CN103657154B - A kind of ion-exchange process - Google Patents
A kind of ion-exchange process Download PDFInfo
- Publication number
- CN103657154B CN103657154B CN201210313803.3A CN201210313803A CN103657154B CN 103657154 B CN103657154 B CN 103657154B CN 201210313803 A CN201210313803 A CN 201210313803A CN 103657154 B CN103657154 B CN 103657154B
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- ion
- exchange resin
- solid matter
- slurries
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a kind of ion-exchange process, the method comprises makes the slurries containing the solid matter with commutative group flow through the ion exchange column being filled with ion exchange resin, the commutative group on described solid matter and the ion-exchange group on described ion exchange resin is made to carry out ion-exchange, and collect the slurries containing solid matter flowed out from described ion exchange column, wherein, the process of at least part of described ion-exchange carries out counter current contacting to realize by making the slurries of described ion exchange resin and the described solid matter containing having commutative group, and ion exchange resin is supplemented in described ion exchange column, remove and the space stayed to fill ion exchange column ion exchange resin.The problem that method of the present invention there will not be ion exchange column to block in ion exchange process, carries out the ion exchange resin after ion-exchange when regenerating, and is easy to cleaning; Further, the stable content of commutative group in the solid matter after 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 occur that ion exchange column blocking and ion exchange resin are difficult to by the problem cleaned up in regenerative process.
Summary of the invention
When the object of the invention is to overcome the ion exchange column that the slurries containing molecular sieve flow through be filled with ion exchange resin to carry out ion-exchange, ion exchange column is easy to blocking and ion exchange resin is difficult to by the problem cleaned up in regenerative process, the invention provides a kind of ion-exchange process, when adopting the method to carry out ion-exchange by ion exchange column to molecular sieve, there will not be the problem that ion exchange column blocks, and the ion exchange resin carried out after ion-exchange is easy to cleaning.
The present inventor conducts in-depth research molecular sieve ion-exchange process disclosed in CN102020288A, when finding to adopt method disclosed in it to carry out ion-exchange to molecular sieve in ion exchange column, be easy to occur that ion exchange column blocking and ion exchange resin are difficult to by the reason of the problem cleaned up may be in regenerative process: the slurries containing molecular sieve, when passing through ion exchange column, sedimentation occur, a large amount of molecular sieve accumulation areas is formed in resin bed, cause ion exchange resin column to block, and make ion exchange resin be difficult to clean up.The present inventor found through experiments, if when being undertaken by ion exchange column carrying out ion-exchange to the slurries containing molecular sieve, the process of at least part of described ion-exchange is realized under the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out the condition of counter current contacting, then can effectively avoid molecular sieve pulp by there is sedimentation during ion exchange column.Complete the present invention on this basis.
The invention provides a kind of ion-exchange process, the method comprises makes the slurries containing the solid matter with commutative group flow through the ion exchange column being filled with ion exchange resin, the commutative group on described solid matter and the ion-exchange group on described ion exchange resin is made to carry out ion-exchange, and collect the slurries containing solid matter flowed out from described ion exchange column, wherein, the process of at least part of described ion-exchange carries out counter current contacting to realize by making the slurries of described ion exchange resin and the described solid matter containing having commutative group, and ion exchange resin is supplemented in described ion exchange column, remove and the space stayed to fill ion exchange column ion exchange resin.
According to method of the present invention, flow through in the process of ion exchange column at the slurries containing the solid matter with commutative group, there will not be the problem that ion exchange column blocks, ion-exchange can be carried out smoothly; Carrying out the ion exchange resin after ion-exchange when regenerating, being easy to cleaning.Further, according to method of the present invention, the stable content of commutative group in the solid matter after ion-exchange.
Accompanying drawing explanation
Fig. 1 for illustration of ion-exchange process according to the present invention one preferred embodiment.
