CN102921319B - Preparation method of hollow fiber diffusion dialysis acid recovery membrane - Google Patents
Preparation method of hollow fiber diffusion dialysis acid recovery membrane Download PDFInfo
- Publication number
- CN102921319B CN102921319B CN201210446999.3A CN201210446999A CN102921319B CN 102921319 B CN102921319 B CN 102921319B CN 201210446999 A CN201210446999 A CN 201210446999A CN 102921319 B CN102921319 B CN 102921319B
- Authority
- CN
- China
- Prior art keywords
- membrane
- basement membrane
- hollow fiber
- diffusion dialysis
- doughnut
- 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 provides a preparation method of a hollow fiber diffusion dialysis acid recovery membrane. According to the preparation method of the hollow fiber diffusion dialysis acid recovery membrane, a hollow fiber ultrafiltration membrane made of polypropylene or polyacrylonitrile is used as a basement membrane, the basement membrane is arranged in a plasma chamber for plasma activation, the activated hollow fiber basement membrane is soaked in a solution of styrene, divinylbenzene and benzoyl peroxide for functional group stem grafting, then the hollow fiber basement membrane after the functional group stem grafting carries out chloromethylation with stannic chloride as a catalyst, and lastly a trimethylamine water solution is used to carry out quaternary ammoniation treatment, and the hollow fiber diffusion dialysis acid recovery membrane is obtained. The preparation method of the hollow fiber diffusion dialysis acid recovery membrane has the advantages that the processing capacity of unit area is strong, the occupied area is small after the hollow fiber diffusion dialysis acid recovery membrane is made into an assembly, and obvious economic benefits and the environmental protection function are provided, thereby having wide application prospects.
Description
Technical field
The invention belongs to chemical production technical field, be specifically related to a kind of preparation method of doughnut diffusion dialysis acid recovery film.
Background technology
The concept of dialysis is that Graham proposed first in 1861, when Graham studies the characteristic of different solute by pellicle (film that parchment or celloidin etc. are made), find the molecule of some solutes or the ion pore by pellicle, larger colloidal particle then not by, Graham claims this phenomenon to be dialysis.The motive force mainly concentration difference of this separation process.Correspondingly, amberplex (being also a kind of pellicle) is applied to dialysis process, and this process is defined by diffusion dialysis.
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.
In industrial production and mining, smelting (as steel and iron industry, titanium dioxide industry, wet type copper smelting industry, the industry of titanium material, electroplating industry, rare-earth industry, wood saccharification industry, gold mining and non-ferrous metal metallurgy industry etc.) process, often to use inorganic acid (as sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid etc.) come clean metal surface or dissolve ore, so just create a large amount of waste acid liquor containing each metal ion species, discharged if do not processed, not only waste natural resources, more seriously pollute the environment, soil and water source.Therefore, take measures them to carry out to be separated, purification processes, recycling, be the focus that people pay close attention to always.
What embrane method waste acid recovery adopted is dialysis principle, and whole diffusion dialysis device is formed by combining by diffusion dialysis film, fluid proportion plate, stiffener, liquid stream sheet frame.The construction unit of varying number is made up of the film of some; Wherein each unit separates into dialysing compartment A and diffuser casing B by an anion-exchange membrane.In the both sides of anion-exchange membrane, when passing into acid pickle and acceptable solution (running water) respectively, the sulfuric acid of acid pickle side and the concentration of salt thereof far above the side of water, therefore, due to the existence of concentration gradient, the trend of spent acid and its esters oriented B room infiltration.But film has selective penetrated property, it can not allow often kind of ion pass through with equal opportunity, first anionic membrane skeleton itself is positively charged, electronegative ion hydration can be attracted in the solution, and repel positively charged ion hydration, therefore under the effect of concentration difference, the anion of spent acid side is attracted and successfully enters the side of water through fenestra road.Simultaneously according to electroneutral requirement, also positively charged ion can be carried secretly, because hydrionic hydrated radius is smaller, electric charge is less, and the ion hydration radius of slaine is comparatively large, is again high price, therefore preferentially can pass through film, just make the acid in waste liquid be separated.Owing to adopting counter-current operation, at waste liquid outlet place, though the acid in acid room reduces concentration greatly because of diffusion, still high than the concentration of acid in import water, add actual when doing film, diffusion dialysis water content and the aperture of controlling diaphragm can be replaced, so can reach more than 80% to the rate of recovery of acid is generally equal by side base.
