CN100439411C - Process for preparing phenolic resin by using waste circuit board pyrolytic oil - Google Patents

Process for preparing phenolic resin by using waste circuit board pyrolytic oil Download PDF

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Publication number
CN100439411C
CN100439411C CNB2006100349658A CN200610034965A CN100439411C CN 100439411 C CN100439411 C CN 100439411C CN B2006100349658 A CNB2006100349658 A CN B2006100349658A CN 200610034965 A CN200610034965 A CN 200610034965A CN 100439411 C CN100439411 C CN 100439411C
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China
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oil
phenol
pyrolysis oil
circuit board
aldehyde
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CN1844180A (en
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彭绍洪
陈烈强
蔡明招
张齐
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • 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

Abstract

The present invention discloses a method for preparing phenolic resin from pyrolytic oil of a waste circuit board, which can be used for preparing industrially useful phenolic resin by utilizing all the components of the pyrolytic oil of a waste circuit board. The method comprises: firstly, the waste circuit board is pyrolyzed or copyrolyzed to obtain the pyrolytic oil; secondly, aldehyde, water and an acid catalyst or an alkali catalyst are added into the pyrolytic oil to react at the temperature of 50 to 60DEG C for 30 to 60 minutes; thirdly, the reaction temperature is raised to 90 to 100DEG C at the rate of temperature rise of 1DEG C/minute, and the reaction is carried out at the temperature for 60 to 120 minutes to recover the phenolic resin through temperature lowering and vacuum dehydration. The method of the present invention has the advantages of no use of a component separation technology or a dehalogenation technology, simple technological process, easy control of technological conditions and environmental hazard elimination. The components in the pyrolytic oil can be almost completely recycled, and all harmful components in the pyrolytic oil can be converted into a part of the phenolic resin.

Description

The method for preparing resol with waste circuit board pyrolytic oil
Technical field
The present invention relates to a kind of method for preparing resol with waste circuit board pyrolytic oil.
Background technology
The printed circuit board (PCB) that is widely used in the electronics is made of matrix material not molten and insoluble epoxy resin fiberglass usually, the brominated flame retardant that wherein contains multiple poisonous and hazardous heavy metal composition and high density, not easy-to-use general Waste recovery technology is handled.Method for pyrolysis is thoroughly to dispose one of effective means of waste and old circuit board, this method is under the high temperature oxygen free condition organic moiety thermolysis in the waste and old circuit board to be converted into small molecules petroleum chemicals (pyrolysis oil), simultaneously Separation and Recovery metal and glass fibre part.Pyrolysis oil generally contains 50～70% phenolic compound, mainly is phenol, isopropyl-phenol, isopropenyl phenol, p-phenyl phenol, dihydroxyphenyl propane etc.In addition, because the existence of brominated flame retardant also contains 5～15% organic bromide in the pyrolysis oil, mainly be bromination phenol and brominated bisphenol A.Organic bromide makes pyrolysis oil have very high environmental organism toxicity, and has seriously limited the further utilization of pyrolysis oil.
The 50th～52 page of " Central China University of Science and Technology's journal " (natural science edition) 2003 the 8th phase discloses a kind of method of utilizing waste circuit board pyrolytic oil to prepare oil fuel, its method is by air distillation obtains 14% light naphthar to pyrolysis oil, 38% heavy naphtha and up to about 48% solid residue, weak point is that the utilization ratio of pyrolysis oil only reaches about 50%, and the organic bromide in the pyrolysis oil is moved in each cut further debrominate processing easily in still-process.
The 57th～60 page of " Shandong science " 2000 the 3rd phase disclose a kind of from circuit board pyrolytic oil rectifying separation go out the method for phenol and isopropyl benzene phenolic product, its method by to pyrolysis oil rectifying isolate phenol and isopropyl-phenol, weak point is utilization and the handling problem that does not solve other low relatively phenols components of organic bromide in the pyrolysis oil and content.
