CN103785303A - Preparation method and application of polypropylene hollow fiber hydrophobic membrane - Google Patents
Preparation method and application of polypropylene hollow fiber hydrophobic membrane Download PDFInfo
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- CN103785303A CN103785303A CN201210434202.8A CN201210434202A CN103785303A CN 103785303 A CN103785303 A CN 103785303A CN 201210434202 A CN201210434202 A CN 201210434202A CN 103785303 A CN103785303 A CN 103785303A
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Abstract
The invention relates to a preparation method and application of a polypropylene hollow fiber hydrophobic membrane, belonging to the field of material science. The method comprises the following steps: 1) adding a polypropylene resin and a diluter into a spinning kettle, heating to 175-200 DEG C, and stirring for 0.5-3 hours to obtain a film casting solution; 2) delivering the film casting solution to a spinneret while introducing an internal setting medium to form a hollow fiber; 3) curing the hollow fiber membrane by cooling with an external setting medium, and carrying out after-drawing rolling according to the drawing ratio of 5-20; 4) extracting in an extractant; and 5) taking out the extracted membrane, and drying to remove the extractant, thereby obtaining the polypropylene hollow fiber hydrophobic membrane. When being subjected to reverse-osmosis concentrated water treatment by external-pressure vacuum membrane distillation in a petrochemical enterprise, the polypropylene hollow fiber hydrophobic membrane has the advantages of high membrane distillation flux, high desalting rate and high sewage recovery rate, and solves the problem of low membrane distillation flux and the problem in reverse-osmosis concentrated water treatment and reclamation in the polypropylene hollow fiber hydrophobic membrane in the prior art.
Description
Technical field
The invention belongs to material science, relate to a kind of preparation and application process of polypropylene hollow fiber hydrophobic membrane, relate more specifically to a kind of preparation and application process of the polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation.
Background technology
The high salt of certain petroleum chemical enterprise, high organic wastewater, remaining reverse osmosis concentrated water after two membrane process are processed reuse, main water quality characteristic is: dense coolant-temperature gage is 55 ~ 65 ℃; Dense water power is led 25000 ~ 35000 μ s/cm, pH 7 ~ 8,20 ~ 50 times of colourities, TOC 100-200 mg/L, NO
3 -10000 ~ 20000 mg/L, SO
4 2-7000 ~ 15000 mg/L, Cl
-300 ~ 500 mg/L, total iron content 1 ~ 5 mg/L.At present, this burst of dense water directly discharge owing to not finding cost-effective method to process reuse, film distillation technology receives much concern in reverse osmosis concentrated water treatment reuse field in recent years.Film distillation is to adopt dewatering microporous film take the poor film separation process as mass transfer driving force of film both sides steam pressure.In the application of film distillation technology, membrane material is basis and the core of membrane technology development and application, the distillatory membrane material of film mainly contains polytetrafluoroethylene (PTFE) (PTFE), polypropylene (PP) and Kynoar (PVDF) at present, wherein polytetrafluoroethylene (PTFE) hydrophobic membrane mostly is Flat Membrane, and hollow fiber hydrophobic membrane material is mainly polypropylene (PP) and Kynoar (PVDF) material.Polypropylene (PP) is as a kind of polyolefine material, and output is large, low price, and there is good acid and alkali resistance and salting liquid performance and chemical stability, therefore become one of polyolefin film materials that should be with the most use.
Widely used polypropylene hollow fiber membrane is prepared by pulling method now, although the problem such as the method easily pore on interior exodermis exists porosity low, and pore-size distribution is wide, and flux is low is difficult to meet the requirement of large-scale application.Water is cheap as one, the liquid of environment-protecting asepsis is conventionally used as outer setting medium and interior setting medium, and easily produces fine and close cortex for TIPS legal system for polypropylene separation membrane in phase inversion film-forming process, make microporous barrier osmotic resistance corresponding higher, be unfavorable for applying of film.Available technology adopting TIPS and unidirectional or biaxial tension method combination, prepare polyolefin micropore battery diaphragm, although can destroy cortex construction, need to first prepare sheet material and stretch again, complex process is high to equipment requirement.
