CN101657246A - Capture of carbon dioxide (CO2) from air - Google Patents

Abstract

Disclosed is a method for removing carbon dioxide from a gas stream, comprising placing the gas stream in contact with a resin, wetting the resin with water, collecting water vapor and carbon dioxidefrom the resin, and separating the carbon dioxide from the water vapor. The resin may be placed in a chamber or a plurality of chambers connected in series wherein the first chamber contains resin that was first contacted by the gas, and each successive chamber contains resin which has been wetted and carbon dioxide collected from for a greater period of time than the previous chamber, and so on,until the last chamber. Secondary sorbents may be employed to further separate the carbon dioxide from the water vapor.

Description

From air, catch carbon dioxide

Technical field

The present invention relates to a kind of method and apparatus that is used for removing selected gas from air.The present invention is particularly useful for extracting carbon dioxide (CO from air ₂), and will get in touch this respect purposes and be illustrated, yet other purposes are also in limit of consideration.

Background technology

There is compellent evidence to show between the corresponding increase of the rapid increase of carbon dioxide level in the atmosphere and global surface temperature and has very strong correlation.This influence is commonly called global warming.CO ₂A large amount of little and widely distributed discharging bodies are arranged in the various sources of discharging, and alleviating them from the source is unpractical.In addition, discharging body such as hydrocarbon fuel power plant on a large scale is not subjected to adequately protecting and prevents the CO that discharges ₂Enter atmosphere.These main sources and other the generation that combines the rapid increment rate that causes atmospheric carbon dioxide concentration.Discharge bodies till its source is repaired, up to all although other technology all needs to catch the Atmospheric CO of the relatively low background level that is increasing ₂People are making great efforts to improve existing discharging minimizing technology and development of new technology, are used for directly catching the CO of surrounding environment ₂These effort need to manage consequent CO with methodology ₂The thickened waste logistics, introduced atmosphere again to prevent it.

CO ₂Generation occur in the various commercial Application, for example power generation factory produces from coal and in the use of hydrocarbon, hydrocarbon is generally the main component of burnt fuel in the burner (as engine).The waste gas of discharging from these burners comprises CO ₂Gas is only discharged into the atmosphere at present simply.Yet, along with growing interest, from the CO in all sources to greenhouse gases ₂Discharging must reduce.For moving source, optimal selection is likely directly collects carbon dioxide from air rather than from the mobile burner of automobile or aircraft.From air, remove CO ₂Advantage be that it no longer needs CO ₂Be stored on the mobile device.

From surrounding air, extract carbon dioxide (CO ₂) make people might utilize carbon-based fuel and handling relevant greenhouse gas emission afterwards.Because carbon dioxide is both nontoxic also harmless by millionth quantity, but only just cause environmental problem, so from air, remove CO by accumulation in atmosphere ₂Might be able to remedy other local onesize discharge capacitys of different time.

Yet the most prior art method causes catching CO from air ₂Efficient poor because heating of these processes or cooling air, or change air pressure in a large number.Therefore, CO in the atmosphere ₂The clean impairment of level can be ignored, because this cleaning course is with CO ₂Introduce in the atmosphere as the electric power accessory substance of giving this process power supply.

Summary of the invention

In our aforesaid patent application, we have described functionalized ion exchange resin and have been used for extracting CO from surrounding air ₂Application.Particularly, in our aforesaid ' 326 applications, described the purposes of strong basic ion exchange resin, had absorption CO when promptly humidity descends with strong humidity function ₂Ability, and appropriateness is emitted CO when raising ₂Ion exchange resin.The invention provides and make the improvement of spent ion exchange resin (IER) the air acquisition equipment.

Term used herein " ion-exchange " refers to a kind of reversible process, and its intermediate ion can discharge from insoluble solid matter, with other ion-exchanges in the solution on every side.For the purpose of this discussion, even to such an extent as to the very little moisture of on ion exchange resin, cannot see of the aquation of ion exchange resin, this term stands good, and therefore, in general water content is not considered as constituting solution.

Hereinafter, we also will consider wetting ion exchange resin.Term " wetting " refers to resin is exposed to the level of aqueous water or enhancing water vapour pressure.Except as otherwise noted, the steam end finger of enhancing (is for example collected CO when it before surpassing resin ₂The time) the steam partial pressure that suffers.

The ion exchange resin that common commerce can get is made by polystyrene or cellulose base skeleton, and it is formed anionic form via chloromethylation by amination usually.In case amino by covalently bound, the ion attribute that just can utilize it is with its site as ion-exchange.Yet other ion exchange resin and these materials also can be used for collecting CO from atmosphere ₂

According to the preparation method, resin can be processed to have special nature, and this resin of design structure is to obtain being applicable to the special properties of special-purpose and one object of the present invention is exactly.The degree of cross linking between the chain that a kind of important control measure are polymer.The crosslinked mode that is a kind of by two polymer chains of common covalent bond connection that Fig. 2 shows.This realizes by the phenyl ring of sharing between two cross linked chains.

In ion exchange resin, the degree of cross linking is represented the water holding capacity of resin.Because the ionic nature of resin, water has high affinity to ion, offset the electric charge that connects, and so water just is adsorbed on the resin.The water yield that balances each other with resin represents to be contained in the relative concentration of the ion salt in the resin.And effectively pH can control kinetics so that absorb CO ₂

The degree of functionalization of polymer can be transferred to be controlled by covalently bound amination by amine by concentration of reactants during the change chloromethylation.The memory capacity of the number of functionalized group decision resin in the per unit volume.Certainly, the amino sites that has is many more, and storable ion is just many more; On the other hand, if the site is too many, the enclosed pasture gravitation in the resin may not allow all polyions to pass through.Sterically hindered in the resin of more combining closely also may be worked to tradable atomic type.

Amino type also is can self-defining attribute.The part that is connected can be simple chemical substance, as ammonia, or complicated molecule, as 2-amino-two propyl alcohol ammonia etc.By with the hydrogen ion in other organic chain substituted-aminos, people can determine to be connected to the alkalescence of the ionic group on the resin to a great extent.Anion, as the ammonia cation opposite charges that connects, its flowability also will influence the CO of resin ₂Absorption dynamics.For example, little anion is (as Cl ^-Or OH ^-), in resin, very easily flow usually, even there are many subunits to link to each other with nitrogen-atoms.Yet big anion is (as CO ₃ ⁼Or NO ₃ ⁼) motionless relatively, and be easier to be fixed by increasing organic subunit on the amino.

The amino type that links to each other with resin influences the ionic dissociation degree that amino may stand widely.Nitrogen-atoms can form three covalent bonds, but as cation, it can form the 4th covalent bond.Ammonia and water reaction form ammonium hydroxide, NH ₃+ H ₂O ← → NH ₄ ⁺OH ^-Yet ammonia is a kind of weak base, because balanced deflection is in NH ₃That side.Yet when ammonia is connected to polymer backbone, can regulate and control the degree that balance shifts.With regard to R-NH ₂, amino can be with neutral state R-NH ₂Exist or can form R-NH ₃ ⁺The cation site of form.The charged degree in this site depends on the selection of R.In addition, might replace the several hydrogen atoms in the molecule, thereby change degree of ionization.A kind of opposite extreme situations is, four organic residues are connected on the nitrogen-atoms-form quaternary ammonium salt-make it forever be in the positive charge state.In a sense, because four all keys are all used fully and are connected on the polymer substrate, nitrogen can not participate in balance again and move back to NH ₃Because hydroxide ion only links to each other with the sites of positive charge of quaternary ammonium salt as ion, the alkali that obtains thus dissociates fully.Therefore quaternary ammonium resin is used as basic resin.When ammonium salt was dissociated fully, it worked as other highly basic such as NaOH.For TMAH or a series of organic liquid that other dissociate fully, this ammonium salt does not need to be connected on the solid polymer to dissociate fully.It is suitable with highly basic earth metal alkali that these compounds are considered to, and observe in these ionic liquids some are CO ₂Strong absorbent.Therefore, might be with many these class ionic liquids as from air, removing CO ₂Adsorbent.

