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Патент USA US3044960

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United States Patent 0 MIce
‘ 1
3,044,950
PROCESS FOR UPGRADING CATALYTICALLY
CRACKED GASOLINE
George B. Swartz, Jr., Penn Hills, Pa., assignor to Gulf
Research & Development Company, Pittsburgh, Pa., a
corporation of Delaware
Filed Dec. 15, 1958, Ser. No. 780,576
4 Claims. (Cl. 208-57)
3,044,950
‘Patented July 17, 1962“
2
high octane ‘rating. The reiormate is then blended with
the fraction enriched in aromatics and with other frac- ,
tions obtained from the cracked gasoline to produce a
gasoline having a considerably higher motor octane rat
ing than the untreated catalytically cracked gasoline.
The charge stock for my process is a full range cata
lytically cracked gasoline. This type of gasoline is pro
duced by contacting a cracking charge stock, for example,
a straight run gas oil, at high temperature, e.g., 8S0~
invention relates to a process -for upgrading ole 10 1000° F., with a cracking catalyst, such as a synthetic
?nic gasoline and more particularly to a process for con—
silicaaalumina composite maintained in a ?xed, ?uidized
verting catalytical-ly cracked gasoline to gasoline of
or moving bed system. Usually a yield of 40 to 50 per
higher octane rating, and especially of higher motor
cent of ole?nic gasoline is produced. The cracked gaso
method octane rating, by a combination of hydrogenation
line product will boil in the range, for example, from
and catalytic reforming of selected fractions.
15 100 to 430° F. and will have an ole?n content from 15
For a number of years the ole?nic gasoline obtained by
to 70 volume percent. The research octane number of
catalytic cracking of hydrocarbon oils has satis?ed the
catalytical-ly cracked gasoline will normally be rather
demand for gasoline blending stock of ‘reasonably high
high, for example, from about 89 to 95 clear, or 94 to
octane rating. However, the increased use of high com
101, leaded. However, a characteristic of such gasolines
pression automobile engines has so greatly increased the 20 is that the motor- method octane rating is rather low,
demand for gasoline of very high octane rating, that it
for example, from 12 to 16 points lower than the corre
has become desirable to develop methods for further up—
grading catalytically cracked gasoline so that the total
gasoline pool can be raised to the required high octane
sponding leaded or clear research octane rating.
.I will now describe my invention with reference to
the drawings, of which FIGURES 1 through 4 are sche
level. Heretofore, processing of catalytically cracked 25 matic ?ow diagrams of four different embodiments of
gasoline for octane improvement has been very limited.
my process.
For instance, catalytic reforming of such stocks has not
In the embodiment of my process illustrated by FIG
been ‘successful because the high ole?nic content causes
URE 1 the entire fulllrange cracked gasoline is subjected
rapid deactivation of reforming catalysts, and especially
to hydrogenation and fractions of the hydrogenated prod
of platinum catalysts. Hydrogenation of the ole?nic
uct are then treated separately. As the drawing shows,
gasoline merely lowers the octane rating by forming sat
an ole?nic gasoline such as the ‘gasoline produced by
urated hydrocarbons of lower octane value than the ole
?ns. I have now developed a process whereby catalyti~
?uid catalytic cracking, otherwise referred to as an FCC
gasoline, is charged by line 10 to a hydrogenation unit
11. In the hydrogenation unit the cracked gasoline in
ly upgraded to a motor fuel of very high octane rating. 35 admixture with hydrogen is contacted with a hydrogena
cally cracked gasolines can be e?iciently and economical~ -
My new process is based on the discovery that the com
bination of hydrogenation and reforming of selected frac
tions of the catalytically cracked gasoline can produce
tion catalyst such as a catalyst composed of minor _
amounts of the oxides of cobalt and molybdenum sup
The hydrogenation con
ported on an alumina carrier.
in high yield a product of higher octane number, espe
ditions include, for example, a hydrogen concentration
cially of higher motor octane number, than the un 40 from about 1,000 to 10,000 standard cubic feet per barrel
treated catalytically cracked gasoline.
of hydrocarbon (abbreviated hereinafter as s.c.f./bbl.),
In this discussion I will use the short terms “motor”
and “researc ” to designate the octane ratings determined
a temperature of 500 to 800° F. and a pressure of 200
High research octane number is desirable for city driving '
5 or less and reduces the sulfur content to less than 0.01
to 800 pounds per square inch gauge (abbreviated here
by the standard ASTM tests, namely, the Test [for Knock
inatter as p.-s.i.g.). The hydrogenation treatment satu
Characteristics of Motor Fuels by the Motor Method 45 rates substantially all of the ole?ns and desulfurizes the
(ASTM D357) and the Test for Knock Characteristics
cracked gasoline. More speci?cally, the hydrogenation
of Motor Fuels by the Research Method (ASTM D908).
reduces the bromine number of the fraction treated to
at low engine speeds and with frequent acceleration, but
weight percent.
high motor octane number is desirable for highway driv 50 In the embodiment of FIGURE 1 the hydrogenated
ing at high engine speeds. The catalytically cracked
full range ole?nic gasoline is fractionally distilled in col
gasoline is not su?ciently high in motor octane rating for
umn 12 to produce three fractions: a light fraction with
present and expected ‘future demand. I shall also refer
drawn overhead by line 14 having a boiling range from
to “clear” octane numbers and “leaded” or “+3 cc. TEL”
the initial boiling point (IBP) of the charge to an end
octane numbers. The “clear” octane number is the'rat 55 point (EP) of 175 to 195° F.; a middle or intermediate
ing of the gasoline without anti-knock additives and the
fraction withdrawn by line 15 having an initial boiling
“leaded” or “+3 cc. TEL” octane number is the octane
rating of the gasoline to which tetraethyl lead has been ‘ point of about the end point of the light fraction (175—
195° F.) and an end point of_290 to 320° F.; and a bot
added in the amount of 3 cc. per gallon of gasoline.
In general, my new process for upgrading an ole?nic 60 toms vor residual fraction withdrawn by line 16 boiling
from about the end point of the middle fraction (290
cracked gasoline comprises hydrogenating at least a resi
320° 'F.) to the end point of the charge. Speci?cally,
dual fraction of‘the ole?nic gasoline having an initial
FIGURE 1 illustrates an embodiment of the process in
boiling point of 290 to 320° F. The hydrogenated resid
ual fraction is subjected to a separation procedure which ' which the three fractions are an IBP—180° F. light frace
is selective for separating aromatics from nonarornatics. 65 tion, a 180-310° F. middle fraction and a 310° F.—EP
A hydrogenated fraction enriched in aromatics and a
residual fraction. The light fraction is characteristically
hydrogenated fraction enriched in nonaromatics are re
improved in motor method octane rating as compared
covered. The fraction enriched in nonarornatics .is sub
with a fraction of the untreated cracked gasoline of the
jected to catalytic reforming to produce a reformate of
same boiling range. In the embodiment of FIGURE 1
3,044,950
3
this fraction is passed directly to gasoline blending unit
17 without further treatment.
