U.S. patent application number 17/140352 was filed with the patent office on 2022-07-07 for systems and processes for treating disulfide oil.
This patent application is currently assigned to Saudi Arabian Oil Company. The applicant listed for this patent is Saudi Arabian Oil Company. Invention is credited to Ki-Hyouk Choi, Mazin M. Fathi.
Application Number | 20220213392 17/140352 |
Document ID | / |
Family ID | |
Filed Date | 2022-07-07 |
United States Patent
Application |
20220213392 |
Kind Code |
A1 |
Fathi; Mazin M. ; et
al. |
July 7, 2022 |
SYSTEMS AND PROCESSES FOR TREATING DISULFIDE OIL
Abstract
A process for treating a disulfide oil composition that includes
combining a supercritical water stream, a hydrogen stream, and a
disulfide oil composition in a mixing device to create a combined
disulfide feed stream; introducing the combined disulfide feed
stream into a supercritical water hydrogenation reactor operating
at a temperature greater than a critical temperature of water and a
pressure greater than a critical pressure of water; and at least
partially converting the combined disulfide feed stream to an
upgraded disulfide product.
Inventors: |
Fathi; Mazin M.; (Dammam,
SA) ; Choi; Ki-Hyouk; (Dhahran, SA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Saudi Arabian Oil Company |
Dhahran |
|
SA |
|
|
Assignee: |
Saudi Arabian Oil Company
Dhahran
SA
|
Appl. No.: |
17/140352 |
Filed: |
January 4, 2021 |
International
Class: |
C10G 45/02 20060101
C10G045/02; C10G 67/02 20060101 C10G067/02 |
Claims
1. A process for treating a disulfide oil composition comprising:
combining a heated water stream, a hydrogen stream, and a disulfide
oil composition in a mixing device to create a combined disulfide
feed stream; introducing the combined disulfide feed stream into a
supercritical water hydrogenation reactor operating at a
temperature greater than a critical temperature of water and a
pressure greater than a critical pressure of water; and at least
partially converting the combined disulfide feed stream to an
upgraded disulfide product.
2. The process of claim 1, further comprising passing the upgraded
product out of the supercritical water hydrogenation reactor to a
gas/water separator and separating the upgraded product in the
gas/water separator to produce a gas fraction and a water
fraction.
3. The process of claim 2, wherein the gas fraction is selected
from the group consisting of H.sub.2, C.sub.2 to C.sub.6
hydrocarbons, H.sub.2S, and combinations thereof.
4. The process of claim 1, further comprising passing the upgraded
product to a cooling device to form a cooled upgraded product.
5. The process of claim 4, further comprising passing the cooled
upgraded product to a depressurizing device.
6. The process of claim 1, wherein the disulfide oil composition is
selected from the group consisting of C.sub.2H.sub.6S.sub.2,
C.sub.3H.sub.8S.sub.2, C.sub.4H.sub.10S.sub.2,
C.sub.5H.sub.12S.sub.2, C.sub.6H.sub.14S.sub.2, and combinations
thereof.
7. The process of claim 1, wherein the disulfide oil compositions
comprises: from 10 wt. % to 20 wt. % C.sub.2H.sub.6S.sub.2; from 20
wt. % to 30 wt. % C.sub.3H.sub.8S.sub.2; from 20 wt. % to 35 wt. %
C.sub.4H.sub.10S.sub.2; from 10 wt. % to 20 wt. %
C.sub.5H.sub.12S.sub.2; and from 1 wt. % to 10 wt. %
C.sub.6H.sub.14S.sub.2.
8. The process of claim 1, wherein the supercritical water
hydrogenation reactor has a temperature of greater than 375.degree.
C. and less than 600.degree. C. and a pressure greater than 22.1
MPa and less than 75 MPa.
9. The process of claim 1, wherein the supercritical water
hydrogenation reactor has a temperature of greater than 390.degree.
C. and less than 470.degree. C. and a pressure greater than 24 MPa
and less than 30 MPa.
10. The process of claim 1, wherein the supercritical water
hydrogenation reactor has a residence time of from 2 to 15 minutes.
Description
TECHNICAL FIELD
[0001] Embodiments of the present disclosure generally relate to
upgrading petroleum-based compositions, and more specifically
relate to supercritical reactor systems, methods, and uses for
upgrading petroleum-based compositions.
BACKGROUND
[0002] Petroleum is an indispensable source of energy; however,
most petroleum is heavy or sour petroleum, meaning that it contains
a high amount of impurities (including sulfur and coke, a high
carbon petroleum residue). Heavy petroleum must be upgraded before
it is a commercially valuable product, such as fuel. Supercritical
water has been known to be an effective reaction medium for heavy
oil upgrading without external supply of hydrogen, at least because
supercritical water upgrading reactions are highly selective
towards breaking of heavy fractions to produce middle distillate
oils without coke generation.
SUMMARY
[0003] Although supercritical water has been known to be an
effective reaction medium for heavy oil upgrading without an
external supply of hydrogen, the upgraded product from a
supercritical water process has a greater aromaticity and
olefinicity than the hydrocarbon feed, which has negative effect on
the stability of the products. Nuclear magnetic resonance (NMR)
analysis has shown that the asphaltene content of supercritical
water treated oil decreased to a large extent, while saturate,
olefin, and aromatic content increased. Additionally, the extent of
hydrocarbon upgrading in conventional supercritical water upgrading
processes may be limited. The high temperature of supercritical
water reactor induces thermal cracking of chemical bonds such as
carbon-sulfur bonds and carbon-carbon bonds. Broken bonds should be
filled with other atoms, preferably hydrogen, to avoid
intermolecular condensation and generation of olefins and
polycondensed aromatics. Although olefins are very valuable
chemicals, the low stability of unsaturated bonds can degrade
products by forming gums. The hydrogen inherently present in the
water molecules can participate in the cracking reaction, but the
extent of hydrogen donation from water is quite limited in
supercritical water conditions due to high hydrogen-oxygen bond
energy.
[0004] Accordingly, a need exists for a hydrocarbon upgrading
process that incorporates the benefits of conventional
supercritical water upgrading processes, while decreasing the large
hydrocarbon radicals and olefins that are hydrothermally generated
by supercritical water. The present disclosure addresses this need
by incorporating hydrogen addition into the supercritical water
hydrocarbon upgrading process.
[0005] Hydrogen addition into the supercritical water process
provides additional yields of middle distillate oils but at
improved stability by saturating heavy hydrocarbon radicals and
olefins that have potential to generate gums. In addition, the
supercritical water process breaks large asphaltene aggregates,
such as aggregates with a size from 1 to 800 microns (.mu.m), to
much smaller scattered radical aggregates, such as aggregates with
a size from 0.1 to 300 nanometers (nm) that can readily be
saturated by hydrogen due to its small size (1.06-1.20 angstrom).
This in turn reduces the asphaltene content in the oil by
converting them into lighter fractions. Therefore, supercritical
water facilitates the hydrogenation of heavy hydrocarbon radicals
including olefins and asphaltenes radicals and prevents their
combination reactions that terminate the upgrading reaction
mechanism. In other words, the hydrogen addition to the
supercritical water process passivates the combination reactions of
large hydrocarbon radicals and olefins that are hydrothermally
generated by supercritical water, thereby preventing gum,
asphaltene, and coke generation, which allows for increasing
process severity for additional oil upgrading.
[0006] In accordance with one embodiment of the present disclosure,
a process for treating a disulfide oil composition is provided. The
process includes combining a supercritical water stream, a hydrogen
stream, and a disulfide oil composition in a mixing device to
create a combined disulfide feed stream; introducing the combined
disulfide feed stream into a supercritical water hydrogenation
reactor operating at a temperature greater than a critical
temperature of water and a pressure greater than a critical
pressure of water; and at least partially converting the combined
disulfide feed stream to an upgraded disulfide product.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The following detailed description of specific embodiments
of the present disclosure can be best understood when read in
conjunction with the following drawings, in which:
[0008] FIG. 1 is a schematic view of a process for upgrading a
hydrocarbon-based composition, according to the present
embodiments; and
[0009] FIG. 2 is a schematic view of a process for treating a
disulfide oil composition, according to the present
embodiments.
DETAILED DESCRIPTION
[0010] Embodiments of the present disclosure are directed to
processes for upgrading hydrocarbon streams in a supercritical
water hydrogenation reactor.
[0011] As used throughout the disclosure, "supercritical" refers to
a substance at or above a pressure and a temperature greater than
or equal to that of its critical pressure and temperature, such
that distinct phases do not exist and the substance may exhibit the
fast diffusion of a gas while dissolving materials like a liquid.
As such, supercritical water is water having a temperature and
pressure greater than or equal to the critical temperature and the
critical pressure of water. At a temperature and pressure greater
than or equal to the critical temperature and pressure, the liquid
and gas phase boundary of water disappears, and the fluid has
characteristics of both liquid and gaseous substances.
Supercritical water is able to dissolve organic compounds like an
organic solvent and has excellent diffusibility like a gas.
Regulation of the temperature and pressure allows for continuous
"tuning" of the properties of the supercritical water to be more
liquid-like or more gas-like. Supercritical water has reduced
density and lesser polarity, as compared to liquid-phase
subcritical water, thereby greatly extending the possible range of
chemistry that can be carried out in water. Water above its
critical condition is neither a liquid nor gas but a single fluid
phase that converts from being polar to non-polar.
[0012] As used throughout the disclosure, "upgrade" means to
increase the API gravity, decrease the amount of impurities, such
as sulfur, nitrogen, and metals, decrease the amount of asphaltene,
and increase the amount of the light fraction.
