CN108840481A - One type Fenton fluidized bed and its wastewater treatment method - Google Patents
One type Fenton fluidized bed and its wastewater treatment method Download PDFInfo
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- CN108840481A CN108840481A CN201810916005.7A CN201810916005A CN108840481A CN 108840481 A CN108840481 A CN 108840481A CN 201810916005 A CN201810916005 A CN 201810916005A CN 108840481 A CN108840481 A CN 108840481A
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- fluidized bed
- class fenton
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000945 filler Substances 0.000 claims abstract description 41
- 238000005243 fluidization Methods 0.000 claims abstract description 40
- 239000003814 drug Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000010865 sewage Substances 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 17
- 230000007246 mechanism Effects 0.000 claims abstract description 6
- 229940079593 drug Drugs 0.000 claims abstract description 5
- 239000002351 wastewater Substances 0.000 claims description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000002699 waste material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 239000008240 homogeneous mixture Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000010802 sludge Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011257 shell material Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to technical field of sewage, disclose a type Fenton fluidized bed, including：Medicine pond comprising medicine pond ontology is connected to the water inlet pipe of medicine pond ontology, and protrudes into the rabbling mechanism of medicine pond ontology；Fluidize pond comprising fluidisation pond ontology, and the effluent trough set on fluidisation pond body upper part；Class fenton catalyst filler is placed in the ontology of the fluidisation pond；And diversion pipe, first end are connected to medicine pond ontology, the second end is connected to the fluidisation pond ontology and protrudes into the class fenton catalyst filler.The present invention also provides a kind of wastewater treatment methods of class Fenton fluidized bed as previously described, and the method for self-cleaning of class Fenton fluidized bed as previously described.The present invention also provides a type fenton catalyst fillers.The present invention can effectively reduce added amount of chemical, reduce sludge yield, reduce operating cost.
Description
Technical field
The present invention relates to technical field of sewage, more particularly, to a type Fenton fluidized bed and its wastewater treatment side
Method.
Background technique
Advanced oxidation processes are a kind of effective ways for handling waste water, are usually used in pretreatment or the depth of industrial wastewater
The reason stage.Fenton oxidation method is the common advanced oxidation processes of current water process.
Fenton oxidation method basic principle is to make catalyst, hydrogen peroxide using ferrous sulfate at acid condition (pH=3-4)
For oxidant, the hydroxyl radical free radical of strong oxidizing property is generated, by the technology of hardly degraded organic substance oxygenolysis, this method treatment effeciency
Height has a wide range of application.Fenton oxidation reaction is used frequently as a kind of homogeneous reaction process, i.e., oxidant and catalyst are dissolved in useless
It is reacted in water, catalyst can not be recycled and reused, and the waste of catalyst is caused.The pH of this method reaction simultaneously is needed
3-4 is maintained, needs after the reaction was completed plus adjusting PH with base value is to alkalinity, then carry out flocculation sedimentation, soda acid consumption is big, and operating cost is high,
A large amount of materialized mud is generated, secondary pollution is caused.
Due to the drawbacks described above of homogeneous catalytic oxidation, added amount of chemical is reduced, reduces sludge yield, reduces operating cost
Just become new research topic.Then, someone begins trying using heterogeneous solid catalyst, in order to reach good catalysis effect
Fruit, catalyst must have big specific surface area, this requires catalyst granules partial size the smaller the better, easily cause since partial size is too small
Catalyst outflows with water, it is easier to cause catalyst blockage, it is unsmooth to cross water.Meanwhile suspended matter is attached to catalyst surface in water
Easily cause catalyst structure and lose activity, effect reduces.Therefore, above-mentioned drawback limits the use of Fenton oxidation method technique.
Summary of the invention
It is an object of the invention to overcome above-mentioned technical deficiency, a type Fenton fluidized bed and its wastewater treatment side are proposed
Method solves the technology that soda acid consumption is big in the prior art, operating cost is high, generates a large amount of materialized mud, causes secondary pollution
Problem.
