U.S. patent number 3,894,938 [Application Number 05/370,265] was granted by the patent office on 1975-07-15 for catalytic dewaxing of gas oils.
This patent grant is currently assigned to Mobil Oil Corporation. Invention is credited to Robert L. Gorring, George F. Shipman.
United States Patent |
3,894,938 |
Gorring , et al. |
July 15, 1975 |
Catalytic dewaxing of gas oils
Abstract
Improved catalytic dewaxing and desulfurization of high pour
point, high sulfur gas oils to lower their pour point to about
10.degree.F or lower and their sulfur content by contacting a high
pour point gas oil first with a ZSM-5 type zeolite hydrodewaxing
catalyst which may contain a hydrogenation/dehydrogenation
component, in the presence or absence of added hydrogen under low
pressure conditions, followed by conventional hydrodesulfurization
processing of the dewaxed intermediate.
Inventors: |
Gorring; Robert L. (Washington
Crossing, PA), Shipman; George F. (Trenton, NJ) |
Assignee: |
Mobil Oil Corporation (New
York, NY)
|
Family
ID: |
23458905 |
Appl.
No.: |
05/370,265 |
Filed: |
June 15, 1973 |
Current U.S.
Class: |
208/97; 208/59;
208/111.3; 208/111.35 |
Current CPC
Class: |
C10G
65/043 (20130101); C10G 2400/06 (20130101) |
Current International
Class: |
C10G
45/58 (20060101); C10G 65/00 (20060101); C10G
45/64 (20060101); C10G 65/04 (20060101); C10G
037/00 () |
Field of
Search: |
;208/97,46 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3438887 |
April 1969 |
Morris et al. |
3472759 |
October 1969 |
Masolocites et al. |
3516925 |
June 1970 |
Lawrence et al. |
3668113 |
June 1972 |
Burbidge et al. |
3700585 |
October 1972 |
Chen et al. |
3764516 |
October 1973 |
Steinmetz et al. |
|
Foreign Patent Documents
|
|
|
|
|
|
|
884,752 |
|
Dec 1961 |
|
GB |
|
1,191,471 |
|
May 1970 |
|
GB |
|
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Hellwege; James W.
Attorney, Agent or Firm: Huggett; Charles A. Gilman; Michael
G.
Claims
What is claimed is:
1. In the process of reducing the pour point of a sulfur and
nitrogen containing gas oil boiling in the range of 400.degree. to
900.degree.F by treating such with a ZSM-5 type of zeolite at about
300.degree. to 1000.degree.F; the improvement, whereby reducing the
pour point of said gas oil and purifying such to reduce the sulfur
and nitrogen content thereof, which comprises subjecting said gas
oil first to said zeolite treatment and then subjecting the whole,
unresolved zeolite treated, reduced pour point intermediate to
desulfurization and denitrogenation.
2. The improved process claimed in claim 1 wherein said
hydrodesulfurization is carried out at about 550.degree. to
800.degree. F, 200 to 1000 psig hydrogen partial pressure, 0.5 to
4.0 LHSV and in effective contact with a cobaltmolybdenum-alumina
catalyst.
3. The improved process claimed in claim 1 wherein said gas oil has
a minimum of 0.1 wt. percent total sulfur and 10 ppm nitrogen
before processing.
4. The improved process claimed in claim 1 wherein said zeolite
treating is carried out at a hydrogen partial pressure of about 0
to 2000 psig and a space velocity of about 0.1 to 10 LHSV.
Description
This invention relates to petroleum processing. It more
particularly refers to upgrading certain gas oil fractions to low
pour point fuels.
Liquid hydrocarbons in the 400.degree. to 850.degree.F boiling
range include kerosine, Diesel fuel and No. 2, or home heating
fuel. Petroleum fractions boiling in this range often have a
significant long chain paraffin content which accounts for their
rather high pour point. It is not unusual for fractions of this
type to have pour points in the 50.degree. to 100.degree.F range.
One significant specification for some No. 2 fuel oil is a pour
point of 0.degree.F or lower. Thus reduction in pour point is
accomplished by dewaxing or removing the long chain normal
paraffins which seem to be principally responsible for this
property.
This dewaxing has traditionally been accomplished by a solvent
dewaxing technique according to which the gas oil is thoroughly
mixed with a suitable solvent, often methyl ethyl ketone, into
which the wax dissolves. In the past, the wax was recovered from
the solvent, by evaporation of the ketone, purified and sold for
seals, candles and other uses. More recently, the petroleum
industry has seen a marked decline in this market and has therefore
sought more profitable and less costly outlets for this wax
constituent.