[0013] Supercritical water has various unexpected properties as it
reaches supercritical boundaries. Supercritical water has very high
solubility toward organic compounds and has an infinite miscibility
with gases. Furthermore, radical species can be stabilized by
supercritical water through the cage effect (that is, a condition
whereby one or more water molecules surrounds the radical species,
which then prevents the radical species from interacting). Without
being limited to theory, stabilization of radical species helps
prevent inter-radical condensation and thereby reduces the overall
coke production in the current embodiments. For example, coke
production can be the result of the inter-radical condensation. In
certain embodiments, supercritical water generates hydrogen gas
through a steam reforming reaction and water-gas shift reaction,
which is then available for the upgrading reactions.
[0014] Moreover, the high temperature and high pressure of
supercritical water may give supercritical water a density of 0.123
grams per milliliter (g/mL) at 27 MPa and 450.degree. C.
Contrastingly, if the pressure was reduced to produce superheated
steam, for example, at 20 MPa and 450.degree. C., the superheated
steam would have a density of only 0.079 g/mL. At that density, the
hydrocarbons may interact with superheated steam to evaporate and
mix into the vapor phase, leaving behind a heavy fraction that may
generate coke upon heating. The formation of coke or coke precursor
may plug the lines and must be removed. Therefore, supercritical
water is superior to steam in some applications.
[0015] Specific embodiments will now be described with references
to the figures. Whenever possible, the same reference numerals will
be used throughout the drawings to refer to the same or like
parts.
[0016] FIG. 1 schematically depicts a process 100 for upgrading a
hydrocarbon-based composition 105, according to embodiments
described herein.
[0017] The hydrocarbon-based composition 105 may refer to any
hydrocarbon source derived from petroleum, coal liquid, or
biomaterials. Possible sources for hydrocarbon-based composition
may include crude oil, distilled crude oil, reduced crude oil,
residue oil, topped crude oil, product streams from oil refineries,
product streams from steam cracking processes, liquefied coals,
liquid products recovered from oil or tar sands, bitumen, oil
shale, asphaltene, biomass hydrocarbons, and the like. Many
compositions are suitable for the hydrocarbon-based composition. In
some embodiments, the hydrocarbon-based composition 105 may
comprise heavy crude oil or a fraction of heavy crude oil. In other
embodiments, the hydrocarbon-based composition 105 may include
atmospheric residue (AR), atmospheric distillates, vacuum gas oil
(VGO), vacuum distillates, or vacuum residue (VR), or cracked
product (such as light cycle oil or coker gas oil). In some
embodiments, the hydrocarbon-based composition may be combined
streams from a refinery, produced oil, or other hydrocarbon
streams, such as from an upstream operation. The hydrocarbon-based
composition 105 may be decanted oil, oil containing 10 or more
carbons (C10+ oil), or hydrocarbon streams from an ethylene plant.
The hydrocarbon-based composition 105 may, in some embodiments, be
liquefied coal or biomaterial-derivatives, such as bio fuel oil. In
some embodiments, used lubrication (lube) oil or brake fluids may
be used.
[0018] The hydrocarbon-based composition 105 may, in some
embodiments, be naphtha or kerosene or diesel fractions. Such
fractions may be used but may not be upgraded as efficiently by the
supercritical water. Contaminated hydrocarbon fractions may also be
used. In some embodiments, fractions with saltwater contamination
may be used as the hydrocarbon-based composition 105. For instance,
crude oil in market typically has a salt content below about 10 PTB
(pounds of salt per 1000 barrels of oil). The salt in saltwater may
be precipitated by the supercritical water to produce a desalted
product, which may be desirable in some embodiments.
[0019] The hydrocarbon-based composition 105 may have a T.sub.5
true boiling point (TBP) of less than 500.degree. C., of less than
450.degree. C., of less than 400.degree. C., of less than
380.degree. C., or of less than 370.degree. C. In embodiments, the
hydrocarbon-based composition 105 may have a T.sub.5 TBP of from
200.degree. C. to 500.degree. C., from 200.degree. C. to
450.degree. C., from 200.degree. C. to 425.degree. C., from
200.degree. C. to 400.degree. C., from 200.degree. C. to
380.degree. C., from 200.degree. C. to 370.degree. C., from
250.degree. C. to 500.degree. C., from 250.degree. C. to
450.degree. C., from 250.degree. C. to 425.degree. C., from
250.degree. C. to 400.degree. C., from 250.degree. C. to
380.degree. C., from 250.degree. C. to 370.degree. C., from
260.degree. C. to 500.degree. C., from 260.degree. C. to
450.degree. C., from 260.degree. C. to 425.degree. C., from
260.degree. C. to 400.degree. C., from 260.degree. C. to
380.degree. C., from 260.degree. C. to 370.degree. C., from
300.degree. C. to 500.degree. C., from 300.degree. C. to
450.degree. C., from 300.degree. C. to 425.degree. C., from
300.degree. C. to 400.degree. C., from 300.degree. C. to
380.degree. C., from 300.degree. C. to 370.degree. C., from
325.degree. C. to 500.degree. C., from 325.degree. C. to
450.degree. C., from 325.degree. C. to 425.degree. C., from
325.degree. C. to 400.degree. C., from 325.degree. C. to
380.degree. C., from 325.degree. C. to 370.degree. C., from
350.degree. C. to 500.degree. C., from 350.degree. C. to
450.degree. C., from 350.degree. C. to 425.degree. C., from
350.degree. C. to 400.degree. C., from 350.degree. C. to
380.degree. C., from 350.degree. C. to 370.degree. C., or
approximately 367.degree. C. The hydrocarbon-based composition 105
may have a T.sub.90 TBP of less than or equal to 750.degree. C.,
less than or equal to 700.degree. C., or less than or equal to
650.degree. C. In embodiments, the hydrocarbon-based composition
105 may have a T.sub.90 TBP from 500.degree. C. to 750.degree. C.,
from 500.degree. C. to 700.degree. C., from 500.degree. C. to
675.degree. C., from 500.degree. C. to 650.degree. C., from
540.degree. C. to 750.degree. C., from 540.degree. C. to
700.degree. C., from 540.degree. C. to 675.degree. C., from
540.degree. C. to 650.degree. C., from 600.degree. C. to
750.degree. C., from 600.degree. C. to 700.degree. C., from
600.degree. C. to 675.degree. C., from 600.degree. C. to
650.degree. C., from 625.degree. C. to 750.degree. C., from
625.degree. C. to 700.degree. C., from 625.degree. C. to
675.degree. C., from 625.degree. C. to 650.degree. C., where the
T.sub.90 TBP is greater than the T.sub.5 TBP previously described.
The hydrocarbon-based composition 105 may have an API gravity from
5.degree. to 23.degree., from 5.degree. to 20.degree., from
5.degree. to 19.degree., from 5.degree. to 15.degree., from
5.degree. to 12.degree., from 8.degree. to 23.degree., from
8.degree. to 20.degree., from 8.degree. to 19.degree., from
8.degree. to 15.degree., from 8.degree. to 12.degree., from
10.degree. to 23.degree., from 10.degree. to 20.degree., from
10.degree. to 19.degree., from 10.degree. to 15.degree., from
10.degree. to 12.degree., or approximately 11.degree.. The
hydrocarbon-based composition 105 may include greater than 2.7
weight percent (wt. %) or greater than 1.7 wt. % total sulfur
content by weight of the hydrocarbon-based composition 105. In
embodiments, the hydrocarbon-based composition 105 may include from
0.1 wt. % to 5 wt. %, from 0.1 wt. % to 4 wt. %, from 0.1 wt. % to
3.5 wt. %, from 0.5 wt. % to 5 wt. %, from 0.5 wt. % to 4 wt. %,
from 0.5 wt. % to 3.5 wt. %, from 1.0 wt. % to 5 wt. %, from 1.0
wt. % to 4 wt. %, from 1.0 wt. % to 3.5 wt. %, from 1.3 wt. % to 5
wt. %, from 1.3 wt. % to 4 wt. %, from 1.3 wt. % to 3.5 wt. %, from
1.6 wt. % to 5 wt. %, from 1.6 wt. % to 4 wt. %, from 1.6 wt. % to
3.5 wt. %, from 1.8 wt. % to 5 wt. %, from 1.8 wt. % to 4 wt. %,
from 1.8 wt. % to 3.5 wt. %, from 2.0 wt. % to 5 wt. %, from 2.0
wt. % to 4 wt. %, from 2.0 wt. % to 3.5 wt. %, from 2.3 wt. % to 5
wt. %, from 2.3 wt. % to 4 wt. %, from 2.3 wt. % to 3.5 wt. %, from
2.6 wt. % to 5 wt. %, from 2.6 wt. % to 4 wt. %, from 2.6 wt. % to
3.5 wt. %, from 2.8 wt. % to 5 wt. %, from 2.8 wt. % to 4 wt. %,
from 2.8 wt. % to 3.5 wt. %, from 3.0 wt. % to 5 wt. %, from 3.0
wt. % to 4 wt. %, from 3.0 wt. % to 3.5 wt. %, or approximately 3.4
wt. % wt. % total sulfur content by weight of the hydrocarbon-based
composition 105. The hydrocarbon-based composition 105 may include
greater than 0.9 wt. % or greater than 0.3 wt. % wt. % total
nitrogen content by weight of the hydrocarbon-based composition
105. In embodiments, the hydrocarbon-based composition 105 may
include from 0.01 wt. % to 2 wt. %, from 0.01 wt. % to 1.3 wt. %,
from 0.1 wt. % to 2 wt. %, from 0.1 wt. % to 1.3 wt. %, from 0.2
wt. % to 2 wt. %, from 0.2 wt. % to 1.3 wt. %, from 0.4 wt. % to 2
wt. %, from 0.4 wt. % to 1.3 wt. %, from 0.6 wt. % to 2 wt. %, from
0.6 wt. % to 1.3 wt. %, from 0.8 wt. % to 2 wt. %, from 0.8 wt. %
to 1.3 wt. %, from 1.0 wt. % to 2 wt. %, from 1.0 wt. % to 1.3 wt.
