CN106186480A - The technique of a kind of compound advanced catalytic oxidation and device - Google Patents
The technique of a kind of compound advanced catalytic oxidation and device Download PDFInfo
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- CN106186480A CN106186480A CN201610802740.6A CN201610802740A CN106186480A CN 106186480 A CN106186480 A CN 106186480A CN 201610802740 A CN201610802740 A CN 201610802740A CN 106186480 A CN106186480 A CN 106186480A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 120
- 230000003647 oxidation Effects 0.000 title claims abstract description 116
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000003814 drug Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 62
- 238000005189 flocculation Methods 0.000 claims description 51
- 230000016615 flocculation Effects 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 19
- 238000005273 aeration Methods 0.000 claims description 19
- 239000002905 metal composite material Substances 0.000 claims description 18
- 239000010802 sludge Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000001117 sulphuric acid Substances 0.000 claims description 13
- 235000011149 sulphuric acid Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940079593 drug Drugs 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 150000002927 oxygen compounds Chemical class 0.000 claims description 3
- 229950000845 politef Drugs 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000701 coagulant Substances 0.000 claims description 2
- 230000010354 integration Effects 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000002335 preservative effect Effects 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 210000005056 cell body Anatomy 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000005260 corrosion Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 claims 1
- 239000000945 filler Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 8
- 231100000719 pollutant Toxicity 0.000 abstract description 8
- -1 hydroxyl radical free radical Chemical class 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010921 garden waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses technique and the device of a kind of compound advanced catalytic oxidation, belong to advanced treatment of wastewater field, the technique of the described compound advanced catalytic oxidation of the present invention and device, combine Fenton, photocatalysis oxidation technique and metal catalytic oxidation technology, under the catalytic condition of metal and light, add the speed that strong production has the hydroxyl radical free radical of Strong oxdiative ability, after hydroxyl radical free radical is formed, by between pollutant occur hydroxyl add and, replace, the chemical reactions such as electron transfer, major part organic compound mineralising or decomposition can be made, a part of mineralising precipitates, macromolecular compound is degraded into low toxicity or nontoxic small-molecule substance by a part, have is the most directly degraded to water and carbon dioxide, thus reach to process the effect of waste water.The present invention is oxidized to basis with catalysis, optimizes catalyst and dosing adds, and uses different classes of catalyst within different times of contact, medicine consumption is greatly decreased, effectively reduces comprehensive energy consumption, be removed hardly degraded organic substance in waste water targetedly.Because using multiple catalysts, efficiency is more than 2 times of common ozone or other strong oxidizers, therefore greatly reduces operating cost.
Description
Technical field
The invention discloses technique and the device of a kind of compound advanced catalytic oxidation, belong to advanced treatment of wastewater field.
Background technology
Along with rapid development of economy and the acceleration of urbanization process, China's Water Basin Water Pollution is on the rise.Whole nation emphasis
The pollutant in basin pollute and widespread pollution from the overuse of fertilizers and pesticides in rural area essentially from industrial pollution, urban life.The industrial wastewater water of different industries
The matter water yield changes greatly, pollutant levels are high, nutrient substance is uneven, and water-quality constituents is extremely complex.Therefore outstanding for industrial park
For it is comprehensive industrial park, waste water quality is considerably complicated, and domestic industrial park is in order to save sewage disposal expense,
The centralized waste water tupe of many employings processes garden waste water, and mostly is biochemical process, thus causes bio-chemical effluent to be difficult to reach
Mark, especially Organic substance and the colourity to bio-refractory, it has also become the environment difficulties that Industrial Wastewater Treatment is urgently to be resolved hurrily.Therefore need
The biochemical tailrace advanced process in Yao Dui industrial park, the most effectively removes the pollutant various of different nature being difficult to degrade,
This key issue that industrial park faces can be solved, thus reduce water environment or even the impact of ecology.
