CN112093988A - Photocatalytic treatment device and method for printing and dyeing wastewater - Google Patents
Photocatalytic treatment device and method for printing and dyeing wastewater Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 78
- 239000002351 wastewater Substances 0.000 title claims abstract description 76
- 238000004043 dyeing Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 238000005273 aeration Methods 0.000 claims abstract description 41
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 238000001556 precipitation Methods 0.000 claims abstract description 37
- 239000011941 photocatalyst Substances 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000005345 coagulation Methods 0.000 claims abstract description 26
- 230000015271 coagulation Effects 0.000 claims abstract description 26
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 20
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 239000000243 solution Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000010802 sludge Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000005192 partition Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000701 coagulant Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000003344 environmental pollutant Substances 0.000 claims description 8
- 231100000719 pollutant Toxicity 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004753 textile Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 229910002900 Bi2MoO6 Inorganic materials 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 3
- 229940107698 malachite green Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
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Abstract
A photocatalytic treatment device and method for printing and dyeing wastewater belong to the technical field of wastewater treatment. Comprises a coagulation stirring area, a precipitation separation area, a photocatalysis area, an aeration oxidation area and a filtering area. The photocatalytic printing and dyeing wastewater treatment device is provided with the photocatalytic lamp tube, and the lamp tube provides sufficient light source for the inside of the photocatalytic area, so that the condition that the catalyst cannot effectively degrade the dye due to insufficient light in rainy days can be effectively avoided; and the device is convenient to operate and operate, does not have the phenomenon of blockage and is convenient to operate and maintain. Bi of optimum proportion2O3/Bi2MoO6Is 1:1.8, 1.8-Bi after 100min irradiation2O3/Bi2MoO6The degradation rate of the composite photocatalyst on the dye reaches 98 percent, which is far higher than that of a single bismuth oxide or bismuth molybdate catalyst.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a photocatalytic treatment device and method for printing and dyeing wastewater.
Background
The textile industry brings great economic benefits and simultaneously causes non-trivial pressure on water environment safety, especially, eight-component pollutants in the whole industrial chain are discharged in an important link of the textile industry chain by printing and dyeing, and according to statistics, the printing and dyeing wastewater generated nationwide every year accounts for more than 24.5 hundred million tons of total discharge of industrial wastewater in China, and accounts for about 12 percent of the total discharge of industrial wastewater in China, and is the third in 41 counted industries. The printing and dyeing wastewater has complex components, main pollutants are derived from a large amount of dyes and chemical agents used in the processing process, and the printing and dyeing wastewater has a great amount of toxic and harmful substances, variable water quality and water quantity and poor biodegradability, and is a kind of recognized industrial wastewater difficult to treat.
At present, the main treatment process of the printing and dyeing wastewater is a traditional physicochemical and biological combined process, wherein an activated sludge method is widely applied, but indexes such as COD, ammonia nitrogen, chromaticity and the like of the printing and dyeing wastewater treated by the traditional method are still high, and the current discharge standard is difficult to achieve.
Meanwhile, with the rapid development of global science and technology, the shortage of energy is also an urgent problem to be solved. In recent years, semiconductor photocatalysis technology is considered as one of the most effective methods for green energy-saving environmental pollution treatment and energy conversion and storage, and has the characteristics of high stability, no secondary pollution in the degradation process, simple process flow and the like, so that the semiconductor photocatalysis technology is widely concerned by researchers.
Bi2O3The photocatalyst has a narrow forbidden band width (about 2.8 eV), can be excited by visible light, and is proved to have good photocatalytic activity and relatively stable photocatalytic performance by research. In addition, Bi2O3The conductivity of the photocatalyst has a change range of more than 5 orders of magnitude, has very high refractive index and dielectric constant, has friendly photoconductivity and hydrophobicity, and is a very potential visible-light photocatalyst for degrading pollutants. Although one is on Bi2O3The research on the catalyst has been extensively explored, but the catalytic effect is still not very ideal. At present, much research is being done on bismuth and othersThe composite photocatalyst consisting of metal or nonmetal has stronger response to visible light and better activity of degrading pollutants by photocatalysis.
