CN105540931B - A kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing method and its device - Google Patents
A kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing method and its device Download PDFInfo
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- CN105540931B CN105540931B CN201610034030.3A CN201610034030A CN105540931B CN 105540931 B CN105540931 B CN 105540931B CN 201610034030 A CN201610034030 A CN 201610034030A CN 105540931 B CN105540931 B CN 105540931B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Engineering & Computer Science (AREA)
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Abstract
The present invention relates to a kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing methods and its device, method to include：Acid and H are added into industrial wastewater2O2, pH is adjusted to 4.5~6.0, into class Fenton's reaction pond；Wherein, multiplexed combination catalytic filler packet is loaded in class Fenton's reaction pond, filler is bundled into point to be made of iron-nickel alloy grain, iron-copper grain, manganeisen grain, zeolite and bloodstone；After waste water reacts 3.0~4.0h in class Fenton's reaction pond, it is 7.8~8.0 to add alkali to pH, adds flocculation aid, into coagulating sedimentation integral pool, is completed after being separated by solid-liquid separation, water discharge, and disposition is arranged outside iron containing sludge.The method raw material of the present invention is easy to get, easy to assembly, of low cost.
Description
Technical field
The invention belongs to process for treating industrial waste water field, more particularly to a kind of industrial wastewater multiplexed combination is catalyzed Zero-valent Iron
Class Fenton processing method and its device.
Background technology
With the increasingly raising that national energy conservation and emission reduction requires, industrial wastewater discharge standard generally improves.Industrial wastewater type
Various, water quality is complicated, and hard-degraded substance is more, is difficult to reach high standard emission request using conventional materialization, life assemblage technique.It is fragrant
Oxidation is advanced oxidation processes based on OH, theoretically can non-selectivity ground most of organic matter in oxidized waste water, because
And obtain relatively broad application in field of industrial waste water treatment.
Zero-valent Iron class Fenton technology is one kind in Fenton oxidation technique, in acid condition, what zeroth order iron rot generated
Fe2+With H2O2Fenton's reaction is formed to achieve the purpose that degradation of organic substances.Zero-valent Iron class Fenton and traditional Fenton oxidation technique
It compares, in addition to the OH generated in processing procedure has compared with strong oxidation, Zero-valent Iron corrodes generation in acid condition
[H] also to have be a kind of Fenton treatment process having both two kinds of oxidation, reduction effects compared with strong reducing action, have effect it is good,
The wide advantage of the scope of application.But there are the reduced levels that inlet flow-patterm need to be adjusted to 3~4 in conventional Zero-valent Iron class Fenton, lead to acid
Alkali adds problem of high cost, that iron cement yield is big.
Invention content
At a kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton
Reason method and its device, this method raw material is easy to get, easy to assembly, of low cost.
A kind of industrial wastewater multiplexed combination of the present invention is catalyzed Zero-valent Iron class Fenton processing method, including：
(1) acid and H are added into industrial wastewater2O2, pH is adjusted to 4.5~6.0, into class Fenton's reaction pond；Wherein,
Multiplexed combination catalytic filler packet is loaded in class Fenton's reaction pond, filler is bundled into point by iron-nickel alloy grain, iron-copper grain, ferromanganese conjunction
Goldc grains, zeolite and bloodstone composition；Wherein, H2O2Dosage be 1.0~2.0mL/L；
(2) after waste water reacts 3.0~4.0h in class Fenton's reaction pond, it is 7.8~8.0 to add alkali to pH, adds flocculation aid,
Into coagulating sedimentation integral pool；
(3) it is completed in coagulating sedimentation integral pool after being separated by solid-liquid separation, water discharge, disposition is arranged outside iron containing sludge.
Industrial wastewater is printing and dyeing, chemical industry or pharmaceutical industry indegradable industrial effluent in the step (1).
Acid is sulfuric acid or spent acid in the step (1)；H2O2Mass concentration be 30.0%.
Acid and H in the step (1)2O2Dosage determination：Because the alkaline buffer ingredient contained in waste water is different, because
The throwing amount of this different waste water quality acid differs, but dosage need to ensure pH being adjusted to accommodation.
Class Fenton's reaction bottom of pond portion is laid with aeration tube in the step (1), is reacted using aeration agitation, gas-water ratio 3：1
~4：1.
Iron-nickel alloy grain in the step (1), iron-copper grain, manganeisen grain, zeolite and bloodstone weight ratio be
5：5：1：1：1.
