CN102284246B - Pervaporation device and method - Google Patents
Pervaporation device and method Download PDFInfo
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- CN102284246B CN102284246B CN2011100355556A CN201110035555A CN102284246B CN 102284246 B CN102284246 B CN 102284246B CN 2011100355556 A CN2011100355556 A CN 2011100355556A CN 201110035555 A CN201110035555 A CN 201110035555A CN 102284246 B CN102284246 B CN 102284246B
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005373 pervaporation Methods 0.000 title abstract description 4
- 230000005686 electrostatic field Effects 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 17
- 230000009471 action Effects 0.000 claims abstract description 9
- 230000008595 infiltration Effects 0.000 claims description 35
- 238000001764 infiltration Methods 0.000 claims description 35
- 238000001704 evaporation Methods 0.000 claims description 31
- 230000008020 evaporation Effects 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 19
- 230000008016 vaporization Effects 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 3
- 239000012465 retentate Substances 0.000 claims 1
- 230000008878 coupling Effects 0.000 abstract description 12
- 238000010168 coupling process Methods 0.000 abstract description 12
- 238000005859 coupling reaction Methods 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 abstract description 12
- 239000012466 permeate Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 2
- 230000005684 electric field Effects 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000012546 transfer Methods 0.000 description 12
- 238000000926 separation method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
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- 238000009792 diffusion process Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 210000000416 exudates and transudate Anatomy 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- -1 dimethylaminoethyl Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
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Abstract
The invention relates to an asymmetric electrostatic field coupling pervaporation device, which comprises a raw material chamber, a permeation chamber, a membrane and electrodes, wherein an asymmetric electrostatic field can be produced by the electrodes; the electrodes comprise a plate electrode and a needle-shaped electrode; and direct current voltage of 101-104V is applied to the electrodes. Polar molecules in raw material liquid permeate through the membrane at a higher speed than that in a case of only using chemical potential gradient as thrust power to be vaporized on the surface of the membrane to form permeate steam under the double actions of chemical potential gradient and electric potential gradient formed by the asymmetric electrostatic field produced by the electrodes. The invention also relates to an asymmetric electrostatic field coupling pervaporation method.
Description
Technical field
The invention belongs to the infiltration evaporation separation field, be specifically related to utilize the apparatus and method of asymmetric Electrostatic Field Coupling infiltration evaporation, improve permeation flux and separating effect.
Background technology
Infiltration evaporation is a kind of novel membrane separation technique.The advantage that this technology is outstanding is to realize with low energy consumption the separation task that the conventional methods such as distillation, extraction, absorption have been difficult to.This technology to minor amount of water in organic solvent and mixed solvent remove and water in de-micro-content organism have significantly technical and economically advantage; Can also reaction product constantly be removed with biology and chemical reaction coupling, improve reaction conversion ratio.Therefore, Pervaporation Technology has broad application prospects and market in the industrial circles such as petrochemical industry, medicine, food, environmental protection.
The motive force of infiltration evaporation is that the film both sides are the chemical potential gradient of material liquid and film opposite side component, and visualize is the steam pressure difference of this component in the film both sides.Penetrant is divided into three steps by the process of film: at first, at the feed liquid side penetrant of film in the film surface is adsorbed and dissolves in film; Then, penetrant diffuses to the opposite side of film in film; Finally, in the desorb of film opposite side penetrant, leave film.The speed that each component sees through film has relation with the character that its quality, geometry, polarity etc. reach film.Some component and film have stronger affinity, more soluble in film (as hydrone in hydrophilic film), are dissolved in film and some component is more difficult; Be dissolved in the component in film, some faster speed in film, spread (molecule as less as diameter), some is with slower VELOCITY DIFFUSION.Due to the difference on solubility and diffusion rate, some component can see through film (being called " preferentially seeing through component ") quickly.Like this " preferentially see through component " the percentage composition that sees through side will be more shared than this component of feed side percentage composition high, so formed the enrichment of " preferentially seeing through component " seeing through side, thereby realize separating.
Dissolving is very fast with desorption process, and the diffusion process in film is slower, is the rate determining step that each component sees through film.Because the mass transfer force spread in film is only the chemical potential gradient, infiltration rate is excessively slow, and permeation flux is little, has restricted infiltration evaporation process applying in actual production.
