CN108067101A - A kind of manufacturing method of cation exchange alloy film - Google Patents
A kind of manufacturing method of cation exchange alloy film Download PDFInfo
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- CN108067101A CN108067101A CN201710878385.5A CN201710878385A CN108067101A CN 108067101 A CN108067101 A CN 108067101A CN 201710878385 A CN201710878385 A CN 201710878385A CN 108067101 A CN108067101 A CN 108067101A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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Abstract
The present invention describes a kind of manufacturing method of cation exchange alloy film.First by thermoplastic polyethylene sulfonated polystyrene storng-acid cation exchange resin powder, not thermoplastic micron order weak-acid cation-exchange resin powder (or not thermoplastic micron order weak-base anion-exchange resin powder), polyethylene powder and polyisobutene powder mixing, using mixing, mill slice, continuous calendering, cooling, severing, individual prefabricated diaphragm is obtained；An enhancing screen cloth finally is clamped with two prefabricated diaphragms, the cation exchange alloy film product is obtained through hot pressing.Film surface is smooth, and contamination resistance is strong；Can thermoplastic component with can not thermoplastic component constitute " starry sky type " high polymer alloy structure, film resistance is low；Enhancing screen cloth limits swelling of the film in highly acid or strong alkali solution, and internal structure is fine and close.Particularly suitable for the electrodialysis application scenario under highly acid or strong alkali solution environment.
Description
Technical field
The invention belongs to functional polymer thin film processing techniques field, enhancing screen cloth has been inlayed in more particularly to a kind of centre
, main membrane material for " starry sky type " high polymer alloy structure therefore can meet under strong acid and strong base solution environment for a long time
The manufacturing method for the cation-exchange membrane that electrodialysis group device uses.
Background technology
Amberplex is widely used in the bitter desalination based on electrodialytic technique, seawater concentration salt manufacturing, food spy
The occasions such as kind separation desalination, industrial wastewater desalination, acid/base recycling.In the past, by not thermoplastic amberlite cosmetics and poly- second
The heterogeneous membrane that the rear surface of the binding agents mixing such as alkene is formed again with enhancing screen cloth compacting, because manufacturing process is very simple and price is non-
It is often cheap, obtain extensive engineer application.But because the structure of ion exchange heterogeneous membrane is loose, performance is bad, especially
It is that the limting concentration that salt concentrates is not high enough, does not for example exceed 12~14% generally directed to the limting concentration of seawater concentration.Therefore,
Substantial amounts of improvement has been carried out to the filming technology of heterogeneous membrane.Particularly Chinese invention patent (application number 201510570174.6) is public
A kind of manufacturing method of half homogeneous phase cation exchange film has been opened, has introduced a kind of thermoplastic polyethylene-sulfonated polystyrene base
Highly acidic cation exchanges compound resin meal component, proposes a kind of four-roll calendaring technique for being capable of continuous membrane along band, not only
Membrane structure is improved, significantly reduce membrane surface resistance and greatly improves concentration performance is (for example dense for the limit of seawater concentration
Degree can reach 16~18%), also significantly improve production efficiency and Product Precision (such as thickness, flatness, finish etc.).
But this half homogeneous phase cation exchange film is still mixed with a high proportion of not thermoplastic highly acidic cation and hands over
Resin-oatmeal (mass percent is up to 40%) is changed, and granularity still (is typically only capable to reach 200~300 mesh, about 50~75 is micro- very much greatly
Rice).This is resulted under highly acid or the solution environmental of strong basicity, and large-sized highly acidic resin powder drastically can be swollen or receive
It contracts (specifically, being swollen in strong acid solution, can then be shunk in strong base solution), membrane structure moment can be caused to be disintegrated when serious.
It, will be because of this " swelling-contraction " drastically during the use switched repeatedly in long-term " Acid-Base-salt " solution environmental
Behavior and cause to be separated between membrane material each component, cause membrane structure compactness decay and concentrated effect decline.Together
When, as heterogeneous membrane, hot pressing enters the method for a relatively thin screen cloth respectively on used by this half homogeneous membrane or upper and lower surface
(general to use thickness as 0.09~0.11 millimeter of terylene mesh).The enhancing effect of screen cloth is therefore or inadequate, it is difficult to really
Limit swelling behavior of the diaphragm under strong acid or strong base solution environment；On the other hand, clip surface net makes film surface rough, holds
Easy adhering contaminant significantly reduces the contamination resistance of film.The result is that：This kind of half homogeneous membrane is as heterogeneous membrane, still
The long-time service under highly acid and strong basicity environment is difficult to, prolonged application is in strong acid after cannot being especially packed into electrodialysis group device
The removing or concentration of (such as hydrochloric acid) and highly basic (such as sodium hydroxide).
The content of the invention
The purpose of the invention is to significantly improve the structure of out-phase cation-exchange membrane or half homogeneous phase cation exchange film
Defect, on the premise of the cost of raw material is not dramatically increased, provide a kind of various film-forming components compatibilities are more preferable, membrane structure more
The cation exchange alloy film that is used for a long time in electrodialysis group device can be fitted into rationally and under strong acid and strong base solution environment
Manufacturing method.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of manufacturer of cation exchange alloy film
Method, this method comprises the following steps：1) by thermoplastic polyethylene-sulfonated polystyrene storng-acid cation exchange resin powder,
Not thermoplastic micron order weak-acid cation-exchange resin powder (or not thermoplastic micron order weak-base anion-exchange resin
Powder), polyethylene powder and polyisobutene powder be uniformly mixed；2) by mixture successively by mixing, two roller open mill slices, four roll-ins
Prolong machine continuous calendering, cooling, severing, obtain individual prefabricated diaphragm；3) an enhancing screen cloth, warp are clamped with two prefabricated diaphragms
Hot press hot pressing fusion, cooling annealing are crossed, obtains the cation exchange alloy film product.
