CN105771700A - Mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and preparation method therefor - Google Patents
Mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and preparation method therefor Download PDFInfo
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Abstract
The invention relates to a mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and a preparation method therefor. An aqueous-phase monomer is prepared through mixing 2,2'-di(1-hydroxyl-1-trifluoromethyl-2,2,2-trifluoroethyl)-4,4'-methylene dianiline with piperazine. The preparation method comprises the following steps: (1) adjusting the temperature and humidity of an experimental environment; (2) carrying out basement membrane pretreatment; (3) preparing an aqueous-phase mixed monomer solution and an organic-phase solution; (4) carrying out an interface polymerization reaction; (5) carrying out heat treatment; (6) preparing an active chlorine solution; and (7) integrally submerging the prepared nanofiltration membrane into the active chlorine solution for oxidation treatment, thereby obtaining the final mixed diamine monomer adopted chlorine-resistant nanofiltration membrane. The mixed diamine monomer adopted chlorine-resistant nanofiltration membrane and the preparation method therefor have the advantages that the process is simple, process scale-up is facilitated, and the range of choice of basement membranes is enlarged, so that the industrial actual application value is remarkable.
Description
[technical field]
The present invention relates to macromolecule member material technical field, specifically, be a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer and preparation method thereof.
[background technology]
Nanofiltration is as a kind of emerging membrane process technology, between reverse osmosis and ultrafiltration, has following significant advantage: high flux, and low operating pressure retains for multivalent ion height and retains low price ion is low, and relatively low operating cost.The trapped molecular weight of NF membrane is usually 200-1000Da, and its aperture size is 0.5nm-2nm.Nanofiltration-membrane technique has been widely used in and has drunk water correction, the removing of heavy metal out of electroplating wastewater ion, separates the molecule of different quality, the purification of bio-pharmaceuticals industry and concentration, petroleum industry is food industry, the process etc. of the strong brine that desalinization produces.
The NF membrane material of current main flow can be largely classified into cellulose family and polyamide-based.Cellulose family NF membrane has chlorine resistance, and more the commercialization NF membrane of main flow is generally polyamide material, but common polyamide material does not have chlorine resistance.And free chlorine is (such as Cl2NaClO etc.) often it is applied in the pretreatment of former water, it it is the degradation agent of dissolved organic matter in excellent efficient bacteria remover and water, former water after generally pretreated often has certain density residual free chlorine, if not removing the free chlorine of these residuals, often cause irreversible oxidation to damage polyamide-based NF membrane, cause that the cutoff performance of film deteriorates.But the free chlorine removing these residuals in follow-up step is played not only increases operating cost, also add the complexity of technique.Therefore development of new high-performance chlorine-resistant NF membrane has become as focus and the difficult point of technical field of membrane.
Caused the concern of researcher in recent years as a kind of novel function monomer containing hexafluoroisopropanol group (double; two) aniline compound and derivant thereof.And it is applied among the preparation of NF membrane.Chinese patent ZLCN102527265B " film function monomer and NF membrane preparation method " containing hexafluoroisopropanol group thereof adopts fluorochemical monomer to carry out the research of chlorine-resistant NF membrane first, it comprises the following steps: first synthesize the monomer 2 containing hexafluoroisopropanol group NF membrane, 2 '-two (1-hydroxyl-1-trifluoromethyls-2, 2, 2,-trifluoroethyl)-4, 4 '-methylene dianiline, prepare the aqueous phase solution of fluorochemical monomer subsequently, and the oil-phase solution containing pyromellitic trimethylsilyl chloride, basement membrane is submerged initially in aqueous phase solution, take out and remove the excessive moisture of membrane surface subsequently, immerse the oil-phase solution containing polynary acyl chlorides again and carry out interface polymerization reaction, carry out heat treatment subsequently, and process with sodium hypochlorite, thus obtaining the strong chlorine-resistant NF membrane containing polyamide.
But all enforcement in polyether sulfone materials of the instantiation of above-mentioned patent formulation, if it was verified that made basement membrane into polysulfone membrane that hydrophobicity is stronger by the good poly (ether sulfone) film of hydrophilic, for identical formula, identical prepares environment, and the flux of the NF membrane obtained is unsatisfactory.For this, for the impact overcoming the kind of basement membrane that fluorochemical monomer is applied, widen the range of application of chlorine-resistant fluorochemical monomer, it is still desirable to the technology of preparing that further exploitation is new.
