CN102716682B - Application of hollow fiber nano-filtration membrane in removal of As in water body - Google Patents
Application of hollow fiber nano-filtration membrane in removal of As in water body Download PDFInfo
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- CN102716682B CN102716682B CN201210224268.4A CN201210224268A CN102716682B CN 102716682 B CN102716682 B CN 102716682B CN 201210224268 A CN201210224268 A CN 201210224268A CN 102716682 B CN102716682 B CN 102716682B
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Abstract
The invention provides an application of a hollow fiber nano-filtration membrane in removal of trivalent As and pentavalent As in a water body at the same time. The hollow fiber nano-filtration membrane is a low pressure hollow fiber sulfonated polymer coating composite nano-filtration membrane prepared by a coating method, and comprises a hollow fiber ultrafiltration base membrane and an effective separation layer coated on the inner surface of the hollow fiber ultrafiltration base membrane; and the effective separation layer is a sulfonated polymer coating containing manganese dioxide micro-nano particles capable of oxidizing the trivalent As. The hollow fiber nano-filtration membrane can be used for effectively intercepting the As in the water body, and the handling capacity of the As in the water body is 10-10000mu g/L. After the hollow fiber nano-filtration membrane is applied, under the condition that the operation pressure of removing the As in the water body is only 3-10bar, the rejection rate of the As is more than 95%, and the osmosis water yield is high and reaches up to more than 10L/m<2>.h.bar; and compared with a commercial flat-plate nano-filtration membrane, the hollow fiber nano-filtration membrane has the advantages that higher osmosis water flux can be obtained under the lower operation pressure, and meanwhile, the rejection rate of the hollow fiber nano-filtration membrane is equivalent to that of the commercial nano-filtration membrane.
Description
Technical field
The invention belongs to water treatment field, be specifically related to a kind of application of hollow fiber nanofiltration membrane material and the preparation of this material and application of simultaneously removing towards trivalent arsenic in water body and pentavalent arsenic.
Background technology
Arsenic and compound thereof are by the subordinate's of the World Health Organization (WHO) the fixed first kind carcinogenic substance of the confessed mankind of many authoritative institutions such as international cancer research institute (IARC), EPA (US-EPA).Due to the enrichment effect of arsenic in organism, even the arsenic of low content, Long Term Contact also can easily cause the generation of the cancers such as liver, lung, bladder and kidney.Arsenic in water source pollutes has become a worldwide important environmental problem.1993, WHO dropped to 10 μ g/L by the standard limited value of Arsenic in Drinking Water by 50 μ g/L.China (GB5749-2006) brings up to the standard limited value of Arsenic in Drinking Water to be no more than 10 μ g/L from the 50 μ g/L that are no more than of former GB from " standards for drinking water quality " that on July 1st, 2007 implements.And " water environment quality standard " (GB3838-2002) in regulation I, II, III class arsenic in water body content must not exceed 50 μ g/L.
In water body, the removal of three valence state arsenic is the most key.The arsenic of three valence states is that toxicity is the strongest, and particularly arsenic trioxide is commonly called as arsenic, is extremely toxic substance.The common way that in water body, three valence state arsenic are removed is by the arsenic oxidation of three valence states, then adopts isolation technics to remove.Current modal arsenic isolation technics comprises absorption method, sedimentation, ion-exchange, bioanalysis processing and membrane technology partition method.Wherein nanofiltration (NF) is the separation process that is often used in multivalent ion in water body.NF membrane comprises screening and Donnan effect for the principle of the centrifugation of multivalent ion.Donnan effect is because the electrostatic repulsion of the active group on ion and NF membrane surface is caused, thus to the crown_interception of multivalent ion significantly higher than monovalention.Because the arsenic of the three valence states existence form in water body is generally neutrality, general Nanofiltration-membrane technique cannot reach complete separating effect.Therefore, be starved of the technology that single process or membrane material just can be removed the arsenic of trivalent and pentavalent state completely.
