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 VWRFNVDVIROORZV RQH0RGHO,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¿QLFDQG1DSKWKHQLF1DSKWKDVIURPDWPRVSKHULF GLVWLOODWLRQDQG1DSKWKDVIURPWKH)&&8V 7DEOH
$OO1DSKWKDVDQG5HVLGXHVIURPHDFK8QLWZHUH THEORETICAL FRAMEWORK HYDOXDWHGLQWKHSLORWSODQWLQDEURDGRSHUDWLQJZLQGRZ XVLQJGLIIHUHQW&2VHYHULWLHVZLWKLQWKHRSHUDWLQJUHV 7KHUHDFWLRQVRFFXUULQJLQWKHFUDFNLQJRI1DSKWKD WULFWLRQVRIWKHLQGXVWULDOSODQW5HDFWLRQWHPSHUDWXUH DUHOHVVFRPSOH[WKDQWKRVHLQYROYHGLQWKHFUDFNLQJ ZDV& ) IRU1DSKWKDVDQG& ) RIKHDY\RLO1HYHUWKHOHVVWKH\LQYROYHKXQGUHGVRI IRU5HVLGXHV$QLQGXVWULDOHTXLOLEULXPFDWDO\VWZDV FRPSRXQGVLQWHUDFWLQJLQWKRXVDQGVRIUHDFWLRQV 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*,/(17 PRGHOFKURPDWRJUDSKIROORZLQJ WKHVWDQGDUG823 ZLWKDUHSHDWDELOLW\UHSRUWHG RESULTS E\WKHODERUDWRU\RIYRORQDYHUDJHIRU HDFKFRPSRXQG7KHOLTXLGSURGXFWZDVFKDUDFWHUL ]HGXVLQJWZRPHWKRGV WKH¿UVWPHWKRGFRQVLVWHGRI 7KHUHVXOWVGLVFXVVHGLQWKLVVWXG\DUH3,$12VRI WKHVLPXODWHGGLVWLOODWLRQGHVFULEHGLQ$670' SLORWSODQWIHHGVWRFNV )&&DQG6WUDLJKWUXQ1DSK- ZKHUHWKHSURGXFWZDVVHSDUDWHGLQWRWKUHHIUDFWLRQV WKDV &KURPDWRJUDSKLFDQG3,$12UHSRUWVIURPWKH DVIROORZV 1DSKWKD ) /&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 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 SURGXFWIRUWKLVUH¿QHU\LWLVLPSRUWDQWWREHFRQVLGHUHG FKDQJHVLQVWUXFWXUDOFRPSRVLWLRQUHVXOWLQJIURPWKH ZKHQWKHREMHFWLYHRI)&&LVQ& VLQFHJUHDWHUQ& cracking reactions. SURGXFWLRQUHVXOWVLQLQFUHDVHGFRQJHVWLRQRIWKHFRP- pression and recovery zone by less-valuable products. LCO, Slurry, and Coke are also produced in the cata- O\WLFFUDFNLQJRI1DSKWKDLQ\LHOGVEHWZHHQDQG 7 7KLVXVXDOO\FRPHVIURPDURPDWLFGHK\GURJHQDWLRQDQG C/O= 18 6 C/O= 15 FRQGHQVDWLRQUHDFWLRQV 7DEOH 1DSKWKDVIURP)&& C/O= 11 5 SURGXFHDKLJKHU\LHOGRIWKHVHSURGXFWVZKLFKLQWXUQ C/O= 8 LVUHODWHGWRLWVJUHDWHU$URPDWLFFRQWHQW 4 C/O= 6 Paraffinic 3 )RUWKHFUDFNLQJRI5HVLGXHVWKHVXPRI/&2 2 6OXUU\DQG&RNH\LHOGVLVQHDUO\7KLVPHDQVWKDW n-Paraffin Yield, %wt WKHUHPDLQLQJFRUUHVSRQGVWRWKH&&IUDFWLRQ 1 DQDO\]HGLQGHWDLODWWKHWRSRI7DEOH 0 nC1 nC2 nC3 nC4 nC5 nC6 nC7 nC8 nC9n C10n C11n C12 Since these Naphthas are injected into the Riser bo- ttom in smaller proportions as compared to Residue, Table VKRZVWKHFRPSDULVRQRI5HDFWRU3URGXFW\LHOGVRI 1DSKWKDVDQG5HVLGXHVDWGLIIHUHQW&2VHYHULWLHV IRU 1DSKWKDVDQGIRU5HVLGXHVOLNHWKH,QGXVWULDO3ODQW ANALYSIS OF RESULTS 6LQFHWKHSRWHQWLDORISHWURFKHPLFDOSURGXFWVDUH