CN103623616B - A kind of ion-exchange process - Google Patents
A kind of ion-exchange process Download PDFInfo
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- CN103623616B CN103623616B CN201210313439.0A CN201210313439A CN103623616B CN 103623616 B CN103623616 B CN 103623616B CN 201210313439 A CN201210313439 A CN 201210313439A CN 103623616 B CN103623616 B CN 103623616B
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Abstract
The invention provides a kind of ion-exchange process, comprise and the slurries feeding containing the solid matter with commutative group is had in the ion exchange column of ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on the ion exchange resin in ion exchange column; Collect the slurries containing solid matter flowed out from ion exchange column; Wherein, before carrying out ion-exchange, on the upper surface of ion exchange resin bed layer, nonactive dielectric layer is formed with at least one non-active particles, make the slurries containing the solid matter with commutative group successively flow through nonactive dielectric layer and ion exchange resin bed layer, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of non-active particles and ion exchange resin bed layer is 1.2-5:1.Method of the present invention can avoid or substantially avoid the solid matter in slurries to be deposited on the upper surface of ion exchange resin bed layer effectively, is applicable to the occasion of carrying out serialization 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 method for ion-exchange is carried out to the commutative group in solid matter.
Background technology
Molecular sieve is very extensive in petrochemical industry application, and the method for current commercial synthesis molecular sieve is all synthesize in alkaline solution, and the molecular sieve be therefore synthesized is sodium form.Catalyst the most large in petroleum refining industry is catalytic cracking catalyst, it adopts Y zeolite as active component mostly, be stable NaY form during Y zeolite Prof. Du Yucang, with center of negative charge during sodium ion is complete in zeolite molecular sieve, cause sodium form molecular sieve there is no acid centre.Therefore, sodium form molecular sieve does not almost have activity in the reaction of carbonium ion type, if be used as catalytic cracking catalyst, must carry out modification, namely remove the sodium ion in NaY molecular sieve to it.In addition, apply the more molecular sieve also having MFI structure, as ZSM-5 and Beta molecular sieve, these molecular sieves also need to be become by sodium ion exchange hydrogen ion could use as catalyst before use.
Sodium ion exchange in molecular sieve is first normally NH with ammonium salt solution by existing molecular sieve method for removing Na
4 +, then 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 needs 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 that molecular sieve ammonium exchange process produces and initial wash water, its ammonia-nitrogen content is more than several times of other ammoniated wastewater (as second wash water, three washings).These waste water needs could discharge after treatment, otherwise can to environment.Therefore, seek new molecular sieve sodium ion exchange method, to reduce the wastewater flow rate produced in process of producing molecular sieve, significant for catalyst plant energy-saving and emission-reduction.
JP63159218A discloses a kind of method making 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 DEG C of temperature, exchange certain hour, after twice exchange process, obtain the hydrogen type molecular sieve that alkali metal content is less than 1wt%.But, the mode that the method Middle molecule sieve and ion exchange resin carry out contacting is for mix molecular sieve with ion exchange resin, cause the resin lost efficacy can not carry out ion-exchange with the sodium ion in molecular sieve again, therefore need to carry out a step raising service life of de-sodium effect and ion exchange resin.
CN101570334A discloses a kind of method of ion exchange resin Modified NaY molecular sieve, and molecular sieve pulp and resin are placed in two reative cells separated with screen cloth by the method respectively, NaY molecular sieve and ion exchange resin are not produced and directly contacts, and H
+and Na
+can screen cloth be passed through, realize exchanging under the promotion of concentration difference.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 to improve further.
Method disclosed in CN101823727A first once exchanges molecular sieve, discharging, in 500-650 DEG C of roasting 1-2h, then naturally cool, after roasted product carries out secondary exchange, continue at 500-650 DEG C 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 NaY molecular sieve pulls an oar by (1) in making beating container, makes part Na
+be free in water, after ceramic membrane separation, be divided into two parts: containing Na
+clear water and dense thick NaY slurries, wherein containing 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 pulling an oar in 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, for subsequent use after resin column regeneration, Na in the molecular sieve of output
2when requiring discharging in O content satisfied (2), simultaneously by throat-fed, continue the process of modification; (4), in exchange process, the addition of resin is 2-4 times of the exchanger resin amounts such as NaY, and resin column water outlet pH value controls between 3 and 6, and exchange temperature is 20-70 DEG C, and swap time is 10-60 minute.Although alkali metal content in molecular sieve can drop to by the method 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 and being contacted with cationic ion-exchange resin by molecular sieve pulp, reclaim the molecular sieve pulp after contacting with cationic ion-exchange resin, described molecular sieve pulp is the mixture containing 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 are one or more cations separately, and the kind of described cation A and described cation B is incomplete same, the condition of molecular sieve pulp and contacts ionic exchange resin make the cation B of cation-bit on molecular sieve at least partly replace by the another kind of cation of cation A.Find in practical application, when ion exchange resin is seated in and carries out ion-exchange with the slurries containing molecular sieve in ion exchange column by employing the method, be easy to the ion exchange resin bed layer surface occurring being deposited on containing the molecular sieve in the slurries of molecular sieve in ion exchange column, and then the phenomenon of plug ion exchange column.