The 723rd～733 page of debrominate treatment process that discloses a kind of circuit board pyrolytic oil and polyolefine copyrolysis of " Journal of Analytical and Applied Pyrolysis " 2003 the 70th volumes, the hydrogen that its method utilizes the polyolefine pyrolysis to produce is converted into hydrogen bromide with the organic bromine in the pyrolysis oil, reach and eliminate the purpose that halogen pollutes, pyrolysis oil behind the dehalogenation can be used as the fuel safe handling, weak point is that pyrolysis oil is higher through polyolefine copyrolysis dehalogenation processing cost, also increased the loss of pyrolysis oil, and because the calorific value of circuit board pyrolytic oil itself is not high, unfavorable economically.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of method for preparing resol with waste circuit board pyrolytic oil is provided.
A kind of method for preparing resol with waste circuit board pyrolytic oil of the present invention, be that waste circuit board pyrolytic or copyrolysis are obtained pyrolysis oil, aldehyde and water are joined in the pyrolysis oil, regulating its pH value with acid is 1～2, with 1 ℃/minute temperature rise rate its temperature is brought up to 90～100 ℃, under this temperature, reacted 60～120 minutes, and be cooled to 80～90 ℃ then, obtain novolac resin through separation, washing, vacuum hydro-extraction; The parts by weight of described each amounts of components are as follows:
Pyrolysis oil 100;
Aldehyde 50～100;
Water 0～10;
Described aldehyde is one or more solids in formaldehyde, the acetaldehyde or the mixture of its aqueous solution.
Described acid is hydrochloric acid or oxalic acid.
The method for preparing resol with waste circuit board pyrolytic oil of the present invention, also waste and old circuit board and alkaline matter copyrolysis can be obtained pyrolysis oil, aldehyde is joined in the pyrolysis oil, reacted 30～60 minutes down at 50～60 ℃, with 1 ℃/minute temperature rise rate temperature of reaction is brought up to 90～100 ℃ then, under this temperature, reacted 60～120 minutes, and be cooled to 60～70 ℃ then, after vacuum hydro-extraction, add the ethanolic soln that dissolve with ethanol obtains resol; The parts by weight of described each amounts of components are as follows:
Pyrolysis oil 100;
Aldehyde 50～100;
Water 0～10;
Described aldehyde is one or more solids in formaldehyde, the acetaldehyde or the mixture of its aqueous solution.
Described alkaline matter is one or more mixtures of lime carbonate, magnesiumcarbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide.
The method for preparing resol with waste circuit board pyrolytic oil of the present invention, also waste circuit board pyrolytic or copyrolysis can be obtained pyrolysis oil, under 45～60 ℃, aldehyde and water are joined in the pyrolysis oil, it is more than 10 that adding alkali is regulated its pH value, react after 30 minutes, with 1 ℃/minute temperature rise rate temperature of reaction is brought up to 90～95 ℃, be incubated 20～40 minutes, cool to 85 ℃ again, and then adding aldehyde, and temperature of reaction is warmed up to 95～100 ℃ once more, and continuing reaction after 60～90 minutes, blowing obtains the aqueous solution of heat-reactive phenolic resin; The parts by weight of described each amounts of components are as follows:
Pyrolysis oil 100;
Aldehyde 50～100;
Water 0～10.
Described aldehyde is one or more solids in formaldehyde, the acetaldehyde or the mixture of its aqueous solution.
Described alkali is a kind of or more than one mixtures in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the magnesium oxide.
The present invention finds through chemical analysis, the main component of waste circuit board pyrolytic oil is 40～60% phenol, 10～20% isopropyl-phenol, 1～5% isopropenyl phenol, 1～5% phenylphenol, 1～10% dihydroxyphenyl propane and 5～15% bromine phenol and brominated bisphenol A contain 10～20% moisture and in addition less than other materials of 10%.Wherein phenol, isopropyl-phenol, isopropenyl phenol, phenylphenol and dihydroxyphenyl propane are the most frequently used industrial chemicals of industrial preparation resol, are feasible technically so utilize pyrolysis oil to prepare resol.