Can find out that from above discussion amino can be used as the degree that alkali plays a role and also can control by the type that is connected to the group on the nitrogen.Can prepare by fill all available reaction site with carbon back as highly basic, weak base can be controlled by limiting continuous group.

The direct application of ion exchange resin (IER) has demonstrated significant character, for example high-hydrophilic and inner ion circulative metabolism.For catching CO ₂, the value of this character is to produce effective OH ^-The surface, and do not need continously wetting.We not only can produce a kind of active OH ^-The surface, and can utilize the pH of above-mentioned feature control surface.In addition, we point out, CO ₂Absorption is based on the water content of resinous substrates.

The ability of the surface of solids that generation is worked as strong base solution has but is not limited to following several advantages:

1, safety: because OH ^-Functional group is connected with the surface of solids, and it can not move or move, and only can remove by replacement.Therefore do not exist the highly basic chemicals to be discharged into harm in the environment unintentionally, in the air stream of handling, do not have free fluid to can be used to form the aerosol that to bring in the environment yet.In fact, production of resins merchant is considered as IER fully useful, unless contact with strong oxidizer.

2, the elimination of the accessory substance of environment: because gatherer is contacted by the air of huge amount, air collector may be collected from the dust of air, pollen and other impurity.This is a problem for solution-air contact structure.Additional filtration in the upstream filtering of the air that enters or the downstream separation process will be required removes pollutant, and increases cost.Because solid OH ^-The surface only with anion Cheng Jian, the surface of solids is easy to be washed off pollutant, as dirt and chip, and does not influence this surface and the anion of catching.Cleaning solution is generally drinking water, can be removed safely then and does not need subsequent treatment, because do not have solid or chemicals in this solution.In fact, this just looks like to wash dirt off from plastic wire.

3, structure:, not only can provide a kind of contact surface, and can be used as actual gatherer because most polymers can directly be applied to amine functional groups constitutionally stable surface by amination.This has simplified Machine Design, has reduced production cost, and accelerates assembling.

4, ion hydromechanics: experiment shows that ion exchange resin comprises a kind of inner surface regenerative system, does not wish to be bound by theory, and this may be because the moisture in the resin keeps and is based upon and ion concentration gradient on air contacts.Work as OH ^-The surface with contain CO ₂Air-flow contact, H ⁺And OH ^-Between acid-base reaction generate water, stay HCO ₃ ^-Group replaces the OH on the resin ^-Owing to have multi-level OH in the resin ^-The surface, concentration gradient produces, and it drives the motion of ion in the resin.The carbonate and the bicarbonate of surface high concentration cause carbonate inwardly to move in this lip-deep high concentration and the low concentration in resin, and opposite concentration gradient also promotes OH simultaneously ^-Anion from the resin internal migration to the surface.Each gradient is supported another, and shows that the enough speed of generation is so that hinder GAS ABSORPTION dynamics not obviously.

5, water loss: when observing gatherer, the important factors of not considering is exactly a water loss usually, and its water loss is relevant with the contactor of aqueous solution base.Usually, in any case water loss all is the CO that collects ₂10-100 doubly or may be more.Suppose dry type operation functional solid surface collection device, then water loss obviously reduces.

6, pH control:, can control effective pH of solid better by the water consumption of crosslinked minimizing aquation.And, by increasing OH on the solid ^-The relative density of group also can be controlled pH.

Can clearly be seen that based on a series of experiments, but do not have that water breakthrough combines with it can absorb a large amount of CO near dried resin ₂, and reaching load condition, in fact have a CO in each amine site this moment ₂Molecule.Per two amino sites of profit resin can not keep surpassing 1 CO ₂Molecule.In the previous case, resin reaches the carbonation state that is equivalent to bicarbonate, and under latter event, equivalent salt is a carbonate.Data show that also under drying regime, the part load condition that lacks from carbonate when system moves to the load condition that obviously surpasses carbonate, kinetics and not obvious change.The system of this and carbonate ion and bicarbonate ion coexistence is contradiction not.

Because the result of this chemical action might (outdoor environment air or room air) absorb a large amount of CO from air ₂, and simply by in the water yield that is exposed to increase, can be the form or steam (water vapor) form of liquid, drive away a large amount of CO from this polymeric adsorbent ₂

Therefore might impel CO ₂Discharge from solid absorbent, and it is caught in the adsorbent near liquid again, can from gas stream, remove CO when this dividing potential drop near the adsorbent of liquid ₂When carrying out ion exchange material wetting with aqueous water, it is moving that we will be called ripples to this effect, and when carry out being called moisture fluctuation when wetting with the dividing potential drop of increase steam.

If resin is exposed in the pure aqueous water, water keeps the CO of this release ₂Ability very limited, and most of CO ₂In the gas phase that accumulates in the moisture film adjacency of wetting this material.Experiment shows, the CO on the wetting ion exchange resin of this liquid ₂The branch pressure energy surpass 50mbar.Yet, if possible contain alkali in the water, therefore make CO ₂Be included in the solution, rather than with its bulk storage to the ambient gas space, this is the basis of our carbonate washing ion exchange resin.Water in the solution impels resin to discharge extra CO ₂, and the CO that discharges ₂Make solution change into bicarbonate solution from carbonate solution.Then, this bicarbonate can be further processed to discharge its CO ₂, and change into carbonate solution again, in order to the ensuing partly or completely load C O of washing ₂Resin.

From bicarbonate separation of C O ₂Another kind of approach be to utilize the electrodialysis battery pack, it is designed to salt (herein for bicarbonate, as sodium acid carbonate) is decomposed to form alkali (being carbonate herein, as sodium carbonate) and sourly (be carbonic acid herein, can resolve into water and CO ₂Thereby, discharge CO ₂).With regard to weak acid, as CO ₂, possible operation only has the salt separator of cationic membrane, and it is transferred to the alkali chamber with cation (as sodium ion) from sour chamber, and the centre needn't produce the salt flowage of dilution.Have in this design and comprise that bipolar and a series of of cationic membrane pile up.Figure X is presented at the specific embodiment of this design that moves on this salt separator.

Also have other method to reclaim CO from bicarbonate solution ₂And regenerative carbon acid salt solution.At first electrochemistry is separated many variations.For example, may utilize the conventional salt separator of a series of bipolar, cations, anionic membrane.In the case, return with the salting liquid dilution and as the current that dilute.Also may utilize and pile up, wherein this is stacked as a series of bipolar and anionic membranes.What in the case, move through film is not cation but bicarbonate ion.

Not all in essence recovery scheme all is an electrochemistry.Possible heated solution, thus CO caused ₂Release; Possible cooling solution, thereby the precipitation of promotion bicarbonate.Bicarbonate is little than the dissolubility of carbonate, and in step subsequently, sodium bicarbonate solid is sintered into CO then ₂, steam and sodium carbonate.

