CN103663869A - Device and method for treating high density organic waste water by multiphase photocatalysis combined film bioreactor - Google Patents
Device and method for treating high density organic waste water by multiphase photocatalysis combined film bioreactor Download PDFInfo
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Abstract
A device for treating high density organic waste water by a multiphase photocatalysis combined film bioreactor, comprises a filter, a primary photocatalyst reactor, a secondary photocatalyst reactor, an acidifying hydrolysis pool, and a film bioreactor; wherein a pipeline is communicated among the filter, the primary photocatalyst reactor, the secondary photocatalyst reactor, the acidifying hydrolysis pool, and the film bioreactor. High density organic matters, under action of ultraviolet light and a catalyst, can be rapidly degraded to be innocuous and unpoisonous small molecules such as CO2, H2O, etc. The device and the method have advantages of: (1) fast catalytic reaction speed, stay time of organic sewage in a photocatalytic reactor can be controlled in 4h; (2) non-selectivity degradation: comprising difficultly-degraded organic matters like chlorinated organic compounds and polycyclic aromatic hydrocarbons; (3) no secondary pollution: the organic matters are thoroughly differentiated and degraded to be harmless substances such as CO2, H2O, etc.; (4) wide application range: the device and the method can almost be applied on all organic sewage, such as papermaking waste water, printing waste water, pesticide waste water, etc., and (5) combination with an MBR film bioreactor technology, small system equipment investment and low operation cost.
Description
Technical field
The present invention relates to technical field of waste water processing, specifically a kind of apparatus and method of multiphase photocatalysis binding film bioreactor for treatment high concentrated organic wastewater.
Background technology
Chemical industry, medicine, in the organic amine liquid waste water producing in the commercial runs such as liquid crystal, contain a large amount of methylamines, methyl alcohol, epoxy chloropropane, toluene, phenol, sodium carbonate, the tens of kinds of organism such as sodium methylate and salt. such high concentrated organic wastewater is the hard nut to crack of water treatment field all the time. water treatment worker is through exploring for many years, the current aeration stripping that mainly contains in industrial utilization, distillation and pretreatment process. although aeration stripping method can effectively be removed COD, but can cause the secondary pollution of environment, briefly, that poisonous and hazardous organism is transferred in atmosphere from water, do not tackle the problem at its root, although rectification method has been avoided the secondary pollution of environment, but a kind of pretreatment process of highly energy-consuming, the height of working cost, causes a lot of manufacturing enterprises to be hung back. TiO in the process of discovery in 1972 at brine electrolysis
2since electrode has photosensitization, TiO
2semi-conductor just receives people's concern and is used widely, and 1976, CAREY etc. found under uviolizing, nano-TiO
2can make the dechlorination of biodegradable organic compounds polychlorobiphenyl, start the new page of semiconductor nano material catalyzed degradation application.
Summary of the invention
The object of the invention is to make full use of TiO
2the principle of photocatalytic degradation, developed the treatment process of utilizing photo catalysis reactor binding film bio-reactor, range of application is for processing organic wastewater with difficult degradation thereby, COD content can be up to 10000-50000mg/L, component can reach tens of kinds, as contained tetrahydrofuran (THF), ethanol, triphenyl phosphorus, the trimethyl carbinol, methylene dichloride, toluene, Isosorbide-5-Nitrae Resorcinol, sherwood oil, methyl and butyl ether, sodium carbonate etc. simultaneously.Effectively solved the processing problem of high density organic amine waste water, both non-secondary pollution, had reduced again the high problem of such cost for wastewater treatment of tradition widely.
The present invention is a kind of device of multiphase photocatalysis binding film bioreactor for treatment high concentrated organic wastewater, comprising: strainer, one-level photocatalyst reactor, secondary light hydrogen-catalyst reactor, acidizing hydrolyzation tank, membrane bioreactor; Between above-mentioned device, pond, use pipeline communication.
