CN102389888B - Molten salt gasification method for treating waste printed circuit board, and applied apparatus thereof - Google Patents
Molten salt gasification method for treating waste printed circuit board, and applied apparatus thereof Download PDFInfo
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- CN102389888B CN102389888B CN201110121628.3A CN201110121628A CN102389888B CN 102389888 B CN102389888 B CN 102389888B CN 201110121628 A CN201110121628 A CN 201110121628A CN 102389888 B CN102389888 B CN 102389888B
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- Prior art keywords
- printed circuit
- circuit boards
- gasification furnace
- discarded printed
- gasification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Abstract
The invention relates to a molten salt gasification method for treating waste printed circuit boards. According to the invention, a molten salt gasification furnace is adopted; crushed waste printed circuit board particles and a gasification agent are mixed, heated and gasified in molten salt with a temperature of 900 to 1000 DEG C; a gas state product is cooled and clarified, such that clean synthetic gas is obtained; halogens in the waste printed circuit boards are subject to a reaction with the molten salt, such that stable harmless inorganic salt is produced; the inorganic salt is dissolved in water, and is recovered by using a flash evaporator; metal deposed on the bottom of the reactor is discharged, separated from the molten salt through quenching, and recovered. With the method provided by the invention, the reaction is stable, gas yield can be improved, tar and residues can be reduced, and secondary pollution can be controlled.
Description
Technical field
The present invention relates to a kind of fused salt gasification process of discarded printed circuit boards and device used thereof disposed.
Background technology
The general method of disposing discarded printed circuit boards has hydrometallurgy, directly burns and three kinds of pyrolysis.
Hydrometallurgy disposal technology is with strong acid or oxidizer treatment discarded printed circuit boards such as sulfuric acid and nitric acid, obtains the solution that contains metal, and then is restored; Or the ground of discarded printed circuit boards is dissolved with corrosion liquid, insoluble metal is directly reclaimed.This method simple to operate, more difficult but the spent acid and the waste water etc. that produce are processed, once dispose not thoroughly, will cause severe contamination to environment.
Directly incineration technology is to make the organic principles such as plastics in discarded printed circuit boards be transformed into CO through combustion process
2with the gaseous products such as water, the non-combustible composition such as metal is discharged with the form of lime-ash.The problem that this method exists is that the halogen such as bromine and chlorine contained in discarded printed circuit boards is converted into HBr and HCl in combustion process, equipment is had to very strong corrosiveness, and easily generate the high toxic material such as brominated phenol and Polychlorinated biphenyls.
Pyrolytic technique is, under the condition of isolated air, discarded printed circuit boards is carried out to heating pyrolyze, obtains tar, pyrolysis gas and residue.The problem that the method exists is that the many kinds of substance such as coke, metal and glass fibre that pyrolytic process produces mixes and is bundled together, and the separation of useful component is reclaimed and had certain difficulty; The complicated component of pyrolytic tar, if directly accepted by general user as fuel is still difficult, the potentiality of its value and reformation modification etc. are also indefinite.
Summary of the invention
For the problems referred to above, the object of this invention is to provide a kind of discarded printed circuit boards method of disposal, make disposal process more meet the requirement of minimizing, innoxious and resource, effectively control secondary pollution.
