CN102580546A - Method evaluating membrane chemical cleaning recovery performance - Google Patents
Method evaluating membrane chemical cleaning recovery performance Download PDFInfo
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- CN102580546A CN102580546A CN2011100205830A CN201110020583A CN102580546A CN 102580546 A CN102580546 A CN 102580546A CN 2011100205830 A CN2011100205830 A CN 2011100205830A CN 201110020583 A CN201110020583 A CN 201110020583A CN 102580546 A CN102580546 A CN 102580546A
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Abstract
The invention discloses a method for evaluating membrane bioreactor (MBR) membrane chemical cleaning recovery performance, which comprises the steps of arranging a stirring type ultrafiltering cup on a magnetic stirrer, connecting the stirring type ultrafiltering cup with a sealed container, connecting the sealed container with a pressure reduction regulation valve, connecting the pressure reduction regulation valve with a nitrogen steel bottle, installing a pressure meter on an air outlet of the pressure reduction regulation valve, connecting a water outlet of the stirring type ultrafiltering cup with a balance, and connecting the balance with a computer. A small evaluation device is used for evaluating initial membrane resistance R1 of a membrane, membrane resistance R2 after the membrane is polluted and membrane resistance R3 after the membrane is chemically cleaned, and then the chemical cleaning recovery performance of the membrane which is cleaned on chemical conditions is judged after slurry is filtered. The method is simple in operation, low in cost and capable of quickly judging membrane chemical cleaning recovery performance, choosing appropriate chemical cleaning chemicals and confirming optimized cleaning schemes.
Description
Technical field
The invention belongs to the membrane technology field, be specifically related to a kind of method of evaluated for film Chemical cleaning restorability.
Background technology
Membrane technology has obtained using widely and having shown vast potential for future development as a kind of new separation technology in wastewater treatment, obtain increasing popularization in recent years.Membrane bioreactor (MBR) is a kind of novel water technology that is combined with biological processing unit by film separation unit; Replace second pond with membrane module; In bioreactor, can keep the high activity sludge concentration; Reduce the sewage treatment facility floor space, and through keeping low sludge loading to reduce sludge yield.Compare with traditional biochemical water technology, membrane bioreactor has following main feature: treatment effeciency is high, effluent quality is good; Facility compact, floor space are little; Easy realization is controlled automatically, operational management is simple.But the MBR technology also comes with some shortcomings, and especially inevitably membrane pollution problem is the principal element that restriction MBR technology is applied in a wider context always.
For MBR system handles waste water; The film pollution can cause the rising of membrane resistance, the decline of membrane flux and the raising of operating pressure; This carries out Chemical cleaning with regard to inevitable requirement to film; To recover the runnability of film, promptly membrance chemistry cleans restorability, guarantees that the actual treatment amount of engineering project reaches design scale.Membrance chemistry cleans restorability and characterizes through membrance chemistry cleaning recovery rate; It is an important indicator of evaluated for film treatment system that membrance chemistry cleans recovery rate; Be related to the service life of film and the replacement cycle of membrane module, and then influence the investment operating cost of whole project.Film after contaminated passes through Chemical cleaning, and film pollutes effectively to be removed, and to recover the runnability of film, the MBR technology could be by effective application in relevant wastewater treatment.In case and film pollutes and can not effectively be removed by Chemical cleaning, promptly film properties can't be restored, and then means the MBR technology is applied in this kind wastewater treatment, can face very big risk.
In addition, cause the normally mixture of various materials in the waste water of pollutant that the MBR film pollutes in the wastewater treatment, thereby cause that dissimilar films pollutes, for example: the biological pollution that causes by microorganism, bacterial extracellular polymer thing etc.; The organic contamination that causes by oil, fat, hardly degraded organic substance etc.; By CaCO
3, CaSO
4, BaSO
4Deng the face fouling that causes; By iron, the metal oxide that aluminium, manganese etc. cause pollutes; And the pollution that causes by silt and silicon etc.Therefore, must reach according to the polluter type that contains in the waste water, select suitable Chemical cleaning medicament, and optimize cleaning program to different wastewater characteristics.