Described strainer, comprising: filter body, is provided with flocculation agent grug feeding jar A, mixing tank B, precipitate and separate tank C, filter canister D in filter body.Aforesaid device connects with pipeline successively, and forms a sled block structure.In its middle filtrator, inner member is a kind of in activated carbon or quartz sand or ceramic element.
Described one-level photocatalyst reactor, comprising: reactor body E1, is provided with dividing plate G1, TiO2 carrier of photocatalyst F1, ultraviolet source H1 in reactor body.Its median septum adopts baffle plate type, and traverse baffle form is rectangle, circle, arc; Preferred rectangle.Carrier of photocatalyst form is structured packing, dumped packing, board-like; Preferred dumped packing.Filler material material is SiO
2glass, 304L stainless steel plate, 316L stainless steel, pottery, silicon carbide, tetrafluoroethylene.
Described secondary light hydrogen-catalyst reactor, comprising: reactor body E2, is provided with dividing plate G2, TiO2 carrier of photocatalyst F2, ultraviolet source H2 in reactor body E2.Its median septum adopts baffle plate type, and traverse baffle form is rectangle, circle, arc; Preferred rectangle.Carrier of photocatalyst form is structured packing, dumped packing, board-like; Preferred dumped packing.Filler material material is SiO
2glass, 304L stainless steel plate, 316L stainless steel, pottery, silicon carbide, tetrafluoroethylene.
Described acidizing hydrolyzation tank, comprising: acidizing hydrolyzation tank body Q(pond body is concrete structure), in acidizing hydrolyzation tank body, be provided with partition wall S and partition wall T.1. acidizing hydrolyzation tank is decomposed into district, 2. district, 3. district by partition wall.1. district is inhalant region, is inside provided with a plurality of water stream thruster R.2. district is acidication district.3. district is exhalant region, will process water extract out by pump.1. district, 2. district, 3. district is connected with hole W by the hole U of partition wall lower curtate.
Described membrane bioreactor, comprising: reactor body O, is provided with membrane module I and K, aeration fluidic device L and M in reactor body.Wherein membrane module is submerged hollow fiber, the preferred PVDF of material or PP, and aperture is 0.04～0.2um preferably.Membrane bioreactor is MBR, and pattern can be in overall skid-mounted or pond and installs, can in parallel or series connection.
The method of a kind of multiphase photocatalysis binding film of the present invention bioreactor for treatment high concentrated organic wastewater, its step is as follows:
(1) high concentrated organic wastewater enters into effective integrated strainer after pre-treatment, and organic waste water is removed after turbidity through effective integrated strainer sled block structure, through volume pump, delivers in one-level photocatalyst reactor.In Integral filter sled block structure, pretreated organic waste water fully mixes in mixing tank with the water flocculation agent from flocculation agent tank, and after the separation of precipitate and separate tank, enters into filter canister, and after filtering, delivery turbidity is less than 1NTU;
(2) in one-level photocatalyst reactor, at catalyzer, oxygenant H
2o
2and under ultraviolet effect, most carbonaceous organic materials is decomposed into CO
2and H
2o, waste water COD is significantly reduced, and biodegradability significantly strengthens, wherein oxygenant H
2o
2add-on be 10～20kg/t water;
(3) after one-level photo catalysis reactor, the waste water after processing is further delivered in secondary light oxidation reactor, and under the compound action of ultraviolet ray and catalyzer, the organism decomposing not yet is completely at oxygenant H
2o
2effect under almost all degraded, oxygenant H wherein
2o
2add-on be 10～20kg/t water.Note: photo catalysis reactor one-level is the same with secondary, is series connection;
(4) waste water after degraded can reach the requirement of biochemical treatment substantially.Waste water from secondary light oxidation catalysis reactor enters the further acidifying of acidizing hydrolyzation tank, and in pond, acidication bacterium utilizes the H of H2O ionization
+and OH
-c-C key in organism is opened, and one end adds H
+, one end adds OH
-thereby, long-chain is hydrolyzed to short chain, improve the biodegradability of sewage, be more conducive to biochemical treatment;
(5) waste water from acidizing hydrolyzation tank enters into membrane bioreactor, microbial film is to improving containing dirt water, realize mud-water separation, utilize film to high-performance bio bacterium as the crown_interception of nitrifier, microorganism is trapped in biofilm reactor, thereby the degree of depth of organism nitrogen is removed in assurance sewage, and reach emission standard and enter and produce pond;
(6) wastewater biochemical is processed and is reached drainage requirement and is discharged in product pond, and producing pond has water containing pool.Pool inner water reaches certain liquid level, just to the external world, discharges.
