CN115976875B - Continuous production method of solvent-method functional regenerated cellulose membrane - Google Patents
Continuous production method of solvent-method functional regenerated cellulose membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000010924 continuous production Methods 0.000 title claims abstract description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 131
- 239000001913 cellulose Substances 0.000 claims abstract description 131
- 238000001035 drying Methods 0.000 claims abstract description 72
- 239000002608 ionic liquid Substances 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000005406 washing Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
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- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000839 emulsion Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002082 metal nanoparticle Substances 0.000 claims description 5
- 239000012802 nanoclay Substances 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- -1 nano-oxide Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005728 strengthening Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 238000004806 packaging method and process Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000008204 material by function Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of functional regenerated cellulose membrane production, and discloses a continuous production method of a solvent-method functional regenerated cellulose membrane, which comprises the following steps: uniformly mixing the ionic liquid, the cellulose pulp and the functional material according to a proportion to obtain a mixed material; after the mixed material is dehydrated, cellulose is dissolved and defoamed, and then impurities are removed by filtering to obtain cellulose ionic liquid solution; spraying the cellulose ionic liquid solution into the coagulating bath through a slit to form a wet cellulose film; after washing and softening the wet cellulose film, coating a functional auxiliary agent on the surface of the wet cellulose film, wherein the functional auxiliary agent at least comprises an anti-adhesion agent, and then predrying the wet cellulose film in a drying channel at 80-120 ℃ and strengthening the drying at 80-150 ℃ close to the surface of a drying cylinder; and finally, performing humidity control treatment on the cellulose membrane to obtain the product. Can solve the problems of long and complex preparation process and obviously higher cost of the traditional regenerated cellulose-based membrane viscose method.
Description
Technical Field
The invention relates to the technical field of functional regenerated cellulose membrane production, in particular to a continuous production method of a solvent-method functional regenerated cellulose membrane.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The regenerated cellulose membrane is prepared from natural cellulose serving as a raw material, can be naturally degraded, is an environment-friendly packaging material, and meanwhile, as the current environment-friendly requirements are stricter and stricter, the degradable material is more and more important, and the regenerated cellulose membrane also meets the development opportunity. However, the characteristics of high cost, non-water resistance, non-heat sealing and the like of the regenerated cellulose membrane limit the application and popularization of the regenerated cellulose membrane in the packaging field, and the functionalization of the regenerated cellulose membrane is an effective way for solving the problem.
The regenerated cellulose membrane functionalization application mainly comprises two modes of adding functional auxiliary agents into the glue and coating or compounding the surface of the cellulose membrane. The traditional regenerated cellulose membrane preparation technology adopts a viscose method technology, and only various functional additives in the form of emulsion can be added into the viscose, so that the additives are ensured to be added into a viscose solution to be dispersed easily and have no adverse effect on subsequent solidification and regeneration, thereby endowing the viscose regenerated cellulose membrane with a certain function; the traditional regenerated cellulose film surface coating process is a two-step method, namely, a dry cellulose film product is firstly prepared, functional coating emulsion is coated on the surface of the dry cellulose film product after edge cutting treatment, and after the coating is finished, edge cutting is carried out again to obtain a finished functional cellulose film meeting the requirements of customers. In addition, the dry film needs to be dried for the second time after being coated, so that the problem of energy consumption increase further increases the product cost, and the popularization and application difficulty is further increased.
In addition, the traditional regenerated cellulose base film is prepared by adopting a viscose method, the technology is long and complex, the high quality requirement on raw material pulp can only use high-quality dissolved pulp, a large amount of chemicals such as caustic soda, sulfuric acid, carbon disulfide and the like are used in the production process, and the toxic and harmful gases such as sulfur dioxide, hydrogen sulfide and the like are generated to discharge, and a large amount of acid wastewater is generated, so the cost of the regenerated cellulose base film prepared by the technology is obviously higher due to the characteristics of the production technology and the environmental protection treatment problem.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a continuous production method of a solvent-method functional regenerated cellulose membrane, which adopts ionic liquid as a solvent to dissolve cellulose to prepare the regenerated cellulose membrane, thereby effectively solving the problems of environmental protection and high cost existing in the preparation of a regenerated cellulose base membrane by the traditional viscose process; the continuous functional treatment process is adopted to realize one-step preparation of the functional regenerated cellulose membrane, shortens the functional preparation process and effectively solves the problem of high cost of the functional regenerated cellulose membrane.