Detailed description of the invention
The invention provides a kind of ion-exchange process, the method comprises makes the slurries containing the solid matter with commutative group flow through the ion exchange column being filled with ion exchange resin, the commutative group on described solid matter and the ion-exchange group on described ion exchange resin is made to carry out ion-exchange, and collect the slurries containing solid matter flowed out from described ion exchange column, wherein, the process of at least part of described ion-exchange carries out counter current contacting to realize by making the slurries of described ion exchange resin and the described solid matter containing having commutative group, and ion exchange resin is supplemented in described ion exchange column, remove and the space stayed to fill ion exchange column ion exchange resin.
According to method of the present invention, described in there is commutative group solid matter can be various types of solid matter containing 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 the molecular sieve containing, for example one or more ions in hydrogen ion, ammonium radical ion and rare earth ion, such as hydrogen type molecular sieve, ammonium type molecular sieve, rare earth metal type molecular sieve, alkaline-earth metal type molecular sieve and mixed type molecular sieve (that is, the molecular sieve containing 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 containing 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 matter containing having commutative group contain water.Described water is preferably deionized water.The present invention is not particularly limited the ratio of solid matter and water in described slurries, 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.
According to method of the present invention, the kind being seated in the ion-exchange group on the ion exchange resin in described ion exchange column is not particularly limited, and 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 radical 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 resin of ion exchange resin, such as: polystyrene resin or acrylic resin.
According to method of the present invention, be filled with the ion exchange column of ion exchange resin described in the method that this area can be adopted to commonly use provides, repeat no more herein.
According to method of the present invention, various method can be adopted to make the slurries containing the solid matter with commutative group flow through the ion exchange column being filled with ion exchange resin, such as: when described ion exchange column is for vertically arranging, the described slurries of solid matter containing having a commutative group can be made under gravity and applying or the effect of applied external force that do not apply by the ion exchange resin in described ion exchange column; Described ion exchange column be non-vertical (as: tilt or level) arrange time, can under the effect of applied external force and presence or absence gravity, make described containing there are the slurries of solid matter of commutative group by the ion exchange resin in described ion exchange column.
According to method of the present invention, the process of at least part of described ion-exchange carries out counter current contacting to realize by making the slurries of described ion exchange resin and the described solid matter containing having commutative group, and ion exchange resin is supplemented in described ion exchange column, remove and the space that stays to fill ion exchange column ion exchange resin.Described counter current contacting refers to that ion exchange resin flows with the direction contrary with the flow direction of slurries of the described solid matter containing having commutative group.
According to method of the present invention, can, in the whole process of described ion-exchange, the slurries of described ion exchange resin and the described solid matter containing having commutative group be made to carry out counter current contacting.That is, the process of whole described ion-exchange is carried out under making the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out the condition of counter current contacting.
According to method of the present invention, also can according to flow out from described ion exchange column containing in the slurries of solid matter, the amount of the commutative group on described solid matter determines to make the slurries of described ion exchange resin and the described material containing having commutative group to carry out opportunity of counter current contacting and described counter current contacting lasting time.Such as: can in ion exchange process, detect the content of the commutative group on the solid matter in the slurries flowed out from ion exchange column, 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, make the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting, the degree of described ion-exchange is defined by formula (I):
In formula I, c
1for the content without the commutative group on the solid matter of ion-exchange;
C
2for the content of the commutative group on the solid matter 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 solid matter, repeat no more herein.
According to method of the present invention, when the degree of described ion-exchange meets the demands, can stop carrying out described counter current contacting, that is, make described ion exchange resin be in first valve state.
According to method of the present invention, when the slurries of described ion exchange resin and the described solid matter containing having commutative group are carried out counter current contacting, the flowing velocity of described ion exchange resin can carry out suitable selection according to the flowing velocity of described slurries.From the angle of the utilization rate of the further ion exchange resin improved in ion exchange column, described ion exchange resin in volume/hour flowing velocity with described containing have commutative group solid matter slurries in volume/hour the ratio of flowing velocity be preferably 1:1-15, be more preferably 1:4-12, more preferably 1:5-10.
