CN103086475B - Industrial ultrafiltration membrane device pollutant online extraction and analysis method - Google Patents
Industrial ultrafiltration membrane device pollutant online extraction and analysis method Download PDFInfo
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- CN103086475B CN103086475B CN201110339013.8A CN201110339013A CN103086475B CN 103086475 B CN103086475 B CN 103086475B CN 201110339013 A CN201110339013 A CN 201110339013A CN 103086475 B CN103086475 B CN 103086475B
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Abstract
The invention relates to an industrial ultrafiltration membrane device pollutant online extraction and analysis method. The invention belongs to the field of membrane-method sewage deep processing and recycling method. The method comprises the steps that: (1) an ultrafiltration membrane with a relatively compact skin structure is used for manufacturing a lateral line membrane assembly; (2) the lateral line membrane assembly is connected in parallel into an industrial ultrafiltration membrane device; and inlet water membrane-surface flow velocity at the lateral line assembly is controlled at 0-8m/s; (3) during an operation process, lateral line membrane assembly water production variation is recorded with timed frequency; when water production is reduced by 50-95% relative to an initial water production, the polluted lateral line membrane assembly is fetched; (4) part of polluted ultrafiltration membrane is fetched and is subjected to low-temperature bake-drying; and membrane-surface pollutant observation and analysis are carried out; and (5) acid and alkali are respectively used for soaking and washing the polluted ultrafiltration membrane, and contents of specific pollutants in the washing liquid are detected. When the method provided by the invention is used in washing the polluted ultrafiltration membrane, water production of the washed polluted ultrafiltration membrane can be restored to higher than 95% of that of the initial water production.
Description
Technical field
The invention belongs to embrane method advanced treatment of wastewater and reuse field, relate to pollutant in industrial ultra filtration membrane application of installation process at line drawing and method for decomposing, relate more specifically to that a kind of embrane method sewage appropriateness is processed and reuse process in membrane contaminant at line drawing, identification and pollutant cleaning method.
Background technology
Ultrafiltration is one of important membrane separation technique, the fields such as the energy, environmental protection, electronics, medicine, food have been widely used at present, with conventional separation method ratio, ultrafiltration has the advantages such as energy consumption is low, efficiency is high, process is simple, free from environmental pollution, is the important technology that solves the contemporary energy, resources and environment problem.But because ultra filtration membrane is very easily subject to the pollution of solute in application, the decline of membrane flux problem causing has therefrom become a key issue that hinders its process of industrialization, therefore, to the rapid extraction of Pollution of Ultrafiltration Membrane thing in industrial membrane device,, the identification of pollutant, and take suitable preprocess method to carry out effectively cleaning actual commercial Application being had to stronger directive significance to Pollution of Ultrafiltration Membrane according to the type of pollutant and content.
The pollution of ultra filtration membrane mainly refers to due to physics or chemistry, causes particulate, the colloidal particle in treating material or forms and precipitate obstruction or the resistance of membrane filtration increase causing because adsorbing, be deposited in film surface or fenestra compared with large solute molecule.The film that can be divided into three types according to the degree of Pollution of Ultrafiltration Membrane pollutes: 1. pollution of surface: a pollutant coverlay surface, film still keeps higher permeable amount---and it is surface filtration that this kind of filter process can be described as, and reversibility film succession is in the case larger.2. deep layer is polluted: pollutant is not only covered in film surface, fenestra interior section hole is also blocked, cause the water flux of film seriously to decay, this kind of phenomenon may be due to the pore size of selected film itself and pore diameter distribution is inhomogeneous causes, also be likely the particle diameter skewness of particle in pending feed liquid in addition, and for the improper pollution causing of selection of membrane aperture and pore diameter distribution, this part irreversible membrane fouling proportion in polluting is relatively high.3. " necrosis " contact scar: due to deep layer severe contamination, preserve or improper use, dehydration, the reason such as dry cause, and with the change of membrane structure, lose separating property.
According to the kind of Pollution of Ultrafiltration Membrane, can be divided into three types: 1. the deposition main manifestations of particle is colloid pollution, and common pollutant mainly contains ferric hydroxide, aluminium hydroxide, silicon dioxide colloid etc.; 2. the adhesion of microorganism and growth, common pollutant has bacterium, algae class etc.; 3. the Organic Pollution that organic macromolecule or organic polymer cause in the absorption of face.
