Korean Chemical Engineering Research
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(2) T §Ð÷. †. KD@HõCò @HD¬z D ·ÉòD¬õC¤ 305-600 ¬MQ K C ß 100 (2004¸ 6ö 8³ [¤, 2004¸ 10ö 11³ >) Effect of Organic Residue on the Continuous/Pyrolysis of Waste Polystyrene Byung Tae Yoon, Seong Bo Kim, Sang Bong Lee and Myoung Jae Choi † Advanced Chemical Technology Division, Korea Research Institute of Chemical Technology, 100, Jang-dong, Yuseong-gu, Daejeon 305-600, Korea (Received 8 June 2004; accepted 11 October 2004). ß È. ·-)W ù~gäÑ ~gä Ú @ æ2 1³ OÑ WKê )WHôËQ zí³ »´(2 Ñ j, <²è)W, «Ë, T¶«Ë Ùo ä5 Ú äQÑ Ù ñ6 Í( ¡¤ËÑ g s çIk, U ¾ äQÑÑ ¶ ä Ú )W ¤So Qo ó«õ Ý. « ê2 ù~g äê_Ñ @ æ2 KD ÍÍíê Ê@! )éÑ D¯G. õù~gQÑ ,}ê Wÿ @ æ2 1³ ¤S« IGæÉk 1³Ñ WKæ´À2 )W >2 ÝGk zí¯ <²è)W, Ñj, j, PÕ Ù zí @ o ÍG. á õCê³z *³Ò õäs .K ù~gäDõ ÄG. Abstract − Oil formation rate, composition of crude oil and formation of side products such as α-methyl styrene, ethyl benzene, benzene, toluene, dimer and trimer on thermal degradation of polystyrene were affected by various factors. Especially, formation of organic residue formed during reaction gave an important influence on formation of oil and composition of crude oil. Also, composition of formed crude oil showed a significant difference on reaction time. These results were caused by organic residue and carbonized solid formed during continuous reaction. Increase of residue and carbonized solid gave a decrease of yield of styrene and an increase of formation of α-methyl styrene, ethyl benzene, benzene, toluene. New reaction system was proposed for continuous operation at the thermal degradation of polystyrene. Key words: Polystyrene, Styrene Monomer, Pyrolysis, Waste PS, Carbonized Solid. 1.. C «. o !d¤¯ U÷ D HYí³ »´( « !d¤Ëo õ0÷ ñ6 Æ ò0³ Äî ¤ À. ñ¶) éÉò dD¬ y Íß àÆ)K öro William Ù[1]« f8K àQ ç« ñ¶) èí0¯ Hô˳ ¡¤G2 ör« ·-)W Î Íß Ò ak³ <s À. ·-)Wª ñ¶) Î ¬z~« è¯ ·-)W(EPS, expanded polystyrene)k³ ù é 2 ³¡Ä ¯ßé Ùk³ Äæ J« ³äJ¯ ·)W(GPPS, general purpose polystyrene)Ý 50 _ è æ´ À´ Dí ÝÄ Ú élÄ +
(3) Ñ « ÁêJ¯ s-Í Q K 8 ]« æÊ À[2-4]. ·-)Wk³z )WHôË ¡¤Ñ îK õg2 Qo õg ÉÑ g ¤}æÊ Àk Nishizima Ù[5]o 350 C 5Ñ ñkõ ÄG( :Ê u 50% ¤S³ )WHô˳ ¡¤G k ñkõ ÄG
(4) 70% « ¤S³ ¡¤O ¤ À{s ÝÊG [6-7]. U¾ Zhang Ù[8]o barium oxideõ ñk³ ÄGñ 85% « ¤S³ )WHôËõ ¡¤G{s ÝÊG.. 16ÿ ñ¶)o ³ @lÑ Q« ÄæÊ À(O é ¬ z~ ñ¶)Ëo é¨hæ( :Ê k?«÷ ÎæÊ Àk k?Ñ K öro ¬z~ ñ¶)« @~gÍ ´sî ~gæ 2) 1Ú QÑ« 1®O O 4n¶ ~g@ í« 1s ³ k. K, ÎÑ K öro Îê_Ñ è@G2 «2U Ùê ço ñ6 ÜÍ Í) 1ís öG³ «6K éf gs .g élÄör« MÑ î[ ðY« æÊ À. ñ¶)s élÄG2 örk³ ¨K í-J¯ Í÷ Í àÝ2 JQK Ft, 5Q l ~.DÑ ù~görÑ g zÍÍjÍ À2 õ0K Ú ò0í0³ é Äör« h éf÷ fJ¯
(5) Ñ Íß àÆ)K örk³ @ÎæÊ À. « ê_Ñ Ê~ÉgÆ2 Êo yѳ ~g æÊ « í0o
(6) Ê. o. † To. whom correspondence should be addressed. E-mail: [email protected]. 125.
