CN102120149B - Method for preparing acid-proof polysulfonamide nanofiltration composite film - Google Patents
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- CN102120149B CN102120149B CN201110033868.8A CN201110033868A CN102120149B CN 102120149 B CN102120149 B CN 102120149B CN 201110033868 A CN201110033868 A CN 201110033868A CN 102120149 B CN102120149 B CN 102120149B
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Abstract
The invention relates to a method for preparing a polymer separating film, and in particular relates to a method for preparing an acid-proof polysulfonamide nanofiltration composite film, wherein a polysulfonamide ultra-thin functional separating layer is condensed and compounded through an interface between heterocyclic polyamine and poly-naphthalene sulfonyl chloride on a porous support film according to certain processing steps by controlling certain technological conditions. The method has the following advantages: the selective separating performance and the penetrating quality of the nanofiltration composite film are not lower than those of the existing polysulfonamide nanofiltration composite film; moreover, the acid resistance is superior; and simultaneously, the preparation method is relatively simple. The acid-proof polysulfonamide nanofiltration composite film can be widely applied to the separation of various types of liquids, specifically the separation of acid industrial fluids; and the method is wide in application.
Description
Technical field
The present invention relates to a kind of polymeric membrane for separation, specifically refer to a kind of acid-proof polysulfonamide nanofiltration composite film and preparation method thereof.
Technical background
NF membrane is a kind of Novel separation film of aperture between reverse osmosis membrane and milipore filter, because it has multi-band electric charge on nano level membrane aperture, film, allow low minute alite by holding back organic matter and the multivalent ion of higher molecular weight, there is unique separating property, higher separation accuracy.Compare with other diffusion barrier, NF membrane has that membrane flux is larger, process infiltration forces down, selects isolating ions, operating pressure power low, system to require the features such as low.At present, Nanofiltration-membrane technique has been widely used in the fields such as water softening and brackish water desalination, drink water purifying, feed separation purifying and concentrated, wastewater treatment and middle water reuse, cleaner production, has obtained good economic and social benefit.But the development of NF membrane is not also very ripe at present, is mainly reflected in: the needs that the manufacturing cost of NF membrane is relatively high, NF membrane performance cannot meet practical application.Thereby, develop high performance nanofiltration film very crucial and necessary to applying of Nanofiltration-membrane technique.
Nano filtering composite membrane is that one deck ultrathin functional layer is deposited to suitable micropore support membrane surface, aperture, and depositional mode mainly contains surface and applies, interfacial polycondensation and in-situ polymerization etc.Composite membrane has many advantages than asymmetric membrane: it can make every layer by optimization, to reach optimum performance.Ultrathin functional layer can be optimized to desirable selection permeability, and support membrane can reach best intensity and pressure tightness.In addition, the material that composite membrane can make to be difficult to form asymmetric membrane forms ultrathin membrane, as formed composite membrane by in-situ polymerization or interfacial polycondensation due to solvent limitation and crosslinking polymer.The ultra-thin share of Nano filtering composite membrane is intended to layer material and require good hydrophilic property, and its mechanical stability, heat endurance and hydrolytic stability are all fine.At present, business-like Nano filtering composite membrane is all on polysulfones support membrane, by the interfacial polycondensation between polyamines and polynary acyl chlorides, is prepared from
Fibiger etc., in the US Patent 4,769,148 of 1987, adopt interfacial polymerization to prepare Nano filtering composite membrane.Water is the aqueous solution containing piperazine function monomer and wetting agent, and organic phase is containing crosslinking agent pyromellitic trimethylsilyl chloride.Its preparation method is that polysulfones porous support membrane is immersed containing certain hour in the aqueous phase solution of piperazine, after taking-up is extracted, in covering, contain the organic solution of pyromellitic trimethylsilyl chloride, reaction a period of time after-baking, and through rinsing and post processing, obtain the Nano filtering composite membrane that ultrathin functional layer is polypiperazine-amide, particular chemical formula can be expressed as:
Cadotte etc., in the US Patent 4,812,270 of 1989, adopt interfacial polymerization and strong acid treatment method to prepare Nano filtering composite membrane.Water is the aqueous solution containing m-phenylene diamine (MPD) function monomer and wetting agent, organic phase is containing crosslinking agent pyromellitic trimethylsilyl chloride, through interface, obtain polyamide composite ultra-thin functional layer, then with strong acid, aramid layer is processed, finally with removal efficiency reinforcing agent, film is processed and waited until the NF membrane that is applicable to water softening.Its preparation method is that polysulfones support membrane is immersed to certain hour in aqueous phase solution, after taking-up is extracted, in covering, containing the organic solution of pyromellitic trimethylsilyl chloride, reacts a period of time after-baking, and through rinsing and post processing, obtains polyamide composite film.The chemical structural formula of the polyamide being obtained by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride polymerization is as follows:
Hodgdon etc., in the US Patent 5,152,901 of 1992, adopt interface polycondensation to prepare Nano filtering composite membrane.Water is the aqueous solution of bridged piperazine derivatives class polyamine and wetting agent, and organic phase is pyromellitic trimethylsilyl chloride and m-phthaloyl chloride mixture containing crosslinking agent.The composite ultra-thin functional layer obtaining is polypiperazine-amide.