Filler outer packing material is nylon net bag in the step (1), and width of mesh is 20-60 mesh；Filler packet is suspended to
In class Fenton's reaction pond.
It is laid with grid in vertical shaft in flocculation basin in flocculation sediment integrated apparatus in the step (2), with enhancing flocculation effect
Fruit is precipitated as sloping plate deposition.
Flocculation aid is PAM in the step (2).
A kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing unit, including class Fenton's reaction pond, wherein institute
Class Fenton's reaction pond multiplexed combination catalytic filler packet, the class Fenton's reaction pond both sides point are equipped in the class Fenton's reaction pond stated
Not She You class Fenton's reaction pond water inlet pipe and class Fenton's reaction pond outlet pipe, the class Fenton's reaction pond side successively be equipped with drum
Wind turbine, alkali add medicine dissolving tank, flocculation aid adds medicine dissolving tank, acid adds medicine dissolving tank and H2O2Add medicine dissolving tank, the other side is equipped with coagulation
Integral pool is precipitated, the air blower is connect by air hose with class Fenton's reaction pond, and the alkali adds medicine dissolving tank upper end and sets
Have that alkali adds medicine dissolving tank blender and alkali adds metering pump, the flocculation aid add medicine dissolving tank upper end added equipped with flocculation aid it is molten
Medicine pond blender and flocculation aid add metering pump, and the acid adds medicine dissolving tank upper end and adds medicine dissolving tank blender and acid equipped with acid
Add metering pump, the H2O2It adds medicine dissolving tank upper end and is equipped with H2O2Add medicine dissolving tank blender and H2O2Metering pump is added, institute
The alkali stated adds medicine dissolving tank and flocculation aid adds medicine dissolving tank respectively by alkali drug tube and flocculation aid drug tube and class Fenton's reaction
Pond outlet pipe connection, the acid add medicine dissolving tank and H2O2Medicine dissolving tank is added respectively by sour drug tube and H2O2Drug tube with
The water inlet pipe connection of class Fenton's reaction pond and sour drug tube and H2O2Drug tube is set with class Fenton's reaction pond water inlet pipe junction lower end
Have a class Fenton's reaction pond water inlet pipe regulating valve, the coagulating sedimentation integral pool side upper end be equipped with coagulating sedimentation outlet pipe, under
End is equipped with sludge from sedimentation tank pipe, and the sludge from sedimentation tank pipe is equipped with sludge from sedimentation tank pipe regulating valve, the coagulating sedimentation
The integral pool other side is connect by tube mixer with class Fenton's reaction pond outlet pipe, the tube mixer upper and lower ends point
It She You not tube mixer regulating valve.
The air hose is equipped with blower air pipe regulating valve and blower air pipe check-valves.
For the deficiency of conventional Zero-valent Iron class Fenton oxidation technique, the present invention proposes a kind of industrial wastewater multiplexed combination catalysis
Zero-valent Iron class Fenton oxidation treatment process.It is catalyzed by the multiplexed combination that multiple catalysts form by being loaded in Fenton's reaction pond
Filler packet makes the Fenton's reaction pH scope of applications improve to 4.5~6.0, can effectively reduce soda acid throwing amount and expense, reduces iron content
Sludge yield.Meanwhile this kind of multiplexed combination catalytic filler raw material is easy to get, is easy to make, is of low cost, and there is no catalyst hardly possiblies
The problem of to recycle, is easy to implement in engineer application.
It is required for the low pH of traditional Zero-valent Iron class Fenton oxidation waste water treatment process, soda acid adds of high cost, iron cement and generates
Big deficiency is measured, the invention discloses a kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing method and is set
It is standby.Its principle is：Combination catalyst is formed with iron-nickel alloy grain, iron-copper grain, manganeisen grain, zeolite, bloodstone etc.,
Under the polynary concerted catalysis effect of the catalyst such as iron system, manganese systems, zeolite and transition metal, class Fenton's reaction can be made in pH=4.5
~6.0 higher range plays efficiency, and effectively reduces soda acid dosage and follow-up iron cement yield；Simultaneously because being exposed in acidity
Zero-valent Iron reduction system can discharge OH under the conditions of gas-, thus after class Fenton's reaction pH can rise to 6.5~7.0 compared with
High scope is greatly saved flocculated stage alkali and adds expense.