At present, to wastewater treatment MBR project, generally all will be through carrying out the MBR pilot plant test; After moving continuously for a long time; Cause that film pollutes and membrane resistance rises, select different chemical agents that film is carried out Chemical cleaning then, the recovery rate of film properties after the investigation Chemical cleaning.Judge the feasibility that adopts this kind of MBR technical finesse waste water according to the recovery effects of film properties after the Chemical cleaning, and confirm adopt any or the number of chemical cleaning agent, and make feasible cleaning program.The operator scheme of even now can obtain result relatively reliably, but often needs long test period, and the bigger man power and material who drops into.And, influence the popularization and the sale of product often because aspects such as a lot of equipment and field condition restriction can not be carried out pilot scale very soon smoothly, thereby can't be made the judgement that can adopt MBR to handle this kind waste water in the short period of time rapidly.
Summary of the invention
The objective of the invention is under the existing situation; The problem that the judgement of MBR membrance chemistry cleaning restorability and the selection of cleaning agent are wasted time and energy; Provide a kind of simple to operate, with low cost, can reflect fast that membrance chemistry cleans restorability and the reliable method of selecting suitable cleaning agent.
The object of the invention can reach through following measure:
A kind of method of estimating flat sheet membrane Chemical cleaning restorability may further comprise the steps:
(1) use small-sized evaluating apparatus to confirm that the initial film resistance R1 of flat sheet membrane, film are at membrane resistance R2 after the pollution and the membrane resistance R3 of film after Chemical cleaning;
(2) according to the initial film resistance R1 of film, film the membrane resistance R2 after the pollution and film the membrane resistance R3 after the Chemical cleaning judge film in sludge filtration after the Chemical cleaning restorability under the Chemical cleaning condition;
Wherein, Described small-sized evaluating apparatus is: stirring-type ultrafiltration cup is placed on the agitator, and the ultrafiltration cup is connected with airtight container, and airtight container is connected with decompression valve; Decompression valve is connected with the nitrogen steel cylinder; Setting pressure table on the decompression valve escape pipe, the water outlet of stirring-type ultrafiltration cup is connected with balance, and balance is connected with computer.
Use small-sized evaluating apparatus to confirm that the initial film resistance R1 of flat sheet membrane, film in the method for membrane resistance R2 after the pollution and the membrane resistance R3 of film after Chemical cleaning are in the described step (1):
1. dull and stereotyped diaphragm is cut into diaphragm according to the specification of stirring-type ultrafiltration cup; Diaphragm is placed stirring-type ultrafiltration cup and fixes; Pure water is inserted in stirring-type ultrafiltration cup and the airtight container; Stirring and regulating system pressure filtered 5-20 minute to fixed value, calculated the initial film resistance R1 of film behind the flux J1 of test diaphragm in pure water;
2. after stirring-type ultrafiltration cup and being connected of airtight container being broken off; Stirring-type ultrafiltration cup directly is connected with decompression valve; With concentration is that the mud of 1000-3000mg/L is poured in the stirring-type ultrafiltration cup and filtered 10-30 minute; Clean the diaphragm in the stirring-type ultrafiltration cup with pure water after the sludge filtration, accomplish once film is carried out the circulation that pure water cleans after the sludge filtration, repeat this circulation 10-30 time;
3. the diaphragm after above-mentioned pure water 2. being cleaned places stirring-type ultrafiltration cup and fixes; Stirring-type ultrafiltration cup is connected with airtight container; Airtight container is connected with decompression valve, and pure water is inserted in stirring-type ultrafiltration cup and the airtight container, and stirring and regulating system pressure are to fixed value; Filtered 5-20 minute, and calculated the membrane resistance R2 of film after pollution behind the flux J2 of test diaphragm in pure water;
4. the diaphragm in the above-mentioned stirring-type ultrafiltration cup is 3. taken out, be immersed in the chemical agent solution, carry out 3-24 hour Chemical cleaning;
5. the diaphragm after the Chemical cleaning is placed stirring-type ultrafiltration cup and fix; Stirring-type ultrafiltration cup is connected with airtight container; Airtight container is connected with decompression valve, and pure water is inserted in stirring-type ultrafiltration cup and the airtight container, and stirring and regulating system pressure are to fixed value; Filtered 5-20 minute, and calculated the membrane resistance R3 of film after Chemical cleaning behind the flux J3 of test diaphragm in pure water.
