CN102908916A - 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
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- CN102908916A CN102908916A CN201210447326XA CN201210447326A CN102908916A CN 102908916 A CN102908916 A CN 102908916A CN 201210447326X A CN201210447326X A CN 201210447326XA CN 201210447326 A CN201210447326 A CN 201210447326A CN 102908916 A CN102908916 A CN 102908916A
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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 reclamation film.
Background technology
All can produce a large amount of salkali waste in processes such as papermaking, cast aluminium, chemical fibre, ion exchange resin regenerations.If let alone direct discharging, will cause serious environmental pollution.If adopt the method for neutralization to process salkali waste, will consume a large amount of acid, and cause a large amount of inorganic salts of shape in the waste water, so reclaiming, alkali must carry out.Alkali recovery technology is take boiling, burning as main at present, and the minority field adopts Nanofiltering membrane to reclaim, and these methods have the high shortcoming of the operating cost of recovery.Diffusive dialysis method reclaims alkali, owing to substantially without operating cost, be a kind of novel, the economic method that alkali reclaims.
Diffusion dialysis is to utilize pellicle or perm-selective ion-ex-change membrane, the process that the solute in the solution is moved to low concentration one side by film by high concentration one side.This process is take concentration difference as power, so be also referred to as concentration difference dialysis or natural dialysis.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.
The beginning of the fifties in 19th century, Englishize scholar T. Graham Sodd method of investing begins systematically to study the diffusion of solution, different solutes have been studied again subsequently by the characteristic of pellicle (film that parchment or celloidin etc. are made), find then intransitable phenomenon of can be by the pore of the pellicle larger colloidal particle of the molecule of some solutes or ion, Graham Sodd method of investing claims that this phenomenon is dialysis.The equipment of around this principle making is called dialyzer, the purification that is usually used in the concentrated of colloidal solution and examines the macromolecular compounds such as sour ﹑ protein.The 1950's, occurred with the diffusion dialysis device of amberplex as barrier film.
The domestic diffusion dialysis film of just having developed as far back as 1964.But because the restriction of film preparation technique, the structure of the similar homogeneous phase ionic membrane of resulting film is all this type of film such as polysulfones quaternary ammonium cavity block S203, DF120 and chlorinated polyvinyl chloride type weak alkaline ionexchange memberanes.
In the diffusion dialysis process, the motive force of ion transfer is the concentration difference of film both sides, uses homo-ion repulsion and the electroneutral of Donnan (Donnan) balance and keeps correlation theory, thereby realize that the selectively penetrating of ion reaches the purpose of separation.This process is divided into anode membrane diffusion dialysis (as being used for the recovery of alkali) and cavity block diffusion dialysis (as being used for the recovery of acid).Wherein cavity block diffusion dialysis technology utilizes anion-exchange membrane to hydrogen ion and the different realization acid of selection permeability of metal ion and separating of salt, the both sides that for example mixed solution and the water of hydrochloric acid and aluminium chloride placed respectively anion-exchange membrane, because the acid of solution side and the concentration of salt are far above the water side, the trend of the oriented water side infiltration of acid and salt, but anion-exchange membrane has the selection permeability, can not allow every kind of ion pass through with equal opportunity; At first anionic membrane skeleton itself is positively charged, in solution, has the characteristic that attracts electronegative ion hydration and repel positively charged ion hydration, so under the effect of concentration difference, the chlorion of solution side is attracted and successfully sees through the side that the fenestra road enters water; Simultaneously according to electroneutral requirement, also can carry the ion with positive charge secretly, but because the hydrated radius of H+ is smaller, electric charge is less, and aluminum ions ion hydration radius is larger, and again with high valence charge, so hydrogen ion can preferentially pass through film, acid in the solution will be separated into water inlet side like this, and passing through of this Hydrogen ion is the key of diffusion dialysis.Used amberplex need to possess some suitable performances, and such as the stability in acid solution, high hydrogen ion percent of pass is to the high rate of rejection of metal ion and low water percent of pass etc.The anode membrane diffusion dialysis process that is used for the alkali recovery is similar with it.
Abroad, the technical development of diffusion dialysis recovered acid is comparatively rapid, and wherein representative country is the U.S. and Japan.The Exergy technique company of the U.S. has developed a kind of new online diffusion dialysis technology, and has pushed commercial Application to.This process using amberplex is processed Waste Sulfuric Acid, and it is recycled.System utilizes flowmeter and liquid level gauge control, and is designed to full-automatic mode, is provided with grid spacer between the film, and is stable to keep lamination.The rate of recovery of acid can reach 88%, and the metal rejection reaches 95%, has greatly reduced the dialysis liquid measure of delivering to Waste Water Treatment, thereby has reduced the consumption of neutralization chemicals, and energy consumption also greatly reduces.