Summary of the invention
The object of the invention is to overcome existing when ion-exchange being carried out to the slurries containing molecular sieve by ion exchange column, be easy to the surface occurring being deposited on ion exchange resin bed layer containing the molecular sieve in the slurries of molecular sieve, plug ion exchange column, cause the problem that ion exchange process cannot normally carry out, a kind of ion-exchange process is provided, when adopting method of the present invention to carry out ion-exchange by ion exchange column to the slurries containing solid matter, even if slurries are added in ion exchange column in a large number, slurry layer is formed in ion exchange column, also solid matter can not or be substantially there will not be to be deposited on the surface of ion exchange resin bed layer, the phenomenon of plug ion exchange column.
The present inventor finds in practice process, when the slurries adopting ion exchange column to the solid matter containing commutative group carry out ion-exchange, before described slurries are sent into ion exchange column, first form nonactive dielectric layer with on the upper surface of the ion exchange resin bed layer of non-active particles in ion exchange column, and be 1.2-5:1 for the formation of the average grain diameter of non-active particles of described nonactive dielectric layer and the ratio of the average grain diameter of ion exchange resin, then by when carrying out ion-exchange in described slurries feeding ion exchange column, even if described slurries are sent in ion exchange column in a large number, and slurry layer is formed in ion exchange column, also the solid matter generation sedimentation in slurries can or substantially can be avoided.This completes the present invention.
The invention provides a kind of ion-exchange process, the method comprises the following steps:
(1) ion exchange column with ion exchange resin bed layer is provided;
(2) slurries containing the solid matter with commutative group are sent in described ion exchange column;
(3) make the described slurries containing the solid matter with commutative group flow through described ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on ion exchange resin; And
(4) slurries containing solid matter flowed out from described ion exchange column are collected;
Wherein, the method is also included in that to carry out step (2) front, on the upper surface of described ion exchange resin bed layer, form nonactive dielectric layer with at least one non-active particles, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described non-active particles and described ion exchange resin bed layer is 1.2-5:1.
According to method of the present invention, sending into containing the solid matter with commutative group before ion exchange column, be first that the non-active particles of 1.2-5:1 forms nonactive dielectric layer on the upper surface of described ion exchange resin bed layer with the ratio of the average grain diameter with the ion-exchange resin particles in described ion exchange resin bed layer, slurries containing the solid matter with commutative group enter in ion exchange resin bed layer by described nonactive dielectric layer, can effectively avoid or substantially avoid containing the solid matter generation sedimentation in the slurries of the solid matter with commutative group, even and if then the described slurries containing having commutative group are sent in ion exchange column by method according to the present invention in a large number, also can not plug ion exchange column, be applicable to the occasion of carrying out serialization ion-exchange.
Accompanying drawing explanation
Fig. 1 is for illustration of the mode of the slurry layer containing the solid matter with commutative group being carried out to disturbance;
Fig. 2 is for illustration of the another kind of mode of the slurry layer containing the solid matter with commutative group being carried out to disturbance;
Fig. 3 is placed in a kind of embodiment in slurry layer for illustration of by pipeline stabilization; And
Fig. 4 for illustration of ion-exchange process of the present invention one preferred embodiment.
Detailed description of the invention
The invention provides a kind of ion-exchange process, the method comprises the following steps:
(1) ion exchange column with ion exchange resin bed layer is provided;
(2) slurries containing the solid matter with commutative group are sent in described ion exchange column;
(3) make the described slurries containing the solid matter with commutative group flow through described ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on ion exchange resin; And
(4) slurries containing solid matter flowed out from described ion exchange column are collected;
Wherein, the method is also included in that to carry out step (2) front, on the upper surface of described ion exchange resin bed layer, form nonactive dielectric layer with at least one non-active particles, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described non-active particles and described ion exchange resin bed layer is 1.2-5:1.
