CN104841279A - Method and device for low-temperature membrane distillation by using heat-sensitive hydrogel as absorbing agent - Google Patents
Method and device for low-temperature membrane distillation by using heat-sensitive hydrogel as absorbing agent Download PDFInfo
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- CN104841279A CN104841279A CN201510247867.1A CN201510247867A CN104841279A CN 104841279 A CN104841279 A CN 104841279A CN 201510247867 A CN201510247867 A CN 201510247867A CN 104841279 A CN104841279 A CN 104841279A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention belongs to the technical field of membrane distillation and relates to a method and a device for low-temperature membrane distillation by using heat-sensitive hydrogel as an absorbing agent, in particular to a method and a device for performing desalination treatment to saline water or polluted water by using heat-sensitive hydrogel and a hydrophobic microporous membrane. The method and the device for low-temperature membrane distillation by using heat-sensitive hydrogel as the absorbing agent provided by the invention realize the effect of directly obtaining distilled water from the saline water or the polluted water by fully using the temperature-sensitive property of the heat-sensitive hydrogel; the method comprises the following steps: uniformly coating with the heat-sensitive hydrogel onto the surface of the hydrophobic microporous membrane; fixing the hydrophobic microporous membrane on a membrane component; enabling the membrane component to be in contact with the saline water or the polluted water; stopping the contact with the water bodies when a membrane flux produced by water absorption through the heat-sensitive hydrogel reduces to be less than 50 percent of an initial membrane flux; phase separating the heat-sensitive hydrogel. The method and the device for low-temperature membrane distillation by using the heat-sensitive hydrogel as the absorbing agent are mainly applied to the aspect of desalination and distillation.
Description
Technical field
The invention belongs to film distillation technology field, relate to a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method and device, be specifically related to a kind of thermosensitive hydrogel and hydrophobic microporous membrane of utilizing and method and the device of desalting processing carried out to brackish water or polluted water body.
Background technology
Shortage of water resources is one of fundamental realities of the country of China.The water resources ownership per capita of China only has 1/4 of world's per capita share, and relatively lagging behind of water pollution control exacerbates the shortage of water resource, becomes the bottleneck factor of restriction China economic development.Film distillation technology, as a kind of new and effective waste-water purification technology, is just receiving increasing concern, all having a wide range of applications in desalinization, wastewater treatment and food industry etc.
Membrane Materials be the hydrone in stoste under the driving of the vapor partial pressure difference of film both sides, with gaseous form through the separation process of microporous hydrophobic membrane.Conventional film distillation utilizes the side of film directly to contact (being called hot side) with the pending solution of heat, the person's character of film hydrophobic makes the aqueous solution not permeate via hole, and gas-liquid contact is formed in porch, each hole, opposite side contacts with the cold aqueous solution directly or indirectly (being called cold side), in the solution of hot side, at face place, vaporization enters cold side by film and is condensed into liquid phase volatile component, other components are then blocked in hot side by hydrophobic membrane, thus realize the object of mixture isolation andpurification.
Permeable membrane distillation is as a kind of Optimization Technology of conventional film distillation, usually the cooling water of conventional film distillation cold side is substituted as drawing agent using the inorganic of hyperosmosis or organic solvent, be that driving force realizes the separation of effective salt solution with steam pressure difference, needed for distilling compared to conventional film, energy consumption is lower, relative temperature difference is less, affect little by concentration polarization, temperature difference polarization, and as drawing the inorganic of agent or organic solvent by recycling utilization, there is good application prospect." the Membrane contactor processes for wastewater reclamation in space II. Combined direct osmosis that the people such as Tzahi Y. Cath deliver, osmotic distillation, and membrane distillation for treatment of metabolic wastewater " (Journal of Membrane Science, 2005, 257:111 – 119) compared for and just permeate, permeable membrane distills, Membrane Materials three kinds of different process are to the treatment effect of simulation aviation sanitary wastewater, show that permeable membrane distillation is under the double action of concentration difference and temperature difference, the requirement that the highest flux meets aviation waste water recycling can be produced, illustrate that permeable membrane distillation has certain advantage compared to other membrane separation technique." permeable membrane distillation equipment and method " (number of patent application 200910175513.5) of Kemi Tex Co., Ltd. of Canada research and development with chlor-alkali factory liquor natrii hypochloritis to be diluted for drawing agent, with crude salt solution to be concentrated for water inlet, realize producing the dilution of water side solution and the concentrated of influent side solution simultaneously." a kind of technique by two Membrane Materials process reverse osmosis concentrated water and device " (number of patent application 201210425431.3) of the equality people invention of Zhao is first by Membrane Materials concentrated reverse osmosis concentrated water further, again using the reverse osmosis concentrated water after concentrated as drawing agent, for thermally sensitive solutions to be concentrated such as beverage concentrates in permeable membrane distilling apparatus.As can be seen from document, the selection of drawing agent is the committed step in permeable membrane distillation, and routine is that the permeable membrane still-process drawing agent often still needs to draw agent by process recovers such as counter-infiltrations with strong brine, and complex process mostly, energy demand advantages is not remarkable, is difficult to realize large-scale application.
