CN103816817B - Alkali-resistant cellulose membrane and preparation method thereof - Google Patents
Alkali-resistant cellulose membrane and preparation method thereof Download PDFInfo
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- CN103816817B CN103816817B CN201410041578.1A CN201410041578A CN103816817B CN 103816817 B CN103816817 B CN 103816817B CN 201410041578 A CN201410041578 A CN 201410041578A CN 103816817 B CN103816817 B CN 103816817B
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Abstract
The invention relates to an alkali-resistant cellulose membrane and a preparation method thereof. The alkali-resistant cellulose membrane is characterized by comprising an alkali-resistant regenerated cellulose ultrafiltration membrane, an alkali-resistant regenerated cellulose nanofiltration membrane, an alkali-resistant regenerated cellulose hollow fiber membrane and an alkali-resistant regenerated cellulose flat membrane. The preparation method comprises the following steps: directly dissolving cellulose pulp and an additive by using NMMO containing 5 to 15 weight percent of water as a solvent, preparing the regenerated cellulose membranes by adopting a gel immersion phase inversion method, and performing sodium hydroxide post-treatment, washing and glycerin post-treatment. The prepared alkali-resistant regenerated cellulose membrane has an aperture of more than 0.001 micron and less than 0.1 micron, and can intercept an organic substance with the molecular weight more than 500 WM. The alkali-resistant cellulose membrane can be used for the treatment of viscose fiber pressing wastewater, black liquor produced by alkali papermaking, yarn boiling and mercerizing washing water of the printing and dyeing industry, lime-alkali hair removal wastewater of the leatherworking industry, wastewater produced by partial petroleum and chemical production processes and the like.
Description
Technical field
The present invention relates to a kind of alkali resistant cellulose film and preparation method thereof.
Background technology
Alkaline waste water refers to be higher than 9 waste water containing certain bases, pH value, is divided into strong basicity waste water, alkalescence waste water, low
Concentration alkaline waste water and high concentration basic waste water.In alkaline waste water, in addition to the alkali containing certain variable concentrations, generally also contain big
The harmful substances such as the Organic substance of amount, inorganic salt.The wide material sources of alkaline waste water, essentially from the squeezing waste water of viscose rayon, alkali
The black liquor of method papermaking, printing and dyeing industry boil yarn, mercerising wash water, the ash alkali unhairing waste water of leather industry and oil, the Ministry of Chemical Industry are mitogenetic
Waste water of product process etc..The processing method of alkaline waste water has acid-base neutralization method, flocculence, chemical precipitation method, combustion method, crystallization
Method, microbial method, electroosmose process etc..Water treatment by membrane has the advantages that efficient, practical, adjustable, energy-conservation and simple process with it
It is expected to be widely used in and process containing alkali waste water.
Cellulose has the advantages that wide material sources, good biocompatibility, physical and chemical performance be stable, acid and alkali-resistance is it is considered to be reason
The membrane material thought.Generally cellulose membrane is used for the neck such as desalinization, hemodialysis, gas separation, oil-water separation, packaging film
Domain.The preparation method of cellulose membrane has viscose process, cuprammonium process and solvent method.The Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences is in cellulose made by soloent process
The applied research of empty film（Middle outer energy, 2006,11（4））In compare the performance of film prepared by solvent method and cuprammonium process, result
The cellulose membrane representing solvent method preparation, either in the acid of higher concentration or alkaline solution, all shows good steady
Qualitative, and the cellulose membrane alkali resistance of cuprammonium process preparation is poor, can be dissolved it is therefore necessary to develop in 18% NaOH solution
Solvent method prepares cellulose membrane for processing containing alkali waste water.
Content of the invention
It is an object of the invention to provide a kind of preparation method of regenerated cellulose film, the method film-forming process is simple, solvent
Recyclable, pollution-free, this cellulose membrane alkaline resistance properties is good, can be used for processing containing alkali waste water.
For reaching above-mentioned purpose, the technical solution used in the present invention is：
Alkaline-resisting regenerated cellulose film includes alkaline-resisting regenerated cellulose ultrafilter membrane and alkaline-resisting regenerated cellulose NF membrane, also includes
Alkaline-resisting regenerated cellulose hollow fiber film and alkaline-resisting regenerated cellulose Flat Membrane, are to adopt the NMMO containing 5～15wt% water to be solvent
Directly dissolving cellulose pulp and additive, are then spun into regenerated cellulose hollow fiber film using the gel phase inversion that soaks
Or be cast into regenerated cellulose Flat Membrane, then through sodium hydroxide post processing, washing, glycerol post processing and be obtained.