Chinese patent CN101862601 discloses a kind of polypropylene hollow fiber microporous membrane and preparation method thereof, it is raw material that the method adopts polypropylene, dibutyl phthalate, fatty amine, calcium stearate, vegetable oil, different Propanolamine, methylbenzene propyl ester, or diphenyl ether is diluent, polyethylene glycol, methylphenol, polyvinylpyrrolidone, polyvinyl alcohol, isosorbite or double thioether are additive, in, outer gel media is nitrogen, water or for containing 20 ~ 100wt% diluent solution, prepare by solution, the spinning of heating, cooling, extraction series of steps is prepared polypropylene hollow fiber microporous membrane, the outer gel media adopting in the method easily causes the densification of hollow fiber microporous membrane outer surface, or the problem such as inner surface hole rate is low.
Chinese patent CN102228804A discloses a kind of hydrophobic microporous polypropylene membrane and preparation method thereof, the method adopts scrapes embrane method, preparation efficiency is low, Chinese patent CN102284404A discloses a kind of tubular membrane for film distillation, diameter reaches 10-20mm, and much larger than hollow-fibre membrane, Flat Membrane and tubular membrane can cause assembly loading density low for film distillation assembly, separative efficiency is lower, and floor space is large.
Chinese patent CN102172478A discloses a kind of hydrophobic ceramic hollow fibrous membrane and has distilled for film, not only complicated process of preparation, and also stability is lower, is using ion rejection rate after 20h to drop to 92% from 99%.
The disclosed hydrophobically modified film distillation of Chinese patent CN102228801A material require carries out low pressure plasma pretreatment to membrane material, and equipment requirement is high, and variant to the surfaces externally and internally treatment effect of hollow-fibre membrane, is difficult to continuous processing.
Existing hollow fiber hydrophobic membrane is in petrochemical industry reverse osmosis concentrated water reuse process, during for the operation of external-compression type vacuum membrane distillation technique, because existing polyvinylidene fluoride dewatering film product mechanical strength is lower than hydrophobic polypropylene film product, therefore the external-compression type vacuum membrane distillation technique operation hydrophobic polypropylene film products that adopt more, but the film distillation when the external-compression type vacuum membrane distillation technique of existing hydrophobic polypropylene film is on the low side, cannot meet application requirements.
Summary of the invention
In order to solve polypropylene hollow fiber hydrophobic membrane prepared by prior art being applied to the problems such as in external-compression type vacuum membrane distillation process, rejection is unstable, flux of membrane distillation is low, the invention provides a kind of preparation method of polypropylene hollow fiber hydrophobic membrane, and this film is used for to the processing of reverse osmosis concentrated water external-compression type vacuum membrane distillation technique.
A preparation method for polypropylene hollow fiber hydrophobic membrane, comprises the following steps:
1) in the spinning still with agitating device, add acrylic resin, diluent and additive, be heated to 175 ~ 200 ℃, and stir 0.5 ~ 3 hour under logical condition of nitrogen gas, after stopping stirring, temperature is maintained to 175 ~ 200 ℃, standing and defoaming 0.5 ~ 2 hour, obtains casting solution; Wherein, the mass percent of described acrylic resin is 10 ~ 40%, and the mass percent of described diluent is 60 ~ 90%, and described additive addition is 0.1 ~ 1% of acrylic resin quality; The melt index of described acrylic resin is 0.1 ~ 20g/10min; Described additive is polypropylene nucleater;
2) adopting gear wheel metering pump that described casting solution is delivered to temperature is 140 ~ 180 ℃ of spinning heads, is that the interior setting medium of 30 ~ 90 ℃ is incorporated in spinning head by temperature simultaneously, forms hollow-fibre membrane;
3) by described hollow-fibre membrane through excess temperature be the outer setting medium cooling curing of 10-80 ℃, described hollow-fibre membrane carried out to drawing-off simultaneously, draw ratio is 5 ~ 20, then rolling;
4) hollow-fibre membrane after rolling is put into extractant and extract, extraction time is 3 ~ 48 hours;
5) take out the film having extracted, be dried and remove extractant, obtain polypropylene hollow fiber hydrophobic membrane.
