CN103611433A - Chitosan/lithium chloride composite membrane, preparation method and applications thereof - Google Patents
Chitosan/lithium chloride composite membrane, preparation method and applications thereof Download PDFInfo
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- CN103611433A CN103611433A CN201310529761.1A CN201310529761A CN103611433A CN 103611433 A CN103611433 A CN 103611433A CN 201310529761 A CN201310529761 A CN 201310529761A CN 103611433 A CN103611433 A CN 103611433A
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Abstract
The invention discloses a chitosan/lithium chloride composite membrane, a preparation method and applications thereof. The main components of the composite membrane are chitosan and lithium chloride. In the membrane, through the interaction forces between hydrogen bonds, a compact structure which is formed by drying is enable to have a high separation property, and the dampness eliminating property of chitosan membrane is changed at the same time, wherein the mass ratio of the chitosan to the lithium chloride is 20:1 to 5:2. The invention also discloses a preparation method of the chitosan/lithium chloride composite membrane. The preparation method comprises the following steps: preparing a membrane casting solution, removing insoluble substances in the membrane casting solution, eliminating the bubbles in the membrane casting solution, carrying out a tape casting process, and finally drying so as to obtain the membrane. The prepared chitosan/lithium chloride composite membrane with a proper mass ratio has a better dampness removing property, can be applied to the field of air dampness removing and cooperatively used with a membrane dampness removing technology, overcomes the shortages of large equipment, high energy consumption, and requirement on a regeneration process, and has the advantages of high performance, environment-friendliness, and economic profit.
Description
Technical field
The present invention relates to a kind of hybrid films and its preparation method and application, relate in particular to a kind of preparation method of shitosan/lithium chloride hybrid films and the application in air dewetting.
Background technology
Suitable humidity is controlled has become ubiquitous problem in the fields such as daily life, specific environment, agricultural production, industrial production, bridge construction gradually.In daily life, air humidity need to be controlled within limits, and the too high or too low human body discomfort that all can cause of relative humidity even can cause damage to health; The special interior too high meeting of environment such as museum, natatorium and civil air defense constructions and installations causes loss to drawing, sculpture, file and plant equipment etc. precious in place; In southern area of China, can cause large greenhouse to stop production in hot and humid 7-9 month, and high humility can suppress plant growth and bring out insect disease winter; In the industrial processes such as semiconductor, precision instrument, metrical instrument, electronics, need humidity strictly to control; Although there are a lot of modes to postpone main rope of suspension bridge steel wire corrosion phenomenon, the only way that can prevent main rope of suspension bridge steel wire corrosion completely that is proved to be is that the air that makes to enter whole main push-towing rope is dry air.
In recent years; understanding to dehumidifying importance is more and more deep; especially the requirement at aspects such as environmental protection, energy conservations is subject to people's attention gradually, and the shortcoming of simultaneously traditional dehumidification mode highlights day by day, and the improvement of dehumidifying technology and innovation become inevitable trend.Compare with above-mentioned dehumidification mode, membrane method dehumidifying is as a kind of emerging dehumidification mode, the advantage that is its obvious technique, power consumption, economic dispatch aspect makes this dehumidifying technology have very large development potentiality, and membrane gas dehumidifying has been applied in the systems such as monomer gas, natural gas and waste gas.
Shitosan is not only the very abundant natural polymer in a kind of source, has good film forming, has many good physicochemical properties simultaneously: biological degradability, preferably hydrophily, enough heat endurance.Researcher shows that chitosan film has lower permeability to some gas componants such as nitrogen, oxygen etc., shitosan has a large amount of amino and hydroxyl hydrophilic active group simultaneously, can to hydrone, carry out effectively separated by hydrogen bond, the hydrophily of restricted shitosan group own, the effect of the air dewetting that the technology of chitosan film by membrane method dehumidifying is applied to contain steam is not ideal enough.Therefore, need carry out modification to chitosan film, by the direct chemical modification of shitosan or with other the compound blend with good nature, form multi-functional hybrid films, enable, when keeping good separation, more stable character such as heat endurance, can effectively improve the wet-out property of film.
