CN106693717A - Salt-dye separating nanofiltration membrane as well as preparation method and application thereof - Google Patents
Salt-dye separating nanofiltration membrane as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN106693717A CN106693717A CN201710044095.0A CN201710044095A CN106693717A CN 106693717 A CN106693717 A CN 106693717A CN 201710044095 A CN201710044095 A CN 201710044095A CN 106693717 A CN106693717 A CN 106693717A
- Authority
- CN
- China
- Prior art keywords
- membrane
- salt
- dye
- preparation
- salt dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- 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
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
Abstract
The invention discloses a salt-dye separating nanofiltration membrane as well as a preparation method and application thereof. According to the preparation method, an ultrafiltration membrane is used as a basement membrane; 2,2'-benzidinedisulfonic acid is used as a water-phase monomer; trimesoyl chloride is used as an organic-phase monomer to be dissolved in an organic solvent; a polyamide selecting layer is prepared and obtained through a water phase-organic phase interfacial polymerization method. According to the preparation method, the nanofiltration membrane with suitable charge performance and an appropriate membrane aperture is obtained through the regulation of monomer concentration, polymerization time, pH (potential of Hydrogen) and the like; by means of a Donnan effect and aperture sieving action, a dye and an inorganic salt are subjected to separation treatment; while an organic macromolecular dye can be effectively intercepted, ions of the inorganic salt are enabled to pass through to a greater extent; in comparison with a conventional commercial membrane, the water consumption is greatly reduced; the operating time is also obviously shortened. In addition, the nanofiltration membrane prepared by the preparation method has the advantages of being higher in mechanical strength, better in stability and easy to wash, and the like; the treatment of salt-dye wastewater can be effectively realized.
Description
Technical field
The invention belongs to NF membrane preparing technical field, it is related to a kind of salt dye to separate NF membrane and preparation method thereof and answer
With.
Background technology
Industrial wastewater has turned into topmost water pollution source, especially dyeing waste water.As shown by data, production 1t dyestuffs are needed
Expend 200-350m3Pure water, so as to produce substantial amounts of dyeing waste water, huge harm is caused to environment.Dyeing waste water has
There is salinity (NaCl high：6.0wt%, Na2SO4：5.6wt%), the features such as COD high, high chroma, the recycling of dyestuff and salt is not
The preparation of dyestuff and the waste of salt can only be significantly reduced, it is also possible to substantially reduce pollution and harm of the waste water to environment, but
Many printing-dyeing waste water treatment process (such as absorption, sedimentation, biodegradable, oxidation) are mainly removing dyestuff or destroy dyestuff knot
Structure, is extremely difficult to the reuse of dyestuff and inorganic salts and reclaims, it is therefore desirable to find other handling process realize it is valuable or
The recovery of harmful resource or recycling.
Current membrane separating be used to contaminate the separation and reuse of salt waste water, wherein fine and close milipore filter, loose NF membrane and
Forward osmosis membrane is frequently used in membrane separating dyeing waste water.NF membrane is the molecular cut off between ultrafiltration and counter-infiltration
A kind of film based on polyamide selection layer of 200-1000Da.In order to obtain more accessories or purer recovery
Thing, it will usually select embrane method to be combined with other techniques, such as nanofiltration-bipolar membrane electrodialysis (NF-BMED) GC-MS, reclaim dyestuff
While, clean manufacturing bronsted lowry acids and bases bronsted lowry etc..But embrane method there is also many deficiencies, such as anisotropic membrane easily causes concentration polarization and shows
As less, pure water waste is excessive etc. in infiltration process for flux in separation process.Large-scale promotion membrane separating dyeing waste water,
Need emphasis solve concentration polarization, flux is too small, water consumption is excessive, not easy cleaning the problems such as.Existing method is often using commercial film pair
Dye salt waste water carries out separating treatment.Woods is supported wait using commercialization film Sepro NF 6, Sepro NF 2A to different dyes (DR long
80th, DR 23, CR) and the mixed solution of salt (NaCl) carried out separating treatment, find these commercial films have to dyestuff well cut
Stay (99.9%), but the transmission ability of salt is general, easily causes concentration polarization phenomenon, causes water consumption in processing procedure, power consumption ratio
More serious (Lin, J.Y et.al.J.Memb.Sci.2015).King's exhibition etc. is separated using loose NF membrane to dye salt waste water, to first
The blue and Congo red retention of base reaches 97.3%, 97.1%, there is a preferable dyestuff interception capacity, but in separation process flux compared with
Small, the used time is more long, Membrane cleaning and is only studied low concentration dyestuff (Wang, Z et.al.J.Memb.Sci.2016).
