CN102698612A - Automatic device and method for preparing prior-alcohol-permeable composite membrane - Google Patents
Automatic device and method for preparing prior-alcohol-permeable composite membrane Download PDFInfo
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- CN102698612A CN102698612A CN201210159100XA CN201210159100A CN102698612A CN 102698612 A CN102698612 A CN 102698612A CN 201210159100X A CN201210159100X A CN 201210159100XA CN 201210159100 A CN201210159100 A CN 201210159100A CN 102698612 A CN102698612 A CN 102698612A
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Abstract
The invention provides an automatic device and a method for preparing a prior-alcohol-permeable composite membrane, belonging to the field of membrane separation technology. The automatic device for preparing the alcohol-permeation-prior composite membrane comprises a constant-temperature low-temperature drying oven, an air compressor, a filtering pressure-reducing valve, a three-way valve, an atomizing nozzle, an electromagnetic valve, a loading tray, a baking lamp, an electrical box, a motor, and a membrane loader; a macromolecular polymer solution is spayed on the surface of a porous support body; a cross-linker agent and a catalyst solution are sprayed to the surface of the membrane on the support body and react with the macromolecular polymer on the surface of the membrane by chemical crosslinking action to form the dense prior-alcohol-permeable composite membrane; a plurality of separation layers can form on the surface of the support body by alternative repetition of the above operations. The automatic device and the method provided by the invention automatically finishes spaying and crosslinking of a membrane casting solution with different components, effectively overcomes the problem of large thickness of the existing dipping composite membrane, greatly increases permeation flux and also improves the membrane forming stability.
Description
Technical field
The present invention relates to a kind of automatics and method of preferentially passing through pure composite membrane that prepare, belong to the membrane separation technique field.
Background technology
Along with the aggravation of global energy crisis and environmental pollution, the development clean energy resource is imperative, and wherein alcohol fuel obtains people's extensive concern as a kind of biomass energy.Traditional fermentation method can only be produced 5% ~ 10% alcohol dilute solution, and ethanol has had strong inhibitory effects as product to reaction, has reduced fermentation efficiency and productive rate.If ethanol is shifted out from zymotic fluid in time, just improve fermentation efficiency, thereby improve the production efficiency of ethanol.
The infiltration evaporation technology can go out ethanol from the displacement of zymotic fluid Central Plains, have advantages such as itself is pollution-free, low energy consumption.For the ethanol of low concentration, use preferential alcohol permselective membrane to help the separation of ethanol.Compare preferential permeable infiltrating and vaporizing membrane, the maturity of preferential alcohol permselective membrane lags far behind.When the tradition immersion process for preparing was preferentially passed through pure composite membrane, the separating layer thickness that supporting body surface forms was thicker, causes permeation flux lower; And be prone on the surface formation defective, cause unstable properties, thereby limited its application in industry.Therefore, demand development urgently and preferentially pass through pure composite membrane novel preparation method
Summary of the invention
The object of the present invention is to provide a kind of preparation facilities and method that is used for preferentially passing through pure osmosis vaporizing compound membrane; Can through repeatedly automatically spraying technology film surface aggregate thing thickness is reduced; Guarantee the integrality of separating layer simultaneously, thereby when guaranteeing separation factor, improve the permeation flux of film.
The automatics of pure composite membrane is preferentially passed through in preparation of the present invention, it is characterized in that, comprises constant temperature low humidity drying box, air compressor, filtering pressure reducing valve, triple valve, atomizer, magnetic valve, loading dish, roasting lamp, circuit box, motor;
Constant temperature low humidity drying box is formed shell by casing, on shell, has three aperture A, B, C (the preferred 2cm in aperture), also comprises dehumidifier, heating cushion, controller, air exhauster, uviol lamp.