Preferred embodiment is:
In described step (1), the mass percent of acrylic resin is advisable with 15 ~ 35%, preferably 18 ~ 33%, the melt index of acrylic resin is advisable with 1 ~ 8 g/10min, preferably 2 ~ 5 g/10min, and the mass percent of diluent is advisable with 65 ~ 85%, preferably 67 ~ 82%, additive is polypropylene nucleater, preferably adipic acid, benzoic acid, TMB-1, WBG or other beta nucleaters.
In in described step (2), setting medium is selected the high boiling medium that exchange can occur when the hollow-fibre membrane moulding with diluent, has avoided the generation of fine and close endodermis.
Described interior setting medium is the mixture of vegetable oil, phthalic acid ester or vegetable oil and phthalic acid ester.
Described vegetable oil is peanut oil or castor oil or soybean oil, is preferably soybean oil or castor oil.
Described phthalic acid ester is dibutyl phthalate, diamyl phthalate, phthalic acid fat in two heptan or o-phthalic acid dibutyl ester, is preferably dibutyl phthalate or o-phthalic acid dibutyl ester.
Described outer setting medium is the mixture of vegetable oil, a kind of phthalic acid ester or vegetable oil and phthalic acid ester.
Described vegetable oil is peanut oil, castor oil or soybean oil, is preferably soybean oil or castor oil.
Described phthalic acid ester is dibutyl phthalate, diamyl phthalate, phthalic acid fat in two heptan or o-phthalic acid dibutyl ester, is preferably dibutyl phthalate or o-phthalic acid dibutyl ester.
State in the mixture of vegetable oil and phthalic acid ester, the mass percent of described phthalic acid ester is 10 ~ 90%.
Draw ratio described in step 3) is 7 ~ 17.
Drying means described in step 4) adopts conventional drying means in filming technology.
Described hollow-fibre membrane is put into a kind of extractant extraction or multiple extractant extracts successively;
Described extractant is ketone, alcohol or alkane.
Described ketone is acetone; Described alcohol is methyl alcohol, ethanol or isopropyl alcohol; Described alkane is n-hexane or cyclohexane.
The membrane aperture of described polypropylene hollow fiber hydrophobic membrane is 0.10 ~ 0.28 μ m, porosity 52-80%, contact angle 133 ~ 142o, hot strength 3.9 ~ 5.8 MPa.
Use described polypropylene hollow fiber hydrophobic membrane to process the method for reverse osmosis concentrated water, comprise the following steps:
1) described polypropylene hollow fiber hydrophobic membrane assembly 3 is put into the heating water tank 1 of vacuum membrane distillation system;
2) described dense water pumps in heating water tank 1 by feed pump 2, is heated to 65 ℃ ~ 80 ℃;
3) adopt vavuum pump 5 to vacuumizing formation negative pressure in the fenestra of polypropylene hollow fiber hydrophobic membrane assembly 3, under vacuum action, gas, water vapour etc. in dense water in heating water tank 1 forms and produces water through condenser 4 condensations at inlet side through the fenestra that is immersed in the polypropylene hollow fiber hydrophobic membrane assembly 3 in heating water tank 1, and entering product water tank 6, described product water can be used as technique recycle-water;
The operating condition of described vacuum membrane distillation system is: dense water pH 7 ~ 8; 65 ℃ ~ 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.085 ~-0.095MPa.
The preferred operations condition of described vacuum membrane distillation system is: dense water pH 7.5; 68 ~ 72 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.085 ~-0.095MPa.
Described reverse osmosis concentrated water water quality characteristic is: dense coolant-temperature gage is 55 ~ 65 ℃; Dense water power is led 25000 ~ 35000 μ s/cm, pH 7 ~ 8,20 ~ 50 times of colourities, TOC 100-200 mg/L, NO
3-10000 ~ 20000 mg/L, SO
4 2-7000 ~ 15000 mg/L, Cl
-300 ~ 500 mg/L, total iron 1 ~ 5 mg/L.
The polypropylene hollow fiber hydrophobic membrane assembly 3 that described vacuum membrane distillation system adopts above-mentioned technique to prepare, membrane aperture scope is 0.10 ~ 0.28 μ m, preferably 0.15 ~ 0.22 μ m.
Described mode of heating is exhaust steam heating, electrical heating, and industrial waste heat adds a kind of or its combination of hankering.
A small amount of film that described film Distallation systm heating water tank 1 is regularly discharged distills dense water and centrally disposes.
