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Патент USA US3033787

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3,033,777
“
'
Patented May 8, 1902
2
able at a given reactionv temperature when compared with
.
a single treatment of the whole of a catalytic reformate.
Further while the treatment of the lower-boiling fraction
decreases its volatility,’ this is o?set' at least in part by
the increase in volatility of‘ the treated higher-boiling
3,033,777
TREATMENT 9F CATALYTEQ REFGWATES
John Arthur Edgar May and Peter Thomas White, Sun
hury-on-Thames, England, assignors to The British Pe
troleum Company Limited, ‘London, England, a Britis
joint-stock corporation
-
fraction, and a higher octane number is obtainable at a
.
given volatility, or vice versa, than, when treatingfthe
No Drawing. Filed May 11, 1959, Ser. No. 812,139
Claims priority, application Great Britain May 23, 1958
6 Ciaims.
(Cl. 200-79)
whole of a catalytic reformate.
The preferred dehydrogenation and dehydrocyclisation
/
This invention relates to the treatment of the products
10
of a catalytic reforming process, hereinafter referred to as
catalyst for treating both the higher-‘boiling and‘ lower
boiling fractions consists essentially of chromium oxide
supported on alumina. It ispreferably used ata pressure
of up to 50 p.s.i.g. (including atmospheric pressure or
In catalytic reforming processes, a naphtha fraction is
below) and without recycle of the hydrogen-rich gas
contacted at elevated temperature and pressure and in 15 produced or addition of extraneous hydrogen-rich gas
the presence of hydrogen with a dehydrogenation catalyst
produced or addition, of extraneous hydrogen. The space
catalytic reformates.
to produce a gasoline fraction of increased octane number.
' velocityymay be from 0.1 to 1.0 v./v./hr. of liquid feed
Catalysts that are used commercially include molybdenum
stock. The chromia on alumina catalyst may contain
oxide on alumina and catalysts consisting essentially of
a minor proportion of oneor more promoters, for ex
platinum on alumina with or without combined halogen. 20. ample a rare earth or mixture of rare earths,- bismuth,
A cat?ytic reforming process using a platinum-on
boron, germanium, nickel, manganese, iron or beryllium
alumina type catalyst will hereinafter be referred to as
preferably in combination with an alkali metal, such, as
platinum reforming and the products as platinum refor
potassium. Another particularly etfective promoteris a
mates.
minor proportion of a spinel, for example cobalt, chro
Platinum reforming is capable of giving products with 25 mite, copper chromite, zinc titanate, or iron chromite,
octane numbers research (clear) of the order of 90-100,
either as such or in the form of the naturally-occurring
but it has certain limitations. In the ?rst place, beyond
ore’ “chrome ironstone.”
,
a certain octane level, increase in octane number is only
The preferred proportions of the catalyst, by weight
obtainable at the expense of decreased volatility and this
of total catalyst stable at 1020° F.,‘are:
runs contrary to the present emphasis on gasolines having 30
Chromium oxide _______ __ 5-25 % wt.
both high octane number and high volatility. While ad
Total promoters (expressed
justment of the feedstock boiling range can improve prod
uct volatility, treatment of lower-boiling feedstocks re
as oxide in the case of
quires high operating severity and gives lower yields. In
metals)
____________ __ 0.1-—l0% wt. (but less than
the amount of chromium
the second place, there is a practical upper limit of octane 35
oxide).
number, quite irrespective of volatility.
Alumina ______________ .._
According to the present invention, a catalytic refor
Balance.
mate is separated into a higher-boiling fraction and a
The dehydrogenation and dehydrocyclisation process
lower-boiling fraction, at least the higher-boiling fraction
may be carried out with a ?xed bed, a moving bed or a
is contacted at from 840 to 1075“ F. (450 to» 580° C.)
?uidised bed of catalyst. With the preferred catalyst,
which can be readily regenerated by conventional tech
niques, a ?uidised bed is-preferred.
with a dehydrogenation and dehydrocyclisation catalyst
to yield a product of increased volatility and the treated
higher-boiling fraction is recombined either with the
untreated lower-boiling fraction or with the lower-boiling
The preferred catalytic reformate used as feed stock '
is a platinum reformate.
.
The platinum reformate is preferably, produced by a
fraction after it has also‘ been contacted at elevated tem 45
platinum reforming process using a heavy naphtha'feed
perature with a dehydrogenation and dehydrocyclisation
stock and operating under conditions such that regen
catalyst to yield a product of increased octane number.
eration of the catalyst in situ is not required (i.e. a cata
The higher-boiling fraction of a catalyst reformate is
lyst life of at least 40 barrels of feedstock processed per
relatively rich in aromatics andis not, prima facie, a suit
able material for further upgrading by dehydrogenation
lb. of catalyst).
volatility and also, usually, increased octane number.
