U.S. patent number 3,607,961 [Application Number 04/785,248] was granted by the patent office on 1971-09-21 for alkyl transfer of alkyl aromatics with group viii metals on boria-alumina.
This patent grant is currently assigned to Ashland Oil & Refining Company. Invention is credited to Ronald A. Kmecak, Stephen M. Kovach.
United States Patent |
3,607,961 |
Kovach , et al. |
September 21, 1971 |
ALKYL TRANSFER OF ALKYL AROMATICS WITH GROUP VIII METALS ON
BORIA-ALUMINA
Abstract
A process for the alkyl transfer of alkyl aromatics including
contacting an alkyl aromatic feed material, such as toluene, with a
catalyst comprising a Group VIII metal, such as nickel, platinum,
or palladium and boria deposited on an alumina base at a
temperature of about 800.degree. to 1100.degree. F., a pressure of
about 0 to 2000 p.s.i.g., and a liquid hourly space velocity of
about 0.1 to 10, and in the presence of hydrogen introduced at a
rate of about 1 to 10 moles hydrogen per mole of hydrocarbon feed.
Promoters selected from Group I, Group II, Group IV, and the Rare
Earth metals of the Periodic System may be added to the catalyst.
Deactivated catalyst may be periodically rejuvenated by
discontinuing the introduction of aromatic feed material and
purging with hydrogen and the catalyst can be reactivated by
calcination in an atmosphere such as air. Where toluene is the
feed, the alkyl transfer product may be distilled to separate
benzene, toluene and xylenes, the toluene may be recycled to the
alkyl transfer step, the xylenes may be crystallized to separate
para-xylene from the remaining xylenes, the mother liquor from the
crystallization step may thereafter be isomerized to readjust the
para-xylene content and the product of the isomerization may be
recycled to the crystallization zone.
Inventors: |
Kovach; Stephen M. (Ashland,
KY), Kmecak; Ronald A. (Ashland, KY) |
Assignee: |
Ashland Oil & Refining
Company (Houston, TX)
|
Family
ID: |
25134889 |
Appl.
No.: |
04/785,248 |
Filed: |
December 19, 1968 |
Current U.S.
Class: |
585/321; 502/339;
585/470 |
Current CPC
Class: |
C07C
5/2724 (20130101); C07C 5/2724 (20130101); C07C
6/123 (20130101); C07C 15/08 (20130101); C07C
15/00 (20130101) |
Current International
Class: |
C07C
15/00 (20060101); C07C 5/00 (20060101); C07C
5/27 (20060101); C07C 6/00 (20060101); C07C
6/12 (20060101); C07C 15/08 (20060101); C07c
003/58 (); C07c 015/08 (); B01j 011/06 () |
Field of
Search: |
;260/672T |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Schmitkons; G. E.
Claims
We claim:
1. A process for the alkyl transfer of alkyl aromatics; comprising,
contacting an alkyl aromatic feed material with a catalyst
comprising about 0.01 to 5 percent by weight of a Group VIII metal
of the Periodic System and about 5 to 25 percent by weight of boria
and a promoting amount of 1-15 percent by weight of a metal
selected from the group consisting of Group I, Group II, Group IV,
and the Rare Earth metals of the Periodic System and mixtures
thereof deposited on an alumina base, under conditions sufficient
to cause alkyl transfer of said alkyl aromatics including a
temperature of about 800 to 1100.degree. F.
2. A process in accordance with claim 1 wherein the Group VIII
metal is a metal of the first transition series of Group VIII.
3. A process in accordance with claim 1 wherein the metal is
nickel.
4. A process in accordance with claim 1 wherein the Group VIII
metal is a precious metal.
5. A process in accordance with claim 1 wherein the feed material
contains substantial volumes of toluene.
6. A process in accordance with claim 5 wherein unconverted toluene
is separated from the alkyl transfer product and said unconverted
toluene is recycled to the disproportionation step.
7. A process in accordance with claim 5 wherein xylenes are
separated from the alkyl transfer product and paraxylene is
separated from said xylenes.
8. A process in accordance with claim 7 wherein the xylenes
remaining after the separation of paraxylene are subjected to
isomerizaton conditions sufficient to produce additional
paraxylene.
9. A process in accordance with claim 1 wherein the flow of feed
material through the catalyst is interrupted periodically and the
flow of hydrogen is continued for a time sufficient to reactivate
the catalyst.
10. A process in accordance with claim 1 wherein the flow of feed
material and hydrogen through the catalyst is discontinued and the
catalyst is calcined in air under conditions sufficient to
reactivate the catalyst.
