CN103768951A

CN103768951A - Ion exchange method for solid substance with exchangeable ions

Info

Publication number: CN103768951A
Application number: CN201210427687.8A
Authority: CN
Inventors: 刘中清; 周丽娜; 罗一斌; 舒兴田
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2012-10-25
Filing date: 2012-10-25
Publication date: 2014-05-07
Anticipated expiration: 2032-10-25
Also published as: CN103768951B

Abstract

The invention provides an ion exchange method for a solid substance with exchangeable ions, which includes the following steps: bipolar membrane electrodialysis: performing bipolar membrane electrodialysis to a water solution with ions, so as to obtain an acid liquor; ion exchange: performing ion exchanging to the contacted solid substance with exchangeable ions and the acid liquor, wherein ions capable of forming a water insoluble substance with OH<-> are contained in the exchangeable ions in the solid substance; solid-liquid separation: performing solid-liquid separation to slurry of the solid substance subjected to ion exchange, so as to obtain the solid phase and the liquid phase; performing solid-liquid separation after the pH value of the liquid phase is adjusted above 8 and obtaining a conditioning fluid; circulating the conditioning fluid to the step of bipolar membrane electrodialysis, substituting at least part of the water solution with ions with the conditioning fluid for bipolar membrane electrodialysis. In the method provided by the invention, power consumption for bipolar membrane electrodialysis is low, and higher ion exchange efficiency is obtained through the method.

Description

A kind of method of the solid matter that contains exchangeable ion being carried out to ion-exchange

Technical field

The present invention relates to a kind of method of the solid matter that contains exchangeable ion being carried out to ion-exchange, particularly a kind of method that cleans and at low cost the solid matter that contains exchangeable ion is carried out ion-exchange.

Background technology

According to Ministry of Water Resources's data of 2005,78% section of flowing through city, the whole nation has been not suitable for as drinking water source, and 50% of urban groundwater is polluted.Water pollution not only can directly affect industrial and agricultural production, also can produce serious harm to health.In order to realize national sustainable development and the harmonious coexistence of man and nature, country has formulated the standard GB/T 8978-1996 of trade effluent discharge, and wherein regulation petrochemical industry ammonium nitrogen first discharge standard is 15mg/L, and secondary discharge standard is 50mg/L.

In petrochemical industry process, often relate to solid matter is carried out to ion-exchange, there is the solid matter of specific ion solid matter is cleaned to processing or preparation.But there is problem consuming time and that wastewater flow rate is large in the existing method that solid matter is carried out to ion-exchange.Wherein, the most representative example is that molecular sieve is taken off to sodium processing.

Molecular sieve has that specific area is high, heat endurance and water stability is good and the equal first-class design feature in aperture, is widely used as catalysis material, adsorption and separation material and ion exchange material, and in petrochemical industry, tool has been widely used.But artificial synthetic molecular sieve is generally Na type, need be converted into Hydrogen or polyvalent metal ion type molecular sieve by ion-exchange, the active component that could serve as acidic catalyst is used.

At present, in the process of molecular sieve, the method that removes sodium ion mainly contains ammonium switching method.But the ubiquitous problem of ammonium switching method is: molecular screen primary powder need be made NH4 type molecular sieve through ammonium exchange, then roasting just can change hydrogen type molecular sieve into, and still, due to the restriction of chemical balance, NH4+ can not once replace Na completely ⁺, for obtaining low Na ₂the molecular sieve of O content, ammonium exchange process need repeat repeatedly, thereby produces the ammonium nitrogen wastewater exceeding standard in a large number.Be less than the national standard of 15mg/L in order to meet the nitrogen discharged amount of ammonium, need to process waste water, still, not only energy consumption is large but also cost is high for the process that described waste water is processed.In addition, conventional ammonium ion exchange method needs the Acidity of Aikalinity of adjusting ambient repeatedly, and complicated operation and efficiency are low.

Therefore, in order to meet the environmental regulation of increasingly stringent and the requirement that factory increases economic efficiency, the technology that solid matter is carried out to ion-exchange that also can increase economic efficiency in the urgent need to developing green environmental protection.

CN102049193A discloses a kind of method of the solid matter that contains exchangeable ion being carried out to ion-exchange, and the method comprises: adopt bipolar membrane electrodialysis to carry out bipolar membrane electrodialysis to the solution that contains ion, thus preparation acid solution or alkali lye; Described acid solution or alkali lye and the solid matter that contains commutative group are carried out to ion-exchange, and the slurries that exchange is obtained carry out Separation of Solid and Liquid, the liquid phase circulation that Separation of Solid and Liquid is obtained is as the solution that contains ion in bipolar membrane electrodialysis.Adopt the method to carry out ion-exchange to the solid matter containing exchangeable ion, can realize on the one hand the object of ion-exchange, can reduce on the other hand the use amount of chemical reagent, realize the zero-emission of waste liquid.

Summary of the invention

The present inventor finds in practice, and adopting in CN102049193A disclosed method acid solution is cationic solid matter while carrying out ion-exchange to exchangeable ion, has the problem that electrodialysis power consumption is high.

The present inventor finds through research, occurs that the reason of above-mentioned phenomenon may be: containing the solid matter of exchangeable ion contain can with OH ^-form the exchangeable ion of water-insoluble materials, in the time carrying out ion-exchange, these can with OH ^-form exchangeable ion and the H of water-insoluble materials ⁺exchange, thus enter in the liquid phase obtaining by Separation of Solid and Liquid, will contain can with OH ^-the liquid phase circulation of exchangeable ion that forms water-insoluble materials is sent into ion interchange unit and is carried out bipolar membrane electrodialysis, during with acid solution for the preparation of ion-exchange, above-mentioned can with OH ^-the OH producing in the exchangeable ion of formation water-insoluble materials and bipolar membrane electrodialysis process ^-in conjunction with, form precipitation, be deposited on the surface of amberplex, hinder ion migration, cause the resistance of amberplex to increase, electrodialysis starting stage current strength declines, and the power consumption of bipolar membrane electrodialysis device increases.Based on above-mentioned discovery, produce the present invention.

The invention provides a kind of method of the solid matter that contains exchangeable ion being carried out to ion-exchange, the method comprises the following steps:

Bipolar membrane electrodialysis step, this step comprises that the aqueous solution to containing ion carries out bipolar membrane electrodialysis, obtains acid solution;

Ion-exchange step, this step comprises that the solid matter that contains exchangeable ion described in making contacts with described acid solution, carries out ion-exchange, obtains the slurries through the solid matter of ion-exchange, the exchangeable ion in described solid matter contain can with OH ^-form the ion of water-insoluble materials;

Solid-liquid separation step, this step comprises carries out Separation of Solid and Liquid to the slurries of the described solid matter through ion-exchange, obtains the first solid phase and the first liquid phase, and carries out Separation of Solid and Liquid after the pH value of described the first liquid phase is adjusted to more than 8, obtains treatment fluid;

Described treatment fluid is circulated in described bipolar membrane electrodialysis step, replaces the aqueous solution that contains at least partly ion to carry out bipolar membrane electrodialysis, to obtain described acid solution;

Wherein, the anion concentration or the cation concn that described in, contain in the aqueous solution of ion are 0.01-10 mol/L.

