JPH09272876A - Device for thermally decomposing styrenic resin and thermal decomposition of the styrenic resin - Google Patents
Device for thermally decomposing styrenic resin and thermal decomposition of the styrenic resinInfo
- Publication number
- JPH09272876A JPH09272876A JP8489096A JP8489096A JPH09272876A JP H09272876 A JPH09272876 A JP H09272876A JP 8489096 A JP8489096 A JP 8489096A JP 8489096 A JP8489096 A JP 8489096A JP H09272876 A JPH09272876 A JP H09272876A
- Authority
- JP
- Japan
- Prior art keywords
- tank
- thermal decomposition
- styrene
- dissolution
- styrene resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005979 thermal decomposition reaction Methods 0.000 title claims abstract description 141
- 229920001890 Novodur Polymers 0.000 title abstract description 15
- 238000004090 dissolution Methods 0.000 claims abstract description 73
- 239000012263 liquid product Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000007599 discharging Methods 0.000 claims abstract description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 231
- 229920005989 resin Polymers 0.000 claims description 115
- 239000011347 resin Substances 0.000 claims description 115
- 238000003756 stirring Methods 0.000 claims description 29
- 238000000354 decomposition reaction Methods 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000000197 pyrolysis Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 238000011978 dissolution method Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003849 aromatic solvent Substances 0.000 abstract description 2
- 239000003254 gasoline additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000013502 plastic waste Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 239000004794 expanded polystyrene Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical group 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VEAFKIYNHVBNIP-UHFFFAOYSA-N 1,3-Diphenylpropane Chemical compound C=1C=CC=CC=1CCCC1=CC=CC=C1 VEAFKIYNHVBNIP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 241001421775 Thereus Species 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- JKXPOVQDCCOPCZ-UHFFFAOYSA-N [O-2].[Fe+2].O[Si](O)(O)O Chemical compound [O-2].[Fe+2].O[Si](O)(O)O JKXPOVQDCCOPCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001583 allophane Inorganic materials 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
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- Y02W30/20—Waste processing or separation
-
- 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
- Processing Of Solid Wastes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、スチレン系樹脂の熱分
解装置及び熱分解方法に関し、詳しくはスチレン系樹脂
廃棄物から芳香族溶剤、ガソリン添加剤、重油添加剤な
ど付加価値の高い芳香族系炭化水素油を安価で簡単にか
つ高収率で速やかに取得することのできるスチレン系樹
脂の熱分解装置及び熱分解方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pyrolysis apparatus and pyrolysis method for styrenic resins, and more particularly to aromatic hydrocarbons having high added value such as aromatic solvents, gasoline additives and heavy oil additives from styrene resin wastes. TECHNICAL FIELD The present invention relates to a thermal decomposition apparatus and thermal decomposition method for a styrene-based resin, which is capable of quickly and inexpensively obtaining a hydrocarbon-based oil at a high yield.
【０００２】[0002]
【従来の技術】現在、プラスチックは日常生活のあらゆ
る分野に浸透しているとともに、高度技術を支えるのに
不可欠な素材の一つになっているが、生産量の増加とと
もにその廃棄物の処理方法が真剣に検討されている。こ
の解決を図るため、プラスチックの廃棄物対策として
は、マテリアルリサイクル、サーマルリサイクルの開発
と単純焼却、埋め立てなどの諸政策が検討されている。
特に近年、地球環境問題の高まりにより、廃棄物の適性
処分、エネルギーの有効利用、リサイクルといった問題
が強く叫ばれている。例えば、プラスチック廃棄物の再
利用の１つとして、廃棄物を無公害で完全に燃焼させ
て、且つ高効率でエネルギー回収を図る、といった２つ
の目的を同時に叶えるために、廃棄物の燃料化を目的と
した熱分解油化技術の研究開発が盛んに行われている。2. Description of the Related Art At present, plastic is permeating into all fields of daily life and is one of the indispensable materials to support advanced technology. Is being seriously considered. In order to solve this problem, various policies such as material recycling, development of thermal recycling, simple incineration, and landfill are being considered as measures against plastic waste.
Particularly in recent years, due to the increase in global environmental problems, problems such as proper disposal of wastes, effective use of energy, and recycling have been strongly emphasized. For example, as one of the reuses of plastic waste, in order to achieve two purposes at the same time, that is, to burn the waste completely without pollution and to recover energy with high efficiency, it is necessary to convert the waste into fuel. Research and development of pyrolysis technology aimed at are being actively conducted.
【０００３】ところで、プラスチック生産量の大部分を
占める熱可塑性プラスチックのうち、ポリスチレン系樹
脂、ポリオレフィン系樹脂（例えばポリエチレン、ポリ
プロピレン等）等の処理方法を見ると、１部でリペレッ
ト化し成形材料として利用されているものの、分別、再
生処理に多大なコストが発生することが多く、また、再
生樹脂の品質劣化が生じ易く、リペレットの回数が限ら
れること等の問題がある。したがって、小規模な利用は
行われているものの、実用的効果を発揮するには至って
いない。また、埋め立て処分については、年々増大する
混合プラスチック廃棄物は、埋め立てる場所の確保が次
第に困難となりつつあり、その対応が急がれている。こ
の場所の問題を早急に解決するためには、混合プラスチ
ック廃棄物の焼却処分を行うことが考えられるが、一般
焼却炉での焼却は、プラスチックの発熱量が高いため、
一般ゴミ中でのプラスチックの混入量が大となると、炉
壁等の損傷を引き起こし易く、これらの対策を講じた専
用の焼却炉の設置が必要である。Among thermoplastics, which account for the majority of plastic production, polystyrene resins, polyolefin resins (eg, polyethylene, polypropylene, etc.) are treated as a molding material by re-pelletizing them in one part. However, there is a problem that a large cost is often generated in the sorting and the recycling process, the quality of the recycled resin is easily deteriorated, and the number of times of re-pelleting is limited. Therefore, although it is used on a small scale, it has not yet achieved a practical effect. Regarding landfill disposal, it is becoming increasingly difficult to secure a landfill site for mixed plastic waste, which is increasing year by year, and there is an urgent need to deal with it. In order to solve the problem of this place as soon as possible, it is possible to incinerate the mixed plastic waste, but in the case of incineration in a general incinerator, the heating value of plastic is high,
If the amount of plastic mixed in general waste is large, damage to the furnace wall and the like is likely to occur, and it is necessary to install a dedicated incinerator that takes these measures.
【０００４】このため、発泡スチロールに代表される嵩
張るスチレン系樹脂の再利用技術の早期の確立と実用化
が望まれており、資源有効利用のためのリサイクル方法
が数多く試みられ、提案されている。Therefore, early establishment and practical application of a technique for reusing bulky styrenic resins typified by expanded polystyrene are desired, and many recycling methods for effective use of resources have been tried and proposed.
【０００５】これらの再利用方法のうち、プラスチック
廃棄物を熱分解し、ガス、オイル等を回収する装置が数
多く提案されているが、未だ実用化の例は少ない。その
理由として熱分解装置が処理量に比較し大規模となり、
設備費が高額となるためである。そこで、この点を改良
するための小規模設備で効率を上げる熱分解装置の提案
も行われている（特開平５−２３７４６７号）が、加熱
効率を上げて、油の生産性を高めることは、安全上また
装置の制約上、限界があると考えられる。Among these recycling methods, many apparatuses for thermally decomposing plastic waste and recovering gas, oil and the like have been proposed, but there are still few examples of practical application. The reason is that the thermal decomposition equipment becomes large compared to the throughput,
This is because the equipment cost becomes high. Therefore, a proposal has been made for a pyrolysis device that improves efficiency with a small-scale facility to improve this point (Japanese Patent Laid-Open No. 5-237467), but it is not possible to increase heating efficiency and oil productivity. It is considered that there are limits due to safety and device restrictions.
【０００６】一方で、プラスチック廃棄物を熱分解する
際に、分解剤を添加して、熱分解の効率を上げるという
考え方がある。例えば、珪酸−酸化鉄、アルミナ−酸化
鉄（特開昭５９−１７４６８９号）、鉄錆（特開昭４９
−１０９０３号）、カルボン酸−金属酸化物（特開昭５
０−３４３６８号）、アロファンからなる土；シリカ−
アルミナ触媒（特開昭４９−１２１８７９号）等を用い
た方法が提案されている。金属酸化物を添加すること
は、プラスチック廃棄物を熱分解した時に分解槽内部に
生成付着した炭素を酸化還元反応により取り除き、伝熱
効率の低下を防止する点が作用の１つであり、さらに分
解効率を向上するという提案である。しかし、かかる方
法により得られる液状生成物（回収油）は、低沸点芳香
族化合物の含有量が高くなり、燃料用としての利用価値
が低くなると共に、低温、例えば３５０℃程度で分解を
行った場合には、特にベンゼン、トルエン、エチルベン
ゼンの収率が劣るという欠点を有していた。[0006] On the other hand, there is an idea that a thermal decomposition efficiency is increased by adding a decomposing agent when the plastic waste is thermally decomposed. For example, silicic acid-iron oxide, alumina-iron oxide (JP-A-59-174689), iron rust (JP-A-49).
-10903), a carboxylic acid-metal oxide (Japanese Patent Application Laid-Open No. S5-10
0-34368), soil consisting of allophane; silica-
A method using an alumina catalyst (JP-A-49-121879) has been proposed. One of the effects of adding metal oxides is to prevent the reduction of heat transfer efficiency by removing the carbon adhering to the inside of the decomposition tank by redox reaction when the plastic waste is thermally decomposed. It is a proposal to improve efficiency. However, the liquid product (recovered oil) obtained by such a method has a high content of low-boiling point aromatic compounds, lowers its utility value as a fuel, and is decomposed at a low temperature, for example, about 350 ° C. In this case, there was a drawback that the yields of benzene, toluene and ethylbenzene were particularly poor.
