U.S. patent number 3,718,576 [Application Number 05/051,488] was granted by the patent office on 1973-02-27 for gasoline production.
This patent grant is currently assigned to Chevron Research Company. Invention is credited to Thomas R. Hughes, Robert P. Sieg.
United States Patent |
3,718,576 |
Hughes , et al. |
February 27, 1973 |
GASOLINE PRODUCTION
Abstract
A process for producing gasoline from a hexane-rich hydrocarbon
feed which comprises disproportionating the hexane-rich feed to
obtain at least C.sub.5 hydrocarbons and C.sub.7 + hydrocarbons,
and catalytically reforming the C.sub.7 + hydrocarbons to obtain
reformate. Preferably, the normal pentane hydrocarbons obtained
from disproportionating the hexane are fed to a C.sub.5
isomerization process to obtain isopentane. Preferably, a common
fractionation zone is used for the disproportionation, catalytic
reforming and C.sub.5 isomerization processes.
Inventors: |
Hughes; Thomas R. (Orinda,
CA), Sieg; Robert P. (Piedmont, CA) |
Assignee: |
Chevron Research Company (San
Francisco, CA)
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Family
ID: |
21971607 |
Appl.
No.: |
05/051,488 |
Filed: |
July 1, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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3303 |
Jan 16, 1970 |
|
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3306 |
Jan 16, 1970 |
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Current U.S.
Class: |
208/93; 585/310;
585/364; 585/708; 208/79; 208/141; 585/319; 585/646 |
Current CPC
Class: |
C10G
61/06 (20130101); C10L 1/06 (20130101); C10G
59/02 (20130101) |
Current International
Class: |
C10G
59/02 (20060101); C10G 59/00 (20060101); C10G
61/06 (20060101); C10G 61/00 (20060101); C10L
1/00 (20060101); C10L 1/06 (20060101); C10g
039/00 () |
Field of
Search: |
;208/65,92,93,141-149
;260/683D,676 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levine; Herbert
Parent Case Text
CROSS REFERENCES
This application is a continuation-in-part of Applications Ser.
Nos. 3,303 and 3,306, filed Jan. 16, 1970, the disclosures of which
applications are incorporated by reference into the present patent
application.
Claims
We claim:
1. A combination process for converting paraffinic hydrocarbons
into gasoline which comprises:
a. separating a hydrocarbon feed stream into a C.sub.5 rich stream,
a hexane rich stream and a C.sub.7 + stream,
b. isomerizing normal pentane present in the C.sub.5 rich stream to
obtain isopentane,
c. disproportionating the hexane rich stream to obtain at least
C.sub.5 - hydrocarbons and a C.sub.7 + hydrocarbon fraction, and
wherein the disproportionation of the hexane is carried out by
contacting the hexane with a catalytic mass having catalytic
activity for paraffin dehydrogenation as well as catalytic activity
for olefin disproportionation, and
d. catalytically reforming, in the presence of hydrogen gas and
using a catalyst containing platinum, at least a portion of the
C.sub.7 + stream and the C.sub.7 + hydrocarbon fraction from
disproportionation to produce reformate.
2. A process in accordance with claim 1 wherein a normal pentane
rich hydrocarbon stream is separated from the C.sub.5 hydrocarbons
from disproportionation and the normal pentane rich hydrocarbon
stream is isomerized to obtain iC.sub.5.
3. A process in accordance with claim 1 wherein the hexane
disproportionation is carried out by contacting the hexane with a
catalytic mass having catalytic activity for paraffin
dehydrogenation as well as catalytic activity for olefin
disproportionation.
4. A process in accordance with claim 3 wherein the catalytic mass
comprises platinum on alumina and a Group VIB metal on a refractory
support.
5. A process in accordance with claim 4 wherein the
disproportionation reaction is carried out at a temperature below
850.degree.F. and in the presence of no more than 5 weight percent
olefins.
6. A process in accordance with claim 1 wherein at least a portion
of the reformate is separated by solvent extraction into an
aromatics-rich stream and a raffinate stream rich in paraffins, and
at least a portion of the raffinate is disproportionated to obtain
C.sub.7 + hydrocarbons which are catalytically reformed.
Description
BACKGROUND OF THE INVENTION
The present invention relates to disproportionation and catalytic
reforming. More particularly, the present invention relates to the
disproportionation of alkanes, especially hexane, and the catalytic
reforming of hydrocarbons. The present invention also relates to
normal pentane isomerization integrated into combined hexane
disproportionation and naphtha reforming.
