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PENEX PROCESSTECHNOLOGY
OVERVIEW
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PENEX Process Objectives
• Why PENEX???
• Conversion of normal paraffins to iso-paraffins
• Principal application of isomerization is the
conversion of normal C5 and C6 material
• Pentane (C5 ! "e#ane (C6 $somerization
provides hi%her octane (&'-) *+NC
components to the %asoline pool,
• enzene sat.ration reaction helps meet aromatic
concentration standards
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Component Ben!e! Oct"ne V"#es
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Process Bene$ts
• )//0 1enzene sat.ration
• "i%h 2ields
• 3o4 severity reactor operations
! +peratin% press.re (),5 %7cm'(%
! 3o4 8emperat.res (9 '/:°C
• E#cellent catalyst sta1ility
! ;p to )/-)' year catalyst lives
• Capa1le of processin% 4ide ran%e of feedstocs
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C%emistr&
• $somerization
• enzene <at.ration
• *in% +penin%• "ydrocracin%
• "eavies =ormation
Reactions take place over a dual function catalyst - Metal function (platinum)
- Acid function (chloride)
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Isomeri'"tion Re"ctions
C
Methylcyclopentane (MCP)
89.3 RON
96.0 RON
Cyclohexane (CH)
84 RON
84.0 RON
C-C-C-C-C
n-Pentane (nC5)
61.8 RON(RON
!opentane ("C5)
93 RON93.5 RON
C-C-C-CC
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Isomeri'"tion Re"ctions
C-C-C-C-C-Cn-hexane (nC6)
#4.8 RON
31.0 RON
#-Methylpentane (#MP)
$3.4 RONN
C-C-C-C-C
C
3-Methylpentane (3MP)
$4.5 RON
C-C-C-C-C
C
#%3-&"'ethlytane (#%3&M*)
104.3 RON
C-C-C-C
C
C
#%#-&"'ethyltane (#%#&M*)
91.8 RON
C-C-C-C
C
C
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Isomeri'"tion Re"ctions
• *e>.ires metal and acid f.nctions
• E>.ili1ri.m limited
• <li%htly e#othermic
• No hydro%en cons.med• $ncreases octane
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Ben'ene S"t#r"tion
• enzene sat.rates to cyclohe#ane
• Cyclohe#ane (C" in e>.ili1ri.m 4ithmethylcyclopentane (CP
• *e>.ires only metal f.nction
C
MCPentane
96.0 RON
Cyclohexane
84.0 RON
*en+ene
1#0.0 RON
100, 40-60,
3H# Pt
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Ben'ene S"t#r"tion
• $mmediate 4ith platin.m sites and presence of hydro%en
• No acid sites re>.ired• )//0 complete
• "i%hly e#othermic ('5# isomerization@ 5# hydrocracin%
• Cons.mes moles "' per mole of 1enzene
• *ed.ces octane ()'/ z &: C" A 6 CP• 3imit z in feed to B5 vol0
! B))C *# 1ed delta8 7 ) vol0 z
! B55C total delta8 7 reactor
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Rin) Openin) Re"ctions
• C" and CP open to C6 paraffins• Cyclohe#ane (C" in e>.ili1ri.m 4ith
methylcyclopentane (CP
C
MCPentane
96.0 RON
Cyclohexane
84.0 RON
*en+ene
1#0.0 RON
100, 40-60,
3H# Pt
C*C*C*C*C*
C30, 30,
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Rin) Openin) Re"ctions
• Competes for the platin.m sites
• oderately e#othermic
• '/-:/ 4t0 openin%
• Cons.mes ) moles "' per mole of rin% opened• *ed.ces octane
• $ncreases 4ith lead reactor temperat.re increase
• "i%her temperat.res favor CP
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H&!rocr"c+in)
• 3on%er chain molec.les 1rea to smaller ones
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H&!rocr"c+in)
• 8ri%%ered 1y hi%h reactor temperat.res and catalyst
acid sites• E#othermic• Cons.mes ) moles "' per mole of craced material
• C5 and C6paraffin hydrocracin% is minimal
• D1o.t 5/0 of CEF paraffins hydrocrac to C:and C paraffins• C5F yield loss
• Ca.sed 1yG
! "i%her CF in feed
! "i%her r# temperat.res p.shin% e>.ili1ri.m
! 8emperat.re e#c.rsion
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He"vies ,orm"tion
• CF =ormed in PENEX reactors d.e to Dlylation
• =ormation of CF A"ydrocracin% are sim.ltaneo.s,
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Isomeri'"tion C"t"&st
• H.al f.nction catalyst (metal7acid
! etal is platin.m ! Dcid is chloride
• etal impre%nated on a hi%h s.rface area al.mina-o#ide
• Dctive sites are 1o.nd al.mina-chloride
• Iray e#tr.date or %ray trilo1e e#tr.date
• H.al f.nction 1alance is maintained 1yG ! Perchloroethylene inJection