At present, most domestic industrial park Sewage Plant uses secondary biochemical treatment technique, rear termination flocculation process only will
COD is reduced to about 100, far above " urban wastewater treatment firm pollutant emission standard " (GB18918-of current municipal execution
2002) one-level emission standard A, and in water outlet COD, major part belongs to the not biodegradable Organic substance of dissolubility, biological method
Can not continue the hardly degraded organic substance in biochemical tail water of degrading, advanced oxidation processes has high efficiency, ease for operation, non-selectivity
Etc. feature, being widely used in the process of organic wastewater with difficult degradation thereby, high-level oxidation technology fundamentally changes difficult degradation to be had
The molecular structure of machine thing so that it is a middle part is direct oxidation into the little molecular inorganics such as water and carbon dioxide, another part quilt
Mineralising forms precipitation.
Be currently used for advanced oxidation processes mainly has ozone, Fenton, hydrogen peroxide, electrochemical oxidation, ultrasonic, microwave, ultraviolet
Light etc., but there is many deficiencies in existing high-level oxidation technology:
1), ozone
According to domestic and international present Research, high-level oxidation technology based on ozone has become improvement bio-refractory organic toxic
The Main Means of pollutant, and be applied in various sewage treatment process.Its feature is to produce hydroxyl free by reaction
Base (OH), this free radical has extremely strong oxidisability, it is possible to effectively decomposed by organic pollution.But the most do not solve
High-level oxidation technology realize large-scale Industry Promotion application difficult point, problem still exists, major embodiment in the following areas: (1)
Using single ozone oxidation agent, oxidability is not enough；(2) ozone is long with the time of contact of sewage, and floor space is big；(3) ozone
Aeration mode is it cannot be guaranteed that being sufficiently mixed of ozone and water, and utilization rate is low.
2), Fenton reagent
Fenton oxidation application in Industrial Wastewater Treatment at present is relatively broad.But Fenton method chemical feeding quantity is big, hydrogen peroxide is unstable
Fixed degradable, produce sludge quantity big, add Financial cost, which has limited Fenton method expands application further.
3), electrochemical oxidation process
It is high that the method has capacity usage ratio, also can carry out under low temperature, and equipment is relatively easy, it is easy to automatically control, dirty without secondary
The features such as dye, but this technology energy consumption is higher, is not easily formed large-scale industrialized development.
4), photocatalytic oxidation
Photocatalytic oxidation is because the problem such as efficiency of the light transmission of sewage, catalysis uses less in industrial wastewater.
5), ultrasonic radiation edman degradation Edman
At present, the research of ultrasonic radiation degraded water pollutant is still in the experimental exploration stage.
Summarizing above further treatment technique, biological method can not continue the hardly degraded organic substance in biochemical tail water of degrading；
Only high-level oxidation technology could fundamentally change the molecular structure of hardly degraded organic substance so that it is a middle part is by direct oxidation
The little molecular inorganics such as Cheng Shui and carbon dioxide, another part mineralising forms precipitation and is removed.High-level oxidation technology is at present
Become the first-selection that hardly degraded organic substance processes, and in high-level oxidation technology, owing to oxidizer containing chlorine is easily formed carcinogen, double
Oxygen water unstable easily decomposes, and Fenton reagent is easily generated a large amount of mud, electrochemical method energy consumption is higher, ultrasonic radiation is the most immature
Technological deficiency, high-level oxidation technology based on catalysis is increasingly favored by people.
Summary of the invention
The purpose of the present invention: the cost being to overcome existing advanced oxidation processes is high, oxidation effectiveness is poor, clearance is low etc. no
Foot, it is an object of the invention to provide that a kind of system stability is good, efficiency is high, investment and operating cost is low, sludge output is little answers
Mould assembly advanced catalytic oxidation advanced treatment process and device, contain bio-refractory organic enterprise tail for low-cost processes
Water.
