CN110540285A - Heterogeneous ozone catalysis and micro-nano bubble combined sewage treatment method - Google Patents
Heterogeneous ozone catalysis and micro-nano bubble combined sewage treatment method Download PDFInfo
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000010865 sewage Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002101 nanobubble Substances 0.000 title claims abstract description 36
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000011049 filling Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000006385 ozonation reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000005273 aeration Methods 0.000 abstract description 4
- 239000010841 municipal wastewater Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 244000005700 microbiome Species 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000003440 toxic substance Substances 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/26—Reducing the size of particles, liquid droplets or bubbles, e.g. by crushing, grinding, spraying, creation of microbubbles or nanobubbles
Abstract
The invention discloses a sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles, wherein ozone is fully mixed with sewage through a micro-nano bubble generating device to form an ozone saturated emulsion; carrying out oxidation reaction on the sewage in a gas-liquid highly-mixed state in a fixed bed reactor filled with a heterogeneous ozone catalyst; the method adopts the running mode of continuous ozone adding and continuous water inlet and outlet. Compared with the traditional direct aeration technology, the method has the advantages that the catalyst is loaded with novel active metal, the surface area of the catalyst is large, the adsorption capacity is strong, highly dispersed micro-nano ozone bubbles are enriched on the surface of the catalyst, the contact area of the ozone bubbles and liquid and the retention time of the ozone bubbles are greatly increased, the ozone utilization rate is greatly improved, the method has extremely high ozone utilization rate, and pollutants such as organic matters, chromaticity, benzene ring toxic substances, microorganisms and the like in various industrial wastewater and municipal wastewater can be effectively removed.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles.
Background
The rapid development of the industry greatly facilitates the life of people, but a large amount of pollutants are discharged into the environment, and particularly the water pollution condition is not optimistic. The rapid increase of the variety and the content of organic matters in the sewage directly threatens the stability of an ecological system and the human health, and has the characteristics of complex components, difficult degradation, deep chroma, high COD (chemical oxygen demand) and the like. Ozone is widely applied to advanced oxidation treatment technology of sewage due to extremely strong oxidizability, and can mineralize organic matters in water to generate CO2, water and other pollutants-free substances, so that the effect of treating sewage can be achieved by high-efficiency cleaning. Compared with the traditional advanced oxidation and homogeneous ozone catalysis, the heterogeneous ozone catalysis has the advantages of simple operation, difficult loss of active metal, no secondary pollution, good stability, low cost and the like, and has good utilization value and wide market prospect in the field of treating various sewage.
However, the conventional aeration method has the defect of low ozone utilization rate, and ozone is easily decomposed and lost in air and water, so that the cost of ozone catalytic oxygen consumption and ozone production is high, and the development of the technology is limited to a great extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles, and aims to improve the catalysis efficiency and the ozone utilization rate.
The technical scheme is as follows:
A sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles is characterized in that ozone is fully mixed with sewage through a micro-nano bubble generating device to form an ozone saturated emulsion; carrying out oxidation reaction on the sewage in a gas-liquid highly-mixed state in a fixed bed reactor filled with a heterogeneous ozone catalyst; the method adopts the running mode of continuous ozone adding and continuous water inlet and outlet.
Preferably, the preparation process of the heterogeneous ozone catalyst comprises three stages of carrier pretreatment, impregnation and roasting, wherein gamma-Al 2O3 is cleaned and then soaked in a sodium hydroxide solution for pretreatment for 4-8 hours; drying, and then adopting an excessive dipping mode, wherein a dipping solution comprises manganese nitrate and at least one of soluble salts of active metals Ru, Pt and Ni, and mixing and synchronously dipping for 4-12 h; then roasting the mixture for 4 to 8 hours in a muffle furnace at 400-500 ℃.
preferably, the diameter of the carrier gamma-Al 2O3 particle of the heterogeneous ozone catalyst is 3-4mm, the specific surface area of the catalyst is 210-260m2/g, and the ozonization index is 3-5(CODmg/L) · (O3mg/L) -1.