According to the present invention, from improving the angle prevented containing the solid matter generation sedimentation in the slurries of the solid matter with commutative group further, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described non-active particles 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 non-active particles and the average grain diameter of ion exchange resin are respectively naturally by getting 100 particles and measuring the diameter of each particle with slide measure, and the mean value calculating the diameter measured obtains.When calculating the ratio of the average grain diameter of non-active particles and the average grain diameter of ion-exchange resin particles, the two adopts identical dimension.
The present invention is not particularly limited for forming the material of described non-active particles, if this non-active particles can not with the described slurry of solid matter and ion exchange resin generation chemical interaction containing having commutative group.Usually, described non-active particles can be selected from glass particle, quartz particles and inactive resin particle (as polytetrafluoroethylgranule granule).
According to method of the present invention, the slurries of the described solid matter containing having commutative group are being admitted to after in ion exchange column, 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 ion exchange resin bed layer cumulative volume V of slurries that can hold
3for benchmark, the volume V of the slurries containing at least one molecular sieve in described ion exchange column
2v can be remained
1>=V
2> V
3, also can remain V
1< V
2(that is, the upper surface of nonactive dielectric layer forming slurry layer).At V
1< V
2time, the height of the slurry layer that the upper surface of described nonactive dielectric layer is formed 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 the vertical range of the upper surface of slurry layer to the upper surface of nonactive dielectric layer, and the height of described nonactive dielectric layer refers to the vertical range of the upper surface of nonactive dielectric layer to the upper surface of described ion exchange resin bed layer.Can by regulating the speed sent into by the slurries of the described solid matter containing having commutative group in ion exchange column, to control in ion exchange column, containing the amount of slurries of solid matter with commutative group, no longer to describe in detail herein.
According to method of the present invention, when the upper surface of described nonactive dielectric layer is also formed with slurry layer, from improving the angle preventing the effect of solid matter generation sedimentation in described slurry layer further, can also comprise according to method of the present invention and disturbance is carried out to described slurry layer, with the motion making the slurries in described slurry layer also have non-gravity direction.
Conventional various methods can be adopted to carry out disturbance to described slurry layer, with the motion making the slurries in described slurry layer also have non-gravity direction.Such as: as shown in Figure 1, the upper surface of the ion exchange resin bed layer 4 in ion exchange column 1 forms nonactive dielectric layer 3, paddle 9 is set in slurry layer 2, drive paddle 9 to carry out disturbance to slurry layer 2.
One of the present invention 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 the pipeline 5 be immersed in slurries, and in pipeline 5, pass into non-active gas (such as: pass into non-active gas by gas passage 8 in slurry layer 2), Existential Space between the outer wall of pipeline 5 and the inwall of ion exchange column 1, and Existential Space between the upper surface of the lower surface of pipeline 5 and nonactive dielectric layer 3.In slurry layer, pipeline is set, and non-active gas is passed in pipeline, the non-active gas passed into forms bubble in slurries, the uphill process of bubble makes to form negative pressure in pipeline, thus the slurries suction below this pipeline 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 prevented in slurry layer.Further, adopt which to carry out disturbance to slurry layer to be easier to implement in practical operation.
This preferred embodiment in, suitable selection can be carried out according to concrete condition to the distance on upper surface to the surface of described slurry layer of the distance of the upper surface of described nonactive dielectric layer and described pipeline in the lower surface of described pipeline.Usually, the lower surface of described pipeline can be 1:3-10 to the vertical range of upper surface of described nonactive dielectric layer and the ratio of the height of described slurry layer, is preferably 1:5-10.The upper surface of described pipeline can be 1:3-5 to the vertical range on surface of described slurry layer and the ratio of the height of described slurry layer.
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, conventional various methods can be adopted to be placed in slurry layer by described pipeline, such as: as shown in Figure 3 (schematic top plan view for ion exchange column), support 10 can be used stably to be placed in the slurry layer in ion exchange column 1 by pipeline 5, 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, can there is not chemically interactive gas with the described slurries of solid matter and ion exchange resin containing having commutative group for various in the non-active gas passed in described pipeline, such as: 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 is can effectively prevent from being describedly as the criterion containing the solid matter generation sedimentation in the slurries of solid matter.Preferably, described non-active gas in volume/hour the speed that passes into and described slurry layer in the ratio of volume of slurries for 40-100:1.
According to method of the present invention, described in there is the solid matter of commutative group can for various types of solid matter 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 have the colloidal sol of commutative group.According to method of the present invention, described in there is commutative group solid matter be preferably molecular sieve.