To reach above-mentioned technical purpose, technical solution of the present invention provides a type Fenton fluidized bed, including：
Medicine pond comprising medicine pond ontology is connected to the water inlet pipe of medicine pond ontology, and protrudes into the rabbling mechanism of medicine pond ontology；
Fluidize pond comprising fluidisation pond ontology, and the effluent trough set on fluidisation pond body upper part；
Class fenton catalyst filler is placed in the ontology of the fluidisation pond；And
Diversion pipe, first end are connected to medicine pond ontology, and the second end is connected to the fluidisation pond ontology and protrudes into institute
It states in class fenton catalyst filler.
The present invention also provides a kind of wastewater treatment methods of class Fenton fluidized bed as previously described, include the following steps：
Step 1.1, waste water is injected in medicine pond, acid is put into medicine pond, adjust PH to 5；
Step 1.2, oxidant is added into medicine pond according to waste strength, stirred evenly；
Step 1.3, waste water step 1.2 obtained imports fluidisation pond by diversion pipe, fills out waste water with class fenton catalyst
Material comes into full contact with, and the organic matter in class Fenton's reaction degrading waste water occurs；
Step 1.4, waste water flows from bottom to top in fluidisation pond, and the waste water after reaction is discharged by the effluent trough for fluidizing pond.
The present invention also provides a kind of method for self-cleaning of class Fenton fluidized bed as previously described, include the following steps：
Step 2.1, compressed air is sent in the air lift central tube into fluidized bed by compressed air inlet pipe, makes air lift
The three-phase admixture of " air-waste water-class fenton catalyst filler " is formed in central tube, air lift central tube is inside and outside to form density
Difference；
Step 2.2, fluid density is small in air lift central tube, and class fenton catalyst filler is in air lift central tube to upstream
Dynamic, mutual collision friction during rising, the passivating film formed when by catalytic oxidation is removed, and finally arrives at fluidisation
The sewage sump on pond top realizes air lift；
Step 2.3, the passivating film of removing is discharged by sewage pipe；Class fenton catalyst filler after removing passivating film is cleaning
It precipitates and falls in device, return to fluidized bed ontology, so far, class fenton catalyst filler is completed a self-cleaning inside fluidized bed and followed
Ring process, entire cyclic process continue 4~6h.
The present invention also provides a type fenton catalyst fillers, are made by the following method：Active carbon powder is immersed
To nickel nitrate, cerous nitrate, lanthanum nitrate mixed solution in, then active carbon drained, is dried, press matter with iron powder, CuO powder later
Amount ratio is 1：2~3：2~3 mixing are homogeneous mixture through high-temperature fusion, then obtain particle by cooling crush, screening and urge
Agent.
Compared with prior art, beneficial effects of the present invention include：
1, using class fenton catalyst, replace adding for traditional Fenton's reaction system ferrous ions, catalyst is repeatable
It utilizes, does not generate iron containing sludge, prevent secondary pollution；And the reaction system has effectively widened the pH value range of reaction, reaction
It is worth range pH4~7, without adding alkali readjustment after reaction, does not need a large amount of acid, alkali adjust pH value；
2, the inside that waste water is imported to class fenton catalyst filler, the solid of waste water can be intercepted by the gap between filler
Suspended matter plays the role of filtering, effectively reduces the solid suspension of water outlet；
3, using pressure difference, i.e., the density that air-water mixture density is less than water generates pressure difference and rises to carry filler,
Circulation is established in fluidisation pond, one, which carrys out catalyst filling, is in fluidized state in reaction zone, substantially increases catalyst and waste water
Contact area greatly improves mass transfer and catalytic efficiency, effectively prevents filler and accumulates hardened problem；Two make catalyst filling
It is forced mutually to rub, the passivating film that catalyst filling surface is formed peels off, and completes the self-cleaning process of filler, is effectively reduced
The influence that catalyst surface passivation causes catalytic efficiency to reduce.
