CN107891053A - A kind of method and system of old circuit board Pyrolyzation and debromination processing - Google Patents
A kind of method and system of old circuit board Pyrolyzation and debromination processing Download PDFInfo
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- CN107891053A CN107891053A CN201711233014.8A CN201711233014A CN107891053A CN 107891053 A CN107891053 A CN 107891053A CN 201711233014 A CN201711233014 A CN 201711233014A CN 107891053 A CN107891053 A CN 107891053A
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- pyrolysis
- circuit board
- thermal carriers
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
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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 present invention relates to a kind of method of old circuit board Pyrolyzation and debromination processing, comprise the following steps：1) old circuit board crushes；2) solid thermal carriers mix with old circuit board；3) it is pyrolyzed；4) gas-solid separator；5) the isolated pyrolysis gas of chilling and pyrolysis oil.The invention further relates to a kind of system of old circuit board Pyrolyzation and debromination processing, comprising knockout tower, disintegrating machine, blender, rotary kiln, roto-siofter, gas-solid separator, centrifuge, heating furnace and collects tower.The present invention does solid thermal carriers using metal oxide and is sufficiently mixed with old circuit board, using metal oxide such as iron oxide, cupric oxide etc. come Br caused by absorbing pyrolytic reaction2, the material such as HBr, so as to effectively remove halides in old circuit board, generation metal bromate salt dissolving prevents the influence of its corrosion and tar to equipment.
Description
Technical field
The present invention relates to fixed-end forces field, more particularly, to a kind of method of old circuit board Pyrolyzation and debromination processing
And system.
Background technology
Old circuit board is by household electrical appliance such as various waste computers, communication apparatus, television set and refrigerators and eliminated
Precision electronic device instrument etc. caused by a kind of solid waste.China is electronic apparatus production and consumption big country, in recent years electronics
Old circuit board quantity caused by electrical equipment then increases in geometry multiple.On the other hand, China is as wiring board system the biggest in the world
Producing country is made, caused waste material reaches the 30% of total amount in production process, is one of discarded circuit board important sources.
Many research institutions are recycled to old circuit board both at home and abroad at present and recycling is recycled and carried out widely
Research, the recycling treatment process technology of use mainly have mechanical physical processing techniques, hydrometallurgy, biological treatment, overcritical
Fluid processing, heat treatment etc..Mechanical-physical treatment technology makes metal component be filled with nonmetallic ingredient using the method for Mechanical Crushing
Decompose from then separating metal ingredient using the methods of gravity separation, magnetic separation, there is that power consumption is big, and break process technique produces big
Measure dust, the shortcomings of crushing effect is undesirable.Hydrometallurgy general principle is in acid or alkalescence by the metal in useless circuit board
Under the conditions of leach, metal and other materials are separated and reclaimed from liquid phase, but can not be organic in recovery train plate
Thing, and water consumption is big, caused waste water causes environmental pollution.In numerous handling process, it is pyrolyzed as a kind of newer scrap wire
Road plate treatment technology, the resin-bonded layer in waste printed circuit board can be made to decompose, weaken the adhesion between metal and non-metallic layer,
So as to realize the efficient dissociation of metal and non-metallic layer；In addition, caused pyrolysis gas and pyrolysis oil can be used as combustion in pyrolytic process
Gas or industrial chemicals reuse, the pollutions such as bioxin can be effectively avoided to generate.
Traditional pyrolysis processing technique, it is primarily present two problems：1st, because wiring board thermal conductivity is bad, furnace heat transfer effect
Rate is low, causes high energy consumption, and treatment effeciency is not high.2nd, exist in wiring board and contain a large amount of halides inside fire retardant, be pyrolyzed
Cheng Zhonghui generates the poisonous and harmful substances such as more shielding smog, simple substance bromine and hydrogen bromide, brominated phenol.These materials are not only right
Environment causes serious harm difficult to the appraisal, can also corrosion treatment equipment, reduce finished product oil quality.Therefore need to consider new give up
Old wiring board pyrolysis processing technique, improve be pyrolyzed efficiency while as far as possible by wiring board be pyrolyzed caused by bromide remove,
So as to avoid the corrosion to reacting equipment, the influence to later stage oil product is eliminated.
It is pyrolyzed in the prior art using fluid bed process, the big operating procedure complexity of power consumption, waste plastics pyrolysis production is present
Raw fused mass is easily adhered to each other with fluidized bed material quartz sand, and technique normal operation is had an impact.And bromide fire retardant
It is mainly caused in pyrolytic process easily equipment to be caused to corrode for inorganic gas such as hydrogen bromide, bromines, also can be with the heat of generation
Solution oil, which reacts, to be generated brominated organic matter and reduces tar quality.
Another technology removes the bromo element in brominated plastics using ammoniacal liquor supercritical fluid method, and technical process includes
Several workshop sections such as pretreatment of raw material, HTHP debromination, post processing.1) the shortcomings that technology is primarily present is using super
The brominated plastic wastes of critical fluids method processing, operating condition is HTHP, and energy resource consumption is larger, and application in the industry is difficult to
Realize；2) course of reaction produces a large amount of waste water, causes secondary pollution.
