CN103373756A - Siphon catalyst and wastewater catalytic oxidization treatment method thereof - Google Patents
Siphon catalyst and wastewater catalytic oxidization treatment method thereof Download PDFInfo
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- CN103373756A CN103373756A CN2013102884375A CN201310288437A CN103373756A CN 103373756 A CN103373756 A CN 103373756A CN 2013102884375 A CN2013102884375 A CN 2013102884375A CN 201310288437 A CN201310288437 A CN 201310288437A CN 103373756 A CN103373756 A CN 103373756A
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- catalyst
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- film pipe
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Abstract
The invention discloses a siphon catalyst and a wastewater catalytic oxidization treatment method thereof. The wastewater catalytic oxidization treatment method comprises the following steps of: enabling wastewater to enter and exit through the catalyst; adding an oxidant to the outside of the catalyst, and meanwhile, introducing compressed air to stir; enabling the oxidant to generate hydroxyl free radical chain reaction under the action of the catalyst at normal temperature and normal pressure, and enabling the compressed air as an auxiliary oxidant to simultaneously participate in the catalytic oxidization chain reaction; and oxidizing pollutants in the wastewater through multiphase catalytic oxidization reaction, wherein a siphon is used as a catalyst carrier, the active ingredient of the catalyst is selected from one or more of rare metal, precious metal and transition metal oxide, and catalyst back flushing is selected from one or more of water flushing and air flushing. The siphon catalyst and the wastewater catalytic oxidization treatment method thereof have the advantages of large special surface area of the catalyst carrier, high gas, liquid and solid multiphase reaction speed, high mass transfer efficiency, sufficient reaction, low oxidant consumption, capability of introducing cheap oxygen as the oxidant to participate in the chain reaction, mild reaction condition and low operation cost.
Description
Technical field
The present invention relates to the waste water advanced oxidization process field, be specifically related to a kind of film pipe catalyzer and waste water treatment by catalytic oxidation thereof.
Background technology
Along with the increasingly stringent of the increasing and pollutant emission standard of the difficult degradation of waste water mesophytization, toxic pollutant, need a kind of effective pre-treatment and deep treatment method badly.
Advanced oxidation processes is take hydroxyl radical free radical as main oxygenant and organism reacts, the organic free radical that generates in the reaction can continue to participate in the chain reaction of HO, by after generating the organic peroxy free radical, further oxidative decomposition occurs until be degraded to final product CO perhaps
2And H
2O, thus reach the organic purpose of oxygenolysis.Advanced oxidation processes has following characteristics: produce a large amount of very active its oxidation capacities of Hydroxyl radical HO (2.80V) and be only second to fluorine (2.87V), it is as the intermediate product of reaction, can bring out the chain reaction of back, hydroxyl radical free radical differs very little from the reaction rate constant of different organic substances, when having multiple pollutant in the water, a kind of material can not occur and be degraded and the substantially constant situation of another kind of material; HO can't be selectively directly and the pollutant reaction in the waste water it is degraded to carbonic acid gas, water and harmless object, can not produce secondary pollution; The general chemistry oxidation style is because oxidation capacity is poor, react the reason such as selective, often can not directly reach and remove the purpose that organism reduces TOC and COD fully, and there is not this problem substantially in the advanced oxidation rule, intermediate product in the oxidising process all can continue same hydroxyl radical reaction, until be oxidized at last carbonic acid gas and water fully, thereby reached the thorough purpose of removing TOC, COD; Because it is a kind of physical and chemical process, be easy to be controlled, process needs to satisfy, even can reduce by 10
-9The pollutent of level; Compare with common chemical oxidization method, the speed of response of advanced oxidation processes is very fast, and general reaction rate constant is greater than 10
9Mol
-1Ls
-1, can within very short time, reach processing requirements; Both can be used as individual curing, can be complementary with other treating processess again, such as the pre-treatment as biochemical treatment, can reduce processing cost.
But also there is certain limitation in the advanced oxidation processes of having used: many such as the oxygenant consumption, running cost is high; Severe reaction conditions; Catalyzer lacks good carrier, poor activity, easily loss, inactivation, obstruction etc.; Limited its application.If can find a kind of oxygenant consumption few, reaction conditions is gentle, and catalyst performance is good, and the catalysed oxidation processes that running cost is low has important practical significance.
Summary of the invention
The object of the invention is to solve the problem that prior art exists, a kind of film pipe catalyzer and waste water treatment by catalytic oxidation thereof are provided.
