CN109012242A - The preparation method of sodium alginate mixed substrate membrane containing nano-grade molecular sieve for alcohol-water separation - Google Patents
The preparation method of sodium alginate mixed substrate membrane containing nano-grade molecular sieve for alcohol-water separation Download PDFInfo
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- CN109012242A CN109012242A CN201811087201.4A CN201811087201A CN109012242A CN 109012242 A CN109012242 A CN 109012242A CN 201811087201 A CN201811087201 A CN 201811087201A CN 109012242 A CN109012242 A CN 109012242A
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- sodium alginate
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- sodium
- alcohol
- molecular sieve
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/005—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion by thermal diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
Abstract
The invention discloses a kind of for separating the preparation method of the mixed substrate membrane containing nano-grade molecular sieve of alcohol water.The present invention passes through a kind of pre-synthesis redox graphene-sodium lignosulfonate composite material, synthesized composite material is added in sodium alginate preparation liquid again, after being uniformly dispersed, sodium alginate mixed substrate membrane containing nano-grade molecular sieve is prepared on ultrafiltration counterdie, is directly obtained after drying at room temperature, crosslinking and heat treatment containing redox graphene-sodium lignosulfonate composite material sodium alginate infiltrating and vaporizing membrane.The present invention utilizes lamella duct and hydrophily in redox graphene-sodium lignosulfonate composite material, adds it in preparation liquid, and the separating property for making the infiltration evaporation of sodium alginate film separate alcohol-water mixture improves.
Description
Technical field:
The present invention relates to a kind of preparation methods of sodium alginate mixed substrate membrane containing nano-grade molecular sieve for separating alcohol water, especially for oxygen reduction
The preparation for the infiltrating and vaporizing membrane that the ethyl alcohol that graphite alkene-sodium lignosulfonate composite material and sodium alginate are mixed to prepare is concentrated
Method.
Background technique:
Pervaporation Technology is a kind of novel membrane separating process, because it has many advantages, such as that efficient, energy-saving and environmental protection are expected to take
The distillation process of generation traditional high energy consumption, plays a significant role during the separation and improvement fermentation efficiency in situ of bio-alcohol.
Chinese scholar is conducted extensive research and is probed into preferential water permeable membrane, such as Wu Liguang；Zhu Changle；Liu Meie is in
A kind of polyvinyl alcohol and shell have been invented in state patent 94102067.3-- " preparation method and composition of vapor permeable membrance "
Glycan is blended, and the excellent membrane material of water permeability, Lin Xiao is made after crosslinking agent citric acid is added；Xu Nanping；Luo Yan；Zhong Sheng comes
It has been invented in Chinese invention patent 200410041601.3-" a kind of preparation method of high performance permeation evaporation permeable membrane "
The method that perforated tubular ceramic supporting body surface prepares NaA type molecular screen membrane, when separating 90wt% ethanol water, average water
Permeation flux J=2.5~3.2kg/m2H, separation a=5000~10000 or more, in Patent No. 200410015893.3
Chinese patent in, Chen Cuixian；Li Jiding；Liu Shoushan；Zhang Danxia prepares low-temperature plasma graft infiltrating and vaporizing membrane, this infiltration
Saturating vaporization film has good selectivity and permeation flux.Industrialization is had been achieved in high concentration ethanol/water dehydration field at present.
Although preferential permeable infiltration evaporation Separation Research has more report both at home and abroad in current alcohol-water system, seep
Vaporization is used to prepare dehydrated alcohol and comes into industrial application thoroughly.But preferential permeable infiltration evaporation process is adapted only to processing and is rich in
There is alcohols and the low system of water content, as process of anhydrous ethyl alcohol is produced in the ethanol dehydration of concentration 99% (w).And in industrial production
In, there is the lower water solution systems of many alcohol contents, therefore carrying out in-depth study to it has important real value.
Natural polysaccharide, a kind of boiomacromolecule are widely used to the fields such as food, medicine, daily-use chemical industry, meanwhile,
Often it is used as membrane material.Sodium alginate is exactly one kind of natural polysaccharide, has good film forming and preferable hydrophily.With it
He compares organic film, though sodium alginate have the advantages that it is flexible it is good, gas permeability is high, density is low etc., its solvent resistant, heatproof
Degree property and mechanical property are all poor.Therefore it is modified to have carried out blending, compound, grafting, hydridization etc. to sodium alginate by people.Wherein,
Hybrid inorganic-organic is one of the simple effective method for improving polymer comprehensive performance.
