U.S. patent number 3,864,417 [Application Number 05/384,853] was granted by the patent office on 1975-02-04 for saturated hydrocarbon disproportionation at low temperatures.
This patent grant is currently assigned to Chevron Research Company. Invention is credited to Thomas R. Hughes.
United States Patent |
3,864,417 |
Hughes |
* February 4, 1975 |
Saturated hydrocarbon disproportionation at low temperatures
Abstract
A process for disproportionation of saturated hydrocarbons which
comprises contacting the saturated hydrocrarbons at a temperature
below 850.degree.F, and much more preferably below 800.degree.F,
and in the presence of no more than 5 weight percent olefin, with a
catalytic mass having catalytic activity for dehydrogenation as
well as catalytic activity for olefin disproportionation.
Inventors: |
Hughes; Thomas R. (Orinda,
CA) |
Assignee: |
Chevron Research Company (San
Francisco, CA)
|
[*] Notice: |
The portion of the term of this patent
subsequent to November 27, 1990 has been disclaimed. |
Family
ID: |
26671599 |
Appl.
No.: |
05/384,853 |
Filed: |
August 1, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
3303 |
Jan 16, 1970 |
|
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Current U.S.
Class: |
585/708 |
Current CPC
Class: |
C07C
6/10 (20130101) |
Current International
Class: |
C07C
6/10 (20060101); C07C 6/00 (20060101); C07c
009/00 (); C07c 003/00 () |
Field of
Search: |
;260/676R,683D |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Nelson; Juanita M.
Attorney, Agent or Firm: Magdeburger; G. F. Davies; R. H. De
Young; J. J.
Parent Case Text
This is a continuation of application Ser. No. 3,303, filed Jan.
16, 1970.
Claims
I claim:
1. In a process for disproportionation of saturated hydrocarbons
which comprises contacting the saturated hydrocarbons in a
disproportionation reaction zone, with a catalytic mass having a
component with catalytic activity for alkane dehydrogenation and a
second component with catalytic-activity for olefin
disporportionation, the improvement which comprises carrying out
said contacting at a temperature between 400.degree.F and
850.degree.F, and at an elevated pressure of at least 100 psig, and
in the presence of no more than 5 weight percent olefins, and
withdrawing from the disproportionation reaction zone product
saturated hydrocarbons containing no more than 5 weight percent
olefins.
2. A process in accordance with claim 1 wherein the improvement is
made which comprises using as said catalytic mass, a catalytic mass
comprising catalyst particles having both catalytic activity for
dehydrogenation and catalytic activity for olefin
disproportionation.
3. A process in accordance with claim 2 wherein the catalytic mass
comprises a physical mixture of (a) catalyst particles containing a
component which has catalytic activity for alkane dehydrogenation,
and (b) catalyst particles containing a component which has
catalytic activity for olefin disproportionation.
4. A process in accordance with claim 2 wherein the saturated
hydrocarbons consist essentially of alkanes.
5. A process in accordance with claim 4 wherein the saturated
hydrocarbons consist essentially of just one carbon number
hydrocarbon selected from the group consisting of propane, normal
butane, and normal pentane.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the conversion of saturated
hydrocarbon feeds to hydrocarbon products with different
distributions of molecular weights than those of the feeds. More
particularly, the present invention relates to disproportionation
of saturated hydrocarbons.
The term "disproportionation" is used herein to mean the conversion
of hydrocarbons to new hydrocarbons of both higher and lower
molecular weight. For example, a pentane may be disproportionated
according to the reaction:
2C.sub.5 H.sub.12 .revreaction.C.sub.4 H.sub.10 +C.sub.6
H.sub.14
"Saturated hydrocarbon" as used herein includes hydrocarbon
molecules which are completely saturated with hydrogen and/or
hydrocarbon molecules which are partially saturated with hydrogen
but contain at least one alkyl group which is completely saturated
with hydrogen. Thus, the term "saturated hydrocarbon" as used
herein includes alkanes (paraffins); alicyclics (cycloparaffins);
branched-chain alkanes; alicyclic hydrocarbons with one or more
attached alkane groups; and unsaturated hydrocarbons with one or
more attached, completely saturated hydrocarbon groups, as, for
example, an aromatic hydrocarbon with an attached alkane. From the
description hereinbelow, it will become apparent that in the
instance of unsaturated hydrocarbons with an attached, completely
saturated hydrocarbon group the conversion process of the present
invention operates by way of the completely saturated hydrocarbon
group.
