CN103623616A - Ion exchange method - Google Patents
Ion exchange method Download PDFInfo
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- CN103623616A CN103623616A CN201210313439.0A CN201210313439A CN103623616A CN 103623616 A CN103623616 A CN 103623616A CN 201210313439 A CN201210313439 A CN 201210313439A CN 103623616 A CN103623616 A CN 103623616A
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Abstract
The invention provides an ion exchange method. The method comprises steps: a slurry containing solid substances with exchangeable groups is sent to an ion exchange column with an ion exchange resin bed layer, and subjected to ion change with the ion exchange groups of the ion exchange resins in the ion exchange column; the slurry containing the solid substances and flowing out from the ion exchange column is collected. Before the ion exchange, an inactive dielectric layer is formed on the upper surface of the ion exchange resin bed layer by utilization of at least one kind of inactive particles, thus the slurry containing solid substances with exchangeable groups flows through the inactive dielectric layer and the ion exchange resin bed layer successively, and the ratio of the average particle size of the inactive particles to the average particle size of the ion exchange resin particles in the ion exchange resin bed layer is 1.2-5:1. Deposition of the solid substances in the slurry on the upper surface of the ion exchange resin bed layer can avoided or basically avoided effectively through the method. The ion exchange method is suitable for occasions of continuous ion exchange.
Description
Technical field
The present invention relates to a kind of ion-exchange process, particularly, the present invention relates to a kind of ion exchange column that adopts and the commutative group in solid matter is carried out to the method for ion-exchange.
Background technology
Molecular sieve is very extensive in petrochemical industry application, and the method for current industrial synthesis of molecular sieve is all synthetic in alkaline solution, and the molecular sieve being therefore synthesized is sodium type.In petroleum refining industry, the most large catalyst is catalytic cracking catalyst, it adopts Y zeolite as active component mostly, Y zeolite is stable NaY form while manually synthesizing, and sodium ion has neutralized center of negative charge completely in zeolite molecular sieve, causes sodium type molecular sieve there is no acid centre.Therefore, sodium type molecular sieve does not almost have activity in the reaction of carbonium ion type, if as catalytic cracking catalyst, must carry out modification to it, removes the sodium ion in NaY molecular sieve.In addition, apply the more molecular sieve that also has MFI structure, as ZSM-5 and Beta molecular sieve, these molecular sieves also need before use sodium ion to be exchanged into hydrogen ion could be used as catalyst.
Existing molecular sieve method for removing Na is normally first exchanged for NH with ammonium salt solution by the sodium ion in molecular sieve
4 +, then pass through high-temperature roasting, by NH
4 +be converted to H
+, this process can not once complete certainly, in order to obtain Na
+the molecular sieve that content is low, ammonium exchange process need to repeat repeatedly.Existing this switching method can produce a large amount of industrial wastewaters, and in all acid ammoniated wastewaters of catalyst plant, what ammonia nitrogen concentration was the highest is exchange liquid and the first washings that molecular sieve ammonium exchange process produces, and its ammonia-nitrogen content is the more than several times of other ammoniated wastewater (as second wash water, three washings).These waste water need could discharge after treatment, otherwise can be to environment.Therefore, seek new molecular sieve sodium ion switching method, to reduce the wastewater flow rate producing in process of producing molecular sieve, significant for catalyst plant energy-saving and emission-reduction.
JP63159218A discloses a kind of method that makes spent ion exchange resin reduce sodium ions content in NaY molecular sieve, its processing procedure is for fully to contact ion exchange resin with molecular sieve, at 40-80 ℃ of temperature, exchange certain hour obtains the hydrogen type molecular sieve that alkali metal content is less than 1wt% after twice exchange process.But, the mode that in the method, molecular sieve contacts with ion exchange resin is for to mix molecular sieve with ion exchange resin, cause the resin that lost efficacy can not be again with molecular sieve in sodium ion carry out ion-exchange, need to carry out a step raising service life of therefore de-sodium effect and ion exchange resin.
CN101570334A discloses a kind of method of ion exchange resin Modified NaY molecular sieve, and the method is placed in respectively by molecular sieve pulp and resin two reative cells that separate with screen cloth, makes NaY molecular sieve not produce directly and contact with ion exchange resin, and H
+and Na
+can pass through screen cloth, under the promotion of concentration difference, realize exchange.In the method, because molecular sieve does not directly contact with ion exchange resin, ion-exchange is driven by concentration difference, and therefore de-sodium effect needs further to improve.
The disclosed method of CN101823727A is first molecular sieve once to be exchanged, discharging, in 500-650 ℃ of roasting 1-2h, then naturally cooling, roasted product carries out after secondary exchange, continue at 500-650 ℃ of roasting 1-2h, obtain product, wherein once exchange and secondary exchange all adopt resin cation to exchange, wherein, cation resin exchange step is: first pull an oar NaY molecular sieve in making beating container (1), makes part Na
+be free in water, after ceramic membrane separation, be divided into two parts: contain Na
+clear water and dense thick NaY slurries, wherein contain Na
+clear water enter resin column, realize Na
+→ H
+exchange, resin water outlet now contains a large amount of H
+, enter making beating container; (2) dense thick NaY slurries reenter making beating container, carry out H with resin water outlet in making beating container
+→ Na
+exchange, and so forth, Na
+be attracted on resin, and H
+replace Na
+position on NaY, realizes the object of falling sodium modification, until Na in NaY molecular sieve
2o content is not more than 1%, discharging when degree of crystallinity is not less than 80%; (3) when resin column lost efficacy, switch with another one spare resin post, standby after resin column regeneration, Na in the molecular sieve of output
2while requiring discharging in O content satisfied (2), simultaneously by throat-fed, continue the process of modification; (4) in exchange process, doubly, resin column water outlet pH value is controlled between 3-6 the 2-4 of the exchanger resin amount such as the addition of resin is NaY, and exchange temperature is 20-70 ℃, and be 10-60 minute swap time.Although the method can drop to alkali metal content in molecular sieve to be less than 1wt%, the operation of the method is comparatively loaded down with trivial details.
