CN1958135A - Dipolar membranes of middle boundary layer of complexation metal catalysis, and preparation method - Google Patents
Dipolar membranes of middle boundary layer of complexation metal catalysis, and preparation method Download PDFInfo
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Abstract
A bipolar membrane combined with anionic and cationic exchange films for converting ammunium lactate to lactic acid while recovering ammonia water is composed of cationic exchange film, middle interface layer containing complexing metallic catalyst, and anionic exchange film.
Description
Technical Field
The invention belongs to the technical field of electrodialysis, and relates to a bipolar membrane with a complex metal catalytic middle interface layer and a preparation method thereof.
Background
Bipolar membrane (BPM) is a new membrane which has been studied internationally in recent years and is generally composed of a cation exchange layer and an anion exchange layer. Under the action of the electric field, the water generator can play a role of 'dissociating' water to generate hydrogen ions and hydroxide ions, but not hydrogen and oxygen. The bipolar membrane electrodialysis system combining the bipolar membrane with other anion and cation exchange membranes can provide a new way for regeneration and recovery of certain substance resources, reduction of substance and energy consumption, reduction of waste discharge, elimination of environmental pollution, separation and preparation of certain acids and alkalis and the like.
Through research and development for more than 40 years, on the basis of theoretical explanation of ion exchange membrane phenomenon, great achievements are obtained on various membrane preparation methods, physical and chemical properties of membranes and development of new materials, and the electrodialysis technology is rapidly developed. However, the market capacity of these fields is nearly saturated, and it is necessary to develop new application fields. The focus of research and development has been moved to the water dissociation technology in foreign countries, so that the water dissociation technology based on the bipolar membrane has become the primary target of research in the electrodialysis technology, and the preparation and the performance improvement of the bipolar membrane are receiving increasing attention. Compared with traditional electrolysis, the bipolar membrane has the following main characteristics: the bipolar membrane can dissociate water to generate H+And OH-(ii) a No gas is generated in the water dissociation process, and the energy consumption is low; no electrochemical reaction occurs, no undesired products are produced or redox reactions that destroy desired products are produced; in combination with an Anion Exchange Membrane (AEM) and a Cation Exchange Membrane (CEM), bipolar membranes are useful for the electrodialytic generation of acids and bases from salts; initial cost is low and the industrial installation is space saving (no electrodes are needed for the repeating unit). Therefore, the bipolar membrane technology plays its unique role in optimizing the existing industrial process and creating a new industrial process, the appearance of the bipolar membrane technology can thoroughly change the traditional industrial separation and preparation process, and is expected to solve the long-standing technical problems in the fields of environment, chemical industry, biology, marine chemical industry and the like, new vitality and vitality must be injected into the fields, and meanwhile, the bipolar membrane technology is one of effective means for solving the problem of environmental resources and energy faced by human beings, so that the research on manufacturing the bipolar membrane is developed, and the bipolar membrane technology has important practical significance for maintaining the sustainable development of human beings.
In the traditional industry of broth purification, ammonium lactate and electrically neutral species are separated by an anion and cation exchange membrane arrangement to give concentrated lactate, but not lactic acid. Although the ZL87104858 can separate and obtain lactic acid, the adoption of four-compartment electrodialysis increases the resistance of unit electrodialysis, increases the energy consumption of electrodialysis and increases the cost.
Disclosure of Invention
In orderto solve the problem of high cost of separating lactic acid by a four-compartment electrodialysis method, the invention provides a bipolar membrane with a middle interface layer in complex metal catalysis and a preparation method thereof.
The bipolar membrane of the complex metal catalytic middle interface layer consists of a cation exchange membrane layer, a middle interface layer containing a complex metal catalyst and an anion exchange membrane layer. The preparation method comprises the following steps:
a. preparing the anode membrane material: dissolving dried polyphenyl ether in anhydrous alcohol-free chloroform, dropwise adding a mixed solution formed by dissolving a sulfonating agent in the anhydrous alcohol-free chloroform, controlling the molar ratio of the sulfonating agent to the polyphenyl ether to be 0.8: 1-1: 1.4, finishing dropwise adding within about 20-40 minutes, controlling the reaction temperature to be 23-28 ℃, reacting for 3-7 hours, standing for 20-40 minutes, separating out flocculent sticky substances, pouring out an upper clear solution, pouring the remaining sticky substances into deionized water, washing and filtering, then transforming in a NaCl solution, and drying for later use.