ZLWKLQ1DSKWKD/3*DQGGU\JDVVWUHDPVWKHDQDO\VLV RIUHVXOWVIRFXVHVRQWKHGHWDLOHGVWXG\RIFRPSRXQGV &&ZKLFKDUHJURXSHGLQWKHIROORZLQJIDPLOLHV 3DUDI¿QHV2OH¿QV$URPDWLFVDQG1DSKWKHQHV Q3DUDI¿QHV Figure 1. Distribution profile of n-Paraffin Yields )LJXUHDVKRZVWKH\LHOGSUR¿OHRIQ3DUDI¿QHV REWDLQHGE\WKHFDWDO\WLFFUDFNLQJRI3DUDI¿QLF1DSK- CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 MARIA-ELIZABETH GÓMEZ et al. WLRQVZKHUH2OH¿QVVDWXUDWLRQLVRQHRIWKHPRVWOLNHO\ Craking Olefin to occur, considering that there is a high concentration RI2OH¿QVLQWKHVH1DSKWKDV 7DEOH =KDR +DUGLQJ 3(Olefins) + 3(Parafines) + )RUDOO1DSKWKDVWKHDSSOLFDWLRQRI$GGLWLYHLQFUHDVHG Q&\LHOGVE\ )LJXUHD DQGIRU5HVLGXHVE\ 7KHQ>&&@LQ1DSKWKDVIURP)&&GRQRWFUDFN )LJXUHD 1RHIIHFWRIWKH$GGLWLYHLVREVHUYHGRQ )LJXUHE WKHQQ&PXVWEHSURGXFHGIURPRWKHUUHDF- n[C5-C12] (Figures 2b and 3b). Figure 2. n-Paraffin Yields in Catalytic Cracking of Naphthas 4 4 3 C/O= 13 3 C/O= 13 C/O= 11 C/O= 11 C/O= 10 C/O= 10 2 C/O= 9 2 C/O= 9 C/O= 7 C/O= 7 C/O= 6 C/O= 6 nC3 Yield, %wt 1 1 C/O= 5 C/O= 5 n[C5-C12] Yield, %wt 0 0 Base 2% 4% 6% Base 2% 4% 6% Base 2% 4% 6% Base 2% 4% 6% Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Orthoflow UOPII Orthoflow UOPII Figure 3. n-Paraffin Yields in Catalytic Cracking of Residues 150 CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING L3DUDI¿QHV 1DSKWKDIURP0RG,9LVDVSHFLDOFDVHEHFDXVHXQOLNH 6HOHFWLYLW\RIL3DUDI¿QHVLQFDWDO\WLFFUDFNLQJRI others, this plant does not process Residues but Light 1DSKWKDVLVFOHDUO\GLUHFWHGWRZDUGL&DQGL&SUR- Gas Oil. GXFWLRQ )LJXUH 7KHVH\LHOGVSDUWLDOO\FRPHIURP FUDFNLQJRIL>&&@ZKLFKDUHUHGXFHGGXULQJWKH 7KHUHIRUHLQPRVWFDVHVLWVKRZVDQLQWHUPHGLDWHEH- SURFHVV )LJXUHE 1DSKWKHQLFDQG3DUDI¿QLF6WUDLJKW KDYLRUEHWZHHQ6WUDLJKW5XQ1DSKWKDVDQG1DSKWKDV 5XQ1DSKWKDVKDYHKLJKHUFRQWHQWRIL>&&@ IURP)&& DQGKLJKHUVHOHFWLYLW\WRZDUGL&WKDQ1DSKWKDVIURP )&& YV )LJXUHEDQG 7KH$GGLWLYHERRVWVL&\LHOGVZLWKLQSRLQWIRU DOO1DSKWKDV )LJXUHD DQGSRLQWVIRUFUDFNLQJ 7KHPRVWDEXQGDQWL3DUDI¿QLQWKHFDWDO\WLFFUDFNLQJ RI5HVLGXH )LJXUHD KRZHYHUWKHWRWDOFRQWHQWRI RI1DSKWKDVIURP)&&LVL& )LJXUHD UHDFKLQJYDOXHV L3DUDI¿QHVERWKLQ1DSKWKD 7DEOH DQG5HVLGXHV XSWRZW 7DEOH )LJXUHE GHFUHDVHV 10 9 8 C/O= 20 7 C/O= 15 C/O= 11 6 C/O= 8 5 C/O= 6 4 Ortho Pdt 3 2 i-Paraffin Yield, %wt 1 0 I-C4 I-C5 2 3 2 3 2 4 3 Mono Mono § Others methyl methyl methyl methyl methyl methyl methylmethyl Ethyl C5 C5 C6 C6 C7 C7 C7 C8+ C8+ Figure 4. Distribution profile of i-Paraffin Yield 12 C/O= 20 32 C/O= 20 