CN207787253U - A kind of system of old circuit board Pyrolyzation and debromination processing - Google Patents
A kind of system of old circuit board Pyrolyzation and debromination processing Download PDFInfo
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- CN207787253U CN207787253U CN201721633804.0U CN201721633804U CN207787253U CN 207787253 U CN207787253 U CN 207787253U CN 201721633804 U CN201721633804 U CN 201721633804U CN 207787253 U CN207787253 U CN 207787253U
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Abstract
The utility model is related to a kind of systems of old circuit board Pyrolyzation and debromination processing, including knockout tower, crusher, mixer, rotary kiln, roto-siofter, gas-solid separator, centrifuge, heating furnace and collection tower.The utility model does solid thermal carriers using metal oxide and is sufficiently mixed with old circuit board, and the Br of pyrolytic reaction generation is absorbed using metal oxide such as iron oxide, copper oxide etc.2, the substances such as HBr, to effectively remove halides in old circuit board, generating metal bromate salt dissolving prevents it to the corrosion of equipment and the influence of tar.
Description
Technical Field
The utility model relates to a solid useless processing field, more specifically relates to a system that old and useless circuit board pyrolysis debrominated was handled.
Background
The waste circuit board is a solid waste produced by various waste computers, communication equipment, household appliances such as televisions, refrigerators and the like, eliminated precise electronic instruments and meters and the like. China is a large country for producing and consuming electronic appliances, and the number of waste circuit boards produced by the electronic appliances is increased in geometric multiples in recent years. On the other hand, as the world's largest circuit board manufacturing and producing country, waste materials generated in the production process reach 30% of the total amount, and are one of important sources of waste circuit boards.
At present, a plurality of research institutions at home and abroad carry out extensive research on the recovery treatment and resource recycling of the waste circuit boards, and the adopted resource treatment process technology mainly comprises a mechanical physical treatment technology, hydrometallurgy, biological treatment, supercritical fluid treatment, heat treatment and the like. The mechanical physical treatment technology utilizes a mechanical crushing method to fully dissociate metal components and nonmetal components, and then utilizes gravity separation, magnetic separation and other methods to separate the metal components, so that the defects of high energy consumption, large amount of dust generated by a crushing treatment process, unsatisfactory crushing effect and the like exist. The basic principle of hydrometallurgy is to leach out metals on a waste circuit board under acidic or alkaline conditions, separate the metals from other substances and recover the metals from a liquid phase, but organic matters in the circuit board cannot be recovered, the water consumption is high, and the generated waste water causes environmental pollution. In a plurality of treatment processes, pyrolysis is used as a novel waste circuit board treatment technology, so that a resin bonding layer in a waste circuit board can be decomposed, and the bonding force between a metal layer and a nonmetal layer is weakened, so that the high-efficiency dissociation of the metal layer and the nonmetal layer is realized; in addition, pyrolysis gas and pyrolysis oil generated in the pyrolysis process can be recycled as fuel gas or chemical raw materials, and pollution generation of dioxin and the like can be effectively avoided.
The traditional pyrolysis treatment process mainly has two problems: 1. because the circuit board heat conductivity is not good, the heat transfer efficiency in the furnace is low, the energy consumption is high, and the treatment efficiency is not high. 2. In the circuit board, a large amount of halogenated matters are contained in the flame retardant, and more shielding smog, elemental bromine, hydrogen bromide, bromophenol and other toxic and harmful substances can be generated in the pyrolysis process. These substances not only cause immeasurable serious environmental damage, but also corrode processing equipment and reduce the quality of the finished oil. Therefore, a new waste circuit board pyrolysis treatment process needs to be considered, bromide generated by circuit board pyrolysis is removed as far as possible while the pyrolysis efficiency is improved, so that corrosion to reaction equipment is avoided, and influence on later-stage oil products is eliminated.
In the prior art, pyrolysis is carried out in a fluidized bed mode, so that the energy consumption is high, the operation process is complex, and a melt generated by pyrolysis of waste plastics is easy to adhere to fluidized bed material quartz sand, so that the normal operation of the process is influenced. In addition, inorganic gases such as hydrogen bromide, bromine and the like mainly generated in the pyrolysis process of the brominated flame retardant are easy to corrode equipment, and can react with the generated pyrolysis oil to generate bromine-containing organic matters so as to reduce the quality of tar.
The other technology utilizes an ammonia supercritical fluid method to remove bromine in bromine-containing plastics, and the main process flow comprises several sections of raw material pretreatment, high-temperature high-pressure debromination reaction, post-treatment and the like. The technology has the main defects that 1) the bromine-containing plastic waste is treated by a supercritical fluid method, the operation condition is high temperature and high pressure, the energy consumption is large, and the application in the industry is difficult to realize; 2) a large amount of waste water is generated in the reaction process, which causes secondary pollution.
Therefore, the development of a technology for efficiently cleaning and treating the waste circuit board is urgently needed.