The preparation method of the alkaline-resisting regenerated cellulose film of the present invention comprises the following steps：
1）The preparation of casting solution：Under the conditions of 80～100 DEG C, percentage by weight is 5～20：70～93.9：1～8：
0.1～2 cellulose pulp, the NMMO containing 5～15wt% water, additive and antioxidant uniformly mix, and stir, dissolve, deaeration
Filter, the cellulose casting solution of 5～20wt% is obtained；
2）The gel phase inversion that soaks is spun into film：Under the conditions of 70 DEG C, by step 1）Prepared casting solution is in glass plate
On be cast into Flat Membrane, or by step 1）Prepared casting solution and core liquid extrude tubular film by spinneret simultaneously；To be obtained
Flat Membrane set to 0 in a gaseous environment decentralization～120S after enter in coagulating bath solidification 3～5min or by tubular film through 0～
Enter in coagulating bath after the gaseous environment of 20cm and solidify；Deionized water washes away the residual solvent in this film again；
3）Under the conditions of 20～30 DEG C, with 17～22wt% sodium hydrate aqueous solution process step 2）The cellulose membrane of preparation
45～100min；
4）By step 3）It is immersed in 3～24h in the glycerine water solution of 10～50wt%, so after the cellulose membrane washing of preparation
Afterwards film is taken out room temperature and dry i.e. prepared regenerated cellulose film.
Described cellulose pulp is absorbent cotton, bamboo pulp, wood pulps, reed straw, wheat straw waste, rice straw, sweet
The mixture of one of sugarcane straw or two kinds；
The described cellulose pulp degree of polymerization is 500～1200, alpha-cellulose content >=90wt%；
Described antioxidant is propylgallate；
Described additive is macromolecular pore generators, the mixture of small molecule pore former；
The weight of described macromolecular pore generators and small molecule pore former is than for 1～5：1；
Described macromolecular pore generators are the mixture of one of Polyvinylpyrrolidone, Polyethylene Glycol or two kinds, gather
Vinylpyrrolidone model is selected from K12, K17, K25, K30, K60, K90, and molecular weight polyethylene glycol is 200-20000；
Described small molecule pore former is one of glycerol, Methanamide；
Described core liquid is one of water, glycerine water solution of 1～20wt%；
In described gaseous environment, gas is one of air, nitrogen, argon, and air gap temperature is 24 DEG C, and humidity is 30
～90%RH；
Described coagulating bath is water, one of the NMMO containing 5～50wt% water, 5～50wt% formyl amine aqueous solution, temperature
For 10～50 DEG C.
The alkaline-resisting regenerated cellulose film of the present invention has the advantage that：
1）Filming technology of the present invention is simple, pollution-free, solvent NMMO easily reclaims, and is friendly process.
2）The cellulose pulp that the present invention uses is not high to the content requirement of alpha-cellulose, it is possible to decrease the system of cellulose pulp
Standby cost, expand raw material carrys out source range.
3）Sodium hydroxide post processing can reduce the content of the impurity such as hemicellulose in cellulose membrane, lignin, makes regeneration fine
In the plain film of dimension, the content of alpha-cellulose is high as much as possible；The method can also change the pore structure of cellulose membrane, fine for preparation porous
The plain film of dimension provides an approach.
4）The present invention with the addition of macromolecular pore generators and small molecule pore former in preparing regenerated cellulose casting solution, passes through
Macromolecular pore generators and the compounded combination of small molecule pore former, have regulated and controled the pore structure of cellulose membrane respectively or synergistically, have made
The aperture of raw cellulose membrane is more than 0.001 μm, less than 0.1 μm, can retain the molecular weight ＞ 500M of Organic substanceW.
5）The alkaline-resisting regenerated cellulose film of present invention preparation can be used for the squeezing waste water of viscose rayon, alkali paper-making black
Liquid, printing and dyeing industry boil yarn, mercerising wash water, the ash alkali unhairing waste water of leather industry and oil, chemical industry part producing process useless
Water process etc..