In the fire retardant treatment process of polymkeric substance, tribromophenol, tetrabromo-bisphenol Chang Zuowei reactive flame retardant join in the polymkeric substance such as resol, Resins, epoxy, through after the solidification treatment, tribromophenol, tetrabromo-bisphenol can react with the matrix resin molecule, become a part of whole polymkeric substance.The brominated phenol of waste circuit board pyrolytic oil is mainly monobromophenol and dibromophenol and monobromo dihydroxyphenyl propane and dibromo dihydroxyphenyl propane, this composition is compared with above-mentioned fire retardant, there is more position not replaced on its aromatic ring by bromine atoms, thereby should low bromine substituent in solidification process and with formaldehyde condensation processes in all than tribromophenol, tetrabromo-bisphenol is easier to react, so this low bromine substituted phenol can be combined into the part of resin by the active group with resol and lose original environmental organism toxicity, bromine phenol after being cured does not exist because of diffusion yet, volatilization or leached and contaminate environment, and the bromine of the staying resin flame retardant properties that can also improve resin but can not influence other performances of resin.
Compared with prior art, the present invention has following advantage:
(1) method of the present invention is recycled pyrolysis oil efficient height, almost 100% utilization the component in the pyrolysis oil.
(2) method of the present invention is not used component isolation technique and dehalogenation technology, and technological process is simple, easy control of process conditions.
(3) the fine catalyzer that has utilized components such as the hydrogen bromide that produces in the waste circuit board pyrolytic process, ammonia as preparation resol of method of the present invention, both improved the utilization ratio of pyrolysis oil, saved the extra adding of catalyzer again, further reduced and utilized cost, the cost of this pyrolysis oil resol is far below the resol product of phenol production.
(4) method of the present invention utilizes waste circuit board pyrolytic oil to prepare resol, and the unwanted component in the pyrolysis oil all is converted into the part of useful resol, and the hazardness that environment is produced is little.
Embodiment
The invention will be further described below in conjunction with embodiment, the invention is not restricted to this.
Embodiment 1
(1) preparation pyrolysis oil.Waste and old circuit board pyrolysis in 600 ℃ of following nitrogen atmospheres is obtained pyrolysis gas, pyrolysis gas is condensed to obtain pyrolysis oil below the room temperature.
(2) preparation novolac resin
Speed with 1kg/ minute in the 100kg pyrolysis oil slowly adds 50kg formalin (37%) continuously, utilize in the pyrolysis oil contained 1～2% Hydrogen bromide as catalyzer, regulate its pH value to 1～2, simultaneously its temperature is brought up to 92 ℃ with 1 ℃/minute temperature rise rate, reacted 90 minutes, after its viscosity of sampling detection is qualified, cool the temperature to 85 ℃, supernatant liquid is separated in the clarification back, wash with water twice, vacuum hydro-extraction then obtains brownish black solid thermoplastic resol product, and its performance is as shown in table 1:
The performance of the resol of table 1 Hydrogen bromide catalyse pyrolysis oil preparation
Annotate: mechanical property is a resin glass fiber moulding material measured value.
Embodiment 2
(1) preparation pyrolysis oil is with embodiment 1.
(2) preparation novolac resin
Speed with 1kg/ minute in the 100kg pyrolysis oil slowly adds 90kg acetaldehyde solution (40%) continuously, utilize in the pyrolysis oil contained 1～2% Hydrogen bromide as catalyzer, regulate its pH value to 1～2, simultaneously its temperature is brought up to 95 ℃ with 1 ℃/minute temperature rise rate, reacted 70 minutes, after its viscosity of sampling detection is qualified, cool the temperature to 85 ℃, supernatant liquid is separated in the clarification back, wash with water twice, vacuum hydro-extraction then obtains brownish black solid thermoplastic resol product, and its performance is as shown in table 2:
The performance of the resol of table 2 Hydrogen bromide catalyse pyrolysis oil preparation
Annotate: mechanical property is a resin glass fiber moulding material measured value.
Embodiment 3
(1) preparation pyrolysis oil is with embodiment 1.