First preparing Bi2O3Then it is reacted with Bi2MoO6Is compounded to further promote Bi2O3The separation of the photogenerated electrons and the holes enhances the absorption capacity of the photogenerated electrons to visible light and improves the catalytic effect.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at solving the technical problems of the traditional treatment method of the printing and dyeing wastewater and Bi2O3The problem of non-ideal catalytic effect is to provide a photocatalytic treatment device and a method for printing and dyeing wastewater, which can effectively treat the printing and dyeing wastewater.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a photocatalysis treatment device for printing and dyeing wastewater comprises a coagulation stirring area 1, a precipitation separation area 2, a photocatalysis area 3, an aeration oxidation area 4 and a filtering area 5.
The coagulation stirring area 1 is provided with a water inlet pipe 1-1 and a water distribution pipe 1-2, the water distribution pipe 1-2 is connected with the water inlet pipe 1-1, and the water distribution pipe 1-2 is provided with a horizontal radiation water outlet. The coagulating and stirring area 1 is provided with a coagulant adding and metering system 1-3, and the middle part of the coagulating and stirring area 1 is provided with a stirring device 1-4. The lower part of the coagulation stirring area 1 is provided with an inclined bottom plate, and the stirred wastewater flows into the precipitation separation area 2 along the inclined bottom plate.
Further, the water distribution pipes 1-2 are arranged in a concentric circle shape or a cross shape for better wastewater treatment effect.
A flow baffle plate 2-1 is arranged between the coagulation stirring area 1 and the precipitation separation area 2, the lower part of the flow baffle plate 2-1 is provided with a 45-degree corner, the corner turns to one side of the coagulation stirring area 1, the bottom of the precipitation separation area 2 is designed into a conical structure, and the lower part of the conical structure is provided with a precipitation separation area discharge valve 2-2.
A flow guide plate 3-1 is arranged between the photocatalytic area 3 and the precipitation separation area 2, a water flow channel for wastewater to enter the photocatalytic area 3 is formed by the flow guide plate 3-1 and the inner wall of the precipitation separation area 2, a photocatalytic inclined plate 3-2 is arranged in the photocatalytic area 3, a photocatalyst is laid on the upper surface of the photocatalytic inclined plate 3-2, and a lamp tube is arranged on the lower surface of the photocatalytic inclined plate 3-2. The bottom of the photocatalytic area 3 is designed into a conical structure, and the lower part of the conical structure is provided with a photocatalytic area discharge valve 3-3.
The preparation steps of the photocatalyst are as follows:
Step 3, preparing the bismuth oxide/bismuth molybdate composite photocatalyst: respectively adding bismuth oxide and bismuth molybdate into ethanol, performing ultrasonic treatment for 1-2 h, pouring a bismuth oxide solution into a bismuth molybdate solution after the ultrasonic treatment is finished, continuing performing ultrasonic treatment on the mixed solution for 2-3 h, then dropwise adding 15-25 ml of acetone into the mixed solution, stirring for 24-36 h, precipitating, and drying to obtain the composite catalyst. The concentration of bismuth oxide in the mixed solution was 6.67X 10-6mol/L, bismuth molybdate concentration 1.2X 10-5mol/L; the volume ratio of the addition amount of the mixed solution to the acetone is 2: 1.
A first partition plate 4-1 is arranged between the photocatalytic zone 3 and the aeration oxidation zone 4, a first water flow port 4-2 is arranged on the first partition plate 4-1, an aeration disc 4-3 is arranged at the lower part of the aeration oxidation zone 4, and the aeration disc 4-3 is connected with an air blower 4-4 positioned outside the aeration oxidation zone 4 through a pipeline.
Further, the aeration discs 4-3 are microporous aeration discs uniformly provided with micropores.