SUMMERY OF THE UTILITY MODEL
To the problem, the utility model provides a system that old and useless circuit board pyrolysis debrominated and handles. The utility model adopts a pyrolysis method to treat the waste circuit board and recover the useful metal components in the circuit board.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
according to the utility model discloses, a system for old and useless circuit board pyrolysis debromination is handled is provided, contains:
the mixer is used for stirring and uniformly mixing materials and comprises a fragment circuit board inlet, a solid heat carrier first inlet and a mixed material outlet;
the rotary kiln is used for carrying out pyrolysis treatment on the materials and comprises a mixed material inlet and a pyrolysis mixed material outlet; the mixed material inlet is connected with the mixed material outlet of the mixer;
the rotary screen is arranged in the gas-solid separator; wherein,
the rotary screen is used for separating the solid heat carrier from the pyrolysis residue and comprises a solid material inlet, a solid heat carrier first outlet, a pyrolysis residue outlet and a gas outlet; the solid material inlet is connected with the pyrolysis mixing outlet of the rotary kiln; the pyrolysis residue outlet and the gas outlet are communicated with the gas-solid separator;
the gas-solid separator is used for carrying out gas-solid separation on the materials and comprises a solid material outlet and a gas material outlet;
the separation tower is used for spraying ammonia water to carry out quenching separation on the gas materials and comprises a gas material inlet, a pyrolysis gas outlet and a pyrolysis oil outlet; the gas material inlet is connected with the gas material outlet of the gas-solid separator. Meanwhile, the sprayed ammonia water can also absorb acidic gases such as hydrogen bromide and the like which are not absorbed in the pyrolysis process, so that the environment is prevented from being damaged.
Further, the system further comprises:
the centrifugal machine separates attachments on the solid heat carrier through centrifugal friction and comprises a second solid heat carrier inlet, a first separated object outlet and a second separated object outlet; the second inlet of the solid heat carrier is connected with the first outlet of the solid heat carrier of a rotary screen, and the connection between the rotary screen and the centrifuge can be opened or closed, and can be controlled by using a valve well known to a person skilled in the art; when the solid heat carrier and the pyrolysis residue are separated in the rotary screen, the rotary screen is connected and closed with the centrifuge; when the solid heat carrier and the pyrolysis residue are separated in the rotary screen, the rotary screen is connected with a centrifuge and opened; and conveying the solid heat carrier in the rotary screen into a centrifuge in a spiral discharging mode. The first separated substance outlet is used for discharging the separated solid heat carrier; the second separated substance outlet is used for discharging attachments on the solid heat carrier;
the heating furnace is used for heating the solid heat carrier, introducing air to promote pyrolysis residues adhered to the solid heat carrier to be burnt and removed, and comprises a material inlet to be heated and a hot material outlet; the material inlet to be heated is connected with a first separated substance outlet of the centrifugal machine; the hot material outlet is connected with the first inlet of the solid heat carrier of the mixer.
Further, the system further comprises:
the crushing machine is used for shearing the waste circuit board into fragments and comprises a waste circuit board inlet and a fragment circuit board outlet, and the fragment circuit board outlet is connected with the fragment circuit board inlet of the mixer;
and the collection tower comprises a pyrolysis residue inlet, and the pyrolysis residue inlet is connected with the solid material outlet of the gas-solid separator and the second separated matter outlet of the centrifuge.
In addition, the method for carrying out pyrolysis debromination on the waste circuit board by using the system comprises the following steps:
1) crushing the waste circuit board into fragments by a crusher; the smaller the particle size of the fragments, the more fully pyrolyzed during pyrolysis.
2) Preheating a solid heat carrier by a preheating device, and uniformly mixing the solid heat carrier with fragments of the waste circuit board in a mixer to form a mixed material;
3) conveying the mixed material to a rotary kiln for pyrolysis; in the pyrolysis process, the metal oxide is fully contacted with the waste circuit board, and corrosive gases such as hydrogen bromide and the like generated by pyrolysis react with the solid heat carrier to generate metal bromide, and metal bromide salt generated by the reaction exists in pyrolytic carbon or is adhered to metal oxide balls;
4) the method comprises the following steps of sequentially feeding pyrolyzed materials into a rotary screen and a gas-solid separator for separation, separating the materials in the rotary screen to obtain a solid heat carrier and pyrolysis residues, and feeding the pyrolysis residues into the gas-solid separator through a pyrolysis residue outlet of the rotary screen; simultaneously, gas materials in the pyrolyzed materials enter a gas-solid separator through a gas outlet of the rotary screen; the gas materials are tar gas and pyrolysis noncondensable gas; separating the pyrolysis residue and the gas material in a gas-solid separator;
5) the gas material passing through the gas-solid separator in the step 4) enters a separation tower for quenching separation to obtain pyrolysis gas and pyrolysis oil; simultaneously, the pyrolysis residue in the gas-solid separator in the step 4) enters a collecting tower for recovery, and the metal layer and the glass fiber are separated by a mechanical or manual method and are recycled;
6) mechanically separating the solid heat carrier sieved by the rotary sieve in the step 4) from pyrolysis residues and metal bromide salt adhered to the wall by a centrifugal machine; sending the separated pyrolysis residue and metal bromide salt into a pyrolytic carbon treatment process for post-treatment;
7) heating the solid heat carrier obtained in the step 6) in a heating furnace, introducing air into the heating furnace to remove carbon deposition remaining in the solid heat carrier, and then sending the solid heat carrier into a mixer to be used as the solid heat carrier to be mixed with the fragments of the waste circuit board.
