CN103785303B - A kind of preparation method and applications of polypropylene hollow fiber hydrophobic membrane - Google Patents

A kind of preparation method and applications of polypropylene hollow fiber hydrophobic membrane Download PDF

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CN103785303B
CN103785303B CN201210434202.8A CN201210434202A CN103785303B CN 103785303 B CN103785303 B CN 103785303B CN 201210434202 A CN201210434202 A CN 201210434202A CN 103785303 B CN103785303 B CN 103785303B
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hollow fiber
membrane
hydrophobic membrane
polypropylene hollow
fiber hydrophobic
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CN103785303A (en
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张新妙
奚振宇
杨永强
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The preparation method and applications of a kind of polypropylene hollow fiber hydrophobic membrane, belong to material science.Method comprises the steps: 1) in spinning still, add acrylic resin and diluent, it is heated to 175 ~ 200 DEG C, and stirs 0.5 ~ 3 hour, obtain casting solution;2) casting solution is delivered to spinning head, is introduced by interior setting medium simultaneously, form doughnut, 3) hollow-fibre membrane cools and solidifies through outer setting medium, and carries out rolling after drawing-off, and draw ratio is 5 ~ 20,4) put in extractant and extract;5) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber hydrophobic membrane of the present invention.Polypropylene hollow fiber hydrophobic membrane is used for petroleum chemical enterprise uses external-compression type vacuum membrane distillation to carry out reverse osmosis concentrated water process, flux of membrane distillation is big, salt rejection rate and the sewage response rate are high, solve that prior art polypropylene hollow fiber hydrophobic membrane flux of membrane distillation is low and the process of reverse osmosis concentrated water and reuse problem.

Description

A kind of preparation method and applications of polypropylene hollow fiber hydrophobic membrane
Technical field
The invention belongs to material science, relate to preparation and the application process of a kind of polypropylene hollow fiber hydrophobic membrane, Relate more specifically to preparation and the application process of a kind of 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 double membrane process treatment for reuse, main The water quality characteristic is wanted to be: dense coolant-temperature gage is 55 ~ 65 DEG C;Dense water power leads 25000 ~ 35000 μ s/cm, pH 7 ~ 8, colourity 20 ~ 50 times, TOC 100-200 mg/L, NO3 - 10000 ~ 20000 mg/L, SO4 2-7000 ~ 15000 mg/L, Cl- 300 ~ 500 mg/L, always Iron content 1 ~ 5 mg/L.At present, this strand of dense water directly discharges owing to not finding cost-effective method to carry out treatment for reuse, Film distillation technology receives much concern in reverse osmosis concentrated water handling reclamation field in recent years.Membrane Materials is to use dewatering microporous film with film two Side vapor pressure differential is the membrane separating process of mass transfer driving force.In the application of film distillation technology, membrane material is then that membrane technology is sent out The basis opened up and apply and core, the membrane material of current Membrane Materials mainly has politef (PTFE), polypropylene (PP) With Kynoar (PVDF), wherein politef hydrophobic membrane mostly is Flat Membrane, and hollow fiber hydrophobic membrane material is the most poly- Propylene (PP) and Kynoar (PVDF) material.Polypropylene (PP) is as a kind of polyolefine material, and yield is big, and price is just Preferably, and there is good acid and alkali resistance and saline solution performance and chemical stability, therefore become and answer polyolefin with the most use One of membrane material.
The most widely used polypropylene hollow fiber membrane is prepared by pulling method, although the method is held on interior exodermis Easily pore, but it is low to there is porosity, pore-size distribution width, the problems such as flux is low, it is difficult to meet the requirement of large-scale application.Water is made Cheap for one, the liquid of environment-protecting asepsis, in phase inversion film-forming process, generally it is used as outer setting medium and interior solidification Medium, and prepare polypropylene separation membrane for TIPS method and easily produce the cortex of densification so that microporous membrane permeation resistance is corresponding relatively Height, is unfavorable for the popularization and application of film.Prior art uses TIPS and unidirectional or biaxial tension method combination, prepares polyolefin micro- Hole battery diaphragm, although can destroy cortex construction, however it is necessary that first preparing sheet material stretches again, and complex process, to equipment Require height.