Sodium lignosulfonate is to possess a large amount of oxygen-containing group, good water solubility from Sulphonation of Lignin.Currently, since it can
Reproducibility, low cost and containing a large amount of hydrophilic groups, increasingly by as surfactant and water absorbent.In addition, wooden
The hydrophobicity phenylpropane units of plain sodium sulfonate are spontaneously cross-linked into three-dimensional network, this makes the energy during humidification-dehumidifying circulation
Rapid expanding and contraction.
Graphene have excellent optics, electricity, mechanical characteristic, materialogy, micro-nano technology, in terms of have weight
A kind of application prospect wanted, it is considered to be revolutionary material.The graphene of thick 1mm comprises about 3,000,000 layers of graphene.Graphite
Gauze-like is presented compared with carbon nanotube in alkene, more suitable for the research of biomaterial.And the edge and carbon nanotube of graphene
It compares, it is longer, it is easier to be doped and chemical modification, it is easier to receive functional group.
Early period, discovery, sodium lignosulfonate was added in sodium alginate preparation liquid, the separating property of film can be improved.In order to
Redox graphene is carried out compound, preparation reduction-oxidation by the performance for advanced optimizing infiltrating and vaporizing membrane with sodium lignosulfonate
Graphene-sodium lignosulfonate dispersion liquid prepares a kind of infiltrating and vaporizing membrane that performance more optimizes.
Summary of the invention:
The technical problem to be solved in the present invention is to provide a kind of for separating the system of the sodium alginate mixed substrate membrane containing nano-grade molecular sieve of alcohol water
Preparation Method has the characteristics that separating property is high using mixed substrate membrane containing nano-grade molecular sieve prepared by this kind of method.The following steps are included:
1) redox graphene-sodium lignosulfonate dispersion liquid preparation: being 0.03g/ml graphene oxide by concentration
Solution and the mixing of lignosulphonic acid sodium solution, ultrasonic mixing is uniformly added into a small amount of vitamin C, with vigorous stirring by graphite oxide
Alkene-sodium lignosulfonate mixed liquor is cooled to room temperature after reaction in 95 DEG C of reaction certain times, then ultrasound, disperses to obtain reduction
Graphene oxide-sodium lignosulfonate uniform dispersion；
2) configuration of preparation liquid: sodium alginate constant temperature soluble in water is stirred to the seaweed for being completely dissolved configuration 0.03g/ml
Then redox graphene-sodium lignosulfonate dispersion liquid, the volume of added dispersion liquid and sodium alginate is added in sour sodium preparation liquid
Than be for 1:10, by mixed liquor is agitated and ultrasonic disperse uniformly after standing and defoaming obtain preparation liquid；
3) then the preparation liquid stood is equably poured over dry, cleaning, on smooth ultrafiltration counterdie, with scraping hymenotome
The wet film for spreading to certain thickness, is dried at room temperature for, and then places into dried film in 0.5mol/L calcium chloride solution
Crosslinking 10 minutes is carried out, washes film water after crosslinking, is thoroughly dried at room temperature to get infiltrating and vaporizing membrane is arrived.
Further improvement as the sodium alginate mixed-matrix membrane preparation method for separating alcohol-water system of the invention:
Ultrafiltration counterdie is PS membrane, poly (ether sulfone) film and polyacrylonitrile film.
The method of the present invention simple possible, easily operated, prepared infiltrating and vaporizing membrane is a kind of composite membrane, has perfection
Infiltrating and vaporizing membrane structure, have preferable selectivity to alcohol type organic；And stable chemical performance, hydrophobicity is strong, makes for a long time
It can still be kept with separating property stable；Therefore it is considerable to be applied to industrial production prospect.The present invention uses cheap raw material
It is produced, therefore the cost of product can be reduced, make it have the very strong market competitiveness.Using infiltrating and vaporizing membrane of the invention from
Ethyl alcohol is concentrated in fermentation liquid, has the advantages that efficient, low energy consumption, the call of national energy conservation and emission reduction can be sufficiently responded to.
Specific implementation method:
Comparative example 1-3:
Sodium alginate infiltrating and vaporizing membrane:
1) configuration of preparation liquid is stirred 1.2g sodium alginate is molten with constant temperature in 40ml water to being completely dissolved, gained film
Liquid is stood overnight to remove bubble；
2) then the preparation liquid stood is equably poured over dry, cleaning, on smooth ultrafiltration counterdie, with scraping hymenotome
It carries out scraping film process, obtains certain thickness wet film, be completely dried at room temperature；
3) then dried film is placed into the calcium chloride solution of 0.5mol/L and carries out crosslinking 10 minutes, it will after crosslinking
Film water is washed, and is completely dried at room temperature to get infiltrating and vaporizing membrane is arrived.