Based on this, it is badly in need of the technology that exploitation high-efficiency cleaning handles discarded circuit board at present.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of method and system of old circuit board Pyrolyzation and debromination processing.This hair
It is bright that discarded circuit board is handled using pyrolysismethod, useful metal composition in recovery train plate.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：
According to the present invention, there is provided a kind of system of old circuit board Pyrolyzation and debromination processing, comprising：
Blender, the blender is used to handle material stirring mixing, and includes fragment wiring board entrance, solid thermal carriers
First entrance and mixed material outlet；
Rotary kiln, the rotary kiln is used to material carrying out pyrolysis processing, and goes out comprising mixed material entrance and pyrolysis batch mixing
Mouthful；Mixed material entrance is connected with the mixed material outlet of blender；
Roto-siofter and gas-solid separator, roto-siofter are arranged in gas-solid separator；Wherein,
Roto-siofter is used to be separated solid thermal carriers and pyrolysis residue, and is carried comprising solid material inlet, solid thermal
Body first outlet, pyrolysis residue outlet and gas vent；Solid material inlet is connected with the pyrolysis batch mixing outlet of rotary kiln；Heat
Solution solid discharge and gas vent connect with gas-solid separator；
Gas-solid separator is used to material carrying out gas solid separation, and is exported comprising solid matter outlet and gas material；
Knockout tower, the knockout tower be used for spray into ammoniacal liquor to gas material carry out chilling separation, and comprising gas material import,
Pyrolysis gas outlet and pyrolysis oil export；Gas material import is connected with the gas material outlet of gas-solid separator.Meanwhile spray
Ammoniacal liquor can also absorb the sour gas such as unabsorbed hydrogen bromide in pyrolytic process, prevent from damaging environment.
Further, the system also includes：
Centrifuge, the centrifuge are acted on by centrifugal friction and are separated the attachment on solid thermal carriers, and comprising
Solid thermal carriers second entrance, the outlet of the first isolate and the outlet of the second isolate；Solid thermal carriers second entrance and roto-siofter
Solid thermal carriers first outlet be connected, roto-siofter is connected with centrifuge can be arranged to open or close, such as can make
It is controlled with valve well known to those skilled in the art；When solid thermal carriers and pyrolysis residue are separated in roto-siofter
When, roto-siofter and centrifuge connection closed；When solid thermal carriers and pyrolysis residue separated in roto-siofter completion when, roto-siofter with
Centrifuge connection is opened；Solid thermal carriers in roto-siofter are delivered into centrifuge in a manner of spiral discharging.First separation
Thing is exported for discharging the solid thermal carriers after separating；Second isolate is exported for discharging the attachment on solid thermal carriers；
Heating furnace, the heating furnace are used to heat solid thermal carriers, and are passed through air and promote heat carrier adhesion wherein
Pyrolysis residue burning remove, and include material inlet to be heated and material outlet；Material inlet and centrifuge to be heated
The first isolate outlet be connected；Material outlet is connected with the solid thermal carriers first entrance of blender.
Further, system also includes：
Disintegrating machine, the disintegrating machine is used to old circuit board being cut into fragment, and includes useless circuit board entrance and fragment circuit
Plate exports, and fragment circuit board exit is connected with the fragment wiring board entrance of blender；
Tower is collected, the collection tower includes pyrolysis residue entrance, and the solid material of pyrolysis residue entrance and gas-solid separator goes out
Mouth is connected with the second isolate outlet of centrifuge.
According to the present invention, a kind of method that old circuit board Pyrolyzation and debromination is carried out using system as described above is also provided,
Comprise the following steps：
1) waste printed circuit board passes through crusher in crushing into fragment；Fragment particle diameter is smaller be pyrolyzed in pyrolytic process it is more abundant.
2) by solid thermal carriers after preheating device preheats, it is mixed into a mixer with waste printed circuit board fragment mixed
Compound material；
3) mixed material is sent in rotary kiln, be pyrolyzed；Metal oxide is in pyrolytic process because and scrap wire
Road plate fully contact with pyrolysis caused by the corrosive gas such as hydrogen bromide with solid thermal carriers reaction so as to generate metal bromide,
The metal bromate salt dissolving of reaction generation is present in pyrolytic carbon or is adhered on metal oxide spheres；
4) material after pyrolysis is sequentially entered into roto-siofter and gas-solid separator is separated, material is carried out in roto-siofter
Separation, obtains solid thermal carriers and pyrolysis residue, and pyrolysis residue enters gas-solid separator by the pyrolysis residue outlet of roto-siofter；
The gas material in the material of pyrolysis enters gas-solid separator by the gas vent of roto-siofter simultaneously；Gas material is tar gas
With pyrolysis fixed gas；Pyrolysis residue and gas material are separated in gas-solid separator；
5) enter in step 4) by the gas material of gas-solid separator and chilling separation is carried out in knockout tower, obtain pyrolysis gas
And pyrolysis oil；Simultaneously by gas-solid separator in step 4) pyrolysis residue enter collect tower reclaimed, by machinery or
Manual method separation metal level and glass fibre simultaneously recycle；
6) solid thermal carriers that roto-siofter screens out in step 4) by centrifuge it is mechanically decoupled be adhered on wall be pyrolyzed it is residual
Slag and metal bromate salt dissolving；The pyrolysis residue of separation and metal bromate salt dissolving are sent into pyrolytic carbon handling process and carry out post-processing；
7) solid thermal carriers for obtaining step 6) are heated in heating furnace, and air is passed through in heating furnace and removes solid thermal
It is sent into blender after remaining carbon distribution in carrier and is mixed as solid thermal carriers with waste printed circuit board fragment.
Further, solid thermal carriers are metal oxide spheres, and the particle diameter of solid thermal carriers is 20~40mm, and in order to just
In the screening of later stage heat carrier and pyrolysis material, the particle diameter of solid thermal carriers is more than the equivalent grain size of fragment.
Further, the equivalent grain size of the fragment in step 1) is 5mm~15mm.
Further, metal oxide include but are not limited to it is following it is several as iron oxide, ferroso-ferric oxide, calcium oxide,
Cupric oxide.
Further, the mixing quality ratio of the waste printed circuit board fragment in step 2) and solid thermal carriers be (1: 3)~(1:
10).The ratio fed by the charging and metal oxide spheres that control waste printed circuit board so that the mean temperature of mixture reaches pre-
The pyrolysis temperature first set.
