CN102512984B - Preparation method for oxygen removal polymer film for water supplied for boiler - Google Patents
Preparation method for oxygen removal polymer film for water supplied for boiler Download PDFInfo
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- CN102512984B CN102512984B CN201110448930.XA CN201110448930A CN102512984B CN 102512984 B CN102512984 B CN 102512984B CN 201110448930 A CN201110448930 A CN 201110448930A CN 102512984 B CN102512984 B CN 102512984B
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Abstract
The present invention relates to a preparation method for an oxygen removal polymer film for water supplied for a boiler. The preparation method comprises: dissolving a certain proportion of a hydrophobic film material in a good solvent, controlling the temperature to 20-100 DEG C, adding a certain proportion of a pore forming agent and a nonsolvent, uniformly mixing, standing, carrying out deaeration, carrying out spinning or film scraping, and adopting a solvent phase conversion method to carry out film forming. The prepared polymer film has characteristics of high oxygen permeability rate, large oxygen flux, high permselectivity, good mechanical stability, and good chemical stability. The quality of the water treated by using the oxygen removal polymer film can reach the water standard of the industrial boiler. The film preparation process is simple, is easy to commercialize, and has a great application prospect.
Description
Technical field
The invention belongs to water treatment field, particularly a kind of preparation method of oxygen removal polymer film for water supplied for boiler.
Technical background
Dissolved oxygen refers to molecular conformation and is dissolved in the oxygen in water, and the activity of oxygen makes it to cause chemical attack with the direct chemical combination of a lot of metals.In some commercial Application, as semiconductor machining, medicine, food production and boiler water feeding aspect, all need to carry out removing of dissolved oxygen.Especially in boiler feedwater, because boiler working pressure is high, temperature is high, for feedwater quality, require very high, if the dissolved oxygen in water is not controlled, too high levels, extremely easily causes corrosion to the metal of boiler or hydraulic pipeline, and be deposited on inwall, pipeline surface, make boiler be heated inequality and cause booster, therefore in order to guarantee safe operation of the boiler, the dissolved oxygen removing in water is very necessary.
In order to meet the requirement of boiler feedwater to oxygen content, industrial multiple technologies and the equipment taked carries out deoxygenation processing to boiler feedwater.Traditional method that removes oxygen in water has thermal de-aeration, deaeration in condenser, parsing deoxygenation, reducing agent deoxygenation, electrochemical deoxidization, catalytic deoxidation etc.Because current various traditional deoxidation methods all exist certain deficiency, as complex process, occupation area of equipment is large, consume energy larger, and easily to environment, in recent years, along with developing rapidly of membrane separation technique, utilize the separated deoxygenation technology of membrane contactor to have remarkable progress.Embrane method deoxygenation technology is new gas-liquid film separation process that membrane separation technique and Degassing Technology are combined.Compare with traditional method of deoxidation, embrane method deoxidation has many advantages, for example floor space is little, operating cost is low, normal-temperature operation energy consumption is low, cleanliness without any pollution, without chemical cost, effect stability, film long service life, the upgrading that the dilatation after low pressure drop, modularization membrane module are convenient to installation and operation maintenance and flow and are increased and effluent quality require changes.
Abroad, embrane method deoxy technology has business-like application example, but the bibliographical information of correlative study is less.At home, embrane method deoxy technology is also in the starting stage, existing research is mainly deoxygenation mass transport process and the process optimization of investigating the various membrane contactors of commercialization, but to play the rare research of preparation of the high selectivity film of most critical effect and major effect in deaerating effect, the present invention is exactly a kind of preparation method for boiler water embrane method deoxygenation polymeric membrane who explores for above-mentioned situation.
Summary of the invention
Technical problem to be solved by this invention is for the application in industrial boiler feedwater film oxygen-eliminating device, and the preparation method that a kind of deaerating effect is good, oxygen flux large, height is selected the deoxygenation polymeric membrane of permeability is provided.
In embrane method deaeration plant, membrane module is to be made by the elongated hollow-fibre membrane of a lot of roots, and its effect is to strengthen gas-liquid contact area, increases mass-transfer efficiency.Film separates liquid and gas, and water enters after membrane module, at the opposite side of film, vacuumizes, inner chamber is negative pressure, and at this moment in the outside of film, the gases such as the dissolved oxygen in water and carbon dioxide will be under the effect of negative pressure, by fenestra, be drawn out of system, thereby realize gas-liquid separation.
