CN103769250B - A kind of ion-exchange process - Google Patents
A kind of ion-exchange process Download PDFInfo
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- CN103769250B CN103769250B CN201210414004.5A CN201210414004A CN103769250B CN 103769250 B CN103769250 B CN 103769250B CN 201210414004 A CN201210414004 A CN 201210414004A CN 103769250 B CN103769250 B CN 103769250B
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- molecular sieve
- exchange resin
- ion exchange
- ion
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Abstract
The invention provides a kind of ion-exchange process, the method is carried out in a kind of device, described device comprises exchange area and renewing zone and material switch unit, described exchange area and renewing zone have material inlet, material outlet and ion exchange resin bed layer that at least one is formed by form ion exchange resin separately, and ion exchange resin bed layer is between described material inlet and material outlet; The material that material switch unit is configured to make to flow through regional switches by following direction in time: the material flowing through exchange area is switched to renewing zone, and the material flowing through renewing zone is switched to exchange area.In the molecular sieve obtained by method of the present invention, the stable content of commutative group.Method of the present invention can realize the continuous operation of ion-exchange and ion exchange resin regeneration, improves the efficiency of ion-exchange.Method of the present invention has maximally utilised the ion-exchange group in ion exchange resin, improves the effective rate of utilization of ion exchange resin.
Description
Technical field
The present invention relates to a kind of ion-exchange process, particularly a kind of method of molecular sieve being carried out to ion-exchange.
Background technology
Molecular sieve, as solid acid catalyst, is widely used in petrochemical process.Molecular screen primary powder is generally Na type, and need make H type could use as the active component of acidic catalyst.
For Y zeolite production process, molecular screen primary powder NaY first exchanges through ammonium and makes NH
4type molecular sieve NH
4y, more just can be converted into H type molecular sieve HY through roasting.Wherein, ammonium exchange process is mixed with ammonium salt (as ammonium sulfate) solution by molecular screen primary powder NaY, the Na in molecular sieve
+with the NH in solution
4 +exchange, generate NH
4type molecular sieve.Due to the restriction of chemical balance and molecular sieve structure, NH
4 +once can not replace Na completely
+, in order to obtain Na
2the molecular sieve that O content is low, ammonium exchange process needs repeatedly, thus can produce the waste water that a large amount of ammonium nitrogen exceeds standard.Current catalyst plant often produces 1 ton of finished product Y zeolite, produces about 20 tons of NH
4 +mass concentration is about the waste water of 5000 ~ 6000mg/L.
Specify in the industrial wastewater discharge standard GB8978-1996 that country formulates: petrochemical industry ammonium nitrogen wastewater first discharge standard is NH
4 +mass concentration is less than 15mg/L, and secondary discharge standard is NH
4 +mass concentration is less than 50mg/L.In order to meet NH
4 +mass concentration is less than the discharging standards of 15mg/L, needs to process ammonia-nitrogen sewage, and energy consumption is large, cost is high.Therefore, in order to the requirement that the environmental regulation and factory that meet increasingly stringent are increased economic efficiency, to clean and the molecular sieve of low cost takes off Na in the urgent need to exploitation
+technology.
JP63159218A discloses one makes spent ion exchange resin reduce Na in NaY molecular sieve
+the method of content.Its processing procedure fully contacts with molecular sieve for making form ion exchange resin, at the temperature of 40 ~ 80 DEG C, exchanges certain hour.The hydrogen type molecular sieve that NaO content is less than 1 % by weight is obtained after twice exchange process.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.
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.Although the sodium oxide content in molecular sieve can be dropped to less than 3 % by weight at the initial stage of ion-exchange by the method, but along with the carrying out of ion-exchange, sodium oxide content in the molecular sieve obtained constantly rises, and causes sodium oxide content in the zeolite product finally obtained very uneven.
Summary of the invention
The object of the invention is to overcome existing employing ion exchange resin column when ion-exchange is carried out to molecular sieve, there is the carrying out with ion-exchange, sodium oxide content in the molecular sieve obtained constantly rises, and causes the problem that in the zeolite product finally obtained, sodium oxide content is very uneven.
The present inventor finds in research process, if arrange many radical ions exchange column, by the kind of many radical ions exchange column according to the material flow through, be divided into exchange area and renewing zone, and in time the material variety flowing through each district is switched by certain direction, the changes of contents of the commutative group in the molecular sieve of ion-exchange obtained is little, can stably be within preset range; The serialization of ion-exchange and ion exchange resin regeneration and transition can also be realized to run simultaneously.Complete the present invention on this basis.
The invention provides a kind of ion-exchange process, the method is carried out in a kind of device, described device comprises exchange area and renewing zone and material switch unit, described exchange area and renewing zone have material inlet, material outlet and ion exchange resin bed layer that at least one is formed by form ion exchange resin separately, described ion exchange resin bed layer at least part of between described material inlet and material outlet;
The method comprises: in exchange area, the slurries containing molecular sieve are made to flow through ion exchange resin bed layer, make the commutative group in described molecular sieve and the hydrogen ion in ion exchange resin carry out ion-exchange, and collect the slurries containing molecular sieve flowed out from described ion exchange resin bed layer; And
In renewing zone, acid solution is made to flow through ion exchange resin bed layer, with by the ion exchange resin regeneration in ion exchange resin bed layer;
The material that described material switch unit is configured to make to flow through regional switches by following direction in time: the material flowing through exchange area is switched to renewing zone, and the material flowing through renewing zone is switched to exchange area.
