CN109867418A - A kind of method for innocent treatment of the industrial wastewater containing brominated bisphenol-A - Google Patents
A kind of method for innocent treatment of the industrial wastewater containing brominated bisphenol-A Download PDFInfo
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- CN109867418A CN109867418A CN201910292000.6A CN201910292000A CN109867418A CN 109867418 A CN109867418 A CN 109867418A CN 201910292000 A CN201910292000 A CN 201910292000A CN 109867418 A CN109867418 A CN 109867418A
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- brominated bisphenol
- bisphenol
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Abstract
The invention discloses a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A, its main feature is that, first will in waste water brominated bisphenol-A pollutant carry out reduction-debromination processing, then debrominate waste water using candida tropicalis (Candida tropicalis CGMCC-6684) and bacillus subtilis (Bacillus subtilis subsp.Subtilis, CGMCC 1.3358) combines aerobic fermentation, and the waste water harmless treatment can be realized；This method is that microorganism aerobic fermentation in combining is connected by reduction-debromination to handle brominated bisphenol-A industrial wastewater, can efficiently, to fast implement brominated bisphenol-A pollutant in waste water degradable, entire treatment process simple process, will not generate new hazardous contaminant matter again.
Description
Technical field:
The present invention relates to industrial waste water treatment, specifically a kind of industrial wastewater containing brominated bisphenol-A it is innoxious
Processing method, i.e., by catalysis reduction-debromination connect microorganism aerobic fermentation realize waste water in brominated bisphenol-A pollutant it is harmless
Change processing method.
Background technique:
Tetrabromobisphenol A is a kind of most common bromide fire retardant as industrial chemical and is widely used in plastics, building materials, electronics
Etc. industries, it is annual to produce hundreds of thousands ton.It has recently been found that tetrabromobisphenol A is a kind of potential incretion interferent, oestrogen-like hormone,
The endocrine system of humans and animals can be made unbalance and lead to anomalous effect；Meanwhile this pollutant is likely to cause humans and animals
Reproductive organs obstacle, directly influence the procreation and existence of the mankind.At present in atmosphere, water body, soil, organism and human body
Have detected that the presence of tetrabromobisphenol A.
In tetrabromobisphenol A production process, multiply waste water is generated, waste water contains chlorobenzene, tetrabromobisphenol A, tribromo bis-phenol
The halogenated organics pollutant such as A and bisphenol-A, concentration are relatively high.The halogenated organics such as chlorobenzene, tetrabromobisphenol A as contained by waste water are dirty
It is big to contaminate object bio-toxicity, inhibiting effect is generated to biology, therefore biodegradability is poor, it is difficult to directly progress biochemical treatment.Therefore, it needs
Tetrabromobisphenol A waste water joint disposal technology is developed, realizes that it is effectively treated.Chinese patent CN201310441701.4 is reported
Tetrabromobisphenol A waste water is realized in the technical tie-ups such as physics Multistage settling coagulation and recovery, desalination, ozone high grade oxidation and biochemical treatment
Processing；Liu Li equality (" salt industry and chemical industry ", 2015) also reports flash process and effectively removes and recycle tetrabromobisphenol A waste water
In chlorobenzene method.For the phenolic comp ' ds pollutions such as tetrabromobisphenol A, tribromo bisphenol-A, tribromphenol and bisphenol-A in waste water,
Boiling point is high, and volatility is poor, and flash process is difficult to evaporate recycling, mainly passes through two in Chinese patent CN201310441701.4
Grade, burning disposal again after three-level flocculation sedimentation.For the phenolic comp ' ds pollutions such as tetrabromobisphenol A, tribromo bisphenol-A and bisphenol-A, high temperature
The energy consumption of the processing modes such as burning is high, needs to consume a large amount of fuel, while not exclusively burning in treatment process and being easy to cause toxicity more
The generation of strong by-product dioxin.Therefore, contain tetrabromobisphenol A, tribromo bisphenol-A and bis-phenol for chlorobenzene has been removed
The waste water of the phenolic comp ' ds pollutions such as A needs to develop more environmentally friendly, more green disposal technology.
For the brominated bisphenol-As class such as tetrabromobisphenol A, why being difficult to the major reason of biochemical treatment is because of bromo element
Presence result in its have compared with high toxicity and stability, so being difficult to biochemical treatment and oxidation processes；And as tetrabromobisphenol A
Complete its biochemical treatment of debrominate product bisphenol-A and oxidation processes just significantly increase.It is therefore possible to use reduction-debromination is first by tetrabromo
The brominated bisphenol-As pollutant such as bisphenol-A is converted to phenols, is then further carried out the processing such as biochemical or oxidation, to realize four
The harmless treatment of bromine bisphenol-A waste water.For example, Wu Yunxiao et al. [CN106944054A] based on the reducing power of Zero-valent Iron with
And the oxidability of potentiometric titrations, a kind of Zero-valent Iron pillared montmorillonite composite material is prepared, is activated as effective catalyst
Peroxy-monosulfate generates potentiometric titrations, realizes the organic contaminations difficult to degrade such as synchronous redox Combined Treatment tetrabromobisphenol A
The purpose of object.