Further, the solid heat carrier is the metal oxide ball, and the particle size of solid heat carrier is 20 ~ 40mm, and for the convenience of the screening of later stage heat carrier and pyrolysis material, the particle size of solid heat carrier is greater than the equivalent particle size of fragment.
Further, the equivalent particle size of the fragments in the step 1) is 5 mm-15 mm.
Further, the metal oxide includes, but is not limited to, iron oxide, ferroferric oxide, calcium oxide, and copper oxide.
Further, the mixing mass ratio of the waste circuit board fragments and the solid heat carrier in the step 2) is (1: 3) - (1: 10). The average temperature of the mixture reaches the preset pyrolysis temperature by controlling the ratio of the feeding of the waste circuit board to the feeding of the metal oxide balls.
Further, the preheating temperature of the solid heat carrier in the preheating device in the step 2) is 700-1200 ℃; the temperature of the solid heat carrier heated in the heating furnace in the step 7) is 700-1200 ℃.
Further, the temperature of the mixed material in the step 2) is 400-800 ℃.
Further, the pyrolysis temperature in the rotary kiln in the step 3) is 400-800 ℃.
Further, gaseous material spouts into aqueous ammonia rapid cooling separation in the knockout tower, and simultaneously, the aqueous ammonia that sprays can also absorb acidic gas such as hydrogen bromide that the pyrolysis process is not absorbed, prevents to cause the destruction to the environment.
The utility model has the advantages that:
1) there is the interior heat transfer efficiency low of stove to old and useless circuit board pyrolysis process, the incomplete scheduling problem of discarded object pyrolysis, the utility model discloses an adopt solid heat carrier and old and useless circuit board to carry out the pyrolysis, utilize the rotary kiln to rotate and promote circuit board and solid heat carrier fully to contact to improve heat transfer efficiency, improve the pyrolysis effect. The waste circuit board is treated by the rotary kiln solid heat carrier pyrolysis method, the process flow is simple, the solid heat carrier can be recycled, and the waste treatment cost is reduced.
2) To the easy equipment that corrodes that causes of bromine-containing gas that the pyrolysis produced, the easy tar reaction with the pyrolysis production generates contains bromine organic matter, reduces the tar quality, the utility model discloses an adopt metal oxide as solid heat carrier and old and useless circuit board intensive mixing, utilize metal oxide to absorb the Br that the pyrolysis produced like iron oxide, cupric oxide etc.2And HBr and the like, thereby effectively removing halogenated substances in the waste circuit board and generating metal bromide to prevent the metal bromide from corroding equipment and preventing the influence of tar.
3) The traditional pyrolysis treatment process of the waste circuit board is to carry out heating pyrolysis on the circuit board by using an external heating method, and gases such as generated hydrogen bromide and the like are sprayed with ammonia water and the like at the later stage to carry out tail gas treatment. Bromine and hydrogen bromide generated by pyrolysis have strong corrosivity, easily cause corrosion damage to equipment, and easily generate tar to react to generate organic bromide to reduce the quality of the tar. The utility model discloses utilize metal oxide to do the pyrolysis that solid heat carrier method carried out the abandonment circuit board, also participated in the pyrolytic reaction when having improved heat transfer efficiency, utilized metal oxide if materials such as iron oxide, cupric oxide, calcium oxide easily react with materials such as bromine simple substance, hydrogen bromide, generate metal bromide salt and prevent its influence to the corruption of equipment and tar.
Drawings
FIG. 1 is a schematic view of a system for pyrolytic debromination of waste circuit boards in accordance with the present invention;
fig. 2 is a flow chart of a method for pyrolysis debromination treatment of waste circuit boards according to the present invention. Reference numerals
1 crusher, 2 mixer, 3 rotary kiln, 4 rotary sieve, 5 gas-solid separator, 6 separating tower, 7 collecting tower, 8 centrifugal machine and 9 heating furnace.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention.
As shown in fig. 1-2, a system for pyrolysis and debromination treatment of waste circuit boards is shown, which comprises a separation tower 6, a crusher 1, a mixer 2, a rotary kiln 3, a rotary screen 4, a gas-solid separator 5, a centrifuge 8, a heating furnace 9 and a collection tower 7.
The crusher 1 is used for shearing the waste circuit board into fragments and comprises a waste circuit board inlet and a fragment circuit board outlet, and the fragment circuit board outlet is connected with the fragment circuit board inlet of the mixer 2;
the mixer 2 is used for uniformly mixing and processing materials and comprises a fragment circuit board inlet, a solid heat carrier first inlet and a mixed material outlet;
the rotary kiln 3 is used for carrying out pyrolysis treatment on the materials and comprises a mixed material inlet and a pyrolysis mixed material outlet; the mixed material inlet is connected with the mixed material outlet of the mixer 2;
the rotary screen 4 is arranged in the gas-solid separator 5; wherein,
the rotary screen 4 is used for separating the solid heat carrier from the pyrolysis residue and comprises a solid material inlet, a solid heat carrier first outlet, a pyrolysis residue outlet and a gas outlet; the solid material inlet is connected with the pyrolysis mixing outlet of the rotary kiln 3; the pyrolysis residue outlet and the gas outlet are communicated with the gas-solid separator 5;
the gas-solid separator 5 is used for carrying out gas-solid separation on the materials and comprises a solid material outlet and a gas material outlet;
the separation tower 6 is used for spraying ammonia water to carry out quenching separation on gas materials and comprises a gas material inlet, a pyrolysis gas outlet and a pyrolysis oil outlet; the gas material inlet is connected with the gas material outlet of the gas-solid separator 5.