Pure water described in the present invention is meant that its electrical conductivity is less than 10 μ s/cm through reverse osmosis membrane and the later water of ion exchange resin treatment.The pure water amount of inserting when described pure water is inserted stirring-type ultrafiltration cup and airtight container is all less than restriction.
Calculating membrane resistance behind the flux of test diaphragm in pure water described in the present invention all calculates according to Darcy's law.
Described chemical agent solution is one or more in liquor natrii hypochloritis, hydrogenperoxide steam generator, hydrochloric acid solution, sodium hydroxide solution, citric acid solution or the oxalic acid solution.Wherein said multiple being meant earlier soaked in other certain chemical agent solution after the immersion in certain chemical agent solution again.Make up the cleaning recovery effects that film is polluted according to different chemical medicament or medicament, confirm the cleaning program of optimizing.Liquor natrii hypochloritis, hydrogenperoxide steam generator, sodium hydroxide solution are used to clean the biological pollution and the organic contamination of face, and hydrochloric acid solution, citric acid solution and oxalic acid solution are used to clean the pollution of diaphragm fouling and metal oxide formation.To different wastewater characteristics and membrane contaminant type, select suitable Chemical cleaning medicament.The scavenging period of diaphragm in described any chemical agent is 3～24h.Described liquor natrii hypochloritis's concentration is counted 500-2000mg/L with effective chlorine density; The concentration of described hydrogenperoxide steam generator is 1000-5000mg/L; The concentration of described sodium hydroxide solution is 100-1000mg/L; The concentration of described hydrochloric acid solution is 100-1000mg/L, and the concentration of described citric acid solution is 1000mg/L-5000mg/L, and the concentration of described oxalic acid solution is 500mg/L-2000mg/L.
Described (2) according to the initial film resistance R1 of film, film the membrane resistance R2 after the pollution and film the membrane resistance R3 after the Chemical cleaning judge film in sludge filtration after the method for the Chemical cleaning restorability under the Chemical cleaning condition be: calculate membrance chemistry through formula (R2-R3)/(R2-R1) * 100% and clean recovery rate.
Said membrance chemistry cleaned recovery rate more than or equal to 80% o'clock, and the life cycle that is judged as film is long, the replacing frequency is low, was fit to handle this waste water; Said membrance chemistry cleans recovery rate and is lower than at 80% o'clock, and the life cycle that is judged as film is short, it is higher to change frequency, needs to adopt the method for number of chemical cleaning agent combination; After two or more Chemical cleaning medicament combination of process was cleaned, membrance chemistry cleaned recovery rate and still is lower than at 60% o'clock, and the life cycle weak point, the replacing frequency that are judged as film are high, are not suitable for handling this waste water.
The invention solves and existingly clean the problem that the selection of judgement and the cleaning agent of restorability is wasted time and energy to membrance chemistry.Need not implement long wastewater treatment MBR pilot plant test; Adopt stirring-type ultrafiltration cup and other evaluating apparatus that MBR mud is carried out the evaluation that membrance chemistry cleans restorability; Simple to operate; With low cost, can reflect quickly that membrance chemistry cleans restorability, and select suitable Chemical cleaning medicament and the cleaning program of confirming to optimize.
Description of drawings
Installation drawing when Fig. 1 tests the flux of diaphragm in pure water for the present invention.
Installation drawing when Fig. 2 filters in mud for diaphragm of the present invention.
As shown in the figure, 1 is that nitrogen steel cylinder, 2 is that decompression valve, 3 is that Pressure gauge, 4 is that airtight container, 5 is that magnetic stirring apparatus, 6 is that stirring-type ultrafiltration cup, 7 is that diaphragm, 8 is that balance, 9 is that beaker, 10 is a computer.