Chinese patent CN101862601 discloses a kind of polypropylene hollow fiber microporous membrane and preparation method thereof, the method Employing polypropylene is raw material, 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 For additive, inside and outside gel media is nitrogen gas and water or is containing 20 ~ 100wt% diluent solution, prepared by solution, heats and spin Silk, cool down, extract series of steps and prepare polypropylene hollow fiber microporous membrane, during the outer gel media used in the method easily causes Hollow fiber microporous membrane outer surface is fine and close, or the problem such as inner surface porosity is low.
Chinese patent CN102228804A discloses a kind of hydrophobic microporous polypropylene membrane and preparation method thereof, and the method uses Scraping embrane method, preparation efficiency is low, and Chinese patent CN102284404A discloses a kind of tubular membrane for Membrane Materials, and diameter reaches 10-20mm, can cause assembly loading density low much larger than hollow-fibre membrane, Flat Membrane and tubular membrane for membrane component, point From inefficient, floor space is big.
Chinese patent CN102172478A discloses a kind of hydrophobic ceramic hollow-fibre membrane for Membrane Materials, not only prepares work Skill is complicated, and stability is relatively low, and after using 20h, ion rejection rate i.e. drops to 92% from 99%.
Hydrophobically modified Membrane Materials material disclosed in Chinese patent CN102228801A need membrane material is carried out low pressure etc. from Daughter pretreatment, equipment requirements is high and variant to the surfaces externally and internally treatment effect of hollow-fibre membrane, it is difficult to Continuous maching.
Existing hollow fiber hydrophobic membrane is during the reverse osmosis concentrated Water circulation of petrochemical industry, for external-compression type vacuum membrane distillation technique During operation, owing to existing polyvinylidene fluoride dewatering film product mechanical strength is less than hydrophobic polypropylene film product, therefore external-compression type The vacuum membrane distillation technique operation hydrophobic polypropylene film product that uses more, but existing hydrophobic polypropylene film is for external-compression type vacuum During membrane distillation technique, Membrane Materials is on the low side, it is impossible to meet application requirement.
Summary of the invention
The polypropylene hollow fiber hydrophobic membrane prepared to solve prior art is being applied to external-compression type vacuum membrane distillation mistake The problems such as in journey, rejection is unstable, flux of membrane distillation is low, the invention provides the system of a kind of polypropylene hollow fiber hydrophobic membrane Preparation Method, and this film is used for the process of reverse osmosis concentrated water external-compression type vacuum membrane distillation technique.
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane, comprises the following steps:
1) in the spinning still with agitating device, acrylic resin, diluent and additive are added, it is heated to 175 ~ 200 DEG C, and stir 0.5 ~ 3 hour under logical condition of nitrogen gas, after stopping stirring, temperature is maintained 175 ~ 200 DEG C, standing and defoaming 0.5 ~ 2 hour, obtain casting solution;Wherein, the mass percent of described acrylic resin is 10 ~ 40%, the quality of described diluent Percentage ratio is 60 ~ 90%, and described additive addition is the 0.1 ~ 1% of acrylic resin quality;Melting of described acrylic resin Index is 0.1 ~ 20g/10min;Described additive is polypropylene nucleater;
2) using gear wheel metering pump that described casting solution is delivered to temperature is 140 ~ 180 DEG C of spinning heads, by temperature is simultaneously The interior setting medium of 30 ~ 90 DEG C is incorporated in spinning head, forms hollow-fibre membrane;
3) by described hollow-fibre membrane through outer setting medium that excess temperature is 10-80 DEG C cooling and solidifying, simultaneously in described Hollow fiber film carries out drawing-off, and draw ratio is 5 ~ 20, then rolling;
4) being put into by the hollow-fibre membrane after rolling in extractant and extract, extraction time is 3 ~ 48 hours;
5) take out the film extracted, be dried removing 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%, and preferably 18 ~ 33%, acrylic resin Melt index be advisable with 1 ~ 8 g/10min, preferably 2 ~ 5 g/10min, the mass percent of diluent is advisable with 65 ~ 85%, excellent Selecting 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 selection is high boiling can occur when hollow-fibre membrane molding with diluent The medium of exchange, it is to avoid 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 Oleum Arachidis hypogaeae semen or Oleum Ricini or soybean oil, preferably soybean oil or Oleum Ricini.