It is oxidant that arsenious oxidation normally adopts manganese dioxide, in filled column, carries out.To contain arsenious waste water by the filled column of manganese dioxide, arsenic is oxidized to pentavalent arsenic, and further nanofiltration processing.Domestic and international adopted NF membrane preparation method mainly contains solution coatings method, interfacial polymerization, phase inversion, surface grafting technology etc. at present.As United States Patent (USP) 4,769,148 disclose a kind of method that NF membrane is prepared in interfacial polymerization, and adopting water is the water of piperazine and wetting agent, and crosslinking agent is pyromellitic trimethylsilyl chloride; United States Patent (USP) 5,152,90 disclose a kind of preparation method of NF membrane, take pyromellitic trimethylsilyl chloride and m-phthaloyl chloride as crosslinking agent, reacts and prepare NF membrane on polysulfones supports with bridged piperazine derivatives class polyamine; United States Patent (USP) 5,693 in the preparation method of 227 disclosed NF membrane, take 5-isocyanates isophthaloyl chlorine as crosslinking agent, reacts preparation NF membrane on polysulfones support membrane with piperazine; Patent CN1288776 discloses a kind of method of preparing NF membrane, and its raw material is sulfonated polyether sulfone, adopts phase inversion to prepare NF membrane; Patent CN 1586702 discloses a kind of method that surface grafting technology is prepared hydrophily NF membrane, a kind of method that adopts interfacial polymerization to prepare NF membrane is disclosed in patent CN101829508A, on polysulfones support membrane by aromatic rings on the aromatic polycarboxylic acyl chlorides of modification acid chloride groups or with other aromatic polycarboxylic acyl chlorides mixtures and the compound last layer aromatic polyamides of 4-amino piperidine aqueous solution interface polycondensation ultrathin functional layer.
In the whole bag of tricks, coating is to be directly coated in membrane surface by containing electric charge Dilute Polymer Solutions, the superthin layer that plays desalination after processing again at the compound one deck of membrane surface, its superthin layer is the thinnest reaches several nanometers, thereby transmembrane pressure and operating pressure are declined to a great extent; The effective area filtering has also been improved on rough wrinkle shape surface, and flux is improved greatly.Arsenic is As (III) and As (V) in the main existing way of occurring in nature, wherein in surface water, the main existing way of arsenic is As (V), As (V) exists with the negative valency acid group form of arsenate or arsenic acid hydrogen root in water, so the nanofiltration with negative electrical charge coating is because the effectively catching that the Donnan effect of its electrical charge rejection and sieving actoion can realize arsenate separates.And the negative electrical charge coating macromolecule adopting in the inventive method is that the sulfonate radical of sulfonated polymer has higher hydrophily, and therefore operating pressure is lower.
At present nearly all nanofiltration Study on Removal of Arsenic adopts business NF membrane, and the operating pressure of the Flat Membrane adopting in research is generally all at ten a few to tens of bar, and it penetrates the general not enough 5L/m of the water yield
2* h*bar, and lower than the also more difficult separation requirement that reaches of operating condition of 10bar.Higher operating pressure and the relatively lower infiltration water flux of hollow fiber nanofiltration membrane have increased the application cost of dull and stereotyped NF membrane, reduce the treatment effeciency of nanofiltration, improve processing cost, be unfavorable for the application of the method in remote underdeveloped arsenic contaminated area, and the most of arsenic Polluted area of China is positioned at economically less developed region just.With respect to Flat Membrane, the advantage such as hollow-fibre membrane has self-supporting, and packed density is large, easy cleaning.And hollow-fibre membrane has the advantages such as compact conformation floor space is little in application process.But not yet there are research and application for arsenic-containing water processing about hollow fiber nanofiltration membrane.
Sum up preparation method and application's technology of current NF membrane, the material of also about one-step method, the arsenic of the arsenic of three valence states in water body and pentavalent state not being removed.
Summary of the invention
In view of the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of compound hollow fiber nanofiltration membrane and preparation and the application of this hollow fiber nanofiltration membrane in removing arsenic in water that can simultaneously remove three valence state arsenic and pentavalent state arsenic.The present invention can effectively hold back the arsenic in water body, improves water body environment, and saves processing cost.Compound hollow fiber nanofiltration membrane of the present invention has the ability of the arsenic of simultaneously removing three valence states and pentavalent state; Adopt the operating pressure of this hollow fiber nanofiltration membrane lower than existing membrane material, cost is low compared with counter-infiltration NF membrane.
For achieving the above object and other relevant objects, the present invention adopts following technical scheme:
The application of hollow fiber nanofiltration membrane in removing arsenic in water, described removing arsenic in water is for remove trivalent arsenic and pentavalent arsenic in water body simultaneously.
