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Патент USA US3083252

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United States Patent 0 "ice
3,083,244
Patented Mar. 26, 1963
1
2
3,083,244
moving. Reaction systems in which any part of the
products are recycled for further conversion may be used.
NON-CATALYTiC PROCESS FOR THE RECOVERY
OF ALKYLNAPHTHALENES IN THE PRESENCE
OF HYDROGEN
The petroleum hydrocarbon feed materials employed
in our process boil primarily in a temperature range from
about 300 to 800° F., preferably in :a temperature range
.
Robert A. Sanford, Homewood, Henry D. Ballard,
Harvey, and Arvin D. Anderson, South Chicago
Heights, 111., assignors, by mesne assignments, to Sin
clair Research, Inc., New York, N.Y., a corporation of
from about 450 to 600° F., and include petroleum mate
rials such as cracked petroleum fractions and straight run
materials containing naphthenes, para?ins, aromatics and
Delaware
No Drawing. Filed July 22, 1958, Ser. No. 750,082
4 Claims. (Cl. 260-674)
ole?ns in the same boiling range, as well as alkyl naphtha
lenes. Generally the hydrocarbon feed material includes
at least about 20 weight percent and preferably about 35
to 80 weight percent of alkyl naphthalenes.
This invention relates to a process for recovering
In addition the feed preferably should contain only
alkylnaphthalenes of high purity and particularly per
minor amounts of biphenyl and alkylbiphenyls, ?uorine
tains to a thermal process conducted in the presence of
hydrogen for recovering alkylnaphthalenes of high purity 15 and alkyl?uorenes. These compounds appear to react only
slowly under conditions of this process and, therefore,
from petroleum hydrocarbon materials containing these
would have to be separated by other methods.
and other components. Alkylnaphthalenes are valuable
In some operations it may be desirable to fractionate
intermediates for the production of organic chemicals
the feedstock to maximize alkylnaphthalenes'of ‘:a particu
since, for instance, they can be oxidized, sulfonated or
20 lar molecular weight range. In a second type of opera
dealkylated.
tion severity could be adjusted to maximize alkylnaphtha
It has been recognized for some time that naphthalene
lenes of \a particular molecular weight by fractionating
could be produced-by catalytic processing of alkylnaphtha
the products to separate the desired boiling range and
lene containing petroleum hydrocarbon materials in the
recycling higher boiling material.
'
presence of hydrogen. The recovery of alkylnaphthalenes
from the products of these reactions has been suggested. 25 The alkylnaphthalenes susceptible of recovery in the
above-described hydrocarbon materials correspond to the
In these processes, the feedstocks usually include naphtha
following general formula:
lene, alkylnaphthalenes and other materials boiling in
10
the alkylnaphthalene boiling range. Although naphtha
lene and alkylnaphthalenes can be separated using, for
instance, distillation means, the other materials boiling 30
in the alkylnaphthalene boiling range are dif?cult to re
move without converting some of the alkylnaphthalenes
R71.
to naphthalene. This “converting,” obviously, will result
in lower yields of alkylnaphthalenes. However, when
where n is 1 to 8 and R is an alkyl radical containing
generally from about 1 to 13 and preferably from about
presence of hydrogen, petroleum hydrocarbon materials
containing alkylnaphthalenes, naphthalene, and other ma
terials boiling in the alkylnaphthalene boiling range are
in alkyl groups attached to the naphthalene nucleus is
generally from about 1 to'13 and preferably from about
following our thermal process which is conducted in the 35 1 to 5 carbon atoms. The total number of carbon atoms
1 to 5.
The present invention will be more clearly illustrated
converted to fractions rich in alkylnaphthalenes without
40 with the following example.
excessive conversion to naphthalene.
In the process of the present invention, alkylnaphtha
EXAMPLE I
lenes of high purity are recovered from petroleum hydro
(A)
carbon materials under conditions including tempera
Analysis of feedstock:
tures generally from about 1100” to 1350“ F. and, pref
API
20.2
erably from about 1140" to 1220° F.; a hydrocarbon feed 45
Bromine No _________________________ __
13.0
partial pressure generally from about 20 to 200 p.s.i.a and
M.W.
174
preferably from about 60 to 125 p.s.i.a.; and a hydrogen
Percent S
partial pressure generally greater than 200 p.s.i.a. and
preferably greater than 500 p.s.i.=a. and up to about 1000
p.s.i.a. The contact time is generally from about 0.5 to 50
200 and preferably from about 3 to 60 seconds. These
conditions are employed in a relationship according to
the formula
tPH2
55
33.4 Paco-ml: (igga‘g- 26.00)]
t=contact time in seconds
PH2-=parti-al pressure of hydrogen in p.-s.i.
PHI¢=partiaI pressure of hydrocarbon feed in p.s.i.
60
e=the base of natural logarithms ('=2.7l8 . . .)