Preferably, the heterogeneous ozone catalyst has a packing rate of 50-75% in a fixed bed reactor, and the packing mode is bulk packing, and the bulk density is 0.7-0.8g/m 3.
Preferably, the contact time of the sewage in a gas-liquid highly mixed state and the heterogeneous ozone catalyst is 10-30 min.
Preferably, the diameter of the nano bubbles of the micro-nano bubble generating device is 90nm-50 μm, the gas-liquid volume ratio of ozone to sewage is 1:9-2:9, and the water inflow is 0.018-5m 3/h.
The sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles has the main advantages that:
(1) Compared with the traditional direct aeration technology, the method greatly improves the utilization rate and the oxidation capacity of ozone, is very suitable for treating the sewage which has high pollutant concentration and is difficult to degrade, and has the advantages of simple operation management, stable operation state and low cost.
(2) Compared with the traditional catalyst such as Fe2+, Co2+, Cu2+ and the like, the catalyst has the advantages of stronger catalytic effect, large surface area, strong adsorption capacity, and enrichment of highly dispersed micro-nano ozone bubbles on the surface of the catalyst, greatly increases the contact area of the ozone bubbles and liquid and the retention time of the ozone bubbles, greatly improves the ozone utilization rate, has extremely high ozone utilization rate, and can effectively remove pollutants such as organic matters, chromaticity, benzene ring toxic substances, microorganisms, bacteria, heavy metals and the like in various industrial wastewater and municipal wastewater.
(3) In the invention, a specific stage heating mode is adopted in the roasting process of the catalyst, so that the roasting final temperature is reduced, the crystallization effect of the active metal oxide after roasting is better, the active metal oxide is not easy to lose, and compared with the traditional direct high-temperature roasting process, the method not only saves energy, but also enhances the activity of the catalyst.
Drawings
FIG. 1 shows the comparison of COD effect and stability experiment results of dye wastewater removal by conventional ozone catalysis, heterogeneous ozone catalysis and micro-nano bubble combined technology.
FIG. 2 is a comparison result of the advanced treatment of municipal sewage by the conventional aeration and heterogeneous ozone catalysis and micro-nano bubble combined technology.
FIG. 3 is a graph of the fluorescence profile of municipal sewage contaminants.
FIG. 4 shows the result of removing pollutants by the sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles.
Detailed Description
In order to make those skilled in the art better understand the technical scheme of the present invention, the following describes in detail a sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles provided by the present invention with reference to the following embodiments. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
In the heterogeneous ozone catalyzed reaction, the catalytic activity of the catalyst and the oxidation efficiency of ozone directly affect the effect of sewage treatment. Therefore, the invention discloses a sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles from the preparation process of an improved catalyst and an enhanced oxidation reaction process, and the specific flow implementation mode is as follows:
Firstly, ozone is fully mixed with sewage through a micro-nano bubble generating device to form ozone saturated emulsion; secondly, the sewage in a gas-liquid highly mixed state is subjected to oxidation reaction in a fixed bed reactor filled with a catalyst. The method adopts a running mode of continuous ozone adding and continuous water inlet and outlet.
in the first process, after ozone and sewage pass through a micro-nano bubble generator, high mixing of gas and liquid is realized, the diameter of ozone micro-nano bubbles is 90nm-50 mu m, and the volume ratio of the gas to the liquid of the ozone to the sewage is 1:9-2: 9. According to different water qualities and treatment requirements, the change of the size of the nano bubbles and the concentration of the bubbles is realized by regulating and controlling the gas-liquid ratio and the pressure.
