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촉매-크래킹에 의한 나프타로부터 경질 올레핀 제조기술
Catalytic Cracking of Naphtha into Light Olefins
한국화학연구원 화학기술연구부, 305-600 대전시 유성구 장동 100
Advanced Chemical Technology Division, KRICT, 100 Jang-dong, Yuseong-gu, Daejeon 305-600, Korea
chulwee@krict.re.kr
HWAHAK KONGHAK, October 2003, 41(5), 549-557(9), NONE
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Abstract
세계적으로 에틸렌 생산공장에서 배출되는 이산화탄소의 양은 매년 141백만 톤에 이르며, 석유화학산업에서 소비되는 전체 에너지 중 약 40%는 나프타 스팀크래킹에 사용된다. 이로인한 지구 온난화를 막기 위하여 에너지 효율 증대를 통하여 이산화탄소 배출양을 최소화할 수 있는 나프타 크래킹 기술개발이 시급하다. 또한 천연가스로부터 얻어지는 에틸렌의 양이 점점 증가하기 때문에 프로필렌/에틸렌 비를 증대하기 위한 연구가 필요한 실정이다. 그러므로 에틸렌과 프로필렌 수요를 맞추기 위한 thermal cracking의 대안으로 촉매를 이용한 크래킹기술이 시도되고 있다. 본 논문에서는 나트파로부터 에틸렌, 프로필렌 등과 같은 경질 올레핀 제조에 관하여 지난 수 년간 공개된 특허와 실용화 가능한 공정 기술을 소개하고자 한다.
In the whole world, the amount of CO2 emission from the ethylene plant is about 141 million tons per year, and currently about 40% of the energy in petrochemical industry is used for steam cracking of naphtha. So, global warming issues have stimulated the development of new cracking process of naphtha which can minimize CO2 emission through the increase of energy efficiency. Also there is an effort to increase the ratio of propylene/ethylene in naphtha cracking since the natural gas cracker which can produce ethylene preferentially increases more and more. Therefore, catalytic cracking of naphtha has been studied as an alternative of thermal cracking to balance ethylene and propylene demand and to reduce CO2 emission. This paper will review the various routes which have been investigated and applied over the past years, but will focus particularly on the recently patented and commercially demonstrated processes for the production of lower olefins from naphtha.
Keywords
References
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Frillette VJ, Haag WO, Logo RM, J. Catal., 67, 218 (1981)
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Kyotani T, Nagai T, Inoue S, Tomita A, Chem. Mater., 9, 609 (1997)
Blaikley DCW, Jorgensen N, Catal. Today, 7, 277 (1990)
Zou R, Lou Q, Liu H, Niu F, Ind. Eng. Chem. Res., 26, 2528 (1987)
Kumar VA, Pant K, Kunzru D, Appl. Catal. A: Gen., 162(1-2), 193 (1997)
Das P, Prassad D, Kunzru S, Ind. Eng. Chem. Res., 31, 2251 (1992)
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Chae JH, Byun YC, Jeong SM, Lee WH, HWAHAK KONGHAK, 40(1), 75 (2002)
"Petrochemicals," Chemical & Engineering News, 80(11), 21 (2003)
Wallenstein D, Kanz B, Harding RH, Appl. Catal. A: Gen., 178(1), 117 (1999)
Wang DZ, Appl. Catal. A: Gen., 141, N4 (1996)
Lemonidou AA, Vasalos IA, Appl. Catal., 54, 119 (1989)
vanMao RL, "Catalysts for Up-Grading Steam-Cracking Products," U.S. Patent, No. 4,732,881 (1988)
Korea Petrochemical General Book 2000, CISChem.Com.
Gartside RJ, Johnson AR, Ross JL, Duncan DA, "Olefin Production from Heavy Hydrocarbon Feed," U.S. Patent, No. 4,663,019 (1987)
Gartside RJ, "Process for the Production of Olefins and Aromatics," EP 0381870A (1990)
Kolombos AJ, McNeice D, Wood DC, "Olefins Production by Steam Cracking over Manganese Catalyst," U.S. Patent, No. 4,087,350 (1978)
Ueda T, Ohta M, Sugano S, "Process for the Production of Olefins," U.S. Patent, No. 4,259,177 (1981)
Sha Y, Cui Z, Wang G, Wang M, "Optimized Process for the Preparation of Olefins by Direct Conversion of Multiple Hydrocarbons," U.S. Patent, No. 6,420,621, B2 (2002)
Yoshimura Y, Kijima N, Hayakawa T, Murata K, Suzuki K, Mizukami F, Matano K, Konishi T, Oikawa T, Saito M, Shiojima T, Shiozawa K, Wakui K, Sawada G, Sato K, Matsuo S, Yamaoka N, Catal. Surveys Jpn., 4, 157 (2000)
Mao RLV, Melancon S, Gauthier-Campbell C, Kletnieks P, Catal. Lett., 73(2-4), 181 (2001)
Melancon S, Le Van Mao R, Kletnieks P, Ohayon D, Intem S, Saberi MA, McCann D, Catal. Lett., 80(3-4), 103 (2002)
Chen TJ, Martens LRM, "Sequential Catalytic and Thermal Cracking for Enhanced Ethylene Yield," U.S. Patent, No. 6,033,555 (2000)
vanMao RL, Microporous Mesoporous Mater., 28, 9 (1999)
Kikuchi K, Tomita T, Sakamoto T, Ishida T, Chem. Eng. Prog., 81, 54 (1985)
Twofighi J, Zimmermann H, Karimzadeh R, Akbarnejad MM, Ind. Eng. Chem. Res., 41(6), 1419 (2002)
Kolombos AJ, McNice D, Wood DC, "Olefins Production by Steam Cracking over Manganese Catalyst," U.S. Patent, No. 4,087,350 (1978)
Koltz JH, Detzer GA, "Composition of Matter and Method for Conversion of C3 and C4 Hydrocarbons," E.P. 0212320 A2 (1987)
Lemonidou AA, Vasalos IA, Hirschberg EJ, bertolacini RJ, Ind. Eng. Chem. Soc., 28, 524 (1989)
Mamedov EA, Corberan VC, Appl. Catal. A: Gen., 127(1-2), 1 (1995)
Chaar MA, Partel D, Kung MC, Kung HH, J. Catal., 105, 483 (1987)
Nguten KT, Kung HH, J. Catal., 122, 415 (1990)
Lopez Nieto JM, Botella P, Vazquez MI, Dejoz A, Chem. Commun., 2002, 1906 (2002)
Thorsteinson EM, Wilson TP, Young FG, Kasai PH, J. Catal., 52, 116 (1978)
Schuette WL, Schweizer AE, Stud. Surf. Sci. Catal., 134, 263 (2001)
Schuette WL, Schweizer AE, "Crystalline Microporous Oxide Having Increased Lewis Acidity and Fluid Catalytic Cracking Process Using Same," EP 0749781 A2 (1996)
Corma A, Orchilles AV, Microporous Mesoporous Mater., 35-36, 21 (2000)
Kazansky VB, Frash MV, Vansanten RA, Appl. Catal. A: Gen., 146(1), 225 (1996)
Mirodatos C, Bartomeuf D, J. Catal., 114, 121 (1988)
Andrson BG, Schumacher RR, vanDuren R, Singh AP, vanSanten RA, J. Mol. Catal. A-Chem., 181, 291 (2002)
Frillette VJ, Haag WO, Logo RM, J. Catal., 67, 218 (1981)
Cai HY, Krzywicki A, Oballa MC, Chem. Eng. Process., 41(3), 199 (2002)
Kyotani T, Nagai T, Inoue S, Tomita A, Chem. Mater., 9, 609 (1997)
Blaikley DCW, Jorgensen N, Catal. Today, 7, 277 (1990)
Zou R, Lou Q, Liu H, Niu F, Ind. Eng. Chem. Res., 26, 2528 (1987)
Kumar VA, Pant K, Kunzru D, Appl. Catal. A: Gen., 162(1-2), 193 (1997)
Das P, Prassad D, Kunzru S, Ind. Eng. Chem. Res., 31, 2251 (1992)
Song JH, Chen P, Kim SH, Somorjai GA, Gartside RJ, Dautzenberg FM, J. Mol. Catal. A-Chem., 184, 197 (2002)
Chae JH, Lee WH, Jeong SM, Park KH, "Thermal Cracking Reactor and its Utilization," Korean Patent, No. 2002-0071649 (2002)
Chae JH, Lee WH, Jeong SM, "Catalyst for Producing Olefins by Steam Cracking of Hydrocarbon," Korean Patent, No. 2002-0072694 (2002)
Chae JH, Byun YC, Jeong SM, Lee WH, HWAHAK KONGHAK, 40(1), 75 (2002)
