CN103091127B - Industrial reverse osmosis membrane device pollutant online extraction and analysis method - Google Patents
Industrial reverse osmosis membrane device pollutant online extraction and analysis method Download PDFInfo
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- CN103091127B CN103091127B CN201110340055.3A CN201110340055A CN103091127B CN 103091127 B CN103091127 B CN 103091127B CN 201110340055 A CN201110340055 A CN 201110340055A CN 103091127 B CN103091127 B CN 103091127B
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Abstract
The invention relates to an industrial reverse osmosis 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: a commercial reverse osmosis membrane is used for manufacturing a lateral line membrane assembly which serves as a key pollutant extraction carrier; the lateral line membrane assembly is connected in parallel into an industrial reverse osmosis membrane device; lateral line membrane assembly water-access valve opening degree is adjusted, such that inlet water membrane-surface flow velocity is controlled; 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 reverse osmosis membrane reaches an analysis requirement; the polluted reverse osmosis membrane is fetched and is subjected to pollutant observation and analysis; acid and alkali are respectively used for soaking and washing the polluted reverse osmosis membrane; and contents of specific pollutants in the washing liquid are detected. The method provided by the invention has high practicality. With the method, original industrial membrane assembly and operation conditions are not damaged, and reverse osmosis membrane pollution cause can be rapidly searched. Therefore, a good technical prospect is provided for long-term stable operation of actual industrial membrane devices.
Description
Technical field
The invention belongs to embrane method advanced treatment of wastewater and reuse field, relate to pollutant in industrial reverse osmosis membrane apparatus application process at line drawing and method for decomposing, relate more specifically to membrane contaminant in a kind of embrane method advanced treatment of wastewater and reuse process at line drawing, identification and pollutant cleaning method.
Background technology
In recent years, along with increasingly sharpening and the continuous reinforcement of law enforcement for environmental protection dynamics of shortage of fresh water, water-saving and emission-reducing correlation technique has obtained further promotion and application, wherein sewage deep reuse technology in actual commercial Application---and membrane separation technique is developed rapidly and has been widely applied in the middle of various fields under prior art condition.Membrane separation technique has become the current energy of solution, resources and environment problem in a sense, realizes one of technical foundation of sustainable development.In China, along with the introduction of membrane technology and deepening continuously of research work, membrane technology starts in chemical wastewater treatment, seawater, brackish water desalination, the field widespread uses such as environmental pollution improvement.
Reverse osmosis membrane pollutes can be divided into two large classes: a class is that reversible film pollution is concentration polarization, can be alleviated and be improved by the control of the optimization of fluid mechanics condition and the recovery; Another kind of pollution and the surface machinery being caused by charging performance and the absorption on film surface for irreversible membrane fouling stops up the pollution causing, this class pollution there is no at present effective measures and is improved, can only obtain by correlation technique means relevant information and the influence degree of key pollutants content to reverse osmosis membrane system stable operation of counter-infiltration face key pollutants, increase its tolerance degree to key pollutants thereby take suitable preprocessing means key pollutants to be eliminated to or developed high anti-pollution reverse osmosis membrane under certain condition, to reduce its pollution level.Although film pollution is different from concentration polarization concept, the two is closely related, usually occurs simultaneously, and in many occasions, concentration polarization is prelude and the root that causes film to pollute.According to the pollution problem producing in existing industrial membrane device operational process, pollutant composition in existing petrochemical wastewater system advanced treating can be divided into following three kinds by its kind and character: 1. inorganic pollution, often show as multiple situation, one is that colloidal material deposits and accumulation for a long time at face, and common colloidal type inorganic pollutant mainly contains ferric hydroxide, aluminium hydroxide, silicon dioxide colloid etc.; It two is the reason of scale species because of the concentration polarization of counter-infiltration face, causes face fouling class ion concentration to exceed its solubility product, forms two or more inorganic scales and deposits at face, and this common pollutant has CaCO
3, CaSO
4, BaSO
4, SrSO
4deng; 2. organic molecule forms Organic Pollution in counter-infiltration face absorption, this type of pollute not only with organism nature and reverse osmosis membrane own characteristic in close relations outside, this pollutant also with waste water system in organism kinds and relation with contents close; 3. microbial contamination main manifestations is adhesion and the growth of microorganism at face, and common microbial contamination has bacterium, algae class etc.In addition, affect that industrial reverse osmosis membrane apparatus is long-term, the pollutant of stable operation except kind and content thereof, the operating conditionss such as feed temperature in actual motion, pressure, flow velocity, concentration also can produce considerable influence to the pollution of reverse osmosis membrane system.
