CN102451622A - Preparation method of nanofiltration membrane for dye concentration and desalination - Google Patents
Preparation method of nanofiltration membrane for dye concentration and desalination Download PDFInfo
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- CN102451622A CN102451622A CN2010105261601A CN201010526160A CN102451622A CN 102451622 A CN102451622 A CN 102451622A CN 2010105261601 A CN2010105261601 A CN 2010105261601A CN 201010526160 A CN201010526160 A CN 201010526160A CN 102451622 A CN102451622 A CN 102451622A
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Abstract
The invention discloses a preparation method of an aromatic polyamide nanofiltration membrane. The method is mainly characterized by comprising the following steps of: on the basis of utilizing aromatic polyamide as a major polymer membrane preparation material, completely defoaming a membrane casting liquid containing aromatic polyamide, organic solvent and additives; then flatly paving the product on a non-woven fabric by use of a membrane casting machine; evaporating in an oven for certain time; and curing in a gel tank to obtain the membrane. By adopting the preparation method, the nanofiltration membrane has relatively high rejection rate against small-molecular organisms, especially the dye with molecular weight of about 400, and has a penetration rate of greater than 80% for sodium sulfate and sodium chloride, thus being suitable for the concentration and desalination of dye.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the NF membrane of dyestuff concentrating and desalinating, belong to the membrane separation technique field.
Background technology
In recent years, the competition of dye industry is growing more intense, and is also increasingly high, bright in luster to the requirement of dyestuff, and environmental protection dyestuff, salt-free liquid dyes that dye-uptake is high enjoy great popularity.In the traditional processing technology of direct dyes, generally through oversalting, filtration with technical process such as concentrate; Purpose is desalination, removes unreacted raw material, intermediate and secondary dyestuff, sloughs moisture, to obtain the dyestuff of desired concn and purity, carries out spray-drying then, processes powder dye or directly processes liquid fuel.Facts have proved that synthetic impurity, the salinity that brings with salting-out process compiled a large amount of compositions that influence dyestuffs purity, intensity and solubility, have only the impurity that reduces in the dyestuff, tinctorial strength that salinity could improve dyestuff and dyestuffs purity etc.At present, domestic conventional dyes production technology mainly adopts saltouts or acid out separation dyestuff composition, and product purity is not high, and the product quality uniformity of different batches is relatively poor, makes product quality receive considerable restraint.Therefore, how to remove these impurity, salinity, improve the dyestuff quality, energy-saving and cost-reducing, minimizing is polluted, and is one of current urgent problem of direct dyes industry.
It is a kind of energy-efficient parting material that film separates, and is with a wide range of applications, and NF membrane is the novel diffusion barrier of developing energetically both at home and abroad, has become the research focus in the diffusion barrier field at present.Its operating pressure and molecular cut off are between counter-infiltration and the ultrafiltration, and the molecular cut off scope relative narrower (200-1000) of NF membrane, and the aperture is in nanoscale, belong to novel nano-material.NF membrane is very suitable for the production of direct dyes and water-soluble dye.
Summary of the invention
The object of the invention is exactly that a kind of preparation method who is used for the aromatic polyamides NF membrane of dyestuff concentrating and desalinating will be provided.Employing the present invention technology; Made aromatic polyamides NF membrane can be than (0.4-0.6MPa) under the low operating pressure; The acid dyes of molecular weight about 400 had good concentrating and desalinating ability, and the film-forming process of this method is simple, easy to operate; Operating cost is low, is easy to realize suitability for industrialized production.
The present invention realizes through following technical scheme:
(1) preparation of casting solution: the aromatic polyamides of drying is dissolved in the organic solvent; And the adding certain quantity of additive, stir and the constant temperature dissolving, form aromatic polyamides/solvent/additive ternary casting solution; Airtight discontinuous degassing can make required casting solution.Aromatic polyamides is mainly poly in the casting solution, and concentration is 15%-20%.Additive is mainly inorganic salts and organic matter in the casting solution, comprises a kind of in calcium chloride, lithium chloride and the lithium perchlorate etc., preferred lithium chloride, and content is 3%-7%.Organic additive comprises polyethylene glycol-400, polyethylene glycol-600, a kind of in polyvinylpyrrolidone, the acrylic acid etc.Preferably polyethylene pyrrolidones, content are 1%-5%.Organic solvent can adopt N, dinethylformamide, N, a kind of in N-dimethylacetylamide, the N-methyl pyrrolidone.