In order to achieve the above object, the present invention is realized by the following technical scheme:
a continuous production method of a solvent-process functional regenerated cellulose membrane, comprising the steps of: uniformly mixing the ionic liquid, cellulose pulp (dry pulp) and functional materials to obtain a mixed material, wherein the mass ratio of the ionic liquid to the cellulose pulp is 85-95:5-15, and the dosage of the functional materials is 0.1-2% of the mass of the cellulose pulp;
after the mixed material is dehydrated, cellulose is dissolved and defoamed, and then impurities are removed by filtering to obtain cellulose ionic liquid solution;
spraying the cellulose ionic liquid solution into the coagulating bath through a slit to form a wet cellulose film;
after washing and softening the wet cellulose film, coating a functional auxiliary agent on the surface of the wet cellulose film, wherein the functional auxiliary agent at least comprises an anti-adhesion agent, then pre-drying for 5-30s at 80-120 ℃ in a drying channel, and then strengthening and drying the wet cellulose film at 80-150 ℃ close to the surface of a drying cylinder, or directly strengthening and drying the wet cellulose film at 80-150 ℃ close to the surface of the drying cylinder without pre-drying; the cellulose film is pre-dried, so that the coating on the surface of the cellulose film is primarily solidified, the binding force between the coating and the cellulose film is improved, the coating is ensured not to be stuck to a cylinder and fall off in the subsequent reinforced drying process, and the method is specifically determined according to the condition of sticking the coating to the cylinder.
Or washing and softening a wet cellulose film, pre-drying the wet cellulose film at 80-120 ℃ after the wet cellulose film is firstly adhered to the surface of a drying cylinder, the pre-drying time is 5-30s, so that the cellulose film is primarily dried and shaped, then coating a functional auxiliary agent on the surface of the cellulose film, wherein the solid content of the functional auxiliary agent is not less than 15%, at least comprises an anti-adhesion agent, and then adhering the functional auxiliary agent to the surface of the drying cylinder for enhanced drying at 80-150 ℃; the primary drying and shaping of the cellulose membrane means primary hardening of the surface of the cellulose membrane, improves the flatness and stiffness of the membrane surface, is convenient for coating, and has higher water content.
And finally, performing humidity control treatment on the cellulose membrane to obtain the product.
The ionic liquid is AmimCl, bmimCl, emimAc imidazole ionic liquid.
The ionic liquid is an aqueous solution of the ionic liquid, wherein the mass fraction of the ionic liquid is 50-95%.
The functional regenerated cellulose membrane is prepared by taking regenerated cellulose membrane as a matrix and taking nano clay, nano oxide, nano composite oxide or metal nano particles as fillers, wherein the functional composite membrane has specific functions such as magnetic permeability, gas-liquid barrier property, flame retardance, photocatalytic activity, adsorptivity and the like. Therefore, in the prior art, the functional auxiliary agent in the form of commercial emulsion is generally purchased and added into the viscose solution to prepare the regenerated cellulose membrane after simple mixing, but the technical scheme of the invention is limited in using the functional auxiliary agent, so that substances such as an emulsifying agent, a dispersing agent, a stabilizing agent and the like can be brought into washing water when the membrane is washed, the subsequent sewage treatment cost is increased, the membrane performance can be influenced by the residual functional auxiliary agent, and the energy consumption of a cellulose dissolving and dehydrating link can be increased by the water in the emulsion, so that the cost of the base membrane is increased.
According to the invention, the ionic liquid is adopted as the solvent, so that the cellulose pulp and the functional material can be mixed in proportion, the strong shearing and meshing effect and the high viscosity of the mixed material are realized in the mixing process, and the functional nano auxiliary agent is fully dispersed.