Described phthalic acid ester is dibutyl phthalate, diamyl phthalate, phthalic acid two fat in heptan Or o-phthalic acid dibutyl ester, preferably dibutyl phthalate or o-phthalic acid dibutyl ester.
Described outer setting medium is the mixing of vegetable oil, a kind of phthalic acid ester or vegetable oil and phthalic acid ester Thing.
Described vegetable oil is Oleum Arachidis hypogaeae semen, Oleum Ricini or soybean oil, preferably soybean oil or Oleum Ricini.
Described phthalic acid ester is dibutyl phthalate, diamyl phthalate, phthalic acid two fat in heptan Or o-phthalic acid dibutyl ester, preferably dibutyl phthalate or o-phthalic acid dibutyl ester.
To 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) uses drying means conventional in filming technology.
Described hollow-fibre membrane is put in a kind of extractant and is extracted successively in extraction or multiple extractant;
Described extractant is ketone, alcohol or alkane.
Described ketone is acetone;Described alcohol is methanol, ethanol or isopropanol;Described alkane is normal hexane or hexamethylene.
The membrane aperture of described polypropylene hollow fiber hydrophobic membrane is 0.10 ~ 0.28 μm, porosity 52-80%, contact angle 133 ~ 142, hot strength 3.9 ~ 5.8 MPa.
The method using described polypropylene hollow fiber hydrophobic membrane to process reverse osmosis concentrated water, comprises the following steps:
1) described polypropylene hollow fiber hydrophobic membrane assembly 3 is put into the heating water tank 1 in vacuum membrane distillation system;
2) described dense water is pumped in heating water tank 1 by feed pump 2, is heated to 65 DEG C ~ 80 DEG C;
3) use vacuum pump 5 that evacuation in the fenestra of polypropylene hollow fiber hydrophobic membrane assembly 3 is formed negative pressure, true taking out Under empty effect, the gas in dense water in heating water tank 1, water vapour etc. are through being immersed in the hollow polypropylene in heating water tank 1 The fenestra of fiber hydrophobic membrane assembly 3 is formed in the condensation of inlet side condensed device 4 and produces water, and enters product water tank 6, described product water As technique recycle-water;
The operating condition of described vacuum membrane distillation system is: dense water pH 7 ~ 8,;Dense coolant-temperature gage 65 DEG C ~ 80 DEG C;Inlet side is true Reciprocal of duty cycle-0.085 ~-0.095MPa.
The preferred operations condition of described vacuum membrane distillation system is: dense water pH 7.5;Dense coolant-temperature gage 68 ~ 72 DEG C;Inlet side Vacuum-0.085 ~-0.095MPa.
Described reverse osmosis concentrated water water quality characteristic is: dense coolant-temperature gage is 55 ~ 65 DEG C;Dense water power leads 25000 ~ 35000 μ s/cm, PH 7 ~ 8, colourity 20 ~ 50 times, TOC 100-200 mg/L, NO3- 10000 ~ 20000 mg/L, SO4 2- 7000~15000 mg/ L, Cl- 300 ~ 500 mg/L, total ferrum 1 ~ 5 mg/L.
Described vacuum membrane distillation system uses polypropylene hollow fiber hydrophobic membrane assembly 3 prepared by above-mentioned technique, fenestra Footpath scope is 0.10 ~ 0.28 μm, preferably 0.15 ~ 0.22 μm.
Described mode of heating is exhaust steam heating, and electrical heating, industrial waste heat adds the one or a combination thereof hankered.
The dense water of a small amount of Membrane Materials of described Membrane Materials system heating water tank 1 periodic exhaustion centrally disposes.