In order to solve above-mentioned technical problem, the compound advanced catalytic oxidation technique of the present invention and device are organic to difficult degradation
Thing plays and aoxidizes and flocculation two aspect effects, oxidation aspect, in acid aqueous solution, and the catalysis hydrogen peroxide of iron ion so that it is
Decomposite the hydroxyl radical free radical with Strong oxdiative ability efficiently；Micro-wave nonpolar lamp-ultraviolet light lamp box and Fenton are to difficult in water body
The deep oxidation of degradation of organic substances has higher synergism；Metal-oxide can directly affect mechanism of catalytic reaction and effect
Rate, the oh group on common metal oxide surface is the active sites of catalytic reaction, and it is by discharging proton and hydroxyl in water
Base, occur ion-exchange reactions and from water adsorpting anion and cation, formed metal-oxide catalytic center.Above-mentioned not
With all producing the hydroxyl radical free radical that chemism is extremely strong in catalytic reaction process, the organic substance in oxidation water body, by pollutant
Decompose or mineralising.Flocculation aspect, in catalytic oxidation process, the ferric hydroxide colloid that iron ion produces has flocculation net and catches, builds bridge
And adsorption function, strengthen catalytic oxidation to a certain extent to organic removal and decolorization.
The technique of a kind of compound advanced catalytic oxidation of the present invention and device, including water inlet pipe (1), intake pump (2), reaction
Pond group (3), mixed reaction pond 1 (3-1), catalysis oxidation pond 1 (3-2), catalysis oxidation pond 2 (3-3), mixed reaction pond 2 (3-4),
Flocculation sedimentation tank (3-5), sludge pump (4), discharge pipeline (5), agitator (6), metal composite oxide filled column (7), microwave without
Pole lamp-ultraviolet lamp box (8), boring aeration pipe (9), inclined plate packing (10), adding of agent system (11), hydrogen peroxide dosing system
(11-1), ferrous adding of agent system (11-2), sulphuric acid dosing system (11-3), sodium hydroxide dosing system (11-4), flocculation
Agent dosing system (11-5), flocculation aid dosing system (11-6), outlet pipe (12).
For achieving the above object, the present invention adopts the following technical scheme that, specifically includes following steps:
1), secondary biochemical treatment technique tail water is collected to mixed reaction pond 1 (3-1) by intake pump (2)；
2), in mixed reaction pond 1 (3-1), by hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-2),
Sulphuric acid dosing system (11-1) adds the hydrogen peroxide of concentration known, ferrous iron and stream acid, by agitator (6) stirring mixing, makes
Tail water is sufficiently mixed with medicament, and adjustment pH value is to 5.5-6.5, and mixed liquor is in the catalysis at micro-wave nonpolar lamp-ultraviolet light lamp box (8)
Under carry out preliminary catalytic oxidation reaction；
3), mixed liquor enters catalysis oxidation pond 1 (3-2) through metal composite oxide filled column (7), at catalysis oxidation pond 1 (3-
2) first catalytic oxidation is carried out through metal composite oxide filled column (7), subsequently at micro-wave nonpolar lamp-ultraviolet light lamp box in
(8) carry out catalytic oxidation under catalysis, through above-mentioned two steps, complete the catalytic oxidation of 60-80%；
4), mixed liquor through catalysis oxidation pond 1 (3-2) enter catalysis oxidation pond 2 (3-3), the most first flow through composition metal oxygen
Compound filled column (7), then carries out catalytic oxidation under the catalysis of micro-wave nonpolar lamp-ultraviolet light lamp box (8), repeats catalysis
Catalytic oxidation in oxidation pond 1 (3-2), completes the catalytic oxidation of 20-30% in catalysis oxidation pond 2 (3-3)；
5), the mixed liquor after catalysis oxidation enters mixed reaction pond 2 (3-4), then with sodium hydroxide dosing system (11-
1) add sodium hydroxide to mix, until mixed liquor pH value is to 7-7.5, lays boring aeration pipe (9) bottom reaction tank, pass through
Aeration is stirred mixing to mixed liquor, and the end at reaction tank passes through flocculant concentration system (11-1), and flocculation aid adds and is
System (11-1) adds flocculant and flocculation aid, makes mixed liquor fully react with flocculant, flocculation aid, additionally, due to influent quality ripple
Dynamic reason, when organic concentration is on the low side, aeration can make unnecessary hydrogen peroxide and oxygen reaction, thus decomposes dioxygen in water outlet
Water, it is ensured that water outlet will not be affected by unreacted hydrogen peroxide completely；
6), mixed liquor and flocculant, flocculation aid enter flocculation sedimentation tank (3-5) after fully reacting and carry out flocculation sediment, flocculation is heavy
Pond, shallow lake (3-5) top is provided with inclined plate packing (10), and bottom is provided with sludge bucket and sludge pump (4), strengthens solid-liquid separation, supernatant with this
Liquid enters outlet pipe (12) through effluent trough;
7), water outlet can directly be discharged, it is also possible to reuse after conventional filter element processes again.