Further, described hollow fiber nanofiltration membrane is the low pressure hollow sulfonated polymer coating composite nanometer filtering film that adopts coating to make.Doughnut sulfonated polymer coating composite nanometer filtering film of the present invention is the composite nanometer filtering film that scribbles effective separating layer at the inner surface of Hollow Fiber Ultrafiltration basement membrane.
Further, described hollow fiber nanofiltration membrane comprises the effective separating layer scribbling on Hollow Fiber Ultrafiltration basement membrane and Hollow Fiber Ultrafiltration basement membrane inner surface.
Preferably, effective separating layer of described hollow fiber nanofiltration membrane is the sulfonated polymer coating that contains oxidable arsenious manganese dioxide micro-and nano-particles.
Hollow fiber nanofiltration membrane of the present invention is composite film material, and its effective separating layer is by the sulfonated polymer coating that contains manganese dioxide micro-and nano-particles; The function of this coating is mainly manganese dioxide oxidation trivalent arsenic becomes pentavalent state arsenic, then the electrical charge rejection effect of the elecrtonegativity of utilizing polymeric coating layer to pentavalent state arsenate ion and the sieving actoion of NF membrane, remove when realizing in water body three valence state arsenic and pentavalent state arsenic.
The present invention can pass through polymeric coating layer legal system for hollow fiber nanofiltration membrane, and is applied to the removal of arsenic in water body.Hollow fiber nanofiltration membrane of the present invention, can, more low-pressure in the situation that, having higher water yield than business NF membrane, can efficiently process arsenic-containing water body.
Further, when arsenic removal, first regulate the pH value of arsenic-containing water body between 6.5～9, then under the operating pressure of 3～10bar, arsenic-containing water body is squeezed into by compression pump in the assembly of doughnut sulfonated polymer coating composite nanometer filtering film and carried out one or more levels infiltration water outlet.Wherein, when total arsenic concentration in water body adopts one-level to penetrate water treatment when lower than 600 μ g/L; In the time that total arsenic concentration is higher than this 600 μ g/L in water body, can adopt secondary or more multistage infiltration water processing.
Further, the doughnut sulfonated polymer coating composite nanometer filtering film for removing arsenic in water of the present invention is made by the method for following steps: sulfonated polymer is dissolved in to solvent, and adds manganese dioxide particle, be mixed with coating solution; Then coating solution is coated on Hollow Fiber Ultrafiltration basement membrane inner surface, obtain composite membrane, the composite membrane obtaining is carried out to the heat treatment of 5～10 hours in 50～70 ℃ of environment, obtain described doughnut sulfonated polymer coating composite nanometer filtering film, be hollow fiber nanofiltration membrane of the present invention.
Preferably, in described coating solution, the mass percent concentration of sulfonated polymer is 0.5～10%.
Preferably, effective coating layer thickness of described doughnut sulfonated polymer coating composite nanometer filtering film is 0.02～20 μ m.Preferred, the thickness of effective separating layer of described doughnut sulfonated polymer coating composite nanometer filtering film is 1～20 μ m.
Preferably, described sulfonated polymer is selected from sulfonated polyether-ether-ketone, sulfonated polystyrene, sulfonated polyaniline and SPSF.
Preferably, when the above-mentioned inner surface to doughnut ultrafiltration membranes applies, adopt single film inner chamber submergence coating solution to apply or coating solution is repeatedly applied in the circulation of film inner chamber.More excellent, described coating solution is 1～30 second to the coating time of doughnut ultrafiltration membranes.
The material of the Hollow Fiber Ultrafiltration basement membrane preferably, adopting is polyether sulfone PES, polysulfones, polypropylene cyanogen, polyvinyl chloride, polyethylene or Kynoar PVDF.
Coating solution of the present invention is the sulfonated polymer mixed solution that contains manganese dioxide particle, and wherein manganese dioxide particle is 5-80% at the total solids content part by weight of manganese dioxide particle and sulfonated polymer; Be preferably 5-55%.
Preferably, in described coating solution, the part by weight of manganese dioxide particle and sulfonated polymer is 1:10000-1:1, is preferably 1:20-1:1, more preferably 1:5-1:1.
Preferably, the particle size range of described manganese dioxide particle is 1-10000 nanometer; Be preferably 5-1000 nanometer.
Preferably, described solvent is one or more in methyl alcohol, ethanol, acetone, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, hexane, ethyl acetate.