2. Prior Art
A number of processes have been disclosed for converting various
hydrocarbons to higher molecular weight hydrocarbons. For example,
polymerization has been proposed for increasing the molecular
weight of hydrocarbons such as gaseous, or low-boiling olefins.
Various processes for olefin polymerization have been disclosed,
including processes wherein the polymerization reaction is
catalyzed with inorganic acids such as sulfuric or phosphoric.
To obtain the olefinic feed for a polymerization reaction, both
thermal cracking and catalytic dehydrogenation processes have been
proposed. For example, a two-stage process has been proposed
wherein hydrocarbon gases are first cracked to form substantial
amounts of olefins. Then the olefins are polymerized to
higher-boiling compounds by contacting the olefins with a catalyst
adapted to promote the forming of heavier hydrocarbons by
polymerization.
U.S. Pat. No. 1,687,890 is directed to a process of converting
low-boiling point hydrocarbons into higher-boiling point
hydrocarbons by mixing a hydrocarbon vapor with steam and then
contacting the steam-hydrocarbon mixture with iron oxide at
temperatures in excess of 1,112.degree.F. It is theorized in U.S.
Pat. No. 1,687,890 that the following reactions may be involved to
a greater or lesser extent:
"1. Paraffin hydrocarbons on being brought into contact with ferric
oxide at elevated temperatures are oxidized or dehydrogenated,
forming unsaturated hydrocarbons.
"2. Unsaturated hydrocarbons of low molecular weight polymerize
into unsaturated hydrocarbons of higher molecular weight when
subjected to elevated temperatures, the extent of polymerization
depending upon the temperature and duration of treatment.
" . . .
"7. Unsaturated hydrocarbons are hydrogenated by nascent
hydrogen."
Another process which has been proposed for converting hydrocarbons
to higher molecular weight hydrocarbons is olefin
disproportionation. Numerous methods and catalysts have been
disclosed for the disproportionation of olefins. In most of these
processes, the olefin is disproportionated by contacting with a
catalyst such as tungsten oxide or molybdenum oxide on silica or
alumina at a temperature between about 150.degree. and
1,100.degree.F and at a pressure between about 15 and 1,500 psia.
These prior art processes have been directed to an effective method
to convert essentially only olefins, not saturated hydrocarbons, to
higher molecular weight hydrocarbons by disproportionation.
For example, in U.S. Pat. No. 3,431,316, an olefin
disproportionation process is disclosed, and it is stated that, if
desired, paraffinic and cycloparaffinic hydrocarbons having up to
12 carbon atoms per molecule can be employed as diluents for the
reacton; that is, the saturated hydrocarbons are nonreactive and
merely dilute the olefins which are the reactants.
A process for the direct conversion of saturated hydrocarbons to
higher molecular weight hydrocarbons would be very attractive
because in many instances saturated hydrocarbons are available as a
relatively cheap feedstock. For example, in many instances, excess
amounts of propane and/or butanes are available in an over-all
refinery operation.
Processes which have been previously reported wherein saturated
hydrocarbons are disproportionated include contact of saturated
hydrocarbons with solid catalyst comprised of AlCl.sub.3 on
Al.sub.2 O.sub.3 and contact of saturated hydrocarbons with a
promoter comprised of alkyl fluoride and BF.sub.3. The use of the
AlCl.sub.3 solid catalyst was uneconomic because, among other
reasons, the catalyst was nonregenerable. The use of alkyl fluoride
and BF.sub.3 was unattractive because of severe corrosion, sludge
formation and other operating problems.
In the past it has been the practice to convert saturated
hydrocarbons, particularly normal alkanes, to olefins as a separate
or distinct step and then to disproportionate the olefins to
valuable higher molecular weight hydrocarbons.
