CN104147938B - The method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties - Google Patents
The method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties Download PDFInfo
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- CN104147938B CN104147938B CN201410421245.1A CN201410421245A CN104147938B CN 104147938 B CN104147938 B CN 104147938B CN 201410421245 A CN201410421245 A CN 201410421245A CN 104147938 B CN104147938 B CN 104147938B
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Abstract
The invention discloses a kind of method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties, by chemicals dosing plant to former water adds the zeolite after bismuth modification, bismuth-containing modified zeolite pre-coating material solution and former water together pass through hyperfiltration membrane assembly, more effective precoated shet can be formed at ultrafiltration membrane surface, ultrafilter membrane concentrate recirculation is to former pond, after terminating one filter cycle, with water, ultrafilter membrane carried out backwash and just rinsing.This method operation is easily controllable, and equipment requirements is low, can effectively alleviate the decrease speed of membrane flux, improve the contamination resistance of ultrafilter membrane, can improve again organic removal efficiency.
Description
Technical field
The invention belongs to advanced treatment of wastewater and reuse project field, a kind of method relating to ultrafilter membrane advanced treating.
Background technology
Membrane technology is in an increasingly wide range of applications in advanced treatment of wastewater and reuse field, hyperfiltration technique advantage is simple to operate, advantage of lower cost, does not undergo phase transition, and ultrafiltration apparatus floor space is little, system energy consumption is low, operating cost is low, can be effectively improved the performance of enterprises, it is water treatment field one of most important hot spot technology over nearly 20 years that ultrafiltration membrane technique has become.Ultrafiltration group technology has bigger effect on the raising ultrafiltration clearance to waste water, and many researcheres find, by Powdered Activated Carbon and ultrafiltration coupling, to improve organic clearance by absorption.By filtration-reverse osmosis film coupling, be also current technical field of membrane frequently with group technology, treatment effect is better, and ultrafilter membrane can reduce the pollution of follow-up reverse osmosis membrane, but through the operation of certain time, ultrafilter membrane also can inevitably be contaminated.Therefore, ultrafilter membrane still suffers from certain limitation in actual motion, and a critical problem in its application is how to efficiently control fouling membrane, extends the service life of ultrafilter membrane, and meanwhile, ultrafilter membrane there is also the defect that organic removal rate is low.
Summary of the invention
For the problems referred to above existed in process hyperfiltration advanced in prior art and reuse method, the present invention provides a kind of method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows:
The method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties, process step is: add bismuth modified zeolite pre-coating material by chemicals dosing plant in former water, bismuth-containing modified zeolite pre-coating material solution and former water together pass through hyperfiltration membrane assembly, it is effectively formed precoated shet at ultrafiltration membrane surface, ultrafilter membrane concentrate recirculation is to former pond, after terminating one filter cycle, with water, ultrafilter membrane carried out backwash and just rinsing.
The preparation method of above-mentioned bismuth modified zeolite pre-coating material is as follows:
(1) zeolite that particle diameter is 300 ~ 2000 orders is added in 0.05 ~ 0.2mol/L sulphuric acid with solid-to-liquid ratio for 1:10 ~ 1:5,12 ~ 36h is dynamically impregnated with the hunting speed of 100 ~ 300r/min, pour out supernatant, then wash 1 ~ 2 time with pure water, dry when 80 ~ 100 ° of C after pouring out supernatant；
(2) zeolite step (1) prepared fills in 0.01 ~ 0.1mol/L bismuth nitrate solution with solid-to-liquid ratio 1:10 ~ 1:5 addition, dynamically impregnates 12 ~ 36h with the hunting speed of 100 ~ 300r/min, dries after pouring out supernatant when 80 ~ 100 ° of C；
(3) zeolite step (2) prepared roasting 2-4h in 300 ~ 500 ° of C when, obtains bismuth modified zeolite pre-coating material.
As a further improvement on the present invention, in described chemicals dosing plant, bismuth-containing modified zeolite pre-coating material particle diameter is 300 ~ 2000 orders, and chemical feeding quantity is 50 ~ 500mg/L.
As a further improvement on the present invention, described ultrafilter membrane is hollow-fibre membrane, and ultrafilter membrane concentrate recirculation ratio is 0% ~ 10%.