Described photocatalyst adopts TiO
2and TiO
2hotchpotch.
Described TiO
2hotchpotch choose Pt, Ag, B; TiO
2with the proportioning of Pt, Ag, B be: 99:1～98:2(mass ratio).
Carrier of photocatalyst Material texture is SiO
2glass, 304L stainless steel, 316L stainless steel, pottery, silicon carbide, tetrafluoroethylene.
In photo catalysis reactor, inducing light source is UV-light, the preferred 387.5nm of ultraviolet light wavelength.
The advantage of the apparatus and method of a kind of multiphase photocatalysis binding film of the present invention bioreactor for treatment high concentrated organic wastewater is: 1. catalytic is fast; Organic sewage residence time in photo catalysis reactor can be controlled in 4h; 2. the non-selectivity of degrading, comprises the hardly degraded organic substances such as chlorinatedorganic, polycyclic aromatic hydrocarbons; 3. non-secondary pollution, organism is thoroughly degraded to CO by differentiation
2and H
2the innoxious substances such as O; 4. applied range, nearly all organic sewage can adopt, as paper waste, printing wastewater, agricultural chemicals waste water etc.; 5. combine with MBR membrane Bio-reactor Technology, system device investment is little, and running cost is low.
Accompanying drawing explanation
Fig. 1 is process flow diagram;
Fig. 2 is the structural representation of strainer;
Fig. 3 is one-level photocatalyst reactor schematic diagram;
Fig. 4 is secondary light hydrogen-catalyst reactor schematic diagram;
Fig. 5 is acidizing hydrolyzation tank schematic diagram;
Fig. 6 is membrane bioreactor schematic diagram.
In Fig. 6, N is inspection window, and P is aeration spout.
Embodiment
Shown in root Ju Fig. 1-Fig. 6, a kind of device of multiphase photocatalysis binding film bioreactor for treatment high concentrated organic wastewater, comprising: strainer, one-level photocatalyst reactor, secondary light hydrogen-catalyst reactor, acidizing hydrolyzation tank, membrane bioreactor; Between above-mentioned device, pond, use pipeline communication.
Described strainer, comprising: filter body.In filter body, be provided with flocculation agent grug feeding jar A, mixing tank B, precipitate and separate tank C, filter canister D.Aforesaid device connects with pipeline successively, and forms a sled block structure.In its middle filtrator, inner member is a kind of in activated carbon or quartz sand or ceramic element.
Described one-level photocatalyst reactor, comprising: reactor body E1, is provided with dividing plate G1, TiO2 carrier of photocatalyst F1, ultraviolet source H1 in reactor body.Its median septum adopts baffle plate type, and traverse baffle form is rectangle, circle, arc; Preferred rectangle.Carrier of photocatalyst form is structured packing, dumped packing, board-like; Preferred dumped packing.Filler material material is SiO
2glass, 304L stainless steel plate, 316L stainless steel, pottery, silicon carbide, tetrafluoroethylene.
Described secondary light hydrogen-catalyst reactor, comprising: reactor body E2, is provided with dividing plate G2, TiO2 carrier of photocatalyst F2, ultraviolet source H2 in reactor body.Its median septum adopts baffle plate type, and traverse baffle form is rectangle, circle, arc; Preferred rectangle.Carrier of photocatalyst form is structured packing, dumped packing, board-like; Preferred dumped packing.Filler material material is SiO
2glass, 304L stainless steel plate, 316L stainless steel, pottery, silicon carbide, tetrafluoroethylene.