The object that the present invention adds manganese dioxide particle is to make to solidify certain oxidant manganese dioxide particle in sulfonated polymer coating, thereby by oxidation, the arsenic oxidation of three valence states is converted into the arsenic of pentavalent state.Because sulfonated polymer has the very high effect of damming to the arsenate ion of pentavalent state, thereby reach, three valence state arsenic and pentavalent state arsenic are separated to the object of removing simultaneously.
Hollow fiber nanofiltration membrane of the present invention can effectively be held back the arsenic in water body, and the content of the arsenic in water body of processing is 10～10000 μ g/L.Removing arsenic in water of the present invention is in the situation that operating pressure is only 3bar～10bar, and its arsenic rejection, more than 95%, penetrates the water yield large, reaches 10L/m
2more than hbar, with respect to the dull and stereotyped NF membrane of business, can under lower operating pressure, obtain higher infiltration water flux, obtain the arsenic rejection suitable with business NF membrane simultaneously.
The present invention also provides a kind of hollow fiber nanofiltration membrane, this hollow fiber nanofiltration membrane is the hollow fiber nanofiltration membrane that can simultaneously remove trivalent arsenic and pentavalent arsenic in water body, and described hollow fiber nanofiltration membrane comprises the effective separating layer scribbling on Hollow Fiber Ultrafiltration basement membrane and Hollow Fiber Ultrafiltration basement membrane inner surface.
Preferably, described effective separating layer is the sulfonated polymer coating that contains oxidable arsenious manganese dioxide micro-and nano-particles; Preferred, the thickness of described effective separating layer is 0.02～20 μ m.
The present invention further provides a kind of preparation method of hollow fiber nanofiltration membrane, comprise the steps: sulfonated polymer to be dissolved in solvent, and add manganese dioxide particle, be mixed with coating solution; Then coating solution is coated on Hollow Fiber Ultrafiltration basement membrane inner surface, obtains composite membrane; The composite membrane obtaining is carried out to the heat treatment of 5～10 hours in 50～70 ℃ of environment, obtain doughnut sulfonated polymer coating composite nanometer filtering film, be described hollow fiber nanofiltration membrane.
Preferably, in described coating solution, the content of sulfonated polymer and manganese dioxide particle meets one of following condition:
One, in described coating solution, the mass percent concentration of sulfonated polymer is 0.5～10%, and in described coating solution, the part by weight of manganese dioxide particle and sulfonated polymer is 1:10000-1:1;
Two, in described coating solution, manganese dioxide particle is 5-80% at the total solids content part by weight of manganese dioxide particle and sulfonated polymer.
The material of the Hollow Fiber Ultrafiltration basement membrane preferably, adopting is polyether sulfone, polysulfones, polypropylene cyanogen, polyvinyl chloride, polyethylene or Kynoar; Described solvent is one or more in methyl alcohol, ethanol, acetone, oxolane, N, dinethylformamide, N, N-dimethylacetylamide, hexane, ethyl acetate.
The present invention further provides a kind of method of removing arsenic in water, for adopt hollow fiber nanofiltration membrane to remove trivalent arsenic and pentavalent arsenic in water body simultaneously, described hollow fiber NF membrane comprises the effective separating layer scribbling on Hollow Fiber Ultrafiltration basement membrane and Hollow Fiber Ultrafiltration basement membrane inner surface; Described effective separating layer is the sulfonated polymer coating that contains oxidable arsenious manganese dioxide micro-and nano-particles; Preferably, the thickness of described effective separating layer is 0.02～20 μ m.
Preferably, when arsenic removal, first regulate the pH value of arsenic-containing water body between 6.5～9, then under the operating pressure of 3～10bar, arsenic-containing water body is squeezed into by compression pump and in the assembly that contains doughnut sulfonated polymer coating composite nanometer filtering film, carried out one or more levels infiltration water outlet; Wherein, when total arsenic concentration in water body adopts one-level to penetrate water treatment when lower than 600 μ g/L; In the time that total arsenic concentration is higher than this 600 μ g/L in water body, can adopt secondary or more multistage infiltration water processing.
