U.S. patent application number 13/635663 was filed with the patent office on 2013-03-07 for catalytical hydrodesulfurization of kerosene in two steps on cobalt-molybdenum catalyst and intermediate stripping.
This patent application is currently assigned to INDIAN OIL CORPORATION LIMITED. The applicant listed for this patent is Rajesh Muralidhar Badhe, Anand Kumar, Brijesh Kumar, Ravinder Kumar Malhotra, Santanam Rajagopal, Alok Sharma. Invention is credited to Rajesh Muralidhar Badhe, Anand Kumar, Brijesh Kumar, Ravinder Kumar Malhotra, Santanam Rajagopal, Alok Sharma.
Application Number | 20130056391 13/635663 |
Document ID | / |
Family ID | 44120372 |
Filed Date | 2013-03-07 |
United States Patent
Application |
20130056391 |
Kind Code |
A1 |
Badhe; Rajesh Muralidhar ;
et al. |
March 7, 2013 |
CATALYTICAL HYDRODESULFURIZATION OF KEROSENE IN TWO STEPS ON
COBALT-MOLYBDENUM CATALYST AND INTERMEDIATE STRIPPING
Abstract
A process for selective removal of mercaptan from aviation
turbine fuel feed includes mixing aviation turbine fuel feed with
hydrogen, at a pressure in a range from 3 bar to 20 bar to obtain a
reaction mixture. The reaction mixture is heated at a temperature
range of 150.degree. C. to 350.degree. C. to obtain a heated
mixture. The heated mixture is reacted with a hydrotreating
catalyst in a rector to obtain a reactor effluent, and H.sub.2S gas
is stripped from the reactor effluent to obtain a stripper bottom
product. Moisture is removed from the stripper bottom product to
obtain aviation turbine fuel product having less than 10 ppm
mercaptan. The aviation fuel product has improved properties such
as color and acidity. Embodiments also relate to an aviation
turbine fuel product having less than 10 ppm mercaptan prepared by
the described process of the present invention.
Inventors: |
Badhe; Rajesh Muralidhar;
(Faridabad, IN) ; Sharma; Alok; (Faridabad,
IN) ; Kumar; Brijesh; (Faridabad, IN) ;
Rajagopal; Santanam; (Faridabad, IN) ; Malhotra;
Ravinder Kumar; (Faridabad, IN) ; Kumar; Anand;
(Faridabad, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Badhe; Rajesh Muralidhar
Sharma; Alok
Kumar; Brijesh
Rajagopal; Santanam
Malhotra; Ravinder Kumar
Kumar; Anand |
Faridabad
Faridabad
Faridabad
Faridabad
Faridabad
Faridabad |
|
IN
IN
IN
IN
IN
IN |
|
|
Assignee: |
INDIAN OIL CORPORATION
LIMITED
Faridabad, Haryana
IN
|
Family ID: |
44120372 |
Appl. No.: |
13/635663 |
Filed: |
March 16, 2011 |
PCT Filed: |
March 16, 2011 |
PCT NO: |
PCT/IN11/00175 |
371 Date: |
October 30, 2012 |
Current U.S.
Class: |
208/15 ; 208/189;
208/203 |
Current CPC
Class: |
C10G 2300/207 20130101;
C10G 2300/4012 20130101; C10G 2300/202 20130101; C10G 2300/4006
20130101; C10G 45/08 20130101; C10G 2400/08 20130101; C10G 2300/301
20130101; C10G 2300/1051 20130101; C10G 2300/4056 20130101; C10G
2300/42 20130101; B01J 23/28 20130101; C10G 2300/4018 20130101 |
Class at
Publication: |
208/15 ; 208/189;
208/203 |
International
Class: |
C10G 45/08 20060101
C10G045/08; C10L 1/04 20060101 C10L001/04 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 17, 2010 |
IN |
623/DEL/2010 |
Claims
1. A process for selective removal of mercaptan from aviation
turbine fuel (ATF) feed comprising: mixing aviation turbine fuel
feed with hydrogen, at a pressure in range of 3 bar to 20 bar to
obtain a reaction mixture, heating the reaction mixture at a
temperature range of 150.degree. C. to 350.degree. C. to obtain a
heated mixture, reacting the heated mixture with a hydrotreating
catalyst in a rector to obtain a reactor effluent, stripping
H.sub.2S gas from the reactor effluent to obtain a stripper bottom
product, and removing moisture from the stripper bottom product to
obtain aviation turbine fuel product having less than 10 ppm
mercaptan.
2. The process as claimed in claim 1, wherein the hydrogen is in
gaseous state and a ratio between the hydrogen gas and aviation
turbine fuel feed is in the range of 20:1 to 50:1.