Chinese patent CN1379697A, CN1994536A, CN101104537A, CN101596406A, CN101721914A, CN101716465A etc. disclose and have utilized electrostatic field in the film separation process.CN1379697A discloses the surface charge of utilizing electrostatic field to change suspended particulate, reduces biomembranous formation, improves membrane separating property; CN101104537A discloses and under electric field action, has formed the organic matter in strong oxidation source oxidation Decomposition water; CN101721914A discloses and in membrane filtration, has passed through electric field action, makes charged organic matter or the effects such as particle generation electrophoretic migration, electrocoagulation, reduces concentration polarization and film pollution that electrically charged organic matter or particle cause; CN101716465A, CN101596406A disclose under the DC electric field effect, make charged molecule or particulate produce the electrophoresis motion that deviates from or see through face, and the concentration polarization and the film that are suppressed at face pollute; CN1994536A discloses and has utilized electric field action in the separation process of multicomponent polysaccharide membrane, reduces concentration polarization and film and pollutes, and improves separating property.
Retrieve research both domestic and external, also by additional electrostatic force, do not improve the permeation flux of infiltration evaporation and optionally report as mass transfer force.
Summary of the invention
For deficiency of the prior art, the object of the present invention is to provide a kind of device of asymmetric Electrostatic Field Coupling infiltration evaporation, the present invention also provides a kind of method of asymmetric Electrostatic Field Coupling infiltration evaporation, has increased mass transfer force, increase permeation flux, improve separating effect.
A kind of device of asymmetric Electrostatic Field Coupling infiltration evaporation is provided according to an aspect of the present invention.In one embodiment, device comprises feed chamber, sees through chamber, film and electrode, and described electrode produces asymmetric electrostatic field.
According to device provided by the invention, in one embodiment, asymmetric electrostatic field produces between plate electrode and needle electrode, and the DC voltage that described electrode is applied is 10
1～10
4Volt.
According to device provided by the invention, described plate electrode is positioned at feed chamber one side (can in inside or the outside of feed chamber), can be the stainless steel of graphite, stainless steel, titanium, platinum or plating ruthenium, titanium etc.Needle electrode is positioned at through chamber one side (can in the inside or the outside that see through chamber), can have the material same with plate electrode.Enter the polar liquid molecule in the material liquid of feed chamber, under the electric potential gradient and chemical potential gradient double action of described asymmetric electrostatic field, the speed faster of usining when only depending on the chemical potential gradient as motive force sees through film, form and see through thing steam and flow out from seeing through chamber, seepage remaining liquid flows out from feed chamber.
According to device provided by the invention, difference according to separation system, the position of plate electrode and needle electrode can exchange, be that plate electrode is positioned at permeate chamber one side (can in the inside or the outside that see through chamber), needle electrode is positioned at feed chamber one side (can in inside or the outside of feed chamber).
According to device provided by the invention, the infiltration evaporation process is to complete under the effect of asymmetric electrostatic field.Fluid molecule is divided into polar molecule and nonpolar molecule.The symmetrical configuration of nonpolar molecule, without under External Electrical Field, the center of gravity of positive and negative charge overlaps, and dipole moment is zero, as alkane etc.The structure of polar molecule is asymmetric, and without under External Electrical Field, the center of gravity of positive and negative charge does not overlap, and certain distance is arranged between them, has intrinsic dipole moment, as water, ethanol etc.Polar molecule is not when there is no extra electric field, and due to the random warm-up movement of molecule, arrangement is disorderly.Under External Electrical Field, the positive and negative charge center of gravity of nonpolar molecule and polar molecule can be pulled open along direction of an electric field, molecule is deformed and produce an additional dipole, this process is the polarization of molecule, this dipole is induced dipole, and the deformation polarizability of its intensity size and electric-field intensity and molecule is directly proportional.In the available electric field of reality, the induced dipole of nonpolar molecule, apart from less than the dipole moment of polar molecule, is subjected to the electric field force effect very weak.Polar molecule issues to give birth in External Electrical Field and rotates, and trends towards carrying out ordered arrangement along the external electric field direction, and external electric field is stronger, arranges more neat.Under uniform electric field, complete when orientation, namely electric field energy fades to hour, reaches balance, and active force is zero, and dipole can not produce translational motion.When an additional asymmetric electrostatic field, space electric field everywhere is inhomogeneous, and dipole is to the direction migration of electric-field strength under the effect of electric field force, and this dynamics phenomenon caused by electric potential gradient is called the electromigration mass transfer.Electromigration speed is relevant with electric-field intensity, molecular polarity and molecular mass etc., and nonpolar molecule can think substantially there is no electromigration, still take random warm-up movement as main.When the system infiltration evaporation was placed in asymmetric electrostatic field, material liquid was the weak side of field intensity, and it is namely the side that field intensity is stronger through the thing steam side that film sees through side.On the one hand, identical with traditional infiltration evaporation, each component sees through the side diffusion mass transfer by the film of the material liquid side direction low concentration of high concentration, and motive force is the chemical potential gradient; On the other hand, the effect of electric field force causes the electromigration mass transfer that becomes maximum direction to electric field, and motive force is electric potential gradient.This process is called to " asymmetric Electrostatic Field Coupling infiltration evaporation ".When in the liquid of a large amount of polar molecules, containing the liquid of a small amount of nonpolar molecule, can select hydrophobic membrane, nonpolar molecule is preferentially seen through, at this moment can oppositely apply asymmetric electrostatic field, namely plate electrode is positioned at permeate chamber one side, and needle electrode is positioned at feed chamber one side.Now asymmetric electrostatic field applies opposition to polar molecule, makes it be difficult to see through film, and though can not improve the motive force that nonpolar molecule sees through film, the probability that polar molecule sees through film can be reduced, thus improve the ratio that sees through non-polar liquid in liquid.