In the scheme of the invention, after the functional auxiliary agent is compounded with the anti-adhesion agent, the surface of the wet cellulose base film is directly coated, so that the functional treatment in the preparation of the regenerated cellulose base film can be realized, and the functional regenerated cellulose film is obtained in one step; meanwhile, the wet cellulose film is coated in the coating mode, the functional emulsion with any solid content can be selected for coating, the problem that the lower the solid content of the dry film coating is, the more serious the dry film coating is deformed and wrinkled when encountering water in the prior art is avoided, the selection requirement of a coating auxiliary agent is widened, the quality stability of a final product is ensured, the functional emulsion with the solid content of more than or equal to 15 percent can be coated after the wet film is pre-dried, the continuous functional treatment is realized, and the secondary drying of the prior two-step method is not needed. Therefore, the technical scheme of the invention solves a series of problems of low yield, increased energy consumption and easy deformation and wrinkling of the dry film when meeting water in the traditional functional cellulose film two-step method, reduces the cost of the final product and improves the competitiveness of the product.
In some embodiments, the functional material is selected from nanoclay, nano-oxide, nano-composite oxide, or metal nanoparticles.
The nano oxide is nano silicon dioxide or nano titanium dioxide;
the nano composite oxide is nano silicon dioxide and nano ferric oxide composite powder or nano oxide and nano clay composite powder;
the metal nano-particles are silver nano-particles, iron nano-particles, cobalt nano-particles, zinc oxide nano-particles and carbon-coated metal nano-particles.
Preferably, the mass ratio of the ionic liquid to the cellulose pulp is 90-95:5-10, and the dosage of the functional auxiliary agent is 0.5-2% of the mass of the cellulose pulp. The consumption of the ionic liquid is greatly increased, so that the production cost is high, and the uneven mixing, high energy consumption and difficult subsequent cellulose dissolution processing can be caused by the too low consumption of the ionic liquid.
In some embodiments, the coagulation bath is an aqueous ionic liquid solution having an ionic liquid content of 10-60% by mass.
Preferably, the coagulation bath temperature is 30-60 ℃.
In some embodiments, the water wash is a two-stage countercurrent wash with a water wash temperature of 40-70 ℃; the softening is performed by using polyalcohol, wherein the concentration of polyalcohol is 20-100g/l, the temperature is 50-70 ℃, and the pH value is 6-10.
Preferably, the polyol is propylene glycol, glycerol, diethylene glycol, triethylene glycol or polyethylene glycol, etc. Industrial grade and food grade products may be selected depending on the end product requirements.
In some embodiments, the functional aid comprises 0.5-5.0% by mass of the anti-tack agent. The function is to avoid interlayer adhesion of the functional cellulose membrane product.
Preferably, the functional auxiliary agent includes, but is not limited to, a multifunctional modifier, a release agent, a hydrophobic agent, or a heat-seal emulsion.
Preferably, the temperature of the functional auxiliary agent is 30-50 ℃, the solid content is 1-60%, and the coating solid content of the functional auxiliary agent is 0.1-10 g/m.
In some embodiments, the drying tunnel is a suspension type drying oven, and a drying cylinder with special treatment (the surface is subjected to anti-sticking treatment, such as spraying Teflon coating) is arranged in the drying tunnel. The cellulose film is pre-dried, so that the coating is solidified, the binding force with the cellulose film is improved, and the problem of coating sticking in the drying process of the cellulose film is effectively solved.
The intensified drying is to fully dry the pre-dried cellulose film in a conventional dryer, so that uneven film surface caused by rapid shrinkage in the drying process of the cellulose film is effectively solved, the sufficient volatilization of water in the cellulose film is ensured, the long-term stability of the bonding fastness of the coating and the cellulose film is ensured, the drying adopts a hot air circulation drying mode, and the temperature is controlled to be 80-150 ℃.