Film pipe catalyzer is by film pipe catalytic unit composing plate frame, spiral, bridge-type, straight pipe type film pipe catalyzer, film pipe catalytic unit comprises support of the catalyst, catalyst layer, membrane channel, support of the catalyst is provided with catalyst layer outward, is provided with membrane channel in the support of the catalyst.
The material of described support of the catalyst is one or more in fiber-like, synthetic resin or the ceramic-like
Described membrane channel diameter is 0.05～100um.
Adopt the waste water treatment by catalytic oxidation of film pipe catalyzer to be:
In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward, the outside oxygenant that drops into of film pipe catalyzer passes into the pressurized air stirring simultaneously, under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the catalyst layer effect of film pipe catalyzer, pressurized air participates in the catalyzed oxidation chain reaction simultaneously as secondary oxidizer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water, water outlet is discharged through membrane channel after processing; Adopt the film pipe as support of the catalyst, the activeconstituents of catalyst cupport is one or more of rare metal, precious metal and transition metal oxide, and one or more in water flushing or the air scour are adopted in the catalyzer recoil.
Described catalyst cupport adopts one or more in the precipitator method, pickling process, hybrid system or the ion exchange method, and active component content is 1%～15%.
Described oxygenant is hydrogen peroxide, dioxide peroxide, ozone, ultraviolet or ultrasonic one or more.
The beneficial effect that the present invention compared with prior art has:
1, film pipe catalyst performance is good.Adopt the film pipe as the carrier of catalyzer, specific surface area is large, and mass-transfer efficiency is high; The catalyst activity composition is one or more of rare metal, precious metal and transition metal oxide, reduces reaction potential energy; Speed of reaction is fast, sufficient reacting, and the oxygenant consumption is few.
2, reaction efficiency is high, and the oxygenant consumption is low.Go out to lead to the filmed passing tube catalyzer outward in waste water advances, evenly and without short flow; Air not only participated in the catalyzed oxidation chain reaction but also worked the effect of mixing as oxygenant; Under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the effect of catalyzer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water; Gas, liquid, solid heterogeneous reaction speed is fast, can introduce cheap oxygen and participate in chain reaction as oxygenant.
3, can not stop up.One or more of water flushing, air scour are adopted in the catalyzer back flushing; Waste water contains impurity and stops up fenestra by during the film, makes fluid pass through the fenestra difficulty, when the impurity of catalyst surface is too much, can open gas, water back-purge system, washes away removal impurity in the other direction by gas, water, can effectively prevent the obstruction of catalyzer.
Support of the catalyst specific surface area of the present invention is large, and gas, liquid, solid heterogeneous reaction speed is fast, and mass-transfer efficiency is high, sufficient reacting, and the oxygenant consumption is few, can introduce cheap oxygen and participate in chain reaction as oxygenant, and reaction conditions is gentle, and running cost is low, can not stop up.
Description of drawings
Fig. 1 is the structural representation of film pipe catalytic unit;
Among the figure, support of the catalyst 1, catalyst layer 2, membrane channel 3.
Embodiment
As shown in Figure 1, film pipe catalyzer is by film pipe catalytic unit composing plate frame, spiral, bridge-type, straight pipe type film pipe catalyzer, film pipe catalytic unit comprises support of the catalyst 1, catalyst layer 2, membrane channel 3, be provided with catalyst layer 2 outside the support of the catalyst 1, be provided with membrane channel 3 in the support of the catalyst 1.
The material of described support of the catalyst 1 is one or more in fiber-like, synthetic resin or the ceramic-like.Described membrane channel 3 diameters are 0.05～100um.
Adopt the waste water treatment by catalytic oxidation of film pipe catalyzer to be:
In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward, the outside oxygenant that drops into of film pipe catalyzer passes into the pressurized air stirring simultaneously, under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under catalyst layer 2 effects of film pipe catalyzer, pressurized air participates in the catalyzed oxidation chain reaction simultaneously as secondary oxidizer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water, water outlet is discharged through membrane channel 3 after processing; Adopt the film pipe as support of the catalyst 1, the activeconstituents of catalyst cupport is one or more of rare metal, precious metal and transition metal oxide, and one or more in water flushing or the air scour are adopted in the catalyzer recoil.
Described catalyst cupport adopts one or more in the precipitator method, pickling process, hybrid system or the ion exchange method, and active component content is 1%～15%.Described oxygenant is hydrogen peroxide, dioxide peroxide, ozone, ultraviolet or ultrasonic one or more.