Undertaken in the molecular sieve that ion-exchange obtains by ion-exchange process of the present invention, the stable content of commutative group.Meanwhile, method of the present invention can also realize the continuous operation of ion-exchange and ion exchange resin regeneration, improves the efficiency of ion-exchange.In addition, method of the present invention has maximally utilised the ion-exchange group in ion exchange resin, improves the effective rate of utilization of ion exchange resin, extends the service life of ion exchange resin, reduces the cost of ion-exchange.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the schematic diagram that the import and export position of material carries out switching by ion-exchange process of the present invention in time, wherein, (a) for the time be t
0time material import and export position, (b) for the time be t
0material import and export position during+Δ t;
Fig. 2 is according to the one of ion-exchange process of the present invention preferred embodiment;
A kind of mode of Fig. 3 for illustration of the slurries containing molecular sieve obtained in ion-exchange process of the present invention and the cyclone hydraulic separators of which use;
Fig. 4 is for illustration of the concrete operations flow process adopting cyclone hydraulic separators to obtain the slurries containing molecular sieve in method of the present invention;
Fig. 5 carries out a kind of embodiment of disturbance to the slurry layer formed by the slurries containing molecular sieve for illustration of ion-exchange process according to the present invention;
Fig. 6 carries out the one of disturbance preferred embodiment for illustration of ion-exchange process according to the present invention to the slurry layer formed by the slurries containing molecular sieve;
Pipeline stabilization to when carrying out disturbance by the slurry layer formed containing the slurries of molecular sieve, is placed in a kind of embodiment in slurry layer for illustration of ion-exchange process according to the present invention by Fig. 7; And
Fig. 8 is for illustration of a kind of preferred embodiment of the ion exchange resin bed layer in the exchange area of ion-exchange process of the present invention.
Detailed description of the invention
The invention provides a kind of ion-exchange process, the method is carried out in a kind of device, described device comprises exchange area and renewing zone and material switch unit, described exchange area and renewing zone have material inlet, material outlet and ion exchange resin bed layer that at least one is formed by form ion exchange resin separately, described ion exchange resin bed layer at least part of between described material inlet and material outlet;
The method comprises: in exchange area, the slurries containing molecular sieve are made to flow through ion exchange resin bed layer, make the commutative group in described molecular sieve and the hydrogen ion in ion exchange resin carry out ion-exchange, and collect the slurries containing molecular sieve flowed out from described ion exchange resin bed layer; And
In renewing zone, acid solution is made to flow through ion exchange resin bed layer, with by the ion exchange resin regeneration in ion exchange resin bed layer;
(namely described material switch unit is configured to make to flow through the material of regional, the material of regional to be passed through) switch by following direction in time: the material flowing through exchange area is switched to renewing zone, the material flowing through renewing zone is switched to exchange area.
According to method of the present invention, can the ion exchange resin bed layer after regeneration be directly switch in exchange area, for ion-exchange.
One of the present invention preferred embodiment in, described device also comprises flushing one district, described flushing one district has material inlet, material outlet and ion exchange resin bed floor that at least one is formed by form ion exchange resin, described ion exchange resin bed layer at least part of between described material inlet and material outlet; The method also comprises: in flushing one district, makes water flow through ion exchange resin bed layer; The material that described material switch unit is configured to make to flow through regional switches by following direction in time: the material flowing through exchange area is switched to flushing one district, the material flowing through flushing one district is switched to renewing zone, the material flowing through renewing zone is switched to exchange area.
According to this preferred embodiment, by arranging flushing one district, after ion exchange resin after regeneration is first rinsed with water, then in exchange area with containing the slurry liquid contacts of molecular sieve, the acid solution remained in regenerative process in ion exchange resin bed layer can be rinsed well.
In another embodiment of the invention, described device also comprises flushing two district, described flushing two district has material inlet, material outlet and ion exchange resin bed floor that at least one is formed by form ion exchange resin, described ion exchange resin bed layer at least part of between described material inlet and material outlet; The method also comprises: in flushing two district, makes water flow through ion exchange resin bed layer; The material that described material switch unit is configured to make to flow through regional switches by following direction in time: the material flowing through exchange area is switched to renewing zone, the material flowing through renewing zone is switched to flushing two district, the material flowing through flushing two district is switched to exchange area.
By arranging flushing two district, with water, the ion exchange resin bed layer having carried out ion-exchange is rinsed, the molecular sieve remained in ion exchange process in ion exchange resin bed layer can be gone out, reduce the cumulant of molecular sieve in ion exchange resin bed layer, thus extend the continuous operating time of method of the present invention further.From the angle improving the developing result in flushing two district further, the flow direction of water in the ion exchange resin bed floor in flushing two district is contrary with the flow direction of slurries in this ion exchange resin bed floor containing molecular sieve in exchange area.
One of the present invention more preferred embodiment in, described device also comprises described flushing one district and described flushing two district, also comprise according to method of the present invention and described material switch unit is arranged to: the material flowing through exchange area is switched to flushing one district, the material flowing through flushing one district is switched to renewing zone, the material flowing through renewing zone is switched to flushing two district, the material flowing through flushing two district is switched to exchange area.
According to method of the present invention, the water flowing through the ion exchange resin bed floor in flushing one district and flushing 2nd district is preferably deionized water.
According to method of the present invention, described material switch unit is used for switching the flow direction of material, thus the material flowing through regional is switched according to predetermined direction in time.Described material switch unit can be the various parts that can realize above-mentioned functions, such as magnetic valve.
According to method of the present invention, on the opportunity switched the material flowing through regional by material switch unit, can be arranged to switch according to fixed time interval, also can carry out suitable selection according to the ion-exchange degree of exchange area.Such as: can in ion exchange process, detect the content of the commutative group on the molecular sieve in the slurries flowed out from the ion-exchange bed of exchange area, and calculate the degree of ion-exchange, can not meet the demands (namely in the degree of ion-exchange, the degree of described ion-exchange is lower than the degree of predetermined ion-exchange) time, switched the material flowing through regional by material switch unit, the degree of described ion-exchange is defined by formula (I):
In formula I, c
1for the content without the commutative group on the molecular sieve of ion-exchange;
C
2for the content of the commutative group on the molecular sieve after ion-exchange.
According to method of the present invention, the various methods that this area can be adopted to commonly use, to measure the content of the commutative group on molecular sieve, repeat no more herein.
The material flowing through regional is switched by material switch unit according to fixed time interval in the embodiment of the present invention.
Fig. 1 shows according to method of the present invention in time by schematic diagram that material switch unit switches the material flowing through regional.