(2) inversion of phases legal system film
With deaeration fully and the casting solution of insulation after filtering, with scraper striking film forming.In baking oven, carry out getting in the coagulation bath and making its coagulation forming after solvent partly evaporates.In order to keep the performance of NF membrane, must it be preserved under hygrometric state.The relative humidity of system film chamber is at 45%-60%, and temperature is 25 ℃-30 ℃.Adopt the prepared aromatic polyamides NF membrane of said method; It is under lower pressure (0.4-0.6MPa); The little molecular dye of molecular weight about 400 had well hold back effect; And the NaCl of 1000mg/L had lower rejection, and salt rejection rate is 10%-15%, water flux is 97.7-150.8L/ (m
2H), be that the rejection of 460 eriochrome black T is more than 99% to molecular weight.The contamination resistance of this film is strong, and separative efficiency is high, and water flux is big, can be used for the concentrating and desalinating processing that dyestuff is gone up in industry.
Description of drawings
Fig. 1 is the surface scan Electronic Speculum picture of the present invention's NF membrane of being used for the dyestuff concentrating and desalinating
Fig. 2 is the cross section ESEM picture of the present invention's NF membrane of being used for the dyestuff concentrating and desalinating
The specific embodiment
Following instance is used to set forth the present invention, and is not used in interpretation protection scope of the present invention.In an embodiment, permeation flux and salt rejection rate and dyestuff rejection are defined as respectively:
Embodiment 1, and the lithium chloride of 7g and the polyvinylpyrrolidone of 1g are dissolved in 74g N, in the N-dimethylacetylamide, adds the aromatic polyamides of 18g then, and this mixture is dissolved in 90 ℃ of constant temperature, and vacuum defoamation makes casting solution.A certain amount of made casting solution is put into hopper, is supporting layer with the polyester non-woven fabric, is 0.2mm through clearance gauge controlling diaphragm thickness.After being applied to casting solution on the nonwoven, in 90 ℃ of baking ovens, stop 0.3min, evaporate a part of solvent, get into film-forming in the coagulation bath afterwards.It is above to remove unnecessary organic solvent fully that obtained film is put into pure water 24h.Under the pressure of 0.6MPa, this film pure water flux is 150.8L/m
2H. use the Na of 2000mg/L
2S0
4Solution is tested, and its flux is 183.1L/m
2H, rejection is 6.7%.Under the operating pressure of 0.6MPa, this film is 132.7L/m to the flux of the eriochrome black T dyestuff (containing 1g/L NaCl) of 1g/L
2H is 99.5% to the dyestuff rejection, and is 89.6% to the transmitance of NaCl.
Embodiment 2, and the lithium chloride of 5g and the polyvinylpyrrolidone of 3g are dissolved in 74g N, in the N-dimethylacetylamide, add the aromatic polyamides of 18g then, this mixture dissolved vacuum defoamation in 90 ℃ of constant temperature.A certain amount of casting solution is put into hopper, is supporting layer with the polyester non-woven fabric, is 0.2mm through clearance gauge controlling diaphragm thickness.After being applied to casting solution on the nonwoven, in 90 ℃ of baking ovens, stop 0.3min, evaporate a part of solvent, get into film-forming in the coagulation bath afterwards.It is above to remove unnecessary organic solvent fully that obtained film is put into pure water 24h.Under the pressure of 0.6MPa, the pure water flux of this film is 112.1L/m
2H.Na with 2000mg/L
2SO
4Solution is tested, and its flux is 108.2L/m
2H, rejection is 7.9%.Under the operating pressure of 0.6MPa, this film is 94.3L/m to the flux of the eriochrome black T dyestuff (containing 1g/L NaCl) of 1g/L
2H is 99.5% to the dyestuff rejection, and is 85.7% to the transmitance of NaCl.
Embodiment 3, and the lithium chloride of 6g and the polyvinylpyrrolidone of 2g are dissolved in 74g N, in the N-dimethylacetylamide, add the aromatic polyamides of 18g then, this mixture dissolved vacuum defoamation in 90 ℃ of constant temperature.A certain amount of casting solution is put into hopper, is supporting layer with the polyester non-woven fabric, is 0.2mm through clearance gauge controlling diaphragm thickness.After being applied to casting solution on the nonwoven, in 90 ℃ of baking ovens, stop 0.4min, evaporate a part of solvent, get into film-forming in the coagulation bath afterwards.It is above to remove unnecessary organic solvent fully that obtained film is put into pure water 24h.Under the pressure of 0.6MPa, the pure water flux of this film is 97.2L/m
2H.Na with 2000mg/L
2SO
4Solution is tested, and its flux is 99.9L/m
2H, rejection is 7.6%.Under the operating pressure of 0.6MPa, this film is 83.5L/m to the flux of the eriochrome black T dyestuff (containing 1g/L NaCl) of 1g/L
2H is 99.2% to the dyestuff rejection, and is 88.3% to the transmitance of NaCl.