The content of the invention
Small for nanofiltration flux in conventional dyeing waste water separation process, with duration, water consumption is more, the problems such as cleaning is difficult,
The invention provides the preparation method that a kind of salt dye separates NF membrane, the method is made with 2,2 '-disulfonic acid base benzidine (BDSA)
It is aqueous phase monomers, pyromellitic trimethylsilyl chloride (TMC) is dissolved in organic solvent as organic phase monomer, obtains polyamide selection layer.
Technical scheme is as follows：
A kind of salt dye separates the preparation method of NF membrane, using milipore filter as basement membrane, by water phase-oil phase interfacial polymerization
Prepared by method, comprise the following steps that：
Step 1, compound concentration is the 2 of 0.1-0.5wt%, and 2 '-disulfonic acid base benzidine (BDSA) solution mixes as water
Liquid, it is 10-11 to add alkaline reagent regulation pH, and aqueous phase solution is poured onto into membrane surface and 2~5min of complete wetting, removes base
The aqueous phase solution of film excess surface；
Step 2, pyromellitic trimethylsilyl chloride (TMC) is dissolved in organic solvent, and compound concentration is the equal benzene of 0.05-0.20wt%
Three formyl chloride organic phase solutions, are poured onto pyromellitic trimethylsilyl chloride organic phase solution the film surface after step 1 is processed and soak completely
Profit, infiltrating time is no more than 60s, removes the organic phase solution of membrane removal excess surface, after after organic solvent volatilization completely, by salt dye point
Preservation is placed in water from NF membrane.
Described basement membrane is polyether sulfone (PES) or polysulfones (PSF) milipore filter.
Preferably, described alkaline reagent is triethylamine or sodium carbonate.
Preferably, described organic solvent is n-hexane or hexamethylene.
The present invention also provides salt dye obtained in above-mentioned preparation method and separates NF membrane, and described NF membrane is super with PES or PSF
Filter membrane is basement membrane, described membrane surface covering polyamide selection layer, and the structural formula of described polyamide is：
Further, the present invention also provides salt dye separation NF membrane obtained in above-mentioned preparation method in salt dye wastewater treatment
Application.
Salt dye obtained in above-mentioned preparation method separates application of the NF membrane in salt dye wastewater treatment, and concrete application method is such as
Under：Under pressure effect, separating NF membrane using salt dye to salt dye waste water be percolated-concentrate, and after concentration terminates, salt is contaminated and is separated
NF membrane mass ratio is 1:The mixed solution backwash of 4 20% second alcohol and water, the salt dye rinsed well separates NF membrane can
It is continuing with.
Preferably, described backwash is concretely comprised the following steps：It is 1 that the film after pollution is used into mass ratio under 0.3MPa:4
The mixed solution of 20% second alcohol and water is backwashed, and backwashing time is 1-5h.
Compared with prior art, the present invention has following remarkable advantage：
(1) the obtained salt dye of the present invention separates the rejection that NF membrane is not higher than the single sodium chloride solutions of 100g/L to concentration
It is below 2.0%；The rejection that the single metabisulfite solution of 40g/L is not higher than to concentration is below 35%；
(2) to dyestuffs such as direct red 80 (DR 80), Direct Red 23 (DR 23), Congo red (CR), reactive blues 2 (RB 2)
Retention is all higher than 99.0%；
(3) infiltration process is first carried out using self-control NF membrane, the inorganic salts in waste water is percolated infiltration to greatest extent
In liquid, inorganic salt concentration is down to below 0.5g/L in making stoste, after carry out concentration to stoste again, obtain preferably dye salinity
While from effect, water consumption, power consumption are obviously reduced；
(4) concentrated using self-control NF membrane, when dyestuff cycles of concentration reaches 10, NF membrane remains to keep better to dyestuff
Rejection effect.