• <ensitive to contaminants and non-re%enera1le
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C"t"&st Promotor * C%ori!e
CC
C*C*
HH--CC**
C*C*
C*C*
C*C*C*C*
H.H.C/C/
C(C(
C/0 C(0 H.0 HCC/0 C(0 H.0 HC
• Contin.o.s chloride inJection re>.ired to maintain activity,
CC''ClCl
:: F 5" F 5"
'' --------K :"Cl F C--------K :"Cl F C
''""
66 @@ 8K)/58K)/5++CC
• "ydro%en and hydrocar1on can strip 1o.nd chlorides from thecatalyst if the partial press.re of chloride s.rro.ndin% the catalystis too lo4,
• 3o4 or loss of chloride inJection 4ill permanently deactivate thecatalyst,
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• <ensitivity of isomerisation catalyst to o#y%enates
(C+7C+'C+ F "C+ F "'' --------K C"--------K C":: F " F "''+ F "eat @ 8L '/:+ F "eat @ 8L '/:++CC
C+C+'' F :"' --------K C" F :"' --------K C":: F '" F '"''+ F "eat @ 8L )6+ F "eat @ 8L )6++CC
• <ide reactionsG +lefin hydro%enation@ C'F cracin%<ide reactionsG +lefin hydro%enation@ C'F cracin%
• +peratin% temperat.re G '/:+peratin% temperat.re G '/:++CC ! '5/ ! '5/ ++CC
• C+C+'' A moist.re removed 1y ae.p Ias Hriers,A moist.re removed 1y ae.p Ias Hriers,
)&
1ETH2N2TOR
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C/ * C( Isomeri'"tion Terms
• Prod.ct *atios@ 4t0 or mol0 ! iC57C5P L iC57(iC5FnC5 # )//0
! '@'H7C6P L '@'H7C6 Paraffins # )//0
! '@H7C6P L '@ H7C6 Paraffins # )//0
! C6 Paraffins L '@'H F '@H F P F CP F C" F nC6
• P$N (Paraffin $somerization N.m1er@ 4t0
! M (iC57C5P F '@'H7C6P F '@H7C6P
• =eed X-factor@ 4t0
! M (CP F C" F F CF
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i C 5 / C 5 P
iC4 / C4P
3.1P-41P56C(P
#-3 &M*C6P
.*. 71B 6 C(P
1#1 C 149 C 1$$ C
/
a 0 R x
/ e
a 1 R x
#04 C
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Oct"nes o8 E9#iibri#m 1i:t#res
2 o t a l C 5 - C
6
C 5 P a3 a4 4 " n!
C 6 P a 3 a 4 4 " n !
70
72
74
76
78
80
82
84
86
8890
100 150 200 250 300
2e'peate% C
R O N
302ºF 392ºF
/ a 0 R x
/ e a 1 R x
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Le"! "n! L") R: IC/ Pro!#ctR"tio
;<<44<
EOR
EOR
4/<.;<
SOR
SOR
==
;/
=.
Re"ctor O#tet Temper"t#re0 ,
I C / P r o ! # c t R " t i o E 9 # i i b r i # m
I C / 6 C /
P 2 R 2 , , I N S P R
O 7 > C T R 2 T I O 0
W t ?
,ee! 31inim#m5
116 C 16$ C #04 C
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PENEX PROCESS,LOW @
EA>IP1ENTS
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PENEX Process Objectives
• asic flo4 dia%ram
• =eed <ection• *eactor A E#chan%er section,
• <ta1ilizer
• Net Ias <cr.11er
• H$"
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B"sic ,o 7i")r"m
Pro!#ctSide DrawMPs, n-C6
Deisohexanier !D"#$
%o&&o's C7(, 'in n-C6
)*erheadC5+, DM%
Receiver
"so'era&e
Stabilizer
Reboiler
FreshS+en&
Cas&i.
/as&o Fe
Scrubber
MU Gas
Driers
Reactors
Liquid
Driers
Mae-+
#droen
ih&
a+h&ha
Surge
Drum
C2
C4
Steam
Heater
!" H!"
#) Penex
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,EE7 SECTION ,EE7 @ 12DE>P G2S7RIERS
'6
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,EE7 7RIERS
'
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12DE>P G2S 7RIERS
'&
RE2CTOR @ EXCH2NGER SECTION
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RE2CTOR @ EXCH2NGER SECTION
'
Steam
Heater
2o ta"l"+e
Reactors
C2C4
!" H!"
H7&RON :ROM M;<=P
; &RR
N;PH2H; :ROM :& =R
&R=M
L"#D L#G
S bii @ N G S bb
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St"bii'er @ Net G"s Scr#bber
/
o D"#
e.ei*er
o Fe /as
#eader
Cas&i.
o Fe /as
Coaes.er
S & a 9
i 0 i e
r
C
h i 0 0 e r
S.rer
P/ S&ri++er
7 I % i
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)
7IH
7IH
Receiver
1PSte"m
,romSt"biiser
Si!e*!r" to ,ee!7riers
)*erheadC5+, DM%
%o&&o's C7(, 'in n-C6
o&a "so'era&e
Side DrawMPs, n-C6
7e*Iso%e:"ni'er
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Isomeri'"tion Re"ctions
Step 1: Formation of Olen Intermediate
Step 2: Formation of Carbonium Ion
Step 3: Carbonium Ion Rearrangement
Step 4: Formation of Isoolen intermediar!
Step ": #######
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IN7I2N G2SOLINE SPECI,IC2TIONS
Chaacte"!t"c! =n"t *- *-
<.lph.r@ 8otal@a#
PP 5// )5/
3ead Content(asP1@ a#
%7l /,/) /,//5
enzene@ Content 0 Ool.me 5 )
*esearch +ctaneN.m1er
&& )