CN101068610A

CN101068610A - Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals

Info

Publication number: CN101068610A
Application number: CNA2005800387545A
Authority: CN
Inventors: 乔·大卫·琼斯
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-09-23
Filing date: 2005-09-23
Publication date: 2007-11-07
Also published as: ZA200703068B

Abstract

Apparatuses and methods for removing carbon dioxide and other pollutants from a gas stream are provided. The methods include obtaining hydroxide in an aqueous mixture, and mixing the hydroxide with the gas stream to produce carbonate and/or bicarbonate. Some of the apparatuses of the present invention comprise an electrolysis chamber for providing hydroxide and mixing equipment for mixing the hydroxide with a gas stream including carbon dioxide to form an admixture including carbonate and/or bicarbonate.

Description

Carbon dioxide is removed in common generation by carbonate and/or bicarbonate minerals from waste streams

The cross reference of related application

This application requires the priority of following application: No. the 60/718906th, the U.S. Provisional Patent Application sequence of submitting on September 20th, 2005 is entitled as " carbon dioxide (Removing Carbon Dioxide from Waste Streams throughCo-Generation of Synthetic Carbonate Minerals) is removed in the common generation by synthetic carbonate inorganic matter from waste streams "; No. the 60/642698th, the U.S. Provisional Patent Application sequence of submitting on January 10th, 2005; No. the 60/612355th, the U.S. Provisional Patent Application sequence of submitting on September 23rd, 2004.The full text of above-mentioned list of references (comprising appendix) is incorporated into this by reference.

Background of invention

1. invention field

The present invention relates generally to from waste streams, remove carbon dioxide, and be accompanied by the elimination of carbon dioxide, also remove other pollutant.More specifically, the present invention relates to by absorbing carbon dioxide and other pollutant from the flue gas class stream that concentrates, carry secretly by common generation then and the carbonate of any subsidiary pollutant that absorbed of neutralizing and/or bicarbonate material and from waste streams, remove carbon dioxide and other pollutant.

2. correlation technique

In the past in 40 years, no matter in private sector still was commercial department, considerable internal and international concern more and more focused on industrial department to airborne emission problem.Especially, the people's attention point concentrates on the greenhouse gases, and greenhouse gases can make that solar heat is retained in the atmosphere, thereby produces " greenhouse effects ".When the heat that is produced by the sun is trapped within earth atmosphere and the hydrosphere, the average atmospheric temperature of planet earth, ocean temperature and other mean temperature measured value improve, up to and when comprising the point that causes climate change, produce greenhouse effects; Although human depletion rate, consumption degree to material can influence this effect, and people's degree, trend and scale of influencing this effect also be in the state of arguement, generally believes that this effect causes actual influence to earth thermal balance.Although people are still in arguement, everyone agrees if remove CO from the discharging source ₂The cost of (with other chemical substance) is enough low, is favourable to this elimination operation so.

Greenhouse gases mainly are made up of carbon dioxide, be to produce by municipal generating equipment and the extensive factory that is equipped with field electricity generating device, yet any common carbon burning (for example automobile, rainforest disappearance (rain-forestclearing), simple combustion etc.) also can produce greenhouse gases, but their the most concentrated discharging sources are spreading all over the generating equipment of the earth, make to reduce and the discharging of eliminating these fixed-sites becomes the attracting problem that realizes technology for eliminating.Because produce power is the main cause of greenhouse gas emission, so in the past in 30 years, people have taken a broad survey and studied certain methods, for example reduce carbon intensity, raise the efficiency, by various means carbon isolated from generating equipment flue gas.

Reducing carbon intensity relates to the energy that uses the non-carbon energy that substitutes such as atomic energy, water power energy, photoelectricity energy, geothermal energy and other generating and only reduces by consuming the percentage of the electric power that carbon produces.Though above-mentioned generation technology constantly increases in gross energy is produced, in the world wide to the needs of electric power according to estimates with than increasing by these method produce power faster rate.Therefore, although the non-carbon energy expects that in development the discharging of carbon greenhouse gases still can increase.

Raise the efficiency and generally concentrate on the technology of improving the burning of carbon by precombustion, decarburizationization, oxygen catching fire etc., at first reduce the CO that produces ₂Amount, all potential pollutants of oxidation as far as possible fully then.And this technology has improved the amount of the energy that every release one unit carbon dioxide emissions produced, thereby has improved efficient.Though improved efficiency of combustion in the development significantly aspect this, the effort in this field almost can't obtain bigger improvement.

Isolate carbon (initial gaseous state CO ₂Form) trial has produced many different technology, and they generally are divided into geological system, land system or marine systems.These technology relate generally to the carbon dioxide that will produce and are transported to physical location, and carbon dioxide is injected in geology, soil or the ocean bank.These isolation technologies are at preparation CO to be transported ₂, finish transportation and be injected in the operation in " carbon bank " the required cost that expends higher.Therefore, these technology generally are infeasible economically, and the energy of Xiao Haoing is more than original carbon production in many cases.

Isolate and also comprise several commercial runs, comprise scrubbing, barrier film, low-cost O ₂And hydration.But these technology are brought up to uneconomic degree and are affected owing to the fund equipment cost, and CO ₂Catch restriction is also played in the influence of power cost.

At large do not enumerate the shortcoming of reference technique, but pointed out to destroy existing known technology is removed the validity of carbon dioxide from waste streams some shortcomings; But mentioned here shortcoming is enough to confirm that existent method fully can not be satisfactory in the prior art, still needs described in the literary composition and the technology of prescription.

Summary of the invention

The invention provides the method and apparatus of removing carbon dioxide from waste streams, described method and apparatus has overcome the problems referred to above.In general, the present invention relates to use hydroxide to form carbonate and/or bicarbonate and the method for from air-flow, removing carbon dioxide.Described carbonate and/or bicarbonate can be used in the various application or simple discarding subsequently.

Different embodiment of the present invention has provided with existing technology of filtering carbon dioxide from waste streams and has compared the advantage that is had.Some can comprise the following stated by the potential advantage that the present invention realizes.

Be different from carbon physics is transplanted on method at a distance, plant-scale common generation by sodium chloride and synthetic sodium carbonate that obtains of carbon dioxide process and/or sodium acid carbonate directly is converted into chemical substance in the generating position with unwanted carbon dioxide, has eliminated the cost that is transported to the isolated location potentially.

Be different from other removing carbon dioxide that is difficult for improved flue gas stream and handle, embodiments of the present invention can be improved according to existing generating equipment, have greatly reduced and have carried out the required fund cost of removing carbon dioxide processing.In addition, the scale that described removing carbon dioxide is handled can enlarge, and can be adjusted to medium-scale and be adjusted to extensive subsequently from experimental scale by continuous increase reactor assembly.

Other method that is different from prior art, the removing carbon dioxide of some embodiment are handled carbon dioxide sequestration in the available chemicals of economy, and supervene available accessory substance, such as chlorine, sodium carbonate and hydrogen.Because the accessory substance that removing carbon dioxide is handled is available economically, their value has remedied isolates required cost, in the system of suitably design, isolation technology self is brought benefits.

Because subsidiary strong carrying out washing treatment to the flue gas that gives off can be washed other disadvantageous acid contaminant, consumingly such as SO in this processing _X, NO _X, HgO _XIn addition, gas scrubbing can cause other air-flow component and/or pollutant to be trapped and/or to be entrained in (for example coal ash) in the sodium carbonate, thereby they are removed from air-flow.

The specific embodiment of the present invention comprises the method for removing carbon dioxide from air-flow, and described method comprises: obtain the hydroxide in aqueous mixture; Hydroxide is mixed with air-flow, produce carbonate product and (be defined as and contain carbonate CO ₃Product), the bicarbonate product (is defined as and contains bicarbonate radical HCO ₃Product) or carbonate product and bicarbonate mixture of products; Described carbonate and/or bicarbonate product are separated from mixture, thereby remove carbon dioxide in the air-flow.Hydroxide can be any type of hydroxide, includes but not limited to NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide and aluminium hydroxide.Those of ordinary skills will appreciate that the mixture that can use any hydroxide or hydroxide realizes that similar chemical reaction and removing carbon dioxide handle.Some preferred embodiment in, hydroxide is NaOH.

In some embodiments, this method also comprises this method of process control, thereby only produces carbonate product basically or only produce the bicarbonate product basically.In other embodiments, this method also comprises this method of process control, thereby produce carbonate and bicarbonate mixture of products, this mixture by the carbonate of about X% and approximately the bicarbonate of Y% form, the combination of X-Y can be following any: 1-99,2-98,3-97,4-96,5-95,6-94,7-93,8-92,9-91,10-90,15-85,20-80,25-75,30-70,35-65,40-60,45-55,50-50,55-45,60-40,65-35,70-30,75-25,80-20,85-15,90-10,91-9,92-8,93-7,94-6,95-5,96-4,97-3,98-2 or 99-1.

In some embodiments, be blended in two and independently carry out in the chamber, a chamber is used to produce carbonate product, and another chamber is used to produce the bicarbonate product.In other embodiments, be blended in bubble column or the bubble column series and carry out.In other embodiments, carbonate and/or bicarbonate product separate from mixture and relate to the thermal precipitation separation process.In some embodiments, the heat that is used for separation process from the heat exchange of the flue gas that enters.The form of the carbonate that separates can be the water paste or the solution of hydroxide, carbonate and water, and the concentration during separation can be different, if like this, can carry out drying to it by any method.In some embodiments, carbonate does not need drying.For example, the slurry of sodium carbonate can be used for handling hard water.Certainly, those skilled in the art will know that the applicable many aspects of carbonate that the inventive method produces, for example, the slurry mix of sodium acid carbonate and sodium carbonate can be pulled an oar in the tank car, be used for various forms of cleaning agent manufacturings, be used for glass manufacturing as flux, and water treatment applications mentioned above.

In some embodiments, this method also comprises carbonate product is transported to long-range isolating points; Carbonate product is mixed in neutralization reaction with acid, generate pure carbon dioxide; Carbon dioxide is injected in the carbon bank.In other embodiments, other component of air-flow is neutralized and/or holds back in forming the process of carbonate/catches, comprise SO _X, NO _XWith mercurous material.

In some embodiments, obtaining hydroxide comprises: obtain salt; Described salt is mixed with water, steam or water and steam, obtain solution; This solution of electrolysis produces hydroxide.In some embodiments, use, and in other embodiments, use less than about 5 volts voltage electrolytic solution more than or equal to about 5 volts voltage electrolytic solution.In some embodiments, use the voltage electrolytic solution of 1-5 volt, comprise about 1.5 volts, about 2.0 volts, about 2.5 volts, about 3.0 volts, about 3.5 volts, about 4.0 volts or about 4.5 volts, or any two values of these values any scope of drawing.

In some embodiments, before the electrolysis of solutions, in solution, add acid.Acid can be any type ofly can make the protonated acid of solution, includes but not limited to hydrochloric acid.Those skilled in the art will appreciate that and to realize similar chemistry and electrolysis with the mixture of any acid or acid.Some preferred embodiment in, acid is hydrochloric acid.In other embodiments, the amount that joins the acid in the solution is to decide from the best protonated speed that product reclaims highest energy simultaneously according to produce reactant with minimum energy.

In other embodiments, electrolysis step is carried out in electrochemical cell, and described electrolytic cell has catholyte side and anolyte side, and carbonate and/or bicarbonate product are recycled to the catholyte side of electrochemical cell.In other embodiments, the required energy of this method is replenished by the used heat that reclaims from air-flow.

Other embodiment of the present invention comprises the method for removing carbon dioxide from air-flow, and described method comprises: obtain the NaOH in aqueous mixture; NaOH is mixed with air-flow, produce the mixture of sodium carbonate, sodium acid carbonate or sodium carbonate and sodium acid carbonate; Described sodium carbonate and/or sodium acid carbonate are separated from mixture, thereby remove carbon dioxide in the air-flow.

In some embodiments, this method also comprises this method of process control, thereby only produces sodium carbonate basically or only produce sodium acid carbonate basically.In other embodiments, this method also comprises this method of process control, thereby produce the mixture of sodium carbonate and sodium acid carbonate, this mixture can by the sodium carbonate of about X% and approximately the sodium acid carbonate of Y% form, the combination of X-Y can be following any: 1-99,2-98,3-97,4-96,5-95,6-94,7-93,8-92,9-91,10-90,15-85,20-80,25-75,30-70,35-65,40-60,45-55,50-50,55-45,60-40,65-35,70-30,75-25,80-20,85-15,90-10,91-9,92-8,93-7,94-6,95-5,96-4,97-3,98-2 or 99-1.

In some embodiments, be blended in two and independently carry out in the chamber, a chamber is used to produce sodium carbonate, and another chamber is used to produce sodium acid carbonate.In other embodiments, be blended in bubble column or the bubble column series and carry out.In other embodiments, sodium carbonate and/or sodium acid carbonate separate from mixture and relate to the thermal precipitation separation process.In some embodiments, the heat that is used for separation process from the heat exchange of the flue gas that enters.

In some embodiments, this method also comprises sodium carbonate is transported to long-range isolating points; Carbonate product is mixed in neutralization reaction with acid, generate pure carbon dioxide; Carbon dioxide is injected in the carbon bank.

In some embodiments, obtaining NaOH comprises: obtain sodium chloride; Sodium chloride is mixed with water, steam or water and steam, obtain salt solution; Electrolytic brine produces NaOH and chlorine.In some embodiments, use, and in other embodiments, use and carry out electrolysis less than about 5 volts voltage more than or equal to about 5 volts voltage electrolytic brine.In some embodiments, use the voltage electrolytic solution of 1-5 volt, comprise about 1.5 volts, about 2.0 volts, about 2.5 volts, about 3.0 volts, about 3.5 volts, about 4.0 volts or about 4.5 volts, or any two values of these values any scope of drawing.

In some embodiments, before saline electrolysis, in salt solution, add acid.Acid can be any type ofly can make the protonated acid of solution, includes but not limited to hydrochloric acid.Those skilled in the art will appreciate that and to realize similar chemistry and electrolysis with the mixture of any acid or acid.Some preferred embodiment in, acid is hydrochloric acid.In other embodiments, the amount that joins the acid in the salt solution is to decide from the best protonated speed that product reclaims highest energy simultaneously according to produce reactant with minimum energy.

In some embodiments, electrolysis step is carried out in electrochemical cell, and described electrolytic cell has catholyte side and anolyte side, and sodium carbonate and/or sodium acid carbonate are recycled to the catholyte side of electrochemical cell.In other embodiments, the required energy of this method is replenished by the used heat that reclaims from air-flow.In other embodiments, described method also comprises collection chlorine, and in some other embodiment, produces hydrogen.In some embodiments, hydrogen and chlorine burning generate hydrochloric acid, and this hydrochloric acid joins in the salt solution before saline electrolysis.In other embodiments, the oxygen in hydrogen and the atmosphere or from the oxygen combustion of raw material chemicals produce water, and in other embodiments, described method comprises uses the hydrogen produce power.In some embodiments, the separation from mixture of sodium carbonate and/or sodium acid carbonate relates to the thermal precipitation separation process, is used for the energy of the heat of this separation process from the hydrogen generation.In other words, hydrogen and coal cofiring burn the emission behaviour that improves coal combustion, perhaps are used for fuel cell and reclaim galvanic combustion process.

In some embodiments, air-flow is the waste streams from equipment, and in other embodiments, described equipment is to use the generating equipment in carbon-based fuel source.In some embodiments, waste streams comprises CO ₂And H ₂O.

Special embodiment of the present invention also comprises a kind of equipment, and described equipment comprises: comprise the tank house of at least one negative electrode and at least one anode, this chamber is fit in use produce hydroxide; With tank house be fit in use to hold the equipment that mixes that the conduit of air-flow is operably connected, this mixing equipment is fit to the hydroxide from tank house is mixed with air-flow, produce mixture, in this mixture, the carbon in the air-flow, sulphur and/or nitrogen compound can react with hydroxide; With mix the separation chamber that is operably connected of equipment, described separation chamber is fit to mixture is separated into independently gas phase and solid phase and/or liquid phase.

In some embodiments, tank house comprises membrane electrolytic cell, barrier film and/or mercury.In some embodiments, mixing equipment is batch reactor or batch reactor series, and in other embodiments, mixing chamber is gas/liquid absorption/reaction unit or gas/liquid absorption/reaction unit series.In other embodiments, mixing chamber is crystallizing tower or crystallizing tower series, and in other embodiments, mixing chamber is bubble column or bubble column series.

In some embodiments, described equipment also comprises the hothouse that is operably connected with described separation chamber, this hothouse is fit in use remove the liquid in solid phase and/or the liquid phase, and in other embodiments, hothouse is fit in use heat solid phase and/or liquid phase.In other embodiments, described equipment also is defined as with generating equipment and is operably connected.

In some embodiments, tank house is fit in use by sodium chloride and water generates chlorine and NaOH.In other embodiments, mixing equipment is fit in use and will produces carbonate and/or bicarbonate product from the hydroxide of tank house and carbon dioxide mix from air-flow.

In some other embodiment, the present invention includes and determine with respect to the subnormal voltage operation of the area that increases and the optimum operation voltage and current that under given protonation, has the electrochemical cell of given V/I feature.In other embodiments, the present invention includes the method for the thermodynamics lower limit of the given electrolytic cell working voltage that is identified for this process.In some embodiments, provide a kind of method, this method is used for determining to finish from waste streams removing CO ₂Ecological efficiency (the  CO of device of work ₂And other embodiments comprise ecological efficiency (the  CO of the concrete device that determine to use any embodiment of the present invention/ E), ₂/  E) method.Other embodiment is included in the method for the very pure hydrogen of low price-indifference point production, and its cost is equivalent to retrievable energy content.