(2) preparation novolac resin
In the 100kg pyrolysis oil, add sodium hydroxide and regulate about its pH value to 7, add oxalic acid dihydrate 1.5kg then, formalin 50kg, water 10kg.With 1 ℃/minute temperature rise rate its temperature is brought up to 92 ℃, reacted 110 minutes, after its viscosity of sampling detection is qualified, cool the temperature to 82 ℃, supernatant liquid is separated in the clarification back, the final vacuum dehydration, obtain brownish black solid thermoplastic resol product, its performance such as table 3:
The performance of the resol of table 3 oxalic acid catalyse pyrolysis oil preparation
Annotate: mechanical property is a resin glass fiber moulding material measured value.
Embodiment 4
(1) preparation pyrolysis oil.Pyrolysis in 600 ℃ of following nitrogen atmospheres obtains pyrolysis gas with waste and old circuit board and lime carbonate, pyrolysis gas is condensed to obtain pyrolysis oil below the room temperature.
(2) ethanolic soln of preparation heat-reactive phenolic resin
In the 100kg pyrolysis oil, add 60kg formalin (37%), with contained 2% ammonia in the pyrolysis oil is catalyzer, under 50 ℃, mixed afterreaction 30 minutes, be warmed up to 95 ℃ with 1 ℃/minute then, reacted 115 minutes, and after the sampling and measuring viscosity is qualified, be cooled to 65 ℃, add the ethanolic soln that dissolve with ethanol obtains heat-reactive phenolic resin after the vacuum hydro-extraction, its performance is as shown in table 4.
The performance of the heat-reactive phenolic resin of table 4 ammonia catalyse pyrolysis oil preparation
Embodiment 5
(1) preparation pyrolysis oil is with embodiment 4.
(2) ethanolic soln of preparation heat-reactive phenolic resin
In the 100kg pyrolysis oil, add the 25kg solid formaldehyde, with contained 2% ammonia in the pyrolysis oil is catalyzer, under 55 ℃, mixed afterreaction 40 minutes, be warmed up to 92 ℃ with 1 ℃/minute then, reacted 100 minutes, and after the sampling and measuring viscosity is qualified, be cooled to 65 ℃, add the ethanolic soln that dissolve with ethanol obtains heat-reactive phenolic resin after the vacuum hydro-extraction, its performance is as shown in table 5.
The performance of the heat-reactive phenolic resin of table 5 ammonia catalyse pyrolysis oil preparation
Embodiment 6
(1) preparation pyrolysis oil is with embodiment 4.
(2) ethanolic soln of preparation heat-reactive phenolic resin
In the 100kg pyrolysis oil, add 80kg acetaldehyde solution (40%), with contained 2% ammonia in the pyrolysis oil is catalyzer, under 58 ℃, mixed afterreaction 50 minutes, be warmed up to 92 ℃ with 1 ℃/minute then, reacted 115 minutes, and after the sampling and measuring viscosity is qualified, be cooled to 68 ℃, add the ethanolic soln that dissolve with ethanol obtains heat-reactive phenolic resin after the vacuum hydro-extraction, its performance is as shown in table 6.
The performance of the heat-reactive phenolic resin of table 6 ammonia catalyse pyrolysis oil preparation
Embodiment 7
(1) preparation pyrolysis oil is with embodiment 4.
(2) preparation water soluble phenol resin
The water-soluble 10kg of sodium hydroxide of adding 40% in the pyrolysis oil of 100kg, be warming up to 50 ℃, vacuum separation also reclaims ammonia contained in the pyrolysis oil, be cooled to 46 ℃ then and add formalin 56kg, water 10kg, reaction is 30 minutes under this temperature, be warmed up to 92 ℃ with 1 ℃/minute again, be incubated 20 minutes, cool to 85 ℃ again, add 14 kilograms of formalins once more, and then be warmed up to 96 ℃ of reactions 60 minutes, after sampling detection viscosity is qualified, blowing obtains water-soluble brownish black thickness resol, and performance is as shown in table 7.