%, or approximately 1.2 wt. % wt. % total nitrogen content by
weight of the hydrocarbon-based composition 105. The
hydrocarbon-based composition 105 may include greater than 1.7 wt.
% or greater than 0.3 wt. % asphaltene (heptane-insoluble) by
weight of the hydrocarbon-based composition 105. In embodiments,
the hydrocarbon-based composition 105 may include from 0.01 wt. %
to 6 wt. %, from 0.01 wt. % to 5 wt. %, from 0.01 wt. % to 4.9 wt.
%, from 0.1 wt. % to 6 wt. %, from 0.1 wt. % to 5 wt. %, from 0.1
wt. % to 4.9 wt. %, from 0.2 wt. % to 6 wt. %, from 0.2 wt. % to 5
wt. %, from 0.2 wt. % to 4.9 wt. %, from 0.4 wt. % to 6 wt. %, from
0.4 wt. % to 5 wt. %, from 0.4 wt. % to 4.9 wt. %, from 0.6 wt. %
to 6 wt. %, from 0.6 wt. % to 5 wt. %, from 0.6 wt. % to 4.9 wt. %,
from 0.8 wt. % to 6 wt. %, from 0.8 wt. % to 5 wt. %, from 0.8 wt.
% to 4.9 wt. %, from 1.0 wt. % to 6 wt. %, from 1.0 wt. % to 5 wt.
%, from 1.0 wt. % to 4.9 wt. %, from 1.6 wt. % to 6 wt. %, from 1.6
wt. % to 5 wt. %, from 1.6 wt. % to 4.9 wt. %, from 1.8 wt. % to 6
wt. %, from 1.8 wt. % to 5 wt. %, from 1.8 wt. % to 4.9 wt. %, from
2.0 wt. % to 6 wt. %, from 2.0 wt. % to 5 wt. %, from 2.0 wt. % to
4.9 wt. %, from 2.5 wt. % to 6 wt. %, from 2.5 wt. % to 5 wt. %,
from 2.5 wt. % to 4.9 wt. %, from 3.0 wt. % to 6 wt. %, from 3.0
wt. % to 5 wt. %, from 3.0 wt. % to 4.9 wt. %, from 4.7 wt. % to 6
wt. %, from 4.7 wt. % to 5 wt. %, from 4.7 wt. % to 4.9 wt. %, or
approximately 4.8 wt. % asphaltene (heptane-insoluble) by weight of
the hydrocarbon-based composition 105. The hydrocarbon-based
composition 105 may include greater than 9 parts per million (ppm)
or greater than 4 ppm metals. In embodiments, the metals may be
vanadium, nickel, or both. In embodiments, the hydrocarbon-based
composition may include from 1 ppm to 100 ppm, from 1 ppm to 83
ppm, from 5 ppm to 100 ppm, from 5 ppm to 83 ppm, from 10 ppm to
100 ppm, from 10 ppm to 83 ppm, from 50 ppm to 100 ppm, from 50 ppm
to 83 ppm, or approximately 82 ppm metals. The hydrocarbon-based
composition 105 may have a viscosity at 50.degree. C. of greater
than 27 centiStokes (cSt) or greater than 89 cSt. In embodiments,
the hydrocarbon-based composition 105 may have a viscosity at
50.degree. C. from 5 cSt to 1000 cSt, from 5 cSt to 700 cSt, from 5
cSt to 650 cSt, from 10 cSt to 1000 cSt, from 10 cSt to 700 cSt,
from 10 cSt to 650 cSt, from 100 cSt to 1000 cSt, from 100 cSt to
700 cSt, from 100 cSt to 650 cSt, from 300 cSt to 1000 cSt, from
300 cSt to 700 cSt, from 300 cSt to 650 cSt, from 500 cSt to 1000
cSt, from 500 cSt to 700 cSt, from 500 cSt to 650 cSt, or
approximately 640 cSt.
[0020] As shown in FIG. 1, the hydrocarbon-based composition 105
may be pressurized in hydrocarbon pump 112 to create pressurized
hydrocarbon-based composition 116. The pressure of pressurized
hydrocarbon-based composition 116 may be at least 22.1 megapascals
(MPa), which is approximately the critical pressure of water.
Alternatively, the pressure of the pressurized hydrocarbon-based
composition 116 may be between 23 MPa and 35 MPa, or between 24 MPa
and 30 MPa. For instance, the pressure of the pressurized
hydrocarbon-based composition 116 may be between 25 MPa and 29 MPa,
26 MPa and 28 MPa, 25 MPa and 30 MPa, 26 MPa and 29 MPa, or 24 MPa
and 28 MPa.
[0021] The pressurized hydrocarbon-based composition 116 may then
be heated in one or more hydrocarbon pre-heaters 120 to form
pressurized, heated hydrocarbon-based composition 124. In one
embodiment, the pressurized, heated hydrocarbon-based composition
124 has a pressure greater than the critical pressure of water and
a temperature greater than 75.degree. C. Alternatively, the
temperature of the pressurized, heated hydrocarbon-based
composition 124 is between 10.degree. C. and 300.degree. C., or
between 50.degree. C. and 250.degree. C., or between 75.degree. C.
and 225.degree. C., or between 100.degree. C. and 200.degree. C.,
or between 125.degree. C. and 175.degree. C., or between
140.degree. C. and 160.degree. C. According to embodiments, the
pressurized, heated hydrocarbon-based composition 124 should not be
heated above about 350.degree. C., and in some embodiments, the
pressurized, heated hydrocarbon-based composition should not be
heated above 300.degree. C. to avoid the formation of coking
products. See Hozuma, U.S. Pat. No. 4,243,633, which is
incorporated by reference in its entirety. While some coke or coke
precursor products may be able to pass through process lines
without slowing or stopping the process 100, the formation of these
potentially problematic compounds should be avoided if
possible.
[0022] Embodiments of the hydrocarbon pre-heater 120 may include a
natural gas fired heater, heat exchanger, or an electric heater or
any type of heater known in the art. In some embodiments, not
shown, the pressurized, heated hydrocarbon-based composition 124
may be heated in a double pipe heat exchanger. For example, and not
by way of limitation, the double pipe heat exchanger may heat the
pressurized, heated hydrocarbon-based composition 124 after it has
combined with a heated water stream 126 and/or a heated hydrogen
stream 129 to form a combined feed stream 132.
[0023] The water stream 110 may be any source of water, such as a
water stream having conductivity of less than 1 microSiemens
(.mu.S)/centimeters (cm), such as less than 0.1 .mu.S/cm. The water
stream 110 may also include demineralized water, distilled water,
boiler feed water (BFW), and deionized water. In at least one
embodiment, water stream 110 is a boiler feed water stream. Water
stream 110 is pressurized by water pump 114 to produce pressurized
water stream 118. The pressure of the pressurized water stream 118
is at least 22.1 MPa, which is approximately the critical pressure
of water. Alternatively, the pressure of the pressurized water
stream 118 may be between 23 MPa and 35 MPa, or between 24 MPa and
30 MPa. For instance, the pressure of the pressurized water stream
118 may be between 25 MPa and 29 MPa, 26 MPa and 28 MPa, 25 MPa and
30 MPa, 26 MPa and 29 MPa, or 24 MPa and 28 MPa.
[0024] The pressurized water streams 118, 218, and 318 may then be
heated in a water pre-heater 122 to create heated water stream 126.
According to embodiments, the temperature of the heated water
stream 126 is greater than 100.degree. C. In embodiments, the
temperature of the heated water stream 126 may be from 100.degree.
C. to 370.degree. C., from 100.degree. C. to 350.degree. C., from
100.degree. C. to 300.degree. C., from 100.degree. C. to
250.degree. C., from 100.degree. C. to 200.degree. C., from
100.degree. C. to 150.degree. C., from 150.degree. C. to
370.degree. C., from 150.degree. C. to 350.degree. C., from
150.degree. C. to 300.degree. C., from 150.degree. C. to
250.degree. C., from 150.degree. C. to 200.degree. C., from
200.degree. C. to 370.degree. C., from 200.degree. C. to
350.degree. C., from 200.degree. C. to 300.degree. C., from
200.degree. C. to 250.degree. C., from 250.degree. C. to
370.degree. C., from 250.degree. C. to 350.degree. C., from
250.degree. C. to 300.degree. C., from 300.degree. C. to
370.degree. C., from 300.degree. C. to 350.degree. C., or from
350.degree. C. to 370.degree. C.
[0025] Similar to hydrocarbon pre-heater 120, suitable water
pre-heaters 122 may include a natural gas fired heater, a heat
exchanger, and an electric heater. The water pre-heater 122 may be
a unit separate and independent from the hydrocarbon pre-heater
120.
