CN107470317B - Method for debrominating and lightening pyrolysis oil of waste circuit board - Google Patents
Method for debrominating and lightening pyrolysis oil of waste circuit board Download PDFInfo
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- CN107470317B CN107470317B CN201710453326.3A CN201710453326A CN107470317B CN 107470317 B CN107470317 B CN 107470317B CN 201710453326 A CN201710453326 A CN 201710453326A CN 107470317 B CN107470317 B CN 107470317B
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 112
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 60
- 239000000654 additive Substances 0.000 claims abstract description 59
- 230000000996 additive effect Effects 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 50
- 239000000306 component Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 238000007256 debromination reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 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
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000007158 vacuum pyrolysis Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 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
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- 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
- Y02W30/62—Plastics recycling; Rubber recycling
-
- 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]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for debrominating and lightening pyrolysis oil of a waste circuit board, which comprises the following steps: s1, crushing a waste circuit board, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, and adding a composite additive; s2, heating the materials to 400-500 ℃, keeping for 1-2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil; the composite additive comprises the following components in parts by weight: 10-90 parts of molecular sieve, CaCO310-90 parts. The method can simultaneously realize dehalogenation and lightening of the pyrolysis oil of the waste circuit board, can be widely applied to treatment or recycling of the waste circuit board, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of waste circuit board recovery, and particularly relates to a method for debrominating and lightening pyrolysis oil of a waste circuit board.
Background
Printed Circuit Boards (PCBs for short) are thermosetting composite materials, which are used as core components of electronic products and are widely used in various industrial fields such as electronic components and electric control. With the development of science and technology, the frequency of upgrading and eliminating electronic products is accelerated, so that the waste amount of PCBs is increased. According to the national university estimate, the electronic waste in the eu countries reaches 910 ten thousand tons in 2005 and increases at a rate of 2.5% to 2.7% per year. The printed wiring board yield in china in 2008 is up to 26% of the world's total volume, occupying the first place in the world. Meanwhile, the waste circuit board contains various toxic and harmful substances, and the waste circuit board can pollute the environment, threaten the health of human beings and stably develop the society without being treated. Therefore, how to perform effective and harmless treatment on Waste circuit Boards (WPCBs) which are increasing rapidly becomes a common problem in the world.
The waste circuit board, which is called as "urban mine" or "secondary metal rich mine", is mainly characterized in that it contains various valuable metals (such as gold, silver, iron, aluminum, copper, etc.), and the remaining non-metal part is mainly glass fiber and epoxy resin containing halogen. The traditional WPCBs treatment method mainly comprises mechanical physical method, chemical method, pyrometallurgical smelting and the like, aims to recover valuable metals, does not fully utilize the residual non-metallic part, and is easy to generate a large amount of waste gas, waste liquid and waste residue to cause secondary pollution to the environment. In recent years, attention and research are paid to and particularly vacuum pyrolysis treatment technology, however, WPCBs contain halogen-containing flame retardants, so that pyrolysis oil contains a large amount of bromine-containing substances, and further utilization of pyrolysis oil is seriously hindered.
As for the pyrolysis dehalogenation of WPCBs, a great deal of research work is done by scholars at home and abroad. Respectively adding NaOH and Na into Blazs Lou M (Blazs Lou M, et al, 2002)2CO3The CaO, ZnO, 5A molecular sieve, 13X molecular sieve and WPCBs powder are subjected to co-pyrolysis, and Py-GC/MS and Py-GC detection show that the additive can effectively reduce the yield of bromophenol and brominated styrene. Investigation of 12 additives (Al) in Zhanzhihua et Al (2011)2O3、SnO4、CuO、ZnO、Fe2O3Cu, Fe, Al, artificial zeolite, natural zeolite, activated carbon and MCM-41) and waste epoxy circuit boards are subjected to vacuum pyrolysis, and the metal Fe and oxides thereof are found to be capable of effectively reducing the bromide content in the pyrolysis oil. Liuxin et al (2012) co-pyrolyzed with waste circuit board powder using urea, p-diaminodiphenylmethane, hexamethylenetetramine as additives, and the results show that bromine in the bromine-containing flame retardant is mainly removed in the form of HBr, methyl bromide and ethyl bromide. Addition of Fe system (Fe) to Wujiaqi et al (2014)2O3、Fe3O4FeOOH), Ca series (CaO, Ca (OH)2、CaCO3) And Al system (Al)2O3Active Al2O3Molecular sieve) oxide and waste circuit board are subjected to co-pyrolysis debromination experiment, and research shows that Fe3O4And CaCO3The debromination effect is optimal and the bromine content in the pyrolysis oil is reduced from 72.10% (without additives) to 8.91% and 7.69%. Li Shenyong et al (2015) study on Fe, FeOOH and Fe3O4Active Al2O3Performing co-pyrolysis on (the particle size is 3-5 mm, the particles) and diatomite (the silicon content is 88%) and the circuit board powder, wherein Fe3O4The diatomite and the FeOOH can obviously reduce the total bromine content of the liquid product.