Under described optimal operation mode, the film distillation operating flux scope of described vacuum membrane distillation system is 3 ~ 15 L/m
2h, film distillation salt rejection rate is higher than 99%.
Described vacuum membrane distillation system adopts external-compression type operation, i.e. film distillation water inlet, for directly to intake from heating water tank, vacuumizes formation negative pressure and makes vapour transmission fenestra form and produce water through condensation in doughnut fenestra.
The water rate of recovery of the external-compression type vacuum membrane distillation system of polypropylene hollow fiber hydrophobic membrane assembly prepared by the above-mentioned technique of described employing is controlled at 80%.
The essential distinction of the present invention and prior art is, the preparation method of the polypropylene hollow fiber hydrophobic membrane relating in the present invention adopts the mixture of vegetable oil or phthalic acid ester or its combination as outer setting medium, this outer setting medium has the effect of dissolved dilution agent, can exchange when the hollow-fibre membrane moulding with diluent, avoid outer surface to generate dense layer surface, and film is carried out the drawing-off of proper proportion in the process of setting of film, promote that outer surface generates a large amount of micropores, adopt the present invention to prepare outer surface and have the hollow-fibre membrane of a large amount of micropores with easy technique.When the polypropylene hollow fiber hydrophobic membrane relating in the present invention operates for the external-compression type vacuum membrane distillation of certain petrochemical industry reverse osmosis concentrated water, the high porosity of doughnut film outer surface has increased and stoste contact area, improve thus gasification efficiency, and then improved the flux of membrane distillation of external-compression type vacuum membrane distillation, keep high rejection simultaneously.
The invention has the beneficial effects as follows:
Polypropylene hollow fiber hydrophobic membrane outer surface of the present invention has a large amount of microcellular structures (seeing accompanying drawing 1), and outer surface porosity is high, narrow pore size distribution range.Polypropylene hollow fiber membrane prepared by the present invention is for the membrane distillation technique of certain petrochemical industry reverse osmosis concentrated water, be particularly suitable for external-compression type vacuum membrane distillation process, increase and stoste contact area for external-compression type vacuum membrane distillation process, improved gasification efficiency and flux of membrane distillation.The hydrophobic polypropylene film outer surface pore simple process relating in the present invention, easy to operate.Polypropylene hollow fiber membrane prepared by the present invention is for the external-compression type vacuum membrane distillation technique of certain petrochemical industry reverse osmosis concentrated water, having improved this strand of reverse osmosis concentrated water adopts external-compression type vacuum membrane distillation technique to process the flux of membrane distillation in reuse process, solve the processing reuse problem of this strand of reverse osmosis concentrated water, and reduced operation and cost of investment.
Accompanying drawing explanation
Fig. 1 is the outer surface SEM figure of polypropylene hollow fiber hydrophobic membrane;
Fig. 2 is the process flow diagram of external-compression type vacuum membrane distillation;
Wherein: 1: heating water tank; 2: feed pump; 3: membrane module; 4: condenser; 5: vavuum pump; 6: produce water tank;
The specific embodiment
Preparation example 1
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 18%, melt index is 2g/10min, take the mixture of soybean oil and dibutyl phthalate (DBP) as diluent, in mixture, dibutyl phthalate (DBP) mass percent is 90%, the mass percent of diluent is 73%, additive is adipic acid, addition is 0.1% of acrylic resin quality, is heated to 175 ℃, and stirs 3 hours under logical condition of nitrogen gas, stop stirring rear standing and defoaming 1 hour, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the soybean oil that is 60 ℃ using temperature is incorporated in spinning head and forms hollow-fibre membrane as interior setting medium, spinning head temperature is 145 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 40 ℃ of outer setting medium dibutyl phthalate (DBP)s, mass fraction is 80%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 7, then rolling, then hollow-fibre membrane is put into ethanol extract, extraction time is 48 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 1
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is: dense coolant-temperature gage is 65 ℃; Dense water power is led 30000 μ s/cm, pH 7.5,25 times of colourities, TOC 100 mg/L, NO
3 -15000 mg/L, SO
4 2-10000 mg/L, Cl
-300 mg/L, total iron 2 mg/L.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 1 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Application examples 2
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber hydrophobic membrane that adopts preparation example 1 to prepare is carried out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 75 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 2