Compared with heterogeneous membrane or half homogeneous membrane, it is made that and is significantly improved part, and achieve specific advantageous effect.The
One, being only mixed with a small amount of not thermoplastic micron order weak-acid cation-exchange resin powder, (or not thermoplastic micron order is weak
Alkalescence anion-exchange resin powder), instead of the not thermoplastic big grain size strong acid largely used in heterogeneous membrane or half homogeneous membrane
Property cation exchange resin powder, so as to by " fabric of island-in-sea type " structure of both rear main membrane material (can will it is this it is large-sized by force
Acidic resins powder regards it as " island ", and thermoplastic other components that its surrounding is surrounded regard it as " sea "), it is improved to the alloy
Required " starry sky type " structure of film (thermoplastic micron order resin-oatmeal can be regarded it as " point point an array of stars ", it can thermoplastic
Other components regard it as " sky ")；Also, by controlling the exchange capacity appropriateness of micron order resin-oatmeal (without being to try to most
It is high), further limit swellbility of the micron order resin-oatmeal under acid/base solution environmental.In this way, by not thermoplastic tree
Radical species (weak acid and weak base), group content (ion exchange capacity) and being directed to for granule size of fat sexually revise, and result in
The apparent transformation of membrane structure and significantly improving for swelling resistance.Second, by optimization of C/C composites, that is, reduce not thermoplastic tree
The content (therefore cation exchange capacity can reduce) of cosmetics, it is strong accordingly to improve thermoplastic polyethylene-sulfonated polystyrene
The content (cation exchange capacity is therefore again with rise) of acid cation exchange resin powder, adds gained after four-roll calendaring
Plasticity, flexibility and the planarization of prefabricated diaphragm.In this way, even without enhancing screen cloth, it is prefabricated among acid/base solution environmental
Diaphragm will not excessively be swollen and structural collapse occurs, can remain that surface is smooth and diaphragm is smooth.3rd, by using two
A thicker enhancing screen cloth is inlayed in prefabricated diaphragm hot pressing, come two relatively thin nets used by replacing heterogeneous membrane and half homogeneous membrane
Cloth covers the method for lid in surface heat, can play " enhancing " effect of enhancing screen cloth to greatest extent, while can also be greatly
Slow down the acid/base treatment fluid in engineer application directly to the corrosiveness of film surface screen cloth, so as to limit to a greater extent
Degree of swelling of the diaphragm under acid/base solution environmental.Final clear and definite effect, exactly significantly improves film to highly acid and highly basic
The tolerance of property solution environmental, enables electrodialysis removing or concentration process of the prolonged application in strong acid or highly basic.
Specific embodiment
The manufacturing method of cation exchange alloy film of the present invention contains following 3 steps：
1) by thermoplastic polyethylene-sulfonated polystyrene storng-acid cation exchange resin powder, not thermoplastic micron
Grade weak-acid cation-exchange resin powder (or not thermoplastic micron order weak-base anion-exchange resin powder), polyethylene powder and
Polyisobutene powder is uniformly mixed.
The thermoplastic polyethylene-sulfonated polystyrene storng-acid cation exchange resin powder is (hereinafter referred to as strong
Acid resin powder), simultaneously containing thermoplastic inertia polyethylene component and sulfonated polystyrene highly acidic cation exchange polymer
Component.In mixing melt blending, polyethylene component therein can part overflow and the polyethylene powder component with adding in later and
Polyisobutene powder component is bonded together；The sulfonated polystyrene component therein then not thermoplastic micron order with adding in later
Weak-acid cation-exchange resin powder partially compatible leads to not thermoplastic micron order weak-base anion-exchange resin powder
It is attracting and more compatible to cross Acid-Base charge.This i other words, by this thermoplastic strong resin powder by remaining component be bonded,
It combines together, so as to which the sulfonic acid group that ensure that dominant cation exchange interaction can incessantly be connected in diaphragm
It connects, becomes " sky " in " starry sky type " high polymer alloy structure.This strong resin powder is impregnated with by low density polyethylene (LDPE) powder
After styrene polymerization oil phase obtained by suspension polymerisation, sulfonation, crushing, specific manufacturing method and it is required use specification
(including particle size, exchange capacity, each component content etc.), can be with document (Chinese invention patent application number
201510570174.6) described in it is consistent.
