CN117482760A - Cellulose-based nanofiltration membrane and preparation method and application thereof - Google Patents
Cellulose-based nanofiltration membrane and preparation method and application thereof Download PDFInfo
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- CN117482760A CN117482760A CN202311495845.8A CN202311495845A CN117482760A CN 117482760 A CN117482760 A CN 117482760A CN 202311495845 A CN202311495845 A CN 202311495845A CN 117482760 A CN117482760 A CN 117482760A
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- cellulose
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 101
- 239000001913 cellulose Substances 0.000 title claims abstract description 101
- 239000012528 membrane Substances 0.000 title claims abstract description 84
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims abstract description 29
- 229920001661 Chitosan Polymers 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 27
- 239000002608 ionic liquid Substances 0.000 claims description 17
- 239000011521 glass Substances 0.000 claims description 12
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 7
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 238000007790 scraping Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 241001474374 Blennius Species 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- 238000011100 viral filtration Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 2
- IARCGBCZSPZLGK-UHFFFAOYSA-N 1-methyl-1,2-dihydropyridin-1-ium;chloride Chemical compound Cl.CN1CC=CC=C1 IARCGBCZSPZLGK-UHFFFAOYSA-N 0.000 claims description 2
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 241000218631 Coniferophyta Species 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 241000251557 Ascidiacea Species 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- ZAMLGGRVTAXBHI-UHFFFAOYSA-N 3-(4-bromophenyl)-3-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(CC(O)=O)C1=CC=C(Br)C=C1 ZAMLGGRVTAXBHI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 241000251555 Tunicata Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241001397809 Hakea leucoptera Species 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- 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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/08—Apparatus therefor
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a cellulose-based nanofiltration membrane, a preparation method and application thereof, wherein the nanofiltration membrane is prepared from raw materials including acetoacetyl cellulose and a cross-linking agent; the cross-linking agent is at least one of polyethylenimine and chitosan. The invention selects soluble acetoacetyl cellulose as a main material for constructing the nanofiltration membrane. The traditional cellulose material can be processed in a water system by acetoacetylation, and the existence of the acetoacetyl group can regulate and control the hydrophilicity and hydrophobicity of the cellulose membrane, so that the cellulose membrane can be respectively used for filtration scenes of the water system and an organic system, and the group provides a crosslinking site for the cellulose material. The large amount of amino groups in the polyethyleneimine and the chitosan endows the nanofiltration membrane with excellent selective filtration performance and antibacterial performance, and can be used as a cellulose crosslinked green reagent. In general, unlike nanofiltration membranes prepared from traditional cellulose, the composite strategy used in the present application makes the nanofiltration membrane structure more stable and can be used in a variety of different scenarios.
Description
Technical Field
The invention relates to the technical field of nanofiltration membranes, in particular to a cellulose-based nanofiltration membrane, a preparation method and application thereof.
Background
Cellulose is an important natural polymer material and has excellent physical and chemical properties and biocompatibility. Nanofiltration membrane is a membrane separation technology between reverse osmosis and ultrafiltration, has the function of intercepting substances with molecular weight of 100-1000 daltons, and has wide application prospect in the fields of medicine preparation, virus filtration, wastewater treatment and the like. However, the existing cellulose-based nanofiltration membrane has single raw material preparation, complex preparation process and poor performance stability. In particular, the solvents involved in the cellulose processing process are against the environment-friendly concept of cellulose itself, such as alkali urea systems containing strong alkalinity, aqueous systems containing lithium chloride with ultrahigh salt content, and the like. In addition, the use of toxic cross-linking agents, such as epichlorohydrin, glutaraldehyde, etc., has greatly limited the scope of their industrial processes and applications.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a cellulose-based nanofiltration membrane, and a preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a cellulose-based nanofiltration membrane, wherein the nanofiltration membrane is prepared from the following raw materials of acetoacetyl cellulose and a cross-linking agent;
the cross-linking agent is at least one of polyethylenimine and chitosan.
Preferably, the raw material for preparing the acetoacetyl cellulose is at least one of needle wood, broad-leaved wood, gramineous plants, sea squirts and seaweed.
Preferably, the hemicellulose content is 0-20%.
Preferably, the molecular weight of the polyethyleneimine is between 800 and 70000.
Preferably, the chitosan is a water-soluble chitosan having a sulfuric acid group.