11. A process for the alkyl transfer of alkyl aromatics;
comprising, contacting an alkyl aromatic feed with a catalyst
comprising about 0.01 to 5 percent by weight of a metal of the
first transition series of Group VIII of the Periodic System and
about 5 to 25 percent by weight of boria deposited on an alumina
base, under conditions sufficient to cause alkyl transfer of said
alkyl aromatics including a temperature of about 800 to
1100.degree. F., a pressure of about 0 to 2000 p.s.i.g. a liquid
hourly space velocity of about 0.1 to 10, and hydrogen to
hydrocarbon mol ratio between about 1 and 10 to 1.
12. A process in accordance with claim 11 wherein the feed material
contains substantial volumes of toluene.
13. A process in accordance with claim 12 wherein unconverted
toluene is recycled to the disproportionation step,
14. A process in accordance with claim 12 wherein xylenes are
separated from the alkyl transfer product and paraxylene is
separated from said xylenes.
15. A process in accordance with claim 14 wherein the xylenes
remaining after the separation of paraxylene are subjected to
isomerization conditions sufficient to produce additional
paraxylene.
16. A process in accordance with claim 11 wherein the flow of feed
material through the catalyst is interrupted periodically and the
flow of hydrogen is continued for a time sufficient to reactivate
the catalysts.
17. A process in accordance with claim 11 wherein the flow of feed
material and hydrogen through the catalyst is discontinued and the
catalyst is calcined in air under conditions sufficient to
reactivate the catalyst.
Description
BACKGROUND OF THE INVENTION
The present invention relates to a process for the catalytic
conversion of hydrocarbons and, more particularly, to a process for
the catalytic alkyl transfer of alkyl aromatics.
Aromatic hydrocarbons, such as benzene, naphthalene, and their
alkyl derivatives are important building blocks in the chemical and
petrochemical industries. For example, benzene and its derivatives
have numerous uses; cyclohexane is utilized in nylon production;
naphthalene is utilized in the production of phthalic anhydride for
alkyd resins, etc., paraxylene can be used for the production of
terephthalic acid which, in turn, is utilized in the production of
synthetic resins, such as dacron, mylar, etc., etc.
For many years, the primary source of such aromatic hydrocarbons
has been coal tar oils obtained by the pyrolysis of coal to produce
coke. Such coal tar oils contain principally benzene, toluene,
naphthalene, methylnaphthalene and paraxylene. Benzene may be
produced from such oils by direct separation, such as distillation
techniques, the paraxylene may be separated by crystallization, and
the naphthalene fractions by direct separation techniques. Further
alkyl derivatives of benzene and naphthalene can be converted to
increased volumes of benzene and naphthalene can be converted to
increased volumes of benzene and naphthalene by hydrodealkylation.
More recently, however, the petroleum industry has become a leading
source of these aromatic hydrocarbons. The reason for this has been
the availability of the catalytic reforming process in which
naphthene hydrocarbons are dehydrogenated to produce a reformate
rich in aromatics and more efficient processes for separating the
aromatics from the reformate.
Some years ago, there was a high demand for toluene which was used
in the production of TNT. This led to the building of substantial
facilities for its production. However, the advent of nuclear and
fusion weaponry and the use of diesel oil-ammonium nitrate
explosives has left toluene in substantial oversupply, since the
only major uses of toluene are as a solvent, the production of
toluene diisocyanates and the production of benzene. This has
resulted in extensive efforts to develop methods for converting
toluene to benzene. One method of converting toluene to benzene is
by the previously mentioned hydrodealkylation.
Dealkylation has the primary disadvantage that methane is a major
product. Volume yields of benzene are therefore low and carbon
deposition on the catalyst is high. The large amounts of methane,
while useful as a fuel, require expensive techniques for the
removal of the methane from the circulating hydrogen stream
utilized in the hydrodealkylation. In addition, large quantities of
hydrogen are consumed in the dealkylation process and hydrogen is
often in short supply and expensive to produce. Finally, where
catalysts are used in the process, carbon laydown on the catalyst
is a serious problem.
A more profitable reaction for changing alkyl aromatics to other
aromatic products is an alkyl transfer reaction. An alkyl transfer
reaction is a process wherein alkyl groups are caused to be
transferred from the nuclear carbon atoms of one aromatic molecule
to the nuclear carbon atoms of another aromatic molecule. By way of
example, an aromatic hydrocarbon molecule containing one nuclear
alkyl substituent, such as toluene, may be treated by
disproportionation to produce an aromatic hydrocarbon with no alkyl
substituents, namely, benzene, and aromatic hydrocarbon molecules
with two nuclear alkyl substituents, namely, benzene, and aromatic
hydrocarbon molecules with two nuclear alkyl substituents, namely
xylenes. Similarly, product ratios may be shifted by
transalkylation of xylene and benzene to toluene. Such an alkyl
transfer reaction has distinct advantages: methane is no produced
in addition to the desired aromatic hydrocarbon. As a result, there
is very little loss of product in alkyl transfer as opposed to
hydrodealkylation.