30 C/O= 15 11 C/O= 15 28 10 C/O= 11 26 C/O= 11 C/O= 8 9 C/O= 8 24 C/O= 6 22 C/O= 6 8 FEEDS 20 FEEDS 7 18 6 16 14 5 12 4 10 8 iC4 Yield, %wt 3 6 2 i[C7-C12] Yield , %wt 4 1 2 0 0 ADDITIVE ADDITIVE No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Figure 5. i-Paraffin Yields in Catalytic Cracking of Naphthas CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 151 MARIA-ELIZABETH GÓMEZ et al. 4 14 13 3 C/O= 13 C/O= 13 12 C/O= 11 C/O= 11 C/O= 10 11 C/O= 10 2 C/O= 9 C/O= 9 10 C/O= 7 C/O= 7 C/O= 6 9 C/O= 6 iC4 Yield, %wt 1 C/O= 5 C/O= 5 i-Paraffin Yield, %wt 8 0 7 Base 2% 4% 6% Base 2% 4% 6% Base 2% 4% 6% Base 2% 4% 6% Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Orthoflow UOPII Orthoflow UOPII Figure 6. i-Paraffin Yields in Catalytic Cracking of Residues Q2OH¿QV 7KLVLVRQHRIWKHUHDVRQVZK\Q& \LHOGLQFUHDVHV ,QJHQHUDOWRWDOQ2OHILQVLQFUHDVHGXULQJFUD LQRQHSRLQWGXULQJWKHFDWDO\WLFFUDFNLQJRI1DSKWKDV cking and due to a higher severity in C/O (Table 2). IURP)&&H[FHSWLQ0RG,9ZKHQWKH$GGLWLYHLVXVHG (Figure 8). ,QWKLVJURXSQ& LVWKHSURGXFWRIKLJKHUVHOHFWL vity and sensitivity to changes in C/O severity (Figu- UH ,QFDWDO\WLFFUDFNLQJRI1DSKWKDIURP)&& 6WUDLJKW5XQ1DSKWKDVKDYHDOPRVWQLOFRQWHQWRI nC3= production increases in similar proportion to Q>&&@2OH¿QV+RZHYHUZLWKRXW$GGLWLYHWKHLU nC3= yields are similar to that produced by Naphthas WKHGHFUHDVHRIQ>&&@2OHILQVIURPWR IURP)&&7KHVH\LHOGVFRPHPDLQO\IURP1DSKWKHQHV )LJXUH 1RWLFHWKHGLUHFWFRUUHVSRQGHQFHEHWZHHQ FUDFNLQJFRQVLGHULQJWKHKLJKFRQWHQWRIWKHVHFRP- Q& RIKLJKHUVHYHULW\SRLQWV )LJXUHD DQGWKH SRXQGV LQWKHIHHGVWRFNV 7DEOH VWDUVRI)LJXUHEIRUWKHVH1DSKWKDV 7KH$GGLWLYHKDVQRHIIHFWRQ6WUDLJKW5XQ1DSKWKDV Q2OH¿QVDUHKLJKO\UHDFWLYHPROHFXOHVRQ=60 (Figure 8a) siQFHWKH\KDYHQR2OH¿QVDFWLQJDVQ& (Hollander et al. =KDR; 5REHULH7* SURPRWHUVRQWKH$GGLWLYH7KH2OH¿QVIRUPHGE\WKH et al., 2008). %XFKDQDQ-6 :DQJ* FUDFNLQJRI1DSKWKHQHVDUHQRWDEVRUEHGE\WKH$GGL 7 7 C/O= 12 6 C/O= 20 C/O= 11 6 C/O= 15 5 C/O= 10 C/O= 11 5 C/O= 8 4 C/O= 8 4 C/O= 6 C/O= 6 3 C/O= 8 Ortho Pdt 3 2 C/O= 5 n-Olefin Yield, %wt 2 1 n-Olefin Yield, %wt 1 0 C2=C3= 1- i- t- c- 1- t2- C2- 1- t3- c3- t2- c2- 0 C4= C4= C4= C4= C5= C5= C5= C6= C6= C6= C6= C6= C2=C3= 1- i- t- c- 1- t2- C2- 1- t3- c3- t2- c2- C4= C4= C4= C4= C5= C5= C5= C6= C6= C6= C6= C6= Figure 7. Distribution profile of n-Olefin Yields 152 CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING 10 C/O= 20 12 C/O= 15 11 C/O= 20 C/O= 11 9 10 C/O= 