Hollow fiber nanofiltration membrane of the present invention has one-step method and the trivalent arsenic in water body and pentavalent arsenic is separated to the advantage of removing simultaneously, is that a kind of simple and high efficiency arsenic is removed material.Hollow fiber nanofiltration membrane manufacture craft of the present invention is simple, penetrating fluid after treatment can reach the drinking water of World Health Organization's suggestion containing arsenic standard, with respect to current business NF membrane, operating pressure is low, infiltration water flux is high, and the extension of hollow fiber nanofiltration membrane arsenic removal only need increase corresponding membrane module and just can realize.The method can be effectively cost-saving in separating arsenic to improve drinking-water environment, can also further hold back trace suspension thing and bacterium etc. in water body, treatment effeciency is high, running cost is low, facilitate the particularly arsenic IA application of remote or energy deficiency of various occasions, can be applicable to some remote undeveloped or removing arsenic in water that energy deficiency is regional of China.
Accompanying drawing explanation
Fig. 1 is one-level nanofiltration device structural representation of the present invention.
1: feed reservoir;
1-1: penetrating fluid;
2: primary filter;
3: compression pump;
4: nanofiltration assembly;
5: control valve;
6: draining valve.
Fig. 2 is secondary nanofiltration device structural representation of the present invention.
1: feed reservoir;
1-1: secondary nanofiltration liquid pool (one-level penetrating fluid);
1-2 secondary nanofiltration penetrating fluid;
2: primary filter;
3: compression pump;
4: one-level nanofiltration assembly;
4-1: secondary nanofiltration assembly.
The specific embodiment
Below, by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this description.The present invention can also be implemented or be applied by the other different specific embodiment, and the every details in this description also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Sulfonated polymer is dissolved in solvent, by adding manganese dioxide nano particle with the proportioning of sulfonated polymer, is mixed to form uniform coating solution.Coating solution is transported to the inner side of hollow fiber nanofiltration membrane by pump, with the time of contact of hollow fiber nanofiltration membrane be 1～30 second, obtain composite membrane, again the composite membrane obtaining is placed in 50～70 ℃ of environment to heat treatment in 5～10 hours, obtain hollow fiber nanofiltration membrane, this hollow fiber nanofiltration membrane is made to assembly, stand-by.The assembly that above-mentioned hollow fiber nanofiltration membrane is made, packs package shell into by hollow fiber film thread, and termination is adopted to epoxy encapsulation; Feed liquid passes into the endoporus of hollow-fibre membrane, and after the coating segregation of arsenic tunicle inner surface, clean water is penetrated into the outer surface of film by membrane structure.
Below in conjunction with the one-level nanofiltration device shown in Fig. 1, hollow fiber nanofiltration membrane arsenic removal process of the present invention is further elaborated: carry out simple filtration containing the former water of the arsenic in feed reservoir 1 through primary filter 2, after compression pump 3 pressurizations, enter the nanofiltration assembly 4 of hollow fiber nanofiltration membrane, form and produce water and dense draining, dense draining can reflux, also can directly discharge, depend on the rare degree of water resource.Secondary nanofiltration device as shown in Figure 2 can further be processed one-level nanofiltration infiltration water outlet by secondary nanofiltration device.
By specific embodiment, the present invention is further set forth below.
Sulfonated polyether-ether-ketone is dissolved in to the solution that methanol solution preparation sulfonated polymer concentration is 0.5%, then the manganese dioxide nano mix particles that by particle diameter is 10 nanometers forms the coating solution mixing in above-mentioned solution, and the part by weight of controlling manganese dioxide particle and sulfonated polymer is 1/3.Adopt single coating to be coated to (inner and outer diameter is respectively 0.9mm, 1.4mm) on PVDF Hollow Fiber Ultrafiltration basement membrane, in 65 degrees Celsius of environment, film post processing is obtained to there is effective coating for the 6 hours hollow fiber nanofiltration membrane of (being effective separating layer), effective coating layer thickness of sulfonated polyether-ether-ketone composite nanometer filtering film is 5 μ m, and this NF membrane is assembled into hollow fiber nanofiltration membrane assembly and utilizes device as shown in Figure 1 to carry out arsenic removal.
Material liquid is natural water (TDS 550mg/L, hardness CaCO
3650mg/L) add arsenic trioxide and natrium arsenicum and make its trivalent arsenic concentration reach 100 μ g/L, the concentration of pentavalent arsenic reaches 300 μ g/L.Before access to plant, regulate water body pH to 7.6 left and right, implement to regulate compression pump and valve to make pressure reach 4bar in running.In infiltration water outlet, the concentration of pentavalent arsenic is 8 μ g/L, trivalent arsenic cannot detect, " standards for drinking water quality " (GB5749-2006) the one-level drinking water standard that contains arsenic standard and China lower than the drinking water of World Health Organization's suggestion, in device, the water yield of membrane module is 45.7L/m
2h, i.e. 11.4L/m
2hbar.