Do not use inorganic salt solution, also might use amine aqueous solution to catch the CO that from film, discharges ₂In the case, guarantee that the chemical compatibility of resin and amine aqueous solution is very important, because resin might be damaged by the organic amine in the solution.Under the sort of situation, people can use specialized designs to be used for the recovery technology of liquid amine.The use of weak amine becomes easier or very weak base brine as auxiliary, because CO ₂Release is that the existence by water promotes.

Generally speaking, greatly help to reclaim CO from strong basic ion exchange resin ₂Be because CO ₂Release be to promote by the water that exists with liquid state or steam form.If glassware for drinking water has very little alkalescence, the CO of release ₂From water, be discharged into the ambient gas space, at this CO ₂Can be recovered by treatment step subsequently.Use the process of steam rather than the wetting resin surface of aqueous water to also have additional advantage, people can use salt solution or other contaminant water to cause moisture fluctuation.Not only the water loss in resin drying subsequently reduces, and from economic angle, uses the form of salt solution or other so-called buck to have the advantage that the water cost reduces.

For the fluctuation that steam is induced, CO ₂Be released in the gas compartment, so just need collect by additive method.At this recovery several selections are arranged.At first being to use to have the agent of the secondary absorption of extensive selection.Use than dried resin in conjunction with CO ₂More weak adsorbent is good.In general this is feasible, because the existence of the water of liquid state or steam form has improved CO greatly ₂Equilibrium partial pressure, therefore and reduced the needed minimum binding energy of secondary absorption agent.Based on experiment information, water or moisture fluctuation make that the secondary absorption agent can be at CO ₂Dividing potential drop far surpasses 50 millibars of operations down.The secondary absorption agent that there is no need directly to contact with this resin can include but not limited to other resins, for example has or do not have the weakly base resin, liquid amine solution, base brine of part carbonate and/or bicarbonate load, active-carbon bed, zeolite beds etc.

Utilize this technology to catch carbon dioxide (CO for above-mentioned needs being discussed, being the invention describes ₂) several embodiments of method and apparatus.

On the one hand, in one group of embodiment, the present invention includes and to contain CO ₂Gas stream contact with resin so that make its partially or completely load C O ₂, with aqueous water or wetting this resin of steam, so that make the CO of absorption ₂Part discharges, and collects steam and carbon dioxide to extract CO from this gas stream from resin ₂, and a kind of by in the several method, separating carbon dioxide from steam.In another group embodiment, wetting is to be used as CO ₂The alkaline rinse of adsorbent carries out, and wherein the water in the solution stimulates CO ₂Discharge from resin, its alkali that is existed in washing lotion then absorbs or holds.

The invention provides several host materials, its improve carbon dioxide on resin catch and carbon dioxide is released into efficient in the water.Carbonic anhydrase can add in the water with auxiliary and promote this process.Resin is selectively wetting by humid air or steam or aqueous water.Experiment shows, there is no need to produce the surface that liquid covers.In one embodiment, this process is contained in the vertical tower apparatus.

On the other hand, technology of the present invention can comprise uses the secondary absorbent, and for example weak liquid amine or hydrophobic active charcoal are to help to isolate CO ₂With separate steam.Because the secondary absorbent does not make main adsorbent pollute or lost efficacy, might from resin, directly wash CO off ₂

The present invention also provides a kind of technology, wherein ion exchange resin is placed in the chamber of a plurality of series connection, wherein said first chamber comprises the saturated resin of just having used recently from gas stream of carbon dioxide, and each follow-up chamber comprises wetting resin, and the time of therefrom collecting carbon dioxide is all longer than the last chamber time, by that analogy until last chamber.These a plurality of chambers connect by a plurality of valves, and it allows in a plurality of chambers any one as described first chamber.

Another aspect of the present invention comprises the solid of gatherer, its allow the macropore space that is used for the solids-gases exchange and be used for solid-steam and the solid-liquid exchange than the aperture space between change.Realize this variation by adjustment aperture size or by the structure that use has more than one apertures.It also comprises fixing aperture system.

Aspect another, the present invention comprises a kind of CO that is used to catch ₂Technology, wherein use the functionalized medium of alkali liquid washing, produce the effluent have high concentration carbon hydrochlorate or bicarbonate.Then, this effluent can be supplied with and for example discharge CO ₂Electrodialysis cell.

Description of drawings

From following description in conjunction with the accompanying drawings, can find out further characteristics of the present invention and advantage, wherein

Fig. 1 is the diagram of the ion exchange process of prior art;

Fig. 2 is the schematic diagram of the covalent bond in the ion exchange resin that shows prior art;

Fig. 3 is for showing that the present invention is used to catch CO ₂The schematic diagram of ion exchange process, wherein add water from resin, to discharge CO ₂

Fig. 4 adopts weak liquid amine to catch CO for showing the present invention ₂The schematic diagram of process;

Fig. 5 wherein uses a plurality of chambers continuously for showing the schematic diagram that is used to catch the CO2 ion exchange process in one embodiment of the present invention;

Fig. 6 is used to catch CO for showing among the present invention ₂The schematic diagram of ion exchange process, wherein valve is used to control flow;

Fig. 7 adopts active carbon to catch CO for showing in one embodiment of the present invention ₂The schematic diagram of ion exchange process;

Fig. 8 is for showing the figure of right circular cylinder tower of the present invention;

Fig. 9 A and 9B are for showing the figure of the roller solid of adjustable gatherer in one embodiment of the present invention;

Figure 10 A and 10B are for showing the figure of the dull and stereotyped solid of adjustable gatherer in one embodiment of the present invention;

Figure 11 A and 11B are for showing the figure of folding gatherer in one embodiment of the present invention;

Figure 12 A-12F is for showing the figure of the fixedly solid of gatherer in other embodiments of the present invention;

The schematic diagram of Figure 13 for having apparatus of the present invention of electrodialysis cell in one embodiment of the present invention; And

The schematic diagram of Figure 14 for having apparatus of the present invention of electrodialysis cell in the alternate embodiments of the present invention.

The specific embodiment

The present invention is based on and utilize CO ₂Equalizing pressure with the humidity level change, with temperature change and along with the fluctuation of pressure change.The combination of these variations provides many and reclaimed CO from the resin that is exposed to air ₂Method.The device that the present invention describes can removed carbon dioxide under the condition widely from surrounding air, it can also remove carbon dioxide from other admixture of gas.Though this embodiment is preferred for the CO of low concentration ₂(as less than 1%), but also might be from the CO that is rich in of 1%～98% scope ₂Admixture of gas in collect carbon dioxide.

We have found that the dry ion exchanger resin that is exposed in the surrounding air can absorb CO ₂, and reach over time with air in CO ₂The balanced load that dividing potential drop balances each other.Except air, also can use to contain 1～200 the low dividing potential drop CO of 000ppm scope ₂Similar admixture of gas.When resin has been exposed to about 400ppm CO in the mixture ₂Surrounding air the time, might be exposed to the resin material of air by wetting this, and such as 80, reclaim CO under 000ppm or the higher dividing potential drop ₂Therefore, the existence of humidity has increased CO on the resin greatly ₂Equilibrium partial pressure.Therefore, can be in water washing resin and from gas that water contacts catch CO ₂Perhaps, might be from absorbing CO ₂The aqueous solution in catch CO ₂, because it has and the CO that frees from resin ₂The necessary alkalescence that combines.This alkalescence can provide (as NaOH or KOH) with the form of hydroxide solution, and it also can be with the form of carbonate (as Na ₂CO ₃, K ₂CO ₃) or provide with the form of the mixture of carbonate and bicarbonate, the bicarbonate duty factor that it has contacts can reach littler with the resin that is exposed to air.