The performance of the resol of table 7 sodium hydroxide catalyse pyrolysis oil preparation
Embodiment 8
(1) preparation pyrolysis oil is with embodiment 1.
(2) preparation water soluble phenol resin
The water-soluble 1kg of sodium hydroxide of adding 40% in the pyrolysis oil of 100kg, be warming up to 50 ℃, vacuum separation also reclaims ammonia contained in the pyrolysis oil, add formalin 45kg, yellow soda ash 5kg, water 10kg then, reaction is 30 minutes under this temperature, be warmed up to 92 ℃ with 1 ℃/minute again, be incubated 20 minutes, cool to 85 ℃ again, add 15 kilograms of formalins once more, and then be warmed up to 98 ℃ of reactions 60 minutes, after sampling detection viscosity is qualified, blowing obtains water-soluble brownish black thickness resol, and performance is as shown in table 8.
The performance of the resol of table 8 yellow soda ash catalyse pyrolysis oil preparation
Embodiment 9
(1) preparation pyrolysis oil is with embodiment 4.
(2) preparation water soluble phenol resin
The water-soluble 10kg of sodium hydroxide of adding 40% in the pyrolysis oil of 100kg, be warming up to 50 ℃, vacuum separation also reclaims ammonia contained in the pyrolysis oil, add 40% acetaldehyde solution 66kg, water 15kg at 55 ℃ then, reaction is 30 minutes under this temperature, be warmed up to 95 ℃ with 1 ℃/minute again, be incubated 30 minutes, cool to 85 ℃ again, add the 17kg acetaldehyde solution once more, and then be warmed up to 98 ℃ of reactions 90 minutes, after sampling detection viscosity is qualified, blowing obtains water-soluble brownish black thickness resol, and its performance is as shown in table 9.
The performance of the resol of table 9 sodium hydroxide catalyse pyrolysis oil preparation
Embodiment 10
(1) preparation pyrolysis oil is with embodiment 4
(2) preparation novolac resin
Adding hydrochloric acid adjusting PH in the 100kg pyrolysis oil is about 1, slowly add 50kg formalin (37%) continuously with 1kg/ minute speed, guarantee system pH value to 1～2,1 ℃/minute temperature rise rate is brought up to 92 ℃ with its temperature simultaneously, reacted 90 minutes, after its viscosity of sampling detection is qualified, cool the temperature to 85 ℃, supernatant liquid is separated in the clarification back, wash with water twice, vacuum hydro-extraction then obtains brownish black solid thermoplastic resol product, and its performance is as shown in table 10:
The performance of the resol of table 10 hydrochloric acid catalysis pyrolysis oil preparation
Annotate: mechanical property is a resin glass fiber moulding material measured value.
With resol prepared among the embodiment 1～10 160 ℃ of curing, resol after solidifying is obtained soak solution with the acetone immersion, soak solution is carried out gas chromatography-mass spectrometry analysis, do not detect halides such as bromine phenol, the extract of the resol of other component concentrations in the extract and the production of purified petroleum benzin phenol does not have obvious difference.After chromatography-mass spectroscopy analytical results explanation utilized pyrolysis oil to prepare resol, the objectionable impurities in the pyrolysis oil can be because of migration after stable through solidifying, leached and not exert an influence to environment.

Claims (5)

1. method for preparing resol with waste circuit board pyrolytic oil, it is characterized in that waste circuit board pyrolytic or copyrolysis are obtained pyrolysis oil, aldehyde and water are joined in the pyrolysis oil, regulating its pH value with acid is 1～2, with 1 ℃/minute temperature rise rate its temperature is brought up to 90～100 ℃, under this temperature, reacted 60～120 minutes, and be cooled to 80～90 ℃ then, obtain novolac resin through separation, washing, vacuum hydro-extraction; The parts by weight of described each amounts of components are as follows:
Pyrolysis oil 100;
Aldehyde 50～100;
Water 0～10;
Described aldehyde is one or more solids in formaldehyde, the acetaldehyde or the mixture of its aqueous solution;
Described pyrolysis main body of oil is 40～60% phenol, 10～20% isopropyl-phenol, 1～5% isopropenyl phenol, 1～5% phenylphenol, 1～10% dihydroxyphenyl propane and 5～15% bromine phenol and brominated bisphenol A contain 10～20% moisture and in addition less than other materials of 10%.
