JP2004091720A - Method for separating carbon fiber and resin - Google Patents
Method for separating carbon fiber and resin Download PDFInfo
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- JP2004091720A JP2004091720A JP2002257490A JP2002257490A JP2004091720A JP 2004091720 A JP2004091720 A JP 2004091720A JP 2002257490 A JP2002257490 A JP 2002257490A JP 2002257490 A JP2002257490 A JP 2002257490A JP 2004091720 A JP2004091720 A JP 2004091720A
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- resin
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 48
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 48
- 229920005989 resin Polymers 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 44
- 239000004918 carbon fiber reinforced polymer Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011151 fibre-reinforced plastic Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 48
- 239000002904 solvent Substances 0.000 abstract description 32
- 239000011159 matrix material Substances 0.000 abstract description 13
- 230000000704 physical effect Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000002542 deteriorative effect Effects 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 description 31
- 238000000197 pyrolysis Methods 0.000 description 27
- 239000003921 oil Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- 239000000835 fiber Substances 0.000 description 16
- 238000000926 separation method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000005292 vacuum distillation Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 12
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 9
- 239000012263 liquid product Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 5
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2707/00—Use of elements other than metals for preformed parts, e.g. for inserts
- B29K2707/04—Carbon
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、炭素繊維強化プラスチック（ＣＦＲＰ）中の炭素繊維（ＣＦ）と樹脂との分離方法に関するものである。
【０００２】
【従来の技術】
近年、ごみ処理問題などに非常に多くの関心が集まっており、地球環境保全などの面からも早急な対応が望まれている。繊維強化プラスチック（ＦＲＰ）は埋立てや焼却などの処理が主流となっていたが、既にこれらの処理方法自体が埋立地の減少、排気ガスなどの社会問題になっていることから、廃棄されたＦＲＰの再利用（リサイクル）が重要な課題となっている。
【０００３】
これまでプラスチックやＦＲＰを構成するマトリックス樹脂を強化材から分離・除去する技術としては、熱分解〔特許文献１、特許文献２〕、化学分解〔非特許文献１〕、超臨界分解〔非特許文献２〕、光・オゾン分解などが考えられている。
【０００４】
ＦＲＰのマトリックス樹脂材料などとして使用されるフェノール樹脂やエポキシ樹脂などの熱硬化性樹脂は、テトラリンなどの水素供与性溶剤を用いた液相熱分解法により４００℃以上の反応温度で、ほぼ１００％分解され、フェノールなどのモノマーを主成分とする液状生成物に転換される。このことは非特許文献３、非特許文献４に記載されているように公知である。
【０００５】
また、ＣＦＲＰ中のマトリックス樹脂を有機触媒使用のもとに油化し、更に処理後のＣＦを回収する技術については、非特許文献５に記載されている。
【０００６】
しかし、これらの処理方法では使用する溶媒（溶剤）が工業的に広く生産されておらず特殊であり、コストが高いなどの問題を抱えている。加えて、処理後の強化繊維に有機触媒が付着し、その除去が容易でないことが処理の簡便さに欠けている。
【０００７】
また、ＣＦＲＰ中に含まれるＣＦは耐熱性の高い材料ではあるが、１５０℃以上では徐々に酸化・劣化する。ＣＦを回収再利用する観点からはＣＦＲＰ中のＣＦとマトリックス樹脂を分離する際には、極力ＣＦの性能・特徴を保持させたまま、高い分解率、若しくはモノマー成分等への高い転化率で樹脂を除去することが可能である分離技術の確立が求められている。
【０００８】
【特許文献１】