【０００７】また、スチレン系樹脂の再利用に関して研
究された技術として、例えば、スチレン系廃棄物の熱分
解によって得られる液状生成物の特性を改質し、スチレ
ン系樹脂からハイオクタンガソリン基材及び高付加価値
化学品原料を高収率で取得する方法（特開平２−２９４
９２号）が開示されている。かかる方法は、ポリスチレ
ン廃棄物を溶融し、該溶融物を加熱して液状で熱分解さ
せ（熱分解工程）、発生した蒸気状生成物をゼオライト
充填層中において接触転化させて（接触転化工程）、芳
香族炭化水素化合物を生成取得するものである。Further, as a technique studied on the reuse of styrene-based resin, for example, the characteristics of a liquid product obtained by the thermal decomposition of styrene-based waste are modified, and the styrene-based resin is used as a base material for high octane gasoline and Method for obtaining high value-added chemical raw material in high yield (Japanese Patent Laid-Open No. 2-294)
92) are disclosed. In this method, polystyrene waste is melted, the melt is heated to be thermally decomposed in a liquid state (pyrolysis step), and the generated vapor product is catalytically converted in a zeolite packed bed (catalytic conversion step). , To produce and obtain an aromatic hydrocarbon compound.
【０００８】また、発泡ポリスチレンの場合は、水蒸気
処理などにより脱泡した後、熱分解工程、接触転化工程
からなる方法で行っている。この方法によって得られる
液状生成物は、エチルベンゼン、イソプロピルベンゼン
等を主成分とする芳香族炭化水素化合物である。この分
解油は石油化学工業で高い利用価値を有し、必要に応じ
て各成分に分離して化学品原料として利用すると共に、
その成分特性からハイオクタンガソリン基材としても有
効に利用することができる。In the case of expanded polystyrene, defoaming is carried out by steam treatment or the like, and then a method comprising a thermal decomposition step and a catalytic conversion step is used. The liquid product obtained by this method is an aromatic hydrocarbon compound containing ethylbenzene, isopropylbenzene or the like as a main component. This cracked oil has a high utility value in the petrochemical industry, and it is used as a raw material for chemicals by separating it into individual components as necessary.
Due to its component characteristics, it can be effectively used as a high-octane gasoline base material.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、上述の
熱分解装置は、減容品（スチレン系樹脂を取扱い易くす
るために、加熱減容粉砕したもの）を前提とした熱分解
装置であり、本来の熱分解工程のコストに加え、減容工
程のコストが必要となり、トータルのコストは非常に高
いものとなる。また、押出機等により加熱溶融の後、溶
解槽又は分解槽へスチレン系樹脂を供給するものもみら
れる。しかし、それらの方法は複雑で大規模な設備とな
り、設備費が高価になる。このように設備費、維持費等
が高価になると、採算性のために多量のスチレン系樹脂
の回収が必要となる。その結果、例えば軽量である発泡
ポリスチレンを遠隔地から多量に運ぶこととなり、更
に、処理コストを押し上げるという悪循環が生じる。従
って、かかる処理方法の実施は安価に行うことができな
いという問題があった。However, the above-mentioned thermal decomposition apparatus is a thermal decomposition apparatus based on the premise that the volume-reduced product (the styrene resin is heat-reduced and pulverized in order to make it easy to handle) is used. In addition to the cost of the thermal decomposition process, the cost of the volume reduction process is required, and the total cost becomes very high. In some cases, the styrene resin is supplied to a melting tank or a decomposition tank after being heated and melted by an extruder or the like. However, those methods result in complicated and large-scale equipment, and the equipment cost is high. When the equipment cost, maintenance cost, etc. become expensive in this way, it is necessary to recover a large amount of styrene resin for profitability. As a result, for example, a large amount of light-weight expanded polystyrene is carried from a remote place, and a vicious cycle of further increasing the processing cost occurs. Therefore, there is a problem that such a treatment method cannot be implemented at low cost.
【００１０】また、上述の処理方法において用いられる
ゼオライト触媒は塩素、臭素などのハロゲン族元素によ
りその触媒活性が失われてしまうという問題がある。こ
のため、難燃化プラスチックの混在が避けられない廃棄
プラスチックの処理には、実質的に不向きであるという
問題もあった。Further, there is a problem that the zeolite catalyst used in the above treatment method loses its catalytic activity due to halogen group elements such as chlorine and bromine. For this reason, there is also a problem that it is practically unsuitable for treating waste plastics in which flame-retardant plastics cannot be avoided.
【００１１】さらに、かかる処理方法では、熱分解温度
や熱分解材料等の条件により回収油の組成が変動する場
合があり、その結果、回収油の引火点が下がるという問
題もあった。従って、得られた回収油をボイラー等の燃
料油として使用する場合に、危険物取扱い上、その取扱
いが異なるという問題が起き得る。そのため、組成変動
の少ない処理方法が望まれている。また、より多くの廃
棄物を処理するために、処理時間を更に短縮することも
望まれている。Further, in such a treatment method, the composition of the recovered oil may vary depending on the conditions such as the thermal decomposition temperature and the thermal decomposition material, and as a result, the flash point of the recovered oil is lowered. Therefore, when the obtained recovered oil is used as fuel oil for a boiler or the like, there may be a problem that the handling is different in handling dangerous materials. Therefore, a treatment method with less composition fluctuation is desired. It is also desired to further reduce the treatment time in order to treat more waste.
【００１２】そこで、本発明者らは上記問題点を解決す
るために鋭意研究開発を行った結果、スチレン系樹脂の
形状を問わない、即ち、スチレン系樹脂を成形原型品の
まま熱分解することも可能な高生産性を有するスチレン
系樹脂の熱分解装置を開発するに至った。即ち、本発明
により、スチレン系樹脂の減容装置を必要としない極め
て安価な方法で利用価値の高い芳香族炭化水素化合物に
富む液状の生成物が得られることになった。Therefore, as a result of intensive research and development for solving the above problems, the present inventors have found that the shape of the styrene-based resin does not matter, that is, the styrene-based resin is pyrolyzed as it is as a molding prototype. We have developed a thermal decomposition device for styrene resin with high productivity. That is, according to the present invention, a liquid product rich in aromatic hydrocarbon compounds having a high utility value can be obtained by an extremely inexpensive method that does not require a volume reducing device for styrene resins.
【００１３】[0013]
【課題を解決するための手段】本発明に係るスチレン系
樹脂の熱分解装置の要旨とするところは、槽の内部に攪
拌機とバッフル及び槽の外側に加熱装置を有するスチレ
ン系樹脂を溶解する溶解槽と、該溶解槽にスチレン系樹
脂を溶解する溶剤及び／またはスチレン系樹脂の熱分解
液状生成物を投入しまたは循環させる装置と、溶解され
た液を熱分解する熱分解槽へ送液するポンプと、槽の外
側に加熱装置と槽の内側に攪拌機と底部より熱分解残渣
を払い出す装置を有するスチレン系樹脂を熱分解する熱
分解槽と、該熱分解槽において発生した蒸気状生成物を
液化する冷却装置と、該冷却装置によって液化された熱
分解液状生成物を回収し混入した水を分離するタンクか
らなる回分式熱分解装置で構成したことにある。The gist of the thermal decomposition apparatus for styrenic resin according to the present invention is to dissolve a styrenic resin having a stirrer and a baffle inside the tank and a heating device outside the tank. A tank, an apparatus for charging or circulating a solvent and / or a thermally decomposed liquid product of a styrene resin in the dissolution tank, and sending the dissolved liquid to a thermal decomposition tank for thermally decomposing the solution. A pyrolysis tank for pyrolyzing a styrene resin having a pump, a heating device outside the tank, a stirrer inside the tank, and a device for discharging the pyrolysis residue from the bottom, and a vaporous product generated in the pyrolysis tank It is composed of a batch-type thermal decomposition apparatus comprising a cooling device for liquefying water and a tank for recovering the thermally decomposed liquid product liquefied by the cooling device and separating the mixed water.
【００１４】また、本発明に係るスチレン系樹脂の熱分
解装置の他の要旨とするところは、槽の内部に攪拌機と
バッフル及び槽の外側に加熱装置と槽の底部より熱分解
残渣を払い出す装置を有するスチレン系樹脂を溶解する
とともに熱分解する溶解分解槽と、該溶解分解槽にスチ
レン系樹脂を溶解する溶剤及び／またはスチレン系樹脂
の熱分解液状生成物を投入しまたは循環させる装置と、
前記溶解分解槽において発生した蒸気状生成物を液化す
る冷却装置と、該冷却装置によって液化された熱分解液
状生成物を回収し混入した水を分離するタンクからなる
回分式熱分解装置で構成したことにある。Another aspect of the styrene-based resin thermal decomposition apparatus according to the present invention is that a thermal decomposition residue is discharged from an agitator and a baffle inside the tank and a heating apparatus outside the tank and the bottom of the tank. A dissolving and decomposing tank having a device for dissolving and thermally decomposing a styrene resin, and a device for charging or circulating a solvent for dissolving the styrene resin and / or a thermally decomposed liquid product of the styrene resin in the dissolving and decomposing tank ,
It was composed of a batch type thermal decomposition apparatus consisting of a cooling device for liquefying the vaporized product generated in the dissolution and decomposition tank and a tank for collecting the thermally decomposed liquid product liquefied by the cooling device and separating the mixed water. Especially.
【００１５】かかるスチレン系樹脂の熱分解装置におい
て、前記溶解槽又は溶解分解槽における、攪拌翼、およ
び攪拌翼と攪拌翼の間に溶解槽の内壁に固定した１対ま
たは複数対の水平バッフルを有することにある。In such a styrene-based resin thermal decomposition apparatus, a stirring blade and one or more pairs of horizontal baffles fixed to the inner wall of the dissolution tank are provided between the stirring blade and the stirring blade in the dissolution tank or the dissolution decomposition tank. To have.
【００１６】また、かかるスチレン系樹脂の熱分解装置
において、前記対をなす水平バッフルの１個のバッフル
の長さが溶解槽又は溶解分解槽の内径の１０〜４０％に
したことにある。In the styrene resin thermal decomposition apparatus, the length of one baffle of the pair of horizontal baffles is 10 to 40% of the inner diameter of the dissolution tank or the dissolution decomposition tank.