2. method according to claim 1 is characterized in that described acid is hydrochloric acid or oxalic acid.
3. method for preparing resol with waste circuit board pyrolytic oil, it is characterized in that waste and old circuit board and alkaline matter copyrolysis are obtained pyrolysis oil, aldehyde is joined in the pyrolysis oil, reacted 30～60 minutes down at 50～60 ℃, with 1 ℃/minute temperature rise rate temperature of reaction is brought up to 90～100 ℃ then, under this temperature, reacted 60～120 minutes, and be cooled to 60～70 ℃ then, after vacuum hydro-extraction, add the ethanolic soln that dissolve with ethanol obtains resol; The parts by weight of described each amounts of components are as follows:
Pyrolysis oil 100;
Aldehyde 50～100;
Water 0～10;
Described aldehyde is one or more solids in formaldehyde, the acetaldehyde or the mixture of its aqueous solution;
Described alkaline matter is one or more mixtures in lime carbonate, magnesiumcarbonate, calcium oxide, magnesium oxide, calcium hydroxide, the magnesium hydroxide;
Described pyrolysis main body of oil is 40～60% phenol, 10～20% isopropyl-phenol, 1～5% isopropenyl phenol, 1～5% phenylphenol, 1～10% dihydroxyphenyl propane and 5～15% bromine phenol and brominated bisphenol A contain 10～20% moisture and in addition less than other materials of 10%.
4. method for preparing resol with waste circuit board pyrolytic oil, it is characterized in that waste circuit board pyrolytic or copyrolysis are obtained pyrolysis oil, under 45～60 ℃, aldehyde and water are joined in the pyrolysis oil, regulating its pH value with alkali is more than 10, react after 30 minutes, with 1 ℃/minute temperature rise rate temperature of reaction is brought up to 90～95 ℃, be incubated 20～40 minutes, cool to 85 ℃ again, and then adding aldehyde, and temperature of reaction is warmed up to 95～100 ℃ once more, and continuing reaction after 60～90 minutes, blowing obtains the aqueous solution of heat-reactive phenolic resin; The parts by weight of described each amounts of components are as follows:
Pyrolysis oil 100;
Aldehyde 50～100;
Water 0～10;
Described aldehyde is one or more solids in formaldehyde, the acetaldehyde or the mixture of its aqueous solution;
Described pyrolysis main body of oil is 40～60% phenol, 10～20% isopropyl-phenol, 1～5% isopropenyl phenol, 1～5% phenylphenol, 1～10% dihydroxyphenyl propane and 5～15% bromine phenol and brominated bisphenol A contain 10～20% moisture and in addition less than other materials of 10%.
5. method according to claim 4 is characterized in that described alkali is a kind of or more than one mixtures in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, hydrated barta, yellow soda ash, salt of wormwood, the magnesium oxide.
CNB2006100349658A 2006-04-13 2006-04-13 Process for preparing phenolic resin by using waste circuit board pyrolytic oil Expired - Fee Related CN100439411C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602838B (en) * 2009-07-10 2011-01-05 北京林业大学 Method for preparing wood pyrolysis oil modified phenolic resin for artificial board
CN102172600B (en) * 2011-03-14 2013-04-17 广东工业大学 Comprehensive recovery method for vacuum pyrolysis oil using wastes like waste circuit boards
CN102964551B (en) * 2012-11-08 2014-02-26 广州有色金属研究院 Method for preparing modified phenolic resin from waste circuit board pyrolysis oil
CN107099009B (en) * 2017-05-15 2019-01-25 北京林业大学 Boric acid/pyrolysis oil is total to the preparation method of modified artificial plate thermosetting phenolic resin
CN112322060A (en) * 2020-05-22 2021-02-05 中国科学技术大学 Method for preparing wood-plastic material from circuit board non-metal material

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