CN102908916B - Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane - Google Patents
Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane Download PDFInfo
- Publication number
- CN102908916B CN102908916B CN201210447326.XA CN201210447326A CN102908916B CN 102908916 B CN102908916 B CN 102908916B CN 201210447326 A CN201210447326 A CN 201210447326A CN 102908916 B CN102908916 B CN 102908916B
- Authority
- CN
- China
- Prior art keywords
- membrane
- doughnut
- basement membrane
- hollow fiber
- preparation
- 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
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a polymeric membrane and particularly relates to a preparation method of a hollow fiber dispersion and dialysis alkali recycling membrane. The preparation method comprises the steps of selecting a hollow fiber ultra-filtration membrane of polypropylene, polyacrylonitrile or nylon as a hollow fiber base membrane; putting the base membrane into a plasma chamber to carry out plasma activation; immersing the activated hollow fiber base membrane into a solution of styrene, divinylbenzene and benzoyl peroxide to carry out functional group grafting; and sulfonating the hollow fiber base membrane with the grafted functional group by taking silver sulfate as a catalyst and taking concentrated sulfuric acid as a sulfonating agent. The preparation method has the advantages that a membrane material in unit area has the characteristics of large processing amount, small occupied area of an assembly made of the membrane and the like. The preparation method has a wide application prospect.
Description
Technical field
The invention belongs to chemical production technical field, be specifically related to a kind of preparation method of doughnut diffusion dialysis alkali collection film.
Background technology
All a large amount of salkali waste can be produced in processes such as papermaking, cast aluminium, chemical fibre, ion exchange resin regenerations.If let alone direct discharge, serious environmental pollution will be caused.If adopt the method process salkali waste of neutralization, will a large amount of acid be consumed, and cause the inorganic salts that shape in waste water is a large amount of, so alkali collection must carry out.Current alkali recovery technology based on boiling, burn, minority field adopts Nanofiltering membrane to reclaim, and these methods have and reclaim the high shortcoming of operating cost.Diffusive dialysis method reclaims alkali, due to substantially without operating cost, is a kind of novel, the economic method of alkali collection.
Diffusion dialysis utilizes pellicle or perm-selective ion-ex-change membrane, makes the process that the solute in solution is moved to low concentration side by film by high concentration side.This process take concentration difference as power, so also referred to as concentration difference dialysis or natural dialysis.It is mainly used in organic and abstraction and purification that is inorganic electrolyte.In environmental project, be mainly used in process and the recovery of Suan ﹑ alkali wasteliquid at present.
The beginning of the fifties in 19th century, Englishize scholar T. Graham Sodd method of investing starts the diffusion systematically studying solution, have studied again the characteristic of different solute by pellicle (film that parchment or celloidin etc. are made) subsequently, find that the molecule of some solutes or ion are by the larger colloidal particle then intransitable phenomenon of the pore of pellicle, Graham Sodd method of investing claims this phenomenon to be dialysis.The equipment around this principle made is called dialyzer, is usually used in the purification of the macromolecular compounds such as the concentrated of colloidal solution and the sour ﹑ protein of core.The 1950's, there is the diffusion dialysis device using amberplex as barrier film.
Domesticly just have developed diffusion dialysis film as far back as 1964.But due to the restriction of film preparation technique, the structure of the similar homogeneous phase ionic membrane of the film obtained, as polysulfones quaternary ammonium cavity block S203, DF120 and chlorinated polyvinyl chloride type weak alkaline ionexchange memberanes are all this type of film.
In diffusion dialysis process, the motive force of ion transmission is the concentration difference of film both sides, and the homo-ion repulsion that application Donnan (Donnan) balances and electroneutral maintain correlation theory, realizes the selectively penetrating of ion thus reaches the object of separation.This process is divided into anode membrane diffusion dialysis (recovery as alkali) and cavity block diffusion dialysis (recovery as acid).Wherein cavity block diffusion dialysis technology utilizes anion-exchange membrane to realize acid and being separated of salt to hydrogen ion is different from the selective penetrated property of metal ion, such as the mixed solution of hydrochloric acid and aluminium chloride and water are placed in respectively the both sides of anion-exchange membrane, because the acid of solution side and the concentration of salt are far above water side, the trend of acid and salt oriented water side infiltration, but anion-exchange membrane has selective penetrated property, often kind of ion can not be allowed to pass through with equal opportunity; First anionic membrane skeleton itself is positively charged, have in the solution and attract electronegative ion hydration and repel the characteristic of positively charged ion hydration, therefore under the effect of concentration difference, the chlorion of solution side is attracted and successfully enters the side of water through fenestra road; Simultaneously according to electroneutral requirement, also the ion with positive charge can be carried secretly, but because the hydrated radius of H+ is smaller, electric charge is less, and aluminum ions ion hydration radius is comparatively large, again with high valence charge, therefore hydrogen ion preferentially can pass through film, acid in such solution will be separated into water inlet side, the hydrionic key by being diffusion dialysis in this process.Amberplex used needs to possess some suitable performances, such as stability in an acidic solution, and high hydrogen ion percent of pass, to high rate of rejection and the low water percent of pass etc. of metal ion.Anode membrane diffusion dialysis process for alkali collection is similar with it.
