CN103349915A - Preparation method for cationic exchange membrane suitable for diffusion dialysis recycle of squeeze alkali liquor in viscose fibre production - Google Patents
Preparation method for cationic exchange membrane suitable for diffusion dialysis recycle of squeeze alkali liquor in viscose fibre production Download PDFInfo
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Abstract
The invention relates to a preparation method for a cationic exchange membrane suitable for diffusion dialysis recycle of squeeze alkali liquor in viscose fibre production, and belongs to the technical field of membrane preparation of membrane recycle in viscose fibre production. The technology comprises material selection of a basal membrane, irradiation activation of the basal membrane, functional group grafting process and sulfonation process. The preparation method optimizes the basal membrane selection, and carries out an irradiation activation process to the basal membrane; the gained cationic exchange membrane suitable for the diffusion dialysis recycle of squeeze alkali liquor in viscose fibre production is made into membrane group equipment; the membrane group equipment is applied to the squeeze alkali liquor diffusion dialysis recycle in the viscose fibre production, and aims at the squeeze alkali liquor containing sodium hydroxide and hemicellulose simultaneously; the recovery rate of alkali in the squeeze alkali liquor can be increased, the alkaline-resisting concentration can be enhanced, the reject rate to hemicellulose can be increased, the diffusion efficiency can be enhanced, damage to a diffusion dialysis membrane system by the alkali liquor can be reduced, stoppage to the diffusion dialysis membrane can be prevented, and the service life of the membrane can be prolonged.
Description
Technical field
The present invention relates to the preparation method of a kind of diffusion dialysis with cation-exchange membrane, more particularly, the present invention relates to a kind of preparation method that the cation-exchange membrane of press lye in viscose rayon production is reclaimed in diffusion dialysis that is applicable to, belong to the membrane preparation technology field that in viscose rayon production, film reclaims.
Background technology
Production process of viscose fiber in chemical fibre industry, can produce the akaline liquid that contains high-enriched organics (take hemicellulose as main).If let alone direct discharge, will cause serious environmental pollution.Process this alkali lye if adopt the method for neutralization, a large amount of acid will be consumed, and cause a large amount of inorganic salts of formation in alkali lye, therefore the alkali in this alkali lye is reclaimed, and make organic matter wherein become the solid matter that can carry out harmless treatment to be only the processing mode more friendly to environment.
Viscose staple fibre is the cellulose reprocessing product be present in natural products, have the water suction moisturizing, smooth nice and cool, ventilative, antistatic, the characteristic such as gorgeous dyes.Its production process is to use bamboo, wood, cotton, it is raw material that fiber crops etc. are rich in the prepared pulp of cellulosic plant, through caustic soda, flood, yellow, and thereby regeneration obtains the viscose rayon product in acid coagulating bath, at caustic soda, flood, the link of squeezing can produce above-mentioned akaline liquid, this akaline liquid is called press lye, be different from the spent lye that other industry produces, its composition is mainly NaOH and hemicellulose, at present the alkali in this alkali lye is reclaimed and also lacks effective means, although adopt Nanofiltering membrane to reclaim alkali in the minority field, but still exist the rate of recovery low, the shortcoming that operating cost is high.
Diffusion dialysis is to utilize pellicle or perm-selective ion-ex-change membrane, the process that the solute in solution is moved to low concentration one side by film by high concentration one side, and this process is to take concentration difference as power.It is mainly used in separating and purifying of organic and inorganic electrolyte.Aspect environmental project, be mainly used at present processing and the recovery of Suan ﹑ alkali wasteliquid.
But the diffusion dialysis cation-exchange membrane in currently available technology is acid proof cation-exchange membrane, it is mainly to reclaim acid solution that the diffusion dialysis film of its application reclaims, and is not suitable for the recovery of the press lye in viscose rayon production.
It is CN102908916A that State Intellectual Property Office discloses a publication number in 2013.2.6, name is called the patent of invention of " a kind of preparation method of doughnut diffusion dialysis alkali reclamation film ", this patent discloses a kind of preparation method of polymeric membrane, specifically refers to a kind of preparation method of doughnut diffusion dialysis alkali reclamation film.The hollow fiber ultrafiltration membrane of selecting polypropylene, polyacrylonitrile or nylon in the present invention is the doughnut basement membrane, basement membrane is placed in to plasma chamber to carry out plasma-activated, the doughnut basement membrane activated is immersed in the solution of styrene, divinylbenzene, benzoyl peroxide and carries out the functional group grafting, again the doughnut basement membrane after the functional group grafting be take to silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent.Advantage of the present invention be in the membrane material of unit are, have treating capacity large, make the characteristics such as the assembly floor space is little.The present invention is with a wide range of applications.