Preferably the product has a volatility of at least 40%
volume evaporated at 100° C., particularly from 40 to
60%, and an octane number research (clear) of at least
to give a reformate having an octane number research
(clear) of'90 to 100. Any convenient platinurnreform
ing process may be used and the process conditions will
50
The term heavy naphtha means a- naphtha having’ an
and dehydrocyclisation. However, such a treatment gives
ASTM ?nal. boiling point between 150° C. and 200° C.
a product of increased volatility. The octane number can
and, preferably, an ASTM initial boiling point within the
also be increased further. ‘By blending this treated
range 70° C. to 100° C.
,
p
higher-boiling fraction back with the untreated lower
boiling fraction, a ?nal product is obtained of increased 55 The platinum reforming stage is preferably operated
90.
e
' The product may be used as a component of motor
normall'yifall within'the following ranges:
60 Catalyst “an.-- 01-10% wt. platinum on alumina
'
gasolines, but the process is particularly suitable for the
gen, particularly ?uorine and/or
chlorine.
production of high octane number, high volatility motor
gasolines themselves which do not require the’ addition
of further blending components.
,
.
In a further speci?c embodiment of the present in
Temperature ____ 60.051200“
fractions are contacted separately with a dehydrogena
an octane number research (clear) of at least 100. It 70
has been found that higher octane numbers are obtain
preferably 9004000a ’ '
F.
65
vention both the higher-boiling'and the lower boiling
tion and dehydrocyclisation catalyst and the fractions
are re-combined. Preferably the recombined blend has
withor without-0.1-8% wt. ofzhalo
504000 p.s'.i., preferably 300-700
,
p.s.1.
Space velocity __ 0.5-10 v./v./hr.,
v./v:/hr.
preferably"
Molar; hydrogen]
hydrocarbon ra-l
tio ________ __ 0.5-1'5', preferably‘ 640.
1-3
3,033,777
4
The'higher-boiling fraction of the catalytic reformate
lower-boiling fraction having an ASTM ‘boiling range
‘should contain the majority of the alkyl aromatics in the
reformate. A convenient separation point is in the
range 80—l30° 0., more particularly within the range
of 34-108° C. and an octane number research (clear)
of 76.1 and a higher-boiling fraction having an ASTM
boiling range of 128-216“ C., and an octane number re
100-120° C. The separation may be e?ected by simple
search (clear) of 104.6. The lower-boiling fraction rep
resented 41.2% wt. and the higher-boiling fraction
~ distillation.
The invention is illustrated by the following-examples.
- 58.8% wt. of the platinum reformate.
The higher-boiling fraction was treated under the same
conditions and with the same catalyst as that used in
EXAMPLE 1
i . A naphtha of Middle East origin having an ASTM 10 Example 1.
boiling range of 90-171" C. was reformed using a cata
'
Runs were carried out at four different temperatures
lyst of 0.7% wt. platinum, 0.45% Wt. fluorine and 0.34%
and the results are set out in Table 3 below.
Table 3
wt. chlorine on alumina to a research octane level of
‘'93. The reforming conditions used were 925° F., 500'
p.s.i.g., 10 v./v./hr. and a hydrozen/hydrocarbon'mol 15
_'ratio of ‘10:1. The platinum reiormate so produced was
Feed
‘fractionated at 100° C. to 'give a lower-boiling fraction
having an ASTM boiling range of 43497.5“ ‘C. and an
octane number research (clear) of 69.2 and a higher
Yield on feed, percent weight
100
‘
'boiling fraction having an IBP of 115° C. and an octane 20 Speci?c gravity at 60° F./
60°F ____________________ __ 0. 8505
‘1 number research (clear) of 101.9.’ The lower-boiling
Volatility at 140° 0., per—
ccn vol _________________ __
20.0
‘fraction represented 34.4% wt. and the higher-boiling
Octane number research
(clear) ___________________ __
" fraction 65.6% wt. of the platinum reformate.
Reaction temperature ° F.
104.0
837
932
977
1,022
86. 0
84. 0
79. 0
77. 0
0.8700
0.8730
0.8755
'0. 8765
38.0
a
111.0
34.0
33.0
57.0
112.2
112.2
112.8
» The higher-boiling fraction was treated over a ?xed
\ bed of a catalyst consisting of 10% Wt. chromia on alu
25
mina promoted with 1% wt. cerium oxide and 1% wt.
The treated higher boiling fractions were then'blended
. back with the lower-boiling fraction. The blends again
had an increased volatility and octane number as shown
_ potassium oxide under the following conditions:
in Table 4.