The invention also provides a method for preparing the cellulose-based nanofiltration membrane, which comprises the following steps:
(1) Preparation of acetoacetyl cellulose: completely dissolving a cellulose raw material with a certain mass in ionic liquid, adding a proper amount of tert-butyl acetoacetate, and reacting for 3-8 hours at a certain temperature to obtain an end product, namely the acetoacetyl cellulose;
(2) Preparation of cellulose-based nanofiltration membranes: the ionic liquid dissolved with the acetoacetyl cellulose is coated on a clean glass plate in a scraping way, although the ionic liquid is placed in a solution of polyethyleneimine or chitosan with a certain concentration for regeneration, and then the ionic liquid is placed in deionized water for washing until no residue exists, so that the cellulose-based nanofiltration membrane crosslinked by polyethyleneimine or chitosan is obtained.
Preferably, the ionic liquid is any one of 1-butyl-3-methylimidazole chloride (BmimCl), 1-allyl-3-methylimidazole chloride (AmimCl), 1-ethyl-3-methylimidazole acetate (Emimac), N-methylpyridine chloride and 1, 3-dialkylimidazoline diformate.
Preferably, the ratio of the cellulose raw material, the tert-butyl acetoacetate and the ionic liquid is 1: (8-15): (75:120).
Preferably, the reaction temperature is 110℃to 135 ℃.
The invention also provides application of the cellulose-based nanofiltration membrane in medicine filtration, virus filtration and wastewater treatment.
Preferably, the solvent for filtering the medicine is at least one of ethanol, chloroform, tetrahydrofuran and N, N-dimethylformamide.
In addition, the invention also provides a membrane component, and the membrane material of the membrane component comprises the water-soluble chitosan with sulfuric acid groups.
The beneficial effects of the invention are as follows:
the invention selects soluble acetoacetyl cellulose as a main material for constructing the nanofiltration membrane. The traditional cellulose material can be processed in a water system by acetoacetylation, and the existence of the acetoacetyl group can regulate and control the hydrophilicity and hydrophobicity of the cellulose membrane, so that the cellulose membrane can be respectively used for filtration scenes of the water system and an organic system, and the group provides a crosslinking site for the cellulose material. The large amount of amino groups in the polyethyleneimine and the chitosan endows the nanofiltration membrane with excellent selective filtration performance and antibacterial performance, and can be used as a cellulose crosslinked green reagent. In general, unlike nanofiltration membranes prepared from traditional cellulose, the composite strategy used in the application enables the nanofiltration membrane to be more stable in structure, integrated with multiple functions, capable of being used in multiple different scenes, and capable of being used as a nanofiltration layer of a membrane assembly in the filtration field.
In the raw materials used in the invention, the acetoacetyl cellulose, the polyethyleneimine and the chitosan are all derived from natural animals and plants, so that the invention has the advantages of green low carbon, low cost, strong designability and the like, and solves the problem of limited application range caused by the fact that the traditional cellulose-based nanofiltration membrane often uses an environment-friendly solvent and a toxic cross-linking agent in the preparation process.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 shows the microscopic morphology (scanning electron microscope image) of the nanofiltration membrane produced in example 1 of the present invention.
FIG. 2 is an external appearance (optical photograph) of the nanofiltration membrane prepared in example 2 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described below with reference to the accompanying drawings, it being understood that the preferred embodiments described herein are for illustration and explanation of the present invention only, and are not intended to limit the present invention.
A first aspect of the present application provides a cellulose-based nanofiltration membrane. The nanofiltration membrane is prepared from the following raw materials of acetoacetyl cellulose and a cross-linking agent;
the cross-linking agent is at least one of polyethylenimine and chitosan.
The nanofiltration membrane main body raw material is derived from natural animals and plants, and has the advantages of being green, low in carbon, low in cost, strong in designability and the like.
The application selects soluble acetoacetyl cellulose as a main material for constructing the nanofiltration membrane. The traditional cellulose material can be processed in a water system by acetoacetylation, and the existence of the acetoacetyl group can regulate and control the hydrophilicity and hydrophobicity of the cellulose membrane, so that the cellulose membrane can be respectively used for filtration scenes of the water system and an organic system, and the group provides a crosslinking site for the cellulose material. The large amount of amino groups in the polyethyleneimine and the chitosan endows the nanofiltration membrane with excellent selective filtration performance and antibacterial performance, and can be used as a cellulose crosslinked green reagent. In general, unlike nanofiltration membranes prepared from traditional cellulose, the composite strategy used in the application enables the nanofiltration membrane to integrate multiple functions, can be used in multiple different scenes, and can be used in the filtration field as a nanofiltration layer of a membrane module.
Because of the variety of sources of cellulose that can affect the ultimate mechanical and filtration properties of nanofiltration membranes, in some embodiments, cellulose is extracted from conifer wood, hardwood, grasses, sea squirts, seaweed.