(7) O³=ö6 Ýö« óöM é. 126. á õgÑ2 ñ6 ÜÍ ñ¶) yÑ ò0³ élÄ« Í DGñ í0 Y0J¯ ¨h« ÍDGÊ, ò0 zÍÍjÍ o EPS(·-)W)³z SM(styrene monomer)s ñkGÑ ù ~gäs Gñ ò0¯ )WHô˳ ¡¤G2 à_ íès .g õgõ ¤}G. á Y×Ñ2 õR ù~g ßjõ «ÄGñ EPS³ z styrene @ Ñ îK õgõ ¤}Gk äê_ zí³ @ æ2 ÍÍí« ä Ñ kÎ y®K ¡¤»s e¯G. á õgÑ2 ñ6 ÜÍ ñ¶) yÑ ò0³ élÄ« Ê ò0 zÍÍjÍ o ¨¤K ·-)Ws ñk ù~g ä Gñ ò0¯ )WHôËõ ¡¤G2 äÑ ¬K ñ6 ä¯É õ ]G. U¾, ·-)W ~gê_Ñ @ æ2 ÍÍí Ú Êd!Í )W @ Ñ Âj2 Ú ä·J õgõ 0g ·-)Wk³z )W @ ÍÍí s ]G. 2.. / tà. á Y×Ñ ÄK Q0¯ waste EPS2 Í· ¤Qß y [Ñ ¤Mæ2 ÝÄ ingot ²Gís Y×Ñ ÄG. Q0 ¿D2 è³K ½ÉÍ 4nÊ ¬÷ 3 cm « äkK ¿Dõ Í(Ê À. Q0 c½s _
(8) dGD .Gñ extruderÑ 250 C Äa5³ )¿P ¡MÑ ¶ ò0c½QÑÑ ñ à
(9) s Fig. 1sF e?G. á Y× à_o Fig. 2Q ç. äk³z »´(2 Íí s -Î, O ¤ À2 -ÎDÍ zôê 3 liter Ä
(10) õR o. Fig. 2. Apparatus for the continuous operation at the degradation of waste polystyrene.. CSTR äDõ ÄGñ 200 rpm ¡M³ äís GäG äs ,}Gk ò0 c½o )¿P ¡M 2.5 rpm k³ àG. äÑ Gñ ~gê ù~g D2 Dõ 0g Udæ´ 1³³ »´k ä y @ æ2 1³o è)Y1
(11) õ ÄG ñ QÑÑ ñ z)õ +_Gñ ù~g _õ îûG. ù~ gê_ yÑ @ æ2 )W HYí« j æD .Gñ 0 õ 30 ml/min K
(12) k³ äD Ñ àG. ~o capillary column (HP-1, 25 m 0.2 mm 0.11 µm)« ß ôê GC/FID(DONAM Instrument)õ ÄG.. 3.. ûG Z +{. 3-1. ?s£ Lð ·-)W ù~gU s ÊûGD .K JQK ÆQs _G D .Gñ c® 䡤¯ ä5 s ÊûG. · -)W 200 gs ä5 350-390 C p.Ñ 10 C Ñk³ 9Qÿ
(13) ¡~Rk³ ù~g äs YQG. Î ä5 Ñ ñ ä QÑo 150-30~ p.«É. ä5Ñ ñ 1³ @ Ú @ 1³ -Ê ä« ³û á äDÑ 4À2 Êd!Í WKG2 ÍÍís 4§ Ñ ÄgK á ñêG ñ Êd!õ ~-Gñ 9GG. K, ñêí 4§ s è Gñ »´, ÍÍís 9GG. ê Table 1ê ç« ä5 Í 9WÑ ¶ @ æ2 1³ ê @ 2 ÍGk ÷ ÍÍío ÝG. K, 1³ y )WHôË W
(14) o 380 C ä5Ñ M¬às ÷ É. «Q 䬳 9Y(b.p) « K K zí¯ Ñjê <²è)W W
(15) o ÝG o. o. o. Fig. 1. Amounts of feeding material for rpm of screw. Table 1. Effect of reaction temperature on the pyrolysis of polystyrene Reaction temperature (oC) Formation of oil (ml/min) Product oil (%) Residue (%) Carbon (%) Styrene monomer (wt%) α-methyl styrene (wt%) Toluene (wt%) Benzene (wt%) Ethylbenzene (wt%) Others (wt%). ¤@¤ C43× C1 2005 2 . 350 360 110.84 11.32 66.5 77.5 32.0 20.6 11.5 1.9 Chemical composition of oil (wt%) 167.37 67.74 113.87 13.45 114.29 13.77 110.24 10.23 111.90 11.68 122.33 23.13. 370 112.88 85.0 13.7 11.3. 380 4.19 89.0 9.3 1.7. 390 116.86 95.0 13.5 11.5. 070.30 112.84 112.46 110.19 111.09 123.22. 71.07 2.60 2.77 0.16 0.92 22.48. 170.68 112.29 111.96 110.21 110.78 124.08.
(16) EPS. . «Q ç« 380 C ä5Ñ )W ¤S« M¬às Ý «2 «K2 Ê5Ñ ÍÍí @ « ÍæD )ék³ 0 ê. 3-2. ;Ø PS£ ?Ï¿ ? ·-)Ws õJk³ c½G
(17) 380 CÑ ù~g õ ä ÆÆs YQG. äQÑ« êWÑ ¶ Fig. 3ê ç« 1³ @ 2 IGæ, Fig. 4 sF )WHôË2 ÝG k 9Y« K K zí¯ Ñj Ú <²è)Wo Í G2 ak³ ÷
(18) . «6K o O Q ä5Ñ ¸ K àQ ç« äê_Ñ @ æ2 ÍÍí « äÑ Ã s cD )é¯ ak³ @Îê. «Q ço ê2 Table 2Ñ Ý2 àQ ç« ¡~Rä Q) ÊÑ ä QÑÑ ¶ »´(2 ä @ í êQ ³jW s Ý. 6³ «6K ê³z äê_Ñ @ æ2 Ê d!õ 9ÇK ÍÍíËo ä~gí @ Ñ Ã s c2 ak³ @Îæ´ ÍÍí s ]G. o. o. Fig. 3. Oil formation rate on reaction time at the continuous operation of degradation of waste polystyrene.. ù~C ä. 127. Table 3. Element analysis for feedstock and residue obtained from degradation of poly styrene Waste poly styrene Organic residue Carbon. Carbon Hydrogen Ratio of carbon to hydrogen 91.9 8.1 11.34 92.6 7.4 12.51 94.3 5.7 16.54. 3-3. ߣW£ Lð ÍÍí s ]GD .Gñ ¨¤K ò0 GPPS 200 gs ä 5 380 C, åñk GÑ ù~gäs YQGñ ù~g @ í« @ æ( :s )b( 3QÑ 8 äs ,}K á ñD » ´, Êd!Q KD ÍÍís Äk¯ 4§ k³ õ¯ á ñê Gñ Êd!Q KD ÍÍís ~-G. ñêUo Äkõ èQ- KD ÍÍís »Ék, «Q ç« ~-K KD ÍÍ íê Êd!õ ò ~Gñ Table 3ê ço êõ »É. ,Ñ Ý2 àQ ç« ò02 ¤Ñ ! 9Í 11.34Ñ 9g KD ÍÍío 12.51, Êd!2 16.54³ ¤ W
(19) « kÎ JÉ. « ê2 ÍÍío Yó ! c ~ê ç« !Ñ 9g ¤9Í J´(2 Qdzh @ s Ýñg. K, GPCÑ g ~K ~É
(20) ~¯2 Table 4Q ç« ù~ g æ´ è~É
(21) o ò0Í 95,000Ñ 9g KD ÍÍío 1,406 I~É
(22) Ê~ɳ ¡dê as Ýñg. äk³z »´, KD ÍÍíê Êd!Í äÑ Âj2 s ]G. ò0 200 gÑ ¬Gñ ÎÎ 5 wt% o { u 30~ 8 ù~gäs G. ê Table 5Q ç« Ê9Y ÍÍí« Êd!Ñ 9Gñ äÑ Ã s cÉ. Ê9Y K ~s ÍG2 Î 1³ Ú )WHôË ¤S« k´ËÊ <² è)W Ú Ñj W
(23) « ¿j ÍG. K, õÆÆÑ ÍÍí s ]GD .Gñ ÍÍí« À2 =Ñ Semi-BatchRk³ 5¡ õ ù~g äs YQG . k¡ K ò0(waste EPS, 200 g)õ *³ c½G ÍÍío fMG( :Ê ªG. ê Fig. 5Q ç« ä,}¡¤ o. Table 4. Molecular weight of polystyrene, organic residue and carbon formed from thermal degradation Waste polystryrene Organic residue. Mn 95,807 1,406. Mw 207,273 3,352. Polydispersity 2.16 2.37. Table 5. Effects on carbon and residue formed at thermal degradation of polystyrene Catalyst Fig. 4. Composition of crude oil formed at the continuous operation of degradation of waste polystyrene. Table 2. Effect of reaction time on degradation of waste polystyrene Reaction time(min) Styrene monomer (wt%) α-methyl styrene (wt%) Toluene (wt%) Benzene (wt%) Ethylbenzene (wt%) Others (wt%). 30. 60. 90. 120. 150. 73.8 1.25 1.70 0.09 0.15 23.0. 67.8 1.47 1.67 0.14 0.50 28.4. 63.8 1.92 1.60 0.09 0.15 32.4. 59.6 2.62 1.72 0.10 0.06 35.9. 57.2 4.21 2.42 0.08 0.32 35.7. No residue. Carbon 5%. Formation of oil (ml/min) 7.35 6.26 Yield of oil (wt%) 93.9 89.6 Residue (wt%) 6.86 6.40 Carbon (wt%) 0.33 0.98 Chemical composition of oil (wt%) Styrene monomer 60.8 61.6 2.2 9.6 α-methyl styrene Toluene 2.1 3.9 Benzene 0.1 0.1 Ethylbenzene 0.3 2.1 Others 34.5 22.8. Residue 5% 6.76 88.6 4.74 2.08 57.6 7.4 4.0 0.1 2.9 28.2. Korean Chem. Eng. Res., Vol. 43, No. 1, February, 2005.
(24) 128. O³=ö6 Ýö« óöM é. á õäs G. 380 CÑ õäs YQK ê Fig. 6 ê ç« zí¯ Ñjê <²è)W @ s ¿j µf O ¤ ÀÉ. K, Fig. 5sF äQÑÑ ¶ ¾ Ýæ2 )WHôË > UdQ ¤ ÀÉ. o. 4.. EPS ù~g äÑ2 380 C ä5Ñ )WH ôË ¤So M¬às Ýk äQÑ« êWÑ ¶ ) WHôË ¤So ÝGk zí¯ <²è)Wê Ñ j @ o ÍG. (2) MJ õÆÆ ÆQÑ ä IG ò¯o äê_Ñ KD ÍÍíê Êd! @ Ñ D¯G. (3) ä ÍÍís ³_Gj Qÿ
(25) õ ù~g äs Y QO Î äQÑÑ ñ )WHôË K ¤S Ý2 U dî ¤ ÀÉÊ, zí¯ <²è)Wê Ñj @ µ fO ¤ ÀÉ. (4) äê_Ñ @ æ2 ÍÍí s MdGD .Gñ ÍÍís ³_Gj fMG õäs O ¤ À2 *³Ò ù~g äD Q)Ês f8G. (1). Fig. 5. Effects of residue on operation times operation at thermal degradation of polystyrene.. û « o. +S Fig. 6. Composition of crude oil formed at the continuous operation of degradation of waste polystyrene using modified reactor.. ÍQ Wÿ )W W
(26) o ÝæÊ zí¯ <²è)Wê Ñj W
(27) o ¿j ÍG. O êQ ç« ñk Ä ñzÑ îªÇ« äQÑ« êW Ñ ¶ )WHôË W
(28) o IGæÊ, ä
(29) Ñ Fig. 5sF Ñ jê <²è)W W
(30) o ÍG2 k³ ÷
(31) . « ê³z äÑ @ æ2 ÍÍío äs µfG z@ í ¯ <²è)Wê Ñj @ s ÍQÿ³ )WHô Ë ¤Ss ÍQÿD .g2 ÍÍís MdG2 a« y® G. 3-4. Ckg ?Ï¿ ?ï§ £§ ;Ø?Ï¿ ? OÑ ¸K àQ ç« äê_Ñ @ ê äÍÍío ä ¤S Ú @ æ2 )WHôË >õ IGQÿ³ ä Ñ Jæ2 ÍÍí s MdGD .Gñ äDõ íG . Jæ2 ä ÍÍís äê_Ñ õJk³ ³_Gj QÿD .Gñ äD GzÑ 8 mm gõ jK. ¤@¤ C43× C1 2005 2 . 1. Williams, V., Symposium of Waste Plastic Recycle, Tokyo 21 (1993). 2. MOST, Study on Technical Trend for Recycle of Waste Plastics, 37(2000). 3. Shun, D. W., Han, K. H. and Son, J. E., “Technical Trend on Thermal Degradation in Japan,” Chemical Industry and Technology, 14(4), 371-378(1996). 4. Liebman, S. A. and Levy, E. J., “Pyrolysis and GC in Polymer Analysis,” MARCEL DEKKER, Inc., 149-158(1980). 5. Nishizima, H., Sakakibara, M. and Yoshida, K., “Oil Recovery from Atatic Polypropyrene by Fludized Bed Reactor,” Nippon Kagaku Kaishi, 1989-1999(1977). 6. Kim, J. S., Kim, S. J., Yun, J. S., Kang, Y. and Choi, M. J., “Pyrolysis Characteristics of Polystyrene Wastes in a Fludized Bed Reactor,” HWAHAK KONGHAK, 39(4), 465-469(2001). 7. Shun, D. W., Ghim, Y. S., Cho, S. H. and Son, J. E., “Pyrolysis of Polystyrene in a Fludized Bed Reactor,” Korea Solid Wastes Eng. Sci., 10(2), 195-201(1993). 8. Zhang, Z., Hirose, T., Nishio, S., Morioka, Y., Azuma, N. and Ueno, A., “Chemical Recycling of Waste Polystyrene Into Styrene Over Solid Acids and Bases,” Ind. Eng. Chem. Res. 34(12), 4515-4519(1995)..
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