3. (canceled)
4. The process as claimed in claim 1, wherein the aviation turbine
fuel feed has boiling range of about 120.degree. C. to about
300.degree. C., preferably between about 140.degree. C. to about
280.degree. C.
5. The process as claimed in claim 2, wherein the hydrogen gas is
reformer off-gas or recycle gas from diesel hydrotreating (DHDT)
unit or diesel hydrodesulfurisation (DHDS) unit.
6. The process as claimed in claim 1, wherein said process is
performed at a Liquid Hourly Space Velocity in the range of 4.0
hr.sup.''1 to 6.0 hr.sup.''1.
7. The process as claimed in claim 1, wherein the hydrotreating
catalyst is cobalt molybdenum catalyst or nickel molybdenum
catalyst.
8. The process as claimed in claim 7, wherein the catalyst is
supported on alumina.
9. The process as claimed in claim 7, wherein the catalyst is
sulfided prior to use.
10. The process as claimed in claim 1, wherein the pressure is in
the range of about 5 bar to 15 bar, preferably 8 bar to 12 bar.
11. The process as claimed in claim 1, wherein the temperature is
in the range of 225.degree. C.-350.degree. C.
12. An aviation turbine fuel product having less than 10 ppm
mercaptan prepared by a process as claimed in claim 1.
13. The process for selective removal of mercaptan from aviation
turbine fuel (ATF) feed, comprising: (a) mixing aviation turbine
fuel feed with a source of hydrogen, at the hydrogen to aviation
turbine fuel feed ratio in the range of 0.0003:1 to 0.0007:1, and
at a pressure in range of 3 bar to 20 bar to obtain a first
reaction mixture, (b) heating the first reaction mixture at a
temperature range of 150.degree. C. to 350.degree. C. to obtain a
heated mixture, (c) reacting the heated mixture with a
hydrotreating catalyst in a rector to obtain a reactor effluent,
(d) stripping H.sub.2S gas from the reactor effluent in an stripper
to obtain a stripper bottom product, (e) mixing the stripper bottom
product with the heated mixture obtained in step (b), at the
stripper bottom product to heated mixture ratio in the range of 1:1
to 10:1 to obtain a second reaction mixture, (f) reacting the
second reaction mixture with a hydrotreating catalyst in a rector
to obtain a reactor effluent, (g) stripping H.sub.2S gas from the
reactor effluent in an stripper to obtain a stripper bottom
product, (h) repeating steps (e) to (g), and (i) removing moisture
from the stripper bottom product to obtain aviation turbine fuel
product having less than 10 ppm mercaptan.
14. The process as claimed in claim 13, wherein the aviation
turbine fuel feed has boiling range of about 120.degree. C. to
about 300.degree. C., preferably between about 140.degree. C. to
about 280.degree. C.
15. The process as claimed in claim 13, wherein the source of
hydrogen is reformer off-gas or recycle gas from diesel
hydrotreating (DHDT) unit or diesel hydrodesulfurisation (DHDS)
unit.
16. The process as claimed in claim 13, wherein said process is
performed at a Liquid Hourly Space Velocity in the range of 4.0
hr.sup.''1 to 6.0 hr.sup.''1.
17. The process as claimed in claim 13, wherein the hydrotreating
catalyst is cobalt molybdenum catalyst or nickel molybdenum
catalyst.
18. The process as claimed in claim 17, wherein the catalyst is
supported on alumina.
19. The process as claimed in claim 17, wherein the catalyst is
sulfided prior to use.
20. The process as claimed in claim 13, wherein the pressure is in
the range of about 5 bar to 15 bar, preferably 8 bar to 12 bar.
21. The process as claimed in claim 13, wherein the temperature is
in the range of 225.degree. C.-350.degree. C.
22. An aviation turbine fuel product having less than 10 ppm
mercaptan prepared by a process as claimed in claim 13.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a process for selective
removal of mercaptan from aviation turbine fuel (ATF) feed. The
present process provides aviation turbine fuel product having
negligible mercaptan, good colour, moderate sulfur and low acidity.
The process is for selective mercaptan removal with minimum removal
of other sulfur compounds.
BACKGROUND
[0002] Aviation Turbine Fuel (ATF) demand is expected to increase
rapidly in the wake of robust economic growth and major
developments in aviation industry. Air travel is projected to grow
in popularity in the years to come and the refinery that produces
jet fuel at competitive cost and environmentally friendly manner
will be in the best position to compete in this market. The
refiners need to respond promptly to the challenge of producing ATF
meeting stringent specifications. A refiner that produces high
quality jet fuels can find attractive markets for ATF product
throughout the world.