The specific embodiment
In conjunction with accompanying drawing and specific embodiment the present invention is done further explain.
The calculating that the initial film resistance R1 of film, film clean recovery rate at mensuration and the membrance chemistry of membrane resistance R2 after the pollution and the membrane resistance R3 of film after Chemical cleaning, below each embodiment all adopt following steps:
1. as shown in Figure 1, nitrogen steel cylinder 1, decompression valve 2, Pressure gauge 3, airtight container 4, magnetic stirring apparatus 5, stirring-type ultrafiltration cup 6, balance 8, beaker 9 are connected with computer 10.Wherein, Stirring-type ultrafiltration cup 6 is placed on the magnetic stirring apparatus 5, and stirring-type ultrafiltration cup 6 is connected with airtight container 4, and airtight container 4 is connected with decompression valve 2; Decompression valve 2 is connected with nitrogen steel cylinder 1; Setting pressure table 3 on decompression valve 2 escape pipes, the water outlet of stirring-type ultrafiltration cup 6 are received beaker 9 the insides that are placed on balance 8, and balance 8 is connected with computer 10;
2. dull and stereotyped diaphragm is cut into diaphragm 7 according to the specification of stirring-type ultrafiltration cup 6; Diaphragm 7 places stirring-type ultrafiltration cup 6 and fixes; Pure water is inserted in stirring-type ultrafiltration cup 6 and the airtight container 4, opens magnetic stirring apparatus 5 to constant rotational speed, through decompression valve 2 regulating system pressure to fixed value; Filtered 5-20 minute, and calculated the initial film resistance R1 of film behind the flux J1 of test diaphragm 7 in pure water;
3. as shown in Figure 2; Breaking off being connected of stirring-type ultrafiltration cup 6 and airtight container 4, stirring-type ultrafiltration cup 6 directly is connected with decompression valve 2, is that the mud of 1000-3000mg/L is poured in the stirring-type ultrafiltration cup 6 with concentration; Open magnetic stirring apparatus 5 to constant rotational speed;, filtered 10-30 minute to fixed value through decompression valve 2 regulating system pressure, clean the diaphragm 7 in the stirring-type ultrafiltration cup 6 with pure water after the sludge filtration; Accomplish once film is carried out the circulation that pure water cleans after the sludge filtration, repeat this circulation 10-30 time;
4. as shown in Figure 1, the diaphragm 7 after above-mentioned pure water 3. cleaned places stirring-type ultrafiltration cup 6 and fixes, and stirring-type ultrafiltration cup 6 is connected with airtight container 4; Airtight container 4 is connected with decompression valve 2; Pure water is inserted in stirring-type ultrafiltration cup 6 and the airtight container 4, opens magnetic stirring apparatus 5 to constant rotational speed, through decompression valve 2 regulating system pressure to fixed value; Filtered 5-20 minute, and calculated the membrane resistance R2 of film after pollution behind the flux J2 of test diaphragm 7 in pure water;
5. the diaphragm in the above-mentioned stirring-type ultrafiltration cup 6 4. 7 is taken out, behind the type selecting chemical agent solution according to mud, be immersed in the chemical agent solution, carry out Chemical cleaning;
6. as shown in Figure 1, the diaphragm after the Chemical cleaning 7 is placed stirring-type ultrafiltration cup 6 and fixes, stirring-type ultrafiltration cup 6 is connected with airtight container 4; Airtight container 4 is connected with decompression valve 2; Pure water is inserted in stirring-type ultrafiltration cup 6 and the airtight container 4, opens magnetic stirring apparatus 5 to constant rotational speed, through decompression valve 2 regulating system pressure to fixed value; Filtered 5-20 minute, and calculated the membrane resistance R3 of film after Chemical cleaning behind the flux J3 of test diaphragm 7 in pure water;
7. calculate membrance chemistry through formula (R2-R3)/(R2-R1) * 100% and clean recovery rate, estimate diaphragm in this sludge filtration after the Chemical cleaning restorability under the Chemical cleaning condition.