The not thermoplastic micron order weak-acid cation-exchange resin powder (hereinafter referred to as weak acid resin powder), can
It is obtained, can also be exchanged by phenolic aldehyde system Subacidity cation with being crushed by commercially available weakly acidic cationic exchange resin of acrylic series
Resin is crushed and obtain and both resins are according to crushing and obtain after the mixing of arbitrary mass ratio.Also, will use sodium form (and
Hydrogen) wet resin, by drying after crush and obtain.It is well known that the heat-resisting quantity of h type resin is substantially not so good as sodium
Type, it is therefore more likely that being difficult to the high temperature requirement for meeting thermoplastic processing.In general, gel type resin may be employed, such as model
For 110 acrylic weak resin or the phenolic aldehyde system weak acid resin of model 122；Porous type resin can also be used,
Such as the acrylic weak resin of model D110；But it is preferential using gel-type, to avoid the pore structure of porous type resin
(still can partly retain after being pulverized) causes be film-made product not fine and close enough.These Subacidity cations are handed over used by crushing
Sodium form resin is changed, cation exchange capacity is 3~10mmol/g butts, is preferably 4~7mmol/g butts.In general, it is commercially available
Acrylic weak resin exchange capacity can higher (up to more than 10mmol/g butts), high-exchange-capacity weak acid resin
Cubical expansivity also can it is very high (refer to from sodium form be transformed into Hydrogen when volume expansion percentage), so as to cause obtained conjunction
Golden film product volume change when acid/base solution environmental is converted is too big.If too low (the such as less than 3mmol/g of exchange capacity
Butt), then the ion exchange capacity of weak acid resin cannot be given full play of again, the ion exchange capacity for causing film entirety is inadequate,
Therefore membrane surface resistance can be raised significantly.It may be noted that under strong alkali solution environment, weak acid group can play better ion
Exchange interaction；And under sour environment, the ion exchange of weak acid group can significantly weaken.But either in highly acid still
Under strong alkali solution environment, swelling-shrinkage degree of the moderate weak acid resin of exchange capacity (as described above) can be all much smaller than
The strong resin of high-exchange-capacity (as cation exchange heterogeneous membrane and half homogeneous membrane of cation exchange use).Meanwhile ion
Ionic conduction performance of the exchange membrane under acid/base solution environmental will be apparently higher than the situation in salting liquid (because hydrogen ion and sodium
There are apparent migration rate differences between ion, hydroxyl and chlorion).So described is mixed with micron order weak acid tree
The cation-exchange membrane of cosmetics, membrane surface resistance in highly acid and strong alkali solution environment all will not be too high (and in salting liquid
Middle meeting is apparent higher), therefore disclosure satisfy that the requirement of operation electric current density when electrodialysis is applied.Nevertheless, it is mixed with micron
The cation exchange alloy film of grade weak acid resin powder, it should be more suitably applied to strong basicity environment (rather than strong acidic environment, because
For the less swelling of strong basicity environment lower film and ionic conduction performance higher), for example recycled with electrodialytic technique from alkaline waste liquor
Sodium hydroxide.
The not thermoplastic micron order weak-base anion-exchange resin powder (hereinafter referred to as weak base resin powder), can
It is obtained, can also be exchanged by epoxy weakly-basic anion with being crushed by commercially available polystyrene weak-base anion-exchange resin
Resin crush and obtain or crushed by acrylic acid series weak-base anion-exchange resin and obtain and these three resins according to times
It crushes and obtains after meaning mass ratio mixing.Also, to use the wet resin of chlorine type (rather than hydrogen-oxygen type), the powder after drying
It is broken and obtain.It is well known that the heat-resisting quantity of hydrogen-oxygen type resin is substantially not so good as chlorine type.In general, gel type resin may be employed,
Such as the epoxy weak base resin of model 335 or the polystyrene weak base resin of model 301；It can also use more
Pass resin, such as the acrylic acid series weak base resin of model D315；But preferentially using gel-type.Crush used by these
Weakly-basic anion exchanges chloride type resin, and ion exchange capacity is 3~10mmol/g butts, is preferably 4~8mmol/g butts.
In general, weak-base anion-exchange resin transition cubical expansivity (refer to from chlorine type be transformed into hydrogen-oxygen type when volume expansion
Percentage), it is more slightly smaller than the weak-acid cation-exchange resin of the identical degree of cross linking and exchange capacity.Especially it is commercially available
The exchange capacity of acrylic acid series weak base resin is higher (more than 9mmol/g butts), may at this time need to customize, that is, select
The product (such as 4~8mmol/g butts) turned down with exchange capacity is too big to avoid the transition cubical expansivity of resin-oatmeal.For
Do not influence the compactness of the alloy film product, used not thermoplastic Weak-acid cation exchange resin (or can not heat
The weak basic anion exchange resin of modeling) transition cubical expansivity, should all control less than 30%.It is further, it is necessary to logical
Cross the skeleton system (acrylic acid series, epoxy, styrene, phenolic aldehyde system etc.), types of radicals (weak acid and weak base), friendship of customization resin
The technical indicators such as connection degree, ion exchange capacity, the transition cubical expansivity to control them meet above-mentioned requirements.Also it is to be noted, that
Under strongly acidic solution environment, weak base group can play good ion exchange, and far short of what is expected under alkaline environment.
But either under highly acid or strong alkali solution environment, the swelling of the moderate weak base resin of exchange capacity (as described above)-
Shrinkage degree, all can be much smaller than high-exchange-capacity strong resin (such as cation exchange heterogeneous membrane and cation exchange half are homogeneous
Film is used).Even if incorporation weak base resin powder can reduce the exchange capacity of cation-exchange membrane, but as long as the few (ratio of incorporation
Such as less than 10%), influence would not be fairly obvious so that either under the highly acid still solution environmental in strong basicity, institute
The surface resistance that film product is made all will not be too high.It will be appreciated, however, that it is mixed with micron order weak base resin powder (rather than micron
Grade weak acid resin powder) cation exchange alloy film product, more suitable for strong acidic environment (rather than strong basicity environment because
The weak base group of micron order resin-oatmeal institute band can accelerate hydrionic electric drive to conduct due to hydrogen bond action), for example electricity consumption
Osmotic technique recycles the strong acid such as hydrochloric acid, sulfuric acid or nitric acid from acid waste liquid.
Above-mentioned weak-acid cation-exchange resin (or weak-base anion-exchange resin), all need to be converted into sodium form (or
Chlorine type) it dries afterwards, and water content, less than 2%, not so the toughness of resin is too strong, rigidity is insufficient, it is difficult to crush thorough.It can be first
With airflow pulverization method, drying resin is crushed to 100 mesh (150 microns) below, when reloading that grinding 3~8 is small in ball mill.