As described herein, polyethyleneimine and chitosan are used as additives of an acetoacetyl cellulose host material for regulating and controlling the filtration performance of the nanofiltration membrane, and improving the mechanical properties of the nanofiltration membrane, so that the nanofiltration membrane with good filtration performance is obtained.
The second aspect of the present application provides a method for preparing the cellulose-based nanofiltration membrane, which comprises the following steps:
the ionic liquid dissolved with the acetoacetyl cellulose is coated on a clean glass plate in a scraping way, although the ionic liquid is placed in a solution of polyethyleneimine or chitosan with a certain concentration for regeneration, and then the ionic liquid is placed in deionized water for washing until no residue exists, so that the cellulose-based nanofiltration membrane crosslinked by polyethyleneimine or chitosan is obtained. The nanofiltration membrane has simple preparation process and has great industrial prospect in the field of filtration.
A third aspect of the present invention is to provide the use of the above-described biomass-based nanofiltration membrane in organic solvent filtration, drug filtration, virus filtration and wastewater treatment, thereby increasing the versatility of the biomass-based nanofiltration membrane.
In general, the invention provides an environment-friendly and renewable cellulose-based nanofiltration membrane, a preparation method and application thereof, which not only meet the environment-friendly requirement, but also have excellent performance and various application fields, and provide a new solution for the separation and purification fields. Embodiments of the present application will be described in detail below with reference to examples, but the present application is not limited to these examples. The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
Example 1
The embodiment provides a cellulose-based nanofiltration membrane, and the preparation method thereof comprises the following steps:
cellulose derived from wood was taken to be completely dissolved in 1-butyl-3-methylimidazole chloride (BmimCl) solution to form a uniform solution a at a concentration of 3% by mass fraction. To the solution A, an appropriate amount of t-butyl acetoacetate was added. At 120℃for 3 hours, the cellulose and t-butyl acetoacetate were allowed to react well to form solution B. And removing the ionic liquid in the solution B by using ethanol to obtain a solid product, namely the acetoacetyl cellulose. According to mass fraction, 5% of aqueous solution of acetoacetyl cellulose is coated on a clean glass plate in a scraping way, and the glass plate is placed in 30% of polyethyleneimine solution for regeneration for 2 hours. The residue was washed and washed with deionized water to obtain a cellulose-based nanofiltration membrane as shown in fig. one.
Comparative example 1
The comparative example provides a cellulose-based nanofiltration membrane, the preparation method of which comprises the following steps:
cellulose derived from wood was taken to be completely dissolved in 1-butyl-3-methylimidazole chloride (BmimCl) solution to form a uniform solution a at a concentration of 3% by mass fraction. To the solution A, an appropriate amount of t-butyl acetoacetate was added. At 120℃for 3 hours, the cellulose and t-butyl acetoacetate were allowed to react well to form solution B. And removing the ionic liquid in the solution B by using ethanol to obtain a solid product, namely the acetoacetyl cellulose. On a mass fraction basis, 5% aqueous solutions of acetoacetyl cellulose were drawn down on clean glass plates and placed in aqueous solution for regeneration for 2 hours. The residue was washed and washed with deionized water to obtain a cellulose-based nanofiltration membrane as shown in fig. one. The nanofiltration membrane of the scheme has no cross-linking, and cannot meet the normal filtration requirement.
Example 2
The embodiment provides a cellulose-based nanofiltration membrane, and the preparation method thereof comprises the following steps:
cellulose derived from wood was taken to be completely dissolved in 1-butyl-3-methylimidazole chloride (BmimCl) solution to form a uniform solution a at a concentration of 3% by mass fraction. To the solution A, an appropriate amount of t-butyl acetoacetate was added. At 120℃for 3 hours, the cellulose and t-butyl acetoacetate were allowed to react well to form solution B. And removing the ionic liquid in the solution B by using ethanol to obtain a solid product, namely the acetoacetyl cellulose. According to mass fraction, 5% of aqueous solution of acetoacetyl cellulose is coated on a clean glass plate in a scraping way, and the glass plate is placed in 30% of chitosan solution for regeneration for 2 hours. Washing and cleaning the residue by deionized water to obtain the cellulose-based nanofiltration membrane.