Term " comprises " (any type of comprising, for example " comprise " and " comprising "), " having " (any type ofly have, for example " have " and " having "), " containing " (any type of containing, for example " contain " and " containing has ") and " comprising " (for example " comprise " and " comprising " any type of comprising) be open link-verb.As a result, a kind of method or equipment " comprise ", " having ", " containing " or " comprising " one or more steps or element refer to that this method or equipment have this one or more steps or element, but are not limited to only have this one or more steps or element.Equally, a device or a kind of element of method " comprises ", " having ", " containing " or " comprising " one or more features are meant that this element has this one or more features, but are not limited to only have these one or more features.Term " use " should be explained in the same way.Therefore, for example, a step in a kind of method comprises that " use " certain information is meant that described at least information is used, but does not get rid of the possibility that can use other information of not describing.In addition, a kind of structure is constructed and must be constructed at least in the manner described according to certain mode, but also can construct according to the mode of not describing.

Except as otherwise noted, term "/a kind of " be defined as one/a kind of or one/more than one.Term " another/another kind " be defined as at least the second/second kind or more.Term " basically " and " pact " are defined as at least near (comprising) set-point or state (preferably in 10%, more preferably in 1%, most preferably in 0.1%).

Used term " carbonate " or " carbonate product " are commonly defined as and contain carbonate CO in the literary composition ₃Inorganic matter composition (mineral components).Therefore, this term comprises the carbonate mixture and only contains the material of carbanion.Term " bicarbonate " and " bicarbonate product " are commonly defined as and contain bicarbonate radical HCO ₃The inorganic matter composition.Therefore, this term comprises the carbonate mixture and only contains the material of bicarbonate ion.

Using some embodiments of the present invention to form in the process of bicarbonate and carbonate, term " ion ratio " refers to that the sodium ion number is divided by the ratio of the carbonate number that exists in the product in the product.Therefore, by pure carbon acid hydrogen salt (NaHCO ₃) " ion ratio " of the product stream that forms be 1.0 (Na/C), and by pure carbon hydrochlorate (Na ₂CO ₃) " ion ratio " of the product stream that forms be 2.0 (Na/C).According to the extension of above-mentioned definition, the ion ratio of the continuous mixture of any carbonate and bicarbonate is between 1.0-2.0.

In preferred implementations more of the present invention, in the sodium chloride brine charging of chloro-alkali electrolytic cell, add hydrochloric acid, carry out following reaction:

H ₂O+NaCl+aHCl+ energy → NaOH+ (1/2+a/2) H ₂+ (1/2+a/2) Cl ₂

In this equation, term " a " is defined as " the protonated factor ", expression proton (H ⁺Ion) and sodium ion (Na ⁺Ion) ratio.

Term " isolation (sequestration) " used in the literary composition refers generally to remove CO partially or completely from discharging source (point emissionssources) ₂And to prevent that its mode that turns back to atmosphere from storing CO ₂Technology or enforcement behavior, use this term not get rid of to be considered to any type of above-mentioned embodiment of " isolation " technology.

Term " ecological efficiency " used in the literary composition is identical with term " thermodynamic efficiency " meaning, is defined as the CO that every consumption 1 unit energy is isolated in some embodiment of the present invention ₂Amount (with formula "  CO ₂/  E " expression).The CO that isolates ₂Be according to the total CO of generating equipment ₂Percentage define, energy consumption is to define according to the generating equipment total power consumption equally.

Used term " low-voltage electrolysis " and " LVE " are meant being lower than and carry out electrolysis under about 5 volts voltage in the literary composition.

The description of well-known technology, component and equipment is omitted, and there is no need to make because of unwanted details the method and apparatus of the present invention indigestion that becomes.The explanation of the inventive method and device comprises in the appendix those, is exemplary and nonrestrictive.Fall within the scope of the claims, but some replacement that does not offer some clarification in this specification, modification, interpolation and/or rearrangement are conspicuous for those of ordinary skills.

In conjunction with the accompanying drawings, by following detailed description to the specific embodiment, further feature is conspicuous with relevant advantage.

Brief Description Of Drawings

The following drawings is exemplary and nonrestrictive.Accompanying drawing is the part of specification of the present invention, is used to further specify some aspect of the present invention.By with reference to the one or more in these accompanying drawings, again in conjunction with in the literary composition to the explanation of illustrative embodiments, the present invention may be better understood:

Fig. 1 is the process chart of some embodiment of expression the present invention.

Fig. 2 A represents to be used to observe the equipment of principal character of an embodiment of removing carbon dioxide part of the present invention.

Fig. 2 B represents the absorption/conversion results of testing.

Fig. 2 C represents the absorption/conversion results of testing.

Fig. 2 D is that 90%CO is removed in expression ₂The figure of required gas/liquid contact distance (m, fluid depth).

Fig. 2 E is that expression product ion ratio is with the CO that absorbs in the test reactor ₂The figure that percentage changes.

The thermodynamic behavior that Fig. 3 represents approximate fluid in the reative cell with shown in reaction carry out the variation of time.

Fig. 4 represents the overflow research of 5 ' post.

Fig. 5 represents typical voltage/current feature work line under various anolyte pH and the temperature conditions.

Fig. 6 is the calcspar according to a kind of system of embodiments of the present invention, and this system comprises the reactor that does not reclaim hydrogen.

Fig. 7 is the calcspar according to a kind of system of embodiments of the present invention, and this system comprises that the DC by fuel cell returns and reclaims the reactor of hydrogen at this.

Fig. 8 is illustrated under the speed of low interface, the CO that absorbs in the bubble column ₂Percentage and fluid depth, with the relation of gas interface speed.

Fig. 9 A represents according to embodiments of the present invention, CO ₂Theoretical obtained the maximum absorption and experimental result.

Fig. 9 B represents hypothesis and result of calculation in conjunction with the flue gas model of the equipment of some embodiment of the present invention.

Fig. 9 C represent to combine some embodiment of the present invention equipment removing carbon dioxide treating capacity (load) and to the intermediate demand amount of corrodent.

Fig. 9 D represents in conjunction with the treating capacity of the electrolysis section of the equipment of some embodiment of the present invention and requirement.

Fig. 9 E represents to combine the used heat result of calculation of the equipment of some embodiment of the present invention.

Fig. 9 F represents to combine the energy balance and the ecological efficiency result of calculation of the equipment of some embodiment of the present invention.

Figure 10 represents to combine the ecological efficiency of the various pattern generating equipments of embodiment of the present invention.

Figure 11 represents the electric power percentage saved for every square metre of area of normalized LVE design.

The description of illustrated embodiment

The present invention relates to partition method, wherein from waste streams, remove carbon dioxide, and carbon dioxide is converted into carbonate and/or bicarbonate product.The embodiment of method and apparatus of the present invention comprises one or more in the following general part: (1) water-based removing carbon dioxide process, gaseous state CO ₂Be absorbed in the water-based causticity mixture, with the hydroxide reaction, form carbonate and/or bicarbonate product then; (2) separation process separates carbonate and/or bicarbonate product from liquid mixture; (3) saline electrolysis process is produced the NaOH that is used as absorption fluids in the removing carbon dioxide process; (4) generation and use comprise chlorine, sodium carbonate and sodium acid carbonate, hydrogen from the accessory substance of removing carbon dioxide and electrolytic process.To be further explained in detail these general parts hereinafter.

I. the summary of advantage

To realize any other method or the equipment of target, many embodiments of the present invention consume some energy to finish CO as work ₂With the absorption of other chemicals in the flue gas stream, and other purpose of finishing the embodiments of the present invention described in the literary composition.But the advantage of some embodiment of the present invention is that they can provide the ecological efficiency more superior than prior art, as explaining in detail in embodiment 5 and 6.Can obviously find out from the data of

embodiment

5 and 6, the energy that uses Waste Heat Recovery to increase or do not produce greenhouse gases provides energy for described process, use low-voltage electrolysis stably, raising is reclaimed the electric power that obtains by Hydrogen Energy and is returned the ecological efficiency that can further improve method, reach and surpass method is provided energy fully by Waste Heat Recovery (reclaiming with Hydrogen Energy) point, and 100% ground absorbs the CO of generating equipment discharging basically ₂

In addition, use the absorption weak acid CO of some embodiment of the present invention ₂The advantage of limit chemical reaction be that this method virtually completely absorbs strong acid, SO _XAnd NO _XAnd a spot of mercury.In the single phase of electric charge load removing carbon dioxide device, use SO _X/ Ar and NO _XThe test of/Ar confirms to remove these components of 99%+ in the flue gas, and (" 99%+ " refers in handling 14 liters/minute the situation of flue gas, by the existence of gas chromatographic technique detection less than each pollutant in the product gas flow, promptly pollutant is removed effectively).In some embodiments of the present invention, NO _X, SO _XHas important economic implications with the subsidiary scrubbing of mercury compound; That is, the embodiment of the application of the invention, the coal that contains a large amount of these compounds can burn in generating equipment, in some embodiments, produces than not having some embodiment CO of the present invention ₂The high-level coal processing pollution still less of/absorption technique benefit.

In addition, the proportional zoom capabilities of some embodiment of the present invention can proceed to limit rank; That is to say that because in some embodiments, described method is electric power control, in fact power consumption can be adjusted according to the individual molecule of the absorbent that produces any preset time.And, accurately determine the CO that is absorbed ₂The ability of amount be can implement and be easy to: the weight of the carbonate product that weighing forms, by their ion ratio of analysis to measure, calculate the CO that absorbs to determine ₂Molal quantity, can easily confirm and measure the CO that is absorbed ₂(to removing CO in the flue gas ₂Play the factor of certain promotion with other compound).

Some embodiment of the present invention and other CO ₂Another advantage that removing method is compared is under some market conditions, and the value of product substantially exceeds the cost of required reactant or net power or equipment depreciation.In other words, some embodiment is a commercial run of producing chloro-hydrogen-carbonate product beneficially, can remove CO in a large number simultaneously ₂With relevant subsidiary pollutant.All other competing methods only are additionally to increase operating cost.

II. method flow diagram

Fig. 1 is the method flow diagram of simplifying, and the generality example embodiment of equipment of the present invention and method has been described.This figure provides for illustrative purposes, has therefore only described the specific embodiment of the present invention, but limits the scope of claim never in any form.As shown in Figure 1, flue gas (FG) may be after carrying out initial used heat exchange with used heat/DC generation systems, from 901 access method processes.The FG that enters as 300 ℃ admixture of gas at first is transported to FG/ bicarbonate heat exchanger 903 by pipeline 902 in this embodiment, and temperature is reduced to 120-140 ℃ in this embodiment in this heat exchanger.Similarly, FG continues by anolyte/FG heat exchanger 904 and catholyte liquid heat exchanger 905, and temperature drops to 95 ℃, and by water/FG heat exchanger 929, temperature further is reduced to 30 ℃ then.FG with leaving water/FG heat exchanger 929 is incorporated into valving then, the FG that the effluent gas temperature mixture control is 931,30 ℃ mixes with 120-140 ℃ the flue gas that is transported to effluent gas temperature mixture control 931 by hot flue gases processing pipeline 906 in this device.The FG mixture of temperature between 30-140 ℃ can be input to differentially the bottom on carbonation/absorption tower 907 then, carbonation/absorption tower 907 can be to fill or unfilled bubble column, in this device, inject or gas jet, gas forms foam as a result, rise by fluid, accumulate in top outlet (Upper Vent) 908.In this embodiment, the fluid that will partially or completely remove carbon dioxide subsequently injects and by bicarbonate salinization/converter 909, makes foam pass through fluid in the described tower by air blast, and arrives outlet 910.

The fluid of use in FG/ bicarbonate heat exchanger 903 is sodium acid carbonate/sodium carbonate and various sulfate, nitrate, mercury and the particulate and the aerosol that absorb from flue gas in absorption/converter (907 and 909).This liquid fluid is heated to the temperature that is enough to produce sufficient water vapor pressure by contacting with 300 ℃ introducing FG, produces steam when fluid is injected in the storage tank 911, and described steam is condensation in condenser 912 subsequently, and the distilled water that obtains is recycled to H ₂In the O accumulator tank 913, after carrying out any necessary processing, be used for forming salt solution at brine mixer 914.The fluid that is used in anolyte/FG heat exchanger 904 is the salt solution of making by the salt (being NaCl in this embodiment) that adds first family and second family in water, and described water is by water main's 915 supplies or partly or entirely by H ₂O accumulator tank 913 is supplied with.Make salt solution protonated (acidifying) by adding HCl, the form of HCl be the HCl GAS ABSORPTION in water, or from feed chemicals HCl, this operation is all carried out under pH closed loop controller 916 is controlled.This fluid cycles through the anolyte portion 917 of electrolytic cell 933.Similarly, using the fluid in catholyte/FG heat exchanger 905 is the NaOH (aqueous solution) that cycles through the catholyte part 918 of electrolytic cell 933.When the pH of catholyte value surpasses the minimum pH value (as the expression of concentration) at control point 919, dense NaOH is transported in the hydroxide storage tank 920.

The fluid of use in water/FG heat exchanger 929 is from enough big reservoir, and temperature is enough low, to finish heat exchange.In some embodiments, this heat-exchange system can be used for " preheating " of bicarbonate/carbonate solution to be handled, and then carries out heat exchange in flue gas/bicarbonate heat exchanger 905.And, in some embodiments, water main 915 storage tank, H ₂O HX storage tank 937 and H ₂ O accumulator tank 913 can be reinforced partially or completely.

The protonated salt solution that cycles through the anolyte portion 917 of electrolytic cell 933 carries out electrolysis, forms chlorine, collects chlorine, enters sodium hypochlorite reaction device 924 by chlorine pipeline 921 in this embodiment.Sodium ion and hydrogen ion (proton) barrier film by electrolytic cell 933 is transported to catholyte part 918.At this, the hydrogen ion in the sodium ion place of water forms hydrogen, transfers to H by the pure hydrogen pipeline of introducing 922 ₂/ O ₂Fuel cell 923, the O in this hydrogen and atmosphere ₂In conjunction with, producing direct current, direct current is recycled in the electrolytic cell 933 in this embodiment, and pure water is recycled to H by pure water recovery loop 935 ₂In the O accumulator tank 913.The chlorine contact (bubbling) that is transported to sodium hypochlorite reaction device 924 is by being transported to the NaOH of this reactor by hydroxide storage tank 920.Obtain clorox, storage is used for selling or being used as feed chemicals.In chlorine that is produced and the HCl gas some (except covering the loss, will producing the continuous circulation of HCl with superstoichiometric amount a) burnings in HCl fuel cell 925 are recycled in the brine mixer 914 by HCl acid gas reflux line 926 then.

The hydroxide that produces and store is the absorption fluids that is incorporated into carbonation/absorption tower 907 by feed chemicals manufacturing and the hydroxide that is stored in the hydroxide storage tank 920 perhaps.This absorption fluids by bicarbonate salinization/converter 909, is transferred (as the bicarbonate/carbonate mixture in water) in FG/ bicarbonate heat exchanger 903 subsequently then.Remove by evaporation anhydrate after, the product slurry of the bicarbonate/carbonate that concentrates is transported in the product bicarbonate salt bath 927, can further handle or refine at this, perhaps can be discarded or sell with the product slurry.

The equipment of the invention described above shown in Fig. 1 and each vague generalization parts of method are described in further detail hereinafter.

III. from waste streams, remove (absorption) CO with aqueous process ₂And be translated into carbonate and bicarbonate

As mentioned above, in some embodiments, equipment of the present invention and method make use removing carbon dioxide method, wherein gaseous state CO ₂Be absorbed in the water-based causticity mixture, with the hydroxide reaction, form carbonate and bicarbonate product then.In many embodiments of the present invention, be different from other and obtain/isolation scheme, NaOH is as main absorption fluids.The NaOH of various concentration is known as CO ₂Convenient absorbent.When carbon dioxide is contacted with sodium hydrate aqueous solution, can form from pure sodium bicarbonate (NaHCO ₃) to pure sodium carbonate (Na ₂CO ₃) continuous product, and can produce different situations, driven equilibrium moves to either direction, even reach fully (or near fully), and produce bicarbonate, the carbonate deposition of enough concentration (remove anhydrate by process chemistry or by the whole bag of tricks) or contain the mixed precipitation of these two kinds of compounds.

When carbon dioxide is contacted with sodium hydrate aqueous solution, the behavior of reative cell inner fluid as shown in Figure 3, the reaction with the indication time carry out.Two temperature drift stage correspondences also mark two visibly different reactivenesses:

(1) CO ₂The absorbable initial absorption stage.The absorbability of fluid descends along with the decline of OH concentration, after the OH ion concentration is consumed, absorbs termination, can take a turn for the worse in some cases.At this partial reaction is heat release, almost only forms carbonate.

(2) CO ₂Be not easy absorbed second transformation stage.Flue gas can not produce fluid to CO by mixture ₂Any clean absorption, but because any evaporation of water, CO ₂Change any endothermic reaction of any loss of vaporized state and generation into and cause the loss of evaporation heat, the result obviously cools off fluid.In this stage, according to following required purification quantitative relation, the sodium carbonate that has formed in solution is converted into sodium acid carbonate:

Na ₂CO ₃(aqueous solution)+H ₂O (liquid)+CO ₂(aqueous solution) → 2NaHCO ₃(aqueous solution)

By in the equipment shown in Fig. 2 A, repeating, can confirm this at first carbonation with reappearing, the order of bicarbonate salinization (explaining in detail in embodiment 3) can meet and exceed the absorption limit of the fluid that contains the variable concentrations absorbent then.