As long as loading is suitable, it is ensured that granularity after crushing is crushed to the particle more than 99% number substantially conforming to requiring
Grain size be less than 3 microns (being measured with laser particle analyzer).Repetition test uses ball it was demonstrated that crushing effect to above-mentioned resin
Mill method will be good than the method for air-flow crushing or Freezing smashing.Requirement is crushed that absolutely in most cases, can directly reach,
Without using laborious, time-consuming screening process (needing with 5000 mesh screens).Only when the granularity of micron order resin-oatmeal accords with
Above-mentioned requirements are closed, " point point an array of stars sews sky all over the sky " such " starry sky type " high polymer alloy structure could be macroscopically being formed, make
These micron powders are equivalent to " star ".Therefore, the granularity requirements of crushing are most important.
The polyethylene powder refers to by low density polyethylene (LDPE) (LDPE) and linear low density polyethylene (LLDPE), either
The mixture of the two is crushed and obtained.The polyisobutene powder, model B200 (BASF AG's production).Both materials
Specification requirement, can be described consistent with document (Chinese invention patent application number 201510570174.6).
More than the proportionings of four kinds of components must be appropriate, can just obtain described " starry sky type " the Polymer Alloy Membrane product.Four
The optimum ratio of person is：Thermoplastic polyethylene -100 parts of sulfonated polystyrene storng-acid cation exchange resin powder, can not heat
The micron order weak-acid cation-exchange resin powder (or not thermoplastic micron order weak-base anion-exchange resin powder) 5 of modeling~
0~10 part of 20 parts, 10~25 parts of polyethylene powder and polyisobutene powder.In the composition and ratio of half homogeneous phase cation exchange film, no
Thermoplastic strong resin powder addition is maximum (generally more than 40%)；And in the cation exchange alloy described in present patent application
In the composition of film, then main body (generally more than 60%) is accounted for by thermoplastic strong resin powder, it can thermoplastic film forming with play it
Main function.This also illustrates simultaneously, for cation-exchange membrane or obtains main by the sulfonic acid group performance of highly acid
Ion exchange (electric drive conduction) acts on, and not so membrane surface resistance can increased dramatically.And a small amount of weak acid resin powder is mixed, objectively
Play the role of making up the cation exchange capacity (particularly in strong alkali solution) of film on the whole, more primarily to utilizing
The characteristic that weak acid resin is less swollen.If add in the clear and definite effect for very little, not having improvement；It, can be bright if added in too much
The aobvious exchange capacity for reducing film.Another aspect, the usually incorporation of weak base resin powder, the incorporation than weak acid resin powder
It is smaller, the cation exchange capacity of made alloy film product otherwise can be reduced to a greater extent (because weak base group can be with
Strong acid group forms " ion pair ").That is, the not thermoplastic micron particles no matter mixed be weak acid resin powder or
Weak base resin powder should all play " positive interaction " (as reduced swellability of the cubical expansivity so as to improve film), and limit " pair work
With " (such as reducing ion exchange capacity), therefore content all must be suitable；And repetition test is it was demonstrated that above-mentioned 5~20 parts
Addition is suitable.The addition of polyethylene powder is to improve the caking property and compactness between membrane component；If only may be used
The strong resin powder of thermoplastic is still not enough to that thermoplastic micron order resin-oatmeal is bonded together by mixing, and can only incite somebody to action
In the latter is loosely embedded in.But if inert polyethylene powder itself add in it is too many, then can " a presumptuous guest usurps the role of the host ", cause strong acid tree
The plasticity of cosmetics has little time to play, and is separated in molding history, that is, is difficult to form sulfonic acid group and is uniformly covered with film base
The effect of body, runs counter to desire instead.The addition of polyisobutene powder component is then to improve the toughness of rolling out film, be allowed to out
Film is smooth；A small amount of addition of this kind of super high molecular weight elastomer, can generally significantly improve blending plastic cement system bonding characteristic and
The flexibility of sheet material.But if not thermoplastic micron order resin-oatmeal addition is seldom, thus system flexibility it is enough when, this
Class polyisobutene powder can not also add in.Depending on specific processing conditions and status of equipment, a small amount of releasing agent can also be added in (such as
Calcium stearate, polyethylene wax), antioxidant (such as pentaerythritol ester) and pigment (such as methyl orange), but be in most cases not required to
It adds these auxiliary agents and steady production can be completed, obtain qualified film product.It should be noted that the mixing of these four components, most
Handy high speed mixer is implemented.
2) mixture is obtained successively by mixing, two roller open mill slices, four-roll calender continuous calendering, cooling, severing
To individual prefabricated diaphragm.
The mixer can be pressing open type mixer, and mixing temperature is 130~150 DEG C, mixing time 15
~30 minutes.After the completion of mixing, clinkering pockets of " stick together material " is delivered to rapidly to two roller open mills of lasting rotation while hot immediately
On；The temperature of open mill must be previously set as 120~140 DEG C, 10~15 DEG C generally lower than mixing temperature；Then two are adjusted
Roller spacing, it is ensured that slice thickness is 1~3 millimeter.Slice is transmitted to the feed inlet of four-roller machine calender while hot, timely feed supplement,
The temperature (should gradually turn down) of four-roller and each roller spacing are set respectively, realize continuous membrane.Diaphragm thickness control for 0.12~
0.32 millimeter；If too thin, first, membrane is difficult, the unusual conditions such as part, empty piece (bulk vacancy occur) are susceptible to, second is that
The thickness of film product is also inadequate, it is impossible to meet the application requirement of electrodialysis group device, if too thick, but it is not necessary to, can not also
Raw material are wasted, production cost is caused significantly to rise.
3) an enhancing screen cloth is clamped with two prefabricated diaphragms, annealed by hot press hot pressing fusion, cooling, obtained described
Cation exchange alloy film product.