Summary of the invention
The technical problem to be solved in the present invention is: solve limitation and defect that traditional dehumidification mode carries out the form existence of air dewetting.The invention provides a kind of shitosan/lithium chloride hybrid films and preparation method thereof and the application in air dewetting, to make up deficiency and the defect of traditional approach, meet the needs of the aspects such as production, life.
In order to achieve the above object, the present invention has adopted following technical scheme:
Shitosan/lithium chloride hybrid films of the present invention, mainly comprises two kinds of compositions of shitosan and lithium chloride, and shitosan and lithium chloride are dissolved in 1% (v/v) acetic acid solution, forms and mixes Casting solution and be prepared into dense film structure; Described shitosan and the mass ratio of lithium chloride are 20: 1～5: 2.
As preferably, described shitosan and the mass ratio of lithium chloride are 5: 1～5: 2.
The preparation method of shitosan/lithium chloride hybrid films of the present invention, comprises the steps:
(1) weigh deacetylation and be not less than 90% shitosan and the lithium chloride of certain mass, join in the acetic acid aqueous solution of 1% (v/v), be made into mass concentration and be 2% shitosan acetic acid solution, at room temperature at the uniform velocity stir, obtain consoluet shitosan/lithium chloride mixing Casting solution;
(2) consoluet shitosan/lithium chloride mixing Casting solution is carried out to suction filtration, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride mixing Casting solution after removal of impurities is carried out to bubble removing, finally guarantee that shitosan/lithium chloride mixing Casting solution is bubble-free form under a negative atmospheric pressure;
(4) the shitosan mixing Casting solution curtain coating on casting film plate making through above-mentioned steps become to the uniform form of thickness and in vacuum drying chamber, dry also vacuum drying to constant weight.Shitosan/lithium chloride the hybrid films being prepared into is kept in drier and prevents water suction, standby.
For the variation of the wet-out property of shitosan/lithium chloride hybrid films of above-mentioned preparation, the inventor has done detailed research.Adopt membrane method dehumidifying technology, use the mixed airflow of nitrogen and steam to be used for the air of simulating different humidity, using shitosan/lithium chloride hybrid films of above-mentioned preparation as effective diffusion barrier, the water vapour permeability of the nitrogen that contains steam has been carried out to detailed measurement, comprise the steps:
(1) shitosan/lithium chloride hybrid films making through above-mentioned steps is put into the membrane module for membrane method dehumidifying, and guarantee that hybrid films has a good seal in membrane module;
(2) by the air that the contains steam air inlet side that is passed into membrane module at the uniform velocity, simultaneously in per-meate side, using dried air as the sweep gas of dehumidifying use and open the vavuum pump of per-meate side;
(3) by using humidity sensor to measure, the humidity and temperature of the air of the air inlet side of membrane module is carried out to record, simultaneously in per-meate side, record temperature and the pressure change of the vavuum pump of use;
(4) operational system a period of time, the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the side air of giving vent to anger after stablizing;
(5) measure after different humidity air, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out thickness measure to hybrid films, record the average thickness of shitosan/lithium chloride hybrid films of use;
(6) different hybrid films is carried out to the measurement of different humidity air, record the data of different hybrid films.
The invention has the beneficial effects as follows: shitosan and lithium chloride mix in certain proportion and form casting solution, pass through interaction of hydrogen bond, make the dry compact texture forming both and there is higher separating property, changed again the wet-out property of chitosan film simultaneously, the wet-out property of shitosan mixing mould first reduces rear rising, the shitosan of minimum water vapour permeability and the mixed proportion of lithium chloride are 20:1, when being greater than this ratio, increase along with mixed proportion, wet-out property equally also increases, do not destroy the compactness of chitosan film and good heat endurance, can in a high proportion of hybrid films, effectively improve wet-out property again.But, if the mixed proportion of shitosan and lithium chloride is higher than 5:2, shitosan/lithium chloride hybrid films surface of preparation can have more lithium chloride, be placed on for a long time under nature, more water can be adsorbed in surface, and then the lithium chloride that makes shitosan/lithium chloride hybrid films surface dissolves and make hybrid films flavescence, affect the wet-out property of film.Adopt membrane method dehumidifying technology, using shitosan/lithium chloride hybrid films of effective ratio as effective diffusion barrier, not only can avoid using the problems such as higher energy resource consumption that traditional dehumidification mode brings and environmental protection, there is technique simple simultaneously, the advantage such as easy to operate.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the water vapour permeability that uses of the present invention is measured.Wherein, 1 is nitrogen cylinder; 2 is valve; 3 is flowmeter; 4 is mixed instrument; 5 is bubble device; 6 is temperature and humidity inductor; 7 is pressure inductor; 8 is vavuum pump; 9 is membrane module.