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 30%, melt index is 3.1g/10min, take the mixture of soybean oil and o-phthalic acid dibutyl ester as diluent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, the mass percent of diluent is 70%, additive is WBG, addition is 0.8% of acrylic resin quality, is heated to 200 ℃, and stirs 0.5 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 0.5 hour, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and temperature is the o-phthalic acid dibutyl ester of 30 ℃, be incorporated in spinning head and form hollow-fibre membrane as interior setting medium, spinning head temperature is 180 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 10 ℃ of outer setting medium o-phthalic acid dibutyl esters, mass fraction is 10%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 17, then rolling, then hollow-fibre membrane is put into methyl alcohol and n-hexane extracts successively, extraction time is 3 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 3
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 2 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Application examples 4
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber hydrophobic membrane that adopts preparation example 2 to prepare is carried out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.085MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 3
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 33%, melt index is 5g/10min, take dibutyl phthalate as diluent, the mass percent of diluent is 70%, and additive is benzoic acid, and addition is 1% of acrylic resin quality, be heated to 180 ℃, and stir 1 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 2 hours, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the mixture that is the soybean oil of 90 ℃ and DBP using temperature is incorporated into and in spinning head, forms hollow-fibre membrane as interior setting medium, wherein the mass percent of soybean oil is 50%, and spinning head temperature is 140 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 60 ℃ of outer setting medium dibutyl phthalates, mass fraction is 60%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 10, then rolling, then hollow-fibre membrane is put into ethanol and cyclohexane extracts successively, extraction time is 24 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 5
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 3 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Application examples 6
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber hydrophobic membrane that adopts preparation example 3 to prepare is carried out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 65 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 4
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 10%, melt index is 0.1g/10min, take the mixture of soybean oil and o-phthalic acid dibutyl ester as diluent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, the mass percent of diluent is 90%, additive is benzoic acid, addition is 1% of acrylic resin quality, is heated to 180 ℃, and stirs 1 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 1 hour, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the mixture that is the soybean oil of 75 ℃ and DBP using temperature is incorporated into and in spinning head, forms hollow-fibre membrane as interior setting medium, wherein the mass percent of soybean oil is 50%, and spinning head temperature is 140 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 80 ℃ of outer setting medium dibutyl phthalates, mass fraction is 60%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 5, then rolling, then hollow-fibre membrane is put into ethanol and cyclohexane extracts successively, extraction time is 24 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 7
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 4 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 8; 72 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.090MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 5
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 40%, melt index is 20g/10min, take the mixture of soybean oil and o-phthalic acid dibutyl ester as diluent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, the mass percent of diluent is 60%, additive is benzoic acid, addition is 1% of acrylic resin quality, is heated to 180 ℃, and stirs 1 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 2 hours, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the mixture that is the soybean oil of 90 ℃ and DBP using temperature is incorporated into and in spinning head, forms hollow-fibre membrane as interior setting medium, wherein the mass percent of soybean oil is 50%, and spinning head temperature is 160 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 60 ℃ of outer setting medium dibutyl phthalates, mass fraction is 60%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 10, then rolling, then hollow-fibre membrane is put into ethanol and cyclohexane extracts successively, extraction time is 24 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 8
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is: dense coolant-temperature gage is 65 ℃; Dense water power is led 25000 μ s/cm, pH 7.5,25 times of colourities, TOC 100 mg/L, NO