Two stages are obviously different in the characteristic aspect shown in the table 1.

Table 1

Stage	Thermodynamics	Product	CO ₂Absorb	[OH] exists
Stage	Thermodynamics	Product	CO ₂Absorb	[OH] exists	The salinization of carbonation bicarbonate	The heat release heat absorption	Na ₂CO ₃ NaHCO ₃	The abundant minimizing do not have absorption or negative absorption	A large amount of few (De minimis)

Though embodiments of the present invention can use same reative cell to come original position to finish this two processes, the feature difference of reaction means reaction separately at two reative cells and to optimize them respectively are suitable approach of preferred implementation.Do not consider " inner be provided with " (i.e. intermittence-right-continuous degree, the number in chamber, container, stage etc.) of transfer device, these two basic processes according to this in proper order to be enough to the providing molar concentration of good absorption to carry out.

Therefore, because can carry out process control to some embodiments of the inventive method and equipment, to produce pure or approaching pure sodium acid carbonate, therefore some embodiments of the present invention are that the sodium that each electrolysis produces is caught a carbon, rather than  (ecological efficiency of generation is improved, and is the 2X that carbonate is produced).Therefore, compare, when being used to form bicarbonate, being used to produce 1 moles of hydrogen oxide required electrolytic energy and treating capacity and making " normally " absorbability double with the absorption/energy efficiency that forms carbonate.

In different embodiments of the present invention, can produce the bicarbonate/carbonate concentration spectrum of form of ownership.In preferred embodiment, can regulate concentration of fluid, temperature, pressure, flow etc., absorbed CO with optimization " available " ₂Ratio, thereby the formation of optimization bicarbonate.

Some embodiments of the present invention can be controlled the pH (OH ion concentration) of absorption fluids, as control CO ₂Means with other GAS ABSORPTION speed.Some preferred embodiment in, the concentration that improves salt/carbonate can be used for further impelling reaction to develop to the direction that forms bicarbonate.The product that is rich in carbonate is produced in the market price of product and economic factor decision in a period of time, produce the product that is rich in bicarbonate in period at another section, equipment by Na/C is average, form a kind of measurement standard, this standard can be used for absorption/conversion with the ionic substance that produces effectively.

By two processes being separated into two independently in the chamber, and two chambers exhaust at OH, the some conversion of temperature stagnation/decline and attenuation by absorption, can adjust the mode that makes up and optimize removing carbon dioxide equipment.It will be appreciated by those skilled in the art that form such as these simple two stage removing carbon dioxide methods can be designed to intermittently, false continuous, continuous.

In addition, in order to finish absorption with the least possible energy, many preferred implementations of the present invention can adopt bubble-column reactor (filling or unfilled, having/do not have horizontal liquid flows, has or do not have horizontal liquid-flow), the characteristic that this reactor can produce bigger liquid/gas contact surface helps mass transfer, master-plan can obtain level of freedom thus, can use less level high (below 3 meters or 3 meters), and still can under the situation that does not almost have resistance or pressure head, realize the absorption of 90%+, thereby overcome the problem that runs in the pumping fluid, therefore be designed to wide horizontal area to realize commercial scale (wide on-swimmer's pool or the container that is equal to), might move horizontally so that continuous operation to be provided.Some embodiments of the present invention can be used the gas-liquid contactor of many other structures, as long as these devices can be realized required gas-liquid contact.

Fig. 4 has shown that wherein resistance is about 0.01psig, adds the pressure head of 1.52psig to the overflow of 5 ' post research (flooding study), to overcome 5 ' fluid depth.These losses and other cost squeeze estimate that ratio shared in the consumption of generating equipment less than 1%, therefore is considered to atomic little, can ignore in an embodiment.Fig. 4 has confirmed that resistance extremely low in the fluid approach can cause extremely low-energy compression, the ecological efficiency of this sampling device not can owing to spend in the compression or gas-operated on excessive energy be damaged.

Absorb CO by implementing the least possible work ₂Can improve the ecological efficiency of the embodiment of the inventive method and equipment, it is to finish the fluid of the required compression of described method, pumping and the amount of air that this ecological efficiency is caused a factor of adverse effect.For this purpose, two kinds of high efficiency absorbers of design (can be removed in the flue gas stream that enters 99% CO ₂, this flue gas stream is N ₂In contain 60% CO ₂), can realize high CO by the operation of " less level is high " ₂Absorptivity.

Preferred implementation of the present invention is used larger area liquid-cyclostrophic to move the surface and (is filled or unfilled bubble column or its equivalent, in static or mobile fluid container) in highly lower absorbing fluid, to finish high-absorbility, thereby reduce the required resistance of fluid contact, therefore this " the high design of less level " needs wide and short " pond " or their equivalent in pipeline, groove, container etc., is used for effectively absorbing a large amount of CO ₂

Think all in main flow industry and all lists of references that removing carbon dioxide reaction of the present invention is that mass transfer is limited.In fact, in rising by the method for fluid, uses foam filling or unfilled tower with big gas-liquid contact absorption area, as if reaction do not have mass transfer limit, as if perhaps in other words, use the bubble column design that is used for the gas-liquid contact of the inventive method can easily overcome mass transfer limit: verified not have bubbling under the situation of filling can produce the CO of instant 98%+ by the injector that only has 30 centimetres of gas/liquids to contact distances ₂Absorptivity (referring to Fig. 2 B and 2C, as opinion during institute among the embodiment 3), and in industrial 15-25 minute significant time period, fluid keep the ability that on average absorbs up to 80%+.This almost is not subjected to serious mass transfer limit, actual experiment confirm, even at simple loading when finishing, the mass transfer behavior of this chemical absorbing is also carried out easily.

Explained high absorption CO among the embodiment 1-3 in detail ₂Three examples of the design of/NaOH absorption reactor thermally.The conclusion that draws from embodiment 1-3 is, confirmed the high-absorbility of the NaOH that less level is high, but and the verified CO that enters that in the industrial container that can have manufacturing dimension, removes high percentage with lower resistance ₂

Generally speaking, comprise one or more in the following attribute about some embodiment of the present invention of the method and apparatus of removing carbon dioxide part:

(1) uses less level CO in the high carbonation stage of coming realization response ₂High-absorbility;

(2) in bicarbonate salinization process, contain CO by continuous contact ₂Process gas (perhaps other CO ₂Concentration surpasses the CO that is reformed by absorption fluids ₂Dividing potential drop contain CO ₂Gas) separate and handle the fluid of carbonation;

(3) arrange spendable method order by process control state variable and concentration, thereby produce all different mixtures of pure carbon acid hydrogen salt, pure carbon hydrochlorate and bicarbonate and carbonate formation;

(4) when the absorptance of sodium/carbon is 1: 1, embodiments of the present invention are effective; Optimized the CO of the every kilowatt hour correspondence that is used to produce reactant like this ₂Uptake (variable of ecological efficiency, ( CO ₂/  E)).

IV. the separation of product

As mentioned above, in some embodiments, equipment and method that the present invention discloses are used a kind of separation method, separate from liquid solution with the bicarbonate product by this method carbonate.The separation of liquid solution product needs relevant method.In the temperature and pressure scope of broad, form sodium acid carbonate (NaHCO ₃) and sodium carbonate (Na ₂CO ₃Or soda ash) with the fluid balance of NaOH (NaOH or caustic soda), is provided at different CO ₂Divide and depress different balance terminal points.By controlling the degree of alkaline concentration, temperature, pressure, reactor size, fluid depth and carbonation, can form the precipitation of carbonate and bicarbonate.Perhaps, some preferred embodiment in, can be by from the aqueous solution of carbonate product, isolating the carbonate product with the heat exchange of the flue gas that enters.In addition, because the solubility product constant difference between sodium carbonate and the sodium acid carbonate, so can reach the process points of some non-intuitive; For example, one of characteristic of the balance of sodium carbonate in some caustic liquor is the precipitation that heating can promote solid; And, under certain conditions, confirmed that carbonate can high-purity (93%+) autoprecipitation from the aqueous solution.

In addition, in some embodiments, be used for the hydrogen that the heat of separation process can produce from initial electrolysis, perhaps from the creativeness utilization of the used heat that contains in the flue gas stream that enters.By well-known crystallization purifying method through crystallization process purified crystals material.

According to DESIGN OF REACTOR, the liquid stream of discharge can comprise water, NaOH, the NaHCO that exists with various balances ₃, Na ₂CO ₃With other dissolved gases.Can also find the trace emission components of dissolving, such as H ₂SO ₄, HNO ₃And Hg.As shown in Figure 6, in order to separate/remove the liquid stream of discharge, for example from carbonate, remove in one embodiment ,/it is minute dried up that (in the words, " carbonate " refers to the mixture of carbonate and bicarbonate, also may have hydroxide; Any isolation technics that is used for any this class mixture can comprise that heating makes water evaporate from mixture), can use reboiler 106 to make the water boiling, thereby cause the water evaporation.Perhaps, the alkaline solution of reserve part (for example, being about the NaOH of 1 gram molecule (molal)), this solution of heating in the separation chamber makes purer Na then ₂CO ₃Be deposited in the dump tank, remaining NaOH recirculation is got back in the reactor 200.In other embodiments, the mixture that pure carbon hydrochlorate, pure carbon acid hydrogen salt and both can be in equilibrium concentration and/or slurry or conc forms subsequently regularly is transported to truck/tank car.In other embodiments, liquid flow can be moved on to evaporation tank/evaporating field, can be carried by evaporation at the liquid of this water and so on and remove.

With reference to figure 6, DESIGN OF REACTOR shows the energy that can reclaim in the hydrogen that is stored in electrolysis, and these hydrogen are as combustion fuel, boiler gas or be used for H ₂/ O ₂In the fuel cell.Reactor 200 can be used for producing the operation of stable state, i.e. NaOH and NaHCO ₃Produce with about 50: 50 ratio.The hydrogen that produces in initial electrolysis can be used for providing heat, NaHCO ₃Can precipitate in separation chamber 108, remaining NaOH is back in the reactor 200.The slurry of self-separation chamber 108 provides to water treatment room 110 in the future, and water treatment room 110 can be connected with separation chamber 108.Perhaps, slurry is stored, offer water treatment room 110 then as required.

Fig. 7 illustrates the another kind of reactor design according to an embodiment of the present invention.In fact, Fig. 7 has shown obtaining again of excess energy that some produces the hydrogen accessory substance.Use the original position high efficiency fuel cell of series connection can realize that direct current reclaims, the direct current that is reclaimed can be used for replenishing and partly providing Faradaic current.Mixing chamber 300 will include but not limited to NaOH, the NaHCO of certain percentage ₃Offer separation chamber 308 with the mixture of NOX, SOX and Hg.Separation chamber 308 can be separated into solid phase and/or liquid phase with mixture by heat is provided to mixture.The hothouse (not shown) of separation chamber 308 can be removed the liquid in solid phase and/or the liquid phase in the process of heat is provided.The NaOH of the dilute form of gained is offered boiler 306, become conc forms, concentrate is offered mixing chamber 300 by recirculation loop in this rare NaOH boiling.Water from boiler 306 can be offered tank house 302, particularly brine mixer 302A.Can be with the Na from separation chamber 308 of gained ₂CO ₃/ NaHCO ₃(slurry) provides and makes commercial use.In one embodiment, the carbonate slurry can (for example, store NaHCO directly or indirectly ₃, be used for the method that hard water is handled and so on afterwards) and offer water treatment facilities 310.Perhaps, NaHCO ₃Can further purify, dry, transport and offer other industrial use.

The release of gaseous products relates to such problem: NaOH or identical component can discharge safely, i.e. generating equipment discharging " alkali rain " should be avoided equally as discharging " acid rain ".But NaOH is used as the scrubbing composition in the generating equipment production usually, and can use through the EPA approval.The measure of operating NaOH and avoid alkali to discharge in generating equipment is well-known in the art.For example, simple and cheap condenser/reflux can prevent a large amount of releases of NaOH gaseous state effluent.

In the carbonate precipitation separation method of some embodiment of foundation the present invention, carbonate eqrilibrium has spatially retrained carbon dioxide, has absorbed the gas of contact, is converted into carbanion basically immediately.Reaction chain can be a mass transfer limit, in case carbon dioxide is absorbed by alkali like this, ionic reaction just takes place rapidly.

A feature of sodium carbonate balance is along with temperature raises, Na ₂CO ₃Natural sedimentation and gathering make it be extracted as slurry easily, and the NaOH of a part discharges in slurry.In one embodiment, with some wet chlorine that produce in the chlorine circulation this slurry is carried out filtration process NaOH is reduced, to NaHCO ₃The content of the NaCl of middle trace is approximately equal to or less than the content of NaCl in the sodium carbonate that obtains by recovery of subterranean " trona " or deposit.Like this, the balance of sodium carbonate/caustic soda can make carbon be converted into liquid from gas fully, is converted into solid again.In other embodiments, can advantageously use carbonate to circulate and collect the slurry of soda ash, NaOH and other various carbonate and impurity as trapping medium, slurry is transported away as roadbed material.

V. at low-yield electrolytic brine down, produce absorption fluids

As mentioned above, in some embodiments, equipment that the present invention discloses and method use saline electrolysis to produce NaOH, and this NaOH is used as absorption fluids in the removing carbon dioxide process.Saline electrolysis is to be mainly used in the electrochemical method of producing concentrated sodium hydroxide (caustic soda) and chlorine, often represents by following equation in pertinent literature:

2NaCl+2H ₂O+e-→2NaOH+H ₂(g)+Cl ₂(g)

Can finish saline electrolysis by the standard electrolytic cell of three kinds of general types: barrier film, mercury and membrane electrolytic cell.In the electrolytic cell of these types any all produces same output product by same input reactant.Their difference is that mainly reactant and product mode spaced apart from each other is different.

In one embodiment, because some factors can be used membrane electrolytic cell.At first, the environmental problem that relates to of mercury has reduced the demand to mercury cell.The second, diaphragm cell can produce more weak caustic product, and this product contains a large amount of salt and chlorion, needs considerable processing/separating step again to remove salt a large amount of in the corrodent afterwards.The 3rd, the development of fluorinated polymer technology has improved the life-span and the electrical efficiency of membrane electrolytic cell technology, generally can guarantee to surpass the life-span in 5 years in industrial market.In addition, in preferred enforcement, the power efficiency of corrodent per ton surpasses barrier film and mercury cell.

The membrane electrolytic cell treating apparatus is usually but be not limited to have following general input and output:

Anode: 26%NaCl input+2275kwh/ ton Cl ₂→ Cl ₂(g)+24%NaOH

Negative electrode: H2O input+e-→ 30-33%NaOH+H ₂(g)

Notice that power demand (for example, chlorine 2275kwh per ton) depends on the design of each electrolytic cell.Therefore, power demand can change.

Manyly preferred embodiment can in this function, adopt membrane electrolytic cell.Membrane electrolytic cell is compared with other saline electrolysis method has some advantages.At first, membrane electrolytic cell neither contains and does not also produce any environmental sensitivity emission (for example, mercury), and with diaphragm cell compare with mercury cell be electricity effectively.Concentrated/dilution that membrane electrolytic cell can also use/additional NaCl circulation, they are suitable as continuous " salt circulation " treating apparatus like this.Secondly, not further evaporation of the NaOH that membrane electrolytic cell produces/concentrate just has the suitable concentration (for example, the NaOH of 30-33 weight %) that is used for the removing carbon dioxide process.In addition, the hydrogen that membrane electrolytic cell produces is " clean ", approximately is " electron level other ", does not relatively have NaCl or other pollutant.Therefore, can be with hydrogen compressed and storage, as electron level H ₂Be used for in-situ power generation,, perhaps be used for combustion technology and improve for example with low-grade coal mixed combustion.Perhaps, hydrogen can be used for boiler oil, is used for the separation process of carrying out after removing carbon dioxide.The membrane electrolytic cell technology can also make scale expand the plant produced rank to from the laboratory rank by adding midget plant.In addition, the chlorine of producing by film method is littler than the humidity of the chlorine of other standard electrolytic method production.Therefore, the single stage compress circulation is enough to other chlorine of production water treatment level.

More than stated the technology of publishing and implementing that is generally used for manufacture chlorine and caustic soda in this area.But the purpose of some embodiment of the present invention is different aspect some, and the result causes different chemical technologies to be used to finish the various objectives of some embodiment of the present invention.

A. low-voltage electrolysis The Application of Technology

In some embodiments of the present invention, saline electrolysis is in conjunction with low-voltage electrolysis (LVE) technology, thus the thermodynamic efficiency of raising method.Some embodiment of the present invention just preparation but mainly utilize NaOH before flue gas emissions is in the environment, to absorb CO in this flue gas as the caustic soda of end-product as middle absorbent ₂Because chlorine industry is usually directed to that caustic soda is transported to its target from manufacturing works and makes use, it is uneconomic that the big water gaging of caustic soda is followed in transportation, therefore by the big mode that dewaters of this power consumption of evaporation of vapours caustic soda is concentrated to about 55 weight % usually, transport as liquid, in some cases, with caustic soda simmer down to anhydrous solid, normally particle form.This concentrate the most often realized by following steps: surpassing electrolysis under the voltage of 5V (being referred to herein as " under tangible overvoltage "), obtain the NaOH of above-mentioned 30-35%, then by steam-vaporization cycle, obtain 55% (perhaps finish-drying product to the anhydrous particle state, etc.).