According to separate object, be removing of dissolved gas in water, what deaerating membrane was selected is that the Polymer materialspreparation with hydrophobic property forms, thereby it is separated to realize gas-liquid film, finally reaches the object of removing gas.Film is in oxygen removal process, vacuumize pressure reduction motive force to separation process is provided, by Young-Laplace formula, learnt, fenestra radius r is less, the contact angle θ of liquid and film is larger, be that the hydrophobicity of film is stronger, water to penetrate pressure larger, therefore the hydrophobicity of the film of preparation is stronger, can make water-wet less through the possibility of fenestra, the operation that membrane module also can be stable.
The present invention comes controlling diaphragm pore morphology and the apparent character of film by macromolecule member material is added to pore-foaming agent, non-solvent etc., increases oxygen flux, increases the relative migration speed of oxygen molecule in membrane material, stops seeing through of hydrone simultaneously.
In the preparation method of deoxygenation polymeric membrane of the present invention, the raw material of employing and mass fraction thereof are:
Pore-foaming agent: 1% ~ 10%
Good solvent: 45% ~ 87%
Non-solvent: 0% ~ 5%
Hydrophobic membrane material: 12% ~ 40%
Preparation process is as follows:
A in the good solvent of formula ratio, controls temperature at 20 ~ 100 ℃ by the hydrophobic membrane Material Addition of formulation content, and vigorous agitation, is transparent settled solution after dissolving, then adds pore-foaming agent and the non-solvent of formula ratio, is uniformly mixed;
The casting solution that b obtains a step is controlled 20 ~ 100 ℃ and is carried out vacuum defoamation 1 ~ 24h in vacuum drying chamber, and above-mentioned casting solution is carried out to spinning or curtain coating knifing, and 5s ~ 600s volatilizees under 20 ~ 100 ℃ of environment;
Inversion of phases film forming in the bath of c immersion precipitation, goes out solvent with the rinsing of deionized water soak at room temperature, and after the polymeric membrane obtaining soaks with volatile organic solvent, nitrogen blowing dries up film, is finished film oxygen-eliminating device polymeric membrane.
Described pore-foaming agent is one or more the mixture in lithium chloride, sodium chloride, calcium chloride, PEG-4000, polyethylene glycol-600, polyvinylpyrrolidone;
Described good solvent is one or more in DMF, DMA, 1-METHYLPYRROLIDONE;
Described non-solvent is one or more the mixture in water, acetone, ethanol, isopropyl alcohol;
Described hydrophobic membrane material is one or more the mixture in polyethylene, polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile.
Macromolecule deaerating membrane prepared by said method, oxygen flux is large, deaerating effect good, select permeability high, can be for the preparation of the required film of embrane method oxygen-eliminating device.
The present invention is through deoxygenation evidence, and after operation a period of time, polymeric membrane can drop to 0.05mg/L from 9mg/L by the dissolved oxygen in water, can reach industrial boiler water-supply oxygen content standard.Film preparation process is simple, is easy to commercialization, has very large application prospect.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention's scope required for protection is not limited to the related scope of embodiment.
Embodiment 1
A is dissolved into 15g Kynoar in 79g DMA, controls temperature 60 C, and vigorous agitation, is transparent settled solution after dissolving, add 5g anhydrous Lithium chloride and 1g water, is uniformly mixed;
B casting solution is controlled 60 ℃ and is carried out vacuum defoamation 10h in vacuum drying chamber, and above-mentioned casting solution is carried out to spinning or curtain coating knifing, solvent flashing 5s under 60 ℃ of environment;
Inversion of phases film forming in the bath of c immersion precipitation, with the rinsing of deionized water soak at room temperature repeatedly, after the polymeric membrane obtaining is soaked with isopropyl alcohol, nitrogen blowing dries up film, is finished film oxygen-eliminating device polymeric membrane.