Sulfonated polyether-ether-ketone is dissolved in to the coating solution of methanol solution preparation sulfonated polymer concentration 1.0%, be coated to that on PES Hollow Fiber Ultrafiltration basement membrane, (basement membrane MWCO is 100000Da, internal-and external diameter is respectively 0.9/1.3mm), in 65 degrees Celsius of environment, film post processing is obtained having the hollow fiber nanofiltration membrane of effective coating for 6 hours, effective coating layer thickness of sulfonated polyether-ether-ketone composite nanometer filtering film is 5-10 μ m, this NF membrane is assembled into hollow fiber nanofiltration membrane assembly utilization device as shown in Figure 1 and carries out arsenic removal.
Material liquid is natural water (TDS 550mg/L, hardness CaCO
3650mg/L) add arsenic trioxide and natrium arsenicum and make its trivalent arsenic concentration reach 100 μ g/L, the concentration of pentavalent arsenic reaches 300 μ g/L, regulates water body pH to 7.8 before access to plant, implements to regulate compression pump and valve to make pressure reach 6bar in running.In infiltration water outlet, the concentration of pentavalent arsenic is 5 μ g/L, and arsenious concentration is 54 μ g/L.Trivalent arsenic is not dammed by NF membrane, cannot reach the threshold values concentration of drinking water arsenic and " standards for drinking water quality " of China (GB5749-2006) one-level drinking water standard of World Health Organization's suggestion.It is lower that these data show in coating, not add the arsenious clearance of manganese dioxide particle team, cannot reach the standard of drinking water.
SPSF is dissolved in to the solution of methanol solution preparation sulfonated polymer concentration 1.0%, then the manganese dioxide nano mix particles that by particle diameter is 10 nanometers forms the coating solution mixing in above-mentioned solution, and the part by weight of controlling manganese dioxide particle and sulfonated polymer is 1/2.Adopt single coating to be coated to (inner and outer diameter is 0.8/1.3mm) on PES Hollow Fiber Ultrafiltration basement membrane, in 65 degrees Celsius of environment, film post processing is obtained to there is effective coating for the 6 hours hollow fiber nanofiltration membrane of (being effective separating layer), effective coating layer thickness of SPSF composite nanometer filtering film is 9-10 μ m, this NF membrane is assembled into hollow fiber nanofiltration membrane assembly and is encased in the arsenic removal application apparatus of accompanying drawing 1.
In water body, trivalent and pentavalent arsenic concentration are respectively 80 μ g/L and 360 μ g/L, regulate water body acid-base value to 8.0 left and right before access to plant, implement to regulate compression pump and valve to make pressure reach 6bar in running.In infiltration water outlet, the concentration of total arsenic is 6 μ g/L, contains " standards for drinking water quality " (GB5749-2006) one-level drinking water standard of arsenic standard and China lower than the drinking water of World Health Organization's suggestion, and in device, the water yield of membrane module is 67L/m
2h.
Sulfonated polyaniline is dissolved in to the solution of methanol solution preparation sulfonated polymer concentration 5%, then the manganese dioxide nano mix particles that by particle diameter is 15 nanometers forms the coating solution mixing in above-mentioned solution, and the part by weight of controlling manganese dioxide particle and sulfonated polymer is 1/1.5.Be coated on PES Hollow Fiber Ultrafiltration basement membrane, in 70 degrees Celsius of environment, film post processing is obtained to there is effective coating for the 6 hours hollow fiber nanofiltration membrane of (being effective separating layer), effective coating layer thickness of sulfonated polyphenyl amine composite nanofiltration membrane is 10 μ m, and this NF membrane is assembled into hollow fiber nanofiltration membrane assembly and utilizes the device as shown in accompanying drawing 1 to carry out arsenic removal.
In water body, trivalent and pentavalent arsenic concentration are respectively 80 μ g/L and 360 μ g/L, regulate water body pH to 8.0 left and right before access to plant, implement to regulate compression pump and valve to make pressure reach 8bar in running.In infiltration water outlet, the concentration of total arsenic is 1 its value of μ g/L contains arsenic standard and China " standards for drinking water quality " (GB5749-2006) one-level drinking water standard lower than the drinking water of World Health Organization's suggestion, and in device, the water yield of membrane module is 40.4L/m
2h.
