U.S. patent number 3,767,562 [Application Number 05/177,362] was granted by the patent office on 1973-10-23 for production of jet fuel.
This patent grant is currently assigned to The Lummus Company. Invention is credited to James William Reilly, Morgan Chuan-Yuan Sze.
United States Patent |
3,767,562 |
Sze , et al. |
October 23, 1973 |
PRODUCTION OF JET FUEL
Abstract
A process for producing jet fuel from a petroleum fraction
having a boiling range within the temperature range of about
135.degree.F. to about 550.degree.F., such as kerosene. The feed is
mixed with hydrogen, and liquid recycle, preheated if necessary,
and subjected to two-stage hydrogenation of aromatics to reduce the
aromatics content and improve the smoke point. Temperature in the
reactor is also controlled by the operation of the process.
Inventors: |
Sze; Morgan Chuan-Yuan (Upper
Montclair, NJ), Reilly; James William (Westfield, NJ) |
Assignee: |
The Lummus Company (Bloomfield,
NJ)
|
Family
ID: |
22648306 |
Appl.
No.: |
05/177,362 |
Filed: |
September 2, 1971 |
Current U.S.
Class: |
208/57; 208/15;
208/143 |
Current CPC
Class: |
B01J
8/0453 (20130101); C10G 2400/08 (20130101) |
Current International
Class: |
C10G
45/02 (20060101); C10G 65/08 (20060101); C10G
45/52 (20060101); C10G 45/08 (20060101); C10G
45/44 (20060101); C10G 45/48 (20060101); C10G
65/00 (20060101); C10g 023/00 () |
Field of
Search: |
;208/57,89,143,15
;260/667 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levine; Herbert
Claims
We Claim:
1. A process for producing jet fuels by the two-stage hydrogenation
of a hydrocarbon feed having a boiling range within the temperature
range of about 300.degree.F to about 550.degree.F, and
substantially free of sulfur-containing impurities, comprising the
steps of:
a. passing the feed in cocurrent contact with a hydrogen-rich gas
through a first hydrogenation zone operated at a temperature of
from about 250.degree.F to about 575.degree.F and at an elevated
pressure in contact with a hydrogenation catalyst to at least
partially hydrogenate the feed;
b. removing from the first hydrogenation zone a gas phase effluent
comprising hydrogen and vaporized liquid materials, and a partially
hydrogenated liquid hydrocarbon liquid;
c. hydrogenating the liquid hydrocarbon effluent in a second
hydrogenation zone operated at a temperature of from about
200.degree.F to about 500.degree.F and at an elevated pressure by
passing a hydrogen-rich gas having a temperature substantially
lower than that of the liquid hydrocarbon effluent into the second
hydrogenation zone countercurrently to the effluent, in contact
with a hydrogenation catalyst; and
d. drawing off from the second hydrogenation zone a gas phase
effluent comprising hydrogen and vaporized liquid materials and a
liquid phase effluent comprising jet fuel.
2. A process according to claim 1 wherein the feed to the first
hydrogenation zone is subjected to desulfurization prior to being
introduced into said zone.
3. A process according to claim 1 wherein the feed to the first
hydrogenation zone is preheated prior to being introduced into said
zone.
4. A process according to claim 3 wherein the gas phase effluents
from the first and second hydrogenation zones are combined and
passed in indirect heat exchange relationship with the feed to the
first hydrogenation zone, thereby cooling said gas phase effluents
and preheating said feed.
5. A process according to claim 1 wherein the gas phase effluents
from the first and second hydrogenation zones are cooled
sufficiently to condense the vaporized liquid components thereof,
and said vaporized liquid components are separated from the
remaining gas components and returned as liquid feed to the first
hydrogenation zone.
6. A process according to claim 5 wherein a mojor portion of the
remaining gas components is returned to the first hydrogenation
zone.
7. A process according to claim 5 wherein the ratio of recycled
liquid to fresh feed is between 0.05:1 and 0.75:1.
8. A process according to claim 1 wherein the first hydrogenation
zone is operated at a temperature of from about 300.degree.F to
about 575.degree.F.
9. A process according to claim 1 wherein the second hydrogenation
zone is operated at a temperature of from about 250.degree.F to
about 500.degree.F.