According to ion-exchange process of the present invention, to bipolar membrane electrodialysis step, carry out bipolar membrane electrodialysis at the liquid phase circulation that ion-exchange step is obtained, when preparing acid solution, first (the pH value of this liquid phase is adjusted to alkalescence, pH value is more than 8), make in liquid phase can with OH ^-in conjunction with the ion precipitation that forms water-insoluble materials out, and pH value is carried out after Separation of Solid and Liquid for alkaline liquid phase, the treatment fluid obtaining is circulated to send into and in bipolar membrane electrodialysis device, carry out bipolar membrane electrodialysis.Method of the present invention solved dexterously in the liquid phase obtaining due to Separation of Solid and Liquid can with OH ^-in conjunction with forming the OH generating in the ion of water-insoluble materials and bipolar membrane electrodialysis process ^-in conjunction with forming precipitation, be deposited on the surface of amberplex, hinder ion migration, cause the resistance of amberplex to raise, electrodialysis starting stage current strength (, current density) declines, the problem that device power consumption raises.

And, under equal conditions, adopt method of the present invention to carry out ion-exchange to solid matter and can obtain higher ion-exchanging efficiency, obtain having the solid matter of lower commutative group content.Thereby method of the present invention can reduce ion-exchange and electrodialytic number of times, reduce the overall energy consumption of operation.

In addition, method of the present invention has also extended the service life of amberplex, has shortened the downtime causing because change amberplex.

Accompanying drawing explanation

Fig. 1 is applicable to the membrane stack of bipolar membrane electrodialysis device of method of the present invention and the schematic diagram of the first arrangement mode of electrode;

Fig. 2 is applicable to the membrane stack of bipolar membrane electrodialysis device of method of the present invention and the schematic diagram of the second arrangement mode of electrode;

Fig. 3 is applicable to the membrane stack of bipolar membrane electrodialysis device of method of the present invention and the schematic diagram of the third arrangement mode of electrode;

Fig. 4 adopts method of the present invention Na type molecular sieve to be taken off to the process chart of sodium; And

Fig. 5 is according in the ion exchange process of embodiment 1 and comparative example 1, electrodialysis current strength time history plot.

The specific embodiment

The method according to this invention, described solid matter contains commutative group, described commutative group comprise can with OH ^-form the ion of water-insoluble materials.The present invention for described can with OH ^-the kind of ion that forms water-insoluble materials is not particularly limited, and according to the kind difference of solid matter of carrying out ion-exchange, can be various and hydroxide ion (, OH ^-) in conjunction with after can form the ion of water-insoluble materials.Particularly, described can with OH ^-the ion that forms water-insoluble materials can be Ca ²⁺, Mg ²⁺, Fe ³⁺, Al ³⁺, Si ⁴⁺with one or more in the ion (described rare earth metal can be for example lanthanum and/or cerium) of rare earth metal.The content of the described ion that can form water-insoluble materials is not particularly limited, and can change with the kind of the solid matter that carries out ion-exchange.Described water-insoluble materials refer to due in solution can with OH ^-in conjunction with the concentration of ion be greater than this ion and OH ^-solubility in conjunction with the material of rear formation in water, thus in water, form the material of precipitation, for example in solution can with OH ^-in conjunction with ion and OH ^-be slightly water-soluble material (that is, depress at 25 ℃ and 1 normal atmosphere, the solubility in water is the material below 0.1g) in conjunction with the material of rear formation.

Described solid matter can for various sources contain the exchangeable ion that can carry out with acid solution ion-exchange, and at least part of exchangeable ion in described solid matter can with OH ^-form the solid matter of water-insoluble materials.Particularly, the example of described solid matter can include but not limited to: one or more in molecular sieve, ion exchange resin and gel.Described ion exchange resin can be the various ion exchange resin that can carry out with acid solution ion-exchange, is specifically as follows cationic ion-exchange resin and/or amphoteric ion-exchange resin.

The method according to this invention is specially adapted to molecular sieve, particularly Na type molecular sieve is carried out to ion-exchange.Described molecular sieve can be various molecular sieve well known to those skilled in the art, comprises microporous silicon aluminum molecular screen, mesoporous Si-Al molecular sieve and micropore phosphate aluminium molecular sieve.Described microporous silicon aluminum molecular screen and micropore phosphate aluminium molecular sieve refer to that aperture is the Si-Al molecular sieve of 0.3-2nm and the micropore phosphate aluminium molecular sieve that aperture is 0.3-2nm, and described mesoporous Si-Al molecular sieve refers to that aperture is the Si-Al molecular sieve of 2-100nm.

Described microporous silicon aluminum molecular screen can be one or more in Y zeolite, X-type molecular sieve, A type molecular sieve, L-type molecular sieve, Beta type molecular sieve, FER type molecular sieve, MOR type molecular sieve, type ZSM 5 molecular sieve, ZSM-22 type molecular sieve, ZSM-11 type molecular sieve, ZSM-23 type molecular sieve, ZSM-35 type molecular sieve, MCM-22 type molecular sieve, MCM-49 type molecular sieve, MCM-36 type molecular sieve and MCM-56 type molecular sieve.

Described mesoporous Si-Al molecular sieve can be one or more in MCM-41 type molecular sieve, MCM-48 type molecular sieve, MCM-50 type molecular sieve, SBA-15 type molecular sieve, SBA-16 type molecular sieve, MSU-1 type molecular sieve and MSU-2 type molecular sieve.

Described micropore phosphate aluminium molecular sieve can be one or more in SAPO-34 type molecular sieve, SAPO-11 type molecular sieve, SAPO-5 type molecular sieve, SAPO-18 type molecular sieve, APO-5 type molecular sieve, APO-11 type molecular sieve and MeAPO-11 type molecular sieve.

Described gel can be various gel well known to those skilled in the art, comprising: one or more in silica-alumina gel, silicon titanium gel, silicon boron gel, zinc-aluminium gel and magnalium gel.

The above-mentioned solid matter of enumerating is only for exemplary, known in those skilled in the art: the present invention is not limited to the above-mentioned solid matter of enumerating, any contain exchangeable ion and at least partly exchangeable ion can with OH ^-the solid matter that forms water-insoluble materials is all suitable for adopting method of the present invention to carry out ion-exchange.

The method according to this invention comprises bipolar membrane electrodialysis step, and this step comprises that the aqueous solution to containing ion carries out bipolar membrane electrodialysis, obtains acid solution.

Cation in the described aqueous solution that contains ion can be for any cation that can form with hydroxide ion alkali, described in contain ion the aqueous solution in anion can form sour anion with hydrogen ion for any.The concentration of the anion in the described aqueous solution that contains ion or cationic concentration can be 0.01-10 mol/L, are preferably 0.01-8 mol/L, more preferably 0.01-1 mol/L, and most preferably be 0.02-0.2 mol/L.

The method according to this invention, goes into operation the stage, described in contain ion the source of the aqueous solution be not particularly limited.The aqueous solution that for example, contains ion, can be for by the aqueous solution that electrolyte dissolution is obtained in water.

Described electrolyte can be various electrolyte well known to those skilled in the art.Usually, described electrolyte can be inorganic electrolyte and/or organic bath.Described inorganic electrolyte can be one or more in sodium sulphate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium dihydrogen phosphate.Described organic bath can be one or more in formic acid, acetic acid, sodium formate, potassium formate and quaternary ammonium type electrolyte.Described quaternary ammonium type electrolyte can be various water miscible quaternary ammonium type electrolyte, is preferably one or more in tetramethyl ammonium chloride, 4 bromide and TMAH.