Diversity due to commercial production raw material, the reasons such as the non-conversion completely of the complicacy of production technology and chemical reaction, cause containing in waste water system various pollutants, although these pollutants have passed through biochemical treatment, but be not that all organism can be degraded by biology completely, but the material also not fallen by biochemistry is all the reason that the industrial ultra filtration membrane device of impact moves, thereby, how effectively to obtain the key pollutants that has a strong impact on industrial ultra filtration membrane device operation, contaminated ultra filtration membrane is carried out effectively cleaning to recover its performance, reduction increases because of the film cost that changes that severe contamination causes, the operation maintenance that reduces industrial ultra filtration membrane device has stronger realistic meaning and industrial application value.
Although adopt chemically separated method can extract the pollutant in waste water to a certain extent, the contaminant information of extracting is subject to the whether representative impact of extracted water sample larger.In commercial Application process, the acquisition methods of actual pollutant is mainly to dissect and analyze after the industrial hyperfiltration membrane assembly of severe contamination being cut after ultrafiltration system is shut down.The industrial hyperfiltration membrane assembly of described severe contamination is that the relative initial launch state of water production rate declines and is greater than 50%, but water production rate after conventional soda acid cleans is less than original state 80%.The major defect of conventional method comprises following several aspect: (1) can not obtain in time the contaminant information of ultrafiltration face in ultrafiltration system operational process; (2) the membrane module analysis after dissection only just can be carried out the multianalysis of pollutant with sub-fraction polluted membrane, causes because dissecting and causes membrane module to destroy, unrenewable; (3) even by obtaining relevant contaminant information to shutting down the anatomy of rear ultra filtration membrane surface pollution thing, but the selection and optimization process of contaminated ultra filtration membrane cleaning is consuming time longer, can affect normal production and the operation of whole system.
The practical problems existing in pollutant extraction in above-mentioned ultra filtration membrane commercial Application and parsing process, not only caused ultrafiltration membrane system in industrial membrane application process frequently to change the operating cost that membrane module causes and increase because of seriously polluted, and in ultrafiltration membrane system operational process, cannot grasp fast, early ultra filtration membrane surface pollution thing information, cannot be in time provide foundation and reference for long-term, the stable operation of industrial ultrafiltration membrane system and the optimization of key parameter.
Summary of the invention
For ultra filtration membrane surface pollution phase in industrial membrane device operational process, closing technical information cannot quick obtaining, the obtaining of pollutant need to be take the technical matters that the destruction of whole hyperfiltration membrane assembly exists in cost and ultra filtration membrane surface pollution thing dissect, the invention provides a kind of industrial ultra filtration membrane surface pollution thing at line drawing, method for decomposing, not only can realize ultra filtration membrane surface pollution thing in industrial membrane device operational process fast, the leaching process of objective, and by the combination of suitable analysis means, and then the correlation technique information of grasp ultra filtration membrane surface pollution thing that can be comparatively detailed, can provide crucial data reference and foundation for the choice and optimization of the industrial hyperfiltration membrane assembly cleaning of severe contamination on this basis.
The technical solution used in the present invention:
A kind of industrial ultra filtration membrane device pollutant provided by the invention extracts and method for decomposing, comprises the following steps:
(1) select the ultra filtration membrane with relative dense layer surface structure to make side line membrane module, the carrier extracting as key pollutants in industrial ultra filtration membrane device operational process, wherein key pollutants refers to the major pollutants that affect ultra filtration membrane operation, mainly refer to suspension, particle, colloid, microorganism viscosity mud, bacterium class material, herein non-finger dissolved organic matter and inorganic pollutant;
(2) side line membrane module is in parallel with industrial ultra filtration membrane device, regulate the Inlet and outlet water valve aperture size of side line membrane module, take that to control water inlet be 0 ~ 8m/s at the flow velocity of face, wherein said side line membrane module is as the rolled film in Fig. 1 and hollow fiber film assembly;
(3) in operational process, the water production rate of time recording side line membrane module changes, and when the relatively initial water production rate of water production rate declines 50 ~ 95%, thinks that ultra filtration membrane surface pollution thing content and pollution layer thickness reach anatomy requirement;
(4) take out contaminated side line membrane module, and therefrom take out the observation of carrying out ultra filtration membrane surface pollution thing after approximately 1/4 ultrafiltration membrane filaments low temperature drying, in conjunction with energy spectrum analysis, carry out the scanning in contaminated interval, the kind of qualitative definite pollutant;
(5) adopt bronsted lowry acids and bases bronsted lowry to 1/4 of contaminated ultrafiltration membrane filaments in step (4), to carry out soaking and washing respectively, and detect respectively the content size of specific pollutants in acid, alkaline cleaner, wherein specific pollutants refers to the pollutant that detects in step (4) and oil, TOC.