[0003] ATF/Kerosene can be produced through distillation of crude
followed by some post-treatment by processes like Merox or through
hydroprocessing route. The former type of processes can produce ATF
from specific type of crude oils only and requires handling of
chemicals like caustic. Further, the product properties such as
color and acidity are inferior as compared to the present
invention. In conventional hydroprocessing process, severe
operating conditions are used leading to high equipment and
operating costs. In addition, high severity of operation reduces
sulfur content affecting the product's lubricity.
[0004] Mercaptan is the generic name for a family of organic
compounds where sulfur and a hydrogen atom (SH) are bonded to one
of the carbon atoms in the molecule. The hydrogen atom in the SH
radical can ionize and produce a mildly acidic environment, which
may lead to corrosion. The most noticeable characteristic of
mercaptan is their strong, unpleasant odor even when their
concentration is only a few parts per million. Mercaptan need to be
removed from ATF due to corrosion and odour problems. Other
specifications of ATF include acidity, aromatics, olefins, smoke
point, mercaptan, freeze point, color, and water separation index,
etc.
[0005] U.S. Pat. No. 6,231,752 discloses a process for removal of
mercaptan and diolefins from naphtha range feed using reactor
system in hydrogen atmosphere but the process lacks capability for
dealing with higher boiling feed (kerosene/diesel) and no claim for
colour or acidity improvement has been cited.
[0006] U.S. Pat. No. 6,334,948 discloses a process for producing
gasoline with low sulfur content, the process does not suggest that
the same process can be used for aviation turbine fuel. Also the
process disclosed is not for selective removal of mercaptan from
the feed.
[0007] The art relating to the treatment of mercaptan containing
sour hydrocarbon distillate and the regeneration of spent caustic
solutions is well developed and the processes and the apparatus
therefore are subject of many patents e.g. U.S. Pat. Nos.
2,988,500; 3,371,031; 3,413,215; 3,445,380; 3,515,677; 3,574,093;
3,923,645; 3,931,054; 3,972,829; 4,003,827; 4,009,120; 4,018,705;
4,033,860; 4,070,271; 4,087,378; 4,090,954; 4,098,681; 4,107,078;
4,113,604; 4,121,998; 4,121,999; 4,124,531; 4,141,819; 4,206,043;
4,248,694; 4,298,502; 4,364,843; 4,481,106; 4,481,107; 4,490,246;
4,498,977; 4,498,978 and 4,579,121 are representative of catalytic
oxidation processes and catalyst for treating mercaptan containing
sour hydrocarbon distillate. U.S. Pat. Nos. 2,425,414; 2,606,099;
2,740,749; 2,853,432; 2,921,021; 2,937,986; 3,107,213; 4,040,947;
4,081,354; 4,104,155; 4,199,440 and 4,362,614 are representative of
extraction and regeneration processes for removal of mercaptan.
[0008] Certain polar compounds can be removed from jet fuel by clay
treating. In this relatively simple process, the fuel is allowed to
pass through a bed of clay. Certain classes of polar compounds,
especially those that act as surfactants, adsorb onto the surface
of the clay and thus are removed from the fuel. Removal of
surfactants from hydrocarbon distillate using post treatment
methods employing clay is well known in the art.
[0009] In order to meet the growing demand of high quality ATF, the
current invention uses a selective hydroprocessing technology for
production of ATF. The present invention provides all the
advantages of conventional hydroprocessing at low severity and
selectively removes mercaptan thereby not affecting the product's
lubricity. The process has the capability of selectively removing
mercaptan from ATF at low severity. It has been found that the
process can reduce mercaptan to less than 10 ppm from ATF feed
having not more than 350 ppm mercaptan level. Acidity and colour
are also improved in the process. All other critical product
properties are also excellent. The process is flexible and can be
employed for a grass root unit or retrofitting existing unit. For
grass root unit, the process utilizes mixing of hydrotreated
product with feed composition and negligible hydrogen for meeting
chemical hydrogen consumption and losses. The process can also be
operated with excess hydrogen gas for retrofitting in existing
units having recycle gas compressor.
SUMMARY
[0010] The present invention relates to a process for the selective
removal of mercaptan from aviation turbine fuel (ATF) feed
comprising: mixing aviation turbine fuel feed with hydrogen, at a
pressure in range of 3 bar to 20 bar to obtain a reaction mixture,
heating the reaction mixture at a temperature range of 150.degree.
C. to 350.degree. C. to obtain a heated mixture, reacting the
heated mixture with a hydrotreating catalyst in a rector to obtain
a reactor effluent, stripping H2S gas from the reactor effluent to
obtain a stripper bottom product, and removing moisture from the
stripper bottom product to obtain aviation turbine fuel product
having less than 10 ppm mercaptan.