The present invention is for adopting bipolar membrane electrodialysis process to carry out electrodialysis to the aqueous solution that contains ion, thereby prepare the method for corresponding acid solution, there is no particular limitation, adopts method well known to those skilled in the art in bipolar membrane electrodialysis device.The membrane stack of described bipolar membrane electrodialysis device and the arrangement mode of electrode can be the conventional various arrangement modes in this area.

Figure 1 shows that the membrane stack of the bipolar membrane electrodialysis device that is applicable to method of the present invention and the first arrangement mode of electrode.In this arrangement mode, described electric dialyzator comprises the positive pole 4 that is positioned at utmost point frame 7, negative pole 5 and at least two Bipolar Membrane and at least one cation-exchange membrane 3 between positive pole 4 and negative pole 5, and described Bipolar Membrane and cation-exchange membrane 3 alternative arrangements, the described aqueous solution B that contains ion enters the sour chamber between cation exchange floor 2 and the cation-exchange membrane 3 of described Bipolar Membrane, water C enters the alkali chamber between anion exchange floor 1 and the cation-exchange membrane 3 of described Bipolar Membrane, electrode chamber between positive pole 4 and the anion exchange layer 1 of described Bipolar Membrane and the electrolytical water solution A of electrode chamber filling between the cation exchange layer 2 of negative pole 5 and described Bipolar Membrane, and apply direct current to positive pole 4 and negative pole 5, the H that anion in sour chamber and bipolar membrane electrodialysis process are generated ⁺form acid, thereby generate acid solution D in described sour chamber, cation in the aqueous solution B that contains ion moves in alkali chamber by cation exchange 3, with the OH generating in bipolar membrane electrodialysis process ^-in conjunction with forming alkali, thereby generate alkali lye E in described alkali chamber.

Although (the bipolar membrane electrodialysis device shown in Fig. 1 only has a sour chamber and an alkali chamber, a film unit), but it will be understood by those skilled in the art that, (described bipolar membrane electrodialysis device can have multiple sour chambers and multiple alkali chamber, multiple film units), as long as correspondingly increase the quantity of Bipolar Membrane and cation-exchange membrane, and make described Bipolar Membrane and cation-exchange membrane according to the mode alternative arrangement shown in Fig. 1 between positive pole and negative pole.Multiple described sour chambers can be relation in parallel or series relationship, and multiple described alkali chamber can be relation in parallel.

Figure 2 shows that the membrane stack of the bipolar membrane electrodialysis device that is applicable to method of the present invention and the second arrangement mode of electrode.In this arrangement mode, described bipolar membrane electrodialysis device comprises the positive pole 4 that is positioned at utmost point frame 7, negative pole 5 and at least two Bipolar Membrane and at least one anion-exchange membrane 6 between positive pole 4 and negative pole 5, described Bipolar Membrane and anion-exchange membrane 6 alternative arrangements, water C enters the sour chamber between cation exchange floor 2 and the anion-exchange membrane 6 of described Bipolar Membrane, the described aqueous solution B that contains ion enters the alkali chamber between anion exchange floor 1 and the anion-exchange membrane 6 of described Bipolar Membrane, electrode chamber between positive pole 4 and the anion exchange layer 1 of described Bipolar Membrane and the electrolytical water solution A of electrode chamber filling between the cation exchange layer 2 of negative pole 5 and described Bipolar Membrane, and apply direct current to positive pole 4 and negative pole 5, anion in the aqueous solution B that makes to contain ion moves in sour chamber by anion-exchange membrane 6, with the H generating in bipolar membrane electrodialysis process ⁺in conjunction with forming acid, thereby generate acid solution D in described sour chamber, cation in the aqueous solution B that contains ion with bipolar membrane electrodialysis process in the OH that generates ^-form alkali, thereby generate alkali lye E in described alkali chamber.

Although (the bipolar membrane electrodialysis device shown in Fig. 2 only has a sour chamber and an alkali chamber, a film unit), but it will be understood by those skilled in the art that, (described bipolar membrane electrodialysis device can have multiple sour chambers and multiple alkali chamber, multiple film units), as long as correspondingly increase the quantity of Bipolar Membrane and anion-exchange membrane, and make described Bipolar Membrane and anion-exchange membrane according to the mode alternative arrangement shown in Fig. 2 between positive pole and negative pole.Multiple described alkali chamber can be relation in parallel or series relationship, and multiple described sour chambers can be relation in parallel.

Figure 3 shows that the membrane stack of the bipolar membrane electrodialysis device that is applicable to method of the present invention and the third arrangement mode of electrode.In this arrangement mode, described bipolar membrane electrodialysis device comprises the positive pole 4 that is positioned at utmost point frame 7, negative pole 5 and at least two Bipolar Membrane between positive pole 4 and negative pole 5, at least one cation-exchange membrane 3 and at least one anion-exchange membrane 6, and cation-exchange membrane 3 and anion-exchange membrane 6 separate described Bipolar Membrane in pairs between two, the aqueous solution B that contains ion enters the salt chamber between cation-exchange membrane 3 and anion-exchange membrane 6, water C enters the alkali chamber between anion exchange floor 1 and the cation-exchange membrane 3 of sour chamber between cation exchange floor 2 and the anion-exchange membrane 6 of described Bipolar Membrane and described Bipolar Membrane, electrode chamber between positive pole 4 and the anion exchange layer 1 of described Bipolar Membrane and the electrolytical water solution A of electrode chamber filling between the cation exchange layer 2 of negative pole 5 and described Bipolar Membrane, and apply direct current to electrode 4 and 5, thereby generate acid solution D in described sour chamber, generate alkali lye E in described alkali chamber.

Although (the bipolar membrane electrodialysis device shown in Fig. 3 only has a sour chamber, an alkali chamber and a salt chamber, a film unit), but it will be understood by those skilled in the art that, (described bipolar membrane electrodialysis device can have multiple sour chambers, multiple alkali chamber and multiple salt chamber, multiple film units), as long as correspondingly increase the quantity of Bipolar Membrane, cation-exchange membrane and anion-exchange membrane, and described Bipolar Membrane, cation-exchange membrane and anion-exchange membrane are arranged between positive pole and negative pole according to the mode shown in Fig. 3.Multiple described salt chamber can be relation in parallel or series relationship, and multiple described sour chambers and multiple described alkali chamber can be relation in parallel.

Under identical condition of the time of bipolar membrane electrodialysis, with compare for ion-exchange adopting above-mentioned the first and the second way to carry out the acid solution that bipolar membrane electrodialysis obtains, carry out acid solution that bipolar membrane electrodialysis obtains for ion-exchange by adopting above-mentioned the third mode, under the ion-exchange time condition identical with number of times, can obtain higher ion-exchange degree, in the solid matter obtaining, the content of exchangeable ion is lower.In addition, in the time adopting above-mentioned the third mode to carry out bipolar membrane electrodialysis, the pH value of salt chamber remains unchanged substantially, can further reduce due to the trend that in the aqueous solution that contains ion, the responsive ion of pH value is formed on the surface of amberplex precipitation, thereby obtain higher ion-exchange degree, and further extend the service life of amberplex.

The present invention is not particularly limited being filled in electrolytical Enthalpy of Electrolytes in Aqueous Solutions in described electrode chamber and the ratio of water, adopts ratio well known to those skilled in the art.Usually, the weight ratio of described electrolytical Enthalpy of Electrolytes in Aqueous Solutions and water can be 0.001-1:1, is preferably 0.001-0.5:1, more preferably 0.005-0.2:1, and most preferably be 0.01-0.05:1.