The cellulose membrane is subjected to humidity control treatment, so that the cellulose membrane is properly rewetted, the flexibility and the dimensional stability of the final product are improved, the mechanical property is improved, the humidity control temperature is controlled to be 50-90 ℃, and the humidity is controlled to be 60-90%rh. And obtaining the functional regenerated cellulose film meeting the requirements after humidity adjustment, and then cutting, packaging and shipping according to the specification and the size required by customers.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
1. according to the invention, the cellulose is directly dissolved by using the ionic liquid as a solvent to prepare the cellulose membrane, so that the low cost and clean production of the cellulose membrane are realized;
2. functional materials are added in the mixing process, and the functional materials are well and uniformly dispersed under the shearing force of high-speed stirring due to the addition of cellulose pulp in the stirring process, so that the problems of filter blockage caused by poor dispersion and agglomeration of the functional materials are thoroughly solved, and the mechanical properties of the cellulose membrane are not influenced; meanwhile, compared with emulsion products, the cost of directly using the pure functional nano material is lower, and the problems of sewage treatment cost improvement, dehydration energy consumption increase, influence on the performance of a cellulose membrane and the like caused by the introduction of impurities and water are avoided.
3. In the preparation process of the cellulose film, the in-line in-machine coating is realized, the problems of high energy consumption, low yield, poor quality stability and the like in the traditional two-step method for coating the cellulose film are solved, and the coating cost of the functional cellulose film is effectively reduced. And the problem that the traditional cellulose film is difficult to successfully coat the water-based functional material with the solid content less than 15% by a two-step method can be effectively solved, and the selection range of the functional material is increased.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
A continuous process for producing a solvent-process functional regenerated cellulose membrane comprising the steps of:
1) Mixing: the mass ratio of the AmimCl ionic liquid to the cellulose pulp is 90:10, 2632kg of the AmimCl ionic liquid aqueous solution with the concentration of 90 percent, 250kg of dissolved wood pulp (which is dry pulp and contains no solvent) and 1.25kg of nano barium sulfate are put into a premixing machine and stirred and mixed uniformly;
2) Dissolution of cellulose: conveying the mixed materials to a dehydrator for dehydration, conveying the dehydrated materials to a dissolver for cellulose dissolution and defoaming, and removing impurities through a filter to prepare a pure, transparent and uniform cellulose ionic liquid solution;
3) And (3) forming a regenerated cellulose film: spraying the cellulose ionic liquid solution into a coagulating bath through a slit, wherein the coagulating bath is an aqueous solution of AmimCl ionic liquid, the content of the AmimCl ionic liquid is controlled to be 35%, the temperature is controlled to be 40 ℃, and cellulose is separated out to form a regenerated cellulose film;
4) Washing and softening: washing and softening the obtained wet cellulose film, wherein the washing adopts a two-stage countercurrent washing process, the washing temperature is 45-48-50-54-56-58-60-65 ℃ in sequence (the first stage is provided with 4 washing tanks, and the second stage is provided with 5 washing tanks); the softening adopts triethylene glycol, the concentration of the triethylene glycol in the softening bath is 35g/l, the temperature is 55 ℃, and the pH value is 8.5;
5) Coating: coating the surface of the cellulose film with acrylic emulsion, adding 1.2% of slipping agent (which has the functions of anti-adhesion and increasing slipping degree), controlling the temperature of the coating to be 32 ℃, controlling the solid content to be 15%, and controlling the feeding amount of the coating dry material to be 3 g/m;
6) Predrying: the coated cellulose film firstly enters a drying tunnel to be subjected to pre-drying treatment of the coating, the hot air temperature in the drying tunnel is controlled to be 80-100 ℃, so that the coating is solidified, the binding force with the cellulose film is improved, and the problem of sticking to cylinders in subsequent drying is prevented;
7) Drying and humidifying: fully drying and humidifying the cellulose film by a special dryer, wherein the drying adopts a hot air circulation drying mode, and the temperature is controlled to be 100-110 ℃; and controlling the humidity to 55 ℃ and 65%rh, obtaining the functional regenerated cellulose film meeting the requirements after humidity control, and then cutting, packaging and shipping according to the specification and the size required by customers.