As shown in (a) in Fig. 1, be t in the time
0time, the material entered in the ion exchange resin bed layer a of ion exchange resin bed layer a and b be connected in series is the slurries A containing molecular sieve
i, be the slurries A containing molecular sieve through ion-exchange from the material of ion exchange resin bed layer b outflow
o; The material entered in the ion exchange resin bed layer c of ion exchange resin bed layer c and d be connected in series is water B
i, the material flowed out from ion exchange resin bed layer d is water B
o, water B
ocontaining the acid remained in regenerative process in ion exchange resin bed layer; The material entered in the ion exchange resin bed layer e of ion exchange resin bed layer e and f be connected in series is acid solution C
i, the material flowed out from ion exchange resin bed layer f is regeneration liquid waste C
o; The material entered in the ion exchange resin bed layer g of ion exchange resin bed layer g and h be connected in series is water D
i, the material flowed out from ion exchange resin bed layer h is water D
o, water D
obe entrained with in ion exchange process the molecular sieve be deposited in ion exchange resin bed layer.Now, the I district that ion exchange resin bed floor a and b is formed is exchange area, the II district that ion exchange resin bed floor c and d is formed is flushing one district, and the III district that ion exchange resin bed floor e and f is formed is renewing zone, and the IV district that ion exchange resin bed floor g and h is formed is flushing two district.
As shown in (b) in Fig. 1, be t in the time
0during+Δ t, by material switch unit, will at t
0time flow through ion exchange resin bed layer a and b material switch in ion exchange resin bed layer c and d, will at t
0time flow through ion exchange resin bed layer c and d material switch in ion exchange resin bed layer e and f, will at t
0time flow through ion exchange resin bed layer e and f material switch in ion exchange resin bed layer g and h, will at t
0time flow through ion exchange resin bed layer g and h material switch in ion exchange resin bed layer a and b.After switching, the I district that ion exchange resin bed floor a and b is formed is flushing two district, the II district that ion exchange resin bed floor c and d is formed is exchange area, and the III district that ion exchange resin bed floor e and f is formed is flushing one district, and the IV district that ion exchange resin bed floor g and h is formed is renewing zone.
According to method of the present invention, while the material flowing through regional is switched, correspondingly the receiving vessel of the material flowed out from regional is switched by material switch unit.
By being seated in tubular container by ion exchange resin, thus ion exchange resin bed layer can be formed.According to method of the present invention, multistage ion exchange resin bed layer can be formed in a tubular container, and multistage ion exchange resin bed layer is divided into many groups, at each group, material inlet and material outlet are set, according to the difference of the material passed in each group, be divided into exchange area, renewing zone and optional flushing one district and rinse 2nd district; Also ion exchange resin can be seated in different tubular containers, form multiple ion exchange column, and multiple ion exchange column is divided into different districts, ion exchange column in each district is connected in series or in parallel, according to the difference of the material passed in each group, be divided into exchange area, renewing zone and optional flushing one district and rinse 2nd district.
Fig. 2 shows a kind of embodiment of method of the present invention.As shown in Figure 2, arrange the many radical ions exchange column be connected in series, many radical ions exchange column is divided into four groups, often group arranges material inlet and material outlet.Be t in the time
0time, ion exchange column i and j forms exchange area, and its material inlet is communicated with the storage tank E containing molecular sieve pulp by magnetic valve C1, and material outlet is communicated with zeolite product storage tank I by magnetic valve C2; Ion exchange column k and l forms flushing one district, and its material inlet is communicated with tank F by magnetic valve C3, and material outlet is communicated with spent acid liquid bath J by magnetic valve C4; Ion exchange column m and n forms renewing zone, and its material inlet is communicated with acid solution storage tank G by magnetic valve C5, and material outlet is communicated with waste liquid tank K by magnetic valve C6; Ion exchange column p and q forms flushing two district, and its material inlet is communicated with tank H by magnetic valve C7, and material outlet is communicated with waste liquid tank L by magnetic valve C8.In the slurries that the material outlet place of exchange area obtains, the content of the commutative group on molecular sieve higher than predetermined content (namely, the degree of ion-exchange is lower than predetermined value) time or preset time interval of switching, by each magnetic valve above-mentioned, the direction of the material entering material inlet according to two districts → exchange area, one district → renewing zone, exchange area → rinse → rinse is switched, the kind of the storage tank that corresponding switching is simultaneously communicated with material outlet.Wherein, symbol " → " represents the direction switched.
According to method of the present invention, in described exchange area, flow through ion exchange resin bed layer containing in the slurries of molecular sieve, the particle diameter of molecular sieve can be the routine selection of this area.Preferably, the described particle diameter containing the molecular sieve in the slurries of molecular sieve meets following condition:
(1) volume average particle size is less than 15 μm;
(2) D
90be less than 30 μm, D
90particle diameter corresponding when representing that cumulative particle sizes percentile reaches 90 volume %; And
(3) average grain diameter of described ion exchange resin and the ratio of the described volume average particle size containing the molecular sieve in the slurries of molecular sieve are 40 ~ 150.
When the described particle diameter containing the molecular sieve in the slurries of molecular sieve meets above-mentioned condition, can more effectively avoid in ion exchange process, molecular sieve in described slurries is deposited in ion exchange resin bed layer, thus the serialization improving method of the present invention further runs degree.
More preferably, the described volume average particle size containing the molecular sieve in the slurries of molecular sieve is 5 ~ 15 μm, D
90be 10 ~ 30 μm, the average grain diameter of described ion exchange resin and the ratio of the described volume average particle size containing the molecular sieve in the slurries of molecular sieve are 40 ~ 150.Further preferably, the described volume average particle size containing the molecular sieve in the slurries of molecular sieve is 8 ~ 15 μm, D
90be 10 ~ 25 μm, the average grain diameter of described ion exchange resin and the ratio of the described average grain diameter containing the molecular sieve in the slurries of molecular sieve are 40 ~ 125.
The described volume average particle size containing the molecular sieve in the slurries of molecular sieve and D
90adopt to be purchased to measure from the Mastersizer2000 type laser fineness gage of Malvern company of Britain; The average grain diameter of described ion exchange resin is the diameter measuring each particle by getting 100 ion-exchange resin particles slide measures, and the mean value calculating the diameter measured obtains.When calculating the ratio of the average grain diameter of described ion exchange resin and the average grain diameter of molecular sieve, both adopt identical dimension.