Described molecular sieve can be the various molecular sieve carrying out ion-exchange that needs well known to those skilled in the art, such as microporous silicon aluminum molecular screen, micropore phosphate aluminium molecular sieve and mesoporous Si-Al molecular sieve.Finger-hole footpath is the Si-Al molecular sieve of 0.3-2nm and aperture is respectively the phosphate aluminium molecular sieve of 0.3-2nm for described microporous silicon aluminum molecular screen and micropore phosphate aluminium molecular sieve, and 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.
Method according to the present invention is specially adapted to carry out ion-exchange to various Na type molecular sieve, obtain such as 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, there is the molecular sieve of two or more commutative group).That is, according to method of the present invention, described in there is commutative group solid matter be more preferably Na type molecular sieve.
The above-mentioned solid matter enumerated is only exemplary, known in those skilled in the art: the present invention is not limited to the above-mentioned solid matter enumerated, any have commutative group and the solid matter that can be mixed with slurries all can adopt method of the present invention to carry out ion-exchange.
According to method of the present invention, described in there is the solid matter of commutative group slurries can pull an oar by the described solid matter with commutative group is mixed with water, thus containing the slurries of solid matter with commutative group described in obtaining.That is, the slurries of the described solid containing having 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 form slurries.Usually, the weight ratio of described solid matter and water can be 1:5-20, is preferably 1:7-15, is more preferably 1:7-12.The present invention is not particularly limited for the method for making beating, can be that the routine of this area is selected.
The present invention is not particularly limited for providing the method for the ion exchange column with ion exchange resin bed layer, ion exchange resin is filled in the container of tubulose by the various methods that this area can be adopted to commonly use, form ion exchange resin bed layer, thus obtain ion exchange column.Described tubular container can for this area commonly use various for holding ion exchange resin to form the tubular container of ion exchange column.Usually, described tubular container can be such as glass tube or stainless steel tube.The internal diameter of described tubular container, external diameter and length can according to embody rule occasions, and the Conventional wisdom according to this area carries out suitable selection, repeats no more herein.According to method of the present invention, ion exchange column is placed along gravity direction.
Method according to the present 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 the solid matter carrying out ion-exchange.Such as: when the commutative group on the solid matter carrying out ion-exchange is cation, the ion-exchange group on described ion exchange resin is cation exchange group; When commutative group on the solid matter carrying out ion-exchange is anion, the ion-exchange group on described ion exchange resin is anion exchange groups.One of the present invention preferred embodiment in, described solid matter is molecular sieve (is preferably Na type molecular sieve), and described ion exchange resin is cationic ion exchanger 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 the conventional method in this area also can be adopted to obtain by making the transition.Existing ion exchange resin is made the transition, thus the method obtaining the ion exchange resin with predetermined ion-exchange group is known in the field, repeats no more herein.
According to method of the present invention, the exchange capacity of described ion exchange resin is not particularly limited, and can be that the routine of this area is selected.Usually, the CEC of described ion exchange resin can be 0.5-5mmol/mL.The molal quantity of the ion-exchange group of described CEC contained by the ion exchange resin of unit volume, can measure, also can obtain from the product information of the ion exchange resin be commercially available under the condition of GB/T8144-2008 defined.Total exchange content in the embodiment of the present invention obtains from the product information of the ion exchange resin be commercially available.
According to method of the present invention, the pore structure for described ion exchange resin is not particularly limited, and can be that the routine of this area is selected, such as: described ion exchange resin can be gel-type ion-exchange resin, also can be macroreticular ion exchange resin.Method according to the present invention is also not particularly limited for the kind of the matrix resin of described ion exchange resin, can for this area commonly use can as the resin of the matrix of ion exchange resin, such as: polystyrene resin or acrylic resin.
According to method of the present invention, the slurries containing solid matter flowed out from described ion exchange column can filter, and solid phase drying are directly used afterwards; Also again can send in ion exchange column as required and carry out ion-exchange, until the content of commutative group on the solid matter obtained meets the demands; Other ion-exchange process can also be adopted to proceed ion-exchange.
According to method of the present invention, the slurries of the described solid matter containing having commutative group can also contain the ion-exchange initator that can promote ion-exchange commonly used at least one this area.The present invention is not particularly limited for the kind of described ion-exchange initator, can be that the routine of this area is selected, such as: 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 (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 be that the routine of this area is selected.Usually, the amount of described ion-exchange initator can for described containing have commutative group solid matter slurries in the 0.001-2 % by weight of amount of solid matter, be preferably described containing have commutative group solid matter slurries in the 0.01-1 % by weight of amount of solid matter, be more preferably described containing have commutative group solid matter slurries in the 0.1-1 % by weight of amount of solid matter.