【００１７】更に、かかるスチレン系樹脂の熱分解装置
における前記熱分解槽又は溶解分解槽において、該熱分
解槽又は溶解分解槽の底部の熱分解残渣を払い出すバル
ブと、熱分解槽に連結された配管を有し、熱分解槽から
未分解及び炭化物からなる熱分解残渣を払い出す密閉さ
れた装置を有することにある。Further, in the thermal decomposition tank or the dissolution decomposition tank in the thermal decomposition apparatus for the styrene resin, a valve for discharging the thermal decomposition residue at the bottom of the thermal decomposition tank or the dissolution decomposition tank is connected to the thermal decomposition tank. It is to have a closed device having the above-mentioned piping and discharging the pyrolysis residue consisting of undecomposed and carbide from the pyrolysis tank.
【００１８】次に、本発明に係るスチレン系樹脂の熱分
解方法の要旨とするところは、スチレン系樹脂と溶剤及
び／またはスチレン系樹脂の熱分解液状生成物を溶解槽
に投入し、該溶解槽でスチレン系樹脂を減容溶解させた
後、該得られた溶解液を熱分解槽に送液して該熱分解槽
で攪拌下で加熱して熱分解し、発生した蒸気状生成物を
液化して熱分解液状生成物を回収することにある。Next, the gist of the method for thermally decomposing a styrene resin according to the present invention is to put a styrene resin and a solvent and / or a thermally decomposed liquid product of the styrene resin into a dissolution tank and dissolve the solution. After the volumetric dissolution of the styrene-based resin in the tank, the obtained solution is sent to a thermal decomposition tank and heated in the thermal decomposition tank under stirring for thermal decomposition to generate a vapor product. Liquefaction is to recover the thermally decomposed liquid product.
【００１９】かかるスチレン系樹脂の熱分解方法におけ
る前記熱分解槽において、未分解及び炭化物からなる熱
分解残渣を流動性を有する状態で、直接空気に接触しな
いようにしつつ熱分解槽の槽外へ払い出すようにしたこ
とにある。In the above-mentioned thermal decomposition tank in the method for thermally decomposing styrene resin, the thermal decomposition residue consisting of undecomposed and carbide is flowable to the outside of the thermal decomposition tank while avoiding direct contact with air. I tried to pay it out.
【００２０】また、かかるスチレン系樹脂の熱分解方法
において、前記熱分解槽における加熱方法として、バー
ナーを使用して熱風加熱を行う際に、廃熱風を燃焼用空
気と熱交換機を介して熱交換することにある。Further, in the method for thermally decomposing styrene resin, as a heating method in the thermal decomposition tank, when hot air is heated by using a burner, waste hot air is exchanged with combustion air through a heat exchanger. To do.
【００２１】更に、かかるスチレン系樹脂の熱分解方法
において、前記溶解槽に投入されるスチレン系樹脂の５
０重量％以上の溶剤及び／またはスチレン系樹脂を熱分
解して得られる熱分解液状生成物を、スチレン系樹脂に
添加し、投入されたスチレン系樹脂を溶解槽の攪拌翼と
対に配置された水平バッフルで破砕および攪拌すること
にある。Further, in the method for thermally decomposing a styrene resin, the styrene resin 5 charged into the melting tank is added.
A pyrolyzed liquid product obtained by thermally decomposing 0% by weight or more of a solvent and / or a styrene resin is added to the styrene resin, and the charged styrene resin is paired with a stirring blade of a dissolution tank. Crushing and stirring with a horizontal baffle.
【００２２】更に、かかるスチレン系樹脂の熱分解方法
において、前記溶解槽においてスチレン系樹脂を溶解す
るに際し、該溶解液を該溶解槽にポンプで循環させるこ
とにある。Further, in the thermal decomposition method of the styrene resin, when the styrene resin is dissolved in the dissolution tank, the solution is circulated in the dissolution tank by a pump.
【００２３】次に、本発明に係るスチレン系樹脂の熱分
解方法の他の要旨とするところは、攪拌機と１対又は複
数対の水平バッフルとを有し、さらに槽の外側に加熱手
段を有する溶解槽で、溶解減容させたスチレン系樹脂
を、直接当該溶解槽で熱分解させるようにしたことにあ
る。Another aspect of the method for thermally decomposing a styrene resin according to the present invention is that it has a stirrer and one or more pairs of horizontal baffles, and further has heating means outside the tank. The styrene resin whose volume has been dissolved and reduced in the dissolution tank is directly pyrolyzed in the dissolution tank.
【００２４】[0024]
【発明の実施の形態】本発明に係るスチレン系樹脂の熱
分解装置は、槽の内部に攪拌機とバッフル及び槽の外側
に加熱装置を有するスチレン系樹脂を溶解する溶解槽
と、該溶解槽にスチレン系樹脂を溶解する溶剤及び／ま
たはスチレン系樹脂の熱分解液状生成物を投入または循
環する装置と、溶解した液を熱分解する熱分解槽へ送液
するポンプと、槽の外側に加熱装置と槽の内側に攪拌機
と、底部より熱分解残渣を払い出す装置を有するスチレ
ン系樹脂を分解する熱分解槽と、該熱分解槽において発
生した蒸気状生成物を液化する冷却装置と、該冷却装置
によって液化された熱分解液状生成物を回収するととも
に混入した水を分離するタンクからなるスチレン系樹脂
の回分式熱分解装置である。以下、具体的に、実施の形
態を説明する。BEST MODE FOR CARRYING OUT THE INVENTION A thermal decomposition apparatus for styrene resin according to the present invention comprises a dissolution tank for dissolving a styrene resin having a stirrer and a baffle inside the tank and a heating device outside the tank, and a dissolution tank for the dissolution tank. A device for charging or circulating a solvent that dissolves the styrene resin and / or a thermally decomposed liquid product of the styrene resin, a pump that feeds the dissolved liquid to a thermal decomposition tank, and a heating device outside the tank. And a stirrer inside the tank, a thermal decomposition tank for decomposing the styrene resin having a device for discharging the thermal decomposition residue from the bottom, a cooling device for liquefying the vaporous product generated in the thermal decomposition tank, and the cooling It is a batch-type thermal decomposition apparatus for styrene-based resins, which is composed of a tank for collecting the thermally decomposed liquid product liquefied by the apparatus and separating the mixed water. The embodiments will be specifically described below.
【００２５】図１は、本発明に係るスチレン系樹脂の熱
分解方法を実施するための装置の１例を示した概略図で
ある。熱分解装置は、スチレン系樹脂を、溶剤及び／ま
たはスチレン系樹脂を熱分解して得られた熱分解液状生
成物で溶解するための溶解槽１０と、溶解槽１０で溶解
したスチレン系樹脂を熱分解槽２４へ移送する移送ポン
プ２０と、熱分解槽２４において発生した蒸気状生成物
を液化するための冷却装置３４と、冷却装置３４によっ
て液化させた熱分解液状生成物を回収するためのタンク
３８とから構成されている。FIG. 1 is a schematic view showing an example of an apparatus for carrying out the thermal decomposition method of a styrene resin according to the present invention. The thermal decomposition apparatus includes a dissolving tank 10 for dissolving a styrene resin with a solvent and / or a thermally decomposed liquid product obtained by thermally decomposing a styrene resin, and a styrene resin dissolved in the dissolving tank 10. A transfer pump 20 for transferring to the thermal decomposition tank 24, a cooling device 34 for liquefying the vaporous product generated in the thermal decomposition tank 24, and a recovery device for recovering the thermally decomposed liquid product liquefied by the cooling device 34. It is composed of a tank 38.
【００２６】溶解槽１０には、攪拌機１２と、溶解槽１
０の内壁に対になった水平バッフル１４が取り付けら
れ、溶剤または熱分解液状生成物は溶剤投入装置２２に
より供給されるように構成されている。また、溶解槽１
０の加熱は、別途、加熱装置を溶解槽１０の外側に取り
付けても良いが、通常は溶解槽１０の外側にジャケット
１１を設けるとともに、熱分解槽２４からの廃熱風をダ
クトで溶解槽１０のジャケット１１に連結して、加熱す
るように構成するのが好ましい。The dissolution tank 10 includes a stirrer 12 and a dissolution tank 1.
A pair of horizontal baffles 14 are attached to the inner wall of No. 0, and the solvent or pyrolyzed liquid product is configured to be supplied by a solvent charging device 22. Also, dissolution tank 1
For heating 0, a heating device may be separately attached to the outside of the melting tank 10. Normally, the jacket 11 is provided outside the melting tank 10, and the waste hot air from the thermal decomposition tank 24 is ducted. It is preferable to be connected to the jacket 11 and to be heated.
【００２７】溶解槽１０の内部に配設される攪拌機１２
の翼型は、例えば、通常の水平パドル翼でもよく、特に
特殊攪拌羽根は必要としない。また、攪拌翼は槽の大き
さによって決まるが、単数であってもよいが、通常は複
数用いるのが好ましい。攪拌翼の径は全ての翼が内径の
５０％以上９０％以下が好ましい。５０％未満では攪拌
と粉砕の効果は期待できず、９０％を越えると攪拌翼と
溶解槽１０の内壁の距離が短く破砕効果が低減される。A stirrer 12 disposed inside the dissolution tank 10.
The blade shape may be, for example, a normal horizontal paddle blade, and no special stirring blade is required. Although the number of stirring blades is determined by the size of the tank, a single blade may be used, but it is usually preferable to use a plurality of blades. The diameter of the stirring blade is preferably 50% or more and 90% or less of the inner diameter of all the blades. If it is less than 50%, the effect of stirring and crushing cannot be expected, and if it exceeds 90%, the distance between the stirring blade and the inner wall of the melting tank 10 is short and the crushing effect is reduced.