Along with further carrying out of national water-saving and emission-reducing policy and waste water advanced processing and reuse work, membrane separation technique obtains large-scale application in petrochemical wastewater field, the reverse osmosis membrane pollution problem thereupon bringing has further restricted applying of membrane process, therefore, how quick, in time, obtain accurately and effectively and grasp that to affect counter-infiltration system long-term, the correlation technique information of the key pollutants of stable operation, to carrying out sewage deep reuse work and promoting fast the commercial Application process of membrane technology in field of waste water treatment, there is stronger use value and realistic meaning.
Although the pollutant that adopts Chemical Decomposition and concentrated method can realize to a certain extent in waste water extracts, but the contaminant information of extracting is not only subject to the representative influence of water sample larger, and the difference of the contaminant information of obtaining and industrial membrane device service condition is larger, thereby the pollutant extracting is less to the directive significance of industrial reverse osmosis membrane apparatus.In actual commercial Application process, the acquisition methods of the actual pollutant of above-mentioned counter-infiltration face is mainly to dissect and analyze after the industrial reverse osmosis membrane assembly that takes out severe contamination after reverse osmosis membrane system is shut down cuts, and the major defect of the method shows as the following aspects: in (1) reverse osmosis membrane apparatus operational process, can not obtain in time film surface pollution thing information; (2) the membrane module analysis after dissection is only used 1/30 of a membrane area can carry out the multianalysis of pollutant, causes the destruction because dissecting the whole membrane module causing to use; (3) can obtain relevant contaminant information even if the reverse osmosis membrane surface pollution thing after shutting down dissects, but it is consuming time longer to carry out the selection and optimization of cleaning, can affect normal production and the operation of whole system.
The existence of practical problems in above-mentioned reverse osmosis membrane commercial Application, not only cause the wasting of resources and the operating cost that frequent replacing membrane module that in industrial membrane application process, reverse osmosis membrane system causes because of severe contamination causes to increase, and in reverse osmosis membrane system operational process, cannot grasp in time film surface pollution thing information, cannot be in time provide foundation and reference for long-term, the stable operation of industrial reverse osmosis membrane system and the optimization of key parameter.
Summary of the invention
Cannot quick obtaining for reverse osmosis membrane surface pollution thing in industrial reverse osmosis membrane apparatus operational process, obtaining of pollutant need to be taking the destruction of whole membrane module as cost and the film surface pollution thing technical matters that exist in dissecting, the invention provides a kind of industrial reverse osmosis membrane surface pollution thing at line drawing, method for decomposing, not only can realize film 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 reverse osmosis membrane surface pollution thing that can be comparatively detailed, can provide data reference and foundation for the choice and optimization of the industrial reverse osmosis membrane assembly cleaning of severe contamination on this basis.
The technical solution used in the present invention:
The industrial reverse osmosis membrane apparatus pollutant of one provided by the invention extracts and method for decomposing, comprises the following steps:
(1) select commercial reverse osmosis membrane to make side line membrane module, the carrier extracting as key pollutants in industrial reverse osmosis membrane apparatus operational process, wherein key pollutants refers to the pollutant that affects reverse osmosis membrane operation, mainly refers to dissolved organic matter matter, colloid, microorganism, bacterium, scale species etc.
(2) side line membrane module is parallel in industrial reverse osmosis membrane apparatus, regulates the Inlet and outlet water valve aperture size of side line membrane module, to control water inlet crossflow velocity as 0～8m/s;
(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 reverse osmosis membrane surface pollution thing content and pollution layer thickness reach anatomy requirement;
(4) take out contaminated side line diaphragm, carry out the observation of film surface pollution thing after choosing fraction reverse osmosis membrane low temperature drying, and carry out the scanning in contaminated interval in conjunction with energy spectrum analysis, qualitative definite pollutant kind;
(5) adopt bronsted lowry acids and bases bronsted lowry respectively the contaminated reverse osmosis membrane of remaining part in step (4) to be carried out to soaking and washing, and detect the content size of specific pollutants in cleaning fluid, wherein specific pollutants refers to the pollutant detecting in step (4), according to the qualitative detection situation of pollutant in step (4), in this step, again carry out quantitative test.