As a further improvement on the present invention, described filter cycle is 0.5 hour to 3.5 hours.
As a further improvement on the present invention, described is film filtration effluent with water, and backwash and positive washing time are 10 seconds to 80 seconds, and backwash and positive flushing flow rate are 1.5 times to 3.0 times of ultrafiltration flow of inlet water.
Beneficial effects of the present invention:
The method adopting the bismuth modified zeolite precoated shet enhancing ultrafiltration film properties of the present invention, after zeolite is modifiied by bismuth, can widen and dredge the internal gutter of zeolite, increase the adsorption activity center of zeolite, for enhancing ultrafiltration film properties, directly contacting of more effective precoated shet, pollution abatement thing and film is formed at ultrafiltration membrane surface.
The present invention utilizes the method for bismuth modified zeolite precoated shet enhancing ultrafiltration film properties, compared with the method that traditional ultrafilter membrane directly filters, this method operation is easily controllable, and equipment requirements is low, the contamination resistance of ultrafilter membrane can be improved, can improve again organic removal efficiency.For, in advanced treatment of wastewater and reuse, can effectively alleviating the decrease speed of ultrafilter membrane flux, delay the pollution of film, the contamination resistance of reinforced film, it is greatly improved the ultrafilter membrane removal effect to water quality index simultaneously.
Accompanying drawing explanation
Fig. 1 is the membrane flux change comparison diagram of the present invention.
Fig. 2 is COD (COD) the clearance comparison diagram of the present invention.
Fig. 3 is total nitrogen (TN) the clearance comparison diagram of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is described in further detail.
The present invention utilizes the method for bismuth modified zeolite precoated shet enhancing ultrafiltration film properties, it is in former water, add bismuth modified zeolite pre-coating material by chemicals dosing plant, bismuth-containing modified zeolite pre-coating material solution and former water together pass through hyperfiltration membrane assembly, it is effectively formed precoated shet at ultrafiltration membrane surface, ultrafilter membrane concentrate recirculation is to former pond, after terminating one filter cycle, with water, ultrafilter membrane carried out backwash and just rinsing.
As the preferred version of the present invention, the preparation method of bismuth modified zeolite pre-coating material is as follows:
(1) zeolite that particle diameter is 300 ~ 2000 orders is added in 0.05 ~ 0.2mol/L sulphuric acid with solid-to-liquid ratio for 1:10 ~ 1:5,12 ~ 36h is dynamically impregnated with the hunting speed of 100 ~ 300r/min, pour out supernatant, then wash 1 ~ 2 time with pure water, dry when 80 ~ 100 ° of C after pouring out supernatant；
(2) zeolite step (1) prepared fills in 0.01 ~ 0.1mol/L bismuth nitrate solution with solid-to-liquid ratio 1:10 ~ 1:5 addition, dynamically impregnates 12 ~ 36h with the hunting speed of 100 ~ 300r/min, dries after pouring out supernatant when 80 ~ 100 ° of C；
(3) zeolite step (2) prepared roasting 2-4h in 300 ~ 500 ° of C when, obtains bismuth modified zeolite pre-coating material.
As the preferred version of the present invention, wherein, bismuth-containing modified zeolite pre-coating material particle diameter is 300 ~ 2000 orders, and chemical feeding quantity is 50 ~ 500mg/L；Ultrafilter membrane is hollow-fibre membrane, and ultrafilter membrane concentrate recirculation ratio is 0% ~ 10%；Filter cycle is 0.5 hour to 3.5 hours；Being film filtration effluent with water, backwash and positive washing time are 10 seconds to 80 seconds, and backwash and positive flushing flow rate are 1.5 times to 3.0 times of ultrafiltration flow of inlet water.