Most of embodiment of the present invention does not transport NaOH as product, can produce the NaOH (as the water-based absorption fluids) of usable concentration under the voltage that obviously forces down than the 5V+ standard electric of chlor-alkali equipment use in service.Excessively estimated service life LVE is to the influence of thermodynamic efficiency of the present invention, because power consumption can be come accurate Calculation with simple DC equation:

P=V (volt) * I (electric current) * (current efficiency)

Because electric current is fixed (for each molecule, a pair of electronics is arranged, etc.) by electrochemical method, so almost can regulate power (other key factor is a current efficiency, and current efficiency also is the function that applies voltage) fully by the required voltage of electrolysis.Because embodiments of the present invention are used LVE, by change the voltage that is low to moderate 2.1V that service condition is determined easily in standard electrolytic cell, revise by method and structure standard electric chemical films electrolytic cell, embodiments of the present invention are compared with traditional high voltage chloric alkali electrolysis, and the power that NaOH consumed (kilowatt hour) of every formation unit quantity still less.Owing to these reasons, preferred implementation of the present invention comprises and is designed to utilize all available techniques to finish the electrolysis unit of low pressure operation, include but not limited to: the operation of narrow crack, high pressure, the anolyte of large tracts of land barrier film, adjustment and catholyte concentration, protonated ion ratio.In embodiment 4, explain the others of LVE in detail.

B. " indifference point " hydrogen uses

Usually the chlor-alkali operation produces hydrogen, and this hydrogen or combustion (of oil) insitu are used for evaporation of vapours (seeing above) as boiler oil, perhaps in many cases, uses air electrode to suppress hydrogen fully; For example, will contain the oxygen air and be blasted into device on the negative electrode, the result causes the instant restoring reaction to take place:

H ₂(g)+1/2O ₂(g)→H ₂O(l/g)，

This has changed the electrochemical energy summation, has reduced and has produced corrodent and the required voltage (in some cases, being low to moderate 2.8 volts in each technical literature) of chlorine, and cost is not produce hydrogen.Benefit to preferred implementation of the present invention is that they do not need hydrogen as the evaporation of vapours boiler oil.

Some embodiments of the present invention can comprise " air electrode " process (making the ability that recovers energy from hydrogen is zero) that inhibition hydrogen generates, but many chemical raw materials that preferred embodiment utilizes hydrogen production as energy recovery or other method of being used as.

Therefore, use the equipment of some embodiment of the present invention to have " indifference point " that relates to the hydrogen that uses generation like this; Promptly this equipment produces hydrogen, is used for its energy and reclaims (for example, in an example, its energy 60%), the energy of this quantity has certain economic and is worth, and does not use hydrogen to be used for energy and reclaims, and can surpass or equal the amount transaction or the sale hydrogen of the economic worth of energy itself.In this mode, this kind equipment is represented various " hydrogen well (hydrogen well) ".Produce hydrogen, and consume hydrogen and produce electric power and be worth, any people who wishes that hydrogen is used for other purpose this electric power of only need concluding the business is worth or its economic dispatch jljl, just can keep the economy of method.This embodiment has useful prompting for " hydrogen economy " planning in future: have ready-made hydrogen source, the price-non-differential cost point that can be lower than its born energy content obtains, and can prove the useful and favourable feature of this technology.

The application of C. protonated salt solution optimisation technique

Some embodiment of the present invention is intended to optimize the production of hydrogen rather than suppress it by following protonated salt solution optimization.In some cases, common chlorine industry joins the HCl of hydrochloric acid form in salt solution (NaCl) electrolytic cell that is called anolyte chamber." protonation " of this salt solution can reduce produces the needed voltage of a certain amount of escharotic, and this is because this effect has reduced the required energy of reactant/absorbent of some embodiment of preparation the present invention.In the normal operating condition of chlor-alkali equipment, cause that the reason of the effect of this reduction voltage is " NaOH by barrier film is returned in neutralization ", people study this process with respect to selectivity of barrier film etc., and have understood this process well.In general, should " neutralization " allegedly can only produce salt solution [NaOH (returning)+HCl (anolyte) → NaCl+H ₂O], and do not demonstrate the stoichiometric proportion that can change product.But, this area also do not understand well or exploitation a bit be to add the stoichiometric proportion that HCl has fundamentally changed following formula really:

NaCl+aHCl+H ₂O→NaOH+(1/2+a/2)H ₂+(1/2+a/2)Cl ₂

Because embodiments of the present invention depend on the energy of hydrogen and reclaim, (when 1 mole of absorbent NaOH of every preparation, the hydrogen of generation is many more, and then the energy that reclaims increases so the hydrogen of this additional quantity that is produced and chlorine are to particular importance of the present invention, and the chlorine that produces is many more, and then economic benefit increases).Produce the hydrogen that is used for the energy recovery of this additional quantity and the chlorine that is used to sell, reduce total voltage simultaneously (therefore, reduce energy and cost), the result causes some embodiment of the present invention to optimize and the consumption minimum energy produces reactant and reclaims the relevant value " a " of highest energy from product.Best situation is generally 0.5-1.0M HCl in NaCl solution (aqueous solution).But optimization all is specific for each cell design, physical dimension, concentration, temperature and pressure condition.But,, all have the best protonated ratio (" a ") of realizing the minimum energy operation for each electrochemical cell.In fact, very high " a " value (for example, at 90 ℃ greater than 0.15M) may cause most of commercially available barrier film to bubble at short notice.Certainly, though HCl is preferred for the protonated acid of salt solution in the present invention, many other acid well known by persons skilled in the art also can be used for making salt solution protonated.

D. from producing the HCl that is used for protonation

Because some embodiment of the present invention uses the HCl of input, produce H simultaneously ₂And Cl ₂Gas, the protonated of salt solution can the oneself back and forth carry out; That is H, ₂And Cl ₂Product gas burning (in effective fuel cell or simple burner) produces HCl gas, and HCl gas can be recycled in the anolyte, is used for the protonated of salt solution.From H ₂/ Cl ₂The energy that reclaims in the burning is higher than from H ₂/ O ₂The energy that reclaims in the burning.This has increased thermodynamic efficiency of the present invention.

Preferred implementations more of the present invention use absorption/conversion/regeneration approach as " concentrate/absorption process early stage ", and this process then is used for absorbing and concentrated CO ₂, these CO ₂(for example, those are with CO to be used in geology, ocean or land isolation technology ₂Inject the technology of carbon bank), specifically carry out according to following mode or similar mode:

(1) all hydrogen burnings produce HCl gas.

(2) reaction of sodium bicarbonate of all HCl gases and generation.

(3), discharge almost 100% pure CO by relevant neutralization reaction ₂, the salt water reuse (treatment can recycle and is used for other and absorbs circulation.

(4) by this method, the present invention is used for absorbing, transforms and discharges CO ₂, its net effect is that gas is removed from flue gas stream, and concentrated this process isolation technology afterwards that is used for.

E. carbonate of Hun Heing and bicarbonate are got back in the catholyte fluid

The chlorine industry that is different from chlorine/hydrogen electrolytic cell is used, and some embodiments of the present invention also make the mixture of carbonate and bicarbonate be recycled to catholyte (corrodent) side of electrochemical cell.These technology are extensive and various, but each operating point for whole process has the recirculation that best carbonate mixture is got back to catholyte, because under some concentration and condition, can reduce electrolytic cell voltage like this, thereby reduce electrolytic cell power.

F. Waste Heat Recovery is used to add hot fluid

Because some embodiment of the present invention is to have generating equipment, or discharge the CO of the hot gas form of a large amount of flue gas forms or other burning generation ₂Situation under use, so be different from the standard chloralkali process, the present invention has the adequate condition of carrying out heat exchange.For example, the temperature of the flue gas that enters usually (for example, handling the back at electrostatic precipitation) is 300 ℃.With below this flue gas cools to 300 ℃, anolyte and catholyte fluid are heated up (for LVE, usually should remain on greater than 90 ℃), some embodiment of the present invention is moved under the situation of not relevant with the catholyte heater with anolyte power loss.

G. Waste Heat Recovery is used for providing electric power to method equipment

Usually, because the temperature that exports the flue gas that obtains in generating equipment is between 100 ℃ (usually behind scrubbing), 300 ℃ (after precipitation process) and 900 ℃ (precipitation inlets) or other this class numerical value, the flue gas that enters is cooled off by reclaiming the heat exchange that circulates with energy, thereby extract considerable used heat, wherein the example of energy recovery circulation is ammonia-water circulation (for example, " Kalina " patented method), steam circulation or any this type of circulation of finishing identical thermodynamics method.Because some embodiment of the present invention relies on the preparation that DC power is finished reactant/absorbent of the present invention, so can directly, partially or even wholly provide electric power to described method by Waste Heat Recovery, and can under the situation of not relevant conventional transducer loss, finish with DC power being converted into the required AC power of other purposes.In addition, make engine operation, can under the situation of not using generation steps fully, realize effective efficient by using used heat.In some cases, the quantity of these Waste Heat Recovery energy can provide embodiment of the present invention required electric power fully.

VI. the generation and the application of accessory substance in removing carbon dioxide and the electrolytic process

As mentioned above, some embodiment of present device and method produces many useful byproducts in the process of removing carbon dioxide and electrolysis, comprise chlorine, sodium acid carbonate and hydrogen.In some embodiments, the hydrogen that embodiment of the present invention is produced is incorporated in the Hydrogen Energy recovery circulation.In one embodiment, the present invention can comprise present fluorinated polymer membrane technology, to reduce the migration of chlorion to the removing carbon dioxide process.Therefore, this method can be isolated chlorion under the situation that does not add the cost of macro-energy and cost; There is not chloride in removing carbon dioxide and the separating cycle comparatively speaking.Therefore, an embodiment of removing carbon dioxide reactor of the present invention can use common salt, water and carbon dioxide exhaust, and their combinations under the electric power effect form chlorine and sodium acid carbonate, and recover energy by hydrogen burning, and are as follows:

2NaCl+H ₂O+2CO ₂+ e-→ 2NaHCO ₃+ Cl ₂+ [ H ₂+ atmosphere O ₂→ e-]

A. Hydrogen Energy reclaims circulation

After deliberation two kinds of technology, can use the Hydrogen Energy of obtaining by embodiment of the present invention.First kind of technology is that hydrogen burns with coal, improves the emission behaviour of coal combustion, and second kind of technology relates to by hydrogen/oxygen fuel cell recovery DC.Pass through H ₂/ O ₂Burning probably can be reclaimed 22% to 32% of electrolysis energy.Perhaps, H ₂And Cl ₂Can directly or by fuel cell or DC recovery burn into Cl ₂And HCl.From used heat eliminate, the thermal source of cell reaction (producing about 135 ℃ caustic soda, tinning) or removing carbon dioxide process itself (absorbing the heat that discharges in various solution heats, heat of gasification and the exothermic reaction) is used in the generating equipment position by well-known technology (being reboiler etc.) that burning gases preheat or be used as other purposes.

In one embodiment, it is favourable that the technical grade fuel cell is produced the DC electricity, because this process operates easily, and can be lower than safe operation under the atmospheric pressure.The instant hydrogen that consumes generation can also directly reduce the electric load cost of saline electrolysis.In addition, because reclaiming circulation, Hydrogen Energy can produce H period in the generating of non-peak ₂, Cl ₂And NaOH, H ₂Be used in peak hours subsequently electric power is provided,, carry out the removing carbon dioxide process simultaneously so the present invention can produce auxiliary expensive peak value electric power subsequently with low-cost preparation feedback thing.Utilize H economically ₂Energy reclaims circulation and comes by increasing H ₂The peak power that the ability that acts as a fuel or produce electric current in fuel cell improves equipment produces, and the utilization on spontaneous combustion basis can be provided.

Perhaps, because the electron level sources of hydrogen of using clean carbon to produce, municipal communal facility, company of factory and power generating equipment can be succeedd because use the hydrogen that produces in municipal bus system, train and other use the public or private purposes of hydrogen fuel.

B. other purposes of the accessory substance of removing carbon dioxide method

In one embodiment, chlorine can be the main oxidant that is used for killing the bacterium of the water treatment facilities in the worldwide.Chlorine, and, usually quoted from ratio shared in the domestic GDP of the U.S. up to 30%+ by the raw material chemicals that some 100+ that it is derived derive.Chlorine can also be used to prepare the industrial chemical hydrochloric acid of maximum-norm.Chlorine can also be widely used in plastics industry, because it is prevailing non-carbon reactant.

Sodium carbonate is the accessory substance of the method for the invention, and sodium carbonate worldwide is usually used in producing flux used in soap, cleaning agent and shampoo and the glass preparation.In addition, power generating equipment and private residence use the sodium acid carbonate softening of water according to following popular response:

CaCl ₂(aqueous solution)+NaHCO ₃(aqueous solution) → CaCO ₃(precipitation)+NaCl (aqueous solution)+HCl (aqueous solution)

Can adopt similar method, use and carry out ion-exchange, thereby make various carbonate depositions from the sodium carbonate of the inventive method and the salt of sodium acid carbonate and multiple first family and second family.

Another example of the accessory substance that the removing carbon dioxide process produces is a hydrogen.Other hydrogen of electron level is senior energy carrier.On the contrary, the hydrogen fuel of generation can burn with the coal of " dirtier ", reduces the discharging of fuel, and hydrogen fuel can be used as the boiler feed burning and is used for separation process, perhaps is used for the hydrogen vehicles.

In other embodiments, can be by the following method or its equivalent processes carbon dioxide is transported to long-range isolating points:

(1), absorbs CO by described method or any its variant in the generating equipment position ₂With other pollutant, produce hydrogen, chlorine and carbonate simultaneously.

(2),, produce almost pure CO with hydrochloric acid and carbonate combination in neutralization reaction again at long-range isolating points ₂Then will be by the CO of these methods generations ₂Be injected in the carbon bank.

By these methods, can be implemented in equally between generating place and the isolating points and transport CO ₂Net effect, and do not need by liquefaction with physics mode transportation CO ₂, and by transportations such as pipeline, lorries.

Embodiment

Following examples are used for proving preferred implementation of the present invention.That these embodiments provide is feasible, reduce or even eliminate the carbon dioxide that generating equipment produces and the economic means of other pollutant substantially, this method is by providing and the gained reactant is used for commerce or commercial run and/or realizes by circulating energy.

What it will be understood by those skilled in the art that the technology that discloses in following examples represents that the inventor finds can implement technology of the present invention well, therefore can think to constitute and implement optimal way of the present invention.But those skilled in the art's content according to the present invention is to be appreciated that in the specific embodiment that discloses can carry out many variations under the situation that does not deviate from the spirit and scope of the present invention, and still obtains similar or similar result.

Embodiment 1

CO by the diagrammatic representation design ₂/ NaOH bubble-column reactor

In being designed for the bubble-column reactor of this embodiment, four main flow stream are arranged, that is:

(1) flows into the liquid of bubble column fluid with given volume flow (cube volume of V1=unit interval fluid); In situation about selecting, the volume flow that the volume flow that enters equals to flow out.Therefore, all be V1.In this embodiment, V1=0.001 rice ³/ second.

(2) volume flow that enters of Vg0=gas, described gas is absorbed absorption of fluids partially or completely.In this embodiment, Vg0=0.05 rice ³/ second.

(3) volume flow left of Vg=gas.In this embodiment, Vg=0.02 rice ³/ second.

Restriction according to above-mentioned condition designs bubble-column reactor.Remove in the flue gas 60% the CO that enters by strong caustic by bubbling ₂Reaction is a mass transfer limit.The purpose of this embodiment is that 99.9% the required reactor size (height and diameter) of carbon dioxide is removed in calculating.P=2 atmospheric pressure, T=298K.The graphical data that use obtains from Fig. 8, this embodiment has described the design of high reactor (2.36 meters) and short reactor (0.41 meter).Fig. 8 represents under the speed of low interface, CO in the bubble column ₂Absorption percentage and the relation (Schumpe etc., 1979) between the fluid depth, gas interface speed.

2.36 rice height tower scheme

Under the surface velocity (Ug0) of about 0.04 meter per second, conversion ratio reaches 100%.This speed is in the scope that bubbling flows (in the solution in similar water, this value is about 0.05 meter per second).The known gas volume flow requires the Diameter Calculation of (Vg0) and tower as follows:

Ac＝Vg0/Ug0＝0.05/0.04＝1.25m2

Dc = 2 \sqrt{Ac / π} = 2 \sqrt{1.25 / π} = 1.26 m

Therefore, the 60%CO that enters ₂Realize that 99% conversion need highly be 2.36 meters, area is 1.25 square metres, and diameter is 1.26 meters, and cumulative volume is 2.95 cubic metres a tower.

0.41 rice height tower scheme

0.41 the conversion in the rice height tower needs surface gas speed to be about 0.02 meter per second.With above shown in similar:

Ac＝Vg0/Ug0＝0.05/0.02＝2.50m2

Dc = 2 \sqrt{Ac / π} = 2 \sqrt{2.5 / π} = 1.78 m

Therefore, the 60%CO that enters ₂Realize that 99% conversion need highly be 0.41 meter, area is 2.50 square metres, and diameter is 1.78 meters, and cumulative volume is 1.03 cubic metres a tower.

Must, by this embodiment can confirm shorter tower on unit volume from flue gas the efficient of stripping carbon dioxide higher; For example, in this embodiment, factor is 3.Therefore, for preferred implementation of the present invention, the target of design is the high reactor of less level and/or by the less high multistage reactor of forming of level.

Embodiment 2

CO by the design of mass tranfer coefficient method ₂/ NaOH bubble column

The purpose of this embodiment is to calculate to determine mass tranfer coefficient kla (mole/second/volume) by theory.Can determine that by this embodiment this correlation technique may cause indecisive result; That is, this embodiment emphasizes owing to the uncertainty of measuring some important parameters from the difficulty of theoretical prediction actual result.Therefore, have only experiment to amplify the result that can determine large-scale removing carbon dioxide device at last.