Fig. 2 is the scanning electron microscope diagram sheet of chitosan film CM0.
The scanning electron microscope diagram sheet of the hybrid films CM5 that the shitosan that Fig. 3 is and lithium chloride mass ratio are 5:2.
Fig. 4 is the result demonstration figure of wet-out property.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further described in detail:
Embodiment 1
(1) use electronic balance accurately to weigh 2g deacetylation and be not less than 90% shitosan, join in the acetic acid aqueous solution of 1% (v/v), being made into gross mass is the shitosan Casting solution of 100g, at room temperature uses magnetic stirring apparatus at the uniform velocity to stir, and obtains consoluet chitosan solution.
(2) use with the Buchner funnel of two layers of filter paper consoluet shitosan Casting solution is carried out to suction filtration, by the mode of filtering, remove in solution still residual small insoluble matter;
(3) the shitosan Casting solution after using standing and associated form that vacuumize to removal of impurities carries out bubble removing, finally guarantees that shitosan Casting solution is bubble-free form under a negative atmospheric pressure;
(4) the shitosan Casting solution making through above-mentioned steps is become to the uniform form of thickness and at 50 ℃, dries in vacuum drying chamber in casting film plate liquid curtain coating, until to constant weight film forming.The chitosan film CM0 being prepared into is kept in drier and prevents water suction, standby;
(5) chitosan film making through above-mentioned steps is put in membrane module, and guaranteed that chitosan film has a good seal in membrane module;
(6) by the mode of the mixing of nitrogen and steam, simulate the air that contains steam and allow the pressure of air-flow remain an atmospheric pressure, the volume flow that adjusting enters bubble device nitrogen is 120 ml/min, and regulate the nitrogen volume flow for mixing is 70 ml/min simultaneously;
(7) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air-flow that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(8) operational system is after a period of time, and the registration that membrane module is given vent to anger in the humidity sensor of side is stable, records the give vent to anger humidity and temperature of the air that contains steam that side form intends of membrane module;
(9) regulating the volume flow enter bubble device nitrogen is 140 ml/min, regulate the nitrogen volume flow for mixing is 50 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air-flow that contains steam of simulating by adjusting, changes the content of the steam in air-flow;
(10) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(11) operational system is after a period of time, and the registration that membrane module is given vent to anger in side humidity sensor is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(12) regulating the volume flow enter bubble device nitrogen is 160 ml/min, regulate the nitrogen volume flow for mixing is 30 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(13) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air-flow that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(14) operational system is after a period of time, and the registration that membrane module is given vent to anger in side humidity sensor is stable, records the give vent to anger humidity and temperature of the air that contains steam that side form intends of membrane module;
(15) regulating the volume flow enter bubble device nitrogen is 180 ml/min, regulate the nitrogen volume flow for mixing is 10 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(16) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(17) operational system is after a period of time, and the registration that membrane module is given vent to anger in the humidity sensor of side is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(18) measure after the air-flow of different humidity, by complete the taking out from membrane module of chitosan film, use film thickness gauge to carry out side to the live part in membrane module thick, record the average thickness of the composite membrane of use.
Embodiment 2
(1) use electronic balance accurately to weigh 2g deacetylation and be not less than 90% shitosan and the lithium chloride (mass ratio of shitosan and lithium chloride is 20:1) of certain mass, join in the acetic acid aqueous solution of 1% (v/v), being made into gross mass is shitosan/lithium chloride mixing Casting solution of 100g, at room temperature use magnetic stirring apparatus at the uniform velocity to stir, obtain consoluet shitosan/lithium chloride Casting solution.