In the second flow, the filling rate of the catalyst in the fixed bed reactor is 50-75%, the filling mode is stacking filling, and the stacking density is 0.75g/m 3. The preparation method of the catalyst comprises three stages of carrier pretreatment, impregnation and roasting. The carrier of the catalyst is gamma-Al 2O3, and the diameter of the carrier particle is 3-4 mm. The pretreatment process parameters of the carrier are as follows: cleaning gamma-Al 2O3, soaking in sodium hydroxide solution for 4-8h, and naturally drying for later use; an excessive impregnation mode is adopted in the impregnation process of the carrier, the impregnation time is 4-12h, the active metal of the manganese nitrate in the impregnation liquid is one or more of Ru, Pt and Ni, and the impregnation process is mixed synchronous impregnation; the roasting process parameters of the carrier are as follows: roasting in a muffle furnace at 450 ℃ for 4-8 hours. The specific surface area of the catalyst is 210-260m2/g, under the coupling action of strong adsorption capacity of the catalyst and high dispersion of micro-nano bubbles, organic matters and ozone are enriched on the surface of the catalyst, organic pollutants are efficiently and rapidly mineralized, and the ozonization index is 3-5(CODmg/L) · (O3mg/L) -1. The contact time of the sewage and the catalyst in the fixed bed reactor is 10-30 min.
Example 1
Selecting gamma-Al 2O3 with the grain diameter of 3-4mm as a carrier, preparing carrier pretreatment liquid with the pH value of 10 by using a sodium hydroxide solution, soaking the carrier in the solution for 4 hours, and then airing for later use. Preparing a mixed solution of Mn (NO3)2 and RuCl2 with the weight of 1 percent, completely soaking the carrier in the mixed solution, shaking and soaking for 4 hours in a shaking table with the oscillation speed of 120rpm, draining the soaking solution after the soaking is finished, and naturally airing. And roasting the impregnated gamma-Al 2O3 carrier in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst after roasting.
and (3) passing the sewage to be treated and ozone gas through a micro-nano bubble generator to obtain the sewage enriched with nano bubbles, wherein the volume ratio of the gas to the liquid is 1: 9. The contact time of the sewage and the catalyst is 25 min.
Dye wastewater treatment and stability test:
The catalyst is filled in an ozone catalytic reaction column, the water inflow is 1m3/h, the bed layer filling rate is 50%, the catalyst is used for treating industrial printing and dyeing wastewater with the COD of 500mg/L and the chroma of 3000-plus-5000 times, and the ozone adding amount is 100 mg/L.
The experimental result shows that the chroma removal rate is more than 99 percent and the COD removal rate is close to 70 percent after the treatment.
The catalyst was subjected to a continuous stability test, and the results of COD and chromaticity removal were shown in FIG. 1. As can be seen from the experimental results shown in FIG. 1, the catalyst of the present invention still has high COD and chroma removal rates after 30-day continuous sewage treatment tests. And under the same condition, compared with the traditional ozone catalysis method, the sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles improves the COD removal rate by 20%.
Example 2
Selecting gamma-Al 2O3 with the grain diameter of 3-4mm as a carrier, preparing carrier pretreatment liquid with the pH value of 10 by using a sodium hydroxide solution, soaking the carrier in the solution for 4 hours, and then airing for later use. Preparing a mixed solution of Mn (NO3)2 and Ni (NO3)2 with the weight of 1 percent, completely soaking the carrier in the mixed solution, shaking and soaking for 4 hours in a shaking table with the oscillation speed of 120rpm, draining the soaking solution after the soaking is finished, and naturally airing. And roasting the impregnated gamma-Al 2O3 carrier in a muffle furnace at 450 ℃ for 4 hours to obtain the catalyst after roasting.
And (3) passing the sewage to be treated and ozone gas through a micro-nano bubble generator to obtain the sewage enriched with nano bubbles, wherein the volume ratio of the gas to the liquid is 1:9, and the contact time of the sewage and a catalyst is 10 min.