Abroad, the technical development that acid is reclaimed in diffusion dialysis is comparatively rapid, and wherein representative country is the U.S. and Japan.The Exergy technique company of the U.S. develops a kind of online diffusion dialysis technology newly, and pushes commercial Application to.This technique adopts amberplex process Waste Sulfuric Acid, makes it recycle.System utilizes flowmeter and liquid level gauge to control, and is designed to full-automatic mode, is provided with grid spacer between film, stablizes to keep lamination.The rate of recovery of acid can reach 88%, and metal rejection reaches 95%, and greatly reduce the dialysis liquid measure delivering to Waste Water Treatment, thus reduce the consumption of neutralization chemicals, energy consumption also greatly reduces.
The above all shows that the technology of diffusion dialysis reclamation film has other membrane process and the incomparable advantage of the way of distillation, but the diffusion dialysis film of current recovery alkali is substantially based on flat film.One of shortcoming of Flat Membrane diffusion dialysis is exactly that membrane area in unit volume is too small, causes treating capacity less than normal.
Summary of the invention
We are for above present situation, on the basis of forefathers' research, for the requirement of the diffusion dialysis film preparation of recovery alkali, series of studies and exploitation are carried out, through many-sided experimental study, finally have developed the diffusion dialysis film of hollow fiber form, have treating capacity large, make the features such as assembly floor space is little; On this basis, according to the requirement of alkali collection diffusion dialysis film, continue to carry out study to the kind of the type selecting of doughnut basement membrane, the plasma-activated process of basement membrane, grafting process, functionalization monomer and proportioning, reaction kinetic time and temperature and optimizes, finally develop the doughnut diffusion dialysis film that can be used for acid recovery.
The present invention is directed to deficiency of the prior art, propose diffusion dialysis film, have treating capacity large, make the features such as assembly floor space is little.
The present invention is achieved by following technical proposals:
A preparation method for doughnut diffusion dialysis alkali collection film, is characterized in that comprising the steps:
(1) the choosing of doughnut basement membrane
The hollow fiber ultrafiltration membrane of polypropylene, polyacrylonitrile or nylon is selected to be doughnut basement membrane;
(2) doughnut basement membrane is plasma-activated
Doughnut basement membrane is placed in plasma chamber to carry out plasma-activated; Wherein the electrode of gas ions activation adopts high-frequency capacitive lotus root composite electrode, vibration frequency 30-50MC, and plasma oxygen purity used is 99.1-99.8%, and soak time is 10-70 minute;
(3) the functional group grafting of doughnut basement membrane, the functionalization of functional group
The doughnut basement membrane activated is immersed in the solution of styrene, divinylbenzene, benzoyl peroxide and carries out functional group grafting; Wherein styrene, divinylbenzene, benzoyl peroxide mass ratio 75-85:14-25:0.5-1.5 in the solution;
(4) post processing becomes doughnut diffusion dialysis alkali collection film
Be catalyst by the doughnut basement membrane after functional group grafting with silver sulfate again, be that sulfonating agent carries out sulfonation process more than 5 hours with the concentrated sulfuric acid under 40 DEG C of-50 DEG C of conditions, doughnut diffusion dialysis alkali collection anode membrane can be obtained.
As preferably, the doughnut basement membrane described in preparation method of above-mentioned a kind of doughnut diffusion dialysis alkali collection film selects the Hollow Fiber Ultrafiltration product film of polypropylene, polyacrylonitrile or the nylon that internal diameter is 0.2-1.5mm, wall thickness is 0.1-0.5mm, membrane aperture is 0.05-0.15 micron.
Beneficial effect: have in the membrane material of unit are treating capacity large, make the features such as assembly floor space is little, and in use there is better environmental-protection function, remarkable in economical benefits.
Accompanying drawing explanation
Fig. 1 doughnut alkali collection anode membrane reclaims the principle schematic of NaOH
The preparation flow schematic diagram of Fig. 2 doughnut alkali collection anode membrane
Detailed description of the invention
Below in conjunction with accompanying drawing, enforcement of the present invention is illustrated:
Embodiment 1
Select polypropylene hollow fiber ultrafiltration product film to be doughnut basement membrane, the internal diameter of doughnut basement membrane is 0.45mm, wall thickness is 0.2mm, membrane aperture is 0.1 micron.Doughnut basement membrane is placed in plasma chamber to carry out plasma-activated, vibration frequency 40MC, and oxygen purity used is 99.5%, and soak time is 30 minutes.The doughnut basement membrane activated is immersed in styrene is 85%, divinylbenzene 14.5%, benzoyl peroxide are carry out functional group grafting in the mixed solution of 0.5%.