The centrifugal machine 8 separates attachments on the solid heat carrier through centrifugal friction, and comprises a second solid heat carrier inlet, a first separated object outlet and a second separated object outlet; the second inlet of the solid heat carrier is connected to the first outlet of the solid heat carrier of a rotary screen 4, which can be arranged to be opened or closed in connection with the centrifuge, for example, and can be controlled using valves well known to those skilled in the art; when the solid heat carrier and the pyrolysis residue are separated in the rotary screen, the rotary screen is connected and closed with the centrifuge; when the solid heat carrier and the pyrolysis residue are separated in the rotary screen, the rotary screen is connected with a centrifuge and opened; and conveying the solid heat carrier in the rotary screen into a centrifuge in a spiral discharging mode. The first separated substance outlet is used for discharging the separated solid heat carrier; the second separated substance outlet is used for discharging attachments on the solid heat carrier;
the heating furnace 9 is used for heating the solid heat carrier, and introducing air to promote the pyrolysis residue adhered to the heat carrier to be burnt and removed, and comprises a material inlet to be heated and a hot material outlet; the material inlet to be heated is connected with the first separated material outlet of the centrifuge 8; the hot material outlet is connected with a first solid heat carrier inlet of the mixer 2;
the collection tower 7 includes a pyrolysis residue inlet connected to the solid material outlet of the gas-solid separator 5 and the second separated material outlet of the centrifuge 8.
As shown in fig. 1-2, a method for carrying out pyrolysis debromination of waste circuit boards by using the system as described above is also shown, which comprises the following steps:
1) crushing the waste circuit board into fragments by a crusher 1; the smaller the particle size of the fragments, the more fully pyrolyzed during pyrolysis.
2) Preheating a solid heat carrier by a preheating device, and uniformly mixing the solid heat carrier and fragments of the waste circuit board in a mixer 2 to form a mixed material;
3) conveying the mixed material to a rotary kiln 3 for pyrolysis; in the pyrolysis process, the metal oxide is fully contacted with the waste circuit board, and corrosive gases such as hydrogen bromide and the like generated by pyrolysis react with the solid heat carrier to generate metal bromide, and metal bromide salt generated by the reaction exists in pyrolytic carbon or is adhered to metal oxide balls;
4) the method comprises the following steps of sequentially enabling pyrolyzed materials to enter a rotary screen 4 and a gas-solid separator 5 for separation, separating the materials in the rotary screen 4 to obtain a solid heat carrier and pyrolysis residues, and enabling the pyrolysis residues to enter the gas-solid separator 5 through a pyrolysis residue outlet of the rotary screen 4; meanwhile, gas materials in the pyrolyzed materials enter a gas-solid separator 5 through a gas outlet of a rotary screen 4; the gas materials are tar gas and pyrolysis noncondensable gas; the pyrolysis residue and the gas material are separated in a gas-solid separator 5;
5) the gas material passing through the gas-solid separator 5 in the step 4) enters a separation tower 6 for quenching separation to obtain pyrolysis gas and pyrolysis oil; simultaneously, the pyrolysis residue in the gas-solid separator 5 in the step 4) enters a collecting tower 7 for recovery, and the metal layer and the glass fiber are separated by a mechanical or manual method and are recycled;
6) mechanically separating the solid heat carrier sieved by the rotary sieve 4 in the step 4) from pyrolysis residues and metal bromide salt adhered to the wall by a centrifuge 8; sending the separated pyrolysis residue and metal bromide salt into a pyrolytic carbon treatment process for post-treatment;
7) heating the solid heat carrier obtained in the step 6) in a heating furnace 9, introducing air into the heating furnace 9 to remove carbon deposition remaining in the solid heat carrier, and then sending the solid heat carrier into a mixer 2 to be used as the solid heat carrier to be mixed with the fragments of the waste circuit board.
Preferably, the solid heat carrier is metal oxide balls, the particle size of the solid heat carrier is 20-40 mm, and in order to facilitate screening of the heat carrier and pyrolysis materials in the later period, the particle size of the solid heat carrier is larger than the equivalent particle size of the fragments.
Preferably, the crumb in step 1) has an equivalent particle size of from 5mm to 15 mm.
Preferably, the metal oxide includes, but is not limited to, iron oxide, ferroferric oxide, calcium oxide, and copper oxide.
Preferably, the mixing mass ratio of the waste circuit board fragments to the solid heat carrier in the step 2) is (1: 3) - (1: 10). The average temperature of the mixture reaches the preset pyrolysis temperature by controlling the ratio of the feeding of the waste circuit board to the feeding of the metal oxide balls.