After above-mentioned steps is processed; can draw composition and the content of key pollutants in contaminated industrial ultra filtration membrane; avoided, because dissecting the long-time shutdown of the industrial ultra filtration membrane device that pollutant, cleaning optimization cause and the destruction of industrial ultrafiltration module, according to the result in line drawing, anatomy, can carrying out effectively cleaning to recover its performance to contaminated ultra filtration membrane.
Described, the ultra filtration membrane with relative compact texture cortex in step 1 is advisable with hollow-fibre membrane or rolling ultrafiltration membrane, preferably rolling ultrafiltration membrane; Wherein, hollow-fibre membrane with endodermis relatively densification or exodermis relatively densification be advisable, preferably exodermis is relatively fine and close; Hollow-fibre membrane or spiral wound membrane material are advisable with bisphenol-a polysulfone, polyethersulfone, phenolic polyether sulphone and polyetherketone, poly (aryl ether sulfone ketone), Kynoar class, and optimum is Kynoar, polyethersulfone, poly (aryl ether sulfone ketone); The ultra filtration membrane pore size of compact texture cortex is advisable with 0.001-0.02 μ m relatively, and optimum is 0.005-0.01 μ m.
Described, the structure of side line hyperfiltration membrane assembly has and the similar structure of industrial hyperfiltration membrane assembly, and as water inlet end, produce water end (W.E.) and concentrated water discharge end, but the effective film area that the key distinction of itself and industrial hyperfiltration membrane assembly is this side line assembly is at 0.1-0.5m
2;
Described, in step 2, the water inlet of side line membrane module, concentrated water spout and the product mouth of a river adopt mode in parallel to be connected with industrial ultra filtration membrane device, and wherein the method for operation of side line membrane module is with cross-flow or dead end mode, preferably cross-flow mode; In operational process, regulate the flow velocity of ultrafiltration water inlet in side line membrane module to be advisable with 0-8m/s, optimum with 2-6m/s;
Described, the water production rate of the time recording side line membrane module in step 3 changes in 0-5h is once advisable with 5-60min record, and optimum with 15-30min record once; After side line membrane module operation 5h, with 1-4h record, be once advisable, optimum with side line membrane module water production rate size of 2h record;
Described, the relatively initial water production rate of the water production rate of the side line membrane module in step 3 declines and is advisable with 50-95%, optimum 60-90%;
Described, the 20-60 ℃ of low temperature drying of the employing of the pollution ultra filtration membrane to taking-up in step 4, optimum bake out temperature is 30-50 ℃;
Described, the ultra filtration membrane surface pollution thing polluting in step 4 is advisable with direct observation and the anatomy of SEM, SEM-EDS, SEM-XPS and FTIR, optimum with SEM-EDS and FTIR;
Described, it is 1 and the pH acid that is 13, immersion, the stirring and washing that alkaline cleaner carries out respectively 15-45min that the ultra filtration membrane polluting in step 5 adopts respectively pH, optimumly soaks, the stirring and washing time is 25-40min; Analyzing the method for pollutant load in cleaning fluid is advisable with the analytical approach of ICP-Mass and TOC;
Described, in step 5, also can be optimized processing to contaminated ultra filtration membrane cleaning condition, select pH scope to be respectively 1-3 and 10-13, the optimum bronsted lowry acids and bases bronsted lowry for 1.5-3 and 11-12 cleans contaminated ultra filtration membrane respectively, determine best pH scope and soaking and washing time, wherein said acid can be selected any one in hydrochloric acid, oxalic acid, citric acid, and described alkali can be selected any one in NaOH, sodium hypochlorite, and optimum is advisable with hydrochloric acid and sodium hypochlorite respectively.