Technical scheme of the present invention
A kind of discarded printed circuit boards method of disposal, in gasification furnace, alkaline, inorganic salts is heated to after molten condition, it is interior and mix, heat and gasify in alkaline molten salt that broken discarded printed circuit boards particle and gasifying agent enter gasification furnace, the heat discharging is used for maintaining gasification reaction to carry out continuously, and gaseous products is the clean synthesis gas of final acquisition after cooling and purification; Halogen in discarded printed circuit boards forms with reacting in alkaline molten salt to be stablized harmless inorganic salts and soluble in waterly reclaims by flash vessel, metal in discarded printed circuit boards is deposited on gasification furnace bottom after being trapped by alkaline molten salt, quenching separation recovery in water after emitting, it specifically comprises the steps:
(1), in gasification furnace, inorganic salts are heated to 900～1000 ℃ in molten condition, discarded printed circuit boards particle after fragmentation and gasifying agent enter in gasification furnace and mix in alkaline molten salt, enter gasifying agent in gasification furnace and the flow of discarded printed circuit boards by adjusting, control excess air coefficient in gasification furnace and be less than 1, maintaining in reactor is reducing atmosphere;
Described inorganic salts are Na
2cO
3and K
2cO
3in a kind of or its mixture, preferred inorganic salts are Na
2cO
3;
Described gasifying agent is air;
Described discarded printed circuit boards grain diameter is 0～3mm;
In described gasification furnace, fused salt height is 15～25cm;
Described discarded printed circuit boards and the flow of gasifying agent are pressed mass volume ratio and are calculated, preferably the discarded printed circuit boards particle after fragmentation: gasifying agent is 1g:1.3L;
(2), each raw material of step (1) heats and gasifies after mixing in gasification furnace, controlling gasification temperature is 900～1000 ℃, the gas of formation through cooling, purify after, obtain clean synthesis gas;
The empty cross section flow velocity of preferably controlling gasifying agent is 0.3m/s;
Halogen in discarded printed circuit boards reacts with alkaline molten salt and forms and stablize harmless inorganic salts and soluble in waterly reclaim by flash distillation mode;
Metal in discarded printed circuit boards is deposited on gasification furnace bottom after being melted inorganic salts trapping, quenching centrifugation collection in water after emitting.
Another aspect of the present invention provides a kind of above-mentioned a kind of discarded printed circuit boards method of disposal device used of realizing, and this device comprises dispenser, gasification furnace, waste heat boiler, spraying drying and absorbing tower, deduster, quenching pond and flash vessel composition; Also be provided with in addition gasifying agent service;
Together with the bottom discharge pipeline of the service of gasifying agent and dispenser, be 45～60 degree and be incorporated to gasification furnace, the top of gasification furnace pipeline is out connected with deduster successively after waste heat boiler, spraying drying and absorbing tower; After the bottom of gasification furnace is connected with quenching pond, lead up to pipeline and be connected with flash vessel in quenching pond, another road in quenching pond from the bottom in quenching pond out, as the collection conduit of discharge metal.
Beneficial effect of the present invention
A kind of discarded printed circuit boards method of disposal of the present invention, because gasification temperature is high, and fused salt has accumulation of heat effect, can make stable reaction carry out, and improves factor of created gase, reduces tar and residue.
The process of reacting with halogen due to fused salt again to stablizing in harmless inorganic salts, is reducing atmosphere halogen transport in reactor, can further suppress the generation of the high toxic material such as brominated phenol and Polychlorinated biphenyls, has innoxious effect.
In addition, gasification is partial combustion reaction, and the heat of release can maintain the carrying out of reaction, does not need external heat source, has energy-conservation effect.And gasification gained synthesis gas and metal can recycle, there is resource effect.
Accompanying drawing explanation
Fig. 1, be a kind of discarded printed circuit boards method of disposal equipment therefor schematic diagram of the present invention.
The specific embodiment
The detection method of synthesis gas of the present invention is with reference to " GB/T 10410-2008 artificial coal gas and liquefied petroleum gas major constituents gas chromatography ";
The detecting instrument of synthesis gas of the present invention is gas chromatograph, model GC-9310-DM, and Shanghai chaste tree and Analytical Instrument Co., Ltd produce.
Below in conjunction with accompanying drawing 1, the present invention is described in detail.But do not limit the present invention.
The device that discarded printed circuit boards method of disposal is used, its schematic diagram as shown in Figure 1.