The appearance of diffusion dialysis technology has had the history of more than 50 year, but due to the restriction of membrane technology, the extensive use of this technology is restricted.In recent years, membrane technology develop rapidly, various film emerges in an endless stream, and has also promoted the development of diffusion dialysis technology.
At home, the units such as Shanghai organic chemistry research institute, China Science & Technology University, State Oceanic Administration, Hangzhou Water Treatment Technology Research and Development Center, are being devoted to or are working out the ion-exchange cavity block for acid recovery; Shandong Tianwei Membrane Technology Co., Ltd., has developed the diffusion dialysis device being applied to acid recovery, and has the homogeneous membrane production technology with independent intellectual property right, and its product quality reaches international most advanced level.The diffusion dialysis device of this production of units, is widely used in the recovery of the acid pickles such as titanium white waste acid liquid, steel-product acid pickle, hydrometallurgy, creates good economic benefit and social benefit.
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 Sawyerand Smith company of the U.S. is also proposed FORMECO series acid-recovery plant.Its feature is between dividing plate, add small pressure, substantially increases reliability and the life-span of this element.Facility compact, floor space is little, and the equipment of a process 400L/d, floor space is only 1.4m2.Equipment is automation mechanized operation, can realize the continuous 7d free of discontinuities of whole day 24h and run, without the need to personal management, and need only periodic cleaning and replacing medium.The rate of recovery of acid is 85% ~ 90%, and metal rejection is 60% ~ 90%.
The above all shows the advantage that the technology of diffusion dialysis reclamation film has other membrane process incomparable, but the diffusion dialysis film of current recovery acid 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.How to develop a kind of area is large, acid recovery treating capacity is large diffusion dialysis form membrane and become a very urgent thing.
Summary of the invention
We are for above present situation, on the basis of forefathers' research, for the requirement of reclaiming sour diffusion dialysis film preparation, 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 acid recovery 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 a kind of plasma-activated preparation method carrying out diffusion dialysis film.
The present invention is achieved by following technical proposals:
A preparation method for doughnut diffusion dialysis acid recovery film, is characterized in that comprising the steps:
(1) the choosing of doughnut basement membrane
The hollow fiber ultrafiltration membrane of polypropylene or polyacrylonitrile 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, and 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 the process of doughnut diffusion dialysis acid recovery film
Be catalyst by the doughnut basement membrane after functional group grafting with butter of tin again, be that chloromethylation reagents carries out chloromethylation with chloromethyl ether under 40 DEG C of conditions, obtain the chloromethyl doughnut basement membrane of chloromethylation, by mass concentration be finally 16% trimethylamine aqueous solution under 20 DEG C of conditions, carry out season ammonification more than 5 hours, doughnut diffusion dialysis acid recovery film can be obtained.
As preferably, the doughnut basement membrane described in preparation method of above-mentioned a kind of doughnut diffusion dialysis acid recovery film selects the Hollow Fiber Ultrafiltration product film of internal diameter is 0.2-1.5mm, wall thickness is 0.1-0.5mm, membrane aperture is 0.05-0.15 micron polypropylene or polyacrylonitrile.
Beneficial effect: the film prepared by the present invention have unit are disposal ability large, make the features such as assembly floor space is little, there is obvious economic benefit and environment-friendly function.