It has therefore been proposed to use shape selective zeolitic
catalysts to crack, preferably hydrocrack, these paraffinic
components and convert them into smaller, suitably paraffinic
fragments which may be collected as light gas, or larger but not
waxy paraffinic materials which remain in the boiling range of the
gas oil being treated and therefore enhance the yield of the
dewaxing operation. The smaller cracked fragments may be used as
fuel, sold as such or resolved and disposed of by components.
Most recently it has been proposed to utilize the new ZSM-5 type of
zeolite as a cracking or hydrocracking dewaxing catalyst because it
converts not only the normal paraffins but the slightly branched
paraffins as well thereby more efficiently lowering the pour point
of the product with better yields than have heretofore been
achieved. (See U.S. Pat. No. 3,700,585).
ZSM-5 type of zeolite is a group of small pored zeolites, the most
noteworthy members of which are ZSM-5, ZSM-8 and ZSM-11. U.S. Pat.
Nos. 3,702,886 directed to ZSM-5 zeolite and 3,709,979 directed to
ZSM-11 zeolite are in point and are incorporated herein by
reference. Abandoned U.S. Patent application Ser. No. 865,418,
filed Oct. 10, 1969 is directed to ZSM-8 and is also in point and
is incorporated herein by reference. The ZSM-5 family of zeolites
can be used to catalyze cracking of normal or slightly branched
paraffins in the absence of added hydrogen or to catalyze
hydrocracking of such paraffins in the presence of added hydrogen.
Typical cracking conditions include a space velocity of about 0.25
to 200 LHSV, a temperature of about 400.degree.F to 1100.degree.F
and a pressure from subatmospheric to several hundred atmospheres.
Typical hydrocracking conditions include a space velocity of about
0.1 to 10 LHSV, a hydrogen to hydrocarbon mole ratio of about 1 to
20 to 1, a temperature of about 650.degree.F to 1000.degree.F and a
pressure of about 100 to 3000 psig (see U.S. Patent 3,700,585).
For most petroleum processing, it is conventional to pretreat the
charge stock in some manner calculated to remove sulfur and/or
metals and/or nitrogen from the charge stock prior to converting
and upgrading such charge stock. Thus catalytic
hydrodesulfurization is a unit process which is widely used in a
refinery. It precedes reforming and other conversion processes
because sulfur, nitrogen and/or metals present in the charge stock
often have detrimental effects upon hydrocarbon conversion
catalysts. Metals, sulfur and nitrogen tend to concentrate in the
heavier petroleum fractions. Therefore conversion processes
utilizing such heavier petroleum fractions would normally be
considered prime users of the conventional desulfurization followed
by catalytic conversion processing sequence.
Thus in the dewaxing of sulfur containing gas oils boiling in the
400.degree. to 900.degree.F range, or any part thereof, one of
ordinary skill in the art would conventionally think of subjecting
such gas oils to catalytic hydrodesulfurization prior to dewaxing.
Indeed this may be a desirable modus operandi for dewaxing of gas
oils with a "conventional" shape selective catalyst of the erionite
type. It has been most unexpectedly found however that operating
according to this sequence with ZSM-5 type zeolite dewaxing
catalyst leads to a significantly decreased activity as compared to
what one would expect (see Examples 1 and 2 infra). In fact the
evidence would seem to lead one to the conclusion that the more
sulfur and/or nitrogen there is in the gas oil charge stock, the
greater is the diminution of ZSM-5 type zeolite catalyst life. Yet
the product finally produced as a result of this dewaxing operation
must have a reduced sulfur and/or nitrogen content or preferably
substantially no sulfur or nitrogen content at all. This is because
this product goes predominantly into the jet fuel, Diesel fuel and
home heating market, where nitrogen and sulfur emissions must be
closely controlled.
It is therefore an important object of this invention to provide an
efficient gas oil dewaxing, desulfurization and denitrogenation
process.
It is another object of this invention to provide such a process
capable of taking advantage of the use of ZSM-5 type of zeolite
dewaxing catalyst.
It is a further object of this invention to provide such a process
for producing high yields of No. 2 fuel oil having a pour point of
about 0.degree.F.
Other and additional objects of this invention will become apparent
from a consideration of this entire specification including the
claims hereof.