For example, in U.S. Pat. No. 3,431,316, saturated light
hydrocarbons are cracked to form olefins, and then the olefins are
separated from the cracker effluent and fed to a disproportionation
zone wherein the olefins are disproportionated to higher molecular
weight hydrocarbons. Thus, a separate step is used to obtain
olefins, because, according to the prior art, no economically
feasible process is available for the direct disproportionation of
saturated hydrocarbons.
U.S. Pat. No. 3,445,541 discloses a process for the
dehydrogenation-disproportionation of olefins and paraffins, using
a combined dehydrogenation and disproportionation catalyst.
According to U.S. Pat. No. 3,445,541, a hydrocarbon feed which is
either an acyclic paraffin or acyclic olefin having 3-6 carbon
atoms is contacted with the catalyst at conditions of temperature
and pressure to promote dehydrogenation and disproportionation. It
is said that the process can be carried out at temperatures between
800.degree.F and 1,200.degree.F; however, the lowest temperature
used for processing a paraffin in accordance with any of the
examples of U.S. Pat. No. 3,445,541 is 980.degree.F, and typically
the temperature used is between 1,040.degree.F and
1,125.degree.F.
The high temperature process disclosed in U.S. Pat. No. 3,445,541
is shown therein to result in only relatively low yields of
saturated higher molecular weight hydrocarbons. The U.S. Pat. No.
3,445,541 process operates with a substantial amount of olefins in
the reaction zone and thus with about 10 to 50 volume percent or
more olefins in the effluent from the disproportionation reaction
zone.
SUMMARY OF THE INVENTION
According to the present invention, a process is provided for
disproportionation of saturated hydrocarbons at a temperature below
850.degree.F, and much more preferably below 800.degree.F, and in
the presence of no more than 5 weight percent olefins, which
process comprises contacting the saturated hydrocarbons with a
catalytic mass having catalytic activity for dehydrogenation of
hydrocarbon as well as catalytic activity for olefin
disproportionation.
More broadly, the present invention is directed to operating the
saturated hydrocarbon disproportionation zone in the presence of no
more than 5 weight percent olefins.
A catalytic mass comprising a physical mixture of catalyst
particles which are active for dehydrogenation and catalyst
particles which are active for olefin disproportionation has been
found to be effective for disproportionation of saturated
hydrocarbons when employed in accordance with the present
invention. In the process of the present invention, it is important
that the two types of catalysts be in close proximity to one
another. By "close proximity" is meant a distance less than a few
inches and preferably of the order of a few inches or less.
Ordinarily the dehydrogenation component will, of course, be a
dehydrogenation-hydrogenation component in accordance with standard
principles of catalysis.
Although not to be construed as a binding theory of operation
restricting the scope of the present invention or discovery, it is
believed that the process may take place by virtue of the formation
from the reactant saturated hydrocarbons of a relatively small
amount of olefins (reactant olefins) which migrate to the nearby
active sites of the olefin disproportionation catalyst component
and are disproportionated to form different olefins (product
olefins). Although a method might be devised to withdraw the
product olefins at this point, normally the product olefins are not
withdrawn, but instead migrate to active sites of the
dehydrogenation-hydrogenation component where they are
hydrogenated. It is believed that the success of the reaction of
the present invention is partially due to a steady or continued
removal of the product olefins formed in the reaction zone. The
reactant olefins formed as intermediates are disproportionated to
form product olefins and then product olefin removal is generally
accomplished by hydrogenation of the product olefins, thus
achieving a favorable equilibrium situation for the formation of
additional reactant olefins, which olefins, in turn, may be
disproportionated and hydrogenated in the reaction zone to form
additional saturated product hydrocarbons of molecular weights
other than that of the feed components, and so on.
It will, of course, be recalled that for most reversible or
equilibrium limited reactions (such as would be the case with the
reactant olefin formation), the net rate of formation of product is
increased by maintaining low concentration of product in the
reaction system, as opposed to a relatively high concentration of
product in the reaction system. Thus, in the present process, it is
believed that the net reaction rate of reactant saturated
hydrocarbons to form reactant olefins is increased or maintained at
a relatively high level by virtue of the fact that reactant olefins
are constantly being consumed by the olefin disproportionation
reaction which simultaneously occurs in the reaction zone. The
product olefins formed by disproportionation are, in turn,
maintained at low concentration in the reaction zone, preferably by
hydrogenation to product saturated hydrocarbons. This hydrogenation
serves the additional function of consuming the hydrogen originally
produced by dehydrogenation of the feed saturated hydrocarbons.
