CN106315761A

CN106315761A - Method for exchanging and concentrating ions in solution

Info

Publication number: CN106315761A
Application number: CN201510381052.2A
Authority: CN
Inventors: 秦才东
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-06-24
Filing date: 2015-06-24
Publication date: 2017-01-11

Abstract

The invention relates to a method for exchanging and concentrating ions in a solution. By adopting the combination of an anionic membrane and a cationic membrane or the combination of a cationic resin and an anionic resin, a channel for ion transfer is provided to realize the separation of substances in the solution and the exchange reaction of ions. Under the action of different replacement solutions, seawater desalination, waste water recycling and harmless treatment are realized; the method can be widely applied to sewage treatment and industrial production processes, ion concentration, deacidification, dealkalization, desalination, brine desalination process in the industry production process, the production of potassium salt, sodium salt and alkali, and the mutual conversion between acid, alkali and salts.

Description

The exchange of effects of ion and method for concentration

Technical field

The present invention relates to exchange and the method for concentration of a kind of effects of ion, especially relate to one and utilize anionic membrane With cationic membrane, resin anion (R.A.), the combination application method of cationic resin, belong to ion isolation technical field.

Background technology

Process at water, include desalinization, Chemical Manufacture, chemical separating and chemical reaction, light industry and food, former The son industrial circle such as energy, often relates to exchange or the conversion of various zwitterions in water, or separation removal or concentration and recovery, And Organic substance separates, is dehydrated, purifies and concentrates with variety classes materials such as water, acid, alkali, salt and subdivision Solve reaction problem.Because the development of chemical industry, water pollutes and the scarcity of fresh water has had influence on holding of economy Supervention exhibition, water processes and purifies is a field that must have new breakthrough technically.

Summary of the invention

The exchange of the effects of ion of the present invention and method for concentration problem to be solved be: existing diffusion dialysis and The problem not having additional motive power in Donnan diffusion dialysis, and along with the carrying out of diffusion, driving force constantly reduces, Resistance is continuously increased, and has the hypodynamic problem of driving.The method of the present invention, for from solution, especially from useless Water refines valuable resource, or is allowed to innoxious with harmless ion replacement harmful ion, or remove completely in water Zwitterion realizes water purification and processes, or realizes the exchange of ion between different material, the material required for output.

The present invention additionally provides the selective penetrated property utilizing anions and canons exchange membrane, and the concentration difference of ion especially Spreading effect, by the cation in solution is converted to ammonium radical ion, is converted to carbonic acid by the anion in solution Root or bicarbonate ion, make original compound corresponding to zwitterion in solution be converted into readily volatilized precipitation Ammonia, ammonium hydroxide, carbon dioxide, carbonic acid, ammonium carbonate and/or ammonium hydrogen carbonate.Especially, solve how former The ammonium ion of sub-portfolio and carbonic acid hydrogen ion be adverse effect to diffusion dialysis due to self water decomposition.Following is molten Liquid or pending solution and substitutional solution are a kind of relative concepts set up for convenience of description, actually used Time, the most tangible difference.

The exchange of a kind of effects of ion of the present invention and method for concentration, comprising:

Step 1, with the cation in ammonium radical ion substitutional solution；

Step 2, with the anion in bicarbonate ion or carbanion substitutional solution；

The order of above-mentioned steps 1 and step 2 can be exchanged；Described ammonium radical ion, bicarbonate ion or carbon Acid ion comes from substitutional solution；And substitutional solution is as driving solution, ion concentration therein is the highest, Or saturated solution, to increase ion driving force.

Cationic membrane and anionic membrane are passed through in cation and the exchange of anion in solution respectively；Or respectively by sun Ion exchange resin and resin anion (R.A.)；More preferably, cationic membrane is Subacidity cation film, and anionic membrane is alkalescence Anionic membrane；Or more preferably, cationic membrane is neutral cation film, anionic membrane is neutral anion film.

Because, in the case of in substitutional solution, ammonium concentration is higher than sea water or waste water cationic concentration, permissible Speculate, on the path that ammonium ion is spread by cationic membrane, if film is highly acid film, then electronegative with on film Group form the ammonium salt of slant acidity, near the ammonium ion i.e. migrated in film, proton concentration is higher, occurs mobility high Proton reversely migrate, it is impossible to reach the effect making sea water or sewage cationic be exchanged by ammonium ion, in experiment then Find that the salinity in sea water or sewage is the most a small amount of to reduce, but produce substantial amounts of ammonia and separate out.Therefore, highly acid film Actual effect be to promote hydrolysis, entering sea water or during waste water solution, ammonium ion is combined dimension with hydroxide ion Hold electric neutrality, and hydrion reversely migrates into the electric neutrality also maintaining solution in substitutional solution.And it is molten in displacement In liquid, ammonium concentration is less than in the case of film opposite side anions in solution concentration, then described cation can expand Dissipating and enter in substitutional solution, but ammonium ion should be converted into ammonia after deprotonation and separate out, the proton of generation is handed over Swap-in enters in replaced solution.This phenomenon, can apply to include containing ammonia i.e. containing ammonium in ammonium hydroxide water from The decomposed reaction of son or ammonium salt, in order to the ammonium ion in removing solution, such as, the sea after desalinating in the present invention Ammonia in water, is promoted as cationic catalysts by highly acidic cation film especially with the hydrion in various acid The application of ammonium ion deprotonation in water.

Therefore, in order to make full use of in substitutional solution ammonium ion exchange solution in cation, more preferably, sun from Sub-film selects Subacidity cation film, to avoid the impact of the proton of high mobility, or, cationic membrane selects neutrality Cationic membrane, it is to avoid the generation of water decomposition and the impact that film both sides ion is intercoursed.It addition, by displacement The method adding ammonia in ammonium salt solution in solution, regulation pH value more than 7, then plays suppression highly acidic cation On film, the hydrolysis of group proposes protogenic effect, and therefore the ammonium salt solution in substitutional solution is preferably added ammonia.

In like manner, strong alkalinity anion film provides the invalid exchange of hydroxyl and bicarbonate ion, or and carbonate The partial invalidity exchange of ion, i.e. carbonic acid hydrogen ion hydrolysis combines a hydrion, discharges a hydroxide ion, Return and drive in liquid.To maintain its electric neutrality；But it is likewise possible to utilize this phenomenon bicarbonate radical in waste water Or the removing of carbanion；The most therefore, more preferably, anionic membrane selects alkalescence or neutral anion film, with Avoid the invalid exchange of ionic membrane both sides anion.

Described solution is after step 1 processes, then processes through step 2；Optimally, solution is divided into two parts, Each processing through step 1 and step 2 the most respectively, the two parts after process enter in mixing container, mixed Recycling solution after conjunction carries out the process of step 1 and step 2.