According to method of the present invention, conventional various methods can be adopted to make described Ion Exchange Resin Phase carry out counter current contacting for the slurries of the described solid matter containing having commutative group.Such as: described ion exchange column be non-vertical (as tilt or level) arrange time, driving-belt can being set in ion exchange column, making Ion Exchange Resin Phase carry out counter current contacting for the slurries of the described solid matter containing having commutative group by V belt translation.
One of the present invention preferred embodiment in, the mode making described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting comprises: in described ion exchange column, arrange transmission screw rod, and drive described transmission screw rod, to make described Ion Exchange Resin Phase, reverse flow is carried out for the slurries of the described solid matter containing having commutative group.
This preferred embodiment in, described transmission screw rod is preferably matched in clearance with coordinating between described ion exchange column.Usually, maximal clearance between described transmission screw rod and described ion exchange resin column (namely, difference between the large footpath of described transmission screw rod and the internal diameter of described ion exchange column) for having the particle diameter of the solid matter of cation exchange groups described in being less than, such as: can be 0.05-0.45mm, 0.05-0.2mm be preferably.
This preferred embodiment in, described transmission screw rod can for conventional various can the screw rod of transportation of substances, be not particularly limited.The material of described transmission screw rod is also not particularly limited, only otherwise with described slurries and described ion exchange resin generation chemical interaction.Usually, described transmission screw rod can be made up of various carbon steel that commonly using or steel alloy.Hand of spiral on described transmission screw rod is also not particularly limited, and can be conventional selection.
This preferred embodiment in, the length of described transmission screw rod can carry out suitable selection according to the length of the ion-exchange area in described ion exchange column, is as the criterion the ion exchange resin in ion exchange column can be delivered to the other end from one end of ion-exchange area.Described ion-exchange area refers in ion exchange column to have ion exchange resin and containing the slurries of solid matter with commutative group, the region of ion-exchange can occur.
This preferred embodiment in, described transmission screw rod is preferably driven by motor.The ion exchange resin in described ion exchange column can be made to have predetermined flowing velocity (such as previously described flowing velocity) by regulating the driving force size of described motor.
According to method of the present invention, when making the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting, to remove due to ion exchange resin and the space stayed in ion exchange column is filled by supplementing ion exchange resin to ion exchange column.Namely, according to method of the present invention, while making the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting, in described ion exchange column, supplementing ion exchange resin, remove to fill ion exchange column ion exchange resin the space stayed.The supplementary speed of ion exchange resin is removed the space stayed be as the criterion can be filled ion exchange column ion exchange resin in time.Preferably, the supplementary speed of ion exchange resin makes between the ion exchange resin in the ion exchange resin that supplements and ion exchange column is continuous print.That is, be full of ion exchange resin all the time in the ion-exchange area of described ion exchange column, this ion exchange resin comprises original ion exchange resin and supplementary ion exchange resin in ion exchange column.By arranging ion exchange resin outlet on described ion exchange column, the ion exchange resin moving out ion-exchange area because Ion Exchange Resin Phase carries out counter current contacting for the slurries of the described solid matter containing having commutative group can be exported; Described ion exchange column arranges supplementary ion exchange resin entrance, in ion exchange column, supplements ion exchange resin, remove with filling ion-exchange resin and the space that stays.
According to method of the present invention, when making the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting, the ion exchange resin moving out the ion-exchange area of ion exchange column exports from ion exchange column, the ion exchange resin exported preferably carried out regenerating and after optional transition, supplementing enters in ion exchange column, to realize carrying out continuously of ion-exchange and ion exchange resin regeneration.That is, preferably also comprise according to method of the present invention the ion exchange resin exported from described ion exchange column by described counter current contacting is regenerated, and the ion exchange resin after regeneration is added in ion exchange column; Or the ion exchange resin exported from described ion exchange column by described counter current contacting is successively carried out regenerating and making the transition, and the ion exchange resin after transition is added in ion exchange column.
