CN117443197B - Method for offline cleaning MBR hollow fiber membrane by utilizing ozone micro-nano bubbles - Google Patents
Method for offline cleaning MBR hollow fiber membrane by utilizing ozone micro-nano bubbles Download PDFInfo
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- CN117443197B CN117443197B CN202311775425.5A CN202311775425A CN117443197B CN 117443197 B CN117443197 B CN 117443197B CN 202311775425 A CN202311775425 A CN 202311775425A CN 117443197 B CN117443197 B CN 117443197B
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- 238000004140 cleaning Methods 0.000 title claims abstract description 294
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 243
- 239000012528 membrane Substances 0.000 title claims abstract description 150
- 239000002101 nanobubble Substances 0.000 title claims abstract description 149
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims description 29
- 239000000498 cooling water Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002912 waste gas Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 10
- 230000007246 mechanism Effects 0.000 claims description 7
- 238000009827 uniform distribution Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 17
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000013043 chemical agent Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/02—Forward flushing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/168—Use of other chemical agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/28—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling by soaking or impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/40—Automatic control of cleaning processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/42—Chemical regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/44—Specific cleaning apparatus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for offline cleaning of an MBR hollow fiber membrane by utilizing ozone micro-nano bubbles, which is characterized in that ozone micro-nano bubbles are generated by a micro-nano bubble generator to clean the membrane, and the concentration of dissolved ozone is controlled to be 1-5mg/L. The invention solves the problem of excessive residual chemical agent in water in the traditional hollow fiber membrane offline cleaning process, and avoids the problem of disposal of waste liquid after cleaning. Meanwhile, the ozone micro-nano bubbles have the advantages of strong dissolving capacity and high mass transfer efficiency, and can generate more hydroxyl free radicals compared with common ozone water. Can solve the problems of low ozone utilization rate and general cleaning effect of the existing membrane cleaning by using ozone water.
Description
Technical Field
The invention relates to the technical field of membrane cleaning, in particular to a method for offline cleaning of an MBR hollow fiber membrane by utilizing ozone micro-nano bubbles.
Background
The cleaning of the MBR hollow fiber membrane is divided into online cleaning and offline cleaning, wherein the online cleaning refers to cleaning the membrane at the original position by using liquid medicine regularly when the membrane pollution is not serious. If the online cleaning can not effectively recover the membrane performance, the membrane assembly is taken out of the treatment tank and soaked in the liquid medicine for offline cleaning. The traditional offline chemical cleaning of the MBR hollow fiber membrane generally uses acid-base agents, so that a large amount of acid-base cleaning waste liquid is caused, and harmful byproducts and polluted water are generated.
Ozone has strong oxidizing power for oxidizing organic and inorganic compounds, can oxidize most of organic pollutants in wastewater, and is widely applied to industrial wastewater treatment. Ozone oxidizes organics in two ways: firstly, ozone molecules oxidize organic matters selectively, namely directly; secondly, hydroxyl radicals generated by self-decomposition convert pollutants on the surface of the membrane into intermediate products which are easy to biodegrade, and the organic matters are subjected to non-selective rapid oxidation, namely indirect oxidation. In the existing method for cleaning the membrane by utilizing ozone, the concentration of dissolved ozone is generally higher, and the method is suitable for the membrane with ozone resistance and has poor applicability.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for offline cleaning an MBR hollow fiber membrane by using ozone micro-nano bubbles, so as to solve the problem of excessive residual amount of chemical agent in water in the conventional offline cleaning process of the hollow fiber membrane, and avoid the problem of disposal of waste liquid after cleaning. Meanwhile, the ozone micro-nano bubbles have the advantages of strong dissolving capacity and high mass transfer efficiency, and can generate more hydroxyl free radicals compared with common ozone water. Can solve the problems of low ozone utilization rate and general cleaning effect of the existing membrane cleaning by using ozone water.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a method for offline cleaning of MBR hollow fiber membranes by ozone micro-nano bubbles, which comprises the following steps:
s1, device connection
The oxygen generating device, the ozone generator and the micro-nano bubble generator are sequentially connected through a first pipeline and a second pipeline, a liquid inlet of the micro-nano bubble generator is connected with a third pipeline, a gas outlet of the micro-nano bubble generator is connected with a fourth pipeline, and the third pipeline and the fourth pipeline extend into the cleaning pool; immersing the hollow fiber membrane in a cleaning tank, wherein the hollow fiber membrane is sequentially connected with a pressure sensor and a cleaning pump through a fifth pipeline, the cleaning pump is also connected with a sixth pipeline, and the sixth pipeline stretches into the cleaning tank; the cleaning pool also realizes the cooling of water in the pool through a cooling device; the oxygen generating apparatus is not particularly limited as long as it can generate oxygen, for example, an oxygen generator, an industrial oxygen cylinder, and the like; the cooling device is not particularly limited as long as it can control the temperature of the cleaning liquid, for example, a cooling water circulator, a cooling water pipe, a low-temperature constant-temperature tank, and the like; because the temperature of the micro-nano bubble generator is gradually increased in the operation process, the temperature has great influence on the dissolution of ozone gas and the residence time of the micro-nano bubbles in water, so that the control of the water temperature is very important;
s2, membrane cleaning
1) The method comprises the steps of sequentially starting an oxygen generating device and an ozone generator, and inputting oxygen generated by the oxygen generating device into the ozone generator through a first pipeline to produce ozone;
2) Starting the micro-nano bubble generator, inputting ozone into the micro-nano bubble generator through a second pipeline, inputting water in the cleaning pool into the micro-nano bubble generator through a third pipeline, and releasing generated ozone micro-nano bubbles into the cleaning pool through a fourth pipeline, wherein the dissolved ozone concentration is 1-5mg/L;
3) And (3) starting a cleaning pump to enable ozone micro-nano bubbles to positively pass through a membrane for cleaning, and adopting a mode of 'soaking and simultaneously positively cleaning' or 'soaking and positively alternately cleaning', until the descending amplitude of TMP displayed by a pressure sensor is not more than 10% within 30min, so that the cleaning can be stopped.