Municipal wastewater advanced treatment and stability test:
The catalyst is filled in an ozone catalytic reaction column, the water inflow is 0.5m3/h, the bed layer filling rate is 50%, the catalyst is used for treating municipal sewage with COD of 60mg/L and chromaticity of 100 times, and the ozone adding amount is 30 mg/L.
The experimental result shows that the chroma removal rate after treatment is 100 percent, and the COD removal rate is close to 70 percent.
the catalyst was subjected to a continuous stability test, and the results of COD and micro-pollutant removal results are shown in fig. 2. As can be seen from the experimental results shown in FIG. 2, the catalyst of the present invention still has a high water purification effect after 30-day continuous sewage treatment tests. And under the same condition, compared with the traditional ozone catalysis method, the sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles improves the COD removal rate by 15%.
The experimental results shown in fig. 3 and 4 show that the method has good effect of removing pollutants such as humus, protein and antibiotic medicines in the municipal sewage advanced treatment.
the present invention is not limited to the above-described examples, and various changes can be made without departing from the spirit and scope of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. A sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles is characterized in that ozone is fully mixed with sewage through a micro-nano bubble generating device to form an ozone saturated emulsion; carrying out oxidation reaction on the sewage in a gas-liquid highly-mixed state in a fixed bed reactor filled with a heterogeneous ozone catalyst; the method adopts the running mode of continuous ozone adding and continuous water inlet and outlet.
2. The sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles according to claim 1, wherein the preparation process of the heterogeneous ozone catalyst is divided into three stages of carrier pretreatment-impregnation-roasting, and gamma-Al 2O3 is cleaned and then soaked in a sodium hydroxide solution for 4-8 hours for pretreatment; drying, and then adopting an excessive dipping mode, wherein a dipping solution comprises manganese nitrate and at least one of soluble salts of active metals Ru, Pt and Ni, and mixing and synchronously dipping for 4-12 h; then roasting the mixture for 4 to 8 hours in a muffle furnace at 400-500 ℃.
3. The method for treating sewage by using heterogeneous ozone catalysis and micro-nano bubbles in combination as claimed in claim 2, wherein the heterogeneous ozone catalyst has carrier γ -Al2O3 particles with a diameter of 3-4mm, a specific surface area of 210 and 260m2/g, and an ozonization index of 3-5(CODmg/L) · (O3mg/L) -1.
4. The sewage treatment method combining the heterogeneous ozone catalysis and the micro-nano bubbles according to claim 3, wherein the filling rate of the heterogeneous ozone catalyst in the fixed bed reactor is 50% -75%, the filling mode is stacking filling, and the stacking density is 0.7-0.8g/m 3.
5. The heterogeneous ozone catalysis and micro-nano bubble combined sewage treatment method according to claim 4, wherein the contact time of the sewage in a gas-liquid highly-mixed state and the heterogeneous ozone catalyst is 10-30 min.
6. The sewage treatment method combining heterogeneous ozone catalysis and micro-nano bubbles according to any one of claims 1 to 5, wherein the diameter of the nano bubbles of the micro-nano bubble generation device is 90nm to 50 μm, the gas-liquid volume ratio of ozone to sewage is 1:9 to 2:9, and the water inflow is 0.018 to 5m 3/h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112777722A (en) * | 2021-01-11 | 2021-05-11 | 杭州水处理技术研究开发中心有限公司 | Method and device for efficiently catalyzing ozone for advanced sewage treatment |
| CN113060862A (en) * | 2021-03-23 | 2021-07-02 | 武汉希泰环保工程有限公司 | System and method for treating refractory industrial wastewater based on heterogeneous catalytic oxidation process |
| CN113087112A (en) * | 2019-12-23 | 2021-07-09 | 南京延长反应技术研究院有限公司 | System and method for treating industrial alkaline residue wastewater |
| CN117383767A (en) * | 2023-12-08 | 2024-01-12 | 中国科学院大学 | Method for deeply purifying total organic carbon in high-salinity water |
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Application publication date: 20191206 |