Preferably, the preheating temperature of the solid heat carrier in the preheating device in the step 2) is 700-1200 ℃; the temperature of the solid heat carrier heated in the heating furnace 9 in the step 7) is 700-1200 ℃.
Preferably, the temperature of the mixed material in the step 2) is 400-800 ℃.
Preferably, the pyrolysis temperature in the rotary kiln 3 in step 3) is 400-800 degrees celsius.
Preferably, the gas material is sprayed into ammonia water in the separation tower 6 for quenching separation, and meanwhile, the sprayed ammonia water can also absorb the unabsorbed acidic gases such as hydrogen bromide and the like in the pyrolysis process, so that the environment is prevented from being damaged.
Example 1
In the embodiment, waste printed circuit board FR4 is adopted to carry out pyrolysis and debromination of the rotary kiln 3 pyrolysis process by adopting the system.
As shown in fig. 1, collected waste circuit boards are pretreated and enter a crusher 1 to be crushed to have a particle size of 5mm-10mm, wherein the smaller the particle size of the circuit boards, the more uniform the solid heat carrier is mixed with the circuit boards, and the higher the pyrolysis efficiency is.
The crushed circuit board and a solid heat carrier heated by a preheating device (such as a heating furnace 9) are quickly and uniformly mixed in a spiral mixer, and the solid heat carrier adopts iron oxide balls. The equivalent particle size of the iron oxide ball is larger than that of the circuit board, so that the iron oxide ball is conveniently separated from pyrolytic coke in the later period, and the equivalent particle size of the iron oxide ball is 20 mm. The heating furnace 9 heats the iron oxide balls by using a heat accumulating type radiant tube burner in an external heating mode, so that the temperature of the iron oxide balls is over 1000-1200 ℃. In the spiral mixer 2, the feeding ratio of the iron oxide balls to the circuit board is controlled to be 4: 1, so that the temperature of the mixed materials is 600-800 ℃.
And (3) pyrolyzing the mixed materials in a rotary kiln 3, and maintaining the temperature of a reaction system between 400 and 600 ℃. The solid heat carrier in the mixed material is specifically an iron oxide ball, the iron oxide is fully contacted with the waste circuit board in the pyrolysis process, corrosive gas hydrogen bromide and elemental bromine generated by pyrolysis react with the iron oxide to generate ferric bromide and ferrous bromide, and the ferric bromide and the ferrous bromide generated by the reaction exist in pyrolysis residues (such as pyrolysis carbon) or are adhered to the iron oxide ball.
The mixed material enters the rotary screen 4 in the gas-solid separator 5 along with the mixed material, the gas material enters the pyrolysis gas in the gas-solid separator 5 through a gas outlet of the rotary screen 4 and enters the separation tower 6, the pyrolysis residue enters the gas-solid separator 5 through a pyrolysis residue outlet of the rotary screen 4 along with the screening of the rotary screen 4, and the iron oxide balls are remained in the rotary screen 4. And separating the gas material and the pyrolysis residue in a gas-solid separator 5, and quenching the gas material in a separation tower 6 by directly spraying ammonia water to reduce the pyrolysis gas temperature to 80-90 ℃ so as to separate pyrolysis tar and pyrolysis gas. Pyrolysis residues in the gas-solid separator 5 enter a collecting tower 7 to be recovered, the pyrolysis residues of the waste circuit board mainly comprise metal copper, glass fiber, pyrolytic carbon and the like, and the metal layer and the glass fiber are separated by a mechanical or manual method and are recycled.
The flame retardant in the circuit board can generate more elemental bromine and hydrogen bromide in the pyrolysis process, most of the elemental bromine and hydrogen bromide react with the iron oxide balls in the rotary kiln 3 to be removed, and the rest of the elemental bromine is absorbed by ammonia water in the separation tower 6, so that the bromine pyrolysis product of the waste circuit board is effectively removed. Experiments prove that the content of organic bromine in the pyrolysis tar is reduced by over 57.3 percent.
The iron oxide balls in the rotary screen 4 enter a centrifuge 8 to rotate at a high speed, the pyrolytic carbon adhered on the balls is removed through the shearing friction among the iron oxide balls, the separated pyrolytic carbon is sent into a collecting tower 7, the iron oxide balls enter a heating furnace 9, the iron oxide balls are heated by a heat accumulating type radiation burner, part of air is introduced to promote the coke which is not removed from the balls, and the temperature of the iron oxide balls is heated to be more than 1000-1200 ℃. Then enters a mixer 2 to be mixed with the waste circuit board again for pyrolysis.
Example 2
In the embodiment, waste printed circuit board FR4 is adopted to carry out pyrolysis and debromination of the rotary kiln 3 pyrolysis process by adopting the system.
As shown in fig. 1, collected waste circuit boards are pretreated and enter a crusher 1 to be crushed to have the particle size of 10mm-15mm, wherein the smaller the particle size of the circuit boards, the more uniform the solid heat carrier is mixed with the circuit boards, and the higher the pyrolysis efficiency is.