特許第３１８０４６３号公報 （第２頁［０００４］〜第３頁［００２１］）
【特許文献２】
特開平１１−１７２２５８号公報 （第２頁［０００３］〜第３頁［００１４］）
【非特許文献１】
牛越憲治、小松信幸、杉野守彦、材料、４４巻、Ｐ４２８〜４３１（１９９５）
【非特許文献２】
佐古猛、岡島いずみ、菅田猛、プラスチック化学リサイクル研究会、第３回討論会予稿集、Ｐ２７〜２８（２０００）
【非特許文献３】
Ｙ．Ｓａｔｏ、Ｙ．Ｋｏｄｅｒａ、Ｔ．Ｋａｍｏ、Ｅｎｅｒｇｙ ＆ Ｆｕｅｌｓ、１３巻、Ｐ３６４〜３６８（１９９９）
【非特許文献４】
佐藤芳樹、化学と工業、５４（１２）、Ｐ１３４７〜１３５１（２００１）
【非特許文献５】
平成１２年度 新エネルギー・産業技術総合開発機構研究受託成果報告書、リサイクルＣＦＲＰ粉砕品の標準化、Ｐ４５〜６５
【０００９】
【発明が解決しようとする課題】
本発明者等は、上記の問題を解決するために種々検討しているうちに、ＣＦＲＰと、工業的に広く使用されている高級アルコール又はライトサイクルオイル〔Ｌｉｇｈｔ Ｃｙｃｌｅ Ｏｉｌ（ＬＣＯ：石油精製工業においてＦＣＣ装置から製造される生成残油の軽質成分）〕と、触媒との混合物を非酸化性ガス雰囲気下、加圧・加熱することにより、マトリックス樹脂を極力高い転化率にて、かつＣＦの性能を劣化させないで除去できることを知得し本発明を完成するに至った。
【００１０】
よって、本発明の目的とするところは、上記問題を解決したＣＦＲＰからのＣＦとマトリックス樹脂との分離方法を提供することにある。
【００１１】
【課題を解決するための手段】
上記目的を達成する本発明は、以下に記載のものである。
【００１２】
〔１〕 炭素繊維強化プラスチックと、高級アルコール又はライトサイクルオイルと、触媒との混合物を、非酸化性ガス雰囲気下、加圧・加熱して炭素繊維強化プラスチック中の樹脂を分解し、得られた分解樹脂を炭素繊維強化プラスチック中の炭素繊維から分離する炭素繊維と樹脂との分離方法。
【００１３】
〔２〕 触媒が、アルカリ金属若しくはアルカリ土類金属の炭酸塩、元素の周期表１族、２族、３族、１５族及び１６族金属を除く金属の酸化物、又は水素活性化金属を多孔性無機担体に担持させた触媒である請求項１に記載の炭素繊維と樹脂との分離方法。
【００１４】
【発明の実施の形態】
本発明で被処理原料として用いるＣＦＲＰは、マトリックス樹脂にＣＦを分散させた強化複合材料である。マトリックス樹脂には、エポキシ樹脂、フェノール樹脂、ポリウレタン樹脂、不飽和ポリエステル樹脂などの熱硬化性樹脂、並びにポリプロピレン、ナイロンなどの熱可塑性樹脂が包含される。ＣＦにはレーヨン糸、ピッチ糸、アクリル糸などのＣＦが包含される。
【００１５】
ＣＦＲＰ中の樹脂含有量は、特に限定されるものではないが、２０〜５０質量％が好ましい。
【００１６】
本発明においては、上記ＣＦＲＰと、高級アルコール又はＬＣＯと、触媒との混合物を、非酸化性ガス雰囲気下、加圧、加熱してＣＦＲＰから樹脂とＣＦとを分離することを特徴とする。
【００１７】
高級アルコールの純度は９８質量％が好ましい。
【００１８】
高級アルコールは通常、炭素数４以上の脂肪族アルコールを指す。これら脂肪族アルコールのうちでも、炭素数が６〜１２の脂肪族アルコールで樹脂の分解によって得られる低分子化合物よりも高沸点のものが好ましい。このような高級アルコールとしては、ヘキサノール、シクロヘキサノール、１−ヘプタノール、２−エチル−１−ヘキサノール、１−オクタノールなどが挙げられる。
【００１９】
ＬＣＯの純度は９８質量％が好ましい。
【００２０】
これら溶剤の使用割合は、ＣＦＲＰ１００質量部当り、５０〜４００質量部の割合が好ましく、５０〜３００質量部の割合が更に好ましい。
【００２１】
触媒としては、アルカリ金属若しくはアルカリ土類金属の炭酸塩、元素の周期表１族、２族、３族、１５族及び１６族金属を除く金属の酸化物、又は水素活性化金属を多孔性無機担体に担持させた触媒を用いることができる。具体的には、炭酸塩としては、Ｎａ２ＣＯ３、ＫＣＯ３、ＣａＣＯ３、ＭｇＣＯ３、ＢａＣＯ３等が例示でき、酸化物としては、Ｆｅ２Ｏ３、Ｖ２Ｏ５、ＺｒＯ２、ＣｕＯ、Ｃｕ２Ｏ、ＭｏＯ３、ＺｎＯ、Ａｌ２Ｏ３、ＴｉＯ２、Ｃｒ２Ｏ３、ＣｅＯ２、ＭｎＯ２、ＳｎＯ２、ＣｄＯ、ＣｏＯ等が例示でき、水素活性化金属としては、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｏ等が例示でき、多孔性無機担体としては、アルミナ、シリカ、チタン等が例示できる。
【００２２】
上記触媒の使用割合は、ＣＦＲＰ１００質量部当り、２〜８質量部の割合が好ましく、４〜５質量部が更に好ましい。
【００２３】
ＣＦＲＰは最大径で１０ｍｍ以下に破砕することが好ましく、１〜５ｍｍに破砕することが更に好ましい。
【００２４】
次に、上記ＣＦＲＰと溶剤と触媒との混合物を、非酸化性ガス雰囲気下、好ましくは１〜５ＭＰａ、更に好ましくは２〜３ＭＰａに加圧すると共に、好ましくは３００〜５００℃、更に好ましくは３８０〜４４０℃に加熱することにより、液相熱分解させる。
【００２５】
この液相熱分解反応により、ＣＦＲＰのマトリックス樹脂は、低分子化合物にまで分解され、ガス状成分、又は溶剤に溶けて常温で液体の生成油（液状生成物）となる。
【００２６】
例えば、ＣＦＲＰのマトリックス樹脂がエポキシ樹脂の場合、液状生成物としては、樹脂はフェノールやイソプロピルフェノールなどのエポキシ樹脂由来のモノマー成分にまで分解され、それらのモノマー成分の生成量は、ＣＦＲＰ当り１〜１０質量％にまで達する。
【００２７】
上記液相熱分解反応において、非酸化性ガス雰囲気は、Ｎ２、Ａｒなどの不活性ガス雰囲気、又はＨ２ガス雰囲気が好ましい。
【００２８】
液相熱分解の圧力を上記範囲の１〜５ＭＰａにすることにより、ＣＦＲＰと混合した溶剤を、その加熱温度において液相に保持することができる。
【００２９】
液相熱分解の反応温度が３００℃未満の場合は、後述する軽質油収率が低くなるので好ましくない。液相熱分解の反応温度が５００℃を超える場合は、反応生成物中のガス量が多くなる、並びに、回収されるＣＦの強度が低下するなどの不具合を生ずるので好ましくない。
【００３０】
液相熱分解の反応時間は、そのＣＦＲＰが十分に分解油化される時間であれば良く、通常、６０〜９０分程度である。
【００３１】
上記液相熱分解反応においては、ＣＦＲＰと混合された溶剤からは触媒作用によって、水素が脱離する。この水素は樹脂の炭化を防ぐと共に、樹脂の分解を円滑に進行させる。