As a condition of operation of the present invention, it is
critical that the olefin concentration be maintained relatively
low; in accordance with our present findings, the olefin
concentration in the reaction zone is to be maintained below 5
weight percent. For purposes of the present invention, the olefin
concentration in the reaction zone is determined by analysis of the
reaction zone effluent.
As discussed above, it is believed that one reason for the success
of the process of the present invention is that the reactant
olefins are constantly being consumed by disproportionation and the
product olefins by hydrogenation to product saturated hydrocarbons,
thereby establishing a favorable equilibrium situation and allowing
further desired reaction in the reaction zone. We have found that
it is undesirable to have considerable amounts of olefin present in
the reaction zone and that the addition of olefin to the feedstock
to the reaction zone will tend to kill the disproportionation
reactions desired in accordance with the process of the present
invention. This was a surprising finding, especially in view of the
fact that it was initially thought that the desired
disproportionation of reactant saturated hydrocarbons to product
saturated hydrocarbons would be speeded up by the injection of
suitable olefins into the disproportionation reaction zone. To the
contrary, however, we have found that the addition of as little as
one volume percent olefin (specifically propylene) dramatically
reduced the conversion of saturated hydrocarbons (specifically
n-butane) to product saturated hydrocarbon disproportionate. This
is discussed further hereinbelow in conjunction with FIG. 3.
It is believed that the olefins are detrimental to the
disproportionation reactions of the present invention because the
olefins adsorb relatively strongly onto the
hydrogenation-dehydrogenation catalytic sites and thus prevent the
saturated hydrocarbon feedstock molecules from reaching these
catalytic sites. In our laboratory work, we have noted that after
the saturated hydrocarbon disproportionation has been substantially
inhibited by the injection of olefins to the disproportionation
reaction zone, most of the catalytic activity can be recovered by
discontinuing the olefin injection to the reaction zone.
Other theories may be postulated as to why the presence of more
than a few weight percent olefins in the reaction zone poisons the
saturated hydrocarbon disproportionation reaction of the present
invention. For example, certain work by Wood, reported on page 30,
Vol. 11 of the Journal of Catalysis (1968), indicates that the
presence of adsorbed hydrogen is necessary for cyclohexane
dehydrogenation to occur. This adsorbed hydrogen may be selectively
scavenged by substantial quantities of olefins present in the
disproportionation reaction zone, thereby preventing the saturated
hydrocarbon feedstock molecules from being dehydrogenated.
Whether because of a combination of the above theories, or one of
the theories separately, or some other theory, the finding remains
that the process of the present invention requires that the
concentration of olefins in the disproportionation reaction zone be
maintained at a low level.
It is also preferred in the process of the present invention to
operate the reaction zone at a pressure above at least 100 psig.
The elevated pressure has been found advantageous because it leads
to higher disproportionation conversion. The residence time of the
reactant in the reaction zone increases with increasing pressure.
Also, the equilibrium partial pressures of both olefin and H.sub.2
formed from dehydrogenation of saturated hydrocarbons rise in
direct proportion to the square root of the total pressure. The
equilibrium concentrations of olefins, relative to those of the
saturated hydrocarbons from which they are formed, are inversely
proportional to the square root of the total pressure. Relatively
high pressures, of the order of 500-1,500 psig, are particularly
preferred.
While the process of the present invention requires that no more
than 5 weight percent olefins be present in the reaction zone, it
is preferred to maintain the olefin concentration still lower as,
for example, below about 2 weight percent olefins, and still more
preferably, below about 1 weight percent olefins. To maintain the
olefin concentration at a relatively low level, various means may
be employed. Temperatures below about 800.degree.F and elevated
pressures above at least 100 psig are particularly desirable to
maintain the olefin concentration at a relatively low level in the
disproportionation reaction zone. In accordance with one
particularly preferred embodiment of the present invention, the
temperature in the disproportionation reaction zone is maintained
below about 800.degree.F, the pressure is maintained above at least
100 psig, and the olefin concentration is maintained below about
0.5 weight percent.