Specific embodiment
Embodiment 1
At 80 DEG C, the 5g degree of polymerization is 1200, alpha-cellulose content is the reed straw of 90wt%, 0.83gPVP-K90,
0.17g glycerol, 0.1g propylgallate and 93.9g contain the NMMO solvent mixing of 15wt% water, and uniform stirring makes it dissolve, greatly
About need 1h, deaeration is obtained the cellulose casting solution of 5wt% after filtering；At 70 DEG C, this casting solution is cast on a glass
Flat Membrane, this film is put into solidification 5min in deionized water at once；After washing by this film under the conditions of 30 DEG C, use 17wt% hydrogen-oxygen
Change sodium water solution and process 45min, then this film 30wt% glycerine water solution is soaked 3h after washing, then that this film is empty in room temperature
Dry in gas and regenerated cellulose flat plate ultrafiltration membrane is obtained.The water flux of this film is 637L/m2H, to 1% bovine serum albumin
Rejection is 98%.
Embodiment 2
At 100 DEG C, the 20g degree of polymerization is 912, alpha-cellulose content is the bamboo pulp of 93wt%, and 4gPEG8000,4g are sweet
Oil, 2g propylgallate and 70g contain the NMMO solvent mixing of 5wt% water, and uniform stirring makes it dissolve, takes around 2h, deaeration
The cellulose casting solution of 20wt% is obtained after filtration；Will be common through spinneret to this casting solution and 20wt% glycerine water solution at 70 DEG C
It is extruded into tubular film, by this film through 24 DEG C of 15cm, enter 50 DEG C after the argon air gap of 90%RH, the NMMO containing 10wt% water
Solidify in solvent；After washing by this film under the conditions of 25 DEG C, process 100min with 22wt% sodium hydrate aqueous solution, then after washing
Soak this film 24h with 10wt% glycerine water solution, then this film is dried in air at room temperature and regenerated cellulose hollow fibre is obtained
Wiener filter membrane.The water flux of this film is 234L/m2H, squeezes the rejection of the impurity such as hemicellulose in waste water to viscose rayon
Up to 98%.
Embodiment 3
At 90 DEG C, the 24g degree of polymerization is 500, alpha-cellulose content is the wood pulps of 92wt%, 3.75gPVP-K30,
1.25g Methanamide, 2g propylgallate and 169g contain the NMMO solvent mixing of 10wt% water, and uniform stirring makes it dissolve, about
Need 1.5h, deaeration is obtained the cellulose casting solution of 12wt% after filtering；By this casting solution and 1wt% glycerine water solution at 70 DEG C
Jointly it is extruded into tubular film through spinneret, is immediately placed in 30 DEG C, solidify in 5wt% formyl amine aqueous solution；By this film 20 after washing
Under the conditions of DEG C, process 60min with 20wt% sodium hydrate aqueous solution, then soak this film 15h with 30wt% glycerine water solution after washing,
Then this film is dried in air at room temperature and regenerated cellulose hollow fiber ultrafilter membrane is obtained.The water flux of this film is 532L/
m2H, the rejection to 1% bovine serum albumin is 99%.
Claims (7)
1. a kind of alkali resistant cellulose film is it is characterised in that this film includes alkali resistant cellulose hollow-fibre membrane and alkali resistant cellulose flat board
Film, is directly to dissolve cellulose pulp and additive using the NMMO containing 5～15wt% water for solvent, then using the gel that soaks
Phase inversion is spun into regenerated cellulose hollow fiber film or is cast into regenerated cellulose Flat Membrane, then locates after sodium hydroxide
Reason, washing, glycerol post processing and be obtained,
The preparation method of described alkali resistant cellulose film, comprises the following steps：
1) preparation of casting solution：Under the conditions of 80～100 DEG C, percentage by weight is 5～20：70～93.9：1～8：0.1～2
Cellulose pulp, uniformly mix containing the NMMO of 5～15wt% water, additive and antioxidant, stir, dissolve, deaeration is filtered,
The cellulose casting solution of 5～20wt% is obtained；
Described additive is macromolecular pore generators, the mixture of small molecule pore former；
Described small molecule pore former is one of glycerol, Methanamide；
2) the gel phase inversion that soaks is spun into film：Under the conditions of 70 DEG C, by step 1) be obtained casting solution flow on a glass
Prolonging into Flat Membrane, or by step 1) casting solution and the core liquid that are obtained extrudes tubular film by spinneret simultaneously；Flat by be obtained
Plate film one gaseous environment decentralization set to 0～120S after enter coagulating bath in solidification 3～5min or by tubular film through 0～20cm's
Enter in coagulating bath after gaseous environment and solidify；Deionized water washes away the residual solvent in this film again；
Described core liquid is one of water, glycerine water solution of 1～20wt%；
Described coagulating bath is water, one of the NMMO containing 5～50wt% water, 5～50wt% formyl amine aqueous solution, and temperature is
10～50 DEG C；
3) under the conditions of 20～30 DEG C, with 17～22wt% sodium hydrate aqueous solution process step 2) cellulose membrane prepared 45～
100min；
4) by step 3) it is immersed in 3～24h in the glycerine water solution of 10～50wt% after the washing of the cellulose membrane prepared, then will
Film is taken out room temperature and is dried i.e. prepared alkali resistant cellulose film.