(2) use with the Buchner funnel of two layers of filter paper consoluet shitosan/lithium chloride Casting solution is carried out to suction filtration, by the mode of filtering, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride Casting solution after using standing and associated form that vacuumize to removal of impurities carries out bubble removing, finally guarantees that solution is bubble-free form under a negative atmospheric pressure;
(4) shitosan/lithium chloride Casting solution making through above-mentioned steps is become to the uniform form of thickness and at 50 ℃, dries in vacuum drying chamber in casting film plate liquid curtain coating, until to constant weight film forming.Shitosan/lithium chloride hybrid films the CM1 being prepared into is kept in drier and prevents water suction, standby;
(5) shitosan/lithium chloride hybrid films making through above-mentioned steps is put in membrane module, and guaranteed that shitosan/lithium chloride hybrid films has a good seal in membrane module;
(6) by the mode of the mixing of nitrogen and steam, simulate the air that contains steam and allow the pressure of air-flow remain an atmospheric pressure, the volume flow that adjusting enters bubble device nitrogen is 120 ml/min, and regulate the nitrogen volume flow for mixing is 70 ml/min simultaneously;
(7) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(8) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(9) regulating the volume flow enter bubble device nitrogen is 140 ml/min, regulate the nitrogen volume flow for mixing is 50 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(10) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(11) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(12) regulating the volume flow enter bubble device nitrogen is 160 ml/min, regulate the nitrogen volume flow for mixing is 30 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(13) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(14) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(15) regulating the volume flow enter bubble device nitrogen is 180 ml/min, regulate the nitrogen volume flow for mixing is 10 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(16) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(17) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(18) measure after the air-flow of all different humidity, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out side to the live part in membrane module thick, record the average thickness of the composite membrane of use.
Embodiment 3
(1) use electronic balance accurately to weigh 2g deacetylation and be not less than 90% shitosan and 0.2g lithium chloride (mass ratio of shitosan and lithium chloride is 10:1), join in the acetic acid aqueous solution of 1% (v/v), being made into gross mass is shitosan/lithium chloride mixing Casting solution of 100g, at room temperature use magnetic stirring apparatus at the uniform velocity to stir, obtain consoluet shitosan/lithium chloride Casting solution.
(2) use with the Buchner funnel of two layers of filter paper consoluet shitosan/lithium chloride Casting solution is carried out to suction filtration, by the mode of filtering, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride Casting solution after using standing and associated form that vacuumize to removal of impurities carries out bubble removing, finally guarantees that solution is bubble-free form under a negative atmospheric pressure;
(4) shitosan/lithium chloride Casting solution making through above-mentioned steps is become to the uniform form of thickness and at 50 ℃, dries in vacuum drying chamber in casting film plate liquid curtain coating, until to constant weight film forming.Shitosan/lithium chloride hybrid films the CM2 being prepared into is kept in drier and prevents water suction, standby;
(5) shitosan/lithium chloride hybrid films making through above-mentioned steps is put in membrane module, and guaranteed that shitosan/lithium chloride hybrid films has a good seal in membrane module;
(6) by the mode of the mixing of nitrogen and steam, simulate the air that contains steam and allow the pressure of air-flow remain an atmospheric pressure, the volume flow that adjusting enters bubble device nitrogen is 120 ml/min, and regulate the nitrogen volume flow for mixing is 70 ml/min simultaneously;
(7) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(8) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(9) regulating the volume flow enter bubble device nitrogen is 140 ml/min, regulate the nitrogen volume flow for mixing is 50 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(10) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(11) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(12) regulating the volume flow enter bubble device nitrogen is 160 ml/min, regulate the nitrogen volume flow for mixing is 30 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(13) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(14) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(15) regulating the volume flow enter bubble device nitrogen is 180 ml/min, regulate the nitrogen volume flow for mixing is 10 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(16) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(17) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(18) measure after the air-flow of all different humidity, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out side to the live part in membrane module thick, record the average thickness of the composite membrane of use.