To sum up, the obtained NF membrane of the present invention is used to process salinity dyeing waste water high, during by monomer concentration, polymerization
Between, the regulation of pH, obtained that there is suitable charge and appropriate membrane aperture, by road south effect and aperture sieving actoion, to dye
Material and inorganic salts are processed, while its most outstanding feature can be effectively catching organic macromolecule dyestuff, largely
The inorganic ion that makes pass through；Compared with conventional commercial film, water consumption is greatly reduced, and the operating time also substantially shortens.Additionally, this
The obtained NF membrane of invention has the advantages that mechanical strength higher, preferable stability and easy cleaning, can be effectively real
Existing salt dye wastewater treatment.
Brief description of the drawings
Fig. 1 is surface scan electron microscope (a) and cross-sectional scans electron microscope (b) of NF membrane M2.
Fig. 2 is NF membrane M1, M2, M3 to various concentrations sodium chloride solution rejection effect figure.
Fig. 3 is NF membrane M1, M2, M3 to various concentrations metabisulfite solution rejection effect figure.
Fig. 4 is NF membrane M1, M2, M3 to rejection effect figure (the 1g L of different dyes-1)。
Fig. 5 is NF membrane M1 to 20g L-1NaCl+1g L-1The separation process design sketch of the waste water of DR 80.
Fig. 6 is NF membrane M2 to 20g L-1NaCl+1g L-1The separation process design sketch of CR waste water.
Fig. 7 is NF membrane M3 to 20g L-1NaCl+1g L-1The separation process design sketch of the waste water of DR 23.
Fig. 8 is (a) M1 to 20g L-1NaCl+1g L-1Stoste pre-concentration procedure chart after the diafiltrations of DR 80, (b) M2 is to 20g L-1NaCl+1g L-1Stoste pre-concentration procedure chart after CR diafiltrations, (c) M3 is to 20g L-1NaCl+1g L-1Stoste is pre- after DR23 diafiltrations
Concentration process figure.
Fig. 9 is that NF membrane different solvents clean traversing of probe electron microscope, and (a) is cleaned for pure water, and (b) is 20% ethanol/water
Cleaning, (c) is cleaned for 50% ethanol/water.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
The preparation of NF membrane M1
The BDSA aqueous solution of 0.1wt% is configured, and adds triethylamine to adjust pH to 10.The solution is poured onto polysulfones afterwards
(PSF) membrane surface, solution is removed after submergence 5min, is dried naturally in atmosphere.Configure the TMC organic solutions of 0.2wt% (just
Hexane), after pour into above-mentioned film film surface and remove unnecessary organic solvent after contacting 20s.After natural air drying, by film be placed in from
Preserved in sub- water.
Embodiment 2
The preparation of NF membrane M2
The BDSA aqueous solution of 0.2wt% is configured, and adds triethylamine to adjust pH to 11.The solution is poured onto polyether sulfone afterwards
(PES) membrane surface, solution is removed after submergence 3min, is dried naturally in atmosphere.Configure the TMC organic solutions of 0.1wt% (just
Hexane), after pour into above-mentioned film film surface and remove unnecessary organic solvent after contacting 30s.After natural air drying, by film be placed in from
Preserved in sub- water.Shown in NF membrane pattern such as Fig. 1-(a), there is projection on film surface, and this illustrates that membrane surface has aramid layer
Formed；Can significantly see that membrane surface has one layer to select layer than relatively thin polyamide from profile scanning electron microscope 1- (b).
Embodiment 3
The preparation of NF membrane M3
The BDSA aqueous solution of 0.5wt% is configured, and adds sodium carbonate to adjust pH to 11.The solution is poured onto polysulfones afterwards
(PSF) membrane surface, solution is removed after submergence 2min, is dried naturally in atmosphere.Configure the TMC organic solutions of 0.05wt%
(hexamethylene), after pour into above-mentioned film film surface and remove unnecessary organic solvent after contacting 60s.After natural air drying, film is placed in
Preserved in deionized water.