15 C/O= 8 C/O= 11 C/O= 6 9 C/O= 8 8 FEEDS 8 C/O= 6 7 FEEDS 7 6 5 6 4 3 nC3= Yield, %wt 5 2 1 4 0 ADDITIVE ADDITIVE No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes n[C5-C12]Olefins Yield, %wt No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Note: The total content of n-Olefin in Straight Run Naphtha is ZERO a. nC3= b. n[C5-C12]Olefins Figure 8. n-Olefin Yields in Catalytic Cracking of Naphthas WLYH7KLVPHDQVWKDWWKHLQGXVWULDOXVHRIWKH$GGLWLYH RI$GGLWLYH LQWKH&DWDO\VW7KLVPDWFKHVZLWKWKH LVQRWMXVWL¿HGZLWKWKLVW\SHRIIHHGVWRFN5HJDUGLQJ VHOHFWLYLW\VSHFL¿FDWLRQV JUHDWHUWKDQ JLYHQE\ 1DSKWKDVIURP)&&$GGLWLYHLQFUHDVHVQ& \LHOGV $GGLWLYH6XSSOLHUVLQWKHFUDFNLQJRIKHDY\IHHGVWRFNV by more than one point (Figure 8a). (Table 2). &RQFHUQLQJ&UDFNLQJRI5HVLGXHWKH$GGLWLYH $VIDUDV(WK\OHQH & DOO1DSKWKDVVKRZHGD LVPXFKPRUHVHOHFWLYHWRZDUGQ& DVFRPSDUHG VLPLODU\LHOGRIDQG5HVLGXHV )LJXUH WRFUDFNLQJRI1DSKWKDVLQFUHDVLQJ\LHOGE\XSWR 8QOLNHFUDFNLQJRI5HVLGXHVFUDFNLQJRI1DSKWKDLQ- SRLQWVLQ823,,FDVH )LJXUH D ZKHQXVLQJ creases yield to Ethylene upon increase in C/O severity. 11 5 10 C/O= 13 C/O= 13 9 4 C/O= 11 C/O= 11 8 C/O= 10 3 C/O= 10 C/O= 9 7 C/O= 9 C/O= 7 6 2 C/O= 7 C/O= 6 C/O= 6 5 C/O= 5 nC3= Yield, %wt 1 C/O= 5 4 n[C5-C12]Olefins Yield, %wt 3 0 Base 2% 4% 6% Base 2% 4% 6% Base 2% 4% 6% Base 2% 4% 6% Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Adit Orthoflow UOPII Orthoflow UOPII b. n[C5-C12]Olefins Figure 9. n-Olefin Yields in Catalytic Cracking of Residues CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 153 MARIA-ELIZABETH GÓMEZ et al. 4 C/O= 20 4 C/O= 15 C/O= 11 C/O= 13 C/O= 8 3 C/O= 6 3 C/O= 11 FEEDS C/O= 10 C/O= 9 2 2 C/O= 7 C/O= 6 C2= Yield,1 %wt C2= Yield, %wt 1 C/O= 5 0 0 Base 2% 4% 6% Base 2% 4% 6% ADDITIVE No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes Adit Adit Adit Adit Adit Adit Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Orthoflow UOPII )LJXUH& 7KH$GGLWLYHSURPRWHVWKH& \LHOGVIRUDOO1DSK- SURPRWHUVWKDWIDYRUSURSHU$GGLWLYHSHUIRUPDQFH WKDVSDUWLFXODUO\LQ1DSKWKDVIURP)&& )LJXUH (Hollander et al., 2002). )RU5HVLGXHVWKHHIIHFWRI$GGLWLYHVLVEHWWHUREVHUYHG LQ823,,ZKHUHDQLQFUHDVHRI$GGLWLYHUHVXOWVLQD $FFRUGLQJWR%XFKDQDQ-6 L2OH¿QVRQ VOLJKWOLQHDULQFUHDVHRI& 2WKHUSDSHUVRQ*DV2LO $GGLWLYHVH[KLELWWKHKLJKHVWUHDFWLRQUDWH7KH\FUDFN FUDFNLQJKDYHUHSRUWHGWKHVDPHWUHQGIRU& =KDR WRSURGXFHQ2OH¿QVRIORZPROHFXODUZHLJKW1DSKWKDV 5REHULH IURP)&&KDYHKLJKL2OH¿QFRQWHQW )LJXUH D