The middle fraction withdrawn by line 15 is subjected
to catalytic reforming in the reforming unit 18. This is
the conventional catalytic reforming in which the gasoline
in admixture with hydrogen in a concentration, for ex
ample, from about 1,000 to 20,000 s.c.f./bbl. is contacted
at a temperature from 800 to 1050” F. and a pressure
from 250 to 1000 p.s.i.g. with a reforming catalyst such
as platinum on alumina, molybdenum oxide on alumina,
or the like. The previous hydrogenation of the middle
fraction is effective to reduce its ole?n and sulfur content
to an extent that the hydrogenated fraction is an excellent
reforming charge stock, even when using the sensitive
platinum-alumina catalyst. The reformed product of high
octane rating is withdrawn by line 19 and passed to the
gasoline blending unit 17.
I have discovered that the hydrogenated 290-320° F.
IBP residual fraction of the cracked gasoline has a large
content of high octane rating aromatics. Consequently,
I subject this fraction to a separation procedure which is
selective for separating aromatics from nonaromatics. As
illustrated in FIGURE 1, a suitable procedure is to charge
the fraction to a solvent extraction unit 20 wherein the
fraction is contacted with a suitable solvent such as di
ethylene glycol according to the known procedure to pro
duce an extract fraction enriched in aromatics and a
rat?nate fraction enriched in nonaromatics. The extract
fraction enriched in aromatics has a high octane rating
and is passed by line 21 to the gasoline blending unit 17.
The raf?nate fraction enriched in nonaromatics is of low
octane rating and is passed by line 22 to the catalytic
The intermediate fraction of the FCC gasoline with
drawn by line 26 is of reasonably high octane number
as separated from the full range gasoline and is passed
to the blending unit 30 without further treatment.
In accordance with my invention the residual fraction
withdrawn by line 27 is passed to the hydrogenation unit
31 and is subjected to hydrogenation in the manner pre
viously described. The hydrogenated fraction recovered
from hydrogenation unit 31 is then subjected to a selective
10 separation process. For example, as shown in FIGURE
2, the hydrogenation product is passed to solvent extrac
tion unit 32 and is contacted with a suitable extracting
solvent such as diethylene glycol as previously described.
An extract fraction enriched in aromatics is passed by
line 33 to the gasoline blending unit 30. The raf?nate
fraction is enriched in nonaromatics and, having been
hydrogenated previously to saturate ole?ns and remove
sulfur, the fraction is an excellent reforming stock. The
fraction is passed by line 34 to the catalytic reforming
unit ‘35 and is subjected to catalytic reforming as pre~
viously described. The reformate of high octane rating
is then passed by line 36 to the gasoline blending unit 30.
The products of the various operations illustrated in
' FIGURE 2, namely, the hydrogenated light fraction, the
untreated middle fraction, the extracted aromatics frac
tion of the hydrogenated bottoms and the reformed raf
?nate fraction of the hydrogenated bottoms are blended
to form a gasoline having a high research and motor
30 method octane rating.
In a variation of the flow scheme of FIGURE 2 the
light fraction from line 25 can be combined with the
residual fraction of line 27 and the combined stream can
reforming unit 18 in admixture with the hydrogenated 35 be hydrogenated in a single hydrogenation unit 31. This
eliminates the need for two hydrogenation units. How
middle fraction. The products of each of the described
ever, the nonaromatics of the hydrogenated product are
operations, namely, the hydrogenated light fraction of
subsequently subjected to catalytic reforming in reforming
high motor octane rating withdrawn by line 14, the re
unit 35. Since the hydrogenated light fraction has a high
formed hydrogenated middle or intermediate fraction and
the reformed hydrogenated ra?inate Withdrawn by line 40 content of branched chain C5-C6 para?‘ins it is not appre
ciably upgraded by catalytic reforming. The capacity of
19, and the hydrogenated aromatic extract withdrawn by
the reforming unit is, therefore, not most efficiently used
line 21 are blended to produce a gasoline of very high
when this hydrogenated light fraction is charged to it. If
research and motor method octane ratings.
Although the principles of my invention can be applied 45 the light and residual fractions are combined and are
hydrogenated in the same hydrogenation unit, it is pre
to the procedure such as shown in FIGURE 1 in which
ferred to fractionate the hydrogenation product, e.g., in a
the full range cracked gasoline is hydrogenated, in other
distillation column between the hydrogenation and extrac
embodiments of my process only selected fractions of the
tion units, to separate a C5—C8 fraction which is sent
cracked gasoline are hydrogenated. FIGURE 2 is a flow
diagram of an embodiment of the process in which the 50 directly to gasoline blending and a residual fraction which
is passed to the solvent extraction unit. However, it is
ole?nic gasoline, such as an FCC gasoline, Without being
previously hydrogenated, is fractionally distilled in column
24 into three fractions. FIGURE 2 illustrates a speci?c
operation in which the three fractions are: an IBP-180"
usually preferable to hydrogenate the light fraction sepa
rately and pass it directly to the gasoline blending unit
as shown in FIGURE 2.
F. light fraction withdrawn overhead by line 25; a 180 55 FIGURE 3 shows another embodiment of my process
in which the full range cracked gasoline is fractionally
310° F. intermediate fraction Withdrawn by line 26; and
distilled in column 40 into two fractions, a light fraction
a 310° F.—end point residual fraction Withdrawn by line
composed mainly of C5-C6 hydrocarbons which is with
27. However, the end point of the light fraction and
drawn overhead by line 41 and a bottoms fraction with
the initial point of the intermediate fraction can range
60 drawn by line 42. The end point of the light fraction
from 175 to 195° F. The end point of the intermediate
and the initial point of the ‘bottoms fraction will be in
fraction and the initial point of the residual fraction can
the range from 175 to 195° F. In the speci?c operation
range from 290 to 320” F. The light ole?nic fraction
which is composed mainly of C5 and C6 hydrocarbons is
passed by line 25 to a hydrogenation unit 28 and is sub
jected to catalytic hydrogenation, as previously described.
Although hydrogenation of this chie?y C5-C6 fraction
does not appreciably improve its research octane number,
illustrated in FIGURE 3 the two fractions recovered
65 from column 40 are an IBP—180° F. light fraction and
a 180° F.—end point bottoms fraction. The light frac
tion, having a reasonably high research octane number, is
passed directly to gasoline blending unit 43. The bottoms
fraction is hydrogenated in hydrogenation unit 44 and the
I have discovered that it does improve its motor octane
70
hydrogenated
product is fractionally distilled into two frac
number. Consequently, by hydrogenation alone and with
tions in column 46. The end point of the overhead frac
out reforming, the value of the light fraction of the ole
tion withdrawn by line 47 and the initial point of the bot
?nic gasoline can be improved. The hydrogenated light
toms
fraction withdrawn vby line 4-8 will be in the range
fraction is passed by line 29 directly to the gasoline blend
75 from 290 to 320° F. FIGURE 3 demonstrates a speci?c
ing unit 30.