°R=temperature in degrees Rankine
Various types of thermal conversion systems can be
used such ‘as, for instance, coil-type heaters, void reactors,
or reactors packed with inert material, either ?xed or
1.5365
Speci?c
disperson ____________________ __
215.8
Percent aromatics:
F.I.A.
_________________________ _...
ES45A 1
_______________________ __
63.5
48.8
Percent ole?ns:
_________________________ .__
5.8
ES45A 1 ________________________ __
F.I.A.
16.7
Percent naphthalene __________________ __
Percent m-methylnaphthalene ___________ __
Percent B-methylnaphthalene ___________ __
0.58
2.13
1.98
Percent alkylnaphthalenes, M.W. 156 ____ __
Percent kalkylnaphthalenes, M.W. 170 ____ __
Percent alkylnaphthalenes, M.W. 184 ____ __
17.2
12.2
5.0
1HSTM-D8‘78
X, hereinafter referred to as “X value,” must be between
about l-l00, preferably between 2-50.
0.11
11132"
65
(13)
Samples of the feedstock analyzed in (A) above, were
hydrothermally treated in runs 1 to 5 using a thermal
reactor. The conditions as well 'as the results for each
of these runs are presented below in Table I.
e
3,083,244
3
4
Table 1
where t is the contact time in seconds, PH2 is the partial
pressure of hydrogen in psi, VPHIC is the partial pressure
of hydrocarbon feed in p.s.i., e is the base of natural
logarithms, ° R is the temperature in degrees Rankine,
and X is between about ;1 and 100.
2. The process of claim 1 wherein X is between about
Run No ___________________ __ Feed
1
2
3
4
l, 130
1, 180
5
Conditions:
_1, 200
Temperature, ° F _____ __
25
Contact Time, Sec____ .
Hydrocarbon Partial
Pressure, p.s.i.a.______
Pressure, p‘.s.i.a._-____
Concentration of Naphtha
lenes in Fractions, Wt.
percent of Fraction:
450-475“ F. Fraction
2 and 50.
3. A process for the recovery of alkylnaphthalenes
87
Hydrogen Partial
____ __
628
'
from petroleum hydrocarbon materials boiling in the tem
801
310
perature range from about 300 to 800° F., said hydro
carbon materials including aromatics, ole?ns and about
. 20 to 80 weight percent of alkylnaphthalenes, the step
_10
(Naphthalene and
Methylnaphtha
lone
____ _-_ _______ -_'__
100. o
78.9
96. l
86. 8
comprising treating said hydrocarbon materials in the
I
presence of hydrogen, in the absence of a catalyst and
475—520° F. Fraction
(Alkylnaphtha
nes,
.W. 15
.____
520—560° F. Fraction
15 under thermal conditions including a temperature from
about 1100“ to 1350° F., a hydrocarbon partial pressure
from about 20 to 200 p.s.i.a., a hydrogen partial pressure
from about 200 to 1000‘p.~s.i.a., and a contact time from
about 0.5 to’ 200 seconds; said thermal conditions being
(Alkylnaphthalenes,
M.W. 17
85.9
__________ __
"
EGO-600° )3‘. Fraction
(Alkylnaphthalenes,
18
71.7
__________ __
Total Alkylnaphthaleues,
Naphthalene Yield, Wt.
-
62.5
employed in a relationship according to the following
formula:
41.7
Wt. percent Feed _______ __
'
3.3
percent Feed ___________ __
Alkylnaphthalenes Be
X:
covered, Wt. percent of ,
Alkylnaphthalenes in
Feed
108. 3
5. 21
X Values _______________ __
1519112
,
. 33.4 Paco-ml: (‘ii’gi-zeoon
25
where t is the contact time in seconds, P52 isthe partial
pressure of hydrogen in p.s.i., PH'C is the partial pressure
trom petroleum hydrocarbon materials boiling in the tem- ' 30 of hydrocarbon feed in psi, e is the base of natural
logarithms, ° R is the temperature in degrees Rankine,
perature range from about 300 to 800° F., said hydrocar
bon materials including about 20; to 80 Weight percent v _ and X is between about 1 and 100.
lltisclaimed:
1. A process for the
. recovery
r
of alkylnaphthalenes
r.
4. The process of claim 3 wherein X is between about
2 and 50.
of alkylnap'hthalenes, the step comprising treatingsaid
hydrocarbon materials in the presence of hydrogemin the
absence'of a catalyst and under thermal conditions in
cluding a temperature from about 1100° ‘to 1350° F., a
References Cited in the ?le of this patent
UNITED STATES PATENTS’
hydrocarbon partial pressure from about 20 to 200 p.-s.i.a.,
a hydrogen partial pressure from‘ about 200 to 1000
p.s.i.a., and a contact time from about 0.5 to 200 sec
onds; said thermal conditions ‘being employed in afrela-i 40
tionship according 'to the following formula
X
tPHz
45
2,754,340
2,858,348
2,920,116
. Anderson et a1 _________ _; June 10, 1956
Bosmaji'an et a1. ______ __ Oct. 28, 1958'
‘ Riesz et al. ____________ __ Jan. 5, 1960
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