Mixed reaction pond 1 (3-1), catalysis oxidation pond 1 (3-2), catalysis oxidation pond 2 (3-in wherein said reaction tank group (3)
3), mixed reaction pond 2 (3-4) and flocculation sedimentation tank (3-5) are linked in sequence, when wherein mixed reaction pond 1 (3-1) stops successively
Between be 30-45min, catalysis oxidation pond 1 (3-2) hydraulic detention time be 45min, be catalyzed oxidation pond 2 (3-3) hydraulic detention time
For 20-30min, mixed reaction pond 2 (3-4) hydraulic detention time is 30min, wherein adds flocculant and coagulant region waterpower
The time of staying is not less than 15min, and flocculation sedimentation tank (3-5) surface loading is less than 3m/h.
Wherein said reaction tank group (3) main body can use glass steel material and carry out preservative treatment, agitator (6) and microwave
Non-polarized lamp-ultraviolet lamp box (8) all uses glass steel material, and in its mixed reaction pond 1 (3-1), agitator (6) is moderate-speed mixer, urges
Changing oxidation pond 1 (3-2) and catalysis oxidation pond 2 (3-3) is low rate mixing, micro-wave nonpolar lamp-ultraviolet lamp box (8) is arranged on liquid level
Upper 10 centimeters, metal composite oxide filled column (7) unsettled fixed installation, post upper end is less than liquid level 10 centimetres, hybrid reaction
Installing boring aeration pipe (9) in pond 2 (3-4), material is politef, and perforated pipe aerating regulation bore dia is 3mm, flocculation sedimentation tank
(3-5) top arranges swash plate, and bottom arranges sludge bucket, facilitates sludge pump (4) periodically spoil disposal, and package unit can be made as integration
Equipment, by the water inlet of automatic control control realization, dosing, mix, be catalyzed oxidation and flocculation sediment.
Press in the pond groups such as wherein said mixed reaction pond 1 (3-1), catalysis oxidation pond 1 (3-2), catalysis oxidation pond 2 (3-3)
Micro-wave nonpolar lamp-ultraviolet lamp box (8) and metal composite oxide filled column (7), metal composite oxide is laid according to volume fraction
Filled column (7) interior metal-oxide has manganese dioxide, aluminium sesquioxide, manganese dioxide and titanium dioxide.
Wherein said adding of agent system (11) includes hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-
2), sulphuric acid dosing system (11-3), sodium hydroxide dosing system (11-4), flocculant concentration system (11-5) and flocculation aid are thrown
Adding system (11-6), every kind of adding of agent system is independent of one another, and all by dosing pump, drug feeding pipeline, pump early gate and pump after
Valve forms.
The distinguishing feature of the present invention:
1), the present invention has catalysis oxidation efficiency height, flocculation oxidation dual function, operation stability height, investment cost fall low, difficult
Solve the features such as organic removal rate is high, comprehensive energy consumption is low.