[0026] The hydrogen stream 127 may be any source of hydrogen. The
hydrogen stream 127 may be heated in a hydrogen pre-heater 128 to
create heated hydrogen stream 129. According to embodiments, the
temperature of the heated hydrogen stream 129 is greater than
100.degree. C. In embodiments, the temperature of the heated
hydrogen stream 129 may be from 100.degree. C. to 370.degree. C.,
from 100.degree. C. to 350.degree. C., from 100.degree. C. to
300.degree. C., from 100.degree. C. to 250.degree. C., from
100.degree. C. to 200.degree. C., from 100.degree. C. to
150.degree. C., from 150.degree. C. to 370.degree. C., from
150.degree. C. to 350.degree. C., from 150.degree. C. to
300.degree. C., from 150.degree. C. to 250.degree. C., from
150.degree. C. to 200.degree. C., from 200.degree. C. to
370.degree. C., from 200.degree. C. to 350.degree. C., from
200.degree. C. to 300.degree. C., from 200.degree. C. to
250.degree. C., from 250.degree. C. to 370.degree. C., from
250.degree. C. to 350.degree. C., from 250.degree. C. to
300.degree. C., from 300.degree. C. to 370.degree. C., from
300.degree. C. to 350.degree. C., or from 350.degree. C. to
370.degree. C.
[0027] Similar to hydrocarbon pre-heater 120 and water pre-heater
122, suitable hydrogen pre-heaters 128 may include a natural gas
fired heater, a heat exchanger, and an electric heater. The
hydrogen pre-heater 128 may be a unit separate and independent from
the hydrocarbon pre-heater 120 and the water pre-heater 122.
[0028] The heated water stream 126, the heated hydrogen stream 129,
and the pressurized, heated hydrocarbon-based composition 124 may
then be mixed in a feed mixer 130 to produce a combined feed stream
132. The feed mixer 130 can be any type of mixing device capable of
mixing the heated water stream 126 and the pressurized, heated
hydrocarbon-based composition 124. In one embodiment, the feed
mixer 130 may be a mixing tee. The feed mixer 130 may be an
ultrasonic device, a small continuous stir tank reactor (CSTR), or
any suitable mixer. The volumetric flow ratio of each component fed
to the feed mixer 130 may vary. It should also be understood that
in one or more embodiments, which are not shown, multiple feed
mixers may be used to individually mix the pressurized, heated
hydrocarbon-based composition 124, the heated hydrogen stream 129,
and the heated water stream 126 in any combination. In embodiments,
the volumetric flow ratio of the heated hydrocarbon-based
composition 124 to the heated water stream 126 may be from 1:10 to
1:1, from 1:10 to 1:5, from 1:10 to 1:2, from 1:5 to 1:1, from 1:5
to 1:2, or from 1:2 to 1:1 at standard ambient temperature and
ambient pressure (SATP). In embodiments it is desirable that the
volumetric flow rate of water is greater than the volumetric flow
rate of hydrocarbons. Without being bound by any particular theory,
it is believed that heavy oils such as residua and bituminous types
are rich in fractions that contain asphaltenes and heavy
polycondensed aromatic molecules. These fractions yield a high
viscosity. Mixing hot compressed water, such as supercritical
water, reduces the viscosity and improves the oil's mobility
through the developed mixed oil/water phase. Therefore, having a
water flow rate that is higher than an oil flow rate improves the
mixture mobility especially for highly viscous oils. Furthermore,
increasing the water to oil ratio improves the caging effect of
water molecules surrounding the asphaltenic and polycondensed
aromatic molecules and increases the distance between them to
prevent their propagation and association. In embodiments, the
hydrogen to oil volumetric flow can be from 10 to 5000 cubic feet
of heated hydrogen stream 129 to one barrel of heated
hydrocarbon-based composition 124, at SATP.
[0029] The combined feed stream 132 may then be introduced to the
supercritical water hydrogenation reactor 150 that is configured to
upgrade the combined feed stream 132. The supercritical water
hydrogenation reactor 150 may be an upflow, downflow, or horizontal
flow reactor. An upflow, downflow or horizontal reactor refers to
the direction the supercritical water and hydrocarbon-based
composition flow through the supercritical water hydrogenation
reactor 150. An upflow, downflow, or horizontal flow reactor may be
chosen based on the desired application and system configuration.
Without intending to be bound by any theory, in downflow
supercritical reactors, heavy hydrocarbon fractions may flow very
quickly due to having a greater density, which may result in
shortened residence times (known as channeling). This may hinder
upgrading, as there is less time for reactions to occur. Upflow
supercritical reactors have a uniform increased residence time
distribution (no channeling), but may experience difficulties due
to undissolved portion of heavy fraction and large particles, such
as carbon-containing compounds in the heavy fractions, accumulating
in the bottom of the reactor. This accumulation may hinder the
upgrading process and plug the reactor. Upflow reactors typically
utilize catalysts to provide increased contact with the reactants;
however, the catalysts may break down due to the harsh conditions
of supercritical water, forming insoluble aggregates, which may
generate coke. Horizontal reactors may be useful in applications
that desire phase separation or that seek to reduce pressure drop,
however; the control of hydrodynamics of internal fluid is
difficult. Each type of reactor flow has positive and negative
attributes that vary based on the applicable process; however, in
some embodiments, an upflow or downflow reactor may be favored.
[0030] The supercritical water hydrogenation reactor 150 may
operate at a temperature greater than the critical temperature of
water and a pressure greater than the critical pressure of water.
In one or more embodiments, the supercritical water hydrogenation
reactor 150 may have a temperature of between 380.degree. C. to
480.degree. C., or between 390.degree. C. to 450.degree. C. The
supercritical water hydrogenation reactor 150 may be an isothermal
or non-isothermal reactor. The reactor may be a tubular-type
vertical reactor, a tubular-type horizontal reactor, a vessel-type
reactor, a tank-type reactor having an internal mixing device, such
as an agitator, or a combination of any of these reactors.
Moreover, additional components, such as a stirring rod or
agitation device may also be included in the supercritical water
hydrogenation reactor 150.
[0031] The supercritical water hydrogenation reactor 150 may have
dimensions defined by the equation L/D, where L is a length of the
supercritical water hydrogenation reactor 150 and D is the diameter
of the supercritical water hydrogenation reactor 150. In one or
more embodiments, the L/D value of the supercritical water
hydrogenation reactor 150 may be sufficient to achieve a
superficial velocity of fluid greater than 0.5 meter (m)/minute
(min), or an L/D value sufficient to achieve a superficial velocity
of fluid between 1 m/min and 5 m/min. Such relatively high fluid
velocity is desired to attain full turbulence of the internal
fluid. The desired Reynolds number (a measurement of fluid flow) is
greater than 5000. Reynolds number is given by the
relationship:
Re = uD v ##EQU00001##
where u is the superficial velocity, D is the diameter of the
supercritical upgrading reactor, and v is the kinematic viscosity.
If that equation is rewritten as
u = vRe D ##EQU00002##
it can be observed from this relationship that by decreasing the
reactor diameter (D) the superficial velocity (u) is increased
(because u and D are indirectly proportional to each other
( u .times. .times. .alpha. .times. 1 D ) ) . ##EQU00003##
For a fixed reactor length at a reference case, decreasing the
reactor diameter (D) will increase the ratio (L/D). Furthermore, by
increasing the superficial velocity (u), Reynolds Number (Re) is
increased (because u and Re are directly proportional to each other
(u .alpha. Re). Therefore, from the above rationale, in order to
maintain the flow in high flow turbulence regime (Re>5000), it
is required to increase the superficial velocity, and/or decrease
the reactor's diameter, and by decreasing the reactor's diameter,
the ratio (L/D) is also increased.
[0032] In some embodiments, the residence time of the internal
fluid in the supercritical water hydrogenation reactor 150 may be
longer than 5 seconds, such as longer than 1 minute. In some
embodiments, the residence time of the internal fluid in the
supercritical water hydrogenation reactor 150 may be from 1 to 30
minutes, from 1 to 20 minutes, from 1 to 15 minutes, from 1 to 12
minutes, from 1 to 10 minutes, from 1 to 8 minutes, from 1 to 5
minutes, from 1 to 2 minutes, from 2 to 30 minutes, from 2 to 20
minutes, from 2 to 15 minutes, from 2 to 12 minutes, from 2 to 10
minutes, from 2 to 8 minutes, from 2 to 5 minutes, from 5 to 30
minutes, from 5 to 20 minutes, from 5 to 15 minutes, from 5 to 12
minutes, from 5 to 10 minutes, from 5 to 8 minutes, from 8 to 30
minutes, from 8 to 20 minutes, from 8 to 15 minutes, from 8 to 12
minutes, from 8 to 10 minutes, from 10 to 30 minutes, from 10 to 20
minutes, from 10 to 15 minutes, from 10 to 12 minutes, from 12 to
30 minutes, from 12 to 20 minutes, from 12 to 15 minutes, from 15
to 30 minutes, from 15 to 20 minutes, or from 20 to 30 minutes. In
embodiments, the residence time may be no greater than 15 minutes
and no less than 2 minutes.