Disclosure of Invention
The invention aims to provide a method for debrominating and lightening waste circuit board pyrolysis oil aiming at the defects in the prior art, wherein the debromination rate in the pyrolysis oil can exceed 80 percent, so that the recovery rate of the waste circuit board is obviously improved.
The purpose of the invention is realized by the following technical scheme:
a method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a waste circuit board, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, and adding a composite additive;
s2, heating the materials to 400-500 ℃, keeping for 1-2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil;
the composite additive comprises the following components in parts by weight: 10-90 parts of molecular sieve, CaCO310-90 parts.
The method utilizes sodium ions and aluminum ions dissociated from the molecular sieve 5A in the reaction, and simultaneously utilizes the advantages of large specific surface area, high porosity and the like of the molecular sieve 5A to adsorb halogen in the pyrolysis oil, thereby achieving the removal of the halogen. Secondly, CaCO3Dissociated CO3 2-Exchange with bromide ion, and has excellent debromination effect. And Al in 5A molecular sieve2O3Has good catalytic effect on the lightening of pyrolysis oil, CaCO3The content of heavy components in the pyrolysis oil can be reduced to a certain extent. The invention uses the two additives in a composite way and adjusts the two additivesThe proportion reduces the content of heavy components in the pyrolysis oil while reducing the content of bromine in the pyrolysis oil.
Preferably, the composite additive consists of the following components in parts by weight: 30-70 parts of molecular sieve 5A and CaCO330-70 parts.
The weight ratio of the non-metal powder to the composite additive is 1-3: 3-1.
Preferably, the weight ratio of the non-metal powder to the composite additive is 1-2: 2-1.
The adding manner of the composite additive in step S1 includes but is not limited to: uniformly mixing the composite additive, adding the non-metal powder and mixing; adding non-metal powder into the molecular sieve 5A, uniformly mixing, and then adding CaCO3；CaCO3Adding the nonmetal powder, mixing uniformly, and adding the molecular sieve 5A.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the two problems of high bromine content and heavy component content in the waste circuit board pyrolysis oil in the resource recovery process, the invention reduces the bromine content in the pyrolysis oil and simultaneously reduces the heavy component content in the pyrolysis oil by adding the composite modifier in the waste circuit board pyrolysis process. The method utilizes sodium ions and aluminum ions dissociated from the molecular sieve 5A in the reaction, and simultaneously utilizes the advantages of large specific surface area, high porosity and the like of the molecular sieve 5A to adsorb halogen in the pyrolysis oil, thereby achieving the removal of the halogen. Secondly, CaCO3Dissociated CO3 2-Exchange with bromide ion can also remove halogen. And Al in 5A molecular sieve2O3Has good catalytic effect on the lightening of pyrolysis oil, CaCO3The content of heavy components in the pyrolysis oil can be reduced to a certain extent. The invention uses the two additives in a compounding way and adjusts the proportion of the two additives, so that the debromination rate in the obtained pyrolysis oil can exceed 80 percent; the pyrolysis oil contains more than 45% of components at the temperature of less than 200 ℃ and more than 90% of components at the temperature of less than 350 ℃.
Detailed Description
The present invention is further explained with reference to specific embodiments, which are described in detail and specific, but not to be construed as limiting the scope of the invention, and all technical solutions obtained by equivalents or equivalent changes should be included in the scope of the claims of the present invention.
In the following examples and comparative examples, all the raw materials used were commercially available products.
Example 1
The composite additive consists of molecular sieve 5A in 30 weight portions and CaCO in 70 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, and adding a composite additive, wherein the non-metal powder is added and fully mixed after the composite additive is uniformly mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 1: 1.
Example 2
The composite additive consists of molecular sieve 5A in 50 weight portions and CaCO in 50 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, adding a composite additive, adding a molecular sieve 5A, uniformly mixing with the non-metal powder, and adding CaCO3，CaCO3Not mixed with non-metal powder;
s2, after the feeding is finished, heating the pyrolysis furnace to 450 ℃, keeping the temperature for 1.5 hours until the pyrolysis is completed, and collecting pyrolysis oil generated after the pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 1: 2.
Example 3
The composite additive consists of molecular sieve 5A in 80 weight portions and CaCO in 20 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-golden powder, putting the powder into a pyrolysis furnace, and adding a composite additive, wherein CaCO3Firstly, adding the non-golden powder, uniformly mixing, then adding the molecular sieve 5A, wherein the molecular sieve 5A is not mixed with the non-golden powder;
s2, after the feeding is finished, heating the pyrolysis furnace to 500 ℃, keeping for 1 hour until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 2: 1.
Example 4
The composite additive consists of molecular sieve 5A in 10 weight portions and CaCO in 90 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-golden powder, putting the non-golden powder into a pyrolysis furnace, and adding a composite additive, wherein the non-golden powder is added and fully mixed after the composite additive is uniformly mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 1: 1.
Example 5
The composite additive consists of molecular sieve 5A in 90 weight portions and CaCO in 10 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-golden powder, putting the non-golden powder into a pyrolysis furnace, and adding a composite additive, wherein the non-golden powder is added and fully mixed after the composite additive is uniformly mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 1: 1.