Summary of the invention:
The purpose of the present invention is overcoming the shortcomings of above-mentioned prior art, and provide a kind of the harmless of the industrial wastewater containing brominated bisphenol-A
Change processing method；Mainly solve tetrabromobisphenol A production process in the flocculation treatment of industrial wastewater containing brominated bisphenol-A be not thorough, efficiency
Low and subsequent burning disposal leads to the problem of toxic dioxin by-product；Reduction-debromination-microbiological treatment, solution are used simultaneously
It needs to add persulfate during patent of having determined CN106944054A redox Combined Treatment tetrabromobisphenol A and generate big
The problem of measuring the industrial waste salts such as sulfate.
The technical scheme is that a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A, special character
It is, includes the following steps: to be used as joint reduction catalysts system first with iron powder and Pd/C, in 0.1~1.0MPa of pressure, temperature
Under the conditions of 30~80 DEG C of degree, stirring rate are 50~800 turns/min, to the reduction-debromination of industrial wastewater containing brominated bisphenol-A processing 0.5
~3h；Then debrominate waste liquid is filtered and import containing Candida tropicalis (Candida tropicalis CGMCC-6684)
It is aerobic with the fermentor joint of bacillus subtilis (Bacillus subtilis subsp. Subtilis, CGMCC-3358)
Fermented and cultured, 20~50 DEG C of fermentation temperature, stirring rate 10-120 turns/min, aeration rate 0.2L~2.0L/min, when fermentation
Between 4~for 24 hours, realize waste water in brominated bisphenol-A pollutant thorough degradation.
Further, the brominated bisphenol-A pollutant in the waste water mainly include tetrabromobisphenol A, it is tribromo bisphenol-A, double
Phenol A.
Further, the iron powder and wastewater quality ratio are 1:1000~1:100, the Pd/C and wastewater quality ratio
For 1:10000~1:1000.
Further, which is characterized in that Pd content is 0.05%~0.5% in the Pd/C catalysis material, particle size range 3
~15 mesh.
Further, the composition mass parts ratio of the Candida tropicalis and bacillus subtilis is 4:1~1:
2。
The present invention establishes catalysis reduction-debromination series connection microorganism aerobic fermentation harmless treatment Industry Waste containing brominated bisphenol-A
Method in water can efficiently realize that the reduction-debromination of the brominated bisphenol-As pollutant such as tetrabromobisphenol A in waste water, Pd/C are catalyzed material
Material can recycling and reusing, while the phenols such as debrominate product bisphenol-A can be joined by Candida tropicalis and bacillus subtilis
It closes and decomposes, be converted into carbon dioxide and water, so that it is double to realize the toxic bromo such as tetrabromobisphenol A in tetrabromobisphenol A production waste water
The degradable and harmless treatment of phenol A pollutant.
Compared with the prior art a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A of the invention has protrusion
Substantive distinguishing features and marked improvement, 1, compared with the electronations such as traditional Fe, Zn, the addition of Pd/C catalysis material of the present invention
Can complete catalysis reduction-debromination that is more efficient, fast implementing brominated bisphenol-A pollutant in waste water, shorten processing the time, together
When Pd/C catalysis material is recyclable and recycling；2, compared with the processing methods such as burning, oxidation, catalysis reduction of the invention is de-
The degradation of bisphenol-A in waste water may be implemented in bromine series connection microbial fermentation facture, is converted to harmless carbon dioxide and water, handles
Process will not generate high toxicity dioxin pollution object；3, entire treatment process simple process, will not generate again new toxic has
Evil polluter, can especially provide effectively for the processing of the waste water containing tetrabromobisphenol A generated in tetrabromobisphenol A industrial processes
Method.
Specific embodiment:
The following examples are further illustrations of the invention, however, the present invention is not limited thereto.
It is used as joint reduction catalysts system first with iron powder and Pd/C, in 0.1~1.0 MPa of pressure, temperature 30~80
DEG C, stirring rate be 50~800 turns/min under the conditions of, to the reduction-debromination of industrial wastewater containing brominated bisphenol-A processing 0.5~3h；So
Debrominate waste liquid is filtered afterwards and import containing Candida tropicalis (Candida tropicalis ) and withered grass CGMCC-6684
The fermentor joint aerobic fermentation training of bacillus (Bacillus subtilis subsp. Subtilis, CGMCC-3358)
It supports, 20~50 DEG C of fermentation temperature, stirring rate 10-120 turns/min, aeration rate 0.2L~2.0L/min, fermentation time 4~
For 24 hours, the thorough degradation of brominated bisphenol-A pollutant in waste water can be realized.