Dehumidifier is installed in below, casing outside, and the air port is above box house; Heating cushion is positioned at the box house below; Uviol lamp is positioned on the box house end face; Air exhauster is positioned on the box house sidewall, and controller is housed on dehumidifier, and the switch that can control air exhauster and uviol lamp presets the box house temperature; Casing is provided with windowpane, but wherein uviol lamp is surperficial except that the also emitted in ultraviolet line irradiation of illumination film.
A side is arranged to the form of door on casing, on door, offers handle, and the preferred glass window is located on the door.
Air compressor connects filtering pressure reducing valve, and filtering pressure reducing valve is connected an interface of triple valve, and two other interface of triple valve is connected with pressure pot B with pressure pot A through air delivering pipeline respectively, forms two-way output;
First via output is connected to the pressure pot A that holds macromolecule polymer solution through air delivering pipeline; Pressure pot A is connected to atomizer A through infusion pipeline through aperture A; Pressure pot A also is connected to the air delivering pipeline of atomizer A through aperture A; Also be connected with magnetic valve A in turn on the air delivering pipeline from pressure pot A to atomizer A, triple valve A and pressure-reducing valve A; The main blowing mouth of triple valve A is connected to the spray interface of atomizer A, and the secondary blowing mouth of triple valve A is connected with the jettron of atomizer A with pressure-reducing valve A;
The second tunnel output is connected to the pressure pot B that holds crosslinking agent and catalyst solution through air delivering pipeline; Pressure pot B is connected to atomizer B through woven hose through aperture B; Also B is connected to the air delivering pipeline of atomizer B to pressure pot B through the aperture; Also be connected with magnetic valve B in turn on the air delivering pipeline from pressure pot B to atomizer B, triple valve B and pressure-reducing valve B; The main blowing mouth of triple valve B is connected to the spray interface of atomizer B, and the secondary blowing mouth of triple valve B is connected with the jettron of atomizer B with pressure-reducing valve B;
Nozzle A and nozzle B in the first via output and the second tunnel output are all fixed with brandreth, and the central axis of nozzle A and nozzle B forms angle, and the liquid of ejection is uniformly sprayed on the loading dish; The loading dish is made up of nonwoven cloth cover, geometrical clamp, disk; The nonwoven cloth cover is fixed on the disk, and geometrical clamp is used for supporter is fixed on the nonwoven cloth cover; The loading dish is installed on the motor shaft through fixed axis, and motor links to each other with motor shaft, and motor is fixed on the circuit box; Motor is connected to power supply; Between circuit box and loading dish, baffle plate is housed, under circuit box and loading dish, waste liquid tank is housed.
Further, magnetic valve A, magnetic valve A are connected with circuit board (PLC) controller through hole C respectively with roasting lamp; Switch time, blanking time, order and the number of repetition of PLC controller programme-control magnetic valve that configures capable of using and roasting lamp.Simultaneously can set magnetic valve and open simultaneously, also can open respectively; Lamp goes out in the time of can also setting the normal bright or spray of roasting lamp.The electric wire that is connected usefulness on roasting lamp electric wire and the motor is connected on PLC controller and the power supply through the aperture.
Further, from the motor to the power supply, be connected with alignment circuit plate, 24V transformer and switch in turn.On the alignment circuit plate, be connected with the speed governing knob and can control motor speed.
Further; Deacration compressor, filtering pressure reducing valve, triple valve, pressure pot A, pressure pot B, magnetic valve A, magnetic valve B, PLC controller and switch place outside the constant temperature low humidity drying box; And except that pipeline and electric wire, remaining component all places constant temperature low humidity drying box inner.
Further, said air delivering pipeline and infusion pipeline are high pressure resistant flexible pipe or conduit.
Further, the rotating speed of described adjustable slowspeed machine is less than 100rpm.