Further, preheating temperature of the solid thermal carriers in preheating device is 700-1200 degrees Celsius in step 2)；Step
It is rapid 7) in heating furnace heat after solid thermal carriers temperature be 700-1200 degrees Celsius.
Further, the temperature of the mixed material in step 2) is 400-800 degrees Celsius.
Further, the pyrolysis temperature in the rotary kiln in step 3) is 400-800 degrees Celsius.
Further, gas material sprays into the separation of ammoniacal liquor chilling in knockout tower, meanwhile, the ammoniacal liquor of spray can also absorb
The sour gas such as unabsorbed hydrogen bromide in pyrolytic process, prevents from damaging environment.
The beneficial effects of the invention are as follows：
1) the problems such as furnace heat transfer efficiency is low, and pyrolysis of waste is incomplete be present for old circuit board pyrolytic process, this
Invention is pyrolyzed by using solid thermal carriers and old circuit board, is rotated using rotary kiln and is promoted wiring board to be carried with solid thermal
Body fully contacts, and so as to improve heat transfer efficiency, improves pyrolysis effect.Waste-line is handled using rotary kiln solid heat carrier pyrolysis method
Road plate, technological process is simple, and solid thermal carriers can be recycled, and reduces offal treatment cost.
2) for pyrolysis caused by bromine-containing gas easily equipment is caused to corrode, easily with pyrolysis caused by tar reaction generate
Brominated organic matter, reduces tar quality, and the present invention fills by using metal oxide as solid thermal carriers and old circuit board
Point mixing, using metal oxide such as iron oxide, cupric oxide etc. come Br caused by absorbing pyrolytic reaction2, the material such as HBr, so as to
Halides in old circuit board are effectively removed, metal bromate salt dissolving are generated, to prevent the influence of its corrosion and tar to equipment.
3) traditional old circuit board pyrolysis processing technique is to carry out heating pyrolysis to wiring board using external heating, is produced
The gas such as hydrogen bromide carry out vent gas treatment in later stage spray ammoniacal liquor etc..And bromine, hydrogen bromide have deep-etching caused by being pyrolyzed
Property, corrosion harmfulness is easily caused to equipment, and the tar reaction generation organic bromide easily generated reduces tar quality.This hair
The bright pyrolysis that solid heat carrier method progress discarded circuit board is done using metal oxide, is also assisted in while improving heat transfer efficiency
Pyrolytic reaction, using the metal oxide such as material such as iron oxide, cupric oxide, calcium oxide easily with the material such as bromine simple substance, hydrogen bromide
Reaction, generation metal bromate salt dissolving prevent the influence of its corrosion and tar to equipment.
Brief description of the drawings
Fig. 1 is the schematic diagram of the system handled according to the old circuit board Pyrolyzation and debromination of the present invention；
Fig. 2 is the flow chart of the method handled according to the old circuit board Pyrolyzation and debromination of the present invention.
Reference
1 disintegrating machine, 2 blenders, 3 rotary kilns, 4 roto-siofters, 5 gas-solid separators, 6 knockout towers, 7 collection towers, 8 centrifuges, 9
Heating furnace.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with the accompanying drawings and embodiment, it is right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
As shown in Figure 1-2, the system for showing the processing of old circuit board Pyrolyzation and debromination, comprising knockout tower 6, disintegrating machine 1, mix
Clutch 2, rotary kiln 3, roto-siofter 4, gas-solid separator 5, centrifuge 8, heating furnace 9 and collection tower 7.
Disintegrating machine 1 is used to old circuit board being cut into fragment, and comprising useless circuit board entrance and fragment circuit board exit, it is broken
Block circuit board exit is connected with the fragment wiring board entrance of blender 2；
Blender 2 is used to handle material stirring mixing, and includes fragment wiring board entrance, solid thermal carriers first entrance
And mixed material outlet；
Rotary kiln 3 is used to material carrying out pyrolysis processing, and includes mixed material entrance and the outlet of pyrolysis batch mixing；Mixture
Material entrance is connected with the mixed material outlet of blender 2；
Roto-siofter 4 is arranged in gas-solid separator 5；Wherein,
Roto-siofter 4 is used to be separated solid thermal carriers and pyrolysis residue, and is carried comprising solid material inlet, solid thermal
Body first outlet, pyrolysis residue outlet and gas vent；Solid material inlet is connected with the pyrolysis batch mixing outlet of rotary kiln 3；
Pyrolysis residue exports and gas vent connects with gas-solid separator 5；
Gas-solid separator 5 is used to material carrying out gas solid separation, and is exported comprising solid matter outlet and gas material；
The knockout tower 6 is used to spray into ammoniacal liquor to gas material progress chilling separation, and includes gas material import, pyrolysis gas
Outlet and pyrolysis oil export；Gas material import is connected with the gas material outlet of gas-solid separator 5.
Centrifuge 8 is acted on by centrifugal friction and is separated the attachment on solid thermal carriers, and is carried comprising solid thermal
Body second entrance, the outlet of the first isolate and the outlet of the second isolate；Solid thermal carriers second entrance and the solid thermal of roto-siofter 4
Carrier first outlet is connected, and roto-siofter is connected with centrifuge can be arranged to open or close, such as can use this area
Valve is controlled known to technical staff；When solid thermal carriers and pyrolysis residue are separated in roto-siofter, roto-siofter
With centrifuge connection closed；When solid thermal carriers and pyrolysis residue separate completion in roto-siofter, roto-siofter connects with centrifuge
Take out；Solid thermal carriers in roto-siofter are delivered into centrifuge in a manner of spiral discharging.Use the outlet of first isolate
Solid thermal carriers after discharge separates；Second isolate is exported for discharging the attachment on solid thermal carriers；
Heating furnace 9 is used to heat solid thermal carriers, and is passed through air and promotes heat carrier adhesion pyrolysis therein residual
Slag burning removes, and includes material inlet to be heated and material outlet；First point of material inlet to be heated and centrifuge 8
It is connected from thing outlet；Material outlet is connected with the solid thermal carriers first entrance of blender 2；
The collection tower 7 includes pyrolysis residue entrance, the solid matter outlet of pyrolysis residue entrance and gas-solid separator 5 and from
The second isolate outlet of scheming 8 is connected.