According to device provided by the invention, described film is dense film, comprises homogeneous membrane and composite membrane.Needs according to separating different systems, can adopt any suitable known infiltrating and vaporizing membrane.
According to device provided by the invention, in one embodiment, seeing through indoor formation vacuum, the thing steam that sees through diffused into through chamber is taken away, to maintain, see through indoor lower vapour pressure.
In other embodiments of the invention, can see through chamber by inert gas purge, will take away through the exudate steam of film, see through indoor low component vapour pressure to maintain.In addition, also the exudate steam that sees through film can be gone out with suitable solvent absorption, see through indoor low component vapour pressure to maintain.
According to device provided by the invention, asymmetric Electrostatic Field Coupling infiltration evaporation device also can comprise heating or other attemperators, makes the temperature of infiltration evaporation separation process remain on certain scope, and the scope of preferred infiltration evaporation operating temperature is 5～95 ℃.If film can bear, temperature also can be higher.
According to a further aspect in the invention, provide a kind of method of asymmetric Electrostatic Field Coupling infiltration evaporation, comprising: material liquid is introduced into feed chamber; Introduce the polar liquid molecule in the material liquid of described feed chamber, under the electric potential gradient double action of chemical potential gradient and asymmetric electrostatic field, the speed faster of usining when the chemical potential gradient is only arranged as motive force sees through film, and forms and see through thing steam in the vaporization of film surface, flows out from seeing through chamber; Seepage remaining liquid flows out from feed chamber.
According to method provided by the invention, in one embodiment, asymmetric electric field is produced by plate electrode and needle electrode, and the DC voltage preferably applied to described electrode is 10
1～10
4Volt.
According to method provided by the invention, the operating temperature range of described infiltration evaporation is 5～95 ℃.If film can bear, temperature also can be higher.
According to method provided by the invention, in one embodiment, described film is hydrophilic composite separating film.
According to device provided by the invention or method, comparing traditional infiltration evaporation process only has motive force of chemical potential gradient, and process of the present invention has two motive forces, i.e. chemical potential gradient and electric potential gradient.Mass transfer rate is the stack of diffusion rate and electromigration speed.Nonpolar molecule is because the effect that is subjected to electrostatic field is very weak, electrostatic field unmatchful its mass transfer is arranged substantially without impact; And the mass transfer rate of polar molecule after additional electrostatic field is fast than without electric field the time, and the raising of mass transfer rate is relevant with the dipole moment in electrostatic field, so can improve the speed of infiltration evaporation process.
The present invention is applicable to comprise the separating of liquid system (as benzene/aqueous systems) of polarity and nonpolar molecule, and the polarity that also can be used for each component differs the separation of larger liquid system, as the ethanol/water system.
The invention has the advantages that: broken through the pattern that traditional infiltration evaporation only has a mass transfer force (being the chemical potential gradient), propose by additional another mass transfer force (being electric potential gradient) of asymmetric electrostatic field of coupling thus the separation of method and apparatus raising opposed polarity molecule, by the stack of two motive forces, make the further strengthening on the basis of dissolving-diffusive separation of infiltration rate and separating effect.Because modern material is industrial and electrotechniical development is lowered the manufacturing cost of static power supply greatly, realize that the equipment manufacturing cost of coupled field is low.Therefore, can reduce energy consumption of the prior art and cost by the present invention, have applicability and good practicality widely.
The accompanying drawing explanation
Accompanying drawing provides to be convenient to the understanding to present disclosure, and it forms the part of specification but does not form the restriction to any aspect of present disclosure.In the accompanying drawings:
Fig. 1 has shown the infiltration evaporation separator of an example with the form of profile.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but not as limitation of the present invention.
