CN107470317A - A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting - Google Patents
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting Download PDFInfo
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- CN107470317A CN107470317A CN201710453326.3A CN201710453326A CN107470317A CN 107470317 A CN107470317 A CN 107470317A CN 201710453326 A CN201710453326 A CN 201710453326A CN 107470317 A CN107470317 A CN 107470317A
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- China
- Prior art keywords
- pyrolysis
- circuit board
- printed circuit
- pyrolysis oil
- waste printed
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 104
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 230000000996 additive effect Effects 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 46
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 29
- 239000002808 molecular sieve Substances 0.000 claims abstract description 27
- 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 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 4
- 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 18
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002843 nonmetals Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 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
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940006460 bromide ion Drugs 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007158 vacuum pyrolysis Methods 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 class 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-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
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 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
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical group 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
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 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
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 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
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- -1 wherein Substances 0.000 description 1
Classifications
-
- 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 kind of method of waste printed circuit board pyrolysis oil debrominate and lighting, comprise the following steps：S1. waste printed circuit board is crushed, extraction non-metal powder is put into pyrolysis oven, and adds compound additive；S2. above-mentioned material is heated to 400~500 DEG C, kept for 1~2 hour, until pyrolysis, and collect pyrolysis oil completely；The compound additive is made up of the component of following parts by weight：10~90 parts of molecular sieve 5A, CaCO310~90 parts.The present invention can realize waste printed circuit board pyrolysis oil dehalogenation and lighting simultaneously, can be widely applied to processing disposal or the recycling of waste printed circuit board, have good application prospect.
Description
Technical field
The invention belongs to waste printed circuit board recovery technology field, and in particular to a kind of debrominate of waste printed circuit board pyrolysis oil and lighting
Method.
Background technology
Printed substrate（Printed Circuit Boards, abbreviation PCB）It is a kind of same with thermosetting compound material, as electricity
The core component of sub- product, it is widely used among multiple industrial circles such as electronic component and Electronic control.With science and technology
Development, the update of electronic product and superseded frequency are accelerated, and cause the discarded amount aggravations of PCB.Estimate according to United Nations University,
The electronic waste of European Union member countries in 2005 is up to 9,100,000 tons, and is increased every year with 2.5%~2.7% speed.In 2008 years
The printed substrate yield of state is up to the 26% of world's total amount, occupies the position of the first in the world.Meanwhile discarded circuit board contain it is more
The poisonous and hazardous material of kind, it is not acted upon polluting the environment, threatens human health and social stability to develop.Therefore, it is how right
The discarded circuit board sharply increased（Waste Printed Circuited Boards, abbreviation WPCBs）Carry out effective, innoxious
It is treated as the common issue that the whole world is faced.
Discarded circuit board, be known as " city mine " or " secondary metals rich ore ", essentially consist in it contain it is a variety of
Metal values（Such as gold, silver, iron, aluminium, copper）, remaining non-metallic part is mainly glass fibre and halogen-containing asphalt mixtures modified by epoxy resin
Fat.WPCBs traditional treatment methods mainly have mechanical approach, chemical method and pyrometallurgical smelting etc., it is therefore intended that recovery is therein to be had
Valuable metal, remaining non-metallic part are not fully used, and are also easy to produce substantial amounts of waste gas, waste liquid and waste residue, to ring
Cause secondary pollution in border.And metal, organic matter and glass fibre can be effectively separated by pyrolytic technique, pass is enjoyed in recent years
Note and research, especially vacuum pyrolysis treatment technology, still, have halogen-containing fire retardant in WPCBs, cause the heat after pyrolysis
Contain substantial amounts of bromo-containing substance in solution oil, seriously hinder the further utilization of pyrolysis oil.