In order to reduce the ion concentration in solution, it is achieved the desalination of water processes, and increases effective driving force, increase

The ammonium carbonate that in step 3, precipitation step 1 and/or step 2 or generates in the mixing container, ammonium hydrogen carbonate, Carbon dioxide or ammonia；

Solution described in step 4, circulation step 1,2,3, until the content of described effects of ion is reduced to Design requirement.

In order to obtain the extract concentrated from solution, increase

Step 5, separate out in described substitutional solution molten with displacement respectively from the cation in described solution and anion Anion in liquid and the salt of cation generation；

Optional but be not limited to described separation method and have crystallisation by cooling, condensing crystallizing；And

Step 6, circulation solution after step 5 processes, respectively as the substitutional solution in step 1, step 2；

Along with the carrying out of diffusion dialysis, in substitutional solution for the ammonium radical ion of substitutional solution intermediate ion, carbonate from Son or bicarbonate ion concentration constantly reduce, and in order to keep suitable high concentration, increase

Step 7, the ammonium salt supplementing displacement and carbonate, carbonate salt, keep corresponding ion in substitutional solution Concentration；If gained desalination water still containing ammonium ion, then can increase

Step 8, step 3 or 4 are processed after solution carry out dialysis process through highly acidic cation film, corresponding Exchange solution is water, or acid-containing solution；Reduce the carrying out replaced in ammonium ion beneficially step 1 in solution in time；

Wherein, step 6,7,8 be optional and the step carried out can be synchronized.

Above-mentioned ammonium radical ion derives from the mixture of ammonia, ammonium salt or ammonia and ammonium salt；Described ammonium salt is chlorination Ammonium, ammonium carbonate, ammonium hydrogen carbonate, ammonium nitrate, ammonium sulfate, ammonium phosphate, inferior ammonium nitrate, ammonium sulfite, Hydrogen thiocyanate Ammonium；Carbonate or bicarbonate ion derive from carbonate or bicarbonate；Described carbonate is ammonium carbonate, carbon Acid hydrogen ammonium, ammonium carbonate and the mixed solution of ammonia, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate.

The selection of above-mentioned particular compound should be with Financial cost as primary concern, and the setting of target product, holds concurrently Turn round and look at the convenience of industrial operation.

When the exchange of cation and anion is respectively by cationic membrane and anionic membrane, especially, described step In rapid 2, the anion in substitutional solution can also is that hydroxide ion；Described hydroxide ion derives from ammonia or alkali.

The exchange of above-mentioned effects of ion and method for concentration can be used for sea water, pulping sewage, electroplating sewerage, weaving During leather sewage, hydrometallurgy sewage, biomass acid hydrolysis solution, industrial and agricultural production containing electrolyte ion Produce is various containing acid, alkali, the sewage of salt.

When being applied to desalinization, the substitutional solution of preferred step 1 is saturated or the ammonium chloride of high concentration, Optimally, ammonium chloride solution adds ammonia, makes substitutional solution meta-alkalescence, the substitutional solution bicarbonate of step 2 Ammonium, ammonium carbonate or ammonium carbonate and the mixed solution of ammonia.Make the cation in sea water such as sodium, potassium, calcium, magnesium, strontium Etc. being converted into chloride, as product after concentration extraction；Make the anion in sea water such as chloride ion, sulfate ion, Carbanion, nitrate ion, bromide ion, fluorion etc. are converted into ammonium salt and concentrate；This ammonium salt can circulate Reuse is as the donor substance of ammonium radical ion in substitutional solution.

When being applied to process containing alkaline sewage, the ammonium hydroxide generated is utilized to decompose the feature separating out ammonia, logical Cross air-blowing bubble volatilization to separate out, or decompression volatilization separates out ammonia, directly utilizes aforesaid step 1 and need not utilize step 2 purposes that i.e. can reach removing alkalescence, the substitutional solution of preferred step 1 is saturated or the ammonium chloride of high concentration, So that the salt utilizing most of chloride ion is dissolved in the feature of water, it is to avoid in film or film surface formed precipitation；Or root The mixed solution of ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate or ammonium carbonate and ammonia is selected according to product needed. If possibly together with other salt ion in the solution after removing alkalescence, use the most again aforesaid step 1 and step 2 combine into Row processes, and reaches thoroughly to process the purpose of sewage.Typical have pulping back liquor, leather containing alkaline sewage Sewage, cyanide extract the waste water after precious metal.When alkaline pulp-making sewage disposal, optimally, utilize carbonic acid Hydrogen ammonium is as substitutional solution, it is thus achieved that sodium bicarbonate solution, then sodium bicarbonate carbonization is converted into Caustic soda, is back to system Slurry workshop section.After pulping back liquor removing alkalescence, black liquor contains substantial amounts of organic matter, can execute directly as irrigation Fertilizer water.Leather sewage, cyanide extract the waste water after precious metal then after removing alkalescence, in waste water still So containing harmful ion, such as chromate ion, containing arsenate ion, other heavy metal ion etc., therefore, need To use aforesaid step 1 and step 2 to combine further to process, reach thoroughly to process the purpose of sewage.Especially It is the sewage after cyanide extracts precious metal, and after alkalescence removes or during removing, complex occurs Decomposing, precipitable metal cyanides precipitates, or the volatilization precipitation of Blausure (German), ammonium cyanide occurs.

When being applied to containing acid sewage disposal, concentrated acid can first reclaim through diffusion dialysis, remaining diluted acid waste water Utilize aforesaid step 2 can individually be neutralized process, or utilize aforesaid step 1 and step 2 to combine to locate Reason, reaches thoroughly to process the purpose of sewage.The typical sewage containing acid has the acid of electroplating wastewater, pickling sewage, biomass Hydrolysis sugary soln.Ammonium radical ion displacement in the substitutional solution of step 1 concentrates out each metal ion species in waste water, The anion metathesis of the substitutional solution of step 2 concentrates out the harmful ion in waste water as containing chromate ion, containing arsenic acid Radical ion etc..In order to avoid the precipitate infringement to film, acid-bearing wastewater can be initially charged appropriate ammonium carbonate, with precipitation Separate out harmful metal ion.

In a word, if containing ammonium radical ion or hydrion in described pending solution, then described step 1 can save Slightly need not；If described pending solution containing carbanion or bicarbonate ion or hydroxide ion, then Described step 2 can be omitted need not.

The production method of a kind of salt of the present invention, utilizes exchange and the method for concentration of ion in claim 1-5, Comprising: using potassium chloride, sodium chloride solution as the solution described in claim 1, with ammonium carbonate, carbon The mixing of acid hydrogen ammonium, ammonium sulfate, ammonium sulfite, ammonium nitrate or ammonium nilrite solution or aforementioned ammonium salt and ammonia Solution is as the substitutional solution in step 1 in claim 1；With ammonium carbonate or ammonium hydrogen carbonate or ammonium carbonate with The mixed solution of ammonia, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate or ammonia, sodium hydroxide, hydrogen Potassium oxide, Lithium hydrate are as the substitutional solution in step 2 in claim 1；In order to accelerate response speed, instead The concentration answering thing is the highest or saturated.Substitutional solution in step 1 generates respectively correspondence potassium carbonate, Potassium bicarbonate, potassium sulfate, potassium sulfite, potassium nitrate, potassium nitrite, sodium carbonate, sodium bicarbonate, sodium sulfate, Sodium sulfite, sodium nitrate, sodium nitrite.