10. A process according to claim 1 wherein the second hydrogenation
zone is operated at temperature conditions such that the liquid
outlet temperature from said zone is between about 300.degree.F and
500.degree.F.
11. A process according to claim 1 wherein the hydrocarbon feed has
a boiling range within the temperature range of from about
350.degree.F to about 510.degree.F.
12. A process according to claim 1 wherein the hydrocarbon feed has
a boiling range within the temperature range of from about
300.degree.F to about 520.degree.F.
13. A process according to claim 1 wherein the hydrocarbon feed is
a desulfurized straight-run kerosene.
Description
BACKGROUND OF THE INVENTION
This invention relates to the production of jet fuel from
hydrocarbon feedstocks. In general, a number of methods have been
proposed for jet fuel production, from a wide range of feedstocks.
In some processes, various petroleum fractions or products have
been subjected to hydrocracking, reforming, alkylation and other
processes in various combinations. U.S. Pat. No. 3,513,085, which
discloses jet fuel production from coal liquids and petroleum oils
by hydrocracking, solvent extraction, fractionation and
hydrogenation is typical of such processes. Other methods of
producing jet fuel have involved the hydrogenation of aromatics --
containing feeds in various ways, sometimes in combination with
such other processes as hydrocracking. For example, U.S. Pat. No.
3,147,210 discloses the production of jet fuel by catalytic
hydrogenation of high boiling aromatic hydrocarbons, preceded by a
hydrofining or hydrodesulfurization step. The feedstock is
desulfurized in cocurrent flow with added hydrogen in the first
stage, hydrogen sulfide is stripped after the first stage; the
stripped liquid is then subjected to catalytic hydrogenation in
countercurrent flow with hydrogen in a second stage.
Detailed specifications for various types of jet fuels have been
published by the Armed Forces and ASTM. Three jet fuels in common
use today are those designated JP-4, JP-5 and ASTM D-1655 Jet A-1
fuel. With respect to the more critical properties, the
specifications call for a maximum sulfur concentration of 2,000 ppm
(0.2 percent) by weight, a minimum IPT Smoke Point of 25 mm and a
maximum aromatics content of 20 volume per cent. In addition to
methods such as are described in the preceding paragraphs, attempts
have been made to use various kerosene fractions directly as jet
fuels. However, while these fractions may meet many of the
specifications for such fuels, they often do not meet the IPT Smoke
Point specification. Additionally, some kerosenes contain a higher
aromatics content than the specifications permit.
It is an object of this invention, therefore, to provide a method
for producing jet fuel from a hydrocarbon feedstock without the
need for expensive processing steps such as hydrocracking.
It is a further object of this invention to provide a method for
producing jet fuel from a hydrocarbon feedstock having a boiling
range within the temperature range of about 135.degree.F. to about
550.degree.F.
It is a still further object of this invention to provide a process
for producing jet fuel from a hydrocarbon fraction boiling
substantially within the kerosene boiling range, and more
particularly, from a hydrocarbon boiling within the range of from
about 300.degree.F. to about 550.degree.F.
A yet further object of this invention is to provide a method for
producing a jet fuel with a low aromatics content. Additionally, it
is an object of this invention to provide a method for producing a
jet fuel which exceeds the minimum IPT Smoke Point of 25 mm. Other
objects of this invention will become apparent from the
specification, drawings and claims hereof.
SUMMARY OF THE INVENTION
In brief, the invention contemplates the production of jet fuel
from an aromatics-containing petroleum feedstock having a boiling
range within the temperature range of from about 135.degree.F. to
about 550.degree.F. comprising the steps of: (a) passing the
feed-stock in co-current contact with a hydrogen-rich gas through a
first reaction zone operated at a temperature of from about
250.degree.F. to about 575.degree.F. at elevated pressure in
contact with a hydrogenation catalyst; (b) removing from said first
reaction zone a gas phase effluent comprising hydrogen and
vaporized liquid materials, and a partially hydrogenated liquid
effluent; (c) passing said liquid effluent into a second reaction
zone operated at a temperature of from about 200.degree.F. to about
500.degree.F. at elevated pressure; (d) passing a hydrogen-rich gas
into said second reaction zone countercurrently to said liquid
phase effluent in contact with a hydrogenation catalyst, and (e)
drawing off from said second reaction zone a gas phase effluent
comprising hydrogen and vaporized liquid materials and a liquid
phase effluent comprising jet fuel.