Electrolyte in the described electrolytical aqueous solution can be the conventional electrolyte in this area, comprises inorganic electrolyte and/or organic bath.Described inorganic electrolyte can be one or more in sodium sulphate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, NaOH and potassium hydroxide, described organic bath can be one or more in formic acid, acetic acid, sodium formate, potassium formate and quaternary ammonium type electrolyte, described quaternary ammonium type electrolyte can be various water miscible quaternary ammonium type electrolyte, is preferably one or more in tetramethyl ammonium chloride, 4 bromide and TMAH.

Although the present invention only shows the arrangement mode of above-mentioned three kinds of possible membrane stacks and electrode, but be applicable to membrane stack in bipolar membrane electrodialysis device of the present invention and the arrangement mode of electrode and be not limited only to this, as long as the membrane stack in this bipolar membrane electrodialysis device and the arrangement mode of electrode can make bipolar membrane electrodialysis device carry out electrodialysis to the described aqueous solution that contains ion, obtain acid solution.

The concrete operations condition of described bipolar membrane electrodialysis is known in those skilled in the art.Usually, being applied to the voltage between film unit can be 0.5-6V, is preferably 1-5V; The temperature of the described aqueous solution that contains ion can be 0-100 ℃, is preferably 5-80 ℃, more preferably 10-60 ℃.

The method according to this invention comprises ion-exchange step, and this step comprises that the solid matter that contains exchangeable ion described in making contacts with described acid solution, carries out ion-exchange, obtains the slurries through the solid matter of ion-exchange.

Described ion-exchange can be carried out in ion-exchange unit, and the equipment that the present invention uses for described ion-exchange there is no special restriction, can be the conventional various ion-exchange units in this area, for example plate and frame filter or band filter.

Described ion-exchange also can be carried out in bipolar membrane electrodialysis device, for example can be after described bipolar membrane electrodialysis completes, contain in the sour chamber that cationic solid matter is filled to described bipolar membrane electrodialysis device described, thereby the described solid matter acid solution indoor with described acid contacted, carry out ion-exchange.After the described ion-exchange of carrying out in described electric dialyzator completes, the slurries of described solid matter can be discharged from described sour chamber, carry out solid-liquid separation step.

For the condition of described ion-exchange, also there is no particular limitation in the present invention, and usually, the temperature of described ion-exchange can be 0-100 ℃, is preferably 5-80 ℃, more preferably 10-60 ℃.

The method according to this invention also comprises solid-liquid separation step, this step comprises carries out Separation of Solid and Liquid to the slurries of the described solid matter through ion-exchange, obtain the first solid phase and the first liquid phase, and carry out Separation of Solid and Liquid after the pH value of described the first liquid phase is adjusted to more than 8, obtain treatment fluid.In the present invention, for convenience of description, to the liquid phase of carrying out obtaining in the step of Separation of Solid and Liquid through the slurries of the solid matter of ion-exchange be called to the first liquid phase, the slurries of the solid matter to through ion-exchange be carried out to the solid phase that the step of Separation of Solid and Liquid obtains and be called the first solid phase.

The present invention is not particularly limited the method for described Separation of Solid and Liquid, can be the whole bag of tricks well known to those skilled in the art.Usually, the method for described Separation of Solid and Liquid can be decant, filtration or the combination of the two, is preferably filtration.

The slurries of the solid matter through ion-exchange are separated into the first liquid phase and the first solid phase by described Separation of Solid and Liquid.Described the first solid phase being obtained by described Separation of Solid and Liquid can be final product, also can be for proceeding the intermediate product of ion-exchange.When described the first solid phase is need to proceed the intermediate product of ion-exchange time, described the first solid phase can contain water.In described the first solid phase, the weight ratio of solid matter and water can be 1:0.5-10, is preferably 1:0.5-5, more preferably 1:1-3.In described the first solid phase, the weight ratio of solid matter and water can regulate and control by the condition that regulates Separation of Solid and Liquid, also can adjust by supplementing interpolation water, preferably by the condition that regulates Separation of Solid and Liquid, the ratio of solid matter and water in described the first solid phase be regulated and controled.

The method according to this invention, the pH value of described the first liquid phase is adjusted to more than 8 (for example 8-14), is preferably adjusted to 9-13, and carry out obtaining treatment fluid after Separation of Solid and Liquid, the aqueous solution that contains ion by described treatment fluid circulation as described bipolar membrane electrodialysis step, is used for preparing acid solution.By the pH value of described the first liquid phase is adjusted to more than 8, can be for example 8-14, be preferably 9-13, make in described the first liquid phase can with OH ^-form the ion precipitation of water-insoluble materials out, can avoid directly described the first liquid phase circulation being sent in bipolar membrane electrodialysis device time, in described the first liquid phase, contain can with OH ^-form the ion of water-insoluble materials and the OH that bipolar membrane electrodialysis process generates ^-in conjunction with forming precipitation, be deposited on the surface of amberplex, cause the resistance of amberplex to increase; Simultaneously by the acid solution obtaining thus for ion-exchange, can also improve the degree of ion-exchange.

The present invention is not particularly limited for the method for the pH value that regulates described the first liquid phase, can adopt the conventional the whole bag of tricks in this area.For example, can be by add alkaline matter in described the first liquid phase, thus the pH value of described the first liquid phase is adjusted to more than 8 and (can is 8-14, is preferably 9-13).Described alkaline matter can be the conventional various alkaline matters that are applicable to regulate pH value in this area.Preferably, described alkaline matter is alkali-metal hydroxide (for example: NaOH and/or potassium hydroxide) and ammoniacal liquor.More preferably, described alkaline matter is ammoniacal liquor.The present invention is not particularly limited for the concentration of ammoniacal liquor, can be normal concentration.

The first liquid phase that has regulated pH value being carried out to Separation of Solid and Liquid and be not particularly limited with the method that obtains treatment fluid, can be previously described solid-liquid separating method, is not described in detail in this.

In described ion exchange process, hydrogen ion in the commutative group of cation and acid solution in described solid matter carries out ion-exchange, anion in described acid solution is retained in described the first liquid phase owing to not participating in ion-exchange, therefore, do not supplementing and adding under electrolytical condition, described treatment fluid just can be circulated in described bipolar membrane electrodialysis step, as the aqueous solution that contains at least partly ion, carry out bipolar membrane electrodialysis, to obtain acid solution.Certainly, it will be appreciated by persons skilled in the art that in the time that the ion concentration in concentration or the described treatment fluid of wishing the described acid solution of further raising is not enough, can be to the supplementary electrolyte that adds in described treatment fluid, to improve anion or cationic concentration.In addition, in the time of the quantity not sufficient of described treatment fluid, can or contain the electrolytical aqueous solution to supplementing water in described treatment fluid.Described electrolytical kind with describe above can add to described in contain ion the aqueous solution in electrolyte identical, described electrolytical consumption can be for making cation concn in described treatment fluid or anion concentration meet cation concn in the previously described aqueous solution that contains ion or the requirement of anion concentration.