[0011] The present invention relates to a process for selective
removal of mercaptan from aviation turbine fuel (ATF) feed as
claimed in claim 1, comprising: mixing aviation turbine fuel feed
with hydrogen gas at a hydrogen gas to aviation turbine fuel feed
ratio in the range of 20:1 to 50:1, and at a pressure in range of 3
bar to 20 bar to obtain a reaction mixture, heating the reaction
mixture at a temperature range of 150.degree. C. to 350.degree. C.
to obtain heated mixture, reacting the heated mixture with a
hydrotreating catalyst in a reactor to obtain reactor effluent,
stripping H.sub.2S gas from the reactor effluent to obtain stripper
bottom product, and removing moisture from the stripper bottom
product to obtain aviation turbine fuel product having less than 10
ppm mercaptan.
[0012] The present invention also relates a process for selective
removal of mercaptan from aviation turbine fuel (ATF) feed as
claimed in claim 1, comprising: (a) mixing aviation turbine fuel
with hydrogen, at the hydrogen to aviation turbine fuel feed ratio
in the range of 0.0003:1 to 0.0007:1, and at a pressure in range of
3 bar to 20 bar to obtain a first reaction mixture, (b) heating the
first reaction mixture at a temperature range of 150.degree. C. to
350.degree. C. to obtain a heated mixture, (c) reacting the heated
mixture with a hydrotreating catalyst in a reactor to obtain a
reactor effluent, (d) stripping H.sub.2S gas from the reactor
effluent in an stripper to obtain a stripper bottom product, (e)
mixing the stripper product with the heated mixture obtained in
step (b), at the stripper product to heated mixture ratio in the
range of 1:1 to 10:1 to obtain a second reaction mixture, (f)
reacting the second reaction mixture with a hydrotreating catalyst
in a rector to obtain a reactor effluent, (g) stripping H.sub.2S
gas from the reactor effluent in a stripper to obtain a stripper
bottom product, (h) repeating steps (e) to (g), and (i) removing
moisture from the stripper bottom product to obtain aviation
turbine fuel product having less than 10 ppm mercaptan.
[0013] The present invention further relates to an aviation turbine
fuel product having less than 10 ppm mercaptan prepared by a
process of the present invention.
[0014] The process selectively reduces mercaptan to less than 10
ppm while retaining other sulfur compounds from aviation turbine
fuel feed having not more than 350 ppm mercaptan and 2500 ppm
Sulfur level. Acidity and colour are also improved.
[0015] These and other features, aspects, and advantages of the
present subject matter will become better understood with reference
to the following description and appended claims. This summary is
provided to introduce a selection of concepts in a simplified form.
This summary is not intended to identify key features or essential
features of the claimed subject matter, nor is it intended to be
used to limit the scope of the claimed subject matter.
BRIEF DESCRIPTION OF DRAWINGS
[0016] The above and other features, aspects, and advantages of the
subject matter will become better understood with regard to the
following description, appended claims, and accompanying drawings
where:
[0017] FIG. 1 is a schematic illustration of the process of present
invention for new grass root unit. In this figure the reference
numerals represents: exchanger 3, control valve 5, reactor 7,
furnace 8, stripper 9, sand filter 12 and salt dryer 14.
[0018] FIG. 2 is a schematic illustration of the process of present
invention for retrofitting in existing unit. In this figure the
reference numerals represents: exchanger 2, recycle gas compressor
4, furnace 7, reactor 9, separator 11, stripper 14, sand filter 17
and salt dryer 19.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention relates to a process for the selective
removal of mercaptan from aviation turbine fuel (ATF) feed
comprising: mixing aviation turbine fuel feed with hydrogen at a
pressure in range of 3 bar to 20 bar to obtain a reaction mixture,
heating the reaction mixture at a temperature range of 150.degree.
C. to 350.degree. C. to obtain a heated mixture, reacting the
heated mixture with a hydrotreating catalyst in a rector to obtain
a reactor effluent, stripping H.sub.2S gas from the reactor
effluent to obtain a stripper bottom product, and removing moisture
from the stripper bottom product to obtain aviation turbine fuel
product having less than 10 ppm mercaptan.
[0020] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed wherein the aviation turbine fuel feed has boiling range
of about 120.degree. C. to about 330.degree. C.
[0021] Further embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the aviation turbine fuel feed has boiling range
of about 140.degree. C. to about 280.degree. C.
[0022] Yet, another embodiment of the present invention provides a
process for selective removal of mercaptan from a aviation turbine
fuel feed, wherein the aviation turbine fuel feed has mercaptan
content not more than about 350 ppm and sulfur content not more
than about 2500 ppm.
[0023] Still, another embodiment of the present invention provides
a process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the aviation turbine fuel feed is straight run
hydrocarbon stream from crude distillation unit.
[0024] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein aviation turbine fuel feed is a petroleum
fraction.
[0025] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein said process is performed at a Liquid Hourly
Space Velocity in the range of 4.0 hr.sup.-1 to 6.0 hr.sup.-1 with
respect to the fresh feed.