Below be used for gas and be detained the correlation of the equation of (ε g) and mole transmission (kLa) from Akita and Yoshida (1973), can be under the bigger situation of tower height degree and diameter (promptly＞0.1 meter) be used for carbon dioxide and aqueous systems:

Gas is detained

\frac{ϵg}{(1 - ϵg) 4} = C * [g * Dc 2 * ρL / σ] 1 / 8 * [g * Dc 2 / vl 2] 1 / 12 * [μg / \sqrt{g} * Dc]

With

Mass tranfer coefficient

kLa(1/sec)＝[Cco2*Dco2-h20/Dc2]*[vL/Dco2-h20]0.2*

[g*Dc2*ρL/σ]0.62*[g*Dc3/vl2]*ε11

Wherein: ε g=gas retention factor

CO in the Cco2=flue gas ₂Concentration

The diameter of Dc=tower

VL=0.0001 rice ²/ second (sec)

σ＝1cP＝0.1Pa*sec

ρL＝998kg/m3

And, because Dco2-h20P=1.661m2*Pa/ second,

So Dco2-HO=1.661/5.067*10 (5)=3.278*10 (6) m2/ second

Driving force is the difference between carbon dioxide balance concentration (Cco2*) and the actual liquid phase gas concentration lwevel (Cco2), supposes that in this embodiment this species diversity is 0; That is to say that the NaOH of existence at once will neutralized aqueous carbon dioxide " acid ".Therefore, the molar transfer rate of reactor unit volume is as follows:

Nco2＝kLa*[Cco2*-Cco2]＝kLa(Cco2*)

The speed that mole transmits needs to remove in the flue gas 99.99% carbon dioxide.Suppose CO ₂Under the tower condition, be perfect gas.

Cube volume/second:

Vg0＝0.05m3/sec∴Vco2＝0.6*Vg0＝0.03m3/s

Mole/second (Mole/Sec):

Vco2*P/RT＝[0.03M3/sec*5Atm]/

[0.082m3atm/kmolK*298]*1000gmmole/1kmole＝6.14mole/sec

6.14 moles/second=6.13 moles/second of Nco2 (mole/second)=0.999 (the CO2 molal quantity of the CO2 molal quantity/existence of removing) *

Other fluid properties that model dependency is required

With the limit (Vg0=0.05m/s) that the initial surface rate setting flows at bubbling, calculate the area and the diameter of tower:

Ac＝Vg0/UgO＝0.05/0.05＝1.0m2

Dc = 2 \sqrt{Ac / π} = 2 \sqrt{1.0 / π} = 1.13 m

Be detained reaction for gas phase, set C=0.2 among this embodiment, suppose that surface velocity (Ug) is the mean value that enters and leave speed; Ug=0.035m/s=is average, and (0.05m/s 0.02m/s), uses equation solver, finds ε g=0.055.

Then, obtain the molar transfer rate constant according to following equation:

kLa (1 / \sec) = \frac{0.6 * 3.278 * 10 - 6 m 2 / \sec}{[0.6 m] 2} * \frac{0.0001 m 2 / \sec}{3.278 x 10 - 6 m 2 / \sec} * [\frac{9.8 m / s 2 * (0.6 m) 2 * 998 kg / m 3}{0.0696 kg / \sec 2}] *

[\frac{(9.8 m / \sec 2) * (0.6 m) 3}{[0.0001 m 2 / \sec] 2}] * (0.055) 1.1 = 0.386 / \sec

kLa＝0.386/sec

Get back to the driving force equation, obtain reactor volume (V) by following equation:

V＝Nco2/[(kLa)(Cco2*)]＝6.13mole/sec/(0.386/sec*(103.6mole/m3))＝0.15m3

With

Hc＝0.15m3/1m2＝0.15M

Therefore, bubble column is of a size of Dc=1.13 rice, Hc=0.15 rice, and the result is obviously different with the actual result of true bubble column.

Several hypothesis can be used to explain the difference between correlation model (thinking the best model of the behavior) and the actual result:

(1) supposes that NaOH has the character of water (density, surface tension etc.);

(2) CO in the solution ₂Concentration may not can just in time be 0; This more similarly is an operand; For example, if CO ₂Valid density is not 0, and then driving force is less, needs higher tower.

It should be noted that this theory relation can be affected under certain condition but also be its strong point: because term as (vL=0.0001m2/sec) as frequent square of denominator, so the very little variation of these numerical value can produce very big influence.The theoretical calculating of this class is favourable to curve match afterwards, but can not be well in order to design the prediction mass transfer situation that needs.In addition, for CO ₂Absorption/conversion rate have tangible fluid flowing effect, this effect is amplified in the design and can be showed at difference and progressive (at-differing-and-progressive).

Embodiment 3

The CO that obtains by experimental data ₂/ NaOH bubble column design (degree of depth)

Notice, two kinds of different, consistent with actual Chemical Engineering computing techniques have confirmed that some embodiment of the present invention is to (3 meters or less than 3 meters gas-liquid contact distance of the dependences of " the less level high theoretical efficiency " described in the literary composition, or the fluid level is high, with the absorption of realization＞90%).But (as mentioned above) in some cases carried out some and simplified hypothesis in these designing and calculating, so carried out experimental verification, the results are shown among Fig. 2 B and the 2C and (will explain in detail hereinafter)

These engineer testings all obtain certain CO in certain gas-liquid contact distance (being the height of fluid in the unfilled open bubble column) ₂Absorb; For example, by 30 centimetres fluid, 20% absorption.

If gas is by second tower of same design and the same terms afterwards, identical absorption can take place once more; Be remaining 80% initial CO ₂In 20% be absorbed once more.This relation finally weakens; But, suppose that absorption fluids has high-absorbable matter, this chemical absorbing can continue to absorb consumingly the CO in the flue gas ₂Even, rare CO ₂Can be absorbed, this effect that weakens can not considered in this embodiment, realizes 90% effect of removing yet.

The fluid continuation can be with remaining CO by absorption fluids as can be seen for people ₂Reduce 20% again, the rest may be inferred, up to by enough number of times, reaches required absorption level (being 90% in this case).

Obtain " basic progression " design like this, this design decision realize 90% required fluid depth (the multiple degree of depth that 30 Centimeter Level are high).Suppose the %CO that absorptions at different levels are same as described above ₂/ distance then obtains the result of Fig. 2 B and 2C, and maps shown in Fig. 2 D and 2E.

Fig. 2 A has shown the equipment of the principal character of an embodiment that is used to observe removing carbon dioxide part of the present invention.Can be according to the equipment among following description operation Fig. 2 A (or equipment) with similar effect:

(1) NaOH (for example, the NaOH of 1M in 25 ℃ of water) of adding test volume in carbonation device 801, the degree of depth is 30 centimetres, fills or does not fill.

(2) simulation or actual flue gas in this case, will typically be burnt coal smoke road waste gas (16%CO ₂,, 84%N2, SO _X/ NO _X＜1% or exist with natural ppm ratio) be incorporated in the carbonation device 801, effectively be ejected in the unfilled tower, effectively spray or be assigned in the tower of filling, by fluid, discharge.Gas is 25 ℃, CO ₂Be 2 liters/minute, mix pro rata, upwards flow through 4 with other gas " recycle column of diameter; System pressure is equal to or less than 1atm psig.

(3) enter CO by measurement ₂Concentration (for example, by the gas chromatographic analysis sample, perhaps on-line measurement CO ₂Concentration) notice CO ₂By absorption of fluids, temperature raises (exothermic reaction), and the analysis of fluid sample is shown the balance that has carbonate/hydroxide, shows CO not only takes place ₂Absorption, CO ₂Also be converted into carbonate or bicarbonate form.Actual operating experience shows that " transition point " of these keys depends on the pH balance:

A. when pH＜=8.3, help forming bicarbonate.

B. when pH＞=10, help forming carbonate.

(4) because the hydrodynamics of gas, with any speed absorption/conversion CO ₂, absorb/be converted into the reaction of carbonate can be strongly and heat release ground carry out, finish up to the exothermic phase of reaction, temperature platform at first raises, descend then, the absorbability of fluid reduces along with the decline of OH ion concentration, and being equivalent to effect when heat release finishes is zero.When the absorption level began to descend, pH was usually very near 8.3, perhaps near 8.3; In pH＞8.3 o'clock, absorbability is stronger.

(5) fluid is transferred in the bicarbonate salinization tower 803, flue gas is introduced described fluid once more.CO ₂Absorption stop, in some cases, show CO ₂The negative value that is absorbed as (fluid discharges number of C O to the gas by it ₂).The temperature of fluid continues to descend, and is converted into mobile air-flow in part because of some subsidiary evaporations, but also because at sodium carbonate and remaining " dissociating " CO that is dissolved in the fluid of producing before ₂Between bicarbonate salinization reaction takes place.

(6) balance continues to move to the bicarbonate direction, can realize the optimization of initial hydroxide concentration, fluid and gas temperature, pressure, flow and speed, curvature etc., even reaches the point that produces pure carbon acid hydrogen salt (99%+).

Fig. 2 B and 2C have described the result of several test series of carrying out with useful load (being placed into the concrete concentration of the NaOH in the removing carbon dioxide system shown in Fig. 2 A).Data acknowledgement among Fig. 2 B and the 2C several Key Points:

(1) abundant adjusting condition, thus pure carbon hydrochlorate (the 4th and 14) or pure carbon acid hydrogen salt (the 28th and 32) can be produced with reappearing, can regulate obtaining Different Results (or " ion ratio " is between 1.0-2.0).

(2) have the situation of obvious absorption for all, obtained by this research, the size of reactor is that gas-liquid contact distance is enough to realize to entering the absorption of gas 90% less than 3 meters usually.Therefore, the less level that can design lower resistance is high, to realize and the corresponding to high-absorbility of thermodynamic efficiency limit.In other words, remove CO ₂Physical process carry out obviously meeting or surpassing under the absorption level of system thermodynamic efficiency.This high-absorbility (air inlet, exhaust) is irrelevant with energy, so and CO ₂Produce irrelevant.Therefore, keep CO ₂The thermodynamic efficiency of absorptivity (by absorption of fluids) and equipment is important as two kinds of visibly different tolerance, to avoid confusion.

(fluid is to CO for the result of Fig. 2 B and 2C ₂Absorption) and product ion be plotted among Fig. 2 D and the 2E than (1.0=bicarbonate, 2.0=carbonate).Obtain several important conclusions by Fig. 2 B and 2C:

(1) entering CO ₂Single-stage absorb in instantaneous absorptivity up to 98%.

A. be in the single-stage bubble column gas-liquid contactor of 0.30 meter fluid depth/gas-liquid contact distance in the degree of depth, enter CO in absorption 25% ₂Condition under, produce pure carbon acid hydrogen salt (NaHCO with the solution form ₃).Be extrapolated to 90% and absorb, 3 meters long contact distance is enough to absorb 90% the CO that enters ₂

B. be in the single-stage bubble column gas-liquid contactor of 0.30 meter fluid depth/gas-liquid contact distance in the degree of depth, enter CO in absorption 70% ₂Condition under, produce pure carbon hydrochlorate (Na with the solution form ₂CO ₃).Be extrapolated to 90% and absorb, be enough to absorb 90% the CO that enters less than 2 meters contact distances ₂

C. absorb with product in carbanion than between different correlations show and in these limiting case, have continuous solution.

(2) absorption fluids (for example, is 15-240 minute in these embodiments) and keeps its absorbent properties in the industrial valuable time.

(3) input variable (concentration, temperature, pressure, gas flow, time of contact etc.) that can the conditioned reaction device is to produce pure carbon acid hydrogen salt, pure carbon hydrochlorate or both any mixture.

(4) use these laboratory results to design 90%CO ₂Reactor, (for example, approximate fluid depth, tower height degree obtaining solution under) the condition, is to obtain solution under 1 meter in many industrial valuable method 3 meters gas-liquid contact distances.

Embodiment 4

The LVE of various chemical situations analyzes

Fig. 5 represents the low-voltage electrolysis active line under the various chemical situations.Describing some model experiments as a result the time, the film chlor-alkali electrolysis cell moves under non-standard situation, that is:

(1) adding pH by closed loop pH control is the pH that 1.0,2.5 and 5.0 HCl (hydrogen chloride in water) regulates anolyte fluid (protonated salt solution);

(2) closed-loop fluid circuit by electric heater heating remains on set point with the temperature of anolyte fluid;

(3) regulate voltage under each fluid/protonation/temperature conditions, record is by 0.01m ₂The electric current that chlor-alkali electrolysis cell obtains.

In Fig. 5, write down the experimental data of one group of embodiment, according to 0.01m ₂The actual experiment voltage and the electric current of electrolytic cell (13 millimeters gaps) (can be converted into current density, kA/m ₂, the mapping of as indicated in FIG.) relation, electrolytic cell is in the various various combinations operation down of the protonated degree of temperature and anolyte brine fluids (in these experimentalists and technicians, join in salt water ring control by closed loop pH control HCl (1)).

These typical consequence among Fig. 5 are as follows:

(1) under the high voltage (5V) that this class chlor-alkali electrolysis cell is used always, obtains maximum current (, being maximum current density) for given electrolytic cell.

(2) brine temp of same pH value is high more, and the current density under the given voltage is good more.

(3) compare with the salt solution of higher pH value, the current density of salt solution under given voltage of low pH value is better.

(4) these general trends (higher temperature, higher acid concentration) can be by the standard test designing technique of how much/composition of each electrochemical cell design optimization so that electrolytic cell has optimum efficiency (kA/m2V).The similar result of experiment of carrying out with any chlor-alkali electrolysis cell under the raising operating voltage shows that improving operating voltage also can play increase effect (kA/m2V).

(5) slope of straight line (Δ V/ Δ A) beginning is bigger, and electric current/current density descended by a small margin when voltage reduced significantly; But, reach flex point (approximately (and 2.5 volts, 10A/.01m2) after, voltage further reduces and causes electric current to reduce more sharp, so causes current density to reduce more sharp.

(6) near the ruuning situation flex point and the flex point is represented voltage-to-current density compromise best on the business efficiency.For any physics electrolytic cell of embodiment of the present invention, the standard test design optimization can obtain best low-voltage condition.

(7) in this embodiment, 1.0pH, 90 ℃ anolyte condition have superior current/voltage character, therefore are that these are through active lines best in the different operating line of proof.

(8) major defect of low-voltage electrolysis is to follow reducing of current density; Along with voltage descends, kA/m2 descends.Because system must produce the Na+ ion of similar number to absorb the carbon dioxide of same amount, so the surface area of barrier film (m2) must correspondingly increase; For example, if current density descends 50%, then need the diaphragm area of twice to produce enough absorption fluids.This has for equipment cost and seriously influences, because the cost of chlor-alkali equipment and diaphragm area are almost proportional.Low-voltage electrolysis has some advantages, In some embodiments of the present invention, and can be obviously or solve the large-area shortcoming of this needs fully along the optimization of low-voltage line.That is to say that barrier film and electrolytic cell parts move under the less service condition of more optimum/power consumption, so obtain prolonging the life-span of electrolytic cell and/or barrier film.The low pressure condition is carried out specific design can loosen requirement unessential some material and aspect of performance in using the embodiment of low pressure.The free degree of these design aspects can obtain low-cost electrolytic cell, cuts down partially or completely because the increase of low pressure/diaphragm of electrolyzer cost that the low current density operation causes.In these and many other methods, the LVE system though need bigger diaphragm area for the NaOH that produces same amount than standard chlor-alkali electrolysis cell, can completely or partially alleviate these extra costs and the operation part in spending.

(9) this compromise between benefit (low-voltage, so low-power) and the harm (area is than current density big and decay) can come optimization by embodiment 7 described technology.For 1.0/90 ℃ of active line shown in Figure 5 (for this example, setting is the more excellent V/I feature of LVE operation), can calculates Voptlve, and, can obtain Ioptlve by above-mentioned relation.Therefore, geometry designs for given electrolytic cell, the conditions such as temperature, pressure, brine strength, protonated degree, diaphragm type of can regulating produce preferable V/I curve or active line, can calculate best point on this curve by the method for embodiment 7 then.In this case, Voptlve is 2.88 volts, and current density Ioptlve is 1.04kA/m2.

(10) in embodiment 7, in protonated slightly and/or low temperature situation, the electric current when Vopt=2.88V is about 5A.In this embodiment, electric current (so current density) is more than 2 times, reaches 10.4A.

(11) in addition, conditions such as how much settings of protonated, the temperature of salt solution, pressure, concentration, electrolytic cell parts, electric field are optimization similarly, produce preferable (kA/m2V) variable, but the protonated stoichiometry that has increased the hydrogen that produces itself, thereby improved the energy compensating of system.Should be noted that especially, physical electrochemistry electrolytic cell for given concrete structure, can be by (kA/m2V) of optimization system, thereby reduced the required energy of preparation absorption fluids, optimization can utilize the energy of hydrogen to reclaim (optimization can be utilized the organic efficiency of Hydrogen Energy then) simultaneously, whole energy optimizations of this process are arrived its potential minimum, can realize minimum energy CO ₂The optimization of absorption/conversion.

(12) suppose that embodiments of the present invention can make CO ₂Be absorbed in effectively with chlor-alkali preparation in the normal dense hydroxide of producing (33-35 weight % usually, further concentrate by evaporation of vapours then) be in a ratio of in extremely rare hydroxide (proved equal and less than 0.2M), then the design for the chlor-alkali electrolysis cell of low concentration operation (and low pressure operation) can provide the bigger free degree to the design optimization under these non-standard conditions.