The crushed circuit board and a solid heat carrier heated by a preheating device (such as a heating furnace 9) are quickly and uniformly mixed in a horizontal mixer, and the solid heat carrier adopts calcium oxide balls. The equivalent particle size of the calcium oxide ball is larger than that of the circuit board, so that the calcium oxide ball is conveniently separated from pyrolytic coke in the later period, and the equivalent particle size of the calcium oxide ball is 40 mm. The heating furnace 9 heats the calcium oxide ball by using a heat accumulating type radiant tube burner in an external heating mode, so that the temperature of the calcium oxide ball is above 700-900 ℃. In the spiral mixer 2, the temperature of the mixed material is controlled between 400 and 600 ℃ by controlling the feeding ratio of the calcium oxide balls to the circuit board to be 3: 1.
And (3) pyrolyzing the mixed materials in a rotary kiln 3, and maintaining the temperature of a reaction system between 400 and 600 ℃. The solid heat carrier in the mixed material is specifically a calcium oxide ball, calcium oxide is in full contact with a waste circuit board in the pyrolysis process, corrosive gas hydrogen bromide and elemental bromine generated by pyrolysis react with calcium oxide to generate calcium bromide, and the calcium bromide generated by the reaction exists in pyrolysis residues (such as pyrolytic carbon) or adheres to the calcium oxide ball.
The mixed material enters a rotary screen 4 in a gas-solid separator 5 along with the mixed material, the gas material enters pyrolysis gas in the gas-solid separator 5 through a gas outlet of the rotary screen 4 and enters a separation tower 6, pyrolysis residues enter the gas-solid separator 5 through a pyrolysis residue outlet of the rotary screen 4 along with the screening of the rotary screen 4, and calcium oxide balls are left in the rotary screen 4. And separating the gas material and the pyrolysis residue in a gas-solid separator 5, and quenching the gas material in a separation tower 6 by directly spraying ammonia water to reduce the pyrolysis gas temperature to 80-90 ℃ so as to separate pyrolysis tar and pyrolysis gas. Pyrolysis residues in the gas-solid separator 5 enter a collecting tower 7 to be recovered, the pyrolysis residues of the waste circuit board mainly comprise metal copper, glass fiber, pyrolytic carbon and the like, and the metal layer and the glass fiber are separated by a mechanical or manual method and are recycled.
The flame retardant in the circuit board can generate more elemental bromine and hydrogen bromide in the pyrolysis process, most of the elemental bromine and hydrogen bromide react with the calcium oxide balls in the rotary kiln 3 to be removed, and the rest of the elemental bromine is absorbed by ammonia water in the separation tower 6, so that the bromine pyrolysis product of the waste circuit board is effectively removed. Experiments prove that the content of organic bromine in the pyrolysis tar is reduced by over 52.9 percent.
The calcium oxide balls in the rotary screen 4 enter a centrifuge 8 to rotate at a high speed, the pyrolytic carbon adhered on the balls is removed through the shearing friction among the calcium oxide balls, the separated pyrolytic carbon is sent into a collecting tower 7, the calcium oxide balls enter a heating furnace 9, the calcium oxide balls are heated by a heat accumulating type radiation burner, part of air is introduced to promote the coke which is not removed from the balls, and the temperature of the calcium oxide balls is heated to be more than 700-900 ℃. Then enters a mixer 2 to be mixed with the waste circuit board again for pyrolysis.
Example 3
In the embodiment, waste printed circuit board FR4 is adopted to carry out pyrolysis and debromination of the rotary kiln 3 pyrolysis process by adopting the system.
As shown in fig. 1, collected waste circuit boards are pretreated and enter a crusher 1 to be crushed to have a particle size of 5-15mm, wherein the smaller the particle size of the circuit boards, the more uniform the solid heat carrier is mixed with the circuit boards, and the higher the pyrolysis efficiency is.
The crushed circuit board and a solid heat carrier heated by a preheating device (such as a heating furnace 9) are quickly and uniformly mixed in a V-shaped mixer, and the solid heat carrier adopts copper oxide balls. The equivalent particle size of the copper oxide ball is larger than that of the circuit board, so that the copper oxide ball is conveniently separated from pyrolytic coke in the later period, and the equivalent particle size of the copper oxide ball is 30 mm. The heating furnace 9 heats the copper oxide ball by using a heat accumulating type radiant tube burner in an external heating mode, so that the temperature of the copper oxide ball is above 900-1100 ℃. In the spiral mixer 2, the temperature of the mixed material is controlled to be 600-800 ℃ by controlling the feeding ratio of the copper oxide balls to the circuit board to be 10: 1.
The mixed materials enter a rotary kiln 3 for pyrolysis, and the temperature of a reaction system is maintained between 600 ℃ and 800 ℃. The solid heat carrier in the mixed material is specifically a copper oxide ball, the copper oxide is fully contacted with the waste circuit board in the pyrolysis process, corrosive gas hydrogen bromide and elemental bromine generated by pyrolysis react with the copper oxide to generate copper bromide, and the copper bromide generated by the reaction exists in pyrolysis residues (such as pyrolytic carbon) or is adhered to the copper oxide ball.