The term "disproportionation" is used herein to mean the conversion
of hydrocarbons to new hydrocarbons of both higher and lower
molecular weight. For example, hexane may be disproportionated
according to the reaction:
2C.sub.6 H.sub.4 .revreaction. C.sub.4 H.sub.10 +C.sub.8
H.sub.18
Disproportionation, particularly disproportionation of alkanes, is
discussed further in Applications Ser. Nos. 3,303 and 3,306.
The disproportionation processes disclosed in Ser. Nos. 3,303 and
3,306 are preferably carried out at relatively low temperatures,
usually below 850.degree. F. and more preferably below
800.degree.F. The Ser. Nos. 3,303 and 3,306 processes are
particularly directed to the disproportionation of alkanes to
higher and lower molecular weight hydrocarbons with the reaction
preferably being carried out in the presence of no more than a
small amount of olefins.
Catalytic reforming has been practiced increasingly in petroleum
refineries since about 1940. Nearly all of the conventional present
catalytic reforming processes use a catalyst comprising platinum on
alumina. Usually, the reaction temperature for catalytic reforming
is between about 850.degree. and 1100.degree.F., and the reaction
is carried out in the presence of hydrogen. Catalytic reforming in
general, and a particularly preferred catalytic reforming process,
are described in U.S. Pat. No. 3,415,737, the disclosure of which
patent is incorporated by reference into the present
application.
The present invention is particularly concerned with the
integration of alkane disproportionation and catalytic reforming
and the present invention is especially concerned with the
upgrading of hexane or hydrocarbon feedstocks containing hexane, to
obtain higher octane gasoline boiling range hydrocarbons.
The hexane isomers present a unique problem among the alkanes of
the gasoline boiling range. The butanes have high blending octane
numbers and are limited as gasoline components only by their high
vapor pressure. Normal pentane can be isomerized to produce a blend
with a fairly acceptable octane number. The C.sub.7 to C.sub.9
alkanes can be converted into high octane number aromatic
hydrocarbons by catalytic reforming. However, isomerization of
hexanes produces a blend with low octane number, and reforming of
hexanes produces only low yields of benzene. One purpose of the
present invention is to provide a means for conversion of hexanes
into compounds with higher octane numbers.
SUMMARY OF THE INVENTION
According to the present invention, a process is provided for
producing gasoline from a hexane-rich hydrocarbon feed stream which
process comprises disproportionating the hexane-rich feed to obtain
C.sub.5 - hydrocarbons and C.sub.7 + hydrocarbons, and
catalytically reforming at least a portion of the C.sub.7 +
hydrocarbons to obtain reformate.
The term "hexane-rich" is used herein to connote a stream
containing a substantial amount of C.sub.6 hydrocarbons, usually at
least one or two weight percent hexane and preferably at least 5 or
10 weight percent hexane. The process of the present invention can,
of course, be applied to pure hexane streams, but in most
instances, the hexane will be present together with other
hydrocarbons.
The disproportionation of the hexane will result in hydrocarbons
having lower molecular weight than the hexane, i.e., C.sub.5 and
lower hydrocarbons, as well as hydrocarbons having a molecular
weight higher than the hexane, i.e., C.sub.7 and higher boiling
hydrocarbons. The C.sub.5 and lighter hydrocarbons are herein
sometimes referred to as C.sub.5 - hydrocarbons and the C.sub.7 and
higher boiling hydrocarbons are sometimes referred to herein as
C.sub.7 + hydrocarbons. The C.sub.5 - hydrocarbons are primarily
C.sub.5, C.sub.4, C.sub.3 and C.sub.2 hydrocarbons. The C.sub.7 +
hydrocarbons are primarily C.sub.7, C.sub.8, C.sub.9, C.sub.10,
C.sub.11 and C.sub.12 hydrocarbons, but the C.sub.7 + hydrocarbons
can boil as high as about 400.degree. to 500.degree.F.
Preferably, the disproportionation is carried out by contacting the
hexane with a catalytic mass having catalytic activity for paraffin
dehydrogenation as well as catalytic activity for olefin
disproportionation. A particularly preferred catalyst for the
disproportionation of hexane or in general, for the
disproportionation of the hexane-rich feed to the
disproportionation zone in the present invention comprises platinum
on alumina and a Group VIB metal on a refractory support.