The method that ion exchange resin through ion-exchange is carried out regenerating and make the transition is known in the field.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 make the transition as required to be become as alkali metal type ion exchange resin, alkaline-earth metal type ion exchange resin, ammonium type ion exchange resin, rare earth metal type ion exchange resin or mixed type ion exchange resin (that is, the ion exchange resin containing two or more ion-exchange group); 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.
According to method of the present invention, the ion exchange resin exported from ion exchange column before regeneration, preferably cleans with water.Carry out the method for cleaning with water and condition is known in the field, repeat no more herein.
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 weight of solid matter, be preferably described containing have commutative group solid matter slurries in the 0.01-1 % by weight of weight of solid matter, be more preferably described containing have commutative group solid matter slurries in the 0.1-1 % by weight of weight 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 25-100 DEG C, preferably carry out at the temperature of 50-80 DEG C.
Fig. 1 shows according to the one of ion-exchange process of the present invention preferred embodiment.As shown in Figure 1, transmission screw rod 2 is provided with in ion exchange column 1, the axis 3 of transmission screw rod 2 is driven by motor 4, ion exchange column 1 is provided with the injection point 7 containing the solid matter with commutative group and the outlet 5 of slurries containing solid matter of flowing out from ion exchange column, slurries containing the solid matter with commutative group enter ion exchange column 1 from entrance 7, flow through the ion exchange resin in ion exchange column 1, carry out ion-exchange with the ion-exchange group in ion exchange resin, the slurries through ion-exchange flow out from outlet 5.In the process of ion-exchange, or when the degree of ion-exchange can not meet the demands, the axis 3 of transmission screw rod 2 is driven to rotate by motor 4, and then drive the slurries of the ion exchange resin in ion exchange column 1 and the described solid matter containing having commutative group to carry out counter current contacting, in ion exchange column 1, supplement ion exchange resin by ion exchange resin entrance 6 simultaneously, with fill remove due to ion exchange resin and the space that stays in ion exchange column 1 (preferably, it is continuous print that the feeding speed of ion exchange resin of supplementing makes between the ion exchange resin in the ion exchange resin that supplements and ion exchange column 1, namely the ion-exchange area in ion exchange column 1 all the time be full of by ion exchange resin).The ion exchange resin shifting out the ion-exchange area of ion exchange column 1 because Ion Exchange Resin Phase carries out reverse movement for described slurries is exported from ion exchange column 1 by ion exchange resin outlet 8.The ion exchange resin exported successively is undertaken washing, regenerating and optional transition by ion exchange resin drip washing tank 9 and ion exchange resin regeneration tank 10, to obtain ion exchange resin or the ion exchange resin of transition of regeneration, the ion exchange resin of the regeneration obtained or the ion exchange resin of transition enter in ion exchange resin storage tank 11, and ion exchange resin circulation is sent in ion exchange column 1 as a supplement when needed.
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 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 be by by sample 800 DEG C roasting temperature 2 hours and measure.
Following examples adopt the method shown in Fig. 1 to carry out ion-exchange.
Embodiment 1-7 is for illustration of ion-exchange process of the present invention.
Embodiment 1
(1) height be 25cm, internal diameter is that the glass tube of 3.1cm (is equipped with transmission screw rod in this glass tube, this transmission screw rod is made up of No. 45 steel, large footpath is 3cm, the transmission axis of screw rod overlaps with the axis of glass tube) middle fill 150mL ammonium type polystyrene storng-acid cation exchange resin and (be purchased from Chemical Plant of Nankai Univ., the trade mark is 001 × 7, gel-type, CEC is 1.8mmol/mL).
(2) in beaker, add 2000mL deionized water, and add 200g NaY molecular sieve (in butt) wherein, stir the slurries obtained containing molecular sieve, and these slurries are heated to 70 DEG C.