3,044,950
6
operation in which a 180-310" 'F. intermediate fraction is
Withdrawn overhead by line 47 and a 310° ‘Fa-end point
bottoms fraction is withdrawn by line 48. The bottoms
fraction is then treated to selectively separate aromatics
from nonaromatics. For example, the fraction is sub
jected to solvent extraction in solvent extraction unit 49, as
previously described. The extract fraction enriched in
ra?inate fraction enriched in nonaromatics' is’ passed by: ' "
line 63 to the catalytic reforming unit 64. The reformate'
of high octane rating is then passed by line'65 to the '
blending unit 58. A ?nal product of high octane rating?
is formed by blending the untreated IBP—310° F. ole?nic‘ ~i
fraction, the'reformate, and ‘the aromatics-enriched ex
tract fraction. Marked improvement in octane rating is
thus obtained although only a minor part of the total
cracked gasoline is subjected to the upgrading treatment.
aromatics is of high octane rating and is'passed by line 52,
to the gasoline blending unit 43. The rai?nate ‘fraction en
riched in nona-romatics is withdrawn by line 53 and is com 10
bined with the hydrogenated intermediate ‘fraction of line
47 to form the feed for the catalytic reforming stage.
These two fractions of low octane rating, having been hy
EXAMPLE
I have carried out a series of runs which demonstrate
the unexpected advantages of my new procedure for
cellent reforming stocks. The combined stream is passed 15 upgrading ole?nic gasoline. The nins include fractiona
tion of a catalytically cracked ‘gasoline followed by hy
to catalytic reforming in the reforming unit 50. The high
drogenation, extraction and reforming of certain of the
octane reformate withdrawn by line 51 is passed to the
‘ resulting fractions. The charge stock was a blend ‘of
blending unit 43. A ?nal high octane product is ob
tained by blending the untreated light fraction, the ex— " light and heavy FCC gasolines and had an ASTM boil- tract fraction from the extraction stage,’ and the reformate 20 ing range from £112 to 380° 'F., a gravity of 60.9'° API,
drogenated to saturate ole?ns and remove sulfur, are ex
obtained by catalytically reforming the hydrogenated
and a bromine number of 114. This gasoline was frac
intermediate fraction and the raf?nate fraction from the
extraction stage.
tionally distilled to produce three fractions: an IBP~180°
F. light fraction, a 180° F.—310° F. intermediate fraction
and a 310° F.—end point residual fraction. The fraction
FIGURE 4 illustrates still another embodiment of my
process in which the only fraction of the catalytically
cracked gasoline to be subjected to further treatment is
the residual fraction having an initial boiling point in the
ation was carried out by a procedure substantially accord
ing to the procedure of a true boiling point distillation
and in a manner that produced fractions similar to those‘
range from 290 to 320° F. FIGURE 4 shows a speci?c
obtainable in a conventional commercial tractionating
column. This included using a fractionating column hav-‘
operation in which the FCC gasoline charged to distilla
tion column 55 is separated into an lIBP-3l0" F. fraction 30 ing a packed section, employing re?ux and measuring
overhead vapor temperature to determine the cut points.
withdrawn overhead by line ‘56 and a 310° F.—end point
residual fraction withdrawn from the bottom of the
In this manner, the light fraction was obtained by col
column by line 57. The overhead fraction is passed di
lecting distillate until the overhead vapor temperature
rectly to ‘gasoline blending unit 58. The 310° F.—end 35 reached 180° F. The middle fraction was then obtained
point fraction is subjected to catalytic hydrogenation in
by separately collecting the next portion of distillate until
the hydrogenation unit 60. The hydrogenated product is
then passed to the selective separation stage. For ex
ample, theihydrogenated fraction is passed to the oslvent
?nally the undistilled portion of the charge stock boiling
extraction unit 61 and is extracted with a solvent such
as diethylene glycol, as previously described. An extract
fraction enriched in aromatics is withdrawn by line 62
and is passed to the gasoline blending unit 58.
The
the overhead vapor temperature reached 310° F. and
below the cut point of 310° F. was collected as a residual
fraction.
V
Table I below provides inspection data for the full
range FCC ‘gasoline and for the three fractions thereof
obtained by distillation as described in the above example.
Table 1
Fraction.‘ ____________________ __
Charge
IBP—180° F.
180—310° F.
310° F.~EP
Yield, percent by Volume of
Full-Range FOO Gasoline---
100.0
Inspections:
Gravity, °API ___________ __
Sulfur, percent by Weight“
Bromine Number ________ __
Hydrocarbon Type, percent
by Volume:
41. 4
42. 6
15. 9
78.2
54.3
38. 6
‘
60. 9
0. 091
114
>
0.042
160
0.124
106
AromaticsOle?ns-___
0. 189
44
52. 1
29. 4
18. 5
saturates...“
N aphthenes-
____________ __
Para?in
............ ..
Podbielniak Analysis, per
cent by Weight:
Butanes-Butenes ....... ..
0. 2
Isopentane _____________ _.
4. 6
n-Pentane_-__
1. 4
3. 6
Pentenes _______________ __
12. 8
31. 7
HeX-anes and Heavier..___
81. 0
54. 2
Reid Vapor Pressure Lb__
5. 7
10. 5
Dislitillation
(ASTM D-86
5 :
Over Point, ° F ...... ._
End Point, ° F _______ _.
112
380
115
163
208
287
325
420
10% at: ° F
144
208
133
145
220
234
334
347
328
158
266
373
Motor Method
.
Clear _____________ ..
+3 cc. TEL ______ __
79. 0
83.0
81. 1
85. 6
78. 4
82. 7
80. 1
84. 2
92.0
94. 3
92.0
89. 9 V
97. 5
100; 0
98. 0
95. 1
Research Method
3,044,950
8
Table Il—-Continned
The table includes ASTM distillation data obtained by
the procedure of ASTM D~86-54. It will be noted that
{h
‘
‘
‘
‘
'
Run Number ____________ _.
8 over you?“ an? end Polnts fpr the ASTM fhstlilaltl9ns
1
2
Fraction Treated _________ __ {BF-180%“,
3
180-310°F,
310°I<‘,-EP
do not co1nc1de with the cut points employed In distilling
the FCC. gasoline into. three fractions
as described
above '
.
.
.
.
5
The disagreement is a result of lnherent limitations of
the ASTM distillation method.