Wherein micro-nano bubbles refer to micro-bubbles with a diameter smaller than 100 μm, and the micro-nano bubbles are divided into micro-bubbles with a diameter of 1-100 μm and nano-bubbles with a diameter smaller than 1 μm. The ozone micro-nano bubble technology refers to micro-nano level bubbles formed by ozone passing through a micro-nano bubble generator. The ozone micro-nano bubble technology utilizes the characteristics of large specific surface area, slow rising speed, negatively charged surface and capability of promoting ozone to generate more hydroxyl radicals.
The ozone micro-nano bubbles have strong dissolving capability in water and long ozone retention time: under the condition of the same dissolved ozone concentration, the gas content of the ozone micro-nano bubbles is far higher than that of the ozone macro-bubbles, and the difference of the gas content of the ozone micro-nano bubbles and the ozone macro-bubbles is larger and larger along with the increase of the dissolved ozone concentration.
Ozone micro-nano bubble mass transfer efficiency is high: the saturation dissolved ozone concentration achieved by the ozone micro-nano bubbles is larger than that of ozone large bubbles. Ozone microbubbles take more time to reach saturated dissolved ozone concentrations than ozone macrobubbles.
Ozone micro-nano bubbles have high ozone utilization efficiency, more hydroxyl radicals are generated, the zeta potential of the surface is relatively high, compared with conventional ozone aeration, the ozone micro-nano bubbles can remarkably promote the degradation of organic pollutants, and the unique interface structure of the ozone micro-nano bubbles has unique advantages in the membrane cleaning process.
In addition, the process of generating micro-nano bubbles is an exothermic process, and the temperature of the micro-nano bubble generator is gradually increased in the operation process, so that the dissolution of ozone gas and the residence time of the micro-nano bubbles in water are greatly affected by the temperature, and the control of the water temperature is very important.
Further, the specific steps of the mode of 'soaking while cleaning forward' are as follows: and (3) starting the cleaning pump, keeping the hollow fiber membrane immersed in the cleaning liquid, enabling the ozone micro-nano bubbles to positively pass through the membrane for cleaning, measuring the dissolved ozone concentration in the ozone micro-nano bubble cleaning liquid in the cleaning pool every ten minutes, water temperature and TMP (transmembrane pressure difference) in the membrane cleaning process until the TMP displayed by the pressure sensor is reduced by not more than 10% within 30 minutes, and stopping cleaning for 2 hours at most.
Further, the specific steps of the mode of 'soaking and forward alternate cleaning' are as follows:
a. starting the cleaning pump, keeping the hollow fiber membrane immersed in the cleaning liquid, and enabling the ozone micro-nano bubbles to positively pass through the membrane for cleaning for 30min, and measuring the dissolved ozone concentration in the ozone micro-nano bubble cleaning liquid in the cleaning tank, water and TMP (transmembrane pressure difference) in the membrane cleaning process every ten min;
b. closing the cleaning pump to enable the ozone micro-nano bubbles to soak and clean the hollow fiber membrane for 30min, and measuring the dissolved ozone concentration in the ozone micro-nano bubble cleaning liquid in the cleaning pool, water and TMP in the membrane cleaning process every ten min;
c. and c, repeating the steps a and b until the descending amplitude of the TMP displayed by the pressure sensor is not more than 10% within 30min, and stopping cleaning for at most 2h.
Further, the temperature of the cleaning liquid in the cleaning tank is kept at 25 ℃ + -2 ℃ by the cooling device.
Further, a cleaning tank upper cover is arranged at the top of the cleaning tank, and a first jack for a third pipeline to pass through, a second jack for a fourth pipeline to pass through, a third jack for a fifth pipeline to pass through and a fourth jack for a sixth pipeline to pass through are arranged on the cleaning tank upper cover; when in use, each pipeline is inserted into the cleaning pool through the corresponding jack. The ozone waste gas treatment device is not limited any more, and the ozone waste gas can be discharged after being treated by the device.