A second partition plate 5-1 is arranged between the aeration oxidation area 4 and the filtering area 5, a second water flow port 5-2 is arranged on the second partition plate 5-1, a filtering material rack is arranged in the middle of the filtering area 5, filtering materials 5-3 are placed on the filtering material rack, the filtering materials 5-3 are quartz sand or ceramsite, and the filtering materials 5-3 need to be replaced when the filtering speed is low. The bottom of the filtering area 5 is designed into a conical structure, and the lower part of the conical structure is provided with a sludge discharge valve 5-4. The upper part of the filtering area 5 is provided with an overflow weir 5-5, the overflow weir 5-5 is connected with a water outlet pipe, and water discharged by the water outlet pipe is discharged or recycled after reaching the standard.
The heights of the guide plate 3-1, the flow baffle 2-1, the first clapboard 4-1 and the second clapboard 5-1 are all consistent and are all higher than the inner wall of the precipitation separation zone 2.
The method for treating the waste water by adopting the photocatalytic treatment device for the printing and dyeing waste water comprises the following steps:
firstly, wastewater enters a coagulation stirring area 1 through a water inlet pipe 1-1 and a water distribution pipe 1-2 to be mixed with a coagulant from a coagulant adding and metering system 1-3, a stirring device 1-4 is used for stirring the wastewater, and the wastewater is subjected to coagulation reaction.
Secondly, the waste water enters a precipitation separation area 2 through an inclined bottom plate arranged at the lower part of the coagulation stirring area 1, the solid with larger specific gravity sinks to the lower part of the precipitation separation area 2 under the action of gravity and is discharged through a discharge valve 2-2 of the precipitation separation area at the bottom.
Thirdly, the wastewater after precipitation and separation enters a photocatalytic area 3, a lamp tube is opened, the photocatalyst is contacted with the wastewater, and pollutants in the wastewater are decomposed under the photocatalytic condition. The photocatalyst falling off from the photocatalytic sloping plate 3-2 is naturally precipitated and discharged through the photocatalytic region discharge valve 3-3, and then the photocatalyst is centrifugally collected and regenerated for recycling.
Fourthly, the wastewater after the photocatalytic reaction enters an aeration oxidation zone 4 through a first water flow port 4-2, an aeration disc 4-3 arranged in the aeration oxidation zone 4 aerates the wastewater, and the printing and dyeing wastewater is aerobically oxidized.
And fifthly, the wastewater after aerobic oxidation enters a filtering area 5 through a second water flow port 5-2, the wastewater is filtered by a filter material 5-3 and then is discharged through an overflow weir 5-5 and a water outlet pipe, and the sludge is discharged through a sludge discharge valve 5-4 at the bottom. Part of the sludge flows back to the aeration oxidation zone 4.
Compared with the prior art, the invention has the following beneficial effects:
1. the photocatalytic printing and dyeing wastewater treatment device is provided with the photocatalytic lamp tube, and the lamp tube provides sufficient light source for the inside of the photocatalytic area, so that the condition that the catalyst cannot effectively degrade the dye due to insufficient light in rainy days can be effectively avoided; and the device is convenient to operate and operate, does not have the phenomenon of blockage and is convenient to operate and maintain.
2. Bi of optimum proportion2O3/Bi2MoO6Is 1:1.8, 1.8-Bi after 100min irradiation2O3/Bi2MoO6The degradation rate of the composite photocatalyst on the dye reaches 98 percent, which is far higher than that of a single bismuth oxide or bismuth molybdate catalyst.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic structural view of a photocatalytic treatment apparatus for textile printing wastewater according to an embodiment of the present invention;
in fig. 1:1, a coagulation stirring area; 1-1 water inlet pipe; 1-2 water distribution pipes; 1-3 coagulant addition metering system; 1-4 stirring device; 2, a precipitation separation area; 2-1 flow baffle; 2-2 a sedimentation separation zone discharge valve; 3 a photocatalytic region; 3-1 a flow guide plate; 3-2 photocatalytic sloping plates; 3-3 photocatalytic zone exhaust valve; 4, aerating and oxidizing the mixture; 4-1 a first separator plate; 4-2 a first water flow port; 4-3, an aeration disc; 4-4 of a blower; 5 a filtering area; 5-1 second separator; 5-2 second water flow port; 5-3, filtering; 5-4 sludge discharge valves; 5-5 overflow weir.