As is well known, the
Y
.
to,
4
V‘.
P
t
hjntreageliuiigraogg?nLigf
Hgglriggducg-d?s-?? ----- --
ASTM mitial boiling point of a mixture will be 'con-
sot/“b
srderably higher than the initial boiling point as determined
mspécig‘glilti,l‘l.qfgfwducti
by true boiling point distillation and the ASTM end point 10
Sulfur, ' Percent
Wlll be considerably lower than the end point determined
by true boiling point distillation. (See Perry, Chemical
Engineers’ Handbook, 3d Ed., pages 606-607.) The
B,‘Y,‘§§§§?;,5;,;5;_-_-_j:
Hydrocarbon Type.
1’T§,I;,E,Pgc§f‘j‘_‘ff?__
helpful in characterizing the fractions. However, it 15
sm§3f§§ggg3¢ :
orme
d .
_
that in de?ning
.
.
.
.
‘
the
.
fractions
.
, _
.
128s
83 4
57 s
40 0
0' (1)95
0'
0'
(,8
m
0.5
1.9
M
3.4
93:;
lfar??ins ----- --
‘13f’;
89-2
DistrllatmnQtS’I‘M D
1n my p1 ocess in terms of 1n1t1al boiling points and
101-3
54s
_
Ole?nsnm
f
102-9
863
by
ASTM data are included because they are in some degree
should be understood
104-4
53-3
36-2
-54 z
,
end points, I refer not to ASTM distillation data but to
gggrlg’gzirgtj
12;
£08
2;;
the cut points that would be employed for obtaining such
10 pefcailt gtmjjjjj
112
215
330
fracilons by atmospheric pressure fractionation of the 20
-------- --
rrnovorilidi?iémti'o'ro'ff
typical commercial distillation column provided with
M°ig§e1g§eth°d—
vapor-liquid contacting means such as packing or bubble
cap trays and employing normal re?ux ratios.
+‘3 ooT'i‘T?IIIII
These
76 3
61 8
71 8
9314
8117
e011
R°S%‘{§§Melh°d“
77 8
64 6
so 1
+3 oo‘iiE'LIIIII
93:4
84:9
9110
remarks apply also to the distillation data of the other 25
tables of this application.
The three fractions of Table I were subjected to catalytic
hydrogenation over a ?xedbed, cobalt_molybdenum ca_
3%
-
olefimc gasoline or hydrogenated fractions thereof in a
3 Cobalt-Molydenum on Alumina._
_
based on changemhydrocarbon composltlondurmg
talyst at temperatures ranging from 635 to 678° F., a
m
a
_
pressure of 600 p.s.i.g., a liquid-hourly space velocity of 30
lable II Shows thaf; hydrogenation red?ced the Octane
about 2 volumgs of hydrocarbon Per volume of catalyst
numbers of all fractions, except for raising the leaded
per hour, and at a hydrogen rate of about 6,000 standard
“actor Octane number 0_£_ "1}?- light fraclloll fmm 855 to
cubic feet per barrel of hydrocarbon‘ The Catalyst had
93.4. The octane sensitivity, or the dl?erence between
the following approximate composition: cobalt oxide, 2.8
research and m°t°r.°°tane number? 9f. an fractlons was
Weight percent; molybdenum Oxide, 141) weight percent; 35 greatly reduced while lead susceptrb?ity, or the octane
Silica’ L6 Weight percent; and alumina, 8L6 Weight pep
improvement obtained by addition of tetraethyl lead, was
cent. Further details of the reaction conditions for each
lncreased- ‘In adfhtlon to the effect on motor and 1'5‘
hydrogenation run and the yields and inspections of the
hydrogenatgd products are given in Table 11 below
Table II
1
FREiZgEHiBZZiTJdIIIIIIIIII rnr-isonr.
.
2
3
180-3l0°F.
awn-Er
(1)
0)
.
.
.
.
.
?ve automobiles with high compression engines.
Operating Conditions:
(igglayg—?-ééégér--,i.-c?l;-
sfimch Octal“? fatlllgs,_as Shown lI1_ Table II, hydrogena
tron of the light fraction resulted in anrarked unprove
40 ment of the road performance characteristics of the leaded
light fraction when tested In premium gasoline blends in
I have further subjected the hydrogenated fractions of
Table II to catalytic reforming. The catalyst for these
45 runs ‘was a pelleted, ?xed-bed, platinum-alumina catalyst
(l)
containing essentially about 0.6 weight percent platmum,
peroiure, °_F.'--.‘;-1_-sP$§§‘_,§’§;1_"f‘ffj___fj_-_/_
greecrséreehrg-ss-i-gnm-m
hire-notion Rate,
?ig'r?sélggl-dégtégtf
635
Z0
600
678
2_1
60°
611°
5810
664
0.5 weight percent chlorine and 98.9 weight percent alu
20
mina. The reaction conditions included temperatures of
60° 50 about 900 and about 950° F., pressure of 300 p.s.i.g.,
space velocity of 2 volumes per volume of catalyst per
5950
hour and hydrogen concentration ranging from about
Percent by Vol-
66 3
68 7
_2 a
1,000 to 7,000 s.c.f./bbl. Details of each of the reforming
obo
500
‘5b5
runs and of the yields and inspections of the reformate
nleedolrltntqi'as'fs'fcii'lbhl:
See footnotes at and of table‘
products are given 1n Table III below.
Table III
Run Number ________________________________ _.
FCC Gasoline Boiling Range, ° F ___________ _.
4
5A
5B
6A
6B
IBP~180
180-310
1s0~3r0
sin-BF
1
2
2
3
3lO-EP
Charge to Reformer, Hydrogenated Fraction
of Table II, Run No _______________________ __
Operating Conditions
at
(1)
(1)
(‘)
(1)
3
0)
2.0
1.8
3.0
.0
3.8
.
.
.
300
809
300
001
300
948
300
000
300
951
“a
as
.18;
,
.a;
,
0,5 7
Debutanizcd Reforninte _________________ __
82. 5
77. 5
68. 6
96.5
88. 8
Pentnncs-Pentcncs- -__ _
Butanes-Butcncs _____ __
_
_
39. 5
8. 7
8. 8
8. S
8. 8
11.9
1.0
0.9
5. 6
3. 4
Net Aromatics ProducetL
.
6.4
31. 7
34. 0
7. 8
18.1
Pressure, p.s.i.g ________________ __
Average Catalyst Temperature, ‘’ F _____ __
Hydrogen/Hydrocarbon Ratio:
---------------------------- --
S.c. . Bbl ............................ __
1,
8-.‘
Yields, percent by Volume of Reformer
Charge:2
-
.
a
-_.
101. 3
97. 3
09. G
00. 6
0. 0
Hydrogen in Reactor Gas, Mol percent.“
See footnotes at end of table.
