, film
Partition method, membranes, cryogenic fractionation etc..Current Technical comparing is ripe, be expected to obtain the trapping technique of large-scale industrial application chemical suction
Receipts method and adsorption method of separation.But, chemical absorption method generally existing trapping high cost, regeneration energy consumption is big, absorbent degraded, corruption
The problems such as erosion, volatilization.For example using MEA solwution methods trapping power plant carbon dioxide, its regeneration energy consumption is 3～4MJ/kg CO2, by
This causes power plant efficiency to decline about 12%.Using cold ammonia process power plant efficiency can be made to decline 10% or so, but it is serious to there is ammonia volatilization
The problems such as.Adsorbing separation is expected to significantly reduce the trapping cost of carbon dioxide, but the carbon dioxide purity that adsorbing separation is obtained
Relatively low, regeneration technology is complicated, and its energy consumption and trapping cost are still higher.
In recent years, one kind is reported in document by regulating environmental humidity to realize adsorption-desorption cycle adsorbing separation
Method, referred to as wet reclamation technology.In this method, by the surface hydration water of adsorbing material of the change with particular functional group
Content adjusting its adsorption binding energy power with carbon dioxide, so as to change the adsorption equilibrium partial pressure of carbon dioxide.Due to this
Method is chemisorbed separation, therefore the carbon dioxide purity for obtaining is higher；Compared with alternating temperature regeneration or pressure swing regeneration, wet method is again
Raw process is simple, response is very fast.
As Sun Yimin (is based on Atmospheric CO2The wet reclamation adsorbent experimentation of trapping, Zhejiang University's master's degree opinion
Text) wet reclamation technology is adopted, modified commercial anionic exchange resin membrane (I-200) material in surface is have studied in air
CO2Absorption property.But, the super low concentration that the method for grandson is only applicable in dry air is carbon dioxide enriched, if directly should
For power plant's high humility, the flue gas trapping of high carbon dioxide partial pressure, will produce circulation volume reduces, regenerates difficult, energy consumption surge
A series of problems, such as.
In consideration of it, method of this area in the urgent need to carbon dioxide in a kind of new and effective trapping power-plant flue gas.
The content of the invention
The invention provides a kind of be based on wet reclamation technology, using the ion exchange resin membrane material of functionalization, pass through
The method for going out high-pureness carbon dioxide with power plant thermal system organic combination, efficient, inexpensive adsorbing separation.
A kind of technique based on wet reclamation technology collecting carbon dioxide from fuel gas, step is as follows：
(1) pretreatment：Flue gas Jing cooling and dehumidifyings post-heating to 40～45 DEG C, with adjust the relative humidity of flue gas as 8.7～
11.8%；
(2) adsorb：Pretreated flue gas is passed through into adsorption tower, is contacted with the adsorbing material being placed on adsorbent bed, removed
Carbon dioxide in flue gas；
Described adsorbing material is anion-exchange resin membrane；
(3) displacement is rinsed：The carbon dioxide that concentration is 50～85% is passed through into adsorption tower, adsorbent bed is forward flow through, is replaced
Nitrogen in adsorbent bed, the displacement gas for obtaining send into displacement gas tank；
(4) water spray desorbing：From adsorption tower top spray water, the carbon dioxide and the gaseous mixture of water vapour that desorbing is obtained is entered
Product gas tank；
(5) product gas purging：Gaseous mixture in portioned product gas tank is passed through into adsorption tower, adsorbent bed is inversely purged, is reclaimed
The carbon dioxide of remaining, then lead to back product gas tank；
(6) displacement gas purging：Displacement gas in displacement gas tank are passed through into adsorption tower, adsorbent bed is inversely purged, are further returned
Lead to back displacement gas tank after the carbon dioxide for receiving remaining；
(7) it is dried regeneration：Flue gas after step (2) carbon dioxide removal is passed through into the adsorbent bed after displacement gas purging, it is right
Adsorbing material carries out primary drying and regenerates, and the hot-air that waste heat and used heat are obtained in recycling power plant carries out two to adsorbing material
Level is dried regeneration, and adsorbing material is dried after regeneration, starts next cyclic process.
The present invention adopts wet reclamation technology, and the balance point of adsorbing material absorbing carbon dioxide is changed by adjusting humidity
Pressure, makes full use of the waste heat and used heat in power plant, and continuous dividing is realized using multi-tower type circulation absorption-desorbing-regeneration techniques
The purpose of carbon dioxide in separable flue gas.
In order to ensure being continuously separated for carbon dioxide in flue gas, the present invention adopts multi-tower type, the circulation absorption mistake of six steps
Journey.Preferably, in described technical process include at least three adsorption towers, adsorption tower series circulation carry out step (2)～
(7).After previous adsorption tower completes adsorption step, pretreated flue gas enters next adsorption tower, by that analogy, realizes flue gas
Middle carbon dioxide is continuously separated.
Preferably, described technical process is divided into three time periods, adsorption process required time is first time period, is rushed
Wash displacement, water spray desorbing, product gas purging to take time altogether as second time period, displacement gas purging and be dried regeneration take time altogether for
3rd time period.
In order that its dynamic performance matches, and ensures being continuously separated for carbon dioxide in flue gas, preferably, first
Time period, second time period are equal with the time required to the 3rd time period.
Preferably, in step (1), described flue gas is exported from desulfurizing tower of electric power plant, gas concentration lwevel is 10～
15%, temperature is 45～50 DEG C, and pressure is normal pressure, and humidity is less than the wet cigarette of saturation under (i.e. close to) relevant temperature and pressure
Gas.
Preferably, in step (1), flue gas Jing regenerators first are cooled to 35～40 DEG C, then it is water cooled to 25～
30 DEG C, again Jing electricity be cooled to 4～8 DEG C, finally using power plant's used heat and regenerator to the flue gas after dehumidifying to 40～45 DEG C.
The flue gas of desulfurizing tower outlet is the wet flue gas containing a large amount of saturated vapors, by the cold of regenerator and water cooler
But, flue-gas temperature can be cooled to 25～30 DEG C by 45～50 DEG C, now appoint in flue gas and contain more water vapour；It is cold by electricity
Device, flue-gas temperature is further reduced to 4～8 DEG C, substantial amounts of water vapour condensation, now water vapor partial pressure be only 0.81～
1.07KPa.Relatively low flue-gas temperature can substantially reduce the dynamic performance of adsorption process, therefore the flue gas after cooling and dehumidifying needs
It is reheated to 40～45 DEG C.Using the flue gas after power plant's used heat and regenerator heating cooling and dehumidifying, whole system is remarkably improved
The heat-economy of system.
Preferably, in step (2), described anion-exchange resin membrane, anion selected from fluorion, acetate from
One kind in son, oxalate denominationby, phosphate anion, sulfur hydrogen radical ion.Above-mentioned preferred anion-exchange resin membrane material can
Higher adsorption capacity, and its balance in a wetted condition are reached in the dry environment that gas concentration lwevel is 10～15%
Partial pressure increases 1～2 order of magnitude.
Preferably, in step (2), adsorption process is entered under the normal pressure that 35～45 DEG C, relative humidity are 8.7～11.8%
OK.
Contain nitrogen in flue gas, Jing after the adsorption process of step (2), under part nitrogen also can be adsorbed by exchange resin membrane
Come, or be trapped in the hole of adsorbent bed, can be carbon dioxide by nitrogen displacement Jing after the flushing displacement of step (3),
Ensure Jing after water spray desorbing to obtain the carbon dioxide of higher concentration.
Preferably, in step (4), desorption process is carried out under 35～45 DEG C, condition of normal pressure, adsorption tower top spray
Water temperature is 40～45 DEG C.
