CN114918232A - Method for efficient catalytic pyrolysis recovery of waste circuit board - Google Patents
Method for efficient catalytic pyrolysis recovery of waste circuit board Download PDFInfo
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- CN114918232A CN114918232A CN202210370666.0A CN202210370666A CN114918232A CN 114918232 A CN114918232 A CN 114918232A CN 202210370666 A CN202210370666 A CN 202210370666A CN 114918232 A CN114918232 A CN 114918232A
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- circuit board
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- 239000002699 waste material Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000007233 catalytic pyrolysis Methods 0.000 title claims description 7
- 238000011084 recovery Methods 0.000 title description 14
- 238000000197 pyrolysis Methods 0.000 claims abstract description 93
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 46
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010881 fly ash Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000002386 leaching Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052794 bromium Inorganic materials 0.000 abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 5
- 238000007256 debromination reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010793 electronic waste Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JBCUKQQIWSWEOK-UHFFFAOYSA-N 2-(benzenesulfonyl)aniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 JBCUKQQIWSWEOK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- 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
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/17—Printed circuit boards [PCB]
-
- 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]
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for efficiently catalyzing, pyrolyzing and recycling waste circuit boards belongs to the technical field of resource utilization of waste circuit boards. The invention mixes the high-alumina fly ash and copper oxide according to a certain proportion to prepare the composite catalyst, and the composite catalyst is pyrolyzed with the broken particles of the waste circuit board, thereby improving the pyrolysis rate of the waste circuit board, inhibiting the migration of bromine in the pyrolysis reaction and improving the content of phenol and homologues thereof in the pyrolysis oil component. Pyrolysis volatile components can be directly combusted and converted into heat energy for recycling through mixing oxygen. And (3) leaching the pyrolysis residues with alkali to obtain a bromine salt solution and solid residues, wherein the bromine salt solution can be used for recovering bromine salt through evaporation and crystallization, and the solid residues can be recycled as the composite catalyst after oxidation and roasting.
Description
Technical Field
The invention belongs to the technical field of resource utilization of waste circuit boards, and mainly relates to a method for efficient catalytic pyrolysis recovery of a waste circuit board.
Background
Printed circuit boards are the foundation of the electronics and information industries and are important carriers for various electronic components such as chips, integrated circuits, resistors, capacitors, and the like. With the rapid development of the technology level, the electronic products are updated more and more quickly. The waste circuit board is composed of about 70% of non-metal materials, has low material value, contains various harmful substances such as Brominated Flame Retardants (BFRs) and the like, and can cause serious environmental pollution if not reasonably and effectively treated. The waste circuit board contains 30% of metal components such as copper, and in consideration of the shortage of copper resources in China, a large amount of imports are still needed to maintain industrial needs at present, and if the metal components in the waste circuit board can be effectively recycled, the situation of shortage of copper resources can be relieved to a great extent.
Pyrolysis is one of the most potential electronic waste treatment modes, has the characteristics of low cost, small pollution and high efficiency, and is superior to most of the conventional electronic waste recovery treatment technologies. However, the industrial application of the pyrolysis technology to treat the waste circuit boards has three problems at present: firstly, the problem of low pyrolysis efficiency exists when the waste circuit board is treated by the existing pyrolysis process, and the lower pyrolysis rate can cause incomplete pyrolysis of resin components in the waste circuit board, so that the recycling difficulty of pyrolysis residues is increased; secondly, condensed ring components in the pyrolysis volatile components are easy to condense into high-viscosity oily liquid in the pipeline, the pipeline is easy to block in long-term operation, and the pyrolysis volatile components contain a small amount of water, so that the direct combustion efficiency is low; thirdly, the flame retardant in the waste circuit board contains a large amount of organic bromine, and the common pyrolysis mode can cause the bromine to be completely escaped to the pyrolysis volatile component, thereby increasing the treatment difficulty of the pyrolysis volatile component.