Accompanying drawing explanation
Fig. 1 doughnut alkali collection film reclaims hydrochloric acid principle schematic
The preparation flow schematic diagram of Fig. 2 doughnut acid recovery film
Detailed description of the invention
Below in conjunction with accompanying drawing, enforcement of the present invention is illustrated:
Embodiment 1
Preparation process schematic diagram as shown in Figure 2, selects polypropylene hollow fiber ultrafiltration product film to be doughnut basement membrane, and 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%.
Be catalyst by the basement membrane of grafting with butter of tin, be that chloromethylation reagents carries out chloromethylation 7 hours with chloromethyl ether at 40 DEG C, obtain the chloromethane basement membrane of chloromethylation, finally carry out season ammonification 5 hours with the trimethylamine aqueous solution of 16% in 20 DEG C, can obtain doughnut diffusion dialysis acid recovery film, ion exchange capacity is 0.8 milliequivalent/gram film.
Film prepared in the present embodiment schematic diagram in the application as shown in Figure 1.
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%.
Be catalyst by the basement membrane of grafting with butter of tin, be that chloromethylation reagents carries out chloromethylation 7 hours with chloromethyl ether at 40 DEG C, obtain the chloromethane basement membrane of chloromethylation, finally carry out season ammonification 5 hours with the trimethylamine aqueous solution of 16% in 20 DEG C, can obtain doughnut diffusion dialysis acid recovery film, ion exchange capacity is 1.0 milliequivalents/gram film.
Claims (1)
1. a preparation method for doughnut diffusion dialysis acid recovery film, is characterized in that comprising the steps:
(1) the choosing of doughnut basement membrane
The hollow fiber ultrafiltration membrane of polypropylene or polyacrylonitrile 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, and 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 the process of doughnut diffusion dialysis acid recovery film
Be catalyst by the doughnut basement membrane after functional group grafting with butter of tin again, be that chloromethylation reagents carries out chloromethylation with chloromethyl ether under 40 DEG C of conditions, obtain the chloromethyl doughnut basement membrane of chloromethylation, by mass concentration be finally 16% trimethylamine aqueous solution under 20 DEG C of conditions, carry out season ammonification 5 hours, doughnut diffusion dialysis acid recovery film can be obtained;
Described doughnut basement membrane selects the Hollow Fiber Ultrafiltration product film of internal diameter is 0.2-1.5mm, wall thickness is 0.1-0.5mm, membrane aperture is 0.05-0.15 micron polypropylene or polyacrylonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210446999.3A CN102921319B (en) | 2012-11-09 | 2012-11-09 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210446999.3A CN102921319B (en) | 2012-11-09 | 2012-11-09 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102921319A CN102921319A (en) | 2013-02-13 |
| CN102921319B true CN102921319B (en) | 2015-02-25 |
Family
ID=47636329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210446999.3A Active CN102921319B (en) | 2012-11-09 | 2012-11-09 | Preparation method of hollow fiber diffusion dialysis acid recovery membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102921319B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349915B (en) * | 2013-07-24 | 2015-08-19 | 宜宾海丝特纤维有限责任公司 | A kind of preparation method being applicable to the cation-exchange membrane of press lye in the production of diffusion dialysis recovery viscose rayon |
| CN112456697A (en) * | 2020-12-08 | 2021-03-09 | 杭州水处理技术研究开发中心有限公司 | Forward osmosis acid recovery system |
Citations (5)
| 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 |
| CN102061004A (en) * | 2010-09-14 | 2011-05-18 | 北京廷润膜技术开发有限公司 | Method for manufacturing monolithic bipolar membrane |
| CN102068919A (en) * | 2011-01-11 | 2011-05-25 | 北京廷润膜技术开发有限公司 | Method for manufacturing homogeneous ion exchange membrane |