Detailed description of the invention
Fig. 1 is class Fenton fluidized-bed structure schematic diagram of the invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention provides a type Fenton fluidized beds, as shown in Figure 1, including：Medicine pond 10, fluidizes pond 20, and class Fenton is urged
Agent filler 30 and diversion pipe 40.
Medicine pond 10 includes medicine pond ontology 11, is connected to the water inlet pipe 12 of medicine pond ontology 11, and protrudes into the stirring of medicine pond ontology 11
Mechanism 13.
Fluidizing pond 20 includes fluidisation pond ontology 21, and the effluent trough 22 set on fluidisation 21 top of pond ontology.
Class fenton catalyst filler 30 is placed in fluidisation pond ontology 21, the effective packed height 2m of filler, partial size 1
~3mm.
40 first end of diversion pipe is connected to medicine pond ontology 11, and the second end is connected to fluidisation pond ontology 11 and protrudes into
In the class fenton catalyst filler 30.
This programme is mainly come into full contact with using oxidant and the heterogeneous class fenton catalyst filler in reactor, is aoxidized
The Fe of agent in the catalyst2+、Cu2+、Ni2+Under the catalytic action of plasma, decomposes and generate hydroxyl radical free radical (OH), utilize hydroxyl
The strong oxidizing property of base free radical, the organic matter in oxidative degradation waste water.Cu2+、Ni2+Introducing so that pH needed for reacting is to neutrality
It is mobile.The introducing of rare-earth elements of lanthanum and cerium, the catalytic efficiency of copper and mickel in the Fenton-like of raising.PH is adjusted to 5 before reacting,
PH weakly acidic pH after reaction greatly reduces soda acid dosage, generates substantially without sludge without adding alkali to adjust back pH value.
Preferably, the rabbling mechanism 13 is mechanical stirring or air stirring, it is therefore intended that fill waste water with medicament
Divide mixing；The lower part of the fluidisation pond ontology 21 is tapered, and cone bucket bottom area is small, will not generate dead angle, can be avoided catalysis
Agent filler is deposited in lower part.
Preferably, the second end connection guide shell 41 or water distributor 42, guide shell 41 of the diversion pipe 40 can be
It is horn-like, and its Open Side Down, to realize better water distribution, come into full contact with waste water with class fenton catalyst filler 30, contact
Time is as long as possible, reacts more abundant.When the second end of the diversion pipe 40 connects guide shell 41, the guide shell 41 goes out
Water end (W.E.) is also connected with water distributor 42, and guide shell 41 and water distributor 42 cooperate water distribution, further expand water distribution range, improve
Water distribution effect, that is, improve purifying water effect.Perforation water distributor can be used in the water distributor 42.
Preferably, perforated pipe of the water distributor 42 using UPVC material, is arranged in rice font, water distributor 42
Reflecting plate is arranged in lower part, to guarantee that water distribution is uniform.
Preferably, the fluidisation pond further includes self-cleaning component, which includes being set to the fluidisation pond
The sewage sump 23 on 21 top of ontology, one end is connected to the sewage sump 23 and the other end protrudes into 30 bottom of class fenton catalyst filler
The air lift central tube 24 in portion, the collision part 28 at 24 port of air lift central tube in the sewage sump 23, is connected to the dirt collection
The washer 25 of slot 23 and fluidisation pond ontology 21, and the compressed air inlet pipe 27 being connected to the air lift central tube 24；It is described
Sewage sump 23 is connected to sewage pipe 26.
The impingement area of the collision part 28 can be plane or curved surface, preferably spherical surface or class spherical surface, be set in air lift
24 upper opening of heart pipe is formed anti-when the mixture of gas and water and catalyst filling comes out from stripping tube with the collision of collision part 28
Penetrate, the separative efficiency of gas and water and catalyst on the one hand can be improved, when air capacity on the other hand can be prevented excessive catalyst with
Water flow is lost.