Embodiments of the present invention can not produce the more Hydrogen Energy of energy that consumes than in the preparation hydrogen.Otherwise, will violate the second law of thermodynamics.Therefore restricted for the minimum voltage that can be applied to electrochemical cell.The efficient of returning of supposing hydrogen is 100%, then uses 39000 kilowatt hours/ton H ₂It is 1.55V that energy content (EIA reference value) obtains minimum voltage.For having any system that given hydrogen/electricity returns efficient and system energy content selective value, those skilled in the art can calculate the minimum voltage that this system can realize.

In fact, thermodynamics inefficiency (including but not limited to I2R loss, electric current inefficiency in the electrolytic cell, waste heat losses etc.) and needs overvoltage are slightly moved, and have improved the minimum voltage that can access for given electrolytic cell.Above-mentioned feature can be protonated ratio and varied slightly along with " a " value, and this is because this value has changed the amount that can be used for the hydrogen that energy reclaims.

It is said that current density has under low pressure determined to produce the required electrolysis area of a certain amount of corrodent (considering preferable invariant from fund cost aspect), when minimum voltage, required area is very big.Therefore, need move under certain voltage on the minimum voltage, numerical value depends on the compromise of the fund cost/ecological efficiency of selecting in the design.Current efficiency (percentage of the electric current that is spent during the preparation product) descends when low-voltage, so optimization low-voltage electrolysis operation is not to be equal to the independent a kind of subnormal voltage operation condition that obtains.Present method is design operation (being lower than 5 volts) under the LVE condition, moves under these are lower than the voltage of 5V, and power consumption is compared obvious increase with conventional art.

Embodiment 5

The thermodynamics of large-scale equipment design

For this embodiment, explained the analog machine (combining some embodiment of the present invention) of the equipment behavior that shows oepration at full load, and by various means and method to extracting the CO of specified rate ₂Required energy quantizes, and is limited in the statistics limit, and these means and method comprise:

(1) in enough short E (energy) interval, thermodynamic efficiency ( CO ₂/  E) can be approximated to be Δ CO ₂/ Δ E.

(2) can suppose some simplification that the equipment design is carried out shown in Fig. 9 A, wherein:

A. main energy consumption is at electrolytic process; It is extremely small that pumping, compression, control etc. are considered to spending in that preparation feedback thing (electrolysis) and the Hydrogen Energy energy in reclaiming compares.These numerical value are assumed to be 0 or less than 0.1% of the energy of electrolysis consumption in service.

B. the energy that can represent the electrolysis cost by following formula approx:

Eout=V*I*EFF _{Electric current}

Wherein: the voltage of V=operation electrolytic cell

I=produces the required electric current of chemical substance by the electrochemistry half-reaction, comprises and the protonated stoichiometric proportion above 1: 1 that causes of salt solution.In this embodiment, the ratio of the protonated ion that consumes in the electrolysis is 0.05HCl/NaCl.

EFF electric current=current efficiency is defined as the amount of the electric current that uses in the actual production chemical substance, and remaining loses in I2R consumes etc.This value among this embodiment is 97%; Each electrolytic cell has own unique current efficiency, and this efficient decays in the valid period of electrolytic cell and changes.

C. the energy that reclaims from hydrogen burning (by any way, as the boiler gas combustion, burning in fuel cell etc.) is as follows:

Ein=39000 kilowatt hour/ton compression H2* ton H2*EFFdc

Wherein: the tonnage of the hydrogen that produces in the ton H2=method comprises because the hydrogen that surpasses 1: 1 stoichiometric proportion of the protonated generation of salt solution.

In the EFFdc=hydrogen recovery method hydrogen primary power is converted into the efficient of DC electric current.60% is converted into the recovery of DC electric current in the Hydrogen Energy that produces.This is the DC efficient that the stock of present hydrogen/aerial oxygen fuel cell provides; In the method for compressed hydrogen, can obtain similar numerical value (consume 15% energy realize), suppose in consumption such as hydrogenation treatment, gasoline reforming processing processing, to have 85% Hydrogen Energy to return.

D. the energy that returns from Waste Heat Recovery has obtained the heat of the flue gas stream that enters.I.e. cooling after in a single day the heated air that enters enters in this process.In some embodiments of the present invention, absorption that can be by used heat and heat is converted into the DC electric energy realizes above-mentioned cooling, these DC electric energy can be used for providing auxiliary/whole power/overpowers to forming process of the present invention.In this embodiment, do not comprise additional Waste Heat Recovery.

The device model that is used for this embodiment comprises the simulation of the flue gas of discharging from the generating equipment that is under the normal operating condition, shown in Fig. 9 B.This simulation relates to fuel composition, the efficient of combustion process itself, the relative scale of each composition in the combustion process, or the like important hypothesis.Hypothesis among this embodiment has been described among Fig. 9 B, and with typical hear rate be that the flue gas output of generating equipment of use subbituminous coal of 10,000 BTU/ kilowatt hours is consistent.

For given flue gas output, can calculate the demand of hydroxide.Need some hypothesis here.Ion ratio (" ion ratio " is meant the ratio of Na/C in absorption/conversion reaction) is identical with the ratio of each element in the solid product that forms.In the situation of pure carbon acid hydrogen salt, this value is 1.0, and in the situation of pure carbon hydrochlorate, this value is 2.0, and for the mixture of bicarbonate and carbonate, this is worth between 1.0 to 2.0.The result of calculation of the demand of corrodent is shown among Fig. 9 C among this embodiment.For the embodiment described in Fig. 9 C, ion ratio is 1.0.

For given hydroxide demand, there is corresponding electrolysis requirement, depend on that the amount of water and salt, the area of membrane surface (square metre, the invariant of this class electrochemical cell), current density (itself are the functions of battery design, chemistry and ruuning situation; Value is 3kA/m as used herein ²).The result of calculation that these electrolysis require among this embodiment is shown among Fig. 9 D.

For the electrolysis under the protonated condition of specified rate, produce the hydrogen of specified rate, the hydrogen of generation itself is represented a certain amount of energy that can be used for reclaiming, perhaps with chemical mode with hydrogen applications in other technology.In this embodiment, use the fuel cell that under EFFdc=60%, moves that hydrogen is converted into direct current.

For the treated flue gas of specified rate, certain being converted under the galvanic efficient, can from this flue gas, obtain a certain amount of used heat, the electric power that is reclaimed can be used for replenishing the direct current that electrolytic process consumes.The used heat that is used for this embodiment is shown in Fig. 9 E, and the efficient of Xuan Zeing is 25% in this case, and this numerical value surpasses existing various used heat/DC generation technology in this area.

Shown in Fig. 9 F,, can sum up the net effect that these energy shift according to the individual values of these energy input and output.At this, energy is represented with kilowatt hour, as the percentage of infrastructure device power, has also shown the result of calculation of the ecological efficiency of this embodiment.

In some embodiments of the present invention,, can use extra H in order to be used in the protonated HCl recirculation of salt solution ₂/ Cl ₂Fuel cell makes hydrogen and chlorine burning.Particularly the HCl of " hyperstoichiometry " amount can recycle, and in theory, has got rid of the necessity that adds raw material chemicals HCl in system.In reality is implemented, must regularly add a certain amount of additional HCl to system.H ₂And Cl ₂The energy that burning is held compares H ₂/ O ₂The energy that burning is held is many.Thus, the energy that can be increased a little.But fuel cell itself more or less can't reach perfect efficient, and therefore the energy " increase " that uses chlorine to obtain as oxidant is far smaller than loss intrinsic in the recovery method.Therefore, in this embodiment, these effects are considered to cancel each other, and are equivalent to not effect.Therefore, two kinds of more or less compensation mutually of effect, but still cause net loss.But the effect that has other proton in electrolysis is the production of NaOH under the obvious catalysis low-voltage and the height (kA/m under these low-voltages ²V).Therefore, for any given equipment, can carry out optimization, so that the H of specified rate ₂/ Cl ₂Recirculate to HCl, make the salt solution that enters protonated with the HCl of this quantity.In some optimum values (usually between a=0.05 and a=1.0M, perhaps 90 ℃ the time pH near 1), hydrogen/chlorine fuel cell loss (is compared with the oxidation reaction of carrying out with oxygen with the oxidation reaction that chlorine carries out, the energy that obtains increases slightly, surpasses this increase and should lose) and hydroxide energy benefit (better kA/m ²V) can be for whole system while optimization.It should be noted that in this embodiment, only calculated H ₂/ O ₂Burning; H ₂/ Cl ₂Burning is because the additional strength of oxychloride has thermodynamics increase slightly, but the inefficient cancellation effect of fuel cell causes negative effect, is considered to atomic little effect.

A. the calculating of ecological efficiency

Finish (the  CO of ecological efficiency among this embodiment according to following steps ₂/  E) and Δ CO ₂The calculating of/Δ E:

(1) suppose to have three kinds of equipment:

A. basic generating equipment (the flue gas model is exemplified among Fig. 9 B)

B.CO ₂Absorption/converting apparatus (need auxiliary energy to handle flue gas from basic generating equipment, the part of energy intrinsic in the hydrogen of the energy of hydrogen burning or calculating is returned, the prerequisite of latter event is that hydrogen is end-product and does not burn).

C. the 3rd auxiliary generating plant, this equipment provides CO ₂The energy that absorption/converting apparatus is required.In this embodiment, the feature of this generating equipment is that hypothesis itself and infrastructure device are identical.

(2) calculating infrastructure device then reaches 100% and relates to CO when handling ₂Following several respects with energy consumption:

A. from the CO of infrastructure device ₂(flue gas model);

B. the energy that produces by infrastructure device;

C.CO ₂The net energy that absorption/conversion process is required;

D. hypothesis is replenished required net energy and the CO of generating equipment ₂The required net energy of absorption/conversion process equates;

E. hypothesis is replenished the CO that generating equipment produces ₂Proportional with the energy that ancillary equipment produces, and with the Δ CO of infrastructure device ₂/ Δ E is identical.

(3) obtain the following result of aforementioned calculation:

A. infrastructure device-10000 hear rate equipment produces 1Gw every year continuously, and annual production 8.76Bkw-hour produced 7446068 tons of CO every year ₂, average out to 1176 kilowatt hours/ton CO ₂

B.CO ₂Absorption/converting apparatus-for the calculating (a=0.10 of this embodiment, 2.1V operation, produce pure carbon acid hydrogen salt, 15% Hydrogen Energy consumption is in compression, except pumping/cost squeeze and the Waste Heat Recovery benefit), needed absorb in 3.648BKw-hour/100% (carbon dioxide) of conversion base equipment.

C. the equipment that replenishes among generating equipment-this embodiment produces CO ₂The power that absorption/converting apparatus is required, 3.648Bkw-hour, itself produced (with above-mentioned 1176 kilowatt hours/ton CO ₂Value is calculated) totally 3101209 tons of CO ₂, suppose these CO ₂All be discharged in the air.

D. therefore, the general power of generation is 12.48Gw-hour.Therefore, gross output is 8.76Gw-hour.Therefore, the CO of generation ₂Be 10.55 megatons altogether.Therefore, the CO of discharging ₂Be 3.101 megatons.29.1% of general power consumes at CO ₂In the absorption/conversion process.Whole CO ₂71.9% be consumed.

By aforementioned calculation Several Key Problems has been described:

(1) arithmetically, confirm following equation establishment:

The CO that the power %=1-that consumes consumes ₂%

The CO that consumes ₂The power % that %=1-consumes

Form straight line like this, be called single device active line (One Unit Operating line), shown in Fig. 9 A.

(2) for this embodiment, ( CO ₂/  E) and Δ CO ₂/ Δ E is identical on algebra, that is:

ΔCO ₂/ΔE＝(CO ₂/E)＝0.291/0.719＝0.41

Can further simulate other extrapolation situation, wherein, by the CO of auxiliary generating plant discharge ₂Own with another less relatively CO of capacity ₂Absorption/conversion treatment device #2 handles, and this absorption/reforming unit #2 correspondingly provides energy by auxiliary generating plant #2, or the like, first group of five repetition that the result is as shown in table 2.

Table 2

	Output	Output	Amount	Inc power
	Output	Output	Amount	Inc power	Iteration
2 iteration 3 iteration 4 generating equipments basis, generating equipment basis iteration 2 iteration 3 iteration 4	CO ₂The CO that (megaton) 7,446,068 assisted ₂ 3101209 1291621 537947 224049	Power (kilowatt hour) 8,760,000,000 %tot E 29% 37% 40% 41%	7 of absorption, 446,068 3,101,209 1,291,621 537947 %tot CO ₂ 71％ 89％ 96％ 98％	3 of needs, 648,448,267 1,519,540,497 632,872,705 263584854 ecological efficiency ( CO ₂/E) 2.40 2.40 2.40 2.40	Iteration

Some that relates in the table 2 is very important to this model:

(1) no matter notice the efficient of this method, be in base case, and still in the situation of any successive iterations, all producing for system is identical ( CO ₂/  E) value; The constant of system thought in this term, approaches the limit of this model, is called the ecological efficiency of method for this reason.

(2) clearly ( CO ₂/  E) value all is constant in all solutions, so be assumed to be when unlimited when iterations, can derive a kind of solution; Promptly as the CO of equipment with this equipment generation ₂When 100% situation about consuming is moved, use following equation simply to calculate (expedient):

1/ ( CO ₂/  E)=absorb/catch 100% CO that produces ₂Required plant capacity %

In this embodiment, this result of calculation is 41.6%.

(3) or, clearly find out, when the net power that consumes in the absorption/conversion is zero (not considering Waste Heat Recovery) for given treatment conditions, the CO that absorbs and transform ₂Be similarly 0.Therefore, all working line of this kind equipment is in theory at (0% power, 0%CO ₂) locate to intersect.

(4) by given any two points in the straight line system, can set up the straight line solution of active line by the following method, thus definition CO ₂The operation characteristic of absorption/conversion process:

A. for each service condition, finish finding the solution of base case, with single the device situation value of separating (power %, the CO of gained ₂%) according to CO ₂% (y axle) is with respect to net power % (x axle) mapping that consumes;

B. for the sort of situation, calculate ( CO ₂/  E), x sits target value when finding the solution y=100%;

C. suppose that all straight lines all pass through initial point.In practical systems, even some energy consumption (contrast, environment etc.) can be arranged all when 0 absorbs, confirm ideal situation with this.In fact, these straight lines can be slightly crooked, and can not stop at initial point.

(5) in this way, can obtain a series of CO ₂The active line of absorption/conversion process.

(6) according to the mapping mode of same-type, can map, and carry out chart relatively competing technology, for example:

A. competitive MEA (methyl ethylamine) absorption techniques need consume 30% plant capacity, to finish the preceding CO that discharges is carried out in absorption ₂58% absorption.

B. follow, estimate 15% of consumer device power, make CO by limiting pressure and refrigerant cycles ₂Liquefaction (45% power/58%CO ₂).

C. then, confirm ( CO ₂/  E) value is 1.24; But, need the extra energy that does not count with CO ₂Carry/inject/remain on isolating points.

D. find out from figure, this competing technology with as the CO of embodiment of the present invention ₂Absorption/converting apparatus operation method is compared, and efficient is lower; That is to say that this models show competing technology needs the generating equipment of 70%+ to come 100% to eliminate the CO that produces ₂Notice that these relate to the point of competing technology, they are presented at (referring to the legend in the chart) among Fig. 9 A with diagrammatic form:

I. according to the estimation of 2005EIA, by MEA absorption of technology CO ₂Need 30% plant capacity to absorb the flue gas CO of 58% generation ₂(note (30%, 58%) position among Fig. 9 A, handle for independent absorption.)

Ii. according to identical estimation, CO ₂Compression/liquefaction consumer device power other 15% moves to the operating point of this equipment (45%, 58%).

Iii. to carrying liquid CO by pipeline or other transport means ₂Required energy is indefinite to be estimated, and to CO ₂Pumping or be injected into amount of energy required in various types of carbon banks and with CO ₂Forever remain on the also indefinite estimation of amount of energy required in the described bank.Although these extra energy are inestimable, have reason to suppose that they are not 0.Therefore, from logic, the ecological efficiency of this kind equipment is lower than (45%/58%), is to guarantee certain CO ₂Reduce the compromise of the power that benefit spent.Be extrapolated to 100% situation about eliminating, MEA/ liquefaction/isolation technology need consume and surpass 70% plant capacity.It should be noted that typical competitive absorption techniques can not reach 100% and absorb; Promptly for the equipment of handling 100% flue gas of discharging, CO ₂Absorbing numerical value is 58%.

B. calculate limiting value [(the  CO of ecological efficiency ₂/  E) max]

In fact, for passing through to absorb CO ₂The NaOH of all outputs is converted into NaHCO effectively ₃Given system, main energy ingredient is kilowatt hour/moles of NaOH.Although the power of every moles of NaOH and voltage and current are proportional, electric current by the metering of chemical reaction compare fix.Therefore, every mole of CO ₂The power that consumes is mainly by realizing that the minimum voltage condition that effectively produces hydroxide comes optimization.

Can be by observation system current density (kA/m ²) with the relation of V feature, and definite minimum voltage (obtaining preparing the required enough non-zero current density of product at this voltage) is determined the minimum voltage (according to factor settings such as the concentration that changes, physical dimension, flows) according to the electrolysis system operation of embodiment of the present invention.Change physical size, electric field generation device, battery geometry, material composition and treatment conditions and optimize this characteristic measure (kA ²/ m ²V) be the main means of optimizing these systems, typical experimental design technology can be used for optimizing the industrial process of given physical equipment.