[0033] The supercritical water upgrading process is aided by the
addition of the heated hydrogen stream 129 to convert a greater
amount of heavy hydrocarbons into lighter hydrocarbons. The
supercritical water upgrading process and the addition of the
heated hydrogen stream have a synergistic effect because the
supercritical water dissolves the oil; maximizes mixing of the
combined feed stream 130 (oil, water, and hydrogen components);
ruptures hydrocarbon and heteroatom chemical bonds; cages
asphaltenes and large hydrocarbon radicals (preventing their
polymerization); and provides high pressure that brings hydrogen to
hydrocarbon and heteroatom radicals' moieties to further rupture
chemical bonds and saturate the free hydrocarbon and heteroatoms
radicals; and the hydrogen addition facilitates rupturing
hydrocarbon and heteroatoms chemical bonds and saturates the free
hydrocarbon and heteroatoms radicals generated by the combined
effect of supercritical water and the added hydrogen. Specifically,
the hydrogen addition may suppress gummy olefin, asphaltene, and
coke generation; increase the conversion of the heavy fraction
(hydrocarbons having a T.sub.5 of greater than 540.degree. C.
and/or an API gravity of less than 17.degree.) in the combined feed
stream 130 to lighter fractions; allow for increasing operating
severity by either increasing temperature or reducing flow rate,
thereby increasing the heavy fraction conversion; and provide
hydrotreating to the combined feed stream 130 by converting
heteroatoms such as sulfur to H.sub.2S.
[0034] Thermal processes are temperature driven chemical processes
that convert and upgrade petroleum heavy hydrocarbons via radical
mechanism. The typical thermal cracking processes temperature range
is between 495 and 540.degree. C. and typical pressure is in the
range of 10 and 40 atmospheres. The severities of thermal processes
determine the extent of feed conversion. Process severity refers to
the levels of operating conditions in terms of combinations of
temperature and space times. Thermal processes utilize heat to
crack heavy hydrocarbons into lighter end products, thereby
reducing the oil viscosity without catalyst addition. However, the
presence of asphaltenes in the heavy hydrocarbons limits
upgradability. The amount of asphaltene in the hydrocarbon stream
is directly related to its affinity to form coke, due to asphaltene
condensation reactions. See Yan, T. Y., Characterization of
visbreaker feeds. Fuel, 1990. 69(8): p. 1062-1064. The reactions
taking place in thermal processes are a combination of endothermic
reactions that proceed according to free radical mechanisms. The
chemistry of thermal cracking is rather complex, and the degree of
complexity increases with increase in process severity for heavier
feedstocks. Through thermal cracking, chemical bonds of different
species present in the oil are subjected to endothermic homolytic
dissociation reactions. During this bond cleavage procedure the
asphaltene solvating appendages are detached and the aliphatic
bridges, connecting the polyaromatic clusters within the asphaltene
molecules, are broken. This makes the asphaltene aggregates prone
to precipitation in a less peptizing environment. In addition,
dehydrogenation reactions of asphaltene aggregates result in
increasing C/H ratios, which increase the molecular weight of the
asphaltene molecules. Thermal processes proceed by initiation
reactions where a portion of feed hydrocarbon molecules (M) break
into multiple hydrocarbon radicals (R.), by homolytic cleavage of
the C--C bonds. As a result, free radicals are accumulated until
reaching a steady-stable concentration that allows the thermal
cracking propagation reactions to continue. The generated free
radicals shown by Equation 1 below drive the rest of the
reactions.
M.fwdarw.R.+R.sub.n. (1)
[0035] The above reaction step is followed by a chain of reactions,
which includes hydrogen abstraction and addition, and radical
cracking and recombination. The produced free radicals abstract
hydrogen from nearby molecules, as shown by Equation 2.
R.+M.fwdarw.R.sub.1.+RH (2)
[0036] Generated radicals are also dealkylated, simultaneously, to
produce smaller alkane radicals, as shown by Equation 3.
R.sub.1.fwdarw.R.sub.2.+R.sub.3. (3) [0037] where,
R.sub.1>R.sub.2>R.sub.3, meaning that the R.sub.1 radical is
larger than the R.sub.2 radical, which is larger than the R.sub.3
radical.
[0038] Under constant flow, reactions 1-3 continue to take place
unless interrupted by major change in feedstock properties or
operating conditions. If the temperature or space time increases
beyond the stability limit, heavy free radicals combination
reactions escalate to produce larger and heavier molecules. These
combination reactions terminates the reaction mechanism and cause
asphaltene condensation, hence called condensation reactions, as
shown by Equation 4.
R.+R..fwdarw.M (4)
[0039] The combinations resulting from termination reactions may
produce heavier compounds than the ones present originally in the
feedstock. The cleavage of C--C bond in alkanes requires lower
energy than the cleavage of C--H and H--H bonds. For example while
the cleavage of the C--C bond in ethane (CH.sub.3--CH.sub.3)
requires dissociation energy of 360 KJ/mole, the cleavage of the
C--H bond (C.sub.2H.sub.5--H) requires dissociation energy of 410
KJ/mole, as shown Table 1. The same observation is noticed for the
bond energy of H-Aromatics, which is higher than the bond energy of
C-Aromatics. The data in Table 1 are given at standard ambient
temperature and ambient pressure (SATP) (see Raseev, S., Thermal
and catalytic processes in petroleum refining, page 37, 2003: CRC
Press, 1.sup.st ed.)
TABLE-US-00001 TABLE 1 Chemical Bond Dissociation Energies for
Different Hydrocarbons. Bond Dissociation Energy (kJ/mole) H--H 435
CH.sub.2--H 356 CH.sub.3--H 431 C.sub.2H.sub.5--H 410
n-C.sub.3H.sub.7--H 398 i-C.sub.3H.sub.7--H 394 n-C.sub.4H.sub.9--H
394 i-C.sub.4H.sub.9--H 390 CH.sub.3--CH.sub.3 360
C.sub.2H.sub.5--CH.sub.3 348 n-C.sub.4H.sub.9--C.sub.2H.sub.5 322
C.sub.6H.sub.5--C.sub.6H.sub.5 415
(C.sub.6H.sub.5).sub.3C-C(C.sub.6H.sub.5).sub.3 46 ##STR00001## 364
423
[0040] It is also observed from Table 1 that the dissociation
energy of the C--H bond in alkanes tends to decrease as the alkane
molecular size increases. This indicates that lower molecular
weight hydrocarbon species are kinetically more stable than heavier
ones.
[0041] The dissociation energies at different temperatures, such as
at supercritical temperatures, may be calculated from
thermodynamics starting from the tabulated dissociation enthalpies
at 298K. For example to estimate the oxygen-hydrogen bond (O--H)
dissociation enthalpy starting from 298K at a fixed pressure the
following expression estimates the bond dissociation enthalpy at a
supercritical temperature of 450.degree. C. (723K):
.DELTA.H.sub.(723K)=.DELTA.H.sub.(298K)+.DELTA.C.sub.p.DELTA.T.
After finding the heat capacities (.DELTA.C.sub.P) from
thermodynamic data references such as Brunner, G., Hydrothermal and
supercritical water processes. Vol. 5. 2014: Elsevier, at the
required temperature, the bond dissociation enthalpy at 723K is
estimated to be 442 KJ/mol.
[0042] Non-carbon rejection processes, at relatively higher
operating cost such as hydrocracking, upgrade oil to produce stable
products distant from, gummy olefin generation, asphaltene
precipitation, and/or coke formation reactions. These products are
believed to retain sufficient H/C ratios to preserve their
stability. Hydrogen based routes include hydrocracking (a
hydrogenolysis process), operated at around 200 bars and 350 to
400.degree. C., allows refiner to produce hydrocarbons having a
lower molecular weight with higher H/C ratios and a lower yield of
coke. The mechanism of hydrogenolysis is basically similar to that
of thermal cracking, but the cracking is promoted by high hydrogen
partial and catalyst with concurrent hydrogenation. Hydrotreating
is a mild hydrogen based process that operates at 30 to 130 bars
and 300 to 400.degree. C., allows reducing impurities from the oil
like sulfur and metals without major cracking to the oil. Overall,
olefins and coke formation is very low in hydrogenous processes
since the large hydrocarbon radicals' combination reactions and the
formation of coke precursors are suppressed as the hydrogen
pressure is increased. Oil upgrading and quality improvements by
hydrogenous processes have been vastly practiced in industry to
generate light products (hydrocracking) and/or to remove impurities
(hydrotreating). Hydrogen-based upgrading processes typically
utilize bi-metallic catalysts and hydrogen at different pressures,
which result in high operating cost due to high hydrogen partial
pressure requirement and catalyst and related regeneration Testing
and Inspection (T&I) costs. Furthermore, hydrocracking is a
catalytic process that necessitates treating the feedstock ahead of
the process to prevent catalyst poisoning. Therefore, hydrocracker
feed is usually treated by catalytic hydrotreating at lower
pressures to remove sulfur, nitrogen, metals, and other catalyst
poisoning materials. This hydrotreating step adds to the cost of
the catalytic hydrocracking process. In addition to hydrogen
consumption of 1200 to 2400 standard cubic foot per oil barrel
(SCFB), hydrocracking process conventionally requires high hydrogen
partial pressure of around 200 bars to facilitate cracking the
hydrocarbon molecules.
[0043] Water above its critical condition (about 374.degree. C. and
about 221 bar), termed supercritical water, is neither a liquid nor
gas but a single fluid phase that converts from being polar to
non-polar. Supercritical water can diffuse through semi-solid
materials that are insusceptible to penetration otherwise at lower
conditions, such as polynuclear aromatics and asphaltenes.