Thermosensitive hydrogel is that a class can the polymer that responds of thermal stimulus to external world, can produce by hydrophilic to hydrophobic phase in version near lower critical solution temperature.1978, people (the Collapse of Gels and the Critical Endpoint such as Toyoichi Tanaka, Phys. Rev. Lett. 1987,40:820) Late Cambrian is by N, there is the phenomenon of volume phase transition in the hydrogel of the polyacrylamide that N-methine bisacrylamide is cross-linked, and then cause the concern of large quantities of scholar and carried out a series of research about heat-sensitive gel near a certain specified temp.Thermosensitive hydrogel is applied in control medicament slow release close to human body temperature at about 35 DEG C due to its phase transition temperature at first, and the application of thermosensitive hydrogel in the separation and extraction of material in recent years also more and more comes into one's own.The people such as Hoffman are at " Langmuir " (2007,23, Temperature-Swing Solid-Phase Extraction of Heavy Metals on a Poly (N-isopropylacrylamide) Hydrogel 13104-13108) delivered, using poly-N-isopropyl acrylamide as solid extracting agent, by the Adsorption and desorption copper ion that control temperature is reversible from the aqueous solution.Dan Li seminar (Stimuli-responsive polymer hydrogels as a new class of draw agent for forward osmosis desalination, Chem. Commun. 2011, 47 (6): 1710.1712) first have studied Sodium Polyacrylate (PSA), N-isopropylacrylamide (PNIPAM), the thermosensitive aquagel made of polyacrylamide (PAM) and composition thereof is as the water suction dehydrating effect drawing agent of positive process of osmosis, find that the water absorbing properties of PSA is better, the water flux produced is higher, and the dehydration rate of PNIPAM is higher, convenient recycling.They also add the black carbon particles that can absorb heat in gel subsequently, expand gel networks, are conducive to the raising of water flux, the thermal efficiency during dehydration simultaneously strengthened, and gel can be dewatered under lower intensity of illumination.
Existing document and patent report show, thermosensitive hydrogel are applied to water treatment field and have certain realistic feasibility, but also do not draw the research of agent as Membrane Materials infiltration about heat-sensitive gel so far.Thermosensitive hydrogel is combined with permeable membrane still-process, not only energy consumption can be reduced, overcome the shortcoming drawing the easy inverse osmosis of agent in permeable membrane distillation, the sensitive characteristic of thermosensitive hydrogel more can be utilized to make it transmit in cumulative process at Membrane Materials heat and to realize dehydration, simplifying conventional film distil process, is a kind of novel process with better application prospect.
Summary of the invention
In order to solve that film distillation technology energy consumption under current cryogenic conditions is high, the problem that agent not easily regenerates is drawn in permeable membrane distillation, the invention provides a kind of utilize thermosensitive hydrogel as draw agent cryogenic film distillation method and device, make full use of the temperature-sensing property of thermosensitive hydrogel, realize directly obtaining distilled water from brackish water or polluted water body.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
Take thermosensitive hydrogel as a method for the cryogenic film distillation of drawing agent, carry out according to following steps:
A, thermosensitive hydrogel are evenly coated in the step on dewatering microporous film surface;
B, dewatering microporous film are fixed on the step on membrane module;
The step that c, membrane module contact with brackish water or polluted water body;
The decline of membrane flux that the water suction of d, thermosensitive hydrogel produces to initial film flux less than 10% time stop the step that contacts with above-mentioned water body;
E, thermosensitive hydrogel carry out the step be separated.