Under described optimal operation mode, the Membrane Materials operating flux scope of described vacuum membrane distillation system is 3 ~ 15 L/ m2H, Membrane Materials salt rejection rate is higher than 99%.
Described vacuum membrane distillation system uses external-compression type operation, i.e. Membrane Materials to intake as directly to intake from heating water tank, In doughnut fenestra, evacuation forms negative pressure and makes vapour transmission fenestra condensed formation product water.
The external-compression type vacuum membrane distillation system of polypropylene hollow fiber hydrophobic membrane assembly prepared by the above-mentioned technique of described employing Water Sproading rate control 80%.
The present invention is with the essential distinction of prior art, the polypropylene hollow fiber hydrophobic membrane related in the present invention Preparation method uses the mixture of vegetable oil or phthalic acid ester or a combination thereof as outer setting medium, and this outer setting medium has There is the effect of dissolved dilution agent, can exchange when hollow-fibre membrane molding with diluent, it is to avoid outer surface generates and causes Close cortex, and in the process of setting of film, film is carried out the drawing-off of proper proportion, promote that outer surface generates a large amount of micropores, use The present invention prepares outer surface with easy technique and has the hollow-fibre membrane of a large amount of micropore.The hollow polypropylene related in the present invention When fiber hydrophobic membrane is used for the external-compression type vacuum membrane distillation operation of certain petrochemical industry reverse osmosis concentrated water, the high hole of doughnut film outer surface Gap rate increases and stock solution contact area, which thereby enhances gasification efficiency, and then the film that improve external-compression type vacuum membrane distillation steams Evaporate flux, keep high rejection simultaneously.
The invention has the beneficial effects as follows:
The polypropylene hollow fiber hydrophobic membrane outer surface of the present invention has a large amount of microcellular structure (see accompanying drawing 1), outer surface aperture Gap rate is high, narrow pore size distribution range.The polypropylene hollow fiber membrane present invention prepared is used for the film of certain petrochemical industry reverse osmosis concentrated water Distillation technique, is particularly suitable for external-compression type vacuum membrane distillation process, increases and stock solution for external-compression type vacuum membrane distillation process Contact area, improves gasification efficiency and flux of membrane distillation.The hydrophobic polypropylene film outer surface pore technique related in the present invention Simplicity, easily operates.The polypropylene hollow fiber membrane present invention prepared is used for the external-compression type vacuum diaphragm of certain petrochemical industry reverse osmosis concentrated water Distillation technique, improves the Membrane Materials during this strand of reverse osmosis concentrated water employing external-compression type vacuum membrane distillation technique treatment for reuse and leads to Amount, solves the treatment for reuse problem of this strand of reverse osmosis concentrated water, and reduces 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: vacuum pump;6: produce water tank;
Detailed description of the invention
Preparation example 1
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 18%, melt index is 2g/10min, with the mixture of soybean oil and dibutyl phthalate (DBP) for dilution Agent, in mixture, dibutyl phthalate (DBP) mass percent is 90%, and the mass percent of diluent is 73%, and additive is for oneself Diacid, addition is the 0.1% of acrylic resin quality, is heated to 175 DEG C, and stirs 3 hours under logical condition of nitrogen gas, stops After stirring, standing and defoaming 1 hour, obtains casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and the soybean oil that temperature is 60 DEG C is situated between as interior solidification Matter is incorporated in spinning head formation hollow-fibre membrane, and spinneret temperature is 145 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 40 DEG C of outer setting medium dibutyl phthalate (DBP)s, matter Amount mark is 80%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 7, then rolling, then by doughnut Film is put in ethanol and is extracted, and extraction time is 48 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 1
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is: dense coolant-temperature gage is 65 DEG C;Dense water power leads 30000 μ s/cm, pH 7.5, colourity 25 times, TOC 100 mg/L, NO3 - 15000 mg/L, SO4 2-10000 mg/L, Cl- 300 mg/L, total ferrum 2 mg/L。
The polypropylene hollow fiber membrane using preparation example 1 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 7.5;Dense coolant-temperature gage 80 DEG C;Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Application examples 2