2), the present invention COD and colourity can effectively be removed, water outlet COD and colourity can stably reach " urban wastewater treatment firm
Pollutant emission standard " one-level emission standard A in (GB18918-2002).
3), the present invention uses multiple catalysts, organic matter removal efficiency to be the twices of common ozone or other strong oxidizers
Above, operating cost is therefore greatly reduced.
4), technological process scientific and reasonable, the suitability is extensive, and compact equipment installation, technique front end can coordinate kinds of processes
It is used in combination.
Accompanying drawing illustrates:
In Fig. 1, each assembly is: (1) water inlet pipe, (2) intake pump, (3) reaction tank group, (3-1) mixed reaction pond 1, and (3-2) is catalyzed
Oxidation pond 1, (3-3) is catalyzed oxidation pond 2, (3-4) mixed reaction pond 2, (3-5) flocculation sedimentation tank, (4) sludge pump, (5) spoil disposal
Pipe, (6) agitator, (7) metal composite oxide filled column, (8) micro-wave nonpolar lamp-ultraviolet lamp box, (9) boring aeration pipe,
(10) inclined plate packing, (11) adding of agent system, (11-1) hydrogen peroxide dosing system, (11-2) ferrous adding of agent system,
(11-3) sulphuric acid dosing system, (11-4) sodium hydroxide dosing system, (11-5) flocculant concentration system, (11-6) flocculation aid is thrown
Adding system, (12) outlet pipe.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is discussed in detail further, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
1), secondary biochemical treatment technique tail water is collected to mixed reaction pond 1 (3-1) by intake pump (2)；
2), in mixed reaction pond 1 (3-1), by hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-2),
Sulphuric acid dosing system (11-1) adds the hydrogen peroxide of concentration known, ferrous iron and stream acid, by agitator (6) stirring mixing, makes
Tail water is sufficiently mixed with medicament, and adjustment pH value is to 5.5-6.5, and mixed liquor is in the catalysis at micro-wave nonpolar lamp-ultraviolet light lamp box (8)
Under carry out preliminary catalytic oxidation reaction；
3), mixed liquor enters catalysis oxidation pond 1 (3-2) through metal composite oxide filled column (7), at catalysis oxidation pond 1 (3-
2) first catalytic oxidation is carried out through metal composite oxide filled column (7), subsequently at micro-wave nonpolar lamp-ultraviolet light lamp box in
(8) carry out catalytic oxidation under catalysis, through above-mentioned two steps, complete the catalytic oxidation of 60-80%；
4), mixed liquor through catalysis oxidation pond 1 (3-2) enter catalysis oxidation pond 2 (3-3), the most first flow through composition metal oxygen
Compound filled column (7), then carries out catalytic oxidation under the catalysis of micro-wave nonpolar lamp-ultraviolet light lamp box (8), repeats catalysis
Catalytic oxidation in oxidation pond 1 (3-2), completes the catalytic oxidation of 20-30% in catalysis oxidation pond 2 (3-3)；
5), the mixed liquor after catalysis oxidation enters mixed reaction pond 2 (3-4), then with sodium hydroxide dosing system (11-
1) add sodium hydroxide to mix, until mixed liquor pH value is to 7-7.5, lays boring aeration pipe (9) bottom reaction tank, pass through
Aeration is stirred mixing to mixed liquor, and the end at reaction tank passes through flocculant concentration system (11-1), and flocculation aid adds and is
System (11-1) adds flocculant and flocculation aid, makes mixed liquor fully react with flocculant, flocculation aid, additionally, due to influent quality ripple
Dynamic reason, when organic concentration is on the low side, aeration can make unnecessary hydrogen peroxide and oxygen reaction, thus decomposes dioxygen in water outlet
Water, it is ensured that water outlet will not be affected by unreacted hydrogen peroxide completely；
6), mixed liquor and flocculant, flocculation aid enter flocculation sedimentation tank (3-5) after fully reacting and carry out flocculation sediment, flocculation is heavy
Pond, shallow lake (3-5) top is provided with inclined plate packing (10), and bottom is provided with sludge bucket and sludge pump (4), strengthens solid-liquid separation, supernatant with this
Liquid enters outlet pipe (12) through effluent trough;
7), water outlet can directly be discharged, it is also possible to reuse after conventional filter element processes again.