Further, an ozone waste gas discharge hole is further formed in the upper cover of the cleaning pool, seven ozone waste gas discharge Kong Tongdi pipelines are connected with the ozone waste gas treatment device, and generated waste gas is discharged after being treated by the ozone waste gas treatment device.
Further, the cooling device is a low-temperature constant-temperature tank, and the cleaning tank is placed in a water tank of the low-temperature constant-temperature tank. This approach is suitable for cleaning small hollow fiber membranes.
Further, the cooling device comprises a cooling water circulating machine, an eighth pipeline, a ninth pipeline and a cooling water pipe, wherein the eighth pipeline is connected with a water inlet of the cooling water circulating machine, the ninth pipeline is connected with a water outlet of the cooling water circulating machine, the cooling water pipe is positioned inside the cleaning pool and is arranged in an adherence manner, and two ends of the cooling water pipe are respectively connected with the eighth pipeline and the ninth pipeline. This approach is suitable for cleaning larger hollow fiber membranes.
Further, a bubble uniform distribution mechanism is arranged above the cleaning pool and comprises a connecting pipe, a plurality of guide pipes and a plurality of spray heads, wherein the connecting pipe is vertically arranged, the guide pipes are horizontally arranged, the connecting pipe is connected with a fourth pipeline, the guide pipes are communicated with the connecting pipe, and the spray heads are uniformly distributed on the guide pipes; the generated ozone micro-nano bubbles are uniformly released in the cleaning pool through a plurality of spray heads.
Compared with the prior art, the method for offline cleaning the MBR hollow fiber membrane by utilizing the ozone micro-nano bubbles has the following advantages:
1. environmental protection type: the halogenated disinfection byproducts generated when the ozone micro-nano bubbles clean the membrane are less than NaClO, so that the problem that the residual amount of chemical agents in water is excessive in the traditional hollow fiber membrane offline cleaning process is solved, and the problem of waste liquid disposal after cleaning is avoided. The cost is as follows: the ozone micro-nano bubble technology can also save money, and raw materials are water and ozone, because the ozone is produced on site, and the transportation and storage requirements are eliminated. And (3) real-time processing: ozone micro-nano bubbles can be generated immediately when water is used, and no chemical reagent is required to be stored and added. Thus, the processing efficiency can be improved, and the waiting time in the processing process can be reduced.
2. The existing patent for cleaning by utilizing the ozone micro-nano bubbles or the ozone micro-bubbles does not consider that the ozone micro-nano bubbles are exothermic in the production process, and the too high temperature has great influence on the residence time of the micro-nano bubbles and the dissolution of ozone.
3. The invention selects the ozone micro-nano bubble water with the dissolved ozone concentration of 1-5mg/L, and when the ozone micro-nano bubble water with the dissolved ozone concentration of 1mg/L is used for cleaning the membrane in a 'soaking and forward cleaning' mode, the cleaning effect is better than 2000ppm of sodium hypochlorite.
4. The saturation dissolved ozone concentration of the ozone micro-nano bubbles is larger than that of the ozone macro-bubbles, and the required time is faster than that of the ozone macro-bubbles. Compared with the conventional ozone aeration, the more hydroxyl free radicals generated by the ozone micro-nano bubbles are, the degradation of organic pollutants can be obviously promoted, and the unique interface structure of the ozone micro-nano bubbles has unique advantages in the membrane cleaning process.
5. The invention searches the optimal membrane passing mode of the ozone micro-nano bubbles, and discovers that the effect of cleaning the ozone micro-nano bubbles by passing the membrane in the forward direction is better than that of cleaning the ozone micro-nano bubbles by passing the membrane in the reverse direction. Therefore, the mode of cleaning the membrane by the ozone micro-nano bubbles is 'soaking and forward cleaning', and 'soaking and forward alternate cleaning' can be adopted if the energy consumption is considered. Different from the traditional cleaning mode of soaking and cleaning the hollow fiber membrane by adopting cleaning liquid and reversely cleaning the hollow fiber membrane by the cleaning liquid.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of an apparatus used in the method for offline cleaning of MBR hollow fiber membranes using ozone micro-nano bubbles according to embodiment 1 of the present invention;
FIG. 2 is a top view of a cleaning tank top cover used in the method for offline cleaning MBR hollow fiber membranes by using ozone micro-nano bubbles according to the embodiment 1 of the present invention;
FIG. 3 is a schematic diagram of an apparatus used in the method for offline cleaning of MBR hollow fiber membranes using ozone micro-nano bubbles according to embodiment 2 of the present invention;
FIG. 4 is a top view of a cleaning tank top cover used in the method for offline cleaning MBR hollow fiber membranes by using ozone micro-nano bubbles according to the embodiment 2 of the present invention;
FIG. 5 is a schematic structural diagram of a bubble uniformly-distributing mechanism used in the method for offline cleaning of MBR hollow fiber membranes by ozone micro-nano bubbles according to embodiment 2 of the present invention;
FIG. 6 is a schematic illustration of the reverse and forward cleaning of hollow fiber membranes;
FIG. 7 is a graph of TMP change during "forward cleaning" of hollow fiber membranes with ozone micro-nanobubbles;
FIG. 8 is a graph showing TMP change during "soak and forward alternate cleaning" of ozone micro-nano bubbles in a hollow fiber membrane;
FIG. 9 is a graph showing the surface morphology of the membrane after cleaning the hollow fiber membrane for 2h with ozone micro-nano bubbles of 4 different dissolved ozone concentrations; (a) is dissolved ozone concentration of 1mg/L ozone micro nano bubbles, (b) is dissolved ozone concentration of 3mg/L ozone micro nano bubbles, (c) is dissolved ozone concentration of 5mg/L ozone micro nano bubbles, (d) is dissolved ozone concentration of 7mg/L ozone micro nano bubbles;
FIG. 10 is a graph comparing elongation at break after membrane cleaning;
FIG. 11 is a graph showing a comparison of tensile strength after film cleaning.