Adopt mixing polyamine monomers to prepare NF membrane, as the new focus of NF membrane research in the last few years, often obtain that there is novel performance.WangxiFang is by mixing the polymine of branching (PEI) with piperazine both aqueous phase monomers, prepare PEI/PIP composite nanometer filtering film, by the synergism of PEI and PIP both monomers, prepared NF membrane not only improves flux and also improves the rejection of salt simultaneously.(WangxiFang, LeiShi, RongWang.Mixedpolyamide-basedcompositenanofiltrationholl owfibermembraneswithimprovedlow-pressurewatersofteningca pability, JournalofMembraneScience.2014,468:52-61).Chinese patent ZLCN1817423A mentions and being mixed with piperazine by m-diaminobenzene., prepares the reverse osmosis membrane with special nature, and this reverse osmosis membrane operates under pressure at 300-370psi, at 28 DEG C to 32 DEG C, processes NaCl concentration 50-250g/L, SO4 2-Concentration 5-60g/L, pH7-11, reached NaCl removal efficiency less than 8%, SO4 2-Removal efficiency is more than 95%；Operating under pressure at 150-300psi, at 25 DEG C to 32 DEG C, the removal efficiency processing NaCl concentration 250-2000mg/L, pH6-10, NaCl is 90-94%.
[summary of the invention]
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer and preparation method thereof；The method has widened the basement membrane kind of the adaptation of fluorochemical monomer greatly, and while keeping the chlorine resistance of original fluorochemical monomer NF membrane, further improves its separating property.
It is an object of the invention to be achieved through the following technical solutions:
A kind of chlorine-resistant NF membrane adopting hybrid diamine monomer, its aqueous phase monomers is (1-hydroxyl-1-trifluoromethyl-2,2,2 ,-trifluoroethyl)-4 by 2,2 '-two, and 4 '-methylene dianiline and piperazine mix；Its general structure respectively formula 1 and formula 2；
A kind of chlorine-resistant NF membrane adopting hybrid diamine monomer and preparation method thereof, it concretely comprises the following steps:
(1) regulate between the temperature to 15～35 DEG C of experimental situation, and the relative humidity of Control release room is 45～65%；
(2) with many porous ultrafiltration membranes for counterdie, soak more than 5 hours with deionized water, take out by naturally drying or nitrogen purging, remove the moisture of counterdie excess surface, do not have the obvious globule to dry the basement membrane time for the best with membrane surface；
The molecular cut off of described many porous ultrafiltration membranes is 1～10W.
Described many porous ultrafiltration membranes are polysulphones hyperfiltration membrane or poly (ether-sulfone) ultrafiltration membrane.
(3) preparation aqueous phase mixed monomer solution, 2 in aqueous phase, 2 '-two (1-hydroxyl-1-trifluoromethyl-2,2,2 ,-trifluoroethyl)-4, the content of 4 '-methylene dianiline is 0～2%w/v, and the content of the piperazine in aqueous phase is 0～2%w/v；Wherein content be 100ml volumetric flask in add the meaning of solute of respective quality；
In embodiment 5 and embodiment 8, embodiment 5 is pure piperazine, namely 2,2 '-two (1-hydroxyl-1-trifluoromethyl-2,2,2,-trifluoroethyl)-4,4 '-methylene dianiline content is 0, and embodiment 8 is pure 2,2 '-two (1-hydroxyl-1-trifluoromethyls-2,2,2 ,-trifluoroethyl)-4,4 '-methylene dianiline, the content of piperazine is 0)；The reason that content in this patent is expressed by this mode: for adding the solute of respective quality in the volumetric flask of 100ml, so being this expression way.
In described aqueous phase solution, it is necessary to the sodium hydroxide adding 0.01～0.2%w/v promotes the dissolving of fluorochemical monomer；
In described aqueous phase solution, add surfactant and acid accepting agent；
Surfactant is the sodium lauryl sulphate of 0.01～1%w/v；
Acid accepting agent is the triethylamine of 0.1～1%w/v, sodium carbonate, sodium bicarbonate or its mixture.
(4) preparation organic phase solution, organic facies is the pyromellitic trimethylsilyl chloride organic solution of 0.05～0.3%w/v；
In described organic phase solution, organic solvent is hexamethylene, toluene, normal hexane, one or several mixture in chloroform.