The essential distinction of the present invention and prior art is:
The essential distinction of patent of the present invention and prior art is to adopt the ultra filtration membrane with dense layer surface structure to make the side line assembly that ultra filtration membrane surface pollution thing extracts, can be in the situation that not affecting existing industrial membrane device operation, on affecting the key pollutants of ultra filtration membrane operation in actual waste water system, extract, and can dissect the pollutant extracting, can obtain in time the correlation technique information of ultra filtration membrane surface pollution thing, and on this basis, carry out the optimization of ultra filtration membrane surface pollution thing cleaning.
The invention has the beneficial effects as follows:
The invention provides a kind of extraction and method for decomposing of industrial ultra filtration membrane device key pollutants, solved the defect problem of the static rapid extraction of pollutant in existing waste water system, the present invention is by introducing side line membrane module, be connected in parallel in film device, had advantages of that extracting method is simple, pollutant situation is true, practical.Be applicable in existing industrial membrane device operational process various because polluting the hydraulic performance decline cause, at the cause investigation not destroying under original industrial membrane assembly and service condition.By enforcement of the present invention, can obtain timely and effectively the key pollutants in industrial ultra filtration membrane device operational process, and by the use in conjunction of relevant method for decomposing, can provide stronger technical basis and reference for optimization and the selection of the chemical cleaning technology scheme in industrial ultra filtration membrane device operational process.Thereby, for long-term, the stable operation of actual industrial membrane device and the commercial Application of industrial membrane device, promote and there is good technical prospect.The method according to this invention is cleaned polluting ultra filtration membrane, and the contaminated ultra filtration membrane water production rate after cleaning can revert to the more than 95% of initial water production rate.
Accompanying drawing explanation
Fig. 1 is the hyperfiltration membrane assembly schematic diagram that industrial ultra filtration membrane device pollutant extracts, and wherein Fig. 1 .1 is hollow fiber ultrafiltration membrane side line assembly, and Fig. 1 .2 is rolled film side line assembly.Wherein in Fig. 1 .2, A is side line base (101 base vertical views; 102 produce water flow passage; 103 diaphragm set bolts; 104 produce water collects mouth); B is flat sheet membrane back up pad (201 stainless steel 5 μ m porous plate vertical views); C is side line top cover (301 capping top views; 302 concentrated water drainage outlets; 303 water inlets; 304 O-ring seals)
Fig. 2 is that pollutant is at the connected mode schematic diagram of line drawing side line assembly.
Fig. 3 is the ultrafiltration face key pollutants pattern extracting in embodiment 1.
Fig. 4 is the face particle extracting in embodiment 1, the SEM-EDS result of colloid.
Fig. 5 is the FTIR result of the Organic Pollution that extracts in embodiment 5.
Fig. 6 is the SEM pattern of the microbial contamination of extracting in embodiment 7.
Embodiment
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) adopting 150 50cm length, pore sizes is 0.02 μ m, and the polyvinylidene fluoride hollow fiber ultrafiltration membrane with fine and close exodermis structure is prepared the side line assembly that key pollutants is extracted;
(2) by the water inlet, dense water of the side line assembly of preparation in step 1 and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, regulate the aperture size of the concentrated water discharge valve of side line assembly, regulating the flow velocity of ultrafiltration water inlet in side line assembly is 2m/s;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 5min; After operation 5h, according to water production rate of interval 1h record, change.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 90%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change a untapped ultra filtration membrane side line pollutant extraction assembly, and take out in contaminated side line membrane module approximately 1/4 ultrafiltration membrane filaments and be placed in 25 ℃ of low-temperature bake ovens and dry, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, the ultra filtration membrane surface pollution thing pattern and the pollutant SEM-EDS analysis result that extract are shown in respectively Fig. 3, Fig. 4 and table 1, and hence one can see that, and ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out acid, alkali soaking and washing 45min(acid, each soaking and washing of alkali 45min to the part ultra filtration membrane in remaining contaminated side line membrane module respectively), to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 1 HCl and 10 NaOH carries out the optimization of acid, alkali cleaning condition to the ultra filtration membrane of the remainder in contaminated side line membrane module, described optimization aim is: by the optimization of cleaning condition, make the ultra filtration membrane flux recovery after polluting arrive original state or the more than 95% of original state, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 97% of initial water production rate.