77. 3
84. 2
77.2
85. 0
78. 4
ogen,
u.
.
__-_-
Ptgcovery, percent by Weight _______ _-
1a:
a
,
o
3,044,950
Table III-Continued
Run Number ________________________________ __
4
5A
5B
6A
6B
Yield: Percent by Volume of Untreated Frac
tion; Debutanized Reformate _____________ __
86. 1
79. 7
70. 6
97. 7
89.9
Gasoline,2 Debutanized Reformate ________ _.
35.6
34.0
30.1
15.6
14.3
75. 4
48. 4
42. 8
39.1
35. 8
Yield, Percent by Volume of Full-Range FOO
Inspections:
1
' ‘r
Stabilized Reformate—
Gravity, ° API ______________________ __
Hydrocarbon Type, percent by
Aromat‘
11. 4
Ole?n
55. 9
1. 7 _
saturates---
86.9
Naphthenes--Parai?ns _________ __
____.
____
Reid Vapor Pressure, Pounds ___________ -_
67. 6
57. 8
0.7
2. 4
1. 5
31. 7
39. 8
24. 0
3. 0
36. 8
1.1
22. 9
2. 0
3. 6
2. 4 ______________________ __
84. 5
7. 0
6.0
~Over Point, ° F
108
104
102
End Point, ‘’ F
253
364
375
436
450 ,
10% at, ° F__
120
160
159
316
238
Distillation (ASTM D—86‘54)—-
9. 6
74. 5
1. 2
42. 9
'
50 _________ __
,
134
90 _________________ __
242
147
251
130
341
340
__._
166
300
297
376
390
Recovery Percent ___________________ --
96. 6
98.5
98. 5
98.7
98.0
Debutanized Reformate-Knock Rating: 3
Motor Method, Octane N umber—
Clear_______ __
+3 cc.TEL_. _
_____ _
77.0
86. 5
91. 2
79. 9
89. 1
91.6
92.1
' 94.1
87.8
92.7
79. 2
93. 7
98.0
103. 6
101. 9
106. 0
89. 3
97. 7
101. 2
103. 5
Research Method, Octane Numbe
Clear _______ __
+3 cc. TEL _____________________ __
1 Platinum-Alumina.
2 Yields are corrected to 100% weight balance.
8 Calculated from octane numbers of the stabilized reformate, Octane Numbers ‘over 100 are in terms or,
the Wiese octane number extension scale.
Table III shows that the hydrogenated light ‘fraction was 30 the flow schemes of FIGURES 2 and 4 in which the middle
not appreciably improved by reforming. The only octane
rating of the reformed hydrogenated ‘light fraction that
fraction is not catalytically reformed would be preferred.
Table III shows that hydrogenation and reforming of
was higher than the corresponding rating of the untreated
the entire residual 310° F.-end point FCC gasoline frac- _
light fraction was the motor (+3 cc. TEL) octane rating.
tion produced yields of debutanized reformate of 97.7 vol
However, the motor (+3 cc. TEL) octane rating of the 35 ume percent based on the ole?nic fraction in the 900° F.
reformed hydrogenated light fraction was not as high
run 6A and 89.9 volume percent in the 951° F. run 6B.
as that of the hydrogenated light fraction prior to reform
Runs 6A and 6B both produced reformates of reasonably
mg. These results demonstrate the signi?cance of my .
high octane ratings',-the octane ratings for the product
procedure of subjecting the light fraction only to hydro
of the 951" F. run 63 being higher than those for the
genation and not to catalytic reforming.
40 product of the 900° F. run 6A.
Table
shows that hydrogenation and subsequent cat
In accordance with my invention I have subjected the
alytic reforming of the 180-310” P. fraction of the ole
hydrogenated 310° F.-end point fraction of run 3, Table
?nic gasoline raised all octane ratings of the ole?nic inter
II, to single-stage, batch, solvent extraction with diethyl
ene glycol at 11:1 solven-t-to-oil ratio. The ra?inate
mediate fraction markedly. For example, the research
clear octane rating of the middle fraction was raised from 45 and extract were separated from the solvent and the raf?n
ate vfraction enriched in nonaromatics was then subjected
92.0 to 101.9 in run 5B which was carried out at the pre- '
to catalytic reforming over a platinum-alumina catalyst
ferred reforming conditions. Run 5A was carried out at
yless suitable reforming conditions, namely, ‘low hydrogen
concentration and moderate temperature. However,
containing ‘a small amount of ?uorine at a pressure of 500
p.s.i.g,'a space velocity of 2 vol./vol./hr., a hydrogen re
even this run increased the research octane number from 50 cycle ratio of about 6,000 standard cubiofeet per barrel
in two reforming runs ‘at temperatures of 898 and 948°
92.0 to 98.0. In both reforming runs of the hydrogenated
F.-, respectively. Table 'IV below gives the properties of
middle fraction the liquid product yield wasrather low,
speci?cally 79.7 volume percent of the ole?nic fraction in
the 901° F. run 5A and 76.6 volume percent in the 948°
F. run 5B. This shows that when high gasoline yield
rather than high octane rating is the main consideration
the ‘aromatics-enriched extract fraction and the nonaro
matics-enriched ra?inate fractions obtained in the extrac
tion stage, as well as the reaction conditions and product
inspections for the two reforming runs conducted ‘with
the ra?'inate fraction.
Table IV
Run Number ________________________________ __
7
8 >
9
Solvent Extraction
of Hydrogenated
310° F.—End Point
Fraction
Extract Ra?inate
Fraction Fraction
Charge Stock
Catalyst. _
Reforming Conditions:
Pressure, p.s.i.g_
1)
1
E!)
El;
500
500
Space Velocity:
V ./Vol./Hr-__
2.0 .
.
2.0
Wt./Hr./Wf
Average Catalyst Temperature, ° F
3.0
898
2. 9
948
Hydrogen/Hydrocarbon Ratio:
Mol./Mol_ _
Cu. Ft./Bbl
Recycle Gas Treatment
See footnotes at end of table.
8. 0
6, 241
(I)
7. 3
5, 645
' (8)
3,044,950
Table I V—C0nt1nued
Run Number ................................ ..