The method according to this invention, described bipolar membrane electrodialysis step, ion-exchange step and solid-liquid separation step can loop repeatedly, so that the described solid matter that contains exchangeable ion is carried out to multistage exchange.The present invention there is no special restriction to the number of times of described circulation, and the number of times of general described circulation can meet the demands with the amount of guaranteeing the exchangeable ion in the final solid matter obtaining.In the time that solid matter is repeatedly exchanged, in the liquid phase being obtained by ion-exchange for the first time, the content of various ions is generally higher, therefore needs the pH value of the liquid phase being obtained by ion-exchange to be for the first time adjusted within previously described scope; For ion exchange process and later ion exchange process for the second time, the pH value of the liquid phase that each ion-exchange can be obtained is adjusted within previously described scope, also can be in the liquid phase being obtained by ion-exchange can with OH ^-the content of ion that forms water-insoluble materials within certain limit (for example: can with OH ^-the concentration that forms the ion of water-insoluble materials is 1-10 mM/l, is preferably 1-5 mM/l) time, the pH value of the liquid phase that ion-exchange is obtained is adjusted within previously described scope.

The method according to this invention is in the time implementing, can first the solid matter that contains commutative group be mixed with water, the slurries that obtain are carried out to Separation of Solid and Liquid, obtain second solid phase and the second liquid phase (object that the present invention describes for convenience, the liquid phase obtaining is thus called to second liquid phase, and the solid phase obtaining is thus called second solid phase); The aqueous solution that contains ion using described second liquid phase as the stage of going into operation is sent in bipolar membrane electrodialysis device and is carried out bipolar membrane electrodialysis, obtains acid solution; The acid solution obtaining and second solid phase are carried out, after ion-exchange, carrying out Separation of Solid and Liquid, obtain the first liquid phase and the first solid phase; The pH value of described the first liquid phase is adjusted to more than 8 (for example 8-14, be preferably 9-13), and the first liquid phase that has regulated pH value is carried out to Separation of Solid and Liquid, obtain treatment fluid, the treatment fluid circulation obtaining is sent in bipolar membrane electrodialysis device and carried out bipolar membrane electrodialysis, to obtain acid solution.Wherein, second liquid phase can directly be sent in bipolar membrane electrodialysis device, also its pH value can be adjusted to more than 8 (for example 8-14, be preferably 9-13) and carry out sending in bipolar membrane electrodialysis device after Separation of Solid and Liquid, preferably its pH value is adjusted to more than 8 (for example 8-14, be preferably 9-13) after, carry out Separation of Solid and Liquid, and the liquid phase obtaining is sent in bipolar membrane electrodialysis device, carry out bipolar membrane electrodialysis as the aqueous solution that contains at least partly ion, to obtain acid solution, can avoid like this due to second liquid phase contain can with OH ^-form water-insoluble materials ion, and the electrodialysis starting stage current strength causing reduces.Cation concn or anion concentration in described second liquid phase are lower, can not meet above-mentioned requirements time, can make anion in described second liquid phase or cationic amount in previously described scope by add electrolyte in described second liquid phase.Described electrolyte can be previously described electrolyte, no longer describes in detail herein.

Figure 4 shows that the method according to this invention takes off the process chart of sodium to Na type molecular sieve.As shown in Figure 4, the technological process that adopts method of the present invention to take off sodium to Na type molecular sieve mainly comprises the slurries of first preparing described Na type molecular sieve in material fluid bath, described slurries are filtered, obtain molecular sieve and filtrate, in the filtrate obtaining, supplement interpolation electrolyte (being preferably sodium sulphate), and preferably adopt previously described method, its pH value is adjusted to more than 8, be generally 8-14, be preferably 9-13, then carry out following steps: described filtrate is sent into bipolar membrane electrodialysis device and carry out bipolar membrane electrodialysis, obtain acid solution and the aqueous solution that contains NaOH (described in contain NaOH the aqueous solution can be used as the raw material of synthesis of molecular sieve), described acid solution is contacted in material fluid bath with described molecular sieve, carry out ion-exchange, obtain the slurries through the molecular sieve of ion-exchange, by the described molecular sieve filtration through ion-exchange, obtain molecular sieve and filtrate through ion-exchange, described filtrate regulates above (for example 8-14 of pH value to 8 with alkaline matter, preferably 9-13) after, circulation is sent in described bipolar membrane electrodialysis device and is carried out bipolar membrane electrodialysis, described molecular sieve returns liquid bath is proceeded ion-exchange, so circulation, until the sodium ion in described Na type molecular sieve meets the demands.

According to ion-exchange process of the present invention, not only can significantly reduce the energy consumption of bipolar membrane electrodialysis device, extend the service life of amberplex; And can obtain higher ion-exchanging efficiency, under the identical condition of all the other conditions, method of the present invention can obtain having the solid matter of lower exchangeable ion content.

Method of the present invention is specially adapted to molecular sieve, and particularly Na type molecular sieve carries out ion-exchange.

Below in conjunction with embodiment, present invention is described.

In following examples and comparative example, adopt x ray fluorescence spectrometry (XRF) to measure the cations in molecular sieve on Rigaku 3271E type Xray fluorescence spectrometer.Concrete test process is: molecular sieve is crushed into powder, by this pressed powder pellet, measures the intensity of the characteristic spectral line of element on Xray fluorescence spectrometer, obtain the content of element by external standard method.

In following examples and comparative example, the method for recording according to " Petrochemical Engineering Analysis method (RIPP experimental technique) " (Yang Cuiding etc., Science Press, 1990) 414-415 page is measured the relative crystallinity of molecular sieve.

In following examples and comparative example, the model of the bipolar membrane electrodialysis device of employing is: ACILYZER-02 type electrodialysis plant, and membrane stack is of a size of 100 × 400mm; Bipolar Membrane is purchased the company from Japanese Ya Sitong, and model is BP-1; Cation-exchange membrane is purchased from Shanghai Chemical Plant, and model is 3362-BW; Anion-exchange membrane is purchased from Shanghai Chemical Plant, and model is 3361-BW.In following examples using the beaker of 5000mL as exchanger cell.

In following examples and comparative example, using plasma emission spectrometry (ICP) is measured the content of effects of ion.

In following examples and comparative example, adopt multitester measuring electrodialysis electric current.

Embodiment 1-9 is used for illustrating ion-exchange process of the present invention.

In following examples and comparative example, if not otherwise specified, all use bipolar membrane electrodialysis device as shown in Figure 3 to carry out bipolar membrane electrodialysis, wherein, in described bipolar membrane electrodialysis device, be provided with 40 Bipolar Membrane, 20 cation-exchange membranes and 20 anion-exchange membranes.

Embodiment 1

(1) take 10kg REUSY molecular sieve (Na ₂o content is 4.96 % by weight, and relative crystallinity is 58%) join in 130kg deionized water, stir, obtain slurries.These slurries are filtered, obtain filtrate and filter cake, in filter cake, the weight ratio of molecular sieve and water is 1:3.

(2) by the 100kg filtrate and the 800g Na that obtain ₂sO ₄mix, obtain the aqueous solution that contains ion, be to carry out Separation of Solid and Liquid after the ammoniacal liquor of 17 % by weight is adjusted to 12.5 by the pH value of this aqueous solution by concentration, the liquid phase obtaining is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the sour chamber storage tank of bipolar membrane electrodialysis device and alkali chamber storage tank, respectively add 50kg deionized water, in electrode chamber storage tank, add the Na of 2 % by weight of 20kg ₂sO ₄the aqueous solution.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage was 60V, 30 ℃ of operations 30 minutes.The variation of the electrodialysis current strength in monitoring bipolar membrane electrodialysis process, result provides in Fig. 5.