Supercritical water completely dissolves hydrocarbon oils, and
therefore, thereby both phases become totally miscible. The
distinctive characteristics of water in supercritical state improve
liquid yield and properties of cracking, desulfurization, and
demetallization reactions. Hydrocarbon oil cracking via
supercritical water proceeds by a similar free radicals mechanism
as that of thermal cracking, and is highly selective towards
breaking of heavy fractions to produce middle distillate oils
without coke generation. Furthermore, during upgrading,
supercritical water molecules isolate and separate the most heavy
oil fraction molecules by the caging effect, which extends the
upgrading reaction at the expense of condensation reactions. NMR
analysis has revealed that the asphaltene content of supercritical
water treated oil decreased to a large extent, while saturate,
olefin, and aromatic content increased. When supercritical water is
mixed with oil it dissolves all the oil constituents, including
asphaltene. The dissolution takes place by swelling and breaching
the asphaltene aggregates, thereby reduces the asphaltene aggregate
particles size from about 1 to 800 microns to much smaller
molecules having a particle size of from 0.1 to 300 nanometers (nm)
that are distributed throughout the water/oil mixture. These
relatively smaller asphaltenes molecules are caged by water
molecules surrounding them, which prevent them from association,
aggregation, and deposition during the upgrading reactions.
[0044] As stated above, processes using supercritical water can
generate olefins and polycondensed aromatics, which can lead to
gumming. As stated previously, the high temperature of the
supercritical water reactor induces thermal cracking of chemical
bonds that may be filled with hydrogen to avoid intermolecular
condensation and generation of olefins and polycondensed aromatics.
Although the hydrogen inherently present in the water molecules can
participate in the cracking reaction, the extent of hydrogen
donation from water is quite limited in supercritical water
conditions due to high hydrogen-oxygen bond energy. The
hydrogen-oxygen dissociation energy at supercritical conditions can
be calculated as provided above. Thus, the upgraded product from a
supercritical water process has a greater aromaticity and
olefinicity than the hydrocarbon feed, which has negative effect on
the stability of the products.
[0045] Supercritical water prevents the asphaltenes and heavy
molecules from association and precipitation by breaking the large
molecules into smaller ones and by caging the polycondensed
aromatic clusters (asphaltenes) molecules and breaking bridging
bonds (such as carbon-sulfur-carbon) between large polyaromatic
compounds and keeping them apart. Moreover, the supercritical water
fully dissolves and converts the kinetically active hydrocarbon
species such as large molecules. The upgrading reaction mechanism
involves hydrocarbon and hydrogen abstraction reactions, which
generates numerous free radicals. Appreciable portion of these
generated radicals are subjected to cracking reactions, reforming
reactions, combination reactions, addition reactions, substitution
reactions, and others. The overall result of these reactions is the
generation of new improved quality product fractions that improves
the overall supercritical water product quality including API and
asphaltenes reduction. However, after departing from the water
supercritical conditions, after cooling and pressure let down, some
of the molecules and light hydrocarbon radicals that requires
longer time to complete their conversion reactions tend to
associate and/or form double bonds to fulfill their unpaired
electrons in the absence of hydrogen. These species are generated
by hydrogen and light hydrocarbon abstraction reactions, which
increase their C/H ratios. This increase is translated by increase
in aromaticity, which is the conversion of cyclic hydrocarbons
(having no double bonds or a single double bond) and to some extent
straight chain hydrocarbons into aromatics, and by cleavage of
alkyl appendages that are cross linking different smaller
aromatics. Once their alkyl appendages are cleaved, the different
smaller aromatics radicals combines into larger aromatics clusters,
which also increases the oil aromaticity. Similarly, hydrogen
abstraction reactions in supercritical water process generates
radicals, which tend to form double bonds species (olefins) in the
absence of hydrogen. Availing enough hydrogen during upgrading
saturates these molecules that then require increased time for
conversion into valuable products, which minimizes their
interaction and limits their double bonds formation. This issue may
be addressed by using a catalyst in the supercritical water
process, but no catalysts have been used in supercritical water
process due to the harsh conditions of supercritical water that
makes most catalysts unstable in the presence of supercritical
water. The disintegration of heterogeneous catalysts is frequently
observed in the presence of supercritical water. Additionally,
homogeneous catalysts, such as organometallic compounds, can be
transformed to an inactive form under supercritical water
conditions. Conventionally, this problem has been addressed by
adding catalysts to be used in a separate process downstream the
supercritical water process as a post treatment option. However,
using a downstream process requires major capital investment for
dedicated infrastructure, such as reactor(s), pumps and compressor,
and cooler(s) and heat exchanger(s) in addition to catalyst with
its costs of purchasing, replacement, and regenerating due to
deactivation.
[0046] Consequently, the processes described in this disclosure do
not use a catalyst. Supercritical water processes hydrothermally
crack the hydrocarbon molecules under high operating pressures, as
previously described, which are greater than conventional
hydrocracking pressures. Under this high pressure range,
hydrogenation can suppress gummy olefin generation, heavy
hydrocarbon radical polymerization, and condensation reactions that
lead to coke formation in thermal cracking. The supercritical water
process high pressure can be exploited by adding a low amount of
hydrogen to the supercritical water at hydrogen partial pressure of
1-30 bar, more specifically at 2-6 bar (based on oil type). The
hydrogen partial pressure may be dependent on the hydrocarbons
present. For example, highly viscous oils such as residua and
bituminous oils require relatively greater amounts of hydrogen
because they are highly deficient in hydrogen content (very high
C/H ratio) because they contain abundance of heavy hydrocarbon
molecules. In order to generate lighter hydrocarbon fractions out
of these heavy oils, their generated free radicals must be
saturated with abundant hydrogen. In addition to forming double
bond species, the generated free radicals, especially the heavy
ones, in the absence of hydrogen, tend to associate and form bigger
and heavier molecules and aggregates that are prone to
precipitation. The hydrogen to oil volumetric flow may be between
(10 to 5000 ft.sup.3) H.sub.2 to one barrel of oil, at standard
ambient temperature and ambient pressure (SATP).
[0047] In addition to rupturing different types of bonds in the
oil, supercritical water facilitates hydrogen availability in the
vicinities of the cracked hydrocarbon and heteroatoms moieties,
through hydrogen, water, and oil mixing in high pressure
environments. Therefore, in addition to hydrothermally generated
free hydrocarbon and heteroatoms radicals by supercritical water,
the added hydrogen facilitates further cracking of hydrocarbon and
heteroatoms molecule into free radicals and saturates the overall
generated radicals including heteroatoms (for example converts S to
H.sub.2S), simultaneously, under the supercritical water process
conditions. The disclosed process combines carbon rejection and
non-carbon rejection processes in a single process that combines
the benefits of operating at lower cost than conventional
hydrocracking processes to produce more stable products than
thermal cracking. In this disclosure, the non-catalytically
produced free large hydrocarbon radicals by the combined effect of
supercritical water hydrothermal and hydrogenolysis are saturated
and prevented from combination reactions that terminate the
upgrading reaction mechanism and lead to, gummy olefin, asphaltene,
and coke formations. Furthermore, the presence of hydrogen in the
supercritical water hydrogenation process will treat the oil by
saturating the generated free heteroatoms radicals, such as
converting sulfur to H.sub.2S.
[0048] Hydrogenolysis processes such as hydrocracking require high
hydrogen partial pressure and catalysts to rupture the
carbon-sulfur and carbon-carbon, and carbon-metal bonds. In the
present disclosure the supercritical water hydrogenation reactions
rupture hydrocarbon and heteroatoms bonds and provide the required
high pressure for hydrogenation reactions at low hydrogen partial
pressure. It is contemplated that low hydrogen partial pressure is
desirable because it eliminates the need for dedicated gas
compressors and thereby reduces maintenance and utilities costs.
Additionally, in embodiments, low hydrogen partial pressure
eliminates high hydrogen consumption that is needed to maintain
high hydrogen partial pressure. Under the supercritical water
hydrogenation process conditions, the relatively lower molecular
weight hydrocarbon species of C.sub.1 to C.sub.7 hydrocarbons
(paraffins, cycloparaffins, and aromatics) are kinetically more
stable than the heavier ones. Therefore, supercritical water
hydrogenation process is highly selective towards breaking of heavy
fractions to produce middle distillate oils without gummy olefin,
asphaltene, and coke generation. Furthermore, during upgrading,
supercritical water molecules isolate and separate the most heavy
oil fraction molecules by the caging effect, which extends the
upgrading reaction at the expense of condensation reactions,
thereby decreasing condensation reactions.
[0049] Hydrogen addition into the supercritical water process
provides additional yields of middle distillate oils but at
improved stability by saturating heavy hydrocarbon radicals and
olefins that has potential to generate gums. In addition, the
supercritical water process breaks large asphaltenes aggregates of
size 1 to 800 microns to much smaller scattered radical aggregates
of size 0.1 to 300 nm that can readily be approached and saturated
by hydrogen due to its small size (1.06-1.20 angstrom). This in
turn reduces the asphaltene content in the oil by converting them
into lighter fractions. Therefore, supercritical water facilitates
the hydrogenation of heavy hydrocarbon radicals including olefins
and asphaltenes radicals and prevents their combination reactions
that terminate the upgrading reaction mechanism. In other words,
the hydrogen addition to the supercritical water process passivates
the combination reactions of large hydrocarbon radicals and olefins
that are hydrothermally generated by supercritical water, thereby
preventing gum, asphaltene, and coke generation, which allows for
increasing process severity for additional oil upgrading.
[0050] Large hydrocarbon molecules cracking and radicals'
saturation reactions in supercritical water hydrogenation are
favored by high operating pressure; therefore, increasing process
severity in terms of higher pressures will facilitate large
hydrocarbon and heteroatoms bonds rupturing and hydrogenation of
the generated radicals as well as increasing oil conversion.