Above-mentioned patent is to be applicable to the diffusion dialysis film that alkali reclaims, although solved the problem that film in the past is not suitable for the alkali environment, but still have the defect that intensity is low, the life-span is short, operating cost is high, the viscose rayon that can not be applicable to simultaneously to contain NaOH and hemicellulose produce in the recycling of press lye.
Summary of the invention
The present invention is intended to solve the problem that the viscose rayon that for diffusion dialysis alkali reclamation film, can not be applicable to simultaneously to contain NaOH and hemicellulose of the prior art is produced the recycling of press lye, a kind of preparation method that the cation-exchange membrane of press lye in viscose rayon production is reclaimed in diffusion dialysis that is applicable to is provided, make its product can be used in the recycling of press lye in viscose rayon production, and reach the increase film-strength, extend membrane lifetime, reduce the purpose of operating cost.
In order to realize the foregoing invention purpose, its concrete technical scheme is as follows:
A kind of preparation method who is applicable to the cation-exchange membrane of press lye in the production of diffusion dialysis recovery viscose rayon is characterized in that: comprise following processing step:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is placed under electron beam irradiation and is activated under nitrogen atmosphere, and described activation adopts the electron linear accelerator of 10Mev, and irradiation dose is controlled as 2-20kgy.
C, functional group grafting are processed
Basement membrane through irradiation activation in step B is carried out to the functional group grafting;
D, sulfonation are processed
To in step C, through the basement membrane of grafting, take silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent, then through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye
.
In step C of the present invention, describedly by step B, through the basement membrane of irradiation activation, carrying out the functional group grafting, refer to and will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 70-90:10-20:0.1-1.
In step D of the present invention, in described sulfonation process, sulfonation temperature is 40-60 ℃.
In step D of the present invention, in described sulfonation process, the sulfonation time is 5-7 hour.
The useful technique effect that the present invention brings:
1, of the present inventionly be applicable to preparation method that diffusion dialysis reclaims the cation-exchange membrane of press lye in viscose rayon production the selection of basement membrane is optimized, and basement membrane has been carried out to the irradiation activation processing, the cation-exchange membrane that is applicable to press lye in the production of diffusion dialysis recovery viscose rayon obtained is made into film group device, be applied to viscose rayon produce in press lye diffusion dialysis while reclaiming, for the press lye that contains NaOH and hemicellulose simultaneously, can improve the rate of recovery of alkali in press lye, improve alkaline-resisting concentration, improve half-and-half cellulosic rejection, improve diffuser efficiency, reduce the damage of alkali lye to diffusion dialysis film system, prevent the obstruction to the diffusion dialysis film, improve the service life of film, and guaranteed carrying out smoothly of diffusion dialysis and subsequent handling, in use can guarantee film strength in addition, and operating cost is cheap.
2, in the present invention for the optimization of functional group grafting treatment fluid and sulfonation process technological parameter, more optimized the performance of its product, when reclaiming viscose rayon production press lye for diffusion dialysis, rise appreciably service life, reduced production cost, and make the preparation technology's Energy Intensity Reduction of itself, efficiency improves.
The specific embodiment
embodiment 1
A kind of preparation method who is applicable to the cation-exchange membrane of press lye in the production of diffusion dialysis recovery viscose rayon comprises following processing step:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is placed under electron beam irradiation and is activated under nitrogen atmosphere, and described activation adopts the electron linear accelerator of 10Mev, and irradiation dose is controlled as 2kgy.
C, functional group grafting are processed
Basement membrane through irradiation activation in step B is carried out to the functional group grafting;
D, sulfonation are processed
To in step C, through the basement membrane of grafting, take silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent, then through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye
.
embodiment 2
A kind of preparation method who is applicable to the cation-exchange membrane of press lye in the production of diffusion dialysis recovery viscose rayon comprises following processing step:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is placed under electron beam irradiation and is activated under nitrogen atmosphere, and described activation adopts the electron linear accelerator of 10Mev, and irradiation dose is controlled as 20kgy.
C, functional group grafting are processed
Basement membrane through irradiation activation in step B is carried out to the functional group grafting;
D, sulfonation are processed
To in step C, through the basement membrane of grafting, take silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent, then through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye
.
embodiment 3
A kind of preparation method who is applicable to the cation-exchange membrane of press lye in the production of diffusion dialysis recovery viscose rayon comprises following processing step:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is placed under electron beam irradiation and is activated under nitrogen atmosphere, and described activation adopts the electron linear accelerator of 10Mev, and irradiation dose is controlled as 11kgy.
C, functional group grafting are processed
Basement membrane through irradiation activation in step B is carried out to the functional group grafting;
D, sulfonation are processed
To in step C, through the basement membrane of grafting, take silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent, then through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye
.
embodiment 4
A kind of preparation method who is applicable to the cation-exchange membrane of press lye in the production of diffusion dialysis recovery viscose rayon comprises following processing step:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is placed under electron beam irradiation and is activated under nitrogen atmosphere, and described activation adopts the electron linear accelerator of 10Mev, and irradiation dose is controlled as 5kgy.