Dehalogenation is pyrolyzed on WPCBs, domestic and foreign scholars have made many research work to this.Blazsó M（Blazsó M,
et al. 2002）Deng addition NaOH, Na respectively2CO3, CaO, ZnO, 5A molecular sieve and 13X molecular sieves and WPCBs powder heat altogether
Solution, show that additive can effectively reduce brominated phenol and the yield of brominated styrene through Py-GC/MS and Py-GC detections.Profound will China
Deng（2011）Study 12 kinds of additives（Al2O3、SnO4、CuO、ZnO、Fe2O3, Cu, Fe, Al, artificial zeolite, natural zeolite, activity
Charcoal and MCM-41）With waste epoxy circuit board vacuum pyrolysis, it is found that metal Fe and its oxide can effectively reduce bromine in cracked oil
Compound content.Liu Xin etc.（2012）By the use of urea, p- MDA, hexa as additive with it is waste and old
Circuit board powder copyrolysis, the results showed that bromine is mainly removed in the form of HBr and bromomethane, bromoethane in brominated flame-retardant.Wu Jia
Qi etc.（2014）Add Fe systems（Fe2O3、Fe3O4、FeOOH）, Ca systems（CaO、Ca(OH)2、CaCO3）With Al systems（Al2O3, activity
Al2O3Molecular sieve）Oxide and discarded circuit board carry out copyrolysis debrominate experiment, and research shows Fe3O4And CaCO3Debrominate effect
Most preferably, bromine content and in pyrolysis oil is from 72.10%（It is additive-free）Drop to 8.91% and 7.69%.Lee is extraordinarily brave etc.（2015）Grind
Study carefully Fe, FeOOH, Fe3O4, active Al2O3（3~5mm of particle diameter, graininess）And diatomite（Silicon mass fraction is 88%）With wiring board
Powder carries out copyrolysis, wherein Fe3O4, diatomite and FeOOH can significantly reduce the total bromine content of product liquid.
The content of the invention
It is an object of the invention to the drawbacks described above for prior art, there is provided a kind of waste printed circuit board pyrolysis oil debrominate and light
The method of matter, debrominate rate can exceed that 80% in pyrolysis oil so that the recovery utilization rate of waste printed circuit board significantly improves.
The object of the invention is achieved through the following technical solutions：
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. waste printed circuit board is crushed, extraction non-metal powder is put into pyrolysis oven, and adds compound additive；
S2. above-mentioned material is heated to 400~500 DEG C, kept for 1~2 hour, until pyrolysis, and collect pyrolysis oil completely；
The compound additive is made up of the component of following parts by weight：10~90 parts of molecular sieve 5A, CaCO310~90 parts.
The present invention using molecular sieve 5A dissociate in the reaction come sodium ion, aluminium ion, while utilization molecular sieve 5A ratios
The advantages such as surface area is big, porosity is high are adsorbed to the halogen in pyrolysis oil, so as to reaching the removing to halogen.Secondly,
CaCO3Dissociate the CO come3 2-Exchanged with bromide ion, debrominate excellent effect.And the Al in 5A molecular sieves2O3To the lightweight of pyrolysis oil
Change has good catalytic effect, CaCO3The content of heavy constituent in pyrolysis oil can be also reduced to a certain extent.The present invention passes through
Both additives are used in combination and adjust both ratios, while reducing bromine content in pyrolysis oil, are also reduced in pyrolysis oil
Heavy constituent content.
Preferably, the compound additive is made up of the component of following parts by weight：30~70 parts of molecular sieve 5A, CaCO3
30~70 parts.
The non-metal powder is 1~3 with compound additive weight ratio:3~1.
Preferably, the non-metal powder and compound additive weight ratio are 1~2:2~1.
The feed postition of compound additive includes but is not limited to described in step S1：Added after compound additive is well mixed non-
Metal dust mixes；Molecular sieve 5A first adds that non-metal powder is well mixed to add CaCO3；CaCO3First add non-metal powder
It is well mixed to add molecular sieve 5A.