We also show in experiment, ion exchange resin are exposed under the humidity level of increase just enoughly, rather than directly they are exposed to aqueous water and influence CO ₂Get release in a large number from resin.Experiment shows, its CO ₂Load has reached surrounding air on the resin of balance, CO ₂Equilibrium partial pressure is approximately the function of the absolute humidity in the system, but not relative humidity.In fact, CO on this resin ₂Dividing potential drop with temperature range big variation does not take place, but it is very responsive to the variation of the absolute humidity of the gas that contacts.

Experiment shows that also the exposure in water vapor pressure can stimulate CO ₂Discharge from resin, even lacking other components of air for example under the situation of oxygen and nitrogen.Therefore in one aspect of the present invention, we are filled into cylinder with resin material or are placed in the chamber.This chamber can tolerant be exposed to steam or/and be cleared before the aqueous water within it.

In one aspect of the invention, we are exposed to air with multiple solid and design with resin.When resin by airborne CO ₂Thereby saturated or fractional saturation and CO less than 400ppm ₂After dividing potential drop balanced each other, we were with CO ₂Be discharged in the gas-phase space, wherein CO ₂Dividing potential drop reach 50,000 microbars or more.

In our some previous patent applications, we have described tertiary amine and functionalized 1 type and the 2 type basic resins of quaternary amines are used for absorbing CO from air ₂Purposes.As described therein, CO ₂Be extracted and be stored on the resin as carbonate or bicarbonate.More specifically, of U.S. Patent application 11/866,326, a distinguishing feature of these basic resins is, they absorb more CO when more moistening than them when drying ₂Though this performance depends on the temperature of airborne humidity, resin and the CO of resin ₂Load condition, but we have found that equilibrium partial pressure on the wet resin is compared with having similar CO ₂The dried resin of load goes out about 200 times greatly.For example, we have found that, be exposed to the airborne resin of environmental drying during drying regime, behind contact water, can fill a CO ₂Dividing potential drop surpasses the little air chamber of 60mbar (60,000 microbar).Resin and sodium carbonate/bicarbonate solution equilibria, its conversely with airborne CO ₂Balance each other, for per two positive charges on the surface that is attached to resin, this resin only combines and is slightly more than a carbon atom, as carbonate or bicarbonate ion.On the other hand, if resin balances each other at the air that lacks under the situation of aqueous water with low humidity, the number that is attached to the carbon atom on each adion is near one.This character of resin can be used for the transformation that realizes that humidity is induced, so that catch and collect carbon dioxide.

Along with humidity in the air increases, CO on the matrix ₂Equilibrium partial pressure significantly raise.For example, we after tested the resin sample of 6g ion exchange membrane material, available from San Clemente ¹SnowPure Co., Ltd ( ¹The manufacturer is the anion exchange resin that comprises pulverizing with its product description, is mixed in the polypropylene-base and according to U.S. Patent No. 6503957 and No.6716888 it is pressed into thin plate).This film be torn into 1mm thick * line of the wide noodles shape of 1mm.The amount of this material in atmosphere at room temperature in the 3ppt water with the CO of 40ppm ₂Balance each other, when airborne water vapour content rose to 30ppt, it can be with the CO in 20 liters of bell-jars ₂Dividing potential drop is increased to more than the 1200ppm.In addition, this membrane material of 10g has been used to discharge the CO of about 100cc ₂, dry back absorbs the CO of other 100cc ₂, then wetting back in CO ₂Period 1 in, promote the CO of bell-jar ₂Content reaches 3700ppm.In view of this dried resin material itself is reset, and has held bicarbonate ion and is not only carbanion.Because the CO that this obvious fluctuation of carbon capacity, the humidity that improves resin are enough to that resin is discharged have been absorbed ₂

Yet do not wish bound by theory, think that this resin is beneficial to hold bicarbonate ion along with it parches resetting to small part, but not carbanion itself.Yet we observe along with load increases, CO ₂Uptake rate progressively descends.For dried resin, do not have obvious limit between carbonate/hydroxide and the carbonate/bicarbonate system, show when this system when a side who has the residual hydrogen oxide is transported to a side who has the residual carbon acid ion, the mechanism of taking in does not change.A kind of possible explanation is, in dry system more or less, carbanion can be separated into bicarbonate ion and hydroxide ion, even in the aqueous solution, the balance of this reaction helps carbonate greatly and surpasses bicarbonate.A kind of possible mode, bicarbonate radical will earlier be deposited in the surface of resin than carbanion, thus they can remove some carbonate with the form of bicarbonate from solution.Under any circumstance, as if effective pH on this surface is higher than its level based on the carbonating in the aqueous systems.

Because this obvious fluctuation of carbon dioxide memory capacity is said in principle, the humidity that improves resin is enough to make this resin to discharge the CO that has absorbed ₂A kind of possibility is that this resin is immersed in the water, so that discharge CO ₂This process as shown in Figure 3.The of short duration wetting CO that may be not enough to discharge most of combination of material itself ₂CO ₂Continue considerable time from this material release, but discharged most of CO that can be incorporated into this resin surface ₂Another embodiment of the invention is that wetting resin is exposed in the air, at CO ₂The duration that discharges goes up with the immersion resin-shaped and shines in pairs.Because the time is the main restricting factor to this design, therefore advises that this device is relatively large, and allow the exhaust of volume to carry out the longer time.

In the dynamics of this process that do not slow down near operation under the vacuum, this moment, airborne nitrogen and oxygen in fact were removed from this system.Therefore, might produce gas stream from wetting resin material, it is steam and the CO that discharges from resin ₂Mixture.The latter's dividing potential drop can be up to 60 millibars.The former dividing potential drop depends on temperature, but should be about 30 millibars or lower.The volume of this system should be with the formal construction of throttling, when keeping this system near equilibrium condition with box lunch, and CO ₂Slow release can continue.If CO ₂Removed too soon, steam produces the CO that dynamics will change release rapidly ₂With the ratio of the steam that discharges, help excessive water and discharge.Can cool off this system like this, need extra heat input.If water is hunted down in condensation trap, the energy that is used to cool off will increase fast.Therefore it is very important keeping near equalization point, and it has set acceptable to greatest extent flow rate.

Under the atmospheric conditions of drying, from air, collect CO ₂In case it is high-caliber saturated that resin reaches, wherein it is to change saturated bicarbonate form into from its carbonate form in essence, this resin material is packed in the chamber, and this chamber is cleared, is full of then steam and aqueous water earlier, stirs up to all resin surfaces by complete wetting.Perhaps, this resin only can be contacted with steam.Yet, compare CO when this resin is got wet when only being exposed to steam with it ₂Much higher from the speed that resin discharges.In fact, not only rate of release increases, CO ₂Dividing potential drop also rise.

It may be useful in the water that a spot of carbonic anhydrase is added in discovery to, so that improve CO ₂From the resin transfer to water and the kinetics in the ambient gas space.In some designs, maybe advantageously, by the CO that will load ₂Resin material be collected in and at first be cleared to begin in the container of removing excess air.Wetting then this resin is so that it discharges CO ₂This causes CO in the chamber ₂Be 50 millibars, H in addition ₂O is about 20 to 30 millibars.Might change water content by the temperature that raises or reduce this system.