Conventional various methods can be adopted to meet the slurries of above-mentioned requirements to the particle diameter obtaining slurries Middle molecule sieve.Such as: molecular sieve can be sieved, obtain the molecular sieve that particle diameter meets described requirement above, and this molecular sieve is dispersed in water, thus the particle diameter obtaining molecular sieve wherein meets the slurries containing molecular sieve of described requirement above; Molecular sieve can also be dispersed in water, the dispersion liquid obtained is carried out homogenize in homogenizer, thus the particle diameter obtaining molecular sieve wherein meets the slurries containing molecular sieve of described requirement above.Adjust the service condition of homogenizer, to carry out homogenize to the dispersion liquid containing molecular sieve, thus the method making the particle diameter of the molecular sieve in dispersion liquid meet pre-provisioning request is known in those skilled in the art, repeats no more herein.The present invention is not particularly limited for the consumption of water, as long as can form uniform dispersion liquid.
The angle of degree is run from the serialization improving method of the present invention further, the described slurries containing molecular sieve are obtained: be scattered in water by molecular sieve and form dispersion liquid preferably by the method comprised the following steps, described dispersion liquid is sent in cyclone hydraulic separators, carry out rotary filter press, obtain the described slurries containing molecular sieve from the overfall of described cyclone hydraulic separators.Particularly, as shown in Figure 3, can described dispersion liquid be entered the tangential feeding cyclone hydraulic separators of the cylindrical portions of opening's edge cyclone hydraulic separators from cyclone hydraulic separators, rotation limit, described dispersion liquid limit is moved downward, molecular sieve in dispersion liquid is thrown to wall under the effect of rotary centrifugal force, carry out sedimentation separation, the solid particle of the sedimentation by centrifugal intertia force is drawn off by the underflow opening of the vertex of a cone, the liquid comparatively clarified is with internal layer spiral, and discharge at the overfall place that top center is offered, thus obtain the described slurries containing molecular sieve.
The present invention is not particularly limited for the structure of described cyclone hydraulic separators and operating condition, conventional various cyclone hydraulic separators can be adopted, the kind containing the molecular sieve in the slurries of molecular sieve according to carrying out rotary filter press selects suitable operating condition, meets previously described requirement be as the criterion to make the particle diameter containing the molecular sieve in the slurries of molecular sieve of acquisition.In one embodiment of the invention, with reference to Fig. 3, the intake port d of described cyclone hydraulic separators
ican be the drum diameter D's of this cyclone hydraulic separators
the drum diameter D of described cyclone hydraulic separators, overflow diameter d
0and underflow tap diameter d
upreferably meet
(wherein, D is preferably 0.1 ~ 0.5m); The cone angle of the conical section of described cyclone hydraulic separators can be 10 ° ~ 20 °, is preferably 10 ° ~ 15 °; The length L of overfall can be (0.33 ~ 0.45) D, is preferably (0.37 ~ 0.45) D.Those skilled in the art can select suitable operating condition according to the concrete structure of cyclone hydraulic separators and the character of carrying out the dispersion liquid be separated under the guidance of Conventional wisdom, to obtain the spillage meeting instructions for use, repeat no more herein.
The conventional various methods in this area can be adopted to obtain described dispersion liquid, such as: by molecular sieve and water being carried out mixing in beater pulling an oar, thus described dispersion liquid can be obtained.The slurries flowed out from the underflow opening of described cyclone hydraulic separators again can be sent into beater and pull an oar, and then send in cyclone hydraulic separators and be separated.
According to method of the present invention, when adopting cyclone hydraulic separators to obtain the described slurries containing molecular sieve, as shown in Figure 4, the slurries pump 2 exported by making beating tank 1 can be delivered in cyclone hydraulic separators 3 and be separated, the slurries containing molecular sieve obtained by overfall from cyclone hydraulic separators 3 are sent in exchange area, carry out ion-exchange, the slurries exported from the underflow opening of cyclone hydraulic separators 3 are again sent into making beating tank 1 and are pulled an oar.
In the process of ion-exchange, be generally formed on the upper surface of the ion exchange resin bed layer of exchange area by the described slurry layer formed containing the slurries of molecular sieve.The present inventor find to adopt in following two kinds of modes in research process one or both can effectively avoid or substantially avoid the molecular sieve in slurry layer to be deposited on the surface of ion exchange resin bed layer further: (1) is before by the slurries feeding ion exchange column containing molecular sieve, be 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, the slurries containing molecular sieve are made to enter in ion exchange resin bed layer by described nonactive dielectric layer, (2) disturbance is carried out to described slurry layer, with the motion making the slurries in described slurry layer also have non-gravity direction.
One of the present invention preferred embodiment in, ion-exchange process of the present invention also comprises: in exchange area, disturbance is carried out, with the motion making the slurries in described slurry layer also have non-gravity direction to the slurry layer formed on the upper surface of described ion exchange resin bed layer by the described slurries containing molecular sieve.
The conventional various methods in this area 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 5, can, by arranging paddle 6 in the slurry layer 5 in the container 4 holding ion exchange resin bed layer, paddle 6 be driven to carry out disturbance to described slurry layer 5.
One of the present invention preferred embodiment in, as shown in Figure 6, the mode of described slurry layer being carried out to disturbance comprises: in slurry layer 5, arrange the pipeline 7 be immersed in slurries, and in pipeline 7, pass into non-active gas (such as: pass into non-active gas by gas passage 8 in pipeline 7), Existential Space between the inwall of the outer wall of pipeline 7 and the container 4 of accommodation ion exchange resin bed layer, and Existential Space between the upper surface of the lower surface of pipeline 7 and ion exchange resin bed layer, Existential Space between the upper surface of pipeline 7 and the upper surface of slurry layer 5.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 rising 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 molecular sieve 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.Pipeline particular location in slurry layer is not particularly limited, and is as the criterion can realize above-mentioned functions.
The external diameter of described pipeline can carry out suitable selection according to the internal diameter of described ion exchange column.Preferably, the external diameter of described pipeline is 0.4 ~ 0.6:1 with the ratio of the internal diameter of the container of the described ion exchange resin bed layer of accommodation.
Conventional various methods can be adopted to be placed in slurry layer by described pipeline, such as: as shown in Figure 7, in the slurry layer that support 14 can be used stably to be placed in by pipeline 7 in the container 4 holding ion exchange resin bed layer, with support 13, gas passage 8 is stably placed in slurry layer, wherein, support 14 is supported by the inwall of the container 4 holding ion exchange resin bed layer, and support 13 is supported by the inwall of pipeline 7.
Can there is not chemically interactive gas with the described slurries containing molecular sieve and ion exchange resin 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).