The FIGURE is a diagrammatic illustration of the process of this
invention.
DETAILED DESCRIPTION
As shown in the FIGURE, the hydrogenation zones are preferably
contained in one hydrogenation vessel, which has the form of a
vertical cylinder having disched ends and pressure sustaining
walls. The interior of the vessel is divided by horizontal
partitions 12, 14, and 24, which are preferably perforated or
foraminous plates or the like, into a plurality of chambers or
zones including an upper reaction chamber 16, an intermediate
vapor-disengaging zone 20, and a lower reaction chamber 18. The
reaction chambers 16 and 18 are packed with a suitable
hydrogenation catalyst 22, which may be of any of the well known
hydrogenation-dehydrogenation catalysts, including such as Raney
nickel, or nickel, platinum or palladium, preferably on a support
such as alumina, silica, kieselguhr, diatomaceous earth, magnesia,
zirconia or other inorganic oxides, alone or in combination. The
catalyst in zone 16 is supported on partition 12. The catalyst in
zone 18 is supported on a similar partition 24. Partition 24 is
preferably spaced somewhat above the bottom of the converter, thus
defining the upper boundary of an additional lower chamber or zone
26.
Fresh aromatics-containing feed, such as is hereinafter described,
is introduced into the system at line 46, into a hydrogen stream in
line 40, and the mixture proceeds in line 40 as indicated by the
arrows until it joins line 44, from which is added a condensed
recycle liquid from separator 34. The resulting mixture then passes
through line 42 into the top of the hydrogenation vessel, at a
temperature of from about 250.degree.F. to about 575.degree.F. and
a pressure of from about 400 to about 1,500 psi, depending on the
boiling range of the feedstock and the severity of the
hydrogenation. The lower temperature and pressure correspond to
lower boiling feeds and lower severity of treatment.
The mixture of feed recycle liquid and hydrogen passes downwardly
through the catalyst bed in zone 16, under adiabatic reaction
conditions in which a substantial amount of the aromatics present
in the total liquid charge are hydrogenated to the corresponding
naphthenic compounds. The reaction mixture which passes out of zone
16 is a two-phase mixture. The liquid phase is a mixture of
paraffins, naphthenes and some unreacted aromatics. The gas phase
effluent is a mixture of hydrogen, inert gaseous impurities, and
vaporized liquid hydrocarbons of a composition generally similar to
that of the liquid phase effluent.
The liquid phase of the effluent passes downwardly through the
vapor-disengaging zone 20 into the second hydrogenation zone 18
(through partition 14, which serves as a distributor plate).
In reaction chamber 18, hydrogen introduced through line 48 and
passing through chamber 26 contacts the liquid phase effluent
countercurrently, hydrogenating the remaining aromatics to the
corresponding naphthenes. The hydrogen is introduced without being
preheated, at a relatively low temperature, compared to that of the
liquid phase effluent from zone 16; generally the hydrogen
temperature is no higher than about 100.degree.-120.degree.F.
The liquid portion which emerges from hydrogenation zone 18 is
briefly accumulated in chamber 26 of the reactor, permitting
disengagement of vapors and sealing the outlet to line 50 to
prevent escape of hydrogen. The liquid product is collected in line
50 and contains a very minor portion, generally less than 1.5
volume per cent, of residual unhydrogenated aromatics. The gas
phase effluent from hydrogenation zone 18 contains excess hydrogen,
inert gaseous impurities, and vaporized hydrocarbons of a
composition similar to those contained in the gas phase effluent
from hydrogenation zone 16.