The washer 25 has the runner for being connected to the sewage sump 23 and fluidisation pond ontology 21, and the catalyst after cleaning is filled out
Material falls in this runner, while being driven in the wrong direction and cleaning up by the water opposite with catalyst falling direction, and the flowing of clear liquid is by fluidizing
Liquid level difference driving between pond ontology 21 and sewage sump 23.
The present invention also provides a kind of wastewater treatment methods of class Fenton fluidized bed as previously described, include the following steps：
Step 1.1, waste water is injected in medicine pond, acid is put into medicine pond, adjust PH to 5；
Step 1.2, oxidant is added into medicine pond according to waste strength, stirred evenly；
Step 1.3, waste water step 1.2 obtained imports fluidisation pond by diversion pipe, fills out waste water with class fenton catalyst
Material comes into full contact with, and the organic matter in class Fenton's reaction degrading waste water occurs；Effective packed height of class fenton catalyst filler is excellent
Select 2m, packing material size preferably 1~3mm.
Step 1.4, waste water flows from bottom to top in fluidisation pond, and the waste water after reaction is discharged by the effluent trough for fluidizing pond.
Preferably, the oxidant is hydrogen peroxide in step 1.2, mass concentration is 27~31%, the throwing of hydrogen peroxide
Dosage and waste water COD concentration to be processed are 3~6 in mass ratio：1 adds；After dosing, being stirred the time is 15~30min.Step
In rapid 1.3, the reaction time that class Fenton's reaction occurs is 2~3h, to react fully.
The present invention also provides a kind of method for self-cleaning of class Fenton fluidized bed as previously described, include the following steps：
Step 2.1, compressed air is sent in the air lift central tube into fluidized bed by compressed air inlet pipe, makes air lift
The three-phase admixture of " air-waste water-class fenton catalyst filler " is formed in central tube, air lift central tube is inside and outside to form density
Difference；
Step 2.2, fluid density is small in air lift central tube, and class fenton catalyst filler is in air lift central tube to upstream
Dynamic, mutual collision friction during rising, the passivating film formed when by catalytic oxidation is removed, and finally arrives at fluidisation
The sewage sump on pond top realizes air lift；
Step 2.3, the passivating film of removing is discharged by sewage pipe；Class fenton catalyst filler after removing passivating film is cleaning
It precipitates and falls in device, return fluidized bed ontology (returning reaction zone), so far, class fenton catalyst filler is complete inside fluidized bed
At a self-cleaning cycle process, entire cyclic process continues 4~6h.
The present invention also provides a type fenton catalyst fillers, are made by the following method：Active carbon powder is immersed
To nickel nitrate, cerous nitrate, lanthanum nitrate mixed solution in, then active carbon drained, is dried, press matter with iron powder, CuO powder later
Amount ratio is 1：2~3：2~3 mixing are homogeneous mixture through high-temperature fusion, then obtain particle by cooling crush, screening and urge
Agent.
Preferably, 1~3mm of the beaded catalyst partial size, hole holds 0.39~0.42ml/g, the ratio of catalyst granules
Surface area reaches 300m2/g.Catalyst granules intensity is greater than 120N/, wears away less than 0.2%, and bulk density 0.68~
0.75g/ml。
Embodiment 1：Advanced treating, secondary clarifier effluent COD are carried out to the biochemical treatment water outlet of certain printing and dyeing enterpriseCrConcentration
110mg/L, is respectively adopted Fenton oxidation method and herein described class Fenton fluidized bed is handled by 100 times of coloration, pH 7.2.
This strand of waste water is handled using Fenton oxidation method, waste water is promoted to Fenton oxidation device through pump, successively add the concentrated sulfuric acid,
Ferrous sulfate, hydrogen peroxide.Adjust PH to 4, the concentrated sulfuric acid dosage 5mg/L, ferrous sulfate (FeSO4·7H2O) dosage 120mg/
L, hydrogen peroxide (mass concentration 30%) dosage 220mg/L, air stirring reaction time 2h.After the reaction was completed, liquid alkaline is first added
(mass concentration 30%) adjusts pH to 8, then adds PAC, PAM and carry out coagulating sedimentation reaction.Liquid alkaline (mass concentration 30%) adds
Measure 130mg/L, PAC dosage 120mg/L, PAM dosage 2mg/L.Waste water after treatment, CODCrConcentration 56mg/L, color
10 times of degree, pH 7.3.Using about 0.96 yuan/ton of waste water of reagent cost of traditional Fenton oxidation technique, while the sludge quantity generated
About 0.17kg/ tons of waste water.