7
S
9
Solvent Extraction
of Hydrogenated
310° F.—End Point
Fraction
Extract Ra?inate
Fraction Fraction
Yields, Percent by Volume of Charge: 4
Debutanized Reiorruate ______________________________________ __
83. 7
Pentane-Pentene
6. 7
Butane-Bufcnc
-__
Net Aromatics Produced
Gas, C1-C3: Cu. Ft./Bbl ................. _-
7. 6
11.0
19. 7
23. 2
232
Hydrogen, Cu. Ft./Bbl_-_..__
76. 2
8. 4
392
420
436
Recovery, Percent by Weight ........... __
93. 3
95. 4
Hydrogen in Reactor Gas, Moi. Percent---
84. 0
72. 1
90. 0
85. 4
Liquid Yield, Percent by Volume of Hydro
genated 310° F.—E.P. Fraction of FCC Gaso
line,4 Debutanlzed Reformate Plus Extract
Products from Solvent Extraction __________ __
38. 5
61. 5
39. 0
62. 3
30. 9
45.0
98
44 1
Liquid Yield, Percent by Volume of Untreated
310° I<‘.—E.P. Fraction of FCC Gasoline 4
Products from Solvent Extraction .......... ._
__________________ __
Inspections:
Stabilized Reiormate
Gravity, ‘’ API ....................... ..
Hydrocarbon Type, Percent by Vol
unlgez thus
are
......................... -_
.
41. 9
38. 5
.
Naphthencs ...................... _Ole?ns
10. 6
19. 7 }
3.9
37- 7
1.1
26-1
0.8
Aromatics ........................ -Reid Vapor Pressure, Lbs ............ ..
79. 6
0. 1
32. 3
0.0
61. 2
4. 5
73. 1
4. 5
Distillation (ASTM D-86-54):
Over Point ° F .................. __
306
316
113
113
End Point, F--10 Percent at: ° F
_
410
328
388
328
458
184
498
180
50 .............. .-
-
346
341
327
________________ --
.
322
304
365
374
382
99. 0
98. 7
98. 7
98.4
_
-
88. 2
91.0
52. 5
75. 0
86. 6
91.0
89.9
95. 4
_
100. 9
103. 2
64. 3
81. 4
97. 7
100.1
101. 2
104. 2
Recovery, Percent ........ __
Debutanized Reiormate—-—Knock Ra
Motor Method: Octane N o.-—~
Clear _________________ .+3 cc. TEL _______ ._
Research Method: Octane
Clear ............. __
+3 cc. TEL ........ -_
1 Rai?nate Fraction from Run 7.
I Platinum-on-Alumina.
1 Dried with Solid Desiccant.
_
4 Yields are corrected to 100% weight balance.
It should be noted that the reforming runs 8 and 9 of 50
In runs 8 and 9 the ra?inate fraction was subjected to
catalytic reforming under conditions that differed mainly
Table IV were carried out at a higher pressure than the re
in the reaction temperature, run 8 being at the moderate
forming runs 6A and 6B of Table III and used a different
temperature of 898° F. and run 9 being at the higher tem
catalyst. In fact, the conditions for runs 6A and 6B of
perature of 948° F. The combined yield of the extract
Table III were more favorable for a good yield—octane
relationship than the conditions for runs 8 and 9. Fur 55 fraction from run 7 and the debutanizcd reformed ra?inate
thermore, it should be noted that the extraction stage
fraction from run 8 was 90.0 volume percent, based on
(run 7) was carried out as a single-stage solvent extrac
the hydrogenated 310° F.-end point fraction. The de~
tion. Better separation of aromatics from nonaromatics
butanized reformate (not including the extract) had
would have been obtained by multi-stage solvent extrac
a Research, clear, octane number of 97.7 as compared
tion. This is mentioned so that it will be understood 60 with 64.3 for the rai?nate before reforming. In run 9
that even though the results of reforming only the ra?inate,
which was carried out at a higher temperature than run 8
as recorded in Table IV, showed an improvement over
the liquid yield of debutanized reformate plus the extract
the results of reforming the entire hydrogenated residual
fraction from run 7 was 85.4 volume percent, based on
fraction, as recorded in Table III, the improvement
the hydrogenated 310° F.-end point fraction. The de
would have been even greater had the same reforming 65
butanized reformate (not including the extract) had a
pressure and catalyst been used in runs 8 and 9, as were
Research, clear, octane rating of 101.2. These results
used in runs 6A and 6B, and had a more e?icient extrac
tion procedure been employed.
show that a fraction of very high octane rating was sepa
rated by selective extraction from the hydrogenated
Table IV shows that the solvent extraction run 7 pro
duced an extract fraction and a ra?inate fraction of widely 70 ole?nic bottoms fraction and that the low octane ra?inate
fraction from the extraction stage was greatly improved
differing properties. Thus, the extract fraction contained
79.6 volume percent aromatics as compared with 32.3
aromatics in the rai?nate'fraction. The Research, clear,
octane number of the extract fraction was 100.9 as com
pared with 64.3 for the ra?inate fraction.
in octane rating by catalytic reforming.
Table V below lists the octane ratings of gasoline ob
tained by blending the extract fraction from run 7 with the
75 reformed ra?inate fractions from runs 8 and 9.
3,044,950
16
15
2. The process for upgrading a gasoline consisting es
sentially of a full range, catalytically cracked, ole?nic‘
gasoline boiling in the range 100 to 430° F. which‘com
gasoline, particular catalytic hydrogenation conditions,
particular reforming conditions, and a particular method,
namely, solvent extraction, for separating the hydro
genated bottoms fraction into a fraction enriched in non
aromatics and a fraction enriched in aromatics. It should
prises. fractionally distilling said gasoline to produce ‘a
light fraction boiling from the initial boiling point to ‘an
The reforming stage can also he carried out by any
hydrogenation at a temperature of 5 00 to 800° F., a pres
sure of 2.00 to 800 p.s.i.g. and with a hydrogen concen
end point of 175 to 195° F., an intermediate fraction boil
be understood, however, that considerable variation is
ing from about the end point of the light fraction to an
possible within the individual process stages, except as
end point of 290 to 320° F., ‘and a residual fraction boil
limited by the appended claims. I have already indicated
ing from about the end point of the intermediate fraction
that the catalytically cracked gasoline charge can in gen
eral be prepared by the known processes for catalytically 10 to the end point of the ole?nic gasoline, subjecting said
light fraction to catalytic hydrogenation at a temperature
cracking gas oil to produce ole?nic gasoline and I have
of 500 to 800° F, a pressure of 200 to 800 psig. and‘
indicated in general the conditions and catalysts that can
with a hydrogen concentration of 1,000. to 10,000
be used for hydrogenation of the ole?nic gasoline or frac
s.c.f./bbl., subjecting said residual fraction to catalytic
tions thereof.
of the conventional procedures [for catalytically reform
ing straight run or hydrogenated naphtha fractions. In
general, these known processes use catalysts comprising
tration of 1,000 to 10,000 s.c.f./bbl., subjecting the hy
drogenated residual ‘fraction to solvent ‘extraction, re
covering from said solvent extraction a ra?iuate fraction
a minor amount of a hydrogenating component, such as
enriched in nonaromatics and an extract fraction en
one or more metals or oxides of metals from group VI
riched in aromatics and having essentially the same boil
ing range ‘as said ra?inate fraction, subjecting said ra?i
nate fraction to catalytic reformingin the presence of
or group VIII of the periodic table, such as platinum,
molybdenum, chromium, tungsten or nickel, the hydro
genating component being supported on a porous carrier
such as alumina, silica-alumina, silica-magnesia, or the
like. The reforming operation is usually carried out by.
contacting the naphtha or gasoline fraction with the cat
alyst in the presence of hydrogen in a concentration from
hydrogen and blending the hydrogenated light fraction,
25 the untreated intermediate fraction, the reformed raf?n-ate
1,000 to 20,000 s.c.f./bbl. at a temperature from 800 to
1050° F. and a pressure from 250 to ‘1000 p.s.i.g. This
results in conversion of the gasolinenange hydrocarbons
to hydrocarbons of higher octane rating without much
change in average molecular weight.