Furthermore, supercritical water process has been reported to
desulfurize and demetalize hydrocarbon oil. Adding hydrogen to the
supercritical water process will further enhance the sulfur and
metals removal by hydrogenating the heteroatoms (hydrotreating).
Therefore, adding hydrogen to the supercritical water process will
expand the application of the supercritical water technology for
treating sulfur rich streams (such as disulfide oils) besides
upgrading by facilitating C--S and S--S bond rupturing and
hydrogenating the sulfur radicals in Supercritical water to
generate hydrogen sulfide and light hydrocarbons, as shown by
equation 5.
CH.sub.3--S--S-CH.sub.3+2H.sub.2.fwdarw.CH.sub.3--CH.sub.3+2H.sub.2S
(5)
[0051] Therefore, there exists recognizable synergy between
supercritical water and added hydrogen to upgrade and improve
hydrocarbon oils. It is contemplated that the supercritical water
hydrogenation reactor 150 may dissolve the hydrocarbons and
hydrogen in supercritical water and break the M-S bonds (having a
bond energy of approximately 290 kJ/mol), M-M bonds, H--H bonds,
and MS-SM bonds (having a bond energy of approximately 260 kJ/mol),
and hydrogenate the generated hydrocarbon and heteroatoms radicals.
Within the supercritical water hydrogenation reactor 150, it is
contemplated that large hydrocarbon molecules (including asphaltene
aggregates) are dissolved, broken, dispersed, and hydrogenated in
the oil medium, in addition to hydrocarbon upgrading by improving
properties such as API gravity and reducing properties such as
density, viscosity, and heteroatoms (including metals).
[0052] Upon exiting the supercritical water hydrogenation reactor
150, the upgraded product 152 may have a T.sub.5 true boiling point
(TBP) of less than 500.degree. C., of less than 400.degree. C., of
less than 350.degree. C., of less than 325.degree. C., of less than
310.degree. C., or of less than 300.degree. C. In embodiments, the
upgraded product 152 may have a T.sub.5 TBP of from 25.degree. C.
to 350.degree. C., from 25.degree. C. to 325.degree. C., from
25.degree. C. to 300.degree. C., from 25.degree. C. to 275.degree.
C., from 25.degree. C. to 250.degree. C., from 25.degree. C. to
225.degree. C., from 25.degree. C. to 200.degree. C., from
25.degree. C. to 175.degree. C., from 25.degree. C. to 150.degree.
C., from 25.degree. C. to 125.degree. C., from 25.degree. C. to
100.degree. C., from 25.degree. C. to 75.degree. C., from
25.degree. C. to 50.degree. C., from 50.degree. C. to 350.degree.
C., from 50.degree. C. to 325.degree. C., from 50.degree. C. to
300.degree. C., from 50.degree. C. to 275.degree. C., from
50.degree. C. to 250.degree. C., from 50.degree. C. to 225.degree.
C., from 50.degree. C. to 200.degree. C., from 50.degree. C. to
175.degree. C., from 50.degree. C. to 150.degree. C., from
50.degree. C. to 125.degree. C., from 50.degree. C. to 100.degree.
C., from 50.degree. C. to 75.degree. C., from 75.degree. C. to
350.degree. C., from 75.degree. C. to 325.degree. C., from
75.degree. C. to 300.degree. C., from 75.degree. C. to 275.degree.
C., from 75.degree. C. to 250.degree. C., from 75.degree. C. to
225.degree. C., from 75.degree. C. to 200.degree. C., from
75.degree. C. to 175.degree. C., from 75.degree. C. to 150.degree.
C., from 75.degree. C. to 125.degree. C., from 75.degree. C. to
100.degree. C., from 100.degree. C. to 350.degree. C., from
100.degree. C. to 325.degree. C., from 100.degree. C. to
300.degree. C., from 100.degree. C. to 275.degree. C., from
100.degree. C. to 250.degree. C., from 100.degree. C. to
225.degree. C., from 100.degree. C. to 200.degree. C., from
100.degree. C. to 175.degree. C., from 100.degree. C. to
150.degree. C., from 100.degree. C. to 125.degree. C., from
125.degree. C. to 350.degree. C., from 125.degree. C. to
325.degree. C., from 125.degree. C. to 300.degree. C., from
125.degree. C. to 275.degree. C., from 125.degree. C. to
250.degree. C., from 125.degree. C. to 225.degree. C., from
125.degree. C. to 200.degree. C., from 125.degree. C. to
175.degree. C., from 125.degree. C. to 150.degree. C., from
150.degree. C. to 350.degree. C., from 150.degree. C. to
325.degree. C., from 150.degree. C. to 300.degree. C., from
150.degree. C. to 275.degree. C., from 150.degree. C. to
250.degree. C., from 150.degree. C. to 225.degree. C., from
150.degree. C. to 200.degree. C., from 150.degree. C. to
175.degree. C., from 175.degree. C. to 350.degree. C., from
175.degree. C. to 325.degree. C., from 175.degree. C. to
300.degree. C., from 175.degree. C. to 275.degree. C., from
175.degree. C. to 250.degree. C., from 175.degree. C. to
225.degree. C., from 175.degree. C. to 200.degree. C., from
200.degree. C. to 350.degree. C., from 200.degree. C. to
325.degree. C., from 200.degree. C. to 300.degree. C., from
200.degree. C. to 275.degree. C., from 200.degree. C. to
250.degree. C., from 200.degree. C. to 225.degree. C., from
225.degree. C. to 350.degree. C., from 225.degree. C. to
325.degree. C., from 225.degree. C. to 300.degree. C., from
225.degree. C. to 275.degree. C., from 225.degree. C. to
250.degree. C., from 250.degree. C. to 350.degree. C., from
250.degree. C. to 325.degree. C., from 250.degree. C. to
300.degree. C., from 250.degree. C. to 275.degree. C., from
275.degree. C. to 350.degree. C., from 275.degree. C. to
325.degree. C., from 275.degree. C. to 300.degree. C., from
300.degree. C. to 350.degree. C., from 300.degree. C. to
325.degree. C., or from 325.degree. C. to 350.degree. C. The
upgraded product 152 may have a T.sub.90 TBP of less than or equal
to 650.degree. C., less than or equal to 610.degree. C., or less
than or equal to 600.degree. C. In embodiments, upgraded product
152 may have a T.sub.90 TBP from 200.degree. C. to 650.degree. C.,
from 200.degree. C. to 600.degree. C., from 200.degree. C. to
575.degree. C., from 200.degree. C. to 550.degree. C., from
200.degree. C. to 540.degree. C., from 200.degree. C. to
530.degree. C., from 200.degree. C. to 525.degree. C., from
200.degree. C. to 500.degree. C., from 200.degree. C. to
450.degree. C., from 200.degree. C. to 400.degree. C., from
200.degree. C. to 300.degree. C., from 300.degree. C. to
650.degree. C., from 300.degree. C. to 600.degree. C., from
300.degree. C. to 575.degree. C., from 300.degree. C. to
550.degree. C., from 300.degree. C. to 540.degree. C., from
300.degree. C. to 530.degree. C., from 300.degree. C. to
525.degree. C., from 300.degree. C. to 500.degree. C., from
300.degree. C. to 450.degree. C., from 300.degree. C. to
400.degree. C., from 400.degree. C. to 650.degree. C., from
400.degree. C. to 600.degree. C., from 400.degree. C. to
575.degree. C., from 400.degree. C. to 550.degree. C., from
400.degree. C. to 540.degree. C., from 400.degree. C. to
530.degree. C., from 400.degree. C. to 525.degree. C., from
400.degree. C. to 500.degree. C., from 450.degree. C. to
650.degree. C., from 450.degree. C. to 600.degree. C., from
450.degree. C. to 575.degree. C., from 450.degree. C. to
550.degree. C., from 450.degree. C. to 540.degree. C., from
450.degree. C. to 530.degree. C., from 450.degree. C. to
525.degree. C., from 450.degree. C. to 500.degree. C., from
500.degree. C. to 650.degree. C., from 500.degree. C. to
600.degree. C., from 500.degree. C. to 575.degree. C., from
500.degree. C. to 550.degree. C., from 500.degree. C. to
540.degree. C., from 500.degree. C. to 530.degree. C., from
500.degree. C. to 525.degree. C., from 525.degree. C. to
650.degree. C., from 525.degree. C. to 600.degree. C., from
525.degree. C. to 575.degree. C., from 525.degree. C. to
550.degree. C., from 525.degree. C. to 540.degree. C., from
525.degree. C. to 530.degree. C., from 530.degree. C. to
650.degree. C., from 530.degree. C. to 600.degree. C., from
530.degree. C. to 575.degree. C., from 530.degree. C. to
550.degree. C., from 530.degree. C. to 540.degree. C., from
540.degree. C. to 650.degree. C., from 540.degree. C. to
600.degree. C., from 540.degree. C. to 575.degree. C., from
540.degree. C. to 550.degree. C., from 550.degree. C. to
650.degree. C., from 550.degree. C. to 600.degree. C., from
550.degree. C. to 575.degree. C., from 575.degree. C. to
650.degree. C., from 575.degree. C. to 600.degree. C., or from
600.degree. C. to 650.degree. C., where the T.sub.90 TBP is greater
than the T.sub.5 TBP previously described. The upgraded product 152
may have an API gravity from 12.degree. to 45.degree., from
12.degree. to 35.degree., from 12.degree. to 30.degree., from
12.degree. to 27.degree., from 12.degree. to 25.degree., from
12.degree. to 23.degree., from 12.degree. to 21.degree., from
12.degree. to 20.degree., from 15.degree. to 45.degree., from
15.degree. to 35.degree., from 15.degree. to 30.degree., from
15.degree. to 27.degree., from 15.degree. to 25.degree., from
15.degree. to 23.degree., from 15.degree. to 21.degree., from
15.degree. to 20.degree., from 18.degree. to 45.degree., from
18.degree. to 35.degree., from 18.degree. to 30.degree., from
18.degree. to 27.degree., from 18.degree. to 25.degree., from
18.degree. to 23.degree., from 18.degree. to 21.degree., from
18.degree. to 20, from 20.degree. to 45.degree., from 20.degree. to
35.degree., from 20.degree. to 30.degree., from 20.degree. to
27.degree., from 20.degree. to 25.degree., from 20.degree. to
23.degree., from 20.degree. to 21.degree., from 21.degree. to
45.degree., from 21.degree. to 35.degree., from 21.degree. to
30.degree., from 21.degree. to 27.degree., from 21.degree. to
25.degree., from 21.degree. to 23.degree., from 23.degree. to
45.degree., from 23.degree. to 35.degree., from 23.degree. to
30.degree., from 23.degree. to 27.degree., from 23.degree. to
25.degree., approximately 20.degree., or approximately
19.8.degree.. The upgraded product 152 may include less than 3.4
wt. % total sulfur content by weight of the upgraded product 152.