b. Preparing a negative film material: dissolving polysulfone in anhydrous dichloroethane, then dropwise adding chloromethyl methyl ether, controlling the molar ratio of the chloromethyl methyl ether to the polysulfone to be 0.8: 1-1: 1.5, adding zinc chloride (accounting for 0.5-3% of the mass of the polysulfone), gradually heating to 55-65 ℃, reacting at constant temperature for 2-5 hours, controlling the chlorine content in the resin to be 3-8 wt.%, then pouring into boiling water, adjusting the water bath temperature to 88-92 ℃, evaporating dichloroethane, separating out chloromethylated high polymer, and drying at 55-75 ℃ for later use.
c. Preparing the solar membrane: dissolving sulfonated polyphenyl ether converted into Na type in DMF (N, N-dimethylformamide) to form 15-25 wt.% solution, casting the solution on a clean glass plate to form a film, then placing the film in an oven at 120-130 ℃ for drying for 2-8 minutes, taking out the film, cooling, and then removing the film in deionized water to obtain the cation exchange membrane.
d. Preparing a negative film: dissolving chloromethylated polysulfone in DMF to form a 10-20 wt% solution, filtering to remove insoluble substances, uniformly mixing Tetramethylethylenediamine (TMEDA), controlling the molar ratio of the chloromethylated polysulfone to the TMEDA to be 10: 3-10: 4, scraping a film on a glass plate, standing at room temperature for 20-40 minutes, drying in an oven at 120-130 ℃ for 5-9 minutes, cooling, and removing the film in deionized water to obtain the homogeneous anion exchange membrane.
e. Fixing the catalyst: preparing 1000ml of solution containing 0.05-0.20 mol/L of complex metal catalyst, soaking the cation exchange membrane in the solution, slowly dripping NaOH solution (1-3 ml/min) while stirring, and enabling the precipitated complex metal catalyst to be uniformly attached to the surface of the cation exchange membrane.
f. Preparing a bipolar membrane: preparing the dried cation exchange membrane and the dried anion exchange membrane into a bipolar membrane by the following processes: loose lamination, hot pressing, tape casting or bonding.
The chemical reaction equation of the synthetic membrane material is as follows:
1. and (3) sulfonation reaction:
2. chloromethylation reaction:
3. amination reaction:
the invention prepares the bipolar membrane by using chemically stable organic materials, combines an anion-cation exchange membrane and a cation-anion exchange membrane, and adds a catalyst into an intermediate interface layer to reduce the potential of the bipolar membrane, so that the bipolar membrane is improved.
The principle of the catalyst for reducing the bipolar membrane potential is as follows:
the water dissociation is a proton transfer reaction weakly alkalized by weak acid, and the reaction equilibrium of the water dissociation to generate hydroxide ions and protons (hydronium ions) is as follows:
using immobilized neutral weak acid AH or acid BH corresponding to neutral weak base B+As a catalyst, this reaction can be decomposed into two successive reactions.
Under the action of electric field, the interface region can move charged ions OH-And H+Is moved out of the reaction site; similar to in aqueous solution, their mobility is greatly enhanced due to the tunneling effect of protons and hydroxide ions.
The key point of the invention is to select the optimal catalyst from a plurality of catalysts to be attached to the middle layer of the bipolar membrane so as to reduce the potential of the bipolar membrane, thereby reducing the energy consumption of electrodialysis of the bipolar membrane and effectively separating lactic acid in fermentation liquor.
The method and the prepared two-stage membrane have the advantages that: the bipolar membrane has low membrane resistance; the catalyst has strong adhesive force in the middle layer of the bipolar membrane, is not easy to fall off or dissolve, so the service life is long, and the preparation cost is low.
Detailed Description
The first embodiment is as follows: the bipolar membrane of the complex metal catalytic intermediate interface layer in the present embodiment is composed of a cation exchange membrane layer, an intermediate interface layer containing a complex metal catalyst, and an anion exchange membrane layer.
Wherein: the complex metal catalyst is a metal complex containing Sn, Cr, Ni, Fe, Ru, Mn, Ti, Co, Cu, Pt, Rb or Zn; the cation exchange membrane layer contains 15-25 wt.% of sulfonated polyphenyl ether; the anion exchange membrane layer contains 15-25 wt.% of chloromethylated polysulfone.