(3) step (2) is obtained containing the slurries of molecular sieve pump into prepared by step (1) from top to bottom in the ion exchange column that arranges along gravity direction, drive transmission screw rod that ion exchange resin is moved from bottom to top with motor, ion-exchange is carried out at the temperature of 70 DEG C simultaneously.Wherein, the flow velocity containing the slurries of molecular sieve is 6mL/min, and the translational speed of the ion exchange resin in ion exchange column in ion exchange column is 60mL/h.
(4) at the slurries containing molecular sieve that ion exchange column received down flows out, sample 30mL at interval of 30min, get 9 times altogether.The slurries containing molecular sieve flowed out from ion exchange column at every turn obtained are carried out suction filtration respectively, the filter cake obtained is carried out drying at 120 DEG C, obtains 9 parts of molecular sieves.
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 9th time, result is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike, drive the axis of transmission screw rod without motor, when test proceeds to 80min, ion exchange column is blocked, and the slurries containing molecular sieve cannot pass through ion exchange column smoothly, and test stops.The sodium oxide content of the molecular sieve obtained is listed in Table 1.
Embodiment 2
(1) method identical with the step (1) of embodiment 1 is adopted to prepare ion exchange column, unlike, use ion exchange resin be purchased from the trade mark of Chemical Plant of Nankai Univ. be 001 × 14.5 ammonium type polystyrene storng-acid cation exchange resin (gel-type, CEC is 1.8mmol/mL).
(2) in beaker, add 2000mL deionized water, and add 200g NaY molecular sieve (in butt) wherein, stir the slurries obtained containing molecular sieve, and these slurries are heated to 50 DEG C.
(3) step (2) is obtained containing the slurries of molecular sieve pump into prepared by step (1) from top to bottom in the ion exchange column that arranges along gravity direction, drive transmission screw rod that ion exchange resin is moved from bottom to top with motor, ion-exchange is carried out at the temperature of 50 DEG C simultaneously.Wherein, the flow velocity containing the slurries of molecular sieve is 6mL/min, and the translational speed of the ion exchange resin in ion exchange column in ion exchange column is 50mL/h.
(4) at the slurries containing molecular sieve that ion exchange column received down flows out, sample 30mL at interval of 30min, get 9 times altogether.The slurries containing molecular sieve flowed out from ion exchange column at every turn obtained are carried out suction filtration respectively, the filter cake obtained is carried out drying at 120 DEG C, obtains 9 parts of molecular sieves.
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 9th time, result is listed in Table 1.
Embodiment 3
(1) method identical with the step (1) of embodiment 1 is adopted to prepare ion exchange column, unlike, the ion exchange resin used is the Hydrogen weakly acidic cationic exchange resin of acrylic series (macroporous type, CEC is 4.2mmol/mL) that to be purchased from the trade mark of Chemical Plant of Nankai Univ. be D113.
(2) in beaker, add 2000mL deionized water, and add 200g NaY molecular sieve (in butt) wherein, stir the slurries obtained containing molecular sieve, and these slurries are heated to 45 DEG C.
(3) step (2) is obtained containing the slurries of molecular sieve pump into prepared by step (1) from top to bottom in the ion exchange column that arranges along gravity direction, drive transmission screw rod that ion exchange resin is moved from bottom to top with motor, ion-exchange is carried out at the temperature of 45 DEG C simultaneously.Wherein, the flow velocity containing the slurries of molecular sieve is 6mL/min, and the translational speed of the ion exchange resin in ion exchange column in ion exchange column is 35mL/h.
(4) at the slurries containing molecular sieve that ion exchange column received down flows out, sample 30mL at interval of 30min, get 9 times altogether.The slurries containing molecular sieve flowed out from ion exchange column at every turn obtained are carried out suction filtration respectively, the filter cake obtained is carried out drying at 120 DEG C, obtains 9 parts of molecular sieves.
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 9th time, result is listed in Table 1.