(3) acid solution that obtained by sour chamber is injected to the filter cake that exchanger cell and step (1) obtain and at 30 ℃, carried out the ion-exchange of 35 minutes.

(4) slurries in exchanger cell are filtered, obtain filtrate and filter cake, in described filter cake, the weight ratio of molecular sieve and water is 1:3.In the filtrate obtaining, add the ammoniacal liquor that concentration is 17 % by weight, the pH value of filtrate is adjusted to 11, obtain treatment fluid.

(5) described treatment fluid is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, method is carried out bipolar membrane electrodialysis as described above, and the filter cake that step (4) is obtained is sent in exchanger cell method as described above and carried out ion-exchange.

REUSY molecular sieve is carried out to 2 secondary ion exchanges (that is, carrying out altogether 2 circulations) afterwards, by the molecular sieve output obtaining.

The molecular sieve of output is dried to 20 hours at 100 ℃, thereby obtains hydrogen type molecular sieve, the Na in this molecular sieve ₂o content is 0.49 % by weight, and relative crystallinity is 56%.

Filtrate and treatment fluid that the ion-exchange step of first circulation is obtained detect, measure wherein can with OH ^-the content that forms the ion of water-insoluble materials, result provides in table 1.

Comparative example 1

Adopt the method identical with embodiment 1 to carry out ion-exchange, different, the filtrate in step (2) and step (4) does not regulate pH value, directly sends in the salt chamber of bipolar membrane electrodialysis device; And in each circulation, the time of bipolar membrane electrodialysis is 50 minutes.

Na in the hydrogen type molecular sieve finally obtaining ₂o content is 1.5 % by weight, and relative crystallinity is 56%.

The variation of the electrodialysis current strength in monitoring bipolar membrane electrodialysis process, result provides in Fig. 5.

As can be seen from Figure 5, under the constant condition of the voltage applying between the positive pole of electrodialysis plant and negative pole, adopt method of the present invention to carry out ion-exchange, the current strength of the electrodialysis starting stage (, electrodialysis starts latter 5 minutes) of each circulation is basic identical; But, the first liquid phase is directly sent into while carrying out electrodialysis in bipolar membrane electrodialysis device, compared with the electrodialysis starting stage current strength of last circulation, the electrodialysis starting stage current strength of a rear circulation is obvious downward trend.Therefore, directly the first liquid phase is sent into while carrying out electrodialysis in bipolar membrane electrodialysis device, not only needed to extend the time of bipolar membrane electrodialysis; And the content of sodium oxide molybdena in the molecular sieve that obtains of ion-exchange is higher, is difficult to obtain the ion-exchange effect identical with method of the present invention.In addition, the stage of going into operation (, in first circulation), the molecular sieve of pending exchange is mixed with to slurries, and slurries are filtered, by the filtrate obtaining (, second liquid phase) as the aqueous solution that contains ion during for bipolar membrane electrodialysis, preferably first the pH value of described second liquid phase is adjusted to alkalescence, then carry out bipolar membrane electrodialysis, can obtains so higher electrodialysis starting stage current strength.

Table 1

Metal ion	Filtrate (mgkg ^-1）	Treatment fluid (mgkg ^-1）
			Fe	<0.1	<0.1
Ni	<0.1	<0.1
			Cu	<0.1	<0.1
Ca	50.8	13.7
			Mg	22.2	3.3
Pb	<0.1	<0.1
			Al	233	1.8
Si	204	1.2
			La	30	<0.1
Ce	75	<0.1

As can be seen from Table 1, can obtain higher electrodialysis starting stage current strength and make the electrodialysis starting stage current strength of each circulation be worth essentially identical reason according to ion-exchange process of the present invention and may be: (be for example 8-14 by the pH value of the first liquid phase and second liquid phase being adjusted to respectively more than 8, be preferably 9-13), make in described the first liquid phase and second liquid phase can with OH ^-form the ion precipitation of water-insoluble materials out, and then the liquid phase obtaining sent in bipolar membrane electrodialysis device and carried out bipolar membrane electrodialysis, can effectively avoid in the first liquid phase and second liquid phase can with OH ^-the ion that forms water-insoluble materials due to bipolar membrane electrodialysis process in the OH that produces ^-in conjunction with forming precipitation, be deposited on the surface of amberplex, cause the resistance of amberplex to increase, electrodialysis starting stage current strength reduces; Can also obtain purity and the higher acid solution of concentration, thereby can obtain better ion-exchange effect simultaneously.

Embodiment 2

(1) take 10kg NaY molecular sieve (Na ₂o content is 13.0 % by weight, and relative crystallinity is 85%) join in 80kg deionized water, stir, obtain slurries.These slurries are filtered, obtain filtrate and filter cake, wherein, in filter cake, the weight ratio of molecular sieve and water is 1:3.

(2) by the 50kg filtrate and the 200g Na that obtain ₂sO ₄mix, obtain the aqueous solution that contains ion, be to carry out Separation of Solid and Liquid after the ammoniacal liquor of 20 % by weight is adjusted to 9 by the pH value of this aqueous solution by concentration, the liquid phase obtaining is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the sour chamber storage tank of bipolar membrane electrodialysis device and alkali chamber storage tank, respectively add 80kg deionized water, in electrode chamber storage tank, add the Na of 3 % by weight of 20kg ₂sO ₄the aqueous solution.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage, control voltage is 40V, moves 20 minutes at 30 ℃.

(3) acid solution that obtained by sour chamber is injected to the filter cake that exchanger cell and step (1) obtain and at 30 ℃, carried out the ion-exchange of 30 minutes.

(4) molecular sieve pulp in exchanger cell is filtered, obtain filtrate and filter cake, in described filter cake, the weight ratio of molecular sieve and water is 1:3.In the filtrate obtaining, add the ammoniacal liquor that concentration is 20 % by weight, the pH value of filtrate is adjusted to 10, obtain treatment fluid.

(5) described treatment fluid is sent in the salt chamber storage tank of electric dialyzator, method is carried out bipolar membrane electrodialysis as described above, and the filter cake that step (4) is obtained is sent in exchanger cell method as described above and carried out ion-exchange.

After NaY molecular sieve is carried out to 2 secondary ion exchanges, by the molecular sieve output obtaining.Wherein, the electrodialysis starting stage current strength of first circulation is 32A, and the electrodialysis starting stage current strength of second circulation is 33A.

The molecular sieve of output is dried to 20 hours at 100 ℃, thereby obtains hydrogen type molecular sieve, the Na in this molecular sieve ₂o content is 4.5 % by weight, and relative crystallinity is 75%.

Embodiment 3

(1) take 8kg ZSM-5 molecular sieve (Na ₂o content is 1.2 % by weight, and relative crystallinity is 95%) join in 100kg deionized water, stir, obtain slurries.These slurries are filtered, obtain filtrate and filter cake, in filter cake, the weight ratio of molecular sieve and water is 1:3.

(2) by the 76kg filtrate and the 500g Na that obtain ₂sO ₄mix, obtain the aqueous solution that contains ion, be to carry out Separation of Solid and Liquid after the ammoniacal liquor of 30 % by weight is adjusted to 12 by the pH value of this aqueous solution by concentration, the liquid phase obtaining is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the alkali chamber storage tank of bipolar membrane electrodialysis device and sour chamber storage tank, respectively add 50kg deionized water, in electrode chamber storage tank, add the Na of 3 % by weight of 20kg ₂sO ₄the aqueous solution.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage, control voltage is 40V, moves 20 minutes at 30 ℃.