The above shows that all 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 present recovery alkali is basically take flat film as main.It is too small that one of shortcoming of Flat Membrane diffusion dialysis is exactly the interior membrane area of unit volume, causes treating capacity less than normal.
Summary of the invention
We are for above present situation, on the basis of forefathers' research, requirement for the diffusion dialysis film preparation of reclaiming alkali, series of studies and exploitation have been carried out, through many-sided experimental study, finally developed the diffusion dialysis film of doughnut form, have treating capacity large, make the characteristics such as the assembly floor space is little; On this basis, reclaim the requirement of diffusion dialysis film according to alkali, continuation is studied the kind of the plasma-activated processing of type selecting, basement membrane of doughnut basement membrane, grafting processing, functionalization monomer and proportioning, reaction kinetic time and temperature and is optimized, and final exploitation can be used for the doughnut diffusion dialysis film that acid recovery is used.
The present invention is directed to deficiency of the prior art, proposed the diffusion dialysis film, have treating capacity large, make the characteristics such as the assembly floor space is little.
The present invention is achieved by following technical proposals:
A kind of preparation method of doughnut diffusion dialysis alkali reclamation film is characterized in that comprising the steps:
(1) the doughnut basement membrane chooses
The hollow fiber ultrafiltration membrane of selecting polypropylene, polyacrylonitrile or nylon is the doughnut basement membrane;
(2) the doughnut basement membrane is plasma-activated
It is plasma-activated to place plasma chamber to carry out the doughnut basement membrane; Wherein the electrode of gas ions activation adopts high-frequency capacitive lotus root composite electrode, vibration frequency 30-50MC, and the used oxygen purity of plasma is 99.1-99.8%, soak time is 10-70 minute;
(3) the functional group grafting of doughnut basement membrane, the functionalization of functional group
The doughnut basement membrane that activated is immersed in the solution of styrene, divinylbenzene, benzoyl peroxide and carries out the functional group grafting; Mass ratio 75-85:14 in solution of styrene, divinylbenzene, benzoyl peroxide-25:0.5-1.5 wherein;
(4) post processing becomes doughnut diffusion dialysis alkali reclamation film
Again with the doughnut basement membrane after the functional group grafting take silver sulfate as catalyst, under 40 ℃ of-50 ℃ of conditions, carry out sulfonation take the concentrated sulfuric acid as sulfonating agent and process more than 5 hours, can obtain doughnut diffusion dialysis alkali and reclaim anode membrane.
As preferably, it is that 0.2-1.5mm, wall thickness are that 0.1-0.5mm, membrane aperture are the Hollow Fiber Ultrafiltration product film of polypropylene, polyacrylonitrile or the nylon of 0.05-0.15 micron that the doughnut basement membrane described in the preparation method of above-mentioned a kind of doughnut diffusion dialysis alkali reclamation film is selected internal diameter.
Beneficial effect: have in the membrane material of unit are treating capacity large, make the characteristics such as the assembly floor space is little, and in use have better environmental-protection function, remarkable in economical benefits.
Description of drawings
Fig. 1 doughnut alkali reclaims the principle schematic that anode membrane reclaims NaOH
Fig. 2 doughnut alkali reclaims the preparation flow schematic diagram of anode membrane
The specific embodiment
Below in conjunction with accompanying drawing, enforcement of the present invention is specified:
Embodiment 1
Selecting polypropylene hollow fiber ultrafiltration product film is the doughnut basement membrane, and the internal diameter of doughnut basement membrane is that 0.45mm, wall thickness are that 0.2mm, membrane aperture are 0.1 micron.It is plasma-activated to place plasma chamber to carry out the doughnut basement membrane, and vibration frequency 40MC, used oxygen purity are 99.5%, and soak time is 30 minutes.With the doughnut basement membrane that activated be immersed in that styrene is 85%, divinylbenzene 14.5%, benzoyl peroxide be to carry out the functional group grafting in 0.5% the mixed solution.
The basement membrane of grafting take silver sulfate as catalyst, was carried out sulfonation 8 hours at 45 ℃ take the concentrated sulfuric acid as sulfonating agent, and through cooling, separate, take out and can obtain doughnut diffusion dialysis alkali reclamation film, ion exchange capacity is 0.7 milliequivalent/gram film.
In the present embodiment, doughnut diffusion dialysis film reclaims the alkali schematic diagram as shown in Figure 1, and the preparation process in the present embodiment as shown in Figure 2.