Might extract the gas that produces out this system now, along with gas is compressed, the water in the gas gets off condensation, simultaneously CO ₂More and more compression becomes.Finally we can promote this pressure and reach CO ₂Pipeline pressure.If desired, this CO ₂Can be dry with its bottling or before delivering to the client.

Even wetting this resin material allows to discharge CO from resin ₂, this release is also slow relatively.The of short duration wetting CO that is not enough to discharge most of combination of material itself ₂Yet we find the CO in this material ₂Discharge last very long, but it has related to most of CO that can be incorporated into this resin surface ₂

In an experiment of carrying out, use the 6g membrane material, be cut into bar, and in DI water, washing this resin after 15 minutes, resin will be emitted CO ₂And make CO in the clock container of sealing ₂Level is increased to about 1200ppm.Placement is spent the night, but allows drying, all these CO of this resin reacquisition ₂, but also more, make the CO in the clock container ₂Level is reduced to about 40ppm.Humidity in this clock container is increased to 30ppm causes CO ₂Release reaches more than the 1400ppm.Discharge this CO ₂And the washing resin bar will cause CO in DI water ₂Discharge more rapidly, it makes the pressure in the bell jar be increased to about 1800ppm.Experiment for the second time produces and surpasses 1100ppm, and still reaches 700ppm for the third time.This system is emitted 1000+1400+500+300～3300ppm at least altogether.This changes into the CO of about 66cc again ₂Perhaps at first by the CO of carbonate washing film collection ₂About 2/3 of capacity.The total capacity of this membrane material should be about 6 mMs or about 120cc.Therefore, can think and only can cause the CO that is attached on the matrix with pure water ₂Big fluctuation.It is unclear that how many CO were arranged in washing cycle ₂Be discharged into the outside of bell-jar from matrix.When this system is placed a few minutes in water, a large amount of extra CO ₂Can be removed.Data during end of run show CO ₂Some descends the speed that discharges in washing cycle, shows and removes extra CO with faster rate this washing cycle ₂Yet, consider that some emits the CO that removes washing cycle in the silent period of centre ₂Total amount inevitable less relatively.

When membrane material was in water, its decarbonization rate did not detect.Yet, observed carbonic anhydrase to CO ₂Little from the speed influence that wet film discharges, this shows that the slow step in this process is CO suddenly ₂Release from film.

Perhaps, as shown in Figure 4, we can extract CO with other separation schemes from gas stream ₂, for example be used for the weak liquid amine of secondary absorption step.This amine must be able to make the CO of admixture of gas ₂Content reduces, so that CO ₂Differential pressure drop is to for example about 20 to 30 millibars.Therefore, it can be to be used for catching CO than us ₂The weak many adsorbents of main resin, and this allows us to use very weak amine, or weak amine resin.Under the situation that resin is destroyed by rosin mixture, might make the amine irrigation flow through other surfaces, these surfaces are owing to can be absorbed a large amount of CO by resin wetted ₂

In another embodiment of the invention, we can be used in the resin of same type on the air acquisition equipment, but operate on the load curve of varying level.It is moving to remove CO that this resin will keep moistening and will experience thermal change ₂

Though high-caliber steam or moisture should be enough to make CO in the air ₂Discharge, we also can be at CO ₂Use aqueous water in the release.But be to use steam and non-liquid water can reduce the wearing and tearing to resin.Also may use the water that contains salt or other impurity.

Usually useful is, by to gas pressurized so that make steam become supersaturation and cohesion, with too much steam from CO ₂Remove in the steam mixture.Yet, might be used for CO by using cold-trap (cold trap) except that anhydrating, can connecing in principle then ₂Second cold-trap.If get back to lower environment temperature by heating the resin cooling, can partly realize water condensation at least, then the method is especially useful.If this device uses buck or salt solution to come work at first, water condensation can provide independent cleaning current, and it can be used as byproduct and is emitted.

Reduce water consumption several different methods is arranged.For example, can carry the short pulse steam to pass resin,, but be enough to discharge CO from resin surface to such an extent as to the very short steam of control impuls can not deeply enter resin ₂Afterwards, the diffusion in the resin will be redistributed the load of resin inside, and the steam pulse can repeat several times, until total CO ₂Content significantly descends.

By dry resin being exposed to water saturated air or, can removing the most of CO that has been collected by dried resin again by immersing in the aqueous water ₂Particularly, very little to the wearing and tearing of material in relying on the moving embodiment of ripples, this material can be by the moving repeatedly circulation of ripples.Fluctuating range can relate to the CO of resin ₂Half of bearer cap, but actual design can be at low slightly load fluctuation.

Numeral general for film is, rate of release is about 1 mM CO in every 10g sample 15 minutes ₂, or about 1e-4 mM/Grams Per Second.Because for our employed material, macro surface is long-pending to be about 40cm ²/ g, we obtain 2.5e-5mole/m ²The release rate of/sec.Absorption rate is similar, though a bit slow usually.This means that also the 50g sample will produce the gas of about 0.1cc/sec or about 100cc in about 15 minutes.

Based on theory, by operating under the environment of nearly vacuum, this moment, airborne nitrogen and oxygen were in fact removed from this system, and the dynamics of this process does not slow down.Test verified this viewpoint.Under the low pressure condition, might from wetting resin material, produce gas stream, its come down to chamber in the steam that balances each other of temperature and the CO that discharges from resin ₂Mixture.CO in the chamber ₂Pressure can be up to 60 millibars, but along with having CO ₂The load of resin reduce and descend.At room temperature, steam partial pressure is about 30 millibars.Might improve the dividing potential drop of steam in the chamber by the rising temperature.In fact this produce humidity/ripples are moving and temperature fluctuation a combines hybrid system.In the system of heating, the temperature by the relative environment of cooling output stream can reduce water vapour pressure.This will reduce the concentration of steam in the chamber and reach equalizing pressure under the environment temperature.

Because CO ₂Discharge to reach with environmental gas from resin and balance each other and need take a long time, the volume of this system should make up in the mode of throttling, so that CO ₂Slow release can the maintenance system near CO ₂Partial balanced condition.If fluid can very rapidly move, then steam production dynamics will change the CO that discharges ₂And the ratio between the steam that discharges helps excessive water and discharges.This can unnecessarily cool off this system, thereby needs extra heat input.If water is removed in condensation trap, as if steam and CO in the admixture of gas ₂Ratio become unfavorable, the energy requirement that then is used for cooling gas flow will increase rapidly.CO ₂Can have 1: 1 ratio with the suitable mixture of water.Therefore, preferably keep this system near equalization point, it has set the acceptable maximum flow rate.

Water can be removed from this low pressure mixture by several modes.First kind is that this gas of cooling is to get off water condensation.As long as the projecting environment of temperature of system, this just can not cause actual energy loss, takes place if still be condensate under the inferior environmental condition, and then loss is very serious.A kind of mode of avoiding it is compression H ₂O/CO ₂Admixture of gas.When the dividing potential drop of water rises, it will promote in the condensation that is higher than under the temperature of environmental condition, anhydrate thereby may remove with extremely little energy loss.In fact, in a cover embodiment, people can promote condensation under the temperature of (rising) operating temperature that is higher than chamber, and heat demand greatly is provided from the heat of condensation thus.In fact, this system moves with high-efficiency heat pump, and it is transferred to condensation heat in this system at elevated temperatures.