According to method of the present invention, the condition of described ion-exchange can be the routine selection of this area, is not particularly limited.Such as: described ion-exchange can 20-100 DEG C, preferably carry out at the temperature of 50-80 DEG C.According to method of the present invention, can adopt the conventional various methods in this area that described ion-exchange is carried out at the temperature disclosed above, repeat no more herein.
According to method of the present invention, the ion exchange resin in ion exchange resin bed layer can carry out regenerating and optional transition after inefficacy, then recycles.Known in the field by the method that the ion exchange resin of inefficacy carries out regenerating and make the transition.Such as: can soak with acid solution the ion exchange resin that exports from ion exchange column or with acid solution, drip washing (flow velocity of acid solution is preferably 1-100mL/min) be carried out to the ion exchange resin exported from ion exchange column and regenerate, to obtain form ion exchange resin; The form ion exchange resin obtained can carry out becoming 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 containing two or more ion-exchange group) as required transition; The salt (as sodium salt) generated in regenerative process can be recycled.The various acid solutions that described acid solution can be commonly used for this area can be such as 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 the routine selection of this area.Usually, the temperature of described regeneration can be 0-30 DEG C, and the time of described regeneration can be 1-300 minute.
Fig. 4 shows according to the one of ion-exchange process of the present invention preferred embodiment.This preferred embodiment in, there is in ion exchange column 1 ion exchange resin bed layer 4, the nonactive dielectric layer 3 be formed on the upper surface of ion exchange resin bed layer 4, to be placed in above nonactive dielectric layer 3 and the pipeline 5 of the upper surface Existential Space of its lower surface and nonactive dielectric layer 3, for carrying containing the slurries conveyance conduit 7 of the slurries of the solid matter with commutative group and the gas passage 8 for passing into non-active gas.During use, slurries containing the solid matter with commutative group are sent in ion exchange column 1 by slurries conveyance conduit 7, the upper surface of nonactive dielectric layer 3 forms slurry layer 2, slurries are made to flow through ion exchange resin bed layer 4 through nonactive dielectric layer 3, to carry out ion-exchange, in pipeline 5, pass into non-active gas by gas passage 8, to carry out disturbance to slurry layer 2 simultaneously.
Can effectively avoid on the surface of ion exchange resin bed layer, sedimentation occurring containing the slurries of the solid matter with commutative group according to method of the present invention, method of the present invention is specially adapted to adopt ion exchange column by the mode of serialization, the solid matter containing commutative group to be carried out to the occasion of ion-exchange.The various methods that this area can be adopted to commonly use are carried out to the serialization realizing ion-exchange.Such as: the ion exchange column that can arrange more than two or two, 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.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, adopt the content being purchased and being measured commutative group in solid matter from the D/MAX-IIIA type X-ray fluorescence spectrometer of Rigaku by X fluorescence spectrum method, wherein, adopt rhodium target, excitation power source is 50kV, and excitation current is 50mA.
In following examples and comparative example, the average grain diameter of described non-active particles and the average grain diameter of ion exchange resin are the diameters measuring each particle by getting 100 particle slide measures, and the mean value calculating the diameter measured 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 μm; The ZSM-5 molecular sieve used 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 μm.Wherein, the particle diameter of molecular sieve adopts to be purchased and measures from the Mastersizer 2000 type laser fineness gage of Malvern company of Britain.
In following examples and comparative example, butt is by by sample at the temperature of 800 DEG C dry 2 hours and measure.
The method shown in Fig. 4 is adopted to carry out ion-exchange in following examples if not otherwise specified.
Embodiment 1-10 is for illustration of ion-exchange process of the present invention.
Embodiment 1
(1) height be 40cm, internal diameter is fill 150mL ammonium type polystyrene storng-acid cation exchange resin in the glass column of 3.1cm (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.(be purchased from Ningbo Li Ming Glass Co., Ltd. with glass particle, 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 to settle a glass tube above nonactive dielectric layer, 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 200g NaY molecular sieve (in butt) wherein, stir 30 minutes, obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve step (2) obtained are heated to 70 DEG C, then pump in the ion exchange column that step (1) obtains from top to bottom with the flow velocity of 5mL/min, form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, carry out ion-exchange at 70 DEG C.Meanwhile, pass into air by gas passage in glass tube, intake velocity is 30mL/min.At the slurries through ion-exchange that the received down of ion exchange column flows out from ion exchange column, sample 40mL at interval of 20min, get 10 times altogether.
(4) the slurries suction filtration through ion-exchange flowed out from ion exchange column step (3) obtained, and the filter cake obtained is carried out drying at 120 DEG C, obtain 10 parts of molecular sieves.