Adopt above-mentioned automatics preparation preferentially to pass through pure composite membrane method, it is characterized in that, may further comprise the steps:
(a) high molecular polymer, crosslinking agent and catalyst are dissolved in respectively in the solvent,, are made into preparation liquid through stirring, ultrasonic deaeration;
(b) porous supporting body is fixed on the loading dish, regulates the slowspeed machine rotating speed simultaneously and be not higher than 100rpm;
(c) with macromolecule polymer solution place in the pressure pot A39, crosslinking agent and catalyst place in the pressure pot B40;
(d) start air compressor, regulate filtering pressure reducing valve, keep output pressure constant, set and the startup working procedure;
(e) startup constant temperature low humidity drying box is constant to temperature and humidity;
(f) air compressor (preferred 0.3MPa) under 0.2～0.4MPa pressure is sprayed into the porous supporting body surface with the high molecular polymer preparation liquid, forms the high molecular polymer thin layer in supporting body surface.
(g) under 0.2～0.4MPa pressure, crosslinking agent and catalyst preparation liquid are sprayed into high molecular polymer thin layer surface, high molecular polymer and crosslinking agent are reacted, form individual layer and preferentially pass through pure diffusion barrier;
(h) open roasting lamp etc. to the film skin drying;
(i) repeating step (f)～(h) forms multilayer in supporting body surface and preferentially passes through pure diffusion barrier.
(j) after spraying finishes, film is taken off and dries from the loading dish.
The preferred dimethyl silicone polymer of above-mentioned high molecular polymer, the preferred 0.1%-25% of its mass concentration; The preferred ethyl orthosilicate of crosslinking agent, its mass concentration preferred 1%; The preferred dibutyl tin laurate of catalyst, its mass concentration preferred 0.15%.
Described solvent can be normal heptane, n-decane, chloroform and cyclohexane.
Described supporter is micro-filtration membrane, milipore filter or NF membrane; Described support body material can be an organic polymer films, no basement membrane or organic/inorganic composite membrane.
In addition, above-mentioned spraying method also can change high molecular polymer preparation liquid, crosslinking agent and catalyst preparation liquid into and sprays simultaneously.
The preferred 2-3ml/s of spray speed more has the spray speed of selecting the high molecular polymer preparation liquid to equate with the spray speed of crosslinking agent and catalyst preparation liquid.
Described constant temperature low humidity drying box controlled humidity is below 20%, and the temperature of constant temperature low humidity drying box control is 25 ℃.
Above-mentioned spraying assembling process can at first configure spray procedure, realizes operation automatically through digital control system.
In the present invention, said cross-linking reaction is meant porous supporting body is soaked, dries; At its surperficial sprayed with adhesive high molecular polymer, spray crosslinking agent and catalyst more earlier, make it chemical crosslink reaction take place and form long-chain polymer on the film surface; Can form ultra-thin separating layer after the repeated multiple times.
Know-why of the present invention is: under certain pressure, macromolecule polymer solution is sprayed into the porous supporting body surface; Crosslinking agent and catalyst solution are sprayed into the supporter face, and form densification with the high molecular polymer of face through the chemical crosslinking effect and preferentially pass through pure diffusion barrier; So alternate repetition can form the multilayer separating layer in supporting body surface.Because this method can be sprayed into supporting body surface through mechanical atomization with solution; Solution is disperseed very evenly and as thin as a wafer at the thickness on film surface; Whole process can realize control automatically through logical program simultaneously; Therefore can control the face separating layer thickness and the uniformity, thereby improve permeation flux greatly.
The present invention is based on the advantage of the crosslinked compound preferential alcohol permselective membrane method of tradition, proposed automatic assembling device and method that pure composite membrane is preferentially passed through in a kind of more meticulous preparation.Not only can divide spraying successively respectively and can make all solution be sprayed into the support surface simultaneously.The crosslinked compound preferential alcohol permselective membrane method of tradition is combined with traditional industry aerial spraying technology; The material that had both kept crosslinked legal system film is abundant; Advantages such as technology is easy can make film surface thickness attenuate simultaneously again, and repeatedly spraying can guarantee separating layer integrality and uniformity; It is bigger to have overcome traditional system thickness, and flux is low, controllability and repeatability shortcoming such as relatively poor.