Embodiment 2
1), secondary biochemical treatment technique tail water is collected to mixed reaction pond 1 (3-1) by intake pump (2)；
2), in mixed reaction pond 1 (3-1), by hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-2),
Sulphuric acid dosing system (11-1) adds the hydrogen peroxide of concentration known, ferrous iron and stream acid, by agitator (6) stirring mixing, makes
Tail water is sufficiently mixed with medicament, and adjustment pH value is to 5.5-6.5, and mixed liquor is in the catalysis at micro-wave nonpolar lamp-ultraviolet light lamp box (8)
Under carry out preliminary catalytic oxidation reaction；
3), mixed liquor enters catalysis oxidation pond 1 (3-2) through metal composite oxide filled column (7), at catalysis oxidation pond 1 (3-
2) first catalytic oxidation is carried out through metal composite oxide filled column (7), subsequently at micro-wave nonpolar lamp-ultraviolet light lamp box in
(8) carry out catalytic oxidation under catalysis, through above-mentioned two steps, complete the catalytic oxidation of 80-90%；
4), mixed liquor through catalysis oxidation pond 1 (3-2) enter catalysis oxidation pond 2 (3-3), because of Organic substance realized expect clearance,
So metal composite oxide filled column (7) and micro-wave nonpolar lamp-ultraviolet light lamp box (8) are all not turned on, mixed liquor is at catalysis oxygen
Change pond 2 (3-3) and do not carrying out catalytic oxidation, be directly entered next and process pond group;
5), enter mixed reaction pond 2 (3-4) through the mixed liquor of catalysis oxidation pond 2 (3-3), then add with sodium hydroxide and be
System (11-1) adds sodium hydroxide and mixes, until mixed liquor pH value is to 7-7.5, lays boring aeration pipe bottom reaction tank
(9), by aeration, mixed liquor being stirred mixing, the end at reaction tank passes through flocculant concentration system (11-1), helps solidifying
Agent dosing system (11-1) adds flocculant and flocculation aid, makes mixed liquor fully react with flocculant, flocculation aid, additionally, due to entering
The reason of water variation water quality, when organic concentration is on the low side, aeration can make unnecessary hydrogen peroxide and oxygen reaction, thus decomposites
Hydrogen peroxide in water, it is ensured that water outlet will not be affected by unreacted hydrogen peroxide completely；
6), mixed liquor and flocculant, flocculation aid enter flocculation sedimentation tank (3-5) after fully reacting and carry out flocculation sediment, flocculation is heavy
Pond, shallow lake (3-5) top is provided with inclined plate packing (10), and bottom is provided with sludge bucket and sludge pump (4), strengthens solid-liquid separation, supernatant with this
Liquid enters outlet pipe (12) through effluent trough；
7), water outlet can directly be discharged, it is also possible to reuse after conventional filter element processes again.
Dotted lines shown in Fig. 1 is the pipeline of adding of agent system, including hydrogen peroxide dosing system (11-1), ferrous medicament
Dosing system (11-2), sulphuric acid dosing system (11-3), sodium hydroxide dosing system (11-4), flocculant concentration system (11-5)
And flocculation aid dosing system (11-6), every kind of adding of agent system is independent of one another, and all by dosing pump, drug feeding pipeline, pump before
Valve and pump late gate composition.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and modification, these improve and modification
Also should be regarded as protection scope of the present invention.