(5) experiment is carried out stopping after 200 minutes, does not observe the molecular sieve of deposition in ion exchange column.With X fluorescence spectrum method detect the 1st time, the 3rd time, the 5th, the sodium oxide content of molecular sieve that obtains for the 7th time and the 10th time, result is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to carry out ion-exchange to the slurries containing molecular sieve, unlike, 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 that the upper surface of ion exchange resin bed layer is observed the molecular sieve of deposition is 4mm.The sodium oxide content of the molecular sieve obtained is listed in Table 1.
Comparative example 2
The method identical with embodiment 1 is adopted to carry out ion-exchange to the slurries containing molecular sieve, unlike, average grain diameter for the formation of the non-active particles 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 deposited the molecular sieve that thickness is 4mm on the upper surface of nonactive dielectric layer.The sodium oxide content of the molecular sieve obtained is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to carry out ion-exchange to the slurries containing molecular sieve, unlike, in glass tube, do not pass into air.After ion-exchange terminates, the thickness of the molecular sieve that the upper surface of nonactive dielectric layer deposits is 1.5mm.The sodium oxide content of the molecular sieve obtained, result is listed in Table 1.
Embodiment 3
(1) height be 40cm, internal diameter is fill 150mL ammonium type polystyrene storng-acid cation exchange resin in the glass column of 3.1cm (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 × 14.5, gel-type, average grain diameter is 0.75mm, and CEC is 1.8mmol/mL).(be purchased from Shandong fluorine chemical Co., Ltd of China with polyflon particle, 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 to settle a glass tube above nonactive dielectric layer, 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 200g NaY molecular sieve (in butt) and 1.2g NaCl wherein, stir 30 minutes, obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve step (2) obtained are heated to 70 DEG C, then pump into from top to bottom with the flow velocity of 5mL/min in the ion exchange column of step (1), form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, carry out ion-exchange at 70 DEG C.Meanwhile, pass into air by gas passage in glass tube, intake velocity is 30mL/min.At the slurries through ion-exchange that the received down of ion exchange column flows out from ion exchange column, change a receiving vessel at interval of 20min, get 10 times altogether.
(4) the slurry samples suction filtration through ion-exchange flowed out from ion exchange column step (3) obtained, and the filter cake obtained is carried out drying at 120 DEG C, obtain 10 parts of molecular sieves.
(5) experiment is carried out stopping after 200 minutes, and the upper surface of nonactive dielectric layer is not observed the molecular sieve of deposition.Detect the 1st time, the 3rd time, the 5th, the sodium oxide content of molecular sieve that obtains for the 7th time and the 10th time, result is listed in Table 1.
Comparative example 3
The method identical with embodiment 3 is adopted to carry out ion-exchange, unlike, average grain diameter for the formation of the non-active particles 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 that the upper surface of nonactive dielectric layer deposits is 4mm.The sodium oxide content of the molecular sieve obtained is listed in Table 1.
Embodiment 4
The method identical with embodiment 3 is adopted to carry out ion-exchange, unlike, in glass tube, do not pass into air.The thickness of the molecular sieve that the upper surface of nonactive dielectric layer deposits is 1mm.The sodium oxide content of the molecular sieve obtained is listed in Table 1.
Embodiment 5
(1) height be 40cm, internal diameter is fill 150mL ammonium type weakly acidic cationic exchange resin of acrylic series in the glass column of 3.1cm (to be purchased from Chemical Plant of Nankai Univ., the trade mark is D113, macroporous type, average grain diameter is 0.75mm, and CEC is 4.2mmol/mL).(be purchased from Lingshou County, From Shijiazhuang City of Hebei Province Jian Shi quartz sand factory with quartz sand, 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 to settle a glass tube above nonactive dielectric layer, 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 200g NaY molecular sieve (in butt) wherein, stir 30 minutes, obtain the slurries containing molecular sieve.
(3) slurries containing molecular sieve step (2) obtained are heated to 70 DEG C, then pump into from top to bottom with the flow velocity of 5mL/min in the ion exchange column of step (1), form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, carry out ion-exchange at 70 DEG C.Meanwhile, pass into air by gas passage in glass tube, intake velocity is 20mL/min.At the slurries through ion-exchange that the received down of ion exchange column flows out from ion exchange column, change a receiving vessel at interval of 20min, get 10 times altogether.
(4) the slurry samples suction filtration through ion-exchange flowed out from ion exchange column step (3) obtained, and the filter cake obtained is carried out drying at 120 DEG C, obtain 10 parts of molecular sieves.