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber hydrophobic membrane using preparation example 1 preparation carries out the operation bar of external-compression type vacuum membrane distillation technique Part is: dense water pH 7.5;Dense coolant-temperature gage 75 DEG C;Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of saturating dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 2
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 30%, melt index is 3.1g/10min, is dilute with the mixture of soybean oil and o-phthalic acid dibutyl ester Releasing agent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, and the mass percent of diluent is 70%, and additive is WBG, addition is the 0.8% of acrylic resin quality, is heated to 200 DEG C, and stirs 0.5 hour under logical condition of nitrogen gas, stops After stirring, standing and defoaming 0.5 hour, obtains casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by the o-phthalic acid dibutyl ester that temperature is 30 DEG C, make Being incorporated in spinning head formation hollow-fibre membrane for interior setting medium, spinneret temperature is 180 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 10 DEG C of outer setting medium o-phthalic acid dibutyl esters, matter Amount mark is 10%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 17, then rolling, then hollow is fine Dimension film is put in methanol and normal hexane and is extracted successively, and extraction time is 3 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 3
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber membrane using preparation example 2 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 7.5;Dense coolant-temperature gage 80 DEG C;Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Application examples 4
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber hydrophobic membrane using preparation example 2 preparation carries out the operation bar of external-compression type vacuum membrane distillation technique Part is: dense water pH 7.5;Dense coolant-temperature gage 80 DEG C;Inlet side vacuum-0.085MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of saturating dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 3
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 33%, melt index is 5g/10min, with dibutyl phthalate as diluent, the quality of diluent Percentage ratio is 70%, and additive is benzoic acid, and addition is the 1% of acrylic resin quality, is heated to 180 DEG C, and at logical nitrogen Under the conditions of stir 1 hour, stop standing and defoaming 2 hours after stirring, obtain casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by soybean oil that temperature is 90 DEG C and phthalic acid two The mixture of butyl ester is incorporated in spinning head formation hollow-fibre membrane, the wherein mass percent of soybean oil as interior setting medium Being 50%, spinneret temperature is 140 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 60 DEG C of outer setting medium dibutyl phthalates, matter Amount mark is 60%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 10, then rolling, then hollow is fine Dimension film is put in ethanol and hexamethylene and is extracted successively, and extraction time is 24 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 5
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber membrane using preparation example 3 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 7.5;Dense coolant-temperature gage 80 DEG C;Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Application examples 6
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber hydrophobic membrane using preparation example 3 preparation carries out the operation bar of external-compression type vacuum membrane distillation technique Part is: dense water pH 7.5;Dense coolant-temperature gage 65 DEG C;Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of saturating dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 4
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 10%, melt index is 0.1g/10min, is dilute with the mixture of soybean oil and o-phthalic acid dibutyl ester Releasing agent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, and the mass percent of diluent is 90%, and additive is Benzoic acid, addition is the 1% of acrylic resin quality, is heated to 180 DEG C, and stirs 1 hour under logical condition of nitrogen gas, stops After stirring, standing and defoaming 1 hour, obtains casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by soybean oil that temperature is 75 DEG C and phthalic acid two The mixture of butyl ester is incorporated in spinning head formation hollow-fibre membrane, the wherein mass percent of soybean oil as interior setting medium Being 50%, spinneret temperature is 140 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 80 DEG C of outer setting medium dibutyl phthalates, matter Amount mark is 60%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 5, then rolling, then by doughnut Film is put in ethanol and hexamethylene and is extracted successively, and extraction time is 24 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 7