(5) interface polymerization reaction: remove solution after being immersed in the aqueous phase solution of mix monomer 1～10 minute by the ultrafilter membrane counterdie dried, film by gas purging or is dried naturally, after treating that film surface is dried, immerse in organic phase solution and carry out interface polymerization reaction in 5 seconds～1 minute, remove the organic solution on film surface subsequently, and film good for interfacial polymerization is now placed 1～10 minute in atmosphere, it is subsequently placed in the baking oven of 50～100 DEG C and carries out heat treatment 2～15 minutes；After heat treatment is good, take the film out standby.
(6) preparation active chlorine solutions: active chlorine solutions is the aqueous solution of the active chlorine of 0～10000ppm, by adding the pH value of sulphuric acid, nitric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide adjustment solution；Such as embodiment 3, it does not have adopt active chlorine solutions to process, namely it is believed that the content of its practicality is the active chlorine of 0ppm；
(7) the above-mentioned NF membrane entirety prepared being immersed in the solution of active chlorine and carry out oxidation processes, oxidation treatment time is 0～10 hour；After process, carry out rinsing 1～2 time at normal temperatures with deionized water, obtain final hybrid diamine monomer chlorine-resistant NF membrane.
Such as embodiment 3, it does not have adopt active chlorine solutions to process, namely it is believed that the active chlorine that the content of its practicality is 0 hour.
Compared with prior art, the method have the advantages that
Positive effect of the present invention is in that, the price of piperazine is more much lower than fluorochemical monomer, by simple aqueous phase mix monomer, preparing the strong chlorine-resistant NF membrane of hybrid diamine monomer, what decrease fluorochemical monomer makes consumption, reduces production cost and has widened the basement membrane scope of use of fluorochemical monomer, moreover, being also equipped with simple to operate, reaction condition is gentle, has good prospects for commercial application.
[accompanying drawing explanation]
Fig. 1 is the scanning electron microscope sectional view of embodiment 3 NF membrane；
Fig. 2 is the scanning electron microscope sectional view of embodiment 3 NF membrane；
Fig. 3 is the scanning electron microscope plane graph of embodiment 10 NF membrane；
Fig. 4 is the scanning electron microscope sectional view of embodiment 10 NF membrane；
Fig. 5 is the stability test schematic diagram of embodiment 18 NF membrane.
[detailed description of the invention]
The detailed description of the invention of a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer of the present invention presented below and preparation method thereof.
A kind of chlorine-resistant NF membrane adopting hybrid diamine monomer and preparation method thereof, itself particularly as follows:
Prepared Nano filtering composite membrane is all use pure water precompressed half an hour under 0.6MPa, and tests the pure water flux of film respectively with pure water, with the Na of 2000ppm2SO4, MgSO4, the electrolyte solution of NaCl tests cutoff performance and the aquifer yield of film, with the glucose of 300ppm, sucrose, the aperture of the neutral solution test film of cottonseed sugar and molecular cut off.The computing formula of membrane flux is as shown in (1).
Wherein J is the flux (L/ (m of film2H)), V is the volume (L) of the permeate collected, and A is the effective area (m of film2), T is the time (h) required for the permeate collecting V volume.
The cutoff performance computational methods of film are as shown in (2).
Wherein R is the rejection of film, CpFor the concentration through side, CfConcentration for feed side.
The concentration of electrolyte solution measures the electrical conductivity through side and feed side initially with conductivity meter, then passes through the standard curve of electrolyte solution to calculate its concentration, thus obtaining its rejection.The concentration of neutral solution is then obtained by organic total carbon (TOC) analyser, thus obtaining its rejection.
The early-stage preparations of the present invention have following steps:
(1) control of experimental situation: regulate between the temperature to 15 DEG C to 35 DEG C of experimental situation, and the relative humidity of Control release room is 45～65%.
(2) pretreatment of counterdie: with many porous ultrafiltration membranes for counterdie, soaks more than 5 hours with deionized water, takes out by naturally drying or nitrogen purging, removes the moisture of counterdie excess surface, do not have the obvious globule to dry the basement membrane time for the best with membrane surface.
Embodiment 1～4
The preparation of hybrid diamine monomer chlorine-resistant NF membrane:
Selecting molecular cut off is that the polysulphone flat ultrafiltration membrane of 70,000 is as counterdie, solution is removed after being immersed in the aqueous phase solution of mix monomer by counterdie 5 minutes, film by gas purging or is dried naturally, after treating that film surface is dried, immerse in organic phase solution and carry out interface polymerization reaction in 5 seconds, 10 seconds, 15 seconds and 30 seconds, remove the organic solution on film surface subsequently, and film good for interfacial polymerization is now placed 1 minute in atmosphere, be subsequently placed in the baking oven of 80 DEG C and carry out heat treatment 5 minutes.After heat treatment is good, take the film out, use rinsed with deionized water 5 minutes subsequently, prepare NF membrane.