Description of drawings
The front structural map of film carrier device in Fig. 1, the automatics of the present invention;
The sectional structural map of film carrier device in Fig. 2, the automatics of the present invention;
The front structural map of constant temperature low humidity drying box 26 in Fig. 3, the automatics of the present invention;
The side surface configurations figure of constant temperature low humidity drying box 26 in Fig. 4, the automatics of the present invention;
Fig. 5, multilayer are preferentially passed through the automatics figure of pure diffusion barrier;
Under Fig. 6,100,000 times, the sem photograph of polysulfones ultrafiltration basement membrane;
Under Fig. 7,100,000 times, the sem photograph after the compound five layers of 1wt% dimethyl silicone polymer of polysulfones membrane surface are crosslinked;
Among the figure: 1. nonwoven cloth cover, 2. geometrical clamp, 3. loading dish, 4. baffle plate, 5. waste liquid tank, 6. fixed axis, 7. motor shaft; 8. adjustable slowspeed machine, 9. speed governing knob, 10. alignment circuit plate, 11.24V transformer, 12. switches, 14. circuit box, 15. electric wires; 16. dehumidifier, 17. heating cushions, 18. uviol lamps, 19. handles, 20. air exhausters, 21. low-humidity chamber controllers, 22. windowpanes; 23.2CM diametric hole A, 24.2CM diametric hole B, 25.2CM diametric hole C, 26. constant temperature low humidity drying boxes, 27. atomizer A, 28. atomizer B; 29. pressure-reducing valve A, 30. pressure-reducing valve B, 31. triple valve A, 32. triple valve B, 33. infusion pipeline A, 34. infusion pipeline B; 35. magnetic valve A, 36. magnetic valve B, 37. air delivering pipeline A, 38. air delivering pipeline B, 39. pressure pot A, 40. pressure pot B; 41. triple valve, 42. filtering pressure reducing valves, 43. air compressors, 44. roasting lamps, 45.PLC controller, 46. roasting lamp electric wires.
The specific embodiment
Through specific embodiment the present invention is elaborated below, but the present invention is not limited to following examples.
A kind of automatics of preferentially passing through pure composite membrane for preparing comprises constant temperature low humidity drying box, air compressor, filtering pressure reducing valve, triple valve, atomizer, magnetic valve, loading dish, roasting lamp, circuit box, motor;
Constant temperature low humidity drying box 26 is formed shell by casing, on shell, has three aperture A, B, C, also comprises dehumidifier 16, heating cushion 17, controller 21, air exhauster 20, uviol lamp 18.
Dehumidifier 16 is installed in below, casing outside, and the air port is above box house; Heating cushion 17 is positioned at the box house below, and uviol lamp is positioned on the box house end face, and air exhauster 20 is positioned on the box house sidewall.Controller 21 is housed on dehumidifier 16, the switch that can control air exhauster 20 and uviol lamp 18 with set the box house temperature, casing is provided with windowpane 22, but wherein uviol lamp 18 is surperficial except that the also emitted in ultraviolet line irradiation of illumination film.
A side is arranged to the form of door on casing, on door, offers handle 19, and the preferred glass window is located on the door.