FIG. 2 shows XRD patterns of the single-type photocatalyst and the composite photocatalyst prepared by the present invention.
FIG. 3 is a graph of the degradation efficiency of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
Example 1
The photocatalytic treatment device for printing and dyeing wastewater disclosed by the invention as shown in figure 1 comprises a coagulation stirring area 1, a precipitation separation area 2, a photocatalytic area 3, an aeration oxidation area 4 and a filtering area 5.
The coagulation stirring area 1 is provided with a water inlet pipe 1-1 and a water distribution pipe 1-2, the water distribution pipe 1-2 is connected with the water inlet pipe 1-1, for better wastewater treatment effect, the water distribution pipe 1-2 is arranged in a concentric circle shape or a cross shape, and the water distribution pipe 1-2 is provided with a horizontal radiation water outlet. The coagulating and stirring area 1 is provided with a coagulant adding and metering system 1-3, and the middle part of the coagulating and stirring area 1 is provided with a stirring device 1-4. The lower part of the coagulation stirring area 1 is provided with an inclined bottom plate, and the stirred wastewater flows into the precipitation separation area 2 along the inclined bottom plate.
A flow baffle plate 2-1 is arranged between the coagulation stirring area 1 and the precipitation separation area 2, the lower part of the flow baffle plate 2-1 is provided with a 45-degree corner, the corner turns to one side of the coagulation stirring area 1, the bottom of the precipitation separation area 2 is designed into a conical structure, and the lower part of the conical structure is provided with a precipitation separation area discharge valve 2-2.
A guide plate 3-1 is arranged between the photocatalytic area 3 and the precipitation separation area 2, the guide plate 3-1 and the inner wall of the photocatalytic treatment device for printing and dyeing wastewater form a water flow channel for wastewater to enter the photocatalytic area 3, a photocatalytic inclined plate 3-2 is arranged in the photocatalytic area 3, a photocatalyst is laid on the upper surface of the photocatalytic inclined plate 3-2, and a lamp tube is arranged on the lower surface of the photocatalytic inclined plate 3-2. The bottom of the photocatalytic area 3 is designed into a conical structure, and the lower part of the conical structure is provided with a photocatalytic area discharge valve 3-3. The photocatalyst falling off from the photocatalytic sloping plate 3-2 is naturally precipitated and discharged through the photocatalytic region discharge valve 3-3, and then the photocatalyst is centrifugally collected and regenerated for recycling.
The preparation steps of the photocatalyst are as follows:
Step 3, preparing the bismuth oxide/bismuth molybdate composite photocatalyst: respectively adding 0.1g of bismuth oxide and 0.18g of bismuth molybdate into 15ml of ethanol, carrying out ultrasonic treatment for 1h, pouring the bismuth oxide solution into the bismuth molybdate solution after the ultrasonic treatment is finished, continuing the ultrasonic treatment for 2h on the mixed solution, then dropwise adding 15ml of acetone into the mixed solution by using a rubber head dropper, stirring for 24h, precipitating, and drying to obtain the composite catalyst. The concentration of bismuth oxide in the mixed solution was 6.67X 10-6mol/L, bismuth molybdate concentration 1.2X 10-5mol/L; the volume ratio of the addition amount of the mixed solution to the acetone is 2: 1.
A first partition plate 4-1 is arranged between the photocatalytic zone 3 and the aeration oxidation zone 4, a first water flow port 4-2 is arranged on the first partition plate 4-1, an aeration disc 4-3 is arranged at the lower part of the aeration oxidation zone 4, the aeration disc 4-3 is connected with an air blower 4-4 outside the aeration oxidation zone through a pipeline, and the aeration disc 4-3 is a microporous aeration disc with micropores uniformly arranged.