C, functional group grafting are processed
Basement membrane through irradiation activation in step B is carried out to the functional group grafting;
D, sulfonation are processed
To in step C, through the basement membrane of grafting, take silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent, then through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye
.
embodiment 5
On the basis of embodiment 1-4, preferred:
In step C, describedly by step B, through the basement membrane of irradiation activation, carrying out the functional group grafting, refer to and will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 70:10:0.1.
In step D, in described sulfonation process, sulfonation temperature is 40 ℃.
In step D, in described sulfonation process, the sulfonation time is 5 hours.
embodiment 6
On the basis of embodiment 1-4, preferred:
In step C, describedly by step B, through the basement membrane of irradiation activation, carrying out the functional group grafting, refer to and will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 90:20:1.
In step D, in described sulfonation process, sulfonation temperature is 60 ℃.
In step D, in described sulfonation process, the sulfonation time is 7 hours.
embodiment 7
On the basis of embodiment 1-4, preferred:
In step C, describedly by step B, through the basement membrane of irradiation activation, carrying out the functional group grafting, refer to and will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 80:15:0.55.
In step D, in described sulfonation process, sulfonation temperature is 50 ℃.
In step D, in described sulfonation process, the sulfonation time is 6 hours.
embodiment 8
On the basis of embodiment 1-4, preferred:
In step C, describedly by step B, through the basement membrane of irradiation activation, carrying out the functional group grafting, refer to and will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
The amount ratio of above-mentioned styrene, divinylbenzene and benzoyl peroxide is 85:12:0.88.
In step D, in described sulfonation process, sulfonation temperature is 55 ℃.
In step D, in described sulfonation process, the sulfonation time is 5.5 hours.
Claims (5)
1. one kind is applicable to the preparation method that the cation-exchange membrane of press lye in viscose rayon production is reclaimed in diffusion dialysis, it is characterized in that: comprise following processing step:
The selection of A, basement membrane
Select with a kind of cloth in nylon, polypropylene and polyvinyl chloride, or the cloth of any two cospinning shape is basement membrane;
The irradiation activation of B, basement membrane
The basement membrane of steps A is placed under electron beam irradiation and is activated under nitrogen atmosphere, and described activation adopts the electron linear accelerator of 10Mev, and irradiation dose is controlled as 2-20kgy;
C, functional group grafting are processed
Basement membrane through irradiation activation in step B is carried out to the functional group grafting;
D, sulfonation are processed
To in step C, through the basement membrane of grafting, take silver sulfate as catalyst, the concentrated sulfuric acid of take carries out sulfonation as sulfonating agent, then through cooling, separate, take out obtain of the present invention be applicable to diffusion dialysis reclaim viscose rayon produce in the cation-exchange membrane of press lye
.
According to claim 1 a kind of be applicable to diffusion dialysis reclaim viscose rayon produce in the preparation method of cation-exchange membrane of press lye, it is characterized in that: in step C, describedly by step B, through the basement membrane of irradiation activation, carrying out the functional group grafting, refer to and will be in step B through the basement membrane of irradiation activation, be soaked in the mixed solution of styrene, divinylbenzene and benzoyl peroxide and carry out the functional group grafting.
According to claim 2 a kind of be applicable to diffusion dialysis reclaim viscose rayon produce in the preparation method of cation-exchange membrane of press lye, it is characterized in that: the amount ratio of described styrene, divinylbenzene and benzoyl peroxide is 70-90:10-20:0.1-1.
According to claim 1 a kind of be applicable to diffusion dialysis reclaim viscose rayon produce in the preparation method of cation-exchange membrane of press lye, it is characterized in that: in step D, in described sulfonation process, sulfonation temperature is 40-60 ℃.
5. according to the described a kind of preparation method that the cation-exchange membrane of press lye in viscose rayon production is reclaimed in diffusion dialysis that is applicable to of claim 1 or 4, it is characterized in that: in step D, in described sulfonation process, the sulfonation time is 5-7 hour.
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| CN106994304A (en) * | 2017-05-08 | 2017-08-01 | 厦门大学 | A kind of homogeneous phase cation exchange film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921319A (en) * | 2012-11-09 | 2013-02-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102921319A (en) * | 2012-11-09 | 2013-02-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106994304A (en) * | 2017-05-08 | 2017-08-01 | 厦门大学 | A kind of homogeneous phase cation exchange film and preparation method thereof |
| CN106994304B (en) * | 2017-05-08 | 2020-05-12 | 厦门大学 | Homogeneous cation exchange membrane and preparation method thereof |
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