Described a step is specially: the thermosensitive hydrogel being 5 ~ 25 by swelling ratio initial after water absorption and swelling is evenly coated in dewatering microporous film surface, and thickness is 5mm ~ 30mm, and the use amount of elementary membrane surface gel powder is 0.03 ~ 0.2g/cm
2.
The phase transition temperature of described thermosensitive hydrogel is 30 ~ 50 DEG C, absorbs water under phase transition temperature, exceedes phase in version 20 ~ 30 DEG C of realizations and to be separated dehydration; Described dewatering microporous film is inorganic or organic hydrophobic membrane, can be polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), polyethylene, poly(4-methyl-1-pentene) (PMP) or perfluorodimethyldioxole-tetrafluoroethene (PDD-TFE), average pore size be 0.1-1.0 μm.
Described b step is specially: the dewatering microporous film being covered with thermosensitive hydrogel can be screwed on plate film assembly, also can be fixed in hollow fiber film assembly or tubular membrane component by marine glue, and blend compounds circle seals.
Described step c is specially: by normal temperature or can be heated to the brackish water of 30 ~ 50 DEG C or polluted water by membrane module, also membrane module can be placed in above-mentioned water body, the thermosensitive hydrogel in membrane module absorbs moisture and occurs swelling.
Described Step d is specially: measure the gain in weight after thermosensitive hydrogel water suction, be pure water volume, and pass through formula according to density conversion
calculate membrane flux, in formula, V is the water volume of certain hour t through dewatering microporous film, and A is the effective area that thermosensitive hydrogel contacts with dewatering microporous film; Continuous monitoring membrane flux, when the decline of membrane flux that thermosensitive hydrogel water suction produces to initial film flux less than 10% time, stop the water inlet of brackish water or polluted water, or membrane module taken out from water body.
Described step e is specially: the membrane module after will stopping water suction being heated to exceed phase transition temperature 20 ~ 30 DEG C, and thermosensitive hydrogel is separated dehydration, realizes distilled water recovery.
A kind of is the device that the cryogenic film drawing agent is distilled with thermosensitive hydrogel, comprise thermosensitive hydrogel 1, dewatering microporous film 2 and membrane module 3, described thermosensitive hydrogel 1 is coated on dewatering microporous film 2, described dewatering microporous film 2 is fixed on membrane module 3, and described membrane module 3 contacts with brackish water or polluted water body 4.
Described membrane module 3 is plate film assembly, and described dewatering microporous film 2 is fixed on membrane module 3 by screw 5, and described dewatering microporous film 2 is provided with sealing frame 6 by the part that screw 5 is fixing.
Described membrane module 3 is hollow fiber film assembly or tubular membrane component, and described dewatering microporous film 2 is fixed on membrane module 3 by marine glue 7, and by the sealing of O type circle.
The beneficial effect that compared with prior art the present invention has is:
The present invention utilizes thermosensitive hydrogel that the characteristic of reversible phase in version spontaneously can occur in the scope of 30 ~ 50 DEG C, using thermosensitive hydrogel as drawing agent in Membrane Materials, water suction at normal temperatures also with transmission and the accumulation of heat, realizes spontaneous dehydration after simply heating.And conventional film distillation needs the object having been reached fresh water recovery by cooling water or the continuous circulating condensing of cold steam more, flux is low under cryogenic, thus all comparatively large to the loss of energy and the energy, and technique is comparatively complicated.Adopt method of the present invention and device, the fresh-water recovery rate of more than 95% can not only be reached, the salt-stopping rate of more than 96%, the cold insulation characteristic of gel more can be utilized to make distillation film both sides there is steam pressure difference all the time and maintain initial film flux between 1.0 ~ 3.0LMH.
Accompanying drawing explanation
Below by accompanying drawing, the specific embodiment of the present invention is described in further detail.
The structural representation of Fig. 1 to be membrane module of the present invention be plate film assembly;
The structural representation of Fig. 2 to be membrane module of the present invention be hollow fiber film assembly or tubular membrane component.
1 be thermosensitive hydrogel, 2 be dewatering microporous film in figure, 3 be membrane module, 4 be brackish water or polluted water body, 5 be screw, 6 be sealing frame.
Detailed description of the invention
The invention will be further described by reference to the accompanying drawings for embodiment below.