Accuracy for checking the method for the invention; In each embodiment, all carried out corresponding pilot plant test; Wherein the initial film resistance R1 of the film in the method for the invention, film are represented at membrane resistance S2 after the pollution and the membrane resistance S3 of film after Chemical cleaning with initial film resistance S1, the film of film respectively in corresponding pilot scale at membrane resistance R2 after the pollution and the membrane resistance R3 of film after Chemical cleaning.
Embodiment 1
Test mud is the mud of certain paper waste treatment plant, and sludge concentration is 2000mg/L.At first recording the flux J1 of diaphragm in pure water is 9.39m/d 5KPa, calculates the initial film resistance R1 of diaphragm through Darcy's law; Pure water cleaned diaphragm after the repetition sludge filtration was tested 20 times, and recording the flux J2 of diaphragm in pure water is 0.84m/d 5KPa, calculates the membrane resistance R2 of diaphragm after pollution through Darcy's law; Diaphragm is taken out; Be immersed in 20h in the oxalic acid solution that concentration is 1000mg/L; Recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 6.35m/d 5KPa; Calculate the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law, test data is as shown in table 1, learns that through calculating the membrance chemistry of diaphragm cleans recovery rate and is (R2-R3)/(R2-R1) * 100%=95.3%.
Table 1
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.6 | 51.3 | 6.8 |
Below carry out the pilot scale checking.Adopt this paper waste of MBR PROCESS FOR TREATMENT, treating capacity is 20m
3/ d moved after three months, and pollution has taken place the MBR film, and employing concentration is that the oxalic acid solution of 1500mg/L cleans film, and is as shown in table 2, learns that through calculating the Chemical cleaning recovery rate of film is (S2-S3)/(S2-S1) * 100%=90.0%.
Table 2
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 0.32 | 7.72 | 1.06 |
The data that data and small-sized evaluating apparatus through pilot scale obtains can be found out; The result who is obtained by small-sized evaluating apparatus conforms to the result that pilot plant test obtains: MBR is used for the wastewater treatment of this paper waste factory; After the MBR film pollutes, only adopt oxalic acid solution to clean, just obtaining preferably, membrance chemistry cleans recovery rate; Explain that the MBR technology should be applied in this technological process of treating papermaking preferably, it is the cleaning method that is fit to that oxalic acid solution cleans.
Test mud is the mud of certain treatment of dyeing wastewater factory, and sludge concentration is 3000mg/L, and at first recording the flux J1 of diaphragm in pure water is 9.00m/d 5KPa, calculates the initial film resistance R1 of diaphragm through Darcy's law; Pure water cleaned diaphragm after the repetition sludge filtration was tested 20 times; Recording the flux J2 of diaphragm in pure water is 0.93m/d 5KPa; Calculate the membrane resistance R2 of diaphragm after pollution through Darcy's law, diaphragm is taken out, be immersed in 10h among the liquor natrii hypochloritis of effective chlorine density 1000mg/L; Recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 3.13m/d 5KPa; Calculate the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law, test data is as shown in table 3, and it is (R2-R3)/(R2-R1) * 100%=78.4% that the membrance chemistry of diaphragm cleans recovery rate.Be immersed in 8h in the hydrochloric acid solution of 500mg/L then; Recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 6.97m/d 5KPa; Calculate the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law; Test data is as shown in table 4, learns that through calculating the membrance chemistry of diaphragm cleans recovery rate and is (R2-R3)/(R2-R1) * 100%=96.6%.