[0026] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is cobalt molybdenum catalyst or
nickel molybdenum catalyst.
[0027] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is supported on a support material
such as alumina.
[0028] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is sulfided prior to use.
[0029] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the physical surface area of the support
material is between 150-200 m.sup.2/g, the pore volume of the
catalyst is between 0.3-0.6 cc/gm. The average pore diameter is
between 60-100.degree. A. The metal content in the cobalt
molybdenum catalyst is 2.5-3.5 wt % cobalt oxide and 13-15 wt % of
molybdenum oxide.
[0030] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the partial pressure is in the range of about 5
bar to about 15 bar.
[0031] Yet another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the partial pressure is in the range of about 8
bar to about 12 bar.
[0032] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the temperature is in the range of 225.degree.
C.-300.degree. C.
[0033] An embodiment of the present invention relates to a process
for selective removal of mercaptan from aviation turbine fuel (ATF)
feed comprising: mixing aviation turbine fuel feed with hydrogen
gas at a hydrogen gas to aviation turbine fuel feed ratio in the
range of 20:1 to 50:1, and at a partial pressure in range of 3 bar
to 20 bar to obtain a reaction mixture, heating the reaction
mixture at a temperature range of 150.degree. C. to 350.degree. C.
to obtain heated mixture, reacting the heated mixture with a
hydrotreating catalyst in a reactor to obtain reactor effluent,
stripping H2S gas from the reactor effluent to obtain stripper
bottom product, and removing moisture from the stripper bottom
product to obtain aviation turbine fuel product having less than 10
ppm mercaptan.
[0034] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed wherein the aviation turbine fuel feed has boiling range
of about 120.degree. C. to about 330.degree. C.
[0035] Further embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the aviation turbine fuel feed has boiling range
of about 140.degree. C. to about 280.degree. C.
[0036] Yet, another embodiment of the present invention provides a
process for selective removal of mercaptan from a aviation turbine
fuel feed, wherein the aviation turbine fuel feed has mercaptan
content not more than about 350 ppm and sulfur content not more
than about 2500 ppm.
[0037] Still, another embodiment of the present invention provides
a process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the aviation turbine fuel feed is straight run
hydrocarbon stream from crude distillation unit.
[0038] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein aviation turbine fuel feed is a petroleum
fraction.
[0039] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein said process is performed at a Liquid Hourly
Space Velocity in the range of 4.0 hr.sup.-1 to 6.0 hr.sup.-1 with
respect to the fresh feed.
[0040] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is cobalt molybdenum catalyst or
nickel molybdenum catalyst.
[0041] Yet, another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is supported on a support material
such as alumina.
[0042] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is sulfided prior to use.
[0043] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the physical surface area of the support
material is between 150-200 m.sup.2/g, the pore volume of the
catalyst is between 0.3-0.6 cc/gm. The average pore diameter is
between 60-100.degree. A. The metal content in the cobalt
molybdenum catalyst is 2.5-3.5 wt % cobalt oxide and 13-15 wt % of
molybdenum oxide.
[0044] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the partial pressure is in the range of about 5
bar to about 15 bar.
[0045] Yet another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the partial pressure is in the range of about 8
bar to about 12 bar.
[0046] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the temperature is in the range of 225.degree.
C.-300.degree. C.
[0047] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the hydrogen gas is a reformer off-gas or
recycled gas from other hydroprocessing units such as diesel
hydrotreating (DHDT) unit or diesel hydrodesulfurisation (DHDS)
unit.
[0048] An embodiment of the present invention provides a process
for selective removal of mercaptan from aviation turbine fuel (ATF)
feed, comprising: (a) mixing aviation turbine fuel with hydrogen,
at the hydrogen to aviation turbine fuel feed ratio in the range of
0.0003:1 to 0.0007:1, and at a pressure in range of 3 bar to 20 bar
to obtain a first reaction mixture, (b) heating the first reaction
mixture at a temperature range of 150.degree. C. to 350.degree. C.
to obtain a heated mixture, (c) reacting the heated mixture with a
hydrotreating catalyst in a rector to obtain a reactor effluent,
(d) stripping H.sub.2S gas from the reactor effluent in an stripper
to obtain a stripper bottom product, (e) mixing the stripper
product with the heated mixture obtained in step (b), at the
stripper product to heated mixture ratio in the range of 1:1 to
10:1 to obtain a second reaction mixture, (f) reacting the second
reaction mixture with a hydrotreating catalyst In a rector to
obtain a reactor effluent, (g) stripping H.sub.2S gas from the
reactor effluent In an stripper to obtain a stripper bottom
product, (h) repeating steps (e) to (g), and (i) removing moisture
from the stripper bottom product to obtain aviation turbine fuel
product having less than 10 ppm mercaptan.