In step (6), using the carbon dioxide of remaining in the nitrogen displacement adsorbent bed in displacement gas, two are further reclaimed
Carbonoxide.Preferably, the displacement gas in displacement gas tank are back to use in step (3), displacement is rinsed, when in displacement gas tank
After gas concentration lwevel is higher than 85%, the medium carbon dioxide to be recycled of product gas tank is sent into.
Compared with prior art, the invention has the advantages that：
Compared with conventional physical adsorbing separation, wet reclamation technology separate produced carbon dioxide have it is higher pure
Degree；Compared with alternating temperature regenerates, wet reclamation response time is short, and equipment is simple；The waste heat and used heat in power plant is fully utilized, heat
Better economy；Corrosion-free, avirulence, will not produce secondary pollution.
Description of the drawings：
Fig. 1 be flue gas is carried out cooling and dehumidifying and backheat heating process chart, wherein 1- pressure fan, 2- regenerators,
3- water coolers, 4- point coolers, 5- heater utilizing waste heats；
The step of Fig. 2 is the circulation absorption-desorbing-Regenerating Trap carbon dioxide based on wet reclamation is schemed；
Fig. 3 is the process chart of three tower circulation absorption-desorbing-Regenerating Trap carbon dioxide, each digitized representation in figure
Different valves.
Specific embodiment
Further detailed description is done to the present invention below in conjunction with accompanying drawing.
The working environment sorbent used in order to adapt to wet reclamation, carries out cooling and removes to the flue gas of desulfurizing tower outlet first
Wet process, as shown in Figure 1.The flue gas of desulfurizing tower outlet is the wet flue gas containing a large amount of saturated vapors, by regenerator and
The cooling of water cooler, flue-gas temperature can be cooled to 25～30 DEG C by 45～50 DEG C, and more water vapour is now still contained in flue gas.
By electric cooler, flue-gas temperature can be down to 4～8 DEG C, substantial amounts of water vapour condensation, now water vapor partial pressure be only 0.81～
1.07KPa.Relatively low flue-gas temperature can substantially reduce the dynamic performance of adsorption process, therefore the flue gas after cooling and dehumidifying needs
It is reheated to 40～45 DEG C.Using the flue gas after power plant's used heat and regenerator heating cooling and dehumidifying, whole system is remarkably improved
The heat-economy of system.
In order to ensure being continuously separated for carbon dioxide in flue gas, the present invention adopts three-tower type circulation absorption-desorbing-regeneration skill
Art, three adsorption tower series circulations carry out step step following six, as shown in Figure 2：
Adsorption treatment：Pretreated flue gas is passed through into adsorption tower, is 35～45 DEG C in temperature, pressure is the drying of normal pressure
In environment, contact for the anion-exchange resin membrane of fluorion with the functional group being placed on adsorbent bed, remove the dioxy in flue gas
Change carbon, the flue gas after carbon dioxide removal is stand-by.
The preparation process of the anion-exchange resin membrane is：
Drying pretreatment will be carried out from the I type strong-base anion-exchange resin film purchased on the market, be then placed in 1mol/
Repeated washing in the NaOH solution of L, until Cl-By OH-Cement out completely.After washing the NaOH of residual with water, by this resin
Membrane material is put in the HF solution of 1mol/L, makes OH-Completely by F-Substitute, wash the HF of residual with water, sense is obtained after being dried
Group is the anion-exchange resin membrane of fluorion.
The adsorption mechanism of anion-exchange resin membrane used is chemisorbed in the present invention, in 10～15% titanium dioxide
Higher adsorption saturation degree is can reach under the conditions of concentration of carbon.
Rinse replacement Treatment：The carbon dioxide of high concentration is passed through into adsorption tower, adsorbent bed is forward flow through, in displacement sorption bed
Nitrogen, the displacement gas that obtain send into displacement gas tank, in displacement gas purge step.