2. a kind of alkali resistant cellulose film described in a kind of claim 1 preparation method it is characterised in that the method include following
Step：
1) preparation of casting solution：Under the conditions of 80～100 DEG C, percentage by weight is 5～20：70～93.9：1～8：0.1～2
Cellulose pulp, uniformly mix containing the NMMO of 5～15wt% water, additive and antioxidant, stir, dissolve, deaeration is filtered,
The cellulose casting solution of 5～20wt% is obtained；
2) the gel phase inversion that soaks is spun into film：Under the conditions of 70 DEG C, by step 1) be obtained casting solution flow on a glass
Prolonging into Flat Membrane, or by step 1) casting solution and the core liquid that are obtained extrudes tubular film by spinneret simultaneously；Flat by be obtained
Plate film one gaseous environment decentralization set to 0～120S after enter coagulating bath in solidification 3～5min or by tubular film through 0～20cm's
Enter in coagulating bath after gaseous environment and solidify；Deionized water washes away the residual solvent in this film again；
Described core liquid is one of water, glycerine water solution of 1～20wt%；
Described coagulating bath is water, one of the NMMO containing 5～50wt% water, 5～50wt% formyl amine aqueous solution, and temperature is
10～50 DEG C；
3) under the conditions of 20～30 DEG C, with 17～22wt% sodium hydrate aqueous solution process step 2) cellulose membrane prepared 45～
100min；
4) by step 3) it is immersed in 3～24h in the glycerine water solution of 10～50wt% after the washing of the cellulose membrane prepared, then will
Film is taken out room temperature and is dried i.e. prepared alkali resistant cellulose film.
3. a kind of alkali resistant cellulose film according to claim 1 it is characterised in that described cellulose pulp be absorbent cotton,
The mixture of one of bamboo pulp, wood pulps, reed straw, wheat straw waste, rice straw, Caulis Sacchari sinensis straw or two kinds.
4. a kind of alkali resistant cellulose film according to claim 1 or 3 is it is characterised in that the described cellulose pulp degree of polymerization
For 500～1200, alpha-cellulose content >=90wt%.
5. a kind of alkali resistant cellulose film according to claim 1 it is characterised in that described macromolecular pore generators with little point
The weight of sub- pore former is than for 1～5：1.
6. according to claim 1 or 5 a kind of alkali resistant cellulose film it is characterised in that described macromolecular pore generators are poly-
The mixture of one of vinylpyrrolidone, Polyethylene Glycol or two kinds, Polyvinylpyrrolidone model be selected from K12, K17,
K25, K30, K60, K90, molecular weight polyethylene glycol is 200-20000.
7. a kind of alkali resistant cellulose film according to claim 1 is it is characterised in that step 2) described in gaseous environment in
Gas is one of air, nitrogen, argon, and air gap temperature is 24 DEG C, and humidity is 30～90%RH.
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| CN105597551B (en) * | 2015-10-16 | 2019-05-10 | 福建农林大学 | A kind of preparation method of regenerated cellulose nanofiltration membrane |
| CN106474944B (en) * | 2016-11-08 | 2019-04-23 | 福建农林大学 | A kind of preparation method of antibacterial cellulose plate nanofiltration membrane |
| CN111437740B (en) * | 2020-03-09 | 2022-07-01 | 哈尔滨工业大学 | Preparation method of sodium lignosulfonate-based high-flux high-interception nanofiltration membrane |
| CN112538777B (en) * | 2020-12-07 | 2023-05-16 | 广东省东莞市质量监督检测中心 | Regenerated cellulose film coated green food packaging paper and preparation method and application thereof |
| CN115025630A (en) * | 2021-06-02 | 2022-09-09 | 赛普(杭州)过滤科技有限公司 | Preparation method and product of hollow cellulose virus removal filtering membrane |
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