Above-mentioned mixed substrate membrane containing nano-grade molecular sieve is used for separating alcohol-water, concrete operations are as follows:
Manufactured infiltrating and vaporizing membrane is fitted into the osmotic cell of infiltration evaporation device, 90% ethyl alcohol is added in feed liquid bottle
Aqueous solution, heating make feed liquid temperature maintain 70 DEG C, and film downstream vacuum degree is controlled in 180Pa.Receiving flask is put into cold in liquid nitrogen
Freeze, open vacuum pump, alcohol vapour is condensed collections, by quality in weighing receiving flask and with gas chromatographic analysis permeate
The concentration of middle ethyl alcohol, so that the permeation flux and separation factor of the infiltrating and vaporizing membrane separating alcohol-water system are obtained, as a result such as table
1。
Embodiment 1-3:
A kind of preparation method of the sodium alginate mixed substrate membrane containing nano-grade molecular sieve for separating alcohol-water system, successively follows the steps below:
1) redox graphene-sodium lignosulfonate dispersion liquid preparation: being 0.03g/ml graphene oxide by concentration
Solution and the mixing of lignosulphonic acid sodium solution, ultrasonic mixing is uniformly added into a small amount of vitamin C, with vigorous stirring by graphite oxide
Alkene-sodium lignosulfonate mixed liquor is cooled to room temperature after reaction in 95 DEG C of reaction certain times, then ultrasound, disperses to obtain reduction
Graphene oxide-sodium lignosulfonate uniform dispersion；
2) configuration of preparation liquid: sodium alginate is dissolved in constant temperature in water and is stirred to the sea for being completely dissolved configuration 0.03g/ml
Then redox graphene-sodium lignosulfonate dispersion liquid, the body of added dispersion liquid and sodium alginate is added in mosanom preparation liquid
Product than be for 1:10, by mixed liquor is agitated and ultrasonic disperse uniformly after standing and defoaming obtain preparation liquid.
Subsequent process steps are consistent with comparative example.Above-mentioned mixed substrate membrane containing nano-grade molecular sieve is used for separating alcohol-water, to obtain the infiltration
The permeation flux and separation factor of vaporization UF membrane ethanol-water system thoroughly, as a result such as table 1.
The permeation flux and separation factor of table 1SA film and LS/SA composite membrane separating alcohol-water system
Claims (2)
1. the preparation method of the sodium alginate mixed substrate membrane containing nano-grade molecular sieve for alcohol-water separation, it is characterized in that the following steps are included:
1) redox graphene-sodium lignosulfonate dispersion liquid preparation: being 0.03g/ml graphene oxide solution by concentration
It is mixed with lignosulphonic acid sodium solution, ultrasonic mixing is uniformly added into a small amount of vitamin C, with vigorous stirring by graphene oxide-wood
Plain sodium sulfonate mixed liquor is cooled to room temperature after reaction in 95 DEG C of reaction certain times, then ultrasound, disperses to obtain oxygen reduction fossil
Black alkene-sodium lignosulfonate uniform dispersion；
2) configuration of preparation liquid: sodium alginate constant temperature soluble in water is stirred to the sodium alginate for being completely dissolved configuration 0.03g/ml
Preparation liquid, is then added redox graphene-sodium lignosulfonate dispersion liquid, and the volume ratio of added dispersion liquid and sodium alginate is equal
For for 1:10, by mixed liquor is agitated and ultrasonic disperse uniformly after standing and defoaming obtain preparation liquid；
3) then the preparation liquid stood is equably poured on dry, clean, smooth ultrafiltration counterdie, is spread to hymenotome is scraped
The wet film of certain thickness, is dried at room temperature for, and then places into 0.5mol/L calcium chloride solution dried film and carries out
Crosslinking 10 minutes, washes film water after crosslinking, is thoroughly dried at room temperature to get infiltrating and vaporizing membrane is arrived.
2. the preparation method of the sodium alginate mixed substrate membrane containing nano-grade molecular sieve according to claim 1 for separating alcohol water, feature
Be: the ultrafiltration counterdie is PS membrane, poly (ether sulfone) film and polyacrylonitrile film.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110548414A (en) * | 2019-08-28 | 2019-12-10 | 南京工业大学 | Separation membrane based on zwitterion functionalized graphene oxide and preparation method thereof |
| CN110711491A (en) * | 2019-11-20 | 2020-01-21 | 北京林业大学 | Preparation of calcium lignosulphonate/sodium alginate pervaporation membrane for alcohol-water separation |
| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
| CN114539646A (en) * | 2022-01-24 | 2022-05-27 | 谢辉辉 | High-strength wear-resistant rubber and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
| CN114539646A (en) * | 2022-01-24 | 2022-05-27 | 谢辉辉 | High-strength wear-resistant rubber and preparation method thereof |
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Application publication date: 20181218 |