This strand of waste water is handled using the wastewater treatment method of the application class Fenton fluidized bed, waste water injects this through water inlet pipe 12
In the medicine pond 10 for applying for the class Fenton fluidized bed, and the concentrated sulfuric acid (98%) first being added to medicine pond 10 and adjusts PH to 5, the concentrated sulfuric acid is thrown
Dosage 1mg/L, then hydrogen peroxide is added, hydrogen peroxide concentration 30%, dosage 300mg/L.After waste water is mixed with hydrogen peroxide, from water conservancy diversion
Pipe 40 enters the guide shell 41 of fluidisation 20 lower part of pond or water distributor 42 realizes that water distribution, waste water are urged during rising with class Fenton
Agent filler comes into full contact with reaction, fluidizes catalyst filling in pond 20 and is dispersed with fluidizing state, and with the help of self-cleaning component
Formation circulates.Residence time of the waste water in fluidisation pond 20 is 2.5h, then from 22 row of effluent trough at 20 top of fluidisation pond
Out.Waste water after treatment, CODCrConcentration 65mg/L, 10 times of coloration, pH 6.9.The present apparatus is removing removal organic polluter
Meanwhile the coloration of waste water is effectively reduced, no sludge generates.About 0.55 yuan/ton of waste water of reagent cost of device processing.
By above-mentioned case as it can be seen that the removal efficiency of class Fenton fluidized bed is substantially close to traditional Fenton oxidation technique, but medicine
Agent expense is far below traditional Fenton oxidation technique, and generates without sludge.
Embodiment 2：Certain waste water processing station of viscose rayon manufacturing enterprise need to carry out proposing mark transformation, using the application class Fenton
The wastewater treatment method of fluidized bed carries out advanced treating to secondary clarifier effluent.Secondary clarifier effluent COD concentration 90mg/L, SS50mg/
L, pH 7.8.Waste water is injected through water inlet pipe 12 in the medicine pond 10 of herein described class Fenton fluidized bed, adjusts PH to 5, then add
Hydrogen peroxide, hydrogen peroxide concentration 30%, dosage 350mg/L.After waste water is mixed with hydrogen peroxide, enter fluidisation pond 20 from diversion pipe 40
The guide shell 41 or water distributor 42 of lower part realize that water distribution, waste water come into full contact with during rising with class fenton catalyst filler
Reaction fluidizes catalyst in pond 20 and fills out guide shell material to fluidize state dispersion, and forms recycle stream with the help of self-cleaning component
It is dynamic.Then waste water residence time 3.0h in fluidisation pond 20 is discharged from the effluent trough 22 at 20 top of fluidisation pond.After treatment
Waste water, CODCrConcentration 48mg/L, SS20mg/L, pH 7.2.Device is while removing removal organic polluter, to consolidating in waste water
Body suspended matter has carried out effective interception.
The above described specific embodiments of the present invention are not intended to limit the scope of the present invention..Any basis
Any other various changes and modifications that technical concept of the invention is made should be included in the guarantor of the claims in the present invention
It protects in range.
Claims (10)
1. a type Fenton fluidized bed, it is characterised in that including：
Medicine pond comprising medicine pond ontology is connected to the water inlet pipe of medicine pond ontology, and protrudes into the rabbling mechanism of medicine pond ontology；
Fluidize pond comprising fluidisation pond ontology, and the effluent trough set on fluidisation pond body upper part；
Class fenton catalyst filler is placed in the ontology of the fluidisation pond；And
Diversion pipe, first end are connected to medicine pond ontology, and the second end is connected to the fluidisation pond ontology and protrudes into the class
In fenton catalyst filler.
