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Патент USA US3071639

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United States atent @ce
Patented Jan. 1, 1963
The relative proportions of the catalyst components by
weight of total catalyst material stable at 550° C. are
Chromium oxide (expressed
Peter Thomas White and Frederick William Bertram
Porter, Sunhury-on-Thames, England, assignors to The
as CI‘203)
British Petroleum (Iompany Limited, London, England,
a joint-stock corporation of Great Britain
as oxide) ____________________ _. 0.1 to 10% but less
No Drawing. Filed Dec. 1, 1959, Ser. No. 856,343
Claims priority, application Great Britain Dec. 3, 1958
2 Claims. (Cl. 260-668)
than the CI'203.
Alumina ______________________ _. Balance.
Preferred conditions, which are particularly suitable for
This invention relates to the production of alkyl aryl
compounds and in particular to the production of such
compounds suitable for use in the production of detergents
and wetting agents which comprise salts of sulphonated
use with the preferred chromium oxide on alumina cata
the production of such sulphonates may be produced by
the treatment of aryl hydrocarbons with ole?nic hydro
process may be carried out without such recycle or the
addition of extraneous hydrogen to the reaction zone.
In the case of regenerable catalysts the process is ad
vantageously carried out with a ?uidised or moving bed
lyst are pressures of up to 200 p.s.i.g., including atmos
pheric pressure or below, and space velocities of the liquid
feedstock of from 0.1 to 2.0 v./v./hr. A hydrogen~rich
alkyl aryl compounds.
15 gas is produced in the process and may be recycled to
the reaction zone although it is to be understood that the
It is well known that alkyl aryl compounds suitable for
carbons having from 8 to 20 carbon atoms per molecule.
Such processes involve the preparation of a suitable ole
?nic hydrocarbon and the treatment of an aryl hydrocar
bon therewith.
In accordance with the present invention, alkyl aryl
hydrocarbons are produced by a process which comprises
of catalyst although the use of stationary beds of catalyst
is also possible.
The cycle oils used as feedstock in the present inven
tion may be derived from any catalytic cracking feedstock,
contacting alkyl naphthenes having from 14 to 26 carbon 25 for example a gas oil fraction or a wax distillate fraction.
atoms per molecule with a dehydrogenation catalyst at a
temperature of from 370° C. to 580° C.
Cycle oils, particularly when wax distillate fractions are
used as cat. cracker fcedstocks, may contain an appreciable
quantity of ole?ns. They may also contain an appreciable
The feedstock need not consist entirely of alkyl naph
quantity of sulphur compounds. If such unsaturated and
thenes, and may contain for example a minor proportion
of paraf?nic and/ or ole?nic hydrocarbons. A particular 30 sulphur containing cycle oils were to be solvent extracted
the ole?ns would be partitioned between ra?inate and ex
ly preferred feedstock is the ra?‘inate Obtained by the sol
tract and the sulphur compounds would go into the ex
vent extraction of a cycle oil, and the present invention in
tract. When the cycle oil contains olefins and/or sul
cludes a process for the production of alkyl aryl hydro
phur compounds, therefore, it is preferred to subject it
carbons comprising subjecting a cycleioil to seiective sol
to a hydrogenation treatment prior to solvent extraction.
vent extraction, and contacting the rafiinate with a de
In this way ole?ns are hydrogenated to para?ins and
hydrogenation catalyst at a temperature of from 370° C.
to 580° C.
During the catalytic cracking of hydrocarbon oils,
whether gas oils or oils boiling above that range e.g. wax
sulphur compounds are decomposed, thereby increasing
the yield of ra?inate.
The hydrogenation treatment may use any conven
distillate fractions, it is customary to fractionate the cata 40 ient hydrogenation catalyst which should, however, be
sulphur-insensitive and have desulphurising properties if
lytically cracked products so as to give a heavy gas oil
fraction boiling above 275° C. which together with the
fractionator bottoms, if desired, may be recycled to the
cat. cracker. This so-called “cycle oil” is not normally
recycled to destruction, however, and in consequence ap
preciable quantities of the oil may be available, for which
the normal outlet would be fuel oil.