The second embodiment is as follows: the embodiment prepares the bipolar membrane of the complex metal catalytic middle interface layer according to the following steps:
a. preparing the anode membrane material: dissolving dried polyphenyl ether in anhydrous alcohol-free chloroform, dropwise adding a mixed solution formed by dissolving a sulfonating agent in the anhydrous alcohol-free chloroform, controlling the molar ratio of the sulfonating agent to the polyphenyl ether to be 0.8: 1-1: 1.4, controlling the reaction temperature to be 23-28 ℃ after dropwise adding for about 20-40 minutes, reacting for 3-7 hours, standing for 20-40 minutes, separating out flocculent sticky substances, pouring out an upper clear solution, pouring the remaining sticky substances into deionized water, washing and filtering, then transforming in a NaCl solution, and drying for later use.
b. Preparing a negative film material: dissolving polysulfone in anhydrous dichloroethane, then dropwise adding chloromethyl methyl ether, controlling the molar ratio of the chloromethyl methyl ether to the polysulfone to be 0.8: 1-1: 1.5, adding zinc chloride (accounting for 0.5-3% of the mass of the polysulfone, gradually heating to 55-65 ℃, reacting at constant temperature for 2-5 hours, controlling the chlorine content in the resin to be 3-8 wt.%, then pouring into boiling water, adjusting the water bath temperature to 88-92 ℃, evaporating the dichloroethane, separating out a chloromethylated high polymer, and drying at 55-75 ℃ for later use.
c. Preparing the solar membrane: dissolving sulfonated polyphenyl ether converted into Na type in DMF (N, N-dimethylformamide) to form 15-25 wt.% solution, casting the solution on a clean glass plate to form a film, then placing the film in an oven at 120-130 ℃ for drying for 2-8 minutes, taking out the film, cooling, and then removing the film in deionized water to obtain the cation exchange membrane.
d. Preparing a negative film: dissolving chloromethylated polysulfone in DMF (dimethyl formamide) to form a 10-20 wt% solution, filtering to remove insoluble substances, uniformly mixing Tetramethylethylenediamine (TMEDA), controlling the molar ratio of the chloromethylated polysulfone to the TMEDA to be 10: 3-10: 4, scraping a film on a glass plate, standing at room temperature for 20-40 minutes, drying in an oven at 120-130 ℃ for 5-9 minutes, cooling, and removing the film in deionized water to obtain the homogeneous anion exchange membrane.
e. Fixing the catalyst: preparing 1000ml of solution containing 0.05-0.20 mol/L of complex metal catalyst, soaking the cation exchange membrane in the solution, slowly dripping NaOH solution (1-3 ml/min) while stirring, and enabling the precipitated complex metal catalyst to be uniformly attached to the surface of the cation exchange membrane.
f. Preparing a bipolar membrane: preparing the dried cation exchange membrane and the dried anion exchange membrane into a bipolar membrane by the following processes: loose lamination, hot pressing, tape casting or bonding.
In this embodiment, the sulfonating agent is chlorosulfonic acid or oleum; the complex metal catalyst is a metal complex containing Sn, Cr, Ni, Fe, Ru, Mn, Ti, Co, Cu, Pt, Rb or Zn; the concentration of the NaCl solution is 0.5-2 mol/L; the concentration of the NaOH solution is 0.05-0.20 mol/L.
The third concrete implementation mode: the embodiment prepares the bipolar membrane of the complex metal catalytic middle interface layer according to the following steps:
a. preparing the anode membrane material: dissolving dried polyphenyl ether in anhydrous alcohol-free chloroform, dropwise adding a mixed solution formed by dissolving a sulfonating agent in the anhydrous alcohol-free chloroform, controlling the molar ratio of the sulfonating agent to the polyphenyl ether to be 0.9: 1, controlling the reaction temperature to be 26 ℃ and the reaction time to be 5 hours after 25 minutes of dropwise addition, standing for 20-40 minutes, separating out flocculent sticky substances, pouring out supernatant liquid, pouring the remaining sticky substances into deionized water, washing and filtering, then transferring in 0.5-2 mol/L NaCl solution, and drying for later use.
b. Preparing a negative film material: dissolving polysulfone in anhydrous dichloroethane, then dropwise adding chloromethyl methyl ether, controlling the molar ratio of the chloromethyl methyl ether to the polysulfone to be 0.9: 1, adding2g of zinc chloride, gradually heating to 60 ℃, reacting at a constant temperature for 5 hours, controlling the chlorine content in the resin to be 3-8 wt.%, then pouring into boiling water, adjusting the water bath temperature to 88-92 ℃, evaporating the dichloroethane to separate out chloromethylated high polymer, and drying at the temperature of 55-75 ℃ for later use.
