CN104028120A - Method for preparing carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane - Google Patents
Method for preparing carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane Download PDFInfo
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Abstract
The invention discloses a method for preparing a carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane. The method comprises the steps: preparing a carboxymethylcellulose sodium composite by an ionic crosslinking method, adding the carboxymethylcellulose sodium composite into an aqueous phase monomer solution for synthesis of a polyamide membrane, and preparing the carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane by an interfacial polymerization method. With utilization of good hydrophilicity, charge performance and a unique nano pore structure of the composite, the water permeation flux of the membrane is greatly improved while the high selectivity of the polyamide membrane on an inorganic salt is kept. Under an operating pressure of 0.6 MPa, the nanofiltration membrane has the water flux of 50-65 L.m<-2>.h<-1>, has quite high interception rate on divalent ions and the highest reaching 97%, and has the interception rate on monovalent ions of generally less than 25%. Therefore, the prepared carboxymethylcellulose sodium composite-filled polyamide nanofiltration membrane has high separation selectivity and water permeation flux, and has the advantages of simple and feasible membrane preparation method, low cost, and good industrialized application prospects.
Description
Technical field
The invention belongs to NF membrane separation field, relate in particular to the preparation method that a kind of sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane.
Background technology
Nanofiltration is as a kind of novel isolation technics, compares with isolation technics such as traditional distillation, rectifying, has the advantages such as low energy consumption, high separating efficiency, environmental protection.NF membrane be aperture between milipore filter and reverse osmosis membrane, a kind of novel pressure-actuated diffusion barrier.According to Coulomb repulsion and aperture screening principle, NF membrane can be held back highly charged ions and organic macromolecule, and lower valency ion and organic molecule are seen through, be particularly suitable for inorganic salts, inorganic salts and the organic matter of different valence state, and the organic separation of different molecular weight, now be used to gradually water correction, wastewater treatment, the aspect such as concentrated and separated of material in food, chemical industry, medicine and other fields.
At present, commercialization NF membrane is mainly prepared by interfacial polymerization, is generally to utilize that in water, in polyamine and organic phase, polynary acyl chlorides monomer is at two-phase interface place polymerization reaction take place, and (US Patent 5,693,227 to form fine and close polyamide cortex; US Patent 5,152,901; US Patent 4,769,148).Although polyamide nanofiltration membrane has higher salt rejection and water flux, in order further to reduce the operating cost of nanofiltration separation process, the water flux and the separating property that improve film are the eternal theme of NF membrane development.Macromolecular material (PVA, the PEG) original position that existing report has hydrophily and a stain resistance by some such as introduces in PA membrane at the Nomenclature Composition and Structure of Complexes of method regulation and control film, improve separating property and stain resistance (the Macromol. Chem. Phys. of film, 2005,206:1934-1940; Polymer, 2007,48:1165 – 1170; J. Membr. Sci., 2011,367:158-165).In addition, also have the inorganic nano materials such as zeolite, nano silicon, CNT are introduced to polyamide nanofiltration membrane, to improve its water permeability and stain resistance (J. Membr. Sci., 2007,294:1-7; Desalination, 2008,219:48 – 56).Yet with regard to existing report, these material modified modified effects that still exist are not obvious, nano material manufacturing cost is higher, in film, easily assembles, and makes film produce the problems such as defect.Therefore, developing that some are novel material modified, is very necessary for the performance of improving with improving polyamide nanofiltration membrane.
Compound polyelectrolyte is the class multicomponent macromolecular material that the polyelectrolyte molecules chain of oppositely charged is combined togather and formed by electrostatic force, and it is controlling release, and papermaking strengthens, flocculation, and extensive use has been obtained in a plurality of fields such as microcapsules.In recent years, we adopt ionic cross-linking successfully to make the compound polyelectrolyte of water dispersible, and by it successfully for preparation (J. Membr. Sci., 2009, the 329:175 – 182 of infiltrating and vaporizing membrane; J. Membr. Sci., 2009,333:68 – 78).Research discovery, a large amount of ion pair cross-linked structures had both been contained in compound polyelectrolyte inside, and a certain amount of charged group is freely contained again on surface, and its infiltrating and vaporizing membrane has high separation factor and permeation flux simultaneously.As compound polyelectrolyte is incorporated in polyamide nanofiltration membrane, not only can utilize its good hydrophily and charge, also can rely on its unique nano aperture structure, when keeping the separation selectivity that film is good, significantly improve the water permeability of film, can meet better the needs of practical application.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of sodium carboxymethylcellulose compound to fill the preparation method of polyamide nanofiltration membrane.