First via output is connected on the liquid level of the pressure pot A39 that holds macromolecule polymer solution through air delivering pipeline; Pressure pot A39 is connected to atomizer A27 through infusion pipeline 33 (under liquid level) through aperture A24; Pressure pot A39 also is connected to the air delivering pipeline 37 of atomizer A27 through aperture A24; Also be connected with magnetic valve A35 in turn on the air delivering pipeline from pressure pot A39 to atomizer A27, triple valve A31 and pressure-reducing valve A29; The main blowing mouth of triple valve A31 is connected to the spray interface of atomizer A27, and the secondary blowing mouth of triple valve A31 is connected with the jettron of atomizer A27 with pressure-reducing valve A29;
The second tunnel output is connected to the pressure pot B40 (on the liquid level) that holds crosslinking agent and catalyst solution through air delivering pipeline; Pressure pot B40 is connected to atomizer B28 through woven hose 34 (under the liquid level) through aperture B23; Also B23 is connected to the air delivering pipeline 38 of atomizer B28 to pressure pot B40 through the aperture; Also be connected with magnetic valve B36 in turn on the air delivering pipeline from pressure pot B40 to atomizer B28, triple valve B32 and pressure-reducing valve B30; The main blowing mouth of triple valve B32 is connected to the spray interface of atomizer B28, and the secondary blowing mouth of triple valve B32 is connected with the jettron of atomizer B28 with pressure-reducing valve B30;
Nozzle A27 and nozzle B 28 in the first via output and the second tunnel output are all fixed with brandreth, and the central axis of nozzle A27 and nozzle B 28 forms angle, and the liquid of ejection is uniformly sprayed on the loading dish; (following modular construction is called for short the film carrier device) loading dish is made up of nonwoven cloth cover 1, geometrical clamp 2, disk 3; Nonwoven cloth cover 1 is fixed on the disk, and geometrical clamp 2 is used for supporter is fixed on nonwoven cloth cover 1; The loading dish is installed on the motor shaft 7 through fixed axis 6, and motor 8 links to each other with motor shaft 7, and motor 8 is fixed on the circuit box 14; Motor 8 is connected to power supply; Between circuit box 14 and loading dish, baffle plate 4 is housed, under circuit box 14 and loading dish, waste liquid tank 5 is housed.
Magnetic valve A35, magnetic valve A36 are connected with circuit board (PLC) controller 45 respectively with roasting lamp 44; Switch time, blanking time, order and the number of repetition of PLC controller 45 programme-control magnetic valves that configure capable of using and roasting lamp.Simultaneously can set magnetic valve and open simultaneously, also can open respectively; Lamp goes out in the time of can also setting the normal bright or spray of roasting lamp.The electric wire 15 that is connected usefulness on roasting lamp electric wire 46 and the motor is connected on PLC controller 45 and the power supply through aperture 25.
Be connected with alignment circuit plate 10,24V transformer 11 and switch 12 in turn from motor 8 to power supply.On alignment circuit plate 10, be connected with speed governing knob 9 and can control motor speed.
Said air delivering pipeline 37,38 and infusion pipeline 33,34 are high pressure resistant flexible pipe or conduit.
See also Fig. 1, Fig. 2, Fig. 3, Fig. 4 and Fig. 5.At first supporter is fixed on the nonwoven cloth cover 1 through four geometrical clamps 2.Control the rotating speed of loading dish 3 through speed governing knob 9.Constant temperature low humidity drying box 26 is opened, is regulated the casing internal temperatures through controller 21, treat in the casing that temperature and humidity is constant after.Air compressor 43 gas vents are connected with filtration under diminished pressure valve 42, triple valve 41 and pressure pot A39, B40 through air delivering pipeline; To belong to magnetic valve A35, the B36 of branch road more respectively through two air delivering pipelines; Triple valve A31, B32; Pressure-reducing valve A29, B30 and atomizer A27, B28 are connected, and respectively two infusion pipelines directly are being connected with the atomizer of place branch road then, thereby are forming air supply system and spraying system.Set magnetic valve A35, the opening time of B36, opening sequence, stand-by period, number of repetition through PLC controller 45, and the roasting lamp opening time.Select automatic running program then, and then form the automatics of whole preparation composite membrane.Spray speed is 2-3ml/s, and constant temperature low humidity drying box controlled humidity is at (preferred 15%) below 20%, and the temperature of constant temperature low humidity drying box control is 25 ℃.
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on the nonwoven cloth cover of loading dish, regulating the slowspeed machine rotating speed simultaneously is 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 3275gm
-2H
-1, see through ethanol content 28.28wt% in the liquid, separation factor 7.49.