[0049] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed wherein the aviation turbine fuel feed has boiling range
of about 120.degree. C. to about 330.degree. C.
[0050] Further embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the aviation turbine fuel feed has boiling range
of about 140.degree. C. to about 280.degree. C.
[0051] Yet, another embodiment of the present invention provides a
process for selective removal of mercaptan from a aviation turbine
fuel feed, wherein the aviation turbine fuel feed has mercaptan
content not more than about 350 ppm and sulfur content not more
than about 2500 ppm.
[0052] Still, another embodiment of the present invention provides
a process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the aviation turbine fuel feed is straight run
hydrocarbon stream from crude distillation unit.
[0053] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein aviation turbine fuel feed is a petroleum
fraction.
[0054] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein said process is performed at a Liquid Hourly
Space Velocity in the range of 4.0 hr.sup.-1 to 6.0 hr.sup.-1 with
respect to the fresh feed.
[0055] Further embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is cobalt molybdenum catalyst or
nickel molybdenum catalyst.
[0056] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is supported on a support material
such as alumina.
[0057] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the catalyst is sulfided prior to use.
[0058] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the physical surface area of the support
material is between 150-200 m.sup.2/g, the pore volume of the
catalyst is between 0.3-0.6 cc/gm. The average pore diameter is
between 60-100.degree. A. The metal content in the cobalt
molybdenum catalyst is 2.5-3.5 wt % cobalt oxide and 13-15 wt % of
molybdenum oxide.
[0059] Further an embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the partial pressure is in the range of about 5
bar to about 15 bar.
[0060] Yet another embodiment of the present invention provides
a-process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the partial pressure is in the range of about 8
bar to about 12 bar.
[0061] Still another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed, wherein the temperature is in the range of 225.degree.
C.-300.degree. C.
[0062] An embodiment of the present invention provides an aviation
turbine fuel product having less than 10 ppm mercaptan prepared by
a process of the present invention.
[0063] Yet another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed which in addition to selective mercaptan removal,
improves other product properties such as colour, acidity thereby
providing flexibility of processing feed composition with high
mercaptan as well as high acidity and does not require handling of
caustic.
[0064] An embodiment of the present invention provides an aviation
turbine fuel product having superior properties in comparison to
the products obtained through Merox process (known process). These
superior properties of the aviation turbine fuel product of the
present invention are given in the table below:
TABLE-US-00001 Product Properties Merox Process Present Invention
1. Mercaptan (ppm) 10-20 0-5 2. Acidity ~40% reduction ~70%
reduction (mg KOH/g) 3. Colour (Saybolt) worse than the feed Better
than the feed 4. Doctors Test Negative to Slightly +ve Negative 5.
Sulfur (ppm) Same as Feed Can be controlled
[0065] Another embodiment of the present invention provides a
process for selective removal of mercaptan from aviation turbine
fuel feed which employs a Ni--Mo or Co--Mo type hydrotreating
catalyst at low severity.
[0066] The feed for the process of the present invention is an
aviation turbine fuel containing mercaptan not more than about 350
ppm and sulfur content not more than about 2500 ppm, with a boiling
point ranges from about 120.degree. C. to about 330.degree. C.
[0067] The product of the process of the present invention is an
aviation turbine fuel containing less than 10 ppm of mercaptan.
[0068] The process of the present invention is flexible and can be
employed for a grass root unit or retrofitting existing
conventional hydrotreating units. For grass root unit, the process
utilizes mixing of hydrotreated product with feed composition and
negligible hydrogen for meeting chemical hydrogen consumption and
losses. The process can also be operated with excess hydrogen gas
for retrofitting in existing units having recycle gas
compressor.
[0069] The process of the present invention selectively removes
mercaptan from feed composition with minimum removal of other
sulfur compounds thereby not affecting the product lubricity. Also,
selective removal helps in minimizing chemical hydrogen consumption
compared to conventional hydroprocessing technologies for ATF. The
process is particularly suitable for production of commercial ATF.
The process has distinct advantage over competing Merox process in
terms of improved colour, acidity of the product and does not
require handling of caustic.
[0070] Liquid Hourly Space Velocity (LHSV) is the ratio of the
hourly volume of oil processed to the volume of catalyst. It is
generally expressed as v/v/hr or h.sup.-1.
[0071] This invention is illustrated in the accompanying drawings,
throughout which like reference letters indicate corresponding
parts in the various figures.