Reference numerals illustrate:
1. an oxygen generating device; 2. a first pipe; 3. an ozone generator; 4. a second pipe; 5. a micro-nano bubble generator; 6. a third conduit; 7. a fourth conduit; 8. a cooling device; 9. a cleaning pool; 10. a hollow fiber membrane; 11. a fifth pipe; 12. a pressure sensor; 13. a cleaning pump; 14. a sixth conduit; 15. cleaning an upper cover of the pool; 16. a seventh pipe; 17. an ozone waste gas treatment device; 18. an eighth conduit; 19. a ninth conduit; 20. a cooling water pipe; 21. a connecting pipe; 22. a flow guiding pipe; 23. a spray head;
a. a first jack; b. a second jack; c. ozone exhaust gas discharge holes; d. a third jack; e. a fourth jack; f. a fifth jack; g. and a sixth jack.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first", "a second", etc. may explicitly or implicitly include one or more such feature. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art in a specific case.
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for offline cleaning of MBR hollow fiber membranes by ozone micro-nano bubbles, which comprises the following steps:
s1, device connection
The oxygen generating device 1, the ozone generator 3 and the micro-nano bubble generator 5 are sequentially connected through a first pipeline 2 and a second pipeline 4, a liquid inlet of the micro-nano bubble generator 5 is connected with a third pipeline 6, a gas outlet of the micro-nano bubble generator 5 is connected with a fourth pipeline 7, and the third pipeline 6 and the fourth pipeline 7 extend into a cleaning pool 9; immersing the hollow fiber membrane 10 in the cleaning tank 9, wherein the hollow fiber membrane 10 is sequentially connected with a pressure sensor 12 and a cleaning pump 13 through a fifth pipeline 11, the cleaning pump 13 is also connected with a sixth pipeline 14, and the sixth pipeline 14 extends into the cleaning tank 9; the cleaning pool 9 also realizes the cooling of water in the pool through a cooling device 8; the cooling device 8 is not particularly limited as long as it can control the temperature of the cleaning liquid, for example, a cooling water circulator, a cooling water pipe, a low-temperature constant-temperature tank, and the like; because the temperature of the water of the micro-nano bubble generator 5 is gradually increased in the operation process, the temperature has a great influence on the dissolution of ozone gas and the residence time of micro-nano bubbles in the water, so that the control of the water temperature is very important; the cooling device 8 of the embodiment is a low-temperature constant-temperature tank, and the cleaning pool is placed in a water tank of the low-temperature constant-temperature tank.
The top of the cleaning tank 9 is provided with a cleaning tank upper cover 15, as shown in fig. 2, the cleaning tank upper cover is provided with a first jack a for the third pipeline 6 to pass through, a second jack b for the fourth pipeline 7 to pass through, a third jack d for the fifth pipeline 11 to pass through and a fourth jack e for the sixth pipeline 14 to pass through; in use, each pipe is inserted into the cleaning tank 9 through the corresponding jack.
The upper cover of the cleaning pool is also provided with an ozone waste gas discharge hole c, the ozone waste gas discharge hole c is connected with an ozone waste gas treatment device 17 through a seventh pipeline 16, and the generated waste gas is discharged after being treated by the ozone waste gas treatment device 17.
The connected device is shown in fig. 1.
S2, membrane cleaning
1) The oxygen generating device 1 and the ozone generator 3 are sequentially started, and oxygen generated by the oxygen generating device 1 is input into the ozone generator 3 through the first pipeline 2 to produce ozone;
2) Starting the micro-nano bubble generator 5, inputting ozone into the micro-nano bubble generator 5 through the second pipeline 4, inputting water in the cleaning tank 9 into the micro-nano bubble generator 5 through the third pipeline 6, and releasing generated ozone micro-nano bubbles in the cleaning tank 9 through the fourth pipeline 7, wherein the concentration of dissolved ozone can be selected to be 1-5mg/L according to actual conditions in consideration of different pollution degrees of membranes cleaned in reality; the cleaning pool 9 is placed in a constant temperature tank of a cooling water circulating machine, and the temperature of cleaning liquid in the cleaning pool 9 is kept to be 25 ℃ through a cooling device 8;
3) The hollow fiber membrane module is connected with the pressure sensor 12 and the cleaning pump 13 through the fifth pipeline 11, and water after membrane filtration flows back to the cleaning tank 9 through the sixth pipeline 14.