【００３２】
樹脂からの分解生成物は低分子化して溶剤に溶ける。しかし、触媒を加えない液相熱分解反応では、樹脂からの分解生成物は、ある程度低分子化するものの、常温で液体になるまでは低分子化できない。
【００３３】
次に、液状生成物については、３３０℃、４００Ｐａでの真空蒸留を行い、留出油（軽質油Ｏｉｌ）と、水と、残渣（重質成分ＶＲ）とに分離することが好ましい。
【００３４】
上記の本発明のＣＦＲＰからのＣＦと樹脂の分離方法によって得られたスラリー中の反応生成物は、濾過法などの固液分離によって固体（回収ＣＦを含む）と液状生成物とに分離することができる。
【００３５】
一方の固液分離物である固体は、必要に応じ脱イオン水とアセトンを用いて洗浄し、付着している溶媒、触媒を除去することができる。本発明のＣＦＲＰからのＣＦと樹脂の分離方法によれば、回収されたＣＦは、光学顕微鏡観察、比重、強度とも未処理の原糸と変わらないことを特徴としている。
【００３６】
他方の固液分離物である液状生成物は、真空蒸留などの蒸留分離によって、留出油（軽質油）と、水と、残渣（重質成分）とに分離することができる。本発明のＣＦＲＰからのＣＦと樹脂の分離方法によれば、水や重質油の生成量が少なく、リサイクルとして適した軽質油の生成量が多いことを特徴としている。
【００３７】
なお、上記軽質油は、ＣＦＲＰのマトリックス樹脂から液相熱分解反応で得られた軽質油成分と、溶剤と、脱水素された溶剤との混合物になっているため、液相熱分解反応で得られた生成物の組成解析をする際には、溶剤の仕込量を差し引いた数値として示すものである。
【００３８】
【実施例】
次に本発明を実施例により更に詳細に説明する。
【００３９】
（ＣＦＲＰの液相分解）
実施例１
内容積２００ｍＬの電磁攪拌式オートクレーブにより、溶剤としてシクロヘキサノールを５５．７５ｇと、ＣＦＲＰ２２．２９ｇと、触媒としてＣａＣＯ３を０．９６ｇ仕込み、２ＭＰａの窒素加圧下、反応温度４４０℃、反応時間１ｈｒ、攪拌数１０００ｒｐｍの条件で液相熱分解反応を行った。
【００４０】
ＣＦＲＰは、東邦テナックス（株）製・ＣＦ〔Ｂｅｓｆｉｇｈｔ（登録商標）〕プリプレグ（原糸：ＨＴＡ−１２Ｋ、エポキシ樹脂３７質量％含有）を５０×５０ｍｍに切断し、熱風乾燥機にて２ｈｒ硬化させたものを使用した。
【００４１】
上記液相熱分解反応によって生成したガスの容量は湿式ガスメーターによって測定し、その組成はＴＣＤ検出器を備えたガスクロマトグラフによって定量した。
【００４２】
未反応ＣＦＲＰを含むスラリー状の反応生成物は、濾過法によって固体〔未反応ＣＦＲＰ（回収ＣＦを含む）〕と液状生成物とに分離した。液状生成物については、３３０℃、４００Ｐａでの真空蒸留を行い、留出油（軽質油Ｏｉｌ）と、水と、残渣（重質成分ＶＲ）とに分離した。軽質油中のフェノール、イソプロピルフェノール及びビスフェノールＡについてはＦＩＤ検出器及びガラスキャピラリーカラムを備えたガスクロマトグラフによって組成解析を行った。
【００４３】
以上の液相熱分解反応で得られた生成物の各成分組成を、ＣＦＲＰの仕込量に対する質量％として表１に示している。なお、軽質油については溶剤の仕込量を差引いた数値として示している。また、後述する「回収ＣＦの外観と性状」において回収ＣＦの生成物各成分の付着量を求め、各成分組成に加えた。
【００４４】
実施例２
液相熱分解反応における触媒をＮａ２ＣＯ３にした以外は、実施例１と同様にして、液相熱分解反応、液固分離、真空蒸留、成分組成分析を行い、それらの結果を表１に示した。
【００４５】
実施例３
液相熱分解反応における反応温度を３８０℃にし、触媒をＮａ２ＣＯ３にした以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表１に示した。
【００４６】
実施例４
溶剤としてシクロヘキサノールの代わりにＬＣＯ５５．７５ｇを、触媒としてＣａＣＯ３の代わりにＮａ２ＣＯ３０．９６ｇを、オートクレーブに仕込み、反応温度を４４０℃とした以外は、実施例１と同様にして、液相熱分解反応、液固分離、真空蒸留、成分組成分析を行い、それらの結果を表１に示した。
【００４７】
【表１】
実施例５
溶剤としてシクロヘキサノールの代わりに２−エチル−１−ヘキサノール５５．７５ｇを、オートクレーブに仕込んだ以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表２に示した。
【００４９】
実施例６
溶剤としてシクロヘキサノールの代わりに１−オクタノール５５．７５ｇを、オートクレーブに仕込んだ以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表２に示した。
【００５０】
実施例７
溶剤としてシクロヘキサノールの代わりに１−オクタノール５５．７５ｇを、触媒としてＣａＣＯ３の代わりにＮａ２ＣＯ３０．９６ｇを、オートクレーブに仕込んだ以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表２に示した。
【００５１】
比較例１
オートクレーブに触媒を仕込まなかった以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表２に示した。
【００５２】
【表２】
比較例２
オートクレーブに触媒を仕込まなかった以外は、実施例４と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表３に示した。
【００５４】
比較例３
オートクレーブに、触媒を仕込まず、溶剤としてシクロヘキサノールの代わりに１−ヘプタノール５５．７５ｇを仕込み、反応温度を３５０℃とした以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表３に示した。
【００５５】
比較例４
オートクレーブに、触媒を仕込まず、溶剤としてシクロヘキサノールの代わりに１−ヘプタノール５５．７５ｇを仕込み、反応温度を４４０℃とした以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表３に示した。
【００５６】
比較例５
オートクレーブに、触媒を仕込まず、溶剤としてシクロヘキサノールの代わりに２−エチル−１−ヘキサノール５５．７５ｇを仕込み、反応温度を３５０℃とした以外は、実施例１と同様にして、液相熱分解反応、固液分離、真空蒸留、成分組成解析を行い、それらの結果を表３に示した。