The index of the prepared functional cellulose film is shown in table 1.
Example 2
A continuous process for producing a solvent-process functional regenerated cellulose membrane comprising the steps of:
1) Mixing: the ratio of the BmimCl ionic liquid to the cellulose pulp is 88:12, 2157kg of water solution of BmimCl ionic liquid with the concentration of 85 percent, 250kg of dissolved wood pulp and 0.8kg of nano montmorillonite are put into a premixing machine and stirred and mixed uniformly;
2) Dissolution of cellulose: conveying the mixed materials to a dehydrator for dehydration, conveying the dehydrated materials to a dissolver for cellulose dissolution and defoaming, and removing impurities through a filter to prepare a pure, transparent and uniform cellulose ionic liquid solution;
3) And (3) forming a regenerated cellulose film: spraying the cellulose ionic liquid solution into a coagulating bath through a slit, wherein the coagulating bath is a BmimCl ionic liquid aqueous solution, the BmimCl ionic liquid content is controlled to 45%, the temperature is controlled to 50 ℃, and cellulose is separated out to form a regenerated cellulose film;
4) Washing and softening: washing and softening the obtained wet cellulose membrane, wherein the washing adopts a two-stage countercurrent washing process, and the washing temperature is 48-49-50-52-54-57-59-62-64 ℃; diethylene glycol is adopted for softening, the concentration of diethylene glycol in a softening bath is 50g/l, the temperature is 58 ℃, and the pH value is 7.2;
5) Pre-drying the washed and softened cellulose membrane in a drying tunnel at 90 ℃ for 15s to preliminarily dry and shape the cellulose membrane;
6) Coating: coating the surface of the cellulose film with pvdc emulsion, adding 3% of slipping agent into the emulsion, controlling the temperature of the coating to be 35 ℃, controlling the solid content to be 30%, and controlling the feeding amount of the coating dry material to be 6 g/m;
7) Drying and humidifying: fully drying and humidifying the cellulose film by a special dryer, wherein the drying adopts a hot air circulation drying mode, and the temperature is controlled to be 100-120 ℃; and controlling the humidity to be 60 ℃ and controlling the humidity to be 75%rh, obtaining the functional regenerated cellulose film meeting the requirements after humidity control, and then cutting, packaging and shipping according to the specification and the size required by customers.
Example 3
A continuous process for producing a solvent-process functional regenerated cellulose membrane comprising the steps of:
1) Mixing: 2257kg of aqueous solution of AmimCl ion liquid with concentration of 85%, 220kg of dissolved wood pulp and 0.9kg of nano montmorillonite are put into a premixing machine and stirred and mixed uniformly;
2) Dissolution of cellulose: conveying the mixed materials to a dehydrator for dehydration, conveying the dehydrated materials to a dissolver for cellulose dissolution and defoaming, and removing impurities through a filter to prepare a pure, transparent and uniform cellulose ionic liquid solution;
3) And (3) forming a regenerated cellulose film: spraying the cellulose ionic liquid solution into a coagulating bath through a slit, wherein the coagulating bath is an aqueous solution of AmimCl ionic liquid, the content of the AmimCl ionic liquid is controlled to be 60%, the temperature is controlled to be 40 ℃, and cellulose is separated out to form a regenerated cellulose film;
4) Washing and softening: washing and softening the obtained wet cellulose membrane, wherein the washing adopts a two-stage countercurrent washing process, and the washing temperature is 40-43-48-52-56-60-62-66-70 ℃; the softening adopts triethylene glycol, the concentration of the triethylene glycol in the softening bath is 90g/l, the temperature is 50 ℃, and the pH value is 6.2;
5) Coating: coating the surface of the cellulose film with a hydrophobic agent emulsion, adding 1.5% of an anti-adhesion agent into the emulsion, controlling the temperature of the coating to be 30 ℃, controlling the solid content to be 5%, and controlling the feeding amount of a coating dry material to be 1.0 g/m;
6) Predrying: the coated cellulose film firstly enters a drying tunnel to be pre-dried for 5s, the hot air temperature in the drying tunnel is controlled to be 100-120 ℃, so that the coating is solidified, the binding force with the cellulose film is improved, and the problem of sticking cylinders in subsequent drying is prevented;
7) Drying and humidifying: fully drying and humidifying the cellulose film by a special dryer, wherein the drying adopts a hot air circulation drying mode, and the temperature is controlled to be 100-120 ℃; and controlling the humidity to be 60 ℃ and controlling the humidity to be 75%rh, obtaining the functional regenerated cellulose film meeting the requirements after humidity control, and then cutting, packaging and shipping according to the specification and the size required by customers.