Sulfonated polyether-ether-ketone is dissolved in to the solution of methanol solution preparation sulfonated polymer concentration 1.5%, then the manganese dioxide nano mix particles that by particle diameter is 100 nanometers forms the coating solution mixing in above-mentioned solution, the part by weight of controlling manganese dioxide particle and sulfonated polymer is that 1/3 employing circulation coating is coated to (internal-and external diameter is 0.7/1.1mm) on polypropylene cyanogen Hollow Fiber Ultrafiltration basement membrane, 60 degrees Celsius of left and right hot-air blowings obtain having effective coating for the 6 hours hollow fiber nanofiltration membrane of (being effective separating layer), effective coating layer thickness of sulfonated polyether-ether-ketone composite nanometer filtering film is 5-6 μ m, this NF membrane is assembled into hollow fiber nanofiltration membrane assembly and utilizes device as shown in Figure 1 to carry out arsenic removal.
In water body, trivalent arsenic and pentavalent arsenic concentration are respectively 25 μ g/L and 250 μ g/L, regulate water body pH to 8 left and right before access to plant, implement to regulate compression pump and valve to make pressure reach 8bar in running.In infiltration water outlet, arsenic rejection has reached 100%, and water yield is 80.4L/m
2h.
Sulfonated polyether-ether-ketone is dissolved in to the solution of methanol solution preparation sulfonated polymer concentration 10%, then the manganese dioxide nano mix particles that by particle diameter is 30 nanometers forms the coating solution mixing in above-mentioned solution, the part by weight of controlling manganese dioxide particle and sulfonated polymer is that 1/1 employing circulation coating is coated to (internal-and external diameter is 1.5/2.60mm) on polyvinyl chloride hollow fiber ultrafiltration membranes, 66 degrees Celsius of left and right hot-air blowings obtain having effective coating for the 8 hours hollow fiber nanofiltration membrane of (being effective separating layer), effective coating layer thickness of sulfonated polyether-ether-ketone composite nanometer filtering film is 4-5 μ m, this NF membrane is assembled into hollow fiber nanofiltration membrane assembly and utilizes device as shown in Figure 1 to carry out arsenic removal.
In water body, trivalent arsenic and pentavalent arsenic concentration are respectively 25 μ g/L and 250 μ g/L, regulate water body pH to 7.5 left and right before access to plant, implement to regulate compression pump and valve to make pressure reach 8bar in running.In infiltration water outlet, arsenic rejection has reached 100%, and water yield is 82.4L/m
2h.
Embodiment 7
Sulfonated polystyrene is dissolved in to the solution that methanol solution preparation sulfonated polymer concentration is 0.5%, then the manganese dioxide nano mix particles that by particle diameter is 10 nanometers forms the coating solution mixing in above-mentioned solution, and the part by weight of controlling manganese dioxide particle and sulfonated polymer is 1/3.Adopt single coating to be coated to (inner and outer diameter is respectively 0.9mm, 1.4mm) on PVDF Hollow Fiber Ultrafiltration basement membrane, in 65 degrees Celsius of environment, film post processing is obtained to there is effective coating for the 6 hours hollow fiber nanofiltration membrane of (being effective separating layer), effective coating layer thickness of sulfonated polystyrene compounded NF membrane is 5 μ m, and this NF membrane is assembled into hollow fiber nanofiltration membrane assembly and utilizes device as shown in Figure 1 to carry out arsenic removal.
Material liquid is natural water (TDS 550mg/L, hardness CaCO
3650mg/L) add arsenic trioxide and natrium arsenicum and make its trivalent arsenic concentration reach 100 μ g/L, the concentration of pentavalent arsenic reaches 300 μ g/L.Before access to plant, regulate water body pH to 7.6 left and right, implement to regulate compression pump and valve to make pressure reach 4bar in running.In infiltration water outlet, the concentration of pentavalent arsenic is 8 μ g/L, trivalent arsenic cannot detect, " standards for drinking water quality " (GB5749-2006) the one-level drinking water standard that contains arsenic standard and China lower than the drinking water of World Health Organization's suggestion, in device, the water yield of membrane module is 45.7L/m
2h, i.e. 11.4L/m
2hbar.