3 -10000 mg/L, SO
4 2-7000 mg/L, Cl
-300 mg/L, total iron 2 mg/L.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 5 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 7; 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 6
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 15%, melt index is 1g/10min, take the mixture of soybean oil and dibutyl phthalate (DBP) as diluent, in mixture, dibutyl phthalate (DBP) mass percent is 50%, the mass percent of diluent is 85%, additive is benzoic acid, addition is 1% of acrylic resin quality, is heated to 180 ℃, and stirs 1 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 2 hours, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the mixture that is the soybean oil of 90 ℃ and DBP using temperature is incorporated into and in spinning head, forms hollow-fibre membrane as interior setting medium, wherein the mass percent of soybean oil is 50%, and spinning head temperature is 170 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 60 ℃ of outer setting medium dibutyl phthalates, mass fraction is 60%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 10, then rolling, then hollow-fibre membrane is put into ethanol and cyclohexane extracts successively, extraction time is 24 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 9
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 6 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 8; 72 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.090MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 7
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 35%, melt index is 8g/10min, take the mixture of soybean oil and dibutyl phthalate (DBP) as diluent, in mixture, dibutyl phthalate (DBP) mass percent is 50%, the mass percent of diluent is 65%, additive is benzoic acid, addition is 1% of acrylic resin quality, is heated to 180 ℃, and stirs 1 hour under logical condition of nitrogen gas, stop stirring rear standing and defoaming 2 hours, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the mixture that is the soybean oil of 90 ℃ and DBP using temperature is incorporated into and in spinning head, forms hollow-fibre membrane as interior setting medium, wherein the mass percent of soybean oil is 50%, and spinning head temperature is 165 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 60 ℃ of outer setting medium dibutyl phthalates, mass fraction is 60%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 10, then rolling, then hollow-fibre membrane is put into ethanol and cyclohexane extracts successively, extraction time is 24 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 10
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is: dense coolant-temperature gage is 65 ℃; Dense water power is led 25000 μ s/cm, pH 7.5,25 times of colourities, TOC 100 mg/L, NO
3 -10000 mg/L, SO
4 2-7000 mg/L, Cl
-300 mg/L, total iron 2 mg/L.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 7 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 7; 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
Preparation example 8
For a preparation method for the polypropylene hollow fiber hydrophobic membrane of external-compression type vacuum membrane distillation, concrete steps are as follows:
(1) in the spinning still with agitating device, add acrylic resin, diluent and additive, the mass percent of acrylic resin is 30%, melt index is 0.1g/10min, take the mixture of soybean oil and dibutyl phthalate (DBP) as diluent, in mixture, dibutyl phthalate (DBP) mass percent is 60%, the mass percent of diluent is 70%, additive is adipic acid, addition is 0.5% of acrylic resin quality, is heated to 200 ℃, and stirs 3 hours under logical condition of nitrogen gas, stop stirring rear standing and defoaming 2 hours, obtain casting solution;
(2) adopt measuring pump that casting solution is delivered to spinning head, and the mixture that is the soybean oil of 90 ℃ and DBP using temperature is incorporated into and in spinning head, forms hollow-fibre membrane as interior setting medium, wherein the mass percent of soybean oil is 50%, and spinning head temperature is 175 ℃;
(3) by the hollow-fibre membrane obtaining in step (2) through 60 ℃ of outer setting medium dibutyl phthalates, mass fraction is 60%, cooling curing, hollow-fibre membrane is carried out to drawing-off simultaneously, draw ratio is 20, then rolling, then hollow-fibre membrane is put into ethanol and cyclohexane extracts successively, extraction time is 24 hours;
(4) take out the film that extract, be dried after removing extractant and obtain polypropylene hollow fiber diffusion barrier of the present invention, its performance is shown in Table 1.
Application examples 3
The main water quality characteristic of certain petrochemical industry reverse osmosis concentrated water is with application examples 1.
The operating condition that the polypropylene hollow fiber membrane that adopts preparation example 8 to prepare carries out external-compression type vacuum membrane distillation technique is: dense water pH 7.5; 68 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation is processed the water rate of recovery 80% of this reverse osmosis concentrated water.
Under this condition, external-compression type vacuum membrane distillation technique treatment effect is listed in table 2.