Being catalyst by the basement membrane of grafting with silver sulfate, is that sulfonating agent carries out sulfonation 8 hours at 45 DEG C with the concentrated sulfuric acid, and through cooling, be separated, take out and can obtain doughnut diffusion dialysis alkali collection film, ion exchange capacity is 0.7 milliequivalent/gram film.
In the present embodiment, doughnut diffusion dialysis film reclaims alkali schematic diagram as shown in Figure 1, and the preparation process in the present embodiment as shown in Figure 2.
Embodiment 2
Select polyacrylonitrile hollow fiber ultrafiltration product film to be doughnut basement membrane, the internal diameter of doughnut basement membrane is 0.6mm, wall thickness is 0.3mm, membrane aperture is 0.15 micron.Doughnut basement membrane is placed in plasma chamber to carry out plasma-activated, vibration frequency 50MC, and oxygen purity used is 99.8%, and soak time is 40 minutes.The doughnut basement membrane activated is immersed in styrene is 75%, divinylbenzene 24%, benzoyl peroxide are carry out functional group grafting in the mixed solution of 1%.
Being catalyst by the basement membrane of grafting with silver sulfate, is that sulfonating agent carries out sulfonation 6 hours at 50 DEG C with the concentrated sulfuric acid, and through cooling, be separated, take out and can obtain doughnut diffusion dialysis alkali collection film, ion exchange capacity is 0.6 milliequivalent/gram film.
Embodiment 3
Select nylon Hollow Fiber Ultrafiltration product film to be doughnut basement membrane, the internal diameter of doughnut basement membrane is 0.7mm, wall thickness is 0.4mm, membrane aperture is 0.1 micron.Doughnut basement membrane is placed in plasma chamber to carry out plasma-activated, vibration frequency 45MC, and oxygen purity used is 99.5%, and soak time is 50 minutes.The doughnut basement membrane activated is immersed in styrene is 80%, divinylbenzene 20%, benzoyl peroxide are carry out functional group grafting in the mixed solution of 1%.
Being catalyst by the basement membrane of grafting with silver sulfate, is that sulfonating agent carries out sulfonation 7 hours at 50 DEG C with the concentrated sulfuric acid, and through cooling, be separated, take out and can obtain doughnut diffusion dialysis alkali collection film, ion exchange capacity is 0.7 milliequivalent/gram film.
Claims (1)
1. a preparation method for doughnut diffusion dialysis alkali collection film, is characterized in that comprising the steps:
(1) the choosing of doughnut basement membrane
The hollow fiber ultrafiltration membrane of polypropylene, polyacrylonitrile or nylon is selected to be doughnut basement membrane; Doughnut basement membrane selects the Hollow Fiber Ultrafiltration product film of polypropylene, polyacrylonitrile or the nylon that internal diameter is 0.2-1.5mm, wall thickness is 0.1-0.5mm, membrane aperture is 0.05-0.15 micron;
(2) doughnut basement membrane is plasma-activated
Doughnut basement membrane is placed in plasma chamber to carry out plasma-activated; Wherein the electrode of gas ions activation adopts high-frequency capacitive coupling electrode, vibration frequency 30-50MC, and plasma oxygen purity used is 99.1-99.8%, and soak time is 10-70 minute;
(3) the functional group grafting process of doughnut basement membrane
The doughnut basement membrane activated is immersed in the solution of styrene, divinylbenzene, benzoyl peroxide and carries out functional group grafting; Wherein styrene, divinylbenzene, benzoyl peroxide mass ratio 75-85:14-25:0.5-1.5 in the solution;
(4) post processing becomes the sulfonation process of doughnut diffusion dialysis alkali collection film
Be catalyst by the doughnut basement membrane after functional group grafting with silver sulfate again, be that sulfonating agent carries out sulfonation process more than 5 hours with the concentrated sulfuric acid under 40 DEG C of-50 DEG C of conditions, doughnut diffusion dialysis alkali collection anode membrane can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447326.XA CN102908916B (en) | 2012-11-09 | 2012-11-09 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447326.XA CN102908916B (en) | 2012-11-09 | 2012-11-09 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102908916A CN102908916A (en) | 2013-02-06 |
| CN102908916B true CN102908916B (en) | 2015-04-01 |
Family
ID=47607632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210447326.XA Active CN102908916B (en) | 2012-11-09 | 2012-11-09 | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102908916B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349908B (en) * | 2013-07-24 | 2015-07-01 | 宜宾海丝特纤维有限责任公司 | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture |
| CN105819588B (en) * | 2016-04-01 | 2018-11-20 | 中国环境科学研究院 | The method for reducing pollutant emission in phenol-acetone production |
| CN114345146A (en) * | 2022-01-06 | 2022-04-15 | 中国科学技术大学 | Modified polypropylene oil-water separation membrane and preparation method thereof |
| CN114345141A (en) * | 2022-01-06 | 2022-04-15 | 中国科学技术大学 | Super-wettability modified polyolefin porous membrane, preparation method and application |
| CN115043466B (en) * | 2022-08-10 | 2022-12-09 | 杭州水处理技术研究开发中心有限公司 | High-salt high-concentration organic wastewater treatment device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114237A (en) * | 1994-06-20 | 1996-01-03 | 中国科学院化学研究所 | Ionic exchange membrane using polypropylene micro-porous membrane as basal membrane and making method thereof |
| CN1640532A (en) * | 2004-01-13 | 2005-07-20 | 中国科学院化学研究所 | Method for modifying polyolefin hollow fiber microporous membrane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2153973A1 (en) * | 1993-01-15 | 1994-07-21 | Christopher Andreola | Process for producing ion exchange membranes, and the ion exchange membranes produced thereby |
| CN101352657B (en) * | 2008-02-29 | 2011-07-20 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
| CN101845149A (en) * | 2010-05-11 | 2010-09-29 | 河北科技大学 | Modified polystyrene homogeneous membrane, modification method and application in separation of glycine |
-
2012
- 2012-11-09 CN CN201210447326.XA patent/CN102908916B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114237A (en) * | 1994-06-20 | 1996-01-03 | 中国科学院化学研究所 | Ionic exchange membrane using polypropylene micro-porous membrane as basal membrane and making method thereof |
| CN1640532A (en) * | 2004-01-13 | 2005-07-20 | 中国科学院化学研究所 | Method for modifying polyolefin hollow fiber microporous membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102908916A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102908916B (en) | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane | |
| CN102941026B (en) | Ion exchange composite film with selectivity on single cation | |
| CN207375760U (en) | A kind of device that lithium is carried from salt lake brine with high magnesium-lithium ratio | |
| KR101528777B1 (en) | Bipolar ion exchange sheet for recovering valuables, method of manufacturing the same and apparatus for recovering valuables | |
| CN104495991A (en) | Efficient membrane capacitive deionizing array based on flowing electrodes | |
| CN112159902A (en) | Electricity-water lithium extraction co-production system based on capacitance method | |
| CN112717731B (en) | Ion conductive film and preparation method thereof | |
| CN103349909B (en) | Post-processing method for squeezed alkali liquid in diffusion dialysis recycling viscose manufacture | |
| CN111115770A (en) | Electrode material for capacitive deionization and capacitive deionization device | |
| CN103349908B (en) | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture | |
| CN212669467U (en) | Catalytic cracking wet flue gas desulfurization waste water cyclic utilization system | |
| CN103663808B (en) | Heavy metal wastewater thereby film integrated treating device | |
| Yu et al. | Preparation and research progress of anion exchange membranes | |
| CN102921319B (en) | Preparation method of hollow fiber diffusion dialysis acid recovery membrane | |
| CN204400676U (en) | A kind of high performance membrane capacitor deionizing instrument based on flowing-type electrode | |
| CN114471177A (en) | Anion exchange driven cation selective separation hybrid membrane and preparation and application thereof | |
| CN111825266A (en) | Catalytic cracking wet desulphurization waste water recycling system and method | |
| CN103349910A (en) | Pre-treatment method for pressed alkali liquor in manufacturing of recycling viscose by diffusion dialysis | |
| CN103397408B (en) | The preprocess method of press lye in viscose production is reclaimed in a kind of diffusion dialysis | |
| CN103362011B (en) | The preprocess method of black digestion liquid in pulp manufacture is reclaimed in diffusion dialysis | |
| CN103352388B (en) | The pretreating process of black digestion liquid in pulp manufacture is reclaimed in a kind of diffusion dialysis | |
| CN103352389B (en) | The preprocess method of black digestion liquid during pulp manufactures is reclaimed in a kind of diffusion dialysis | |
| CN214060200U (en) | Salt lake lithium extraction system based on membrane separation | |
| CN103361769B (en) | Viscose sodium sulfate waste liquor reclaims the method for soda acid through bipolar membrane electrodialysis method | |
| CN114950135B (en) | Acid-resistant nanofiltration membrane, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |