US 20050082201A1

( 19 ) United Sta tes

( 12) Pa tent Applica tion Publica tion ( 10) Pub. N o. : US 2005/ 0082201 A1
Groten et a l. ( 4 3 ) Pub. D a te: Apr. 21, 2005
( 54 )
( 7 5)
( 7 3 )
( 21)
( 22)
( 6 3 )
PROCESS FOR THE PROD UCTION OF LOW
BEN ZEN E GASOLIN E
Inv entors : Willibrord A. Groten, Hous ton, TX
( US) ; K erry L. Rock , Hous ton, TX
( Us )
Corres pondence Addres s :
K enneth H. Johns on
P. O. Box 6 3 07 08
Hous ton, TX 7 7 26 3 ( US)
As s ig nee: CATALYTIC D ISTILLATION TECH
N OLOGIES
Appl. N o. : 10/ 9 83 , 56 2
Filed: N ov . 8, 2004
Rela ted US Applica tion D a ta
Continua tion of a pplica tion N o. 10/ 3 53 , 3 3 1, ? led on
Ja n. 29 , 2003 , noW Pa t. N o. 6 , 855, 853 .
( 6 0) Prov is iona l a pplica tion N o. 6 0/ 4 11, 810, ? led on Sep.
18, 2002.
Publica tion Cla s s i? ca tion
( 51) Int. Cl? . . . . . . . . . . . . . . . . . . . . . . . . . . . C10G 4 5/ 02; C10G 6 7 / 02
( 52) U. S. c1. . . . . . . . . . . . . . . . . . . . . . . . . . . . 208/ 211; 208/ 212; 208/ 213
( 57 ) ABSTRACT
A proces s f or the production of 10W benzene content g a s o
line is dis clos ed Wherein a f ull boiling ra ng e na phtha is
f ra ctiona ted to produce a lig ht na phtha , a medium na phtha
a nd a hea v y na phtha . The benzene is conta ined in the
medium na phtha a nd this s trea m is s ubj ected to hy drog ena
tion to conv ert the benzene to cy cloheXa ne Which ma y be
is omerized to improv e the octa ne. The v a lua ble ole? ns a re
remov ed in the lig ht na phtha a nd the v a lua ble hea v ier
a roma tics ( toluene a nd Xy lenes ) a re remov ed in the hea v y
na phtha . In a pref erred embodiment a ll of the rea ctions a re
ca rried out in dis tilla tion column rea ctors .
Pa tent Applica tion Publica tion Apr. 21, 2005 Sheet 1 0f 2 US 2005/ 0082201 A1
Pa tent Applica tion Publica tion Apr. 21, 2005 Sheet 2 0f 2 US 2005/ 0082201 A1
4 03
I! ! ! >
4 01
FIG. 2
US 2005/ 0082201 A1
PROCESS FOR THE PROD UCTION OF LOW
BEN ZEN E GASOLIN E
BACK GROUN D OF THE IN VEN TION
[ 0001] 1. Field of the Inv ention
[ 0002] The pres ent inv ention rela tes to a proces s f or the
production of loW benZene content g a s oline. More pa rticu
la rly the inv ention rela tes to a proces s Wherein a f ull boiling
ra ng e na phtha is f ra ctiona ted to s epa ra te out a lig ht na phtha
f ra ction, a medium na phtha f ra ction conta ining the benZene
a nd a hea v y na phtha . More pa rticula rly the inv ention rela tes
to a proces s Wherein the medium na phtha is hy drog ena ted to
conv ert the benZene to cy clohexa ne.
[ 0003 ] 2. Rela ted Inf orma tion
[ 0004 ] Petroleum dis tilla te s trea ms conta in a v a riety of
org a nic chemica l components . Genera lly the s trea ms a re
de? ned by their boiling ra ng e Which determines the com
pos ition. The proces s ing of the s trea ms a ls o a f f ects the
compos ition. For ins ta nce, products f rom either ca ta ly tic
cra ck ing or therma l cra ck ing proces s es conta in hig h con
centra tions of ole? nic ma teria ls a s Well a s s a tura ted
( a lk a nes ) ma teria ls , a roma tic compounds a nd poly uns a tu
ra ted ma teria ls ( diole? ns ) . Additiona lly , thes e components
ma y be a ny of the v a rious is omers of the compounds .
[ 0005] The compos ition of untrea ted na phtha a s it comes
f rom the crude s till, or s tra ig ht run na phtha , is prima rily
in? uenced by the crude s ource. N a phtha s f rom pa ra f ? nic
crude s ources ha v e more s a tura ted s tra ig ht cha in or cy clic
compounds . As a g enera l rule mos t of the s Weet ( loW
s ulf ur) crudes a nd na phtha s a re pa ra f f inic. The na phthenic
crudes conta in more uns a tura tes a nd cy clic a nd poly cy lic
compounds . The hig her s ulf ur content crudes tend to be
na phthenic. Trea tment of the dif f erent s tra ig ht run na phtha s
ma y be s lig htly dif f erent depending upon their compos ition
due to crude s ource.
[ 0006 ] Ref ormed na phtha or ref orma te g enera lly req uires
no f urther trea tment except perha ps dis tilla tion or s olv ent
extra ction f or v a lua ble a roma tic product remov a l. Ref ormed
na phtha s ha v e es s entia lly no s ulf ur conta mina nts due to the
s ev erity of their pretrea tment f or the proces s a nd the proces s
its elf .
[ 0007 ] Cra ck ed na phtha a s it comes f rom the ca ta ly tic
cra ck er ha s a rela tiv ely hig h octa ne number a s a res ult of the
ole? nic a nd a roma tic compounds conta ined therein. In s ome
ca s es this f ra ction ma y contribute a s much a s ha lf of the
g a s oline in the re? nery pool tog ether With a s ig ni? ca nt
portion of the octa ne.
[ 0008] Ca ta ly tica lly cra ck ed na phtha g a s oline boiling
ra ng e ma teria l currently f orms a s ig ni? ca nt pa rt ( - 1/ 3 ) of the
g a s oline product pool in the United Sta tes a nd it prov ides the
la rg es t portion of the s ulf ur. The s ulf ur impurities ma y
req uire remov a l, us ua lly by hy drotrea ting , in order to com
ply With product s peci? ca tions or to ens ure complia nce With
env ironmenta l reg ula tions . Some us ers req uire the s ulf ur of
the ? na l product to be beloW 50 Wppm. In a ddition the EPA
req uires tha t the benZene content of the g a s oline be loW, i. e. ,
1 v ol. %.
[ 0009 ] The mos t common method of remov a l of the s ulf ur
compounds is by hy drodes ulf uriZa tion ( HD S) in Which the
petroleum dis tilla te is pa s s ed ov er a s olid pa rticula te ca ta ly s t
Apr. 21, 2005
compris ing a hy drog ena tion meta l s upported on a n a lumina
ba s e. Additiona lly copious q ua ntities of hy drog en a re
included in the f eed. The f olloWing eq ua tions illus tra te the
rea ctions in a ty pica l HD S unit:
[ 0010] Ty pica l opera ting conditions f or the HD S rea ctions
a re:
Tempera ture, F. 6 00- 7 80
Pres s ure, ps ig 6 00- 3 000
H2 recy cle ra te, SCF/ bbl 1500- 3 000
Fres h H2 ma k eup, SCF/ bbl 7 00- 1000
[ 0011] Af ter the hy drotrea ting is complete, the product
ma y be f ra ctiona ted or s imply ? a s hed to relea s e the hy dro
g en s ul? de a nd collect the noW des ulf uriZed na phtha . The
los s of ole? ns by incidenta l hy drog ena tion is detrimenta l by
the reduction of the octa ne ra ting of the na phtha a nd the
reduction in the pool of ole? ns f or other us es .
[ 0012] Genera lly re? ners tend to prev ent benZene f rom
entering the g a s oline blending s tock . For exa mple a s men
tioned a bov e the cra ck ed na phtha s ma y be s ubj ected to
a roma tic remov a l by s olv ent extra ction. This , hoWev er,
remov es a ll a roma tic ma teria l not j us t the benZene. One
method of prev enting the introduction of benZene into the
g a s oline pool is to remov e the benZene precurs or ( is ohex
a ne) f rom the cha rg e to the ca ta ly tic ref orming units . This
does not s olv e the problem of s trea ms Which conta in ben
Zene a s Well a s hea v ier a roma tic compounds s uch a s toluene
a nd xy lenes . The hea v ier a roma tics contribute g rea tly to the
octa ne pool a nd to da te ha v e not been f ound to be detri
menta l to the env ironment.
[ 0013 ] US. Pa t. N o. 5, 7 7 3 4 , 6 7 0 dis clos es a proces s f or the
hy drog ena tion of a roma tics in a petroleum s trea m. HoWev er,
lik e s olv ent extra ction, the proces s is not s electiv e to only
the benZene. US. Pa t. N o. 5, 856 , 6 02, dis clos es the hy dro
g ena tion of a roma tics in a hy droca rbon s trea m utiliZing a
dis tilla tion column rea ctor Wherein the pla cement of the
ca ta ly s t bed a nd opera tion of the dis tilla tion column controls
Which a roma tic is reta ined in the ca ta ly s t bed f or hy drog e
na tion. US. Pa t. N o. 6 , 187 , 9 80 B1 dis clos es a proces s f or
the hy drog ena tion of benZene to cy clohexa ne in a dis tilla tion
column rea ctor Wherein es s entia lly pure benZene is us ed a s
the f eed to the rea ctor.
[ 0014 ] In a ddition to s upply ing hig h octa ne blending com
ponents the cra ck ed na phtha s a re of ten us ed a s s ources of
ole? ns in other proces s es s uch a s etheri? ca tion. The condi
tions of hy drotrea ting of the na phtha f ra ction to remov e
s ulf ur Will a ls o s a tura te s ome of the ole? nic compounds in
the f ra ction reducing the octa ne a nd ca us ing a los s of s ource
ole? ns .
[ 0015] Va rious propos a ls ha v e been ma de f or remov ing
s ulf ur While reta ining the more des ira ble ole? ns . Since the
ole? ns in the cra ck ed na phtha a re ma inly in the loW boiling
f ra ction of thes e na phtha s a nd the s ulf ur conta ining impu
rities tend to be concentra ted in the hig h boiling f ra ction the
US 2005/ 0082201 A1
mos t common s olution ha s been pref ra ctiona tion prior to
hy drotrea ting . The pref ra ctiona tion produces a lig ht boiling
ra ng e na phtha Which boils in the ra ng e of C5 to a bout 250
F. a nd a hea v y boiling ra ng e na phtha Which boils in the
ra ng e of f rom a bout 250- 4 50 F.
[ 0016 ] The predomina nt lig ht or loWer boiling s ulf ur com
pounds a re merca pta ns While the hea v ier or hig her boiling
compounds a re thiophenes a nd other heterocy clic com
pounds . The s epa ra tion by f ra ctiona tion a lone Will not
remov e the merca pta ns . In the pa s t the merca pta ns ha v e
been remov ed by oXida tiv e proces s es inv olv ing ca us tic
Wa s hing . A combina tion oXida tiv e remov a l of the merca p
ta ns f olloWed by f ra ctiona tion a nd hy drotrea ting of the
hea v ier f ra ction is dis clos ed in US. Pa t. N o. 5, 3 20, 7 4 2. In
the oXida tiv e remov a l of the merca pta ns the merca pta ns a re
conv erted to the corres ponding dis ul? des .
[ 0017 ] US. Pa t. N o. 5, 510, 56 8 dis clos es a proces s in
Which na phtha is f ed to a dis tilla tion column rea ctor Which
a cts a s a depenta niZer or deheXa niZer With the lig hter ma te
ria l conta ining mos t of the ole? ns a nd merca pta ns being
boiled up into a dis tilla tion rea ction Zone Where the mer
ca pta ns a re rea cted With diole? ns to f orm s ul? des Which a re
remov ed in the bottoms a long With a ny hig her boiling s ulf ur
compounds .
SUMMARY OF THE IN VEN TION
[ 0018] Brie? y , the pres ent inv ention is a proces s f or the
production of loW benZene content g a s oline compris ing
f ra ctiona ting a f ull boiling ra ng e na phtha to produce a lig ht
na phtha conta ining ole? ns , a medium na phtha conta ining
benZene a nd a hea v y na phtha conta ining toluene a nd Xy lenes
a nd hy drog ena ting s a id medium na phtha to conv ert the
benZene to cy cloheXa ne. The cy cloheXa ne ma y be is omer
iZed to improv e the octa ne. Pref era bly a ll of the rea ctions a re
ca rried out under conditions of ca ta ly tic dis tilla tion.
[ 0019 ] As us ed herein the term ca ta ly tic dis tilla tion
mea ns a rea ction ca rried out With a ca ta ly s t s uch tha t
rea ction a nd dis tilla tion a re g oing on concurrently . In a
pref erred embodiment the ca ta ly s t is prepa red a s a dis tilla
tion s tructure a nd s erv es a s both the ca ta ly s t a nd dis tilla tion
s tructure.
BRIEF D ESCRIPTION OF THE D RAWIN G
[ 0020] FIG. 1 is a How dia g ra m in s chema tic f orm of one
embodiment of the pres ent inv ention.
[ 0021] FIG. 2 is a How dia g ra m in s chema tic f orm- of a
s econd embodiment of the pres ent inv ention.
D ETAILED D ESCRIPTION OF THE
IN VEN TION
[ 0022] The f eed to the proces s compris es a benZene
conta ining petroleum f ra ction Which boils in the g a s oline
boiling ra ng e ( C5 to 4 50 F. or f ull boiling ra ng e na phtha ) .
The f ra ction ca n be f rom a ca ta ly tic ref orming unit or f rom
a ? uid ca ta ly tic cra ck ing unit. Genera lly the proces s is us ef ul
on the na phtha boiling ra ng e ma teria l f rom ca ta ly tic cra ck er
products beca us e they conta in the des ired ole? ns a nd
hea v ier a roma tic compounds a nd the unWa nted benZene. In
a ddition the cra ck ed na phtha s a ls o conta in unWa nted s ulf ur
compounds Which a re remov ed in one embodiment of the
Apr. 21, 2005
inv ention. Stra ig ht run na phtha s ha v e v ery little ole? nic
ma teria l, a nd unles s the crude s ource is s our , v ery little
s ulf ur.
[ 0023 ] Both f ull boiling ra ng e ref ormed na phtha a nd f ull
boiling ra ng e cra ck ed na phtha ha v e s ig ni? ca nt q ua ntities of
the hea v ier a roma tics .
[ 0024 ] The s ulf ur content of the ca ta ly tica lly cra ck ed
f ra ctions Will depend upon the s ulf ur content of the f eed to
the cra ck er a s Well a s the boiling ra ng e of the s elected
f ra ction us ed a s f eed to the proces s . Lig hter f ra ctions Will
ha v e loWer s ulf ur contents tha n hig her boiling f ra ctions . The
f ront end of the na phtha conta ins mos t of the hig h octa ne
ole? ns but rela tiv ely little of the s ulf ur. The s ulf ur compo
nents in the f ront end a re ma inly merca pta ns a nd ty pica l of
thos e compounds a re: methy l merca pta n ( b. p. 4 3 F. ) , ethy l
merca pta n ( b. p. 9 9 F. ) , n- propy l merca pta n ( b. p. 154 F. ) ,
is o- propy l merca pta n ( b. p. 13 5- 14 0 F. ) , is o- buty l merca p
ta n ( b . p. 19 0 F. ) , tert- buty l merca pta n ( b . p. 14 7 F. ) , n- buty l
merca pta n ( b. p. 208 F. ) , s ec- buty l merca pta n ( b. p. 203 F. ) ,
is o- a my l merca pta n ( b. p. 250 F. ) , n- a my l merca pta n ( b. p.