Embodiment 4, and the lithium chloride of 4g and the polyvinylpyrrolidone of 4g are dissolved in 74g N, in the N-dimethylacetylamide, add the aromatic polyamides of 18g then, this mixture dissolved vacuum defoamation in 90 ℃ of constant temperature.A certain amount of casting solution is put into hopper, is supporting layer with the polyester non-woven fabric, is 0.2mm through clearance gauge controlling diaphragm thickness.After being applied to casting solution on the nonwoven, in 90 ℃ of baking ovens, stop 0.3min, evaporate a part of solvent, get into film-forming in the coagulation bath afterwards.It is above to remove unnecessary organic solvent fully that obtained film is put into pure water 24h.Under the pressure of 0.6MPa, the pure water flux of this film is 98.4L/m
2H.Na with 2000mg/L
2SO
4Solution is tested, and its flux is 94.2L/m
2H, rejection is 8.5%.Under the operating pressure of 0.6MPa, this film is 83.4L/m to the flux of the eriochrome black T dyestuff (containing 1g/L NaCl) of 1g/L
2H is 99.6% to the dyestuff rejection, and is 84.6% to the transmitance rate of NaCl.
Embodiment 5, and the lithium chloride of 5g and the polyvinylpyrrolidone of 3g are dissolved in 74g N, in the N-dimethylacetylamide, add the aromatic polyamides of 18g then, this mixture dissolved vacuum defoamation in 90 ℃ of constant temperature.A certain amount of casting solution is put into hopper, is supporting layer with the polyester non-woven fabric, is 0.2mm through clearance gauge controlling diaphragm thickness.After being applied to casting solution on the nonwoven, in 100 ℃ of baking ovens, stop 0.4min, evaporate a part of solvent, get into film-forming in the coagulation bath afterwards.It is above to remove unnecessary organic solvent fully that obtained film is put into pure water 24h.Under the pressure of 0.6MPa, the pure water flux of this film is 47.7L/m
2H.Na with 2000mg/L
2SO
4Solution is tested, and its flux is 47.3L/m
2H, rejection is 6.8%.Under the operating pressure of 0.6MPa, this film is 38.5L/m to the flux of the eriochrome black T dyestuff (containing 1g/L NaCl) of 1g/L
2H is 99.1% to the dyestuff rejection, and is 86.5% to the transmitance rate of NaCl.
Embodiment 6, and the lithium chloride of 6g and the polyvinylpyrrolidone of 2g are dissolved in 74g N, in the N-dimethylacetylamide, add the aromatic polyamides of 18g then, this mixture dissolved vacuum defoamation in 90 ℃ of constant temperature.A certain amount of casting solution is put into hopper, is supporting layer with the polyester non-woven fabric, is 0.2mm through clearance gauge controlling diaphragm thickness.After being applied to casting solution on the nonwoven, in 90 ℃ of baking ovens, stop 0.5min, evaporate a part of solvent, get into film-forming in the coagulation bath afterwards.It is above to remove unnecessary organic solvent fully that obtained film is put into pure water 24h.Under the pressure of 0.6MPa, the pure water flux of this film is 59.5L/m
2H.Na with 2000mg/L
2SO
4Solution is tested, and its flux is 58.5L/m
2H, rejection is 10.6%.Under the operating pressure of 0.6MPa, this film is 51.8L/m to the flux of the eriochrome black T dyestuff (containing 1g/L NaCl) of 1g/L
2H is 99% to the dyestuff rejection, and is 87.7% to the transmitance rate of NaCl.
Claims (6)
1. the preparation method of an aromatic polyamides NF membrane is characterized in that: will contain the casting solution of aromatic polyamides, organic solvent and additive, and after forming film with phase transformation method, preserve down in hygrometric state.
2. the preparation method of aromatic polyamides NF membrane according to claim 1, it is characterized in that: wherein used aromatic polyamides membrane material is mainly poly.Contain the aromatic polyamides of 15%-20%, the additive of 1%-8% in the casting solution.