【００５７】
【表３】
前述のようにＣＦＲＰサンプル中には３７質量％のエポキシ樹脂が含まれているため、すべての樹脂が分解された場合の転化率も３７質量％であり、表中にはフェノールなどのエポキシ樹脂の分解によって生成する主な成分の収率も付記してある。
【００５９】
表１乃至３によると、比較例２のＬＣＯ を溶剤として使用した場合を除くと、いずれの場合もガスの生成率は０．２〜５質量％と低く、主な組成は二酸化炭素、一酸化炭素、メタン及び低級炭化水素などであった。
【００６０】
シクロヘキサノールやＬＣＯ、他の高級アルコールへＣａＣＯ３あるいはＮａ２ＣＯ３などの触媒を併用した場合には、熱分解反応では樹脂を十分分解・除去することができた。
【００６１】
転化率については、ＣａＣＯ３あるいはＮａ２ＣＯ３などの触媒を添加した実施例１乃至４では何れも３７質量％前後と高い値を示した。実施例５の２−エチル−１−ヘキサノールについては、転化率が３３．８質量％と少し低めの値であった。しかし、比較例５と比べるとＣａＣＯ３を触媒として加え、温度を３０℃上げることによって、転化率にして１９．４質量％もの上昇を示した。
【００６２】
反応後、ＣａＣＯ３あるいはＮａ２ＣＯ３など触媒は、水洗によって容易に除去できることから、残渣としてのＣＦの物性に影響を及ぼすことはないどころか、後述の「回収ＣＦの外観と性状の評価」で示すように、残渣としてのＣＦの物性は非接触反応の場合よりも高く維持されるため、熱分解反応における接触反応は効果的である。
【００６３】
反応温度の違いについては、実施例２と実施例３更には実施例４との比較で示されるように、転化率への影響は少なかった。
【００６４】
なお、液体の反応生成物（軽質油、重質成分、及び水）の収率（樹脂からの転化率）は、反応後の総液体生成物（軽質油、重質成分、及び水に加えて、反応後の溶剤も含まれる）の質量から反応前の溶剤の質量を差し引いて算出した。また、軽質油の収率は、上記液体反応生成物の収率から、重質成分の収率、及び水の収率を差し引いて算出した。
【００６５】
そのため、軽質油収率の値が負の値を示すことがある。このことは熱的に分解された樹脂成分からの活性成分（ラジカル）が溶剤と縮重合反応を起こし、多量の重質成分（ＶＲ）を生成したためと考えられる。
【００６６】
液体の反応生成物中にはフェノール、イソプロピルフェノールなどエポキシ樹脂由来のモノマー成分が認められた。水素を放出した後の溶剤が縮重合反応によって重質化するため、計算上、軽質油の収率は低くなる場合があるが、エポキシ樹脂の分解で生成したラジカルは溶剤からの水素によって、エポキシ樹脂由来のモノマー成分として低分子のまま安定化されていると考えられる。
【００６７】
液体の反応生成物は蒸留可能な炭化水素類であり、燃料あるいは石油化学用の原料などとしての利用が可能である。
【００６８】
（回収ＣＦの外観と性状の評価）
実施例１〜７、並びに、比較例１〜５に示す液相熱分解法により処理した後の回収ＣＦは、脱イオン水及びアセトンを用いて洗浄し、付着している溶剤、触媒を除去した。その後、８０℃で１ｈｒの加熱乾燥を施し各種解析を実施した。
【００６９】
原材料ＣＦＲＰ、並びに、実施例３及び４における回収ＣＦについて、その外観をそれぞれ図１（ａ）、図１（ｂ）、並びに、図１（ｃ）に示す。
【００７０】
回収ＣＦの表面の解析には光学顕微鏡を用いて観察を、実施例１〜４、並びに、比較例１及び２における各回収ＣＦについて行い、その光学顕微鏡写真をそれぞれ図２（ａ）、図２（ｂ）、図２（ｃ）、図２（ｄ）、図２（ｅ）、並びに、図２（ｆ）に示した。
【００７１】
さらに、繊維の劣化を評価するために、各回収ＣＦの比重及び単繊維強度の測定を、実施例１〜７、並びに、比較例１〜５について行った。これらの比重測定、単繊維強度測定の結果を表４に示した。
【００７２】
なお、繊維劣化の比較対照としては、未処理の原糸（ＨＴＡ−１２Ｋ、サイズ剤なし、比重１．７７、単繊維強度：４．０ＧＰａ）を用いて優位差を判断した。
【００７３】
【表４】
表４によると、溶剤としてシクロヘキサノールやＬＣＯを使用し、ＣａＣＯ３やＮａ２ＣＯ３などの触媒を併用した場合には、繊維比重の値が１．７７、単繊維強度も４．３〜３．９ＧＰａと繊維劣化は認められず、物性的には十分再利用可能である。しかし、ＣａＣＯ３やＮａ２ＣＯ３などの触媒を併用しない場合には、繊維比重の値が１．７７であるものの、単繊維強度が３．６、３．７ＧＰａであり、物性が劣化している。
【００７５】
また、表４によると、溶剤として２−エチル−１−ヘキサノール、１−オクタノール及び１−ヘプタノールを使用し、ＣａＣＯ３やＮａ２ＣＯ３などの触媒を併用した場合にも、繊維比重の値が１．７７、単繊維強度も３．９〜３．８ＧＰａと繊維劣化は認められず、物性的には十分再利用可能である。しかし、ＣａＣＯ３やＮａ２ＣＯ３などの触媒を併用しない場合には、繊維比重の値が１．７７であるものの、単繊維強度が３．６〜３．４ＧＰａであり、物性が劣化している。
【００７６】
更に、図２（ａ）、図２（ｂ）、図２（ｃ）、図２（ｄ）、図２（ｅ）、並びに、図２（ｆ）によると、実施例１〜４では光学顕微鏡での観察において樹脂が除去されている様子が窺える。しかし、比較例１及び２においては、ＣＦ表面に樹脂が残存している。
【００７７】
【発明の効果】
本発明によれば、ＣＦＲＰと、高級アルコール又はＬＣＯと、触媒との混合物を、非酸化性ガス雰囲気下、加圧・加熱することから、ＣＦＲＰ中のマトリックス樹脂を高い転化率で分解することができると共に、ＣＦの物性劣化させることなく、ＣＦＲＰから樹脂とＣＦとを分離することができる。
【図面の簡単な説明】
【図１】原材料ＣＦＲＰ、並びに、実施例３及び４における回収ＣＦの外観について撮影した図面代用の写真であって、（ａ）は原材料ＣＦＲＰ、（ｂ）は実施例３における回収ＣＦ、（ｃ）は実施例４における回収ＣＦの外観写真である。
【図２】実施例１〜４、並びに、比較例１及び２において撮影した図面代用の光学顕微鏡写真であって、（ａ）は実施例１、（ｂ）は実施例２、（ｃ）は実施例３、（ｄ）は実施例４、（ｅ）は比較例１、（ｆ）は比較例２における顕微鏡写真である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for separating carbon fiber (CF) and resin in carbon fiber reinforced plastic (CFRP).