The intake of described non-active gas is as the criterion effectively can prevent the molecular sieve generation sedimentation in the described slurries containing molecular sieve.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 30 ~ 100:1.
According to method of the present invention, can all arrange above-mentioned pipeline in regional, the material passed into when the material inlet in this region is the slurries containing molecular sieve, when becoming exchange area, in pipeline, pass into non-active gas, disturbance is carried out to the slurry layer formed by the slurries containing molecular sieve.
In another preferred embodiment of the present invention, before method of the present invention is also included in and carries out described ion-exchange, on the upper surface of described ion exchange resin bed layer, nonactive dielectric layer is formed with non-active particles, make the described slurries containing molecular sieve successively flow through described nonactive dielectric layer and described ion exchange resin bed layer, the ratio of the average grain diameter of described non-active particles and the average grain diameter of described ion-exchange resin particles is 1.2 ~ 5:1.From the angle improving further the molecular sieve generation sedimentation prevented in slurry layer, 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.The average grain diameter of described non-active particles is the diameter measuring each non-active particles by getting 100 non-active particles slide measures, 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 containing at least one molecular sieve and ion exchange resin generation chemical interaction.Usually, described non-active particles can be selected from glass particle, quartz particles and inactive resin particle (as polytetrafluoroethylgranule granule).
When the upper surface being also included in ion exchange resin bed layer according to method of the present invention forms nonactive dielectric layer, slurries containing molecular sieve are being admitted to after in ion exchange column, first flow through the gap between non-active particles in 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 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 upper surface of nonactive dielectric layer to the upper surface of ion exchange resin bed layer vertical range (namely, the height of nonactive dielectric layer) with the upper surface of slurry layer to the upper surface of nonactive dielectric layer vertical range (namely, the height of slurry layer) ratio can be 1:1.1 ~ 5, be preferably 1:1.5 ~ 3.5.By regulating the speed in the container of the slurries feeding accommodation ion exchange resin bed layer containing molecular sieve, the amount containing the slurries of molecular sieve in ion exchange column can be controlled, no longer describes in detail herein.In the present invention, when the upper surface of ion exchange resin bed layer does not have nonactive dielectric layer, slurry layer refers to the layer that the upper surface of the ion exchange resin bed layer of the slurries containing molecular sieve is formed; When the upper surface of ion exchange resin bed layer is formed with nonactive dielectric layer, slurry layer refers to the layer that the slurries containing molecular sieve are formed on the upper surface of nonactive dielectric layer.
According to method of the present invention, when the upper surface of described nonactive dielectric layer is also formed with slurry layer, from the further angle improving the effect of the molecular sieve generation sedimentation prevented in described slurry layer, method according to the present invention comprises the previously described mode of employing and carries out disturbance (as illustrated in Figures 5 and 6 to described slurry layer, the upper surface of the ion exchange resin bed layer 10 in the container 4 holding ion exchange resin bed layer forms nonactive dielectric layer 11 with described non-active particles, and paddle 6 is set in slurry layer 5, or pipeline 7 is set in slurry layer 5, non-active gas is passed into) in pipeline 7, and preferably by settling pipeline and pass into non-active gas in described slurry layer in described pipeline, disturbance is carried out to described slurry layer.
By in described slurry layer, settle pipeline and pass in described pipeline non-active gas disturbance is carried out to described slurry layer time, 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 upper surface of vertical range and the slurry layer of the upper surface of described nonactive dielectric layer to the ratio of the vertical range of the upper surface of nonactive dielectric layer, preferably 1:5 ~ 10.The ratio of the vertical range on the upper surface of described pipeline to the surface of described slurry layer and the upper surface of the slurry layer extremely vertical range of the upper surface of nonactive dielectric layer can be 1:2 ~ 5.In described slurry layer, settle pipeline and in pipeline, pass into non-active gas and described slurry layer is carried out to all the other conditions of disturbance with described identical above, do not repeat them here.
Fig. 8 shows a kind of preferred embodiment of the ion exchange column in exchange area.As shown in Figure 8, hold in the container 4 of ion exchange resin bed layer and there is ion exchange resin bed layer 10, the nonactive dielectric layer 11 be formed on the upper surface of ion exchange resin bed layer 10, being placed in above nonactive dielectric layer 11 and its lower surface with the pipeline 7 of the upper surface Existential Space of nonactive dielectric layer 11, for carrying this slurries conveyance conduit of slurries conveyance conduit 12(of the slurries containing molecular sieve to be preferably communicated with the overfall of previously described cyclone hydraulic separators) and gas passage 8 for passing into non-active gas.During operation, slurries containing molecular sieve are sent into by slurries conveyance conduit 12 in the container 4 holding ion exchange resin bed layer, the upper surface of nonactive dielectric layer 11 forms slurry layer 5, slurries are made to enter ion exchange resin bed layer 10 by nonactive dielectric layer 11, to carry out ion-exchange, in pipeline 7, pass into non-active gas by gas passage 8, to carry out disturbance to slurry layer 5 simultaneously.
According to method of the present invention, 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.
According to method of the present invention, described molecular sieve is preferably the molecular sieve except Y zeolite and X-type molecular sieve, its instantiation can include but not limited to: 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, MCM-56 type molecular sieve, 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, MeAPO-11 type molecular sieve, 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, obtains hydrogen type molecular sieve.
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: the temperature of ion-exchange can be 25 ~ 100 DEG C, 50 ~ 80 DEG C are preferably.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.The described flow velocity of slurries in ion exchange resin bed layer containing molecular sieve can be conventional selection.Usually, the described flow velocity of slurries in ion exchange resin bed layer containing molecular sieve can be 2 ~ 20mL/min, is preferably 2 ~ 10mL/min.In the described slurries containing molecular sieve, the ratio of molecular sieve and water can be that the routine of this area is selected.Usually, the weight ratio of molecular sieve and water can be 1:5 ~ 50, is preferably 1:5 ~ 20.