After above-mentioned steps is processed, can draw composition and the content of key pollutants in industrial reverse osmosis membrane, avoid shutting down because of the device that the anatomy of industrial reverse osmosis membrane assembly and the optimization of cleaning cause, and the economic loss causing thus.Can effectively clean and performance recovery contaminated reverse osmosis membrane according to the result in line drawing, anatomy.
Described, the commercial reverse osmosis membrane in step 1 is advisable with the antipollution RO film of polyamide composite film and various hydrophilic modifying thereof (mainly comprising sulfonation, carboxylated and PVA coating etc.), and preferred lower pressure anti-pollution reverse osmosis membrane is as PROC10, PROC20;
Described, commercial reverse osmosis membrane in step 1 with commercial reverse osmosis membrane widgets comprise 1812,2540,4040 and the nonstandard reverse osmosis membrane assembly of other size be advisable, preferably 1812,2540 reverse osmosis membrane assemblies or the corresponding counter-infiltration diaphragm of corresponding industrial membrane assembly;
Described, the structure of side line reverse osmosis membrane assembly has and the similar structure of industrial reverse osmosis 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 reverse osmosis membrane assembly is this side line assembly is at 100cm
2-2m
2;
Described, in step 2, side line assembly adopts mode in parallel to be connected with industrial reverse osmosis membrane apparatus, and wherein the method for operation of side line membrane module is cross-flow; In operational process, regulate the flow velocity of water inlet in side line membrane module to be advisable with 4-10m/s, optimum with 5-8m/s;
Described, the water production rate of the time recording side line membrane module in step 3 changes, and 1-4h record is once advisable, and optimum records primary side line component water production rate with 2-3h;
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 contaminated reverse osmosis membrane in step 4 adopts 25-60 DEG C of low temperature drying, and optimum bake out temperature is 30-50 DEG C;
Described, the contaminated reverse osmosis membrane surface pollution thing 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 15-45min that the contaminated reverse osmosis membrane 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 reverse osmosis 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 reverse osmosis 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 NaOH, Na
4eDTA, Na-SDS, NaOH/Na
4the composite clean-out system that EDTA or NaOH/Na-SDS form etc., bronsted lowry acids and bases bronsted lowry optimum is respectively with hydrochloric acid and NaOH and the composite clean-out system of EDTA;
In the optimization of described contaminated reverse osmosis membrane cleaning condition, comprise methyl alcohol, ethanol, vinyl ethylene glycol only son hydrochlorate etc. for the clean-out system of organic pollutant, optimum with ethanol, vinyl ethylene glycol only son hydrochlorate;
Patent of the present invention and the essential distinction of prior art are to adopt the counter-infiltration diaphragm that the reverse osmosis module model in industrial membrane device is consistent/little membrane module or low pressure, the side line assembly that anti-pollution reverse osmosis membrane sheet/membranelle assembly extracts as reverse osmosis membrane surface pollution thing, can be in the situation that not affecting existing industrial membrane device operation, key pollutants in actual waste water system is extracted, and can be to the pollutant extracting in the situation that not destroying original industrial membrane assembly, can obtain in time the correlation technique information of film surface pollution thing, on this basis, carry out the optimization of reverse osmosis membrane surface pollution thing cleaning.
The invention has the beneficial effects as follows:
Extraction, anatomy and the application process of a kind of industrial reverse osmosis membrane apparatus key pollutants of the present invention, solve the defect problem of the static rapid extraction of pollutant in existing waste water system, as the contaminant information of extracting is subject to the representative influence of institute's water sampling larger, can not be from the objective reaction waste system of the ruuning situation of the fluctuation of the variation of long period, actual water quality and industrial membrane device the correlation technique information of pollutant; Can obtain timely and effectively the operating major pollutants of industrial reverse osmosis membrane apparatus by enforcement of the present invention, and by the use in conjunction of relevant method for decomposing, the selection and the optimization that can be industrial reverse osmosis membrane apparatus chemical cleaning technology scheme provide stronger technical basis and reference.The inventive method is simple, practical, be applicable in existing industrial membrane device operational process various because of pollute cause hydraulic performance decline problem, at the cause investigation not destroying under original industrial membrane assembly and service condition, thereby, promote and there is good technical prospect for long-term, the stable operation of actual industrial film device and commercial Application.