【００２８】また、水平バッフル１４は溶解槽１０の内
壁に対を成して固定されていて、１対の水平バッフル１
４の個数は、溶解槽１０の大きさによって決まるが、単
数でもよいが、通常は複数対設置するのが好ましい。水
平バッフル１４はこのように同一水平面になって配設さ
れているのが好ましいが、同一水平面に１個あるいは３
個または複数対を設けることも可能である。The horizontal baffles 14 are fixed to the inner wall of the melting tank 10 in pairs, and the pair of horizontal baffles 1
Although the number of 4 is determined by the size of the dissolution tank 10, it may be a single number, but it is usually preferable to install a plurality of pairs. The horizontal baffles 14 are preferably arranged in the same horizontal plane as described above, but one or three horizontal baffles 14 are arranged in the same horizontal plane.
It is also possible to provide individual or multiple pairs.
【００２９】対になった水平バッフル１４の１個の長さ
は、全てが内径の１０〜４０％、好ましくは２０〜４０
％が必要である。また、水平バッフル１４の厚みは、強
度を損なわない範囲で投入されたスチレン系樹脂の成形
体を破砕（切断）するためにできるだけ薄いほうがよ
い。例えば、水平バッフル１４の形状は刃物状を成して
いるのが好ましいが、その他、斧や日本刀形状、あるい
は楔状などいずれでもよく、特に限定されない。更に、
バッフルの取り付け角度は通常は水平であるが、水平に
対し傾斜を付けて取り付けてもよいが、水平に対し４５
度以上上向き又は下向きにすると効果は著しく低減す
る。The length of one of the paired horizontal baffles 14 is all 10-40% of the inner diameter, preferably 20-40.
%is required. In addition, the thickness of the horizontal baffle 14 is preferably as thin as possible in order to crush (cut) the styrene resin molded product that is input within a range that does not impair the strength. For example, the shape of the horizontal baffle 14 is preferably in the shape of a knife, but may be in the shape of an ax, a Japanese sword, or a wedge, and is not particularly limited. Furthermore,
The mounting angle of the baffle is usually horizontal, but it may be installed at an angle to the horizontal,
If it is turned upward or downward more than once, the effect is significantly reduced.
【００３０】このように水平バッフル１４を配設し、水
平バッフル１４の間を攪拌翼が回転することにより、溶
解槽１０に投入されたスチレン系樹脂の成形体は水平バ
ッフル１４と攪拌翼で剪断され、または圧縮破壊され
る。そして、それらの効果により、スチレン系樹脂は迅
速且つ確実に破砕され、更に、投入された溶剤や熱分解
液状生成物によって迅速に溶解させられる。By thus disposing the horizontal baffles 14 and rotating the stirring blades between the horizontal baffles 14, the molded product of the styrene resin charged into the dissolution tank 10 is sheared by the horizontal baffles 14 and the stirring blades. Or compressed and destroyed. Due to these effects, the styrene-based resin is crushed quickly and surely, and further, the styrene resin is quickly dissolved by the charged solvent and the thermally decomposed liquid product.
【００３１】溶解槽１０で溶解させられたスチレン系樹
脂は熱分解槽２４へ移送されて、熱分解槽２４で熱分解
される。溶解させられたスチレン系樹脂の移送は、溶解
槽１０の下部に開閉弁１６を介して移送管１８が配設さ
れていて、その移送管１８に設けられた移送ポンプ２０
により行われる。この開閉弁１６を適宜開閉させ、溶解
槽において溶解されたスチレン系樹脂の溶解液の熱分解
槽２４への供給量を調整する。なお、この移送ポンプ２
０は、高粘度液用の汎用ポンプ例えばスネーク型ポンプ
がよいが、レイアウト上許されるのであれば、分解槽２
４の上部に溶解槽１０を設置し、重力で分解槽２４に溶
解液を払い出すように構成することも可能である。The styrene resin dissolved in the dissolution tank 10 is transferred to the thermal decomposition tank 24 and is thermally decomposed in the thermal decomposition tank 24. For the transfer of the dissolved styrene-based resin, a transfer pipe 18 is disposed below the dissolution tank 10 via an opening / closing valve 16, and a transfer pump 20 provided in the transfer pipe 18 is provided.
It is performed by The on-off valve 16 is appropriately opened and closed to adjust the supply amount of the solution of the styrene resin dissolved in the dissolution tank to the thermal decomposition tank 24. In addition, this transfer pump 2
0 is a general-purpose pump for high-viscosity liquids such as a snake type pump, but if the layout allows it, the decomposition tank 2
It is also possible to install the dissolving tank 10 on the upper part of 4 and to discharge the dissolving liquid to the decomposition tank 24 by gravity.
【００３２】次に、溶解させられたスチレン系樹脂を熱
分解する熱分解槽２４は、加熱装置２６を備えており、
加熱装置２６により熱分解槽２４内に投入されたスチレ
ン系樹脂が加熱されてスチレンモノマー、α−メチルス
チレン、トルエン等に分解するように構成されている。
加熱装置２６は、バーナー、電気、スチーム等のいかな
る手段により加熱するように構成されていてもよく、特
に限定されるものではない。加熱装置２６によって熱分
解槽２４を加熱した後の廃熱風は熱分解槽２４の外側に
設けられたジャケット２５により集められ、その出口に
接続した廃熱風ダクト２７により溶解槽１０に供給され
るのが好ましい。Next, the thermal decomposition tank 24 for thermally decomposing the dissolved styrene resin is equipped with a heating device 26,
The heating device 26 is configured to heat the styrene resin charged into the thermal decomposition tank 24 and decompose it into styrene monomer, α-methylstyrene, toluene and the like.
The heating device 26 may be configured to heat by any means such as a burner, electricity, steam, etc., and is not particularly limited. The waste hot air after heating the pyrolysis tank 24 by the heating device 26 is collected by the jacket 25 provided outside the pyrolysis tank 24 and supplied to the melting tank 10 by the waste hot air duct 27 connected to the outlet thereof. Is preferred.
【００３３】熱分解槽２４の加熱装置２６としてバーナ
ーを用いる場合、図に示すように、ジャケット２５の出
口に接続した廃熱風ダクト２７に熱交換機３２を取り付
け、送風機３３により送られてくるバーナーの燃焼用空
気を予熱し、廃熱風の熱回収を図ることも可能である。
なお、この熱交換機３２の型式はいかなるものでもよ
く、特に限定されるものではない。When a burner is used as the heating device 26 of the thermal decomposition tank 24, a heat exchanger 32 is attached to a waste hot air duct 27 connected to the outlet of the jacket 25, and a burner sent by a blower 33 is installed as shown in the figure. It is also possible to preheat the combustion air and recover the heat of the waste hot air.
The heat exchanger 32 may be of any type and is not particularly limited.
【００３４】また、熱分解槽２４の内部には攪拌翼２８
が設けられているのが好ましい。この攪拌翼２８は、溶
融されたスチレン系樹脂が均一に混合され、均一な温度
となるように攪拌し、また外側のジャケット２５からの
熱伝達を促進する役割を有する。A stirring blade 28 is provided inside the thermal decomposition tank 24.
Is preferably provided. The stirring blade 28 has a role of stirring the molten styrene-based resin so as to be uniformly mixed and having a uniform temperature, and promoting heat transfer from the outer jacket 25.
【００３５】ここで、熱分解槽２４における熱分解温度
は、２００〜５５０℃で行うのが好ましい。２００℃以
下では熱分解反応が進行せず、５５０℃以上では炭化が
進行して熱分解液状生成物の回収率が低下するといった
不都合が起きやすいからである。熱分解液状生成物の回
収率及び分解反応速度の点から好ましくは３００℃〜４
３０℃で熱分解することが好ましい。なお、温度調整は
通常用いられる攪拌槽の温度調整方法によればよく、特
に限定されるものではない。The thermal decomposition temperature in the thermal decomposition tank 24 is preferably 200 to 550.degree. This is because the thermal decomposition reaction does not proceed at 200 ° C or lower, and the carbonization proceeds at 550 ° C or higher to lower the recovery rate of the thermally decomposed liquid product. From the viewpoint of recovery rate and decomposition reaction rate of the thermally decomposed liquid product, it is preferably 300 ° C to 4
Pyrolysis at 30 ° C. is preferred. It should be noted that the temperature adjustment may be performed according to a temperature adjustment method for a stirring tank that is usually used, and is not particularly limited.
【００３６】更に、熱分解槽２４には、熱分解残渣を外
部へ払い出すための熱分解残渣払出し装置３０が設けら
れており、熱分解槽２４と熱分解残渣払出し装置３０は
開閉弁２９を介して配管で連結されている。残渣払出し
装置３０は、着火温度以上の蒸気状生成物が空気と接触
し静電気によって着火し燃焼することを回避するため、
また密閉する必要があるため、熱分解残渣などに付着し
発生させられる蒸気状生成物を熱分解槽２４に戻すため
の連結配管３１が設けられている。これら残渣払い出し
装置３０及び連結配管３１は、金属製であれば、特に限
定されるものではない。Further, the thermal decomposition tank 24 is provided with a thermal decomposition residue dispensing device 30 for discharging the thermal decomposition residue to the outside. The thermal decomposition tank 24 and the thermal decomposition residue dispensing device 30 have an opening / closing valve 29. It is connected by piping. The residue dispensing device 30 avoids that the vaporous product having a temperature higher than the ignition temperature comes into contact with air and ignites and burns due to static electricity.
Further, since it is necessary to hermetically close it, a connecting pipe 31 is provided for returning the vaporous product that adheres to the thermal decomposition residue or the like and is generated to the thermal decomposition tank 24. The residue dispensing device 30 and the connection pipe 31 are not particularly limited as long as they are made of metal.
【００３７】次に、本発明に係る熱分解装置には、熱分
解槽２４において発生させられた蒸気状生成物を液化す
るための冷却装置３４と、その冷却装置３４によって液
化された液状分解物を回収するためのタンク３８とが設
けられていて、これら冷却装置３４とタンク３８は移送
管３６により接続されている。冷却装置３４は蒸気状生
成物と冷却水が直接接触しない型式であり、蒸気状生成
物をその各成分ガスの凝縮温度以下に冷却するものであ
ればいかなる構成の装置でもよく、特に限定されるもの
ではない。Next, in the thermal decomposition apparatus according to the present invention, a cooling device 34 for liquefying the vaporous product generated in the thermal decomposition tank 24, and a liquid decomposition product liquefied by the cooling device 34. And a tank 38 for recovering the water, and the cooling device 34 and the tank 38 are connected by a transfer pipe 36. The cooling device 34 is of a type in which the vaporous product and the cooling water do not come into direct contact with each other, and may be any device as long as it cools the vaporous product to a temperature equal to or lower than the condensation temperature of each component gas thereof, and is not particularly limited. Not a thing.
【００３８】また、蒸気状生成物を液化する冷却装置に
おいて、凝縮しなかった蒸気状生成物を加熱装置へ戻し
て、燃焼せしめることも可能であり、たとえば図に示す
ように冷却装置３４に配管３５を設け、送風機３３の空
気吸引部に接続してもよい。このようにすれば、未凝縮
蒸気状生成物の大気中への放出量を低減することも可能
である。Further, in the cooling device for liquefying the vaporous product, it is possible to return the vaporized product which has not condensed to the heating device and burn it. For example, as shown in the figure, the cooling device 34 is connected to the pipe. 35 may be provided and connected to the air suction part of the blower 33. By doing so, it is possible to reduce the amount of uncondensed vapor product released into the atmosphere.
【００３９】次に、タンク３８は蒸気状生成物が液化さ
れた熱分解液状生成物を蒸発させたり、酸化などによっ
て変質させたりしないように構成されているものが好ま
しく、その構造などは特に限定されるものではない。タ
ンク３８には熱分解液状生成物が貯留されて、熱分解液
状生成物の生成過程で混入した水分を分離した後、熱分
解液状生成物はポンプ４０により貯槽に送られる。貯槽
に送られる熱分解液状生成物の一部は溶解槽１０に戻さ
れ、溶剤とともに、あるいは溶剤に代えて溶解槽１０に
入れられてもよい。Next, the tank 38 is preferably constructed so as not to evaporate the pyrolyzed liquid product in which the vapor-like product is liquefied or to be deteriorated by oxidation or the like, and its structure is particularly limited. It is not something that will be done. The pyrolyzed liquid product is stored in the tank 38, the water mixed in the process of producing the pyrolyzed liquid product is separated, and then the pyrolyzed liquid product is sent to the storage tank by the pump 40. A part of the thermally decomposed liquid product sent to the storage tank may be returned to the dissolution tank 10 and may be put in the dissolution tank 10 together with the solvent or in place of the solvent.
【００４０】以上、本発明に係るスチレン系樹脂の熱分
解装置の１例を図１に詳述したが、本発明はかかる実施
装置の構成に限定されるものではない。Although one example of the styrene-based resin thermal decomposition apparatus according to the present invention has been described in detail above with reference to FIG. 1, the present invention is not limited to the configuration of such an apparatus.
【００４１】以下に、本発明に係るスチレン系樹脂の熱
分解装置の使用方法について説明する。上述の処理装置
において、まず、溶解槽１０に、溶剤またはスチレン系
樹脂を熱分解して得られた液状生成物のいずれか一方ま
たは双方を溶剤投入装置２２から投入する。The method of using the styrene resin thermal decomposition apparatus according to the present invention will be described below. In the above-described processing apparatus, first, either or both of the solvent and the liquid product obtained by thermally decomposing the styrene resin are charged into the dissolution tank 10 from the solvent charging device 22.
【００４２】溶剤としてのスチレン系樹脂の熱分解液状
生成物を投入する装置２２は、その装置を単独で設置し
てもよいが、前述したように本発明に係る熱分解装置に
よって得られたスチレン系樹脂の熱分解液状生成物をタ
ンク３８から貯槽に送液するポンプ４０から一部または
全部を取り出す枝取りし、溶解槽１０に投入してもよ
い。このとき、スチレン系樹脂の熱分解液状生成物を計
量しながら投入する計量機を備えることも可能である。The device 22 for introducing the thermally decomposed liquid product of the styrene resin as the solvent may be installed alone, but as described above, the styrene obtained by the thermal decomposition device according to the present invention is used. A part or all of the thermally decomposed liquid product of the system resin may be taken out from a pump 40 that feeds it from the tank 38 to the storage tank, and may be put into the dissolution tank 10. At this time, it is also possible to provide a weighing machine for feeding the thermally decomposed liquid product of the styrene resin while measuring it.
【００４３】このスチレン系樹脂の熱分解液状生成物は
後述する表１及び表２の実施例及び比較例に代表例を示
すように、芳香族化合物からなっており、スチレン系樹
脂の良好な溶剤でもある。従って、本発明によって得ら
れる熱分解液状生成物はスチレン系樹脂の溶剤として繰
り返して利用することが可能である。The pyrolyzed liquid product of the styrene resin is composed of an aromatic compound as shown in the examples and comparative examples of Tables 1 and 2 described later, and is a good solvent for the styrene resin. But also. Therefore, the thermally decomposed liquid product obtained by the present invention can be repeatedly used as a solvent for the styrene resin.
【００４４】また、本発明に用いられる溶剤はスチレン
系樹脂を溶解するものであればよいが、塩酸、硫酸等の
無機酸類、及び有機化合物であっても、蟻酸、酢酸等の
カルボン酸は装置を腐食させるため、使用できない。ま
た、塩化メチル、塩化エチル等のハロゲン化化合物も、
ハロゲンが装置を腐食させるため、使用できない。従っ
て、芳香族化合物、アセトン、シクロヘキサン及びシク
ロヘキサノン等の環状化合物がスチレン系樹脂の溶剤と
して好ましいが、これら物質に限定されるものではな
く、天然に存在する物質であってもスチレン系樹脂を溶
解し、装置を腐食しなければ使用可能である。The solvent used in the present invention may be any solvent which can dissolve the styrene resin, but inorganic acids such as hydrochloric acid and sulfuric acid, and organic compounds such as carboxylic acid such as formic acid and acetic acid can be used as a solvent. Can not be used because it corrodes. In addition, halogenated compounds such as methyl chloride, ethyl chloride,
Cannot be used as halogen corrodes equipment. Therefore, aromatic compounds, cyclic compounds such as acetone, cyclohexane, and cyclohexanone are preferable as the solvent for the styrene resin, but are not limited to these substances, and even a naturally occurring substance can dissolve the styrene resin. It can be used if it does not corrode the device.
【００４５】更に、溶解槽１０の加熱方法は、スチレン
系樹脂を溶解するときの温度は５０〜８０℃であり、通
常は熱分解槽２４の廃熱風を溶解槽１０のジャケット１
１に連結して加熱する。温度は５０℃未満では溶解性が
劣り、８０℃を越えると溶剤の蒸気により溶解作業性が
悪くなるため、好ましくない。Further, in the heating method of the melting tank 10, the temperature at which the styrene resin is melted is 50 to 80 ° C. Usually, the waste hot air of the thermal decomposition tank 24 is heated by the jacket 1 of the melting tank 10.
Connect to 1 and heat. If the temperature is lower than 50 ° C., the solubility is poor, and if it exceeds 80 ° C., the solvent workability deteriorates due to the vapor of the solvent, which is not preferable.
【００４６】溶解槽１０へ添加する溶剤またはスチレン
系樹脂の熱分解液状生成物の量は、投入するスチレン系
樹脂の５０重量％以上、好ましくは１００重量％以上で
２００重量％以下が好ましい。５０重量％未満ではスチ
レン系樹脂を溶解するに従い溶解液の粘度が上昇し、溶
解速度が遅くなる。また、２００重量％をこえると、溶
剤の蒸発に必要なエネルギーが大きくなり、燃料油のコ
ストが高く実用的でない。The amount of the solvent or the thermally decomposed liquid product of the styrene resin added to the dissolution tank 10 is 50% by weight or more, preferably 100% by weight or more and 200% by weight or less of the styrene resin to be charged. If it is less than 50% by weight, the viscosity of the solution increases as the styrene resin is dissolved, and the dissolution rate becomes slow. On the other hand, if it exceeds 200% by weight, the energy required for evaporation of the solvent becomes large, and the cost of fuel oil is high, which is not practical.
【００４７】次いで、スチレン系樹脂の成形体を溶解槽
１０に投入し、溶解槽１０の攪拌機１２及び水平バッフ
ル１４によって適当な大きさに破砕しつつ、溶剤または
熱分解液状生成物によって溶解させる。Next, the molded product of styrene resin is put into the dissolution tank 10 and is crushed into an appropriate size by the stirrer 12 and the horizontal baffle 14 of the dissolution tank 10 and dissolved by the solvent or the thermally decomposed liquid product.
【００４８】ここで、本発明に供されるスチレン系樹脂
は、フィルム、シート、成形品、塊等、いかなる形状の
ものでもよく、発泡ポリスチレン成形品も好適に処理す
ることが可能である。また、本発明では、これらスチレ
ン系樹脂の合成時又は加工成形時に難燃剤、帯電防止
剤、印刷剤等が添加されたスチレン系樹脂も熱分解液化
の対象として使用することが可能である。Here, the styrene resin used in the present invention may have any shape such as a film, a sheet, a molded product, and a lump, and a foamed polystyrene molded product can be suitably treated. Further, in the present invention, a styrene resin to which a flame retardant, an antistatic agent, a printing agent, or the like is added at the time of synthesizing or molding these styrene resins can also be used as a target of thermal decomposition and liquefaction.
【００４９】更には、本発明の目的を損なわない範囲
で、スチレン系樹脂に、例えば５０重量％未満、好まし
くは３０重量％以下、更に好ましくは、２０重量％以下
の他の合成樹脂が混入した樹脂混合物（廃棄物）であっ
て、広い概念のものをも熱分解液化の対象として使用す
ることができる。他の合成樹脂としては、例えばポリエ
チレン、ポリプロピレン等のオレフィン系樹脂、塩化ビ
ニール系樹脂（廃棄物）がある。Further, within a range not impairing the object of the present invention, for example, less than 50% by weight, preferably 30% by weight or less, more preferably 20% by weight or less of other synthetic resin is mixed in the styrene resin. A resin mixture (waste) having a broad concept can also be used as a target of thermal decomposition liquefaction. Examples of other synthetic resins include olefin resins such as polyethylene and polypropylene and vinyl chloride resins (waste).
【００５０】詳しくは、本発明でいうスチレン系樹脂と
は、ポリスチレン、優位量のスチレンモノマーと劣位量
のハロゲン又は置換基で置換された置換スチレンとの共
重合体、又はスチレンモノマーに劣位量、好ましくは３
０重量％（以下、単に％と略記する。）以下、更に好ま
しくは２０％以下の他の単量体、たとえばブタジエン等
のジエン類、アクリル酸、メタアクリル酸等の（メタ）
アクリル酸エステル類およびその誘導体、アクリロニト
リル等を共重合した共重合体類（例えば、スチレン−ブ
タジエンゴム（ＳＢＲ）、ハイインパクトポリスチレ
ン、ＡＢＳ樹脂、メチルメタアクリレート−ブタジエン
−スチレン系樹脂（ＭＢＳ）等）の廃棄物が良好に使用
することができ、これらは、単独でも混合でも使用する
ことが可能である。More specifically, the styrenic resin in the present invention means polystyrene, a copolymer of a predominant amount of styrene monomer and a subordinate amount of halogen or a substituted styrene substituted with a substituent, or a subordinate amount of styrene monomer, Preferably 3
0% by weight (hereinafter simply abbreviated as%) or less, more preferably 20% or less of other monomers, for example, dienes such as butadiene, acrylic acid, methacrylic acid (meth)
Acrylic esters and their derivatives, copolymers obtained by copolymerizing acrylonitrile, etc. (for example, styrene-butadiene rubber (SBR), high-impact polystyrene, ABS resin, methylmethacrylate-butadiene-styrene resin (MBS), etc.) The wastes of can be used satisfactorily, and they can be used alone or in a mixture.
【００５１】更に、これらスチレン系樹脂にポリフェニ
レンエーテル及びその誘導体、ポリサルホン、ポリアセ
タール、ポリカーボネード、ポリアミド、ポリイミド、
芳香族ポリエステル等のエンジニアリングプラスチック
やＳＢＲ、ＡＢＳ、ＭＢＳ等のポリマーを添加して使用
することも可能である。Furthermore, polyphenylene ether and its derivatives, polysulfone, polyacetal, polycarbonate, polyamide, polyimide, etc. are added to these styrene resins.
Engineering plastics such as aromatic polyester and polymers such as SBR, ABS and MBS may be added and used.
【００５２】これらスチレン系樹脂を溶解させた溶解液
を熱分解槽２４内に供給した後、熱分解槽２４内を密閉
する。密閉した熱分解槽２４において、雰囲気を必要に
応じて脱酸、窒素置換した後、熱分解槽２４内で溶解液
を加熱して熱分解し、蒸気状生成物を発生させる。After the solution containing the styrene resin dissolved therein is supplied into the thermal decomposition tank 24, the inside of the thermal decomposition tank 24 is closed. In the sealed thermal decomposition tank 24, the atmosphere is deoxidized and replaced with nitrogen as necessary, and then the solution is heated in the thermal decomposition tank 24 to be thermally decomposed to generate a vapor product.
【００５３】熱分解により発生した蒸気状生成物は熱分
解槽２４の上部から配管を通り冷却装置３４に送られ、
その冷却装置３４において冷却液化され、熱分解液状生
成物がタンク３８に回収される。The vaporous product generated by the thermal decomposition is sent from the upper part of the thermal decomposition tank 24 through the pipe to the cooling device 34,
It is liquefied by cooling in the cooling device 34, and the thermally decomposed liquid product is recovered in the tank 38.
【００５４】回収された熱分解液状生成物は、タンク３
８の底部より水を分離した後、貯槽に貯蔵される。この
油水分離タンクには、底部に水を抜くバルブ、直胴部に
液状生成物を抜き出すバルブを取り付ければよい。The recovered thermal decomposition liquid product is stored in the tank 3
After separating water from the bottom of No. 8, it is stored in a storage tank. The oil / water separation tank may be equipped with a valve for draining water at the bottom and a valve for draining the liquid product at the straight body.
【００５５】一方、熱分解槽２４の熱分解残渣は、熱分
解終了後、熱分解温度または流動性を損なわない温度ま
で冷却した後、熱分解槽２４の底部の開閉弁２９を開に
し、密閉された熱分解残渣払出し装置３０に空気に接触
しないように払い出される。熱分解槽２４の熱分解残渣
は、着火温度（火源がなくても着火する温度）以上の状
態で払い出されるため、空気に接触すると燃焼してしま
うため、密閉容器に払い出さなければならない。払い出
すときの熱分解残渣の温度は、熱分解終了時の熱分解温
度でもよいし、冷却してから払い出してもよい。ただ
し、冷却しすぎると、熱分解残渣の粘度が上昇し、もは
や流動性を有しなくなるので、流動性を損なわない温度
で払い出せばよい。On the other hand, the thermal decomposition residue in the thermal decomposition tank 24 is cooled to the thermal decomposition temperature or a temperature at which the fluidity is not impaired after completion of the thermal decomposition, and then the opening / closing valve 29 at the bottom of the thermal decomposition tank 24 is opened and sealed. The pyrolysis residue dispensing device 30 is dispensed so as not to come into contact with air. The thermal decomposition residue in the thermal decomposition tank 24 is discharged at a temperature higher than the ignition temperature (the temperature at which ignition occurs even if there is no fire source), so that it burns when it comes into contact with air, so it must be discharged into a closed container. The temperature of the thermal decomposition residue at the time of discharging may be the thermal decomposition temperature at the end of thermal decomposition, or may be cooled and then discharged. However, if it is cooled too much, the viscosity of the thermal decomposition residue increases and it no longer has fluidity, so that it may be dispensed at a temperature at which fluidity is not impaired.
【００５６】上記のようにして得られた本発明に係るス
チレン系樹脂の熱分解装置及び熱分解方法により生成さ
れた液状生成物は、芳香族炭化水素化合物であり、その
主成分はスチレンモノマー、α−メチルスチレン、トル
エン、イソプロピルベンゼン、スチレンダイマー、スチ
レントリマー、１，３−ジフェニルプロパン等である。The liquid product produced by the thermal decomposition apparatus and thermal decomposition method of the styrene resin according to the present invention obtained as described above is an aromatic hydrocarbon compound, the main component of which is styrene monomer, Examples include α-methylstyrene, toluene, isopropylbenzene, styrene dimer, styrene trimer, and 1,3-diphenylpropane.
【００５７】以上のようにして得られた熱分解液状生成
物は通常、やや褐色を呈した透明性のある液体であり、
後述する表１及び表２の実施例及び比較例に示すよう
に、大部分が芳香族化合物であり、安定な物質である。
また、この熱分解液状生成物は常温保管であれば、液状
のスチレンモノマーが重合することはなく、安定である
特質を有する。The thermal decomposition liquid product obtained as described above is usually a slightly brownish transparent liquid,
As shown in Examples and Comparative Examples in Tables 1 and 2 described later, most of them are aromatic compounds and stable substances.
Further, this pyrolyzed liquid product has a characteristic of being stable without being polymerized with a liquid styrene monomer when stored at room temperature.
【００５８】このようにして、得られた液状生成物は、
そのまま燃料として使用してもよく、あるいはＡ重油と
混合して燃料として使用してもよい。更に、精留により
有用な成分に分離精製して、再利用に供してもよい。The liquid product thus obtained is
It may be used as it is as a fuel, or may be mixed with A heavy oil and used as a fuel. Further, it may be reused after being separated and purified into useful components by rectification.
【００５９】以上、本発明に係るスチレン系樹脂の熱分
解装置及び熱分解方法のいくつかの実施の態様を説明し
たが、本発明はこれらの実施の形態に限定されるもので
はない。特に、上述の熱分解方法を実施するための装置
は例示した装置に限定されるものではない。例えば、熱
分解槽２４の攪拌翼２８は必ずしも必要ではない。Although some embodiments of the thermal decomposition apparatus and the thermal decomposition method for the styrene resin according to the present invention have been described above, the present invention is not limited to these embodiments. In particular, the device for carrying out the above-mentioned thermal decomposition method is not limited to the illustrated device. For example, the stirring blade 28 of the thermal decomposition tank 24 is not always necessary.
【００６０】また、かかるスチレン系樹脂の熱分解装置
において、比較的小規模のプラントでは、スチレン系樹
脂の溶解槽と熱分解槽を分離して２つ設置しなくて、溶
解槽と熱分解槽とを１つの溶解分解槽で構成することも
可能である。即ち、溶解分解槽で、スチレン系樹脂の減
容および溶解をした後、次いで同じ槽内で加熱装置によ
り加熱温度を変えて熱分解を行うことができる。このよ
うに構成すれば、更に設備費が安価になる。Further, in such a styrene-based resin thermal decomposition apparatus, in a relatively small-scale plant, it is not necessary to separately install two styrene-based resin dissolution tanks and thermal decomposition tanks. It is also possible to configure and in one dissolution and decomposition tank. That is, after the styrene resin is reduced in volume and dissolved in the dissolution / decomposition tank, the heating temperature can be changed by a heating device in the same tank to perform thermal decomposition. With this configuration, the equipment cost is further reduced.
【００６１】その他、熱分解槽２４に温度や圧力などを
検知するセンサーや、溶融廃棄物をサンプリングして成
分分析をするための装置などを配設するなど、本発明が
その趣旨を逸脱しない範囲内で当業者の知識に基づき、
種々なる改良、変更、修正を加えた態様で実施しうるも
のである。Other than the above, the thermal decomposition tank 24 is provided with a sensor for detecting temperature, pressure and the like, a device for sampling the molten waste and analyzing the components, and the like without departing from the scope of the present invention. Based on the knowledge of those skilled in
The present invention can be implemented with various improvements, changes, and modifications.
【００６２】以下に、実施例により本発明をより具体的
に説明するが、本発明はこれら実施例によって限定され
るものではない。Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.
【００６３】〔実施例１〕内径８００ミリの溶解槽で、
内部に翼径が６００ミリの三段パドル翼及び長さが３０
０ミリで、先端を鋭利にした対となった水平バッフルを
パドル翼間に三対取り付け、液状生成物を２００Ｋｇ投
入した。攪拌しながら、スチレン系樹脂として発泡ポリ
スチレン製の生協等で使用する通箱（大きさ３８０×３
１５×２３０ミリ）１１０Ｋｇを、溶解槽にそのまま投
入した。投入と同時に、通箱は攪拌翼と水平バッフル間
で激しく破砕され、次いで溶解槽内の液状生成物で速や
かに溶解を開始した。投入後約３時間で１１０Ｋｇの通
箱は全て溶解した。Example 1 In a melting tank having an inner diameter of 800 mm,
Inside is a 3-stage paddle blade with a blade diameter of 600 mm and a length of 30
At 0 mm, three pairs of horizontal baffles with sharp tips were attached between the paddle blades, and 200 kg of the liquid product was charged. While stirring, a box made of expanded polystyrene as a styrene-based resin (size 380 x 3)
110 × 15 × 230 mm) was directly added to the dissolution tank. Simultaneously with the charging, the through box was violently crushed between the stirring blade and the horizontal baffle, and then the liquid product in the dissolution tank immediately started to dissolve. Approximately 3 hours after the addition, all of the 110 Kg boxes were dissolved.
【００６４】次いで、溶解液をポンプにて熱分解槽に送
液し、熱分解槽を密閉した後、脱酸素並びに窒素にて置
換し、その後、熱風にて熱分解槽を昇温して、溶解液を
熱分解し、蒸気状生成物を冷却して液状生成物を得た。
また、熱分解残渣は分解終了後直ぐに、分解槽とつなが
った配管を有するステンレス製の密閉容器に２分で払い
出した。また、溶解結果、熱分解結果及びガスクロマト
グラフ磁場型質量分析装置を用いて定量、定性分析を行
い、各成分の含有率を求めた液状生成物の組成を表１に
示す。Then, the dissolved solution was sent to the thermal decomposition tank by a pump, the thermal decomposition tank was sealed, and then deoxygenated and replaced with nitrogen, after which the temperature of the thermal decomposition tank was raised by hot air, The solution was pyrolyzed and the vapor product was cooled to give a liquid product.
Immediately after completion of the decomposition, the thermal decomposition residue was discharged into a stainless steel closed container having a pipe connected to the decomposition tank in 2 minutes. Further, Table 1 shows the composition of the liquid product in which the content of each component was determined by carrying out quantitative and qualitative analysis using a dissolution result, a thermal decomposition result and a gas chromatograph magnetic field type mass spectrometer.
【００６５】[0065]
【表１】 [Table 1]
【００６６】〔実施例２〕実施例１と同様の装置で同様
の方法で、ポリスチレンペーパートレー１１０Ｋｇをそ
のまま溶解槽に投入した。通箱と同様に、投入と同時に
トレーは攪拌翼と水平バッフル間で激しく破砕され、次
いで溶解槽内の液状生成物で速やかに溶解を開始した。
投入後２時間で１１０Ｋｇのトレーは全て溶解した。次
いで実施例１と同様の方法で、熱分解し、液状生成物を
得た。Example 2 Using the same apparatus as in Example 1 and using the same method, 110 kg of polystyrene paper tray was directly charged into the melting tank. Similar to the through box, the tray was violently crushed between the stirring blades and the horizontal baffle at the same time as the loading, and then the liquid product in the dissolution tank immediately started to dissolve.
Two hours after the addition, all of the 110 kg tray was dissolved. Then, it was thermally decomposed in the same manner as in Example 1 to obtain a liquid product.
【００６７】溶解結果、熱分解結果及びガスクロマトグ
ラフおよびガスクロマトグラフ磁場型質量分析装置を用
いて定量、定性分析を行い、各成分の含有率を求めた液
状生成物の組成を表１に示す。The results of dissolution, the results of thermal decomposition, and quantitative and qualitative analysis using a gas chromatograph and a gas chromatograph magnetic field type mass spectrometer, and the composition of the liquid product for which the content of each component was determined are shown in Table 1.
【００６８】〔比較例１〕実施例１と同様の溶解槽で水
平バッフルを取り付けないで、実施例１と同様に通箱を
投入した。通箱は攪拌翼と溶解槽の内壁で破砕はされる
が、溶解速度は著しく低下し、１１０Ｋｇ全量を溶解す
るのに６時間を要した。次いで、実施例１と同様の方法
で、熱分解し、液状生成物を得た。[Comparative Example 1] The same melting tank as in Example 1 was used, but the horizontal baffle was not attached. Although the through box was crushed by the stirring blade and the inner wall of the dissolution tank, the dissolution rate was remarkably reduced, and it took 6 hours to dissolve the total amount of 110 kg. Then, it was thermally decomposed in the same manner as in Example 1 to obtain a liquid product.
【００６９】溶解結果、熱分解結果及びガスクロマトグ
ラフおよびガスクロマトグラフ磁場型質量分析装置を用
いて定量、定性分析を行い、各成分の含有率を求めた液
状生成物の組成を表１に示す。分解挙動、液状生成物組
成については実施例１と差は無かった。Table 1 shows the composition of the liquid product obtained by quantifying and qualitatively analyzing the dissolution result, the thermal decomposition result and the gas chromatograph and the gas chromatograph magnetic field mass spectrometer. There was no difference in decomposition behavior and liquid product composition from Example 1.
【００７０】〔比較例２〕実施例２と同様の溶解槽で水
平バッフルを取り付けないで、実施例２と同様にポリス
チレンペーパートレーを投入した。比較例１の通箱程度
の溶解速度の低下は無かったが、１１０Ｋｇ全量を溶解
するのに４時間を要した。次いで、実施例１と同様の方
法で、熱分解し、液状生成物を得た。[Comparative Example 2] A polystyrene paper tray was put in the same manner as in Example 2 except that the horizontal baffle was not attached in the same dissolution tank as in Example 2. Although there was no decrease in the dissolution rate in the case of Comparative Example 1, it took 4 hours to dissolve the total amount of 110 kg. Then, it was thermally decomposed in the same manner as in Example 1 to obtain a liquid product.
【００７１】溶解結果、熱分解結果及びガスクロマトグ
ラフおよびガスクロマトグラフ磁場型質量分析装置を用
いて定量、定性分析を行い、各成分の含有率を求めた液
状生成物の組成を表１に示す。分解挙動、液状生成物組
成については実施例１と差は無かった。Table 1 shows the composition of the liquid product obtained by the quantitative analysis and the qualitative analysis using the results of dissolution, the result of thermal decomposition and the gas chromatograph and the gas chromatograph magnetic field type mass spectrometer. There was no difference in decomposition behavior and liquid product composition from Example 1.
【００７２】〔比較例３〕実施例１と同様の溶解槽で水
平バッフル長を、槽内径の５％に短くしたものを取り付
け、実施例１と同様に通箱を投入した。通箱は攪拌翼と
溶解槽の内壁で破砕はされるが、溶解速度は低下し、１
１０Ｋｇ全量を溶解するのに５時間を要した。次いで実
施例１と同様の方法で、熱分解し、液状生成物を得た。[Comparative Example 3] A melting tank similar to that of Example 1 with a horizontal baffle length shortened to 5% of the inner diameter of the tank was attached, and a through box was put in the same manner as in Example 1. The through box is crushed by the stirring blade and the inner wall of the dissolution tank, but the dissolution rate decreases and
It took 5 hours to dissolve the total amount of 10 kg. Then, it was thermally decomposed in the same manner as in Example 1 to obtain a liquid product.
【００７３】溶解結果、熱分解結果及びガスクロマトグ
ラフおよびガスクロマトグラフ磁場型質量分析装置を用
いて定量、定性分析を行い、各成分の含有率を求めた液
状生成物の組成を表２に示す。分解挙動、液状生成物組
成については実施例１と差は無かった。Table 2 shows the composition of the liquid product obtained by quantifying and qualitatively analyzing the dissolution result, the thermal decomposition result and the gas chromatograph and the gas chromatograph magnetic field mass spectrometer. There was no difference in decomposition behavior and liquid product composition from Example 1.
【００７４】[0074]
【表２】 [Table 2]
【００７５】〔比較例４〕実施例１と同様の溶解槽で、
溶剤の量は同一で、廃プラの投入量を２５０Ｋｇに増量
し、実施例１と同様に通箱を投入した。通箱は攪拌翼と
溶解槽の内壁で破砕はされるが、溶解速度は低下し、２
５０Ｋｇ全量を溶解するのに８時間を要した。次いで実
施例１と同様の方法で、熱分解し、液状生成物を得た。[Comparative Example 4] In the same dissolution tank as in Example 1,
The amount of solvent was the same, the amount of waste plastic added was increased to 250 Kg, and the container was put in the same way as in Example 1. The through box is crushed by the stirring blade and the inner wall of the dissolution tank, but the dissolution rate decreases and
It took 8 hours to dissolve the entire 50 kg. Then, it was thermally decomposed in the same manner as in Example 1 to obtain a liquid product.
【００７６】溶解結果、熱分解結果及びガスクロマトグ
ラフおよびガスクロマトグラフ磁場型質量分析装置を用
いて定量、定性分析を行い、各成分の含有率を求めた液
状生成物の組成を表２に示す。分解挙動、液状生成物組
成については実施例１と差は無かった。Table 2 shows the composition of the liquid product obtained by the quantitative analysis and qualitative analysis using the dissolution result, the thermal decomposition result and the gas chromatograph and the gas chromatograph magnetic field type mass spectrometer. There was no difference in decomposition behavior and liquid product composition from Example 1.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成８年９月２日[Submission date] September 2, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】図面の簡単な説明[Correction target item name] Brief description of drawings
【補正方法】追加[Correction method] Added
【補正内容】[Correction contents]
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明に係るスチレン系樹脂の熱分解装置及び
熱分解方法を示す説明図である。FIG. 1 is an explanatory view showing a thermal decomposition apparatus and a thermal decomposition method for a styrene resin according to the present invention.
