CN106390351A - Efficient degradation method for polybrominated diphenyl ethers fire retardant - Google Patents
Efficient degradation method for polybrominated diphenyl ethers fire retardant Download PDFInfo
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- CN106390351A CN106390351A CN201610697187.4A CN201610697187A CN106390351A CN 106390351 A CN106390351 A CN 106390351A CN 201610697187 A CN201610697187 A CN 201610697187A CN 106390351 A CN106390351 A CN 106390351A
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/178—Microwave radiations, i.e. radiation having a wavelength of about 0.3 cm to 30cm
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/02—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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- A—HUMAN NECESSITIES
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- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
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- A—HUMAN NECESSITIES
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- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
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Abstract
The invention discloses an efficient degradation method for a polybrominated diphenyl ethers fire retardant. The degradation method comprises the specific steps that a surfactant is added into the fire retardant, then the mixture is added into a microwave reactor, non-pulse microwave continuous heating is conducted at the temperature of 250-300 DEG C for 1-2 h, and ctivation and enrichment of polybrominated diphenyl ethers are facilitated; then the microwave reactor is put in an ultrasonic environment, and sponge iron/Ag bimetallic catalysts are added, hydrogen is led in; and then strong light with the intensity of 50000 lux irradiates the microwave reactor, and the polybrominated diphenyl ethers fire retardant is degraded through reduction reaction. According to the efficient degradation method, the sponge iron/Ag bimetallic catalysts are combined with the surfactant, the polybrominated diphenyl ethers can be degraded efficiently through reduction reaction, the efficient degradation method is simple, and the degradation efficiency is high.
Description
Technical field
The present invention relates to environmental protection technical field is and in particular to a kind of efficient degradation side of PBDE based flame retardant
Method.
Background technology
PBDE (abbreviation PBDEs), has 209 kinds of homologues such as tetrabromo Biphenyl Ether, pentabromo-, hexabromo, eight bromines, ten bromines.
PBDE is a kind of brominated flame-retardant of excellent performance, is widely used in various industry and consumer products, simultaneously many
Bromo biphenyl ether is also the persistent organic pollution of a class, highly stable in the environment, difficult degradation, and has highly lipophilic, low
Water solublity, has bioaccumulation and can be enriched with along food chain.The at present degraded with regard to PBDE and technology for eliminating
Research is widely paid attention to.
PBDE is our traditional fire retardant kinds, and the PBDE kind of industrialized production has：Tetrabromo joins
Phenylate, pentabromo- Biphenyl Ether, hexabromobiphenyl ether, seven bromo biphenyl ethers, octa-BDE, nine bromo biphenyl ethers and decabromodiphenyl oxide, wherein
Conventional for pentabromo- Biphenyl Ether, octa-BDE and three kinds of decabromodiphenyl oxide.An a kind of big class as bromide fire retardant
Fire retardant matter, due to its excellent fire resistance, has increasingly been widely used in the middle of various consumer products.
Research shows, it is in even that multiple proportion increases, in animal even that PBDEs has notable rising in various environmental matrices
Human fatty tissue, blood, breast milk all have detection, have therefore become the ubiquitous pollutant in ecosystem of a class.Right
The influence research of human body finds, the workman's thyroid function being engaged in production PBDEs substantially weakens.PBDEs under certain condition, can
It is changed into poisonous many bromos that can be carcinogenic dibenzo to mutter (PBDFs) and many bromos two and two.
Content of the invention
The technical problem to be solved in the present invention be provide that a kind of speed is fast, efficiency high and do not result in the many of environmental pollution
The efficient degradation method of bromo biphenyl ethers fire retardant.
For solving above-mentioned technical problem, the technical solution used in the present invention is：
The concretely comprising the following steps of a kind of efficient degradation method of PBDE based flame retardant：Add in described fire retardant
With respect to the surfactant of fire retardant percentage by weight 0.1%, it is then added in microwave reactor, non-at 250～300 DEG C
Pulse microwave laser heating 1～2h, promotes PBBs ethers to activate and be enriched with, then microwave reflecting device is placed in ultrasound environments
In and add sponge iron/Ag bimetallic catalyst with respect to 0.2 times of quality of fire retardant, and press 0.05～0.08m3The speed of/h
It is passed through hydrogen, the strong illumination microwave reactor being simultaneously 50000lux with intensity, by reduction reaction by PBBs ethers
Fire retardant is degraded.
Further, described surfactant is sodium lauryl sulphate, sodium laurylsulfate, sodium glycocholate, poly- second
The mixture to any two kinds in isooctyl phenyl ether for the glycol, mixed proportion is mass ratio 1:1.
Further, the chemical reaction equipment in described microwave reactor is provided with surface and contains 35% in-situ preparation
Cu TiO2 conduction band, wherein Cu irradiated by high light, and Cu ion can capture light on TiO2 conduction band and excite generation to be reduced
Electronics, PBDE based flame retardant can be subject to light activated Hole oxidation on TiO2 conduction band, and the many bromines of simultaneous catalytic reduction join
Phenylate.
Further, also contain magnetic stirrer in described microwave reactor, mixing speed continuously adjustabe simultaneously shows in real time
Show.
Further, the ultrasonic frequency in described ultrasound environments is 25KHz～40KHz.
Further, the preparation method of described sponge iron/Ag bimetallic catalyst is：By sponge iron be immersed in respect to
In the deionized water of sponge iron 10 times amount, it is subsequently adding and stirs under ultrasound environments with respect to the silver nitrate solution of sponge iron 5 times amount
Mix to reaction completely, filter and remove excessive silver nitrate solution, be subsequently placed in magnetic separator and carry out Magnetic Isolation, spend after separating
Ionized water is cleaned multiple times, and is then dried under vacuum and obtains final product described sponge iron/Ag bimetallic catalyst.
Further, the PBBs ethers of degraded in microwave reactor is cooled in mass ratio 8 after 25～40 DEG C:
1 bacterial strain adding pseudomonass thereto and anaerobic fungi bacterial strain, stand 24～36h in closed environment, carry out biological fall
Solution.Biodegradation can prevent chemical degradation not exclusively, can greatly degrading polybrominated diphenyl etherss based flame retardant.
Beneficial effects of the present invention are embodied in：The present invention utilizes sponge iron/Ag bimetallic catalyst mating surface activating agent
With microwave reactor, surfactant can guarantee that PBBs ethers activates and is enriched with to auxiliary, sponge iron/Ag bimetallic catalyst
There is preferable dispersibility and surface energy, be subject to electrostatic force, capillary effect under ultrasound environments, to PBDE in addition
Class has good reducing power, and microwave reactor can lift response speed, and can be heated by non-pulse microwave continuous, protects
Demonstrate,prove PBBs ethers efficient-decomposition.
Specific embodiment
Embodiment 1
A kind of efficient degradation method of PBDE based flame retardant, the concretely comprising the following steps of described biodegrading process：To institute
Add the surfactant with respect to fire retardant 0.1% in the fire retardant stated, be then added in microwave reactor, at 250 DEG C
Non-pulse microwave continuous heat 1h, promote PBBs ethers to activate and be enriched with, then microwave reflecting device are placed in ultrasound environments
In and add sponge iron/Ag bimetallic catalyst with respect to 0.2 times of quality of fire retardant, and press 0.05m3The speed of/h is passed through hydrogen
The strong illumination microwave reactor that then gas be 50000lux with intensity, by reduction reaction by PBDE based flame retardant
Decompose and remove.
Wherein, described surfactant is sodium lauryl sulphate, the mixture of two kinds of sodium laurylsulfate；Mixing ratio
Example is mass ratio 1:1.Being provided with surface on chemical reaction equipment in described microwave reactor, to contain 35% generated in-situ
The TiO2 conduction band of Cu, wherein Cu is irradiated by high light, and Cu ion can capture light on TiO2 conduction band and excite generation to be reduced
Electronics, PBDE based flame retardant can be subject to light activated Hole oxidation, simultaneous catalytic reduction PBBs on TiO2 conduction band
Ethers；Magnetic stirrer is also contained, mixing speed continuously adjustabe simultaneously shows in real time in described microwave reactor；Described is ultrasonic
Ultrasonic frequency in environment is 25KHz.
Wherein, the preparation method of described sponge iron/Ag bimetallic catalyst is：Sponge iron is immersed in deionized water
In, it is subsequently adding excessive silver nitrate solution and stirs under ultrasound environments to reaction completely, filter the excessive silver nitrate of removal molten
Liquid, is subsequently placed in magnetic separator and carries out Magnetic Isolation, and after separating, deionized water is cleaned multiple times, and is then dried under vacuum and obtains final product
Described sponge iron/Ag bimetallic catalyst.
Wherein, the PBBs ethers of degraded in microwave reactor is cooled in mass ratio 8 after 25 DEG C:1 thereto
Add bacterial strain and the anaerobic fungi bacterial strain of pseudomonass, stand 24h in closed environment, carry out biodegradation.Biodegradation
Chemical degradation can be prevented not exclusively, can greatly degrading polybrominated diphenyl etherss based flame retardant.
Embodiment 2
A kind of efficient degradation method of PBDE based flame retardant, the concretely comprising the following steps of described biodegrading process：To institute
Add the surfactant with respect to fire retardant 0.1% in the fire retardant stated, be then added in microwave reactor, at 275 DEG C
Non-pulse microwave continuous heat 1.5h, promote PBBs ethers to activate and be enriched with, then microwave reflecting device are placed in ultrasonic ring
In border and add sponge iron/Ag bimetallic catalyst with respect to 0.2 times of quality of fire retardant, and press 0.065m3The speed of/h is led to
Enter hydrogen, PBBs ethers is hindered by the strong illumination microwave reactor being then 50000lux with intensity by reduction reaction
Removal is decomposed in combustion agent.
Wherein, described surfactant be sodium glycocholate, the mixture to two kinds of isooctyl phenyl ether for the Polyethylene Glycol；Mixed
Composition and division in a proportion example is mass ratio 1:1.Surface is provided with the chemical reaction equipment in described microwave reactor and contains 35% life in situ
The TiO2 conduction band of the Cu becoming, wherein Cu is irradiated by high light, and Cu ion can capture light on TiO2 conduction band and excite generation to be gone back
Former electronics, PBDE based flame retardant can be subject to light activated Hole oxidation, the many bromines of simultaneous catalytic reduction on TiO2 conduction band
Biphenyl Ether；Magnetic stirrer is also contained, mixing speed continuously adjustabe simultaneously shows in real time in described microwave reactor；Described is super
Ultrasonic frequency in acoustic environment is 32.5KHz.
Wherein, the preparation method of described sponge iron/Ag bimetallic catalyst is：Sponge iron is immersed in deionized water
In, it is subsequently adding excessive silver nitrate solution and stirs under ultrasound environments to reaction completely, filter the excessive silver nitrate of removal molten
Liquid, is subsequently placed in magnetic separator and carries out Magnetic Isolation, and after separating, deionized water is cleaned multiple times, and is then dried under vacuum and obtains final product
Described sponge iron/Ag bimetallic catalyst.
Wherein, the PBBs ethers of degraded in microwave reactor is cooled in mass ratio 8 after 32.5 DEG C:1 to it
In add bacterial strain and the anaerobic fungi bacterial strain of pseudomonass, stand 30h in closed environment, carry out biodegradation.Biological fall
Solution can prevent chemical degradation not exclusively, can greatly degrading polybrominated diphenyl etherss based flame retardant.
Embodiment 3
A kind of efficient degradation method of PBDE based flame retardant, the concretely comprising the following steps of described biodegrading process：To institute
Add the surfactant with respect to fire retardant 0.1% in the fire retardant stated, be then added in microwave reactor, at 300 DEG C
Non-pulse microwave continuous heat 2h, promote PBBs ethers to activate and be enriched with, then microwave reflecting device are placed in ultrasound environments
In and add sponge iron/Ag bimetallic catalyst with respect to 0.2 times of quality of fire retardant, and press 0.08m3The speed of/h is passed through hydrogen
The strong illumination microwave reactor that then gas be 50000lux with intensity, by reduction reaction by PBDE based flame retardant
Decompose and remove.
Wherein, described surfactant is that sodium lauryl sulphate, Polyethylene Glycol mix for two kinds to isooctyl phenyl ether
Compound；Mixed proportion is mass ratio 1:1.It is provided with surface on chemical reaction equipment in described microwave reactor and contain 35%
The TiO2 conduction band of generated in-situ Cu, wherein Cu is irradiated by high light, and Cu ion can capture light on TiO2 conduction band and excite product
The electronics that is reduced of life, PBDE based flame retardant can be subject to light activated Hole oxidation on TiO2 conduction band, and catalysis simultaneously is also
Former PBDE；Magnetic stirrer is also contained, mixing speed continuously adjustabe simultaneously shows in real time in described microwave reactor；Institute
Ultrasonic frequency in the ultrasound environments stated is 40KHz.
Wherein, the preparation method of described sponge iron/Ag bimetallic catalyst is：Sponge iron is immersed in deionized water
In, it is subsequently adding excessive silver nitrate solution and stirs under ultrasound environments to reaction completely, filter the excessive silver nitrate of removal molten
Liquid, is subsequently placed in magnetic separator and carries out Magnetic Isolation, and after separating, deionized water is cleaned multiple times, and is then dried under vacuum and obtains final product
Described sponge iron/Ag bimetallic catalyst.
Wherein, the PBBs ethers of degraded in microwave reactor is cooled in mass ratio 8 after 40 DEG C:1 thereto
Add bacterial strain and the anaerobic fungi bacterial strain of pseudomonass, stand 36h in closed environment, carry out biodegradation.Biodegradation
Chemical degradation can be prevented not exclusively, can greatly degrading polybrominated diphenyl etherss based flame retardant.
Finally it should be noted that：Above example only in order to technical scheme to be described, is not intended to limit；Although
With reference to the foregoing embodiments the present invention is described in detail, it will be understood by those within the art that：It still may be used
To modify to the technical scheme described in previous embodiment, or equivalent is carried out to wherein some technical characteristics；And
These modifications or replacement, do not make the essence of appropriate technical solution depart from spirit and the model of embodiment of the present invention technical scheme
Enclose.
Claims (7)
1. a kind of efficient degradation method of PBDE based flame retardant is it is characterised in that the concrete step of described biodegrading process
Suddenly it is：Add the surfactant with respect to fire retardant percentage by weight 0.1% in described fire retardant, be then added to micro-
In ripple reactor, heat 1～2h in 250～300 DEG C of non-pulse microwave continuous, promote PBBs ethers to activate and be enriched with, so
Afterwards microwave reflecting device is placed in ultrasound environments and adds the sponge iron/Ag bimetallic catalytic with respect to 0.2 times of quality of fire retardant
Agent, and press 0.05～0.08m3The speed of/h is passed through hydrogen, the strong illumination microwave reactor being simultaneously 50000lux with intensity,
By reduction reaction, PBDE based flame retardant is degraded.
2. as claimed in claim 1 a kind of efficient degradation method of PBDE based flame retardant it is characterised in that described
Surfactant is sodium lauryl sulphate, sodium laurylsulfate, sodium glycocholate, Polyethylene Glycol are to any in isooctyl phenyl ether
Two kinds of mixture, mixed proportion is mass ratio 1:1.
3. as claimed in claim 1 a kind of efficient degradation method of PBDE based flame retardant it is characterised in that described
The TiO2 conduction band that 35% generated in-situ Cu is contained on surface is provided with the chemical reaction equipment in microwave reactor.
4. as claimed in claim 1 a kind of efficient degradation method of PBDE based flame retardant it is characterised in that：Preferably
Ground, also contains magnetic stirrer, mixing speed continuously adjustabe simultaneously shows in real time in described microwave reactor.
5. as claimed in claim 1 a kind of efficient degradation method of PBDE based flame retardant it is characterised in that：Preferably
Ground, the ultrasonic frequency in described ultrasound environments is 25KHz～40KHz.
6. as claimed in claim 1 a kind of efficient degradation method of PBDE based flame retardant it is characterised in that described
The preparation method of sponge iron/Ag bimetallic catalyst is：Sponge iron is immersed in the deionized water with respect to sponge iron 10 times amount
In, it is subsequently adding and stirs under ultrasound environments to reaction completely with respect to the silver nitrate solution of sponge iron 5 times amount, be placed in after filtration
Carry out Magnetic Isolation in magnetic separator, after separating, deionized water is cleaned multiple times, be then dried under vacuum and obtain final product described sponge
Ferrum/Ag bimetallic catalyst.
7. as claimed in claim 1 a kind of efficient degradation method of PBDE based flame retardant it is characterised in that will be micro-
In mass ratio 8 after in ripple reactor, the PBBs ethers of degraded is cooled to 25～40 DEG C:1 adds pseudomonass thereto
Bacterial strain and the hybrid bacterial strain of anaerobic fungi bacterial strain, stand 24～36h in closed environment, carry out biodegradation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462679A (en) * | 2021-06-30 | 2021-10-01 | 生态环境部华南环境科学研究所 | Method for degrading polybrominated diphenyl ether flame retardant by utilizing biological sponge iron |
| CN113913853A (en) * | 2021-11-23 | 2022-01-11 | 浙江工业大学 | Electrochemical deep degradation method of brominated phenolic compounds under synergistic adsorption of surfactant |
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| CN102502985A (en) * | 2011-10-25 | 2012-06-20 | 南京大学 | Method for removing typical bromide flame retardant based on Fe/Ag reduction-class Fenton oxidization |
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| CN102351297A (en) * | 2011-09-15 | 2012-02-15 | 山东大学 | Treatment method of halogenated organic pollutant waste water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462679A (en) * | 2021-06-30 | 2021-10-01 | 生态环境部华南环境科学研究所 | Method for degrading polybrominated diphenyl ether flame retardant by utilizing biological sponge iron |
| CN113913853A (en) * | 2021-11-23 | 2022-01-11 | 浙江工业大学 | Electrochemical deep degradation method of brominated phenolic compounds under synergistic adsorption of surfactant |
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