259 F. ) , a - methy lbuty l merca pta n ( b. p. 23 4 F. ) , a - ethy l
propy l merca pta n ( b. p. 29 3 F. ) , n- heXy l merca pta n ( b. p.
3 04 F. ) , 2- merca pto heXa ne ( b. p. 284 F. ) , a nd 3 - merca pto
heXa ne ( b . p. 13 5 Ty pica l s ulf ur compounds f ound in the
hea v ier boiling f ra ction include the hea v ier merca pta ns ,
thiophenes s ul? des a nd dis ul? des .
[ 0025] The rea ction of org a nic s ulf ur compounds in a
re? nery s trea m With hy drog en ov er a ca ta ly s t to f orm HZS is
ty pica lly ca lled hy drodes ulf uriZa tion. Hy drotrea ting is a
broa der term Which includes s a tura tion of ole? ns a nd a ro
ma tics a nd the rea ction of org a nic nitrog en compounds to
f orm a mmonia . HoWev er hy drodes ulf uriZa tion is included
a nd is s ometimes s imply ref erred to a s hy drotrea ting .
[ 0026 ] The loWer boiling portion of the na phtha Which
conta ins mos t of the ole? ns is theref ore not s ubj ected to
hy drodes ulf uriZa tion ca ta ly s t but to a les s s ev ere trea tment
Wherein the merca pta ns conta ined therein a re rea cted With
diole? ns conta ined therein to f orm s ul? des ( thioetheri? ca
tion) Which a re hig her boiling a nd ca n be remov ed With the
hea v ier na phtha . The thioetheri? ca tion rea ctor ca n be either
bef ore or a f ter a ca ta ly tic dis tilla tion hy drodes ulf uriZa tion
rea ctor s o long a s the hy drodes ulf uriZa tion occurs in the
s tripping s ection of the ca ta ly tic dis tilla tion hy drodes ulf ur
iZa tion rea ctor s uch tha t the loWer boiling point ma teria ls a re
not conta cted With the hy drodes ulf uriZa tion ca ta ly s t.
[ 0027 ] Thioetheri? ca tion Ca ta ly s ts
[ 0028] A s uita ble ca ta ly s t f or the thioetheri? ca tion rea c
tion is 0. 3 4 Wt. % Pd on 7 to 14 mes h Al2O3 ( a lumina )
s pheres , s upplied by Siid- Chemie des ig na ted a s G- 6 8C.
Ty pica l phy s ica l a nd chemica l properties of the ca ta ly s t a s
prov ided by the ma nuf a cturer a re a s f olloWs :
TABLE I
D es ig na tion G- 6 8C
Form Sphere
N omina l s ize 7 x 14 mes h
Pd. Wt % 0. 3 ( 0. 27 - 0. 3 3 )
Support Hig h purity a lumina
[ 0029 ] The ca ta ly s t is believ ed to be the hy dride of pa l
la dium Which is produced during opera tion. The hy drog en
US 2005/ 0082201 A1
ra te to the rea ctor mus t be s uf f icient to ma inta in the ca ta ly s t
in the a ctiv e f orm beca us e hy drog en is los t f rom the ca ta ly s t
by hy drog ena tion, but k ept below tha t Which Would ca us e
? ooding of the column Which is unders tood to be the
ef f ectua ting a mount of hy drog en a s tha t term is us ed
herein. Genera lly the mole ra tio of hy drog en to diole? ns a nd
a cety lenes in the f eed is a t lea s t 1. 0 to 1. 0 a nd pref era bly 2. 0
to 1. 0.
[ 003 0] The thioetheri? ca tion ca ta ly s t a ls o ca ta ly Zes the
s electiv e hy drog ena tion of poly ole? ns conta ined Within the
lig ht cra ck ed na phtha a nd to a les s er deg ree the is omeriZa
tion of s ome of the mono- ole? ns . Genera lly the rela tiv e ra tes
of rea ction f or v a rious compounds a re in the order of f rom
f a s ter to s loWer:
[ 003 1] ( 1) rea ction of diole? ns With merca pta ns
[ 003 2] ( 2) hy drog ena tion of diole? ns
[ 003 3 ] ( 3 ) is omeriZa tion of the mono- ole? ns
[ 003 4 ] ( 4 ) hy drog ena tion of the mono- ole? ns .
[ 003 5] The rea ction of interes t is the rea ction of the
merca pta ns With diole? ns . In the pres ence of the ca ta ly s t the
merca pta ns Will a ls o rea ct With mono- ole? ns . HoWev er,
there is a n exces s of diole? ns to merca pta ns in the lig ht
cra ck ed na phtha f eed a nd the merca pta ns pref erentia lly rea ct
With them bef ore rea cting With the mono- ole? ns . The eq ua
tion of interes t Which des cribes the rea ction is :
- - - - - >
P
[ 003 6 ] This ma y be compa red to the HD S rea ction
des cribed beloW Which cons umes hy drog en. The only
hy drog en cons umed in the remov a l of the merca pta ns in the
pres ent inv ention is tha t neces s a ry to k eep the ca ta ly s t in the
reduced hy dride s ta te. If there is concurrent hy drog ena tion
of the dienes , then hy drog en Will be cons umed in tha t
rea ction.
[ 003 7 ] HD S a nd Hy drog ena tion Ca ta ly s t
[ 003 8] A pref era ble ca ta ly s t f or the hy drog ena tion of
benZene a nd the des tructiv e hy drog ena tion of the s ulf ur
compounds ( hy drodes ulf uriZa tion) is 58 Wt % N i on 8 to 14
mes h a lumina s pheres , s upplied by Ca lcica t, des ig na ted a s
E4 7 5- SR. Ty pica l phy s ica l a nd chemica l properties of the
ca ta ly s t a s prov ided by the ma nuf a cturer a re a s f olloWs :
TABLE II
D es ig na tion E- 4 7 5- SR
Form Spheres
N omina l s ize 8 x 14 Mes h
N i Wt % 54
Support Alumina
[ 003 9 ] Ca ta ly s ts Which a re us ef ul f or either the hy drog e
na tion of benZene or the hy drodes ulf uriZa tion rea ction
Apr. 21, 2005
include Group VIII meta ls s uch a s coba lt, nick el, pa lla dium,
a lone or in combina tion With other meta ls s uch a s moly b
denum or tung s ten on a s uita ble s upport Which ma y be
a lumina , s ilica - a lumina , tita nia - Zirconia or the lik e. N or
ma lly the meta ls a re prov ided a s the oxides of the meta ls
s upported on extruda tes or s pheres a nd a s s uch a re not
g enera lly us ef ul a s dis tilla tion s tructures .
[ 004 0] The ca ta ly s ts ma y a dditiona lly conta in components
f rom Group V a nd VIB meta ls of the Periodic Ta ble or
mixtures thereof . The us e of the dis tilla tion s y s tem reduces
the dea ctiv a tion a nd prov ides f or long er runs tha n the ? xed
bed hy drog ena tion units of the prior a rt. The Group VIII
meta l prov ides increa s ed ov era ll a v era g e a ctiv ity . Ca ta ly s ts
conta ining a Group VIB meta l s uch a s moly bdenum a nd a
Group VIII s uch a s coba lt or nick el a re pref erred. Ca ta ly s ts
s uita ble f or the hy drodes ulf uriZa tion rea ction include coba lt
moly bdenum, nick el- moly bdenum a nd nick el- tung s ten. The
meta ls a re g enera lly pres ent a s oxides s upported on a neutra l
ba s e s uch a s a lumina , s ilica - a lumina or the lik e. The meta ls
a re reduced to the s ul? de either in us e or prior to us e by
expos ure to s ulf ur compound conta ining s trea ms .
[ 004 1] The properties of a ty pica l hy drodes ulf uriZa tion
ca ta ly s t a re s hoWn in Ta ble I beloW.
TABLE III
Ma nuf a cturer Criterion Ca ta ly s t Co.
D es ig na tion C- 4 4 8
Form Tri- lobe Extruda te
N omina l s ize 1. 2 mm dia meter
Meta l, Wt. %
Coba lt 25%
Moly bdenum 520%
Support Alumina
[ 004 2] The ca ta ly s t ty pica lly is in the f orm of extruda tes
ha v ing a dia meter of 1/ s , 1/ 16 or 1/ 3 2 inches a nd a n UD of 1. 5
to 10. The ca ta ly s t a ls o ma y be in the f orm of s pheres ha v ing
the s a me dia meters . In their reg ula r f orm they f orm too
compa ct a ma s s a nd a re pref era bly prepa red in the f orm of
a ca ta ly tic dis tilla tion s tructure. The ca ta ly tic dis tilla tion
s tructure mus t be a ble to f unction a s ca ta ly s t a nd a s ma s s
tra ns f er medium.
[ 004 3 ]
[ 004 4 ] Ty pica lly is omeriZa tion ca ta ly s ts a re of the Freidel
Cra f ts chlorided a lumina ca ta ly s t ha v ing a Group VIII,
pa rticula rly pla tinum. Such ca ta ly s ts a re Well k noWn in the
a rt a nd a re dis cus s ed in US. Pa t. N o. 4 , 7 83 , 57 5 Which is
incorpora ted herein by ref erence.
[ 004 5] Ca ta ly tic D is tilla tion Structure
[ 004 6 ] When the ca ta ly s ts a re us ed Within a dis tilla tion
column rea ctor, they a re pref era bly prepa red in the f orm of
a ca ta ly tic dis tilla tion s tructure. The ca ta ly tic dis tilla tion
s tructure mus t be a ble to f unction a s ca ta ly s t a nd a s ma s s
tra ns f er medium. The ca ta ly s t mus t be s uita bly s upported
a nd s pa ced Within the column to a ct a s a ca ta ly tic dis tilla tion
s tructure. Ca ta ly tic dis tilla tion s tructures us ef ul f or this
purpos e a re dis clos ed in US. Pa t. N os . 4 , 7 3 1, 229 , 5, 07 3 ,
23 6 , 5, 4 3 1, 89 0 a nd 5, 26 6 , 54 6 Which a re incorpora ted by
ref erence.
[ 004 7 ] The mos t pref erred s tructure is tha t s hoWn in US.
Pa t. N o. 5, 7 3 0, 84 3 Which is incorpora ted by ref erence. As
Is omeriZa tion Ca ta ly s t
US 2005/ 0082201 A1
dis clos ed therein the s tructure compris es a rig id f ra me ma de
of tWo s ubs ta ntia lly v ertica l duplica te g rids s pa ced a pa rt a nd
held rig id by a plura lity of s ubs ta ntia lly horizonta l rig id
members a nd a plura lity of s ubs ta ntia lly horizonta l Wire
mes h tubes mounted to the g rids to f orm a plura lity of ? uid
pa thWa y s a mong the tubes . At lea s t a portion of the Wire
mes h tubes conta in a pa rticula te ca ta ly tic ma teria l. The
ca ta ly s t Within the tubes prov ides a rea ction Zone Where
ca ta ly tic rea ctions ma y occur a nd the Wire mes h prov ides
ma s s tra ns f er s urf a ces to ef f ect a f ra ctiona l dis tilla tion. The
s pa cing elements prov ide f or a v a ria tion of the ca ta ly s t
dens ity a nd loa ding a nd s tructura l integ rity .
[ 004 8] Proces s Conditions
[ 004 9 ] Conditions f or the hy drog ena tion of benZene to
cy clohexa ne in a s ing le pa s s doWn? oW ? xed bed rea ctor a re
k noWn in the a rt. Tempera tures of a bout 4 00 F. a nd pres
s ures in the ra ng e of 3 00- 500 ps ig a re a deq ua te When us ing
a nick el ca ta ly s t. HoWev er, copious q ua ntities of hy drog en,
es pecia lly betWeen beds , a re need to control the tempera ture
of the hig hly exothermic rea ction. Conditions in a dis tilla
tion column rea ctor a re cons idera bly dif f erent. Ca ta ly s t bed
tempera tures of betWeen 250 a nd 3 00 F. a t pres s ures of
a bout 7 5 ps ig ( a bout 3 0 ps ia hy drog en pa rtia l pres s ure) a re
a deq ua te. In a ddition the boiling of the liq uid Within the bed
dis s ipa tes the hea t of rea ction Which is remov ed in the
ov erhea ds by condens a tion a nd re? ux.
[ 0050] Proces s conditions f or s ta nda rd hy drodes ulf uriZa
tion of a ? uid cra ck ed na phtha s trea m a re a ls o k noWn.
Tempera tures in the ra ng e of a bout 6 00- 7 00 F. a long With
pres s ures in the ra ng e of 7 00- 1000 ps ig a nd s pa ce v elocities
in the ra ng e of 1- 10 v olume of na phtha per unit v olume of
ca ta ly s t. Hy drog en ra tes in the ra ng e of 1000 to 1500
s ta nda rd cubic f oot per ba rrel of f eed a re commonly us ed.
[ 0051] Proces s f or the conditions f or the hy drodes ulf ur
iZa tion of a hea v y ? uid cra ck ed na phtha s trea m in a dis til
la tion column rea ctor include tempera tures in the ra ng e of
500 F. a nd pres s ures s uf f icient to k eep a portion of the
na phtha in the liq uid s ta te ( boiling ) or a bout 200- 3 00 ps ig .
Hy drog en ra tes s imila r to tha t in s ta nda rd units a re s uita ble.
[ 0052] Proces s conditions f or the thioetheri? ca tion of a
lig ht na phtha in a s ta nda rd ? xed bed rea ctor a re a bout 150
ps ig pres s ure, a bout 3 00 F. , a nd a 10 WHSV ( Weig ht hourly
s pa ce v elocity , in Wt of f eed per Wt of ca ta ly s t per hour,
hr_ 1) . About 6 . 25 v olume of hy drog en per v olume of f eed is
us ef ul to k eep the ca ta ly s t in the hy dride s ta te.
[ 0053 ] Conditions in a dis tilla tion column us ed a s a thio
etheri? ca tion rea ctor include a bout 125 ps ig ov erhea d pres
s ure, middle ca ta ly s t bed tempera ture of a bout 26 5 F. With
hy drog en f eed a t a bout the s a me a s f or the s ta nda rd rea ctor.
[ 0054 ] The is omeriZa tion of cy clohexa ne to hig her octa ne
components is dis clos ed in Us . Pa t. N o. 4 , 7 83 , 57 5 Which is
incorpora ted herein by ref erence. Genera lly the cy clohexa ne
ring is ? rs t brok en a nd is omeriZed to is ohexa ne. Any methy l
cy clo penta ne ca n a ls o be conv erted to is ohexa ne. The
conditions include 29 0- 4 4 0 F. With pres s ures of a bout 3 7 0
ps ig . Spa ce v elocities of 0. 5 to 3 a re pref erred. Hy drog en is
f ed in a n a mount to prov ide a mola r ra tio of f rom 0. 01 to 10
moles of hy drog en per mole of hy droca rbon in the outlet of
the rea ctor. Thes e conditions a re s uita ble f or both s ta nda rd
? xed bed opera tion a nd dis tilla tion column rea ctor.
Apr. 21, 2005
[ 0055] Ref erring noW to the ? g ures s peci? c embodiments
of the proces s of the inv ention a re s hoWn.
[ 0056 ] In FIG. 1 there is s hoWn a g eneric proces s s cheme
to produce loW benZene content g a s oline While a t the s a me
time reducing the s ulf ur lev els . The f ull boiling ra ng e
na phtha is f ed v ia ? oW line 101 to a dis tilla tion column 10
ha v ing s ta nda rd dis tilla tion s tructure 12 conta ined therein.
The s ta nda rd dis tilla tion s tructure ma y be s iev e tra y s , v a lv e
tra y s , bubble ca p or pa ck ing a s is norma l in the indus try . A
lig ht na phtha boiling beloW the boiling point of benZene
( a bout 17 5 F. a nd lig hter) is ta k en a s ov erhea ds v ia ? oW line
102. A mid ra ng e na phtha boiling in the ra ng e of a bout 17 0
to 180 F. is ta k en a s a s ide dra W v ia ? oW line 104 . This mid
ra ng e na phtha conta ins the benZene Which ha s a boiling
point of 17 6 F. The ra ng e is neces s a ry to ins ure tha t a ll of
the benZene is remov ed. A hea v y na phtha is boiling a bov e
the boiling point of benZene ( a bout 180 F. a nd hea v ier) is
ta k en a s bottoms v ia ? oW lined 103 . The bottoms Will
conta in a ny octa ne rich toluene a nd xy lenes .
[ 0057 ] The lig ht na phtha ma y conta in v a lua ble ole? ns but
a ls o diole? ns a nd org a nic s ulf ur compounds Which a re
mos tly merca pta ns . To remov e the merca pta ns the na phtha
ca n be s ubj ected to a ty pica l s Weetening proces s s uch a s
MEROX or by rea ction With the diole? ns ov er a thioetheri
? ca tion ca ta ly s t 22 in a thioetheri? ca tion rea ctor 20. Hy dro
g en is a dded to the thioetheri? ca tion rea ctor v ia ? oW line
201 a nd product is remov ed v ia ? oW line 202.
[ 0058] The mid ra ng e na phtha in ? oW line 104 is s ubj ected
to hy drog ena tion in a hy drog ena tion rea ctor 3 0 conta ining a
hy drog ena tion ca ta ly s t 3 2 With hy drog en being a dded v ia
? oW line 3 01. The mid ra ng e na phtha ma y a ls o conta in
org a nic s ulf ur compounds Which Would g enera lly be
thiophene in the boiling ra ng e ta k en. The hy drog ena tion
ca ta ly s t a ls o a cts a s a hy drodes ulf uriZa tion ca ta ly s t to con
v ert the thiophene to hy drog en s ul? de a t the s a me time a s the
benZene is conv erted to cy clohexa ne. The mid ra ng e na phtha
ha v ing reduced benZene content is remov ed v ia ? oW line
3 02 a nd ma y then be s ubj ected to is omeriZa tion ca ta ly s t 4 2
in is omeriZa tion rea ctor 4 0 to improv e the octa ne With
product being remov ed v ia ? oW line 4 02.
[ 0059 ] The hea v y na phtha in the bottoms ma y be s ub
j ected to hy drodes u? uriZa tion in rea ctor 50 conta ining
hy drodes ulf uriZa tion ca ta ly s t 52 With hy drog en being a dded
v ia ? oW line 501. D es ulf uriZed hea v y na phtha is remov ed
v ia ? oW line 502. If des ire a ll of the product s trea ms in ? oW
lines 202, 4 02 a nd 502 ca n be combined to produce a
g a s oline Which is loW in benZene a nd s ulf ur.
[ 006 0] Ref erring noW to FIG. 2 a pref erred embodiment
of the inv ention is s hoWn. A ? rs t dis tilla tion column rea ctor
10 is s hoWn to conta in a bed 12 of thioetheri? ca tion ca ta ly s t
in the recti? ca tion s ection. The rema inder of the column
conta ins s ta nda rd dis tilla tion s tructure 13 a s dis cus s ed
a bov e. The f ull ra ng e na phtha is f ed to the dis tilla tion
column 10 v ia ? oW line 101 With the hy drog en neces s a ry to
k eep the thioetheri? ca tion ca ta ly s t in the hy drided s ta te
being s upplied v ia ? oW line 102. The diole? ns Within the
lig ht na phtha rea ct With the merca pta ns to f orm s ul? des
Which a re dis tilled doWnWa rd a nd remov ed in the bottoms .
The noW loW s ulf ur lig ht na phtha Which boils beloW the
boiling point of benZene ( a bout 17 0 F. a nd lig hter) is
remov ed a s ov erhea ds v ia ? oW line 103 .
[ 006 1] A mid ra ng e na phtha boiling in the ra ng e of 17 0
180 F. is ta k en a s a s ide dra W v ia ? oW line 104 a nd f ed to
US 2005/ 0082201 A1
a s econd dis tilla tion column rea ctor 20 Which conta ins a bed
22 of hy drog ena tion ca ta ly s t With hy drog en being f ed ? oW
line 201. The recti? ca tion s ection of the dis tilla tion column
conta ins s ta nda rd dis tilla tion s tructure 24 a s dis cus s ed
a bov e. Any lig hter na phtha boiling beloW the boiling point
of benZene or cy cloheXa ne ( a bout 17 4 F. a nd lig hter) a nd
conta ining v a lua ble ole? ns is s tripped out of the mid ra ng e
na phtha a nd remov ed a s ov erhea ds v ia ? oW line 202 a long
With the hy drog en s ul? de produced. The rema inder of the
mid ra ng e na phtha conta ining the benZene a nd pos s ible
thiophene is s ubj ected to hy drog ena tion in the loWer portion
of the column Wherein benZene is conv erted to cy cloheXa ne
a nd thiophene is conv erted to hy drog en s ul? de. The mid
ra ng e na phtha noW s tripped of a ny lig hter products a nd
conta ining les s benZene a nd thiophene is remov ed a bottoms
v ia ? oW line 203 .