Contrast case 1(direct ultra-filtration, writes a Chinese character in simplified form UF):
Former water is certain Industrial Waste Water Treatments plant tail water (COD58mg/L, TN19.2mg/L).Former water is either directly through hyperfiltration membrane assembly, ultrafilter membrane is hollow-fibre membrane, ultrafilter membrane concentrate recirculation ratio is 3%, ultrafilter membrane concentrate recirculation is to former pond, filter cycle is 3 hours, after terminating a filter cycle, adopts film filtration effluent ultrafilter membrane is sequentially carried out backwash and is just rinsing, backwash and positive washing time are 50 seconds, and backwash and positive flushing flow rate are 2 times of ultrafiltration flow of inlet water.Filter 4 cycles, membrane flux change as it is shown in figure 1, major pollutants clearance as shown in Figures 2 and 3.
The method that contrast case 2(improves ultrafilter membrane performance merely with zeolite precoated shet, writes a Chinese character in simplified form Z-UF):
Former water is certain Industrial Waste Water Treatments plant tail water (COD58mg/L, TN19.2mg/L).In former water, unmodified natural zeolite is added by chemicals dosing plant, zeolitic material solution and former water together pass through hyperfiltration membrane assembly, ultrafilter membrane is hollow-fibre membrane, ultrafilter membrane concentrate recirculation ratio is 3%, and ultrafilter membrane concentrate recirculation is to former pond, and filter cycle is 3 hours, after terminating one filter cycle, adopting film filtration effluent ultrafilter membrane is sequentially carried out backwash and is just rinsing, backwash and positive washing time are 50 seconds, and backwash and positive flushing flow rate are 2 times of ultrafiltration flow of inlet water.Filtering 4 cycles, membrane flux changes as it is shown in figure 1, major pollutants clearance as shown in Figures 2 and 3, compares direct ultra-filtration, can alleviate the decrease speed of ultrafilter membrane flux, but the clearance of COD and TN is only respectively increased 41.6% and 40.5%.
Embodiment 1(utilizes the method for bismuth modified zeolite precoated shet enhancing ultrafiltration film properties of the present invention, writes a Chinese character in simplified form 0.03Bi-Z-UF):
Former water is certain Industrial Waste Water Treatments plant tail water (COD58mg/L, TN19.2mg/L).The preparation method of bismuth modified zeolite pre-coating material is as follows: the zeolite that particle diameter is 1000 orders is added in 0.1mol/L sulphuric acid with solid-to-liquid ratio for 1:5 by (1), 18h is dynamically impregnated with the hunting speed of 20r/min, pour out supernatant, then wash 1 time with pure water, dry when 85 ° of C after pouring out supernatant；(2) zeolite step (1) prepared fills in 0.03mol/L bismuth nitrate solution with solid-to-liquid ratio 1:5 addition, dynamically impregnates 18h with the hunting speed of 200r/min, dries after pouring out supernatant when 85 ° of C；(3) zeolite step (2) prepared roasting 3h in 450 ° of C when, obtains bismuth modified zeolite pre-coating material.In former water, bismuth modified zeolite pre-coating material is added by chemicals dosing plant, zeolitic material solution and former water together pass through hyperfiltration membrane assembly, ultrafilter membrane is hollow-fibre membrane, ultrafilter membrane concentrate recirculation ratio is 3%, and ultrafilter membrane concentrate recirculation is to former pond, and filter cycle is 3 hours, after terminating one filter cycle, adopting film filtration effluent ultrafilter membrane is sequentially carried out backwash and is just rinsing, backwash and positive washing time are 50 seconds, and backwash and positive flushing flow rate are 2 times of ultrafiltration flow of inlet water.Filtering 4 cycles, membrane flux changes as it is shown in figure 1, major pollutants clearance as shown in Figures 2 and 3, compares direct ultra-filtration, can effectively alleviate the decrease speed of ultrafilter membrane flux, and the clearance of COD and TN has been respectively increased 102.5% and 103.8%.