The production method of a kind of alkali of the present invention, utilizes exchange and the method for concentration of ion in claim 1-5, Comprising: using sodium chloride, potassium chloride or lithium chloride solution as the solution described in claim 1, with ammonia Aqueous solution is as the substitutional solution in step 1 in claim 1；With ammonium carbonate, ammonium hydrogen carbonate, ammonium carbonate and ammonia The mixed solution of water, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, hydroxide Potassium or Lithium hydrate are as the substitutional solution in step 2 in claim 1；

Substitutional solution in step 1 generates the sodium hydroxide of correspondence, potassium hydroxide, Lithium hydrate respectively；For Reduce the alkali that generated on the electrolysis of ammonia from impact, in time product alkali should be removed out substitutional solution or carry out showing Field is applied to the chemical reaction that alkali participates in.Gained alkali can be as the substitutional solution of step 2 in above-mentioned desalinization, sea The ammonia separated out in water desalination process, as the raw material of production alkali, forms process capable of circulation.

Or, using sodium chloride, potassium chloride or lithium chloride concentrated solution or saturated solution as institute in claim 1 State the solution in step 2, using ammonia spirit as step 2 in substitutional solution, in the solution in this step 2 Generate the sodium hydroxide of correspondence, potassium hydroxide, Lithium hydrate and corresponding remaining salt respectively；

Further, using the gained solution containing alkali and remaining salinity as hydroxyl required in claim 7 from The source of son；

Further, simultaneously independent by 2 with sodium chloride, potassium chloride or lithium chloride concentrated solution or saturated solution With ammonia and sea water or useless while of anionic membrane [both sides being i.e. equivalent to container are made up of anionic membrane] difference Water swaps, and indirectly improves the hydroxide ion concentration swapped with sea water or waste water, solves weak electrolyte The problem that in ammonia, ammonium concentration is low.

Detailed description of the invention

Embodiment 1

The present embodiment provides a kind of method of new desalinization, sewage disposal containing acid-alkali salt, illustrates as demonstration The exchange of any effects of ion of model and method for concentration, be to use simple diffusion dialysis or Donnan dialysis. This new method has concentrated the advantage of Donnan diffusion dialysis and ion exchange, also overcomes Donnan dialysis The problem that driving force is low, i.e. can open up new application, it is also possible to certain applications are in current ion exchange resin Already field.Comprising:

In step 1, experiment, preferably faintly acid or neutral cation film is that the diffusion in Donnan electrodialysis apparatus is oozed Analysis film, it is that between 3 centimetres and the nylon part that docks, the effective area of film is that this film is clamped at two opening diameters 3 cm diameter circles, each nylon part perforate degree of depth is 1.5 centimetres, reduces the degree of depth and is conducive to the Uniform Flow of solution Property.Film both sides form the first and second 2 film rooms, and film room avris is respectively arranged with 2 connectors and connects leading of turnover current Pipe.With edible sodium chloride solution simulated seawater, optimally, the substitutional solution being this step with ammonium chloride solution, if Cationic membrane used is highly acid film, then add ammonia in ammonium chloride solution, makes pH value be more than 7, and through every Membrane pump is pumped to the first film room, and circulating reflux, flow velocity 25ml/min；The sea water of simulation is pumped to the through micropump Two film rooms, and circulating reflux, flow velocity 1000ml/min.In this circulation, sea water oozes through the cation described in contact After analysis film dialysis, part sodium ion is replaced by ammonium ion.

Step 2, utilization and another nylon part of step 1 same structure, with ammonium hydrogen carbonate or sal volatile or carbon The mixed solution of acid ammonium and ammonia or the moon that ammonia spirit is the substitutional solution of this step, preferably alkalescence or neutrality Ionic membrane is the diffusion dialysis film in Donnan electrodialysis apparatus.Carbonate substitutional solution is pumped to first through membrane pump Film room, and circulating reflux, flow velocity 25ml/min；Sea water is pumped to the second film room, and circulating reflux through micropump, Flow velocity 1000ml/min.In this step, sea water through contact described in anion dialyser dialysis after, part sea water In anion, predominantly chloride ion is replaced by carbanion.Utilizing highly acidic cation film and strong basicity When anionic membrane is as exchange membrane, optimally, after first making the anion metathesis rate in sea water reach more than 10%, Carry out again from step 1 to step 2 again to the circulation of step 1；Or the first cation in step 1 makes sea water After being reached more than 10% by ammonium ion replacement rate, enter back into and step 2 is circulated process.

Step 3, every 1 hour or 3 hours, the sea water after step 2 processes is aided with aeration, stirring decompression Volatilization, promotes the reaction between ammonium chloride and sodium bicarbonate, sodium carbonate or the sodium hydroxide in solution, also promotes molten Ammonium carbonate in liquid decomposes precipitation products gaseous ammonia and carbon dioxide；During actual production, after ammonia and carbon dioxide recovery Recycle；Or make the second film room in step 2 be in aeration or stirring decompression volatileness all the time, continuously Remove ammonium carbonate product, and reclaim and be back in ammonium carbonate substitutional solution.

Step 4, by the solution in step 3 after fully removing ammonium carbonate or ammonia product, be back in step 1, Or part returns step 1, part returns in step 2 and carries out synchronous circulating process, or carries out from step 1 to step The circular treatment of 3, until the solutes content in pending solution is reduced to the requirement set.

Ammonium chloride in said process or ammonium chloride ammonia spirit or sal volatile are preferably saturated solution, at least than Ion concentration to be exchanged in sea water is high.Anion in sea water concentrates through displacement and enters ammonium carbonate substitutional solution The ammonium chloride of middle formation, ammonium sulfate etc. can crystallized separation and Extraction, or directly as in step 2 ammonium chloride replace Solution recycles, and the most remaining ammonium carbonate can separate out in first heated volatilization.Cation in sea water is dense through displacement Indentation enter ammonium chloride substitutional solution is formed sodium chloride, potassium chloride, the salinity such as magnesium chloride to concentrate, crystallisation by cooling Mode separates out.