Two prefabricated diaphragms, in order to ensure uniformity of the film product in thickness direction, thickness must be the same, best
It is front and rear adjacent that two obtained from severing after same batch four-roll calendaring.Otherwise, two prefabricated membranes are on thickness
Nuance can be amplified by subsequent hot-pressing processing, ultimately result in film product and bend in the solution to being swollen the small side,
The planarization of film is bad.The enhancing screen cloth, twine material are terylene (polyester), polyamide fibre (nylon) or polypropylene fibre (poly- third
Alkene), it can also be obtained by the twine mixed weaving of these materials.For highly acid or the solution environmental of strong basicity, screen cloth material
It should be distinguished：If being mainly used for strong acidic environment, twine material should select terylene that can be acidproof；If it is mainly used for highly basic
Property environment, then polyamide fibre that preferably can be alkaline-resisting；If two class environment all can frequently be related to, consider to select polypropylene fibre.It may be noted that
Though polypropylene fibre screen cloth can be resistant to highly acid and the solution environmental of strong basicity simultaneously, terylene and brocade are not so good as to the enhancing effect of diaphragm
Synthetic fibre, i.e., the twine tensile strength of identical string diameter is not as good as both rear.Common polyethylene material screen cloth on the market, then cannot apply
In the enhancing of the alloy film product, first, (even if material is ultra-high molecular weight polyethylene) can be melted under hot pressing temperature, two
It is tensile strength or not as good as terylene, polyamide fibre and polypropylene fibre.The thickness of screen cloth will generally be slightly larger than the thickness of prefabricated membrane, too thin
Will insufficient strength, be as a result not enough to limitation diaphragm swelling；But the thickness of prefabricated diaphragm that can not be more than 2 times, otherwise, heat
The twine marking can be fairly obvious after pressure, the out-of-flatness of film surface pole.The perforation density of screen cloth should be between 20~60 mesh, and mesh number is too big
(eyelet is too small) will cause two prefabricated membranes to be difficult to realize complete welding through screen cloth, not have qualified enhancing effect；Mesh
It counts too small (eyelet is too big) and the twine in the range of unit width can be made very few, enhancing effect on the whole is still not achieved.Together
When, the too small screen cloth of mesh number (such as less than 20 mesh), often string diameter is very big (such as larger than 0.3 millimeter), twine as a result can be caused just to go up,
The diaphragm material of lower section is very few, and be swollen in the solution occur afterwards the twine significantly fallen in print (because membrane material is less,
Swelling is also few), lose the planarization of film surface.The hot pressing and the process conditions of cooling annealing may be referred to half homogeneous sun
The processing method of amberplex, it is described consistent with document (Chinese invention patent application number 201510570174.6).Finally, institute
The thickness of dry film of cation exchange alloy film obtained is 0.3~0.6 millimeter.Further, such as have no special requirements, may be referred to
The professional standard of heterogeneous membrane, generally 0.38~0.42 millimeter；Higher such as is required to film-strength or consistency, can suitably be increased
The thickness of blooming product, such as 0.5~0.6 millimeter.
The present invention is further explained below by way of specific embodiment, but therefore can not think this hair
It is bright to be only limitted among these embodiments.
Embodiment 1：
Raw material prepare：1) thermoplastic strong resin powder (polyethylene-sulfonated polystyrene strongly acidic cation exchange tree
Cosmetics)：It can refer to document (Chinese invention patent application number 201510570174.6) the method to be prepared, by Hangzhou Ai Er
Environmental Protection Technology Co., Ltd provides (granularity is below 50 mesh, cation exchange capacity is 2.58mmol/g butts).It 2) can not heat
The weak base resin powder of modeling：By epoxy weak-base anion-exchange resin, (particle size range is 0.325~1.25mm, and anion is handed over
Capacity is changed as 7.5mmol/g butts, model 335 is customized by Shanghai Huazhen Science and Technology Co., Ltd.), with 4% salt acid soak, water
Neutrality is washed till, that is, switchs to chlorine type, forced air drying is to constant weight at 60~70 DEG C；100 mesh can be passed through by being first crushed to airslide disintegrating mill
Stainless steel mesh, then with ball mill grinding 6 it is small when；Sampling analysis is measured with laser particle size analysis：Grain size is less than 3 microns of
Grain number amount is more than 99.2%, that is, is determined as qualification.3) polyethylene powder：Reference literature (Chinese invention patent application number
201510570174.6) the method is prepared, by Hangzhou Ai Er Environmental Protection Technology Co., Ltd provide (granularity for 50 mesh with
Under, crushed by LDPE particles (Yanshan Petrochemical, model 1I20A) and obtained).4) polyisobutene powder：(Chinese invention is special for reference literature
Sharp application number 201510570174.6) the method is prepared, provide that (granularity is by Hangzhou Ai Er Environmental Protection Technology Co., Ltd
It below 50 mesh, is obtained by the block polyisobutene powder of model B200 (BASF)).5) screen cloth is enhanced：Terylene material, model
DPP12S, The concrete specification are listed in table 1, are purchased from Shanghai Xintielian Sieve Manufacturing Co., Ltd.