Embodiment 4
The separating effect of NF membrane M1, M2, M3 to different sodium chloride concentrations
Under pressure, respectively using NF membrane M1, M2, M3 to the sodium chloride solution of various concentrations (10,20,40,60,80,
100g L-1) carry out separation test, testing time 30-60min, the content of sodium chloride in record stoste and penetrating fluid, and solution
Permeation flux.Fig. 2 reflects separating effect of three kinds of NF membranes to various concentrations sodium chloride solution, as we can see from the figure three kinds
NF membrane rejection M3 all the time>M1>M2, the rejection that the single sodium chloride solutions of 100g/L are not higher than to concentration is below 2.0%；
And with the increase of sodium chloride concentration, rejection has declined；It can also be seen that with the increase of concentration, flux in figure
Decline, this is mainly concentration increase, film surface penetration pressure increase, true actuating pressure reduces what is caused.
Embodiment 5
The separating effect of NF membrane M1, M2, M3 to different sodium sulfate concentrations
Under pressure, respectively using NF membrane M1, M2, M3 to the metabisulfite solution of various concentrations (10,20,30,40g L-1)
Tested, testing time 30-60min, the content of sodium sulphate in record stoste and penetrating fluid, and solution permeation flux.Fig. 3
Separating effect of three kinds of NF membranes to various concentrations metabisulfite solution is reflected, as we can see from the figure rejection M3 all the time>M1>
M2, the rejection that the single metabisulfite solutions of 40g/L are not higher than to concentration is below 35%；And with the increasing of sodium sulfate concentration
Greatly, rejection has declined；It can also be seen that with the increase of concentration, flux has also declined in figure.
Embodiment 6
The separating effect of NF membrane M1, M2, M3 to different dyes
Under pressure, respectively using NF membrane M1, M2, M3 to different dyes (DR 80, DR 23, CR, RB 2,1g L-1) enter
Row separates test, and testing time 45-60min records the content of stoste and dyestuff in penetrating fluid using ultraviolet specrophotometer.Figure
4 reflect three kinds of NF membranes to 1g L-1The separating effect of the different dyes under same concentrations, it can be seen that NF membrane M2 pairs in figure
The rejection effect of different dyes is relatively poor, and three kinds of NF membranes are also relatively poor to Congo red retention, reach
99.45%, this is primarily due to Congo red molecules amount minimum, and bear is electrically worst, due to road south effect and aperture screening effect
Should be caused.Generally, three kinds of NF membranes are preferable to the rejection effect of different dyes.
Embodiment 7
Separating experiments of the NF membrane M1 to salinity dyeing waste water high
(1) configuration 1L 20g/L NaCl+1g/L DR 80 simulate salinity dyeing waste water high, as stoste；
(2) operating pressure is 1MPa, when stoste volume is down to 500mL, NaCl, DR 80 in record stoste and penetrating fluid
The change of concentration, and 500mL pure water to stoste is supplemented simultaneously.Above procedure is repeated until NaCl concentration is less than 0.5g/ in stoste
L；
(3) stoste after salt dye is separated further is concentrated, and by (highest is concentrated into when recording different cycles of concentration
10g/L) in stoste and penetrating fluid DR 80 change in concentration.
Fig. 5 reflects separating effects of the NF membrane M1 to waste water, as seen from the figure when in stoste sodium chloride concentration reach
0.5g L-1When, it is necessary to by 4 times diafiltration, water consumption 1800mL, used time 1174min.Fig. 8-(a) show NF membrane M1 to oozing
The pre-concentration process of stoste after filter, can be clearly seen that the sodium chloride in stoste contains when stoste is concentrated to 3.5 times from figure
Amount improves 61.3%, illustrates that NF membrane M1 has transmission ability higher to sodium chloride；And dyestuff theoretical values of DR 80 and true in figure
Real-valued gap very little, illustrates that NF membrane M1 has good interception capacity to DR 80.
Embodiment 8
Separating experiments of the NF membrane M2 to salinity dyeing waste water high
(1) configuration 1L 20g/L NaCl+1g/L CR simulate salinity dyeing waste water high, as stoste；
(2) operating pressure is 1MPa, record stoste and NaCl in penetrating fluid, Congo red when stoste volume is down to 500mL
The change of concentration, and 500mL pure water to stoste is supplemented simultaneously.Above procedure is repeated until NaCl concentration is less than 0.5g/ in stoste
L；
(3) stoste after salt dye is separated further is concentrated, and by (highest is concentrated into when recording different cycles of concentration
10g/L) change in concentration Congo red in stoste and penetrating fluid.