Based on these conditions, we have designed water (or humidity) fluctuation system, and collect CO this moment from air under drying condition ₂It seems that from experiment humidity level's principal character is an absolute humidity, rather than relative humidity.This is based on observes, under constant absolute humidity, when temperature from move to for example 10 to 20 ℃ or when high of much higher temperature, the CO in the bell-jar of sealing near dew point ₂Level can not change, and air contacts with resin in bell-jar.On the other hand, the variation of humidity will cause CO ₂The fluctuation of equilibrium level.This results suggest, the wet cycle of doing all is possible in moistening/nice and cool weather and desert climate.In case it is high-caliber saturated that resin reaches, it means that in dry climate it transfers to bicarbonate form completely from its carbonate form in fact, this resin material is loaded into and at first empties in the chamber that charges into steam and/or aqueous water then, and it is stirred up to all resin surface complete wetting.This system discharges CO then ₂, and if enough materials are arranged in the chamber, this system can reach the CO that is higher than water vapour pressure in the chamber ₂Pressure.In order to reach high CO ₂Pressure (about 30 to 60 millibars) can be provided with a succession of chamber, as shown in Figure 5, its near environmental condition but under different temperatures with steam-laden (steam of about 30mb), so that water saturation pressure is from upstream extremity (steam enters at this) arrival downstream (CO ₂Be removed at this with steam).In this system, gas flow is held, because steam and CO ₂Downstream at this chain is extracted.Last chamber contains the resin that has just returned from the saturation of the air in the chain, and it can promote CO ₂Dividing potential drop reach the same with water vapour pressure high or even higher.The resin that exposes the long period in the warm moist environment is contained in the higher upstream of chamber.

Chamber preferably almost completely is full of resin material, because interstitial space is big more, reaches high CO in the system ₂Dividing potential drop is just difficult more.Chamber can physically move in chain, because new resin is the gas outflow end interpolation in chain, and CO ₂The resin that exhausts is to be removed at the other end.Do not spend the box that moves other chamber or put into those chambers, we also can change the valve of chamber.By this way, each chamber can be connected to its downstream adjacent body or last extraction system.Each chamber also can be connected or be connected to the source and the tail gas input of steam at upstream extremity with the upstream adjacent body.Might open the valve of a unit, empty and recharge and shut valve, make that see in logic is the other end at chain now.By this way, resin can move through chain, and the position is never with moving.

Unless with CO ₂Absorb from fluid, stay stable steam simultaneously, unless perhaps two kinds of gas components are all extracted out simply and compressed, the steam condensation that is bound to is got off, with from CO ₂Separate in the stream.Condensation will take place in the downstream of chain, perhaps along with air-flow advances, when temperature descends between chamber when causing the water vapor pressure reduction from chamber, more may take place in the chamber of centre.The condensation of steam will produce the fluid towards system low-voltage.

At (between 80 ° and-100 ℃) under the low-down temperature or by compressor pump, by condensation/distillation, can be with CO ₂Remove from the downstream of last chamber, this pump moves to gas in the cistern under another elevated pressures.Perhaps, can remove CO by adsorbent ₂, for example cold liquid methanol, liquid amine or sodium carbonate.Other selections comprise the active carbon of hydrophobic form.

With reference to figure 6,6g SnowPure anion-exchange material is arranged, and this resin of washing is after 15 minutes in DI water in single chamber, resin still can be emitted CO ₂And make CO in the system ₂Level is increased to about 1200ppm.Placement is spent the night, but allow dry, this resin reacquisition all these and more CO ₂, make the CO in the container ₂Level is reduced to about 40ppm.Humidity in the rising container will cause CO to 30ppm ₂Emit, reach more than the 1400ppm.Discharge this CO ₂And the washing resin bar causes higher CO in DI water ₂Release rate makes the pressure in the bell be increased to about 1800ppm.For the second time repeat still to reach more than the 1100ppm, and repeat still to reach 700ppm for the third time.This system emits about 3300ppm altogether.This transforms the CO into about 66cc ₂Or the CO that collects by carbonate washing film at first ₂About 2/3 of capacity.The total capacity of this membrane material is about 6 mMs or about 120cc.Therefore think that list can cause the CO that is attached on the matrix with pure water ₂Fluctuation.It is unclear that how many CO were arranged in washing cycle ₂Be discharged into the outside of bell-jar measuring system from matrix.When this system has spent a few minutes in water, at these a large amount of extra CO ₂May be removed, the terminal data that obtain of operation show CO ₂Some descends the speed that discharges in washing cycle, shows that the water washing circulation removed extra CO at faster speed ₂Yet, consider in the quiet period of centre and emit, the CO that removes washing cycle ₂Total amount inevitable less relatively.

Numeral general for film is, the speed of release is about 1 mM CO in the 10g sample 15 minutes ₂, perhaps about 1e-4 mM/g/sec.For the long-pending about 40cm of macro surface ²The material of/g, we have reached 2.5e-5mole/m ²The rate of release of/sec.Absorptivity is much the same, though a bit slow usually.Experiment shows that also the 50g sample will produce the gas of about 0.1cc/sec or about 100cc in about 15 minutes.

A design feature is that many chambers are arranged in this sequence.Resin in the different chamber has exposed different time spans in degassing procedure.Resin moves between can be from the chamber to the chamber, perhaps more likely, changes valve so that a chamber leaves the purification end of chain, removes and fills thing in it, and fill with resin, and this moment, it was positioned at the not purification end of chain.Gas in each chamber comprises steam, CO ₂, and have inertia tail gas (sweep gas).Downstream from the upstream extremity of system to system, the summation of three's dividing potential drop are dull declines.Can reduce tail gas pressure by accelerating flowing velocity, but the similar aqueous water with this moment of steam partial pressure balances each other.CO ₂Divide on the direction that is pressed in process and should increase.If steam is the major part of gross pressure, the water vapour pressure gradient has been controlled this fluid, and this can confirm to Next reduction from a chamber by temperature, this moment CO ₂Pressure will rise to next from a chamber, because each chamber all adds number of C O in fluid ₂The contribution of each chamber can discharge CO by material ₂Speed and the specific resin equilibrium pressure that can reach limit.The resin of upstream extremity has almost exhausted its all CO ₂, therefore be the output aggregate increase seldom; Last downstream units can be added nearly 60 millibars in principle.Accomplish this point, upstream extremity or have and surpass 70 millibars vapour pressure, or contain in a large number and still need from CO ₂The tail gas that separates.

The final step of supposing this system is to collect CO in cold methanol ₂, then wherein a kind of tail gas of this system of condensation can be methanol vapor.Other ways are to depend on water, and the upstream temperature of water must enough high dividing potential drop with at least 60 millibars of generations in this case.Along with steam moves to the next one from a chamber, it will run into more low temperature, thereby partly condense, and produce a kind of pressure curve, and it orders about the low CO of pure qi (oxygen) (net gas) from system ₂End flows to high CO ₂End.

In one embodiment, all remaining water condensations are got off, take out CO then ₂Other embodiments will depend on CO ₂Absorb and the recovery of adsorbent subsequently.These adsorbents can be cold methanol, liquid amine or ammoniacal liquor or sodium carbonate.Other selections comprise the active carbon of hydrophobic form.

Fig. 7 has shown another invention scheme.This invention scheme is observed active carbon and absorb CO when moistening based on an observation ₂, and its discharges CO when dry ₂This is the performance opposite with ion exchange resin.Therefore, this makes successively that coupled ion exchanger resin and active carbon become possibility.Begin with dried active carbon and wetting resin material, air is passed through this system.Along with dry this resin of air, it is transported to carbon with steam.Resin carries CO when drying ₂, and active carbon carries CO when accepting moisture ₂In case resin drying, this system reverses, the fresh air active carbon of flowing through then, and discharge moisture and get back to ion exchange resin.Along with the carbon drying, it emits CO ₂, rising CO ₂Dividing potential drop, CO at this moment ₂Can be concentrated and remove.The characteristics of coupled ion exchanger resin and active carbon and advantage are by this way, and water is retained, and mounted valve also is a simple thing to reverse air stream.