Embodiment 4
(1) method identical with the step (1) of embodiment 1 is adopted to prepare ion exchange column, unlike, use ion exchange resin be purchased from the trade mark of Chemical Plant of Nankai Univ. be 001 × 14.5 ammonium type polystyrene storng-acid cation exchange resin (gel-type, CEC is 1.8mmol/mL).
(2) in beaker, add 2000mL deionized water, and add 200g NaY molecular sieve (in butt) wherein, stir the slurries obtained containing molecular sieve, and these slurries are heated to 80 DEG C.
(3) step (2) is obtained containing the slurries of molecular sieve pump into prepared by step (1) from top to bottom in the ion exchange column that arranges along gravity direction, drive transmission screw rod that ion exchange resin is moved from bottom to top with motor, ion-exchange is carried out at the temperature of 80 DEG C simultaneously.Wherein, the flow velocity containing the slurries of molecular sieve is 6mL/min, and the translational speed of the ion exchange resin in ion exchange column in ion exchange column is 49mL/h.
(4) at the slurries containing molecular sieve that ion exchange column received down flows out, sample 30mL at interval of 30min, get 9 times altogether.The slurries containing molecular sieve flowed out from ion exchange column at every turn obtained are carried out suction filtration respectively, the filter cake obtained is carried out drying at 120 DEG C, obtains 9 parts of molecular sieves.
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 9th time, result is listed in Table 1.
Embodiment 5
(1) method identical with the step (1) of embodiment 1 is adopted to prepare ion exchange column, unlike, use ion exchange resin be purchased from the trade mark of Chemical Plant of Nankai Univ. be 001 × 14.5 Hydrogen polystyrene storng-acid cation exchange resin (gel-type, CEC is 1.8mmol/mL).
(2) in beaker, add 1400mL deionized water, and add 200g ZSM-5 molecular sieve (in butt) wherein, stir the slurries obtained containing molecular sieve, and these slurries are heated to 70 DEG C.
(3) step (2) is obtained containing the slurries of molecular sieve pump into prepared by step (1) from top to bottom in the ion exchange column that arranges along gravity direction, drive transmission screw rod that ion exchange resin is moved from bottom to top with motor, ion-exchange is carried out at the temperature of 70 DEG C simultaneously.Wherein, the flow velocity containing the slurries of molecular sieve is 6mL/min, and the translational speed of the ion exchange resin in ion exchange column in ion exchange column is 35mL/h.
(4) at the slurries containing molecular sieve that ion exchange column received down flows out, sample 30mL at interval of 30min, get 9 times altogether.The slurries containing molecular sieve flowed out from ion exchange column at every turn obtained are carried out suction filtration respectively, the filter cake obtained is carried out drying at 120 DEG C, obtains 9 parts of molecular sieves.
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 9th time, result is listed in Table 1.
Embodiment 6
(1) method identical with the step (1) of embodiment 1 is adopted to prepare ion exchange column, unlike, use ion exchange resin be purchased from the trade mark of Chemical Plant of Nankai Univ. be 001 × 14.5 ammonium type polystyrene storng-acid cation exchange resin (gel-type, CEC is 1.8mmol/mL).
(2) in beaker, add 2000mL deionized water, and add 200g NaY molecular sieve (using butt) and 1.2g NaCl wherein as ion-exchange initator, stir the slurries obtained containing molecular sieve, and these slurries are heated to 70 DEG C.
(3) step (2) is obtained containing the slurries of molecular sieve pump into prepared by step (1) from top to bottom in the ion exchange column that arranges along gravity direction, drive transmission screw rod that ion exchange resin is moved from bottom to top with motor, ion-exchange is carried out at the temperature of 70 DEG C simultaneously.Wherein, the flow velocity containing the slurries of molecular sieve is 8mL/min, and the translational speed of the ion exchange resin in ion exchange column in ion exchange column is 56mL/h.