According to method of the present invention, by acid solution, the method that the ion exchange resin bed layer through ion-exchange regenerates is not particularly limited, can regenerates under the normal condition of this area.Particularly, the various acidic aqueous solutions that described acid solution can be commonly used for this area, such as can for containing HCl, H
2sO
4and HNO
3in one or more the aqueous solution.The present invention is also not particularly limited for the concentration of described acid solution, and usually, the concentration of described acid solution can be 0.1 ~ 3mol/L, is preferably 1 ~ 3mol/L.The temperature of described acid solution can be 0 ~ 30 DEG C.The flow velocity in ion exchange resin bed layer of described acid solution can be 1 ~ 50mL/min, is preferably 5 ~ 20mL/min.
According to the inventive method, the operating condition for flushing one district and flushing 2nd district is not particularly limited, as long as the molecular sieve be deposited in ion exchange resin bed layer and the acid solution remained in ion exchange resin bed layer can be gone out.Usually, the flow velocity of water in flushing one district can be 1 ~ 50mL/min, is preferably 10 ~ 40mL/min; The temperature of rinsing a district can be 0 ~ 30 DEG C.The flow velocity of water in flushing two district can be 1 ~ 50mL/min, is preferably 5 ~ 40mL/min; The temperature of rinsing 2nd district can be 0 ~ 30 DEG C.
According to method of the present invention, from guaranteeing when switching, regeneration task in renewing zone, rinse a district and rinse 2nd district all completed prerequisite of flushing task under, from reducing the use amount of acid solution in renewing zone and rinsing a district and rinse the angle of consumption of water in 2nd district, the slurries containing molecular sieve in exchange area: rinse the water in 2nd district: the acid solution in renewing zone: the ratio rinsing the flow velocity of the water in a district is preferably 1:1 ~ 2:1 ~ 4:1 ~ 4.
According to method of the present invention, the exchange capacity forming the form ion exchange resin of ion exchange resin bed layer 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.CEC 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 resin of ion exchange resin, such as: polystyrene resin or acrylic resin.
According to method of the present invention, the ion-exchange initator that can promote ion-exchange that the described slurries containing molecular sieve can also be commonly used containing 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.Preferably, described ion-exchange initator is selected from the water soluble salt of organic acid water soluble salt and inorganic acid.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 be described containing 0.001 ~ 2 % by weight of the molecular sieve in the slurries of molecular sieve, be preferably described containing 0.01 ~ 1 % by weight of the molecular sieve in the slurries of molecular sieve, be more preferably described containing 0.1 ~ 1 % by weight of the molecular sieve in the slurries of molecular sieve.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, adopt the content being purchased and being measured commutative group in molecular sieve from Rigaku D/MAX-IIIA type X-ray fluorescence spectrometer by X fluorescence spectrum method, wherein, adopt rhodium target, excitation power source is 50kV, and excitation current is 50mA.
In following examples, the average grain diameter of described non-active particles and ion exchange resin is the diameter 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 described volume average particle size containing the molecular sieve in the slurries of molecular sieve and D
90adopt to be purchased to measure from the Mastersizer2000 type laser fineness gage of Malvern company of Britain.
In following examples and comparative example, X-ray diffraction (that is, XRD) method is adopted to measure the degree of crystallinity of molecular sieve.
The molecular sieve that following examples and comparative example use is purchased from Chemical Plant of Nankai Univ., wherein:
The trade mark be 001 × 7 polystyrene storng-acid cation exchange resin be gel-type, average grain diameter is 0.65mm, and volume CEC is 1.8mmol/mL;
The trade mark be 001 × 14.5 polystyrene storng-acid cation exchange resin be gel-type, average grain diameter is 0.75mm, and volume CEC is 1.8mmol/mL;
The trade mark is the weakly acidic cationic exchange resin of acrylic series of D113 is macroporous type, and average grain diameter is 0.75mm, and volume CEC is 4.2mmol/mL.
In following examples and comparative example, the ZSM-5 molecular sieve of use 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 ~ 200 μm;
The beta-molecular sieve used is purchased from China Petrochemical Industry's catalyst Chang Ling branch company, Na
2o content is 2.2wt%, and degree of crystallinity is 78%, and particle diameter is 1 ~ 300 μm.
In following examples and comparative example, butt is by by sample at the temperature of 800 DEG C dry 2 hours and measure.
In following examples, flow through flushing one district and rinse 2nd district be deionized water, the temperature of deionized water is normal temperature (being 25 DEG C).
Embodiment 1 ~ 11 is for illustration of ion-exchange process of the present invention.
Embodiment 1
8 radical ion exchange columns are used in the present embodiment, as shown in Figure 1,8 radical ion exchange columns are divided into four districts: I district, II district, III district and IV district, there are 2 ion exchange columns be connected in series in each district, and material inlet and the material outlet place in each district are provided with magnetic valve.Wherein, every root internal diameter is load the form ion exchange resin that the 60mL trade mark is 001 × 7 in the ion exchange column of 2cm.
In beaker, add 5000mL deionized water, and add 500gZSM-5 molecular sieve (butt) and 9g wherein as the NaCl of ion-exchange initator, obtain dispersion liquid.The dispersion liquid obtained is sent into cyclone hydraulic separators (with reference to Fig. 3, drum diameter D=0.2m, intake port d with the flow velocity of 600mL/min
i=0.028m, taper angle theta=15 °, overflow pipe length L=0.09m, cylinder heights H
1=0.2m, d
0=d
u=0.04m) in, and obtain the slurries containing molecular sieve from the overfall of cyclone hydraulic separators.After testing, the average grain diameter containing the molecular sieve in the slurries of molecular sieve obtained is 12 μm, D
90it is 20 μm.
Compound concentration is the HCl aqueous solution of 1mol/L, as acid solution, for renewing zone.
(1) send in I district, II district, III district and IV district respectively by the slurries containing molecular sieve obtained, water, acid solution and water, the time is t
0time, I district is exchange area, and II district is flushing one district, III district is renewing zone, IV district is flushing two district.Send into exchange area, rinse 2nd district, the flow velocity of the material in renewing zone and flushing one district is respectively 5mL/min, 6mL/min, 5mL/min and 8mL/min.Wherein, temperature containing the slurries of molecular sieve is 70 DEG C, and the temperature of acid solution is 25 DEG C, in exchange area, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, the thickness of the slurry layer that the slurries containing molecular sieve are formed on the upper surface of the first radical ion exchanger resin bed is 50mm.
Material is switched according to the direction of two districts → exchange area, one district → renewing zone, exchange area → rinse → rinse every 70min magnetic valve.