Described acidizing hydrolyzation tank, comprising: acidizing hydrolyzation tank body Q, pond body is concrete structure, is provided with partition wall S and T in acidizing hydrolyzation tank body.1. acidizing hydrolyzation tank is decomposed into district, 2. district, 3. district by partition wall.1. district is inhalant region, is inside provided with a plurality of water stream thruster R.2. district is acidication district.3. district is exhalant region, will process water extract out by pump.1. district, 2. district, 3. district is connected with W by the hole U of partition wall lower curtate.
Described membrane bioreactor, comprising: reactor body O, is provided with membrane module I and K, aeration is penetrated dispensing device L and M in reactor body.Wherein membrane module is submerged hollow fiber, the preferred PVDF of material or PP, and aperture is 0.04～0.2um preferably.Membrane bioreactor is MBR, and pattern can be in overall skid-mounted or pond and installs, can in parallel or series connection.
The method of a kind of multiphase photocatalysis binding film of the present invention bioreactor for treatment high concentrated organic wastewater, its step is as follows:
(1) high concentrated organic wastewater enters into effective integrated strainer after pre-treatment, and organic waste water is removed after turbidity through effective integrated strainer sled block structure, through volume pump, delivers in one-level photocatalyst reactor.In Integral filter sled block structure, pretreated organic waste water fully mixes in mixing tank with the water flocculation agent from flocculation agent tank, and after the separation of precipitate and separate tank, enters into filter canister, and after filtering, delivery turbidity is less than 1NTU;
(2) in one-level photocatalyst reactor, at catalyzer, oxygenant H
2o
2and under ultraviolet effect, most carbonaceous organic materials is decomposed into CO
2and H
2o, waste water COD is significantly reduced, and biodegradability significantly strengthens, wherein oxygenant H
2o
2add-on be 10～20kg/t water;
(3) after one-level photo catalysis reactor, the waste water after processing is further delivered in secondary light oxidation reactor, and under the compound action of ultraviolet ray and catalyzer, the organism decomposing not yet is completely at oxygenant H
2o
2effect under almost all degraded, oxygenant H wherein
2o
2add-on be 10～20kg/t water.Note: photo catalysis reactor one-level is the same with secondary, is series connection;
(4) waste water after degraded can reach the requirement of biochemical treatment substantially.Waste water from secondary light oxidation catalysis reactor enters the further acidifying of acidizing hydrolyzation tank, and in pond, acidication bacterium utilizes the H of H2O ionization
+and OH
-c-C key in organism is opened, and one end adds H
+, one end adds OH
-thereby, long-chain is hydrolyzed to short chain, improve the biodegradability of sewage, be more conducive to biochemical treatment;
(5) waste water from acidizing hydrolyzation tank enters into membrane bioreactor, microbial film is to improving containing dirt water, realize mud-water separation, utilize film to high-performance bio bacterium as the crown_interception of nitrifier, microorganism is trapped in biofilm reactor, thereby the degree of depth of organism nitrogen is removed in assurance sewage, and reach emission standard and enter and produce pond;
(6) wastewater biochemical is processed and is reached drainage requirement and is discharged in product pond, and producing pond has water containing pool.Pool inner water reaches certain liquid level, just to the external world, discharges.
Be below specific embodiments of the invention, technical scheme of the present invention is further described, but protection scope of the present invention is not limited to these embodiment.Every do not deviate from the change of the present invention design or be equal to substitute include within protection scope of the present invention.
The know-why that the present invention processes waste water is: TiO
2hotchpotch (Pt is 1%) under the condition that is having ultraviolet light (wavelength n=387.5nm) to participate in, and between hardly degraded organic substance, can there is a kind of chemical reaction and redox processes in oxygenant H2O2 and sewage.Through a series of reaction, the various free radicals with strong oxidation or reducing power have been produced.The activity of these particles is high, to reactant non-selectivity almost, can destroy organic C-C, C-N, and C-H, C-O, N-H and O-H key, thereby can be oxidized and TiO
2a lot of organic mediums of particle contact, finally reduce to CO by it
2and H
2the innoxious substances such as O.