The present invention is easy to change.For example, available other materials for example zeolite replace active carbon.

This shows, make spent ion exchange resin, moisture fluctuation can be used for separating and capturing ambient CO ₂By several air acquisition equipments being chained together the environment CO that removes ₂Can be concentrated.

Make spent ion exchange resin remove CO to combine successively individually or with active carbon or zeolite ₂The advantage that has is to avoid eroding chemical, for example passes by typically to be used for the NaOH of CO2 washer.In addition, substantially use moisture fluctuation in Feng Bi the system, water is retained.

With reference to figure 8, CO ₂The air acquisition equipment can comprise a plurality of CO of containing ₂The right circular cylinder tower 100 of capture material.Preferably, but not necessarily, CO ₂Capture material comprises the ion exchange material of humidity sensitive as described before.Each tower 100 contiguous its have a plurality of air inlets 102 than low side, and there are a plurality of gas outlets 104 on contiguous its top.Perhaps, the wall of tower can be opened to allow air pass through on any level in ground.Air enters in import 102, upwards flows and CO in tower 100 from here ₂The capture material contact.Air stream can perhaps if desired, provide power by fan by free convection.Inlet 102 and outlet 104 make that optionally by the sealing of shield (not shown) the humidity in the tower can raise, and the CO that catches ₂From resin, be removed and concentrate.Perhaps, available liquid water washing resin is to remove the CO that catches ₂, it is concentrated in bases, and bases also comprises (not shown)s such as water pipe facility and valve.Perhaps, CO ₂Capture material can comprise wet adsorbent, as amine or carbonate or other CO ₂Adsorbent, it is stamped by pump and drips or flow into host material in the tower downwards.In a kind of preferred implementation of the present invention, several towers 100 are to link together underground, in this liquid handling that tower 100 is flowed out to remove CO ₂, and the CO that removes ₂Be concentrated.Yet other variations also are possible.

In another aspect of this invention, the functional solid structure in the gatherer can be optimized for gas exchange, steam exchange, fluid exchange and mechanical performance.For the gas exchange, interstitial space/passage should make turbulent flow reduce to minimum enough greatly with the reduction that keep-ups pressure, and prevents that the boundary layer is increased to obstruction CO ₂The thickness of supplying with to functional group.For example, when gas stream is surrounding air,, then need 22.4 liters of pure CO with saturated those sites of bicarbonate if one liter of functional solid has one mole of exchange site ₂If we think that the per unit volume of air on average absorbs the CO of 100 parts of per 1,000,000 volumes (ppmV) ₂, then we need move 224,000 litres of air by one liter of solid with saturated functional group.When solid is saturated, need reduce air mass flow, because CO ₂Absorption is with saturated reduction.

For steam and fluid exchange, the ratio of solid and hole is bigger typically.For example, in the water treatment system of commercialization, typical ion exchange resin bed has about void space of 30 to 40%.Pearl is about 0.5mm size, stays more closely spaced interstitial space.Therefore, for many application, gatherer should be for having the changeable structure of the primary and secondary pore that varies in size.

This design also comprises a system at constant power size under the various situations, uses the system in the power space that identical aperture or mechanical factor help fixing in this gas, steam and fluid exchange.

On the other hand, the invention provides the embodiment of the solid of gatherer, it utilizes functional solid gatherer medium to remove CO from gas stream ₂For example, this catch medium can by be fixed on the solid/in amine groups form.

Referring to Fig. 9 A and 9B, the invention provides the gatherer of the adjustable aperture of roller solid, comprise that one has the inertia central shaft 205 of locking mechanism; The porous media 206 of inertia net or other sheet form; And the functionalized gatherer medium 207 of sheet form.Multihole lamina and gatherer medium thin plate are fixed and are centered around on the axle, so that the innermost layer of roller and outermost layer are made up of porous plate.Guarantee that like this gatherer medium always is clipped between the porous plate to allow gas, steam or liquid on the both sides with gatherer medium thin plate to contact.According to the diameter of roller, use more than a film and porous layer so that interstitial space widen the less rotation that needs central shaft.For example, three layers need 1/3rd of individual layer rotation.

Multihole lamina provides the path for gas, steam and/or liquid stream.This flow path can be the design of straight, spiral, crooked, laminar flow or turbulent flow.Multihole lamina has also been set the minimum widith of interstitial space, when roller can be realized when axle is tightened.By the direction turning cylinder against coil, interstitial space can broaden, and perhaps towards the direction turning cylinder of coil, interstitial space narrows down.Axle and multihole lamina are made by the material that gas, steam and liquid stream that it exposed is inertia.

In the alternate embodiments of Figure 10 A and 10B demonstration, the invention provides the gatherer of the adjustable aperture of dull and stereotyped solid, comprise the porous material 211 of inertia net or other sheet form or as compressible stratum 212, and the functionalized gatherer medium 213 of sheet form.This flat board solid gatherer has the alternating layer of net or other porous medias and gatherer medium.Between liquid flow/commutation period, these layers are pressed together to reach the minimum fluid channel thickness between the gatherer medium thin plate.Void space in the minimum thickness of fluid passage and this passage is determined by the porous media that uses.Between gas flow/commutation period,, thin plate this fluid passage can be adjusted to optimum thickness by being drawn back.Optimal spacing is to be determined by the flow rate of the exchange rate of gatherer medium and liquid or gas stream and liquids and gases stream.

In the another kind of alternate embodiments that Figure 11 A and 11B show, the invention provides and have elementary and the folding gatherer secondary hole.Elementary hole is optimized for gas stream.The wall that is used for the passage of gas stream is made up by the gatherer medium.The gatherer medium itself has the secondary hole that is optimized for liquid stream.In case the gas exchange is finished, and the gatherer medium is by CO ₂Saturated, then elementary hole subsides, and only stays the secondary hole and is used for fluid or fluid exchange.

The simple geometric body of this gatherer is a series of medium collection device thin plates that have open cell (open-cell) hole.For the gas exchange, this thin plate is spaced apart certain distance, and it can be at CO ₂The length of uptake ratio and thin plate is optimized.For fluid or fluid exchange, this thin plate stack up and liquid flow are by the hole of this gatherer medium.Other solids and comprise folding square or rectangular channel etc. shown in Figure 12 A-12F.

Fixing gatherer will adopt one or more fixing apertures.The pore geometry body can change.The example of pore geometry body is circle, square, rectangle, triangle, hexagon or difform passage.This design also comprises the open cell foam solid, or the shape of other irregular connections of being determined by the form of this gatherer medium.

In another aspect of the present invention shown in Figure 13, ion exchange process can utilize electrodialysis (ED) unit to finish.Ion exchange resin can be used alkaline solution washing, as sodium carbonate (Na ₂CO ₃), preferably have the pH of 11-12.Consequent effluent preferably has the pH of 9-10, and it is mainly sodium acid carbonate (NaHCO in the example of sodium carbonate washing ₃).