Brief description of the drawings
Fig. 1 is the side line assembly schematic diagram that industrial reverse osmosis membrane apparatus pollutant extracts, and wherein A is side line base (101 base vertical views; 102 produce water flow passage; 103 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 the counter-infiltration face key pollutants pattern extracting in embodiment 1.
Fig. 3 is face key pollutants pattern and the power spectrum result of extracting in embodiment 1.
Fig. 4 is face key pollutants pattern and the power spectrum result of extracting in embodiment 1.
Fig. 5 is the counter-infiltration face microbial contamination pattern extracting in embodiment 2.
Fig. 6 is the organic contaminant FTIR result of extracting in embodiment 3.
Embodiment
Embodiment 1
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 100cm by effective film area
2tao Shi BW30HRLE counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter electricity of feed water by reverse osmosis is led as 1500us/cm, COD
crfor 120mg/L, regulating side line assembly concentrated water discharge valve opening and intake pressure is 0.5MPa, and regulating the crossflow velocity of water inlet in side line assembly is 4m/s;
(3) produce water from side line assembly and start to record initial water production rate, change according to water production rate of interval 1h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 98%, reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, be cut into 4 block sizes and a low-temperature bake oven that is placed in 25 DEG C is wherein dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, the reverse osmosis membrane surface pollution thing pattern and the SEM-EDS analysis result that extract are shown in respectively Fig. 2-Fig. 4, and hence one can see that, and counter-infiltration face major pollutants are Al, Si colloid pollution and CaCO
3, Ca
3(PO
4)
2inorganic scale pollutes;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 45min (acid, alkali respectively clean 45min) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) adopt pH to be respectively 1 HCl and 0.1w% NaOH/0.025w%Na-SDS and carry out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 98% of initial water production rate.
Embodiment 2
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 100cm by effective film area
2tao Shi XLE counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) the side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter electricity of feed water by reverse osmosis is led as 2000us/cm, COD
crfor 80mg/L, regulating concentrated water discharge valve opening and the intake pressure of side line assembly is 0.8MPa, and regulating the crossflow velocity of water inlet is 5m/s;
(3) produce water from side line assembly and start to record its initial water production rate, change according to water production rate of interval 2h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 90%, think that reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, be cut into 4 block sizes and will be wherein one be placed in 30 DEG C 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, it is Al, Si colloid pollution and CaCO that the pollutant pattern extracting and SEM-EDS analyze known counter-infiltration face major pollutants
3, Ca
3(PO
4)
2inorganic scale pollutes, and wherein microbial contamination pattern is as Fig. 5;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 30min (acid, alkali respectively clean 30min) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) employing pH is respectively 2 oxalic acid and 0.1w% NaOH/1.0w%Na
4eDTA carries out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 95% of initial water production rate.
Embodiment 3
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 500cm by effective film area
2tao Shi LP counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) the side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter electricity of feed water by reverse osmosis is led as 4000us/cm, COD
crfor 60mg/L, regulating concentrated water discharge valve opening and the intake pressure of side line assembly is 1.0MPa, and regulating the crossflow velocity of water inlet is 6m/s;
(3) produce water from side line assembly and start to record its initial water production rate, change according to water production rate of interval 3h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 95%, think that reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, be cut into 4 block sizes and a low-temperature bake oven that is placed in 35 DEG C is wherein dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, it is Al, Si colloid pollution and CaCO that the reverse osmosis membrane surface pollution thing pattern extracting and SEM-EDS analyze known counter-infiltration face major pollutants
3, Ca
3(PO
4)
2inorganic scale pollutes, and wherein the results of IR of Organic Pollution is as Fig. 6;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 25min (each 25min of cleaning in acid, alkali) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) adopt pH to be respectively 3 citric acid and 12 NaOH carries out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 95% of initial water production rate.