A second partition plate 5-1 is arranged between the aeration oxidation area 4 and the filtering area 5, a second water flow port 5-2 is arranged on the second partition plate 5-1, a filtering material 5-3 is arranged in the middle of the filtering area, the filtering material 5-3 is made of quartz sand and ceramsite, the filtering material 5-3 is placed on a filtering material rack, and the filtering material 5-3 needs to be replaced when the filtering speed is low. The bottom of the filtering area 5 is designed into a conical structure, and the lower part of the conical structure is provided with a sludge discharge valve 5-4. The upper part of the filtering area 5 is provided with an overflow weir 5-5, the overflow weir 5-5 is connected with a water outlet pipe, and water discharged by the water outlet pipe is discharged or recycled after reaching the standard.
The heights of the guide plate 3-1, the flow baffle 2-1, the first clapboard 4-1 and the second clapboard 5-1 are all consistent and are all higher than the inner wall of the precipitation separation zone 2.
The method for treating the waste water by adopting the photocatalytic treatment device for the printing and dyeing waste water comprises the following steps:
preparing 20MG/L malachite green solution as simulated printing and dyeing wastewater, and evaluating the degradation rate of the whole device by degrading organic dye Malachite Green (MG). Measuring absorbance C of wastewater before water inflow0And the absorbance measured at the maximum absorption wavelength is 2.48, the wastewater enters a coagulation stirring area 1 through a water inlet pipe 1-1 and a water distribution pipe 1-2 and is mixed with a coagulant from a coagulant adding and metering system 1-3, a stirring device 1-4 is used for stirring the wastewater, and the wastewater undergoes coagulation reaction.
Secondly, the waste water enters a precipitation separation area 2 through an inclined bottom plate arranged at the lower part of the coagulation stirring area 1, the solid with larger specific gravity sinks to the lower part of the precipitation separation area 2 under the action of gravity and is discharged through a discharge valve 2-2 of the precipitation separation area at the bottom.
Thirdly, the wastewater after precipitation and separation enters a photocatalytic area 3, a lamp tube is opened, the photocatalyst is contacted with the wastewater, and pollutants in the wastewater are decomposed under the photocatalytic condition. The photocatalyst falling off from the photocatalytic sloping plate 3-2 is naturally precipitated and discharged through the photocatalytic region discharge valve 3-3, and then the photocatalyst is centrifugally collected and regenerated for recycling.
Fourthly, the wastewater after the photocatalytic reaction enters an aeration oxidation zone 4 through a first water flow port 4-2, an aeration disc 4-3 arranged in the aeration oxidation zone 4 aerates the wastewater, and the printing and dyeing wastewater is aerobically oxidized.
The wastewater after aerobic oxidation enters a filtering area 5 through a second water flow port 5-2, the wastewater is filtered by a filter material 5-3 and then is discharged through an overflow weir 5-5 and a water outlet pipe, and sludge is discharged through a sludge discharge valve 5-4 at the bottom; part of the sludge flows back to the aeration oxidation zone 4. Measuring the absorbance C of the wastewater discharged from the water outlet pipe againtThe absorbance measured at the maximum absorption wavelength was 0.05.
Sixthly, calculating the degradation efficiency of the sample on the pollutants by the following formula:
D＝(1-Ct/C0)×100％
D＝(1-0.05/2.48)×100％＝98％
wherein C is0And CtThe absorbance of the wastewater before water inlet and after water outlet is respectively shown.
Example 2
For comparison, in the preparation of the photocatalyst of example 2, only bismuth oxide was added as a catalyst for photocatalytic reaction, and no bismuth molybdate was added.
The rest of the structure and method are the same as those of example 1.
Example 3
For comparison, in example 3, the photocatalyst was prepared by adding only bismuth molybdate as a catalyst for the photocatalytic reaction and not bismuth oxide.
The rest of the structure is the same as in example 1.
Comparative example 1
For comparison, in comparative example 1, no photocatalyst was applied to the upper surface of the photocatalytic sloping plate, and the wastewater directly passed through the photocatalytic region without photocatalytic reaction. As shown in fig. 3, the degradation rate of the bismuth oxide/bismuth molybdate composite photocatalyst prepared in example 1 to the printing and dyeing wastewater can reach 98%, the degradation rates of the catalysts prepared in examples 2 and 3 to the printing and dyeing wastewater are 49% and 62%, and the degradation rate of the catalyst to the wastewater is only 23% without adding the catalyst in comparative example 1. Therefore, the photocatalytic performance of the 1.8-Bi2O3/Bi2MoO6 composite material is far higher than that of a single catalyst.
The rest of the structure is the same as in example 1.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (5)
1. A photocatalytic treatment device for printing and dyeing wastewater is characterized by comprising a coagulation stirring area (1), a precipitation separation area (2), a photocatalytic area (3), an aeration oxidation area (4) and a filtering area (5);
the coagulation stirring area (1) is provided with a water inlet pipe (1-1) and a water distribution pipe (1-2), the water distribution pipe (1-2) is connected with the water inlet pipe (1-1), and the water distribution pipe (1-2) is provided with a horizontal radiation water outlet; the coagulating and stirring area (1) is provided with a coagulant adding and metering system (1-3), and the middle part of the coagulating and stirring area (1) is provided with a stirring device (1-4); an inclined bottom plate is arranged at the lower part of the coagulation stirring area (1), and the stirred wastewater flows into the precipitation separation area (2) along the inclined bottom plate;
a flow baffle plate (2-1) is arranged between the coagulation stirring area (1) and the precipitation separation area (2), the lower part of the flow baffle plate (2-1) is provided with a 45-degree corner, the corner turns to one side of the coagulation stirring area (1), the bottom of the precipitation separation area (2) is designed into a conical structure, and the lower part of the conical structure is provided with a precipitation separation area discharge valve (2-2);
a flow guide plate (3-1) is arranged between the photocatalytic area (3) and the precipitation separation area (2), a water flow channel which is used as wastewater to enter the photocatalytic area (3) is formed by the flow guide plate (3-1) and the inner wall of the precipitation separation area (2), a photocatalytic sloping plate (3-2) is arranged in the photocatalytic area (3), a photocatalyst is laid on the upper surface of the photocatalytic sloping plate (3-2), and a lamp tube is arranged on the lower surface of the photocatalytic sloping plate (3-2); the bottom of the photocatalytic area (3) is designed into a conical structure, and the lower part of the conical structure is provided with a photocatalytic area discharge valve (3-3);
a first partition plate (4-1) is arranged between the photocatalytic zone (3) and the aeration oxidation zone (4), a first water flow port (4-2) is formed in the first partition plate (4-1), an aeration disc (4-3) is arranged at the lower part of the aeration oxidation zone (4), and the aeration disc (4-3) is connected with an air blower (4-4) positioned outside the aeration oxidation zone (4) through a pipeline;
a second partition plate (5-1) is arranged between the aeration oxidation area (4) and the filtering area (5), a second water flow port (5-2) is formed in the second partition plate (5-1), a filtering material rack is arranged in the middle of the filtering area (5), filtering materials (5-3) are placed on the filtering material rack, the filtering materials (5-3) are quartz sand or ceramsite, and the filtering materials (5-3) need to be replaced when the filtering speed is low; the bottom of the filtering area (5) is designed into a conical structure, and the lower part of the conical structure is provided with a sludge discharge valve (5-4); an overflow weir (5-5) is arranged at the upper part of the filtering area (5), the overflow weir (5-5) is connected with a water outlet pipe, and water discharged by the water outlet pipe is discharged or recycled after reaching the standard;
the heights of the guide plate (3-1), the baffle plate (2-1), the first clapboard (4-1) and the second clapboard (5-1) are all consistent and are all higher than the inner wall of the precipitation separation area (2).