FRQVHTXHQWO\WKH\KDYHKLJKQ& \LHOGVZLWK L2OH¿QV WKHXVHRIWKH$GGLWLYH )LJXUHD )RUFUDFNLQJRI L2OH¿QVDUHYHU\UHDFWLYHDQGDUHDOPRVWIXOO\ 5HVLGXHV )LJXUHE RQO\823,,WKDWKDVKLJKHU FRQVXPHGGXULQJFUDFNLQJUHDFWLRQVIURP WR Q& \LHOGVVKRZVDSURJUHVVLYHUHGXFWLRQLQL2OH¿QV )LJXUHD L2OH¿QVOLNHQ2OH¿QVDUHQ& \LHOGVDVWKHXVHRI$GGLWLYHLQFUHDVHV )LJXUH D 22 C/O= 20 8 20 C/O= 15 7 C/O= 13 18 C/O= 11 C/O= 11 16 C/O= 8 6 C/O= 6 C/O= 10 14 5 12 FEEDS C/O= 9 4 10 C/O= 7 8 3 C/O= 6 6 2 C/O= 5 4 i-Olefin Yield, %wt i-Olefin Yield, %wt 2 1 0 0 ADDITIVE Base 2% 4% 6% Base 2% 4% 6% No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes Adit Adit Adit Adit Adit Adit Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Orthoflow UOPII Figure 11. i-Olefin Yields in Catalytic Cracking of Naphthas and Residues 154 CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING NaphWKHQH2OH¿QV coPSRXQGVLQ1DSKWKDVDUHJHQHUDOO\WKHUHVXOWRI 1DSKWKHQH2OH¿QVFRQWHQWLVKLJKHULQ1DSKWKDV K\GURJHQWUDQVIHUUHDFWLRQVEHWZHHQ2OH¿QVDQG1DSK- IURP)&& H[FHSW0RG,9 WKDQLQ6WUDLJKW5XQ1DSK- WKHQHV :DQJet al.,:DQJ/ 4 6 C/O= 20 C/O= 15 C/O= 11 C/O= 13 5 C/O= 8 3 C/O= 11 C/O= 6 4 FEEDS C/O= 10 2 C/O= 9 3 C/O= 7 2 C/O= 6 1 C/O= 5 1 Naphthen-Olefin Yield, %wt 0 Naphthen-Olefin Yield, %wt 0 ADDITIVE Base 2% 4% 6% Base 2% 4% 6% No Yes No Yes No Yes No Yes No Yes No Yes No Yes No Yes Adit Adit Adit Adit Adit Adit Naphthenic Paraffinic ModIVDBP ModIV Liv UOPII Liv UOPII Pdt Ortho Pdt UOPI Liv Orthoflow UOPII a. Naphtha feedstock b. Residue feedstock Figure 12. Naphthen-Olefin Yields in Catalytic Cracking of Naphthas and Residues 9 3,0 C/O= 12 8 C/O= 19 2,5 C/O= 11 7 C/O= 16 C/O= 10 C/O= 8 6 C/O= 11 2,0 C/O= 9 C/O= 8 5 C/O= 6 C/O= 6 1,5 4 C/O= 5 UOPII Pdt 3 1,0 2 Aromatic Yield, %wt Aromatic Yield, %wt 0,5 1 0 0,0 BenceneToluene ethyl m p o 1methyl1methyl 1,3,5 1methyl 1,2,4 1,2,3 BenceneToluene ethyl m p o 1methyl 1methyl 1,3,5 1methyl 1,2,4 1,2,3 Bencene Xylene Xylene Xylene 3ethyl 4ethyl Trimethyl 2ethyl TrimethylTrimethyl Bencene Xylene Xylene Xylene 3ethyl 4ethyl Trimethyl 2ethyl TrimethylTrimethyl Benc Benc Benc Benc Benc Benc Benc Benc Benc Benc Benc Benc a. Cracking of UOPII Naphtha b. Cracking of UOPII Residue Figure 13. Distribution profile of Aromatic Yields CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 155 MARIA-ELIZABETH GÓMEZ et al. ,Q1DSKWKDVIURP)&&WRWDO7ROXHQHDQG;\OHQHV\LHOGV 7KH\LHOGVRI7ROXHQHDQG;\OHQHLQWKHFUDFNLQJRI are greater than in Straight