Pressure ___________________________ __ Atmospheric.
Space velocity __________ .._ __________ __ 0.2 v./v./hr.
Recycle
Table 4
30
Untreated
gas ________ -1 ______ _; ______ __ None.
Heavy end treated at—
platinum
.Process period ______________________ __ 5 hours.
'
refer-mate
'
.
887° F. 932° F. 977° F. 1,022“ F.
Runs were carried out at two different temperatures
35. Yield on total platinum
and the results are set out in Table 1 below.
ret‘orrnate, percent
7
7
Weight ______________ ._
Volatility at 100° 0.,
percent vol __________ __
Table 1
Reaction temper
032
' ‘Yield on feed, percent Weight _________ __~
Speci?c gravity at 60° FJSO“ F ____ _;
-.
. ' Volatility at 140° 0. percent volume
_
7’
Octane number research (clear) ______ -_
.
40'
ature, ° F.
92. 1
90. 0
39. 5
51. 8
52. 4
53. 8
89. 0
54. 5
92. 8
-95. 6
06. 3
95. 8
95. 0
'
(clear) ............... _.
Feed
93. 2
_
Octane number research
7
100
EXAMPLE 3
’ Comparative experiments were carried out in which
1,022
100
' 87. 9
75. 2
0. 8405
‘0. 8700
0. 8732
48
47. 5
51. 7
101.9
108.4
108.4
the whole of the platinum reformate of Example 2, and
the higher-boiling fraction and the lower-boiling .frac
45 tions (also as obtained in Example 2) were treated sep
arately under the same conditions and with the same
' catalyst as that used in Example 1. The treated higher
and lower-boiling fractions were subsequently re-com
The treated higher-boiling fractions were then blended"
back with the lower-boiling fraction. The blends had the 50
7 characteristics shown in Table 2.
bined. .
The reaction temperatures used and the results ob
tained are set out in Table 5 below.
Table 57
Table 2
Treating total platinum reformate
Untreated Heavy end Heavy end 55
7 relormate
treated at
treated a
932° F.
1022° F.
Reaction temperature ° 1:‘.
Feed
.
° F.
887
Yield on total platinum reformate,
percent weight _____________ _V____
.Vnlatility at 100° 0., percent. vol_Octane number research (clear)..-_
100
34.5
v03. 0
7
5
8
60
Yield on feed, percent weight.
Volatility at 100° 0., percent
100
volume...‘ _______________ __
39. E
Octane
number
From the table‘ it will 'be seen that the ‘volatility of
the ?nal product and also thero'ctane number has been
increased as compared withvthe original platinum re 65
'
formate.
_
7
EXAMPLE 2
977
86
83
32. 6
33. 6
,7 100. 4
102. 3
1,022
70 ______ -_
.
research
(clear) ___________________ __
932
.
92. 8
27
...... -.
103. 5
______ __
'
Treating lower-boiling fraction (SG 0.69)-—Yield on total reformate
‘
53.6% vo1., 41.2% weight
Yield on feed, percent weight. .--_-'.-_ i
Volatility at 100° 0., percent vol. __
1
.
72. 6
01. 6
67. 0
74
67. 2
62:0
59. 0
. 7360
. 7610
.7900
.7970
Octane numberrresearch (clear) ____ .. ' - 94.3
90.0
102.1
103.0
seat; 60° E160“ F-__ .............
__
A naphtha of Middle East origin having an ASTM
boiling range of 100 to, 175° C; was reformed using a 70 Treating higher-boiling traction '(SG .8565)——-Yie1d
catalyst of platinum, alumina and combined halogen to
an octane level research (clear) of 92.8. The reforming
conditions were 940° F., 450 p.s.i.g., 1.8 v./v.‘/hr. and
a hydrogen/hydrocarbon mol ratio of 9:1. The plati
num'reformate was fractionated at 115° C. to give a 75
I
a
on total reformate
46.5% VOL, 58.8 0 weight
Yield on feed, percent Weight
86
70
77
SG at 60° F./60° F _________ _.
. 8700
.8730
. 8755
.8765
Octane number research (clea
111.0
112. 2
84 '
112.2
112.8
3,033,777
5.