The invention has the advantages that adopting hollow-fibre membrane is basement membrane, utilize sulfonated polymer coating to make hollow fiber nanofiltration membrane, the application by it at removing arsenic in water.The manufacture craft of NF membrane is simple, penetrating fluid after treatment can reach the World Health Organization and China " standards for drinking water quality " drinking water (GB5749-2006) containing arsenic standard, and with respect to current business NF membrane, operating pressure is low, water flux is high, can be effectively cost-saving in separating arsenic to improve water body environment.
The above; it is only preferred embodiment of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of the inventive method, also can make some improvement and supplement, these improvement and the supplementary protection scope of the present invention that also should be considered as.All those skilled in the art, without departing from the spirit and scope of the present invention, a little change of making when utilizing disclosed above technology contents, the equivalent variations of modifying and developing, be equivalent embodiment of the present invention; Meanwhile, the change of any equivalent variations that all foundations essence technology of the present invention is done above-described embodiment, modification and differentiation, all still belong in the scope of technical scheme of the present invention.
Claims (7)
1. the application of hollow fiber nanofiltration membrane in removing arsenic in water, described removing arsenic in water is for remove trivalent arsenic and pentavalent arsenic in water body simultaneously;
Described hollow fiber nanofiltration membrane is the doughnut sulfonated polymer coating composite nanometer filtering film that adopts coating to make;
Described hollow fiber nanofiltration membrane comprises the effective separating layer scribbling on Hollow Fiber Ultrafiltration basement membrane and Hollow Fiber Ultrafiltration basement membrane inner surface;
Effective separating layer of described hollow fiber nanofiltration membrane is the sulfonated polymer coating that contains oxidable arsenious manganese dioxide micro-and nano-particles.
2. the application of hollow fiber nanofiltration membrane as claimed in claim 1 in removing arsenic in water, is characterized in that, the thickness of effective separating layer of described doughnut sulfonated polymer coating composite nanometer filtering film is 0.02～20 μ m.
3. the application of hollow fiber nanofiltration membrane as claimed in claim 1 in removing arsenic in water, it is characterized in that, when arsenic removal, first regulate the pH value of arsenic-containing water body between 6.5～9, then under the operating pressure of 3～10bar, arsenic-containing water body is squeezed into by compression pump and in the assembly that contains doughnut sulfonated polymer coating composite nanometer filtering film, carried out one or more levels infiltration water outlet; Wherein, when total arsenic concentration in water body adopts one-level to penetrate water treatment when lower than 600 μ g/L; In the time that total arsenic concentration is higher than 600 μ g/L in water body, can adopt secondary or more multistage infiltration water processing.
4. the application of hollow fiber nanofiltration membrane as claimed in claim 1 in removing arsenic in water, it is characterized in that, described doughnut sulfonated polymer coating composite nanometer filtering film is specifically made by the method for following steps: sulfonated polymer is dissolved in solvent, and add manganese dioxide particle, be mixed with coating solution; Then coating solution is coated on Hollow Fiber Ultrafiltration basement membrane inner surface, obtains composite membrane; The composite membrane obtaining is carried out to the heat treatment of 5～10 hours in 50～70 ℃ of environment, obtain described doughnut sulfonated polymer coating composite nanometer filtering film.
5. the application of hollow fiber nanofiltration membrane as claimed in claim 4 in removing arsenic in water, is characterized in that, described sulfonated polymer is sulfonated polyether-ether-ketone, sulfonated polystyrene, sulfonated polyaniline or SPSF; The particle size range of described manganese dioxide particle is 1-10000 nanometer.
6. the application of hollow fiber nanofiltration membrane as claimed in claim 4 in removing arsenic in water, is characterized in that, in described coating solution, the content of sulfonated polymer and manganese dioxide particle meets one of following condition:
One, in described coating solution, the mass percent concentration of sulfonated polymer is 0.5～10%, and in described coating solution, the part by weight of manganese dioxide particle and sulfonated polymer is 1:10000-1:1;
Two, in described coating solution, manganese dioxide particle is 5-80% at the total solids content part by weight of manganese dioxide particle and sulfonated polymer.
7. the application of hollow fiber nanofiltration membrane as claimed in claim 4 in removing arsenic in water, is characterized in that, the material of the Hollow Fiber Ultrafiltration basement membrane adopting is polyether sulfone, polysulfones, polypropylene cyanogen, polyvinyl chloride, polyethylene or Kynoar; Described solvent is one or more in methyl alcohol, ethanol, acetone, oxolane, DMF, DMA, hexane, ethyl acetate.
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