The preparation method that sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane comprises the steps:
(1) cationic polyelectrolyte of the sodium carboxymethylcellulose of 1～3 mass parts and 0.5～2 mass parts is dissolved in respectively in the acidic aqueous solution of 100～500 mass parts, again above-mentioned cationic polyelectrolyte acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, obtain sodium carboxymethylcellulose compound after dry; Then the compound of above-mentioned 0.1～0.5 mass parts is joined in the alkaline aqueous solution of 100～500 mass parts and be made into compound dispersion liquid;
(2) polyamine monomer is dissolved in the water, then adds compound dispersion liquid and sodium hydrate solid, be made into aqueous phase solution; Polynary acyl chlorides monomer is dissolved in organic solvent, is made into organic phase solution;
(3) porous polysulfones support membrane is flooded 1～4 minute in aqueous phase solution, take out and remove the excessive aqueous phase solution in surface; Be immersed in again in organic phase solution 0.5～2 minute, take out and remove the remaining organic phase solution in surface; 45～75
ounder C, solidify 15～35 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane;
Cationic polyelectrolyte described in step 1) is PDDA, polymethyl acyl-oxygen ethyl-trimethyl salmiac, quaternized polyvinylpyridine or cationic cellulose; Step 2) the polyamine monomer described in is piperazine, m-phenylene diamine (MPD) or 1,3,5-triaminobenzene; Step 2) the polynary acyl chlorides monomer described in is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride or biphenyl tetracarboxylic acyl chlorides; Acidic aqueous solution described in step 1) is that mass percent concentration is 0.01～0.1% hydrochloric acid, acetic acid or aqueous sulfuric acid; Drying condition described in step 1) is 40～60
ounder C, heat 8～16 hours; Alkaline aqueous solution described in step 1) is that mass percent concentration is 0.1～0.5% NaOH or potassium hydroxide aqueous solution; Step 2) in the aqueous phase solution described in, the mass percent concentration of polyamine monomer is 0.2～3%; Step 2) in the aqueous phase solution described in, the mass percent concentration of compound is 0.01～0.5 %; Step 2) in the aqueous phase solution described in, the mass percent concentration of NaOH is 0.01～0.2%; Step 2) in the organic phase solution described in, the mass percent concentration of polynary acyl chlorides monomer is 0.1～1%; The solvent of the organic phase solution step 2) is n-hexane, cyclohexane or heptane.
Described sodium carboxymethylcellulose compound is filled separation and inorganic salts and the organic separation field that polyamide nanofiltration membrane can be used for desalinization, water softening, different valence state inorganic salts.
The separating property method of testing that a kind of sodium carboxymethylcellulose compound of the present invention is filled polyamide nanofiltration membrane is as follows: NF membrane is placed in to the conventional nanofiltration testing arrangement in this area, and test cephacoria precompressed 1 h under 0.7 MPa operating pressure, then 25
ounder C and 0.6 MPa test condition, the rejection (R) of the water permeation flux (J) of film and material is measured, its computing formula is suc as formula being: J=V/ (A.t); R=1-C
pc
f; Wherein, V-feed liquid sees through the volume of film, and the effective area of A-film is 22.4 cm
2, t-running time, C
p-penetrating fluid concentration, C
f-feeding liquid concentration; By measuring conductivity value, obtain inorganic salt solution concentration.