Example 4
A continuous process for producing a solvent-process functional regenerated cellulose membrane comprising the steps of:
1) Mixing: 2257kg of aqueous solution of BmimCl ion liquid with the concentration of 85 percent, 330kg of dissolved wood pulp and 1.5kg of nano clay are put into a premixing machine and stirred and mixed uniformly;
2) Dissolution of cellulose: conveying the mixed materials to a dehydrator for dehydration, conveying the dehydrated materials to a dissolver for cellulose dissolution and defoaming, and removing impurities through a filter to prepare a pure, transparent and uniform cellulose ionic liquid solution;
3) And (3) forming a regenerated cellulose film: spraying the cellulose ionic liquid solution into a coagulating bath through a slit, wherein the coagulating bath is a BmimCl ionic liquid aqueous solution, the ionic liquid content is controlled to 10%, the temperature is controlled to 30 ℃, and cellulose is separated out to form a regenerated cellulose film;
4) Washing and softening: washing and softening the obtained wet cellulose membrane, wherein the washing adopts a two-stage countercurrent washing process, and the washing temperature is 40-43-48-52-56-60-62-66-70 ℃; the softening adopts 90 percent triethylene glycol and 10 percent polyethylene glycol, the concentration of mixed components in the softening bath is 30g/l, the temperature is 55 ℃, and the pH value is 10;
5) Coating: coating the surface of the cellulose film with a release agent emulsion, controlling the temperature of the release agent emulsion to 25 ℃, controlling the solid content to 2%, and controlling the feeding amount of a coating dry material to 0.3 g/m;
6) Predrying: the coated cellulose film firstly enters a drying tunnel to be pre-dried for 30s, the hot air temperature in the drying tunnel is controlled to be 100-120 ℃, so that the coating is solidified, the binding force with the cellulose film is improved, and the problem of sticking cylinders in subsequent drying is prevented;
7) Drying and humidifying: fully drying and humidifying the cellulose film by a special dryer, wherein the drying adopts a hot air circulation drying mode, and the temperature is controlled to be 100-120 ℃; and controlling the humidity to be 60 ℃ and controlling the humidity to be 75%rh, obtaining the functional regenerated cellulose film meeting the requirements after humidity control, and then cutting, packaging and shipping according to the specification and the size required by customers.
Example 5
A continuous process for producing a solvent-process functional regenerated cellulose membrane comprising the steps of:
1) Mixing: 2257kg of aqueous solution of AmimCl ion liquid with concentration of 85%, 300kg of dissolved wood pulp and 0.6kg of nano silver particles are put into a premixing machine and stirred and mixed uniformly;
2) Dissolution of cellulose: conveying the mixed materials to a dehydrator for dehydration, conveying the dehydrated materials to a dissolver for cellulose dissolution and defoaming, and removing impurities through a filter to prepare a pure, transparent and uniform cellulose ionic liquid solution;
3) And (3) forming a regenerated cellulose film: spraying the cellulose ionic liquid solution into a coagulating bath through a slit, wherein the coagulating bath is an aqueous solution of an AminCl ionic liquid, the content of the ionic liquid is controlled to be 20%, the temperature is controlled to be 50 ℃, and cellulose is separated out to form a regenerated cellulose film;
4) Washing and softening: washing and softening the obtained wet cellulose membrane, wherein the washing adopts a two-stage countercurrent washing process, and the washing temperature is 40-43-48-52-56-60-62-66-70 ℃; glycerol is adopted for softening, the concentration of the glycerol in the softening bath is 70g/l, the temperature is 70 ℃, and the pH value is 8;
5) Coating: coating the surface of the cellulose film with a hydrophobic agent emulsion, adding 2% of a slipping agent into the emulsion, controlling the temperature of the coating to 45 ℃, controlling the solid content to 10%, and controlling the feeding amount of a coating dry material to 0.8 g/m;
6) Predrying: the coated cellulose film firstly enters a drying tunnel to be pre-dried for 10s, the hot air temperature in the drying tunnel is controlled to be 100-120 ℃, so that the coating is solidified, the binding force with the cellulose film is improved, and the problem of sticking cylinders in subsequent drying is prevented;
7) Drying and humidifying: fully drying and humidifying the cellulose film by a special dryer, wherein the drying adopts a hot air circulation drying mode, and the temperature is controlled to be 100-120 ℃; and controlling the humidity to be 60 ℃ and controlling the humidity to be 75%rh, obtaining the functional regenerated cellulose film meeting the requirements after humidity control, and then cutting, packaging and shipping according to the specification and the size required by customers.