Fig. 6 reflects separating effects of the NF membrane M2 to simulated wastewater, and compare Fig. 5, corresponding NF membranes M1, M2 of Fig. 7
Separating effect, NF membrane M2 diafiltration number of times it is few, water consumption is few, and the operating time is short, with separating property very high.Fig. 8-(b)
The pre-concentration process of NF membrane M2 is shown, be can be clearly seen that from figure when stoste is concentrated to 3.5 times, in stoste
NaCl contents only improve 26.88%, illustrate that NF membrane M2 has transmission ability very high to sodium chloride；And CR dyestuffs reason in figure
It is smaller by value and actual value gap, illustrate that NF membrane M2 has relatively good interception capacity to CR dyestuffs, meet very much dye salt and separate
Imagination.
Embodiment 9
Separating experiments of the NF membrane M3 to salinity dyeing waste water high
(1) configuration 1L 20g/L NaCl+1g/L DR 23 simulate salinity dyeing waste water high, as stoste；
(2) operating pressure is 1MPa, when stoste volume is down to 500mL, NaCl, DR 23 in record stoste and penetrating fluid
The change of concentration, and 500mL pure water to stoste is supplemented simultaneously.Above procedure is repeated until NaCl concentration is less than 0.5g/ in stoste
L；
(3) stoste after salt dye is separated further is concentrated, and by (highest is concentrated into when recording different cycles of concentration
10g/L) in stoste and penetrating fluid DR 23 change in concentration.
Fig. 7 is separating effects of the NF membrane M3 to waste water, and NF membrane M3 is percolated 4 times in separation process, water consumption 2000mL, is used
When 1231min.Fig. 8-(c) shows the pre-concentration process to stoste after diafiltration of NF membrane M3, and original is worked as we can see from the figure
During liquid cycles of concentration 3.5, the sodium chloride content in stoste improves 108.5%, illustrates that NF membrane M3 has to sodium chloride and preferably cuts
Stay；And the dyestuff theoretical values of DR 23 and actual value gap are very small in figure, illustrate that NF membrane M3 has very to the dyestuffs of DR 23
Good interception capacity, it is contemplated that the retention to salt is also preferable, NF membrane M3 is more weaker than M2 in dye salt waste water separating effect.
Embodiment 10
Separating experiments of the NF membrane M2 to salinity dyeing waste water high
(1) configuration 1L 20g/L Na2SO4+ 1g/L RB 2 simulate salinity dyeing waste water high, as stoste；
(2) operating pressure is 1MPa, when stoste volume is down to 500mL, Na in record stoste and penetrating fluid2SO4, RB2 it is dense
The change of degree, and 500mL pure water to stoste is supplemented simultaneously.Above procedure is repeated up to Na in stoste2SO4Concentration is less than 0.5g/L；
(3) stoste after salt dye is separated further is concentrated, and by (highest is concentrated into when recording different cycles of concentration
10g/L) in stoste and penetrating fluid RB2 change in concentration.
Embodiment 11
Separating experiments of the NF membrane M2 to salinity dyeing waste water high
(1) configuration 1L 20g/L Na2SO4+ 1g/L CR simulate salinity dyeing waste water high, as stoste；
(2) operating pressure is 1MPa, when stoste volume is down to 500mL, Na in record stoste and penetrating fluid2SO4, the Congo
The change of red concentration, and 500mL pure water to stoste is supplemented simultaneously.Above procedure is repeated up to Na in stoste2SO4Concentration is less than
0.5g/L；
(3) stoste after salt dye is separated further is concentrated, and by (highest is concentrated into when recording different cycles of concentration
10g/L) change in concentration Congo red in stoste and penetrating fluid.
Embodiment 12
Film when using dyestuff cycles of concentration being 2.5 times, as object, is mixed solvent with 20% ethanol/water, under 0.3MPa
Carry out backwash 2h.Fig. 9-(b) is the cleaning performance of 20% ethanol/water mixing cleaning fluid, finds the organic pollution on film surface
Substantially cleaning is all gone.
Comparative example 1
Film when using dyestuff cycles of concentration being 2.5 times, with pure water as solvent, is backwashed as object under 0.3MPa
1h.Fig. 9-(a) is the cleaning performance of pure water, it can be seen that film surface contaminant residual is more.