Alloy film manufactures：A) 30 kilograms of thermoplastic strong resin powder, 2.4 kilograms of not thermoplastic weak base resins are weighed
Powder, 3.6 kilograms of polyethylene powders, 3 kilograms of polyisobutene powder (raw material proportioning is shown in Table 1), are uniformly mixed with high speed mixer；B) put into
In mixer, mixing of pressurizeing, temperature rises to 145 DEG C from 120 DEG C naturally, stops mixing, discharging；Pockets of " stick together material " is transported
To lasting rotation, roll surface temperature be continuously to pull out diaphragm on 120~125 DEG C of two roller open mills, thickness is about 2.0~
3.0 millimeter；Diaphragm while hot, is uninterruptedly put into four-roll calender feed inlet (four-roller synchronization for 6~7 meters/
Minute, temperature is followed successively by 122,119,115,112 DEG C), continuous membrane, width is 90~95 centimetres, and thickness is 0.19~0.20
Millimeter；Diaphragm from the bottom roller of four-roll calender remove after immediately by five roller coolers, with the continuous cutting edge of cutter, until width is 81
~82 centimetres, end is blocked automatically with pulse cutting machine, obtains the prefabricated diaphragm that length is 162~164 centimetres；C) it is membrane is suitable
Two adjacent prefabricated diaphragms of sequence clamp enhancing screen cloth (84 × 168 centimetres), are integrally placed at and cover polyester protective film in advance
Stainless steel plate (180 centimetres of length, 90 centimetres of width, the thickness of (180 centimetres of length, 90 centimetres of width, 0.125 millimeter of thickness)
2.0 millimeters) on, then a kind of same polyester protective film and stainless steel plate are covered, it is sent into oil pressure after being so superimposed 8~10 layers
Machine, hot pressing 60 minutes under 155~160 DEG C, 15~18MPa are passed through circulating cooling water cooling, take out, successively remove steel plate and
Polyester protective film is made the cation exchange alloy film, can be cut into according to electrodialytic group of device standard of heterogeneous membrane
800 × 1600 millimeters, average thickness is 0.43 millimeter.
With reference to the assay method described in professional standard (HY/T 034.2-1994), the performance detection data of gained film product
It is listed in table 2.It can be seen that its size swellbility in brine and strong acid is all little, the dry and wet on length and width direction
Size increment rate is below 3%；And in highly basic, since polyester screen cloth can slowly be degraded, humidification can gradually weaken, and lead
Swellbility is caused to be continuously increased with soaking time.Nonetheless, 15 days rear films are impregnated in highly basic and still keeps apparent intact, tieed up
Planarization and tensile strength have been held, has not occurred significantly being disintegrated sign.It is said that membrane surface resistance testing number is bright, the film is in strong acid
Surface resistance be less than 5 Ω cm2, the requirement of electrodialysis application can be met；And in highly basic, due to being constantly swollen, testing number
According to unstable (compactness is less and less, therefore loses actual application value).This it is stated that, it is obtained under the formulation condition
Cation exchange alloy film product, be more suitably applied to electrodialysis removing or the concentration process of strong acid (rather than highly basic).
Embodiment 2：
By the epoxy weak base resin of the model 335 in embodiment 1, the acrylic acid series weak base tree of model D315 is changed into
(particle size range is 0.325~1.25mm to fat, and anion-exchange capacity 6.5mmol/g is determined by Shanghai Huazhen Science and Technology Co., Ltd.
System)；By the terylene mesh of model DPP12S, the terylene mesh of model DPP20S is changed into (from the new iron chains sieve manufacture in Shanghai
Co., Ltd purchases)；Remaining raw material and proportioning constant compared with Example 1 (being specifically shown in Table 1).According to described in embodiment 1
Identical alloy film manufacturing process, is first made the prefabricated diaphragm that thickness is 0.12 millimeter, and it is 0.30 millimeter that thickness is made after hot pressing
Alloy film product.
Assay method with reference to described in professional standard, the performance detection data of gained film product are listed in table 2, conclusion and
Rule with it is basically identical in embodiment 1.Illustrate simultaneously, reduce film thickness, the qualified products that can still obtain the alloy film are (dry
Film thickness only has 0.3 millimeter, more apparent than embodiment 1 thin).
Embodiment 3：
By the epoxy weak base resin of the model 335 in embodiment 1, the polystyrene weak base tree of model 301 is changed into
(particle size range is 0.325~1.25mm to fat, and anion-exchange capacity 5.2mmol/g is determined by Shanghai Huazhen Science and Technology Co., Ltd.
System)；By " 2.4 kilograms of not thermoplastic weak base resin powder, 3.6 kilograms of polyethylene powders, the 3 kilograms of polyisobutene in embodiment 1
Powder " changes into " 1.5 kilograms of not thermoplastic (301) weak base resin powder, 4.5 kilograms of polyethylene powders, 1.5 kilograms of polyisobutene powder ".
Thickness is first made as 0.18 milli in remaining raw material and alloy film manufacturing process, constant compared with Example 1 (being specifically shown in Table 1)
The alloy film product that thickness is 0.41 millimeter is made in the prefabricated diaphragm of rice after hot pressing.
Assay method with reference to described in professional standard, the performance detection data of gained film product are listed in table 2, conclusion and
Rule with it is basically identical in embodiment 1, illustrate that the system of not thermoplastic micron order weak base resin powder (becomes benzene second from epoxy
Alkene system) it influences to be not obvious.
Embodiment 4：
By the epoxy weak base resin of the model 335 in embodiment 1, the phenolic aldehyde system weak acid resin of model 122 is changed into
(particle size range is 0.325~1.25mm, cation exchange capacity 4.2mmol/g, and by Bengbu TianXing, resin Co., Ltd determines
System)；By " 2.4 kilograms of not thermoplastic weak base resin powder, 3.6 kilograms of polyethylene powders, the 3 kilograms of polyisobutene in embodiment 1
Powder " changes into " 3.6 kilograms of not thermoplastic (122) weak acid resin powder, 4.8 kilograms of polyethylene powders, 1.5 kilograms of polyisobutene powder "；
By the terylene mesh of model DPP12S, the polyamide fibre screen cloth of model JPP24 is changed into (from the limited public affairs of the new iron chains sieve manufacture in Shanghai
Department's buying)；Thickness is first made in remaining raw material and alloy film manufacturing process, constant compared with Example 1 (being specifically shown in Table 1)
For 0.20 millimeter of prefabricated diaphragm, the alloy film product that thickness is 0.46 millimeter is made after hot pressing.