Run Naphthas (Figure 14a 5HVLGXHVDUHWRRPXFKORZHUWKDQWKRVHIURPFUDFNLQJ and 14b). This is not due to higher selectivity but to the RI1DSKWKDV )LJXUH IDFWWKDW1DSKWKDVIURP)&&IHHGVWRFNVKDYHKLJKHU LQLWLDOFRQWHQWRIWKHVHFRPSRXQGVWKDQ6WUDLJKW5XQ 1DSKWKHQHV 1DSKWKDV7ROXHQHDQGP;\OHQH\LHOGVDUHVLJQL¿FDQWO\ DIIHFWHGE\&2VHYHULW\ $FFRUGLQJWR)LJXUH1DSKWKHQHVDUHDOZD\V reduced during cracking reactions (Table 2). Since Naphthenes are the main components in Straight Run 1DSKWKDV WKHLUUHDFWLYLW\LVKLJKHUEHFDXVHWKHUH LVQRFRPSHWLWLRQZLWK2OH¿QVIRUDFWLYHVLWHV 6WUDLJKW 5XQ1DSKWKDVGRQRWKDYH2OH¿QV 7KHLUUHDFWLYLW\LV evident in their sensitivity to C/O severity. %DVHGRQWKHDERYH1DSKWKHQHVEHFRPHLQGLUHFW3UR- S\OHQHSURPRWHUVLQWKHFUDFNLQJRI6WUDLJKW5XQ1DSKWKDV GXHWRWKHIDFWWKDWWKH\KDYHQR2OH¿QVDQGWKHUHIRUH WKH\DUHSURGXFHGE\FUDFNLQJRI1DSKWKHQHV 5 C/O= 13 4 C/O= 11 3 C/O= 10 C/O= 9 2 C/O= 7 C/O= 6 1 C/O= 5 0 Toluene Xylenes Toluene Xylenes Toluene and Xylenes Yield, %wt Orthoflow Base UOPII Base c. Toluene and Xylenes in Residues Figure 15. Naphthene Yields in Catalytic Cracking Figure 14. Aromatic Yields in Catalytic Cracking of Naphthas and Residues of Naphthas and Residues CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 PETROCHEMICAL PROMOTERS IN CATALYTIC CRACKING Due to their molecular size, Naphthenes cannot access Ɣ Straight Run Naphthas are highly selective to- WKH=60=HROLWH7KHUHIRUHWKHUHGXFWLRQREVHUYHG ZDUG3URSDQH7KH\LHOGVDUHDOPRVWGRXEOHZKHQ in Figure 15a can be attributed to additional reactions FRPSDUHGWR1DSKWKDIURP)&& YV 7KH RI1DSKWKHQHVZLWK2OH¿QVEHLQJWKHODWWHUSURPRWHG $GGLWLYHLQFUHDVHVE\DSSUR[LPDWHO\RQHSRLQWIRU E\=60 DOO1DSKWKDV3URSDQH\LHOGVDUHGLUHFWO\FRUUHODWHG ZLWKKLJKQ>&&@FRQWHQWVLQWKHVHIHHGVWRFNV RUZLWK1DSKWKHQHVDQGL3DUDI¿QHVDOVR LQKLJKFRQFHQWUDWLRQ DQGUHVSHFWLYHO\LQ CONCLUSIONS the cases studied). Ɣ CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009 MARIA-ELIZABETH GÓMEZ et al. REFERENCES RULHQWHGOXPSLQJFRPELQHGZLWK0RQWH&DUORInd. Eng. Chem. 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A: Gen., 7LPNHQ+.& $QJHYLQH3- 3URGXFWLRQRI %HQ]HQH7ROXHQHDQG;\OHQH %7; IURP)&&1DSKWKD United States Patent, Patent number: 1RY 823 5H¿QHU\*DV$QDO\VLVE\*DV&KURPD- tography. :DQJ/ :DQJ* :DQJ*DQJ;X&KXQPLQJ *DR-LQVHQ 6WXG\ RIFUDFNLQJ)&&QDSKWKDLQDVHFRQGDU\ULVHURIWKH)&& XQLWIRUPD[LPXPSURS\OHQHSURGXFWLRQFuel Processing Technology, 158 CT&F - Ciencia, Tecnología y Futuro - Vol. 3 Núm. 5 Dic. 2009