Experiment finds, under the conditions of room temperature 25 DEG C, using highly acidic cation film as permeable membrane, salt angle value 61.9ppt Ammonium chloride concentrated solution be 200ml substitutional solution, the tap water 150ml of salt angle value 0.1ppt is pending solution, 3 as a child.The salt angle value of ammonium chloride is reduced to 60.9, and the salt angle value of tap water is upgraded to 0.2ppt, and at ammonium chloride Solution separates out with the Ammonia valatilization of a small amount of alkalescence, it should be that strong acidic ion Membrane catalysis promotes ammonium in ammonium chloride The deprotonation reaction of ion.The sodium chloride solution of salt angle value 33.7ppt is substituted tap water carry out replacing 1 hour Hou Hou, the salt angle value of ammonium chloride solution reduces to 60.5ppt, and still has a small amount of ammonia to separate out, the salt of sodium chloride solution Angle value is upgraded to 34.5ppt, because the salt angle value recorded with the ammonium chloride of molar concentration is higher than the salt angle value of sodium chloride, Illustrate that partial oxidation sodium is converted into ammonium chloride.Experiment finds, when the salt angle value of sodium chloride reduces, as arrived about 15ppt After, ammonium ion is the most weak to the displacement effect of sodium ion, importantly the deprotonation reaction of ammonium ion, and sends ammonia Gas, makes the pH value of saline increase, but the change of the salt angle value of sodium chloride is slowly, and the only salt angle value of ammonium chloride continues It is decreased obviously, it should be the ammonium chloride reason that is converted into hydrogen chloride.For solving this problem, need to use non-strong acid Property cationic membrane or add ammonia in ammonium chloride solution, the pH value of regulation substitutional solution more than 7, surveys chlorine The salinity changing sodium solution increases substantially, and salinity when reaching salinity height gathers way.Same phenomenon also occurs in by force The situation of alkaline anionic membrane, therefore, desalination in the case of Low-salinity, the most non-strong alkalinity anion film, or Person is preferentially by the cation ic-converted process for carrying out anionic membrane after ammonium ion again in sea water.

Experimental result shows, total amount is the simulated seawater solution of 250ml ,～the normal temperature and pressure of 20 DEG C under, through 90 Hour accumulation dialysis, by following steps, especially in the case of using highly acidic cation film, in step 2 In preferentially the sodium chloride in sea water is converted into sodium carbonate, make the weight ratio of sodium chloride and sodium carbonate reach～70: 30, Carry out the dialysis of step 2 again, be stirred continuously precipitation ammonium carbonate gas in step 1.When the carbonic acid sodio in step 1 After this is replaced, when the salinity i.e. shown when salinometer no longer reduces, again return to circular treatment in step 2, salt Degree is down to 2.5 ‰ [salinity is calculated as commercially available salinometer SA287, and is corrected] through saturated brine concentration from 36 ‰. On the premise of not affecting overall dialysis rates, optimum process is to make sodium chloride in sea water as much as possible First it is converted into sodium carbonate, then is converted into ammonium carbonate through step 1.Owing to the ion of film optionally limits, continue fall The concentration of less salt needs to improve the ion selectivity of film.It was also found that there is the carbon of white on the surface of film in experimentation The deposit of hydrochlorate, needs timing acid solution to be carried out removing.Because step 2 need to utilize carbonate as putting Changing solution, and carbonate deposition damages the performance of ionic membrane, therefore, optimally, addition carbonate or ammonia are in advance The material that can form carbonate or alkali precipitation in pending solution is carried out Precipitation, and the carbonate deposition of optimum Agent is ammonium carbonate, to facilitate follow-up precipitation to process.Or, utilize the feature that chloride is soluble in water, utilizing Under conditions of Subacidity cation film is as dialyser, or it is big to add ammonia regulation pH value in ammonium chloride salt solution Under conditions of 7, preferentially carry out step 1, then carry out step 2, and circular treatment.

Experiment finds, if cationic membrane is highly acidic cation film, time in step 1 using ammonium salt as substitutional solution, If the anion in sea water is not the most sufficiently displaced from by carbanion, through Preliminary detection, sodium carbonate Not up to～when more than 20: 80, the ion number ratio～1: 7.3 of carbonate and chloride ion is closed with the weight ratio of sodium chloride, Replaced chloride ion ratio～12%, ammonium salt mainly occurs the dialysis effect of selfdecomposition and auto purification [to answer as one With, may serve as the method containing the process of ammonium ion waste water, and substitutional solution can use any electrolyte solution], And the replacement process carried out with sea water cationic can not occur, i.e. ammonium ion is through electricity in cationic membrane, with sea water There is invalid exchange or send out in the hydrion [be likely to be due to highly acidic cation film dissociative and promote by force hydrolysis] separated out Being conigenous and decompose to give off hydrion, form electric equilibrium, and be partially converted into ammonia release, result demonstrates the salt of sea water Spend the effect that not anti-reflection increases.And in the presence of sea water has enough sodium carbonate, then can reduce hydrogen ion concentration, The decomposition of suppression ammonium ion.It is thus preferable to, cationic membrane preferably selects non-strong-acid type.In like manner, in order to avoid The invalid exchange of carbanion or bicarbonate ion and hydroxide ion, anionic membrane preferably selects non-strong basicity Anionic membrane.

When the ammonium carbonate separated out in step 1 or ammonia are saturated, when i.e. releasing strong ammonia, salinometer shows, Salinity in solution no longer reduces, and display dialysis stops substantially, illustrates to need ammonium carbonate product to be removed out in time to treat Process solution, promote the dialysis of ammonium ion.

When the substitutional solution in step 1 is selected ammonium carbonate, ammonium sulfate, ammonium nitrate, then can give birth to from sea water The products such as output sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate.

Embodiment 2

In order to check the destructive effect of ammonium salt, and the leakage parameters [experiment of the leakage that causes and detection membrane itself Find, because cationic membrane properties of materials, when clamping with nylon part, on the border of contact, be easily caused film Deformation, or cause the leakage problem frequent generation in experimentation], with the city tap-water containing microelectrolysis matter [200ml, the salt angle value recorded is 0.1ppt] is that the exchange solution that pending solution is the most corresponding is diffused dialysis； Highly acidic cation film thickness about 0.28 millimeter used.

When being saturated ammonium chloride solution when driving liquid, after diffusion dialysis half an hour, record ammonium chloride solution and from the beginning Water all there is ammonia separate out, and make pH test paper color development, and the pH value of tap water increases to about 7.5 from about 7, separately Outward, record salinity in tap water and often increase 0.1ppt, time-consuming 10min.After 7 hours, the salt angle value of tap water Reach 4.4ppt, after transpiring moisture, it is seen that ammonia chloride crystal, after calcination, basically form white haze, illustrate there is being ammonia While infiltration, cationic membrane also has the leakage of solute ammonium chloride.

When being saturated ammonium chloride and sal volatile when driving liquid, i.e. adding the basicity driving solution, diffusion is oozed After analysing 1.5 hours, record and tap water has faint ammonia separate out, and make pH test paper color development, and the pH of tap water It is worth micro-aobvious alkalescence, it addition, record salinity in tap water often increase 0.1ppt, time-consuming 18min.