The mixed material enters a rotary screen 4 in a gas-solid separator 5 along with the mixed material, the gas material enters a pyrolysis gas in the gas-solid separator 5 through a gas outlet of the rotary screen 4 and enters a separation tower 6, the pyrolysis residue enters the gas-solid separator 5 through a pyrolysis residue outlet of the rotary screen 4 along with the screening of the rotary screen 4, and the copper oxide balls are remained in the rotary screen 4. And separating the gas material and the pyrolysis residue in a gas-solid separator 5, and quenching the gas material in a separation tower 6 by directly spraying ammonia water to reduce the pyrolysis gas temperature to 80-90 ℃ so as to separate pyrolysis tar and pyrolysis gas. Pyrolysis residues in the gas-solid separator 5 enter a collecting tower 7 to be recovered, the pyrolysis residues of the waste circuit board mainly comprise metal copper, glass fiber, pyrolytic carbon and the like, and the metal layer and the glass fiber are separated by a mechanical or manual method and are recycled.
The flame retardant in the circuit board can generate more elemental bromine and hydrogen bromide in the pyrolysis process, most of the elemental bromine and hydrogen bromide react with the copper oxide balls in the rotary kiln 3 to be removed, and the rest of the elemental bromine is absorbed by ammonia water in the separation tower 6, so that the bromine pyrolysis product of the waste circuit board is effectively removed. Experiments prove that the content of organic bromine in the pyrolysis tar is reduced by over 72.1 percent.
The copper oxide balls in the rotary screen 4 enter a centrifuge 8 to rotate at a high speed, the pyrolytic carbon adhered on the balls is removed through shearing friction among the copper oxide balls, the separated pyrolytic carbon is sent into a collecting tower 7, the copper oxide balls enter a heating furnace 9, the copper oxide balls are heated by a heat accumulating type radiation burner, part of air is introduced to promote the coke which is not removed from the balls, and the temperature of the copper oxide balls is heated to be more than 900-1100 ℃. Then enters a mixer 2 to be mixed with the waste circuit board again for pyrolysis.
Example 4
In the embodiment, waste printed circuit board FR4 is adopted to carry out pyrolysis and debromination of the rotary kiln 3 pyrolysis process by adopting the system.
As shown in fig. 1, collected waste circuit boards are pretreated and enter a crusher 1 to be crushed to have the particle size of 6mm-12mm, wherein the smaller the particle size of the circuit boards, the more uniform the solid heat carrier is mixed with the circuit boards, and the higher the pyrolysis efficiency is.
The crushed circuit board and a solid heat carrier heated by a preheating device (such as a heating furnace 9) are quickly and uniformly mixed in a spiral mixer, and the solid heat carrier adopts ferric oxide balls. The equivalent particle size of the ferroferric oxide ball is larger than that of the circuit board, so that the ferroferric oxide ball is conveniently separated from pyrolytic coke in the later period, and the equivalent particle size of the ferroferric oxide ball is 25 mm. The heating furnace 9 heats the ferroferric oxide ball by using an external heating mode and a heat accumulating type radiant tube burner, so that the temperature of the ferroferric oxide ball is over 800-1000 ℃. In the spiral mixer 2, the temperature of the mixed materials is controlled to be 500-700 ℃ by controlling the feeding ratio of the ferric oxide balls to the circuit board to be 7: 1.
The mixed materials enter a rotary kiln 3 for pyrolysis, and the temperature of a reaction system is maintained between 500 and 700 ℃. The solid heat carrier in the mixed material is specifically a ferroferric oxide ball, the ferroferric oxide is in full contact with a waste circuit board in the pyrolysis process, corrosive gas hydrogen bromide and elemental bromine generated by pyrolysis react with the ferroferric oxide to generate ferric bromide and ferrous bromide, and the ferric bromide and the ferrous bromide generated by the reaction exist in pyrolysis residues (such as pyrolytic carbon) or are adhered to the ferroferric oxide ball.
The mixed material enters a rotary screen 4 in a gas-solid separator 5 along with the mixed material, the gas material enters a pyrolysis gas in the gas-solid separator 5 through a gas outlet of the rotary screen 4 and enters a separation tower 6, the pyrolysis residue enters the gas-solid separator 5 through a pyrolysis residue outlet of the rotary screen 4 along with the screening of the rotary screen 4, and the ferric oxide balls are left in the rotary screen 4. And separating the gas material and the pyrolysis residue in a gas-solid separator 5, and quenching the gas material in a separation tower 6 by directly spraying ammonia water to reduce the pyrolysis gas temperature to 80-90 ℃ so as to separate pyrolysis tar and pyrolysis gas. Pyrolysis residues in the gas-solid separator 5 enter a collecting tower 7 to be recovered, the pyrolysis residues of the waste circuit board mainly comprise metal copper, glass fiber, pyrolytic carbon and the like, and the metal layer and the glass fiber are separated by a mechanical or manual method and are recycled.
The flame retardant in the circuit board can generate more elemental bromine and hydrogen bromide in the pyrolysis process, most of the elemental bromine and hydrogen bromide react with the ferroferric oxide spheres in the rotary kiln 3 to be removed, and the rest of the elemental bromine and hydrogen bromide are absorbed by ammonia water in the separation tower 6, so that the bromine pyrolysis product of the waste circuit board is effectively removed. Experiments prove that the content of organic bromine in the pyrolysis tar is reduced by over 69.3 percent.