Lawrence etc., in the US Patent 5,693,227 of 1997, adopt interfacial polymerization to prepare Nano filtering composite membrane.Water is the aqueous solution containing piperazine function monomer and wetting agent, and organic phase is containing crosslinking agent 5-isocyanates isophthaloyl chlorine, and porous support membrane is polysulphone super-filter membrane.Preparation method immerses polysulfones support membrane in the polyamine aqueous solution, immerses polynary solution of acid chloride after extracting again, reaction a period of time after-baking, and obtain Nano filtering composite membrane through rinsing and post processing.The ultrathin functional layer being obtained by piperazine and the polymerization of 5-isocyanates isophthaloyl chlorine is polypiperazine-amide-polyureas, and particular chemical formula can be expressed as:
In addition, US Patent 6,123,804, US Patent 6,464,873, US Patent6,536,605, US Patent 6,878, the patents such as 278 are also to adopt the interface polymerization reaction between polyamine and polynary acyl chlorides to prepare Nano filtering composite membrane, and the ultra-thin parting absciss layer of NF membrane is polyamide-based material.
At present, commercially produce and the Nano filtering composite membrane of industrial applications is to prepare by the interfacial polymerization between polyamine and polynary acyl chlorides mostly, the desalination functional layer of Nano filtering composite membrane is polyamide-based material, because amido link can be hydrolyzed under low pH condition, restricted the application of Nano filtering composite membrane under some acid conditions.
Thereby preparation has the Nano filtering composite membrane of acidproof function, for application, the especially application in the separation of some acid industrial fluids of expanding Nanofiltration-membrane technique, be very necessary and there is important practical usage.
Summary of the invention
The present invention is directed to deficiency of the prior art, propose a kind of novel polysulfonamide Nano filtering composite membrane and preparation method thereof, can effectively improve the acid resistance of existing composite nanometer filtering film.
The technical issues that need to address of the present invention are, provide a kind of raw material to be easy to get, cheap, select separating property superior, nanofiltration composite membrane that acid resistance is good and preparation method thereof.
Acid-proof polysulfonamide nanofiltration composite film of the present invention, is characterized in that on porous support membrane by heterocycle polyamine and polynary naphthalene sulfonyl chloride through the compound polysulfonamide functional layer obtaining of interfacial polycondensation.The mechanical stability of polysulfonamide functional layer, heat endurance and acidproof hydrolytic stability are all fine, are specially adapted to the nanofiltration separation process of acid industrial fluids.
Above-mentioned acid-proof polysulfonamide nanofiltration composite film, described heterocycle polyamine is piperazine, or 2,5-lupetazin, or N, N '-diaminourea piperazine, or 1,4-bis-(3-aminopropyl)-piperazine, or N-(2-aminoethyl)-piperazine, or their mixture.
Above-mentioned acid-proof polysulfonamide nanofiltration composite film, described polynary naphthalene sulfonyl chloride is 1,3,6-naphthalene, three sulfonic acid chlorides.
Above-mentioned acid-proof polysulfonamide nanofiltration composite film, the part by weight of described heterocycle polyamine and described polynary naphthalene sulfonyl chloride was from 1.5: 1 to 40: 1.
Above-mentioned acid-proof polysulfonamide nanofiltration composite film, interfacial polycondensation is with in the polyamines aqueous solution, and the acid containing 0.5%～4% receives agent, and it is triethylamine that acid receives agent, or NaOH, or sodium carbonate, or tertiary sodium phosphate.