Assay method with reference to described in professional standard, the performance detection data of gained film product are listed in table 2.It can be seen that
Its size swellbility in brine, strong acid and highly basic is all little, and the dry and wet size increment rate on length and width direction is equal
Less than 3%.But it also can slowly degrade it may be noted that polyamide fibre screen cloth is exposed to for a long time under strong acid condition, therefore the swelling in strong acid
Degree still extremely slowly can increase (being difficult to significantly present in a short time) with the extension of soaking time.Membrane surface resistance detects
Show that surface resistance of the film in strong acid and highly basic is below 4 Ω cm2, the requirement of electrodialysis application can be met.It considers
Polyamide fibre screen cloth is easier generation ion exchange intolerant to strong acid characteristic and weak acid resin powder under strong basicity environment, it is proposed that should
Obtained cation exchange alloy film product, the electrodialysis for being more suitably applied to highly basic (rather than strong acid) take off under formulation condition
It removes or concentration process.
Embodiment 5：
By the epoxy weak base resin of the model 335 in embodiment 1, the phenolic aldehyde system weak acid resin of model 110 is changed into
(particle size range is 0.325~1.25mm, cation exchange capacity 4.5mmol/g, and by Bengbu TianXing, resin Co., Ltd determines
System)；By " 2.4 kilograms of not thermoplastic weak base resin powder, 3.6 kilograms of polyethylene powders, the 3 kilograms of polyisobutene in embodiment 1
Powder " changes into " 3.0 kilograms of not thermoplastic (110) weak acid resin powder, 4.2 kilograms of polyethylene powders, 1.5 kilograms of polyisobutene powder "；
By the terylene mesh of model DPP12S, the polyamide fibre screen cloth of model JPP16 is changed into (from the limited public affairs of the new iron chains sieve manufacture in Shanghai
Department's buying)；Remaining raw material and alloy film manufacturing process, are basically unchanged (are specifically shown in Table 1) compared with Example 1, are first made
Thickness is 0.24 millimeter of prefabricated diaphragm, and the alloy film product that thickness is 0.58 millimeter is made after hot pressing.
Assay method with reference to described in professional standard, the performance detection data of gained film product are listed in table 2.With embodiment 4
Comparative illustration, the increase of film thickness can not significantly affect size swellbility of the film in brine, strong acid and highly basic；And
Surface resistance increase in strong acid and highly basic is all less (still less than 5 Ω cm2) it still can meet wanting for electrodialysis application
It asks.The reason for same as Example 4, it is proposed that obtained cation exchange alloy film product under the formulation condition, being more suitable for should
For the electrodialysis removing of highly basic or concentration process.
Embodiment 6：
By the terylene mesh of the model DPP12S in embodiment 1, change into the same polypropylene fibre screen cloth of braiding specification (see
Table 1 is provided by Hai Shuhuatian sieves Co., Ltd of Ningbo City)；Or it is 0.19 millimeter pre- with thickness obtained in embodiment 1
Piece is film-made, uses identical heat pressing process that thickness is made as 0.43 millimeter of alloy film product.
Assay method with reference to described in professional standard, the performance detection data of gained film product are listed in table 2.Show film in salt
Size swellbility in water, strong acid and highly basic, the dry and wet size increment rate on length and width direction are below 3%；And film
Surface resistance in strong acid and highly basic is below 5 Ω cm2.It can be resistant to simultaneously at normal temperatures in view of the screen cloth of polypropylene material
Highly acid and strong alkali solution environment, therefore, obtained cation exchange alloy film product, can answer simultaneously under the formulation condition
Electrodialysis removing or concentration process for strong acid or highly basic.
Embodiment 7：
By the polyamide fibre screen cloth of the model JPP24 in embodiment 4, the polypropylene fibre screen cloth in embodiment 6 is changed into；Or with implementation
Thickness obtained is 0.20 millimeter of prefabricated diaphragm in example 4, uses identical heat pressing process that thickness is made as 0.44 millimeter of conjunction
Golden film product.
Assay method with reference to described in professional standard, the performance detection data of gained film product are listed in table 2, conclusion and
Rule and embodiment 6 are basically identical.And it further illustrates：Either mix micron order weak acid resin powder or micron order weak base
Resin-oatmeal is attained by the purpose for the swellbility being substantially reduced in highly acid and strong alkali solution.
Comparative example：
Method described in reference literature (Chinese invention patent application number 201510570174.6) (specifically refers to embodiment
3) half homogeneous phase cation exchange film, is prepared, obtains the thickness of prefabricated diaphragm as 0.38 millimeter, the thickness that film product is made is
0.43 millimeter.Specific raw material and formula (being shown in Table 1) are as follows：20 kilograms not thermoplastic strong resin powder (by sodium form 001 ×
9 highly acid sulfonic acid type styrene type cation exchange resins are crushed to below 300 mesh, cation exchange capacity 4.37mmol/
G), 9 kilograms of thermoplastic strong resin powder (the same all embodiments of the invention of specification), 5 kilograms of LLDPE powder (model 20100J,
Mitsui Chemicals), 5 kilograms of LDPE powder (model 1I20A, Yanshan Petrochemical), 1.4 kilograms of polyisobutene powder.With the embodiment of the present invention
It compares, has in place of main difference：A) with grain size increase the not thermoplastic strong resin powder of at least one order of magnitude instead of
Micron-sized not thermoplastic weak base resin powder (or weak acid resin powder)；B) " primary and secondary " of specific formula ratio is different, can not heat
The addition for moulding component is maximum instead；C) screen cloth enhancement method is different, is to cover surface heat by two thin net to be press-fitted into Er Feiben
Thick net described in inventive embodiments is embedded in interior method.