Alkyl transfers may be carried out thermally. However, thermal
alkyl transfer results in demethylation due to cracking and
hydrogenation, ultimately resulting in low yields of desired
aromatics. On the other hand, catalytic alkyl transfer has not been
highly successful since it requires an active, rugged, acidic
catalyst. Typical catalysts are solid oxides, such as
silica-alumina, silica-magnesium, etc. These materials, however,
are not active enough to promote disproportionation at high
conversion rates. In addition, as is the case in hydrodealkylation,
carbon deposition on the catalyst and its affect on catalyst
activity with time is a severe problem.
It is therefore an object of the present invention to provide an
improved process for the conversion of alkyl aromatics. Another
object of the present invention is to provide an improved process
for the alkyl transfer of alkyl aromatics. Yet another object of
the present invention is to provide an improved process for the
disproportionation of toluene to produce benzene and xylenes.
Another and further object of the present invention is to provide
an improved process for the disproportionation of alkyl aromatics
which utilizes a novel catalyst system. Another object of the
present invention is to provide an improved process for the
disproportionation of alkyl aromatics with a catalyst system
resistant to carbon laydown. A further object of the present
invention is to provide an improved process for the catalytic
disproportionation of alkyl aromatics utilizing a Group VIII metal
and boria on an alumina base. A further object of the present
invention is to provide an improved process for the
disproportionation of alkyl aromatics utilizing critical conditions
of temperature and pressure which produce maximum
disproportionation and conversion of one aromatic to another. Still
another object of the present invention is to provide an improved
process for the conversion of toluene to benzene and xylenes and
conversion of meta- and ortho- xylenes to additional para-xylene.
These and other objects and advantages of the present invention
will be apparent from the following detailed description.
SUMMARY OF THE INVENTION
Briefly, in accordance with the present invention, alkyl transfer
of alkyl aromatics comprises contacting an alkyl aromatic feed
material with a catalyst comprising a metal of Group VIII of the
Periodic System and boria deposited on an alumina base. Further
improvement of he catalyst is obtained by adding a Group I, Group
II, Group IV, a Rare Earth metal or mixtures thereof. Further
improvements of the process are obtained by maintaining the
temperature between about 800 and 1100.degree. F and the pressure
between about 0 and 2000 p.s.i.g. Where toluene is the feed,
additional para-xylene is produced by isomerizing ortho- and meta-
xylenes .
BRIEF DESCRIPTION OF THE DRAWINGS
The drawing shows a flow diagram of the process system in
accordance with the present invention
DETAILED DESCRIPTION OF THE INVENTION
Alkyl aromatic feed materials for use in accordance with the
present invention can be any alkyl aromatic having at least one
transferrable alkyl group. Primary materials are alkyl aromatics
having from 7 to 15 carbon atoms, mixtures of such alkyl aromatic
hydrocarbons, or hydrocarbon fractions rich in such alkyl aromatic
hydrocarbons. Such feeds include mono- and di- aromatics, such as
alkyl benzenes and alkyl naphthalenes. Preferably, the alkyl group
should contain no more than about 4 carbon atoms. A preferred feed
in accordance with the present invention is toluene. Accordingly,
disproportionation of toluene will be referred to hereinafter in
the detailed description.
The process of the present invention should be conducted at a
temperature between about 800 and 1100.degree. F., and preferably
between 850 and 1000.degree. F. It has been found in accordance
with the present invention that below this temperature range,
substantially decreased conversion occurs due to hydrogenation. On
the other hand, when operating above this temperature range,
thermal demethylation occurs. The pressure utilized in accordance
with the present invention has also been determined to be a
critical factor. Accordingly, the process should be carried out
between about 0 and 2000 p.s.i.g. and preferably, between 300 to
600 p.s.i.g. It has been found that below the desired pressure
range, conversion is low and the aromaticity of the product is
high. On the other hand, at higher pressures, conversion is high,
but liquid recoveries are low due to hydrogenation and
hydrocracking. A liquid hourly space velocity between about 0.1 and
10, and preferably between 0.25 and 1.0, should be utilized and a
hydrogen-to-hydrocarbon mole ratio between about 1 and 10 to 1 and
preferably between 2 and 4 to 1 is desired.