Compared with prior art, the present invention has the advantages that：
There are the brominated and high two large problems of heavy constituent content in the present invention, lead to for waste printed circuit board pyrolysis oil during resource reclaim
Cross and add composite modifier in waste printed circuit board pyrolytic process, while bromine content in reducing pyrolysis oil, reduce in pyrolysis oil
Heavy constituent content.The present invention using molecular sieve 5A dissociate in the reaction come sodium ion, aluminium ion, while utilization molecular sieve 5A
The advantages such as specific surface area is big, porosity is high are adsorbed to the halogen in pyrolysis oil, so as to reaching the removing to halogen.Its
It is secondary, CaCO3Dissociate the CO come3 2-Exchanged with bromide ion, can also remove halogen.And the Al in 5A molecular sieves2O3To pyrolysis oil
Lighting has good catalytic effect, CaCO3The content of pyrolysis oil heavy constituent can be also reduced to a certain extent.The present invention is logical
Cross and both additives are used in combination and adjust both ratios, debrominate rate can exceed that 80% in obtained pyrolysis oil；In pyrolysis oil
Less than 200 DEG C components are more than 45%, and less than 350 DEG C components are more than 90%.
Embodiment
The present invention being further expalined explanation with reference to specific embodiment, its description is more specific and detailed, but
Therefore limitation of the scope of the invention can not be interpreted as, as long as obtained using the form of equivalent substitution or equivalent transformation
Technical scheme, it all should be included within the protection domain of the claims in the present invention.
In following examples and comparative example, raw materials used is commercial goods.
Embodiment 1
A kind of compound additive, by the molecular sieve 5A of the 30 parts by weight and CaCO of 70 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component is crushed, and extraction non-metal powder is put into pyrolysis oven, and adds compound addition
Agent, wherein, add non-metal powder after compound additive is well mixed and be sufficiently mixed；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 1 with compound additive weight ratio:1.
Embodiment 2
A kind of compound additive, by the molecular sieve 5A of the 50 parts by weight and CaCO of 50 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component is crushed, and extraction non-metal powder is put into pyrolysis oven, and adds compound addition
Agent, wherein molecular sieve 5A, which first add to be well mixed with non-metal powder, adds CaCO3, CaCO3Do not mixed with non-metal powder；
S2. after feeding, pyrolysis oven is heated to 450 DEG C, kept for 1.5 hours, until pyrolysis completely, and produced after collecting pyrolysis
Raw pyrolysis oil；
Non-metal powder is 1 with compound additive weight ratio:2.
Embodiment 3
A kind of compound additive, by the molecular sieve 5A of the 80 parts by weight and CaCO of 20 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component crushes, and extracts non-golden powder and is put into pyrolysis oven, and adds compound addition
Agent, wherein CaCO3First add to be well mixed with non-golden powder and add molecular sieve 5A, molecular sieve 5A does not mix with non-golden powder
Close；
S2. after feeding, pyrolysis oven is heated to 500 DEG C, kept for 1 hour, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 2 with compound additive weight ratio:1.
Embodiment 4
A kind of compound additive, by the molecular sieve 5A of the 10 parts by weight and CaCO of 90 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component crushes, and extracts non-golden powder and is put into pyrolysis oven, and adds compound addition
Agent, wherein, add non-golden powder after compound additive is well mixed and be sufficiently mixed；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 1 with compound additive weight ratio:1.
Embodiment 5
A kind of compound additive, by the molecular sieve 5A of the 90 parts by weight and CaCO of 10 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component crushes, and extracts non-golden powder and is put into pyrolysis oven, and adds compound addition
Agent, wherein, add non-golden powder after compound additive is well mixed and be sufficiently mixed；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 1 with compound additive weight ratio:1.
Embodiment 6
A kind of compound additive, by the molecular sieve 5A of the 40 parts by weight and CaCO of 60 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component crushes, and extracts non-golden powder and is put into pyrolysis oven, and adds compound addition
Agent, wherein, add non-golden powder after compound additive is well mixed and be sufficiently mixed；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 1.5 hours, until pyrolysis completely, and produced after collecting pyrolysis
Raw pyrolysis oil；
Non-metal powder is 1 with compound additive weight ratio:3.