CN102020288A discloses a kind of ion-exchange process of molecular sieve, the method comprises molecular sieve pulp is contacted with cationic ion-exchange resin, reclaim the molecular sieve pulp after contacting with cationic ion-exchange resin, described molecular sieve pulp is the mixture that contains molecular sieve and water, the cation-bit of cationic ion-exchange resin comprises cation A, the cation-bit of molecular sieve comprises cation B, described cation A and described cation B one or more cations of respectively doing for oneself, and the kind of described cation A and described cation B is incomplete same, the condition that molecular sieve pulp contacts with ion exchange resin is replaced the cation B of cation-bit on molecular sieve at least partly by the another kind of cation of cation A.In practical application, find, adopt the method that ion exchange resin is seated in ion exchange column while carrying out ion-exchange with slurries containing molecular sieve, be easy to occur being deposited on the ion exchange resin bed layer surface in ion exchange column containing the molecular sieve in the slurries of molecular sieve, and then the phenomenon of plug ion exchange column.
Summary of the invention
The object of the invention is to overcome existing while the slurries containing molecular sieve being carried out to ion-exchange by ion exchange column, be easy to occur being deposited on containing the molecular sieve in the slurries of molecular sieve the surface of ion exchange resin bed layer, plug ion exchange column, the problem that causes ion exchange process normally to carry out, a kind of ion-exchange process is provided, while adopting method of the present invention, by ion exchange column, the slurries that contain solid matter are carried out to ion-exchange, even slurries are added in ion exchange column in a large number, in ion exchange column, form slurry layer, can or substantially not there will not be solid matter to be deposited on the surface of ion exchange resin bed layer yet, the phenomenon of plug ion exchange column.
The present inventor finds in practice process, when adopting ion exchange column to carry out ion-exchange to the slurries of the solid matter containing commutative group, before described slurries are sent into ion exchange column, first with nonactive particle, on the upper surface of the ion exchange resin bed layer in ion exchange column, form nonactive dielectric layer, and be used to form the average grain diameter of nonactive particle of described nonactive dielectric layer and the ratio of the average grain diameter of ion exchange resin is 1.2-5:1, then described slurries are sent into while carrying out ion-exchange in ion exchange column, even described slurries are sent in ion exchange column in a large number, and in ion exchange column, form slurry layer, also can or substantially can avoid the solid matter generation sedimentation in slurries.Completed thus the present invention.
The invention provides a kind of ion-exchange process, the method comprises the following steps:
(1) provide the ion exchange column with ion exchange resin bed layer;
(2) will send in described ion exchange column containing the slurries with the solid matter of commutative group;
(3) make the described slurry stream that contains the solid matter with commutative group cross described ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on ion exchange resin; And
(4) collect the slurries containing solid matter that flow out from described ion exchange column;
Wherein, the method is also included in that to carry out step (2) front, with at least one nonactive particle, form nonactive dielectric layer on the upper surface of described ion exchange resin bed layer, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described nonactive particle and described ion exchange resin bed layer is 1.2-5:1.
The method according to this invention, by before sending into ion exchange column containing the solid matter with commutative group, first use with described ion exchange resin bed layer in the ratio of average grain diameter of ion-exchange resin particles be 1.2-5:1 nonactive particle forms nonactive dielectric layer on the upper surface of described ion exchange resin bed layer, containing the slurries with the solid matter of commutative group, by described nonactive dielectric layer, enter in ion exchange resin bed layer, can effectively avoid or substantially avoid containing the solid matter generation sedimentation having in the slurries of solid matter of commutative group, even and if then the method according to this invention is sent in ion exchange column by described containing the slurries with commutative group in a large number, can plug ion exchange column yet, be applicable to carry out the occasion of serialization ion-exchange.
Accompanying drawing explanation
Fig. 1 is for illustrating the mode to carrying out disturbance containing the slurry layer with the solid matter of commutative group;
Fig. 2 is for illustrating the another kind of mode to carrying out disturbance containing the slurry layer with the solid matter of commutative group;
Fig. 3 for illustrate by pipeline stabilization be placed in a kind of embodiment of slurry layer; And
Fig. 4 is for illustrating the preferred embodiment a kind of of ion-exchange process of the present invention.
The specific embodiment
The invention provides a kind of ion-exchange process, the method comprises the following steps:
(1) provide the ion exchange column with ion exchange resin bed layer;
(2) will send in described ion exchange column containing the slurries with the solid matter of commutative group;
(3) make the described slurry stream that contains the solid matter with commutative group cross described ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on ion exchange resin; And
(4) collect the slurries containing solid matter that flow out from described ion exchange column;
Wherein, the method is also included in that to carry out step (2) front, with at least one nonactive particle, form nonactive dielectric layer on the upper surface of described ion exchange resin bed layer, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described nonactive particle and described ion exchange resin bed layer is 1.2-5:1.
According to the present invention, from further raising, prevent containing the angle with the solid matter generation sedimentation the slurries of solid matter of commutative group, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described nonactive particle and described ion exchange resin bed layer is preferably 1.3-3:1, more preferably 1.3-2.5:1.
The average grain diameter of described nonactive particle and the average grain diameter of ion exchange resin each naturally by getting 100 particles and measuring the diameter of each particle with slide measure, the mean value that calculates the diameter of measuring obtains.While calculating the ratio of the average grain diameter of nonactive particle and the average grain diameter of ion-exchange resin particles, the two adopts identical dimension.