When drive liquid be saturated ammonium chloride, ammonium carbonate add ammonia spirit time, i.e. further increase driving molten The basicity of liquid, after diffusion dialysis 4 hours, records and just has faint ammonia to separate out in tap water, and the pH of tap water Value has increase but changes inconspicuous, it addition, record salinity in tap water often increase 0.1ppt, time-consuming 66min.

The above results shows, chlorination ammonium salt is under the catalysis of highly acidic cation film, and ammonium ion has the anti-of Auto-decomposition Should, its process should be, when ammonium ion is under the effect of Concentraton gradient, after penetrating in cationic membrane, with film In the hydrion that generates via the hydrolysis of strong acidic ion Membrane catalysis swap, make in driving liquid hydrogen ion concentration increase Add, but when ammonium ion leaves cationic membrane, then dissociate hydrion, to maintain the electric neutrality of film, then divide with ammonia Sub-form enters in tap water, also has part random motion to return ammonium salt and drives in solution and separate out solution, and part is molten The salt angle value of measured water is added in water.Or, ammonium ion is combined with hydroxide ion, with electroneutral hydrogen Amine-oxides or ammonium hydrate mode, through cationic membrane, enter back in pending liquid, or return in ammonium salt solution.

When driving that hydroxide ion concentration increases in liquid, the salinity in tap water gathers way reduction, illustrates to drive Hydroxide ion in hydrodynamic is after diffusing in highly acidic cation ionic membrane, due to the limit of the ionization equilibrium of water System, it is suppressed that water decomposition generates hydrionic reaction near acid active group, decreases hydrion and oozes diffusion Saturating impact, thus reduce the decomposition reaction of ammonium ion namely ammonium salt.Certainly, this phenomenon and reaction can be used to Reach to remove effect and the purpose of the ammonium ion in solution, especially, utilize highly acidic cation film or highly acid sun The decomposition of ion exchange resin catalysis ammonium ion, is used for removing in embodiment 1 method for desalting seawater and separates out the most completely in sea water Ammonium carbonate, ammonium hydrogen carbonate, wherein corresponding exchange solution is clear water or acid-containing solution, and acid-containing solution is by providing Hydrion, promotes the decomposition reaction of ammonium ion further.This experiment also illustrate that, is utilizing ammonium ion as friendship When changing ion, it is preferred to use faintly acid or the cationic membrane of neutrality, with minimizing hydrion naturally, other cation is handed over Change the impact of diffusion.

In order to verify the hydroxide ion impact on diffusion dialysis further, with ammonium chloride saturated solution for driving solution, It is pending solution with 200ml salt angle value 4.5ppt sodium carbonate, replaced dialysis through 1.5 hours, sodium carbonate liquor Salt angle value is reduced to 4.0ppt, illustrates that ammonium ion can replace sodium ion, but anti-increasing, warp do not drop in salt angle value thereafter Within 6 hours, increase to 4.1.May is that because balance is reached in the leakage of diffusion dialysis and film, but because salt angle value is from minimum Increasing at Dian, it is also possible to be because, under relatively low concentration of sodium carbonate, hydroxide ion concentration reduces, The effect of strong acidic ion Membrane catalysis hydrone hydrolysis can not be completely inhibited, result in and drive the decomposition of ammonium ion in liquid Penetrate in sodium carbonate liquor.Furthermore, it is contemplated that the leakage of film, real diffusion dialysis speed wanting than actual measurement High.

When being applied to desalinization and reducing salinity, add ammonia with saturated ammonium chloride and drive solution for ammonium ion, with carbon Acid hydrogen ammonium or potassium bicarbonate are that anion drives solution.Experiment finds, when being pending liquid with tap water, and waits to locate Reason liquid is simultaneously diffused dialysis through cationic membrane and anionic membrane and processes, and the most pending liquid is independent miniature by 2 Pump circulates dialysis, in 2 hours, tap water at simultaneous pumping in same container to cationic membrane and anionic membrane Salinity increase to 0.4ppt from 0.1, pH value reaches 8, and has ammonia to separate out, and illustrates that leakage rate is 0.15ppt/hr. Adding sodium chloride in tap water, make salinity increase to 12.0, through dialysis in 1.5 hours, salt angle value increased to 12.2ppt, Increasing to 12.7ppt again after 7 hours, the aobvious alkalescence of solution, pH value is close to 8.By the heating of seawater portion of this simulation After dividing evaporation, adding water to original weight, recording its pH value is between 6 to 7, records salt angle value 11.8ppt, table See salt angle value and be reduced to 0.2pp, but wherein should have the 1.2ppt of leakage, effective salinity decrease 1.4.When evaporating completely And during calcination, wherein have the white haze that ammonium chloride calcination is formed, and residue has sodium bicarbonate, the aobvious alkalescence of detection paper, And sodium chloride cubic crystal granule, therefore, possibly together with the carbon separated out the most completely in the salt angle value of above-mentioned 11.8ppt The salt angle value of acid hydrogen ammonium.

Embodiment 3

The present embodiment provides the demonstration example of the desalination method of a kind of sea water or waste water.By commercially available for 50g highly acidic cation Resin soaks 6 hours with saturated ammonium chloride solution, i.e. regenerative process, by 50g strongly basic anionic resin with full The ammonium carbonate of sum or ammonium bicarbonate soln soak 6 hours.Fully wash with clear water after taking out resin, and take off by centrifugation Moisture removal.First the sea water 150ml of simulation is poured in the cationic resin that ammonium chloride processed, put through 1 hour After changing reaction, sea water is poured in the resin anion (R.A.) of previously processed mistake, after 1 hour displacement reaction, complete one After individual replacement cycles, then pour in cationic resin, after circulating 3 times, record salinity and be reduced to from 35/1000ths 29/1000ths, and separate out with the ammonia of alkalescence.When using acidulous cation resin and weak anion resin instead, There is similar effect, but replacing velocity is slower.About the regeneration of resin, cation exchange resin ammonium salt circulates again Raw, carbanion or bicarbonate ion carbonate or bicarbonate recycle regeneration.Optional main ammonium salt is Ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium sulfate or ammonium nitrate, optional main carbonate or bicarbonate are carbon Acid ammonium, ammonium carbonate and the mixed solution of ammonia, potassium carbonate, sodium carbonate, ammonium hydrogen carbonate, potassium bicarbonate or bicarbonate Sodium.Resin method needs regeneration, cleaning process, is the major defect comparing embrane method.