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber membrane using preparation example 4 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 8;Dense coolant-temperature gage 72 DEG C;Inlet side vacuum-0.090MPa.It is reverse osmosis concentrated that external-compression type vacuum membrane distillation processes this The Water Sproading rate 80% of water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 5
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 40%, melt index is 20g/10min, is dilute with the mixture of soybean oil and o-phthalic acid dibutyl ester Releasing agent, in mixture, o-phthalic acid dibutyl ester mass percent is 50%, and the mass percent of diluent is 60%, and additive is Benzoic acid, addition is the 1% of acrylic resin quality, is heated to 180 DEG C, and stirs 1 hour under logical condition of nitrogen gas, stops After stirring, standing and defoaming 2 hours, obtain casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by soybean oil that temperature is 90 DEG C and phthalic acid two The mixture of butyl ester is incorporated in spinning head formation hollow-fibre membrane, the wherein mass percent of soybean oil as interior setting medium Being 50%, spinneret temperature is 160 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 60 DEG C of outer setting medium dibutyl phthalates, matter Amount mark is 60%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 10, then rolling, then hollow is fine Dimension film is put in ethanol and hexamethylene and is extracted successively, and extraction time is 24 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 8
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is: dense coolant-temperature gage is 65 DEG C;Dense water power leads 25000 μ s/cm, pH 7.5, colourity 25 times, TOC 100 mg/L, NO3 - 10000 mg/L, SO4 2-7000 mg/L, Cl- 300 mg/L, total ferrum 2 mg/ L。
The polypropylene hollow fiber membrane using preparation example 5 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 7;Dense coolant-temperature gage 80 DEG C;Inlet side vacuum-0.095MPa.It is reverse osmosis concentrated that external-compression type vacuum membrane distillation processes this The Water Sproading rate 80% of water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 6
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 15%, melt index is 1g/10min, with the mixture of soybean oil and dibutyl phthalate (DBP) for dilution Agent, in mixture, dibutyl phthalate (DBP) mass percent is 50%, and the mass percent of diluent is 85%, and additive is benzene Formic acid, addition is the 1% of acrylic resin quality, is heated to 180 DEG C, and stirs 1 hour under logical condition of nitrogen gas, stops stirring Mix rear standing and defoaming 2 hours, obtain casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by soybean oil that temperature is 90 DEG C and phthalic acid two The mixture of butyl ester is incorporated in spinning head formation hollow-fibre membrane, the wherein mass percent of soybean oil as interior setting medium Being 50%, spinneret temperature is 170 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 60 DEG C of outer setting medium dibutyl phthalates, matter Amount mark is 60%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 10, then rolling, then hollow is fine Dimension film is put in ethanol and hexamethylene and is extracted successively, and extraction time is 24 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 9
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber membrane using preparation example 6 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 8;Dense coolant-temperature gage 72 DEG C;Inlet side vacuum-0.090MPa.It is reverse osmosis concentrated that external-compression type vacuum membrane distillation processes this The Water Sproading rate 80% of water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 7
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 35%, melt index is 8g/10min, with the mixture of soybean oil and dibutyl phthalate (DBP) for dilution Agent, in mixture, dibutyl phthalate (DBP) mass percent is 50%, and the mass percent of diluent is 65%, and additive is benzene Formic acid, addition is the 1% of acrylic resin quality, is heated to 180 DEG C, and stirs 1 hour under logical condition of nitrogen gas, stops stirring Mix rear standing and defoaming 2 hours, obtain casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by soybean oil that temperature is 90 DEG C and phthalic acid two The mixture of butyl ester is incorporated in spinning head formation hollow-fibre membrane, the wherein mass percent of soybean oil as interior setting medium Being 50%, spinneret temperature is 165 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 60 DEG C of outer setting medium dibutyl phthalates, matter Amount mark is 60%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 10, then rolling, then hollow is fine Dimension film is put in ethanol and hexamethylene and is extracted successively, and extraction time is 24 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 10