The performance parameter of table 1 polypropylene hollow fiber hydrophobic membrane
| Sample | Hot strength (MPa) | Contact angle (o) | Porosity (%) | (μ m) for average pore size |
| Preparation example 1 | 4.3 | 135 | 75 | 0.15 |
| Preparation example 2 | 4.8 | 133 | 65 | 0.20 |
| Preparation example 3 | 4.6 | 138 | 60 | 0.22 |
| Preparation example 4 | 4.2 | 142 | 80 | 0.28 |
| Preparation example 5 | 3.9 | 136 | 52 | 0.10 |
| Preparation example 6 | 4.5 | 135 | 73 | 0.26 |
| Preparation example 7 | 4.0 | 134 | 56 | 0.12 |
| Preparation example 8 | 5.8 | 137 | 65 | 0.15 |
The wastewater treatment efficiency of table 2 external-compression type vacuum membrane distillation technique
| Sample | The dense water water rate of recovery, % | Average salt rejection rate, % | Flux of membrane distillation, L/m 2·h， |
| Application examples 1 | 80 | 99.7 | 7~12 |
| Application examples 2 | 80 | 99.7 | 5~9 |
| Application examples 3 | 80 | 99.5 | 8~14 |
| Application examples 4 | 80 | 99.5 | 4~7 |
| Application examples 5 | 80 | 99.5 | 8~15 |
| Application examples 6 | 80 | 99.5 | 3~6 |
| Application examples 7 | 80 | 99.5 | 3~6 |
| Application examples 8 | 80 | 99.7 | 5~9 |
| Application examples 9 | 80 | 99.5 | 3~5 |
| Application examples 10 | 80 | 99.7 | 5~10 |
| Application examples 11 | 80 | 99.5 | 4~7 |
Claims (17)
1. a preparation method for polypropylene hollow fiber hydrophobic membrane, comprises the following steps:
1) in the spinning still with agitating device, add acrylic resin, diluent and additive, be heated to 175 ~ 200 ℃, and stir 0.5 ~ 3 hour under logical condition of nitrogen gas, after stopping stirring, temperature is maintained to 175 ~ 200 ℃, standing and defoaming 0.5 ~ 2 hour, obtains casting solution; Wherein:
The mass percent of described acrylic resin is 10 ~ 40%, and the mass percent of described diluent is 60 ~ 90%, and described additive addition is 0.1 ~ 1% of acrylic resin quality; The melt index of described acrylic resin is 0.1 ~ 20g/10min; Described additive is polypropylene nucleater;
2) adopting gear wheel metering pump that described casting solution is delivered to temperature is 140 ~ 180 ℃ of spinning heads, is that the interior setting medium of 30 ~ 90 ℃ is incorporated in spinning head by temperature simultaneously, forms hollow-fibre membrane;
3) by described hollow-fibre membrane through excess temperature be the outer setting medium cooling curing of 10 ~ 80 ℃, described hollow-fibre membrane carried out to drawing-off simultaneously, draw ratio is 5 ~ 20, then rolling;
4) hollow-fibre membrane after rolling is put into extractant and extract, extraction time is 3 ~ 48 hours;
5) take out the film having extracted, be dried and remove extractant, obtain polypropylene hollow fiber hydrophobic membrane.
2. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, the mass percent of described acrylic resin is 18 ~ 33%, and the mass percent of described diluent is 67 ~ 82%.
3. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, the melt index of described acrylic resin is 2 ~ 5 g/10min.
4. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, described polypropylene nucleater is adipic acid, benzoic acid, TMB-1, WBG.
5. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, described interior setting medium is the mixture of vegetable oil, phthalic acid ester or vegetable oil and phthalic acid ester.
6. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, described outer setting medium is the mixture of vegetable oil, a kind of phthalic acid ester or vegetable oil and phthalic acid ester.
7. the preparation method of the polypropylene hollow fiber hydrophobic membrane as described in claim 5 or 6, is characterized in that, described vegetable oil is peanut oil, castor oil or soybean oil; Described phthalic acid ester is dibutyl phthalate, diamyl phthalate, phthalic acid fat in two heptan or o-phthalic acid dibutyl ester.
8. the preparation method of the polypropylene hollow fiber hydrophobic membrane as described in claim 5 or 6, is characterized in that, in the mixture of described vegetable oil and phthalic acid ester, the mass percent of described phthalic acid ester is 10 ~ 90%.
9. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, draw ratio described in step 3) is 7 ~ 17.
10. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, is characterized in that, described extractant is ketone, alcohol or alkane.
The preparation method of 11. polypropylene hollow fiber hydrophobic membrane as claimed in claim 10, is characterized in that, described ketone is acetone; Described alcohol is methyl alcohol, ethanol or isopropyl alcohol, and described alkane is n-hexane or cyclohexane.
The polypropylene hollow fiber hydrophobic membrane that the preparation method of 12. polypropylene hollow fiber hydrophobic membrane as claimed in claim 1 makes, it is characterized in that, the aperture of described film is 0.10 ~ 0.28 μ m, porosity 52-80%, contact angle 133 ~ 142o, hot strength 3.9 ~ 5.8 MPa.