The present invention is not particularly limited for the material that forms described nonactive particle, if this nonactive particle not can with described slurry and ion exchange resin generation chemical interaction containing thering is the solid matter of commutative group.Usually, described nonactive particle can be selected from glass particle, quartz particles and inactive resin particle (as polytetrafluoroethylgranule granule).
The method according to this invention, the described slurries of solid matter containing thering is commutative group in being admitted to ion exchange column after, first flow through described nonactive dielectric layer, then enter in ion exchange resin bed layer.The cumulative volume V of the slurries that can hold with described nonactive dielectric layer and ion exchange resin bed layer
1, and the cumulative volume V of the ion exchange resin bed layer slurries that can hold
3for benchmark, the volume V of the slurries containing at least one molecular sieve in described ion exchange column
2can remain V
1>=V
2> V
3, also can remain V
1< V
2(that is, on the upper surface of nonactive dielectric layer, forming slurry layer).At V
1< V
2time, the height of the slurry layer forming on the upper surface of described nonactive dielectric layer can carry out suitable selection according to the actual motion condition of ion exchange column.Usually, the ratio of the height of described nonactive dielectric layer and the height of described slurry layer can be 1:1.1-5, is preferably 1:1.5-2.5.The height of described slurry layer refers to that the upper surface of slurry layer is to the vertical range of the upper surface of nonactive dielectric layer, and the height of described nonactive dielectric layer refers to that the upper surface of nonactive dielectric layer is to the vertical range of the upper surface of described ion exchange resin bed layer.Can by described, containing the slurries with the solid matter of commutative group, send into the speed in ion exchange column by regulating, control the amount that contains the slurries of the solid matter with commutative group in ion exchange column, no longer describe in detail herein.
The method according to this invention, while being also formed with slurry layer on the upper surface of described nonactive dielectric layer, from further raising, prevent the angle of the effect of solid matter generation sedimentation described slurry layer, the method according to this invention can also comprise carries out disturbance to described slurry layer, so that the slurries in described slurry layer also have the motion of non-gravity direction.
Can adopt conventional the whole bag of tricks to carry out disturbance to described slurry layer, so that the slurries in described slurry layer also have the motion of non-gravity direction.For example: as shown in Figure 1, on the upper surface of the ion exchange resin bed layer 4 in ion exchange column 1, form nonactive dielectric layer 3, paddle 9 is set in slurry layer 2, drive paddle 9 so that slurry layer 2 is carried out to disturbance.
Of the present invention a kind of preferred embodiment in, as shown in Figure 2, the mode of described slurry layer being carried out to disturbance comprises: in slurry layer 2, arrange and be immersed in the pipeline 5 in slurries, and pass into non-active gas (for example: pass into non-active gas by gas passage 8 in slurry layer 2) in pipeline 5, Existential Space between the inwall of the outer wall of pipeline 5 and ion exchange column 1, and Existential Space between the lower surface of pipeline 5 and the upper surface of nonactive dielectric layer 3.Pipeline is set in slurry layer, and pass into non-active gas in pipeline, the non-active gas passing into forms bubble in slurries, the uphill process of bubble makes formation negative pressure in pipeline, thereby the slurries suction of this pipeline below is entered in this pipeline, slurries in promotion pipeline flow out along the outer wall of pipeline, and then can obtain the effect of the solid matter generation sedimentation better preventing in slurry layer.And, adopt which to carry out disturbance to slurry layer and in practical operation, be easier to implement.
This preferred embodiment in, the lower surface of described pipeline to the distance of upper surface of described nonactive dielectric layer and the upper surface of described pipeline to the surperficial distance of described slurry layer can be carried out suitable selection according to concrete condition.Usually, the lower surface of described pipeline to the vertical range of upper surface of described nonactive dielectric layer and the ratio of the height of described slurry layer can be 1:3-10, is preferably 1:5-10.The upper surface of described pipeline to the ratio of the surperficial vertical range of described slurry layer and the height of described slurry layer can be 1:3-5.
This preferred embodiment in, the external diameter of described pipeline can carry out suitable selection according to the internal diameter of ion exchange column.Preferably, the ratio of the external diameter of described pipeline and the internal diameter of ion exchange column is 0.4-0.6:1.
This preferred embodiment in, can adopt conventional the whole bag of tricks that described pipeline is placed in slurry layer, for example: (being the schematic top plan view of ion exchange column) as shown in Figure 3, can use support 10 that pipeline 5 is stably placed in the slurry layer in ion exchange column 1, with support 11, gas passage 8 is stably placed in slurry layer, wherein, support 10 is supported by the inwall of ion exchange column 1, and support 11 is supported by the inwall of pipeline 5.
This preferred embodiment in, to the non-active gas passing in described pipeline, can there is not chemically interactive gas with described slurries and ion exchange resin containing thering is the solid matter of commutative group for various, for example: described non-active gas can be selected from air, nitrogen and group 0 element gas (as argon gas).
This preferred embodiment in, the intake of described non-active gas described is as the criterion containing the solid matter generation sedimentation in the slurries of solid matter can effectively prevent.Preferably, described non-active gas take volume/hour the speed that passes into and the ratio of the volume of the slurries in described slurry layer be 40-100:1.
The method according to this invention, described in there is commutative group solid matter can be various types of solid matters with commutative group well known to those skilled in the art.The instantiation of described solid matter can include but not limited to: molecular sieve, hydrotalcite and the colloidal sol with commutative group.The method according to this invention, described in there is commutative group solid matter be preferably molecular sieve.