The present invention forms multi-component system with substances such as iron-nickel alloy grain, iron-copper grain, manganeisen grain, zeolite and bloodstone
Catalyst is closed, since the polynary concerted catalysis of the catalyst such as iron system, manganese systems, zeolite and a variety of transition metal acts on, zeroth order can be made
Higher range of the iron class Fenton's reaction in pH=4.5~6.0 plays efficiency, and effectively reduces soda acid dosage and iron cement production
Amount.Multiplexed combination catalyst is encapsulated to form filler packet after evenly mixing with nylon net bag, and filler packet is outstanding as source of iron and catalyst
It hangs and can be used in Fenton's reaction pond.
Advantageous effect
(1) compared with the ranges of optimum pH=3~4 of traditional Zero-valent Iron class Fenton, multiplexed combination proposed by the present invention is urged
The optimum pH ranging from 4.5~6.0 for changing Zero-valent Iron class Fenton oxidation technique, can be such that soda acid dosage and expense significantly drops
It is low, and make the reduction of iron cement yield；
(2) multiplexed combination catalyst proposed by the present invention is easily prepared, material is cheap and easy to get, and raw material is easy to get, easy to assembly,
It is very suitable for being engineered.
Description of the drawings
Fig. 1 is that industrial wastewater multiplexed combination is catalyzed Zero-valent Iron class Fenton processing unit in the present invention.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
Certain textile and dyeing industry garden waste water secondary biochemical effluent COD is 120-140mg/L, need to be reached after advanced treating
It arrives《Urban wastewater treatment firm pollutant emission standard》(GB18918-2002) level-one B standard (COD≤60.0mg/L).Waste water is thrown
Acid adding and H2O2, enter in Fenton's reaction pond after pH is adjusted to 5.0, loaded in reaction tank iron-nickel alloy grain, iron-copper grain,
Multiplexed combination catalytic filler (iron-nickel alloy grain, iron-copper grain, manganeisen grain, the zeolite of manganese sand, zeolite, bloodstone composition
Weight ratio with bloodstone is 5：5：1：1：1), the residence time is 4.0h in Fenton's reaction pond；Then add alkali and PAM help it is solidifying
After reaction water outlet pH is adjusted to 7.8 by agent, into coagulative precipitation tank, COD stablizes less than 60mg/L waste water after processing.
Industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing unit is as shown in Figure 1, fragrant including class in the present embodiment
Pause reaction tank 20, wherein being equipped with class Fenton's reaction pond multiplexed combination catalytic filler packet 19, institute in the class Fenton's reaction pond 20
20 both sides of class Fenton's reaction pond stated are respectively equipped with class Fenton's reaction pond water inlet pipe 17 and class Fenton's reaction pond outlet pipe 21, described
20 side of class Fenton's reaction pond successively be equipped with air blower 26, alkali adds medicine dissolving tank 1, flocculation aid adds medicine dissolving tank 2, acid add it is molten
Medicine pond 3 and H2O2Add medicine dissolving tank 4, the other side be equipped with coagulating sedimentation integral pool 23, the air blower 26 by air hose 31 with
Class Fenton's reaction pond 20 connects, and the alkali adds that 1 upper end of medicine dissolving tank adds medicine dissolving tank blender 5 equipped with alkali and alkali adds metering
Pump 9, the flocculation aid add that 2 upper end of medicine dissolving tank adds medicine dissolving tank blender 6 equipped with flocculation aid and flocculation aid adds metering pump
10, the acid adds that 3 upper end of medicine dissolving tank adds medicine dissolving tank blender 7 equipped with acid and acid adds metering pump 11, the H2O2It throws
4 upper end of medicine dissolving tank is added to be equipped with H2O2Add medicine dissolving tank blender 8 and H2O2Metering pump 12 is added, the alkali adds 1 He of medicine dissolving tank
Flocculation aid adds medicine dissolving tank 2 and is connected respectively with class Fenton's reaction pond outlet pipe 21 by alkali drug tube 13 and flocculation aid drug tube 14
It connects, the acid adds medicine dissolving tank 3 and H2O2Medicine dissolving tank 4 is added respectively by sour drug tube 15 and H2O2Drug tube 16 is fragrant with class
Pause the connection of reaction tank water inlet pipe 17 and sour drug tube 15 and H2O2Under drug tube 16 and 17 junction of class Fenton's reaction pond water inlet pipe
End is equipped with class Fenton's reaction pond water inlet pipe regulating valve 18, and the 23 side upper end of coagulating sedimentation integral pool goes out equipped with coagulating sedimentation
Water pipe 24, lower end are equipped with sludge from sedimentation tank pipe 25, and the sludge from sedimentation tank pipe 25 is equipped with sludge from sedimentation tank pipe regulating valve 32,
23 other side of coagulating sedimentation integral pool is connect by tube mixer 22 with class Fenton's reaction pond outlet pipe 21, described
22 upper and lower ends of tube mixer are respectively equipped with tube mixer regulating valve 29,30.