The ultrafiltration face particle extracting in table 1 embodiment 1, the EDS analysis result of colloidal material
| Element | C-K | O-K | Na-K | Mg-K | Al-K | Si-K | Cl-K | CaK | FeK | Cu-K | Zn-K |
| Wt % | 8.74 | 26.03 | 0.57 | 1.69 | 1.86 | 4.34 | 0.52 | 17.02 | 32.66 | 2.83 | 3.74 |
| At % | 19.16 | 42.83 | 0.65 | 1.83 | 1.81 | 4.06 | 0.39 | 11.18 | 15.4 | 1.17 | 1.51 |
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) adopting 150 50cm length, pore sizes is 0.05 μ m, and the PES with fine and close endodermis structure is prepared the extraction side line assembly of key pollutants;
(2) by the water inlet, dense water of the side line assembly of preparation in step 1 and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, regulate the aperture size of the concentrated water discharge valve of side line assembly, regulating the flow velocity of ultrafiltration water inlet in side line assembly is 4m/s;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 15min; After operation 5h, according to water production rate of interval 1.5h record, change.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 50%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change a untapped ultra filtration membrane side line pollutant extraction assembly, and take out in contaminated side line membrane module approximately 1/4 ultrafiltration membrane filaments and be placed in 30 ℃ of low-temperature bake ovens and dry, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, known ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out respectively cleaning 15min in acid, alkali soaking and washing 15min(acid, alkali to the part ultra filtration membrane in contaminated side line membrane module respectively, to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 2 oxalic acid and 11 sodium hypochlorite carries out the optimization of cleaning condition to the contaminated ultra filtration membrane of part, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 95% of initial water production rate.
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) adopt that 150 50cm are long, pore sizes are 0.05 μ m, there is the side line assembly of key pollutants extraction in the polyvinylidene fluoride hollow fiber ultrafiltration membrane preparation of inside and outside dense layer surface structure;
(2) by the water inlet of the side line assembly of preparation in step (1), dense water and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, regulate the aperture size of the concentrated water discharge valve of side line assembly, regulating the flow velocity of ultrafiltration water inlet in side line assembly is 6m/s;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 10min; After operation 5h, according to water production rate of interval 2h record, change.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 70%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change a untapped ultra filtration membrane side line pollutant extraction assembly, and take out in contaminated side line membrane module approximately 1/4 ultrafiltration membrane filaments and be placed in 35 ℃ of low-temperature bake ovens and dry, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, known ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out respectively cleaning 25min in acid, alkali soaking and washing 25min(acid, alkali to the part ultra filtration membrane in contaminated side line membrane module respectively), to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 3 citric acid and 12 NaOH carries out the optimization of cleaning condition to the contaminated ultra filtration membrane of part, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 95% of initial water production rate.
Embodiment 4
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) membrane area is about to 80cm
2, pore size is that the poly (aryl ether sulfone ketone) flat plate ultrafiltration membrane of 0.07 μ m is placed in the side line assembly that specific pollutant extraction element extracts as pollutant;
(2) by the water inlet of the side line assembly in step 1, dense water and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, regulate the aperture size of the concentrated water discharge valve of side line assembly, regulating the flow velocity of ultrafiltration water inlet in side line assembly is 8m/s;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 30min; After operation 5h, according to water production rate of interval 3h record, change.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 90%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change a slice membrane area and be about 80cm
2ultrafiltration diaphragm, and 1/4 of the contaminated ultra filtration membrane low-temperature bake oven that is placed in 40 ℃ is dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, known ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out respectively cleaning 40min in acid, alkali soaking and washing 40min(acid, alkali to the part ultra filtration membrane in the side line membrane module polluting respectively), to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 4 hydrochloric acid and 12 sodium hypochlorite carries out the optimization of cleaning condition to the contaminated ultra filtration membrane of part, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 96% of initial water production rate.
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) membrane area is about to 80cm
2, pore size is that the vinylidene difluoride planar ultrafiltration membrane of 0.02 μ m is placed in the side line assembly that specific pollutant extraction element extracts as pollutant;
(2) by the water inlet of the side line assembly in step 1, dense water and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, and close concentrated water discharge valve, carry out the mode of dead-end filtration and extract pollutant;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 10min; The variation of recording a water production rate according to interval 1h after operation 5h.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 95%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change the untapped ultra filtration membrane of a slice, and approximately 1/4 in contaminated side line diaphragm is placed in to 50 ℃ of low-temperature bake ovens dries, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, known ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution; The film surface pollution thing extracting is shown in to Fig. 5 compared with the FTIR analysis result of thickness portion simultaneously;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out respectively cleaning 45min in acid, alkali soaking and washing 45min(acid, alkali to the part ultra filtration membrane in contaminated side line membrane module respectively), to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 1 hydrochloric acid and 13 NaOH carries out the optimization of cleaning condition to the contaminated ultra filtration membrane of part, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 95% of initial water production rate.