Sodium carboxymethylcellulose compound has good hydrophily, charge and special nano aperture structure, added in polyamide nanofiltration membrane, can improve hydrophily and the efficiency of transmission of hydrone in film of film, in the high salt separative efficiency of maintenance, improve the water permeation flux of film.The present invention is by adjusting chemical constitution and the membrance casting condition of sodium carboxymethylcellulose compound, and gained sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane to divalent salts Na
2sO
4rejection can be up to 97%, and to the rejection of monovalent salt NaCl lower than 25%, water flux is higher than 50 L.m
-2.h
-1; In addition, the present invention is used for preparing the functional material sodium carboxymethylcellulose compound of polyamide nanofiltration membrane and can prepares by easy water ionic cross-linking, and the selected raw material of interfacial polymerization film forming are the conventional commercially available chemical reagent in this area.Therefore, raw materials of the present invention is conveniently easy to get, and the preparation technology of film is easy, production cost is low, and film properties is good, has good industrial applicibility.
accompanying drawing explanation:
Fig. 1 is the infared spectrum of sodium carboxymethylcellulose compound of the present invention;
Fig. 2 is the surface topography map that sodium carboxymethylcellulose compound of the present invention is filled polyamide nanofiltration membrane.
The specific embodiment
The preparation method that sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane comprises the steps:
(1) cationic polyelectrolyte of the sodium carboxymethylcellulose of 1～3 mass parts and 0.5～2 mass parts is dissolved in respectively in the acidic aqueous solution of 100～500 mass parts, again above-mentioned cationic polyelectrolyte acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, obtain sodium carboxymethylcellulose compound after dry; Then the compound of above-mentioned 0.1～0.5 mass parts is joined in the alkaline aqueous solution of 100～500 mass parts and be made into compound dispersion liquid;
(2) polyamine monomer is dissolved in the water, then adds compound dispersion liquid and sodium hydrate solid, be made into aqueous phase solution; Polynary acyl chlorides monomer is dissolved in organic solvent, is made into organic phase solution;
(3) porous polysulfones support membrane is flooded 1～4 minute in aqueous phase solution, take out and remove the excessive aqueous phase solution in surface; Be immersed in again in organic phase solution 0.5～2 minute, take out and remove the remaining organic phase solution in surface; 45～75
ounder C, solidify 15～35 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane;
Cationic polyelectrolyte described in step 1) is PDDA, polymethyl acyl-oxygen ethyl-trimethyl salmiac, quaternized polyvinylpyridine or cationic cellulose; Step 2) the polyamine monomer described in is piperazine, m-phenylene diamine (MPD) or 1,3,5-triaminobenzene; Step 2) the polynary acyl chlorides monomer described in is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride or biphenyl tetracarboxylic acyl chlorides; Acidic aqueous solution described in step 1) is that mass percent concentration is 0.01～0.1% hydrochloric acid, acetic acid or aqueous sulfuric acid; Drying condition described in step 1) is 40～60
ounder C, heat 8～16 hours; Alkaline aqueous solution described in step 1) is that mass percent concentration is 0.1～0.5% NaOH or potassium hydroxide aqueous solution; Step 2) in the aqueous phase solution described in, the mass percent concentration of polyamine monomer is 0.2～3%; Step 2) in the aqueous phase solution described in, the mass percent concentration of compound is 0.01～0.5 %; Step 2) in the aqueous phase solution described in, the mass percent concentration of NaOH is 0.01～0.2%; Step 2) in the organic phase solution described in, the mass percent concentration of polynary acyl chlorides monomer is 0.1～1%; The solvent of the organic phase solution step 2) is n-hexane, cyclohexane or heptane.
Provide embodiments of the invention below, but the present invention is not subject to the restriction of embodiment:
Embodiment 1:
Getting 1g sodium carboxymethylcellulose and 0.5g PDDA is dissolved in respectively in the aqueous hydrochloric acid solution that 100g mass percent concentration is 0.01wt%, again above-mentioned PDDA acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 40
oCdry after 16 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.1g is joined in the sodium hydrate aqueous solution that 100g mass percent concentration is 0.1wt% and is made into compound dispersion liquid; Porous polysulfones support membrane is flooded 1 minute in aqueous phase solution, and in aqueous phase solution, the concentration of piperazine is 0.2 wt%, and the concentration of compound is 0.01 wt%, and the concentration of NaOH is 0.01 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 0.1 wt% again, and interface polymerization reaction 0.5 minute, 45
ounder C, solidify 35 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 21.2%, water flux is 50.6L.m
-2.h
-1; To Na
2sO
4rejection be 94.7%, water flux is 49.5L.m
-2.h
-1.