The index of the prepared functional cellulose film is shown in table 1.
Table 1 results of product index detection of examples
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A continuous production method of a solvent-method functional regenerated cellulose membrane is characterized in that: the method comprises the following steps: uniformly mixing the ionic liquid, the cellulose pulp and the functional material to obtain a mixed material, wherein the mass ratio of the ionic liquid to the cellulose pulp is 85-95:5-15, and the dosage of the functional material is 0.1-2% of the mass of the cellulose pulp;
after the mixed material is dehydrated, cellulose is dissolved and defoamed, and then impurities are removed by filtering to obtain cellulose ionic liquid solution;
spraying the cellulose ionic liquid solution into the coagulating bath through a slit to form a wet cellulose film;
after washing and softening a wet cellulose film, coating a functional auxiliary agent on the surface of the wet cellulose film, wherein the solid content of the functional auxiliary agent is more than 1% and less than 15%; the functional auxiliary agent at least comprises an anti-sticking agent, and is pre-dried for 5-30s at 80-120 ℃ in a drying channel, and then is closely adhered to the surface of a drying cylinder for 80-150 ℃ for intensified drying, or is directly closely adhered to the surface of the drying cylinder for 80-150 ℃ for intensified drying without pre-drying;
the functional auxiliary agent is a release agent emulsion, a hydrophobic agent emulsion or a heat sealing emulsion; the mass fraction of the anti-adhesion agent in the functional auxiliary agent is 0.5-5.0%;
and finally, performing humidity control treatment on the cellulose membrane to obtain the product.
2. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 1, characterized in that: the functional material is selected from nanoclay, nano-oxide, nano-composite oxide or metal nano-particles.
3. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 2, characterized in that: the mass ratio of the ionic liquid to the cellulose pulp is 90-95:5-10, and the dosage of the functional material is 0.5-2% of the mass of the cellulose pulp.
4. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 1, characterized in that: the coagulating bath is an ionic liquid aqueous solution, the ionic liquid content is 10-60%, and the percentage is mass percent.
5. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 4, wherein: the coagulation bath temperature is 30-60 ℃.
6. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 1, characterized in that: the water washing is two-stage countercurrent washing, and the water washing temperature is 40-70 ℃; the softening is performed by using polyalcohol, the concentration of the polyalcohol is 20-100g/l, the temperature is 50-70 ℃, and the pH value is 6-10.
7. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 6, wherein: the polyalcohol is glycerol, diethylene glycol, triethylene glycol or polyethylene glycol.
8. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 1, characterized in that: the temperature of the functional auxiliary agent is 30-50 ℃, and the coating solid content of the functional auxiliary agent is 0.1-10 g/m.
9. The continuous production method of a solvent-process functional regenerated cellulose membrane according to claim 1, characterized in that: the drying tunnel is a suspension type drying oven, and a drying cylinder subjected to anti-sticking treatment is arranged in the drying tunnel.
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