Preferred catalysts for use in the disproportionation zone in the
process of the present invention are disclosed in Ser. Nos. 3,303
and 3,306.
As indicated previously, it is advantageous to combine normal
pentane isomerization with the disproportionation and catalytic
reforming steps of the present invention. Thus, according to a
particularly preferred embodiment of the present invention, a
combination process is provided for converting paraffinic
hydrocarbons into gasoline which comprises (a) separating a C.sub.3
+ hydrocarbon feed stream into a C.sub.5 rich stream, a C.sub.6
rich stream and a C.sub.7 + stream, (b) isomerizing the C.sub.5
rich stream to obtain iC.sub.5, (c) disproportionating the C.sub.6
rich stream to obtain at least hydrocarbons lighter than hexane and
C.sub.7 + hydrocarbons, and (d) catalytically reforming at least a
portion of the C.sub.7 + stream and the C.sub.7 + hydrocarbons from
disproportionation to produce reformate. The term "C.sub.5 rich"
connotes a C.sub.5 of at least 20 weight percent C.sub.5 and
usually at least 70 weight percent C.sub.5.
The isomerization step according to the above preferred embodiment
can operate on all or only on a portion of the normal pentane
present in the hexane-rich feed to the process of the present
invention. However, it is particularly preferred to feed at least a
portion of the normal pentane produced in the disproportionation
step to the C.sub.5 isomerization step. Isopentane produced by the
isomerization is a high octane gasoline blending component.
The C.sub.7 + feed to the catalytic reforming step of the process
of the present invention can be altered somewhat by feeding the
C.sub.7 hydrocarbons to the disproportionation step and feeding
only the C.sub.8 + hydrocarbons to the catalytic reforming step. In
either case, the C.sub.7 + or C.sub.8 + feed to the catalytic
reforming step usually will boil in the naphtha boiling range or
from about C.sub.7 or C.sub.8 up to about 400.degree. or
450.degree.F.
The catalytic reforming step is generally carried out using a
platinum on alumina catalyst. Preferably, the catalyst also
contains between about 0.01 and 5 weight percent rhenium. In any
event, the catalytic reforming step will operate to substantially
increase the octane number of the naphtha feed to the reforming
step.
In general, substantial amounts of aromatics including xylenes will
be produced in the catalytic reforming step. According to a
preferred embodiment of the present invention, at least a portion
of the aromatics present in at least a portion of the effluent from
the catalytic reforming step are fractionated or extracted from the
reforming effluent and the remaining paraffinic-rich raffinate is
recycled at least in part to the disproportionation step. Recycling
the paraffinic raffinate to the disproportionation step is
especially advantageous because the paraffinic raffinate usually
has a relatively low octane and the disproportionation step can
operate to substantially raise the quality of the raffinate by
disproportionating the raffinate to C.sub.7 + hydrocarbons, which
hydrocarbons can be advantageously catalytically reformed.
It is particularly advantageous to feed the raffinate to a common
fractionation zone so that C.sub.5 hydrocarbons can be separated
from the raffinate and then isomerized in an isomerization zone.
The C.sub.6 or C.sub.6 and C.sub.7 hydrocarbons in the raffinate
preferably are fractionated from the raffinate and fed to the
disproportionation zone for upgrading, at least in part, to higher
molecular weight hydrocarbons which, in turn, can be fed to the
catalytic reforming step of the present invention.
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a schematic process flow diagram illustrating a
preferred embodiment of the process of the present invention.
DETAILED DESCRIPTION OF THE DRAWING
Referring now more specifically to the drawing, a hydrocarbon
stream preferably rich in paraffins and containing at least hexane
is fed via line 1 to fractionation zone 2. The hydrocarbon fresh
feed stream to the process of the present invention can boil over a
wide range such as C.sub.3 up to C.sub.10 + (C.sub.10 to about
C.sub.16) hydrocarbons. Highly paraffinic feedstocks boiling up to
about 500.degree. or 600.degree.F. are preferred hydrocarbon feeds.
To a large extent, as is schematically indicated in the drawing,
the effluent streams from the processing steps of the present
invention and the fresh feed can be handled in one common
fractionation zone. The fresh feed stream is separated in the
fractionation zone into a number of hydrocarbon cuts, most of which
are indicated on the drawing. In many instances, it is advantageous
to use more than one fractionation column in the fractionation
zone.