This device comprises dispenser 1, gasification furnace 2, waste heat boiler 3, spraying drying and absorbing tower 4, deduster 5, quenching pond 6, flash vessel 7;
Also be provided with in addition gasifying agent service;
Together with the bottom discharge pipeline of the service of gasifying agent and dispenser 1, be 45～60 degree and be incorporated to gasification furnace 2, the top of gasification furnace 2 pipeline is out connected with deduster 5 successively after waste heat boiler 3, spraying drying and absorbing tower 4; After the bottom of gasification furnace 2 is connected with quenching pond 6, lead up to pipeline and be connected with flash vessel 7 in quenching pond 6, another road from the bottom in quenching pond 6 out, as the collection conduit of discharge metal.
Carry out discarded printed circuit boards disposal with above-mentioned device, comprise the steps:
(1), Na
2cO
3add in gasification furnace 2, be heated to 900～1000 ℃ by electrical heating or high-temperature flue gas, make Na
2cO
3reach molten condition, control fused salt height 20cm, with gasifying agent, the discarded printed circuit boards particle after fragmentation is sent in gasification furnace 2 by dispenser 1, the flow-rate ratio of discarded printed circuit boards and gasifying agent is 1g:1.3L, excess air coefficient 0.4 in stove, maintaining in reactor is reducing atmosphere;
Described gasifying agent is air;
(2), control gasification furnace interior reaction temperature at 930 ℃, gasifying agent and discarded printed circuit boards particle mix, heat and gasify in alkaline molten salt; Gasification furnace 2 gaseous products is out cooled to after 260～280 ℃ through waste heat boiler 3, spray-dried absorption tower 4 is sprayed 20%CaO slurries and is absorbed the sour gas such as residual HBr again, then remove dust by deduster 5, must clean synthesis gas, the synthesis gas of gained detects and analyzes through gas chromatograph, and in final synthesis gas, the volume fraction of gas componant is 16.1%CO
2, 18.4%CO, 14.0%H
2, 5.5%CH
4, 1.2%C
2h
4and 44.8%N
2;
Bromine in discarded printed circuit boards reacts with alkaline molten salt, generates and stablizes harmless brominated inorganic salts NaBr etc., is dissolved in water rear by flash vessel 7 dehydration recovery, 39 ℃ of removal process flash vessel final stage temperature, pressure 7kPa;
Metal in discarded printed circuit boards is melted inorganic salts detention, be greater than alkaline molten salt salt by the because of metal density of detention and deposit to the bottom of gasification furnace, after emitting, be by water cooling in the quenching pond 6 of 75～85 ℃ in temperature, metal is water insoluble and separated, reclaims sorting through bottom drain road.
Above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (7)
1. a fused salt gasification process of disposing discarded printed circuit boards, is characterized in that comprising the steps:
(1), in gasification furnace Na
2cO
3and K
2cO
3in a kind of or its mixture be heated to molten condition, temperature of molten salt is 900～1000 ℃, then with gasifying agent, the discarded printed circuit boards particle after fragmentation is sent into from gasification furnace side by dispenser and in gasification furnace and alkaline molten salt, mixed and react, enter gasifying agent in gasification furnace and the flow of discarded printed circuit boards by adjusting, control excess air coefficient in gasification furnace and be less than 1, maintaining in reactor is reducing atmosphere;
(2), each raw material of step (1) heats and gasifies after mixing in gasification furnace, controlling gasification temperature is 930 ℃, the gas of formation through cooling, purify after, obtain clean synthesis gas;
Halogen in discarded printed circuit boards reacts with alkaline molten salt and forms that to stablize harmless inorganic salts soluble in water and reclaim by flash distillation mode;
Metal in discarded printed circuit boards is deposited on gasification furnace bottom after being melted inorganic salts trapping, quenching centrifugation collection in water after emitting.
2. a kind of fused salt gasification process of disposing discarded printed circuit boards as claimed in claim 1, is characterized in that in the gasification furnace described in step (1) excess air coefficient preferably 0.4.
3. a kind of fused salt gasification process of disposing discarded printed circuit boards as claimed in claim 1 or 2, is characterized in that the gasifying agent described in step (1) is air.
4. a kind of fused salt gasification process of disposing discarded printed circuit boards as claimed in claim 3, is characterized in that: the empty cross section flow velocity of controlling gasifying agent in step (1) is 0.3m/s.
5. a kind of fused salt gasification process of disposing discarded printed circuit boards according to claim 4, is characterized in that the discarded printed circuit boards grain diameter described in step (1) is below 3mm.
6. a kind of fused salt gasification process of disposing discarded printed circuit boards as claimed in claim 5, is characterized in that in the gasification furnace described in step (1), fused salt height is 15～25cm.
7. a kind of fused salt gasification process device used of disposing discarded printed circuit boards as claimed in claim 1 or 2, it is characterized in that comprising dispenser, gasification furnace, waste heat boiler, spraying drying and absorbing tower, deduster, quenching pond and flash vessel, be also provided with in addition gasifying agent service; The bottom discharge pipeline of the service of gasifying agent and dispenser be that a pipeline is 45-60 degree and is communicated with gasification furnace side, the top of gasification furnace pipeline is out connected with deduster successively after waste heat boiler, spraying drying and absorbing tower; After the bottom of gasification furnace is connected with quenching pond, lead up to pipeline and be connected with flash vessel in quenching pond, another road in quenching pond from the bottom in quenching pond out, as the collection conduit of discharge metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110121628.3A CN102389888B (en) | 2011-05-12 | 2011-05-12 | Molten salt gasification method for treating waste printed circuit board, and applied apparatus thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110121628.3A CN102389888B (en) | 2011-05-12 | 2011-05-12 | Molten salt gasification method for treating waste printed circuit board, and applied apparatus thereof |
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| CN102389888A CN102389888A (en) | 2012-03-28 |
| CN102389888B true CN102389888B (en) | 2014-05-28 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479756A (en) * | 2014-11-05 | 2015-04-01 | 江西理工大学 | Water-vapor gasification separation apparatus and method for waste printed circuit boards |
| CN104451165A (en) * | 2014-12-18 | 2015-03-25 | 郴州市金贵银业股份有限公司 | Method for recovering nonferrous metals and rare-noble metals |
| CN111171871B (en) * | 2020-03-04 | 2021-05-18 | 梵境新能源科技(浙江)有限公司 | Process for preparing synthetic gas or fuel gas from waste circuit board resin |
| FR3121847B1 (en) | 2021-04-16 | 2023-03-24 | Crymirotech | Process for the gasification of a carbonaceous material by molten salt catalysis |
| CN113351625B (en) * | 2021-06-02 | 2024-02-13 | 山东益众传媒科技有限公司 | Automatic wave frequency melting furnace device for destroying hard disk |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007190551A (en) * | 2006-01-20 | 2007-08-02 | Hsieh Sen Wu | Method of recycling wasted printed-circuit-board |
| CN101905234A (en) * | 2010-07-23 | 2010-12-08 | 中国科学院广州能源研究所 | Method and device for comprehensively recycling waste printed circuit boards |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007190551A (en) * | 2006-01-20 | 2007-08-02 | Hsieh Sen Wu | Method of recycling wasted printed-circuit-board |
| CN101905234A (en) * | 2010-07-23 | 2010-12-08 | 中国科学院广州能源研究所 | Method and device for comprehensively recycling waste printed circuit boards |
Non-Patent Citations (4)
| Title |
|---|
| 废弃印刷线路板熔融盐气化特性研究;李飞等;《环境科学学报》;20071130;第27卷(第11期);第1851-1857页 * |
| 李飞等.废弃印刷线路板熔融盐气化特性研究.《环境科学学报》.2007,第27卷(第11期), |
| 李飞等.熔融盐对印刷线路板热解影响实验研究.《燃料化学学报》.2007,第35卷(第5期), |
| 熔融盐对印刷线路板热解影响实验研究;李飞等;《燃料化学学报》;20071031;第35卷(第5期);第548-552页 * |
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Granted publication date: 20140528 Termination date: 20200512 |