[ 006 2] The bottoms f rom the hy drog ena tion dis tilla tion
column rea ctor in How line 203 a re f ed to a third dis tilla tion
column rea ctor 3 0 conta ining a bed of 3 2 of is omeriZa tion
ca ta ly s t a nd s ta nda rd dis tilla tion s tructure 3 4 . In the rea ctor
3 0 the cy cloheXa ne is is omeriZed to hig her octa ne product
s uch a s methy l cy clopenta ne or is oheXa ne. The a dv a nta g e of
the concurrent dis tilla tion is tha t the is omeriZa tion product is
remov ed f rom the ca ta ly s t bed 3 2 a s f a s t a s it is f ormed thus
improv ing the ov era ll production of the is omers . An ov er
hea ds is ta k en v ia ? oW line 3 02 With bottoms conta ining the
is omeriZa tion product being ta k en v ia ? oW line 3 03 . If
hy drog en is needed, it is s upplied v ia ? oW line 3 01. If
neces s a ry a s econd bed ( not s hoWn) of hy drodes ulf uriZa tion
ca ta ly s t ma y be us ed to conv ert the thiophene to hy drog en
s ul? de.
[ 006 3 ] The bottoms , conta ining the hea v y na phtha includ
ing the hea v ier a roma tic ma teria l s uch a s toluene a nd
Xy lenes is remov ed v ia ? oW line 105 a nd f ed to f ourth
dis tilla tion column rea ctor 4 0 conta ining a bed 4 2 of
hy drodes ulf uriZa tion ca ta ly s t. Hy drog en is a dded v ia ? oW
line 4 01. Sta nda rd dis tilla tion s tructure 4 4 ma y be dis pos ed
a bov e a nd beloW the bed 4 2. The hea v ier org a nic s ulf ur
compounds conta ined Within the hea v y na phtha a re rea cted
With hy drog en to produce hy drog en s ul? de. The dis tilla tion
is run not s o much f or s epa ra tion but to prov ide a condens ing
liq uid Within the bed 4 2 Which a lloWs f or us e of loWer
hy drog en pa rtia l pres s ures tha n otherWis e be neces s a ry . An
ov erhea ds is ta k en v ia ? oW line 4 02 a nd a bottoms v ia ? oW
line 4 03 . The ov erhea ds liq uid product ma y be tota lly
recy cled a s re? uX a f ter the hy drog en s ul? de a nd eXces s
hy drog en a re remov ed.
Apr. 21, 2005
[ 006 4 ] If des ired a ll of the na phtha products in How lines
202, 3 02, 3 03 , 4 02 a nd 4 03 ma y be combined to produce a
loW benZene loW s ulf ur g a s oline.
1. A proces s f or producing loW benZene content g a s oline
compris ing the s teps of :
( a ) f eeding a f ull boiling ra ng e na phtha conta ining ben
Zene, ole? ns , diole? ns , merca pta ns , thiophenes a nd
other org a nic s ulf ur compounds to a dis tilla tion column
Wherein a lig ht na phtha f ra ction is ta k en a s ov erhea ds ,
a medium na phtha f ra ction conta ining s a id benZene is
ta k en a s a s ide dra W a nd a hea v y na phtha f ra ction is
ta k en a s a bottoms ; a nd
( b) f eeding s a id medium na phtha f ra ction conta ining s a id
benZene a nd s a id thiophenes to a hy drog ena tion rea ctor
conta ining a hy drog ena tion ca ta ly s t Wherein a portion
of s a id benZene is hy drog ena ted to cy cloheXa ne a nd
s a id thiophenes a re conv erted to hy drog en s ul? de.
2- 11. ( ca nceled)
12. The proces s a ccording to cla im 1 f urther compris ing
the s tep of :
( c) combining s a id ov erhea ds , s a id bottoms a nd the ef ? u
ent f rom s a id hy drog ena tion rea ctor to produce a g a s o
line loWer in benZene content tha n s a id f ull boiling
ra ng e na phtha f eed.
13 . The proces s a ccording to cla im 1 f urther compris ing
the s teps of :
( d) f eeding s a id ov erhea ds to a thioetheri? ca tion rea ctor
conta ining a thioetheri? ca tion ca ta ly s t Wherein a por
tion of s a id diole? ns a re rea cted With a portion of s a id
merca pta ns to produce s ul? des ;
( e) s epa ra ting s a id s ul? des f rom s a id ov erhea ds ;
( f ) f eeding s a id bottoms a nd hy drog en to a hy drodes ulf u
riZa tion rea ctor conta ining a hy drodes ulf uriZa tion ca ta
ly s t Wherein a portion of s a id other org a nic s ulf ur
compounds a re rea cted With hy drog en to produce
hy drog en s ul? de; a nd
( g ) s epa ra ting s a id hy drog en s ul? de f rom s a id bottoms .
14 . The proces s a ccording to cla im 1 Wherein the ef f luent
f rom s a id hy drog ena tion rea ctor is f ed to a n is omeriZa tion
rea ctor conta ining a n is omeriZa tion ca ta ly s t Wherein a por
tion of s a id cy cloheXa ne is is omeriZed to methy l cy clo
penta ne.