The specific operation is as follows: the cleaning pump 13 is started to enable the ozone micro-nano bubbles to positively pass through the membrane for cleaning, and the mode of 'soaking and simultaneously positive cleaning' or 'soaking and positive alternate cleaning' is adopted until the descending amplitude of TMP displayed by the pressure sensor 12 is not more than 10% within 30min, so that the cleaning can be stopped.
4) The ozone exhaust gas discharge hole c is connected to the ozone exhaust gas treatment device 17 through a seventh pipe 16, and the generated exhaust gas is treated by the ozone exhaust gas treatment device 17 and then discharged.
The method for soaking and simultaneously cleaning in the positive direction comprises the following specific steps of: the cleaning pump 13 is turned on, the hollow fiber membrane 10 is kept immersed in the cleaning liquid, so that the ozone micro-nano bubbles are positively cleaned through the membrane, the dissolved ozone concentration in the ozone micro-nano bubble cleaning liquid in the cleaning pool 9, the water temperature and the TMP (transmembrane pressure difference) in the membrane cleaning process are measured every ten minutes until the TMP displayed by the pressure sensor 12 is reduced by not more than 10% within 30 minutes, the cleaning can be stopped, and the cleaning time is at most 2 hours.
The specific steps of the mode of 'soaking and forward alternate cleaning' are as follows:
a. the cleaning pump 13 is started, the hollow fiber membrane 10 is kept immersed in the cleaning liquid, so that the ozone micro-nano bubbles are positively cleaned through the membrane for 30 minutes, and the dissolved ozone concentration in the ozone micro-nano bubble cleaning liquid in the cleaning tank 9, the water temperature and the TMP (transmembrane pressure difference) in the membrane cleaning process are measured every ten minutes;
b. closing the cleaning pump 13 to enable the ozone micro-nano bubbles to soak and clean the hollow fiber membrane 1030min, and measuring the dissolved ozone concentration, water temperature and TMP in the membrane cleaning process in the ozone micro-nano bubble cleaning liquid in the cleaning pool 9 every ten min;
c. and (c) repeating the steps a and b until the TMP displayed by the pressure sensor 12 does not decrease by more than 10% within 30min, and stopping cleaning for at most 2h.
Example 2
A method for offline cleaning of MBR hollow fiber membranes using ozone micro-nano bubbles, which is different from example 1 in that the equipment connection in step S1 is different: namely, the cooling device 8 adopts a cooling water circulation machine, an eighth pipeline 18, a ninth pipeline 19 and a cooling water pipe 20, the eighth pipeline 18 is connected with a water inlet of the cooling water circulation machine, the ninth pipeline 19 is connected with a water outlet of the cooling water circulation machine, the cooling water pipe 20 is positioned in the cleaning tank 9 and is arranged in a wall-attached surrounding manner, two ends of the cooling water pipe 20 are respectively connected with the eighth pipeline 18 and the ninth pipeline 19, and a fifth jack f and a sixth jack for connecting and inserting the eighth pipeline 18 and the ninth pipeline 19 are respectively arranged on an upper cover of the cleaning tank, as shown in fig. 3 and 4.
The upper part of the cleaning pool 9 is also provided with a bubble uniform distribution mechanism, the bubble uniform distribution mechanism is arranged at the edge of an inner groove of the cleaning pool, as shown in fig. 5, the bubble uniform distribution mechanism comprises a connecting pipe 21 which is vertically arranged, a plurality of guide pipes 22 which are horizontally arranged and a plurality of spray heads 23, the connecting pipe 21 is connected with the fourth pipeline 7, the plurality of guide pipes 22 are communicated with the connecting pipe 21, and the spray heads 23 are uniformly distributed on the guide pipes 22; the generated ozone micro-nano bubbles are uniformly released in the cleaning pool 9 through a plurality of spray heads 23.
Testing
This test example uses the method described in example 1.
The cleaned membrane is a PVDF hollow fiber membrane which is continuously operated in an MBR membrane bioreactor for 9 months, and the sludge concentration of the MBR membrane bioreactor is 5000mg/L.