[0002]
[Prior art]
In recent years, there has been a great deal of interest in garbage disposal issues and the like, and an immediate response is also desired in terms of global environmental conservation and the like. The mainstream of fiber reinforced plastic (FRP) treatment was landfilling and incineration, but these methods have already been discarded due to the reduction of landfills and social problems such as exhaust gas. Reuse (recycling) of FRP is an important issue.
[0003]
Conventionally, techniques for separating and removing matrix resin constituting plastic and FRP from reinforcing materials include thermal decomposition [Patent Document 1, Patent Document 2], chemical decomposition [Non-patent Document 1], and supercritical decomposition [Non-patent Document]. 2), light and ozonolysis are considered.
[0004]
Thermosetting resins such as phenolic resins and epoxy resins used as matrix resin materials for FRP are almost 100% at a reaction temperature of 400 ° C. or more by a liquid phase pyrolysis method using a hydrogen donor solvent such as tetralin. It is decomposed and converted into a liquid product mainly composed of a monomer such as phenol. This is known as described in
[0005]
Further, Non-Patent Document 5 describes a technique for liquefying a matrix resin in CFRP under the use of an organic catalyst and recovering the CF after the treatment.
[0006]
However, in these treatment methods, the solvent to be used (solvent) is not widely produced industrially, is special, and has problems such as high cost. In addition, the simplicity of the treatment is lacking because the organic catalyst adheres to the reinforced fibers after the treatment and the removal thereof is not easy.
[0007]
Further, CF contained in CFRP is a material having high heat resistance, but gradually oxidizes and deteriorates at 150 ° C. or higher. From the viewpoint of recovering and reusing CF, when separating the CF from the matrix resin in the CFRP, the resin must have a high decomposition rate or a high conversion rate to monomer components while maintaining the performance and characteristics of CF as much as possible. There is a demand for the establishment of a separation technique capable of removing methane.
[0008]
[Patent Document 1]
Japanese Patent No. 3180463 (Page 2 [0004] to Page 3 [0021])
[Patent Document 2]
JP-A-11-172258 (Page 2 [0003] to Page 3 [0014])
[Non-patent document 1]
Kenji Ushikoshi, Nobuyuki Komatsu, Morihiko Sugino, Materials, 44 volumes, pp. 428-431 (1995)
[Non-patent document 2]
Takeshi Sako, Izumi Okajima, Takeshi Sugata, Plastic Chemistry Recycling Study Group, Proceedings of the 3rd Symposium, P27-28 (2000)
[Non-Patent Document 3]
Y. Sato, Y .; Kodera, T .; Kamo, Energy & Fuels, Volume 13, P364-368 (1999)
[Non-patent document 4]
Yoshiki Sato, Chemistry and Industry, 54 (12), P1347-1351 (2001)
[Non-Patent Document 5]
FY2000 New Energy and Industrial Technology Development Organization Research Commissioned Results Report, Standardization of Recycled CFRP Pulverized Products, P45-65
[0009]
[Problems to be solved by the invention]
The present inventors have conducted various studies to solve the above-mentioned problems, and found that CFRP and a higher alcohol or light cycle oil widely used industrially [Light Cycle Oil (LCO: FCC Pressurizing and heating a mixture of the residual oil produced from the apparatus) and a catalyst in a non-oxidizing gas atmosphere to convert the matrix resin at the highest possible conversion rate and improve the CF performance. The inventors have learned that they can be removed without deterioration, and have completed the present invention.
[0010]
Accordingly, it is an object of the present invention to provide a method for separating CF from a matrix resin from CFRP, which solves the above problem.
[0011]
[Means for Solving the Problems]
The present invention that achieves the above object is as described below.
[0012]
[1] A mixture of a carbon fiber reinforced plastic, a higher alcohol or light cycle oil, and a catalyst is pressurized and heated under a non-oxidizing gas atmosphere to decompose the resin in the carbon fiber reinforced plastic and obtain the obtained decomposition. A method for separating a carbon fiber and a resin, wherein the resin is separated from the carbon fibers in the carbon fiber reinforced plastic.
[0013]
[2] The catalyst is made of a porous metal such as a carbonate of an alkali metal or an alkaline earth metal, an oxide of a metal other than metals of
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
CFRP used as a raw material to be treated in the present invention is a reinforced composite material in which CF is dispersed in a matrix resin. The matrix resin includes a thermosetting resin such as an epoxy resin, a phenol resin, a polyurethane resin, and an unsaturated polyester resin, and a thermoplastic resin such as polypropylene and nylon. CF includes rayon yarn, pitch yarn, and acrylic yarn.