Described molecular sieve can be the various molecular sieves that need to carry out ion-exchange well known to those skilled in the art, for example microporous silicon aluminum molecular screen, micropore phosphate aluminium molecular sieve and mesoporous Si-Al molecular sieve.The phosphate aluminium molecular sieve that described microporous silicon aluminum molecular screen and the micropore phosphate aluminium molecular sieve Si-Al molecular sieve that finger-hole footpath is 0.3-2nm respectively and aperture are 0.3-2nm, described mesoporous Si-Al molecular sieve refers to that aperture is the Si-Al molecular sieve of 2-100nm.The instantiation of described microporous silicon aluminum molecular screen can include but not limited to: 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.The instantiation of described micropore phosphate aluminium molecular sieve can include but not limited to: 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.The instantiation of described mesoporous Si-Al molecular sieve can include but not limited to: 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.
The method according to this invention is specially adapted to various Na type molecular sieves to carry out ion-exchange, obtain for example hydrogen type molecular sieve, ammonium type molecular sieve, rare earth metal type molecular sieve, alkaline-earth metal type molecular sieve or mixed type molecular sieve (that is the molecular sieve, with two or more commutative group).That is, the method according to this invention, described in there is commutative group solid matter Na type molecular sieve more preferably.
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 solid matter that has commutative group and can be mixed with slurries all can adopt method of the present invention to carry out ion-exchange.
The method according to this invention, described in there are the slurries of the solid matter of commutative group can be by the described solid matter with commutative group is mixed to making beating with water, thereby obtain the described slurries containing thering is the solid matter of commutative group.That is, the described slurries containing having the solid of commutative group contain water.Described water is preferably deionized water.The present invention is in described slurries, and the ratio of solid matter and water is not particularly limited, as long as the amount of water is enough to make described solid matter to form slurries.Usually, the weight ratio of described solid matter and water can be 1:5-20, is preferably 1:7-15, more preferably 1:7-12.The present invention is not particularly limited for the method for making beating, can select for the routine of this area.
The present invention is for providing the method for the ion exchange column with ion exchange resin bed layer to be not particularly limited, can adopt the conventional the whole bag of tricks in this area ion exchange resin to be filled in the container of tubulose, form ion exchange resin bed layer, thereby obtain ion exchange column.Described tubular container can be conventional various for holding ion exchange resin to form the tubular container of ion exchange column in this area.Usually, described tubular container can be for example glass tube or stainless steel tube.The internal diameter of described tubular container, external diameter and length can be carried out suitable selection according to the conventional knowledge of this area according to concrete application scenario, repeat no more herein.The method according to this invention, ion exchange column is placed along gravity direction.
The method according to this invention is not particularly limited for the kind of the ion-exchange group on described ion exchange resin, can carry out suitable selection according to the specific requirement of carrying out the solid matter of ion-exchange.For example: when the commutative group on the solid matter that carries out ion-exchange is cation, the ion-exchange group on described ion exchange resin is cation exchange group; When the commutative group on the solid matter that carries out ion-exchange is anion, the ion-exchange group on described ion exchange resin is anion exchange groups.Of the present invention a kind of preferred embodiment in, described solid matter is molecular sieve (being preferably Na type molecular sieve), described ion exchange resin is cationic ion exchange resin.Particularly, when the described solid matter with commutative group is Na type molecular sieve, the ion-exchange group on described ion exchange resin can be hydrogen ion, ammonium ion (that is, NH
4 +), one or more in alkaline-earth metal ions and rare earth ion.The ion exchange resin with above-mentioned ion-exchange group can be commercially available, and also can adopt the conventional method in this area to obtain by making the transition.Existing ion exchange resin is made the transition, thereby the method that obtains having the ion exchange resin of predetermined ion-exchange group is known in the field, repeats no more herein.
The method according to this invention, the exchange capacity of described ion exchange resin is not particularly limited, and can select for the routine of this area.Usually, the CEC of described ion exchange resin can be 0.5-5mmol/mL.Described CEC is the molal quantity of the contained ion-exchange group of the ion exchange resin of unit volume, can under the condition of GB/T8144-2008 defined, measure, and also can from the product information of the ion exchange resin that is commercially available, obtain.The product information that full exchange content in the embodiment of the present invention is the ion exchange resin from being commercially available, obtain.
The method according to this invention, is not particularly limited for the pore structure of described ion exchange resin, can select for the routine of this area, and for example: described ion exchange resin can be gel-type ion-exchange resin, can be also macroreticular ion exchange resin.The method according to this invention is also not particularly limited for the kind of the matrix resin of described ion exchange resin, can for this area conventional can for example, as the resin of the matrix of ion exchange resin: polystyrene resin or acrylic resin.
The method according to this invention, the slurries containing solid matter that flow out from described ion exchange column can filter, and directly use after solid phase is dry; Also can again send into as required in ion exchange column and carry out ion-exchange, until the content of the commutative group on the solid matter obtaining meets the demands; Can also adopt other ion-exchange process to proceed ion-exchange.
The method according to this invention, the described slurries containing having the solid matter of commutative group can also contain the conventional ion-exchange initator that can promote ion-exchange at least one this area.The present invention is not particularly limited for the kind of described ion-exchange initator, can select for the routine of this area, for example: described ion-exchange initator can be selected from the water soluble salt of organic acid, inorganic acid, organic acid water soluble salt and inorganic acid.Particularly, described ion-exchange initator can be selected from but be not limited to: hydrochloric acid and water soluble salt thereof (as alkali metal salt, alkali salt and ammonium salt), nitric acid and water soluble salt (as alkali metal salt, alkali salt and ammonium salt) thereof, phosphoric acid and water soluble salt (as alkali metal salt, alkali salt and ammonium salt) thereof and sulfuric acid and water soluble salt (as alkali metal salt, alkali salt and ammonium salt) thereof.The instantiation of described ion-exchange initator can include but not limited to: hydrochloric acid, sodium chloride, ammonium chloride, nitric acid, sodium nitrate, ammonium nitrate, phosphoric acid, sulfuric acid, sodium sulphate and ammonium sulfate.The present invention is not particularly limited for the consumption of described ion-exchange initator, can select for the routine of this area.Usually, the amount of described ion-exchange initator can be the described 0.001-2 % by weight containing having the amount of the solid matter in the slurries of solid matter of commutative group, be preferably the described 0.01-1 % by weight containing thering is the amount of the solid matter in the slurries of solid matter of commutative group, more preferably the described 0.1-1 % by weight containing thering is the amount of the solid matter in the slurries of solid matter of commutative group.