The effective volume of the cleaning liquid in the cleaning tank is 1L. The effective area of the washed hollow fiber membrane was 15.1X10 -3 m 2 。
The test example compares the cleaning effect of the cleaning liquid in different film cleaning modes: the 'soaking cleaning' is as follows: the membrane is immersed in a cleaning solution. The soaking is simultaneously and reversely cleaned: the membrane is soaked in a cleaning liquid, and the cleaning liquid is pumped into the membrane filaments of the hollow fiber membrane by a cleaning pump, so that the cleaning liquid passes through the membrane from inside to outside of the membrane filaments of the hollow fiber membrane for cleaning. The soaking is simultaneously and positively cleaned: the membrane is soaked in a cleaning liquid, and then the cleaning liquid is pumped by a cleaning pump, so that the cleaning liquid passes through the membrane from outside to inside to clean the surface of the hollow fiber membrane. The 'soaking and forward alternate cleaning' is as follows: the film is soaked in the cleaning liquid and is cleaned in a forward film passing way every 30 minutes: the membrane is soaked in the cleaning liquid, the cleaning pump is firstly turned on, the cleaning liquid is enabled to positively pass through the membrane to clean for 30min, then the cleaning pump is turned off, the membrane is soaked and cleaned for 30min, and the membrane is circularly operated according to the rule. Specific cleaning direction fig. 6 is a schematic view of cleaning hollow fiber membranes in the reverse direction in fig. 6 (a), and a schematic view of cleaning hollow fiber membranes in the forward direction in fig. 6 (b).
1. The present test example employs cleaning efficiency to evaluate the cleaning effect of the film.
The cleaning efficiency was evaluated as a percentage reduction in the membrane resistance of the hollow fiber membranes. The formula is as follows:
；
wherein:R after cleaning : membrane resistance (m) after contaminated membrane cleaning -1 )；R After pollution : membrane resistance (m) of contaminated membrane -1 )；R Initial initiation : film resistance (m) of original film -1 ). The raw film was immersed in ultrapure water for 24 hours and then measured for pure water permeability coefficient.
The resistance of the membrane was calculated according to the following formula:
；
wherein: r: resistance of Membrane Assembly (m -1 ) The method comprises the steps of carrying out a first treatment on the surface of the Δp: a transmembrane pressure difference (Pa); and (3) a step (mu): the dynamic viscosity (Pa.s) of deionized water at 20 ℃ is selected in the experiment, 1.00 multiplied by 10 -3 The method comprises the steps of carrying out a first treatment on the surface of the J: flux L/(m) of membrane module 2 ·h)。
The test example compares the cleaning effects of ozone micro-nano bubbles, common ozone water and 2000ppm NaClO on cleaning MBR hollow fiber membranes, and 3 repeated test data are selected for each group of cleaning experiments to calculate in order to ensure the accuracy of experimental results.
The film cleaning effect of ozone micro-nano bubbles and common ozone water, which are measured in water and have the same dissolved ozone concentration, is compared. Ozone gas and water are introduced into the micro-nano bubble generator 5, the concentration of the cleaning liquid reaches balance after half an hour of operation, and ozone micro-nano bubbles with the ozone concentration of 1mg/L are dissolved in the water in the cleaning tank. Ozone gas is introduced into the cleaning pool through the aeration stone, and the ozone concentration in the ozone water measured after stabilization is 1mg/L. The principle of ozone micro-nano bubble generation is as follows: the dissolved air releases air and the cross section of the flow is gradually reduced and suddenly expanded. The common ozone water is produced by dissolving ozone gas into water through an aerated stone.
TABLE 1 comparison of cleaning Effect of ozone micro-nano bubbles, common ozone Water, naClO cleaning MBR hollow fiber Membrane
As shown in Table 1, the effects of the ozone micro-nano bubbles of soaking cleaning, soaking, forward alternate cleaning and soaking and forward cleaning are better than those of the hollow fiber membrane cleaned by common ozone water and 2000ppm NaClO. Because the ozone micro-nano bubbles have strong dissolving capability in water, the ozone retention time is long. The ozone utilization efficiency is high, the generation of hydroxyl radicals is more, the cleaning of the membrane holes is facilitated, and the unique interface structure of the micro-nano bubbles is also beneficial to the cleaning of the membrane surface.
2. The test example compares the cleaning efficiency of ozone micro-nano bubbles with dissolved ozone concentration of 1, 3, 5 and 7mg/L for cleaning the hollow fiber membrane for 1 h.
TABLE 2 cleaning efficiency of ozone micro-nano bubbles with different concentrations for 1h
The test example compares the cleaning efficiency of ozone micro-nano bubbles with dissolved ozone concentration of 1, 3, 5 and 7mg/L in water for cleaning the hollow fiber membrane for 2 hours.
TABLE 3 cleaning efficiency of ozone micro-nano bubbles with different concentrations for 2h
From tables 2 and 3, it was found that the cleaning effect of different cleaning modes was achieved at the same concentration: "soaking while forward cleaning" > "soaking, forward alternate cleaning" > "soaking while reverse cleaning". It follows that: the optimal cleaning mode of the ozone micro-nano bubbles is as follows: "forward through-film cleaning while soaking". If energy consumption is a consideration, a "soak, forward alternate rinse" may be used.