Collect the slurries containing molecular sieve flowed out from exchange area, and, sample 40mL every 30min, get 10 times altogether.
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the average thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 0.5mm.
(3) carry out suction filtration by what get at every turn containing the slurries of molecular sieve, by the filter cake that obtains 120 DEG C of oven dry, obtain 10 parts of molecular sieves.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Comparative example 1
Adopt the method identical with embodiment 1 to load 2 radical ion exchange resin columns, and 2 radical ion exchange resin columns are connected in series, the slurries containing molecular sieve identical with embodiment 1 are sent in ion exchange column, carries out ion-exchange.What flow out at ion exchange resin column received down contains molecular sieve pulp, wherein, samples 40mL, get 10 times altogether, thus obtain 10 parts of molecular sieves every 30min.
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 2.4mm.
Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result illustrates in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike, (wherein, the average grain diameter containing the molecular sieve in the dispersion liquid of molecular sieve is 30 μm to the dispersion liquid obtained, D
90be 70 μm) do not carry out rotary filter press and directly send in exchange area, carry out ion-exchange.
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 2.5mm.
Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result illustrates in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike:
Use ion exchange resin for the trade mark be the form ion exchange resin of 001 × 14.5;
The dispersion liquid obtained is sent in cyclone hydraulic separators with the flow velocity of 800mL/min, and obtains the slurries containing molecular sieve from the overfall of cyclone hydraulic separators.After testing, the average grain diameter containing the molecular sieve in the slurries of molecular sieve obtained is 6 μm, D
90it is 10 μm;
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 0.4mm.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 4
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike:
The form ion exchange resin that the ion exchange resin used is D113 for the trade mark.
Dispersion liquid is sent into cyclone hydraulic separators (with reference to Fig. 1, drum diameter D=0.2m, intake port d with the flow velocity of 600mL/min
i=0.028m, taper angle theta=15 °, overflow pipe length L=0.09m, cylinder heights H
1=0.2m, d
0=d
u=0.04m) in, and obtain the slurries containing molecular sieve from the overfall of cyclone hydraulic separators.After testing, the average grain diameter containing the molecular sieve in the slurries of molecular sieve obtained is 9 μm, D
90it is 15 μm.
Send into exchange area, rinse 2nd district, the flow velocity of the material in renewing zone and flushing one district is respectively 4mL/min, 8mL/min, 4mL/min and 6mL/min.
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 0.6mm.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 5
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike:
Use ion exchange resin for the trade mark be the form ion exchange resin of 001 × 14.5.
Dispersion liquid is sent in cyclone hydraulic separators (with embodiment 3) with the flow velocity of 400mL/min, and obtains the slurries containing molecular sieve from the overfall of cyclone hydraulic separators.After testing, the average grain diameter containing the molecular sieve in the slurries of molecular sieve obtained is 15 μm, D
90it is 25 μm;
The molecular sieve used is beta-molecular sieve;
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 0.6mm.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 6
The method identical with embodiment 5 is adopted to carry out ion-exchange, unlike, the dispersion liquid obtained is sent in cyclone hydraulic separators with the flow velocity of 200mL/min, and obtains the slurries containing molecular sieve from the overfall of cyclone hydraulic separators.After testing, the average grain diameter containing the molecular sieve in the slurries of molecular sieve obtained is 18 μm, D
90it is 35 μm.
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 2.8mm.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 7
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike, be not used as the NaCl of ion-exchange initator.
Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 0.6mm.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 8
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike, (be purchased from Lingshou County, Hebei province hundred arsenic in a natural state sand processing factory with quartz sand, average grain diameter is 2mm) on the upper surface of ion exchange resin bed layer, load the nonactive dielectric layer that thickness is 2cm, 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).At the slurries that the material flowing through ion exchange resin bed layer is containing molecular sieve, the thickness of the slurry layer formed on the nonactive dielectric layer upper surface of the first radical ion exchanger resin bed containing the slurries of molecular sieve is 50mm, when this ion exchange resin bed layer forms exchange area, in glass tube, air is passed into by gas passage, intake velocity is 30mL/min, then the slurries containing molecular sieve are pumped in ion exchange column, carry out ion-exchange.
Stop ion-exchange after 5.5 hours, on the upper surface of exchange area ion exchange resin bed layer, during switching, do not observe the molecular sieve of deposition.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 9
The method identical with embodiment 8 is adopted to carry out ion-exchange, unlike, in glass tube, do not pass into air.Ion-exchange is stopped after 5.5 hours, along the flow direction of slurries in ion exchange resin bed layer containing molecular sieve, measure the thickness of the molecular sieve that the upper surface of first ion exchange resin bed layer in exchange area deposits when switching, the thickness at every turn obtained is averaged as 0.2mm.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 10
The method identical with embodiment 8 is adopted to carry out ion-exchange, unlike, the upper surface of ion exchange resin bed layer does not form nonactive dielectric layer.Stop ion-exchange after 5.5 hours, on the upper surface of exchange area ion exchange resin bed layer, during switching, do not observe the molecular sieve of deposition.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 11
The method identical with embodiment 5 is adopted to carry out ion-exchange, unlike, (be purchased from Lingshou County, Hebei province hundred arsenic in a natural state sand processing factory with quartz sand, average grain diameter is 1mm) on the upper surface of ion exchange resin bed layer, form the nonactive dielectric layer that thickness is 1.5cm, and above nonactive dielectric layer, settle a glass tube (with embodiment 8).At the slurries that the material flowing through ion exchange resin bed layer is containing molecular sieve, when this ion exchange resin bed layer forms exchange area, in glass tube, nitrogen is passed into by gas passage, intake velocity is 20mL/min, then pumped in ion exchange column by the slurries containing molecular sieve and carry out ion-exchange, the thickness of the slurry layer that the slurries containing molecular sieve are formed on the nonactive dielectric layer upper surface of the first radical ion exchanger resin bed is 50mm.
Stop ion-exchange after 5.5 hours, on the upper surface of exchange area ion exchange resin bed layer, during switching, do not observe the molecular sieve of deposition.Detect the sodium oxide content in the molecular sieve at every turn obtained by X fluorescence spectrum method, result is listed in Table 1.