Then, this effluent being fed to the acidic side of ED unit, is by bipolar or cationic membrane control in this reaction.After the initial launch, the acidic side of this unit is stabilized in nearly neutral pH, at this moment CO ₂Release also is hunted down.Osmotic pressure is pushed to water alkalescence one side of this unit.Alkaline solution remains on the pH near 12, and also can be used for replenishing cleaning solution.

Because the difference of the composition of pH and cleaning solution and effluent can be used independent pond (basin) separately.

Perhaps, as shown in figure 14, the alkaline solution and the cleaning solution that are used for the ED unit can be included in identical pond.This pond can comprise a separator, is used to separate two kinds of alkaline solutions that two different pH scopes are arranged.A kind of preferred embodiment in, the pH of cleaning solution is 12, and the pH that offers the alkaline solution of ED unit is 11.Before the acidic side that enters the ED unit, this effluent can be included in the independent pond.In addition, this effluent, it is preferably pH 9-10, can be used for diluting the part alkaline solution, so that this washing lotion reaches pH 11.

What should emphasize is, embodiments of the present invention described above specifically and " preferably " embodiment, only are possible embodiment, and only are used to be expressly understood principle of the present invention.At the many different embodiments that under the situation of the spirit and scope of the present invention, can design and/or make technology described herein.The modifications and variations of all these and other all comprise at this, belong to the scope of this specification and by following claims protection.Therefore, scope of the present invention is not subjected to the restriction except that shown in additional claims.

Claims (40)

1, a kind of method of from gas, removing carbon dioxide, comprise described gas is contacted with resin in the chamber, from this chamber, discharge gas, wetting described resin, collect steam and carbon dioxide from described resin, and separate described carbon dioxide from described steam.

2, the described method of claim 1, wherein said resin is next wetting by immersing in the water.

3, the described method of claim 1, wherein said resin is next wetting by being exposed in the malaria.

4, the described method of claim 1, wherein said resin is wetting by coming in the steam that is exposed to short pulse.

5, the described method of claim 2, wherein said water also comprises carbonic anhydrase.

6, the described method of claim 1 is wherein separated described carbon dioxide by reducing temperature from steam.

7, the described method of claim 1 is wherein separated described carbon dioxide by the pressure that increases steam and carbon dioxide mixture from steam.

8, the described method of claim 1 is wherein utilized secondary absorption agent separating carbon dioxide from steam.

9, the described method of claim 8, wherein said secondary absorption agent is weak liquid amine.

10, the described method of claim 8, wherein said carbon dioxide is released from the secondary absorption agent when temperature raises.

11, a kind of method of removing carbon dioxide from gas comprises:

Resin in making described gas and being contained in a plurality of chambers contacts, and wherein a plurality of chambers are connected;

With the described resin of water-wet, wherein water enters first chamber, and discharges through last chamber;

Collect steam and carbon dioxide from described resin; With

From described steam, separate described carbon dioxide.

12, the described method of claim 11, wherein said a plurality of chambers are to connect by a plurality of valves, and this valve allows in described a plurality of chamber any as described first chamber or described last chamber.

13, the described method of claim 11, wherein said first chamber comprises by the resin from the up-to-date saturated or fractional saturation of the carbon dioxide of described gas, and each follow-up chamber comprises wetting resin, and the last chamber of the time ratio of therefrom collecting carbon dioxide is longer, and the like until described last chamber.

14, a kind of method of removing carbon dioxide from gas comprises described gas introducing is comprised in the chamber of resin and active carbon that wetting this resin and active carbon are discharged gas, and collect carbon dioxide from active carbon from this chamber.

15, the described method of claim 14, wherein zeolitic material is used to replace or use outside active carbon.

16, a kind of device of catching carbon dioxide from air comprises upright tower, and each tower has at least one air inlet in the bottom near tower, and at the top near tower at least one gas outlet is arranged; Chamber between at least one air inlet and at least one gas outlet, described chamber comprises the ion exchange resin that is used to catch carbon dioxide; And the water source, be used for wetting this resin to discharge described carbon dioxide.

17, the described device of claim 16, wherein said water is the form of humid air.

18, the described device of claim 16 further comprises a plurality of shields that are used for optionally closing at least one air inlet and/or gas outlet.

19, the described device of claim 16 further comprises the fan that is used to control by the air stream of this tower.

20, a kind of gatherer of catching carbon dioxide from gas stream comprises the gatherer medium of porous material and sheet form, and wherein said gatherer medium has adjustable solid, so that gas exchange and fluid exchange to be provided continuously.

21, the described gatherer of claim 20, the solid of wherein said gatherer is adjustable, so that the exchange rate maximization.

22, the gatherer of claim 20, wherein said porous material are placed between a plurality of thin plates of gatherer medium, and wherein this porous material is compressed to adapt to the solid of this gatherer.

23, the described gatherer of claim 20, wherein said porous material is the form of compressible thin plate, it alternately is positioned between a plurality of thin plates of gatherer medium, and wherein the compressible thin plate of this porous material is compressed to adapt to the solid of this gatherer.

24, the described gatherer of claim 20, wherein said porous material is a sheet form, and wherein at least one thin plate of this porous material and at least one thin plate of trapping medium are connected on the central shaft.

25, the described gatherer of claim 24, the solid of wherein said gatherer is regulated by rotary middle spindle.

26, a kind of gatherer of catching carbon dioxide from gas is included in the functionalised materials in the collapsible solid, and wherein this gatherer has elementary hole that is used for the gas exchange and the secondary hole that is used for fluid exchange.

27, a kind of method of from gas, removing carbon dioxide, comprise the carbon dioxide of catching on the main sorbent material, wash main adsorbent to produce effluent with cleaning solution, this effluent is placed the acidic side of electrodialysis cell, and impel the pH of the acidic side of this electrodialysis cell to reach neutral pH with release of carbon dioxide.

28, the described method of claim 27, the pH of wherein said cleaning solution is between 11-12, and the pH of described effluent is 9-10.

29, the described method of claim 27 wherein uses liquid from the alkaline side of electrodialysis cell as cleaning solution.

30, the described method of claim 27, wherein osmotic pressure is urged to alkaline side with water from the acidic side of electrodialysis cell.

31, a kind of method of from gas, removing carbon dioxide, comprise and make described gas flow, in first chamber, contact with resin, from described first chamber, discharge described gas, with the described resin of water-wet, collect steam and carbon dioxide from described resin, and from described steam, separate described carbon dioxide.

32, the described method of claim 31 further is included in before the step of discharging described gas from described first chamber, and this resin is placed described first chamber.

33, the described method of claim 31, wherein when the described gas of discharge flowed, described first chamber was near vacuum pressure.

34, the described method of claim 31, wherein said resin comes wetting by the water of steam form.

35, the described method of claim 31, wherein said resin is next wetting by immersing in the water.

36, the described method of claim 31 wherein increases pressure and with the condensate water steam described carbon dioxide is separated from described steam.

37, the described method of claim 31 wherein uses alkalescent amine that described carbon dioxide is separated from described steam.

38, the described method of claim 32, wherein a plurality of chamber series connection, and wherein water enters first chamber and flows out by last chamber, collects described carbon dioxide and steam from described last chamber.

39, the described method of claim 38, wherein said a plurality of chambers are to connect by a plurality of valves, and this valve allows in described a plurality of chamber any as described first chamber or described last chamber.

40, the described method of claim 38, wherein said first chamber comprises by the up-to-date saturated resin of carbon dioxide from described gas stream, and each follow-up chamber comprises wetting resin, and the last chamber of the time ratio of therefrom collecting carbon dioxide is longer, and the like until described last chamber.

Images