Through tables 2 and 3, the cleaning effect of the membrane with the dissolved ozone concentration of 5mg/L and 7mg/L in the ozone micro-nano bubbles is almost similar, and the cleaning effect at 7mg/L is slightly lower than the cleaning effect at 5mg/L, which indicates that when the dissolved ozone concentration in the ozone micro-nano bubbles is 5mg/L, the cleaning requirement of the membrane is met, and the resource waste is caused by increasing the ozone concentration, the cost is increased, and the performance of the membrane is also affected. Considering that the pollution degree of the membranes cleaned in reality is different, the concentration of dissolved ozone in the ozone micro-nano bubbles is selected to be 1-5mg/L according to the actual situation. The membrane cleaned by the method is a PVDF hollow fiber membrane suitable for MBR water treatment.
It is also found from tables 2 and 3 that the cleaning effect of the polluted film selected in the test example reaches more than 90% after the polluted film is soaked and cleaned for 1 h.
3. Ozone micro-nano bubbles with dissolved ozone concentration of 1, 3 and 5mg/L in water change of TMP in the processes of soaking, forward cleaning and soaking and forward alternate cleaning.
It was found in connection with fig. 7 and 8 that after 2h of membrane cleaning, the change in TMP had tended to stabilize, indicating that the cleaning effect was saturated. Considering the difference in contamination level of the films, the cleaning time is referred to as: and the TMP in the membrane cleaning process is measured every ten minutes until the descending amplitude of the TMP displayed by the pressure sensor is not more than 10% within 30 minutes, the cleaning can be stopped, and the cleaning time is at most 2 hours, so that the membrane can be cleaned under the cleaning time of 2 hours even if the pollution degree of the membrane is serious.
4. Cleaning cost
TABLE 4 operating power of various devices during cleaning
TABLE 5 run time of various devices during cleaning
TABLE 6 cleaning cost (Yuan/m 2 ）
The power consumption E=P×t, and the electric charge is calculated according to 0.8 yuan/kW.h.
From the above table, it can be seen that under the same cleaning mode and the same cleaning time, the greater the concentration of dissolved ozone in the used ozone micro-nano bubble cleaning liquid, the greater the energy consumption and the higher the corresponding cleaning cost. The cleaning effect of the ozone micro-nano bubbles when the dissolved ozone concentration is 7mg/L is slightly lower than that of the ozone micro-nano bubbles when the dissolved ozone concentration is 5mg/L, and the cleaning cost is low: ozone micro-nano bubbles (7 mg/L) > ozone micro-nano bubbles (5 mg/L) > ozone micro-nano bubbles (3 mg/L) > ozone micro-nano bubbles (1 mg/L). Therefore, from the cost point of view, dissolved ozone concentration of 1-5mg/L is selected.
5. Film surface topography analysis
As shown in fig. 9, a film surface morphology diagram of the hollow fiber film after the hollow fiber film is cleaned by the ozone micro-nano bubbles with 4 different dissolved ozone concentrations is shown; (a) is a graph of ozone micro-nano bubbles with dissolved ozone concentration of 1mg/L, (b) is a graph of ozone micro-nano bubbles with dissolved ozone concentration of 3mg/L, (c) is a graph of ozone micro-nano bubbles with dissolved ozone concentration of 5mg/L, and (d) is a graph of ozone micro-nano bubbles with dissolved ozone concentration of 7 mg/L; analysis finds that: after the membrane is cleaned by dissolving ozone micro-nano bubbles with the ozone concentration of 7mg/L, cracks appear on the surface of the membrane, and the ozone micro-nano bubbles with the ozone concentration of 7mg/L are not suitable for cleaning the membrane for a long time.
6. Mechanical strength after film cleaning
As can be seen from fig. 10 and 11, after the membrane was cleaned with ozone micro-nano bubbles having a dissolved ozone concentration of 7mg/L for 2 hours, the tensile strength and elongation at break of the membrane were significantly reduced, and the decrease in mechanical strength of the membrane suggests that the membrane performance was changed after the membrane was cleaned with ozone micro-nano bubbles having a dissolved ozone concentration of 1-5mg/L, while the mechanical strength of the membrane was not greatly affected after the membrane was cleaned with ozone micro-nano bubbles having a dissolved ozone concentration of 1-5mg/L.