Embodiment 2
Selecting polyacrylonitrile Hollow Fiber Ultrafiltration product film is the doughnut basement membrane, and the internal diameter of doughnut basement membrane is that 0.6mm, wall thickness are that 0.3mm, membrane aperture are 0.15 micron.It is plasma-activated to place plasma chamber to carry out the doughnut basement membrane, and vibration frequency 50MC, used oxygen purity are 99.8%, and soak time is 40 minutes.With the doughnut basement membrane that activated be immersed in that styrene is 75%, divinylbenzene 24%, benzoyl peroxide be to carry out the functional group grafting in 1% the mixed solution.
The basement membrane of grafting take silver sulfate as catalyst, was carried out sulfonation 6 hours at 50 ℃ take the concentrated sulfuric acid as sulfonating agent, and through cooling, separate, take out and can obtain doughnut diffusion dialysis alkali reclamation film, ion exchange capacity is 0.6 milliequivalent/gram film.
Embodiment 3
Selecting nylon Hollow Fiber Ultrafiltration product film is the doughnut basement membrane, and the internal diameter of doughnut basement membrane is that 0.7mm, wall thickness are that 0.4mm, membrane aperture are 0.1 micron.It is plasma-activated to place plasma chamber to carry out the doughnut basement membrane, and vibration frequency 45MC, used oxygen purity are 99.5%, and soak time is 50 minutes.With the doughnut basement membrane that activated be immersed in that styrene is 80%, divinylbenzene 20%, benzoyl peroxide be to carry out the functional group grafting in 1% the mixed solution.
The basement membrane of grafting take silver sulfate as catalyst, was carried out sulfonation 7 hours at 50 ℃ take the concentrated sulfuric acid as sulfonating agent, and through cooling, separate, take out and can obtain doughnut diffusion dialysis alkali reclamation film, ion exchange capacity is 0.7 milliequivalent/gram film.
Claims (2)
1. the preparation method of a doughnut diffusion dialysis alkali reclamation film is characterized in that comprising the steps:
(1) the doughnut basement membrane chooses
The hollow fiber ultrafiltration membrane of selecting polypropylene, polyacrylonitrile or nylon is the doughnut basement membrane;
(2) the doughnut basement membrane is plasma-activated
It is plasma-activated to place plasma chamber to carry out the doughnut basement membrane; Wherein the electrode of gas ions activation adopts high-frequency capacitive lotus root composite electrode, vibration frequency 30-50MC, and the used oxygen purity of plasma is 99.1-99.8%, soak time is 10-70 minute;
(3) the functional group grafting of doughnut basement membrane is processed
The doughnut basement membrane that activated is immersed in the solution of styrene, divinylbenzene, benzoyl peroxide and carries out the functional group grafting; Mass ratio 75-85:14 in solution of styrene, divinylbenzene, benzoyl peroxide-25:0.5-1.5 wherein;
(4) post processing becomes the sulfonation process of doughnut diffusion dialysis alkali reclamation film
Again with the doughnut basement membrane after the functional group grafting take silver sulfate as catalyst, under 40 ℃ of-50 ℃ of conditions, carry out sulfonation take the concentrated sulfuric acid as sulfonating agent and process more than 5 hours, can obtain doughnut diffusion dialysis alkali and reclaim anode membrane.
2. the preparation method of a kind of doughnut diffusion dialysis alkali reclamation film according to claim 1, it is characterized in that it is that 0.2-1.5mm, wall thickness are that 0.1-0.5mm, membrane aperture are the Hollow Fiber Ultrafiltration product film of polypropylene, polyacrylonitrile or the nylon of 0.05-0.15 micron that described doughnut basement membrane is selected internal diameter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349908A (en) * | 2013-07-24 | 2013-10-16 | 宜宾海丝特纤维有限责任公司 | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture |
| CN105819588A (en) * | 2016-04-01 | 2016-08-03 | 中国环境科学研究院 | Method for reducing pollutant discharge in phenol-acetone production |
| 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 |
| 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 |
| CN115043466A (en) * | 2022-08-10 | 2022-09-13 | 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 |
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| CN101352657A (en) * | 2008-02-29 | 2009-01-28 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103349908A (en) * | 2013-07-24 | 2013-10-16 | 宜宾海丝特纤维有限责任公司 | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture |
| 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 |
| CN105819588A (en) * | 2016-04-01 | 2016-08-03 | 中国环境科学研究院 | Method for reducing pollutant discharge in phenol-acetone production |
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| US10974981B2 (en) | 2016-04-01 | 2021-04-13 | Chinese Research Academy Of Environmental Sciences | Method for reducing pollutant discharge in phenol and acetone production |
| 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 |
| 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 |
| CN115043466A (en) * | 2022-08-10 | 2022-09-13 | 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 |
| 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 |
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