[0015]
Although the resin content in CFRP is not particularly limited, it is preferably 20 to 50% by mass.
[0016]
The present invention is characterized in that a mixture of the above CFRP, higher alcohol or LCO, and a catalyst is pressurized and heated in a non-oxidizing gas atmosphere to separate resin and CF from CFRP.
[0017]
The purity of the higher alcohol is preferably 98% by mass.
[0018]
The higher alcohol usually refers to an aliphatic alcohol having 4 or more carbon atoms. Among these aliphatic alcohols, aliphatic alcohols having 6 to 12 carbon atoms and having a higher boiling point than low molecular weight compounds obtained by decomposition of a resin are preferable. Such higher alcohols include hexanol, cyclohexanol, 1-heptanol, 2-ethyl-1-hexanol, 1-octanol and the like.
[0019]
The purity of LCO is preferably 98% by mass.
[0020]
The use ratio of these solvents is preferably from 50 to 400 parts by mass, more preferably from 50 to 300 parts by mass, per 100 parts by mass of CFRP.
[0021]
Examples of the catalyst include a carbonate of an alkali metal or an alkaline earth metal, an oxide of a metal excluding metals of
[0022]
The use ratio of the above catalyst is preferably 2 to 8 parts by mass, more preferably 4 to 5 parts by mass, per 100 parts by mass of CFRP.
[0023]
The CFRP is preferably crushed to a maximum diameter of 10 mm or less, more preferably 1 to 5 mm.
[0024]
Next, the mixture of the CFRP, the solvent, and the catalyst is pressurized under a non-oxidizing gas atmosphere to preferably 1 to 5 MPa, more preferably 2 to 3 MPa, and preferably 300 to 500 ° C., and more preferably 380 to 380 ° C. By heating to 440 ° C., liquid phase pyrolysis is performed.
[0025]
By this liquid-phase thermal decomposition reaction, the matrix resin of CFRP is decomposed into low molecular compounds, and dissolved in gaseous components or solvents to form liquid oil (liquid product) at room temperature.
[0026]
For example, when the matrix resin of CFRP is an epoxy resin, as a liquid product, the resin is decomposed into monomer components derived from an epoxy resin such as phenol or isopropylphenol, and the amount of these monomer components generated is 1 to 1 per CFRP. It reaches up to 10% by weight.
[0027]
In the liquid phase pyrolysis reaction, the non-oxidizing gas atmosphere is preferably an inert gas atmosphere such as N 2 or Ar, or an H 2 gas atmosphere.
[0028]
By setting the pressure of liquid phase pyrolysis to the above range of 1 to 5 MPa, the solvent mixed with CFRP can be kept in the liquid phase at the heating temperature.
[0029]
When the reaction temperature of the liquid phase thermal decomposition is lower than 300 ° C., the light oil yield described below is undesirably low. When the reaction temperature of the liquid phase pyrolysis exceeds 500 ° C., it is not preferable because problems such as an increase in the amount of gas in the reaction product and a decrease in the strength of the recovered CF are caused.
[0030]
The reaction time of the liquid phase pyrolysis may be any time as long as the CFRP is sufficiently decomposed into oil, and is usually about 60 to 90 minutes.
[0031]
In the liquid phase pyrolysis reaction, hydrogen is desorbed from the solvent mixed with CFRP by a catalytic action. The hydrogen prevents carbonization of the resin and promotes the decomposition of the resin.
[0032]
Decomposition products from the resin are reduced in molecular weight and dissolved in the solvent. However, in the liquid phase pyrolysis reaction without adding a catalyst, the decomposition products from the resin are reduced to a certain degree in molecular weight, but cannot be reduced to a liquid state at room temperature.
[0033]
Next, the liquid product is preferably subjected to vacuum distillation at 330 ° C. and 400 Pa to separate a distillate (light oil), water, and a residue (heavy component VR).
[0034]
The reaction product in the slurry obtained by the method for separating CF and resin from CFRP of the present invention is separated into a solid (including recovered CF) and a liquid product by solid-liquid separation such as filtration. Can be.
[0035]
The solid, which is one of the solid-liquid separation products, can be washed with deionized water and acetone as necessary to remove the attached solvent and catalyst. According to the method for separating CF and resin from CFRP of the present invention, the recovered CF is characterized in that it is not different from untreated raw yarn in optical microscopic observation, specific gravity and strength.
[0036]
The other liquid product, which is a solid-liquid separation product, can be separated into a distillate (light oil), water, and a residue (heavy component) by distillation separation such as vacuum distillation. According to the method for separating CF and resin from CFRP of the present invention, the amount of water and heavy oil generated is small, and the amount of light oil suitable for recycling is large.
[0037]
Since the light oil is a mixture of a light oil component obtained from a matrix resin of CFRP in a liquid phase pyrolysis reaction, a solvent, and a dehydrogenated solvent, the light oil is obtained in a liquid phase pyrolysis reaction. When the composition of the obtained product is analyzed, it is shown as a value obtained by subtracting the charged amount of the solvent.
[0038]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0039]
(Liquid phase decomposition of CFRP)
Example 1
55.75 g of cyclohexanol as a solvent, 22.29 g of CFRP, and 0.96 g of CaCO 3 as a catalyst were charged by a magnetic stirring autoclave having an internal volume of 200 mL, and a reaction temperature of 440 ° C. and a reaction time of 1 hr were applied under nitrogen pressure of 2 MPa. The liquid phase pyrolysis reaction was performed under the conditions of a stirring number of 1,000 rpm.
[0040]
CFRP is a product of Toho Tenax Co., Ltd., CF [Besfight (registered trademark)] prepreg (raw yarn: HTA-12K, containing 37% by mass of epoxy resin), cut into 50 × 50 mm, and cured with a hot air drier for 2 hours. Was used.