Although it is advantageous to maintain the temperature in the
reaction zone below about 850.degree.F and more preferably below
about 800.degree.F in order to maintain relatively low olefin
concentration, it is also particularly important to maintain the
temperature below about 850.degree.F, and more preferably below
about 800.degree.F in order to obtain a relatively high yield of
saturated hydrocarbons which are of higher molecular weight than
the feed-saturated hydrocarbons. Thus, for example, when butanes or
propane are fed to the disproportionation reaction zone, a much
better ultimate yield of C.sub.5 + material is obtained when
operating at the relatively low temperatures. Temperatures in the
range of 500.degree. to 700.degree.F are particularly desirable.
This aspect of the present invention is discussed hereinbelow in
conjunction with FIG. 1.
Still further, the relatively low temperature, particularly below
800.degree.F, have been found by us to be extremely advantageous
from the standpoint of catalyst stability. That is, the fouling
rates of catalysts used in the process of the present invention
have been found to be considerably lower when operating at the
relatively low temperatures, i.e., below about 800.degree.F, as
opposed to operating temperatures above 800.degree.F and
particularly operating temperatures above 850.degree.F. This aspect
of the present invention is discussed further hereinbelow in
conjunction with FIG. 2.
In a preferred embodiment of the process of the present invention,
the catalytic mass is comprised of catalyst particles having both
catalytic activity for dehydrogenation and catalytic activity for
olefin disproportionation. In certain instances, rather than
forming the catalytic mass in the reaction zone by physical
admixture of the two types of catalyst particles, it is more
convenient and more desirable to use only one type of catalyst
particle but, in accordance with the process of the present
invention, this catalyst particle must have substantial catalytic
activity for dehydrogenation as well as for olefin
disproportionation.
Temperatures employed in the reaction zone usually are maintained
between 400.degree. and 850.degree.F, preferably between
500.degree. and 800.degree.F, and still more preferably between
500.degree. and 750.degree.F. Feed to the disproportionation
reaction zone is preferably butanes and/or propane, as a large
increase in the value of these particular hydrocarbon feedstocks is
obtained by the disproportionation reaction.
Another particularly preferred feed is the highly paraffinic
raffinate resulting from the extraction of aromatics from a portion
of the effluent from a catalytic reforming process. Typically, the
raffinate is mostly C.sub.8 and C.sub.9 alkanes and has a
relatively low motor fuel octane rating. By the disproportionation
reaction of the present invention, the raffinate may be converted
to higher octane light gasoline and to jet fuel.
The direct disproportionation of propane gives a relatively low
yield of C.sub.5 + paraffins, whereas the yield from butanes is
much higher.
As defined previously, the term "saturated hydrocarbons" is used
herein to include a large number of types of hydrocarbons. However,
the process of the present invention is preferably carried out
using alkanes as the feed-saturated hydrocarbons. As used herein,
the term "alkanes" is used to mean hydrocarbons from the group of
aliphatic hydrocarbons of the series C.sub.n H.sub.2n.sub.+2,
excluding methane.
Feed hydrocarbons which are not converted in the disproportionation
reaction zone preferably are recycled to the disproportionation
reaction zone. Lower and higher molecular weight hydrocarbons
formed in the disproportionation reaction zone preferably are
removed from the unconverted feed prior to recycling the
unconverted feed. For example, generally all of the ethane formed
is removed in the disproportionation of propane, or of propane plus
butanes. The low molecular weight hydrocarbons are removed in order
to prevent their accumulation in the recycle stream to the
disproportionation zone.
The catalytic mass used in the disproportionation reaction zone,
according to the process of the present invention, must contain
substantial activity for dehydrogenation of hydrocarbons such as
alkanes, as well as substantial catalytic activity for olefin
disproportionation. Preferably, the catalytic mass is comprised of
a noble metal or a noble metal compound on a refractory support.
Thus, preferred catalyst masses include platinum-on-alumina
particles mixed with tungsten oxide-on-silica particles.