The method according to this invention, the condition of described ion-exchange can be selected for the routine of this area, is not particularly limited.For example: described ion-exchange can 20-100 ℃, preferably at the temperature of 50-80 ℃, carry out.The method according to this invention, can adopt the conventional the whole bag of tricks in this area that described ion-exchange is carried out under said temperature, repeats no more herein.
The method according to this invention, the ion exchange resin in ion exchange resin bed layer can be regenerated and optional transition after inefficacy, then recycles.The method of the ion exchange resin of inefficacy being regenerated and making the transition is known in the field.For example: can soak the ion exchange resin of exporting or with acid solution, the ion exchange resin of exporting is carried out to drip washing (flow velocity of acid solution is preferably 1-100mL/min) and regenerate from ion exchange column from ion exchange column with acid solution, to obtain Hydrogen ion exchange resin; The Hydrogen ion exchange resin obtaining can make the transition as required to be become as alkali metal type ion exchange resin, alkaline-earth metal type ion exchange resin, ammonium type ion exchange resin, rare earth metal type ion exchange resin or mixed type ion exchange resin (that is the ion exchange resin that, contains two or more ion-exchange group); The salt generating in regenerative process (as sodium salt) can be recycled.Described acid solution can for the conventional various acid solutions in this area, for example, can be aqueous hydrochloric acid solution and/or aqueous sulfuric acid.The present invention is also not particularly limited for the concentration of described acidic aqueous solution, can be generally 1-20 % by weight.According to the present invention, the temperature and time of described regeneration can be selected for the routine of this area.Usually, the temperature of described regeneration can be 0-30 ℃, and the time of described regeneration can be 1-300 minute.
Fig. 4 shows preferred embodiment a kind of according to ion-exchange process of the present invention.This preferred embodiment in, in ion exchange column 1, there is ion exchange resin bed layer 4, be formed at nonactive dielectric layer 3 on the upper surface of ion exchange resin bed layer 4, be placed in the upper surface Existential Space of nonactive dielectric layer 3 tops and its lower surface and nonactive dielectric layer 3 pipeline 5, for delivery of containing have commutative group solid matter slurries slurries conveyance conduit 7 and for passing into the gas passage 8 of non-active gas.During use, to by slurries conveyance conduit 7, send in ion exchange column 1 containing the slurries with the solid matter of commutative group, on the upper surface of nonactive dielectric layer 3, form slurry layer 2, make slurries flow through ion exchange resin bed layer 4 through nonactive dielectric layer 3, to carry out ion-exchange, by gas passage 8, in pipeline 5, pass into non-active gas, so that slurry layer 2 is carried out to disturbance simultaneously.
The method according to this invention can be avoided on the surface of ion exchange resin bed layer, sedimentation occurring containing the slurries with the solid matter of commutative group effectively, and method of the present invention is specially adapted to the occasion that adopts ion exchange column, by the mode of serialization, the solid matter containing commutative group is carried out to ion-exchange.The serialization that can adopt the conventional the whole bag of tricks in this area to realize ion-exchange is carried out.For example: two or two above ion exchange columns can be set, make the ion exchange column that cannot obtain gratifying ion-exchange effect stop ion-exchange, carry out regeneration of ion-exchange resin, ion-exchange is carried out in remaining ion exchange column.
Below in conjunction with embodiment and comparative example, describe the present invention in detail.
In following examples and comparative example, employing is purchased the content that passes through commutative group in X-fluorescence spectrographic determination solid matter from the D/MAX-IIIA of Rigaku type X-ray fluorescence spectrometer, wherein, adopts rhodium target, excitation power source is 50kV, and excitation current is 50mA.
In following examples and comparative example, the average grain diameter of described nonactive particle and the average grain diameter of ion exchange resin are with slide measure, to measure the diameter of each particle by getting 100 particles, and the mean value of the diameter of calculating mensuration obtains.
In following examples and comparative example, the NaY molecular sieve of use is purchased from China Petrochemical Industry's catalyst Chang Ling branch company, wherein, and Na
2o content is 12 % by weight, and degree of crystallinity is 84.1%, and lattice constant is
particle diameter is 0.5-1.2 μ m; The ZSM-5 molecular sieve using is purchased from China Petrochemical Industry's catalyst Chang Ling branch company, Na
2o content is 5 % by weight, and degree of crystallinity is 95%, and silica alumina ratio is 60, and particle diameter is 1-2 μ m.Wherein, the particle diameter of molecular sieve adopts to be purchased from the Mastersizer of Britain Ma Erwen company 2000 type laser fineness gages and measures.
In following examples and comparative example, butt is by sample is dried and is measured for 2 hours at the temperature of 800 ℃.
In following examples, adopt if not otherwise specified the method shown in Fig. 4 to carry out ion-exchange.
Embodiment 1-10 is used for illustrating ion-exchange process of the present invention.
(1) at height, be in 40cm, the internal diameter glass column that is 3.1cm, to fill 150mL ammonium type polystyrene storng-acid cation exchange resin (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 * 7, gel-type, average grain diameter is 0.65mm, CEC is 1.8mmol/mL), form ion exchange resin bed layer.With glass particle, (be purchased from Ningbo Li Ming Glass Co., Ltd., average grain diameter is 3mm) on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 20mm, and (internal diameter is 12mm above nonactive dielectric layer, to settle a glass tube, length is 20mm, external diameter is 13mm, distance between the outer wall of this glass tube and the inwall of ion exchange column is 9mm, and the distance between the lower surface of this glass tube and the upper surface of nonactive dielectric layer is 5mm).