Aiming at the difficult problem of pyrolysis treatment of waste circuit boards, the existing research mainly focuses on the catalytic pyrolysis technology and equipment. Zhang et al (Journal of Hazaedos materials.2021,402:123749.) carried out the pyrolysis of waste circuit boards using a microwave-assisted process and showed that the addition of K was done with the aid of microwaves 2 CO 3 And Na 2 CO 3 The debromination effect is best, but the microwave assistance has high requirements on equipment, and the accurate control of the reaction temperature of the resin component in the pyrolysis process is difficult, so that the resin component is not beneficial to full conversion and decomposition. Ma and Kamo (Journal of Analytical and Applied Pyrolysis,2018,134:614-620.) use Fe and Ni as catalysts for Pyrolysis of waste wire boards to successfully reduce the concentration of brominated compounds in the produced oil, especially organic bromineThe effect of the compound is more obvious, but the addition of catalysts such as iron and nickel leads new components to be mixed in the pyrolysis residue, which is not beneficial to the reutilization of the pyrolysis residue, and meanwhile, the catalyst is difficult to realize the recycling. The invention patent CN 101829666A develops a method for pyrolysis and debromination of waste circuit boards, bromine is fully escaped by adding any one of urea, hexamethylenetetramine, aminodiphenylsulfone and dicyandiamide, but the method can cause bromine to exist in pyrolysis volatile components in various forms, increase the recycling difficulty of the pyrolysis volatile components and hardly solve the problem of resource utilization of pyrolysis products. The invention patent CN 112978765A develops a device and a method for the pyrolysis and debromination purification of a waste circuit board, which mainly aims to recycle debrominated gas after pyrolysis volatile components are subjected to debromination treatment preferentially by a molten salt purification tower filled with molten sodium/potassium hydroxide, but the cost of the pyrolysis and recycling treatment of the waste circuit board is increased due to the addition of a component unit of a pyrolysis system.
Disclosure of Invention
The invention aims to provide a method for efficiently catalyzing, pyrolyzing and recycling waste circuit boards, aiming at solving the application problem of treating the waste circuit boards by a pyrolysis technology, so as to realize efficient pyrolysis of the waste circuit boards and inhibit the migration of bromine in the pyrolysis process.
The purpose of the invention is realized by the following technical scheme:
a method for recycling waste circuit boards through efficient catalytic pyrolysis is characterized by comprising the following steps:
(1) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate;
(2) crushing the waste circuit board substrate obtained in the step (1);
(3) uniformly mixing the waste circuit board substrate particles obtained in the step (2) with composite catalyst powder;
(4) placing the mixture prepared in the step (3) in a pyrolysis device for anaerobic pyrolysis to obtain volatile components and pyrolysis residues;
(5) fully mixing and burning the volatile matter obtained in the step (4) with oxygen to obtain heat which can provide energy for the step (4);
(6) carrying out alkaline leaching treatment on the pyrolysis residue obtained in the step (4) to obtain a bromine salt solution and solid residue;
(7) evaporating and crystallizing the bromine salt solution obtained in the step (6), and recovering crude bromine salt;
(8) heating and drying the solid residue obtained in the step (6), and oxidizing and roasting the solid residue to be used as a composite catalyst to be recycled in the step (3);
further, in the step (2), the particle size of the crushed waste circuit board substrate is 5-25 mm.
Furthermore, in the step (3), the mass ratio of the waste circuit board substrate to the composite catalyst is 10 (2-5).
Further, in the step (3), the composite catalyst is formed by uniformly mixing high-alumina fly ash (fly ash with alumina content of more than 37% in terms of industry) and copper oxide powder, and the mass ratio of the components is as follows: high-alumina fly ash (60-70 wt%), and copper oxide powder (30-40 wt%).
Further, in the step (3), the nitrogen flow is 50-100 ml/min, the pyrolysis reaction temperature is 500-600 ℃, and the heat preservation time is 30-60 min.
Compared with the prior art, the invention has the advantages that:
(1) the composite catalyst used in the invention can improve the pyrolysis rate of the waste circuit board and inhibit the migration of bromine in the pyrolysis process.
(2) The composite catalyst used in the invention can not generate new impurities to the pyrolysis solid phase, and the pyrolysis residue can be used as a new composite catalyst for recycling after alkaline leaching, filtering, heating, drying and oxidizing roasting.
(3) The pyrolysis volatile component obtained by the invention can be directly introduced into the combustion chamber to be combusted by mixed oxygen to generate heat for recycling, thereby reducing the energy consumption.
Drawings
Fig. 1 is a process route diagram provided in an embodiment of the present invention.
Detailed Description
Example 1
The recovery is carried out according to the following steps:
and (3) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 100ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 98.8 percent, the bromine content of pyrolysis residue is 99.2 percent of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 51.1 percent.
Example 2
The recovery is carried out according to the following steps:
and (3) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 70 wt% of high-alumina fly ash and 30 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 95ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 98.5%, the bromine content of pyrolysis residue is 98.8% of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 49.4%.
Example 3
The recovery is carried out according to the following steps:
and removing the electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 65 wt% of high-alumina fly ash and 35 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 90ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 98.4%, the bromine content of pyrolysis residue is 98.9% of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 50.3%.