Embodiment 6
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) adopting 150 50cm length, pore sizes is 0.01 μ m, and the PVC hollow fiber ultrafiltration membrane with fine and close exodermis structure is prepared the side line assembly that key pollutants is extracted;
(2) by the water inlet, dense water of the side line assembly of preparation in step 1 and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, regulate the aperture size of the concentrated water discharge valve of side line assembly, regulating the flow velocity of ultrafiltration water inlet in side line assembly is 6m/s;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 20min; The variation of recording a water production rate according to interval 4h after operation 5h.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 90%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change a untapped ultra filtration membrane side line pollutant extraction assembly, and take out the low-temperature bake oven that approximately 1/4 ultrafiltration membrane filaments in contaminated side line membrane module is placed in 60 ℃ and dry, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, hence one can see that, and ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out respectively cleaning 40min in acid, alkali soaking and washing 40min(acid, alkali to the part ultra filtration membrane in the side line membrane module polluting respectively), to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 2 HCl and 10 sodium hypochlorite carries out the optimization of cleaning condition to the contaminated ultra filtration membrane of part, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 96% of initial water production rate.
Embodiment 7
A kind of industrial ultra filtration membrane device pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) membrane area is about to 80cm
2, pore size is that the polyethersulfone flat plate ultrafiltration membrane of 0.05 μ m is placed in the side line assembly that specific pollutant extraction element extracts as pollutant;
(2) by the water inlet of the side line assembly in step 1, dense water and produce water successively according to industrial ultra filtration membrane in membrane module water inlet, dense water and produce water with connected mode, be parallel in industrial ultra filtration membrane device, and close concentrated water discharge valve, carry out the mode of dead-end filtration and extract pollutant;
(3) from side line assembly, produce water and start to record its initial water production rate size, the water production rate variation of recording primary side line component in 0-5h according to interval 10min; The variation of recording a water production rate according to interval 1h after operation 5h.When the relatively initial water production rate decline of water production rate of side line assembly is greater than 95%, ultra filtration membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) again change the ultra filtration membrane in a slice step (1), and approximately 1/4 ultra filtration membrane in contaminated membrane module is placed in to the low-temperature bake oven of 55 ℃ dries, treat that it is fully dried and carries out observation and the energy spectrum analysis that metal spraying is processed laggard line scanning Electronic Speculum, known ultrafiltration face major pollutants are Fe, Cu, Zn, Al and Si colloid pollution; The microbial contamination pattern simultaneously extracting is shown in Fig. 6;
(5) NaOH that the hydrochloric acid that employing pH is 1 and pH are 13 carries out respectively cleaning 45min in acid, alkali soaking and washing 45min(acid, alkali to the part ultra filtration membrane in the side line membrane module polluting respectively), to be cleanedly to acid and alkali cleansing solution, adopt ICP-Mass to carry out the quantitative test of Fe, Cu, Zn, Al and Si colloidal content and organic content respectively after fully, in cleaning fluid, the analysis result of key pollutants is in Table 2;
(6) adopt pH to be respectively 3 hydrochloric acid and 13 sodium hypochlorite carries out the optimization of cleaning condition to the contaminated ultra filtration membrane of part, regulate scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated ultra filtration membrane, the contaminated ultra filtration membrane water production rate after cleaning can revert to 98% of initial water production rate.