In accordance with one preferred embodiment of the present
invention, the feed-saturated hydrocarbons consist essentially of,
or at least mostly of, just one carbon number saturated hydrocarbon
such as propane; or normal butane with or without isobutane; or
normal pentane with or without other C.sub.5 carbon number
saturated hydrocarbons such as the branched-chain pentanes;
however, mixtures thereof, i.e., mixtures of any of the previously
mentioned hydrocarbons, may also be disproportionated. The term
"branched-chain" is used herein to connote hydrocarbons such as
2-methyl-pentane or 2,2-dimethyl-butane, either of which would be
referred to in accordance with common practice as branched-chain
hexanes or branched-chain C.sub.6 alkanes.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a graph showing the utimate yield of C.sub.5 +
hydrocarbons versus temperature for the disproportionation of
normal butane in curve A and percent total conversion versus
temperature in curve B.
FIG. 2 is a graph showing catalyst fouling rate versus temperature
for the disproportionation of normal butane.
FIG. 3 is a graph showing relative C.sub.5 + yield versus the
weight percent olefin added to a normal butane feed to a
disproportionation reaction zone.
DETAILED DESCRIPTION OF THE DRAWINGS
Referring now in more detail to FIG. 1, the data tabulated below in
Table I shows the yield of various products for four different
temperatures.
TABLE I
__________________________________________________________________________
Weight % Product Yields at Various Operating Temperatures Product
650.degree.F 700.degree.F 750.degree.F 800.degree.F 875.degree.F
__________________________________________________________________________
He + CH.sub.4 0.2 0.2 0.5 1.1 3.2 C.sub.2 H.sub.6 0.8 1.3 2.1 2.8
7.5 C.sub.3 H.sub.8 5.9 11.6 15.7 19.8 16.0 iC.sub.4 H.sub.10 0.1
0.1 0.2 0.4 0.5 nC.sub.4 H.sub.10 83.1 67.7 56.7 46.9 53.1 .SIGMA.
C.sub.4 H.sub.8 0.5 0.4 0.5 0.5 N.M..sup.4 .SIGMA. branched C.sub.5
H.sub.12 0.06 0.1 0.2 0.5 0.8 nC.sub.5 H.sub.12 4.7 9.5 11.7 13.9
7.2 .SIGMA. C.sub.5 H.sub.10 0.1 0.1 0.2 0.2 N.M..sup.4 .SIGMA.
branched C.sub.6 H.sub.14 0.03 0.1 0.3 0.8 0.9 nC.sub.6 H.sub.14
2.3 4.4 5.7 6.3 3.7 .SIGMA. C.sub.6 H.sub.12 0.1 0.1 0.2 0.4
N.M..sup.4 .SIGMA. branched C.sub.7 H.sub.16 0.009 0.05 0.2 0.3 0.6
nC.sub.7 H.sub.16 1.1 2.1 2.8 2.9 1.9 .SIGMA. C.sub.7 H.sub.14 0.02
0.05 0.08 0.06 N.M..sup.4 .SIGMA. branched C.sub.8 H.sub.18 -- 0.05
0.1 0.5 0.4 nC.sub.8 H.sub.18 0.5 1.0 1.3 1.3 1.0 .SIGMA. branched
C.sub.9 H.sub.20 -- 0.05 0.1 -- 0.7 nC.sub.9 H.sub.20 0.3 0.4 0.7
-- 0.5 .SIGMA. C.sub.10 + -- 0.3 0.5 -- 2.0 .SIGMA. C.sub.1
-C.sub.3 6.9 13.2 18.3 23.8 26.7 .SIGMA. C.sub.5 + 9.4 18.4 24.2
28.4 19.7 C.sub.5 + Ultimate Yield.sup.1 57.7 58.3 56.9 54.4 42.4
.SIGMA. Olefins.sup.2 0.7 0.8 0.9 1.2 N.M..sup.4 [% branched chain
in C.sub.5 -C.sub.9 range].sup.3 1.1 2.0 4.3 7.4 19.2
__________________________________________________________________________
.sup.1 C.sub.5 + Ultimate Yield = .SIGMA. C.sub.5 +/(.SIGMA.
C.sub.1 -C.sub.3 + .SIGMA. C.sub.5 +). .sup.2 All olefins analyses
are from an approximate chromatographic analysis. .sup.3 The
decrease in branching with decreasing temperature indicates th
process of the present invention is more selective for pure
disproportionation without isomerization at lower temperatures.