'
'
fraction ‘and the extract fraction of the hydrogenated
residual fraction to produce a gasoline ‘of high octane
rating.
.
3. The process for upgrading a gasoline consisting es
sentially of a full range, catalytic-ally cracked, ole?nic
gasoline boiling in the range 100 to 430° F. which com
/ prises fractionally distilling said gasoline to'produce a
I have described solvent extraction as a preferred
light fraction boiling from the initial boiling point to an
method of separating the hydrogenated residual fraction
end point of 175 to 195° F, anda bottoms fraction boil
glycol as a preferred extracting solvent. Other suitable
ing from about the end point of the light fraction to the
end point of the ole?nic gasoline, subjecting said bottoms
fraction to catalytic hydrogenation at a temperature of
extracting solvents include dimethyl sulfoxide, triethyl
ene glycol and polyethylene glycol. Other suitable meth
500‘ to 800° F, a pressure of ‘200 to 800 p.s.i.g. and with
a hydrogen concentration of 1,000 to 10,000 s.c.f./bbl.,
end point of the hydrogenated gasoline, subjecting said
prises fractionally distilling said gasoline to produce
the same boiling range as said ra?‘inate fraction, subject
ture of 500 to 800° F., ‘a pressure of 200 to 800 p.s.i.lg.
‘fraction, the reformed intermediate hydrogenated frac
tion, the reformed ra?inate fraction of the hydrogenated
to solvent extraction and recovering a raf?uate fraction
into 1a traction enriched in nonaromatics and a fraction ‘
enriched in aromatics and have described diethylene
ods for selectively separating the aromatics and non 40 fractionally distilling the hydrogenated bottoms fraction
to produce a hydrogenated intermediate fraction boiling,
aromaticsinclude adsorption separation methods, extrac
from the initial boiling point of the hydrogenated bottoms
tive crystallization and molecular sieve separation.
fraction to an end point of 290 to 320° F. and a hydro
Obviously many modi?cations and variations of the in
genated residual fraction boiling from about the end point
vention as hereinbefore set forth may be made without
departing from the spirit and scope thereof ‘and therefore 45 of the intermediate fraction to the end point of the hy
drogenated bottoms fraction, subjecting the hydrogenated
only such limitations should be imposed as are indicated
intermediate fraction to catalytic reforming in the pres
in'the appended claims.
ence of hydrogen, subjecting the hydrogenated residual
i claim:
fraction to solvent extraction to produce a raf?nate frac
\1. The process ‘for upgrading a gasoline consisting es
sentially of a full range, catalytically cracked, ole?nic gas 50 tion enriched in nonaromatics and an extract fraction
enriched in aromatics and having essentially the same,
oline boiling in the range 100 to 430° P. which comprises
boiling range as said raf?nate fraction,’ subjecting said
cat-alytically hydrogenating said full range gasoline at a
ra?inate fraction to catalytic reforming in the presence of
temperature of 500 to 800° F., a pressure of 200 to 800
hydrogen and blending the untreated light fraction, the
p.s.i.g. and with a hydrogen concentration of 1,000 to
10,000 s.c.f./bbl., fractionally distilling the hydrogenated 55 reformed intermediate hydrogenated fraction, the ‘re
formed ra?inate fraction of the hydrogenated residual
gasoline to produce a light fraction boiling from the initial
fraction and the extract fraction of the residual fraction
boiling point of the hydrogenated gasoline to an end point
to produce a gasoline of high octane rating.
of 175 to 195° R, an intermediate fraction boiling from
‘4. The process for upgrading a vgasoline consisting es
about the end point of the light fraction to an end point
of 290 to 320° F. and a residual fraction- hoiling from 60 sentially‘ of a full range, catalytically cracked, ole?nic
gasoline boiling in the range 100 to 430° F. which com
about the end point of the intermediate fraction to the
overhead fraction boiling from the initial boiling point to
intermediate fraction to catalytic reforming in the pres
an end point of 290 to 320° F. and a residual fraction,
ence of hydrogen, subjecting said residual‘fraction to
solvent extraction, recovering from said solvent extraction 65 boiling from about the end point of the Overhead fraction . V
to the end point of the ole?nic gasoline, subjecting said
a ra?inate fraction enriched in nonaromatics and an ex
residual fraction to catalytic hydrogenation at a tempera
tract fraction enriched in aromatics and having essentially
and with ‘a hydrogen concentration of 1,000 to 10,000
ing said ra?lnate fraction to catalytic reforming in the
presence of hydrogen and blending the hydrogenated light 70 s.c.f./ibb1., subjecting the hydrogenated residual fraction
residual fraction and the extract fraction of the hydro
genated residual fraction to produce a gasolineof high
octane rating,
enriched in non-aromatics ‘and an extract fraction enriched ‘ ,y ‘a
in aromatics and having essentially the same boiling range
as said ra?inate traction, subjecting said raf?nate fraction,
to catalytic ‘reforming in the presence of hydrogen and
3,044,950
13
.
Table V
14
.
has the properties shown in Table I. This fraction is of
about the same quality as the ‘full range ole?nic gasoline
Run Number ___________________ -_
Retormate Plus Extract ________ ._
8
9
Charge to
Extraction,
Hyld?igen
eavy
ate
FC C
and can suitably be passed to gasoline blending with the
fractions which are upgraded. The product obtained
from the bottoms fraction by hydrogenation, extraction
‘and catalytic reforming of the ra?inate has the excellent
properties described above in connection with FIGURE
1. Thus, the procedure of FIGURE 2 has the advan
tages of producing a light fraction with a high motor
Gasoline
Stabilized Reformate Plus Ex
tract‘
10 octane rating and a bottoms fraction of very high octane
Gravity, ° API ............. _.
Vapor Pressure, Reid, Lb.___
rating but omits treatment of the middle fraction, so that
in comparison with FIGURE 1 there is an improvement
in yield and a lower processing expense although there is
a sacri?ce in the octane improvement which would be
Debuttanized
Reformate Plus Ex
tra 0 :
Knock Rating—
Mloqtor
Method, Octane
0..
obtained by reforming the hydrogenated middle fraction
Clear _______________ __
+3 cc. TEL ________ __
as in FIGURE 1.