Claims (10)
1. the technique of compound advanced catalytic oxidation and a device, including water inlet pipe (1), intake pump (2), reaction tank group (3),
Mixed reaction pond 1 (3-1), catalysis oxidation pond 1 (3-2), catalysis oxidation pond 2 (3-3), mixed reaction pond 2 (3-4), flocculation sediment
Pond (3-5), sludge pump (4), discharge pipeline (5), agitator (6), metal composite oxide filled column (7), micro-wave nonpolar lamp-ultraviolet
Lamp box (8), boring aeration pipe (9), inclined plate packing (10), adding of agent system (11), hydrogen peroxide dosing system (11-1), ferrous
Adding of agent system (11-2), sulphuric acid dosing system (11-3), sodium hydroxide dosing system (11-4), flocculant concentration system
(11-5), flocculation aid dosing system (11-6), outlet pipe (12), it is characterised in that comprise the steps:
1), secondary biochemical treatment technique tail water is collected to mixed reaction pond 1 (3-1) by intake pump (2)；
2), in mixed reaction pond 1 (3-1), by hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-2),
Sulphuric acid dosing system (11-1) adds the hydrogen peroxide of concentration known, ferrous iron and stream acid, by agitator (6) stirring mixing, makes
Tail water is sufficiently mixed with medicament, and adjustment pH value is to 5.5-6.5, and mixed liquor is in the catalysis at micro-wave nonpolar lamp-ultraviolet light lamp box (8)
Under carry out preliminary catalytic oxidation reaction；
3), mixed liquor enters catalysis oxidation pond 1 (3-2) through metal composite oxide filled column (7), at catalysis oxidation pond 1 (3-
2) first catalytic oxidation is carried out through metal composite oxide filled column (7), subsequently at micro-wave nonpolar lamp-ultraviolet light lamp box in
(8) carry out catalytic oxidation under catalysis, through above-mentioned two steps, complete the catalytic oxidation of 60-80%；
4), mixed liquor through catalysis oxidation pond 1 (3-2) enter catalysis oxidation pond 2 (3-3), the most first flow through composition metal oxygen
Compound filled column (7), then carries out catalytic oxidation under the catalysis of micro-wave nonpolar lamp-ultraviolet light lamp box (8), repeats catalysis
Catalytic oxidation in oxidation pond 1 (3-2), completes the catalytic oxidation of 20-30% in catalysis oxidation pond 2 (3-3)；
5), the mixed liquor after catalysis oxidation enters mixed reaction pond 2 (3-4), then with sodium hydroxide dosing system (11-
1) add sodium hydroxide to mix, until mixed liquor pH value is to 7-7.5, lays boring aeration pipe (9) bottom reaction tank, pass through
Aeration is stirred mixing to mixed liquor, and the end at reaction tank passes through flocculant concentration system (11-1), and flocculation aid adds and is
System (11-1) adds flocculant and flocculation aid, makes mixed liquor fully react with flocculant, flocculation aid, additionally, due to influent quality ripple
Dynamic reason, when organic concentration is on the low side, aeration can make unnecessary hydrogen peroxide and oxygen reaction, thus decomposes dioxygen in water outlet
Water, it is ensured that water outlet will not be affected by unreacted hydrogen peroxide completely；
6), mixed liquor and flocculant, flocculation aid enter flocculation sedimentation tank (3-5) after fully reacting and carry out flocculation sediment, flocculation is heavy
Pond, shallow lake (3-5) top is provided with inclined plate packing (10), and bottom is provided with sludge bucket and sludge pump (4), strengthens solid-liquid separation, supernatant with this
Liquid enters outlet pipe (12) through effluent trough；
7), water outlet can directly be discharged, it is also possible to reuse after conventional filter element processes again.