As shown in Figure 1-2, further it is shown that the method that old circuit board Pyrolyzation and debromination is carried out using system as described above, bag
Include following steps：
1) waste printed circuit board is broken into fragment by disintegrating machine 1；Fragment particle diameter is smaller be pyrolyzed in pyrolytic process it is more abundant.
2) by solid thermal carriers after preheating device preheats, it is mixed into blender 2 with waste printed circuit board fragment
Mixed material；
3) mixed material is sent in rotary kiln 3, be pyrolyzed；Metal oxide is in pyrolytic process because and scrap wire
Road plate fully contact with pyrolysis caused by the corrosive gas such as hydrogen bromide with solid thermal carriers reaction so as to generate metal bromide,
The metal bromate salt dissolving of reaction generation is present in pyrolytic carbon or is adhered on metal oxide spheres；
4) material after pyrolysis is sequentially entered into roto-siofter 4 and gas-solid separator 5 is separated, material is in roto-siofter 4
Separated, obtain solid thermal carriers and pyrolysis residue, pyrolysis residue is divided by the pyrolysis residue outlet of roto-siofter 4 into gas-solid
From device 5；The gas material in the material of pyrolysis enters gas-solid separator 5 by the gas vent of roto-siofter 4 simultaneously；Gas material
For tar gas and pyrolysis fixed gas；Pyrolysis residue and gas material are separated in gas-solid separator 5；
5) enter in step 4) by the gas material of gas-solid separator 5 and chilling separation is carried out in knockout tower 6, be pyrolyzed
Gas and pyrolysis oil；The pyrolysis residue in gas-solid separator in step 4) 5 is entered into collection tower 7 simultaneously to be reclaimed, by machinery
Or manual method separation metal level and glass fibre and recycle；
6) solid thermal carriers that roto-siofter 4 screens out in step 4) are pyrolyzed by mechanically decoupled be adhered on wall of centrifuge 8
Residue and metal bromate salt dissolving；The pyrolysis residue of separation and metal bromate salt dissolving are sent into pyrolytic carbon handling process and carry out post-processing；
7) solid thermal carriers that step 6) obtains are heated in heating furnace 9, air is passed through in heating furnace 9 and removes solid
It is sent into blender 2 after remaining carbon distribution in heat carrier and is mixed as solid thermal carriers with waste printed circuit board fragment.
Preferably, solid thermal carriers are metal oxide spheres, and the particle diameter of solid thermal carriers is 20~40mm, and for the ease of
The screening of later stage heat carrier and pyrolysis material, the particle diameter of solid thermal carriers are more than the equivalent grain size of fragment.
Preferably, the equivalent grain size of the fragment in step 1) is 5mm~15mm.
Preferably, metal oxide includes but are not limited to following several such as iron oxide, ferroso-ferric oxide, calcium oxide, oxygen
Change copper.
Preferably, the mixing quality ratio of the waste printed circuit board fragment in step 2) and solid thermal carriers be (1: 3)~(1:
10).The ratio fed by the charging and metal oxide spheres that control waste printed circuit board so that the mean temperature of mixture reaches pre-
The pyrolysis temperature first set.
Preferably, preheating temperature of the solid thermal carriers in preheating device is 700-1200 degrees Celsius in step 2)；Step
7) temperature of the solid thermal carriers after being heated in heating furnace 9 is 700-1200 degrees Celsius.
Preferably, the temperature of the mixed material in step 2) is 400-800 degrees Celsius.
Preferably, the pyrolysis temperature in step 3) in rotary kiln 3 is 400-800 degrees Celsius.
Preferably, gas material sprays into the separation of ammoniacal liquor chilling in knockout tower 6, meanwhile, the ammoniacal liquor of spray can also absorb
The sour gas such as unabsorbed hydrogen bromide in pyrolytic process, prevents from damaging environment.
Embodiment 1
The present embodiment carries out the pyrolysis of the pyrolytic process of rotary kiln 3 using said system using waste and old printed circuit board FR4 plates and taken off
Bromine.
As shown in figure 1, the waste printed circuit board of collection is crushed by pretreatment into disintegrating machine 1, its particle diameter is set to exist
5mm-10mm, wherein wiring board particle diameter is smaller, solid thermal carriers mixed with wiring board it is more uniform, pyrolysis efficiency it is higher.
The wiring board crushed and the solid thermal carriers heated by preheating device (such as heating furnace 9) are fast in ribbon mixer
Speed is well mixed, and solid thermal carriers use iron oxide pellet.The equivalent grain size that the equivalent grain size of iron oxide pellet is more than wiring board is easy to
Later stage and the separation of pyrolysis coke, the equivalent grain size of iron oxide pellet is 20mm.Heating furnace 9 utilizes storage using the mode of external heat
Hot type radiant tube burner heats to iron oxide pellet, makes its temperature more than 1000-1200 DEG C.In ribbon mixer 2,
It is 4: 1 by controlling the charge proportion of iron oxide pellet and wiring board so that the temperature of mixed material is at 600-800 DEG C.