Comparative example 2
Film when using dyestuff cycles of concentration being 2.5 times, as object, is mixed solvent with 50% ethanol/water, under 0.3MPa
Carry out backwash 5h.Fig. 9-(c) is the cleaning performance of 50% ethanol/water mixing cleaning fluid, it can be seen that have certain cleaning to imitate
Really, but still there are some pollutants on film surface.
Claims (8)
1. a kind of salt dye separates the preparation method of NF membrane, it is characterised in that comprise the following steps that：
Step 1, compound concentration is the 2 of 0.1-0.5wt%, and 2 '-disulfonic acid base biphenyl amine aqueous solution adds alkalescence as aqueous phase solution
Reagent regulation pH is 10-11, and aqueous phase solution is poured onto into membrane surface and 2~5min of complete wetting, and removal membrane surface is unnecessary
Aqueous phase solution；
Step 2, pyromellitic trimethylsilyl chloride is dissolved in organic solvent, and compound concentration is the pyromellitic trimethylsilyl chloride of 0.05-0.20wt%
Organic phase solution, is poured onto the film surface after step 1 is processed and complete wetting, during infiltration by pyromellitic trimethylsilyl chloride organic phase solution
Between be no more than 60s, remove the organic phase solution of membrane removal excess surface, after organic solvent volatilization completely after, by salt dye separate NF membrane
It is placed in water preservation.
2. salt dye according to claim 1 separates the preparation method of NF membrane, it is characterised in that described basement membrane is polyethers
Sulfone or polysulphone super-filter membrane.
3. salt according to claim 1 dye separates the preparation method of NF membrane, it is characterised in that described alkaline reagent is
Triethylamine or sodium carbonate.
4. salt according to claim 1 dye separates the preparation method of NF membrane, it is characterised in that described organic solvent is
N-hexane or hexamethylene.
5. the salt dye according to obtained in the preparation method that any described salt dye of Claims 1-4 separates NF membrane separates NF membrane.
6. salt dye according to claim 5 separates application of the NF membrane in salt dye wastewater treatment.
7. salt dye according to claim 6 separates application of the NF membrane in salt dye wastewater treatment, it is characterised in that specific
Application process is as follows：Under pressure effect, separating NF membrane using salt dye to salt dye waste water be percolated-concentrate, after concentration terminates,
It is 1 that salt dye is separated into NF membrane mass ratio:The mixed solution backwash of 4 20% second alcohol and water, the salt dye point rinsed well
Can be continuing with from NF membrane.
8. salt dye according to claim 7 separates application of the NF membrane in salt dye wastewater treatment, it is characterised in that described
Backwash concretely comprise the following steps：It is 1 that the film after pollution is used into mass ratio under 0.3MPa:The mixing of 4 20% second alcohol and water
Solution is backwashed, and backwashing time is 1-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710044095.0A CN106693717B (en) | 2017-01-19 | 2017-01-19 | A kind of salt dye separation nanofiltration membrane and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710044095.0A CN106693717B (en) | 2017-01-19 | 2017-01-19 | A kind of salt dye separation nanofiltration membrane and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106693717A true CN106693717A (en) | 2017-05-24 |
| CN106693717B CN106693717B (en) | 2019-06-04 |
Family
ID=58910088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710044095.0A Active CN106693717B (en) | 2017-01-19 | 2017-01-19 | A kind of salt dye separation nanofiltration membrane and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106693717B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899437A (en) * | 2017-11-21 | 2018-04-13 | 贵阳时代沃顿科技有限公司 | A kind of high-performance water-oil separationg film based on interfacial polymerization and preparation method thereof |
| CN109224864A (en) * | 2018-09-12 | 2019-01-18 | 广东产品质量监督检验研究院 | A kind of dark color textiles and leathers extract liquor decoloration novel process for pretreating |
| CN112892249A (en) * | 2019-12-04 | 2021-06-04 | 时代沃顿科技有限公司 | Polyamide reverse osmosis membrane and preparation method thereof |
| CN114272767A (en) * | 2022-01-06 | 2022-04-05 | 天津工业大学 | Diphenyl phenol compound organic solvent nanofiltration composite membrane and preparation method thereof |