Like Fig. 6 and shown in Figure 7, utilize the pure composite membrane surface texture of preferentially passing through of the above-mentioned assembling of scanning electron microscopic observation, can find that the primary surface duct is crosslinked polymer and covers fully.
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 5wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on to regulate the slowspeed machine rotating speed simultaneously on the nonwoven cloth cover of loading dish be 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 1927gm
-2H
-1, see through ethanol content 30.51wt% in the liquid, separation factor 8.34.
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on to regulate the slowspeed machine rotating speed simultaneously on the nonwoven cloth cover of loading dish be 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is the opening time of magnetic valve A35 and B36 to be 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 3373gm
-2H
-1, see through ethanol content 25.56wt% in the liquid, separation factor 6.53.
Embodiment 4
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on to regulate the slowspeed machine rotating speed simultaneously on the nonwoven cloth cover of loading dish be 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 8; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 2117gm
-2H
-1, see through ethanol content 28.23wt% in the liquid, separation factor 7.47.
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on to regulate the slowspeed machine rotating speed simultaneously on the nonwoven cloth cover of loading dish be 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 30s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 3204gm
-2H
-1, see through ethanol content 24.93wt% in the liquid, separation factor 6.3.
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 100), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on to regulate the slowspeed machine rotating speed simultaneously on the nonwoven cloth cover of loading dish be 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 3666gm
-2H
-1, see through ethanol content 21.14wt% in the liquid, separation factor 5.09.
The employing supporter is polysulfones (PS) material, flat milipore filter, and pure water flux 300LMH/bar, membrane area are 92cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, and adds through the ZSM-5 molecular sieve after the modification, silica alumina ratio is 500:1, is mixed with macromolecule polymer solution through stirring, ultrasonic deaeration; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) the polysulfones basement membrane is fixed on to regulate the slowspeed machine rotating speed simultaneously on the nonwoven cloth cover of loading dish be 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to polysulfones membrane surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, composite membrane is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place film that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The pure composite membrane that preferentially passes through of above-mentioned preparation is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 5wt% ethanol/water system, 60 ℃ of experimental temperatures, film downstream pressure 200Pa.
Recording the infiltration evaporation film properties is: permeation flux 3804gm
-2H
-1, see through ethanol content 31.18wt% in the liquid, separation factor 8.61.
The employing supporter is a silicon dioxide substrates, and membrane area is 4cm
2Used macromolecule polymer material is dimethyl silicone polymer (PDMS; Viscosity is 20000), crosslinking agent is ethyl orthosilicate (TEOS, molecular weight are 208); Catalyst is dibutyl tin laurate (molecular weight is 631), and the solvent of dimethyl silicone polymer, ethyl orthosilicate and dibutyl tin laurate is normal heptane.
(1) with normal heptane dimethyl silicone polymer is made into the solution 2000ml of 1wt%, through stir, ultrasonic deaeration is mixed with macromolecule polymer solution; With normal heptane the solution 2000ml that ethyl orthosilicate is made into 1wt% is added 0.015% dibutyl tin laurate, be mixed with cross-linking agent solution through stirring, ultrasonic deaeration;
(2) silicon dioxide substrates is fixed on the nonwoven cloth cover of loading dish, regulating the slowspeed machine rotating speed simultaneously is 100rpm;
(3) dimethyl silicone polymer solution is placed in the pressure pot A39; Ethyl orthosilicate and catalyst solution are placed in the pressure pot B40;
(4) start constant temperature low humidity drying box 26, adjust the temperature to 25 ℃, wait for that temperature in the casing, humidity are constant;
(5) start air compressor 43; Regulate filtering pressure reducing valve 42 pressure to 0.3MPa, setting spraying through PLC controller 45 is that " nozzle 27 → nozzle 28 " and note are done a circulation in proper order, and cycle-index is 5; Spray time is that the opening time of magnetic valve A35 and B36 is 5s and 3s; The loading dish is 1s and 120s in the time of staying of two site, and the lamp state that goes out when roasting lamp is set to spray starts automatic running program;
(6) under the spray pressure of 0.3MPa, with dimethyl silicone polymer solution spraying to silicon dioxide substrates surface;
(7) under the 0.3MPa spray pressure, ethyl orthosilicate and catalyst solution are sprayed into the PS membrane surface, make dimethyl silicone polymer and ethyl orthosilicate generation cross-linking reaction.