The contact angle of polymeric membrane adopts the DSA100 contact angle instrument of German Kruss company to measure, and with evaluated for film surface hydrophobic, the contact angle that experiment records polymeric membrane is 105.6 °;
The porosity ε of film (%) adopts dry wet film gravimetric detemination, and film is fully soaked in organic solvent, and solvent is entered in fenestra completely, and computing formula is:
, wherein,
w 1 wet film quality,
w 2 dry film quality,
ρ solvent density (the kg/m of organic solvent while being 25 ° of C
3),
ρ pVDF pVDF dry film density (kg/m
3), the porosity that records polymeric membrane is 90.15%;
The average pore size of film
r m (m) adopt the water permeable ability of film to measure, according to Guerout-Elford-Ferry formula, measure:
, wherein,
ηthe viscosity of water while being 25 ℃,
lfor the thickness (m) of film,
q t for seeing through the pure water volume (m of film in the unit interval
3/ h),
afor effective filter membrane area (m
2),
Δ Pfor operating pressure (0.1 MPa), the aperture that records polymeric membrane is 22.4nm;
Film deaerating plant adopts vacuum deaeration mode to carry out, and according to conventional film properties, measures oxygen flux
j(g/m
2h), computing formula is:
, wherein,
qfor the infiltration capacity (g) of oxygen in oxygen removal process,
afor effective filter membrane area (m
2),
Δ Tfor filtration time (h).Adopt the variation of the portable dissolved oxygen meter mensuration of the HQ30d type water quality dissolved oxygen content of U.S. HACH company, the deaerating effect of evaluated for film.Test condition: film effective area 51.35cm
2, driving pressure 0.1MPa, 30 ℃ of operating temperatures, flow of inlet water 200L/h, initial dissolution oxygen concentration 9mg/L.The oxygen flux that records polymeric membrane is 973.7mg/m
2h, water quality dissolved oxygen content is reduced to 0.04mg/L.
Embodiment 2
A is dissolved into 40g Kynoar in 45g DMF, controls temperature 50 C, and vigorous agitation, is transparent settled solution after dissolving, add 10g anhydrous calcium chloride and 5g water, is uniformly mixed;
B casting solution is controlled 30 ℃ and is carried out vacuum defoamation 24h in vacuum drying chamber, and above-mentioned casting solution is carried out to spinning or curtain coating knifing, solvent flashing 60s under 60 ℃ of environment;
Inversion of phases film forming in the bath of c immersion precipitation, with the rinsing of deionized water soak at room temperature repeatedly, after the polymeric membrane obtaining is soaked with isopropyl alcohol, nitrogen blowing dries up film, is finished film oxygen-eliminating device polymeric membrane.
According to the method for testing in embodiment 1, the performance of film is tested, the polymeric membrane porosity 18.01% finally obtaining, aperture 12.4nm, contact angle is 102.5 °, oxygen flux is 281.4mg/m
2h, water quality dissolved oxygen content is 0.10mg/L.
Embodiment 3
A is dissolved into 12g Kynoar in 87g DMA, controls temperature 60 C, and vigorous agitation, is transparent settled solution after dissolving, add 1g anhydrous Lithium chloride, is uniformly mixed;
B casting solution is controlled 30 ℃ and is carried out vacuum defoamation 10h in vacuum drying chamber, and above-mentioned casting solution is carried out to spinning or curtain coating knifing, solvent flashing 60s under 60 ℃ of environment;
Inversion of phases film forming in the bath of c immersion precipitation, with the rinsing of deionized water soak at room temperature repeatedly, after the polymeric membrane obtaining is soaked with isopropyl alcohol, nitrogen blowing dries up film, is finished film oxygen-eliminating device polymeric membrane.
According to the method for testing in embodiment 1, the performance of film is tested, the polymeric membrane porosity 87.21% finally obtaining, aperture 13.2nm, contact angle is 102.9 °, oxygen flux is 734.5mg/m
2h, water quality dissolved oxygen content is 0.18mg/L.