(4) molecular sieve pulp in exchanger cell is filtered, obtain filtrate and filter cake, in described filter cake, the weight ratio of molecular sieve and water is 1:3.In the filtrate obtaining, add the ammoniacal liquor that concentration is 30 % by weight, filter after the pH value of filtrate is adjusted to 12, obtain treatment fluid.

(5) described treatment fluid is sent in the salt chamber storage tank of electric dialyzator, method is carried out bipolar membrane electrodialysis as described above.

After ZSM-5 molecular sieve is carried out to 1 secondary ion exchange, by the molecular sieve output obtaining, and do not send in step (3) through the ZSM-5 of ion-exchange a collection of in addition, carry out ion-exchange.Carry out altogether 2 circulations.Wherein, the electrodialysis starting stage current strength of first circulation is 40A, and the electrodialysis starting stage current strength of second circulation is 39A.

The molecular sieve of output is dried to 20 hours at 100 ℃, thereby obtains hydrogen type molecular sieve, the Na in this molecular sieve ₂o content is 0.08 % by weight, and relative crystallinity is 96%.

Embodiment 4

(1) take 30kg silica-alumina gel (solid content is 30 % by weight, in butt, Na ₂the content of O is 15.8 % by weight, wherein, solid content be by by gel at 800 ℃, roasting obtains for 1 hour) join in 100kg deionized water, stir, obtain slurries.These slurries are filtered, obtain filtrate and filter cake, in filter cake, the weight ratio of gel and water is 1:3.

(2) by the 100kg filtrate obtaining and the Na of 800g ₂sO ₄mix, obtain the aqueous solution that contains ion, and sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the sour chamber storage tank of bipolar membrane electrodialysis device and alkali chamber storage tank, respectively add 100kg deionized water, in electrode chamber storage tank, add the Na of 3 % by weight of 20kg ₂sO ₄the aqueous solution.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage, control voltage is 40V, moves 30 minutes at 30 ℃.

(4) slurries in exchanger cell are filtered, obtain filtrate and filter cake, in described filter cake, the weight ratio of gel and water is 1:3.In the filtrate obtaining, add the ammoniacal liquor that concentration is 17 % by weight, filter after the pH value of filtrate is adjusted to 10, obtain treatment fluid.

After gel is carried out to 1 secondary ion exchange, by the solid matter output obtaining, and do not send in step (3) and carry out ion-exchange through the gel of ion-exchange with a collection of in addition.Carry out altogether 2 circulations, the electrodialysis starting stage current strength of first circulation is 46A, and the electrodialysis starting stage current strength of second circulation is 45A.

Na in the gel obtaining through ion-exchange ₂o content is 0.30 % by weight.

Embodiment 5

(1) take 50kg Beta molecular sieve (Na ₂o content is 1.32 % by weight, and relative crystallinity is 95%) join in 650kg deionized water, stir, obtain slurries.These slurries are filtered, obtain filtrate and filter cake, in filter cake, the weight ratio of molecular sieve and water is 1:3.

(2) by the 500kg filtrate and the 2500g Na that obtain ₂sO ₄mix, obtain the aqueous solution that contains ion, be to filter after the ammoniacal liquor of 30 % by weight is adjusted to 11 by the pH value of this aqueous solution by concentration, the liquid phase obtaining is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the alkali chamber storage tank of bipolar membrane electrodialysis device and sour chamber storage tank, respectively add 100kg deionized water, in electrode chamber storage tank, add the Na of 2 % by weight of 20kg ₂sO ₄the aqueous solution.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage, control voltage was 60V, 30 ℃ of operations 35 minutes.

(3) acid solution that obtained by sour chamber is injected to the filter cake that exchanger cell and step (1) obtain and at 30 ℃, carried out the ion-exchange of 25 minutes.

(4) slurries in exchanger cell are filtered, obtain filtrate and filter cake, in described filter cake, the weight ratio of molecular sieve and water is 1:3.In the filtrate obtaining, add the ammoniacal liquor that concentration is 30 % by weight, the pH value of filtrate is adjusted to 12, after filtering, obtain treatment fluid.

After Beta molecular sieve is carried out to 3 secondary ion exchanges, by the molecular sieve output obtaining.Wherein, the electrodialysis starting stage current strength of first circulation is 45A, and the electrodialysis starting stage current strength of the 3rd circulation is 44A.

The molecular sieve of output is dried to 20 hours at 100 ℃, thereby obtains hydrogen type molecular sieve, the Na in this molecular sieve ₂o content is 0.13 % by weight, and relative crystallinity is 98%.

Embodiment 6

Adopt the method identical with embodiment 5 to carry out ion-exchange, different, adopt the bipolar membrane electrodialysis device shown in Fig. 1 to carry out bipolar membrane electrodialysis, wherein, the quantity of Bipolar Membrane and cation-exchange membrane respectively does for oneself 20, the aqueous solution that contains ion is sent in the sour chamber of bipolar membrane electrodialysis device.Wherein, the electrodialysis starting stage current strength of first circulation is 46A, and the electrodialysis starting stage current strength of the 3rd circulation is 47A.Na in the molecular sieve of ion-exchange ₂o content is 0.35 % by weight, and relative crystallinity is 95%.

Embodiment 7

Adopt the method identical with embodiment 5 to carry out ion-exchange, different, adopt the bipolar membrane electrodialysis device shown in Fig. 2 to carry out bipolar membrane electrodialysis, wherein, the quantity of Bipolar Membrane and anion-exchange membrane respectively does for oneself 20, the aqueous solution that contains ion is sent in the alkali chamber of bipolar membrane electrodialysis device.Wherein, the electrodialysis starting stage current strength of first circulation is 45A, and the electrodialysis starting stage current strength of the 3rd circulation is 46A.Na in the molecular sieve of ion-exchange ₂o content is 0.38 % by weight, and relative crystallinity is 96%.

Embodiment 5 and embodiment 6 and embodiment 7 are compared and can be found out, adopt the bipolar membrane electrodialysis device shown in Fig. 3 to carry out electrodialysis, compare with the bipolar membrane electrodialysis device shown in Fig. 2 with adopting Fig. 1, can obtain higher ion-exchanging efficiency, therefore can reduce the number of times of ion-exchange and the number of times of bipolar membrane electrodialysis, further reduce the overall energy consumption of the inventive method.

Comparative example 2

Adopt the method identical with embodiment 5 to carry out ion-exchange, different, in step (2) and step (4), all do not regulate pH value, but directly use the filtrate obtaining.Wherein, the electrodialysis starting stage current strength of first circulation is 30A, and the electrodialysis starting stage current strength of the 3rd circulation is 14A.Na in the molecular sieve of ion-exchange ₂o content is 0.67 % by weight, and relative crystallinity is 97%.

Embodiment 8

(1) take 10kg MCM-22 molecular sieve (Na ₂o content is 2.95 % by weight, and relative crystallinity is 97%) join in 230kg deionized water, stir, obtain slurries.These slurries are filtered, obtain filtrate and filter cake, wherein, in filter cake, the weight ratio of molecular sieve and water is 1:3.

(2) the 300kg filtrate of acquisition is mixed with 3000g NaCl, obtain the aqueous solution that contains ion, be to filter after the ammoniacal liquor of 30 % by weight is adjusted to 12 by the pH value of this aqueous solution by concentration, the liquid phase obtaining is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the alkali chamber storage tank of bipolar membrane electrodialysis device and sour chamber storage tank, respectively add 100kg deionized water, in electrode chamber storage tank, add the aqueous solution of the NaOH of 3 % by weight of 30kg.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage, control voltage was 50V, 35 ℃ of operations 40 minutes.