The gas phase effluents from both the first hydrogenation zone 16
and the second hydrogenation zone 18 collect in vapor-disengaging
zone 20. The combined gas phase fraction is withdrawn through line
28, and first passed through heat exchanger or waste heat boiler
52, in which some of the heat is used to produce steam for use in
other processing steps, or in other processes, or for general
purposes. The still hot vapor mixture is then passed through line
54, then preferably through condenser 30 in which it is used to
preheat the mixture fed to the reactor, then through condenser 32,
where the vaporized liquid phase components remaining in the system
are recondensed to liquids. The resulting two-phase system,
consisting of gaseous hydrogen, inert gases, and reliquefied
hydrocarbons, is passed into separator 34, where the liquid and
gaseous phases are separated. The liquid phase is passed through
line 44 to be mixed with the feed to hydrogenation zone 16 as
previously described. The gaseous phase, comprising hydrogen and
inert gases, may be vented partially, as through line 56, to
prevent build-up of inert inpurities in the system.
The remainder, and majority of this gaseous phase is recycled
through line 36, to be mixed with the feed to the first
hydrogenation zone 16 in line 40. Fresh feed hydrogen gas may be
supplied from line 48 through line 58 into the recycle gas, in the
event that the recycle hydrogen is insufficient to supply the needs
in the first hydrogenation zone.
An important feature of this invention is a built-in temperature
control. Reactions of the type contemplated are exothermic. The
production of the desired jet fuel is favored by low outlet
temperatures. Furthermore, runaway reactions must be prevented or
coke and undesirable side products will be formed. Accordingly,
external temperature control means are usually necessitated in
processes for hydrogenating aromatics for jet fuel production. The
present process, however, provides an inherent temperature control,
particularly in the second hydrogenation zone 18. As the hydrogen
feed from line 58 passes upwardly through this zone, a portion of
the heat present in that chamber is absorbed in the process of
sensibly heating the hydrogen. An additional amount of heat is
absorbed by the vaporization of reaction product liquid in zone 18,
in an amount sufficient to saturate the gas stream emerging from
this zone into vapor-disengaging zone 20. Similarly, the
temperature in the first reaction zone 16 is controlled by the
absorption of heat in partially vaporizing the liquid feed. The
vaporized liquid is removed from the vapor-disengaging zone 20 in
conduit 28, as previously described. A similar process for the
production of cyclohexane from benzene, with this same built-in
temperature control, is described in our U.S. Pat. No.
3,450,784.
The vaporized hydrocarbons recovered from the vapor-disengaging
zone 20 and used as recycle comprise partially hydrogenated feed
containing up to about 5 percent aromatics. Because of the low
concentration of aromatics, the ratio of recycle to fresh feed is
less than 1:1, generally in the range of about 0.05:1 to about
0.75:1, and depends on a number of factors, including hydrogen
partial pressure and purity, desired temperature in the reactor,
etc.
The feed to the process comprises a petroleum fraction having a
boiling range within the temperature range of from about
135.degree.F. to about 550.degree.F. Fractions, for example, with
boiling ranges such as 135.degree.F.-480.degree.F.,
350.degree.F.-510.degree.F. and 300.degree.F.-520.degree.F. are
typical of those within this broad range which are suitable
feedstocks for this process. The feed can be either a straight run
or other petroleum fraction; such fractions as kerosenes, light and
heavy naphthas, catalytically cracked cycle oils and furnace oils
can be utilized. Particularly suitable is a feedstock generally
boiling within the kerosene boiling range, that is, boiling within
the range of from about 300.degree.F. to about 550.degree.F.
When such a feed is utilized, the first hydrogenation zone 16 is
operated at a temperature of from about 300.degree.F. to about
575.degree.F. and the second zone at about 250.degree.F. to about
500.degree.F., within the pressure ranges previously mentioned.
The process of this invention does not accomplish desulfurization
for practical purposes; consequently most feedstocks should be
desulfurized prior to being introduced into the process, generally
in a separate unit (not shown).
If the feed is desulfurized just prior to its admission into the
first hydrogenation zone, it will generally be sufficiently hot
that no further heating is required to bring it up to reaction
temperature. If, however, the feed has been obtained from a simple
fractionation process or has been allowed to cool down prior to
being passed into this process, or has been in storage, preheating
is required. In any case, the hydrogen fed to the first
hydrogenation zone 16 must be preheated prior to its introduction
into this zone. The liquid recycle to this zone must also be
preheated.