Water spray desorbing is processed：From 40～45 DEG C of warm water of adsorption tower top spray, carry out under 35～45 DEG C, condition of normal pressure
The desorbing of anion-exchange resin membrane, the carbon dioxide and the gaseous mixture of water vapour that desorbing is obtained enters product gas tank；
Product gas purge：Gaseous mixture in product gas tank is passed through into adsorption tower, adsorbent bed is inversely purged, remaining is reclaimed
Carbon dioxide, then lead to back product gas tank；
Displacement gas purge：Displacement gas in displacement gas tank are passed through into adsorption tower, adsorbent bed is inversely purged, are further returned
Lead to back displacement gas tank after the carbon dioxide for receiving remaining；Displacement gas can be back to use in flushing displacement step, two in displacement gas tank
After oxidation concentration of carbon is higher than 85%, the medium carbon dioxide to be recycled of product gas tank is sent into.
It is dried Regeneration Treatment：Flue gas after carbon dioxide removal after adsorption treatment is passed through into the absorption after displacement gas purging
Bed, primary drying is carried out to adsorbing material and is regenerated, and the hot-air that waste heat and used heat are obtained in recycling power plant enters to adsorbing material
Row secondary drying regenerates, and adsorbing material is dried after regeneration, starts next cyclic process.
The technological process of the continuous collecting carbon dioxide from fuel gas of the step of three tower six, as shown in Figure 3.The function of each valve and behaviour
Make state as shown in table 1.In order that its dynamic performance matches, it is equal that each six operating procedure for circulating is divided into the time
Three time periods, (1) adsorption time section, (2) rinse displacement, water spray desorbing, product gas purge time section, (3) displacement gas purging
Be dried recovery time section.
Each adsorbent bed mode of operation explanation is as shown in table 2 in three tower circulation absorption-desorbing-regeneration technology flow processs, and first inhales
Attached tower is adsorbed, and the second adsorption tower is rinsed displacement, water spray desorbing, product gas purging, and the 3rd adsorption tower carries out displacement gas
Purging and dry regeneration.Sequencing valve is automatically controlled, subsequent time period, and the first adsorption tower is rinsed displacement, water spray desorbing, product
Air-blowing is swept, and the second adsorption tower carries out displacement gas purging and is dried regeneration, and the 3rd adsorption tower is adsorbed.Subsequent time period again, journey
Control valve is automatically adjusted, and the first adsorption tower is carried out displacement gas purging and is dried regeneration, and the second adsorption tower is adsorbed, the 3rd absorption
Tower is rinsed displacement, water spray desorbing, product gas purging.By the auto-control of sequencing valve, each adsorbent bed will repeat above-mentioned behaviour
Make, to realize the continuous adsorbing separation of carbon dioxide in flue gas.
Table 1
Table 2
As the above analysis, it is proposed by the invention that carbon dioxide in power-plant flue gas is trapped based on wet reclamation technology
Method can significantly reduce the energy consumption of trapping process.In whole technological process, except electric cooler dehumidifying, pump, blower fan and various
Outside the power consumption of electromagnetic valve, remaining required energy can be provided by the integration with power plant thermal system by its waste heat or used heat,
Comprehensive outside energy consumption is less than 2.3MJ/kg CO2, compared with traditional MEA removing sulfuldioxides, energy consumption declines 20% or so.And by this
The carbon dioxide purity higher (more than 99%) that bright proposed method trapping is obtained, it is also possible to which significantly lowering subsequently carries out dioxy
Change energy consumption and cost that carbon is compressed and liquefied, transported, sealing up for safekeeping.