Mixed material, which enters in rotary kiln 3, to be pyrolyzed, and maintenance reaction system temperature is between 400~600 DEG C.Mixture
Solid thermal carriers in material, specially iron oxide pellet, iron oxide is in pyrolytic process because fully being contacted with waste printed circuit board and heat
Corrosive gas hydrogen bromide caused by solution and simple substance bromine are reacted with iron oxide so as to generate ferric bromide and ferrous bromide, reaction generation
Ferric bromide and ferrous bromide be present in pyrolysis residue (such as pyrolytic carbon) or be adhered on iron oxide pellet.
The roto-siofter 4 that mixed material enters in gas-solid separator 5 therewith, the gas vent that gas material passes through roto-siofter 4
Pyrolysis gas enters in knockout tower 6 into gas-solid separator 5, and with the screening of roto-siofter 4, pyrolysis residue passes through roto-siofter 4
Pyrolysis residue outlet enters gas-solid separator 5, and iron oxide pellet is stayed in roto-siofter 4.Gas material and pyrolysis residue are in gas-solid point
From being separated in device 5, gas material directly sprays carry out chilling in knockout tower 6 using ammoniacal liquor, reduce pyrolysis gas temperature to 80~
90 DEG C, pyrolytic tar is set to be separated with pyrolysis gas.Pyrolysis residue in gas-solid separator 5 enters to collect to be reclaimed in tower 7,
The pyrolysis residue of old circuit board mainly includes metallic copper, glass fibre and pyrolytic carbon etc., by machinery or manual method
Separation metal level and glass fibre simultaneously recycles.
Fire retardant in wiring board be present can generate more simple substance bromine and hydrogen bromide in pyrolytic process, most of to turn round
React and remove with iron oxide pellet in kiln 3, remaining fraction in knockout tower 6 by ammonia absorption, so as to effectively remove waste and old circuit
Plate is pyrolyzed bromine product.Experiments verify that the content of organic bromine reduces more than 57.3% in pyrolytic tar.
Iron oxide pellet in roto-siofter 4 enters to the rotation of the high speed of centrifuge 8, passes through the shearing friction between iron oxide pellet
The pyrolytic carbon being adhered on spheroid is removed, the pyrolytic carbon of separation, which is sent into, to be collected in tower 7, and iron oxide pellet is entered in heating furnace 9, profit
Iron oxide pellet is heated with heat accumulating type radiant burner, and is passed through partial air and promotes not removing clean Jiao in spheroid
Charcoal, heated oxide iron ball temperature is to more than 1000-1200 DEG C.Subsequently into blender 2 again with the discarded circuit board heat of mixing
Solution.
Embodiment 2
The present embodiment carries out the pyrolysis of the pyrolytic process of rotary kiln 3 using said system using waste and old printed circuit board FR4 plates and taken off
Bromine.
As shown in figure 1, the waste printed circuit board of collection is crushed by pretreatment into disintegrating machine 1, its particle diameter is set to exist
10mm-15mm, wherein wiring board particle diameter is smaller, solid thermal carriers mixed with wiring board it is more uniform, pyrolysis efficiency it is higher.
The wiring board crushed and the solid thermal carriers heated by preheating device (such as heating furnace 9) are fast in horizontal mixers
Speed is well mixed, and solid thermal carriers are using oxidation calcisphere.The equivalent grain size that the equivalent grain size of oxidation calcisphere is more than wiring board is easy to
Later stage and the separation of pyrolysis coke, the equivalent grain size for aoxidizing calcisphere are 40mm.Heating furnace 9 utilizes storage using the mode of external heat
Hot type radiant tube burner heats to oxidation calcisphere, makes its temperature more than 700-900 DEG C.In ribbon mixer 2, lead to
It is 3: 1 to cross and control the charge proportion for aoxidizing calcisphere and wiring board so that the temperature of mixed material is at 400-600 DEG C.
Mixed material, which enters in rotary kiln 3, to be pyrolyzed, and maintenance reaction system temperature is between 400~600 DEG C.Mixture
Solid thermal carriers in material, calcisphere is specially aoxidized, calcium oxide is in pyrolytic process because fully being contacted with waste printed circuit board and heat
Corrosive gas hydrogen bromide caused by solution and simple substance bromine are reacted so as to generate calcium bromide with calcium oxide, and the calcium bromide for reacting generation is deposited
It is in pyrolysis residue (such as pyrolytic carbon) or is adhered on oxidation calcisphere.
The roto-siofter 4 that mixed material enters in gas-solid separator 5 therewith, the gas vent that gas material passes through roto-siofter 4
Pyrolysis gas enters in knockout tower 6 into gas-solid separator 5, and with the screening of roto-siofter 4, pyrolysis residue passes through roto-siofter 4
Pyrolysis residue outlet enters gas-solid separator 5, and oxidation calcisphere is stayed in roto-siofter 4.Gas material and pyrolysis residue are in gas-solid point
From being separated in device 5, gas material directly sprays carry out chilling in knockout tower 6 using ammoniacal liquor, reduce pyrolysis gas temperature to 80~
90 DEG C, pyrolytic tar is set to be separated with pyrolysis gas.Pyrolysis residue in gas-solid separator 5 enters to collect to be reclaimed in tower 7,
The pyrolysis residue of old circuit board mainly includes metallic copper, glass fibre and pyrolytic carbon etc., by machinery or manual method
Separation metal level and glass fibre simultaneously recycles.
Fire retardant in wiring board be present can generate more simple substance bromine and hydrogen bromide in pyrolytic process, most of to turn round
Removed in kiln 3 with oxidation calcisphere reaction, remaining fraction in knockout tower 6 by ammonia absorption, so as to effectively remove waste and old circuit
Plate is pyrolyzed bromine product.Experiments verify that the content of organic bromine reduces more than 52.9% in pyrolytic tar.