(8) roasting lamp is opened 120s and is made surperficial normal heptane solvent volatilization;
(9) repeat (6)～(8) step 5 time.
(10) after program running finishes, substrate is taken off and at room temperature place 24h from the loading dish make its solvent evaporates complete.
(11) place substrate that temperature is set is that 8h makes it crosslinked fully in 80 ℃ the baking oven.
The polyelectrolyte multilayer film of above-mentioned assembling is utilized its thickness of ellipsometer measurement, and the gross thickness that records 5 layers is 200nm.Thereby but knowledge capital is invented prepared film thickness about 200 nanometers.
Claims (10)
1. one kind prepares the automatics of preferentially passing through pure composite membrane, it is characterized in that, comprises constant temperature low humidity drying box, air compressor, filtering pressure reducing valve, triple valve, atomizer, magnetic valve, loading dish, roasting lamp, circuit box, motor;
Constant temperature low humidity drying box is formed shell by casing, on shell, has three aperture A, B, C, also comprises dehumidifier, heating cushion, controller, air exhauster, uviol lamp;
Dehumidifier is installed in below, casing outside, and the air port is above box house; Heating cushion is positioned at the box house below, and uviol lamp is positioned on the box house end face, and air exhauster is positioned on the box house sidewall, and controller is housed on dehumidifier, and the switch that can control air exhauster and uviol lamp presets the box house temperature, and casing is provided with windowpane;
Air compressor connects filtering pressure reducing valve, and filtering pressure reducing valve is connected an interface of triple valve, and two other interface of triple valve is connected with pressure pot B with pressure pot A through air delivering pipeline respectively, forms two-way output;
First via output is connected to the pressure pot A that holds macromolecule polymer solution through air delivering pipeline; Pressure pot A is connected to atomizer A through infusion pipeline through aperture A; Pressure pot A also is connected to the air delivering pipeline of atomizer A through aperture A; Also be connected with magnetic valve A in turn on the air delivering pipeline from pressure pot A to atomizer A, triple valve A and pressure-reducing valve A; The main blowing mouth of triple valve A is connected to the spray interface of atomizer A, and the secondary blowing mouth of triple valve A is connected with the jettron of atomizer A with pressure-reducing valve A;
The second tunnel output is connected to the pressure pot B that holds crosslinking agent and catalyst solution through air delivering pipeline; Pressure pot B is connected to atomizer B through woven hose through aperture B; Also B is connected to the air delivering pipeline of atomizer B to pressure pot B through the aperture; Also be connected with magnetic valve B in turn on the air delivering pipeline from pressure pot B to atomizer B, triple valve B and pressure-reducing valve B; The main blowing mouth of triple valve B is connected to the spray interface of atomizer B, and the secondary blowing mouth of triple valve B is connected with the jettron of atomizer B with pressure-reducing valve B;
Nozzle A and nozzle B in the first via output and the second tunnel output are all fixed with brandreth, and the central axis of nozzle A and nozzle B forms angle, and the liquid of ejection is uniformly sprayed on the loading dish; The loading dish is made up of nonwoven cloth cover, geometrical clamp, disk; The nonwoven cloth cover is fixed on the disk, and geometrical clamp is used for supporter is fixed on the nonwoven cloth cover; The loading dish is installed on the motor shaft through fixed axis, and motor links to each other with motor shaft, and motor is fixed on the circuit box; Motor is connected to power supply; Between circuit box and loading dish, baffle plate is housed, under circuit box and loading dish, waste liquid tank is housed.