Embodiment 4
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 200cm by effective film area
2hydranautics ESPA1 counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) the side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter conductivity of feed water by reverse osmosis is 6000us/cm, COD
crfor 40mg/L, regulating concentrated water discharge valve opening and the intake pressure of side line assembly is 1.2MPa, and regulating the crossflow velocity of water inlet in side line assembly is 7m/s;
(3) produce water from side line assembly and start to record its initial water production rate, change according to water production rate of interval 4h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 80%, think that reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, be cut into 4 block sizes and a low-temperature bake oven that is placed in 40 DEG C is wherein dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, it is Al, Si colloid pollution and CaCO that the reverse osmosis membrane surface pollution thing pattern extracting and SEM-EDS analyze known counter-infiltration face major pollutants
3, Ca
3(PO
4)
2inorganic scale pollutes;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 40min (acid, alkali respectively clean 40min) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) employing pH is respectively 4 hydrochloric acid and 0.01w% NaOH 1.0w%Na
4eDTA carries out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 95% of initial water production rate.
Embodiment 5
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 100cm by effective film area
2hydranautics ESPA4 counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) the side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter electricity of feed water by reverse osmosis is led as 8000us/cm, COD
crfor 60mg/L, regulating concentrated water discharge valve opening and the intake pressure of side line assembly is 1.4MPa, and regulating the crossflow velocity of water inlet is 8m/s;
(3) produce water from side line assembly and start to record its initial water production rate, change according to water production rate of interval 4h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 70%, think that reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, be cut into 4 block sizes and a low-temperature bake oven that is placed in 45 DEG C is wherein dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, it is Al, Si colloid pollution and CaCO that the reverse osmosis membrane surface pollution thing pattern extracting and SEM-EDS analyze known counter-infiltration face major pollutants
3, Ca
3(PO
4)
2inorganic scale pollutes;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 45min (acid, alkali respectively clean 45min) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) adopt pH to be respectively 4 hydrochloric acid and 12 NaOH carries out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 95% of initial water production rate.
Embodiment 6
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 100cm by effective film area
2hydranautics PROC10 counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) the side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter electricity of feed water by reverse osmosis is led as 6000us/cm, COD
crfor 80mg/L, regulating concentrated water discharge valve opening and the intake pressure of side line assembly is 1.2MPa, and regulating the crossflow velocity of water inlet is 9m/s;
(3) produce water from side line assembly and start to record its initial water production rate, change according to water production rate of interval 3h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 90%, think that reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, be cut into 4 block sizes and a low-temperature bake oven that is placed in 60 DEG C is wherein dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, it is Al, Si colloid pollution and CaCO that the reverse osmosis membrane surface pollution thing pattern extracting and SEM-EDS analyze known counter-infiltration face major pollutants
3, Ca
3(PO
4)
2inorganic scale pollutes;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 40min (acid, alkali respectively clean 40min) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) employing pH is respectively 2 HCl and 0.1w% NaOH 1.0w%Na
4eDTA carries out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 94% of initial water production rate.
Embodiment 7
A kind of industrial reverse osmosis membrane apparatus pollutant is in the concrete implementation step of line drawing, anatomy and application process thereof:
(1) be 100cm by effective film area
2hydranautics PROC20 counter-infiltration diaphragm be fixed on pollutant and extract in side line component drawings 1;
(2) the side line assembly in step 1 is parallel on industrial reverse osmosis membrane apparatus, the main water quality parameter electricity of feed water by reverse osmosis is led as 10000us/cm, COD
crfor 70mg/L, regulating concentrated water discharge valve opening and the intake pressure of side line assembly is 1.6MPa, and regulating the crossflow velocity of water inlet is 10m/s;
(3) produce water from side line assembly and start to record its initial water production rate, change according to water production rate of interval 4h record.In the time that the relatively initial water production rate decline of water production rate of side line assembly is greater than 60%, think that reverse osmosis membrane surface pollution thing content and pollution level reach anatomy requirement;
(4) the counter-infiltration diaphragm of taking-up severe contamination, and again change the untapped reverse osmosis membrane of a slice and be fixed in side line assembly, the counter-infiltration diaphragm of the severe contamination of taking-up is cut into 4 block sizes and a low-temperature bake oven that is placed in 55 DEG C is wherein dried, treat it is fully dry, metal spraying is processed laggard line scanning Electronic Speculum observation and energy spectrum analysis, it is Al, Si colloid pollution and CaCO that the reverse osmosis membrane surface pollution thing pattern extracting and SEM-EDS analyze known counter-infiltration face major pollutants
3, Ca
3(PO
4)
2inorganic scale pollutes;
(5) NaOH that to adopt pH be 1 hydrochloric acid and pH is 13 carries out acid, alkali soaking and washing 45min (acid, alkali respectively clean 45min) to one in its excess-three piece in step (4) respectively, to be cleanedly adopts ICP-Mass to carry out Al, Si colloid, Ca to acid and alkali cleansing solution respectively after fully
2+, PO
4 3-and organic quantitative test, in cleaning fluid, the analysis result of key pollutants is in table 1;
(6) adopt pH to be respectively 3 hydrochloric acid and 0.1w% NaOH 0.025w%Na-SDS and carry out the optimization of cleaning condition to one that remains in two, regulate detergent concentration, scavenging period, aeration time, aeration intensity, flush time, backwash rate etc. to clean contaminated reverse osmosis membrane, the contaminated reverse osmosis membrane water production rate after cleaning reverts to 90% of initial water production rate.