(4) at the slurries containing molecular sieve that ion exchange column received down flows out, sample 30mL at interval of 30min, get 9 times altogether.The slurries containing molecular sieve flowed out from ion exchange column at every turn obtained are carried out suction filtration respectively, the filter cake obtained is carried out drying at 120 DEG C, obtains 9 parts of molecular sieves.
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 9th time, result is listed in Table 1.
Table 1
*: the sodium oxide content in the molecular sieve obtained for the 70th minute to the 80th minute
Embodiment 7
The method identical with embodiment 1 is adopted to carry out ion-exchange, unlike, when ion-exchange proceeds to 100 minutes and 220 minutes, open motor (each opening time is 60 minutes) respectively, to drive transmission screw rod, ion exchange resin is moved with the speed identical with embodiment 1 from bottom to top.Sodium oxide content in the molecular sieve at every turn obtained is listed in table 2.
Table 2
As can be seen from Table 1 and Table 2, adopt method of the present invention to carry out ion-exchange, the ion-exchange caused due to ion exchange column blocking in ion exchange process can be avoided to interrupt; Further, in the molecular sieve adopting ion-exchange process of the present invention to obtain, the content fluctuation of commutative group is little, can stably remain within preset range.
Claims (12)
1. an ion-exchange process, the method comprises makes the slurries containing the solid matter with commutative group flow through the ion exchange column being filled with ion exchange resin, the commutative group on described solid matter and the ion-exchange group on described ion exchange resin is made to carry out ion-exchange, and collect the slurries containing solid matter flowed out from described ion exchange column, it is characterized in that, the process of at least part of described ion-exchange carries out counter current contacting to realize by making the slurries of described ion exchange resin and the described solid matter containing having commutative group, and ion exchange resin is supplemented in described ion exchange column, remove and the space stayed to fill ion exchange column ion exchange resin.
2. method according to claim 1, wherein, the process of whole described ion-exchange is carried out under making the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out the condition of counter current contacting.
3. method according to claim 1, wherein, during degree lower than predetermined ion-exchange of the degree of described ion-exchange, make the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting, the degree of described ion-exchange is defined by formula (I):
In formula I, c
1for the content without the commutative group on the solid matter of ion-exchange;
C
2for the content of the commutative group on the solid matter after ion-exchange.
4. according to the method in claim 1-3 described in any one, wherein, described ion exchange resin in volume/hour flowing velocity with described containing have commutative group solid matter slurries in volume/hour the ratio of flowing velocity for 1:1-15.
5. according to the method in claim 1-3 described in any one, wherein, the mode making the slurries of described ion exchange resin and the described solid matter containing having commutative group carry out counter current contacting comprises: in described ion exchange column, arrange transmission screw rod, and drive described transmission screw rod, to make described Ion Exchange Resin Phase, reverse flow is carried out for the slurries of the described solid matter containing having commutative group.
6. method according to claim 1, the method also comprises: regenerated by the ion exchange resin exported from described ion exchange column by described counter current contacting, and adds in described ion exchange column by the ion exchange resin after regeneration; Or
The ion exchange resin exported from described ion exchange column by described counter current contacting is successively carried out regenerating and making the transition, and the ion exchange resin after transition is added in described ion exchange column.
7. according to the method in claim 1-3 described in any one, wherein, the slurries of the described solid matter containing having commutative group contain water, and the weight ratio of water and described solid matter is 5-20:1.
8. according to the method in claim 1-3 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 the solid matter in described slurries.
9. method according to claim 8, wherein, described ion-exchange initator is selected from 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.
10. the solid matter according to the method in claim 1-3 described in any one, wherein, with commutative group is molecular sieve.
11. methods according to claim 10, wherein, described molecular sieve is Na type molecular sieve.