The dehydrogenation catalyst may be one or more group
VI or group VIII metals or their oxides or sulphides on
a support, for example, alumina, or silica-alumina. Pre
ferred metals are chromium, molybdenum, cobalt, nickel,
palladium or platinum and particular examples of suit~
the cycle oil contains sulphur. Suitable catalysts are, for
example, cobalt and molybdenum oxides on alumina,
molybdenum oxide on alumina, and tungsten-nickel oxides
or sulphides on alumina and the preferred conditions are
within the range 370~427° C., 600—l500 p.s.i.g., 1/2—4
v./v./h., and 1000-4000 s.c.f./b. gas recycle. 1 to 5%
wt. cobalt oxide, expressed as C00, and 5 to 25% wt.,
molybdenum oxide, expressed as M003, on alumina is
the preferred catalyst, the term “cobalt and molybdenum
oxides” includin‘y either cobalt or molybdenum oxides
as such, or as cobalt molybdate, or both.
When a hydrogenation treatment is given prior to sol
able catalysts are molybdenum oxide on alumina (pref~
vent extraction, the extract from the solvent extraction
erably 5 to 25% Wt. molybdenum oxide expressed as
55 will be a highly aromatic material with a high specific
M003), cobalt and molybdenum oxides on alumina (pref
gravity, low sulphur content and low pour point. It may
erably l to 5% wt. cobalt oxide expressed as C00, and
be used as a source of speci?c aromatics or in small
5 to 25% wt. molybdenum oxide expressed as M003),
amount, as a blending component to increase the speci?c
nickel on alumina (preferably 5 to 15% wt. nickel ex“
gravity and lower the pour point of diesel oils.
pressed as elemental nickel), and platinum on alumina
While a hydrogenation treatment of sulphur or ole
(preferably 0.1 to 5% wt. platinum expressed as ele
?n containing feedstocks prior to solvent extraction is
mental platinum). A particularly effective catalyst is one
consisting essentially of chromium oxide supported on
alumina. This catalyst may contain a minor proportion
preferred, the present invention is not limited to this,
since the extract is also a valuable product and it may
mixture of rare earths, bismuth, boron, germanium,
manganese, iron, beryllium or nickel, preferably in com
not always be desirable to reduce the yield of extract and
increase its aromaticity. In such circumstances it may
be preferable to solvent extract the sulphur or ole?n
containing feedstock and then submit the extract to a hy
bination with an alkali metal such as potassium. Another
drogenation treatment to decompose sulphur compounds
of one or more promoters, for example a rare earth or
particularly effective promoter is a minor proportion of
and hydrogenate ole?ns to para?ins. The hydrogenated
a spinel, for example cobalt chromite, copper chromite, 70 extract will be a high speci?c gravity, low sulphur content
zinc titanate or iron chromite, either as such or in the
and low pour point material suitable for use in diesel
form of the naturally occurring ore chrome ironstone.
oil blends.
sulphonated oil separated and preferably recycled to the
The solvent extraction process may use any convenient
solvent for example furfural, sulphur dioxide, glycols
reaction stage.
such as di- and tri-ethylene glycol with or without Water,
or phenol and water. The preferred solvent is furfural
which may be used at 60-70" C. and a 350% treat
matic extraction step is omitted may be particularly
This latter method in which the aro
suitable for use when a previous selective hydrogena
tion step has been given, since the likelihood of the
sulphonation of compounds other than alkyl aryl com
pounds is minimised.
The invention is illustrated by the following example.
A cycle oil obtained from the catalytic cracking of a
Some ole?nic double bonds may have been formed dur
ing the dehydrogenation process or may have been pres
ent in the original feedstock.
The dehydrogenated material may be selectively hy 10 Wax distillate fraction of a Middle East crude oil had an
drogenated to saturate ole?nic double bonds without sub
ASTM boiling range of 290° C.—467° C. and a speci?c
stantial hydrogenation of aromatic nuclei.
gravity (60° F./60° F.) of 0.932. This oil was solvent
The selective hydrogenation treatment has been found
extracted in a stirred column using furfural as solvent,
to improve the colour and the odour of the product, which
under the following conditions:
is particularly desirable when producing alkyl aryl com 15 Temperature gradient___ 70° C. (top)—60° C. (bottom).
Solventzoil ratio ______ _. 3.5:1.
Suitable catalysts for the hydrogenation include nickel
Stirrer speed _________ __ 650 r.p.rn.
_ pounds for detergent and wetting agent manufacture.
on a support, for example alumina (preferably 5 to 15%
The ra?inate from the solvent extraction which was
or palladium on a support, for example alumina (pref 20 obtained in 45.9% wt. yield was dehydrogcnated using
a catalyst of 10% wt. chromium oxide (expressed as
erably 0.1 to 5% wt. of platinum or palladium expressed
wt. of nickel expressed as elemental nickel), platinum
Cr2O3) on alumina promoted with 1% Wt. lanthanon
as the element), cobalt and molybdenum oxides on a
oxide (expressed as C0203) and 1% wt. potassium oxide
support, for example, alumina (preferably 1 to 5% Wt.
under the following conditions:
cobalt oxide, expressed as C00 and 5 to 25% wt, molyb
denum oxide, expressed as M003), or tungsten and nickel 25 Temperature ________________________ .._° C__ 427
oxides or sulphides (preferably containing tungsten and
Pressure ___________________________ __p.s.i.g__
Space velocity ____________________ __v./v./hr__
nickel in the ratio of 3:1 to 10:1 by weight).
The catalysts are preferably used within the following
Recycle gas
(a) Nickel
Platinum or
(b) Co-Mo or
Ni-W Catalysts
Pressure _____ __
____ __
A comparison between the raf?nate before and after
dehydrogenation is given below.
100 to 1,000.
150 to 480.
Space velocity_
Gas recycle rate__
0.5 to 8.0.
500 to 8,000.
Dehydro- Dehydro
genation genation
Yield, percent wt _______________________________ _.
Bromine N o _____________________________________ __
4. 1
0. 1
Aromatics + ole?ns, percent vol. (AS’I‘M method
D1019) ________________________________________ __
The process preferably includes a distillation step which
serves to remove lower boiling and higher boiling ma
We claim:
terial formed during the dehydrogenation process. Such
material is particularly undesirable in alkyl aryl fractions
for detergent and wetting agent manufacture. In prac
1. A process ‘for production of alkyl aryl hydrocar
bons from a feedstock consisting predominantly of alkyl
naphthenes having from. 14 to 26 carbon atoms per mole
tice a cut boiling within the range 260° C. to 410° C.
cule, said feedstock obtained as a raf?nate stream which
boils at a temperature above 275° C. from the selec
tive solvent extraction of a cycle oil, said process com
will contain the hydrocarbons with the required number
of carbon atoms per molecule. The distillation is pref
erably carried out under vacuum and may be given either
before or after the selective hydrogenation, if such a treat
prising, contacting the said feedstock :with a dehydrogena
tion catalyst at a temperature of from 370° C. to 5 80° C.,
ment is given.
The alkyl aryl compounds produced in accordance with 50 at a pressure of up to 200 p.s.i.g., and a space velocity
of from 0.1 to 2.0 v./v./hr., said catalyst comprising
the invention may be sulphonated and neutralised in
from 5% to 25% -Wt. of chromium oxide, expressed as
known manner to produce alkyl aryl sulphonates suit
Cr2O3, supported on alumina, said process carried out
able for use in the production of detergents and wetting
in the absence of additional hydrogen. agents. When the alkyl aryl compounds are produced
2. A process according to claim 1 wherein ole?nic
from alkyl naphthenes having predominantly straight
double bonds in the alkyl aryl hydrocarbons produced
alkyl chains, the resulting detergents and wetting agents
are selectively hydrogenated without substantial hy
drogenation of the aromatic nuclei.
are biologically soft i.e. they have low resistance to bio
logical breakdown.
The alkyl aryl compounds may be concentrated prior
to sulphonation by subjecting the dehydrogenation reac
tion mixture, after selective hydrogenation and distillation
if such steps are used, to an aromatic extraction process
using for example solvents such as diethylene glycol,
furfural or a sulphur dioxide/benzole mixture or ad
sorbents such as silica gel. Alternatively the sulphona
tion may be carried out on the reaction mixture and non
References Cited in the file of this patent
Linn et al. ____________ __ July 31, 1945
Axe et a1. ____________ __ May 31,
Kirshenbaum ________ __ July 10,
Pasik ________________ __ Oct. 2,
Friedman ____________ __ Ian. 5,
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