A kind of is the device that the cryogenic film drawing agent is distilled with thermosensitive hydrogel, comprise thermosensitive hydrogel 1, dewatering microporous film 2 and membrane module 3, described thermosensitive hydrogel 1 is coated on dewatering microporous film 2, described dewatering microporous film 2 is fixed on membrane module 3, and described membrane module 3 contacts with brackish water or polluted water body 4.
As shown in Figure 1, described membrane module 3 is plate film assembly, and described dewatering microporous film 2 is fixed on membrane module 3 by screw 5, and described dewatering microporous film 2 is provided with sealing frame 6 by the part that screw 5 is fixing.
As shown in Figure 2, described membrane module 3 is hollow fiber film assembly or tubular membrane component, and described dewatering microporous film 2 is fixed on membrane module 3 by marine glue, and by the sealing of O type circle.
Embodiment is only specific embodiments of the invention below, does not limit the scope that the present invention protects.
Embodiment 1
1) by initial swelling ratio be 15 poly-N-isopropyl acrylamide hydrogel be evenly coated in dewatering microporous film surface, make its thickness spreading over hydrophobic membrane surface be 5mm, the hydrophobic membrane being covered with gel be fixed in membrane module, fixing seal;
2) membrane module of good seal is placed in 40 DEG C, concentration is in the NaCl solution of 2000ppm, and Membrane Materials 4h, measures flux every half an hour;
3) gel dewaters after terminating by Membrane Materials process under the condition of 60 DEG C.
Permeant flux reaches 1.6LMH at front 30min, is 0.1LMH at the end of reaction, and after dehydration, Water Sproading rate is 95%, and salt-stopping rate is 99%.
Embodiment 2
1) be 15 by initial swelling ratio, mol ratio is that the NIPA of 4:1 and the copolymer hydrogel of PAA are evenly coated in dewatering microporous film surface, make its thickness spreading over hydrophobic membrane surface be 10mm, the hydrophobic membrane being covered with gel is fixed in membrane module, fixing seal;
2) membrane module of good seal is placed in 40 DEG C, salinity is in the simulated seawater of 3.5%, and Membrane Materials 4h, measures flux every half an hour;
3) gel dewaters after terminating by Membrane Materials process under the condition of 70 DEG C.
Permeant flux reaches 1.2LMH at front 30min, is 0.1LMH at the end of reaction, and after dehydration, Water Sproading rate is 95%, and salt-stopping rate is 96%.
Embodiment 3
1) by initial swelling ratio be 20 poly-N-isopropyl acrylamide hydrogel be evenly coated in dewatering microporous film surface, make its thickness spreading over hydrophobic membrane surface be 10mm, the hydrophobic membrane being covered with gel be fixed in membrane module, fixing seal;
2) membrane module of good seal is placed in 50 DEG C, COD value is about in the coking chemical waste water bio-chemical effluent of 300mg/L, and Membrane Materials 4h, measures flux every half an hour;
3) gel dewaters after terminating by Membrane Materials process under the condition of 80 DEG C.
Permeant flux reaches 1.0LMH at front 30min, is 0.1LMH at the end of reaction, and after dehydration, Water Sproading rate is 95%, and salt-stopping rate is 99%.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that; It still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. be a method for the cryogenic film distillation of drawing agent with thermosensitive hydrogel, it is characterized in that, carry out according to following steps:
A, thermosensitive hydrogel are evenly coated in the step on dewatering microporous film surface;
B, dewatering microporous film are fixed on the step on membrane module;
The step that c, membrane module contact with brackish water or polluted water body;
The decline of membrane flux that the water suction of d, thermosensitive hydrogel produces to initial film flux less than 10% time stop the step that contacts with above-mentioned water body;
E, thermosensitive hydrogel carry out the step be separated.
2. according to claim 1 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method, it is characterized in that, described a step is specially: the thermosensitive hydrogel being 5 ~ 25 by swelling ratio initial after water absorption and swelling is evenly coated in dewatering microporous film surface, thickness is 5mm ~ 30mm, and the use amount of elementary membrane surface gel powder is 0.03 ~ 0.2g/cm
2.
3. according to claim 2 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method, it is characterized in that, the phase transition temperature of described thermosensitive hydrogel is 30 ~ 50 DEG C, absorbs water below phase transition temperature, realizes being separated dehydration when exceeding phase transition temperature 20 ~ 30 DEG C; Described dewatering microporous film is inorganic or organic hydrophobic membrane, can be polytetrafluoroethylene (PTFE) (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), polyethylene, poly(4-methyl-1-pentene) (PMP) or perfluorodimethyldioxole-tetrafluoroethene (PDD-TFE), average pore size be 0.1-1.0 μm.