13. use polypropylene hollow fiber hydrophobic membrane as claimed in claim 12 to process the method for reverse osmosis concentrated water, comprise the following steps:
1) described polypropylene hollow fiber hydrophobic membrane assembly (3) is put into the heating water tank (1) of vacuum membrane distillation system;
2) described dense water pumps in heating water tank (1) by feed pump (2), is heated to 65 ℃ ~ 80 ℃;
3) adopt vavuum pump (5) to vacuumizing formation negative pressure in the fenestra of polypropylene hollow fiber hydrophobic membrane assembly (3), gas in described dense water, the fenestra that water vapour sees through polypropylene hollow fiber hydrophobic membrane assembly (3) form and produce water through condenser (4) condensation at inlet side, and enter product water tank (6);
Described vacuum membrane distillation system adopts external-compression type operation; The operating condition of described vacuum membrane distillation system is: dense water pH 7 ~ 8; 65 ℃ ~ 80 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.085 ~-0.095MPa.
14. use polypropylene hollow fiber hydrophobic membrane as claimed in claim 13 are processed the method for reverse osmosis concentrated water, it is characterized in that, the membrane aperture scope of described polypropylene hollow fiber hydrophobic membrane assembly (3) is 0.10 ~ 0.28 μ m.
15. use polypropylene hollow fiber hydrophobic membrane as claimed in claim 13 are processed the method for reverse osmosis concentrated water, it is characterized in that, the operating condition of described vacuum membrane distillation system is: dense water pH 7.5; 68 ~ 72 ℃ of dense coolant-temperature gages; Inlet side vacuum-0.085 ~-0.095MPa.
16. use polypropylene hollow fiber hydrophobic membrane as claimed in claim 13 are processed the method for reverse osmosis concentrated water, it is characterized in that, described mode of heating is exhaust steam heating, electrical heating, and industrial waste heat adds a kind of or its combination of hankering.
17. use polypropylene hollow fiber hydrophobic membrane as claimed in claim 13 are processed the method for reverse osmosis concentrated water, it is characterized in that, the film after regularly discharge of described film Distallation systm heating water tank (1) is concentrated distills dense water.
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| CN201210434202.8A CN103785303B (en) | 2012-11-02 | A kind of preparation method and applications of polypropylene hollow fiber hydrophobic membrane |
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| CN201210434202.8A CN103785303B (en) | 2012-11-02 | A kind of preparation method and applications of polypropylene hollow fiber hydrophobic membrane |
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| CN103785303A true CN103785303A (en) | 2014-05-14 |
| CN103785303B CN103785303B (en) | 2016-11-30 |
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| CN104357927A (en) * | 2014-11-27 | 2015-02-18 | 天津华清健坤膜科技有限公司 | Spinning nozzle |
| CN105983350A (en) * | 2015-01-27 | 2016-10-05 | 天津科技大学 | Preparation method of hydrophobic polypropylene-polyethylene glycol terephthalate blended micropore membrane |
| CN109231365A (en) * | 2018-08-31 | 2019-01-18 | 浙江工业大学 | A kind of application of PIMs superthin layer composite hollow fiber membrane in separation alcohol water |
| WO2019017486A1 (en) | 2017-07-21 | 2019-01-24 | 日立化成株式会社 | Porous membrane for membrane distillation, membrane module, and membrane distillation device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104357927A (en) * | 2014-11-27 | 2015-02-18 | 天津华清健坤膜科技有限公司 | Spinning nozzle |
| CN105983350A (en) * | 2015-01-27 | 2016-10-05 | 天津科技大学 | Preparation method of hydrophobic polypropylene-polyethylene glycol terephthalate blended micropore membrane |
| WO2019017486A1 (en) | 2017-07-21 | 2019-01-24 | 日立化成株式会社 | Porous membrane for membrane distillation, membrane module, and membrane distillation device |
| CN109231365A (en) * | 2018-08-31 | 2019-01-18 | 浙江工业大学 | A kind of application of PIMs superthin layer composite hollow fiber membrane in separation alcohol water |
| CN109231365B (en) * | 2018-08-31 | 2021-07-27 | 浙江工业大学 | Application of PIMs (platelet-enhanced membranes) ultrathin layer composite hollow fiber membrane in separation of alcohol water |
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