The ferroferric oxide balls in the rotary screen 4 enter a centrifuge 8 to rotate at a high speed, the pyrolytic carbon adhered on the balls is removed through the shearing friction among the ferroferric oxide balls, the separated pyrolytic carbon is sent into a collecting tower 7, the ferroferric oxide balls enter a heating furnace 9, the ferroferric oxide balls are heated by a heat accumulating type radiation burner, and part of air is introduced to promote the coke which is not removed from the balls, so that the temperature of the ferroferric oxide balls is heated to be more than 800-1000 ℃. Then enters a mixer 2 to be mixed with the waste circuit board again for pyrolysis.
The above are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and equivalent arrangements as is within the spirit and scope of the present invention.
Claims (3)
1. The utility model provides a system for old and useless circuit board pyrolysis debromination is handled which characterized in that contains:
the mixer is used for stirring and uniformly mixing materials and comprises a fragment circuit board inlet, a solid heat carrier first inlet and a mixed material outlet;
the rotary kiln is used for carrying out pyrolysis treatment on the materials and comprises a mixed material inlet and a pyrolysis mixed material outlet; the mixed material inlet is connected with the mixed material outlet of the mixer;
the rotary screen is arranged in the gas-solid separator; wherein,
the rotary screen is used for separating the solid heat carrier from the pyrolysis residue and comprises a solid material inlet, a solid heat carrier first outlet, a pyrolysis residue outlet and a gas outlet; the solid material inlet is connected with the pyrolysis mixing outlet of the rotary kiln; the pyrolysis residue outlet and the gas outlet are communicated with the gas-solid separator;
the gas-solid separator is used for carrying out gas-solid separation on the materials and comprises a solid material outlet and a gas material outlet;
the separation tower is used for spraying ammonia water to carry out quenching separation on the gas materials and comprises a gas material inlet, a pyrolysis gas outlet and a pyrolysis oil outlet; the gas material inlet is connected with the gas material outlet of the gas-solid separator.
2. The system for the pyrolysis and debromination treatment of waste circuit boards according to claim 1,
the system further comprises:
the centrifuge is used for separating attachments on the solid heat carrier and comprises a solid heat carrier second inlet, a first separated object outlet and a second separated object outlet; the second solid heat carrier inlet is connected with the first solid heat carrier outlet of the rotary screen; the first separator outlet is used for discharging the separated solid heat carrier; the second separated substance outlet is used for discharging attachments on the solid heat carrier;
the heating furnace is used for heating the solid heat carrier and comprises a material inlet to be heated and a hot material outlet; the material inlet to be heated is connected with the first separated object outlet of the centrifuge; the hot material outlet is connected with the first inlet of the solid heat carrier of the mixer.
3. The system for pyrolytic debromination of scrap board according to claim 2, further comprising:
the crushing machine is used for shearing the waste circuit board into fragments and comprises a waste circuit board inlet and a fragment circuit board outlet, and the fragment circuit board outlet is connected with the fragment circuit board inlet of the mixer;
a collection column comprising a pyrolysis residue inlet connected to the solid feed outlet of the gas-solid separator and the second separator outlet of the centrifuge.
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| CN201721633804.0U CN207787253U (en) | 2017-11-29 | 2017-11-29 | A kind of system of old circuit board Pyrolyzation and debromination processing |
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| CN201721633804.0U CN207787253U (en) | 2017-11-29 | 2017-11-29 | A kind of system of old circuit board Pyrolyzation and debromination processing |
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Cited By (6)
| 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 |
| CN109366796A (en) * | 2018-11-13 | 2019-02-22 | 蒋遂安 | A kind of scrap glass steel processing equipment for recycling |
| JP2020138141A (en) * | 2019-02-28 | 2020-09-03 | 三菱マテリアル株式会社 | Waste electronic board processing method |
| CN112139201A (en) * | 2020-07-30 | 2020-12-29 | 广州维港环保科技有限公司 | Resource recovery processing method for waste circuit board |
| 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 |
| CN115646999A (en) * | 2022-10-21 | 2023-01-31 | 昆明理工大学 | Method for converting calcium hydroxide pyrolysis waste circuit board into organic bromine |
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2017
- 2017-11-29 CN CN201721633804.0U patent/CN207787253U/en not_active Expired - Fee Related
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 |
| CN109366796A (en) * | 2018-11-13 | 2019-02-22 | 蒋遂安 | A kind of scrap glass steel processing equipment for recycling |
| JP2020138141A (en) * | 2019-02-28 | 2020-09-03 | 三菱マテリアル株式会社 | Waste electronic board processing method |
| JP7146176B2 (en) | 2019-02-28 | 2022-10-04 | 三菱マテリアル株式会社 | Disposal method for waste electronic substrates |
| CN112139201A (en) * | 2020-07-30 | 2020-12-29 | 广州维港环保科技有限公司 | Resource recovery processing method for waste circuit board |
| 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 |
| CN115646999A (en) * | 2022-10-21 | 2023-01-31 | 昆明理工大学 | Method for converting calcium hydroxide pyrolysis waste circuit board into organic bromine |
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