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is: dense coolant-temperature gage is 65 DEG C;Dense water power leads 25000 μ s/cm, pH 7.5, colourity 25 times, TOC 100 mg/L, NO3 - 10000 mg/L, SO4 2-7000 mg/L, Cl- 300 mg/L, total ferrum 2 mg/ L。
The polypropylene hollow fiber membrane using preparation example 7 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 7;Dense coolant-temperature gage 80 DEG C;Inlet side vacuum-0.095MPa.It is reverse osmosis concentrated that external-compression type vacuum membrane distillation processes this The Water Sproading rate 80% of water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
Preparation example 8
The preparation method of a kind of polypropylene hollow fiber hydrophobic membrane for external-compression type vacuum membrane distillation, concrete steps are such as Under:
(1) in the spinning still with agitating device, acrylic resin, diluent and additive, acrylic resin are added Mass percent be 30%, melt index is 0.1g/10min, is dilute with the mixture of soybean oil and dibutyl phthalate (DBP) Releasing agent, in mixture, dibutyl phthalate (DBP) mass percent is 60%, and the mass percent of diluent is 70%, and additive is Adipic acid, addition is the 0.5% of acrylic resin quality, is heated to 200 DEG C, and stirs 3 hours under logical condition of nitrogen gas, stops Only standing and defoaming 2 hours after stirring, obtain casting solution;
(2) use dosing pump that casting solution is delivered to spinning head, and by soybean oil that temperature is 90 DEG C and phthalic acid two The mixture of butyl ester is incorporated in spinning head formation hollow-fibre membrane, the wherein mass percent of soybean oil as interior setting medium Being 50%, spinneret temperature is 175 DEG C;
(3) by the hollow-fibre membrane that obtains in step (2) through 60 DEG C of outer setting medium dibutyl phthalates, matter Amount mark is 60%, and cooling and solidifying carries out drawing-off to hollow-fibre membrane simultaneously, and draw ratio is 20, then rolling, then hollow is fine Dimension film is put in ethanol and hexamethylene and is extracted successively, and extraction time is 24 hours;
(4) take out the film extracted, after being dried removing extractant, obtain the polypropylene hollow fiber separation membrane of the present invention, Its performance is shown in Table 1.
Application examples 3
Certain main water quality characteristic of petrochemical industry reverse osmosis concentrated water is with application examples 1.
The polypropylene hollow fiber membrane using preparation example 8 preparation carries out the operating condition of external-compression type vacuum membrane distillation technique For: dense water pH 7.5;Dense coolant-temperature gage 68 DEG C;Inlet side vacuum-0.095MPa.External-compression type vacuum membrane distillation processes this reverse osmosis The Water Sproading rate 80% of dense water.
Under the conditions of this, external-compression type vacuum membrane distillation technique treatment effect is shown in Table 2.
The performance parameter of table 1 polypropylene hollow fiber hydrophobic membrane
Sample Hot strength (MPa) Contact angle () Porosity (%) Average pore size (m)
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 Dense water Water Sproading rate, % Average salt rejection rate, % Flux of membrane distillation, L/m2H,
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 (16)

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 DEG C, And stir 0.5~3 hour under logical condition of nitrogen gas, after stopping stirring, temperature is maintained 175~200 DEG C, standing and defoaming 0.5 ~2 hours, obtain casting solution;Wherein:
The mass percent of described acrylic resin is 10~33%, and the mass percent of described diluent is 60~90%, institute State that additive addition is acrylic resin quality 0.1~1%;The melt index of described acrylic resin is 0.1~20g/ 10min;Described additive is polypropylene nucleater;Described polypropylene nucleater is adipic acid, benzoic acid, TMB-1 or WBG;
2) using gear wheel metering pump, described casting solution is delivered to temperature is 140~180 DEG C of spinning heads, simultaneously by temperature be 30~ The interior setting medium of 90 DEG C is incorporated in spinning head, forms hollow-fibre membrane;
3) by described hollow-fibre membrane through the outer setting medium cooling and solidifying that excess temperature is 10~80 DEG C, simultaneously fine to described hollow Dimension film carries out drawing-off, and draw ratio is 5~20, then rolling;
4) being put into by the hollow-fibre membrane after rolling in extractant and extract, extraction time is 3~48 hours;
5) take out the film extracted, be dried removing extractant, obtain polypropylene hollow fiber hydrophobic membrane.
2. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, it is characterised in that described polypropylene tree The mass percent of fat 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, it is characterised in that described polypropylene tree The melt index of fat is 2~5g/10min.
4. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, it is characterised in that described interior solidification is situated between Matter is the mixture of vegetable oil, phthalic acid ester or vegetable oil and phthalic acid ester.
5. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, it is characterised in that described outer solidification is situated between Matter is the mixture of vegetable oil, a kind of phthalic acid ester or vegetable oil and phthalic acid ester.
6. the preparation method of the polypropylene hollow fiber hydrophobic membrane as described in claim 4 or 5, it is characterised in that described plant Oil is Oleum Arachidis hypogaeae semen, Oleum Ricini or soybean oil;Described phthalic acid ester is dibutyl phthalate, phthalic acid diamyl Ester, phthalic acid two fat in heptan or o-phthalic acid dibutyl ester.
7. the preparation method of the polypropylene hollow fiber hydrophobic membrane as described in claim 4 or 5, it is characterised in that described plant Oil is with the mixture of phthalic acid ester, and the mass percent of described phthalic acid ester is 10~90%.
8. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, it is characterised in that step 3) described in Draw ratio is 7~17.
9. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 1, it is characterised in that described extractant is Ketone, alcohol or alkane.
10. the preparation method of polypropylene hollow fiber hydrophobic membrane as claimed in claim 9, it is characterised in that described ketone is third Ketone;Described alcohol is methanol, ethanol or isopropanol, and described alkane is normal hexane or hexamethylene.
The polypropylene hollow fiber that the preparation method of 11. polypropylene hollow fiber hydrophobic membrane as claimed in claim 1 prepares is dredged Moisture film, it is characterised in that the aperture of described film is 0.10~0.28 μm, porosity 52-80%, contact angle 133~142 °, stretching Intensity 3.9~5.8MPa.
12. use polypropylene hollow fiber hydrophobic membrane as claimed in claim 11 process reverse osmosis concentrated water methods, including with Lower step:
1) described polypropylene hollow fiber hydrophobic membrane assembly (3) is put into the heating water tank (1) in vacuum membrane distillation system;
2) described dense water is pumped in heating water tank (1) by feed pump (2), is heated to 65 DEG C~80 DEG C;
3) use vacuum pump (5) that evacuation in the fenestra of polypropylene hollow fiber hydrophobic membrane assembly (3) is formed negative pressure, described dense Gas, water vapour in water condense at the condensed device of inlet side (4) through the fenestra of polypropylene hollow fiber hydrophobic membrane assembly (3) Formed and produce water, and enter product water tank (6);
Described vacuum membrane distillation system uses external-compression type operation;The operating condition of described vacuum membrane distillation system is: dense water pH7 ~8;Dense coolant-temperature gage 65 DEG C~80 DEG C;Inlet side vacuum-0.085~-0.095MPa.
13. use the method that polypropylene hollow fiber hydrophobic membrane processes reverse osmosis concentrated water, its feature as claimed in claim 12 Being, the membrane aperture scope of described polypropylene hollow fiber hydrophobic membrane assembly (3) is 0.10~0.28 μm.
14. use the method that polypropylene hollow fiber hydrophobic membrane processes reverse osmosis concentrated water, its feature as claimed in claim 12 Being, the operating condition of described vacuum membrane distillation system is: dense water pH 7.5;Dense coolant-temperature gage 68~72 DEG C;Inlet side vacuum- 0.085~-0.095MPa.
15. use the method that polypropylene hollow fiber hydrophobic membrane processes reverse osmosis concentrated water, its feature as claimed in claim 12 Being, described mode of heating is exhaust steam heating, and electrical heating, industrial waste heat adds the one or a combination thereof hankered.
16. use the method that polypropylene hollow fiber hydrophobic membrane processes reverse osmosis concentrated water, its feature as claimed in claim 12 It is, the dense water of Membrane Materials after the concentration of described Membrane Materials system heating water tank (1) periodic exhaustion.
CN201210434202.8A 2012-11-02 A kind of preparation method and applications of polypropylene hollow fiber hydrophobic membrane Active CN103785303B (en)

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US4708799A (en) * 1980-07-15 1987-11-24 Klaus Gerlach Hollow fiber membrane for plasma separation
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