Embodiment 4
(1) use electronic balance accurately to weigh 2g deacetylation and be not less than 90% shitosan and 0.4g lithium chloride (mass ratio of shitosan and lithium chloride is 5:1), join in the acetic acid aqueous solution of 1% (v/v), being made into gross mass is shitosan/lithium chloride mixing Casting solution of 100g, at room temperature use magnetic stirring apparatus at the uniform velocity to stir, obtain consoluet shitosan/lithium chloride Casting solution.
(2) use with the Buchner funnel of two layers of filter paper consoluet shitosan/lithium chloride Casting solution is carried out to suction filtration, by the mode of filtering, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride Casting solution after using standing and associated form that vacuumize to removal of impurities carries out bubble removing, finally guarantees that solution is bubble-free form under a negative atmospheric pressure;
(4) shitosan/lithium chloride Casting solution making through above-mentioned steps is become to the uniform form of thickness and at 50 ℃, dries in vacuum drying chamber in casting film plate liquid curtain coating, until to constant weight film forming.Shitosan/lithium chloride hybrid films the CM3 being prepared into is kept in drier and prevents water suction, standby;
(5) shitosan/lithium chloride hybrid films making through above-mentioned steps is put in membrane module, and guaranteed that shitosan/lithium chloride hybrid films has a good seal in membrane module;
(6) by the mode of the mixing of nitrogen and steam, simulate the air that contains steam and allow the pressure of air-flow remain an atmospheric pressure, the volume flow that adjusting enters bubble device nitrogen is 120 ml/min, and regulate the nitrogen volume flow for mixing is 70 ml/min simultaneously;
(7) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(8) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(9) regulating the volume flow enter bubble device nitrogen is 140 ml/min, regulate the nitrogen volume flow for mixing is 50 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(10) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(11) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(12) regulating the volume flow enter bubble device nitrogen is 160 ml/min, regulate the nitrogen volume flow for mixing is 30 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(13) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(14) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(15) regulating the volume flow enter bubble device nitrogen is 180 ml/min, regulate the nitrogen volume flow for mixing is 10 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(16) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(17) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(18) measure after the air-flow of all different humidity, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out side to the live part in membrane module thick, record the average thickness of the composite membrane of use.
?
(1) use electronic balance accurately to weigh 2g deacetylation and be not less than 90% shitosan and 0.6g lithium chloride (mass ratio of shitosan and lithium chloride is 10:3), join in the acetic acid aqueous solution of 1% (v/v), being made into gross mass is shitosan/lithium chloride mixing Casting solution of 100g, at room temperature use magnetic stirring apparatus at the uniform velocity to stir, obtain consoluet shitosan/lithium chloride Casting solution.
(2) use with the Buchner funnel of two layers of filter paper consoluet shitosan/lithium chloride Casting solution is carried out to suction filtration, by the mode of filtering, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride Casting solution after using standing and associated form that vacuumize to removal of impurities carries out bubble removing, finally guarantees that solution is bubble-free form under a negative atmospheric pressure;
(4) shitosan/lithium chloride Casting solution making through above-mentioned steps is become to the uniform form of thickness and at 50 ℃, dries in vacuum drying chamber in casting film plate liquid curtain coating, until to constant weight film forming.Shitosan/lithium chloride hybrid films the CM4 being prepared into is kept in drier and prevents water suction, standby;
(5) shitosan/lithium chloride hybrid films making through above-mentioned steps is put in membrane module, and guaranteed that shitosan/lithium chloride hybrid films has a good seal in membrane module;
(6) by the mode of the mixing of nitrogen and steam, simulate the air that contains steam and allow the pressure of air-flow remain an atmospheric pressure, the volume flow that adjusting enters bubble device nitrogen is 120 ml/min, and regulate the nitrogen volume flow for mixing is 70 ml/min simultaneously;
(7) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(8) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(9) regulating the volume flow enter bubble device nitrogen is 140 ml/min, regulate the nitrogen volume flow for mixing is 50 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(10) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(11) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(12) regulating the volume flow enter bubble device nitrogen is 160 ml/min, regulate the nitrogen volume flow for mixing is 30 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(13) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(14) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(15) regulating the volume flow enter bubble device nitrogen is 180 ml/min, regulate the nitrogen volume flow for mixing is 10 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(16) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(17) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(18) measure after the air-flow of all different humidity, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out side to the live part in membrane module thick, record the average thickness of the composite membrane of use.