(2) in beaker, add 2000mL deionized water, and add wherein 200g NaY molecular sieve (in butt), stir 30 minutes, obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve that step (2) obtained are heated to 70 ℃, then with the flow velocity of 5mL/min, pump into from top to bottom in the ion exchange column that step (1) obtains, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, at 70 ℃, carry out ion-exchange.Meanwhile, by gas passage, in glass tube, pass into air, intake velocity is 30mL/min.Below ion exchange column, receive the slurries through ion-exchange that flow out from ion exchange column, at interval of 20min sampling 40mL, get altogether 10 times.
(4) the slurries suction filtration through ion-exchange flowing out from ion exchange column step (3) being obtained, and the filter cake obtaining is dried at 120 ℃, 10 parts of molecular sieves obtained.
(5) experiment is carried out stopping after 200 minutes, does not observe the molecular sieve of deposition in ion exchange column.With X-fluorescence spectroscopic methodology detect the 1st time, the 3rd time, the 5th, the sodium oxide content of the molecular sieve that obtains for the 7th time and the 10th time, result is listed in table 1.
Comparative example 1
Adopt the method identical with embodiment 1 to carry out ion-exchange to the slurries containing molecular sieve, different is, nonactive dielectric layer is not set on the upper surface of ion exchange resin bed layer and in glass tube, does not pass into air, when experiment proceeds to 90min, ion exchange column is blocked, cannot carry out ion-exchange, experiment stops.The thickness of observing the molecular sieve of deposition on the upper surface of ion exchange resin bed layer is 4mm.The sodium oxide content of the molecular sieve obtaining is listed in table 1.
Comparative example 2
Adopt the method identical with embodiment 1 to carry out ion-exchange to the slurries containing molecular sieve, different is, the average grain diameter that is used to form the nonactive particle of nonactive dielectric layer is 4mm, and in glass tube, do not pass into air, when experiment proceeds to 120min, ion exchange column is blocked, cannot carry out ion-exchange, and experiment stops.Observe and on the upper surface of nonactive dielectric layer, deposited the molecular sieve that thickness is 4mm.The sodium oxide content of the molecular sieve obtaining is listed in table 1.
Adopt the method identical with embodiment 1 to carry out ion-exchange to the slurries containing molecular sieve, different, in glass tube, do not pass into air.After ion-exchange finishes, the thickness of the molecular sieve depositing on the upper surface of nonactive dielectric layer is 1.5mm.The sodium oxide content of the molecular sieve obtaining, result is listed in table 1.
(1) at height, be in 40cm, the internal diameter glass column that is 3.1cm, to fill 150mL ammonium type polystyrene storng-acid cation exchange resin (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 * 14.5, gel-type, average grain diameter is 0.75mm, CEC is 1.8mmol/mL).With polyflon particle, (be purchased from Shandong China fluorine chemical Co., Ltd, average grain diameter is 1mm) on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 20mm, and (internal diameter is 12mm above nonactive dielectric layer, to settle a glass tube, length is 20mm, external diameter is 13mm, the axis of this glass tube and the dead in line of glass tube, the distance between the lower surface of this glass tube and the upper surface of nonactive dielectric layer is 5mm).
(2) in beaker, add 2000mL deionized water, and add wherein 200g NaY molecular sieve (in butt) and 1.2g NaCl, stir 30 minutes, obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve that step (2) obtained are heated to 70 ℃, then the flow velocity with 5mL/min pumps in the ion exchange column of step (1) from top to bottom, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, at 70 ℃, carry out ion-exchange.Meanwhile, by gas passage, in glass tube, pass into air, intake velocity is 30mL/min.Below ion exchange column, receive the slurries through ion-exchange that flow out from ion exchange column, at interval of 20min, change a receiving vessel, get altogether 10 times.
(4) the slurry samples suction filtration through ion-exchange flowing out from ion exchange column step (3) being obtained, and the filter cake obtaining is dried at 120 ℃, 10 parts of molecular sieves obtained.
(5) experiment is carried out stopping after 200 minutes, does not observe the molecular sieve of deposition on the upper surface of nonactive dielectric layer.The sodium oxide content of the molecular sieve that detect the 1st time, the 3rd time, the 5th, obtains for the 7th time and the 10th time, result is listed in table 1.
Comparative example 3
Adopt the method identical with embodiment 3 to carry out ion-exchange, different is, the average grain diameter that is used to form the nonactive particle of nonactive dielectric layer is 0.8mm, and in glass tube, do not pass into air, when experiment proceeds to 100min, ion exchange column is blocked, cannot carry out ion-exchange, and experiment stops.The thickness of the molecular sieve depositing on the upper surface of nonactive dielectric layer is 4mm.The sodium oxide content of the molecular sieve obtaining is listed in table 1.
Adopt the method identical with embodiment 3 to carry out ion-exchange, different, in glass tube, do not pass into air.The thickness of the molecular sieve depositing on the upper surface of nonactive dielectric layer is 1mm.The sodium oxide content of the molecular sieve obtaining is listed in table 1.
(1) at height, be in 40cm, the internal diameter glass column that is 3.1cm, to fill 150mL ammonium type weakly acidic cationic exchange resin of acrylic series (to be purchased from Chemical Plant of Nankai Univ., the trade mark is D113, macroporous type, average grain diameter is 0.75mm, CEC is 4.2mmol/mL).With quartz sand, (be purchased from Lingshou County, From Shijiazhuang City of Hebei Province Jian Shi quartz sand factory, average grain diameter is 1.3mm) on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 20mm, and (internal diameter is 12mm above nonactive dielectric layer, to settle a glass tube, length is 20mm, external diameter is 13mm, the axis of this glass tube and the dead in line of glass tube, the distance between the lower surface of this glass tube and the upper surface of nonactive dielectric layer is 7mm).