Embodiment
Certain Liquid crystal production waste water, contains the gas chromatography molecules such as tetrahydrofuran (THF), ethanol, ethylene dichloride, sherwood oil, Glacial acetic acid in water.Molecular structure is comparatively stable, belongs to a kind of high concentrated organic wastewater of difficult degradation, and water quality and quantity is as follows:
The factory effluent water yield: 40m
3/ h.
Waste water quality: COD=10000mg/L, BOD
5 =3000mg/L, PH=6～8, main organic content mark (quality): tetrahydrofuran (THF) 6.67%, ethanol 1.21%, methylene dichloride 0.09%, sherwood oil 0.02%, Isosorbide-5-Nitrae Resorcinol 0.01% etc.
After above-mentioned waste water regulates by equalization basin, with being pumped into integrated high-efficiency strainer, remove turbidity, then deliver in one-level photocatalyst reactor by volume pump, add H
2o
2400kg/h, under the effect of TIO2 catalyzer (containing Pt1%) and ultraviolet ray (wavelength is 387.5nm), 84% carbonaceous organic material is decomposed into CO
2and H
2o, waste water COD is significantly reduced, and biodegradability significantly strengthens, and after one-level photo catalysis reactor, the waste water after processing is further delivered in secondary light oxidation reactor, adds H
2o
2200kg/h, under the compound action of TIO2 catalyzer (containing Pt1%) and ultraviolet ray (wavelength is 387.5nm), remaining 14.5% still undecomposed organism degraded.Waste water energy after degraded reaches the requirement of biochemical treatment.Waste water from secondary light oxidation catalysis reactor enters the further acidifying of hydrolysis acidification pool, remaining 1.5% organism is all degraded, waste water from acidizing hydrolyzation tank enters into membrane bioreactor, take under the biological bacteria effect that film is carrier, and wastewater biochemical is processed and reached drainage requirement.
After processing by said apparatus and method, by for some time average sample assay, discharge water quality is: COD=386mg/L, BOD5=279mg/L, ss=300mg/L, petroleum-type=15 mg/L, pH=7.8.
Claims (9)
1. a device for multiphase photocatalysis binding film bioreactor for treatment high concentrated organic wastewater, is characterized in that: comprising: strainer, one-level photocatalyst reactor, secondary light hydrogen-catalyst reactor, acidizing hydrolyzation tank, membrane bioreactor; Between above-mentioned device, pond, use pipeline communication.
2. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, it is characterized in that: described strainer, comprise: filter body, is provided with flocculation agent grug feeding jar A, mixing tank B, precipitate and separate tank C, filter canister D in filter body; Aforesaid device connects with pipeline successively, and forms a sled block structure; In its middle filtrator, inner member is a kind of in activated carbon or quartz sand or ceramic element.
3. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, it is characterized in that: described one-level photocatalyst reactor, comprise: reactor body E1, in reactor body, be provided with dividing plate G1, TiO2 carrier of photocatalyst F1, ultraviolet source H1 and reactor upper space J1, TiO2 carrier of photocatalyst is housed in reactor body, these support of the catalyst separate with dividing plate, form a kind of baffling structure; In reactor head, a plurality of ultraviolet lamps are housed, separately also have a gas collection cavity J1.
4. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, it is characterized in that: described secondary light hydrogen-catalyst reactor, comprise: reactor body E2, in reactor body, be provided with dividing plate G2, TiO2 carrier of photocatalyst F2, ultraviolet source H2 and reactor upper space J2, TiO2 carrier of photocatalyst is housed in reactor body, these support of the catalyst separate with dividing plate, form a kind of baffling structure; In reactor head, a plurality of ultraviolet lamps are housed, separately also have a gas collection cavity J2.
5. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, it is characterized in that: described acidizing hydrolyzation tank Q, comprise: acidizing hydrolyzation tank body Q, pond body is concrete structure, in acidizing hydrolyzation tank body, be provided with partition wall S and partition wall T, 1. acidizing hydrolyzation tank is decomposed into district, 2. district, 3. district by partition wall S, T; 1. district is inhalant region, is inside provided with a plurality of water stream thruster R; 2. district is acidication district; 3. district is exhalant region, will process water extract out by pump; 1. district, 2. district, 3. district is connected with hole W by the hole U of partition wall bottom, 1. district, 2. district, 3. district is separated by partition wall S and partition wall T in order.
6. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, it is characterized in that: described membrane bioreactor, comprise: reactor body O, is provided with in reactor body that membrane module 1I and membrane module 2K, aeration are penetrated dispensing device 1L and aeration is penetrated dispensing device 2M; Wherein membrane module 1 and membrane module 2 are submerged hollow fiber, the preferred PVDF of material or PP, and aperture is 0.04～0.2um preferably, and membrane bioreactor is MBR, and pattern can be in overall skid-mounted or pond and installs, can in parallel or series connection.
7. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, is characterized in that: described dividing plate adopts baffle plate type, and traverse baffle form is rectangle, circle, arc; Preferred rectangle.
8. the device of Ju multiphase photocatalysis binding film claimed in claim 1 bioreactor for treatment high concentrated organic wastewater, is characterized in that described carrier of photocatalyst form is structured packing, dumped packing, board-like, preferably dumped packing; Filler material material is SiO
2glass, 304L stainless steel plate, 316L stainless steel, pottery, silicon carbide, tetrafluoroethylene.
9. a method for multiphase photocatalysis binding film bioreactor for treatment high concentrated organic wastewater, is characterized in that: its step is as follows:
(1) high concentrated organic wastewater enters into effective integrated strainer after pre-treatment, organic waste water is removed after turbidity through effective integrated strainer sled block structure, through volume pump, deliver in one-level photocatalyst reactor, in Integral filter sled block structure, pretreated organic waste water fully mixes in mixing tank B with the water flocculation agent from flocculation agent tank A, and after precipitate and separate tank C separation, enter into filter canister D, after filtering, delivery turbidity is less than 1NTU;
(2) in one-level photocatalyst reactor, at catalyzer, oxygenant H
2o
2and under ultraviolet effect,
Most carbonaceous organic materials is decomposed into CO
2and H
2o, waste water COD is significantly reduced, and biodegradability significantly strengthens, wherein oxygenant H
2o
2add-on be 10～20kg/t water;
(3), after one-level photo catalysis reactor, the waste water after processing is further delivered to secondary light oxidation reactor
In, under the compound action of ultraviolet ray and catalyzer, the organism decomposing not yet is completely at oxygenant H
2o
2effect under almost all degraded, oxygenant H wherein
2o
2add-on be 10～20kg/t water;
(4) waste water after degraded can reach the requirement of biochemical treatment substantially, from secondary light oxidation catalysis reactor
Waste water enter the further acidifying of acidizing hydrolyzation tank, in pond, acidication bacterium utilizes the H of H2O ionization
+and OH
-c-C key in organism is opened, and one end adds H
+, one end adds OH
-thereby, long-chain is hydrolyzed to short chain, improve the biodegradability of sewage, be more conducive to biochemical treatment;
(5) waste water from acidizing hydrolyzation tank enters into membrane bioreactor, and microbial film is to carrying out containing dirt water
Improve, realize mud-water separation, utilize film to high-performance bio bacterium as the crown_interception of nitrifier, microorganism is trapped in biofilm reactor, thereby guarantees that the degree of depth of organism nitrogen in sewage removes, and reach emission standard and enter and produce pond;
(6) wastewater biochemical is processed and is reached drainage requirement and is discharged in product pond, and producing pond has water containing pool,
Pool inner water reaches certain liquid level, just to the external world, discharges.
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