Embodiment 6
(1) use electronic balance accurately to weigh 2g deacetylation and be not less than 90% shitosan and 0.8g lithium chloride (mass ratio of shitosan and lithium chloride is 5:2), join in the acetic acid aqueous solution of 1% (v/v), being made into gross mass is shitosan/lithium chloride mixing Casting solution of 100g, at room temperature use magnetic stirring apparatus at the uniform velocity to stir, obtain consoluet shitosan/lithium chloride Casting solution.
(2) use with the Buchner funnel of two layers of filter paper consoluet shitosan/lithium chloride Casting solution is carried out to suction filtration, by the mode of filtering, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride Casting solution after using standing and associated form that vacuumize to removal of impurities carries out bubble removing, finally guarantees that solution is bubble-free form under a negative atmospheric pressure;
(4) shitosan/lithium chloride Casting solution making through above-mentioned steps is become to the uniform form of thickness and at 50 ℃, dries in vacuum drying chamber in casting film plate liquid curtain coating, until to constant weight film forming.Shitosan/lithium chloride hybrid films the CM5 being prepared into is kept in drier and prevents water suction, standby;
(5) shitosan/lithium chloride hybrid films making through above-mentioned steps is put in membrane module, and guaranteed that shitosan/lithium chloride hybrid films has a good seal in membrane module;
(6) by the mode of the mixing of nitrogen and steam, simulate the air that contains steam and allow the pressure of air-flow remain an atmospheric pressure, the volume flow that adjusting enters bubble device nitrogen is 120 ml/min, and regulate the nitrogen volume flow for mixing is 70 ml/min simultaneously;
(7) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(8) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(9) regulating the volume flow enter bubble device nitrogen is 140 ml/min, regulate the nitrogen volume flow for mixing is 50 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(10) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(11) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(12) regulating the volume flow enter bubble device nitrogen is 160 ml/min, regulate the nitrogen volume flow for mixing is 30 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(13) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(14) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(15) regulating the volume flow enter bubble device nitrogen is 180 ml/min, regulate the nitrogen volume flow for mixing is 10 ml/min simultaneously, the volume flow of two strands of air-flows and allow the pressure of air-flow remain an atmospheric pressure in the air that contains steam of simulating by adjusting, and then change the content of the steam in air-flow;
(16) by using humidity sensor to measure, the air that contains steam of simulation is carried out moisture measurement and records concrete humidity and temperature, then the gas dehumidifying the air that contains steam of simulation as needs, be passed into the air inlet side of membrane module, simultaneously in per-meate side, use the sweep gas that dry air is membrane module per-meate side and open the vavuum pump of per-meate side, record temperature and the pressure of the vavuum pump of use;
(17) operational system is after a period of time, and the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the air that contains steam that the side form of giving vent to anger of membrane module intends;
(18) measure after the air-flow of all different humidity, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out side to the live part in membrane module thick, record the average thickness of the composite membrane of use.
Table 1 is shitosan/lithium chloride hybrid films (CM0, CM1, CM2, CM3, CM4, the measurement result of water vapour permeability CM5), the result of wet-out property is gathered to drawing (as shown in Figure 4), the water vapour permeability of shitosan mixing mould is with the increase of lithium chloride addition, totally present and first reduce the trend rising afterwards, the shitosan of minimum water vapour permeability and the mixed proportion of lithium chloride are 20:1, when being greater than this ratio, increase along with mixed proportion, wet-out property equally also increases, do not destroy the compactness of chitosan film and good heat endurance, can in a high proportion of hybrid films, effectively improve wet-out property again.
Table 1:
In above-mentioned all embodiment, use except the moist air mixed airflow that is nitrogen and steam, in order to be convenient for measuring the wet-out property of different hybrid films, as long as in actual application, meet shitosan hybrid films to air in composition there is higher separation, do not affect the subsequent treatment of air, can apply above-mentioned hybrid films and dehumidify simultaneously.
Claims (5)
1. shitosan/lithium chloride hybrid films, is characterized in that: main component comprises shitosan and lithium chloride, and shitosan and lithium chloride are dissolved in 1% (v/v) acetic acid solution, forms and mixes Casting solution and be prepared into dense film structure; The mass ratio of described shitosan and described lithium chloride is 20: 1～5: 2.