Table 3
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.8 | 46.5 | 13.8 |
Table 4
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.8 | 46.5 | 6.2 |
Below carry out the pilot scale checking.Adopt this dyeing waste water of MBR PROCESS FOR TREATMENT, treating capacity is 20m
3/ d; Move after three months; Pollution has taken place in the MBR film; Adopt liquor natrii hypochloritis that film is cleaned earlier in effective chlorine density 2000mg/L, as shown in table 5, learn that through calculating the Chemical cleaning recovery rate that adopts the film after clorox cleans is (S2-S3)/(S2-S1) * 100%=77.6%.Adopting concentration then is that the hydrochloric acid solution of 1000mg/L cleans film, as shown in table 6, learns through calculating and adopts the Chemical cleaning recovery rate of the film after hydrochloric acid cleans to be (S2-S3)/(S2-S1) * 100%=94.4%.
Table 5
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 1.01 | 10.92 | 3.23 |
Table 6
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 1.01 | 10.92 | 1.56 |
The data that data and small-sized evaluating apparatus through pilot scale obtains can be found out; The result who is obtained by small-sized evaluating apparatus conforms to the result that pilot plant test obtains: MBR is used for the wastewater treatment of this dyeing waste water factory; After the MBR film pollutes; Only adopt the liquor natrii hypochloritis to clean, can not obtain the recovery rate of membrance chemistry cleaning preferably, obtained desirable membrance chemistry after increase hydrochloric acid cleans and cleaned recovery rate; Explain that the MBR technology should be applied in the processing of this dyeing waste water preferably, it is the cleaning method that is fit to that clorox combines the hydrochloric acid combination to clean.
Test mud is the mud of certain percolate treatment plant, and sludge concentration is 2000mg/L, and at first recording the flux J1 of diaphragm in pure water is 9.39m/d 5KPa; Calculate the initial film resistance R1 of diaphragm through Darcy's law; Pure water cleaned diaphragm after the repetition sludge filtration was tested 15 times, and recording the flux J2 of diaphragm in pure water is 0.57m/d 5KPa, calculates the membrane resistance R2 of diaphragm after pollution through Darcy's law; Diaphragm is taken out; At first be immersed in 20h among the liquor natrii hypochloritis of effective chlorine density 600mg/L, recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 1.05m/d 5KPa, calculates the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law; Test data is as shown in table 7, and it is (R2-R3)/(R2-R1) * 100%=48.7% that the membrance chemistry of diaphragm cleans recovery rate.Be immersed in 15h in the citric acid solution of 2000mg/L then; Recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 1.27m/d 5KPa; Calculate the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law; Test data is as shown in table 8, learns that through calculating the membrance chemistry of diaphragm cleans recovery rate and is (R2-R3)/(R2-R1) * 100%=58.8%.
Table 7
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.6 | 76.2 | 41.3 |
Table 8
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.6 | 76.2 | 34.1 |
Below carry out the pilot scale checking.Adopt this percolate of MBR PROCESS FOR TREATMENT, treating capacity is 10m
3/ d; Move after 20 days, pollution has taken place in the MBR film, adopts the liquor natrii hypochloritis in effective chlorine density 2000mg/L that film is cleaned earlier; As shown in table 9, learn that through calculating the Chemical cleaning recovery rate that adopts the film after clorox cleans is (S2-S3)/(S2-S1) * 100%=48.3%.Adopting concentration then is that the citric acid solution of 5000mg/L cleans film, as shown in table 10, learns through calculating and adopts the Chemical cleaning recovery rate of the film after citric acid cleans to be (S2-S4)/(S2-S1) * 100%=56.1%.
Table 9
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 1.64 | 8.95 | 5.42 |
Table 10
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 1.64 | 8.95 | 4.85 |
The data that data and small-sized evaluating apparatus through pilot scale obtains can be found out; The result who is obtained by small-sized evaluating apparatus conforms to the result that pilot plant test obtains: MBR is used for this percolate to be handled; After the MBR film pollutes; The effect of Chemical cleaning is unsatisfactory, explain the MBR technology be applied to the feasibility that this percolate handles little, have a big risk.