| CN102120829A (en) * | 2010-12-30 | 2011-07-13 | 中国科学院等离子体物理研究所 | Preparation method of polymer alkaline anion-exchange membrane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5996135A (en) * | 1982-11-24 | 1984-06-02 | Nok Corp | Anion exchange membrane and its production |
| JPH0817917B2 (en) * | 1987-12-10 | 1996-02-28 | 株式会社トクヤマ | Diffusion dialysis method |
| JPH01275639A (en) * | 1988-04-28 | 1989-11-06 | Agency Of Ind Science & Technol | Surface modification |
-
2012
- 2012-11-09 CN CN201210446999.3A patent/CN102921319B/en active Active
Patent Citations (5)
| 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 |
| CN102061004A (en) * | 2010-09-14 | 2011-05-18 | 北京廷润膜技术开发有限公司 | Method for manufacturing monolithic bipolar membrane |
| CN102120829A (en) * | 2010-12-30 | 2011-07-13 | 中国科学院等离子体物理研究所 | Preparation method of polymer alkaline anion-exchange membrane |
| CN102068919A (en) * | 2011-01-11 | 2011-05-25 | 北京廷润膜技术开发有限公司 | Method for manufacturing homogeneous ion exchange membrane |
Non-Patent Citations (2)
| Title |
|---|
| 张丹霞等.聚丙烯腈超滤膜的等离子体接枝改性 (Ⅰ )膜材料的表面结构与性能.《膜科学与技术》.2003,第23卷(第05期),第15-18页. * |
| 徐铜文.扩散渗析法回收工业酸性废液的研究进展.《水处理技术》.2004,第30卷(第02期),第63-66页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102921319A (en) | 2013-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Recovery of hydrochloric acid from simulated chemosynthesis aluminum foils wastewater: an integration of diffusion dialysis and conventional electrodialysis | |
| Jiang et al. | Production of lithium hydroxide from lake brines through electro–electrodialysis with bipolar membranes (EEDBM) | |
| CN102941026B (en) | Ion exchange composite film with selectivity on single cation | |
| Qiu et al. | Study on recovering high-concentration lithium salt from lithium-containing wastewater using a hybrid reverse osmosis (RO)–electrodialysis (ED) process | |
| CN102908916B (en) | Preparation method of hollow fiber dispersion and dialysis alkali recycling membrane | |
| CN102321908A (en) | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution | |
| Pourcelly et al. | Applications of charged membranes in separation, fuel cells, and emerging processes | |
| CN202272954U (en) | System for acid chloride etching liquid cycle regeneration and metallic copper recycling | |
| EP3041598B1 (en) | Apparatus and method for product recovery and electrical energy generation | |
| CN107512806A (en) | Ion exchange resin waste water zero discharge processing method | |
| CN106345304A (en) | Cathodic solution protection type electrodialysis device | |
| Calvo | Direct lithium recovery from aqueous electrolytes with electrochemical ion pumping and lithium intercalation | |
| CN201614411U (en) | Printed-board acid etching waste liquid regenerating and copper recycling device | |
| CN102921319B (en) | Preparation method of hollow fiber diffusion dialysis acid recovery membrane | |
| CN206592241U (en) | A kind of ocean salinity energy utilization system | |
| CN103663808B (en) | Heavy metal wastewater thereby film integrated treating device | |
| Asadi et al. | Electrodialysis of lithium sulphate solution: model development and validation | |
| CN105056763A (en) | Method for removing salt in water through double-membrane dialysis under no-voltage condition and reactor | |
| Loza et al. | Electrodialysis concentration of sulfuric acid | |
| CN117819771A (en) | Recycling treatment process for lead storage battery dismantling waste acid | |
| CN103349908B (en) | Method for squeezing alkali liquid in diffusion dialysis recycling viscose manufacture | |
| CN103318862B (en) | Five Room electroosmose processs prepare the technique of Hypophosporous Acid, 50 | |
| CN113025829A (en) | Method for treating copper ore smelting waste residues by applying bipolar membrane electrodialysis | |
| CN109231379B (en) | Method for selectively recovering target ions from organic wastewater | |
| Li et al. | Design of Photothermal “Ion Pumps” for Achieving Energy-Efficient, Augmented, and Durable Lithium Extraction from Seawater |
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 |