Embodiment 4

The present embodiment provides a kind of method that new simple alkaline water processes, as a example by pulp and paper making sewage, its Its alkaline waste water such as weaving, leather, hydrometallurgy waste water etc. can carry out the operation being similar to.By enforcement row 1 middle mold The sea water intended replaces with the pulp and paper making sewage of alkalescence, with the highly acidic cation film of 0.28mm thickness for expanding Dissipate dialyser, optimally, using ammonium hydrogen carbonate, ammonium carbonate as substitutional solution, it is provided that ammonium radical ion, only through above-mentioned Step 1, under normal temperature and pressure, 200ml black liquor of pulp making is measured with salinometer, and it is per hour that its salt angle value reduces speed 0.3ppt, the cationic membrane closing every square metre can displace about 120g from containing alkali about 5% (weight) waste water per hour Sodium hydroxide, replacing velocity, apparently higher than the displacement to sodium ion of the ammonium ion in sea water, further illustrates, strong basicity The solution suppression to strong acidic ion Membrane catalysis water decomposition.Time actually used, enter through diffusion dialysis in advance containing alkali waste water After row alkali collection, then carry out the replacement Treatment of ammonium radical ion and sodium ion；And in substitutional solution obtained by have valency The carbonate of the sodium of value, can sink through the soda bath and calcium carbonate of producing slurrying with the reaction of lime water Form sediment, it is achieved whole recyclings of sodium ion.During calcination of calcium carbonate obtains calcium hydroxide, the two of generation After carbon oxide gas reclaims, with the ammonia reclaimed row reaction again, the ammonium carbonate salts of generation circulates as in substitutional solution Ammonium salt.In order to avoid in waste water, the metal ion such as calcium, magnesium, silicate form the precipitation impact on film, the most in advance First it is filled with carbon dioxide [or to be filled with air, utilize the carbon dioxide in air, and utilize air to be formed The Organic substances such as steel foams separate section lignin] or add carbonic acid ammonia salt, make these metal ions, silicate Ion and the leading Precipitation of part larger molecular organics.

Embodiment 5

The present embodiment provides a kind of new simple acid-containing solution or the method for the process containing acid sewage, with biomass diluted acid As a example by solution, waste water such as other acid waste water such as plating, pickling sewage, chemosynthesis etc. can carry out the operation being similar to. The sea water implementing to simulate in row 1 is replaced with the sugary soln obtained by 3% sulphuric acid acid hydrolysis agricultural crop straw, Excellently, using ammonium hydrogen carbonate, ammonium carbonate as substitutional solution, it is provided that bicarbonate with or carbanion, only through above-mentioned Step 2, under normal temperature and pressure, make sulfate ion and bicarbonate ion displacement, and sugary soln because of carbonic acid point Solving, and realize deacidification, the ammonium sulfate in substitutional solution realizes it as chemical fertilizer and is worth.Time actually used, useless containing acid Water is in advance after diffusion dialysis carries out acid recovery, then carries out replacement Treatment.

In experiment as a example by 200ml salpeter solution, with ammonia, ammonium hydrogen carbonate or potassium bicarbonate saturated solution for driving Liquid or the mixed solution with ammonia, anionic membrane is strong alkalinity anion film, through dialysis in 1 hour, part nitric acid quilt Carbonic acid is replaced and volatilizees precipitation, and with salinometer salt angle value for metering, the salt angle value of nitric acid is reduced to from 22.3ppt 20.7ppt.When low concentration salpeter solution, through 17min dialysis, the salt angle value of nitric acid is reduced to 7.1ppt from 7.3ppt； During lower concentration concentration, through dialysis in 1 hour, the salt angle value of nitric acid was reduced to 2.5ppt from 2.9ppt.Actually used Time, appropriate ammonium carbonate can be initially charged, the precipitation by metallic ion that can form carbonate deposition in solution is separated out, to keep away Precipitation is formed during exempting from dialysis.

Embodiment 6

The present embodiment provides the production method of a kind of salt.Using potassium chloride, sodium chloride solution as pending solution, With ammonium carbonate, ammonium hydrogen carbonate, ammonium carbonate and the mixed solution of ammonia, ammonium sulfate, ammonium sulfite, ammonium nitrate or Ammonium nilrite solution is as the substitutional solution in step 1, and cationic membrane is preferably non-strong-acid type film；With ammonium carbonate, Or ammonium hydrogen carbonate or ammonium carbonate and the mixed solution of ammonia, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, Or ammonia, sodium hydroxide, potassium hydroxide, Lithium hydrate are as the substitutional solution in step 2, and anionic membrane is It it is well non-strong base film；

The substitutional solution of step 1 generates respectively correspondence potassium carbonate, potassium bicarbonate, potassium sulfate, potassium sulfite, Potassium nitrate, potassium nitrite, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium sulfite, sodium nitrate, sodium nitrite.

When the driving solution with 200ml ammonium carbonate saturated solution as cationic membrane, saturated ammonium hydrogen carbonate or bicarbonate Potassium is that anionic membrane drives solution, and cationic membrane and anionic membrane are in embodiment 6 highly acid used and highly basic Property film, 200ml Klorvess Liquid is corresponding exchange solution, and this solution is delivered to by 2 micropump circulating pumps simultaneously Anionic membrane side and cationic membrane side, its initial stage salt angle value is reduced to the time-consuming 10min of 109.0ppt from 109.5ppt, Through dialysis in 1 hour, the salt angle value recorded in potassium chloride was reduced to 107.7ppt, time-consuming 99min from 109.5ppt, Wherein there is ammonia to separate out, it should to be the ammonia partially decomposed forming of ammonium hydrogen carbonate, utilize carbonic acid hydrogen ion to reduce chlorine Change the purpose of ammonium concentration in potassium, be to reach to maintain cationic membrane side ammonium ion and potassium ion high the driving of exchange The purpose of power.After calcination ammonium carbonate drives solution, completely volatilization ammonium carbonate, obtain the pressed powder of alkalescence, directly Contact records pH and reaches 14, it should be solid carbonic acid potassium.During actual production, the ammonium ion in ammonium carbonate should be made complete Entirely replaced by potassium ion, reduce the trouble needing to separate ammonium carbonate when obtaining potassium carbonate, it addition, use saturated Klorvess Liquid, as corresponding exchanger, improves the driving force of ion exchange, shortens swap time.Certainly, as Not considering the displacement completely of ammonium ion and potassium ion, anionic membrane switching part can omit need not.When ammonium carbonate is molten After in liquid, addition ammonia increases its pH value, due to the further suppression of effect that highly acidic cation film water is dissociated, Exchange velocity increases, and in the test of different batches, the salt angle value of initial stage potassium chloride has from the 44.8ppt fall started Low to the time-consuming 7min of 44.2ppt；It is reduced to the time-consuming 4min of 103.0ppt from the 103.8ppt started.Start salt The sample of angle value 103.8ppt is after total dialysis 7 hours, and recording salt angle value is 106.5ppt；Evaporated de- Water, and after calcination makes the ammonium chloride that exists on a small quantity form white haze volatilization, add water recovery original weight, records salt angle value For 100.2ppt.After dialysis is described, containing ammonium hydrogen carbonate and ammonium chloride in Klorvess Liquid.