(2) in beaker, add 2000mL deionized water, and add wherein 200g NaY molecular sieve (in butt), stir 30 minutes, obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve that step (2) obtained are heated to 70 ℃, then the flow velocity with 5mL/min pumps in the ion exchange column of step (1) from top to bottom, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, at 70 ℃, carry out ion-exchange.Meanwhile, by gas passage, in glass tube, pass into air, intake velocity is 20mL/min.Below ion exchange column, receive the slurries through ion-exchange that flow out from ion exchange column, at interval of 20min, change a receiving vessel, get altogether 10 times.
(4) the slurry samples suction filtration through ion-exchange flowing out from ion exchange column step (3) being obtained, and the filter cake obtaining is dried at 120 ℃, 10 parts of molecular sieves obtained.
(5) experiment is carried out stopping after 200 minutes, does not observe the molecular sieve of deposition on the upper surface of nonactive dielectric layer.The sodium oxide content of the molecular sieve that detect the 1st time, the 3rd time, the 5th, obtains for the 7th time and the 10th time, result is listed in table 1.
Embodiment 6
(1) at height, be in 40cm, the internal diameter glass column that is 3.1cm, to fill 150mL Hydrogen polystyrene storng-acid cation exchange resin (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 * 14.5, gel-type, average grain diameter is 0.75mm, CEC is 1.8mmol/mL).With polytetrafluoroethylgranule granule (be purchased from Shandong China fluorine chemical Co., Ltd, average grain diameter is 1.5mm), on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 15mm.As shown in Figure 1, with rubber stopper, at the upper surface of ion exchange resin bed layer, fix a paddle.
(2) in beaker, add 2000mL deionized water, and add wherein 200g NaY molecular sieve (in butt) and 2g NaCl, by mechanical agitation, stir and obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve that step (2) obtained are heated to 70 ℃, then the flow velocity with 5mL/min pumps in the ion exchange column of step (1) from top to bottom, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, at 70 ℃, carry out ion-exchange, in ion exchange process, with motor, drive paddle to stir slurry layer.Below ion exchange column, receive the slurries through ion-exchange that flow out from ion exchange column, at interval of 20min, change a receiving vessel, get altogether 10 times.
(4) the slurry samples suction filtration through ion-exchange flowing out from ion exchange column step (3) being obtained, and the filter cake obtaining is dried at 120 ℃, 10 parts of molecular sieves obtained.
(5) experiment is carried out stopping after 200 minutes, does not observe the molecular sieve of deposition on the upper surface of nonactive dielectric layer.The sodium oxide content of the molecular sieve that detect the 1st time, the 3rd time, the 5th, obtains for the 7th time and the 10th time, result is listed in table 1.
Embodiment 7
Adopt the method identical with embodiment 6 to carry out ion-exchange, different, paddle replaces with the glass tube in embodiment 1, and the speed that passes into of gas is 30mL/min.Experiment is carried out stopping after 200 minutes, does not observe the molecular sieve of deposition in ion exchange column.The sodium oxide content obtaining in molecular sieve is listed in table 1.
(1) at height, be in 40cm, the internal diameter glass column that is 3.1cm, to fill 150mL Hydrogen polystyrene storng-acid cation exchange resin (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 * 14.5, gel-type, average grain diameter is 0.65mm, quality CEC is 1.8mmol/mL).With quartz sand, (be purchased from Lingshou County, From Shijiazhuang City of Hebei Province Jian Shi quartz sand factory, average grain diameter is 1.3mm) on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 15mm, and (internal diameter is 12mm above nonactive dielectric layer, to settle a glass tube, length is 20mm, external diameter is 13mm, the axis of this glass tube and the dead in line of glass tube, the distance between the lower surface of this glass tube and the upper surface of nonactive dielectric layer is 5mm).
(2) in beaker, add 2000mL deionized water, and add wherein 200g ZSM-5 molecular sieve (in butt), by mechanical agitation, stir and obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve that step (2) obtained are heated to 70 ℃, then the flow velocity with 5mL/min pumps in the ion exchange column of step (1) from top to bottom, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, at 70 ℃, carry out ion-exchange.Meanwhile, by gas passage, in glass tube, pass into air, intake velocity is 40mL/min.Below ion exchange column, receive the slurries through ion-exchange that flow out from ion exchange column, at interval of 20min, change a receiving vessel, get altogether 9 times.
(4) the slurry samples suction filtration through ion-exchange flowing out from ion exchange column step (3) being obtained, and the filter cake obtaining is dried at 120 ℃, 9 parts of molecular sieves obtained.
(5) experiment is carried out stopping after 180 minutes, does not observe the molecular sieve of deposition on the upper surface of nonactive dielectric layer.The sodium oxide content of the molecular sieve that detect the 1st time, the 3rd time, the 5th, obtains for the 7th time and the 9th time, result is listed in table 1.
(1) at height, be in 40cm, the internal diameter glass column that is 3.1cm, to fill 150mL Hydrogen polystyrene storng-acid cation exchange resin (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 * 14.5, gel-type, average grain diameter is 0.65mm, CEC is 1.8mmol/mL).With glass particle, (be purchased from Ningbo Li Ming Glass Co., Ltd., average grain diameter is 1.5mm) on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 20mm, and (internal diameter is 12mm above nonactive dielectric layer, to settle a glass tube, length is 20mmm, external diameter is 13mm, the axis of this glass tube and the dead in line of glass tube, the distance between the lower surface of this glass tube and the upper surface of nonactive dielectric layer is 5mm).