The high severity conditions required to obtain disproportionation
of alkyl aromatics, particularly the disproportionation of toluene,
has been found to lead to catalyst deactivation due to selective
adsorption and condensation of aromatics on the catalyst surface
and carbon laydown on the catalyst. It was found that the
condensation and adsorption of aromatics on the catalyst is a
temporary poison and that this condition can be alleviated by
utilizing high hydrogen partial pressures. In addition, this
temporary deactivation of the catalyst can be overcome to
completely rejuvenate the catalyst to near virgin activity by
hydrogen-purging of the catalyst in the absence of aromatic
hydrocarbon feed. While coke or carbon deposition on the catalyst
is a permanent poison, it has been found, in accordance with the
present invention, that carbon laydown can be decreased by
utilizing the catalysts of the present invention. Further, it was
found that when these catalysts become deactivated by carbon
laydown, they can be restored to near virgin activity by
regeneration in air.
The catalyst employed in accordance with the present invention is a
multifaceted cure for many of the ills of catalytic
disproportionation reactions. First, it has been found that boria
deposited on an alumina base is vastly superior to a silica-alumina
base catalyst; the former consistently proving to be twice as
active as the latter. The amount of boria deposited on the alumina
may vary between about 5 and 25 percent by weight of the finished
catalyst. The alumina is preferably a gamma alumina. Such gamma
aluminas are very stable up to temperatures of about 1800.degree.
F. One such alumina, Boehmite, may be prepared in a variety of
ways, one of the simplest being the addition of ammonium hydroxide
to a water solution of aluminum chloride. The material originally
precipitated is an amorphous alumina flock which rapidly grows to
crystal size yielding crystalline Boehmite. Aging of Boehmite in
ammonium hydroxide solution transforms the Boehmite first to the
meta-stable Bayerite and finally to the highly stable Gibbsite. The
Bayerite is preferred any may be in its beta- or eta- form.
The active Group VIII metal added to the boria-alumina may be
broken down into two families; namely, the ferrous or first
transition series, such as nickel and cobalt, and the precious
metals or second and third transition series, such as platinum,
palladium, rhodium, ruthenium, etc. A ferrous group metal should be
present on the finished catalyst in amounts between about 0.5 and 5
percent by weight while a precious metal component should be
present in amounts between about 0.01 and 1 percent by weight.
It has also been found that conversion may be improved and, more
significantly, carbon laydown on the catalyst may be reduced by the
addition thereto of a promotor. Such promoters may be selected from
Group I of the Periodic System, such as potassium, rubidium,
cesium, etc., Group II of the Periodic System, such as calcium,
magnesium, strontium, etc., a Rare Earth metal of the Periodic
System, such as cerium, thorium, etc., a Group IV metal of the
Periodic System, such as tin or lead, or mixtures of these, and
particularly mixtures of a Group IV metal with one of the other
groups mentioned. The promoters are preferably in their oxide form
and are present in amounts of about 1 to 15 percent by weight based
on the weight based on the weight of the finished catalyst.
The catalysts may be prepared by techniques well known in the art.
For example, such preparation may include coprecipitation or
impregnation techniques. One can employ extrudates or pellets for
impregnation or powders followed by pelletization or extrusion to
yield the finished catalyst. When employing impregnation
techniques, the metals may be added to the base singly or in
combination, utilizing water soluble salts such as borates, boric
acid, halides, nitrates, sulfates, acetates, etc. Easily hydrolyzed
salts can be kept in solution without decomposition by employing
the appropriate inorganic acids. Well-known procedures for drying
and calcination of the catalyst will also be employed. For example,
vacuum drying at a temperature of about 250.degree. F and
calcination in an oxidative, neutral or reductive atmosphere,
utilizing a calcination temperature of about 800 to 1200.degree. F
can be practiced.
Preparation of a specific catalyst is illustrated below. To 200 ml.
of distilled water was added 18 grams of nickel nitrate,
hexahydrate and 42 grams of boric acid. he solution was heated
until all the metal salts went into solution. This hot solution was
added slowly to 250 mls. of Bayerite alumina and allowed to stand
for 15 minutes. At the end of this period, the liquid was decanted
from the impregnated alumina. The resulting catalyst was dried at
250.degree. F for one hour in a vacuum oven and then calcined in a
muffle furnace at 950.degree. F in air for 8 hours. The resultant
catalyst contained 1 percent nickel oxide, 10 percent boria and the
remainder alumina.