Above-mentioned acid-proof polysulfonamide nanofiltration composite film, described porous support membrane is the UDEL P3500 LCD polysulfones with 13.5%, 0.2% water and 0.1% surfactant are dissolved in N, N-dimethylacetylamide, painting is scraped on polypropylene non-woven fabric, after being then immersed in the water gel and removing desolventizing, obtains; Surfactant wherein at least comprises alkyl phenol polyoxy Acetoxon acid esters, or dodecyl sodium sulfate, or a kind of in alkyl phenol polyoxy Acetoxon hydrochlorate.UDEL P3500 LCD is a kind of conventional polysulfones product of public offering on existing market.
The preparation method of acid-proof polysulfonamide nanofiltration composite film, that the polysulfones porous support membrane first polypropylene non-woven fabric being strengthened is immersed in certain hour in the above-mentioned polyamines aqueous solution, then with containing the organic solution of polynary naphthalene sulfonyl chloride, carry out that one side contacts and interface polymerization reaction occurs on surface, generate polysulfonamide active layer, nascent state composite membrane dries in the shade 1～5 minute in air, through heat treatment, rinsing afterwards obtains Nano filtering composite membrane again.
The preparation method of above-mentioned acid-proof polysulfonamide nanofiltration composite film, the described time of soaking the polyamines aqueous solution is 1-20 minute; The described one side haptoreaction time is 0.5-10 minute; Described heat treatment comprises two steps, and the first step is to process 3-10 minute at 60-80 ℃, and second step is to process 3-6 minute at 90-110 ℃; Described rinsing refers to rinsing 10-40 minute in the pure water of 40-50 ℃.
The preparation method of above-mentioned acid-proof polysulfonamide nanofiltration composite film, polynary naphthalene sulfonyl chloride solution organic solvent used is IsoparG, or trifluorotrichloroethane, or n-hexane, or heptane, or dodecane.
Acid-proof polysulfonamide nanofiltration composite film described in the present invention is Flat Membrane, or hollow-fibre membrane, or tubular membrane.
Beneficial effect: selection separating property and the permeance property of acid-proof polysulfonamide nanofiltration composite film of the present invention are not less than existing compound nanometer filtering membrane of polyamide, acid resistance is superior simultaneously, and preparation method is also simpler.
The specific embodiment
Below enforcement of the present invention is illustrated:
Following examples provide the explanation of acid-proof polysulfonamide nanofiltration composite film and their separating property.Yet these embodiment are only to provide as explanation rather than limit the present invention.
Porous support membrane preparation: 13.5% Udel PS3500 LCD polysulfones, 0.2% water and 0.1% surfactant are dissolved in to N, in N-dimethylacetylamide, painting is scraped on polypropylene non-woven fabric, then being immersed in the water gel, is the support membrane of 80,000 left and right except obtaining molecular cut off (MWCO) after desolventizing; Surfactant wherein at least comprises alkyl phenol polyoxy Acetoxon acid esters, or dodecyl sodium sulfate, or a kind of in alkyl phenol polyoxy Acetoxon hydrochlorate.
The preparation of Nano filtering composite membrane: the polysulfones support membrane of hygrometric state is immersed in containing 1-20 minute in the polyamine aqueous solution of acid reception agent, take out rear with squeegee roll extrusion support membrane surface and after drying up with compressed air, carry out interface polymerization reaction with the organic solution one side contact of 1,3,6-naphthalene, three sulfonic acid chlorides; It is triethylamine that acid wherein receives agent, or NaOH, or sodium carbonate, or tertiary sodium phosphate, and content is 0.5%～4%; Polyamine is wherein piperazine, or 2,5-lupetazin, or N, N '-diaminourea piperazine, or Isosorbide-5-Nitrae-bis-(3-aminopropyl)-piperazine, or N-(2-aminoethyl)-piperazine, or their mixture; Polynary naphthalene sulfonyl chloride solution organic solvent used is wherein Isopar
g, or trifluorotrichloroethane, or n-hexane, or heptane, or dodecane; The one side haptoreaction time is wherein 0.5-10 minute.Nascent state composite membrane stopped after 1-5 minute in air, then through two step heat treatments: the first step is to process 3-10 minute at 60-80 ℃, and second step is to process 3-6 minute at 90-110 ℃.Finally use the pure water of 40-50 ℃ to composite membrane rinsing 10-40 minute.
The acid resisting test of acid-proof polysulfonamide nanofiltration composite film: the aqueous hydrochloric acid solution with 0.5mol/l, NF membrane is carried out to immersion treatment, at the temperature of 25 ℃, soak 100 hours, then use pure water rinsing clean.