c. Preparing the solar membrane: and (2) dissolving the sulfonated polyphenyl ether converted into the Na type in DMF to form a solution of 15-25 wt%, casting the solution on a clean glass plate to form a film, then placing the film in a drying oven at 120-130 ℃ for drying for 2-8 minutes, taking out the film, cooling, and then removing the film in deionized water to obtain the cation exchange membrane.
d. Preparing a negative film: according to the weight parts, 2 parts of chloromethylated polysulfone are dissolved in 12-18 parts of DMF, insoluble substances are removed by filtration, then 0.32-0.36 part of Tetramethylethylenediamine (TMEDA) is added and uniformly mixed, a film is scraped on a glass plate, the glass plate is placed at room temperature for standing for 20-40 minutes, then the glass plate is placed in a drying oven at 120-130 ℃ for drying for 5-9 minutes, and the membrane is removed in deionized water after cooling, so that the homogeneous phase anion exchange membrane is obtained.
e. Fixing the catalyst: preparing 1000ml of solution containing 0.05-0.20 mol/L of complex metal catalyst, soaking the cation exchange membrane in the solution, slowly dropwise adding 0.05-0.20 mol/L of NaOH solution (1-3 ml/min) while stirring, and enabling the precipitated complex metal catalyst to be uniformly attached to the surface of the cation exchange membrane.
f. Preparing a bipolar membrane: the bipolar membrane is prepared by adopting a hot-press forming method or a tape casting forming method, andthe specific method comprises the following steps:
and (3) pressing and forming: stacking the obtained dried anion and cation exchange membrane layers, removing internal air bubbles, spreading between two rollers of a two-roller open mill, adjusting the spacing, and heating and pressurizing to obtain bipolar membrane.
Tape casting: and covering the prepared anion exchange membrane layer with a layer of polymer solution dispersed with cation exchange resin, or covering the prepared cation exchange membrane layer with a layer of polymer solution dispersed with anion exchange resin, and drying to obtain the bipolar membrane.
Claims (9)
1. A bipolar membrane with a middle interface layer catalyzed by a complex metal is characterized by consisting of a cation exchange membrane layer, a middle interface layer containing a complex metal catalyst and an anion exchange membrane layer.
2. The bipolar membrane according to claim 1, wherein said complex metal catalyst is a metal complex containing Sn, Cr, Ni, Fe, Ru, Mn, Ti, Co, Cu, Pt, Rb or Zn.
3. The bipolar membrane of claim 1 wherein said cation exchange membrane layer comprises 15 to 25 wt.% of a sulfonated polyphenylene ether.
4. The bipolar membrane of claim 1, wherein said anion exchange membrane layer comprises 15-25 wt.% chloromethylated polysulfone.
5. A process for the preparation of a bipolar membrane of a complex metal catalyzed intermediate interfacial layer according to claim 1, wherein said process is carried out according to the following steps:
a. preparing the anode membrane material: dissolving dried polyphenyl ether in anhydrous alcohol-free chloroform, dropwise adding a mixed solution formed by dissolving a sulfonating agent in the anhydrous alcohol-free chloroform, controlling the molar ratio of the sulfonating agent to the polyphenyl ether to be 0.8: 1-1: 1.4, after dropwise adding for 20-40 minutes, controlling the reaction temperature to be 23-28 ℃ and the reaction time to be 3-7 hours, standing for 20-40 minutes, separating out flocculent sticky substances, pouring out an upper clear solution, pouring the remaining sticky substances into deionized water, washing and filtering, then transforming in a NaCl solution, and drying for later use;
b. preparing a negative film material: dissolving polysulfone in anhydrous dichloroethane, then dropwise adding chloromethyl methyl ether, controlling the molar ratio of the chloromethyl methyl ether to the polysulfone to be 0.8: 1-1: 1.5, adding zinc chloride accounting for 0.5-3% of the mass of the polysulfone, gradually heating to 55-65 ℃, reacting at constant temperature for 2-5 hours, controlling the chlorine content in resin to be 3-8 wt.%, then pouring into boiling water, adjusting the water bath temperature to 88-92 ℃, evaporating dichloroethane, separating out chloromethylated polysulfone, and drying at 55-75 ℃ for later use;
c. preparing the solar membrane: dissolving sulfonated polyphenyl ether converted into Na type in N, N-dimethylformamide to form a solution of 15-25 wt%, casting the solution on a clean glass plate to form a film, then placing the film in an oven at 120-130 ℃ for drying for 2-8 minutes, taking out the film, cooling, and then removing the film in deionized water to prepare a cation exchange membrane;
d. preparing a negative film: dissolving chloromethylated polysulfone in N, N-dimethylformamide to form a 10-20 wt% solution, filtering to remove insoluble substances, uniformly mixing with tetramethylethylenediamine, controlling the molar ratio of the chloromethylated polysulfone to the tetramethylethylenediamine to be 10: 3-10: 4, scraping a film on a glass plate, standing at room temperature for 20-40 minutes, drying in an oven at 120-130 ℃ for 5-9 minutes, cooling, and removing the film in deionized water to obtain a homogeneous anion exchange membrane;
e. fixing the catalyst: preparing 1000ml of 0.05-0.20 mol/L solution containing the complex metal catalyst, soaking the cation exchange membrane in the solution, slowly dropwise adding NaOH solution while stirring to enable the precipitated complex metal catalyst to be uniformly attached to the surface of the cation exchange membrane;
f. preparing a bipolar membrane: the bipolar membrane is prepared by adopting a loose superposition method, a hot pressing method, a casting method or an adhesion method.