Changing above-mentioned ammonium carbonate saturated solution into ammonium nitrate solution, potassium chloride is saturated solution, with ammonium carbonate itself Aobvious alkalescence is different, the aobvious acidity of ammonium nitrate, because the hydrolysis of the strong acid group of cationic membrane, molten from ammonium nitrate Liquid separates out a large amount of ammonia, from Klorvess Liquid, also separates out part ammonia, and the pH value of ammonium nitrate solution increases To 8, through dialysis in 1 hour, the salinity of ammonium nitrate solution increased to 37.0ppt, Klorvess Liquid from 35.0ppt PH value increases to about 7.2, and pH increases explanation ammonia or amino molecule or the existence of ammonium hydrogen carbonate, illustrate potassium from Sub-reality importantly with hydrionic exchange, and the most less amount of exchange with ammonium ion, and hydrion directly or Indirectly deriving from the hydrion that ammonium ion dissociates, ammonium ion itself is converted into amino molecule and meets water and show alkalescence, or Generate ammonium hydrogen carbonate and show alkalescence.When evaporating and burning ammonium nitrate solution, residue ammonium nitrate is completely decomposed of volatile, Gained potassium nitrate solid finally decomposes, remaining potassium oxide detection display alkalescence.Because the exchange of potassium ion is restricted In the dissociation process of ammonium ion, therefore, dialysis rates is limited.For making ammonium ion and potassium ion occur the most quickly Exchanging, cationic membrane should select faintly acid or neutral film, and anionic membrane is preferably also selection alkalescence or neutral film, Or in ammonium nitrate solution, add ammonia, increase its pH value, to suppress the highly acidic cation film rush to hydrolysis Enter effect.When by ammonium nitrate solution enrichment to saturated solution and when adding ammonia instead, potassium chloride is used weak solution, warp Dialysis half an hour, the salinity of Klorvess Liquid drops to 50.7ppt from 50.8ppt, and pH value increases to 8, hereafter Salt angle value then carrying out and increase with dialysis, it should be the ammonium ion displacement potassium ion salt angle value that reduces potassium chloride, and The salt angle value of carbonic acid hydrogen ion displacement chloride ion increase potassium chloride, and the combined influence of ammonium hydrogen carbonate evaporation rate Result.The difference that this Klorvess Liquid is saturated or pH increases during weak solution state, illustrates with potassium ion as height During dense driving ion, the potassium concentration in cationic membrane is high, when part potassium ion enters ammonium nitrate solution, also Permitted to be the main hydrion exchange separated out with ammonium ion, and when using highly concentrated ammonium ion as when driving ion, positive In ionic membrane, ammonium concentration is higher, and ammonium ion enters in Klorvess Liquid with ammonium ion form and hands over potassium ion Change, be combined with the carbonic acid hydrogen ion exchanged from anionic membrane and show alkalescence.

Above-mentioned ammonium nitrate saturated solution is changed into same aobvious acid ammonium sulfate, finds that same ammonium ion divides Solve phenomenon；Through dialysis in 1 hour, ammonium sulfate records salinity increased to 17.2ppt from 15.9ppt, because with The salt angle value of mol sulfuric acid potassium is more than with the salt angle value of mol sulfuric acid ammonium, it addition, also in vitriolization ammonium salt solution Ammonia, the salinity of potassium chloride is then reduced to 107.9ppt from 109.0ppt, because potassium chloride is by carbonic acid or ammonium hydrogen carbonate Replaced, and precipitation can be decomposed.If changing potassium chloride into saturated solution, then obtain the phenomenon of similar ammonium nitrate dialysis, The most saturated pH in potassium chloride increases situation about being less than with during potassium chloride weak solution.

In the conversion production process of above-mentioned salt, along with the carrying out of dialysis, dialysis rates reduces, and estimation is owing to being oozed The ammonium hydrogen carbonate generated in Klorvess Liquid that analysis processes is not separated out in time completely, adds the dense of ammonium ion Degree and pH value, the increase of ammonium concentration reduces the ammonium ion concentration difference driving force of cationic membrane exchange, and pH value The exchange that is unfavorable between carbonic acid hydrogen ion and chloride ion of increase, although the anionic membrane of alkalescence or neutrality is permissible Improve this situation.But potassium chloride is molten optimally, to utilize highly acidic cation film or cationic resin synchronously to promote The decomposition of the ammonium ion in liquid separates out.

After above-mentioned potassium chloride is changed to sodium chloride, all detects the sodium salt of corresponding generation, therefore repeat no more.By chlorination The sodium salt of potassium and carbonic acid or sulphuric acid or nitric acid is replaced by cationic membrane, then can also obtain corresponding potassium salt, But purity is limited.

Embodiment 7

The present embodiment provides the production method of a kind of alkali, utilizes exchange and the method for concentration of ion, including: with chlorination Sodium, potassium chloride or lithium chloride solution respectively as pending solution, using ammonia spirit as step 1 in displacement Solution；With ammonium carbonate, ammonium hydrogen carbonate, ammonium carbonate and the mixed solution of ammonia, potassium carbonate, potassium bicarbonate, carbonic acid Sodium, sodium bicarbonate, ammonia, sodium hydroxide, potassium hydroxide or Lithium hydrate are as the substitutional solution in step 2； Substitutional solution in step 1 generates the sodium hydroxide of correspondence, potassium hydroxide, Lithium hydrate respectively；In order to subtract Few alkali generated on the electrolysis of ammonia from impact, in time product alkali should be removed out substitutional solution or carry out on-the-spot answering The chemical reaction participated in for alkali.Gained alkali can be molten as the displacement of step 2 in desalinization in above-described embodiment 1 Liquid, the ammonia separated out in desalting process, as the raw material of production alkali, forms process capable of circulation.Utilizing embodiment When device demonstration in 6 is tested, record strong aqua ammonia the putting as step 1 of salt angle value about 0.2ppt using salinometer Change solution, unsaturated carbonate hydrogen ammonium or the potassium bicarbonate substitutional solution as step 2, the chlorination of salt angle value 80.8ppt Sodium, as pending liquid, is pumped to anions and canons film side through 2 independent micropumps and swaps, through 3 hours Dialysis, the salt angle value of sodium chloride increases to 81.3ppt, and this solution volatilizees ammonium hydrogen carbonate through burning or has ammonium chloride, The salt angle value recorded after recovering the water yield again is 79.3ppt；The salt angle value of strong aqua ammonia increases to 1.8ppt, heated evaporation After burning, obtaining white solid powder, detection paper pH value reaches 14, illustrates that white powder is sodium hydroxide, then The salt angle value recorded after recovering the water yield is 1.5ppt, is the concentration of the sodium hydroxide of gained.Should tie up during actual production Holding sodium chloride all the time in saturation, ammonia is also maintained at saturation, and suitably pressurizes.