Except the restriction of reality, also there is a basic restriction for having given H/Na all systems, that is: than (protonated ratio)

(1) there is not equipment to reclaim the energy that the energy that produces can surpass the system that inputs in the electrolysis by Hydrogen Energy.The people who is familiar with thermodynamic principles should be noted that otherwise will be " violating second law ".

(2) based on this fact, be used for the H/Na ratio that anolyte consumes according to selecting, elementary heat mechanics limit is limited:

A. for this embodiment, suppose that H/Na is 0.10.

B. the Hydrogen Energy organic efficiency is set at 100%.

C. calculating the minimum voltage that can move, is 0 (" Vmintheo ") (being the point of the electrolysis cost 100% hydrogen organic efficiency that equals to suppose) by the net energy of this system consumption wherein.

D. in this embodiment, low-voltage is 1.5526 volts.This numerical value is the function of Na/C ratio, H/C ratio and Hydrogen Energy organic efficiency.In optimal cases, Na/C is 1.0, and H/C is 1.0.

E. these computational methods are extended to its ecological efficiency, the result of single device scheme is the CO for 93% ₂Absorption/conversion is about 7% power.

F. can carry out than theoretical minimum value more efficient operation point by the following stated:

I. consume by Waste Heat Recovery supplemental capacity;

Ii. can not cause CO with its generation partially or completely ₂The mode of discharging provides energy (water power, solar energy, wind-force, nuclear energy etc.) to absorption/conversion process.

Similarly, suppose it is aforesaid desirable hydrogen organic efficiency etc., calculate operation and be " ecological " maximum voltage (" Vmaxeco ") (i.e. CO wherein ₂The CO that absorption/conversion process is removed ₂More than what produce):

A. as mentioned above, H/Na, Na/C and Hydrogen Energy organic efficiency are set in 1.0,1.0 and 100% respectively.

B. calculate CO ₂Removing is 50% o'clock voltage.

C. in this embodiment, Vmaxeco is 4.457 volts.When this voltage and situation, this process is according to straight line  CO ₂= E (boundary between the useful and ecological harmful operation of ecology) operation.

Therefore, when electrolysis system moves, will ecological useful operation take place between Vmintheo (1.5526 volts) and Vmaxeco (4.457 volts).Many typical electrolysis systems can repeat the operation between these two points.The physical dimension, concentration, temperature, pressure, flow etc. of the electrochemical cell of design can easily be reappeared the laboratory result that is equal to or less than 2.1V in this way by control.

C. non-greenhouse generates the influence of power to ecological efficiency

When the energy-provision way by can not discharging greenhouse gases (GHG) (for example wind-power electricity generation, water power, solar energy, nuclear energy etc.) produces makeup energy (with this energy to the method energy supply), then there is not extra CO ₂Discharge, can improve ecological efficiency of the present invention greatly.For this embodiment, 3101209 tons of CO of the term in the table 2 ₂Along with after all iterative process be eliminated, obtain following simple result: all CO ₂Be absorbed/transform (7446069 tons), the whole power that need only are that 8,760,000,000 of basis adds the CO that finishes the basis amount ₂3,648,448,267 required kilowatt hours of absorption/conversion, with need general power in the GHG energy supply method 41% fix 100% CO ₂Discharging is compared, and in non-GHG energy supply method, only needs 29% of whole power promptly can fix 100% CO ₂Discharging.This means that embodiments of the present invention provide important " lever " factor when this method provides energy by non-GHG discharging.With to use non-GHG energy to substitute the energy that generates GHG with 1%: 1% benchmark opposite, if use non-GHG energy to provide energy to the method for some embodiments of the present invention, then 1% the energy that does not generate GHG substitutes the energy that generates GHG with the form that doubles factor, even surpasses the example of the energy of the generation GHG described in the literary composition.People can easily predict such situation, promptly for given country, state or tissue, when using a certain proportion of energy that does not produce GHG according to the mode of this amplification, can more effectively realize reducing CO ₂Purpose; Be that people can use " clean " energy thoroughly to change the emission behaviour of other " the dirty energy " efficiently.

Because in some applications, the energy generation that does not produce GHG is (for example, solar energy, wind-power electricity generation " field " etc.) utilized in the mode that cuts in and out sometimes, and it is very favorable can utilizing this energy to prepare a large amount of absorbents at non-peak period.

Embodiment 6

The ecological efficiency of various typical generating equipments

Figure 10 has shown the ecological efficiency in conjunction with the various typical generating equipments of embodiment of the present invention, and this Figure 10 has described as decision ecological efficiency ( CO ₂The various conditions of principal element/ E).

From these result of calculation, can obtain usually to draw a conclusion:

(1) form sodium carbonate, use standard chlor-alkali condition, the ecological efficiency of this method is greater than 1, and operation although it is so may be feasible economically, but the CO that produces ₂Than its absorb many.

(2) change the product balance, help producing sodium acid carbonate, thus the ecological efficiency of raising method.Produce in the situation of in fact pure sodium acid carbonate in the change condition, this advantage is optimized fully.

(3) adopt the low-voltage electrolysis behavior, make reaction enter ecological efficiency less than (promptly ecological useful CO in 1.0 the operation area ₂Absorb and method for transformation).Optimize each physical analogy amount of electrolysis system, obtain best (kA/m ²V) and maximum Hydrogen Energy production, the result further improves ecological efficiency.

(4), put into the primary power of DC electrolysis and AC pumping etc. and can replenish or all provide by Waste Heat Recovery by Waste Heat Recovery with the absorption/conversion process of embodiment of the present invention and the available of any number or used heat can being converted into galvanic machine and linking to each other of manufacturing for this purpose.

Should be noted that the invention provides, can make described method directly reach 100%CO from the energy of the generator of emission greenhouse gas not ₂Absorb (referring to the discussion among the embodiment 5).

Embodiment 7

Determine Voptlve (with respect to the best subnormal voltage operation voltage of electrolytic cell capacity or area) and Ioptlve (electric current when this working voltage) according to the V/I feature work line of the LVE chlor-alkali electrolysis cell of optimizing

Confirmed in the literary composition that subnormal voltage operation has reduced the NaOH required energy of preparation as absorption fluids.Table 3 has shown the result of calculation (discussing) that the VI active line by 1.0/90 ℃ of anolyte situation among Fig. 5 obtains in the foregoing description 4.

For the content of table 3 should note following some:

(1) is used to produce the ratio of the electric current of chemical product in the electric current that the current efficiency of third column (dimensionless) expression produces; The loss (for example, 12R loss) and the used heat of electrolysis fluid are inefficient main causes.Current efficiency descends and descends along with voltage.

(2) for the situation of 3.975V, (current density, and the area that needs of relevant therewith this method are and at 3.0kA/m to make the electrolytic cell area normalization ²The standard 5V electrolysis that moves under the feature is identical).Calculate A2/A1 (dimensionless).

At last, according to the power % mapping that unit dimensionless area is saved, see Figure 11.For this function, the maximum point of slope (variation that power uses and the relation of voltage change) is represented the best; Promptly when low-voltage (for example 2.1-2.5 volt), slope (Δ power/Δ m2) is lower, and when voltage higher (for example 2.5 volts to about 3 volts), slope (Δ power/Δ m2) is increased to bigger numerical, continues to raise along with voltage then, and slope descends.This explanation all has low slope region in the both sides of high slope region; I.e. any side of ordering at Voptlve, the variation of voltage value is so unobvious to the influence of the variation that power uses.

At first draw the function that is in close proximity to agenda (noting the equation of the polynomial trend line that produces by least square fitting).In this embodiment: y=-10.164x3+88.256x2-235.06x+198.37 is very approaching.Then, handle first derivative that calculates this function by the multinomial of routine: dy/dx=(3) (10.164) x2+ (2) (88.256) x-235.06=max.The value of x (volt) can iteration, up to the maximum that draws this first derivative, can finish this computing by various technology, and the result who finds the solution is 2.894 volts.

Attention can be used the voltage less than 2.894 volts, and the result further saves energy.Some preferred embodiment carry out optimization to being lower than this " best naturally point " low power run.In these situations, the extra area that is used for barrier film can obtain " suboptimization " electrolysis system, but for given electrolysis subsystem, the low power run of whole removing carbon dioxide process can be owing to further be benefited in this operation below best naturally point.But, move like this, can weaken the benefit of voltage/power afterwards, the while area factor can continue proportional efficient of unit are operation that makes and reduce.

Can be by forming similar V and I least square relation, perhaps by using illustrated operation curve to determine that Ioptlve determines electric current and the current density corresponding to Voptlve.In this embodiment, calculated value is 10.419A (perhaps for 0.01 square metre an electrolytic cell area in this situation), 1.042kA/m ²

Table 3

I, electric current (A)	Volt, V service condition: 1.0,90 ℃ of anolyte pH	Current efficiency	Δ(kA/m ²)/Δ V	Δ power/Δ (kA/m ²)	Power=VIEff
I, electric current (A)	Volt, V service condition: 1.0,90 ℃ of anolyte pH	Current efficiency	Δ(kA/m ²)/Δ V	Δ power/Δ (kA/m ²)	Power=VIEff	30 25 20 15 10 7.5 5 4 3 2 1.5 1 0.7 0.5 0.4 0.3 0.2 0.1	3.975 3.7 3.433 3.165 2.887 2.747 2.603 2.544 2.477 2.407 2.365 2.309 2.262 2.229 2.213 2.182 2.164 2.12	97％ 96％ 94％ 91％ 88％ 83％ 78％ 73％ 67％ 60％ 54％ 49％ 44％ 40％ 36％ 32％ 29％ 26％	1.82 1.87 1.87 1.80 1.79 1.74 1.69 1.49 1.43 1.19 0.89 0.64 0.61 0.62 0.32 0.56 0.23 0.00	0.55 0.53 0.54 0.56 0.56 0.58 0.59 0.67 0.70 0.84 1.12 1.57 1.65 1.60 3.10 1.80 4.40 212.00	115.67 88.83 64.62 43.34 25.30 17.15 10.19 7.41 4.98 2.90 1.92 1.13 0.70 0.44 0.31 0.21 0.12 0.05
I, electric current (A)	Electrolytic cell area A 2/A1	STD power %/kg-moles	By reducing the power % that V saves	Power/m that Δ is saved ²		30 25 20 15 10 7.5 5 4 3 2 1.5 1 0.7 0.5 0.4 0.3 0.2 0.1
I, electric current (A)	Electrolytic cell area A 2/A1	STD power %/kg-moles	By reducing the power % that V saves	Power/m that Δ is saved ²		30 25 20 15 10 7.5 5 4 3 2 1.5 1 0.7 0.5 0.4 0.3 0.2 0.1	1.000 1.302 1.790 2.669 4.572 6.744 11.357 15.619 23.248 39.873 60.121 102.631 166.292 262.506 367.228 551.770 927.267 2103.359	77％ 71％ 65％ 58％ 51％ 46％ 41％ 37％ 33％ 29％ 26％ 23％ 20％ 18％ 16％ 14％ 12％ 11％	23％ 29％ 35％ 42％ 49％ 54％ 59％ 63％ 67％ 71％ 74％ 77％ 80％ 82％ 84％ 86％ 88％ 89％	22.22 19.77 15.82 10.80 8.05 5.22 4.03 2.87 1.78 1.24 0.75 0.48 0.31 0.23 0.16 0.09 0.04

******

The content that discloses according to the present invention can be under the situation of too much not testing, all method and apparatus of disclose and prescription in enforcement and the execution literary composition.Though according to preferred embodiment method and apparatus of the present invention being described, but it will be apparent for a person skilled in the art that under the situation that does not deviate from notion of the present invention, spirit and scope, can change the method and apparatus described in the literary composition and the sequence of steps of method step or method.More specifically, obviously some composition that chemistry is relevant can substitute the composition described in the literary composition, and obtains same or similar result.All these conspicuous for a person skilled in the art similar substitute and modification is considered to belong to spirit of the present invention, scope and notion, and spirit of the present invention, scope and notion are defined by the following claims.

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" modern chlor-alkali technology (Modern Chlor-Alkali Technology), " edited by M.O.Coultier, Society for the Chemical Industry, London, 1980.

" modern chlor-alkali technology (Modern Chlor-Alkali Technology), " 1-7 volume, The RoyalSociety of Chemistry Information Services, 1998.

" some guidances of the analysis of bubble-column reactor, design and operating principle (Some Guidelines forAnalysis; Design; and Operational Principles of Bubble Column Reactors); " and other selection information that comprises in " bubble-column reactor (Bubble Column Reactors) ", Wolf-DieterDeckwer, Gesellschaft fur Biotechnologische Forschung mbH, Braunsweig, Germany, by Robert Field translation, 1991 ISBN 0-471-91811-3.

" transmission of fuel battery proton exchange film and structure (Transport and Structure in Fuel CellProton Exchange Membranes); " Michael Anthony Hickner, the paper of submitting to Virginia PolytechnicInstitute and State University faculty, 2003.

Fig. 8. " at various tower heights is the CO of 0.18 meter sodium hydroxide solution in unfilled injection bubble tower ₂Absorb relation (CO with (low) interfacial gases speed ₂Absorption vs. (Low) Interfacial GasVelocity at Various Column Heights of 0.18M Sodium Hydroxide Solution in anUnpacked Sparged Bubble Column; " from the A.Schumpe paper, University ofHanover, 1978.

Klara in: the EIA discharging (EIA Emissions ofGreenhouse Gases in the U.S.2000) of the U.S.'s greenhouse gases in 2000, EPGA 3rd Annual Power GenerationConference, Hershey PA, 2002.

Mandal etc., J.Chem.Engineering (Canada), 81:212-219,2003.

Shah etc., AiCHE J., 28 (3): 353-379,1982.

The unit operations of Chemical Engineering (Unit Operations of Chemical Engineering), McGraw-Hill, the 3rd edition  1976, " Gas Absorption " 707-743 page or leaf is after Eckert.

Wie-rong etc., J.Zhejiang University Science, ISSN 1009-3095,2004.

Claims

1. method of from air-flow, removing carbon dioxide, it comprises:

Obtain the hydroxide of aqueous mixture form;

Described hydroxide is mixed with described air-flow, produce carbonate product, bicarbonate product or carbonate and bicarbonate mixture of products; And

Described carbonate and/or bicarbonate product are separated from described mixture, from described air-flow, remove carbon dioxide thus.

2. the method for claim 1 is characterized in that, also comprises described method is carried out process control, thereby has to have to carbonate product, basically to the bicarbonate product basically or obtain carbonate and the bicarbonate mixture of products.

3. method as claimed in claim 1 or 2, it is characterized in that generation comprises about 50% carbonate product and about 50% bicarbonate product, about 25% carbonate product and about 75% bicarbonate product or about 75% carbonate product and about 25% bicarbonate mixture of products.

4. as each described method in the claim 1 to 3, it is characterized in that describedly be blended in two and independently carry out in the chamber, one of them chamber is used for the production carbonate product, another chamber is used to produce the bicarbonate product.

5. as each described method in the claim 1 to 4, it is characterized in that described being blended in bubble column or the bubble column series carried out.

6. as each described method in the claim 1 to 5, it is characterized in that described carbonate and/or the separation of bicarbonate product from mixture relate to the thermal precipitation separation process.

7. as each described method in the claim 1 to 6, it is characterized in that, the heat that is used for described separation process from the heat exchange of the flue gas that enters.

8. as each described method in the claim 1 to 7, it is characterized in that described method also comprises:

Carbonate product is transported to long-range isolating points;

Carbonate product is mixed in neutralization reaction with acid, generate pure carbon dioxide; And

Carbon dioxide is injected in the carbon bank.

9. as each described method in the claim 1 to 8, it is characterized in that, other component in the described air-flow is neutralized and/or carries secretly in forming the process of carbonate/catches.

10. method as claimed in claim 9 is characterized in that, in forming the process of carbonate, be neutralized and/or carry secretly/other component of the described air-flow of catching comprises SO _X, NO _XWith mercurous material.

11. as each described method in the claim 1 to 10, it is characterized in that, obtain described hydroxide and comprise:

Obtain salt;

Described salt is mixed with water, steam or water and vapor phase, obtain solution; And

The described solution of electrolysis obtains hydroxide.

12. method as claimed in claim 11 is characterized in that, uses more than or equal to about 5 volts described solution of voltage electrolysis.

13. method as claimed in claim 11 is characterized in that, uses approximately less than 5 volts for example about 1.5 volts to 4 volts or about 2 volts to 3 volts described salt solution of voltage electrolysis.

14. as each described method in the claim 11 to 13, it is characterized in that, before the described electrolysis of solutions, to wherein adding acid, preferably add hydrochloric acid earlier.

15. as each described method in the claim 11 to 14, it is characterized in that,

Described electrolysis step is carried out in the electrochemical cell with catholyte side and anolyte side;

Carbonate and/or bicarbonate product are recycled to the catholyte side of electrochemical cell.

16. as each described method in the claim 11 to 15, it is characterized in that, use the used heat that from described air-flow, reclaims to replenish the required energy of described method.

17., be further defined as the method for from air-flow, removing carbon dioxide that may further comprise the steps as each described method in the claim 1 to 16:

Obtain the NaOH of aqueous mixture form;

Described NaOH is mixed with described air-flow, obtain the mixture of sodium carbonate, sodium acid carbonate or sodium carbonate and sodium acid carbonate; And

Described sodium carbonate and/or sodium acid carbonate are separated from mixture, from described air-flow, remove carbon dioxide thus.

18. method as claimed in claim 17 is characterized in that, described method also comprises:

Sodium carbonate is transported to long-range isolating points;

Carbon dioxide is injected in the carbon bank.