The air hose 31 is equipped with blower air pipe regulating valve 27 and blower air pipe check-valves 28.
Embodiment 2
Certain textile and dyeing industry garden waste water secondary biochemical effluent COD is 60~80mg/L, need to be after advanced treating《Cities and towns
Wastewater Treatment discharge standard》(GB18918-2002) level-one A standards (COD≤50.0mg/L).Waste water add acid and
H2O2, enter in Fenton's reaction pond after pH is adjusted to 4.8, iron-nickel alloy grain, iron-copper grain, manganese sand, boiling loaded in reaction tank
Multiplexed combination catalytic filler (iron-nickel alloy grain, iron-copper grain, manganeisen grain, zeolite and the bloodstone of stone, bloodstone composition
Weight ratio be 5：5：1：1：1), the residence time is 3.0h in Fenton's reaction pond, and then adding alkali and PAM flocculation aids will react
After water outlet pH is adjusted to 8.0, into coagulative precipitation tank, COD stablizes less than 50mg/L waste water after processing.
Claims (7)
1. a kind of industrial wastewater multiplexed combination is catalyzed Zero-valent Iron class Fenton processing method, including：
(1) acid and H are added into industrial wastewater2O2, pH is adjusted to 4.5~6.0, into class Fenton's reaction pond (20)；Wherein,
Load multiplexed combination catalytic filler packet in class Fenton's reaction pond (20), it point is 5 by weight ratio that filler, which is bundled into,:5:1:1:1 iron nickel
Alloy granule, iron-copper grain, manganeisen grain, zeolite and bloodstone composition；Wherein, H2O2Dosage be 1.0~2.0mL/L；
(2) after class Fenton's reaction pond (20) react 3.0~4.0h, it is 7.8~8.0 to add alkali to pH, adds PAM flocculation aids, into
Enter coagulating sedimentation integral pool (23), wherein coagulating basin is to be laid with grid in vertical shaft, is precipitated as sloping plate deposition；
(3) it is completed in coagulating sedimentation integral pool (23) after being separated by solid-liquid separation, water discharge, disposition is arranged outside iron containing sludge.
2. a kind of industrial wastewater multiplexed combination according to claim 1 is catalyzed Zero-valent Iron class Fenton processing method, feature
It is, industrial wastewater is printing and dyeing, chemical industry or pharmaceutical industry indegradable industrial effluent in the step (1).
3. a kind of industrial wastewater multiplexed combination according to claim 1 is catalyzed Zero-valent Iron class Fenton processing method, feature
It is, acid is sulfuric acid or spent acid in the step (1)；H2O2Mass concentration is 30.0%.
4. a kind of industrial wastewater multiplexed combination according to claim 1 is catalyzed Zero-valent Iron class Fenton processing method, feature
It is, class Fenton's reaction pond (20) bottom is laid with aeration tube in the step (1), is reacted using aeration agitation, gas-water ratio 3:1
~4:1.
5. a kind of industrial wastewater multiplexed combination according to claim 1 is catalyzed Zero-valent Iron class Fenton processing method, feature
It is, filler outer packing material is nylon net bag in the step (1), and width of mesh is 20-60 mesh；Filler packet is suspended to class sweet smell
Pause in reaction tank.