Example 3
The embodiment provides a cellulose-based nanofiltration membrane, and the preparation method thereof comprises the following steps:
cellulose derived from seaweed was completely dissolved in 1-butyl-3-methylimidazole chloride (BmimCl) solution to form a uniform solution a at a concentration of 3% by mass fraction. To the solution A, an appropriate amount of t-butyl acetoacetate was added. At 120℃for 3 hours, the cellulose and t-butyl acetoacetate were allowed to react well to form solution B. And removing the ionic liquid in the solution B by using ethanol to obtain a solid product, namely the acetoacetyl cellulose. According to mass fraction, 5% of aqueous solution of acetoacetyl cellulose is coated on a clean glass plate in a scraping way, and the glass plate is placed in 30% of polyethyleneimine solution for regeneration for 2 hours. Washing and cleaning the residue by deionized water to obtain the cellulose-based nanofiltration membrane.
To further describe the filtration performance of the biomass-based nanofiltration membrane, the present invention provides the retention performance of the nanofiltration membrane in the water system as described in examples 1-3, and specific data are shown in the following table.
| Examples | Trapped material | Concentration (mg/L) | Flux (L h) -1 m -2 bar -1 ） | Retention rate of |
| 1 | Methyl yellow | 20 | 17.6 | 92.6% |
| 2 | Methyl yellow | 20 | 19.7 | 91.0% |
| 3 | Methyl yellow | 20 | 20.8 | 89.7% |
Likewise, the present invention provides the retention properties of nanofiltration membranes in organic solvent systems as described in examples 1-3, with specific data as shown in the following table.
The data show that the cellulose-based nanofiltration membrane shows excellent material interception performance in a water treatment system and an organic solvent treatment system such as ethanol, chloroform and the like through the regulation and control of a formula, can intercept small molecules with the molecular weight of about 200 and Da in a solvent, and has great potential in the fields of organic solvent filtration, medicine filtration and the like.
Finally, it should be noted that: the above is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that the present invention is described in detail with reference to the foregoing embodiments, and modifications and equivalents of some of the technical features described in the foregoing embodiments may be made 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 (10)
1. The cellulose-based nanofiltration membrane is characterized in that the preparation raw materials of the nanofiltration membrane comprise acetoacetyl cellulose and a cross-linking agent; the cross-linking agent is at least one of polyethylenimine and chitosan.
2. The cellulose-based nanofiltration membrane according to claim 1, wherein the cellulose raw material for preparing acetoacetyl cellulose is derived from at least one of conifer wood, hardwood wood, graminaceous plants, ascidians, seaweed.
3. The cellulose-based nanofiltration membrane according to claim 1 or 2, wherein the hemicellulose content of the cellulose raw material is 0-20%.
4. The cellulose-based nanofiltration membrane according to claim 1, wherein the polyethyleneimine has a molecular weight of between 800 and 70000.
5. The cellulose-based nanofiltration membrane of claim 1, wherein the chitosan is a water-soluble chitosan having sulfate groups.
6. The cellulose-based nanofiltration membrane according to any one of claims 1 to 5, wherein the nanofiltration membrane is prepared by a process comprising:
preparation of acetoacetyl cellulose: completely dissolving a cellulose raw material with a certain mass in ionic liquid, adding a proper amount of tert-butyl acetoacetate, and reacting for 3-8 hours at a certain temperature to obtain an end product, namely the acetoacetyl cellulose;
preparation of cellulose-based nanofiltration membranes: and (3) scraping the ionic liquid dissolved with the acetoacetyl cellulose on a clean glass plate, placing the glass plate in a polyethyleneimine or chitosan solution with a certain concentration for regeneration, and then placing the glass plate in deionized water for washing until no residue exists, thus obtaining the cellulose-based nanofiltration membrane.
7. The method for preparing the cellulose-based nanofiltration membrane according to claim 6, wherein the ionic liquid is any one of 1-butyl-3-methylimidazole chloride (BmimCl), 1-allyl-3-methylimidazole chloride (amicl), 1-ethyl-3-methylimidazole acetate (EmimAc), N-methylpyridine chloride and 1, 3-dialkylimidazoline diformate.
8. The method for preparing a cellulose-based nanofiltration membrane according to claim 7, wherein the ratio of the cellulose raw material, the tert-butyl acetoacetate and the ionic liquid is 1: (8-15): (75:120), the concentration of the polyethyleneimine or chitosan aqueous solution is 1-30% by mass fraction.
9. The method for preparing a cellulose-based nanofiltration membrane according to claim 8, wherein the nanofiltration membrane is prepared to have a thickness of 65-250 μm.
10. Use of a cellulose-based nanofiltration membrane prepared by the method for preparing a cellulose-based nanofiltration membrane as claimed in any one of claims 6 to 9 in drug filtration, virus filtration and wastewater treatment.
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