Claims (4)
1. a kind of technique based on wet reclamation technology collecting carbon dioxide from fuel gas, it is characterised in that step is as follows：
(1) pretreatment：Flue gas Jing regenerators first are cooled to 35～40 DEG C, then water cooled to 25～30 DEG C, and again Jing electricity is cooled to 4
～8 DEG C, finally using power plant's used heat and regenerator to the flue gas after dehumidifying to 40～45 DEG C, to adjust the relatively wet of flue gas
Spend for 8.7～11.8%；
Described flue gas is exported from desulfurizing tower of electric power plant, and gas concentration lwevel is 10～15%, and temperature is 45～50 DEG C, and pressure is
Normal pressure, humidity is less than the saturation wet flue gas under relevant temperature and pressure；
(2) adsorb：Pretreated flue gas is passed through into adsorption tower, is contacted with the adsorbing material being placed on adsorbent bed, remove flue gas
In carbon dioxide, adsorption process carries out under the normal pressure that 35～45 DEG C, relative humidity are 8.7～11.8%；
Described adsorbing material be anion-exchange resin membrane, anion selected from fluorion, acetate ion, oxalate denominationby,
One kind in phosphate anion, sulfur hydrogen radical ion；
(3) displacement is rinsed：The carbon dioxide that concentration is 50～85% is passed through into adsorption tower, adsorbent bed, displacement sorption is forward flow through
Nitrogen in bed, the displacement gas for obtaining send into displacement gas tank；
(4) water spray desorbing：From adsorption tower top spray water, the carbon dioxide and the gaseous mixture of water vapour that desorbing is obtained enters product
Gas tank, desorption process is carried out under 35～45 DEG C, condition of normal pressure, and the water temperature of adsorption tower top spray is 40～45 DEG C；
(5) product gas purging：Gaseous mixture in portioned product gas tank is passed through into adsorption tower, adsorbent bed is inversely purged, remaining is reclaimed
Carbon dioxide, then lead to back product gas tank；
(6) displacement gas purging：Displacement gas in displacement gas tank are passed through into adsorption tower, adsorbent bed is inversely purged, further reclaim residual
Lead to back displacement gas tank after the carbon dioxide deposited；
(7) it is dried regeneration：Flue gas after step (2) carbon dioxide removal is passed through into the adsorbent bed after displacement gas purging, to absorption
Material carries out primary drying and regenerates, and the hot-air that waste heat and used heat are obtained in recycling power plant carries out two grades to adsorbing material and does
Dry regeneration, adsorbing material is dried after regeneration, starts next cyclic process.
2. the technique based on wet reclamation technology collecting carbon dioxide from fuel gas according to claim 1, it is characterised in that
In step (6), the displacement gas replaced in gas tank are back to use in step (3), are rinsed displacement, the titanium dioxide in displacement gas tank
After concentration of carbon is higher than 85%, the medium carbon dioxide to be recycled of product gas tank is sent into.
3. the technique based on wet reclamation technology collecting carbon dioxide from fuel gas according to claim 1, it is characterised in that
At least three adsorption towers are included in described technical process, adsorption tower series circulation carries out step (2)～(7).
4. the technique based on wet reclamation technology collecting carbon dioxide from fuel gas according to claim 1 or 3, its feature exists
In described technical process is divided into three time periods, and adsorption process required time is first time period, rinses displacement, water spray and solves
Inhale, product gas purging takes time altogether as second time period, displacement gas purging and be dried regeneration and take time altogether as the 3rd time period, the
One time period, second time period are equal with the time required to the 3rd time period.
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| CN108821288B (en) * | 2018-07-03 | 2020-08-07 | 杭州快凯高效节能新技术有限公司 | Preparation device and preparation process for producing high-quality liquid carbon dioxide |
| CN114290511B (en) * | 2021-12-23 | 2023-01-03 | 湖南大学 | Method for enhancing carbon dioxide solid existence in cement-based material |
| CN114452768A (en) * | 2022-03-03 | 2022-05-10 | 霖和气候科技(北京)有限公司 | CO based on wet-process regenerated adsorption material2Direct air capture system and method |
| CN114558414A (en) * | 2022-03-09 | 2022-05-31 | 霖和气候科技(北京)有限公司 | Method for decarbonizing concentrated carbon dioxide emission source based on wet-process regeneration carbon dioxide capture material |
| CN117463111B (en) * | 2023-12-28 | 2024-03-05 | 山西格瑞思科技有限公司 | CO (carbon monoxide) 2 Gas separation apparatus and method of use thereof |
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