Key pollutants analysis result (unit: mass concentration) in the contaminated reverse osmosis membrane cleaning fluid of table 1
| Al | Si | CaCO 3 | Ca 3(PO 4) 2 | TOC | |
| Embodiment 1 | 0.21 | 4.8 | 31.3 | 4.5 | 0.16 |
| Embodiment 2 | 0.13 | 3.5 | 20.8 | 3.1 | 0.12 |
| Embodiment 3 | 0.15 | 4.2 | 27.5 | 3.9 | 0.11 |
| Embodiment 4 | 0.11 | 3.1 | 19.5 | 2.6 | 0.09 |
| Embodiment 5 | 0.12 | 2.9 | 15.2 | 1.9 | 0.13 |
| Embodiment 6 | 0.14 | 3.3 | 22.1 | 2.7 | 0.12 |
| Embodiment 7 | 0.09 | 1.5 | 9.8 | 1.6 | 0.08 |
Claims (10)
1. industrial reverse osmosis membrane apparatus pollutant, at line drawing and a method for decomposing, comprises the following steps:
Step (1) selects reverse osmosis membrane to make side line membrane module, the carrier extracting as key pollutants in industrial reverse osmosis membrane apparatus operational process;
Step (2) is parallel to side line membrane module in industrial reverse osmosis membrane apparatus, regulates the Inlet and outlet water valve aperture size of side line membrane module, taking control water inlet at the flow velocity of face as 4～10m/s;
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%, reverse osmosis membrane surface pollution thing content and pollution layer thickness reach anatomy requirement;
Step (4) is taken out observation and the anatomy of carrying out pollutant after contaminated counter-infiltration diaphragm low temperature drying;
Step (5) adopts bronsted lowry acids and bases bronsted lowry respectively contaminated reverse osmosis 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, is characterized in that the reverse osmosis membrane in step (1) is selected polyamide composite film or antipollution RO film or low-pressure reverse osmosis membrane to polyamide composite film hydrophilic modifying.
3. method according to claim 2, is characterized in that described hydrophilic modifying mainly comprises any one in sulfonation, carboxylated and PVA coating.
4. method according to claim 1, is characterized in that the Operation Mode Selection cross-flow mode of side line membrane module.
5. method according to claim 1, is characterized in that the water production rate time recording of the side line membrane module in step (3) with 1-4h once.
6. method according to claim 1, is characterized in that the contaminated counter-infiltration diaphragm in step (4) adopts 25-60 DEG C of low temperature drying.
7. method according to claim 1, is characterized in that in step (4) that contaminated reverse osmosis membrane surface pollution thing adopts in SEM, SEM-EDS, SEM-XPS or FTIR any one or multiplely observes 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 reverse osmosis 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 reverse osmosis 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 NaOH, Na
4eDTA, Na-SDS, NaOH/Na
4the composite clean-out system of any one in EDTA or NaOH/Na-SDS or multiple formation.
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| CN106770403B (en) * | 2016-11-15 | 2020-07-14 | 中国科学院上海高等研究院 | Method for detecting influence of different pollutants on reverse osmosis membrane on performance of membrane device |
| CN112147475B (en) * | 2020-11-03 | 2023-05-02 | 国网四川省电力公司电力科学研究院 | Method for identifying state of room temperature vulcanized silicone rubber material |
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