Embodiment 2:
Getting 3 g sodium carboxymethylcelluloses and 2 g PDDAs, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous hydrochloric acid solution of 0.1 wt%, again above-mentioned PDDA acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 60
oCdry after 8 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.5 g is joined in the sodium hydrate aqueous solution that 500 g mass percent concentrations are 0.5 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 4 minutes in aqueous phase solution, and in aqueous phase solution, the concentration of piperazine is 3 wt%, and the concentration of complex compound is 0.5 wt%, and the concentration of NaOH is 0.2 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 1 wt% again, and interface polymerization reaction 2 minutes, 75
ounder C, solidify 15 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 23.5%, water flux is 53.8L.m
-2.h
-1; To Na
2sO
4rejection be 95.2%, water flux is 52.5L.m
-2.h
-1.
Embodiment 3:
Getting 2 g sodium carboxymethylcelluloses and 1 g PDDA, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous hydrochloric acid solution of 0.05 wt%, again above-mentioned PDDA acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 50
oCdry after 12 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.25 g is joined in the sodium hydrate aqueous solution that 500 g mass percent concentrations are 0.25 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 2 minutes in aqueous phase solution, and in aqueous phase solution, the concentration of piperazine is 1 wt%, and the concentration of compound is 0.25 wt%, and the concentration of NaOH is 0.1 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 0.5 wt% again, and interface polymerization reaction 1 minute, 60
ounder C, solidify 30 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Comparative example 1
With reference to embodiment 3 steps, without preparing sodium carboxymethylcellulose compound, directly take piperazine and pyromellitic trimethylsilyl chloride and prepare polyamide nanofiltration membrane as raw material (adding proportion is with reference to embodiment 3).
Comparative example 2
With reference to embodiment 3 steps, with sodium carboxymethylcellulose, replace sodium carboxymethylcellulose compound to add (adding proportion is with reference to embodiment 3) in PA membrane preparation process to, prepare polyamide nanofiltration membrane.
Comparative example 3
With reference to embodiment 3 steps, with PDDA, replace sodium carboxymethylcellulose compound to add (adding proportion is with reference to embodiment 3) in PA membrane preparation process to, prepare polyamide nanofiltration membrane.
Table 1 embodiment 3, the separating property comparison of PA membrane prepared by comparative example 1-3
| ? | Na 2SO 4Rejection (%) | Water flux (L.m -2.h -1） | NaCl rejection (%) | Water flux (L.m -2.h -1） |
| Embodiment 3 | 96.7 | 63.5 | 19.8 | 65.7 |
| Comparative example 1 | 94.5 | 28.5 | 38.7 | 30.1 |
| Comparative example 2 | 92.8 | 35.2 | 27.5 | 36.8 |
| Comparative example 3 | 85.9 | 37.5 | 22.8 | 39.5 |
Table 1 result shows, 4 kinds of methods all can make polyamide nanofiltration membrane, but it has larger difference to the rejection of divalence, monovalent salt and water flux, and reason is that microstructure for the preparation of the interpolation material of PA membrane is different with hydrophily and causes.
In comparative example 1, do not add that other is material modified, its PA membrane is comprised of the rigidity cross-linked structure of cycloalkane and aromatic hydrocarbon, and this film is finer and close; In comparative example 2, it is material modified adding sodium carboxymethylcellulose, introduces flexible, hydrophilic macromolecular material in its PA membrane, the compactness of film is decreased, hydrophily increases; In comparative example 3, it is material modified adding PDDA, and this kind of cationic polyelectrolyte do not participate in interface polymerization reaction, and it can not stable existence in PA membrane, can cause film to produce defect.
In embodiment 3, take sodium carboxymethylcellulose compound as material modified, utilize the nanostructured of himself uniqueness and good hydrophily, be introduced in PA membrane, not only can improve the hydrophily of film, can also in film, form " aquaporin " structure, promote that hydrone transmits in film; Meanwhile, due to complex particle favorable dispersibility, can guarantee that the compactness of film is unaffected, there is high selection separation property.Therefore, take sodium carboxymethylcellulose compound as material modified, the polyamide nanofiltration membrane of preparation has high separation selectivity and water permeability.