19. method as claimed in claim 17 is characterized in that, obtains NaOH and comprises:

Obtain sodium chloride;

Sodium chloride is mixed with water, steam or water and vapor phase, obtain salt solution; And

The described salt solution of electrolysis produces NaOH and chlorine.

20. method as claimed in claim 19 is characterized in that, uses more than or equal to about 5 volts described salt solution of voltage electrolysis.

21. method as claimed in claim 19 is characterized in that, uses approximately less than 5 volts for example about 1.5 volts to 4 volts or about 2 volts to 3 volts described salt solution of voltage electrolysis.

22., it is characterized in that as each described method in the claim 19 to 21, before described saline electrolysis, in this salt solution, add acid earlier, preferably add hydrochloric acid.

23. as each described method in the claim 19 to 22, it is characterized in that,

Sodium carbonate and/or sodium acid carbonate product are recycled to the catholyte side of electrochemical cell.

24. as each described method in the claim 19 to 23, it is characterized in that, use the used heat that from described air-flow, reclaims to replenish the required energy of described method.

25., it is characterized in that described method also comprises collection chlorine as each described method in the claim 19 to 24.

26. as each described method in the claim 19 to 25, it is characterized in that, produce hydrogen.

27., it is characterized in that hydrogen and chlorine burning form hydrochloric acid as each described method in the claim 19 to 26, described hydrochloric acid joins in the salt solution before saline electrolysis.

28., it is characterized in that the oxygen in described hydrogen and the atmosphere or from the burning of the oxygen of chemical raw material produces water as claim 26 or 27 described methods.

29., it is characterized in that described method also comprises uses the hydrogen produce power as each described method in the claim 26 to 28.

30., it is characterized in that the separation from mixture of described sodium carbonate and/or sodium acid carbonate relates to the thermal precipitation process as each described method in the claim 19 to 29, wherein be used for the energy of the heat of this separation process from the combustion of hydrogen generation.

31., it is characterized in that described hydrogen burns improve to burn the emission behaviour of coal with coal as claim 29 or 30 described methods, perhaps hydrogen is used for fuel cell and reclaims galvanic combustion process.

32., it is characterized in that described air-flow is a kind of discharge stream of equipment as each described method in the claim 1 to 31, described equipment comprises the generating equipment of using the carbon-based fuel source, preferred described discharge stream comprises CO ₂And H ₂O.

33. an equipment, it comprises:

Tank house, it comprises at least one negative electrode and at least one anode, this tank house is fit in use produce hydroxide;

Mix equipment, it is operably connected with tank house and the suitable conduit that in use holds air-flow, described mixing equipment is fit to the hydroxide from described tank house is mixed with described air-flow, produce mixture, wherein the carbon in the air-flow, sulphur and/or nitrogen compound can react with hydroxide; And

The separation chamber, it is operably connected and is fit to described mixture is separated into independently gas phase and solid phase and/or liquid phase with the described equipment that mixes.

34. equipment as claimed in claim 33 is characterized in that, described tank house comprises membrane electrolytic cell, barrier film and/or mercury.

35. as claim 33 or 34 described equipment, it is characterized in that described mixing equipment comprises batch reactor or batch reactor series, gas/liquid absorption/reaction unit or gas/liquid absorption/reaction unit series, crystallizing tower or crystallizing tower series or bubble column or bubble column series.

36., it is characterized in that described equipment also comprises as each described equipment in the claim 33 to 35:

Hothouse, it is operably connected with described separation chamber and the suitable liquid of in use removing in solid phase and/or the liquid phase.

37. equipment as claimed in claim 36 is characterized in that, described hothouse is fit in use solid phase and/or liquid phase be heated.

38., it is characterized in that described equipment also is defined as with generating equipment and is operably connected as each described equipment in the claim 33 to 37.

39., it is characterized in that described tank house is fit in use by sodium chloride and water generates chlorine and NaOH as each described equipment in the claim 33 to 38.

40., it is characterized in that described mixing equipment is fit in use to make from the hydroxide of tank house and carbon dioxide mix from air-flow, produces carbonate and/or bicarbonate product as each described equipment in the claim 33 to 39.

41. a method of removing carbon dioxide from air-flow, it comprises:

Obtain the hydroxide of aqueous mixture form;

Described carbonate and/or bicarbonate product are separated from mixture, from air-flow, remove carbon dioxide thus.

42. method as claimed in claim 41 is characterized in that, also comprises described method is carried out process control, only produces carbonate product basically.

43. method as claimed in claim 41 is characterized in that, also comprises described method is carried out process control, only produces the bicarbonate product basically.

44. method as claimed in claim 41 is characterized in that, also comprises described method is carried out process control, produces carbonate and bicarbonate mixture of products.

45. method as claimed in claim 44 is characterized in that, described mixture comprises about 50% carbonate product and about 50% bicarbonate product.

46. method as claimed in claim 44 is characterized in that, described mixture comprises about 25% carbonate product and about 75% bicarbonate product.

47. method as claimed in claim 44 is characterized in that, described mixture comprises about 75% carbonate product and about 25% bicarbonate product.

48 methods as claimed in claim 41 is characterized in that, describedly are blended in two and independently carry out in the chamber, and one of them chamber is used for the production carbonate product, and another chamber is used to produce the bicarbonate product.

49. method as claimed in claim 41 is characterized in that, described being blended in bubble column or the bubble column series carried out.

50. method as claimed in claim 41 is characterized in that, described carbonate and/or the separation of bicarbonate product from mixture relate to the thermal precipitation separation process.

51. method as claimed in claim 50 is characterized in that, the heat that is used for described separation process from the heat exchange of the flue gas that enters.

52. method as claimed in claim 41 is characterized in that, described method also comprises:

Carbonate product is transported to long-range isolating points;

Carbon dioxide is injected in the carbon bank.

53. method as claimed in claim 41 is characterized in that, other component in the described air-flow is neutralized and/or carries secretly in forming the process of carbonate/and catches.

54. method as claimed in claim 53 is characterized in that, in forming the process of carbonate, be neutralized and/or carry secretly/other component of the described air-flow of catching comprises SO _X, NO _XWith mercurous material.

55. method as claimed in claim 41 is characterized in that, obtains hydroxide and comprises:

Obtain salt;

The described solution of electrolysis obtains hydroxide.

56. method as claimed in claim 55 is characterized in that, uses more than or equal to about 5 volts described solution of voltage electrolysis.

57. method as claimed in claim 55 is characterized in that, uses approximately the described solution of voltage electrolysis less than 5 volts.

58. method as claimed in claim 57 is characterized in that, uses about 1.5 volts to 4 volts described solution of voltage electrolysis.

59. method as claimed in claim 57 is characterized in that, uses about 2 volts to 3 volts described solution of voltage electrolysis.

60. method as claimed in claim 55 is characterized in that, before the described electrolysis of solutions, earlier to wherein adding acid.

61. method as claimed in claim 60 is characterized in that, described acid is hydrochloric acid.

62. method as claimed in claim 60 is characterized in that, the amount of the acid that adds in described solution is based on determining of minimum energy of realize producing reactant and the best protonated ratio that reclaiming highest energy from product.

63. method as claimed in claim 55 is characterized in that:

64. method as claimed in claim 55 is characterized in that, uses the used heat that reclaims from air-flow to replenish the required energy of described method.

65. a method of removing carbon dioxide from air-flow, it comprises:

Obtain the NaOH of aqueous mixture form;

66., it is characterized in that as the described method of claim 65, also comprise described method is carried out process control, only produce sodium carbonate basically.

67., it is characterized in that as the described method of claim 65, also comprise described method is carried out process control, only produce sodium acid carbonate basically.

68., it is characterized in that as the described method of claim 65, also comprise described method is carried out process control, produce the mixture of sodium carbonate and sodium acid carbonate.

69., it is characterized in that described mixture comprises about 50% sodium carbonate and about 50% sodium acid carbonate as the described method of claim 68.

70., it is characterized in that described mixture comprises about 25% sodium carbonate and about 75% sodium acid carbonate as the described method of claim 68.

71., it is characterized in that described mixture comprises about 75% sodium carbonate and about 25% sodium acid carbonate as the described method of claim 68.

72., it is characterized in that describedly be blended in two and independently carry out in the chamber, one of them chamber is used to produce sodium carbonate as the described method of claim 65, another chamber is used to produce sodium acid carbonate.

73., it is characterized in that described being blended in bubble column or the bubble column series carried out as the described method of claim 65.

74., it is characterized in that the separation from mixture of described sodium carbonate and/or sodium acid carbonate relates to the thermal precipitation separation process as the described method of claim 65.

75. as the described method of claim 74, it is characterized in that, the heat that is used for described separation process from the heat exchange of the flue gas that enters.

76., it is characterized in that described method also comprises as the described method of claim 65:

Sodium carbonate is transported to long-range isolating points;

Carbon dioxide is injected in the carbon bank.

77. as the described method of claim 65, it is characterized in that, obtain NaOH and comprise:

Obtain sodium chloride;

Sodium chloride is mixed with water, steam or water and steam, obtain salt solution; And

The described salt solution of electrolysis produces NaOH and chlorine.

78. as the described method of claim 77, it is characterized in that, use more than or equal to about 5 volts described salt solution of voltage electrolysis.

79. as the described method of claim 77, it is characterized in that, use approximately the described salt solution of voltage electrolysis less than 5 volts.

80. as the described method of claim 79, it is characterized in that, use about 1.5 volts to 4 volts described salt solution of voltage electrolysis.

81. as the described method of claim 79, it is characterized in that, use about 2 volts to 3 volts described salt solution of voltage electrolysis.

82. as the described method of claim 77, it is characterized in that, before described saline electrolysis, in this salt solution, add acid earlier.

83., it is characterized in that described acid is hydrochloric acid as the described method of claim 82.

84., it is characterized in that the amount of the acid that adds is based on determining of minimum energy of realize producing reactant and the best protonated ratio that reclaiming highest energy from product as the described method of claim 82 in described salt solution.

85., it is characterized in that as the described method of claim 77:

Sodium carbonate and/or sodium acid carbonate are recycled to the catholyte side of electrochemical cell.

86. as the described method of claim 77, it is characterized in that, use the used heat that from air-flow, reclaims to replenish the required energy of described method.

87., it is characterized in that described method also comprises collection chlorine as the described method of claim 77.

88. as the described method of claim 77, it is characterized in that, produce hydrogen.

89., it is characterized in that hydrogen and chlorine burning form hydrochloric acid as the described method of claim 88, described hydrochloric acid joins in the salt solution before saline electrolysis.

90., it is characterized in that the oxygen in described hydrogen and the atmosphere or from the burning of the oxygen of chemical raw material produces water as the described method of claim 88.

91., it is characterized in that described method also comprises uses the hydrogen produce power as the described method of claim 88.

92., it is characterized in that the separation from mixture of sodium carbonate and/or sodium acid carbonate relates to the thermal precipitation separation process as the described method of claim 91, wherein be used for the energy of the heat of this separation process from the hydrogen generation.

93., it is characterized in that the emission behaviour that described hydrogen burns and burns coal to improve with coal as the described method of claim 91.

94., it is characterized in that described hydrogen is used for fuel cell and reclaims galvanic combustion process as the described method of claim 91.

95., it is characterized in that described air-flow is a kind of discharge stream of equipment as the described method of claim 65.

96., it is characterized in that described equipment is to use the generating equipment in carbon-based fuel source as the described method of claim 95.

97., it is characterized in that described discharge stream comprises CO as the described method of claim 95 ₂And H ₂O.

98. an equipment, it comprises:

Mix equipment, it is operably connected with tank house and the suitable conduit that in use holds air-flow, described mixing equipment is fit to the hydroxide from tank house is mixed with described air-flow, produce mixture, the carbon in the wherein said air-flow, sulphur and/or nitrogen compound can react with hydroxide; And

The separation chamber, it is operably connected with mixing equipment, and described separation chamber is fit to mixture is separated into independently gas phase and solid phase and/or liquid phase.

99., it is characterized in that described tank house comprises membrane electrolytic cell, barrier film and/or mercury as the described equipment of claim 98.

100., it is characterized in that described tank house comprises membrane electrolytic cell as the described equipment of claim 99.

101., it is characterized in that described mixing equipment is batch reactor or batch reactor series as the described equipment of claim 98.

102., it is characterized in that described mixing equipment is gas/liquid absorption/reaction unit or gas/liquid absorption/reaction unit series as the described equipment of claim 98.

103., it is characterized in that described mixing equipment is crystallizing tower or crystallizing tower series as the described equipment of claim 98

104., it is characterized in that described mixing equipment is bubble column or bubble column series as the described equipment of claim 98.

105. as the described equipment of claim 98, it is characterized in that, also comprise:

Hothouse, it is operably connected with described separation chamber, and described hothouse is fit in use remove the liquid in solid phase and/or the liquid phase.

106., it is characterized in that described hothouse is fit in use solid phase and/or liquid phase be heated as the described equipment of claim 104.

107., it is characterized in that described equipment also is defined as with generating equipment and is operably connected as the described equipment of claim 98.

108., it is characterized in that described tank house is fit in use by sodium chloride and water generates chlorine and NaOH as the described equipment of claim 98.

109., it is characterized in that described mixing equipment is fit in use to make from the hydroxide of described tank house and carbon dioxide mix from described air-flow, produces carbonate and/or bicarbonate product as the described equipment of claim 98.

110. a method of removing carbon dioxide from air-flow, it comprises:

Obtain the hydroxide of aqueous mixture form;

111., it is characterized in that as the described method of claim 110, also comprise described method is carried out process control, only produce carbonate product basically, only produce bicarbonate product or produce carbonate and the bicarbonate mixture of products basically.

112., it is characterized in that describedly be blended in two and independently carry out in the chamber, one of them chamber is used for the production carbonate product as the described method of claim 110, another chamber is used to produce the bicarbonate product.

113., it is characterized in that described being blended in bubble column or the bubble column series carried out as the described method of claim 110.

114., it is characterized in that described carbonate and/or the separation of bicarbonate product from mixture relate to the thermal precipitation separation process as the described method of claim 110.

115. as the described method of claim 114, it is characterized in that, the heat that is used for described separation process from the heat exchange of the flue gas that enters.

116. as the described method of claim 110, it is characterized in that, also comprise:

Carbonate product is transported to long-range isolating points;

Carbon dioxide is injected in the carbon bank.

117. as the described method of claim 110, it is characterized in that, other component in the described air-flow is neutralized and/or carries secretly in forming the process of carbonate/catches.

118. as the described method of claim 110, it is characterized in that, obtain hydroxide and comprise:

Obtain salt;

Described salt is mixed with water, steam or water and steam, obtain solution; And

The described solution of electrolysis obtains hydroxide.

119., it is characterized in that as the described method of claim 118, before the described electrolysis of solutions, in this solution, add acid earlier, preferably add hydrochloric acid.

120., it is characterized in that the amount of the acid that adds is based on determining of minimum energy of realize producing reactant and the best protonated ratio that reclaiming highest energy from product as the described method of claim 119 in described solution.

121., it is characterized in that as the described method of claim 118:

122. as the described method of claim 118, it is characterized in that, use the used heat that from air-flow, reclaims to replenish the required energy of described method.

123., it is characterized in that described salt is sodium chloride as the described method of claim 118, the solution that is produced is salt solution, electrolysis described salt water generates NaOH and chlorine.

124. as the described method of claim 123, it is characterized in that, produce hydrogen.

125., it is characterized in that hydrogen and chlorine burning form hydrochloric acid as the described method of claim 124, described hydrochloric acid joins in the salt solution before saline electrolysis.

126., it is characterized in that the oxygen in described hydrogen and the atmosphere or from the burning of the oxygen of chemical raw material produces water as the described method of claim 124.

127., it is characterized in that described method also comprises uses the hydrogen produce power as the described method of claim 124.

128., it is characterized in that carbonate and/or the separation of bicarbonate product from mixture relate to the thermal precipitation separation process as the described method of claim 127, wherein be used for the energy of the heat of this separation process from the hydrogen generation.

129., it is characterized in that the emission behaviour that described hydrogen burns and burns coal to improve with coal as the described method of claim 127.

130., it is characterized in that described hydrogen is used for fuel cell and reclaims galvanic combustion process as the described method of claim 127.

131., it is characterized in that described air-flow is a kind of discharge stream of equipment as the described method of claim 110.

132., it is characterized in that described equipment is to use the generating equipment in carbon-based fuel source as the described method of claim 131.

133. an equipment, it comprises:

Tank house, it comprises at least one negative electrode and at least one anode, this chamber is fit in use produce hydroxide;

134., it is characterized in that described tank house comprises membrane electrolytic cell, barrier film and/or mercury as the described equipment of claim 133.

135. as the described equipment of claim 133, it is characterized in that described mixing equipment is batch reactor or batch reactor series, gas/liquid absorption/reaction unit or gas/liquid absorption/reaction unit series, crystallizing tower or crystallizing tower series or bubble column or bubble column series.

136. as the described equipment of claim 133, it is characterized in that, also comprise:

Hothouse, it is operably connected with the separation chamber, and described hothouse is fit in use remove the liquid in solid phase and/or the liquid phase.

137., it is characterized in that described hothouse is fit in use solid phase and/or liquid phase be heated as the described equipment of claim 136.

138., it is characterized in that described equipment also is defined as with generating equipment and is operably connected as the described equipment of claim 133.

139., it is characterized in that described tank house is fit in use by sodium chloride and water generates chlorine and NaOH as the described equipment of claim 133.

140., it is characterized in that described mixing equipment is fit in use to make from the hydroxide of tank house and carbon dioxide mix from air-flow, produces carbonate and/or bicarbonate product as the described equipment of claim 133.