This attribute is important when it is desired to produce
n-paraffins, as, for example, in wax production. .sup.4 N.M. = not
measured because products were hydrogenated prior to analysis.
The data upon which FIG. 1 was based were obtained by contacting
normal butane with a saturated hydrocarbon disproportionation
catalyst masss under the following conditions: Volume of Catalyst
in Reactor: 9 cubic centimeters (cc.) Type of Catalyst: 2 cc. of
0.5 wt.% Pt; 0.5 wt.% Re; 0.5 wt.% Li on Al.sub.2 O.sub.3 7 cc. of
8.0 wt.% WO.sub.3 on SiO.sub.2 Both catalyst particles were 28 to
60 Tyler mesh size. Operating Conditions: Temperature.sup.1 :
650.degree., 700.degree., 750.degree., 800.degree., 875.degree.F
Pressure: 900 psig Feed Rate: 9 cc./hour .sup.1 Successive runs, of
several hours each with no regeneration in between, were made at
the temperatures specified, except that the catalys was reactivated
by flushing the catalyst overnight with hydrogen before the run at
875.degree.F.
As can be seen from curve A in FIG. 1, the ultimate yield of
C.sub.5 + decreases considerably in moving from particularly
preferred temperatures below 800.degree.F to temperatures in excess
of 800.degree.F as, for example, temperatures as high as
875.degree.F where the ultimate yield of C.sub.5 + drops to about
42 percent versus approximately 57 percent at 750.degree.F.
The term "ultimate yield" is used herein to mean the yield of the
specified material (e.g., C.sub.5 +) which would be obtained by
recycling unconverted feed back to the disproportionation reaction
zone, assuming no loss occurs due to the recycling. In particular,
the data points used to obtain curve A in FIG. 1 are the calculated
ultimate yield of C.sub.5 + material, based on the amount of normal
butane which was converted by a single pass through the
disproportionation reaction zone at the various respective
temperatures. Thus, the ultimate yield of C.sub.5 + is determined
from the single pass laboratory data by dividing the percent
C.sub.5 + yield by the fraction of total conversion of the normal
butane fed to the disproportionation reaction zone. The fractional
conversion of normal butane includes, of course, the quantity of
normal butane which was converted to lower molecular weight
hydrocarbons, as well as that portion of the normal butane which
was converted to more valuable higher molecular weight
hydrocarbons.
Curve B of FIG. 1 shows the total conversion of normal butane to
the higher and lower molecular weight products for single pass
operation through the disproportionation reaction zone. The data
for curve B were obtained in essentially the same manner as that
for curve A. The data are tabulated in Table I. As can be seen from
curve B, the conversion rises sharply in moving from relatively low
temperatures such as 650.degree.F to reach a maximum at a point
somewhere between 800.degree. and 850.degree.F. However, although
the conversion is higher, according to the graph, at a temperature
somewhat in excess of 800.degree.F, it is clear that our findings
establish that it is much preferable to operate at a temperature
below about 800.degree.F in order to achieve relatively high yields
of the valuable higher molecular weight hydrocarbons. As the
temperatures are raised up to 800.degree.F and above, the
conversion goes up, largely because substantial light hydrocarbons
are generated, possibly due to cracking. However, at the preferred
operating temperatures of below 800.degree.F, there is
substantially greater ultimate yield of C.sub.5 + material, as in
indicated by curve A of FIG. 1.
Furthermore, the relatively high olefin concentration in the
product from the reaction zone when operated at 857.degree.F versus
the relatively low olefin concentration when operating at the lower
temperatures, as can be seen from the data tabulated in Table I
above, illustrates the advantage of operating the saturated
hydrocarbon disproportionation zone in the presence of no more than
about 5 weight percent olefins and preferably substantially less
olefins, as, for example, less than 1 weight percent olefins.
Results which are qualitatively similar to those shown in FIG. 1
were obtained using a catalyst mass consisting of Pd on Al.sub.2
O.sub.3 particles mixed with WO.sub.3 on SiO.sub.2 particles. These
results are tabulated in summary form in Table II.