4. according to claim 1 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method, it is characterized in that, described b step is specially: the dewatering microporous film being covered with thermosensitive hydrogel can be screwed on plate film assembly, also can be fixed in hollow fiber film assembly or tubular membrane component by marine glue, blend compounds circle seals.
5. according to claim 1 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method, it is characterized in that, described step c is specially: by normal temperature or can be heated to the brackish water of 30 ~ 50 DEG C or polluted water passes through membrane module, also membrane module can be placed in above-mentioned water body, the thermosensitive hydrogel in membrane module absorbs moisture and occurs swelling.
6. according to claim 1 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method, it is characterized in that, described Step d is specially: measure thermosensitive hydrogel water suction after gain in weight, be pure water volume according to density conversion, and pass through formula
calculate membrane flux, in formula, V is the water volume of certain hour t through dewatering microporous film, and A is the effective area that thermosensitive hydrogel contacts with dewatering microporous film; Continuous monitoring membrane flux, when the decline of membrane flux that thermosensitive hydrogel water suction produces to initial film flux less than 10% time, stop the water inlet of brackish water or polluted water, or membrane module taken out from water body.
7. according to claim 1 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation method, it is characterized in that, described step e is specially: be heated to exceed phase transition temperature 20 ~ 30 DEG C by the membrane module after stopping water suction, thermosensitive hydrogel is separated dehydration, realizes distilled water and reclaims.
8. one kind is the device that the cryogenic film drawing agent is distilled with thermosensitive hydrogel, it is characterized in that: comprise thermosensitive hydrogel (1), dewatering microporous film (2) and membrane module (3), described thermosensitive hydrogel (1) is coated on dewatering microporous film (2), described dewatering microporous film (2) is fixed on membrane module (3), and described membrane module (3) contacts with brackish water or polluted water body (4).
9. according to claim 8 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation device, it is characterized in that: described membrane module (3) is plate film assembly, described dewatering microporous film (2) is fixed on membrane module (3) by screw (5), and described dewatering microporous film (2) is provided with sealing frame (6) by the part that screw (5) is fixing.
10. according to claim 8 a kind of with thermosensitive hydrogel be draw agent cryogenic film distillation device, it is characterized in that: described membrane module (3) is hollow fiber film assembly or tubular membrane component, described dewatering microporous film (2) is fixed on membrane module (3) by marine glue, and by the sealing of O type circle.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417596A (en) * | 2015-12-08 | 2016-03-23 | 华南理工大学 | Method for using hydrogel to continuously desalinate seawater |
| CN108939937A (en) * | 2018-09-11 | 2018-12-07 | 济南大学 | A kind of method of polyvinyl alcohol hydrogel enhancing membrane distillation flux system |
| EA031763B1 (en) * | 2016-12-20 | 2019-02-28 | Ибрагим Эсенович Сулейменов | Solution demineralization method |
| CN112299578A (en) * | 2019-07-23 | 2021-02-02 | 宝山钢铁股份有限公司 | Forward osmosis wastewater recycling method |
| CN113877492A (en) * | 2021-11-17 | 2022-01-04 | 华侨大学 | Porous MoS2Hydrogel, preparation method and application thereof |
| CN114100370A (en) * | 2021-11-29 | 2022-03-01 | 中新国际联合研究院 | Forward osmosis and draw liquid regeneration modular device using temperature-sensitive hydrogel as draw liquid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417596A (en) * | 2015-12-08 | 2016-03-23 | 华南理工大学 | Method for using hydrogel to continuously desalinate seawater |
| EA031763B1 (en) * | 2016-12-20 | 2019-02-28 | Ибрагим Эсенович Сулейменов | Solution demineralization method |
| CN108939937A (en) * | 2018-09-11 | 2018-12-07 | 济南大学 | A kind of method of polyvinyl alcohol hydrogel enhancing membrane distillation flux system |
| CN112299578A (en) * | 2019-07-23 | 2021-02-02 | 宝山钢铁股份有限公司 | Forward osmosis wastewater recycling method |
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| CN114100370A (en) * | 2021-11-29 | 2022-03-01 | 中新国际联合研究院 | Forward osmosis and draw liquid regeneration modular device using temperature-sensitive hydrogel as draw liquid |
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