Oxidation calcisphere in roto-siofter 4 enters to the rotation of the high speed of centrifuge 8, by aoxidizing the shearing friction between calcisphere
The pyrolytic carbon being adhered on spheroid is removed, the pyrolytic carbon of separation, which is sent into, to be collected in tower 7, and oxidation calcisphere is entered in heating furnace 9, profit
Oxidation calcisphere is heated with heat accumulating type radiant burner, and is passed through partial air and promotes not removing clean Jiao in spheroid
Charcoal, heated oxide calcisphere temperature is to more than 700-900 DEG C.Subsequently into blender 2 again with discarded circuit board mixed pyrolysis.
Embodiment 3
The present embodiment carries out the pyrolysis of the pyrolytic process of rotary kiln 3 using said system using waste and old printed circuit board FR4 plates and taken off
Bromine.
As shown in figure 1, the waste printed circuit board of collection is crushed by pretreatment into disintegrating machine 1, make its particle diameter in 5-
15mm, wherein wiring board particle diameter is smaller, solid thermal carriers mixed with wiring board it is more uniform, pyrolysis efficiency it is higher.
The wiring board crushed and the solid thermal carriers heated by preheating device (such as heating furnace 9) are fast in V-type blender
Speed is well mixed, and solid thermal carriers are using oxidation copper ball.The equivalent grain size that the equivalent grain size of oxidation copper ball is more than wiring board is easy to
Later stage and the separation of pyrolysis coke, the equivalent grain size for aoxidizing copper ball are 30mm.Heating furnace 9 utilizes storage using the mode of external heat
Hot type radiant tube burner heats to oxidation copper ball, makes its temperature more than 900-1100 DEG C.In ribbon mixer 2,
It is 10: 1 by controlling the charge proportion of oxidation copper ball and wiring board so that the temperature of mixed material is at 600-800 DEG C.
Mixed material, which enters in rotary kiln 3, to be pyrolyzed, and maintenance reaction system temperature is between 600-800 DEG C.Mixture
Solid thermal carriers in material, copper ball is specially aoxidized, cupric oxide is in pyrolytic process because fully being contacted with waste printed circuit board and heat
Corrosive gas hydrogen bromide caused by solution and simple substance bromine are reacted so as to generate copper bromide with cupric oxide, and the copper bromide for reacting generation is deposited
It is in pyrolysis residue (such as pyrolytic carbon) or is adhered on oxidation copper ball.
The roto-siofter 4 that mixed material enters in gas-solid separator 5 therewith, the gas vent that gas material passes through roto-siofter 4
Pyrolysis gas enters in knockout tower 6 into gas-solid separator 5, and with the screening of roto-siofter 4, pyrolysis residue passes through roto-siofter 4
Pyrolysis residue outlet enters gas-solid separator 5, and oxidation copper ball is stayed in roto-siofter 4.Gas material and pyrolysis residue are in gas-solid point
From being separated in device 5, gas material directly sprays carry out chilling in knockout tower 6 using ammoniacal liquor, reduce pyrolysis gas temperature to 80~
90 DEG C, pyrolytic tar is set to be separated with pyrolysis gas.Pyrolysis residue in gas-solid separator 5 enters to collect to be reclaimed in tower 7,
The pyrolysis residue of old circuit board mainly includes metallic copper, glass fibre and pyrolytic carbon etc., by machinery or manual method
Separation metal level and glass fibre simultaneously recycles.
Fire retardant in wiring board be present can generate more simple substance bromine and hydrogen bromide in pyrolytic process, most of to turn round
Removed in kiln 3 with oxidation copper ball reaction, remaining fraction in knockout tower 6 by ammonia absorption, so as to effectively remove waste and old circuit
Plate is pyrolyzed bromine product.Experiments verify that the content of organic bromine reduces more than 72.1% in pyrolytic tar.
Oxidation copper ball in roto-siofter 4 enters to the rotation of the high speed of centrifuge 8, by aoxidizing the shearing friction between copper ball
The pyrolytic carbon being adhered on spheroid is removed, the pyrolytic carbon of separation, which is sent into, to be collected in tower 7, and oxidation copper ball is entered in heating furnace 9, profit
Oxidation copper ball is heated with heat accumulating type radiant burner, and is passed through partial air and promotes not removing clean Jiao in spheroid
Charcoal, heated oxide copper ball temperature is to more than 900-1100 DEG C.Subsequently into blender 2 again with the discarded circuit board heat of mixing
Solution.
Embodiment 4
The present embodiment carries out the pyrolysis of the pyrolytic process of rotary kiln 3 using said system using waste and old printed circuit board FR4 plates and taken off
Bromine.
As shown in figure 1, the waste printed circuit board of collection is crushed by pretreatment into disintegrating machine 1, its particle diameter is set to exist
6mm-12mm, wherein wiring board particle diameter is smaller, solid thermal carriers mixed with wiring board it is more uniform, pyrolysis efficiency it is higher.
The wiring board crushed and the solid thermal carriers heated by preheating device (such as heating furnace 9) are fast in ribbon mixer
Speed is well mixed, and solid thermal carriers use ferroso-ferric oxide ball.The equivalent grain size of ferroso-ferric oxide ball is more than the equivalent of wiring board
Particle diameter is easy to the separation of later stage and pyrolysis coke, and the equivalent grain size of ferroso-ferric oxide ball is 25mm.Heating furnace 9 utilizes external heat
Mode, ferroso-ferric oxide ball is heated using regenerative radiant tube burner, makes its temperature more than 800-1000 DEG C.
It is 7: 1 by controlling the charge proportion of ferroso-ferric oxide ball and wiring board so that the temperature of mixed material in ribbon mixer 2
At 500-700 DEG C.