The following table shows the the results of the treatment of
toluene in accordance with the present invention utilizing three of
the catalysts contemplated herein. ##SPC1##
It will be seen from the preceding Table that all of the catalysts
are highly effective in the conversion of toluene to benzene and
xylenes. However, the precious metals have one disadvantage in this
process, namely, rather high hydrogenation activity which results
in the production of naphthalenes and cracked products. On the
other hand, while nickel from the ferrous metal group gives a lower
conversion, liquid recoveries are much higher than those obtained
with the precious metal catalysts. Hence, the catalysts of the
precious metal group are superior. It has also been found that
keeping the ferrous metal group metal between about 1 and 4 percent
is highly desirable. At 1 percent this catalyst gives a high
selectivity whereas, at 4 percent this catalyst is approximately
equivalent to the precious metal group catalysts. It has also been
found that when utilizing the precious metal catalysts, process
conditions should be maintained within the narrower limits
specified. Hence, the temperature should be between about 925 and
1000.degree. F, the pressure between about 300 and 600 p.s.i.g. a
liquid hourly space velocity between 0.25 and 1, and
hydrogen-to-hydrocarbon mole ratio between 1 and 3 to 1.
The improvements obtained by adding a promoter to either a precious
metal or a first transition metal catalyst is illustrated by Table
II below; ##SPC2##
It is to be observed from the above that the severity of operation
can be increased without penalizing conversion or carbon laydown on
the catalyst.
In accordance with the present invention, an integrated process for
the production of benzene and paraxylene from toluene can be
carried out with resultant high yields of these two valuable
products. This process is best described by reference to the
drawing.
In accordance with the drawing, toluene is introduced to the system
through line 10, hydrogen is added through line 12 and these
materials are passed over the catalyst of the present invention in
the disproportionation reactor 14. The effluent passing through
line 16 is passed to a flash drum for the removal of hydrogen and
any light gases produced. These materials are discharged through
line 18. Since little or no demethanation occurs, the hydrogen is
substantially pure and may be recycled to the disproportionaton
reaction without further treatment. However, in some instances,
further purification of the hydrogen is necessary before recycle or
reuse. The liquid product passes through line 20 to a first
distillation unit 22. In distillation unit 22, benzene is recovered
as an overhead through line 24. The bottoms product from
distillation unit 22 passes through line 26 to a second
distillation unit 28. In distillation unit 28, toluene in removed
as an overhead product and recycled to the disproportionation
section through line 30. The bottoms product from distillation unit
28 is a mixture of xylenes which is discharged through line 32.
This product may be withdrawn, as such, through line 34.
Preferably, however, the xylene product is passed through line 36
to crystallization unit 38. In crystallization unit 38, para-xylene
is selectively removed and withdrawn through line 40. The mother
liquor from the crystallization secton is passed through line 42 to
an isomerization unit 44. Hydrogen is added through line 46. In the
isomerization unit 44, the equilibrium concentration of paraxylene
is reestablished and the material may then be recycled through line
48 to crystallization unit 38 for further paraxylene
separation.
The isomerization reaction should be carried out under more mild
conditions that the disproportionation. Catalysts useful in the
disproportionation reaction might also be used in the isomerization
or conventional catalysts, such as, platinum on silica-alumina, can
be used. The isomerization may be carried out at temperatures of
about 500 to 900.degree. F, and preferably 550 to 650.degree. F,
pressures of 50 to 2000 p.s.i.g., and preferably 300 to 600
p.s.i.g., at a liquid hourly space velocity of 0.1 to 10, and
utilizing a hydrogen-to-hydrocarbon mole ratio between about 1 and
20 to 1.
When reference is made herein to the Periodic System of Elements,
the particular groupings referred to are as set forth in the
Periodic Chart of the Elements in "The Merck Index," Seventh
Edition, Merck & Co., Inc., 1960.
The term "alkyl transfer" of alkyl aromatics as used herein is
meant to include disproportionation and transalkylation.
Disproportionation, in turn, is meant to include conversion of two
moles of a single aromatic, such as toluene, to one mole each of
two different aromatics, such as xylenes and benzene.
Transalkylation is meant to include conversion of one mole each of
two different aromatics, such as xylenes and benzene, to one mole
of a single different aromatic, such as toluene. The alkyl transfer
defined above is also to be distinguished from isomerization where
there is no transfer of alkyl groups from one molecule to another
but simply a shifting of alkyl group around the aromatic ring, such
as isomerization of xylenes, or rupture of the rings or the alkyl
side chain and rearrangement of slip-off carbon atoms on the same
molecule. The alkyl transfer is also to be distinguished from a
hydrogen transfer reaction, such as the hydrogenation of aromatics,
the dehydrogenation of cyclo-paraffins and like reactions.
* * * * *