(5) experiment is carried out stopping after 200 minutes, and the upper surface of nonactive dielectric layer is not observed the molecular sieve of deposition.Detect the 1st time, the 3rd time, the 5th, the sodium oxide content of molecular sieve that obtains for the 7th time and the 10th time, result is listed in Table 1.
Embodiment 6
(1) height be 40cm, internal diameter is fill 150mL Hydrogen polystyrene storng-acid cation exchange resin in the glass column of 3.1cm (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 × 14.5, gel-type, average grain diameter is 0.75mm, and CEC is 1.8mmol/mL).On the upper surface of ion exchange resin bed layer, the nonactive dielectric layer that thickness is 15mm is formed with polytetrafluoroethylgranule granule (be purchased from Shandong fluorine chemical Co., Ltd of China, average grain diameter is 1.5mm).As shown in Figure 1, a paddle is fixed with rubber stopper at the upper surface of ion exchange resin bed layer.
(2) in beaker, add 2000mL deionized water, and add 200g NaY molecular sieve (in butt) and 2g NaCl wherein, stirring by mechanical agitation obtains containing the slurries of molecular sieve.
(3) slurries containing molecular sieve step (2) obtained are heated to 70 DEG C, then pump into from top to bottom with the flow velocity of 5mL/min in the ion exchange column of step (1), form slurry layer, the height of the slurry layer in ion exchange column is made to remain 35mm, ion-exchange is carried out at 70 DEG C, in ion exchange process, paddle is driven to stir slurry layer with motor.At the slurries through ion-exchange that the received down of ion exchange column flows out from ion exchange column, change a receiving vessel at interval of 20min, get 10 times altogether.
(4) the slurry samples suction filtration through ion-exchange flowed out from ion exchange column step (3) obtained, and the filter cake obtained is carried out drying at 120 DEG C, obtain 10 parts of molecular sieves.
(5) experiment is carried out stopping after 200 minutes, and the upper surface of nonactive dielectric layer is not observed the molecular sieve of deposition.Detect the 1st time, the 3rd time, the 5th, the sodium oxide content of molecular sieve that obtains for the 7th time and the 10th time, result is listed in Table 1.
Embodiment 7
The method identical with embodiment 6 is adopted to carry out ion-exchange, unlike, the glass tube of paddle in embodiment 1 replaces, 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 obtained in molecular sieve is listed in Table 1.
Embodiment 8
(1) height be 40cm, internal diameter is fill 150mL Hydrogen polystyrene storng-acid cation exchange resin in the glass column of 3.1cm (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 × 14.5, gel-type, average grain diameter is 0.65mm, and quality CEC is 1.8mmol/mL).(be purchased from Lingshou County, From Shijiazhuang City of Hebei Province Jian Shi quartz sand factory with quartz sand, 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 to settle a glass tube above nonactive dielectric layer, 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 200g ZSM-5 molecular sieve (in butt) wherein, stirring by mechanical agitation obtains containing the slurries of molecular sieve.
(3) slurries containing molecular sieve step (2) obtained are heated to 70 DEG C, then pump into from top to bottom with the flow velocity of 5mL/min in the ion exchange column of step (1), form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, carry out ion-exchange at 70 DEG C.Meanwhile, pass into air by gas passage in glass tube, intake velocity is 40mL/min.At the slurries through ion-exchange that the received down of ion exchange column flows out from ion exchange column, change a receiving vessel at interval of 20min, get 9 times altogether.
(4) the slurry samples suction filtration through ion-exchange flowed out from ion exchange column step (3) obtained, and the filter cake obtained is carried out drying at 120 DEG C, obtain 9 parts of molecular sieves.
(5) experiment is carried out stopping after 180 minutes, and the upper surface of nonactive dielectric layer is not observed the molecular sieve of deposition.Detect the 1st time, the 3rd time, the 5th, the sodium oxide content of molecular sieve that obtains for the 7th time and the 9th time, result is listed in Table 1.
Embodiment 9
(1) height be 40cm, internal diameter is fill 150mL Hydrogen polystyrene storng-acid cation exchange resin in the glass column of 3.1cm (to be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 × 14.5, gel-type, average grain diameter is 0.65mm, and CEC is 1.8mmol/mL).(be purchased from Ningbo Li Ming Glass Co., Ltd. with glass particle, 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 to settle a glass tube above nonactive dielectric layer, 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 200g NaX molecular sieve (in butt) wherein, stirring by mechanical agitation obtains containing the slurries of molecular sieve.