12. methods according to claim 11, wherein, the ion-exchange group on described ion exchange resin is one or more in hydrogen ion, ammonium ion and rare earth ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210313803.3A CN103657154B (en) | 2012-08-29 | 2012-08-29 | A kind of ion-exchange process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210313803.3A CN103657154B (en) | 2012-08-29 | 2012-08-29 | A kind of ion-exchange process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103657154A CN103657154A (en) | 2014-03-26 |
| CN103657154B true CN103657154B (en) | 2015-08-26 |
Family
ID=50296667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210313803.3A Active CN103657154B (en) | 2012-08-29 | 2012-08-29 | A kind of ion-exchange process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103657154B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111175891B (en) * | 2019-12-30 | 2020-10-23 | 浙江大学 | Method for manufacturing optical waveguide by continuous electric field assisted ion migration |
| CN111045150B (en) * | 2019-12-30 | 2021-04-20 | 浙江大学 | Method for realizing continuous production of glass-based ion exchange surface optical waveguide chip |
| CN114210375B (en) * | 2021-10-23 | 2024-04-12 | 苏州思萃同位素技术研究所有限公司 | Preparation method of hydrogen isotope substituted acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2646171A (en) * | 1949-06-14 | 1953-07-21 | John M Weiss And Co | Process for separation and recovery of components of a solution |
| CN1950327A (en) * | 2004-04-07 | 2007-04-18 | 旭化成化学株式会社 | Method of purifying amino acid |
| CN101367852A (en) * | 2008-09-09 | 2009-02-18 | 王德骥 | High-efficiency method for continuously extracting stevioside from stevia leaf |
| 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 |
-
2012
- 2012-08-29 CN CN201210313803.3A patent/CN103657154B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2646171A (en) * | 1949-06-14 | 1953-07-21 | John M Weiss And Co | Process for separation and recovery of components of a solution |
| CN1950327A (en) * | 2004-04-07 | 2007-04-18 | 旭化成化学株式会社 | Method of purifying amino acid |
| CN101367852A (en) * | 2008-09-09 | 2009-02-18 | 王德骥 | High-efficiency method for continuously extracting stevioside from stevia leaf |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103657154A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102173436B (en) | Preparation method of rare earth (RE) yttrium (Y) molecular sieve | |
| EP2802533B1 (en) | Uzm-39 aluminosilicate zeolite | |
| CN103771434B (en) | A kind of molecular sieve ion-exchange techniques | |
| CN103657154B (en) | A kind of ion-exchange process | |
| CN1115298C (en) | Y-type molecular sieve and its prepn. | |
| CN103771436B (en) | A kind of molecular sieve ion-exchange techniques and application thereof | |
| EP1756004A1 (en) | High silica zeolites uzm-5hs | |
| WO2004039725A2 (en) | 'crystalline aluminosilicate zeolitic composition: uzm-4m' | |
| CN107001056A (en) | Mesoporous zeolite is prepared with the processing of reduction | |
| CN101538051B (en) | Method for preparing ZSM-5 zeolite catalyst | |
| CN109775716B (en) | Hierarchical pore Y-type molecular sieve rich in L acid and preparation method thereof | |
| RU2624443C2 (en) | Catalyst for catalytic cracking of hydrocarbons | |
| CN105502433A (en) | Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5 | |
| CN103769249B (en) | A kind of ion-exchange process | |
| CN103623616B (en) | A kind of ion-exchange process | |
| CN105121356A (en) | Use of zeolitic materials for removing mercury (+2) ions from liquid streams | |
| CN1335258A (en) | Synthesis of nanometer size beta-zeolite | |
| CN103657153B (en) | A kind of ion-exchange process | |
| EP2874944A2 (en) | Layered conversion synthesis of zeolites | |
| CN1142022C (en) | Transalkylation catalyst and its prepn. | |
| CN103769250B (en) | A kind of ion-exchange process | |
| CN103623617B (en) | The preparation method of ion-exchange process and hydrogen type molecular sieve | |
| CN102872898A (en) | Preparation method for Fe-containing mesoporous mordenite with high catalytic activity | |
| CN104338566B (en) | A kind of ion-exchange process | |
| CN100404432C (en) | Method of reducing ammonia and nitrogen pollution in process of zeolite modification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |