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Petrochemical Promoters in Catalytic Cracking

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Petrochemical Promoters in Catalytic Cracking PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING Ciencia, Tecnología y Futuro PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING Maria-Elizabeth Gómez*1, Clemencia Vargas1 and Javier Lizcano2 1 Ecopetrol S.A - Instituto Colombiano del Petróleo, A.A. 4185 Bucaramanga, Santander, Colombia 2 UT TIP - Petrolabin, Piedecuesta, Santander, Colombia e-mail: [email protected] (Received May 5, 2009; Accepted October10, 2009) his study is based on the current scheme followed by a refinery with available Catalytic Cracking capacity to Tprocess new feedstocks such as Straight Run Naphtha and Naphthas from FCC. These feedstocks are of pe- trochemical interest to produce Ethane, Ethylene, Propylene, i-Butane, Toluene and Xylene. To evaluate the potential of these new streams versus the Cracking-charged Residues, it was performed a detailed chemical analysis on the structural groups in carbons [C1-C12] at the reactor product obtained in pilot plant. A catalyst with and without Propylene - Promoter Additive was used. This study analyzes the differences in the chemical composition of the feedstocks, relating them to the yield of each petrochemical product. Straight Run Naphthas with a high content of Naphthenes, and Paraffines n[C5-C12] and i[C7-C12] are selective to the production of i-Butane and Propane, while Naphthas from FCC with a high content of n[C5-C12]Olefins, i-Olefins, and Aromatics are more selective to Propylene, Toluene, and Xylene. Concerning Catalytic Cracking of Naphthas, the Additive has similar selectivity for all the petrochemical products, their yields increase by about one point with 4%wt of Additive, while in cracking of Residues, the Additive increases in three SRLQWV3URS\OHQH\LHOGFRUUHVSRQGLQJWRDVHOHFWLYLW\RI ¨& ¨/3* Keywords: propylene, catalytic cracking, i-butane, ethylene, naphthas, petrochemicals, Residues, ZSM-5. * To whom correspondence may be addressed CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 143 MARIA-ELIZABETH GÓMEZ et al. l presente estudio se basa en el esquema actual de una refinería con capacidad disponible en Cracking ECatalítico, para procesar nuevas cargas tales como Naftas Vírgenes y Naftas de URC (Unidad de 5XSWXUD&DWDOtWLFD ODVFXDOHVVRQGHLQWHUpV3HWURTXtPLFRHQSURGXFWRVWDOHVFRPR(WDQR(WLOHQR Propileno, i-Butano, Tolueno y Xilenos. Para evaluar el Potencial Petroquímico de estas corrientes frente al de los Residuos cargados a Cracking, se realizó un análisis químico detallado de los Grupos Estructurales de los Carbonos [C1-C12] en el producto reactor obtenido en planta piloto, utilizando un catalizador con y sin Aditivo promotor de Propileno. El estudio analiza las marcadas diferencias en la composición química de las cargas, y las relaciona con los rendimientos de cada uno de los productos petroquímicos. Las Naftas Vírgenes con mayor contenido de Naftenos y de Parafinas n[C5-C12] e i[C7-C12] son selectivas hacia la producción de i-Butano y Propano, mientras que las Naftas de URC con altos contenidos de n[C5-C12] Olefinas, i-Olefinas, y Aromáticos son más selectivas hacia Propileno, Tolueno y Xilenos. En el craqueo de las Naftas, el Aditivo tiene la misma selectividad para todos los productos petroquímicos, sus rendimientos incrementan en valores cercanos a un punto con 4% peso de Aditivo; mientras que en el craqueo de los Residuos el aditivo incrementa en 3 puntos el rendimiento de Propileno, lo que corresponde DXQDVHOHFWLYLGDGGHO ¨& ¨/3* Palabras Clave: propileno, craqueo, i-butano, etileno, naftas, petroquímicos, residuos, ZSM-5 144 CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING NOMENCLATURE LCO Light Cycle Oil C/O Catalyst / Oil ratio DCR Davison Circulating Riser FCCU Fluid Catalytic Cracking Unit LPG /LTXH¿HG3HWUROHXP*DV H2 Hydrogen iC4 i-Butane iC5 L3HQWDQH i[C4-C6] L3DUDI¿QHV&& i[C7-C12] L3DUDI¿QHV&& iP L3DUDI¿QHV Naft Naphthenes nC2 Ethane C2= Ethylene nC3 3URSDQH nC3 3URS\OHQH nC4 Butane n>&&@ Q3DUDI¿QHV&& n>&&@2OH¿QV Q2OH¿QV&& Q>&&@ Q3DUDI¿QHV&& Q>&&@2OH¿QV Q2OH¿QV&& Q3 Q3DUDI¿QHV 3,$12 3DUDI¿QHVL3DUDI¿QHV$URPDWLFV1DSKWKHQHV DQG2OH¿QV SimDis Simulated distillation 899,6 9LVLEOHXOWUDYLROHW VGO Vacuum Gas Oil ǻ& ǻ/3* 3URS\OHQH6HOHFWLYLW\ZLWK$GGLWLYH >& LQFUHDVH@>/3*LQFUHDVH@ CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 145 MARIA-ELIZABETH GÓMEZ et al. INTRODUCTION 6WXGLHVFRQGXFWHGRQFDWDO\WLFFUDFNLQJRI*DV2LO ZLWKFDWDO\VWVXVLQJ3URS\OHQH$GGLWLYH=60 =KDR 7KHRSHUDWLRQDOFRQVWUDLQWVRID)OXLG&DWDO\WLF ; +DUGLQJ5+ GHPRQVWUDWHGWKDWWKH\LHOG Cracking Unit (FCCU) to produce certain products not RI2OH¿QVLQGXFHGE\WKH$GGLWLYHGHFUHDVHVZLWKWKH only depend on its technology or operating conditions, but FRQWHQWRI1DSKWKHQHVLQWKHIHHGVWRFN7KLVEHKDYLRULV DOVRRQWKHFKDUDFWHULVWLFVDQGTXDOLW\RIWKHIHHGVWRFNWKDW DWWULEXWHGWRWKHIDFWWKDW1DSKWKHQHVSDUWLFLSDWHLQWKH determine its potential to produce the desired product. K\GURJHQWUDQVIHUUHDFWLRQVWKDWVDWXUDWH2OH¿QV,WLV WKHUHIRUHFRQFOXGHGWKDWWKH$GGLWLYHHIIHFWLVPD[LPL]HG ZKHQFDWDO\VWVRIORZDFWLYLW\LQK\GURJHQWUDQVIHUUHDF- 7KHREMHFWLYHRIWKLVVWXG\LVWRGHWHUPLQHDQGFRP- tions are used. These catalysts are characterized by the SDUHWKHSHWURFKHPLFDOSRWHQWLDORIGLIIHUHQWW\SHVRI 1DSKWKDVIRUD5H¿QHU\WKDWKDVIRXUXQLWVRIGLIIHUHQW ORZGHQVLW\RIDFLGVLWHVDQGORZFRQWHQWRIUDUHHDUWK )&&8WHFKQRORJ\SURFHVVLQJGLIIHUHQWW\SHRIIHHG- HOHPHQWV5HJDUGLQJWKHFDWDO\WLFFUDFNLQJRI1DSKWKD VWRFNVDVIROORZVRQH0RGHO,9SURFHVVLQJ9DFXXP IURP)&&WKHZRUNGRQHE\+ROODGHU0$et al. (2002) *DV2LO 9*2 WZR8QLYHUVDO2LO3URGXFW8QLWV 823 FRQFOXGHVWKDWWKHRQO\VLJQL¿FDQWO\UHDFWLYHFRPSRXQGV DQGRQH2UWKRÀRZ8QLWSURFHVVLQJDPL[WXUHRI5HVL- LQ1DSKWKDIURP)&&DUHWKHROH¿QVZLWKPRUHWKDQ GXHVZLWK9*2DQG9DFXXP%RWWRPVZLWKRUZLWKRXW DWRPVRIFDUERQ,WLVDOVRGHPRQVWUDWHGWKDWELPROHFXODU IXUWKHUK\GURWUHDWPHQW UHDFWLRQVRIK\GURJHQWUDQVIHURFFXURQWKHFDWDO\VWDQG QRWRQWKH$GGLWLYH%\FRQWUDVWWKH$GGLWLYHZLWKVPDOOHU pore size promotes monomolecular reactions only to 7KHSURGXFWVRILQWHUHVWDUH(WKDQH(WK\OHQH3URS\ lene, i-Butane, Toluene and Xylene. Ethane is pyrolized SURGXFHOLJKWROH¿QV,WLVLPSRUWDQWWRXQGHUVWDQGKRZ 1DSKWKDFRPSRVLWLRQFDQDIIHFWSURGXFWVHOHFWLYLW\GX DQGFRQYHUWHGLQ(WK\OHQH7KH3URSDQH3URS\OHQHFX UUHQWLVVHSDUDWHGLQDVSOLWWHUDQGWKH3URS\OHQHLVVHQW ULQJFDWDO\WLFFUDFNLQJUHDFWLRQV7KHUHIRUHWKHDSSURDFK WRDSRO\PHUL]DWLRQSODQWZKLOHL%XWDQHLVUHTXLUHGDV LQWKLVVWXG\LVWRDQDO\]HWKHEHKDYLRURIHDFKW\SHRI DIHHGVWRFNIRUDON\ODWLRQ7KHFXUUHQWVFKHPHRIWKH hydrocarbon in detail. 