Research Method, 00
tane N 0.:
In FIGURE 3 the light fraction is untreated. It has
the properties indicated in Table I. All of its octane
ratings are higher than those of the charge stock, al
Comparison of the yield-octane relationships for the 20 though the motor octane rating is not nearly so high as
Clear _______________ ._
+3 cc. TEL ________ __
9.
2. 8
products of runs 8 and 9 as listed in Tables IV and V with
the products of runs 6A and 6B as listed in Table II shows
a marked superiority for my procedure of separating the
is obtained by the hydrogenation procedures of FIG
URES 1 and 2. The middle and heavy fractions receive
the same treatment as in FIGURE 1, namely, the hydro
genation and reforming of the middle fraction ‘and hy
only the nonaromatics-enriched portion thereof to cata 25 drogenation, extraction and reforming of the raf?nate of
the residual fraction. Thus, the procedure of FIGURE
lytic reforming instead of reforming the entire fraction as
hydrogenated 310° F.—end point fraction and subjecting
in runs 6A and 6B. The motor method octane numbers
(+3 cc. TEL) of the products of runs 6A and 6B were
87.8 and 92.7, ‘respectively. As shown in Table V the
octane numbers of the blends of extract with a refor
mates from runs 8 and 9 had motor method octane num
3 has most of the advantages of FIGURE 1 but does not
gain the motor octane improvement of the light fraction
which is obtained by hydrogenation of this fraction in
30 FIGURE 1.
FIGURE 4 represents the minimum upgrading in ac
cordance with the invention but shows that a consider
bers (+3 cc. TEL) of 92.0 and 93.4, respectively. The
able improvement of the full range gasoline is accom
other octane ratings of the products of Table V were simi
plished by treating only the residual fraction thereof.
larly superior to those of runs 6A and 6B. As previously
mentioned, the superiority of the products of Table V 35 This fraction, as in each of the other schemes, is hydro
would have been even greater had the reforming procedure
genated and solvent extracted, the ra?inate then being
in runs 8 and 9Vbeen the same as in runs 6A and 6B. This
can be stated with con?dence inasmuch as I have de
cataly-tically reformed. This selective treatment of a nar
row portion of the full range gasoline, provides an eco
termined previously that the use of the catalyst employed
nomical method of making a marked improvement in the
overall gasoline.
The speci?c example describes particular initial and
in runs 6A and 6B and the use of lower pressure results
in a yield-octane relationship clearly superior to that oh
tainable with the catalyst and higher pressure used in
end points for the fractions formed in my process. How
runs 8 and 9.
ever, ‘as I have indicated, these can extend over certain
Advantages of each of the embodiments of my process
shown in the drawing can be seen from the data of
Tables I through V. Thus, the tables show that the pro
cedure of FIGURE 1 greatly improved the ole?nic gaso
mentioned ranges. Thus, the light fraction can have an
end point from 175 to 195° F. The middle fraction,
which has an initial boiling point of about that of the
end point of the light fraction, can have an end point
from 290 to 320° F. The residual fraction will have an
line. Considering the qualities of each fraction, the hydro
initial point of about that of the end point of the middle
genated light fraction, as shown in Table II was greatly
fraction. Within these ranges certain speci?c cut points
superior in motor method octane rating to the full range
are preferred for certain modi?cations of the process.
ole?nic gasoline and to the untreated light fraction of the
Thus, the end point of the light ‘fraction of the ole?nie
ole?nic gasoline as shown in Table I. Furthermore, the
gasoline is preferably at or near the upper end of the
leaded octane sensitivity of the hydrogenated light frac
range 175-195° P. if the middle fraction is to be sub
tion Was zero. The catalytically reformed hydrogenated
intermediate fraction of run 5A, as shown in Table III, 55 jected to catalytic reforming. Giving the light fraction
the highest end point will insure that at least part of the
was greatly superior to the full range FCC gasoline and
C7 branched chain para?ins, and especially the dimethyl
to the untreated intermediate fraction of the FCC gaso
pentanes, are recovered in the light fraction instead of in
line in all octane ratings. The leaded octane sensitivity
was also considerably better than that of either the full
the middle fraction. This will avoid subjecting to eat
alytic reforming branched chain heptanes which are al
range FCC gasoline or of its intermediate fraction. The
similar reformate obtained in run 5B was even more
ready of high octane rating.
superior to the untreated fractions. The product obtained
from the residual hydrogenated fraction in FIGURE 1,
Similarly, if the middle fraction is not to be subjected
to catalytic. reforming, as in FIGURE 2, it is preferred
to give the residual fraction of the ole?nic gasoline an
namely, the blend of the aromatics-enriched extract and
the reformed rai?nate was also greatly superior to the 65 initial ‘boiling point at or ‘near the lower end of the range
starting materials as shown in Table V. Thus, the blends
290-320“ F. This will place the C9 normal paraf?n,
produced from the runs 8 and 9' reformates had motor
n-nonane, or at least part of the same, in the residual
and research octane numbers markedly superior to those
fraction from which it will subsequently be recovered with
of full range FCC gasoline or of the residual fraction
other nonaromatics and subjected to catalytic reform
thereof. Furthermore, the leaded octane sensitivities were
ing. This will contribute to maximum upgrading of the
10.8 and 10.9, respectively, as compared with 14.5 for
charge stock because n-nonane, although a minor com
the full range FCC gasoline.
ponent, has a rather low octane rating and can be im
Referring to FIGURE 2, the hydrogenated light frac
tion will have the same properties as discussed in con
proved by reforming.
‘I‘he runs of the speci?c example described above used
nection with FIGURE 1. The untreated middle fraction 75 a particular cracking process for preparing the cracked
3,044,950
17
blending the untreated overhead traction, the reformed 9’
2,409,695
2,419,029
Laughlin ____________
18
__ Oct. 22, 1946
Oberfell _____________ _.. Apr. 15, 1947
ra?inate fraetion of the hydrogenated residuval- fraction
and the extract fraction of the hydrogenated residual ‘frac
tion to produce a gasoline of high octane rating.
2, 69 6,460
Hemmimger __________ .. Dec. 7, 1954
2,703,308
Oblad ________________ __' Mar. 1, 1955
References Cited in the ?le of this patent
UNITED STATES PATENTS
2, 8 62,870
Voorhies ______________ __ Dec. 2, 1958 "
2,905,620
2,925,373
Haensel ____________ _._. Sept. 22, 1959,
Annable et ‘a1. ____, ____ __ Feb. 16, 1960
2,946,73 6
Muiiat et ‘a1 ___________ __ July 26, 1960
2,324,295
Goldsby ______________ __ July 13, 1943
V
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