Example 6
The composite additive consists of molecular sieve 5A in 40 weight portions and CaCO in 60 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-golden powder, putting the non-golden powder into a pyrolysis furnace, and adding a composite additive, wherein the non-golden powder is added and fully mixed after the composite additive is uniformly mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping the temperature for 1.5 hours until the pyrolysis is completed, and collecting pyrolysis oil generated after the pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 1: 3.
Example 7
A composite additive is prepared from molecular sieve (5A) 35 wt% and CaCO 65 wt%3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-golden powder, putting the non-golden powder into a pyrolysis furnace, and adding a composite additive, wherein the non-golden powder is added and fully mixed after the composite additive is uniformly mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 3: 1.
Example 8
The composite additive consists of molecular sieve 5A in 60 weight portions and CaCO in 40 weight portions3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-golden powder, putting the non-golden powder into a pyrolysis furnace, and adding a composite additive, wherein the non-golden powder is added and fully mixed after the composite additive is uniformly mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the composite additive is 1.5: 1.
Comparative example 1
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-metal powder and putting the non-metal powder into a pyrolysis furnace;
s2, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis.
Comparative example 2
An additive, which consists of 100 parts by weight of 5A.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, and adding an additive molecular sieve 5A, wherein the additive and the non-gold powder are fully mixed;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the additive is 1: 1.
Comparative example 3
A composite additive, which consists of 100 parts by weight of CaCO3And (4) forming.
A method for debrominating and lightening pyrolysis oil of a waste circuit board comprises the following steps:
s1, crushing a circuit board with electronic components removed, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, and adding an additive CaCO3Wherein, the additive is fully mixed with the non-metal powder and the non-golden powder;
s2, after the feeding is finished, heating the pyrolysis furnace to 400 ℃, keeping for 2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil generated after pyrolysis;
the weight ratio of the non-metal powder to the additive is 1: 1.
Application example 1
The pyrolysis oils collected after the complete pyrolysis of examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests including a debromination rate test and a pyrolysis oil composition analysis, and the results are shown in tables 1 and 2. And (3) testing the debromination rate: bromine content was determined by a combination of bomb combustion and ion chromatography.
TABLE 1 Debrominating Rate test results
| Debromination rate | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| % | 82 | 91 | 87 | 84 | 81 | 84 | 86 | 88 |
| Debromination rate | Comparative example 1 | Comparative example 2 | Comparative example 3 | |||||
| % | 0 | 27 | 31 |
TABLE 2 analysis results of pyrolysis oil composition
| Pyrolysis oil component | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| >360℃ | 25 | 21 | 18 | 20 | 23 | 25 | 21 | 23 |
| 240-360℃ | 19 | 20 | 25 | 23 | 20 | 21 | 21 | 22 |
| 120-240℃ | 48 | 49 | 48 | 50 | 47 | 45 | 47 | 47 |
| ＜120℃ | 8 | 10 | 9 | 7 | 10 | 9 | 11 | 8 |
| Pyrolysis oil component | Comparative example 1 | Comparative example 2 | Comparative example 3 | |||||
| >360℃ | 35 | 17 | 32 | |||||
| 240-360℃ | 9 | 31 | 10 | |||||
| 120-240℃ | 48 | 50 | 49 | |||||
| ＜120℃ | 8 | 2 | 9 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A method for debrominating and lightening pyrolysis oil of a waste circuit board is characterized by comprising the following steps:
s1, crushing a waste circuit board, extracting non-metal powder, putting the non-metal powder into a pyrolysis furnace, and adding a composite additive;
s2, heating the materials to 400-500 ℃, keeping for 1-2 hours until complete pyrolysis is achieved, and collecting pyrolysis oil;
the composite additive comprises the following components in parts by weight: 10-90 parts of molecular sieve, CaCO310-90 parts.
2. The method according to claim 1, wherein the composite additive is composed of the following components in parts by weight: 5A 30-70 parts of molecular sieve, CaCO330-70 parts.
3. The method according to claim 1, wherein the weight ratio of the non-metal powder to the composite additive is 1-3: 3-1.
4. The method according to claim 1, wherein the weight ratio of the non-metal powder to the composite additive is 1-2: 2-1.
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| JPH06859A (en) * | 1992-06-22 | 1994-01-11 | Diafoil Co Ltd | Production of laminated film |
| CN103831287A (en) * | 2014-03-13 | 2014-06-04 | 北京神雾环境能源科技集团股份有限公司 | Method for treating circuit board |
| CN103846272A (en) * | 2014-02-27 | 2014-06-11 | 广东工业大学 | Two-step debromination method for waste printed circuit board |
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| JPH04163005A (en) * | 1990-10-23 | 1992-06-08 | Matsushita Electric Works Ltd | Base material for prepreg |
| JPH06859A (en) * | 1992-06-22 | 1994-01-11 | Diafoil Co Ltd | Production of laminated film |
| CN103846272A (en) * | 2014-02-27 | 2014-06-11 | 广东工业大学 | Two-step debromination method for waste printed circuit board |
| CN103831287A (en) * | 2014-03-13 | 2014-06-04 | 北京神雾环境能源科技集团股份有限公司 | Method for treating circuit board |
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