-
2017
- 2017-01-19 CN CN201710044095.0A patent/CN106693717B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| JIAHUI HU ET AL.: "Fabrication of a high-flux sulfonated polyamide nanofiltration membrane: Experimental and dissipative particle dynamics studies", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899437A (en) * | 2017-11-21 | 2018-04-13 | 贵阳时代沃顿科技有限公司 | A kind of high-performance water-oil separationg film based on interfacial polymerization and preparation method thereof |
| CN109224864A (en) * | 2018-09-12 | 2019-01-18 | 广东产品质量监督检验研究院 | A kind of dark color textiles and leathers extract liquor decoloration novel process for pretreating |
| CN109224864B (en) * | 2018-09-12 | 2021-02-19 | 广东产品质量监督检验研究院 | Novel process for decoloring dark textile and leather extract liquor |
| CN112892249A (en) * | 2019-12-04 | 2021-06-04 | 时代沃顿科技有限公司 | Polyamide reverse osmosis membrane and preparation method thereof |
| WO2021109621A1 (en) * | 2019-12-04 | 2021-06-10 | 时代沃顿科技有限公司 | Polyamide reverse osmosis membrane and production method therefor |
| CN114272767A (en) * | 2022-01-06 | 2022-04-05 | 天津工业大学 | Diphenyl phenol compound organic solvent nanofiltration composite membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106693717B (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Effective dye purification using tight ceramic ultrafiltration membrane | |
| CN106693717B (en) | A kind of salt dye separation nanofiltration membrane and its preparation method and application | |
| CN106731841B (en) | A kind of supermolecule composite nanometer filtering film and its preparation method and application | |
| US11623182B2 (en) | Nanofiltration membrane with high flux for selectively removing hydrophobic endocrine disrupting chemicals and preparation method thereof | |
| CN106823854A (en) | A kind of preparation method of polymer-based metal organic backbone hybridized film | |
| CN105148752A (en) | Polyamide reverse-osmosis composite membrane containing MIL type metal-organic framework material and preparation method thereof | |
| CN110787644B (en) | Loose nanofiltration membrane based on branched polyethyleneimine, and preparation and application thereof | |
| CN114100374B (en) | Monovalent ion selective cation exchange membrane and preparation method and application thereof | |
| CN109173737A (en) | A kind of preparation method of novel highly selective positive charged composite nanofiltration membrane | |
| CN102580561B (en) | Tubular composite nanofiltration membrane | |
| CN108176241A (en) | A kind of composite nanometer filtering film containing aquaporin and preparation method thereof | |
| CN103785301B (en) | A kind of Cellulose acetate forward osmotic membrane material and preparation method thereof | |
| CN113797763B (en) | Cellulose gel layer modified loose nanofiltration membrane for high-flux dye separation and preparation method and application thereof | |
| CN110465211B (en) | Polyphenol functionalized composite membrane with sandwich structure separation layer and preparation method thereof | |
| CN110339724B (en) | Composite polyamide membrane with salt concentration responsiveness and preparation method and application thereof | |
| CN114887486A (en) | Mannitol-based polyester loose composite nanofiltration membrane and preparation method and application thereof | |
| CN109647222B (en) | Method for preparing high-flux high-rejection-rate aromatic polyamide composite reverse osmosis membrane by using tannic acid modified base membrane | |
| CN107376667B (en) | Method and device for preparing nano-filtration/forward-osmosis amphibious-performance CTA (CTA) membrane | |
| CN113522039A (en) | Preparation method of forward osmosis membrane based on PVA (polyvinyl alcohol) grafting modification | |
| CN108176260A (en) | A kind of preparation method of the hydrophilic seperation film of pressure response type | |
| CN114259891B (en) | Graphene oxide nanofiltration membrane as well as preparation method and application thereof | |
| CN109603564A (en) | The method of preparing nano-filtration membrane from tree polyamide-amine embedded inorganic nano particles | |
| CN111437740B (en) | Preparation method of sodium lignosulfonate-based high-flux high-interception nanofiltration membrane | |
| CN108358371B (en) | Cationic dye wastewater separation method | |
| DE102004045848B3 (en) | Process for producing hollow fiber membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |