CN103239975A - Treatment method of heat-treatment tail gas containing brominated flame retardant material - Google Patents
Treatment method of heat-treatment tail gas containing brominated flame retardant material Download PDFInfo
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- CN103239975A CN103239975A CN2013101508986A CN201310150898A CN103239975A CN 103239975 A CN103239975 A CN 103239975A CN 2013101508986 A CN2013101508986 A CN 2013101508986A CN 201310150898 A CN201310150898 A CN 201310150898A CN 103239975 A CN103239975 A CN 103239975A
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Abstract
The invention relates to a treatment method of a heat-treatment tail gas containing a brominated flame retardant material. The method comprises the following steps: heating a reactor and fusing the fused salt in the reactor; diluting the heat-treatment tail gas containing the brominated flame retardant material by utilizing air or oxygen; adjusting the gas intake volume concentration to reach 30% to 90%; and continuously leading the mixed gas into the reactor under the speed rate of 0.1L/min to 0.5L/min. After the reaction is finished, the destruction removal rate of the harmful component in the discharged tail gas can reach 80% to 100%. In the reactor, peroxy ions O2<2->, superoxy ions O<2-> and the like, which are generated by the reaction between the high-temperature fused salt and oxygen, can quickly destroy the brominated organic matter in the tail gas, thereby generating CO2, H2O, NaBr and the like without dioxin and other by-products. The method has the advantages of being rapid and complete in reaction, free of secondary pollution, easy to operate and the like.
Description
Technical field
The present invention relates to environmental protection technical field, especially a kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas.
Background technology
Present global fire retardant consumption figure is about 2,000,000 tons, and wherein 65～70% are used for flame retardant plastics.Flame retardant plastics is fire retardant with PBDEs (PBDEs), PBBs (PBB) and tetrabromobisphenol A (TBBA) usually, is widely used in printed circuit board (PCB), plastics, coating, electric wire and the resinae electronic component.Present China has entered household electrical appliance and has scrapped the peak period, and annual learies surpasses 5,000 ten thousand, and learies increases by 20% every year.The waste electronic electric equipment products are disassembled process and are produced a large amount of bromination flame retardant materials that contain, as waste plastics, useless circuit board, electric wire etc.
Brominated flame retardant has good flame retardancy, enters environment but spin off easily in electronic waste processing disposal process, and health and ecological environment are constituted a threat to.PBDEs has neurotoxicity, particularly is easy to generate many bromos benzo bioxin (PBDD) and many bromos benzofuran (PBDF) poisonous, carcinogenic, teratogenesis when polymer combustion, cracking.Buser in 1986 measures and finds that PBDEs can form PBDD and PBDF 510～630 ℃ of following pyrolysis.Steric effect that it is generally acknowledged the tetrabromobisphenol A molecular structure can not produce Xiu Dai bioxin in processing procedure, but Wichmann, Thoma, Dumler etc. show the pyrolysis of tetrabromobisphenol A experiment, and tetrabromobisphenol A can produce dioxins materials being higher than 600 ℃.Except the dioxin pollutant, contain and also can produce brominated organic matter and hydrogen bromides such as bromobenzene, bromine phenol in the bromination flame retardant materials heat treatment process.Barontini etc. have studied hydrogen bromide and brominated organic formation in the wiring board heat treatment process, find that bromine mainly is present in the gas-phase product with the form of hydrogen bromide and bromophenol.Grause etc. study at the pyrolysis gas under the different temperatures paper substrate FR-1 type wiring board, fire retardant began to decompose and discharge hydrogen bromide and bromination aromatic hydrocarbon when the result showed 270-370 ℃, was higher than 370 ℃ of resins and began coking and produce with bromize hydrogen gas simultaneously.In addition, still exist simple and easy baking to disassemble the primitive operation mode that circuit board reclaims metal in components and parts or incineration disposal retrieving circuit board, the electric wire in some areas of China, caused serious environmental pollution.Because passing a resolution to forbid the 4th conference of contracting party in May, 2009, a series of harm features such as persistence, biological accumulation and genotoxicity of PBDEs, " Convention of Stockholm " comprise a series of brominated flame retardants such as tetrabromodiphenyl ether, penta-BDE, hexabromo diphenyl ether and seven dibromodiphenyl ethers.On April 25th, 2011, " Convention of Stockholm " the 5th conference of contracting party of holding at Geneva, Switzerland, representative potential environmental pollution and environmental risk that the recovery problem of brominated flame retardant is brought debate actively, and the suggestion various countries will contain bromination fire retardant refuse as early as possible, come out and will properly dispose as waste plastics, useless foam go-no-go from waste stream.
Contain a large amount of brominated organic matter of meeting generation in the bromination flame retardant materials heat treatment process, processing procedure faces dehalogenation and purifies a difficult problem.The method that dehalogenation purifies roughly can be summarized globality dehalogenation and destructive dehalogenation two classes.Under the prerequisite of not destroying plastic or other material, carry out dehalogenation, as supercritical CO
2TBBA and HBCD in the extract and separate polybutylene terephthalate (PBT) (PBT).Plastics behind the dehalogenation can be used as the raw material of raw product again, and also recyclable utilization of halogen, but this technology requires height to equipment, and disengaging time is long, and operating cost is a key factor that influences this technical applicationization.Compare with the globality dehalogenation, interpolation alkali or basic anhydride carry out dehalogenation in cracking such as plastics, burning process, have and remove the acidic components ability preferably, but the affiliation that adds of basic component causes to a certain degree damage to materials such as the metal that reclaims, glass fibres, is unfavorable for pyrolysis residue subsequent treatment.Therefore, it is imperative that research and development contain the terminal purification techniques of bromination flame retardant materials thermal treatment exhaust gas.
Fused salt oxidation processes technology is a kind of heat treatment technics that U.S. Rockwell International company (existing Boeing) took the lead in proposing in nineteen sixty-five, is used for coal gasification at first.This technology is reaction medium with the fuse salt, utilizes it to organic strong oxidizing property and high thermoconductivity discarded object to be decomposed rapidly.In recent years, fused salt oxidation processes technology is applied to organic waste, and especially the processing of hazardous waste causes world's extensive concern.Li Fei etc. carry out waste printed circuit board gasification experiment in the fused salt gasification furnace, investigated the influence of air equivalent comparison gas yield, gas heating value, efficiency of carbon con version and gasification efficiency, delay and the distribution situation of metal in fuse salt in the gasification, and set up the reaction Kinetics Model of gasification reaction process.Korea S Yang etc. adopt two-part fuse salt stove to handle chloro-carbon solvent CCl
4, C
6H
5Cl has obtained very good effect.U.S. Hsu etc. handle ABS plastic, leather and active carbon to fused salt and study.Because media and the catalytic action of fuse salt, fused salt oxidation processes technology can effectively be decomposed debirs, and the sour gas that discharges in the course of reaction can be absorbed by fused salt, simultaneously other inorganic matter and metal is trapped in the fused salt.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas, simple and easy, efficient, non-secondary pollution.
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
4 to 300～900 ℃ of reactor heatings, make fused salt 3 fusings in the reactor 4, utilize air or oxygen 2 dilutions to contain bromination flame retardant materials thermal treatment exhaust gas 1, adjusting charge volume concentration is 30～90%, mist is introduced reactor 4 continuously with the speed of 0.1～0.5L/min, after reaction finished, the destruction clearance of harmful constituent reached 80～100% in the discharge tail gas.
The described bromination flame retardant materials that contains comprises in flame retardant plastics, useless circuit board, useless circuit board non-metal material, electric wire, the brominated chemicals one or more.
Described heat treatment comprises pyrolysis, burning or baking.
The mixture of one or more in the carbonate that described fused salt 3 is alkali metal and its nitrate, nitrite, villaumite, the hydroxide.
The present invention compared with prior art have be swift in response thoroughly, advantages such as non-secondary pollution, easy operating.In reactor 4, high-temperature molten salt and oxygen reaction produce peroxide radical ion O
2 2-With super oxygen radical ion O
2-Deng, can destroy the brominated organic matter in the tail gas rapidly, generate CO
2, H
2O and NaBr etc., accessory substances such as no bioxin produce.
Description of drawings
Accompanying drawing is for realizing device schematic diagram of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is described in detail.
With reference to accompanying drawing, realization the inventive system comprises reactor 4, is placed with fused salt 3 in the reactor 4, and air or oxygen 2 dilutions contain bromination flame retardant materials thermal treatment exhaust gas 1 back and introduce reactor 4, the top of reactor 4 is provided with the exhaust emissions pipeline, and the bottom of reactor 4 is provided with the waste sludge discharge pipeline.
The present invention is described further below in conjunction with embodiment, but content of the present invention is not limited only to content related among the embodiment.
Embodiment 1
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 900 ℃, the fused salt Na in the reactor
2CO
3Fusing utilizes the useless circuit board pyrolytic tail gas of air dilution, and adjusting charge volume concentration is 30%, and mist is introduced reactor continuously with the speed of 0.5L/min, and after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 80% in the discharge tail gas.
Embodiment 2
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 900 ℃ makes the fused salt K in the reactor
2CO
3Fusing utilizes the useless circuit board pyrolytic tail gas of oxygen dilution, and adjusting charge volume concentration is 90%, and mist is introduced reactor continuously with the speed of 0.1L/min, and after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 100% in the discharge tail gas.
Embodiment 3
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 750 ℃ makes the fused salt Li in the reactor
2CO
3Fusing, utilize the useless household electrical appliances plastic casing pyrolysis tail gas of air dilution, adjusting charge volume concentration is 60%, and mist is introduced reactor continuously with the speed of 0.4L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 85% in the discharge tail gas.
Embodiment 4
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 750 ℃ makes the fused salt 56Na in the reactor
2CO
3-44K
2CO
3(mol%) fusing, utilize the useless household electrical appliances plastic casing pyrolysis tail gas of oxygen dilution, adjusting charge volume concentration is 70%, and mist is introduced reactor continuously with the speed of 0.4L/min, after reaction finished, destruction and the clearance (DRE) of main harmful constituent reached 90% in the discharge tail gas.
Embodiment 5
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 650 ℃ makes the fused salt 35Na in the reactor
2CO
3-65NaCl(mol%) fusing, utilize the useless circuit board non-metal material pyrolysis tail gas of air dilution, adjusting charge volume concentration is 75%, mist is introduced reactor continuously with the speed of 0.3L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 90% in the discharge tail gas.
Embodiment 6
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 400 ℃ makes the fused salt 29.8Na in the reactor
2CO
3-44.1Li
2CO
3-26.1K
2CO
3(mol%) fusing, utilize the useless circuit board non-metal material pyrolysis tail gas of oxygen dilution, adjusting charge volume concentration is 75%, and mist is introduced reactor continuously with the speed of 0.3L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 95% in the discharge tail gas.
Embodiment 7
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 300 ℃ makes the fused salt 7.2Na in the reactor
2CO
3-92.8NaOH(mol%) fusing, utilize the useless circuit board incineration tail gas of air dilution, adjusting charge volume concentration is 85%, and mist is introduced reactor continuously with the speed of 0.2L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 90% in the discharge tail gas.
Embodiment 8
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 600 ℃ makes the fused salt 18.1Na in the reactor
2CO
3-43.3K
2CO
3-42.5KCl(mol%) fusing, utilize the useless circuit board incineration tail gas of oxygen dilution, adjusting charge volume concentration is 85%, and mist is introduced reactor continuously with the speed of 0.5L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 80% in the discharge tail gas.
Embodiment 9
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 350 ℃ makes the fused salt 2K in the reactor
2CO
3-98KNO
3(mol%) fusing, utilize air to dilute brominated chemical incineration tail gas, adjusting charge volume concentration is 70%, and mist is introduced reactor continuously with the speed of 0.4L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 90% in the discharge tail gas.
Embodiment 10
A kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas comprises the steps:
Reactor heating to 350 ℃ makes the fused salt 1.8Na in the reactor
2CO
3-98.2NaNO
3(mol%) fusing, utilize oxygen to dilute brominated chemical incineration tail gas, adjusting charge volume concentration is 80%, and mist is introduced reactor continuously with the speed of 0.3L/min, after reaction finished, the destruction of harmful constituent and clearance (DRE) reached 90% in the discharge tail gas.
Claims (4)
1. a processing method that contains bromination flame retardant materials thermal treatment exhaust gas is characterized in that, comprises the steps:
Reactor heating (4) is to 300～900 ℃, make fused salt (3) fusing in the reactor (4), utilize air or oxygen (2) dilution to contain bromination flame retardant materials thermal treatment exhaust gas (1), adjusting charge volume concentration is 30～90%, and mist is introduced reactor (4) continuously with the speed of 0.1～0.5L/min.
2. a kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas according to claim 1 is characterized in that: the described bromination flame retardant materials that contains comprises in flame retardant plastics, useless circuit board, useless circuit board non-metal material, electric wire, the brominated chemicals one or more.
3. a kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas according to claim 1, it is characterized in that: described heat treatment comprises pyrolysis, burning or baking.
4. a kind of processing method that contains bromination flame retardant materials thermal treatment exhaust gas according to claim 1 is characterized in that: described fused salt (3) is one or more the mixture in the carbonate of alkali metal and its nitrate, nitrite, villaumite, the hydroxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964099A (en) * | 2016-06-07 | 2016-09-28 | 刘杰 | Method and device for treating dioxin contained in incineration exhaust gas |
| CN106237800A (en) * | 2016-09-05 | 2016-12-21 | 上海理工大学 | Volatile organic compounds melting salt oxidation system |
| CN108996524A (en) * | 2018-09-09 | 2018-12-14 | 寿光富康制药有限公司 | A kind of method that brominated waste prepares Bromide |
| CN114288837A (en) * | 2021-12-13 | 2022-04-08 | 中国科学院上海应用物理研究所 | Chemical decarburization device and chemical decarburization method for halide molten salt |
| CN114870590A (en) * | 2022-05-05 | 2022-08-09 | 苏州清咨威特环保科技有限公司 | Device for oxidation treatment of halogenated organic waste gas |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964099A (en) * | 2016-06-07 | 2016-09-28 | 刘杰 | Method and device for treating dioxin contained in incineration exhaust gas |
| CN106237800A (en) * | 2016-09-05 | 2016-12-21 | 上海理工大学 | Volatile organic compounds melting salt oxidation system |
| CN108996524A (en) * | 2018-09-09 | 2018-12-14 | 寿光富康制药有限公司 | A kind of method that brominated waste prepares Bromide |
| CN114288837A (en) * | 2021-12-13 | 2022-04-08 | 中国科学院上海应用物理研究所 | Chemical decarburization device and chemical decarburization method for halide molten salt |
| CN114288837B (en) * | 2021-12-13 | 2022-09-16 | 中国科学院上海应用物理研究所 | Chemical decarburization device and chemical decarburization method for halide molten salt |
| CN114870590A (en) * | 2022-05-05 | 2022-08-09 | 苏州清咨威特环保科技有限公司 | Device for oxidation treatment of halogenated organic waste gas |
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| CN103239975B (en) | 2015-02-18 |
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