Embodiment 2(utilizes the method for bismuth modified zeolite precoated shet enhancing ultrafiltration film properties of the present invention, writes a Chinese character in simplified form 0.08Bi-Z-UF):
Former water is certain Industrial Waste Water Treatments plant tail water (COD58mg/L, TN19.2mg/L).The preparation method of bismuth modified zeolite pre-coating material is as follows: the zeolite that particle diameter is 1000 orders is added in 0.1mol/L sulphuric acid with solid-to-liquid ratio for 1:5 by (1), 18h is dynamically impregnated with the hunting speed of 20r/min, pour out supernatant, then wash 1 time with pure water, dry when 85 ° of C after pouring out supernatant；(2) zeolite step (1) prepared fills in 0.08mol/L bismuth nitrate solution with solid-to-liquid ratio 1:5 addition, dynamically impregnates 18h with the hunting speed of 200r/min, dries after pouring out supernatant when 85 ° of C；(3) zeolite step (2) prepared roasting 3h in 450 ° of C when, obtains bismuth modified zeolite pre-coating material.In former water, bismuth modified zeolite pre-coating material is added by chemicals dosing plant, zeolitic material solution and former water together pass through hyperfiltration membrane assembly, ultrafilter membrane is hollow-fibre membrane, ultrafilter membrane concentrate recirculation ratio is 3%, and ultrafilter membrane concentrate recirculation is to former pond, and filter cycle is 3 hours, after terminating one filter cycle, adopting film filtration effluent ultrafilter membrane is sequentially carried out backwash and is just rinsing, backwash and positive washing time are 50 seconds, and backwash and positive flushing flow rate are 2 times of ultrafiltration flow of inlet water.Filtering 4 cycles, membrane flux changes as it is shown in figure 1, major pollutants clearance as shown in Figures 2 and 3, compares direct ultra-filtration, can effectively alleviate the decrease speed of ultrafilter membrane flux, and the clearance of COD and TN has been respectively increased 116.8% and 119.2%.
As fully visible, the method utilizing this bismuth modified zeolite precoated shet enhancing ultrafiltration film properties, compares direct ultra-filtration and the method improving ultrafilter membrane performance merely with zeolite precoated shet, can the decrease speed of more effective alleviation membrane flux, delay the pollution of film, be greatly improved the film removal effect to water quality index simultaneously.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention.All any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.
Claims (5)
1. the method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties, it is characterized in that: processing step is: add bismuth modified zeolite pre-coating material by chemicals dosing plant in former water, bismuth-containing modified zeolite pre-coating material solution and former water together pass through hyperfiltration membrane assembly, it is effectively formed precoated shet at ultrafiltration membrane surface, ultrafilter membrane concentrate recirculation is to former pond, after terminating one filter cycle, with water, ultrafilter membrane carried out backwash and just rinsing；The preparation method of described bismuth modified zeolite pre-coating material is:
(1) zeolite that particle diameter is 300～2000 orders is added in 0.05～0.2mol/L sulphuric acid with solid-to-liquid ratio for 1:10～1:5,12～36h is dynamically impregnated with the hunting speed of 100～300r/min, pour out supernatant, wash 1～2 time with pure water again, dry under 80～100 DEG C of conditions after pouring out supernatant；
(2) zeolite step (1) prepared fills in 0.01～0.1mol/L bismuth nitrate solution with solid-to-liquid ratio 1:10～1:5 addition, dynamically impregnate 12～36h with the hunting speed of 100～300r/min, dry under 80～100 DEG C of conditions after pouring out supernatant；
(3) zeolite roasting 2 4h under 300～500 DEG C of conditions step (2) prepared, obtains bismuth modified zeolite pre-coating material.
2. the method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties according to claim 1, it is characterised in that: in described chemicals dosing plant, bismuth modified zeolite pre-coating material particle diameter is 300～2000 orders, and chemical feeding quantity is 50～500mg/L.
3. the method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties according to claim 1, it is characterised in that: described ultrafilter membrane is hollow-fibre membrane, and ultrafilter membrane concentrate recirculation ratio is 0%～10%.
4. the method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties according to claim 1, it is characterised in that: described filter cycle is 0.5 hour to 3.5 hours.
5. the method utilizing bismuth modified zeolite precoated shet enhancing ultrafiltration film properties according to claim 1, it is characterized in that: described is film filtration effluent with water, backwash and positive washing time are 10 seconds to 80 seconds, and backwash and positive flushing flow rate are 1.5 times to 3.0 times of ultrafiltration flow of inlet water.
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| EP2604330A1 (en) * | 2011-12-16 | 2013-06-19 | Samsung Electronics Co., Ltd | Semi-permeable separation membrane including coated nanoporous particles in a polymer matrix, and method of manufacturing the same |
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