The waste water of processing in this example is the former water of pharmacy corporation discharging, the design influent COD
CrBe 5106mg/L, BOD
5Be 1277mg/L, B/C is 0.25.This example utilizes the film pipe as the carrier of catalyzer, and film pipe catalyzer is straight pipe type; The material of support of the catalyst 1 is ceramic-like; Membrane channel 3 diameters are 100um; The activeconstituents of catalyst cupport is iron Fe, manganese Mn, nickel, cobalt Co oxide compound, and active component content is 15%; Catalyst cupport adopts the precipitator method; In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward; Oxygenant adopts hydrogen peroxide; Air not only participated in the catalyzed oxidation chain reaction but also worked the effect of mixing as oxygenant; Under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the effect of catalyzer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water; The water flushing is adopted in the catalyzer back flushing; Water outlet COD
CrBe 465mg/L, BOD
5Be 167mg/L, B/C is 0.36; After treatment, waste water COD
CrClearance be that 90.9%, B/C has improved 44%.
The waste water of processing in this example is the tail water of town sewage plant discharging, the design influent COD
CrBe 85mg/L.This example utilizes the film pipe as the carrier of catalyzer, and film pipe catalyzer is straight pipe type; The material of support of the catalyst 1 is synthetic resin; Membrane channel 3 diameters are 0.05um; The activeconstituents of catalyst cupport is iron Fe, copper Cu, silver-colored Ag, cobalt Co oxide compound, and active component content is 1%; Catalyst cupport adopts pickling process; In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward; Oxygenant adopts dioxide peroxide; Air not only participated in the catalyzed oxidation chain reaction but also worked the effect of mixing as oxygenant; Under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the effect of catalyzer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water; Air scour is adopted in the catalyzer back flushing; Water outlet COD
CrBe 43mg/L, waste water COD
CrClearance be 49.4%.
The waste water of processing in this example is the former water of chemical enterprise emission, the design influent COD
CrBe 1250mg/L, BOD
5Be 250mg/L, B/C is 0.2.This example utilizes the film pipe as the carrier of catalyzer, and film pipe catalyzer is plate and frame; The material of support of the catalyst 1 is fiber-like; Membrane channel 3 diameters are 5um; The activeconstituents of catalyst cupport is iron Fe, nickel, cobalt Co oxide compound, and active component content is 5%; Catalyst cupport adopts the precipitator method; In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward; Oxygenant adopts ozone; Air not only participated in the catalyzed oxidation chain reaction but also worked the effect of mixing as oxygenant; Under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the effect of catalyzer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water; The catalyzer back flushing adopts water, gas to unite flushing; Water outlet COD
CrBe 320mg/L, BOD
5Be 99mg/L, B/C is 0.31; After treatment, waste water COD
CrClearance be that 74.4%, B/C has improved 55%.
Embodiment 4
The waste water of processing in this example is the former water of agricultural chemicals enterprise discharging, the design influent COD
CrBe 3480mg/L, BOD
5Be 766mg/L, B/C is 0.22.This example utilizes the film pipe as the carrier of catalyzer, and film pipe catalyzer is spiral; The material of support of the catalyst 1 is fiber-like; Membrane channel 3 diameters are 20um; The activeconstituents of catalyst cupport is manganese Mn, nickel, cobalt Co oxide compound, and active component content is 10%; Catalyst cupport adopts ion exchange method; In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward; Oxygenant adopts ultraviolet; Air not only participated in the catalyzed oxidation chain reaction but also worked the effect of mixing as oxygenant; Under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the effect of catalyzer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water; The water flushing is adopted in the catalyzer back flushing; Water outlet COD
CrBe 700mg/L, BOD
5Be 280mg/L, B/C is 0.4; After treatment, waste water COD
CrClearance be that 79.9%, B/C has improved 81.8%.
Embodiment 5
The waste water of processing in this example is the tail water of printing and dyeing enterprise discharging, the design influent COD
CrBe 165mg/L.This example utilizes the film pipe as the carrier of catalyzer, and film pipe catalyzer is bridge-type; The material of support of the catalyst 1 is synthetic resin; Membrane channel 3 diameters are 3um; The activeconstituents of catalyst cupport is iron Fe, copper Cu, silver-colored Ag, nickel oxide compound, and active component content is 3%; Catalyst cupport adopts hybrid system; In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward; Oxygenant adopts ultrasonic; Air not only participated in the catalyzed oxidation chain reaction but also worked the effect of mixing as oxygenant; Under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under the effect of catalyzer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water; Air scour is adopted in the catalyzer back flushing; Water outlet COD
CrBe 92mg/L, waste water COD
CrClearance be 44.2%.