The technique of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: reaction tank group (3)
Middle mixed reaction pond 1 (3-1), catalysis oxidation pond 1 (3-2), catalysis oxidation pond 2 (3-3), mixed reaction pond 2 (3-4) and flocculation
Sedimentation tank (3-5) is linked in sequence successively, and wherein mixed reaction pond 1 (3-1) time of staying is 30-45min, is catalyzed oxidation pond 1 (3-
2) hydraulic detention time is 45min, and catalysis oxidation pond 2 (3-3) hydraulic detention time is 20-30min, mixed reaction pond 2 (3-4)
Hydraulic detention time is 30min, wherein adds flocculant and coagulant region hydraulic detention time and sinks not less than 15min, flocculation
Pond, shallow lake (3-5) surface loading is less than 3m/h.
The device of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: reaction tank group (3)
Main body can use glass steel material and carry out preservative treatment, and agitator (6) and micro-wave nonpolar lamp-ultraviolet lamp box (8) all use glass
Glass steel matter, in its mixed reaction pond 1 (3-1), agitator (6) is moderate-speed mixer, catalysis oxidation pond 1 (3-2) and catalysis oxidation pond
2 (3-3) are low rate mixing, and micro-wave nonpolar lamp-ultraviolet lamp box (8) is arranged on 10 centimeters on liquid level, and metal composite oxide is filled out
Stock column (7) unsettled fixed installation, post upper end is less than in liquid level 10 centimetres, mixed reaction pond 2 (3-4) installs boring aeration pipe (9),
Flocculation sedimentation tank (3-5) top arranges swash plate, and bottom arranges sludge bucket, facilitates sludge pump (4) periodically spoil disposal, and package unit can be made
As integration apparatus, by the water inlet of automatic control control realization, dosing, mix, be catalyzed oxidation and flocculation sediment.
The device of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: mixed reaction pond 1
(3-1), micro-wave nonpolar lamp-purple is laid according to volume fraction in the pond group such as catalysis oxidation pond 1 (3-2), catalysis oxidation pond 2 (3-3)
Outer lamp box (8).
The device of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: catalysis oxidation pond 1
(3-2) and in being catalyzed the pond groups such as oxidation pond 2 (3-3), metal composite oxide filled column (7), metal composite oxide filler are installed
Post (7) interior metal-oxide has manganese dioxide, aluminium sesquioxide, manganese dioxide and titanium dioxide.
The device of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: adding of agent system
(11) hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-2), sulphuric acid dosing system (11-3), hydroxide are included
Sodium dosing system (11-4), flocculant concentration system (11-5) and flocculation aid dosing system (11-6), every kind of adding of agent system
System independently of one another, and is all made up of dosing pump, drug feeding pipeline, pump early gate and pump late gate, dosing pump, drug feeding pipeline, pump
Early gate and the equal acid-fast alkali-proof of pump late gate are corrosion-resistant, all use politef material.
The device of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: mixed reaction pond 2
(3-4) installing boring aeration pipe (9) in, material is politef, and perforated pipe aerating regulation bore dia is 3mm.
The technique of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: 6 kinds of adding of agents
Order is followed successively by ferrous medicament, sulphuric acid, hydrogen peroxide, sodium hydroxide, flocculant and flocculation aid.
The technique of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: at mixed reaction pond
In 1 (3-1), adding the hydrogen peroxide of concentration known, ferrous iron and stream acid, the toss area of 3 kinds of medicaments respectively sulphuric acid adds and
Hose nozzle, ferrous adding of agent is in cell body middle part, and hydrogen peroxide adds at cell body top nearly micro-wave nonpolar lamp-ultraviolet lamp box
(8) place.
The technique of a kind of compound advanced catalytic oxidation the most according to claim 1, it is characterised in that: in hybrid reaction
In pond 1 (3-1), by hydrogen peroxide dosing system (11-1), ferrous adding of agent system (11-2), sulphuric acid dosing system (11-1)
Adding the hydrogen peroxide of concentration known, ferrous iron and stream acid, in controlling pond, pH value enters mixed reaction pond 2 to 5.5-6.5, mixed liquor
(3-4), after, sodium hydroxide, control ph to 7-7.5 are added by sodium hydroxide dosing system (11-1).
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