To aid in the use of a common fractionation zone, in some instances
it is preferable to employ vapor side draws from the fractionation
column or columns, as well as liquid side draws. Thus, the
hexane-rich withdrawal from the fractionation zone schematically
indicated by arrow 7 from the fractionation zone to
disproportionation zone 8 can be a vapor withdrawal.
The C.sub.5 - feed to the fractionation zone via line 19 from
disproportionation zone 8 usually will contain substantial amounts
of C.sub.2 and C.sub.3 hydrocarbons in addition to butanes and
pentanes. The C.sub.2, C.sub.3 and C.sub.4 hydrocarbons can be
withdrawn from the fractionation zone via line 3 and processed
further, if necessary, to obtain liquified petroleum gas (LPG).
Isopentane present in the fresh feed to the fractionation zone
and/or isopentane recycled together with normal pentane via line 22
to the fractionation zone is preferably withdrawn as an isopentane
rich stream via line 21.
C.sub.5 hydrocarbons, particularly normal pentanes, are withdrawn
via line 4 from the fractionation zone. Preferably, this C.sub.5
rich hydrocarbon stream is fed to isomerization zone 5 for the
conversion of normal pentane into isopentane, which is a much
higher octane constituent for gasoline. The isopentane is
advantageously blended with high octane reformate produced in
catalytic reforming zone 11.
A number of different catalysts can be used for normal pentane
isomerization. Catalysts such as two percent aluminum chloride
dissolved in antimony trichloride have been used for pentane
isomerization carried out under a hydrogen pressure of about 60 -
100 psig to suppress side reactions. Other acidic-type solid
isomerization catalysts can be used to effect the normal pentane
isomerization. Particularly preferred catalysts comprise layered
clay-type crystalline aluminosilicate catalysts, such as described
in U.S. Pat. No. 3,252,757.
A hexane-rich hydrocarbon stream is withdrawn via line 7 from the
fractionation zone and is fed to disproportionation zone 8. The
hexane-rich feed usually contains at least about 10 weight percent
hexane and preferably 35 weight percent or more hexane. The
hexane-rich stream can contain both lighter and heavier
hydrocarbons than hexane. According to the present invention, the
two most preferred hexane-rich feed streams are (a) a predominantly
C.sub.6 paraffin stream boiling between about 136.degree. and
156.degree.F. or (b) predominantly C.sub.6 and C.sub.7 paraffins
boiling between about 136.degree. and 209.degree.F.
As indicated previously, preferably the disproportionation of the
hexane is carried out at a temperature below 850.degree.F., and
more preferably, below 800.degree.F., and in the presence of no
more than about five weight percent olefins, by contacting the
hexane with a catalytic mass having catalytic activity for
dehydrogenation of hydrocarbons as well as catalytic activity for
olefin disproportionation. The catalytic mass can comprise a
physical mixture of catalyst particles which are active for
hydrocarbon dehydrogenation and catalyst particles which are active
for olefin disproportionation. Preferably, the catalytic mass
comprises a noble metal or a noble metal compound on a refractory
support, in addition to an olefin disproportionation component.
Thus, preferred catalyst masses include platinum on alumina
particles mixed with tungsten oxide on silica particles. Catalyst
masses comprising a Group VIII component in addition to a Group VIB
component are generally suitable in the process of the present
invention.
It is preferred in the process of the present invention to operate
the disproportionation reaction zone at a pressure above about 200
psig, more preferably above about 400 psig, and still more
preferably above about 800 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. Thus, relatively high pressure, of the order
of 500-1,500 psig, are particularly preferred.
C.sub.7 + or C.sub.8 + hydrocarbons produced in disproportionation
zone 8 are removed via line 9 and fed to fractionation zone 2. It
is to be understood that in most instances, there will be some
fractionation or separation facilities as part of
disproportionation zone 8 in order to separate the lighter
hydrocarbons, for example, C.sub.5 -, from the heavier
hydrocarbons, for example, C.sub.7 +, formed from the
disproportionation of the hexane-rich feed to the
disproportionation zone. In some instances, the C.sub.7 + fraction
from the disproportionation zone is preferably fed directly to
catalytic reforming zone 11. But usually, it is preferred to feed
the C.sub.7 + material from the disproportionation zone to common
fractionation zone 2 so that the desired C.sub.7 + feed comprising
a mixture of C.sub.7 + hydrocarbons in the initial feed added via
line 1 and the C.sub.7 + hydrocarbons obtained by
disproportionation can be withdrawn together from the common
fractionation zone via line 10 and fed to catalytic reforming zone
11. The feed to the reformer in the process of the present
invention preferably boils from about C.sub.7 up to about
300.degree. to 425.degree.F. or from C.sub.8 up to about
300.degree. to 425.degree.F. To increase jet fuel production, the
feed to the reformer preferably boils from about C.sub.8 to
300.degree. or 350.degree.F. Jet fuel boiling range hydrocarbons
(about 350.degree. to 600.degree.F.) are withdrawn from the
fractionation zone via line 17.