2. according to the device of claim 1, it is characterized in that the aperture on the cabinet shell is 2cm.
3. according to the device of claim 1, it is characterized in that a side is arranged to the form of door on casing, on door, offers handle, windowpane is located on the door.
4. according to the device of claim 1, it is characterized in that magnetic valve A, magnetic valve A are connected with the circuit board controller through hole C respectively with roasting lamp; Switch time, blanking time, order and the number of repetition of circuit board controller programme-control magnetic valve that configures capable of using and roasting lamp; Simultaneously can set magnetic valve and open simultaneously, or open respectively; Lamp goes out in the time of can also setting the normal bright or spray of roasting lamp; The electric wire that is connected usefulness on roasting lamp electric wire and the motor is connected on circuit board controller and the power supply through aperture C.
5. according to the device of claim 1, it is characterized in that, from the motor to the power supply, be connected with alignment circuit plate, 24V transformer and switch in turn, on the alignment circuit plate, be connected with the speed governing knob and can control motor speed.
6. according to the said arbitrary device of claim 1-5; It is characterized in that; Deacration compressor, filtering pressure reducing valve, triple valve, pressure pot, magnetic valve, circuit board controller and switch place outside the constant temperature low humidity drying box; And except that pipeline and electric wire, remaining component all places constant temperature low humidity drying box inner.
7. according to the said arbitrary device of claim 1-5, it is characterized in that said air delivering pipeline and infusion pipeline are high pressure resistant flexible pipe or conduit.
8. the method that adopts the described device preparation of claim 1 preferentially to pass through pure composite membrane is characterized in that, may further comprise the steps:
(a) high molecular polymer, crosslinking agent and catalyst are dissolved in respectively in the solvent,, are made into preparation liquid through stirring, ultrasonic deaeration;
(b) porous supporting body is fixed on the loading dish, regulates the slowspeed machine rotating speed simultaneously and be not higher than 100rpm;
(c) with macromolecule polymer solution place in the pressure pot A39, crosslinking agent and catalyst place in the pressure pot B40;
(d) start air compressor, regulate filtering pressure reducing valve, keep output pressure constant, set and the startup working procedure;
(e) startup constant temperature low humidity drying box is constant to temperature and humidity;
(f) air compressor is sprayed into the porous supporting body surface with the high molecular polymer preparation liquid under 0.2～0.4MPa pressure, forms the high molecular polymer thin layer in supporting body surface;
(g) under 0.2～0.4MPa pressure, crosslinking agent and catalyst preparation liquid are sprayed into high molecular polymer thin layer surface, high molecular polymer and crosslinking agent are reacted, form individual layer and preferentially pass through pure diffusion barrier;
(h) open roasting lamp etc. to the film skin drying;
(i) repeating step (f)～(h) forms multilayer in supporting body surface and preferentially passes through pure diffusion barrier;
(j) after spraying finishes, film is taken off and dries from the loading dish.
9. according to the method for claim 1, it is characterized in that above-mentioned spraying method changes high molecular polymer preparation liquid, crosslinking agent and catalyst preparation liquid into and sprays simultaneously.
10. according to the method for claim 1, it is characterized in that above-mentioned high molecular polymer dimethyl silicone polymer, its mass concentration 0.1%-25%; The crosslinking agent ethyl orthosilicate, its mass concentration 1%; The catalyst dibutyl tin laurate, its mass concentration 0.15%; Described solvent can be normal heptane, n-decane, chloroform and cyclohexane; Described supporter is micro-filtration membrane, milipore filter or NF membrane; Described support body material can be an organic polymer films, no basement membrane or organic/inorganic composite membrane; Spray fast 2-3ml/s, the spray speed of high molecular polymer preparation liquid equates with the spray speed of crosslinking agent and catalyst preparation liquid;
Constant temperature low humidity drying box controlled humidity is below 20%, and the temperature of constant temperature low humidity drying box control is 25 ℃.
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