1L waste water containing brominated bisphenol-A is added to the reaction kettle of 2L by embodiment 1, is added and 1g iron powder and 0.1g is then added
3 mesh of 0.05%Pd/C(partial size), reaction pressure 1Mpa, reaction temperature is 80 DEG C, and stirring rate is 50 turns/min, reacts 3h；So
Afterwards by debrominate waste water be added to containing 4 parts of Candida tropicalis (Candida tropicalis CGMCC-6684) and 1 part withered
The fermentor of careless bacillus (Bacillus subtilis subsp. Subtilis, CGMCC-3358) combines aerobic fermentation
Culture, 20 DEG C of fermentation temperature, stirring rate 120 turns/min, aeration rate 0.2L/min, fermentation time for 24 hours, debrominate product bis-phenol
A is degraded completely.
1L waste water containing brominated bisphenol-A is added to the reaction kettle of 2L by embodiment 2, and 10g iron powder and 1g 0.5% is then added
5 mesh of Pd/C(partial size) catalysis material, reaction pressure 0.5Mpa, reaction temperature is 60 DEG C, and stirring rate is 800 turns/min, instead
Answer 0.5h, the conversion bisphenol-A completely such as brominated bisphenol-A；Then debrominate waste water is added to containing 4 parts of Candida tropicalis
(Candida tropicalis ) and 2 parts of bacillus subtilis (Bacillus subtilis subsp. CGMCC-6684
Subtilis, CGMCC-3358) fermentor combine aerobic fermentation culture, 35 DEG C of fermentation temperature, 10 turns/min of stirring rate, expose
Gas velocity rate 2.0L/min, fermentation time 4h, bisphenol-A is degraded completely in waste water.
1L waste water containing brominated bisphenol-A is added to the reaction kettle of 2L by embodiment 3, and 5g iron powder, 0.5g 0.1% is then added
15 mesh of Pd/C(partial size), reaction pressure 0.1Mpa, reaction temperature is 30 DEG C, and stirring rate is 300 turns/min, reacts 2h, bromine
For the conversion bisphenol-A completely such as bisphenol-A；Then by debrominate waste water be added to containing 2 parts of Candida tropicalis (Candida tropicalis CGMCC-6684) and 4 parts of bacillus subtilises (Bacillus subtilis subsp. Subtilis,
CGMCC-3358 fermentor joint aerobic fermentation culture), 50 DEG C of fermentation temperature, 30 turns/min of stirring rate, aeration rate
1.0L/min, fermentation time 16h, bisphenol-A is degraded completely in waste water.
1L waste water containing tetrabromobisphenol A is added to the reaction kettle of 2 L by embodiment 4, and 7g iron powder, 1.0g is then added
8 mesh of 0.3%Pd/C(partial size), reaction pressure 0.5Mpa, reaction temperature is 60 DEG C, and stirring rate is 300 turns/min, 1h is reacted,
The pollutants such as brominated bisphenol-A just can be completely achieved debrominate；Then debrominate waste water is added to containing 4 parts of Candida tropicalis
(Candida tropicalis ) and 2 parts of bacillus subtilis (Bacillus subtilis subsp. CGMCC-6684
Subtilis, CGMCC-3358) fermentor combine aerobic fermentation culture, 45 DEG C of fermentation temperature, 20 turns/min of stirring rate, expose
Gas velocity rate 1.5L/min, fermentation time 8h, the bisphenol-A class after debrominate achieve that degradable.
1L waste water containing tetrabromobisphenol A is added to the reaction kettle of 2L, then compared with above-described embodiment 1-4 by comparative example 1
10g iron powder, reaction pressure 1.0Mpa is added, reaction temperature is 60 DEG C, and stirring rate is 300 turns/min, reacts 10h, only
60% brominated bisphenol-A can realize debrominate；Then by debrominate waste water be added to containing 4 parts of Candida tropicalis (Candida tropicalis CGMCC-6684) and 2 parts of bacillus subtilises (Bacillus subtilis subsp. Subtilis,
CGMCC-3358 fermentor joint aerobic fermentation culture), 45 DEG C of fermentation temperature, 20 turns/min of stirring rate, aeration rate
1.5L/min, fermentation time for 24 hours, still have 20% brominated bisphenol-A can detecte.
1L waste water containing tetrabromobisphenol A is added to the reaction kettle of 2 L, then compared with above-described embodiment 1-4 by comparative example 2
Be added 3 mesh of 1.0g 0.5%Pd/C(partial size), reaction pressure 1.0Mpa, reaction temperature be 80 DEG C, stirring rate be 800 turns/
Min, reacts 10h, and 95% or more brominated bisphenol-A is unable to debrominate；Then the waste water is added to containing 4 parts of Candida tropicalis
(Candida tropicalis ) and 2 parts of bacillus subtilis (Bacillus subtilis subsp. CGMCC-6684
Subtilis, CGMCC-3358) fermentor combine aerobic fermentation culture, 45 DEG C of fermentation temperature, 20 turns/min of stirring rate, expose
Gas velocity rate 1.5L/min, fermentation time for 24 hours, still have 90% or more brominated bisphenol-A not to be degraded by microorganisms.
1L waste water containing brominated bisphenol-A is added to the reaction kettle of 2 L, then compared with above-described embodiment 1-4 by comparative example 3
10g iron powder and 5 mesh of 1g 0.5%Pd/C(partial size is added) catalysis material, reaction pressure 0.5Mpa, reaction temperature is 60 DEG C, is stirred
Mixing rate is 800 turns/min, reacts 0.5h, the conversion bisphenol-A completely such as brominated bisphenol-A；Then debrominate waste water is added to containing 4 parts
Candida tropicalis (Candida tropicalis CGMCC-6684 ferment tank culture), is stirred by 35 DEG C of fermentation temperature
10 turns/min of rate, aeration rate 2.0L/min are mixed, fermentation time for 24 hours, still has 30% bisphenol-A not to be degraded in waste water.
1L waste water containing brominated bisphenol-A is added to the reaction kettle of 2L, then compared with above-described embodiment 1-4 by comparative example 4
10g iron powder and 5 mesh of 1g 0.5%Pd/C(partial size is added) catalysis material, reaction pressure 0.5Mpa, reaction temperature is 60 DEG C, is stirred
Mixing rate is 800 turns/min, reacts 0.5h, the conversion bisphenol-A completely such as brominated bisphenol-A；Then debrominate waste water is added to containing 4 parts
The ferment tank culture of bacillus subtilis (Bacillus subtilis subsp. Subtilis, CGMCC-3358),
35 DEG C of fermentation temperature, stirring rate 10 turns/min, aeration rate 2.0L/min, fermentation time for 24 hours, in waste water 85% or more it is double
Phenol A is not degraded.
1-4 and comparative example 1-4 are only adopted it is found that for the Industrial Wastewater Treatment containing brominated bisphenol-A through the foregoing embodiment
Use iron powder and Pd/C as joint reduction catalysts system, Candida tropicalis and the processing of bacillus subtilis co-fermentation, it should
Industrial wastewater can be by efficient process.
Claims (5)
1. a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A, which comprises the steps of: sharp first
Use iron powder and Pd/C as joint reduction catalysts system, in 0.1~1.0MPa of pressure, 30~80 DEG C of temperature, stirring rate 50
Under the conditions of~800 turns/min, 0.5~3h is handled to the reduction-debromination of industrial wastewater containing brominated bisphenol-A；Then debrominate waste liquid is filtered
And it imports and combines aerobic fermentation culture, fermentation temperature 20~50 containing Candida tropicalis and the fermentor of bacillus subtilis
DEG C, stirring rate 10-120 turns/min, aeration rate 0.2L~2.0L/min, fermentation time 4~for 24 hours, realize bromo in waste water
The thorough degradation of bisphenol-A pollutant.
2. a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A according to claim 1, which is characterized in that
Brominated bisphenol-A pollutant in the waste water mainly includes tetrabromobisphenol A, tribromo bisphenol-A, bisphenol-A.
3. a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A according to claim 1, which is characterized in that
The iron powder and wastewater quality ratio is 1:1000~1:100, and the Pd/C and wastewater quality ratio are 1:10000~1:
1000。
4. a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A according to claim 1 or 3, feature exist
In Pd content is 0.05%~0.5% in the Pd/C catalysis material, 3~15 mesh of particle size range.
5. a kind of method for innocent treatment of industrial wastewater containing brominated bisphenol-A according to claim 1, which is characterized in that
The composition mass parts ratio of the Candida tropicalis and bacillus subtilis is 4:1~1:2.
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Cited By (3)
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| CN113816520A (en) * | 2021-09-06 | 2021-12-21 | 天津长芦汉沽盐场有限责任公司 | Tetrabromo bisphenol A comprehensive wastewater treatment process |
| CN115072933A (en) * | 2022-06-17 | 2022-09-20 | 同济大学 | Method and system for simultaneously removing brominated pollutants and nitrates in sewage |
| CN116606195A (en) * | 2023-07-19 | 2023-08-18 | 天津长芦汉沽盐场有限责任公司 | Resource treatment method for tetrabromobisphenol A wastewater |
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