TABLE II ______________________________________ Temperature 700 750
800 850 C.sub.5 +, ultimate yield 37 41.5 39 31 Deactivation
rate.sup.1 0.04 0.039 0.038 0.069 Pressure, psig 900 900 900 900
LHSV 1.0 1.0 1.0 1.0 Feed nC.sub.4 nC.sub.4 nC.sub.4 nC.sub.4
______________________________________ .sup.1 Deactivation rate =
-d{log (conversion to C.sub.5 +){/dt, i.e., th deactivation rate is
calculated as the rate of change (decrease) of the logarithm of the
per pass conversion to C.sub.5 + per unit time, e.g., pe hour.
Referring now in more detail to FIG. 2, it can be seen from the
curve in FIG. 2 that considerably greater disproportionation
catalyst fouling rates result from operation above 800.degree.F and
that temperatures of 850.degree.F or higher appear to be
particularly undesirable from the standpoint of catalyst fouling
rate. The following conditions were employed to obtain the data
used for plotting the curve in FIG. 2:
Feed: Normal butane Volume of Catalyst in Reactor: 10 cubic
centimeters (cc.) Type of Catalyst: .about.2.2 cc. of 0.5 wt. % Pt;
0.5 wt. % Li on Al.sub.2 O.sub.3 .about.7.8 cc. of 8.0 wt. %
WO.sub.3 on SiO.sub.2 Both catalyst particles were 28 to 60 Tyler
mesh size and were mixed together well. Operating Conditions:
Temperature: 700.degree., 800.degree., 850.degree.F Pressure: 900
psig Feed Rate: 10 cc./hour LHSV: 1.0
Referring now in more detail to FIG. 3, it can be seen that the
injection of olefins to the disproportionation reaction zone is
extremely detrimental when carrying out the disproportionation of
saturated hydrocarbons. The reaction conditions used to obtain the
data to plot curves A and B in FIG. 3 were obtained under
essentially the same conditions as described above with respect to
FIG. 1, except that varying amounts of propylene were added to the
normal butane feed and the temperature was maintained at
650.degree.F for the data points of curves A and B of FIG. 3. As
can be seen from these curves, when operating the reaction zone at
650.degree.F both the conversion and the yield of valuable C.sub.5
+ hydrocarbons was substantially unaffected when only about 0.08
volume percent propylene was added to the normal butane feed to the
disproportionation reaction zone. However, when about 0.4 volume
percent propylene was added to the normal butane feed, the C.sub.5
+ yield dropped about 30 percent relative to what the C.sub.5 +
yield was prior to the addition of propylene to the normal butane
feed. Still further, when about one percent propylene was added,
both the C.sub.5 + yield and the conversion of normal butane
dropped to about 10 percent of what the yield and conversion were
when no propylene was added to the normal butane feed.
Thus, the data presented by curves A and B of FIG. 3 show that it
is undesirable to have substantial amounts of olefins in the feed
to the reaction zone and also indicates that it is preferable to
operate the disproportionation reaction zone in the presence of
less than 1 weight percent olefins when the disproportionation
reaction is carried out at temperatures of about 650.degree.F or
lower. We have found that somewhat higher amounts of olefins may be
tolerated in the disproportionation reaction zone at higher
temperatures. Thus, at temperatures of about 775.degree.F, somewhat
greater amounts of olefins may be present without seriously
retarding the saturated hydrocarbon disproportionation as is
indicated by curves C and D in FIG. 3. But it is important to
maintain the olefins below about 5 weight percent, and still more
preferable to maintain the olefins at less than about 2 weight
percent, in the disproportionation zone when operating at
temperatures of about 750.degree. to 800.degree.F.
In this respect, it can be calculated from dehydrogenation
equilibria data that at temperatures below about 800.degree.F the
olefin concentration resulting from a normal butane-olefin
equilibrium is below about 2 weight percent at 900 psig.
Although various embodiments of the invention have been described,
it is to be understood that they are meant to be illustrative only
and not limiting. Certain features may be changed. It is apparent
that the present invention has broad application to the
disproportionation of saturated hydrocarbons. Accordingly, the
invention is not to be construed as limited to the specific
embodiments or examples discussed but only as defined in the
appended claims.
* * * * *