[0072] The process of present invention for new grass root unit,
which is schematically illustrated in FIG. 1, comprising: mixing
aviation turbine fuel (ATF) feed via line 1 and hydrogen gas for
meeting chemical hydrogen consumption and losses via line 2 to
obtain a mixture, heating the mixture to a reaction temperature of
225-300.degree. C. in an exchanger 3, the heated mixture along with
hydrotreated ATF product from stripper bottom via line 4 and
through control valve 5 is sent to the reactor 7 via line 6, in
reactor 7 mercaptan from ATF feed are selectively removed over a
Co--Mo catalyst and the reactor effluent is then further heated in
a furnace 8 for stripping H.sub.2S in a stripper 9. H.sub.2S is
removed from the top of the stripper via line 10 and part of
stripper bottom product after heat exchange in exchanger 3 is sent
via line 11 to the sand filter 12 and then via line 13 to the salt
dryer 14 for moisture removal. The finished hydrotreated ATF
product is sent to the storage via line 15.
[0073] The process of the present invention for retrofitting in
existing unit, which is schematically illustrated in FIG. 2,
comprising: preheating ATF feed via line 1 in exchanger 2, mixing
preheated ATF feed with recycle gas from recycle gas compressor 4
via line 5 after combining with make up hydrogen gas via line 3 to
obtain a mixture, the mixture of hydrogen gas and ATF feed are
heated in furnace 7 via line 6 to a reaction temperature of
225-300.degree. C. and the heated mixture is sent via line 8 to the
reactor 9. In reactor 9, mercaptan from ATF feed are selectively
removed over a Co--Mo catalyst and the reactor effluent after
exchanging heat in the exchanger 2 is sent to the separator 11. The
liquid product from separator 11 is sent via line 13 to stripper
14. H.sub.2S is removed from the top of the stripper via line 15
and stripper bottom product is sent via line 16 to sand filter 17
and then via line 18 to salt dryer 19 for removal of moisture. The
finished hydrotreated ATF product is sent to the storage via line
20.
EXAMPLES
[0074] The following examples are given by way of illustration of
the present invention and should not be construed to limit the
scope of present disclosure. It is to be understood that both the
foregoing general description and the following detailed
description are exemplary and explanatory only and are intended to
provide further explanation of the claimed subject matter.
Example-1
[0075] The process of the present invention was conducted using
aviation turbine fuel (ATF) feed. Aviation turbine fuel (ATF) feed
and hydrogen gas for meeting chemical hydrogen consumption and
losses are mixed to obtain a mixture, the mixture is heated to a
reaction temperature of 150-300.degree. C. in an exchanger, the
heated mixture along with hydrotreated ATF product from stripper
bottom and through control valve is sent to the reactor. In reactor
mercaptan from ATF feed are selectively removed over a Co--Mo
catalyst and the reactor effluent is then further heated in a
furnace for stripping H.sub.2S in a stripper. H.sub.2S is removed
from the top of the stripper and stripper bottom product after heat
exchange in exchanger is sent to the sand filter and then to the
salt dryer for moisture removal. The finished hydrotreated ATF
product is sent to the storage.
[0076] The properties of ATF feed used for the experiment is given
in Table-1. The summary of operating conditions is provided in
Table-2 and the salient results and products' properties tabulated
as Table-3.
TABLE-US-00002 TABLE 1 Typical Feed (ATF) Properties Properties
Value 1. Mercaptan (ppm) 110 2. Acidity (mg KOH/g) 0.006 3. Colour
(Saybolt) +21 4. Doctors Test Positive 5. Sulfur (ppm) 2000
TABLE-US-00003 TABLE 2 Summary of Operating Conditions Operating
Conditions Low High 1. Reactor Temperature (.degree. C.) 225 300 2.
System Pressure (bar) 3 20 3. H.sub.2 flow, wt % on fresh feed 0.05
0.1 4. Liquid LHSV (h.sup.-1) on fresh feed 4.0 6.0 5. Ratio of
hydrotreated to fresh ATF 1.0 10.0
TABLE-US-00004 TABLE 3 Summary of Results Sl. Hydrotreated/Fresh
Pressure Temp. Mercaptan No. ATF ratio (bar) (deg. C.) (ppm) 1. 1
10 240 9 2. 5 10 240 7 3. 10 20 230 5
Example-2
[0077] The process of the present invention was conducted using
aviation turbine fuel (ATF) feed.
[0078] ATF feed is preheated in an exchanger, preheated ATF feed is
then mixed with recycle gas from recycle gas compressor after
combining with make up hydrogen gas to obtain a mixture, the
mixture of hydrogen gas and ATF feed is heated in furnace to a
reaction temperature of 225-300.degree. C. and the heated mixture
is sent to the reactor. In reactor mercaptan from ATF feed are
selectively removed over a Co--Mo catalyst and the reactor effluent
after exchanging heat in the exchanger is sent to the separator.
The liquid product from separator is sent to stripper. H.sub.2S is
removed from the top of the stripper and stripper bottom product is
sent to sand filter and then to salt dryer for removal of moisture.