6
Blend of treated hlgher- and lower-boiling fractions-Blended in make
1020° F., and balance alumina, at a temperature of 840‘
ratio on total reiormate
to 1075“ F., at a pressure not in excess of 50 p.s.i. ga., at
a space velocity of 0.1 to 1.0 v./v./hr., and in the absence
of added hydrogen, recovering the treated high boiling
Yield on total relormate, percent
70. 5
67. 4
Volatility at 100° 0., percent vol____-
38. 1
32. 2
27. 6
Octane number research (clear) ____ __
Weight _________________________ _-
101. 8
84. 6
105. 8
78. 5
107. 7
25. 4
108. 6
fraction, contacting the separated low boiling fraction
in a reaction zone With a dehydrogenation and dehydro
cyclization catalyst consisting essentially of 5 to 25% wt.
of chromium oxide, by weight of total catalyst stable at
From the table it will be seen that at a reaction tem
perature of 887° F. the blended product has a somewhat
1020” F., and balance alumina, at a temperature of 840
higher octane number and a considerably higher vola 10 to 1075 ° F., at a‘pressure not in excess of 50 p.s.i. ga., at a
tility than the treated total reformate. At the higher
space velocity of ‘0.1 to 1.0 v./v./hr., and in the absence
of added hydrogen, recovering the treated low boiling
reaction temperatures the two products are of equivalent
volatility but the blended product has a considerably
higher octane number.
We claim:
‘
fraction, and combining the treated fractions to produce
a product having an octane number research (clear) of
15 at least 100, and a volatility at least substantially equal
1. A process for the treatment of a catalytic reformate
to produce a product having a high octane number and
to the volatility of the catalytic reformate.
high volatility which comprises separating the catalytic
catalyst includes at least one promoter in an amount of
,
3. A process in accordance with claiml wherein the
reformate into a high boiling fraction and a low boiling
0.1 to 10% wt. by weight of total catalyst stable at 1020°
fraction, the cut point between the fractions being in the
range 80 to 130° C., contacting the high boiling fraction
F., said weight of promoter being less than the weight of
in a reaction zone with a dehydrogenation and dehydro
the chromium oxide.
4. A process in accordance with claim 2 wherein the
cyclization catalyst consisting essentially of 5 to 25% wt.
of chromium oxide by weight of total catalyst stable at
catalyst includes at least one promoter in an amount of
to 1075° F., at a pressure not in excess of 50 p.s.i. ga., at
the chromium oxide.
0.1 to 10% wt. by weight of total catalyst stable at 1020"
1020° F., and balance alumina, at a temperature of 840 25 F., said weight of promoter being less than the weight of
a space velocity of 0.1 to 1.0 v./v.’/hr., and in the absence
'
5. A process in accordance with claim 1 wherein the
of added hydrogen, recovering the treated high boiling
fraction, and combining the low boiling fraction with
said treated high boiling fraction to produce a product
catalytic reformate is a platinum reformate.
6. A process in accordance with claim 5, wherein the
30 platinum reformate is produced by a process using a heavy
naphtha feedstock and operating under conditions such
having an octane number research (clear) of at least 90
and a volatility of at 'least 40% volume evaporated at
that the regeneration of the catalyst in situ is not required.
100° C.
2. A process for the treatment of a catalytic reformate
to produce a product having a high octane number and 3-5
high volatility which comprises separating the catalytic
References Cited in the ?le of this patent
UNITED STATES PATENTS
reformate into a high boiling fraction and a low boiling
fraction, the cut point between the fractions being in the
2,304,183
2,337,191
Greensfelder et al ______ __ Dec. 21, 1943
range 80 to 130° C., contacting the high boiling fraction
2,758,062
Arundale et al. ________ __ Aug. 7, 1956
2,765,264 '
'Pasik _____ __‘ ___________ __ Oct. 2, 1956
in a reaction zone with a dehydrogenation and dehydro
cyclization catalyst consisting essentially of 5 to 25% wt.
of chromium oxide, by weight of total catalyst stable at
Layng et al. __; _________ __ Dec. 8, 1942
' 2,773,917
Coonradt et a1 _________ __ Dec. 11, 1956
2,897,132
Knight ____ -_' _______ _.'___ July 28, 1959
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No, 3,033,777
May 8q 1962
John Arthur Edgar Moy et a1.
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent ehould read as
corrected below.
Column 1, line 48, for "catalyst" read —— catalytic ——;
column 2, line 24, after "cobalt“ strike out the comma; line
66, before "50-1000" insert —- Pressure-———-
-—; column 3, line
15, for "10 v.,/v,./hr-. and a hydrozen/hydrocarbon" read
—— 100 v.,/v.,/hr*u and a hydrogen/hydrocarbon --; column 4,
Tabtl‘e E3, heading to column 2 thereof 1, for "Feed °F." read
-—
ee
——.
Signed and sealed this 9th day of October 1962.
(SEAL)
Attest:
ERNEST W. SWlDER
Attesting Officer
DAVID L. LADD
Commissioner of Patents
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