[0041]
The volume of the gas generated by the liquid phase pyrolysis reaction was measured by a wet gas meter, and the composition was quantified by a gas chromatograph equipped with a TCD detector.
[0042]
The slurry-like reaction product containing unreacted CFRP was separated into a solid [unreacted CFRP (including recovered CF)] and a liquid product by a filtration method. The liquid product was subjected to vacuum distillation at 330 ° C. and 400 Pa to separate a distillate (light oil), water, and a residue (heavy component VR). The composition of phenol, isopropylphenol and bisphenol A in light oil was analyzed by gas chromatography equipped with a FID detector and a glass capillary column.
[0043]
Table 1 shows the composition of each component of the product obtained in the above liquid phase pyrolysis reaction as% by mass with respect to the charged amount of CFRP. Light oil is shown as a value obtained by subtracting the charged amount of the solvent. The amount of each component of the recovered CF was determined in “Appearance and Properties of Recovered CF” described below, and added to each component composition.
[0044]
Example 2
A liquid-phase pyrolysis reaction, liquid-solid separation, vacuum distillation, and component composition analysis were performed in the same manner as in Example 1 except that Na 2 CO 3 was used as the catalyst in the liquid-phase pyrolysis reaction. It was shown to.
[0045]
Example 3
The liquid phase pyrolysis reaction, solid-liquid separation, vacuum distillation, and component composition analysis were performed in the same manner as in Example 1 except that the reaction temperature in the liquid phase pyrolysis reaction was set to 380 ° C. and the catalyst was changed to Na 2 CO 3. The results are shown in Table 1.
[0046]
Example 4
55.75 g of LCO instead of cyclohexanol as a solvent, and 0.96 g of Na 2 CO 3 instead of CaCO 3 as a catalyst were charged into an autoclave, and the reaction temperature was changed to 440 ° C. Liquid phase pyrolysis reaction, liquid-solid separation, vacuum distillation, and component composition analysis were performed. The results are shown in Table 1.
[0047]
[Table 1]
Example 5
Liquid phase pyrolysis reaction, solid-liquid separation, vacuum distillation, component composition analysis in the same manner as in Example 1 except that 55.75 g of 2-ethyl-1-hexanol was charged to the autoclave instead of cyclohexanol as a solvent. And the results are shown in Table 2.
[0049]
Example 6
A liquid phase pyrolysis reaction, solid-liquid separation, vacuum distillation, and component composition analysis were performed in the same manner as in Example 1 except that 55.75 g of 1-octanol was used instead of cyclohexanol as a solvent in the autoclave. Table 2 shows the results.
[0050]
Example 7
Liquid phase pyrolysis was carried out in the same manner as in Example 1 except that 55.75 g of 1-octanol was used instead of cyclohexanol as a solvent, and 0.96 g of Na 2 CO 3 was used as a catalyst instead of CaCO 3 in an autoclave. Reaction, solid-liquid separation, vacuum distillation, and component composition analysis were performed, and the results are shown in Table 2.
[0051]
Comparative Example 1
A liquid phase pyrolysis reaction, solid-liquid separation, vacuum distillation, and component composition analysis were performed in the same manner as in Example 1 except that no catalyst was charged in the autoclave. The results are shown in Table 2.
[0052]
[Table 2]
Comparative Example 2
A liquid phase pyrolysis reaction, solid-liquid separation, vacuum distillation and component composition analysis were performed in the same manner as in Example 4 except that the catalyst was not charged in the autoclave. The results are shown in Table 3.
[0054]
Comparative Example 3
A liquid phase pyrolysis reaction and a solid-liquid reaction were performed in the same manner as in Example 1 except that the autoclave was charged with 55.75 g of 1-heptanol instead of cyclohexanol as a solvent without charging the catalyst, and the reaction temperature was changed to 350 ° C. Separation, vacuum distillation and component composition analysis were performed, and the results are shown in Table 3.
[0055]
Comparative Example 4
A liquid phase pyrolysis reaction and a solid-liquid reaction were performed in the same manner as in Example 1 except that the autoclave was charged with 55.75 g of 1-heptanol instead of cyclohexanol as a solvent and the reaction temperature was changed to 440 ° C without charging the catalyst. Separation, vacuum distillation and component composition analysis were performed, and the results are shown in Table 3.
[0056]
Comparative Example 5
Liquid phase pyrolysis was performed in the same manner as in Example 1 except that the catalyst was not charged into the autoclave, but 55.75 g of 2-ethyl-1-hexanol was charged as a solvent instead of cyclohexanol, and the reaction temperature was 350 ° C. Reaction, solid-liquid separation, vacuum distillation, and component composition analysis were performed, and the results are shown in Table 3.
[0057]
[Table 3]
As described above, since the CFRP sample contains 37% by mass of the epoxy resin, the conversion rate when all the resins are decomposed is 37% by mass, and the epoxy resin such as phenol is shown in the table. The yields of the main components formed by the decomposition are also indicated.
[0059]
According to Tables 1 to 3, except for the case where LCO 2 of Comparative Example 2 was used as a solvent, the gas generation rate was as low as 0.2 to 5% by mass in each case, and the main composition was carbon dioxide and monoxide. Carbon, methane and lower hydrocarbons.
[0060]
When a catalyst such as CaCO 3 or Na 2 CO 3 was used in combination with cyclohexanol, LCO, or other higher alcohols, the resin could be sufficiently decomposed and removed by the thermal decomposition reaction.
[0061]
Regarding the conversion, all of Examples 1 to 4 in which a catalyst such as CaCO 3 or Na 2 CO 3 was added showed a high value of about 37% by mass. The conversion of 2-ethyl-1-hexanol of Example 5 was a slightly lower value of 33.8% by mass. However, when compared with Comparative Example 5, CaCO 3 was added as a catalyst and the temperature was increased by 30 ° C., whereby the conversion was increased by 19.4% by mass.