Embodiment 4:
Getting 2.5 g sodium carboxymethylcelluloses and 0.5 g PDDA, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous hydrochloric acid solution of 0.05 wt%, again above-mentioned PDDA acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 50
oCdry after 12 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.25 g is joined in the sodium hydrate aqueous solution that 500 g mass percent concentrations are 0.25 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 2 minutes in aqueous phase solution, and in aqueous phase solution, the concentration of piperazine is 0.5 wt%, and the concentration of compound is 0.25 wt%, and the concentration of NaOH is 0.1 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 0.2 wt% again, and interface polymerization reaction 1 minute, 50
ounder C, solidify 30 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 17.5%, water flux is 63.8L.m
-2.h
-1; To Na
2sO
4rejection be 96.2%, water flux is 62.5L.m
-2.h
-1.
Embodiment 5:
Getting 2.5 g sodium carboxymethylcelluloses and 0.5 g polymethyl acyl-oxygen ethyl-trimethyl salmiac, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous hydrochloric acid solution of 0.05 wt%, again above-mentioned polymethyl acyl-oxygen ethyl-trimethyl salmiac acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 50
oCdry after 12 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.25 g is joined in the sodium hydrate aqueous solution that 500 g mass percent concentrations are 0.25 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 2 minutes in aqueous phase solution, and in aqueous phase solution, the concentration of m-phenylene diamine (MPD) is 0.5 wt%, and the concentration of complex compound is 0.25 wt%, and the concentration of NaOH is 0.1 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 0.2 wt% again, and interface polymerization reaction 1 minute, 50
ounder C, solidify 30 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 18.3%, water flux is 61.5L.m
-2.h
-1; To Na
2sO
4rejection be 95.8%, water flux is 58.2L.m
-2.h
-1.
Embodiment 6:
Getting 2.5 g sodium carboxymethylcelluloses and 0.5 g PDDA, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous acetic acid of 0.05 wt%, again above-mentioned PDDA acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 50
oCdry after 12 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.25 g is joined in the potassium hydroxide aqueous solution that 500 g mass percent concentrations are 0.25 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 2 minutes in aqueous phase solution, and in aqueous phase solution 1,3, the concentration of 5-triaminobenzene is 0.5 wt%, and the concentration of compound is 0.25 wt%, and the concentration of NaOH is 0.1 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the o-phthaloyl chloride cyclohexane solution of 0.2 wt% again, and interface polymerization reaction 1 minute, 50
ounder C, solidify 30 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 15.6%, water flux is 60.4L.m
-2.h
-1; To Na
2sO
4rejection be 95.6%, water flux is 58.5L.m
-2.h
-1.
Embodiment 7:
Getting 2 g sodium carboxymethylcelluloses and the quaternized polyvinylpyridine of 1 g, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous hydrochloric acid solution of 0.05 wt%, again above-mentioned quaternized polyvinylpyridine acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 50
oCdry after 12 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.25 g is joined in the sodium hydrate aqueous solution that 500 g mass percent concentrations are 0.25 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 2 minutes in aqueous phase solution, and in aqueous phase solution, the concentration of piperazine is 1 wt%, and the concentration of compound is 0.25 wt%, and the concentration of NaOH is 0.1 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 0.5 wt% again, and interface polymerization reaction 1 minute, 60
ounder C, solidify 30 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 18.6%, water flux is 58.2L.m
-2.h
-1; To Na
2sO
4rejection be 96.2%, water flux is 56.5L.m
-2.h
-1.
Embodiment 8:
Getting 2 g sodium carboxymethylcelluloses and 1 g cationic cellulose, to be dissolved in respectively 500 g mass percent concentrations be in the aqueous hydrochloric acid solution of 0.05 wt%, again above-mentioned cationic cellulose acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, in 50
oCdry after 12 hours down, obtain sodium carboxymethylcellulose compound; Then the compound of above-mentioned 0.25 g is joined in the sodium hydrate aqueous solution that 500 g mass percent concentrations are 0.25 wt% and be made into compound dispersion liquid; Porous polysulfones support membrane is flooded 2 minutes in aqueous phase solution, and in aqueous phase solution, the concentration of piperazine is 1 wt%, and the concentration of compound is 0.25 wt%, and the concentration of NaOH is 0.1 wt%, takes out and remove the excessive aqueous phase solution in surface; Being immersed in mass percent concentration is in the pyromellitic trimethylsilyl chloride hexane solution of 0.5 wt% again, and interface polymerization reaction 1 minute, 60
ounder C, solidify 30 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane.