Example 4
The recovery is carried out according to the following steps:
and removing the electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 55 wt% of high-alumina fly ash and 45 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 85ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 98.3 percent, the bromine content of pyrolysis residue is 99.1 percent of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 48.7 percent.
Example 5
The recovery is carried out according to the following steps:
and (3) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 2. Pyrolysis in the absence of oxygen, N 2 The flow rate is 80ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 98.4%, the bromine content of pyrolysis residue is 99.3% of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 50.5%.
Example 6
The recovery is carried out according to the following steps:
and removing the electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 4. Pyrolysis in the absence of oxygen, N 2 The flow rate is 75ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 98.9 percent, the bromine content of the pyrolysis residue is 98.6 percent of the total bromine content of the waste circuit board, and phenol and the like in the pyrolysis oilThe content of the series is 50.9 percent.
Example 7
The recovery is carried out according to the following steps:
and removing the electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 5. Pyrolysis in the absence of oxygen, N 2 The flow rate is 70ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 99.2 percent, the bromine content of pyrolysis residue is 99.3 percent of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 52.1 percent.
Example 8
The recovery is carried out according to the following steps:
and (3) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 65ml/min, the temperature is raised to 550 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board substrate is 98.8%, the bromine content of pyrolysis residue is 99.4% of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 50.3%.
Example 9
The recovery is carried out according to the following steps:
and removing the electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 60ml/min, the temperature is raised to 600 ℃ and the reaction is carried out for 60min at constant temperature. The pyrolysis rate of the waste circuit board is 99.0 percent, and the heatThe bromine content of the decomposition residue is 99.1 percent of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in the pyrolysis oil is 51.3 percent.
Example 10
The recovery is carried out according to the following steps:
and (3) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 55ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 30min at constant temperature. The pyrolysis rate of the waste circuit board is 98.8 percent, the bromine content of pyrolysis residue is 99.5 percent of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 54.1 percent.
Example 11
The recovery is carried out according to the following steps:
and removing the electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate, and crushing the substrate to 5-25 mm. Uniformly mixing the crushed particles of the waste circuit board with composite catalyst powder, wherein the composite catalyst comprises 60 wt% of high-alumina fly ash and 40 wt% of copper oxide powder, and the mass ratio of the waste circuit board substrate to the composite catalyst is 10: 3. Pyrolysis in the absence of oxygen, N 2 The flow rate is 50ml/min, the temperature is raised to 500 ℃ and the reaction is carried out for 45min at constant temperature. The pyrolysis rate of the waste circuit board is 98.6 percent, the bromine content of pyrolysis residue is 98.7 percent of the total bromine content of the waste circuit board, and the content of phenol and homologues thereof in pyrolysis oil is 53.1 percent.
Claims (2)
1. A method for recycling waste circuit boards through efficient catalytic pyrolysis is characterized by comprising the following steps:
(1) removing electronic components on the surface of the waste circuit board after detinning to obtain a waste circuit board substrate;
(2) crushing the waste circuit board substrate obtained in the step (1);
(3) uniformly mixing the crushed particles of the waste circuit board obtained in the step (2) with composite catalyst powder;
(4) placing the mixture prepared in the step (3) in a pyrolysis device for anaerobic pyrolysis to obtain volatile components and pyrolysis residues;
(5) fully mixing and burning the volatile matter obtained in the step (4) with oxygen to obtain heat which can provide energy for the step (4);
(6) performing alkaline leaching treatment on the pyrolysis residue obtained in the step (4) to obtain a bromine salt solution and solid residue;
(7) evaporating and crystallizing the bromine salt solution obtained in the step (6), and recovering crude bromine salt;
(8) heating and drying the solid residue obtained in the step (6);
in the step (3), the mass ratio of the crushed waste circuit board particles to the composite catalyst is 10 (2-5); the composite catalyst is formed by uniformly mixing high-alumina fly ash and copper oxide powder, wherein the mass fraction of the high-alumina fly ash is 60-70 wt%, and the mass fraction of the copper oxide powder is 30-40 wt%;
in the step (4), the nitrogen flow is 50-100 ml/min, the pyrolysis reaction temperature is 500-600 ℃, and the heat preservation time is 30-60 min.
2. The method for recovering the waste circuit board by high-efficiency catalytic pyrolysis according to claim 1, characterized by comprising the following steps: in the step (2), the particle size of the crushed waste circuit board substrate is 5-25 mm.
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