Mixed material, which enters in rotary kiln 3, to be pyrolyzed, and maintenance reaction system temperature is between 500-700 DEG C.Mixture
Solid thermal carriers in material, specially ferroso-ferric oxide ball, ferroso-ferric oxide is in pyrolytic process because abundant with waste printed circuit board
Contact is reacted so as to generate ferric bromide and bromination with corrosive gas hydrogen bromide caused by pyrolysis and simple substance bromine with ferroso-ferric oxide
Ferrous iron, reacts the ferric bromide of generation and ferrous bromide is present in pyrolysis residue (such as pyrolytic carbon) or be adhered to ferroso-ferric oxide ball
On.
The roto-siofter 4 that mixed material enters in gas-solid separator 5 therewith, the gas vent that gas material passes through roto-siofter 4
Pyrolysis gas enters in knockout tower 6 into gas-solid separator 5, and with the screening of roto-siofter 4, pyrolysis residue passes through roto-siofter 4
Pyrolysis residue outlet enters gas-solid separator 5, and ferroso-ferric oxide ball is stayed in roto-siofter 4.Gas material and pyrolysis residue are in gas
Separated in solid separator 5, gas material directly sprays carry out chilling in knockout tower 6 using ammoniacal liquor, reduces pyrolysis gas temperature extremely
80~90 DEG C, pyrolytic tar is set to be separated with pyrolysis gas.Pyrolysis residue in gas-solid separator 5 enters to collect to be carried out in tower 7
Recovery, the pyrolysis residue of old circuit board mainly include metallic copper, glass fibre and pyrolytic carbon etc., by mechanical or craft
Method separates metal level and glass fibre and recycled.
Fire retardant in wiring board be present can generate more simple substance bromine and hydrogen bromide in pyrolytic process, most of to turn round
React and remove with ferroso-ferric oxide ball in kiln 3, remaining fraction in knockout tower 6 by ammonia absorption, it is waste and old so as to effectively remove
Wiring board is pyrolyzed bromine product.Experiments verify that the content of organic bromine reduces more than 69.3% in pyrolytic tar.
Ferroso-ferric oxide ball in roto-siofter 4 enters to the rotation of the high speed of centrifuge 8, by between ferroso-ferric oxide ball
Shearing friction removes the pyrolytic carbon being adhered on spheroid, and the pyrolytic carbon of separation, which is sent into, to be collected in tower 7, and ferroso-ferric oxide ball enters to
In heating furnace 9, ferroso-ferric oxide ball is heated using heat accumulating type radiant burner, and is passed through partial air and promotes in spheroid
Clean coke is not removed, and heating ferroso-ferric oxide ball temperature is to more than 800-1000 DEG C.Subsequently into blender 2 again with
Discarded circuit board mixed pyrolysis.
Presently preferred embodiments of the present invention is these are only, is not used for limiting the practical range of the present invention；If this is not departed from
The spirit and scope of invention, modify or equivalent substitution to the present invention, all should cover the protection in the claims in the present invention
Among scope.
Claims (10)
- A kind of 1. method of old circuit board Pyrolyzation and debromination processing, it is characterised in that comprise the following steps：1) waste printed circuit board passes through crusher in crushing into fragment；2) by solid thermal carriers after preheating device preheats, it is mixed into a mixer with the waste printed circuit board fragment mixed Compound material；3) mixed material is sent in rotary kiln and be pyrolyzed；4) material after pyrolysis is sequentially entered into roto-siofter and gas-solid separator is separated, the material is in the roto-siofter Separated, obtain solid thermal carriers and pyrolysis residue, the pyrolysis residue by the pyrolysis residue of the roto-siofter export into Enter the gas-solid separator；The gas material in the material of pyrolysis enters the gas by the gas vent of the roto-siofter simultaneously Solid separator；The gas material is tar gas and pyrolysis fixed gas；Pyrolysis residue and gas material are in the gas-solid separator In separated；5) enter in step 4) by the gas material of the gas-solid separator and chilling separation is carried out in knockout tower, obtain pyrolysis gas And pyrolysis oil；Simultaneously by gas-solid separator in step 4) pyrolysis residue enter collect tower reclaimed, by machinery or Manual method separation metal level and glass fibre simultaneously recycle.
- 2. the method as described in claim 1, it is characterised in that comprise the following steps：The solid thermal carriers that roto-siofter described in step 4) screens out are adhered to pyrolysis residue on wall by centrifuge is mechanically decoupled And metal bromate salt dissolving；The pyrolysis residue of separation and metal bromate salt dissolving are sent into pyrolytic carbon handling process and carry out post-processing；Solid thermal carriers after centrifuge processing are heated in heating furnace, air is passed through in the heating furnace and is removed admittedly It is sent into after remaining carbon distribution in the blender in body heat carrier and is mixed as solid thermal carriers with waste printed circuit board fragment.
- 3. the method as described in claim 1, it is characterised in that the solid thermal carriers are metal oxide spheres, the solid The particle diameter of heat carrier is 20~40mm, and the particle diameter of the solid thermal carriers is more than the equivalent grain size of the fragment.
- 4. the method as described in claim 1, it is characterised in that the equivalent grain size of the fragment in the step 1) is 5mm ~15mm.
- 5. the method as described in claim 1, it is characterised in that waste printed circuit board fragment and solid thermal carriers in step 2) it is mixed Conjunction mass ratio is (1: 3)~(1: 10).
- 6. the method as described in claim 1, it is characterised in that solid thermal carriers are in preheating device described in the step 2) Preheating temperature be 700-1200 degrees Celsius；The temperature of solid thermal carriers after being heated in the step 7) in heating furnace is 700-1200 degrees Celsius.
- 7. the method as described in claim 1, it is characterised in that the temperature of the mixed material in the step 2) is 400- 800 degrees Celsius；The pyrolysis temperature in the rotary kiln in the step 3) is 400-800 degrees Celsius.