Embodiment 4
Test mud is the mud of certain sanitary sewage disposal factory, and sludge concentration is 2500mg/L, and at first recording the flux J1 of diaphragm in pure water is 9.60m/d 5KPa; Calculate the initial film resistance R1 of diaphragm through Darcy's law; Pure water cleaned diaphragm after the repetition sludge filtration was tested 30 times, and recording the flux J2 of diaphragm in pure water is 1.13m/d 5KPa, calculates the membrane resistance R2 of diaphragm after pollution through Darcy's law; Diaphragm is taken out; Be immersed in 5h among the liquor natrii hypochloritis of effective chlorine density 600mg/L, recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 7.08m/d 5KPa, calculates the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law; Test data is as shown in table 11, and it is (R2-R3)/(R2-R1) * 100%=95.2% that the membrance chemistry of diaphragm cleans recovery rate.Be immersed in 8h in the citric acid solution of 1500mg/L then; Recording the flux J3 of diaphragm in pure water after the Chemical cleaning is 7.45m/d 5KPa; Calculate the membrane resistance R3 of diaphragm after Chemical cleaning through Darcy's law; Test data is as shown in table 12, learns that through calculating the membrance chemistry of diaphragm cleans recovery rate and is (R2-R3)/(R2-R1) * 100%=96.1%.
Table 11
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.5 | 38.2 | 6.1 |
Table 12
| R1 | R2 | R3 | |
| Membrane resistance (E+10l/m) | 4.5 | 38.2 | 5.8 |
Below carry out the pilot scale checking.Adopt this sanitary sewage of MBR PROCESS FOR TREATMENT, treating capacity is 50m
3/ d; Move after five months; Pollution has taken place in the MBR film, adopts earlier the liquor natrii hypochloritis in effective chlorine density 2000mg/L that film is cleaned, and adopting concentration then is that the citric acid solution of 4000mg/L cleans film; As shown in table 13, learn that through calculating the Chemical cleaning recovery rate that adopts the film after clorox cleans is (S2-S3)/(S2-S1) * 100%=91.5%.Adopting concentration then is that the citric acid solution of 4000mg/L cleans film, as shown in table 14, learns through calculating and adopts the Chemical cleaning recovery rate of the film after citric acid cleans to be (S2-S4)/(S2-S 1) * 100%=92.5%.
Table 13
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 0.29 | 6.55 | 0.82 |
Table 14
| S1 | S2 | S3 | |
| Membrane resistance (E+12l/m) | 0.29 | 6.55 | 0.76 |
The data that data and small-sized evaluating apparatus through pilot scale obtains can be found out; The result who is obtained by small-sized evaluating apparatus conforms to the result that pilot plant test obtains: MBR is used for this sanitary sewage disposal; After the MBR film pollutes; Only need to adopt the liquor natrii hypochloritis to clean to film and just can obtain the recovery rate of membrance chemistry cleaning preferably, explain that the MBR technology should be applied in the processing of this sanitary sewage preferably, the liquor natrii hypochloritis is the Chemical cleaning medicament that is fit to.
Can find out through embodiment; Adopt the present invention that the Chemical cleaning restorability of film is estimated; Thereby judge the feasibility that adopts membrane technology to handle certain waste water, and select suitable Chemical cleaning medicament and the cleaning program of confirming to optimize, its method is simple to operate with respect to adopting pilot plant test; With low cost, can clean restorability to membrance chemistry fast and make judgement.And the result of contrast pilot plant test also can find out, adopts the reliability of this method high, is consistent with the result of the test of pilot scale.
Claims (5)
1. method of estimating flat sheet membrane Chemical cleaning restorability is characterized in that: may further comprise the steps:
(1) use small-sized evaluating apparatus to confirm that the initial film resistance R1 of flat sheet membrane, film are at membrane resistance R2 after the pollution and the membrane resistance R3 of film after Chemical cleaning;
(2) according to the initial film resistance R1 of film, film the membrane resistance R2 after the pollution and film the membrane resistance R3 after the Chemical cleaning judge film in sludge filtration after the Chemical cleaning restorability under the Chemical cleaning condition;
Wherein, Described small-sized evaluating apparatus is: stirring-type ultrafiltration cup is placed on the agitator, and stirring-type ultrafiltration cup is connected with airtight container, and airtight container is connected with decompression valve; Decompression valve is connected with the nitrogen steel cylinder; Setting pressure table on the decompression valve escape pipe, the water outlet of stirring-type ultrafiltration cup is connected with balance, and balance is connected with computer.