Nano filtering composite membrane separating property is evaluated: solute removal efficiency and water flux are two important parameters evaluating Nano filtering composite membrane separating property.By cross-flow permeability test, the sodium chloride removal efficiency of Nano filtering composite membrane, sodium sulphate removal efficiency and aquifer yield are carried out to separating property evaluation.
Salt removal efficiency (R) is defined as: under certain operating condition, and feeding liquid salinity (C
f) with penetrating fluid in salinity (C
p) poor, then divided by feeding liquid salinity.
Water flux is defined as: under certain operating condition, the volume ，Qi unit that sees through the water of unit plane integrated membrane in the unit interval is 1/m
2.h.
The operating condition that in the present invention, Nano filtering composite membrane separating property mensuration adopts is: the sodium-chloride water solution that feed liquor is 500mg/l or aqueous sodium persulfate solution, and operating pressure is 1.0MPa, and operating temperature is 25 ℃, and pH value of solution is 6.8.
Result:
Table 1: the performance of prepared Nano filtering composite membrane under different technology conditions
Table 2: the acid resistance of Nano filtering composite membrane
Claims (8)
1. a preparation method for acid-proof polysulfonamide nanofiltration composite film, is characterized in that, it comprises the steps:
(1) 13.5% polysulfones, 0.2% water and 0.1% surfactant are dissolved in to N, in N-dimethylacetylamide, be coated with and scrape on polypropylene non-woven fabric, be then immersed in the water gel, except after desolventizing, obtain polysulfones support membrane, above-mentioned percentage is the mass percent that each component accounts for mixed liquor; Described polysulfones is UDEL P3500 polysulfones;
Described surfactant is a kind of in alkyl phenol polyoxy Acetoxon acid esters, dodecyl sodium sulfate or alkyl phenol polyoxy Acetoxon hydrochlorate;
(2) polysulfones support membrane is immersed in containing 1-20 minute in the heterocycle polyamine aqueous solution of acid reception agent, take out rear with squeegee roll extrusion support membrane surface and after drying up with compressed air, with 1,3, interface polymerization reaction 0.5-10 minute is carried out in the organic solution one side contact of 6-naphthalene three sulfonic acid chlorides, on polysulfones support membrane, generate polysulfonamide functional layer, obtain nascent state composite membrane; The thickness of polysulfonamide functional layer is 0.1～0.5 micron, and the thickness of described polysulfones porous support membrane is 50～200 microns;
(3) nascent state composite membrane stopped after 1-5 minute in air, again through two step heat treatments: the first step is to process 3-10 minute at 60-80 ℃, second step is to process 3-6 minute at 90-110 ℃, finally with the pure water of 40-50 ℃, composite membrane rinsing is obtained to acid-proof polysulfonamide nanofiltration composite film for 10-40 minute.
2. preparation method according to claim 1, it is characterized in that the described heterocycle polyamine of step (2) is piperazine, 2,5-lupetazin, N, the mixture of one or more in N '-diaminourea piperazine, Isosorbide-5-Nitrae-bis-(3-aminopropyl)-piperazine or N-(2-aminoethyl)-piperazine; The mass fraction concentration of described heterocycle polyamine solution is 0.5～8.0%.
3. preparation method according to claim 2, is characterized in that the mass fraction concentration of the described heterocycle polyamine of step (2) solution is 2.0～4.0%.
4. preparation method according to claim 1, is characterized in that in the heterocycle polyamine aqueous solution, containing described in step (2) 1%～4% acid and receives agent; It is triethylamine, sodium carbonate or tertiary sodium phosphate that described acid receives agent.
5. preparation method according to claim 1, is characterized in that, described 1,3, and the mass fraction concentration of 6-naphthalene three sulfonic acid chloride organic solutions is 0.05～2.0%, and organic solvent used is IsoparG, trifluorotrichloroethane, n-hexane, heptane or dodecane.
6. preparation method according to claim 1, is characterized in that the weight ratio of described heterocycle polyamine and 1,3,6-naphthalene, three sulfonic acid chlorides is 1.5: 1～40: 1.
7. preparation method according to claim 8, is characterized in that the weight ratio of described heterocycle polyamine and 1,3,6-naphthalene, three sulfonic acid chlorides is 5: 1～15: 1.
8. preparation method according to claim 1, is characterized in that, described acid-proof polysulfonamide nanofiltration composite film is Flat Membrane, hollow-fibre membrane or tubular membrane.
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