A portion of the disproportionation zone effluent can be withdrawn
via line 20. Build up of highly branched chain hexanes, which are
not as readily disproportionated as straight chain hexanes, can be
avoided by withdrawal of a bleed stream via line 20.
Catalytic reforming zone 11 is preferably operated at a temperature
between 850.degree. and 1,100.degree.F. and at a hydrogen partial
pressure between about 40 and 1,000 psig. Preferred catalysts are
catalysts containing one or more noble metals on a refractory
support such as platinum on alumina. Preferably, the reforming
catalyst also contains a small amount of a halide to promote the
activity of the catalyst for isomerization. The platinum or noble
metal component of the catalyst is believed to be mainly
responsible for the reaction (which may be characterized as a
dehydrocyclization reaction) necessary to convert paraffinic
hydrocarbons to aromatics. The term "catalytic reforming" is used
herein to refer to hydrocarbon processing wherein substantial
amounts of paraffins are converted to aromatics so as to obtain a
reformate which, usually after removal of at least some light ends,
has a substantially increased octane rating relative to the
paraffinic feedstocks to the reforming process. Particularly
preferred catalysts for upgrading the octane level of the
paraffinic feed to catalytic reforming zone 11 are catalysts
comprising platinum and rhenium on alumina such as described in
U.S. Pat. No. 3,415,737.
Product reformate can be withdrawn from zone 11 via line 12,
usually after separating a small amount of light hydrocarbons in
separation or distillation facilities which are a part of zone 11.
However, in the process of the present invention, it is
particularly preferred to feed at least a portion of the effluent
from catalytic reforming zone 11 to fractionation and/or extraction
zone 14 via line 13. Zone 14 is operated so as to separate a
paraffinic-rich hydrocarbon stream from higher octane primarily
aromatic hydrocarbons. The paraffinic-rich stream is recycled via
line 16 to the fractionation zone so that the recycle stream can be
upgraded in octane oevel. The most important means of upgrading the
recycle stream in octane level is by the disproportionation of
hexanes present in the recycle stream followed by catalytic
reforming of the heavier hydrocarbons obtained in the
disproportionation of the hexanes. Also, in the process of the
present invention, normal pentane present in the recycle
paraffin-rich stream can be increased in octane rating by means of
isomerization in zone 5.
It is particularly preferred to separate the paraffinic-rich
recycle stream by solvent extraction in zone 14 using a solvent
which selectively takes aromatics into solution with the solvent
such as glycol-water solutions (frequently referred to as Udex) or
furfural or other aromatic solvents. The material left after the
aromatics have been extracted is generally referred to as
raffinate. The raffinate is a preferred paraffinic-rich hydrocarbon
stream for disproportionation in zone 8, usually after the
raffinate has been further processed by fractionation to obtain a
C.sub.6 rich stream for feed to disproportionation zone 8.
Various aromatic-rich fractions can be withdrawn from zone 14 but
only two withdrawals via line 15 and line 18 are indicated from
zone 14. The two preferred withdrawals are a xylene-rich aromatic
stream for use in a chemical plant such as a paraxylene plant, and
a high octane aromatic gasoline stream for use as motor fuel.
When carrying out high severity reforming in zone 11, producing
predominantly aromatics and using, for example, newly developed
catalysts such as Pt-Re on alumina catalysts, it is usually
preferably in the process of the present invention to employ
fractionation rather than solvent extraction for separating
paraffins from aromatics, especially for newly built low pressure
catalytic reforming units.
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 increasing the
octane rating of hexane-rich hydrocarbons by a combination of at
least hexane disproportionation and catalytic reforming of
hydrocarbons heavier than hexane. 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.
* * * * *