The preheating of the hydrogen, and feed if necessary, can be
accomplished in a number of ways, and can be performed separately
or together. A convenient method, in this process, is to utilize
the heat contained in the vapors in lines 28 and 54, which have
been removed from the vapor-disengaging zone 20. The combined
hydrogen (and feed, if necessary) in stream 42, together with
recycle liquid from line 44, is passed through heat exchanger 30,
in which it is preheated to the desired inlet temperature by
indirect heat exchange with the partially cooled vapors in line 54.
This heat exchange, under some conditions, may have the additional
effect of partially condensing some of the hydrocarbons in the
combined vapor stream, facilitating the separation of hydrocarbons
for recycle from the hydrogen and other gases, in separator 34.
If the fresh feed is already sufficiently hot so as not to require
preheating, it should be by-passed around the preheater to avoid
overheating and undesirable side reactions. The fresh feed will
then enter the system, for example, through line 43 instead of
through line 46, or by-pass can be accomplished in other ways known
in the art. In this case, only the hydrogen and recycled liquid
hydrocarbons will be preheated.
Alternatively, the preheating of the fresh feed, liquid recycle and
hydrogen can be done in separate heat exchangers, and the heated
materials mixed before being introduced into the reactor. This
separate preheating can be done using any source of available heat,
including the hot vapor mixture in line 54.
The ratio of hydrogen to fresh feed in the mixture fed to reaction
zone 16 may vary from a stoichiometric ratio of 1 mole of hydrogen
per double bond to as much as about 300 percent of the
stoichiometric requirement, and the ratio of hydrogen to the liquid
material entering reaction zone 18 may vary from about 0.3 to about
1.0 moles/mole.
The L.H.S.V. in the first zone 16 is preferably maintained between
about 0.5 and about 6.0, based on fresh feed only, while that in
the second zone 18 is generally at a higher level The overall
L.H.S.V. is maintained, however, between 0.5 and 6.0.
The temperature conditions in the second zone should be adjusted to
maintain the temperature of the liquid product at the outlet
between about 300.degree.F. and about 500.degree.F., depending on
the boiling range of the fresh feed, to provide optimum conditions
favoring hydrogenation of the aromatics to naphthenes and close
equilibrium approach.
It should be noted that it is not necessary to saturate all
aromatics in the feed to produce a jet fuel meeting the minimum
smoke point requirement. Saturation of 90 percent of the aromatics
is usually more than sufficient to reach this standard; as pointed
out herein above, the product may have a residual aromatics content
of up to 1.5 volume per cent. However, much lower aromatics
contents can be achieved, as illustrated in the Example.
Most of the fuels produced by the process of this invention, from
the feedstocks mentioned while meeting the specifications for
standard jet fuel, will not possess a low enough freezing point to
be suitable for use in supersonic aircraft (-57.degree.F. or less).
However, in the case of certain feedstocks, even this specification
can be met. It has been found, for example, that such a jet fuel
can be produced from a desulfurized kerosene obtained from a
Bachaquero crude by utilizing the process described herein.
In order to illustrate more fully the nature of this invention, and
the manner of practicing the same, the following specific example
is presented.
EXAMPLE
A desulfurized straight run kerosene having the following
properties:
Astm distillation, ASTM D-86-62
I.b.p., .degree.f..sub.o --345
50 vol..sub.o %, .degree.F.--390
E.p., .degree.f.--460
vol. % Aromatics, ASTM D-1319-65T--16.0
Smoke Point, mm ASTM D-1322-64--18.2
was mixed with hydrogen, then combined with recycled liquid in a
ratio of 16 parts recycle to 100 parts fresh feed, preheated in
heat exchanger 30 and introduced into the top of reactor 10. The
inlet temperature at the top of section 16 was 400.degree.F; the
maximum overall catalyst bed temperature was 525.degree.F. The
reaction was conducted at an overall L.H.S.V. of 2.40 and a
pressure of 900 psig. The hydrogenated product recovered in line 50
had an aromatics content of 0.55 volume per cent. The smoke point
was improved to 36 mm, well above the minimum acceptable limit of
25 mm.
While the above constitutes a description of our invention, it is
by no means intended to limit the invention to the specific items
disclosed herein, as alternatives and equivalents will readily
occur to those skilled in the art. The invention, therefore, is not
to be construed as limited, except as set forth below in the
claims.
* * * * *