- 8. a kind of system for implementing the method as described in claim 1-7, it is characterised in that include：Blender, the blender are used to handle material stirring mixing, and include fragment wiring board entrance, solid thermal carriers the One entrance and mixed material outlet；Rotary kiln, the rotary kiln is used to material carrying out pyrolysis processing, and includes mixed material entrance and the outlet of pyrolysis batch mixing； The mixed material entrance is connected with the mixed material outlet of the blender；Roto-siofter and gas-solid separator, the roto-siofter are arranged in the gas-solid separator；Wherein,The roto-siofter is used to be separated solid thermal carriers and pyrolysis residue, and is carried comprising solid material inlet, solid thermal Body first outlet, pyrolysis residue outlet and gas vent；The solid material inlet and the pyrolysis of the rotary kiln mix Material outlet is connected；The pyrolysis residue outlet and the gas vent connect with the gas-solid separator；The gas-solid separator is used to material carrying out gas solid separation, and is exported comprising solid matter outlet and gas material；Knockout tower, the knockout tower is used to spray into ammoniacal liquor to gas material progress chilling separation, and includes gas material import, heat Vent one's spleen and export and be pyrolyzed oil export；The gas material import is connected with the gas material outlet of the gas-solid separator.
- 9. the system of old circuit board Pyrolyzation and debromination processing as claimed in claim 8, it is characterised in thatThe system also includes：Centrifuge, the centrifuge are separated the attachment on solid thermal carriers, and comprising solid thermal carriers second entrance, First isolate exports and the outlet of the second isolate；The solid thermal carriers second entrance and the solid thermal of the roto-siofter Carrier first outlet is connected；First isolate is exported for discharging the solid thermal carriers after separating；Second isolate Export for discharging the attachment on solid thermal carriers；Heating furnace, the heating furnace is used to heat solid thermal carriers, and includes material inlet to be heated and thermal material Outlet；The material inlet to be heated is connected with first isolate outlet of the centrifuge；The material outlet with The solid thermal carriers first entrance of the blender is connected.
- 10. the system of old circuit board Pyrolyzation and debromination processing as claimed in claim 9, it is characterised in that the system is also wrapped Contain：Disintegrating machine, the disintegrating machine is used to old circuit board being cut into fragment, and includes useless circuit board entrance and fragment circuit board Outlet, the fragment circuit board exit are connected with the fragment wiring board entrance of the blender；Tower is collected, the collection tower includes pyrolysis residue entrance, and the pyrolysis residue entrance is described with the gas-solid separator Solid matter outlet is connected with second isolate outlet of the centrifuge.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711233014.8A CN107891053A (en) | 2017-11-29 | 2017-11-29 | A kind of method and system of old circuit board Pyrolyzation and debromination processing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711233014.8A CN107891053A (en) | 2017-11-29 | 2017-11-29 | A kind of method and system of old circuit board Pyrolyzation and debromination processing |
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| CN107891053A true CN107891053A (en) | 2018-04-10 |
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| CN201711233014.8A Pending CN107891053A (en) | 2017-11-29 | 2017-11-29 | A kind of method and system of old circuit board Pyrolyzation and debromination processing |
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| CN (1) | CN107891053A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180318842A1 (en) * | 2015-11-09 | 2018-11-08 | Eauterre Consulting, Llc | Method and apparatus for separation and size reduction of noble metal containing sources |
| CN112283712A (en) * | 2020-10-21 | 2021-01-29 | 深圳市捷晶能源科技有限公司 | Chlorine-containing and bromine-containing solid waste pyrolysis system |
| CN112735625A (en) * | 2021-01-07 | 2021-04-30 | 广州维港环保科技有限公司 | Equipment and process for treating organic matters by utilizing heat carrier |
| CN112759731A (en) * | 2020-12-22 | 2021-05-07 | 山东省环境保护科学研究设计院有限公司 | Method for separating and recycling pyrolysis oil in waste circuit board and electronic component packaging material |
| CN112812792A (en) * | 2020-12-30 | 2021-05-18 | 南京万德斯环保科技股份有限公司 | Internal heat rotary anaerobic pyrolysis system and method for treating solid waste by using same |
| CN112978765A (en) * | 2021-05-20 | 2021-06-18 | 中国恩菲工程技术有限公司 | Waste circuit board pyrolysis debromination purification device and method |
| CN114231319A (en) * | 2021-12-02 | 2022-03-25 | 中国科学院广州能源研究所 | Method for preparing synthesis gas by co-processing waste printed circuit board and organic waste liquid |
-
2017
- 2017-11-29 CN CN201711233014.8A patent/CN107891053A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180318842A1 (en) * | 2015-11-09 | 2018-11-08 | Eauterre Consulting, Llc | Method and apparatus for separation and size reduction of noble metal containing sources |
| CN112283712A (en) * | 2020-10-21 | 2021-01-29 | 深圳市捷晶能源科技有限公司 | Chlorine-containing and bromine-containing solid waste pyrolysis system |
| CN112759731A (en) * | 2020-12-22 | 2021-05-07 | 山东省环境保护科学研究设计院有限公司 | Method for separating and recycling pyrolysis oil in waste circuit board and electronic component packaging material |
| CN112812792A (en) * | 2020-12-30 | 2021-05-18 | 南京万德斯环保科技股份有限公司 | Internal heat rotary anaerobic pyrolysis system and method for treating solid waste by using same |
| CN112735625A (en) * | 2021-01-07 | 2021-04-30 | 广州维港环保科技有限公司 | Equipment and process for treating organic matters by utilizing heat carrier |
| CN112978765A (en) * | 2021-05-20 | 2021-06-18 | 中国恩菲工程技术有限公司 | Waste circuit board pyrolysis debromination purification device and method |
| CN114231319A (en) * | 2021-12-02 | 2022-03-25 | 中国科学院广州能源研究所 | Method for preparing synthesis gas by co-processing waste printed circuit board and organic waste liquid |
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