5H¿QHU\LQFOXGHVWKHSURGXFWLRQRI0RWRU*DVROLQHDQG WKHUHIRUHWKHUHDUHQRIDFLOLWLHVWRVHSDUDWHWKH$URPDWLF IUDFWLRQ7KLVIUDFWLRQFDQEHVHSDUDWHGE\DSSO\LQJWKH processSDWHQWHGE\7LPNHQ+.& $QJHYLQH EXPERIMENTAL DEVELOPMENT 3- FRQVLVWLQJRI1DSKWKDK\GURWUHDWPHQWWR HOLPLQDWHVXOIXUIROORZHGE\WKHUHFRYHU\RIWKH$UR- PDWLFIUDFWLRQE\GLVWLOODWLRQ7KLVSURFHVVFRSURGXFHV 7KHLQGXVWULDO1DSKWKDVVHOHFWHGIRUWKLVVWXG\ZHUH 1DSKWKDVZLWKORZVXOIXUDQGUHODWLYHO\KLJKRFWDQH 3DUDI¿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used in all cases. et al. 2008). Based on their decreasing reactivity, these UHDFWLRQVDUHXVXDOO\JURXSHGDVIROORZV :DQJ/ <DQJ% :DQJ= $GGLWLRQDOO\LQWKHFDVHRI1DSKWKDWKHHIIHFWRI WKH3URS\OHQH3URPRWHU$GGLWLYH=60ZDVHYDOXD 2OH¿QV!$URPDWLF6LGH&KDLQV!L3DUDI¿QHV! WHGE\XVLQJDFRQFHQWUDWLRQRIDQGIRU5HVLGXHV 1DSKWKHQHV!Q3DUDI¿QHV!!$URPDWLF5LQJV DQG CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING Table 1. Quality of Residues and Naphthas to Pilot Plant Experimental Equipment GHVFULEHGE\$670'WKDWVHSDUDWHVDOOFRP- Pilot Plant.$OOIHHGVWRFNVZHUHHYDOXDWHGLQD SRXQGVOHVVWKDQRUHTXDOWR&ZLWKDUHSHDWDELOLW\ continuous Davison Circulating Riser (DCR). The unit RIZWRQDYHUDJHIRUHDFKFRPSRXQGUHSRUWHG RSHUDWHVZLWKNJRIFDWDO\VWWKDWFRQWLQXRXVO\UHDFWV E\WKHODERUDWRU\&RNH\LHOGZDVFDOFXODWHGIURP DQGUHJHQHUDWHVLWVHOI7KHRSHUDWLRQZDVFDUULHGRXW WKHFRPSRVLWLRQRIWKHÀXHJDVDQDO\]HGIROORZLQJ PDLQWDLQLQJDQLVRWKHUPDOSUR¿OHDORQJWKH5LVHUZLWK WKH$670'ZLWKDUHSHDWDELOLW\UHSRUWHGE\ DIHHGÀRZRINJK WKHODERUDWRU\RIYRORQDYHUDJHIRUHDFK reported compound. Gas Chromatograph.*DVHVZHUHDQDO\]HGLQDQ $1*,/(17PRGHOFKURPDWRJUDSKIROORZLQJ WKHVWDQGDUG823ZLWKDUHSHDWDELOLW\UHSRUWHG RESULTS E\WKHODERUDWRU\RIYRORQDYHUDJHIRU HDFKFRPSRXQG7KHOLTXLGSURGXFWZDVFKDUDFWHUL ]HGXVLQJWZRPHWKRGVWKH¿UVWPHWKRGFRQVLVWHGRI 7KHUHVXOWVGLVFXVVHGLQWKLVVWXG\DUH3,$12VRI WKHVLPXODWHGGLVWLOODWLRQGHVFULEHGLQ$670' SLORWSODQWIHHGVWRFNV )&&DQG6WUDLJKWUXQ1DSK- ZKHUHWKHSURGXFWZDVVHSDUDWHGLQWRWKUHHIUDFWLRQV WKDV &KURPDWRJUDSKLFDQG3,$12UHSRUWVIURPWKH DVIROORZV1DSKWKD ) /&2 ) DQG SLORWSODQWHIÀXHQWV7KHVHUHVXOWVDUHQRUPDOL]HG 6OXUU\ !) WKHVHFRQGLV3,$12 3DUDI¿QHV through a mass balance and reported in Table 2 as L3DUDI¿QHV$URPDWLFV1DSKWKHQHVDQG2OH¿QV DV reactor products. CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 MARIA-ELIZABETH GÓMEZ et al. 7DEOH3LORW3ODQW<LHOGV ZW IURP&DWDO\WLF&UDFNLQJRI1DSKWKDVDQG5HVLGXHV with and without ZSM-5 Additive. 148 CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING 7DEOHVKRZVWKHPRVWUHSUHVHQWDWLYHUHVXOWVRI Even though nC3 is not directly a petrochemical WKLVVWXG\7KLVSURYLGHVDPRUHJHQHUDORXWORRNRIWKH
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