(2) in beaker, add 2000mL deionized water, and add wherein 200g NaX molecular sieve (in butt), by mechanical agitation, stir and obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve that step (2) obtained are heated to 50 ℃, then the flow velocity with 5mL/min pumps in the ion exchange column of step (1) from top to bottom, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, at 50 ℃, carry out ion-exchange.Meanwhile, by gas passage, in glass tube, pass into air, intake velocity is 30mL/min.Below ion exchange column, receive the slurries through ion-exchange that flow out from ion exchange column, at interval of 15min, change a receiving vessel, get altogether 9 times.
(4) the slurry samples suction filtration through ion-exchange flowing out from ion exchange column step (3) being obtained, and the filter cake obtaining is dried at 120 ℃, 9 parts of molecular sieves obtained.
(5) experiment is carried out stopping after 135 minutes, does not observe the molecular sieve of deposition on the upper surface of nonactive dielectric layer.The sodium oxide content of the molecular sieve that detect the 1st time, the 3rd time, the 5th, obtains for the 7th time and the 9th time, result is listed in table 1.
Adopt the method identical with embodiment 9 to carry out ion-exchange, different is, glass tube is not set in ion exchange column, and containing the amount of the slurries of molecular sieve, is retained as identical (that is, the V of total measurement (volume) with nonactive dielectric layer and ion exchange resin bed layer in ion exchange column
1=V
2).Experiment is carried out stopping after 200 minutes, and the thickness of the molecular sieve depositing on the upper surface of nonactive dielectric layer is 0.8mm.The sodium oxide content of the molecular sieve obtaining is listed in table 1.
Table 1
*: the sodium oxide content of the molecular sieve obtaining for the 9th time
As can be seen from Table 1, ion-exchange process of the present invention can be avoided or substantially avoid, containing the slurries with commutative group, sedimentation occurs in ion exchange column effectively.
Claims (15)
1. an ion-exchange process, the method comprises the following steps:
(1) provide the ion exchange column with ion exchange resin bed layer;
(2) will send in described ion exchange column containing the slurries with the solid matter of commutative group;
(3) make the described slurry stream that contains the solid matter with commutative group cross described ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on ion exchange resin; And
(4) collect the slurries containing solid matter that flow out from described ion exchange column;
It is characterized in that, the method is also included in that to carry out step (2) front, with at least one nonactive particle, form nonactive dielectric layer on the upper surface of described ion exchange resin bed layer, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described nonactive particle and described ion exchange resin bed layer is 1.2-5:1.
2. method according to claim 1, wherein, the described slurries containing having the solid matter of commutative group form slurry layer on the upper surface of described nonactive dielectric layer, the method also comprises carries out disturbance to described slurry layer, so that the slurries in described slurry layer also have the motion of non-gravity direction.
3. method according to claim 2, wherein, the mode of described slurry layer being carried out to disturbance comprises: in described slurry layer, arrange and be immersed in the pipeline in described slurries, and pass into non-active gas in described pipeline, Existential Space between the outer wall of described pipeline and the inwall of described ion exchange column, and Existential Space between the lower surface of described pipeline and the upper surface of described nonactive dielectric layer.
4. method according to claim 3, wherein, the lower surface of described pipeline to the vertical range of upper surface of described nonactive dielectric layer and the ratio of the height of described slurry layer is 1:3-10.
5. method according to claim 3, wherein, the upper surface of described pipeline to the ratio of the surperficial vertical range of described slurry layer and the height of described slurry layer is 1:3-5.
6. according to the method described in any one in claim 3-5, wherein, the ratio of the external diameter of described pipeline and the internal diameter of described ion exchange column is 0.4-0.6:1.
7. method according to claim 3, wherein, described non-active gas take volume/hour the speed that passes into and the ratio of the volume of the slurries in described slurry layer be 40-100:1.
8. according to the method described in claim 3 or 7, wherein, described non-active gas is selected from air, nitrogen and group 0 element gas.
9. according to the method described in any one in claim 1-4, wherein, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described nonactive particle and described ion exchange resin bed layer is 1.3-3:1.
10. according to the method described in any one in claim 1-4, wherein, described nonactive particle is selected from glass particle, quartz particles and inactive resin particle.
11. according to the method described in any one in claim 1-5 and 7, wherein, the described slurries containing having the solid matter of commutative group also contain at least one ion-exchange initator, and the amount of described ion-exchange initator is the 0.001-2 % by weight of the amount of solid matter in described slurries.
12. methods according to claim 11, wherein, described ion-exchange initator is hydrochloric acid and water soluble salt, nitric acid and water soluble salt thereof, phosphoric acid and water soluble salt thereof and sulfuric acid and water soluble salt thereof.
13. according to the method described in any one in claim 1-5 and 7, wherein, described in there is commutative group solid matter be molecular sieve.
14. methods according to claim 13, wherein, described molecular sieve is Na type molecular sieve.
15. methods according to claim 14, wherein, the ion-exchange group on described ion exchange resin is one or more in hydrogen ion, ammonium ion and rare earth ion.
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| CN112546674A (en) * | 2020-12-23 | 2021-03-26 | 浙江华康药业股份有限公司 | System and method for inhibiting glucose from isomerizing into fructose in anion exchange column |
| CN115000435A (en) * | 2022-06-24 | 2022-09-02 | 中自环保科技股份有限公司 | CCM material full recovery process for proton exchange membrane fuel cell |
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| CN2775038Y (en) * | 2005-03-11 | 2006-04-26 | 西北电力试验研究院 | High flow speed double chamber ion exchanging device |
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| CN115000435A (en) * | 2022-06-24 | 2022-09-02 | 中自环保科技股份有限公司 | CCM material full recovery process for proton exchange membrane fuel cell |
| CN115000435B (en) * | 2022-06-24 | 2023-06-13 | 中自环保科技股份有限公司 | Complete recovery process for CCM material of proton exchange membrane fuel cell |
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