In accord with and fulfilling these objects, one important aspect
of this invention resides in a processing sequence consisting
essentially of catalytically dewaxing a sulfur and/or nitrogen
containing gas oil having a boiling range in the range of about
400.degree.F to 900.degree.F and thence subjecting at least the
liquid product resulting from such dewaxing to desulfurization
and/or denitrogenation. In a preferred aspect of this invention the
gas oils to which this process is directed have a total sulfur and
nitrogen content of at least 0.1 wt. percent and 10 ppm,
respectively, and a pour point of at least +20.degree.F. It is
preferred to use a ZSM-5 type of zeolite catalyst for dewaxing and
to operate the dewaxing portion of this process at about
300.degree. to 1000.degree.F, 0 to 2000 psig, 0.1 to 10 LHSV and a
hydrogen to hydrocarbon ratio of about 0 to 25 to 1. Where the
dewaxing portion of the process is of the hydrodewaxing type, the
ZSM-5 type zeolite may have incorporated therein a hydrogen
transfer functional component such as nickel, palladium, or
platinum in a proportion of about 0.5 to 5 weight percent based on
the total weight of dewaxing catalyst. The dewaxing catalyst may be
used in a fixed or fluidized bed configuration as desired. In a
fixed bed operation, the catalyst particles should be sized between
one thirty-second and one-eighth inch. In a fluidized bed the
catalyst particles should be about 80 to 400 mesh. The catalyst may
be of the matrix type with alumina, silica, silica-alumina or other
similar known matrix materials. In this matrix embodiment, the
ZSM-5 type zeolite should constitute about 5 to 95 weight percent
of the total catalyst matrix.
The product of catalytic dewaxing may be resolved into a liquid and
gas portion by cooling to a prescribed temperature at an
appropriate pressure to obtain whatever liquid-gas demarcation is
desired. The liquid may then be subjected to desulfurization and
denitrogenation. It is preferred however to subject the entire
dewaxed product, without intermediate product resolution, to
desulfurization and denitrogenation. By not resolving the
intermediate product there is obtained a great saving in energy,
particularly heat, because this resolution requires cooling and the
subsequent desulfurization and denitrogenation requires reheating.
Desulfurization and denitrogenation are usually accomplished
simultaneously, one treatment serving to liberate both sulfur and
nitrogen from the feed stock. This treatment can be carried out in
any manner desired, e.g. conventionally at about 550.degree. to
800.degree. F, 200 to 1000 psig, 0.5 to 4.0 LHSV, 2 to 10 moles of
added hydrogen per mole of feed stock, in effective contact with a
cobalt-molybdenum-alumina-catalyst. This procedure converts sulfur
and nitrogen values in the feed stock to hydrogen sulfide and
ammonia which are later recovered from the gaseous portion of the
final product.
While operating in the manner and sequence set forth results in
excellent dewaxing and pour point reduction to acceptable levels
with liquid yields of over about 80 percent and dewaxing catalyst
life of about 20 to 400 days between regenerations to a total life
of about 6 to 60 months, reversing the sequence of operations, that
is desulfurizing and denitrogenating under the same conditions as
set forth above and directly dewaxing the intermediate product thus
formed to the same final product specifications, permitted
operation of the dewaxing catalyst for about 1 to 24 hours between
regenerations.
This invention will be illustrated by the following Examples which
are not to be considered as limiting on the scope or applicability
thereof. In these Examples parts and percentages are by weight
unless expressly stated to be on some other basis.
EXAMPLE 1 (PRIOR ART)
A gas oil having a boiling range of 500.degree. to 800.degree. F, a
pour point of +50.degree. F, a sulfur content of less than 3 wt. %
and a nitrogen content of less than 3000 ppm was contacted with
ZSM-5 zeolite at 700.degree. F, 400 psig, 5.0 hydrogen to
hydrocarbon mole ratio and 3.0 LHSV. The conversion to 330.degree.F
+ liquid was 84 percent with the pourpoint reduced to 0.degree.F.
Time between catalyst regenerations was 20 days.
EXAMPLE 2 (PRIOR ART)
A gas oil having a boiling range of 500.degree. to 800.degree. F, a
pour point of + 50.degree. F, a sulfur content of 2.5 percent and a
nitrogen content of 0.02 percent was contacted with a
cobalt-molybdenum-alumina catalyst at 700.degree. F, 400 psig, 5.0
hydrogen to hydrocarbon ratio and 1.0 LHSV. The product thus formed
was directly, and without intermediate product resolution,
contacted with ZSM-5 zeolite at 700.degree. F, 400 psig, 5.0
hydrogen to hydrocarbon mole ratio and 3.0 LHSV. The yield of
330.degree.F + liquid was 96 percent. However, its pour point was
reduced only from +50.degree.F to +25.degree.F, indicating that the
ZSM-5 dewaxing catalyst was substantially deactivated.
EXAMPLE 3
Example 2 was exactly repeated except that the sequence of
processing steps was reversed. The yield of 330.degree.F+ liquid
was 84 percent and the pour point was reduced from +50.degree.F to
0.degree.F. Time between ZSM-5 catalyst regenerations was 20
days.
* * * * *