The finished hydrotreated ATF product is sent to the storage.
[0079] The properties of ATF feed used for the experiment are given
in Table-4. This ATF feed was fed along with hydrogen to a tubular
reactor having Co--Mo catalyst. The properties of Co--Mo catalyst,
which is used in the present process, are provided in Table-5. The
summary of operating conditions is provided in Table-6 and the
salient results and product's properties tabulated as Table-7.
TABLE-US-00005 TABLE 4 Typical Feed (ATF) Properties Properties
Value 1. Mercaptan (ppm) 100-350 2. Acidity (mg KOH/g) 0.005-0.02
3. Colour (Saybolt) +16 4. Doctors Test Positive 5. Sulfur (ppm)
1750-2200
TABLE-US-00006 TABLE 5 Typical Catalyst Characteristics Chemical
Composition: Co--Mo/Al.sub.2O.sub.3 Physical Surface area: 200
cm.sup.2/gm Pore volume: 0.42 cc/gm Av. Pore diameter: 80 A.degree.
Cobalt oxide: 2.8% Molybdenum oxide 13.5%
TABLE-US-00007 TABLE 6 Summary of Operating Conditions Operating
Conditions Low High Reactor Temperature (.degree. C.) 150 300
System Pressure (bar) 3 20 H.sub.2:HC Ratio 20 50 Liquid LHSV
(h.sup.-1) 4.0 6.0
TABLE-US-00008 TABLE 7 Summary of Results Sl. H.sub.2:HC Pressure
Temp. Mercaptan Sulfur Acidity No. ratio (bar) (deg. C.) (ppm)
(ppm) mg KOH/g 1. 25:1 3 240 9 1500 0.003 2. 25:1 12 240 7 1420
0.002 3. 50:1 3 240 8 1470 0.003 4. 50:1 12 240 6 1400 0.002 5.*
25:1 12 270 9 1140 0.001 *Feed with higher mercaptan and sulfur
used
[0080] Other Typical Product Properties: [0081] Flash Point (at 12
bar, 270.degree. C. and H2/HC ratio 25)=44.degree. C. [0082]
Freezing Point (at 12 bar, 270.degree. C. and H2/HC ratio
25)=-49.degree. C. [0083] Copper Strip Corrosion Test: 1 [0084]
BOCLE Lubricity test (at 12 bar, 270.degree. C. and H2/HC ratio
25)=0.560 mm
Example-3
[0085] The process of the present invention was conducted using
aviation turbine fuel (ATF) feed. The property of ATF feed used for
the experiment is given in Table-8. ATF feed was fed along with
hydrogen gas to a tubular reactor having Co--Mo catalyst. The
summary of operating conditions is provided in Table-9 and the
salient results are tabulated as Table-10.
[0086] It has been observed that the violation of operating range
in this case with respect to Liquid Hourly Space Velocity (LHSV)
results in product not meeting the desired objective of achieving
less than 10 ppm mercaptan in the product.
TABLE-US-00009 TABLE 8 Typical Feed (ATF) Properties Properties
Value 1. Mercaptan (ppm) 100 2. Acidity (mg KOH/g) 0.008 3. Colour
(Saybolt) +16 4. Doctors Test Positive 5. Sulfur (ppm) 1750
TABLE-US-00010 TABLE 9 Summary of Operating Conditions Operating
Conditions 1. Reactor Temperature (.degree. C.) 240 2. System
Pressure (bar) 12 3. H.sub.2:HC Ratio 25:1 4. Liquid LHSV
(h.sup.-1) 6.5
TABLE-US-00011 TABLE 10 Summary of Results Mercaptan in product,
ppm 30
Example-4
[0087] Experimentation was conducted using ATF feed (Properties in
Table-11) with operating conditions similar to conventional
hydrotreating. The summary of operating conditions and the salient
results and products' properties are tabulated Table-12. It has
been observed that with conventional hydrotreating operating
conditions, the product does not meet the specification with
respect to lubricity.
TABLE-US-00012 TABLE 11 Typical Feed (ATF) Properties Sl. No.
Properties Value 1. Mercaptan (ppm) 110 2. Acidity (mg KOH/g) 0.015
3. Sulfur (ppm) 2000
TABLE-US-00013 TABLE 12 Summary of Results Sl. H2/HC Pressure
Temperature Mercaptan Sulfur Bocle No. ratio (Bar) (.degree. C.)
(ppm) (ppm) Lubricity (mm) 1. 250 30 325 5 80 0.850 2. 250 30 350 3
50 0.900
[0088] Although the subject matter has been described in
considerable detail with reference to certain preferred embodiments
thereof, other embodiments are possible. As such, the spirit and
scope of the appended claims should not be limited to the
description of the preferred embodiment contained therein.
* * * * *