2. shitosan/lithium chloride hybrid films according to claim 1, is characterized in that: the mass ratio of described shitosan and described lithium chloride is 5: 1～5: 2.
3. the preparation method of shitosan/lithium chloride hybrid films according to claim 1, is characterized in that comprising the steps:
(1) weigh deacetylation and be not less than 90% shitosan and the lithium chloride of certain mass, join in the acetic acid aqueous solution of 1% (v/v), be made into mass concentration and be 2% shitosan acetic acid solution, at room temperature at the uniform velocity stir, obtain consoluet shitosan/lithium chloride mixing Casting solution;
(2) consoluet shitosan/lithium chloride mixing Casting solution is carried out to suction filtration, remove in solution still residual small insoluble matter;
(3) shitosan/lithium chloride mixing Casting solution after removal of impurities is carried out to bubble removing, finally guarantee that shitosan/lithium chloride mixing Casting solution is bubble-free form under a negative atmospheric pressure;
(4) the shitosan mixing Casting solution curtain coating on casting film plate making through above-mentioned steps become to the uniform form of thickness and in vacuum drying chamber, dry also vacuum drying to constant weight, shitosan/lithium chloride the hybrid films being prepared into is kept in drier and prevents water suction, standby.
4. the application of shitosan/lithium chloride hybrid films according to claim 3, is characterized in that, for separating of removing airborne steam.
5. the application of shitosan/lithium chloride hybrid films according to claim 4, is characterized in that, described shitosan/lithium chloride hybrid films is applied to by the technology of membrane method dehumidifying the air dewetting that contains steam, comprises the steps:
(1) shitosan/lithium chloride hybrid films making through above-mentioned steps is put into the membrane module for membrane method dehumidifying, and guarantee that hybrid films has a good seal in membrane module;
(2) by the air that the contains steam air inlet side that is passed into membrane module at the uniform velocity, simultaneously in per-meate side, using dried air as the sweep gas of dehumidifying use and open the vavuum pump of per-meate side;
(3) by using humidity sensor to measure, the humidity and temperature of the air of the air inlet side of membrane module is carried out to record, simultaneously in per-meate side, record temperature and the pressure change of the vavuum pump of use;
(4) operational system a period of time, the registration in the humidity sensor of the side of giving vent to anger of membrane module is stable, records the humidity and temperature of the side air of giving vent to anger after stablizing;
(5) measure after different humidity air, by complete the taking out from membrane module of shitosan/lithium chloride hybrid films, use film thickness gauge to carry out thickness measure to hybrid films, record the average thickness of shitosan/lithium chloride hybrid films of use;
(6) different hybrid films is carried out to measurement the record data of different humidity air.
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| CN112808036A (en) * | 2020-12-30 | 2021-05-18 | 中国科学院过程工程研究所 | Gas dehumidification film and preparation method and application thereof |
| CN114441379A (en) * | 2022-01-13 | 2022-05-06 | 中国乐凯集团有限公司 | Dehumidification capacity testing device and testing method for gas dehumidification film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009035413A1 (en) * | 2007-09-10 | 2009-03-19 | National University Of Singapore | A chitosan solution and method of preparing the same |
| CN103342828A (en) * | 2013-06-27 | 2013-10-09 | 华南理工大学 | Efficient moisture-permeable film prepared by a one-step process and application thereof |
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| WO2009035413A1 (en) * | 2007-09-10 | 2009-03-19 | National University Of Singapore | A chitosan solution and method of preparing the same |
| CN103342828A (en) * | 2013-06-27 | 2013-10-09 | 华南理工大学 | Efficient moisture-permeable film prepared by a one-step process and application thereof |
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| CN112808036A (en) * | 2020-12-30 | 2021-05-18 | 中国科学院过程工程研究所 | Gas dehumidification film and preparation method and application thereof |
| CN114441379A (en) * | 2022-01-13 | 2022-05-06 | 中国乐凯集团有限公司 | Dehumidification capacity testing device and testing method for gas dehumidification film |
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