Therefore, from the aspects of the appearance and the mechanical strength, the ozone micro-nano bubbles with the dissolved ozone concentration of 1-5mg/L are selected.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. A method for offline cleaning of an MBR hollow fiber membrane by utilizing ozone micro-nano bubbles is characterized by comprising the following steps: the method comprises the following steps:
s1, device connection
The oxygen generating device, the ozone generator and the micro-nano bubble generator are sequentially connected through a first pipeline and a second pipeline, a liquid inlet of the micro-nano bubble generator is connected with a third pipeline, a gas outlet of the micro-nano bubble generator is connected with a fourth pipeline, and the third pipeline and the fourth pipeline extend into the cleaning pool; immersing the hollow fiber membrane in a cleaning tank, wherein the hollow fiber membrane is sequentially connected with a pressure sensor and a cleaning pump through a fifth pipeline, the cleaning pump is also connected with a sixth pipeline, and the sixth pipeline stretches into the cleaning tank; the cleaning pool also realizes the cooling of water in the pool through a cooling device; maintaining the temperature of the cleaning liquid in the cleaning pool to be 25+/-2 ℃ through a cooling device;
s2, membrane cleaning
1) The method comprises the steps of sequentially starting an oxygen generating device and an ozone generator, and inputting oxygen generated by the oxygen generating device into the ozone generator through a first pipeline to produce ozone;
2) Starting the micro-nano bubble generator, inputting ozone into the micro-nano bubble generator through a second pipeline, inputting water in the cleaning pool into the micro-nano bubble generator through a third pipeline, and releasing generated ozone micro-nano bubbles into the cleaning pool through a fourth pipeline, wherein the dissolved ozone concentration is 1-5mg/L;
3) The cleaning pump is started to enable ozone micro-nano bubbles to positively pass through the membrane for cleaning, and the cleaning is stopped by adopting a mode of 'soaking and simultaneously positively cleaning' or 'soaking and positively alternately cleaning' until the descending amplitude of TMP displayed by the pressure sensor is not more than 10% within 30 min;
the method for soaking and simultaneously cleaning in the positive direction comprises the following specific steps of: starting the cleaning pump, keeping the hollow fiber membrane immersed in the cleaning liquid to enable the ozone micro-nano bubbles to positively pass through the membrane for cleaning, measuring the dissolved ozone concentration, water temperature and TMP in the membrane cleaning process in the ozone micro-nano bubble cleaning liquid in the cleaning pool every ten minutes until the descending amplitude of the TMP displayed by the pressure sensor is not more than 10% within 30 minutes, and stopping cleaning for 2 hours at most;
the specific steps of the mode of 'soaking and forward alternate cleaning' are as follows:
a. starting the cleaning pump, keeping the hollow fiber membrane immersed in the cleaning liquid, enabling the ozone micro-nano bubbles to positively pass through the membrane for cleaning for 30min, and measuring the dissolved ozone concentration, water and TMP in the membrane cleaning process in the ozone micro-nano bubble cleaning liquid in the cleaning pool every ten minutes;
b. closing the cleaning pump to enable the ozone micro-nano bubbles to soak and clean the hollow fiber membrane for 30min, and measuring the dissolved ozone concentration in the ozone micro-nano bubble cleaning liquid in the cleaning pool, water and TMP in the membrane cleaning process every ten min;
c. and c, repeating the steps a and b until the descending amplitude of the TMP displayed by the pressure sensor is not more than 10% within 30min, and stopping cleaning for at most 2h.
2. The method for offline cleaning of the MBR hollow fiber membranes by using ozone micro-nano bubbles according to claim 1, wherein the method comprises the following steps: the top of the cleaning tank is provided with a cleaning tank upper cover, and the cleaning tank upper cover is provided with a first jack for a third pipeline to pass through, a second jack for a fourth pipeline to pass through, a third jack for a fifth pipeline to pass through and a fourth jack for a sixth pipeline to pass through; when in use, each pipeline is inserted into the cleaning pool through the corresponding jack.
3. The method for offline cleaning of the MBR hollow fiber membranes by using ozone micro-nano bubbles according to claim 2, wherein the method comprises the following steps: the upper cover of the cleaning pool is also provided with an ozone waste gas discharge hole, seven ozone waste gas discharge Kong Tongdi pipelines are connected with an ozone waste gas treatment device, and the generated waste gas is discharged after being treated by the ozone waste gas treatment device.
4. The method for offline cleaning of the MBR hollow fiber membranes by using ozone micro-nano bubbles according to claim 1, wherein the method comprises the following steps: the cooling device is a low-temperature constant-temperature tank, and the cleaning pool is placed in a water tank of the low-temperature constant-temperature tank.
5. The method for offline cleaning of the MBR hollow fiber membranes by using ozone micro-nano bubbles according to claim 1, wherein the method comprises the following steps: the cooling device comprises a cooling water circulating machine, an eighth pipeline, a ninth pipeline and a cooling water pipe, wherein the eighth pipeline is connected with a water inlet of the cooling water circulating machine, the ninth pipeline is connected with a water outlet of the cooling water circulating machine, the cooling water pipe is positioned inside the cleaning pool and is arranged in an adherence manner, and two ends of the cooling water pipe are respectively connected with the eighth pipeline and the ninth pipeline.
6. The method for offline cleaning of MBR hollow fiber membranes by utilizing ozone micro-nano bubbles according to claim 5, wherein the method comprises the following steps: the upper part of the cleaning pool is also provided with a bubble uniform distribution mechanism, the bubble uniform distribution mechanism comprises a connecting pipe which is vertically arranged, a plurality of guide pipes which are horizontally arranged and a plurality of spray heads, the connecting pipe is connected with a fourth pipeline, the plurality of guide pipes are communicated with the connecting pipe, and the spray heads are uniformly distributed on the guide pipes; the generated ozone micro-nano bubbles are uniformly released in the cleaning pool through a plurality of spray heads.
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