3. the preparation method of aromatic polyamides NF membrane according to claim 1, it is characterized in that: wherein said organic solvent can be selected N for use, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone a kind of or more than one.
4. the preparation method of aromatic polyamides NF membrane according to claim 1, it is characterized in that: wherein additive therefor is mainly inorganic additive and organic additive.Inorganic additive is selected from one or more of calcium chloride, lithium chloride, lithium bromide or lithium perchlorate.Organic additive is mainly a kind of in polyethylene glycol, polyvinylpyrrolidone, the acrylic acid or more than one.
5. the preparation method of aromatic polyamides NF membrane according to claim 1, it is characterized in that: after being applied to casting solution on the nonwoven, in 90 ℃ of-120 ℃ of heat treatment 0.3min-1min, the coagulation bath composition is a running water in baking oven.
6. the preparation method of aromatic polyamides NF membrane according to claim 1 is characterized in that: under lower pressure (0.4-0.6MPa), the dyestuff of molecular weight about 400 had well hold back effect, and sodium chloride is had than high permeability.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406030A (en) * | 2013-08-23 | 2013-11-27 | 哈尔滨工业大学 | Preparation method of gas-phase crosslinking modified polyetherimide nanofiltration membrane |
| CN105348846A (en) * | 2015-09-25 | 2016-02-24 | 恒升化工有限公司 | Preparation method for acid blue dye 9 with low salt content |
| CN106110908A (en) * | 2016-07-05 | 2016-11-16 | 浙江赛特膜技术有限公司 | The preparation method of aromatic polyamides hydridization NF membrane |
| CN110359298A (en) * | 2019-07-10 | 2019-10-22 | 浙江海印数码科技有限公司 | Preparation method of low-salinization reactive dye and application of low-salinization reactive dye in ink-jet printing ink |
| CN111359458A (en) * | 2020-04-03 | 2020-07-03 | 江西省科学院能源研究所 | Molybdenum disulfide oxide modified flat nanofiltration membrane as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903417A (en) * | 2006-07-14 | 2007-01-31 | 哈尔滨工业大学 | Titanium dioxide granule modified aromatic polyamide separation film and its prepn. method |
| CN101732998A (en) * | 2010-01-25 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Preparation method for cross-linking polyvinyl alcohol furfural nanofiltration membrane |
| CN102114391A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院生态环境研究中心 | Method for preparing polyisophthaloyl metaphenylene diamide nanofiltration membrane |
-
2010
- 2010-10-27 CN CN2010105261601A patent/CN102451622A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903417A (en) * | 2006-07-14 | 2007-01-31 | 哈尔滨工业大学 | Titanium dioxide granule modified aromatic polyamide separation film and its prepn. method |
| CN102114391A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院生态环境研究中心 | Method for preparing polyisophthaloyl metaphenylene diamide nanofiltration membrane |
| CN101732998A (en) * | 2010-01-25 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Preparation method for cross-linking polyvinyl alcohol furfural nanofiltration membrane |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406030A (en) * | 2013-08-23 | 2013-11-27 | 哈尔滨工业大学 | Preparation method of gas-phase crosslinking modified polyetherimide nanofiltration membrane |
| CN105348846A (en) * | 2015-09-25 | 2016-02-24 | 恒升化工有限公司 | Preparation method for acid blue dye 9 with low salt content |
| CN105348846B (en) * | 2015-09-25 | 2017-07-11 | 恒升化工有限公司 | A kind of preparation method of lower salt content acid blue 9 dyestuff |
| CN106110908A (en) * | 2016-07-05 | 2016-11-16 | 浙江赛特膜技术有限公司 | The preparation method of aromatic polyamides hydridization NF membrane |
| CN110359298A (en) * | 2019-07-10 | 2019-10-22 | 浙江海印数码科技有限公司 | Preparation method of low-salinization reactive dye and application of low-salinization reactive dye in ink-jet printing ink |
| CN110359298B (en) * | 2019-07-10 | 2022-05-13 | 浙江海印数码科技有限公司 | Preparation method of low-salinization reactive dye and application of low-salinization reactive dye in ink-jet printing ink |
| CN111359458A (en) * | 2020-04-03 | 2020-07-03 | 江西省科学院能源研究所 | Molybdenum disulfide oxide modified flat nanofiltration membrane as well as preparation method and application thereof |
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Application publication date: 20120516 |