With reference to the assay method (detection data are listed in table 2) of professional standard, show half homogeneous membrane in brine, strong acid and highly basic
In size swellbility it is all bigger, the dry and wet size increment rate on length and width direction is all higher than 3% (if out-phase
Film, toward contact meeting bigger).Moreover, it is present with film quickly because the polyester screen cloth of surface covering dissolves in strong base solution
Net separation, the situation (it is i.e. broken to actually appear tearing) of membrane material disintegration.Further comparative study, such as surface cover nylon or
The thin screen cloth of person's polypropylene, find the screen cloth because of these materials does not tolerate high temperature hot pressing (more apparent than terylene poor), it is difficult to
Half homogeneous membrane product of diaphragm has all intactly been pressed into any surface finish, screen cloth.Even if taking out the preferable position of hot pressing situation,
It (being usually no more than 10 times) after highly acid and strong alkali solution environment multiple conversions, diaphragm will be separated from middle part,
Large-sized strong resin powder can be stripped out, and moment makes soaking solution become muddy.This i.e. illustrate, " fabric of island-in-sea type " structure it is different
Phase film and half homogeneous membrane, it is impossible to as the alloy film of " starry sky type " structure of the present invention, can prolonged application in strong acid
The electrodialytic process of property or strong alkali solution environment.
Above-described embodiment is for the explanation and illustration present invention rather than limits the invention.The present invention's
Within spirit and scope of the claims, as made by those of ordinary skill in the art to any modification of the present invention and
Change, all without departing from protection scope of the present invention.
Claims (8)
1. a kind of manufacturing method of cation exchange alloy film, which is characterized in that this method comprises the following steps：It 1) can thermoplastic
Polyethylene-sulfonated polystyrene storng-acid cation exchange resin powder, thermoplastic micron order Subacidity cation does not exchange
Resin-oatmeal (or not thermoplastic micron order weak-base anion-exchange resin powder), polyethylene powder and the mixing of polyisobutene powder are equal
It is even；2) mixture is obtained into list successively by mixing, two roller open mill slices, four-roll calender continuous calendering, cooling, severing
The prefabricated diaphragm opened；3) an enhancing screen cloth is clamped with two prefabricated diaphragms, anneals, obtain by hot press hot pressing fusion, cooling
To the cation exchange alloy film product.
2. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that in the step 1
The quality proportionings of four kinds of raw materials be：Thermoplastic polyethylene-sulfonated polystyrene storng-acid cation exchange resin powder 100
Part, (or not thermoplastic micron order weakly-basic anion does not exchange for thermoplastic micron order weak-acid cation-exchange resin powder
Resin-oatmeal) 5~20 parts, 0~10 part of 10~25 parts of polyethylene powder and polyisobutene powder.
3. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that in the step 1
Not thermoplastic micron order weak-acid cation-exchange resin powder, can be by acrylic weak cation exchange sodium form tree
Cosmetics is broken and obtains, can also be exchanged by phenolic aldehyde system Subacidity cation sodium form resin crush and obtain and both resins according to
It crushes and obtains after arbitrary mass ratio mixing.These Subacidity cations exchange sodium form resin used by the crushing, sun from
Sub- exchange capacity is 3~10mmol/g butts, is preferably 4~7mmol/g butts.
4. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that in the step 1
Not thermoplastic micron order weak-base anion-exchange resin powder, can by polystyrene weakly-basic anion exchange chlorine type tree
Cosmetics is broken and obtains, and can also be obtained by the exchange chloride type resin crushing of epoxy weakly-basic anion or by acrylic acid series weak base
Property anion exchange chloride type resin crush and obtain and these three resins are obtained according to being crushed after the mixing of arbitrary mass ratio.Institute
These weakly-basic anions exchange chloride type resin used by stating crushing, and ion exchange capacity is 3~10mmol/g butts, preferably
For 4~8mmol/g butts.
5. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that in the step 1
Not thermoplastic micron order weak-acid cation-exchange resin powder (or thermoplastic micron order weakly-basic anion does not exchange tree
Cosmetics), granularity control is that the grain size of the particle more than 99% number is less than 3 microns (being measured with laser particle analyzer).
6. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that in the step 2
Individual prefabricated diaphragm, thickness be 0.12~0.32 millimeter.
7. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that in the step 3
Enhancing screen cloth, twine material be terylene (polyester), polyamide fibre (nylon) or polypropylene fibre (polypropylene), can also be by these three materials
Twine mixed weaving and obtain；The thickness of used screen cloth is greater than the thickness of the prefabricated diaphragm, but pre- less than 2 times
Diaphragm thickness processed.
8. the manufacturing method of cation exchange alloy film according to claim 1, which is characterized in that obtained cation
The thickness of dry film for exchanging alloy film is 0.3~0.6 millimeter.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111087055A (en) * | 2019-12-31 | 2020-05-01 | 佛山市云米电器科技有限公司 | Method for preparing electric desalting device based on two-state low-deformation ion exchange membrane |
| CN115072904A (en) * | 2022-07-14 | 2022-09-20 | 重庆海通环保科技有限公司 | Reverse osmosis membrane for fractional reverse osmosis treatment of treatment liquid |
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| CN115072904A (en) * | 2022-07-14 | 2022-09-20 | 重庆海通环保科技有限公司 | Reverse osmosis membrane for fractional reverse osmosis treatment of treatment liquid |
| CN115072904B (en) * | 2022-07-14 | 2023-10-27 | 重庆海通环保科技有限公司 | Reverse osmosis membrane body for fractional reverse osmosis treatment of treatment fluid |
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