In aqueous phase 2,2 '-two (1-hydroxyl-1-trifluoromethyls-2,2,2,-trifluoroethyl)-4, the content of 4 '-methylene dianiline is 0.5% (w/v), and the content of the piperazine in aqueous phase is 0.5% (w/v), additionally promotes the dissolving of fluorochemical monomer possibly together with the sodium hydroxide of 0.02% (w/v).Organic facies is the pyromellitic trimethylsilyl chloride hexane solution of 0.15% (w/v).
The BHTTM/PIP mix monomer NF membrane that embodiment 1-4 prepares is carried out water flux and the test of salt cutoff performance, and test result is in Table 1
Embodiment 1～4 mainly considers the impact on NF membrane performance of the interfacial polymerization time.
Embodiment 5～8
Substantially the same manner as Example 3, by 2 in aqueous phase monomers, 2 '-two (1-hydroxyl-1-trifluoromethyls-2,2,2 ,-trifluoroethyl)-4, the ratio of 4 '-methylene dianiline and piperazine is adjusted, and in investigation mix monomer, piperazine content is for the impact of NF membrane performance.
The mix monomer NF membrane that embodiment 5～8 prepares is carried out water flux and the test of salt cutoff performance, and test result is as follows.
Embodiment 9～12
Essentially identical with embodiment 3,5～8, but the NF membrane prepared need not be rinsed, directly the NF membrane entirety obtained after heat treatment is immersed oxidation processes 1 hour in the effective liquor natrii hypochloritis of 3000ppm, take out subsequently, rinse with deionized water.
The mix monomer NF membrane that embodiment 9～12 prepares is carried out water flux and the test of salt cutoff performance, and test result is as follows.
Embodiment 13～14
Substantially the same manner as Example 3, but the NF membrane prepared need not be rinsed, directly the NF membrane entirety obtained after heat treatment be immersed in the effective liquor natrii hypochloritis of 3000ppm, carry out oxidation processes 0.5,2 hours, take out subsequently, rinse with deionized water.
The mix monomer NF membrane that embodiment 13～14 prepares is carried out water flux and the test of salt cutoff performance, and test result is as follows.
Embodiment 15～16
Substantially the same manner as Example 3, but the NF membrane prepared need not be rinsed, directly the NF membrane entirety obtained after heat treatment is immersed 1000ppm, in the effective liquor natrii hypochloritis of 5000ppm, carry out oxidation processes 1 hour, take out subsequently, rinse with deionized water.
The mix monomer NF membrane that embodiment 15～16 prepares is carried out water flux and the test of salt cutoff performance, and test result is as follows.
Embodiment 17
Identical with embodiment 10, systematic testing is for the solution cutoff performance of different salt, and not for the cutoff performance of same neutral solution, test result is as follows.
Embodiment 18
Identical with embodiment 10, the stability of film to be investigated, test result is Fig. 5 such as.
The present invention is prepared for high flux by the mixed monomer solution of piperazine and fluorochemical monomer by interfacial polymerization, and height retains, the NF membrane of strong chlorine resistance.Present invention process is simple, it is easy to technique is amplified, and has widened the range of choice of basement membrane, has significant industry actual application value.
The above is only the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, without departing from the inventive concept of the premise; can also making some improvements and modifications, these improvements and modifications also should be regarded as in protection scope of the present invention.
Claims (10)
1. the chlorine-resistant NF membrane adopting hybrid diamine monomer, it is characterised in that its aqueous phase monomers is by having 2,2 '-two (1-hydroxyl-1-trifluoromethyl-2,2,2 ,-trifluoroethyl)-4,4 '-methylene dianiline and piperazine mix；Its general structure respectively formula 1 and formula 2；
2. chlorine-resistant NF membrane adopting hybrid diamine monomer and preparation method thereof, it is characterised in that it concretely comprises the following steps:
(1) regulate between the temperature to 15～35 DEG C of experimental situation, and the relative humidity of Control release room is 45～65%；
(2) with many porous ultrafiltration membranes for counterdie, soak more than 5 hours with deionized water, take out by naturally drying or nitrogen purging, remove the moisture of counterdie excess surface；
(3) preparation aqueous phase mixed monomer solution
(4) preparation organic phase solution
(5) interface polymerization reaction: remove solution after being immersed in the aqueous phase solution of mix monomer 1～10 minute by the ultrafilter membrane counterdie dried, film by gas purging or is dried naturally, after treating that film surface is dried, immerse in organic phase solution and carry out interface polymerization reaction in 5 seconds～1 minute, remove the organic solution on film surface subsequently, and film good for interfacial polymerization is now placed 1～10 minute in atmosphere, it is subsequently placed in the baking oven of 50～100 DEG C and carries out heat treatment 2～15 minutes；After heat treatment is good, take the film out standby；
(6) preparation active chlorine solutions:
(7) the above-mentioned NF membrane entirety prepared being immersed in the solution of active chlorine and carry out oxidation processes, oxidation treatment time is 0～10 hour；After process, carry out rinsing 1～2 time with deionized water at normal temperatures, obtain the chlorine-resistant NF membrane of final hybrid diamine monomer.
3. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterised in that in described step (2), the molecular cut off of described many porous ultrafiltration membranes is 1～10W.
4. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterised in that in described step (2), described many porous ultrafiltration membranes are polysulphones hyperfiltration membrane or poly (ether-sulfone) ultrafiltration membrane.
5. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterized in that, in described step (3), in aqueous phase 2,2 '-two (1-hydroxyl-1-trifluoromethyl-2,2,2,-trifluoroethyl)-4, the content of 4 '-methylene dianiline is 0～2%w/v, and the content of the piperazine in aqueous phase is 0～2%w/v.
6. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterized in that, in described step (3), in described aqueous phase solution, it is necessary to the sodium hydroxide adding 0.01～0.2%w/v promotes the dissolving of fluorochemical monomer.
7. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterised in that in described step (3), in described aqueous phase solution, adds surfactant and acid accepting agent；Surfactant is the sodium lauryl sulphate of 0.01～1%w/v；Acid accepting agent is the triethylamine of 0.1～1%w/v, sodium carbonate, sodium bicarbonate or its mixture.
8. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterised in that in described step (4), organic facies is the pyromellitic trimethylsilyl chloride organic solution of 0.05～0.3%w/v.
9. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterised in that in described step (4), in described organic phase solution, organic solvent is hexamethylene, toluene, normal hexane, one or several mixture in chloroform.
10. a kind of chlorine-resistant NF membrane adopting hybrid diamine monomer as claimed in claim 2 and preparation method thereof, it is characterized in that, in described step (6), active chlorine solutions is the aqueous solution of the active chlorine of 0～10000ppm, by adding sulphuric acid, nitric acid, hydrochloric acid, sodium hydroxide or potassium hydroxide regulate the pH value of solution.
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| CN107754617A (en) * | 2016-08-23 | 2018-03-06 | 华东理工大学 | The preparation method of triple channel milipore filter and endothelium floor height chlorine-resistant NF membrane |
| CN109351190A (en) * | 2018-09-07 | 2019-02-19 | 中国海洋大学 | It is a kind of to be crosslinked the compound solvent resistant nanofiltration membrane of fluorine-containing polyamide, preparation method and applications |
| CN109663511A (en) * | 2017-10-13 | 2019-04-23 | 湖州欧美新材料有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN109833778A (en) * | 2018-12-26 | 2019-06-04 | 天津膜天膜科技股份有限公司 | The method for improving continuous production External Pressure Type hollow fiber nanofiltration membrane rejection |
| CN110545903A (en) * | 2017-04-19 | 2019-12-06 | 香港大学 | Membrane permeability-enhanced thin film composite membranes with nano-sized bubbles, methods of making and uses thereof |
| CN111282458A (en) * | 2020-02-20 | 2020-06-16 | 自然资源部天津海水淡化与综合利用研究所 | Polyamide composite reverse osmosis membrane with chlorine resistance and preparation method thereof |
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| CN107754617A (en) * | 2016-08-23 | 2018-03-06 | 华东理工大学 | The preparation method of triple channel milipore filter and endothelium floor height chlorine-resistant NF membrane |
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| CN109833778A (en) * | 2018-12-26 | 2019-06-04 | 天津膜天膜科技股份有限公司 | The method for improving continuous production External Pressure Type hollow fiber nanofiltration membrane rejection |
| CN111282458A (en) * | 2020-02-20 | 2020-06-16 | 自然资源部天津海水淡化与综合利用研究所 | Polyamide composite reverse osmosis membrane with chlorine resistance and preparation method thereof |
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Application publication date: 20160720 |