(3) slurries containing molecular sieve step (2) obtained are heated to 50 DEG C, then pump into from top to bottom with the flow velocity of 5mL/min in the ion exchange column of step (1), form slurry layer, make the height of the slurry layer in ion exchange column remain 35mm, carry out ion-exchange at 50 DEG C.Meanwhile, pass into air by gas passage in glass tube, intake velocity is 30mL/min.At the slurries through ion-exchange that the received down of ion exchange column flows out from ion exchange column, change a receiving vessel at interval of 15min, get 9 times altogether.
(4) the slurry samples suction filtration through ion-exchange flowed out from ion exchange column step (3) obtained, and the filter cake obtained is carried out drying at 120 DEG C, obtain 9 parts of molecular sieves.
(5) experiment is carried out stopping after 135 minutes, and the upper surface of nonactive dielectric layer is not observed the molecular sieve of deposition.Detect the 1st time, the 3rd time, the 5th, the sodium oxide content of molecular sieve that obtains for the 7th time and the 9th time, result is listed in Table 1.
Embodiment 10
The method identical with embodiment 9 is adopted to carry out ion-exchange, unlike, glass tube is not set in ion exchange column, and the amount containing the slurries of molecular sieve in ion exchange column is retained as (that is, V identical with the total measurement (volume) of ion exchange resin bed layer with nonactive dielectric layer
1=V
2).Experiment is carried out stopping after 200 minutes, and the thickness of the molecular sieve that the upper surface of nonactive dielectric layer deposits is 0.8mm.The sodium oxide content of the molecular sieve obtained is listed in Table 1.
Table 1
*: the sodium oxide content of the molecular sieve obtained for the 9th time
As can be seen from Table 1, ion-exchange process of the present invention can avoid or substantially avoid the slurries containing having commutative group, in ion exchange column, sedimentation occurs effectively.
Claims (15)
1. an ion-exchange process, the method comprises the following steps:
(1) ion exchange column with ion exchange resin bed layer is provided;
(2) slurries containing the solid matter with commutative group are sent in described ion exchange column;
(3) make the described slurries containing the solid matter with commutative group flow through described ion exchange resin bed layer, carry out ion-exchange with the ion-exchange group on ion exchange resin; And
(4) slurries containing solid matter flowed out from described ion exchange column are collected;
It is characterized in that, the method is also included in that to carry out step (2) front, on the upper surface of described ion exchange resin bed layer, form nonactive dielectric layer with at least one non-active particles, the ratio of the average grain diameter of the ion-exchange resin particles in the average grain diameter of described non-active particles and described ion exchange resin bed layer is 1.2-5:1.
2. method according to claim 1, wherein, the slurries of the described solid matter containing having 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, with the motion making the slurries in described slurry layer also have 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 the pipeline be immersed in described slurries, and non-active gas is passed 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 upper surface of the lower surface of described pipeline and described nonactive dielectric layer.
4. method according to claim 3, wherein, the lower surface of described pipeline is 1:3-10 to the vertical range of upper surface of described nonactive dielectric layer and the ratio of the height of described slurry layer.
5. method according to claim 3, wherein, the upper surface of described pipeline is 1:3-5 to the vertical range on surface of described slurry layer and the ratio of the height of described slurry layer.
6. according to the method in claim 3-5 described in any one, 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 in volume/hour the speed that passes into and described slurry layer in the ratio of volume of slurries for 40-100 hour
-1.
8. the method according to claim 3 or 7, wherein, described non-active gas is selected from air, nitrogen and group 0 element gas.
9. the ratio of the average grain diameter of the ion-exchange resin particles according to the method in claim 1-4 described in any one, wherein, in the average grain diameter of described non-active particles and described ion exchange resin bed layer is 1.3-3:1.
10. according to the method in claim 1-4 described in any one, wherein, described non-active particles is selected from glass particle, quartz particles and inactive resin particle.
11. according to the method in claim 1-5 and 7 described in any one, wherein, the slurries of the described solid matter containing having 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 in claim 1-5 and 7 described in any one, 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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|---|---|---|---|---|
| CN2408964Y (en) * | 2000-01-31 | 2000-12-06 | 刘澄清 | Float bed type ion-exchanger |
| 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 |
| CN201124095Y (en) * | 2007-10-24 | 2008-10-01 | 何新华 | Full chamber fixed bed counter-current regeneration ion exchanging apparatus |
| CN102452662A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Molecular sieve alkali metal ion exchange method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2408964Y (en) * | 2000-01-31 | 2000-12-06 | 刘澄清 | Float bed type ion-exchanger |
| 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 |
| CN201124095Y (en) * | 2007-10-24 | 2008-10-01 | 何新华 | Full chamber fixed bed counter-current regeneration ion exchanging apparatus |
| CN102452662A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Molecular sieve alkali metal ion exchange method |
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