2. the method for evaluation flat sheet membrane Chemical cleaning restorability according to claim 1 is characterized in that: use small-sized evaluating apparatus to confirm that the initial film resistance R1 of flat sheet membrane, film in the method for membrane resistance R2 after the pollution and the membrane resistance R3 of film after Chemical cleaning are in the described step (1):
1. dull and stereotyped diaphragm is cut into diaphragm according to the specification of stirring-type ultrafiltration cup; Diaphragm is placed stirring-type ultrafiltration cup and fixes; Pure water is inserted in stirring-type ultrafiltration cup and the airtight container; Stirring and regulating system pressure filtered 5-20 minute to fixed value, calculated the initial film resistance R1 of film behind the flux J1 of test diaphragm in pure water;
2. after stirring-type ultrafiltration cup and being connected of airtight container being broken off; Stirring-type ultrafiltration cup directly is connected with decompression valve; With concentration is that the mud of 1000-3000mg/L is poured in the stirring-type ultrafiltration cup and filtered 10-30 minute; Clean the diaphragm in the stirring-type ultrafiltration cup with pure water after the sludge filtration, accomplish once film is carried out the circulation that pure water cleans after the sludge filtration, repeat this circulation 10-30 time;
3. the diaphragm after above-mentioned pure water 2. being cleaned places stirring-type ultrafiltration cup and fixes; Stirring-type ultrafiltration cup is connected with airtight container; Airtight container is connected with decompression valve, and pure water is inserted in stirring-type ultrafiltration cup and the airtight container, and stirring and regulating system pressure are to fixed value; Filtered 5-20 minute, and calculated the membrane resistance R2 of film after pollution behind the flux J2 of test diaphragm in pure water;
4. the diaphragm in the above-mentioned stirring-type ultrafiltration cup is 3. taken out, be immersed in the chemical agent solution, carry out 3-24 hour Chemical cleaning;
5. the diaphragm after the Chemical cleaning is placed stirring-type ultrafiltration cup and fix; Stirring-type ultrafiltration cup is connected with airtight container; Airtight container is connected with decompression valve, and pure water is inserted in stirring-type ultrafiltration cup and the airtight container, and stirring and regulating system pressure are to fixed value; Filtered 5-20 minute, and calculated the membrane resistance R3 of film after Chemical cleaning behind the flux J3 of test diaphragm in pure water.
3. the method for evaluation flat sheet membrane Chemical cleaning restorability according to claim 1 and 2 is characterized in that: described chemical agent solution is one or more in liquor natrii hypochloritis, hydrogenperoxide steam generator, hydrochloric acid solution, sodium hydroxide solution, citric acid solution or the oxalic acid solution.
4. the method for evaluation flat sheet membrane Chemical cleaning restorability according to claim 1 and 2 is characterized in that: described (2) according to the initial film resistance R1 of film, film the membrane resistance R2 after the pollution and film the membrane resistance R3 after the Chemical cleaning judge film in sludge filtration after the method for the Chemical cleaning restorability under the Chemical cleaning condition be: calculate membrance chemistry through formula (R2-R3)/(R2-R1) * 100% and clean recovery rate.
5. the method for evaluation flat sheet membrane Chemical cleaning restorability according to claim 4 is characterized in that: said membrance chemistry cleaned recovery rate more than or equal to 80% o'clock, and the life cycle that is judged as film is long, the replacing frequency is low, was fit to handle this waste water;
Said membrance chemistry cleans recovery rate and is lower than at 80% o'clock, and the life cycle that is judged as film is short, it is higher to change frequency, needs to adopt the method for number of chemical cleaning agent combination; After two or more Chemical cleaning medicament combination of process was cleaned, membrance chemistry cleaned recovery rate and still is lower than at 60% o'clock, and the life cycle weak point, the replacing frequency that are judged as film are high, are not suitable for handling this waste water.
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