[0062]
After the reaction, since the catalyst such as CaCO 3 or Na 2 CO 3 can be easily removed by washing with water, it does not affect the physical properties of CF as a residue. As shown, since the physical properties of CF as a residue are maintained higher than in the case of the non-contact reaction, the catalytic reaction in the thermal decomposition reaction is effective.
[0063]
Regarding the difference in the reaction temperature, as shown in the comparison between Example 2, Example 3, and Example 4, there was little influence on the conversion.
[0064]
The yield (conversion rate from resin) of liquid reaction products (light oil, heavy components, and water) is calculated by adding the total liquid products (light oil, heavy components, and water) after the reaction. , Including the solvent after the reaction) was subtracted from the mass of the solvent before the reaction. The yield of light oil was calculated by subtracting the yield of heavy components and the yield of water from the yield of the liquid reaction product.
[0065]
Therefore, the value of the light oil yield may show a negative value. This is presumably because the active component (radical) from the thermally decomposed resin component caused a polycondensation reaction with the solvent to generate a large amount of heavy component (VR).
[0066]
Monomer components derived from epoxy resins such as phenol and isopropylphenol were found in the liquid reaction product. Since the solvent after releasing hydrogen becomes heavier due to the polycondensation reaction, the yield of light oil may be calculated lower in some cases, but radicals generated by the decomposition of the epoxy resin are converted into epoxy by hydrogen from the solvent. It is considered that the low molecular weight is stabilized as a resin-derived monomer component.
[0067]
The liquid reaction product is a hydrocarbon which can be distilled, and can be used as a fuel or a raw material for petrochemicals.
[0068]
(Evaluation of appearance and properties of recovered CF)
The recovered CF after the treatment by the liquid phase pyrolysis method shown in Examples 1 to 7 and Comparative Examples 1 to 5 was washed with deionized water and acetone to remove the attached solvent and catalyst. . After that, heating and drying were performed at 80 ° C. for 1 hour, and various analyzes were performed.
[0069]
The appearance of the raw material CFRP and the recovered CF in Examples 3 and 4 are shown in FIGS. 1 (a), 1 (b) and 1 (c), respectively.
[0070]
For the analysis of the surface of the recovered CF, observation was performed using an optical microscope for each of the recovered CFs in Examples 1 to 4 and Comparative Examples 1 and 2, and the optical microscope photographs were respectively shown in FIGS. (B), FIG. 2 (c), FIG. 2 (d), FIG. 2 (e), and FIG. 2 (f).
[0071]
Furthermore, in order to evaluate fiber deterioration, specific gravity and single fiber strength of each recovered CF were measured for Examples 1 to 7 and Comparative Examples 1 to 5. Table 4 shows the results of these specific gravity measurements and single fiber strength measurements.
[0072]
In addition, as a comparative control of fiber deterioration, a superior difference was determined using an untreated raw yarn (HTA-12K, no sizing agent, specific gravity 1.77, single fiber strength: 4.0 GPa).
[0073]
[Table 4]
According to Table 4, when cyclohexanol or LCO is used as a solvent and a catalyst such as CaCO 3 or Na 2 CO 3 is used in combination, the fiber specific gravity value is 1.77 and the single fiber strength is 4.3 to 3 As a result, no fiber deterioration was observed at 0.9 GPa, and the material was sufficiently recyclable. However, when a catalyst such as CaCO 3 or Na 2 CO 3 is not used in combination, although the specific gravity of the fiber is 1.77, the single fiber strength is 3.6 and 3.7 GPa, and the physical properties are deteriorated. I have.
[0075]
According to Table 4, 2-ethyl-1-hexanol, 1-octanol and 1-heptanol were used as solvents, and the value of the fiber specific gravity was also increased when a catalyst such as CaCO 3 or Na 2 CO 3 was used in combination. 1.77, the single fiber strength was 3.9 to 3.8 GPa, and no fiber deterioration was observed. However, when a catalyst such as CaCO 3 or Na 2 CO 3 is not used in combination, although the specific gravity of the fiber is 1.77, the single fiber strength is 3.6 to 3.4 GPa, and the physical properties are deteriorated. I have.
[0076]
Further, according to FIGS. 2 (a), 2 (b), 2 (c), 2 (d), 2 (e), and 2 (f), in Examples 1 to 4, the optical microscope was used. It can be seen that the resin has been removed in the observation. However, in Comparative Examples 1 and 2, the resin remains on the CF surface.
[0077]
【The invention's effect】
According to the present invention, a mixture of CFRP, higher alcohol or LCO, and a catalyst is pressurized and heated under a non-oxidizing gas atmosphere, so that the matrix resin in CFRP can be decomposed at a high conversion rate. The resin and the CF can be separated from the CFRP without deteriorating the physical properties of the CF.
[Brief description of the drawings]
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph instead of a drawing taken of the appearance of a raw material CFRP and the recovered CF in Examples 3 and 4, wherein (a) is the raw material CFRP, (b) is the recovered CF in Example 3, (c) () Is a photograph of the appearance of the recovered CF in Example 4.
FIGS. 2A and 2B are optical microscope photographs taken in Examples 1 to 4 and Comparative Examples 1 and 2 as substitutes for drawings, wherein FIG. 2A is Example 1, FIG. 2B is Example 2, and FIG. Example 3, (d) is a micrograph in Example 4, (e) is a micrograph in Comparative Example 1, and (f) is a micrograph in Comparative Example 2.
Claims (2)
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| JP2002257490A JP2004091720A (en) | 2002-09-03 | 2002-09-03 | Method for separating carbon fiber and resin |
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| JP2002257490A JP2004091720A (en) | 2002-09-03 | 2002-09-03 | Method for separating carbon fiber and resin |
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| CN110922633A (en) * | 2019-11-04 | 2020-03-27 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Carbon fiber resin matrix composite material thermal degradation catalyst and application method thereof |
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