Sodium carboxymethylcellulose compound is filled polyamide nanofiltration membrane 25
oc, under 0.6MPa pressure, for 1g.L
-1naCl and Na
2sO
4the separating resulting of solution is: to the rejection of NaCl, be 20.6%, water flux is 63.5L.m
-2.h
-1; To Na
2sO
4rejection be 96.8%, water flux is 62.5L.m
-2.h
-1.
Claims (9)
1. sodium carboxymethylcellulose compound is filled a preparation method for polyamide nanofiltration membrane, it is characterized in that comprising the steps:
(1) cationic polyelectrolyte of the sodium carboxymethylcellulose of 1～3 mass parts and 0.5～2 mass parts is dissolved in respectively in the acidic aqueous solution of 100～500 mass parts, again above-mentioned cationic polyelectrolyte acidic aqueous solution is added drop-wise to and in sodium carboxymethylcellulose acidic aqueous solution, carries out ionomer, through the precipitation of deionized water repeatedly, washing, obtain sodium carboxymethylcellulose compound after dry; Then the sodium carboxymethylcellulose compound of above-mentioned 0.1～0.5 mass parts is joined in the alkaline aqueous solution of 100～500 mass parts and be made into compound dispersion liquid;
(2) polyamine monomer is dissolved in the water, then adds compound dispersion liquid and sodium hydrate solid, be made into aqueous phase solution; Polynary acyl chlorides monomer is dissolved in organic solvent, is made into organic phase solution;
(3) porous polysulfones support membrane is flooded 1～4 minute in aqueous phase solution, take out and remove the excessive aqueous phase solution in surface; Be immersed in again in organic phase solution 0.5～2 minute, take out and remove the remaining organic phase solution in surface; 45～75
ounder C, solidify 15～35 minutes, after rinsed with deionized water, obtain sodium carboxymethylcellulose compound and fill polyamide nanofiltration membrane;
Cationic polyelectrolyte described in step 1) is PDDA, polymethyl acyl-oxygen ethyl-trimethyl salmiac, quaternized polyvinylpyridine or cationic cellulose;
Step 2) the polyamine monomer described in is piperazine, m-phenylene diamine (MPD) or 1,3,5-triaminobenzene;
Step 2) the polynary acyl chlorides monomer described in is o-phthaloyl chloride, m-phthaloyl chloride, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride or biphenyl tetracarboxylic acyl chlorides.
2. preparation method as claimed in claim 1, is characterized in that the acidic aqueous solution described in step 1) is that mass percent concentration is 0.01～0.1% hydrochloric acid, acetic acid or aqueous sulfuric acid.
3. preparation method as claimed in claim 1, is characterized in that the drying condition described in step 1) is 40～60
ounder C, heat 8～16 hours.
4. preparation method as claimed in claim 1, is characterized in that the alkaline aqueous solution described in step 1) is that mass percent concentration is 0.1～0.5% NaOH or potassium hydroxide aqueous solution.
5. preparation method as claimed in claim 1, is characterized in that step 2) described in aqueous phase solution in the mass percent concentration of polyamine monomer be 0.2～3%.
6. preparation method as claimed in claim 1, is characterized in that step 2) described in aqueous phase solution in the mass percent concentration of compound be 0.01～0.5 %.
7. preparation method as claimed in claim 1, is characterized in that step 2) described in aqueous phase solution in the mass percent concentration of NaOH be 0.01～0.2%.
8. preparation method as claimed in claim 1, is characterized in that step 2) described in organic phase solution in the mass percent concentration of polynary acyl chlorides monomer be 0.1～1%.
9. preparation method as claimed in claim 1, is characterized in that step 2) described in the solvent of organic phase solution be n-hexane, cyclohexane or heptane.
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