【符号の説明】 １０；溶解槽 １２，２８；攪拌機 １４；バッフル ２０；ポンプ ２４；熱分解槽 ２６；加熱装置 ３４；冷却装置 ３８；タンク[Explanation of Codes] 10; Melting tank 12, 28; Stirrer 14; Baffle 20; Pump 24; Thermal decomposition tank 26; Heating device 34; Cooling device 38; Tank
Claims (11)
側に加熱装置を有するスチレン系樹脂を溶解する溶解槽
と、該溶解槽にスチレン系樹脂を溶解する溶剤及び／ま
たはスチレン系樹脂の熱分解液状生成物を投入しまたは
循環させる装置と、溶解された液を熱分解する熱分解槽
へ送液するポンプと、槽の外側に加熱装置と槽の内側に
攪拌機と底部より熱分解残渣を払い出す装置を有するス
チレン系樹脂を熱分解する熱分解槽と、該熱分解槽にお
いて発生した蒸気状生成物を液化する冷却装置と、該冷
却装置によって液化された熱分解液状生成物を回収し混
入した水を分離するタンクからなる回分式熱分解装置で
あることを特徴とするスチレン系樹脂の熱分解装置。1. A dissolution tank for dissolving a styrene resin having a stirrer and a baffle inside the tank and a heating device outside the tank, and a solvent for dissolving the styrene resin and / or heat of the styrene resin in the dissolution tank. A device for charging or circulating the decomposed liquid product, a pump for sending the dissolved liquid to a thermal decomposition tank for thermal decomposition, a heating device outside the tank, a stirrer inside the tank and a thermal decomposition residue from the bottom. A thermal decomposition tank for thermally decomposing a styrene resin having a discharging device, a cooling device for liquefying a vapor-like product generated in the thermal decomposition tank, and a thermally decomposed liquid product liquefied by the cooling device for recovery. A pyrolysis device for styrene-based resins, which is a batch pyrolysis device comprising a tank for separating mixed water.
側に加熱装置と槽の底部より熱分解残渣を払い出す装置
を有するスチレン系樹脂を溶解するとともに熱分解する
溶解分解槽と、該溶解分解槽にスチレン系樹脂を溶解す
る溶剤及び／またはスチレン系樹脂の熱分解液状生成物
を投入しまたは循環させる装置と、前記溶解分解槽にお
いて発生した蒸気状生成物を液化する冷却装置と、該冷
却装置によって液化された熱分解液状生成物を回収し混
入した水を分離するタンクからなる回分式熱分解装置で
あることを特徴とするスチレン系樹脂の熱分解装置。2. A dissolving and decomposing tank for dissolving and thermally decomposing a styrene resin having a stirrer and a baffle inside the tank, a heating device outside the tank and a device for discharging a thermal decomposition residue from the bottom of the tank, and the melting tank. A device for charging or circulating a solvent that dissolves the styrene resin and / or a thermally decomposed liquid product of the styrene resin in the decomposition tank; and a cooling device that liquefies the vapor product generated in the dissolution decomposition tank, A pyrolysis apparatus for styrene-based resin, which is a batch pyrolysis apparatus comprising a tank for collecting a pyrolyzed liquid product liquefied by a cooling device and separating mixed water.
拌翼、および攪拌翼と攪拌翼の間に溶解槽の内壁に固定
した１対または複数対の水平バッフルを有することを特
徴とする請求項１又は請求項２に記載するスチレン系樹
脂の熱分解装置。3. The stirring tank in the melting tank or the melting and decomposition tank, and one or more pairs of horizontal baffles fixed to the inner wall of the melting tank between the stirring blades and the stirring blades. The thermal decomposition apparatus for styrene resin according to claim 1 or claim 2.
フルの長さが溶解槽又は溶解分解槽の内径の１０〜４０
％であることを特徴とする請求項３に記載するスチレン
系樹脂の熱分解装置。4. The length of one baffle of the pair of horizontal baffles is 10 to 40 of the inner diameter of the dissolution tank or dissolution decomposition tank.
%, The thermal decomposition apparatus for styrene-based resin according to claim 3.
該熱分解槽又は溶解分解槽の底部の熱分解残渣を払い出
すバルブと、熱分解槽に連結された配管を有し、熱分解
槽から未分解及び炭化物からなる熱分解残渣を払い出す
密閉された装置を有することを特徴とする請求項１乃至
請求項４に記載するスチレン系樹脂の熱分解装置。5. In the thermal decomposition tank or the dissolution decomposition tank,
A valve for discharging the thermal decomposition residue at the bottom of the thermal decomposition tank or the dissolution decomposition tank and a pipe connected to the thermal decomposition tank are provided, and the thermal decomposition residue composed of undecomposed and carbide is discharged from the thermal decomposition tank and sealed. The thermal decomposition apparatus for styrene-based resin according to any one of claims 1 to 4, further comprising:
レン系樹脂の熱分解液状生成物を溶解槽に投入し、該溶
解槽でスチレン系樹脂を減容溶解させた後、該得られた
溶解液を熱分解槽に送液して該熱分解槽で攪拌下で加熱
して熱分解し、発生した蒸気状生成物を液化して熱分解
液状生成物を回収することを特徴とするスチレン系樹脂
の熱分解方法。6. A styrene-based resin and a solvent and / or a thermally decomposed liquid product of the styrene-based resin are charged into a dissolution tank, and the styrene-based resin is volume-dissolved in the dissolution tank, and then the obtained solution is obtained. Is sent to a thermal decomposition tank and heated under stirring in the thermal decomposition tank for thermal decomposition, and the vaporized product generated is liquefied to recover the thermally decomposed liquid product. Pyrolysis method.
物からなる熱分解残渣を流動性を有する状態で、直接空
気に接触しないようにしつつ熱分解槽の槽外へ払い出す
ようにしたことを特徴とする請求項６に記載するスチレ
ン系樹脂の熱分解方法。7. In the thermal decomposition tank, the thermal decomposition residue consisting of undecomposed and carbide is flowed out to the outside of the thermal decomposition tank while avoiding direct contact with air. The method for thermally decomposing a styrene resin according to claim 6, which is characterized in that.
バーナーを使用して熱風加熱を行う際に、廃熱風を燃焼
用空気と熱交換機を介して熱交換することを特徴とする
請求項６又は請求項７に記載するスチレン系樹脂の熱分
解方法。8. The heating method in the thermal decomposition tank,
The method for thermally decomposing styrene-based resin according to claim 6 or 7, wherein when hot air heating is performed using a burner, waste hot air is heat-exchanged with combustion air through a heat exchanger.
の５０重量％以上の溶剤及び／またはスチレン系樹脂を
熱分解して得られる熱分解液状生成物を、スチレン系樹
脂に添加し、投入されたスチレン系樹脂を溶解槽の攪拌
翼と対に配置された水平バッフルで破砕および攪拌する
ことを特徴とする請求項６乃至請求項８のいずれかに記
載するスチレン系樹脂の熱分解方法。9. A thermal decomposition liquid product obtained by thermally decomposing a solvent and / or styrene resin of 50% by weight or more of the styrene resin charged into the dissolution tank is added to the styrene resin and charged. 9. The thermal decomposition method for styrene-based resin according to claim 6, wherein the styrene-based resin thus prepared is crushed and stirred by a horizontal baffle arranged in pairs with a stirring blade of a melting tank.
溶解するに際し、該溶解液を該溶解槽にポンプで循環さ
せることを特徴とする請求項６乃至請求項９のいずれか
に記載するスチレン系樹脂の溶解方法。10. The styrene resin according to any one of claims 6 to 9, wherein when the styrene resin is dissolved in the dissolution tank, the solution is circulated in the dissolution tank by a pump. Dissolution method.
ルとを有し、さらに槽の外側に加熱手段を有する溶解槽
で、溶解減容させたスチレン系樹脂を、直接当該溶解槽
で熱分解させるようにしたことを特徴とするスチレン系
樹脂の熱分解方法。11. A dissolution tank having a stirrer and one or more pairs of horizontal baffles and further having a heating means outside the tank, the styrene resin whose volume has been dissolved and reduced is directly pyrolyzed in the dissolution tank. A method for thermally decomposing a styrene-based resin, characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8489096A JP3596571B2 (en) | 1996-04-08 | 1996-04-08 | Pyrolysis apparatus and method for styrene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8489096A JP3596571B2 (en) | 1996-04-08 | 1996-04-08 | Pyrolysis apparatus and method for styrene resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09272876A true JPH09272876A (en) | 1997-10-21 |
| JP3596571B2 JP3596571B2 (en) | 2004-12-02 |
Family
ID=13843356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8489096A Expired - Fee Related JP3596571B2 (en) | 1996-04-08 | 1996-04-08 | Pyrolysis apparatus and method for styrene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3596571B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028464A (en) * | 2004-07-12 | 2006-02-02 | Tesco Japan Kk | System and method for oil recovery by multi-step wet polymer decomposition liquefaction process |
| KR101237744B1 (en) * | 2009-09-21 | 2013-02-28 | 한국화학연구원 | Apparatus for recovering styrene monomer using auxiliary solvent |
-
1996
- 1996-04-08 JP JP8489096A patent/JP3596571B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006028464A (en) * | 2004-07-12 | 2006-02-02 | Tesco Japan Kk | System and method for oil recovery by multi-step wet polymer decomposition liquefaction process |
| KR101237744B1 (en) * | 2009-09-21 | 2013-02-28 | 한국화학연구원 | Apparatus for recovering styrene monomer using auxiliary solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3596571B2 (en) | 2004-12-02 |
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