(3) acid solution that obtained by sour chamber is injected to the filter cake that exchanger cell and step (1) obtain and carried out the ion-exchange of 30 minutes at 40 ℃.

(4) molecular sieve pulp in exchanger cell is filtered, obtain filtrate and filter cake, in described filter cake, the weight ratio of molecular sieve and water is 1:3.In the filtrate obtaining, add the ammoniacal liquor that concentration is 30 % by weight, the pH value of filtrate is adjusted to 12, after filtering, obtain treatment fluid.

After MCM-22 molecular sieve is carried out to 4 secondary ion exchanges, by the molecular sieve output obtaining.Wherein, the electrodialysis starting stage current strength of first circulation is 38A, and the electrodialysis starting stage current strength of the 4th circulation is 36A.

The molecular sieve of output is dried to 20 hours at 100 ℃, thereby obtains hydrogen type molecular sieve, the Na in this molecular sieve ₂o content is 0.05 % by weight, and relative crystallinity is 95%.

Embodiment 9

(1) (solid content is 32 % by weight to take 100kg cationic ion-exchange resin, ion exchange capacity is 4mol/kg, the ion exchange resin to be generated producing in process for preparation deionized water, the total content of metal ion is 15 % by weight) join in the deionized water of 100kg, stir, obtain slurries.

(2) by the 100kg filtrate obtaining and the NH of 900g ₄cl mixes, obtain the aqueous solution that contains ion, be to carry out Separation of Solid and Liquid after the ammoniacal liquor of 20 % by weight is adjusted to 12 by the pH value of this aqueous solution by concentration, the liquid phase obtaining is sent in the salt chamber storage tank of bipolar membrane electrodialysis device, simultaneously in the alkali chamber storage tank of bipolar membrane electrodialysis device and sour chamber storage tank, respectively add 100kg deionized water, in electrode chamber storage tank, add the Na of 4 % by weight of 25kg ₂sO ₄the aqueous solution.Connect the circulating pump power initiation circulating pump of bipolar membrane electrodialysis device, after Matter Transfer is normal, the dc source between positive pole and the negative pole of startup bipolar membrane electrodialysis device, regulation voltage, control voltage is 70V, moves 20 minutes at 35 ℃.

(3) acid solution that obtained by sour chamber is injected to the filter cake that exchanger cell and step (1) obtain and at 35 ℃, carried out the ion-exchange of 40 minutes.

(4) slurries in exchanger cell are filtered, obtain filtrate and filter cake.In the filtrate obtaining, add the ammoniacal liquor that concentration is 20 % by weight, the pH value of filtrate is adjusted to 11, obtain treatment fluid.

After ion exchange resin is carried out to 3 secondary ion exchanges, by the solid matter output obtaining.Wherein, the electrodialysis starting stage current strength of first circulation is 56A, and the electrodialysis starting stage current strength of the 3rd circulation is 51A.

The total content of the metal ion in the ion exchange resin obtaining through ion-exchange is 0.1 % by weight.

Claims

1. a method of the solid matter that contains exchangeable ion being carried out to ion-exchange, the method comprises the following steps:

Ion-exchange step, this step comprises that the solid matter that contains exchangeable ion described in making contacts with described acid solution, carry out ion-exchange, obtain the slurries through the solid matter of ion-exchange, the exchangeable ion in described solid matter contains the ion that can form with OH-water-insoluble materials;

2. method according to claim 1, wherein, the method that contains the aqueous solution of ion described in obtaining comprises: after the described solid matter that contains exchangeable ion and water are mixed with to slurries, carry out Separation of Solid and Liquid, obtain second solid phase and second liquid phase, after being adjusted to more than 8, the pH value of described second liquid phase carries out Separation of Solid and Liquid, using the liquid phase obtaining as the described aqueous solution that contains ion, described second solid phase is sent into and in described ion-exchange step, carried out ion-exchange.

3. method according to claim 1 and 2, wherein, described in contain ion the aqueous solution in ion at least partly from electrolyte, described electrolyte is inorganic electrolyte and/or organic bath.

4. method according to claim 3, wherein, described inorganic electrolyte is one or more in sodium sulphate, sodium nitrate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate and potassium dihydrogen phosphate;

Described organic bath is one or more in formic acid, acetic acid, sodium formate, potassium formate and quaternary ammonium type electrolyte.

5. method according to claim 4, wherein, described quaternary ammonium type electrolyte is one or more in tetramethyl ammonium chloride, 4 bromide and TMAH.

6. method according to claim 1 and 2, wherein, is adjusted to 8-14 separately by the pH value of described the first liquid phase and described second liquid phase.

7. method according to claim 6, wherein, is adjusted to 9-13 separately by the pH value of described the first liquid phase and second liquid phase.

8. method according to claim 1, wherein, described solid matter is one or more in molecular sieve, cationic ion-exchange resin, amphoteric ion-exchange resin and gel.

9. method according to claim 8, wherein, described molecular sieve is one or more molecular sieves that are selected from microporous silicon aluminum molecular screen, mesoporous Si-Al molecular sieve and micropore phosphate aluminium molecular sieve.

10. method according to claim 9, wherein, described microporous silicon aluminum molecular screen is one or more in Y zeolite, X-type molecular sieve, A type molecular sieve, L-type molecular sieve, Beta type molecular sieve, FER type molecular sieve, MOR type molecular sieve, type ZSM 5 molecular sieve, ZSM-22 type molecular sieve, ZSM-11 type molecular sieve, ZSM-23 type molecular sieve, ZSM-35 type molecular sieve, MCM-22 type molecular sieve, MCM-49 type molecular sieve, MCM-36 type molecular sieve and MCM-56 type molecular sieve;

Described mesoporous Si-Al molecular sieve is one or more in MCM-41 type molecular sieve, MCM-48 type molecular sieve, MCM-50 type molecular sieve, SBA-15 type molecular sieve, SBA-16 type molecular sieve, MSU-1 type molecular sieve and MSU-2 type molecular sieve;

Described micropore phosphate aluminium molecular sieve is one or more in SAPO-34 type molecular sieve, SAPO-11 type molecular sieve, SAPO-5 type molecular sieve, SAPO-18 type molecular sieve, APO-5 type molecular sieve, APO-11 type molecular sieve and MeAPO-11 type molecular sieve.

Method in 11. according to Claim 8-10 described in any one, wherein, described molecular sieve is Na type molecular sieve.

12. methods according to claim 8, wherein, described gel is one or more in silica-alumina gel, silicon titanium gel, silicon boron gel, zinc-aluminium gel and magnalium gel.

13. methods according to claim 1, wherein, described can with OH ^-the ion that forms water-insoluble materials is Ca ²⁺, Mg ²⁺, Fe ³⁺, Al ³⁺, Si ⁴⁺with one or more in rare earth ion.

14. methods according to claim 1, wherein, described bipolar membrane electrodialysis carries out in bipolar membrane electrodialysis device, described bipolar membrane electrodialysis device comprises positive pole, negative pole and at least two Bipolar Membrane between described positive pole and negative pole, at least one cation-exchange membrane and at least one anion-exchange membrane, and described cation-exchange membrane and described anion-exchange membrane separate described Bipolar Membrane in pairs between two.