Embodiment 1 and comparative example 1 are compared and can be found out, adopts ion-exchange process of the present invention to carry out ion-exchange to molecular sieve, the sodium oxide content in the molecular sieve through exchanging can stably remain within preset range.
Table 1
Claims (14)
1. an ion-exchange process, the method is carried out in a kind of device, described device comprises exchange area and renewing zone and material switch unit, described exchange area and renewing zone have material inlet, material outlet and ion exchange resin bed layer that at least one is formed by form ion exchange resin separately, described ion exchange resin bed layer at least part of between described material inlet and material outlet;
The method comprises: in exchange area, the slurries containing molecular sieve are made to flow through ion exchange resin bed layer, make the commutative group in described molecular sieve and the hydrogen ion in ion exchange resin carry out ion-exchange, and collect the slurries containing molecular sieve flowed out from described ion exchange resin bed layer; And
In renewing zone, acid solution is made to flow through ion exchange resin bed layer, with by the ion exchange resin regeneration in ion exchange resin bed layer;
Described device also comprises flushing one district, described flushing one district has material inlet, material outlet and ion exchange resin bed floor that at least one is formed by form ion exchange resin, described ion exchange resin bed layer at least part of between described material inlet and material outlet;
The method also comprises: in flushing one district, makes water flow through ion exchange resin bed layer;
The material that described material switch unit is configured to make to flow through regional switches by following direction in time: the material flowing through exchange area is switched to flushing one district, the material flowing through flushing one district is switched to renewing zone, the material flowing through renewing zone is switched to exchange area.
2. method according to claim 1, wherein, described device also comprises flushing two district, described flushing two district has material inlet, material outlet and ion exchange resin bed floor that at least one is formed by form ion exchange resin, described ion exchange resin bed layer at least part of between described material inlet and material outlet;
The method also comprises: in flushing two district, makes water flow through ion exchange resin bed layer;
The material that described material switch unit is configured to make to flow through regional switches by following direction in time:
The material flowing through exchange area is switched to flushing one district, the material flowing through flushing one district is switched to renewing zone, the material flowing through renewing zone is switched to flushing two district, the material flowing through flushing two district is switched to exchange area.
3. method according to claim 2, wherein, in flushing two district, the flow direction of water in described ion exchange resin bed layer is contrary with the flow direction of slurries in this ion exchange resin bed layer containing molecular sieve in exchange area.
4. method according to claim 1, wherein, the described particle diameter containing the molecular sieve in the slurries of molecular sieve meets following condition:
(1) volume average particle size is less than 15 μm;
(2) D
90be less than 30 μm, D
90particle diameter corresponding when representing that cumulative particle sizes percentile reaches 90 volume %; And
(3) average grain diameter of described ion exchange resin and the ratio of the described volume average particle size containing the molecular sieve in the slurries of molecular sieve are 40 ~ 150.
5. method according to claim 4, wherein, the described particle diameter containing the molecular sieve in the slurries of molecular sieve meets following condition:
(1) volume average particle size is 5 μm ~ 15 μm;
(2) D
90it is 10 μm ~ 30 μm; And
(3) average grain diameter of described ion exchange resin and the ratio of the described average grain diameter containing the molecular sieve in the slurries of molecular sieve are 40 ~ 125.
6. the method according to claim 4 or 5, wherein, the method obtained containing the slurries of molecular sieve comprises: be scattered in water by molecular sieve and form dispersion liquid, is sent in cyclone hydraulic separators by described dispersion liquid and is separated, and obtains the described slurries containing molecular sieve from the overfall of described cyclone hydraulic separators.
7. method according to claim 1, wherein, in exchange area, the described slurries containing molecular sieve form slurry layer on the upper surface of described ion exchange resin bed 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.
8. method according to claim 7, 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, the outer wall of described pipeline and hold described ion-exchange bed container inwall between Existential Space, and Existential Space between the upper surface of the lower surface of described pipeline and described ion exchange resin bed layer.
9. according to the method in claim 1,2,7 and 8 described in any one, wherein, the upper surface of described ion exchange resin bed layer is formed with nonactive dielectric layer, material enters in described ion exchange resin bed layer through described nonactive dielectric layer, described nonactive dielectric layer is formed by non-active particles, and the ratio of the average grain diameter of described non-active particles and the average grain diameter of described ion-exchange resin particles is 1.2 ~ 5:1.
10. method according to claim 9, wherein, the ratio of the average grain diameter of described non-active particles and the average grain diameter of described ion-exchange resin particles is 1.3 ~ 3:1.
11. methods according to claim 9, wherein, described non-active particles is selected from glass particle, quartz particles and inactive resin particle.
12. according to the method in claim 1,4,5,7 and 8 described in any one, wherein, the described slurries containing molecular sieve are also containing at least one ion-exchange initator, and the amount of described ion-exchange initator is 0.001 ~ 2 % by weight of the amount of described slurries Middle molecule sieve.
13. methods according to claim 12, 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.
14. according to the method in claim 1,4,5,7 and 8 described in any one, and wherein, described molecular sieve is Na type molecular sieve.
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| CN201210414004.5A CN103769250B (en) | 2012-10-25 | 2012-10-25 | A kind of ion-exchange process |
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| CN201210414004.5A CN103769250B (en) | 2012-10-25 | 2012-10-25 | A kind of ion-exchange process |
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| CN101069863A (en) * | 2006-05-11 | 2007-11-14 | 北京大学 | Multi-stage series-connection fluidization-bed alternative changing-over molecular-sieve ion exchanging process |
| CN102020288A (en) * | 2009-09-09 | 2011-04-20 | 北京思践通科技发展有限公司 | Ion exchange method for molecular sieve |
| US20110105770A1 (en) * | 2009-11-05 | 2011-05-05 | Battelle Memorial Institute | Adsorption separation processes for ionic liquid catalytic processes |
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| CN101069863A (en) * | 2006-05-11 | 2007-11-14 | 北京大学 | Multi-stage series-connection fluidization-bed alternative changing-over molecular-sieve ion exchanging process |
| CN102020288A (en) * | 2009-09-09 | 2011-04-20 | 北京思践通科技发展有限公司 | Ion exchange method for molecular sieve |
| US20110105770A1 (en) * | 2009-11-05 | 2011-05-05 | Battelle Memorial Institute | Adsorption separation processes for ionic liquid catalytic processes |
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