Claims (6)
1. film pipe catalyzer, it is characterized in that by film pipe catalytic unit composing plate frame, spiral, bridge-type, straight pipe type film pipe catalyzer, film pipe catalytic unit comprises support of the catalyst 1, catalyst layer 2, membrane channel 3, be provided with catalyst layer 2 outside the support of the catalyst 1, be provided with membrane channel 3 in the support of the catalyst 1.
2. a kind of film pipe catalyzer according to claim 1, it is characterized in that: the material of described support of the catalyst 1 is one or more in fiber-like, synthetic resin or the ceramic-like.
3. a kind of film pipe catalyzer according to claim 1, it is characterized in that: described membrane channel 3 diameters are 0.05～100um.
4. waste water treatment by catalytic oxidation that adopts film pipe catalyzer is characterized in that:
In advancing, waste water goes out to lead to the filmed passing tube catalyzer outward, the outside oxygenant that drops into of film pipe catalyzer passes into the pressurized air stirring simultaneously, under the normal temperature and pressure conditions, oxygenant produces the hydroxyl radical free radical chain reaction under catalyst layer 2 effects of film pipe catalyzer, pressurized air participates in the catalyzed oxidation chain reaction simultaneously as secondary oxidizer, by the pollution substance in the multi-phase catalytic oxidation oxidized waste water, water outlet is discharged through membrane channel 3 after processing; Adopt the film pipe as support of the catalyst 1, the activeconstituents of catalyst cupport is one or more of rare metal, precious metal and transition metal oxide, and one or more in water flushing or the air scour are adopted in the catalyzer recoil.
5. a kind of waste water treatment by catalytic oxidation that adopts film pipe catalyzer according to claim 4, it is characterized in that: described catalyst cupport adopts one or more in the precipitator method, pickling process, hybrid system or the ion exchange method, and active component content is 1%～15%.
6. a kind of waste water treatment by catalytic oxidation that adopts film pipe catalyzer according to claim 4 is characterized in that: described oxygenant is hydrogen peroxide, dioxide peroxide, ozone, ultraviolet or ultrasonic one or more.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841292A (en) * | 2015-05-25 | 2015-08-19 | 哈尔滨工业大学 | Ozone-catalytic functional ceramic membrane, preparation method thereof and circulating coating device |
| TWI726799B (en) * | 2020-08-24 | 2021-05-01 | 膜旺能源科技有限公司 | Wastewater purification system having catalytic membrane tube |
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| JP4312765B2 (en) * | 2005-01-21 | 2009-08-12 | 三星エスディアイ株式会社 | SUPPORT FOR FUEL GAS REFORMING REACTION CATALYST AND ITS MANUFACTURING METHOD, SUPPORTED CATALYST AND FUEL TREATMENT DEVICE INCLUDING THE SAME |
| CN101590370A (en) * | 2009-06-11 | 2009-12-02 | 上海交通大学 | The method of catalytically oxidizing elemental mercury by oxidant controlledly released by porous ceramic membrane |
| CN202315700U (en) * | 2011-08-28 | 2012-07-11 | 常州浩瀚新材料科技有限公司 | Toxic and harmful organic waste gas treatment device |
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2013
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07241575A (en) * | 1994-03-08 | 1995-09-19 | Fuji Electric Co Ltd | Treatment of water using ozone |
| JP4312765B2 (en) * | 2005-01-21 | 2009-08-12 | 三星エスディアイ株式会社 | SUPPORT FOR FUEL GAS REFORMING REACTION CATALYST AND ITS MANUFACTURING METHOD, SUPPORTED CATALYST AND FUEL TREATMENT DEVICE INCLUDING THE SAME |
| CN101148287A (en) * | 2007-08-31 | 2008-03-26 | 南京工业大学 | Enhanced oxidation process and device for treating organic poison wastewater |
| CN101590370A (en) * | 2009-06-11 | 2009-12-02 | 上海交通大学 | The method of catalytically oxidizing elemental mercury by oxidant controlledly released by porous ceramic membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841292A (en) * | 2015-05-25 | 2015-08-19 | 哈尔滨工业大学 | Ozone-catalytic functional ceramic membrane, preparation method thereof and circulating coating device |
| TWI726799B (en) * | 2020-08-24 | 2021-05-01 | 膜旺能源科技有限公司 | Wastewater purification system having catalytic membrane tube |
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Application publication date: 20131030 |