Embodiment 4
A is dissolved into 25g Kynoar in 70g DMF, controls temperature 60 C, and vigorous agitation, is transparent settled solution after dissolving, add 2g polyvinylpyrrolidone and 2g acetone, is uniformly mixed;
B casting solution is controlled 60 ℃ and is carried out vacuum defoamation 24h in vacuum drying chamber, and above-mentioned casting solution is carried out to spinning or curtain coating knifing, solvent flashing 600s under 60 ℃ of environment;
Inversion of phases film forming in the bath of c immersion precipitation, with the rinsing of deionized water soak at room temperature repeatedly, after the polymeric membrane obtaining is soaked with isopropyl alcohol, nitrogen blowing dries up film, is finished film oxygen-eliminating device polymeric membrane.
According to the method for testing in embodiment 1, the performance of film is tested, the polymeric membrane porosity 30.25% finally obtaining, aperture 68.3nm, contact angle is 96.03 °, oxygen flux is 435.2mg/m
2h, water quality dissolved oxygen content is 0.76mg/L.
Claims (4)
1. a preparation method for oxygen removal polymer film for water supplied for boiler, is characterized in that, the raw material of employing and mass fraction thereof are:
Pore-foaming agent 1% ~ 10%, described pore-foaming agent is one or more the mixture in lithium chloride, sodium chloride, calcium chloride, PEG-4000, polyethylene glycol-600, polyvinylpyrrolidone;
Good solvent 45% ~ 87%;
Non-solvent 0% ~ 5%;
Hydrophobic membrane material 12% ~ 40%;
Preparation process is as follows:
A in the good solvent of formula ratio, controls temperature at 20 ~ 100 ℃ by the hydrophobic membrane Material Addition of formulation content, and vigorous agitation, is transparent settled solution after dissolving, then adds pore-foaming agent and the non-solvent of formula ratio, is uniformly mixed;
The casting solution that b obtains a step is controlled 20 ~ 100 ℃ and is carried out vacuum defoamation 1 ~ 24h in vacuum drying chamber, and above-mentioned casting solution is carried out to spinning or curtain coating knifing, and 5s ~ 600s volatilizees under 20 ~ 100 ℃ of environment;
Inversion of phases film forming in the bath of c immersion precipitation, goes out solvent with the rinsing of deionized water soak at room temperature, and after the polymeric membrane obtaining soaks with volatile organic solvent, nitrogen blowing dries up film, is finished film.
2. preparation method according to claim 1, is characterized in that, described good solvent is one or more in DMF, DMA, 1-METHYLPYRROLIDONE.
3. preparation method according to claim 1 and 2, is characterized in that, described non-solvent is one or more the mixture in water, acetone, ethanol, isopropyl alcohol.
4. preparation method according to claim 1 and 2, is characterized in that, described hydrophobic membrane material is one or more the mixture in polyethylene, polypropylene, polysulfones, Kynoar, polytetrafluoroethylene (PTFE), polyacrylonitrile.
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|---|---|---|---|
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| CN109173753A (en) * | 2018-09-20 | 2019-01-11 | 中国乐凯集团有限公司 | Casting solution, ultrafiltration membrane, reverse osmosis composite membrane or Nano filtering composite membrane |
| CN112295409B (en) * | 2019-07-31 | 2022-04-05 | 天津工业大学 | Super-hydrophobic membrane with open network surface structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050773C (en) * | 1995-11-24 | 2000-03-29 | 天津纺织工学院膜天膜技术工程公司 | Polyvinylidene fluoride hollow fibre porous membrane manufacturing method |
| CN2719832Y (en) * | 2004-08-30 | 2005-08-24 | 路宁 | Boiler feedwater special film-process deaerization apparatus |
| CN101279211A (en) * | 2008-01-11 | 2008-10-08 | 北京工业大学 | Preparation of polyvinylidene fluoride dewatering microporous film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8092656B2 (en) * | 2002-10-18 | 2012-01-10 | Aquatech International Corporation | Method and apparatus for high efficiency evaporation operation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050773C (en) * | 1995-11-24 | 2000-03-29 | 天津纺织工学院膜天膜技术工程公司 | Polyvinylidene fluoride hollow fibre porous membrane manufacturing method |
| CN2719832Y (en) * | 2004-08-30 | 2005-08-24 | 路宁 | Boiler feedwater special film-process deaerization apparatus |
| CN101279211A (en) * | 2008-01-11 | 2008-10-08 | 北京工业大学 | Preparation of polyvinylidene fluoride dewatering microporous film |
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