Embodiment 7
A kind of compound additive, by the molecular sieve 5A of the 35 parts by weight and CaCO of 65 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component crushes, and extracts non-golden powder and is put into pyrolysis oven, and adds compound addition
Agent, wherein, add non-golden powder after compound additive is well mixed and be sufficiently mixed；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 3 with compound additive weight ratio:1.
Embodiment 8
A kind of compound additive, by the molecular sieve 5A of the 60 parts by weight and CaCO of 40 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component crushes, and extracts non-golden powder and is put into pyrolysis oven, and adds compound addition
Agent, wherein, add non-golden powder after compound additive is well mixed and be sufficiently mixed；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 1.5 with compound additive weight ratio:1.
Comparative example 1
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component is crushed, and extraction non-metal powder is put into pyrolysis oven；
S2. pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and collect caused pyrolysis oil after pyrolysis.
Comparative example 2
A kind of additive, it is made up of the 5A of 100 parts by weight.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component is crushed, and extraction non-metal powder is put into pyrolysis oven, and adds additive molecule
5A is sieved, wherein, additive is sufficiently mixed with non-golden powder；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 1 with additive weight ratio:1.
Comparative example 3
A kind of compound additive, by the CaCO of 100 parts by weight3Composition.
A kind of method of the debrominate of waste printed circuit board pyrolysis oil and lighting, comprises the following steps：
S1. the circuit board for removing electronic component is crushed, and extraction non-metal powder is put into pyrolysis oven, and adds additive
CaCO3, wherein, additive is sufficiently mixed with the non-golden powder of non-metal powder；
S2. after feeding, pyrolysis oven is heated to 400 DEG C, kept for 2 hours, until pyrolysis completely, and produced after collecting pyrolysis
Pyrolysis oil；
Non-metal powder is 1 with additive weight ratio:1.
Application examples 1
The pyrolysis oil collected will carry out performance test after embodiment 1-5 and comparative example 1-3 pyrolysis completely, including the test of debrominate rate and
Pyrolysis oil constituent analysis, it the results are shown in Table 1 and table 2.Debrominate rate is tested：It is combined using oxygen bomb combustion and the chromatography of ions to survey
Determine bromine content.
The debrominate rate test result of table 1
| Debrominate rate | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| % | 82 | 91 | 87 | 84 | 81 | 84 | 86 | 88 |
| Debrominate rate | Comparative example 1 | Comparative example 2 | Comparative example 3 | |||||
| % | 0 | 27 | 31 |
The pyrolysis oil composition analysis result of table 2
| It is pyrolyzed oil component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 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 DEG C of ＜ | 8 | 10 | 9 | 7 | 10 | 9 | 11 | 8 |
| It is pyrolyzed 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 DEG C of ＜ | 8 | 2 | 9 |
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in the spirit and principles in the present invention
Within any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection.
Claims (4)
1. a kind of waste printed circuit board pyrolysis oil debrominate and the method for lighting, it is characterised in that comprise the following steps：
S1. waste printed circuit board is crushed, extraction non-metal powder is put into pyrolysis oven, and adds compound additive；
S2. above-mentioned material is heated to 400~500 DEG C, kept for 1~2 hour, until pyrolysis, and collect pyrolysis oil completely；
The compound additive is made up of the component of following parts by weight：10~90 parts of molecular sieve 5A, CaCO310~90 parts.
2. according to the method for claim 1, it is characterised in that the compound additive by following parts by weight component group
Into：Molecular sieve 5A30~70 part, CaCO330~70 parts.
3. according to the method for claim 1, it is characterised in that the weight ratio of the non-metal powder and compound additive is
1~3:3~1.
4. according to the method for claim 1, it is characterised in that the weight ratio of the non-metal powder and compound additive is
1~2:2~1.
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