2. class Fenton fluidized bed according to claim 1, it is characterised in that：The rabbling mechanism is mechanical stirring or air
Stirring；The lower part of the fluidisation pond ontology is tapered.
3. class Fenton fluidized bed according to claim 1, it is characterised in that：The second end of the diversion pipe connects water conservancy diversion
Cylinder or water distributor；When the second end of the diversion pipe connects guide shell, the guide shell water outlet is also connected with water distributor.
4. class Fenton fluidized bed according to claim 3, it is characterised in that：The water distributor uses the perforation of UPVC material
Pipe arranges that reflecting plate is arranged in the lower part of water distributor in rice font.
5. class Fenton fluidized bed according to claim 1, it is characterised in that：The fluidisation pond further includes self-cleaning component,
The self-cleaning component includes the sewage sump set on the fluidisation pond body upper part, and one end is connected to the sewage sump and the other end protrudes into
The air lift central tube of the class fenton catalyst filler bottom, set on the collision in the sewage sump at the pipe port of air lift center
Part is connected to the sewage sump and fluidizes the washer of pond ontology, and the compressed air inlet pipe being connected to the air lift central tube；
The sewage sump is connected to sewage pipe.
6. a kind of wastewater treatment method of the class Fenton fluidized bed as described in any in claim 1~6, includes the following steps：
Step 1.1, waste water is injected in medicine pond, acid is put into medicine pond, adjust PH to 5；
Step 1.2, oxidant is added into medicine pond according to waste strength, stirred evenly；
Step 1.3, waste water step 1.2 obtained imports fluidisation pond by diversion pipe, fills waste water with class fenton catalyst filler
Tap touching, occurs the organic matter in class Fenton's reaction degrading waste water；
Step 1.4, waste water flows from bottom to top in fluidisation pond, and the waste water after reaction is discharged by the effluent trough for fluidizing pond.
7. wastewater treatment method according to claim 6, it is characterised in that：In step 1.2, the oxidant is dioxygen
Water, mass concentration are 27~31%, and the dosage of hydrogen peroxide and waste water COD concentration to be processed are 3~6 in mass ratio：1 adds；
In step 1.3, the reaction time that class Fenton's reaction occurs is 2~3h.
8. a kind of method for self-cleaning of class Fenton fluidized bed as claimed in claim 5, includes the following steps：
Step 2.1, compressed air is sent in the air lift central tube into fluidized bed by compressed air inlet pipe, makes air lift center
The three-phase admixture of " air-waste water-class fenton catalyst filler " is formed in pipe, air lift central tube is inside and outside to form density contrast；
Step 2.2, fluid density is small in air lift central tube, and class fenton catalyst filler flows up in air lift central tube, on
Mutual collision friction during rising, the passivating film formed when by catalytic oxidation are removed, and are finally arrived on fluidisation pond
The sewage sump in portion realizes air lift；
Step 2.3, the passivating film of removing is discharged by sewage pipe；Class fenton catalyst filler after removing passivating film is in washer
Precipitating falls, and returns to fluidized bed ontology, so far, class fenton catalyst filler completes a self-cleaning cycle mistake inside fluidized bed
Journey.
9. a type fenton catalyst filler, it is characterised in that be made by the following method：Active carbon powder is immersed in nitric acid
Nickel, cerous nitrate, lanthanum nitrate mixed solution in, then active carbon drained, is dried, later with iron powder, CuO powder example in mass ratio
It is 1：2~3：2~3 mixing are homogeneous mixture through high-temperature fusion, then obtain beaded catalyst by cooling crush, screening.
10. class fenton catalyst filler according to claim 9, it is characterised in that：The beaded catalyst partial size 1~
3mm, hole hold 0.39~0.42ml/g, and the specific surface area of catalyst granules reaches 300m2/g.Catalyst granules intensity is greater than
It 120N/, wears away less than 0.2%, 0.68~0.75g/ml of bulk density.
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