6. the dress used in a kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing method as described in claim 1
It sets, it is characterised in that：Class Fenton's reaction pond multiplexed combination catalytic filler packet (19) is equipped in the class Fenton's reaction pond (20),
Described class Fenton's reaction pond (20) both sides are respectively equipped with class Fenton's reaction pond water inlet pipe (17) and class Fenton's reaction pond outlet pipe
(21), described class Fenton's reaction pond (20) side successively be equipped with air blower (26), alkali adds medicine dissolving tank (1), flocculation aid adds
Medicine dissolving tank (2), acid add medicine dissolving tank (3) and H2O2Add medicine dissolving tank (4), the other side be equipped with coagulating sedimentation integral pool (23), it is described
Air blower (26) connect with class Fenton's reaction pond (20) by air hose (31), the alkali adds medicine dissolving tank (1) upper end and sets
Have that alkali adds medicine dissolving tank blender (5) and alkali adds metering pump (9), the flocculation aid, which adds medicine dissolving tank (2) upper end and is equipped with, to be helped
Solidifying agent adds medicine dissolving tank blender (6) and flocculation aid adds metering pump (10), and the acid adds medicine dissolving tank (3) upper end and is equipped with acid
It adds medicine dissolving tank blender (7) and acid adds metering pump (11), the H2O2It adds medicine dissolving tank (4) upper end and is equipped with H2O2It adds
Medicine dissolving tank blender (8) and H2O2Metering pump (12) is added, the alkali adds medicine dissolving tank (1) and flocculation aid adds medicine dissolving tank (2)
It is connect respectively with class Fenton's reaction pond outlet pipe (21) by alkali drug tube (13) and flocculation aid drug tube (14), the acid is thrown
Add medicine dissolving tank (3) and H2O2Medicine dissolving tank (4) is added respectively by sour drug tube (15) and H2O2Drug tube (16) and class Fenton's reaction
Pond water inlet pipe (17) connection and sour drug tube (15) and H2O2Drug tube (16) and class Fenton's reaction pond water inlet pipe (17) junction
Lower end is equipped with class Fenton's reaction pond water inlet pipe regulating valve (18), and described coagulating sedimentation integral pool (23) the side upper end is equipped with coagulation
Outlet pipe (24), lower end are precipitated equipped with sludge from sedimentation tank pipe (25), the sludge from sedimentation tank pipe (25) is arranged equipped with sedimentation basin
Mud pipe regulating valve (32), coagulating sedimentation integral pool (23) other side pass through tube mixer (22) and class Fenton's reaction pond
Outlet pipe (21) connects, and the tube mixer (22) upper and lower ends are respectively equipped with tube mixer regulating valve (29,30).
7. being used in a kind of industrial wastewater multiplexed combination catalysis Zero-valent Iron class Fenton processing method according to claim 6
Device, it is characterised in that：The air hose (31) is equipped with blower air pipe regulating valve (27) and blower air pipe stops
Return valve (28).
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| CN106242114B (en) * | 2016-08-24 | 2022-12-27 | 厦门嵩湖环保股份有限公司 | High-concentration organic industrial wastewater treatment system and treatment method |
| CN106830312B (en) * | 2017-03-13 | 2020-03-31 | 江苏省环境科学研究院 | Anaerobic composite biological filler with zero-valent iron adsorbed by magnet |
| CN106984316B (en) * | 2017-05-15 | 2019-04-26 | 哈尔滨工业大学 | A kind of preparation method of the dendritic iron-copper of efficient out-phase class fenton catalyst micro-nano |
| CN108558152B (en) * | 2018-02-02 | 2021-05-04 | 东华大学 | Method for recycling river sediment |
| CN112645427A (en) * | 2019-10-11 | 2021-04-13 | 杭州特种纸业有限公司 | Zero-valent iron-ferrous catalysis-based Fenton-like oxidation wastewater treatment method |
| CN111186898B (en) * | 2020-01-13 | 2022-04-26 | 北京工商大学 | Method and device for treating printing and dyeing wastewater through Fenton oxidation by taking scrap iron as iron source |
| CN111646615B (en) * | 2020-06-15 | 2021-02-09 | 北京环球中科水务科技有限公司 | Skid-mounted photo-Fenton water treatment equipment |
| CN114643058B (en) * | 2022-04-20 | 2024-08-16 | 清创人和生态工程技术有限公司 | Ternary nano alloy catalyst for decomposing hydrogen peroxide to generate hydroxyl radical to degrade organic wastewater and preparation method thereof |
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| KR20080051863A (en) * | 2006-12-07 | 2008-06-11 | (주)인간과 환경 | Waste water of food treatment apparatus and using the method |
| CN101147854A (en) * | 2007-07-23 | 2008-03-26 | 南京工业大学 | Continuous iron-carbon micro-electrolysis fluidized bed equipment |
| CN104876319A (en) * | 2015-05-19 | 2015-09-02 | 四川大学 | Fenton-like reactor, and toxic nondegradable wastewater treatment device and method |
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