Embodiment
As shown in Figure 1, an exemplary asymmetric Electrostatic Field Coupling infiltration evaporation device 10, comprise feed chamber 7, see through chamber 8, flat sheet membrane 9.In one embodiment, feed chamber 7 comprises import 1 and the outlet 2 of material liquid.Material liquid is the benzene 6-1 that contains 500ppm water 6-2, material liquid volume 100ml,, the peristaltic pump circulation, flow velocity is 2.1cm/s.Feed side is normal pressure.The infiltration evaporation operating temperature is 60 ℃.Seeing through chamber 8 internal pressures is 1kPa.In feed chamber 7 and through chamber 8, implant respectively plate electrode 4 and needle electrode 5, plate electrode 4 is negative electrode, and needle electrode 5 is anode, and the voltage that imposes on two lateral electrodes is 2000 volts.
Material liquid enters feed chamber 7 by import 1, and (membrane area 16cm contacts with the face of polymethylacrylic acid dimethylaminoethyl/polyacrylonitrile composite compact film 9
2), this diffusion barrier is hydrophilic film, the minor amount of water 6-2 in material liquid sees through film 9 under the electric potential gradient double action of chemical potential gradient and the generation of asymmetric electrostatic field, and, seeing through vaporization formation steam 11 on the face of chamber side, is drawn out of from the outlet 3 through chamber 8.Seepage remaining liquid flows out from the outlet 2 of feed chamber 7.The flow direction of liquid as shown by the arrows in Figure 1.The infiltration direction of water is as shown in arrow horizontal in Fig. 1.In 5 hours infiltration evaporation processing times, the material liquid water content is down to 70ppm, and the average permeation flux of water is 5.41g/m
2.h.
Comparative Examples
Material liquid is the benzene that contains minor amount of water, operating temperature, the same embodiment of moisture content, feed chamber, see through chamber, the same embodiment of film, with the embodiment difference be to electrode, not apply DC voltage, 5 hours infiltration evaporation processing times, the material liquid water content is down to 250ppm, and the average permeation flux of resulting water is 3.28g/m
2.h.
Result: above data can learn, by additional asymmetric electrostatic field, in benzene, the infiltration rate of minor amount of water increases closely 65%, and the minor amount of water in benzene is removed faster.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment, the present invention is had been described in detail, for those skilled in the art, it still can be modified to the technical scheme that aforementioned each embodiment puts down in writing, or part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. an infiltration evaporation separating polar and nonpolar molecule or polarity differ the device of larger molecular liquid, comprise feed chamber, see through chamber, film and electrode, it is characterized in that, described film is dense film, and described electrode can produce asymmetric electrostatic field.
2. device as claimed in claim 1, is characterized in that, described electrode is plate electrode and needle electrode, and described plate electrode is positioned at described feed chamber, and described needle electrode is positioned at the described chamber that sees through.
3. device as claimed in claim 2, it is characterized in that, polar molecule in material liquid, under the electric potential gradient and chemical potential gradient double action of described asymmetric electrostatic field, the speed faster of can usining when the chemical potential gradient is only arranged as motive force sees through described dense film and vaporizes on the face of described dense film, forms and sees through thing steam.
4. device as claimed in claim 1, is characterized in that, the DC voltage applied to described electrode is 10
1～10
4Volt.
5. device as claimed in claim 1, is characterized in that, the operating temperature of described infiltration evaporation is 5～95 ℃.
6. an infiltration evaporation separating polar and nonpolar molecule or polarity differ the method for larger molecular liquid, comprising: material liquid is introduced to feed chamber; In described feed chamber with through between chamber, there is asymmetric electrostatic field, polar molecule in described material liquid is usingd when the chemical potential gradient is only arranged as motive force speed faster and is seen through dense film under the double action of the electric potential gradient of chemical potential gradient and asymmetric electrostatic field, and vaporization forms through thing steam on the face of described dense film, flow out from seeing through chamber; Retentate flows out from described feed chamber.
7. method as claimed in claim 6, is characterized in that, described asymmetric electrostatic field is produced by plate electrode and needle electrode.
8. method as claimed in claim 7, is characterized in that, the DC voltage applied to described plate electrode and needle electrode is 10
1～10
4Volt.
9. method as claimed in claim 6, is characterized in that, the operating temperature of described infiltration evaporation is 5～95 ℃.
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|---|---|---|---|
| CN2011100355556A CN102284246B (en) | 2011-02-10 | 2011-02-10 | Pervaporation device and method |
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|---|---|---|---|
| CN2011100355556A CN102284246B (en) | 2011-02-10 | 2011-02-10 | Pervaporation device and method |
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| CN102284246A CN102284246A (en) | 2011-12-21 |
| CN102284246B true CN102284246B (en) | 2013-11-27 |
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