2. The photocatalytic treatment device for printing and dyeing wastewater according to claim 1, characterized in that the water distribution pipes (1-2) are arranged in concentric circles or in a cross shape for better wastewater treatment.
3. The photocatalytic treatment apparatus for textile printing wastewater according to claim 1, wherein the photocatalyst is prepared by the steps of:
step 1, preparation of bismuth molybdate: respectively dissolving bismuth nitrate and ammonium molybdate in acetic acid and distilled water, mixing the solutions together after the solutions are dissolved, adjusting the pH of the mixed solution to 5-8 by using ammonia water, transferring the obtained suspension into a reaction kettle, reacting at 140-160 ℃ for 18-24 h, cooling, washing, centrifuging and drying to obtain light green bismuth molybdate; the concentration of the bismuth nitrate solution is 0.5mol/L, and the concentration of the ammonium molybdate solution is 0.06 mol/L; the volume ratio of the bismuth nitrate to the ammonium molybdate solution is 1: 6;
step 2, preparing bismuth oxide: dissolving sodium bismuthate in distilled water, transferring the suspension into a reaction kettle, reacting for 6-10 h at 140-180 ℃, cooling to room temperature, washing, drying, and putting the obtained sample into a muffle furnace for calcining; the calcining temperature is 300 ℃, and the time is 3 h;
step 3, preparing the bismuth oxide/bismuth molybdate composite photocatalyst: respectively adding bismuth oxide and bismuth molybdate into ethanol, performing ultrasonic treatment for 1-2 h, pouring a bismuth oxide solution into a bismuth molybdate solution after the ultrasonic treatment is finished, continuing performing ultrasonic treatment on the mixed solution for 2-3 h, then dropwise adding 15-25 ml of acetone into the mixed solution, stirring for 24-36 h, precipitating, and drying to obtain a composite catalyst; the concentration of bismuth oxide in the mixed solution was 6.67X 10-6mol/L, bismuth molybdate concentration 1.2X 10-5mol/L; the volume ratio of the addition amount of the mixed solution to the acetone is 2: 1.
4. The photocatalytic treatment apparatus for printing and dyeing wastewater according to claim 1, characterized in that the aeration disks (4-3) are microporous aeration disks having micropores uniformly formed therein.
5. A method for treating waste water by using the photocatalytic treatment apparatus for textile printing waste water according to any one of claims 1 to 4, characterized by comprising the steps of:
firstly, wastewater enters a coagulation stirring area (1) through a water inlet pipe (1-1) and a water distribution pipe (1-2) and is mixed with a coagulant from a coagulant adding and metering system (1-3), a stirring device (1-4) is used for stirring the wastewater, and the wastewater undergoes coagulation reaction;
secondly, the wastewater enters a precipitation separation area (2) through an inclined bottom plate arranged at the lower part of the coagulation stirring area (1), the solid with larger specific gravity sinks to the lower part of the precipitation separation area (2) under the action of gravity and is discharged through a discharge valve (2-2) of the precipitation separation area at the bottom;
thirdly, the wastewater after precipitation and separation enters a photocatalytic area (3), a lamp tube is opened, a photocatalyst is contacted with the wastewater, and pollutants in the wastewater are decomposed under the photocatalytic condition; the photocatalyst falling off from the photocatalytic sloping plate (3-2) is naturally precipitated and discharged through the photocatalytic region discharge valve (3-3), and then the photocatalyst is centrifugally collected and regenerated for recycling;
fourthly, the wastewater after the photocatalytic reaction enters an aeration oxidation zone (4) through a first water flow port (4-2), an aeration disc (4-3) arranged in the aeration oxidation zone (4) aerates the wastewater, and the printing and dyeing wastewater is aerobically oxidized;
the wastewater after aerobic oxidation enters a filtering area (5) through a second water flow port (5-2), the wastewater is filtered by a filter material (5-3) and then is discharged through an overflow weir (5-5) and a water outlet pipe, and the sludge is discharged through a sludge discharge valve (5-4) at the bottom; part of the sludge flows back to the aeration oxidation zone (4).
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