Or, locate using sodium chloride, potassium chloride or lithium chloride concentrated solution or saturated solution as treating in step 2 Reason solution, using ammonia spirit as step 2 in substitutional solution, in the pending solution in this step 2 respectively Generate corresponding sodium hydroxide, potassium hydroxide, Lithium hydrate and corresponding remaining salt；In utilizing embodiment 6 Device experiment time, when anionic membrane both sides be ammonia with sodium chloride concentrated solution time, through diffusion dialysis in 1 hour, PH value in sodium chloride solution is significantly greater than 7, illustrates there occurs the exchange of anion, in sodium chloride brine Generate part alkali.

Further, gained is contained the solution of alkali and remaining salinity as hydroxyl required in embodiment 1 or 6 When pending solution in the source of ion, especially step 2 can form Ammonia valatilization containing ammonium ion；Enter one Step ground, passes through 2 independent anionic membranes with sodium chloride, potassium chloride or lithium chloride concentrated solution or saturated solution simultaneously, The both sides being i.e. equivalent to a container are made up of two anionic membranes, and the salt being dense or saturated between two films is molten Liquid, the outside of film transforms into the sea water containing ammonium ion with ammonia and displacement respectively simultaneously or waste water carries out contacting friendship Change, pH value can be measured by expectedly increasing, reached indirectly to improve ammonia and sea water or waste water swap Hydroxide ion concentration, solves the problem that in weak electrolyte ammonia, ammonium concentration is low.The alkali generated is by application After or other consumption alkali technique swapping removing in embodiment 1 or 6, it is recycled for the dialysis of the present embodiment Process.

The exchange of the effects of ion that this each embodiment provides and method for concentration apply also for separating various containing dissolving Organic substance in aqueous solution and the sewage of inorganic matter；(such as organic oxygen in the chemical reaction that non-electrolyte participates in Change, halogenation, sulfonation, nitrification, ammonolysis, hydrolysis), make electrolyte that non-electrolyte changes into and product or Ionic compound (such as hydrogen chloride, water and discarded catalyst) in by-product separates out, in time to promote non-electrical Solving matter and be converted into electrolyte, the oxidation such as methanol manufactures formic acid, and in sugar fermentation product, organic acid removes；And Daily drunk Water warfare；The various deionizing containing organic mixed solution concentrate；Replace electrodialysis desalination purification etc..

Claims

1. the exchange of an effects of ion and method for concentration, it is characterised in that comprising:

Step 1, with the cation in ammonium radical ion substitutional solution；

The order of above-mentioned steps 1 and step 2 can be exchanged；Described ammonium radical ion, bicarbonate ion or carbon Acid ion comes from substitutional solution.

2. the exchange of effects of ion as claimed in claim 1 and method for concentration, it is characterised in that comprising: The exchange of cation and anion is respectively by cationic membrane and anionic membrane；Or respectively by cationic resin and the moon Ion exchange resin；More preferably, cationic membrane is Subacidity cation film, and anionic membrane is weakly-basic anion film；Or More preferably, cationic membrane is neutral cation film, and anionic membrane is neutral anion film.

3. the exchange of effects of ion as claimed in claim 1 and method for concentration, it is characterised in that comprising: Described solution is after step 1 processes, then processes through step 2；Optimally, solution is divided into two parts, each Processing through step 1 and step 2 the most respectively, the two parts after process enter in mixing container, after mixing Recycling solution carry out the process of step 1 and step 2.

4. the exchange of effects of ion as claimed in claim 1 and method for concentration, it is characterised in that comprising:

5. the exchange of effects of ion as claimed in claim 1 and method for concentration, it is characterised in that comprising:

Optional but be not limited to described separation method and have crystallisation by cooling, condensing crystallizing；

Step 7, the ammonium salt supplementing displacement and carbonate, carbonate salt, keep corresponding ion in substitutional solution Concentration；

Step 8, by step 3 or 4 process after solution through highly acidic cation film be diffused dialysis process, right The exchange solution answered is water, or acid-containing solution；

Wherein, step 6,7,8 be optional and the step carried out can be synchronized.

6. the exchange of effects of ion as claimed in claim 1 and method for concentration, it is characterised in that described Ammonium radical ion derives from the mixture of ammonia, ammonium salt or ammonia and ammonium salt；Described ammonium salt be ammonium chloride, ammonium carbonate, Ammonium hydrogen carbonate, ammonium nitrate, ammonium sulfate, ammonium phosphate, inferior ammonium nitrate, ammonium sulfite, ammonium thiocyanate；

Described carbonate or bicarbonate ion derive from carbonate or bicarbonate；Described carbonate is carbonic acid Ammonium, ammonium hydrogen carbonate, ammonium carbonate and the mixed solution of ammonia, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate；.

7. the exchange of the effects of ion as described in claim 1 and 2 and method for concentration, it is characterised in that institute The cation stated and the exchange of anion by cationic membrane and anionic membrane, are replaced molten respectively in described step 2 Anion in liquid is hydroxide ion；Described hydroxide ion derives from ammonia or alkali.

8. the exchange of the effects of ion as described in claim 1 and 7 and method for concentration, it is characterised in that if Containing ammonium radical ion or hydrion in described solution, then described step 1 can be omitted need not；If described is molten Contain carbanion or bicarbonate ion or hydroxide ion in liquid, then described step 2 can be omitted need not.

9. a production method for salt, utilizes exchange and the method for concentration of ion in claim 1-5, and it is special Levy and be, comprising: using potassium chloride, sodium chloride solution as the solution described in claim 1, with carbon Acid ammonium, ammonium hydrogen carbonate, ammonium sulfate, ammonium sulfite, ammonium nitrate or ammonium nilrite solution or aforementioned ammonium salt and ammonia The mixed solution of water is as the substitutional solution in step 1 in claim 1；With ammonium carbonate or ammonium hydrogen carbonate or Ammonium carbonate and the mixed solution of ammonia, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate or ammonia, hydrogen-oxygen Change sodium, potassium hydroxide, Lithium hydrate as the substitutional solution in step 2 in claim 1；

Substitutional solution in step 1 generates the potassium carbonate of correspondence, potassium bicarbonate, potassium sulfate, sulfurous acid respectively Potassium, potassium nitrate, potassium nitrite, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium sulfite, sodium nitrate, nitrous acid Sodium.

10. a production method for alkali, utilizes exchange and the method for concentration of ion in claim 1-5, and it is special Levy and be, comprising: molten using sodium chloride, potassium chloride or lithium chloride solution as described in claim 1 Liquid, using ammonia spirit as step 1 in claim 1 in substitutional solution；With ammonium carbonate, ammonium hydrogen carbonate, carbon Acid ammonium and the mixed solution of ammonia, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, Potassium hydroxide or Lithium hydrate are as the substitutional solution in step 2 in claim 1, displacement in step 1 Solution generates the sodium hydroxide of correspondence, potassium hydroxide, Lithium hydrate respectively；

Further, simultaneously independent by 2 with sodium chloride, potassium chloride or lithium chloride concentrated solution or saturated solution Anionic membrane swaps with ammonia and sea water or waste water respectively, indirectly improves and sea water or waste water swap Hydroxide ion concentration.