Key pollutants analysis result (unit: mg/L) in the contaminated ultra filtration membrane cleaning fluid of table 2
| ? | Fe | Cu | Zn | Al | | TOC |
| Embodiment | ||||||
| 1 | 0.7 | 0.3 | 0.39 | 0.2 | 10.5 | 4.9 |
| |
0.3 | 0.2 | 0.05 | 0.05 | 4.4 | 2.6 |
| |
0.21 | 0.19 | 0.23 | 0.15 | 5.6 | 3.8 |
| Embodiment 4 | 0.6 | 0.31 | 0.36 | 0.23 | 6.7 | 5.3 |
| |
0.5 | 0.34 | 0.42 | 0.35 | 5.3 | 9.4 |
| Embodiment 6 | 0.42 | 0.12 | 0.29 | 0.31 | 7.5 | 10.8 |
| Embodiment 7 | 0.35 | 0.15 | 0.44 | 0.41 | 8.6 | 13.7 |
Claims (10)
1. industrial ultra filtration membrane device pollutant, at line drawing and a method for decomposing, comprises the following steps:
Step (1) selects the ultra filtration membrane with relative dense layer surface structure to make side line membrane module, the carrier extracting as key pollutants in industrial ultra filtration membrane device operational process;
Step (2) is parallel to side line membrane module in industrial ultra filtration membrane device, regulates the Inlet and outlet water valve aperture size of side line membrane module, take that to control water inlet be 0～8m/s at the flow velocity of face;
In step (3) operational process, the water production rate of time recording side line membrane module changes, and when the relatively initial water production rate of water production rate declines 50～95%, ultra filtration membrane surface pollution thing content and pollution layer thickness reach anatomy requirement;
Step (4) is taken out the side line membrane module polluting, and takes out the contaminated ultra filtration membrane of part in side line membrane module, carries out observation and the anatomy of key pollutants after low temperature drying;
Step (5) adopts bronsted lowry acids and bases bronsted lowry respectively contaminated ultra filtration membrane in step (4) to be carried out to soaking and washing, detects the content size of specific pollutants in cleaning fluid.
2. method according to claim 1, it is characterized in that the ultra filtration membrane in step (1) with relative compact texture cortex comprises endodermis densification or relatively fine and close hollow-fibre membrane or the rolling ultrafiltration membrane of exodermis relatively, wherein the ultra filtration membrane pore size of dense layer surface is 0.001-0.02 μ m relatively.
3. method according to claim 2, is characterized in that hollow-fibre membrane or spiral wound membrane material select any one in bisphenol-a polysulfone, polyethersulfone, phenolic polyether sulphone and polyetherketone, poly (aryl ether sulfone ketone), Kynoar class.
4. method according to claim 1, is characterized in that Operation Mode Selection cross-flow mode or the dead end mode of side line membrane module.
5. method according to claim 1, is characterized in that the water production rate of the time recording side line membrane module in step (3) changes the interior 5-60min record of 0-5h once, and after side line membrane module operation 5h, 1-4h record once.
6. method according to claim 1, is characterized in that the contaminated ultra filtration membrane to taking out in step (4) adopts 20-60 ℃ of low temperature drying.
7. method according to claim 1, is characterized in that in step (4) contaminated ultrafiltration face adopt in SEM, SEM-EDS, SEM-XPS or FTIR any one or multiplely directly observe and dissect.
8. method according to claim 1, it is characterized in that it is 1 and the pH acid that is 13, immersion, the stirring and washing that alkaline cleaner carries out 15-45min that contaminated ultra filtration membrane in step (5) adopts respectively pH, the method for analyzing pollutant load in cleaning fluid is selected the analytical approach of ICP-Mass and TOC.
9. method according to claim 1, is characterized in that acid, the alkali of in step (5), selecting pH scope to be respectively 1-3 and 10-13 clean contaminated ultra filtration membrane respectively.
10. method according to claim 8 or claim 9, is characterized in that described acid selects any one in hydrochloric acid, oxalic acid, citric acid, and described alkali is selected any one in NaOH, sodium hypochlorite.
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| CN106006845B (en) * | 2016-07-05 | 2020-06-02 | 嘉兴悟净环保科技有限公司 | Method for improving flux of swine wastewater pretreated by ultrafiltration membrane method |
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| CN1657143A (en) * | 2004-12-10 | 2005-08-24 | 沈阳建筑大学 | Method for washing hollow fiber membrane component |
| JP2008183510A (en) * | 2007-01-30 | 2008-08-14 | Toray Ind Inc | Purified water production method and apparatus |
| CN201760237U (en) * | 2010-06-13 | 2011-03-16 | 北京科泰兴达高新技术有限公司 | Offline reverse osmosis membrane cleaning equipment |
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| CN1657143A (en) * | 2004-12-10 | 2005-08-24 | 沈阳建筑大学 | Method for washing hollow fiber membrane component |
| JP2008183510A (en) * | 2007-01-30 | 2008-08-14 | Toray Ind Inc | Purified water production method and apparatus |
| CN201760237U (en) * | 2010-06-13 | 2011-03-16 | 北京科泰兴达高新技术有限公司 | Offline reverse osmosis membrane cleaning equipment |
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