6. The method of claim 5, wherein said sulfonating agent is chlorosulfonic acid or oleum.
7. The method of claim 5, wherein said complex metal catalyst is a metal complex containing Sn, Cr, Ni, Fe, Ru, Mn, Ti, Co, Cu, Pt, Rb or Zn.
8. The method for preparing the bipolar membrane with the complex metal catalytic middle interface layer according to claim 5, wherein the concentration of the NaCl solution is 0.5-2 mol/L.
9. The method of claim 5, wherein the concentration of NaOH solution is 0.05-0.20 mol/L.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899675B (en) * | 2009-10-13 | 2012-02-22 | 福建师范大学 | Bipolar membrane and preparation method thereof |
| CN107737614A (en) * | 2017-09-08 | 2018-02-27 | 武汉理工大学 | It is a kind of that Bipolar Membrane of intermediate layer catalyst and preparation method thereof is used as using aluminium hydroxide |
| CN108031302A (en) * | 2017-11-11 | 2018-05-15 | 北京化工大学 | A kind of Bipolar Membrane and preparation method thereof |
| CN108866567A (en) * | 2018-09-19 | 2018-11-23 | 太原师范学院 | Using zinc-metal-organic framework materials as Bipolar Membrane of intermediate layer and preparation method thereof |
| CN111936223A (en) * | 2018-03-26 | 2020-11-13 | 株式会社亚斯通 | Bipolar membrane and method for producing same |
| CN113398768A (en) * | 2020-03-16 | 2021-09-17 | 佛山市云米电器科技有限公司 | Preparation method of single-network bipolar diaphragm |
| CN115245762A (en) * | 2021-09-16 | 2022-10-28 | 上海三及新材料科技有限公司 | MOF-loaded bipolar membrane and application thereof |
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2006
- 2006-09-28 CN CNB2006101508238A patent/CN100482328C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101899675B (en) * | 2009-10-13 | 2012-02-22 | 福建师范大学 | Bipolar membrane and preparation method thereof |
| CN107737614A (en) * | 2017-09-08 | 2018-02-27 | 武汉理工大学 | It is a kind of that Bipolar Membrane of intermediate layer catalyst and preparation method thereof is used as using aluminium hydroxide |
| CN108031302A (en) * | 2017-11-11 | 2018-05-15 | 北京化工大学 | A kind of Bipolar Membrane and preparation method thereof |
| CN111936223A (en) * | 2018-03-26 | 2020-11-13 | 株式会社亚斯通 | Bipolar membrane and method for producing same |
| CN108866567A (en) * | 2018-09-19 | 2018-11-23 | 太原师范学院 | Using zinc-metal-organic framework materials as Bipolar Membrane of intermediate layer and preparation method thereof |
| CN113398768A (en) * | 2020-03-16 | 2021-09-17 | 佛山市云米电器科技有限公司 | Preparation method of single-network bipolar diaphragm |
| CN115245762A (en) * | 2021-09-16 | 2022-10-28 | 上海三及新材料科技有限公司 | MOF-loaded bipolar membrane and application thereof |
| CN115245762B (en) * | 2021-09-16 | 2024-03-12 | 上海三及新材料科技有限公司 | MOF-loaded bipolar membrane and application thereof |
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