In embodiments, the upgraded product 152 may include from 0.1 wt. %
to 5 wt. %, from 0.1 wt. % to 4 wt. %, from 0.1 wt. % to 3.3 wt. %,
from 0.1 wt. % to 3.0 wt. %, from 0.1 wt. % to 2.8 wt. %, from 0.1
wt. % to 2.6 wt. %, from 0.1 wt. % to 2.3 wt. %, from 0.1 wt. % to
2.0 wt. %, from 0.1 wt. % to 1.8 wt. %, from 0.1 wt. % to 1.6 wt.
%, from 0.1 wt. % to 1.3 wt. %, from 0.1 wt. % to 1.0 wt. %, from
0.1 wt. % to 0.5 wt. %, from 0.5 wt. % to 5 wt. %, from 0.5 wt. %
to 4 wt. %, from 0.5 wt. % to 3.3 wt. %, from 0.5 wt. % to 3.0 wt.
%, from 0.5 wt. % to 2.8 wt. %, from 0.5 wt. % to 2.6 wt. %, from
0.5 wt. % to 2.3 wt. %, from 0.5 wt. % to 2.0 wt. %, from 0.5 wt. %
to 1.8 wt. %, from 0.5 wt. % to 1.6 wt. %, from 0.5 wt. % to 1.3
wt. %, from 0.5 wt. % to 1.0 wt. %, from 1.0 wt. % to 5 wt. %, from
1.0 wt. % to 4 wt. %, from 1.0 wt. % to 3.3 wt. %, from 1.0 wt. %
to 3.0 wt. %, from 1.0 wt. % to 2.8 wt. %, from 1.0 wt. % to 2.6
wt. %, from 1.0 wt. % to 2.3 wt. %, from 1.0 wt. % to 2.0 wt. %,
from 1.0 wt. % to 1.8 wt. %, from 1.0 wt. % to 1.6 wt. %, from 1.0
wt. % to 1.3 wt. %, from 1.3 wt. % to 5 wt. %, from 1.3 wt. % to 4
wt. %, from 1.3 wt. % to 3.3 wt. %, from 1.3 wt. % to 3.0 wt. %,
from 1.3 wt. % to 2.8 wt. %, from 1.3 wt. % to 2.6 wt. %, from 1.3
wt. % to 2.3 wt. %, from 1.3 wt. % to 2.0 wt. %, from 1.3 wt. % to
1.8 wt. %, from 1.3 wt. % to 1.6 wt. %, from 1.6 wt. % to 5 wt. %,
from 1.6 wt. % to 4 wt. %, from 1.6 wt. % to 3.3 wt. %, from 1.6
wt. % to 3.0 wt. %, from 1.6 wt. % to 2.8 wt. %, from 1.6 wt. % to
2.6 wt. %, from 1.6 wt. % to 2.3 wt. %, from 1.6 wt. % to 2.0 wt.
%, from 1.6 wt. % to 1.8 wt. %, from 1.8 wt. % to 5 wt. %, from 1.8
wt. % to 4 wt. %, from 1.8 wt. % to 3.3 wt. %, from 1.8 wt. % to
3.0 wt. %, from 1.8 wt. % to 2.8 wt. %, from 1.8 wt. % to 2.6 wt.
%, from 1.8 wt. % to 2.3 wt. %, from 1.8 wt. % to 2.0 wt. %, from
2.0 wt. % to 5 wt. %, from 2.0 wt. % to 4 wt. %, from 2.0 wt. % to
3.3 wt. %, from 2.0 wt. % to 3.0 wt. %, from 2.0 wt. % to 2.8 wt.
%, from 2.0 wt. % to 2.6 wt. %, from 2.0 wt. % to 2.3 wt. %, from
2.3 wt. % to 5 wt. %, from 2.3 wt. % to 4 wt. %, from 2.3 wt. % to
3.3 wt. %, from 2.3 wt. % to 3.0 wt. %, from 2.3 wt. % to 2.8 wt.
%, from 2.3 wt. % to 2.6 wt. %, from 2.6 wt. % to 5 wt. %, from 2.6
wt. % to 4 wt. %, from 2.6 wt. % to 3.3 wt. %, from 2.6 wt. % to
3.0 wt. %, from 2.6 wt. % to 2.8 wt. %, from 2.8 wt. % to 5 wt. %,
from 2.8 wt. % to 4 wt. %, from 2.8 wt. % to 3.3 wt. %, from 2.8
wt. % to 3.0 wt. %, from 3.0 wt. % to 5 wt. %, from 3.0 wt. % to 4
wt. %, from 3.0 wt. % to 3.3 wt. %, or approximately 2.7 wt. % wt.
% total sulfur content by weight of the upgraded product 152. The
upgraded product 152 may include less than 1.2 wt. % wt. % total
nitrogen content by weight of the upgraded product 152. In
embodiments, the upgraded product 152 may include from 0.01 wt. %
to 2 wt. %, from 0.01 wt. % to 1.1 wt. %, from 0.01 wt. % to 1.0
wt. %, from 0.01 wt. % to 0.8 wt. %, from 0.01 wt. % to 0.6 wt. %,
from 0.01 wt. % to 0.4 wt. %, from 0.01 wt. % to 0.2 wt. %, from
0.01 wt. % to 0.1 wt. %, from 0.1 wt. % to 2 wt. %, from 0.1 wt. %
to 1.1 wt. %, from 0.1 wt. % to 1.0 wt. %, from 0.1 wt. % to 0.8
wt. %, from 0.1 wt. % to 0.6 wt. %, from 0.1 wt. % to 0.4 wt. %,
from 0.1 wt. % to 0.2 wt. %, from 0.2 wt. % to 2 wt. %, from 0.2
wt. % to 1.1 wt. %, from 0.2 wt. % to 1.0 wt. %, from 0.2 wt. % to
0.8 wt. %, from 0.2 wt. % to 0.6 wt. %, from 0.2 wt. % to 0.4 wt.
%, from 0.4 wt. % to 2 wt. %, from 0.4 wt. % to 1.1 wt. %, from 0.4
wt. % to 1.0 wt. %, from 0.4 wt. % to 0.8 wt. %, from 0.4 wt. % to
0.6 wt. %, from 0.6 wt. % to 2 wt. %, from 0.6 wt. % to 1.1 wt. %,
from 0.6 wt. % to 1.0 wt. %, from 0.6 wt. % to 0.8 wt. %, from 0.8
wt. % to 2 wt. %, from 0.8 wt. % to 1.1 wt. %, from 0.8 wt. % to
1.0 wt. %, from 1.0 wt. % to 2 wt. %, from 1.0 wt. % to 1.1 wt. %,
or approximately 0.9 wt. % wt. % total nitrogen content by weight
of the upgraded product 152. The upgraded product 152 may include
less than 4.8 wt. % asphaltene (heptane-insoluble) by weight of the
upgraded product 152. In embodiments, the upgraded product 152 may
include from 0.01 wt. % to 6 wt. %, from 0.01 wt. % to 5 wt. %,
from 0.01 wt. % to 4.7 wt. %, from 0.01 wt. % to 4.0 wt. %, from
0.01 wt. % to 3.0 wt. %, from 0.01 wt. % to 2.5 wt. %, from 0.01
wt. % to 2.0 wt. %, from 0.01 wt. % to 1.8 wt. %, from 0.01 wt. %
to 1.6 wt. %, from 0.01 wt. % to 1.0 wt. %, from 0.01 wt. % to 0.8
wt. %, from 0.01 wt. % to 0.6 wt. %, from 0.01 wt. % to 0.4 wt. %,
from 0.01 wt. % to 0.2 wt. %, from 0.01 wt. % to 0.1 wt. %, from
0.1 wt. % to 6 wt. %, from 0.1 wt. % to 5 wt. %, from 0.1 wt. % to
4.7 wt. %, from 0.1 wt. % to 4.0 wt. %, from 0.1 wt. % to 3.0 wt.
%, from 0.1 wt. % to 2.5 wt. %, from 0.1 wt. % to 2.0 wt. %, from
0.1 wt. % to 1.8 wt. %, from 0.1 wt. % to 1.6 wt. %, from 0.1 wt. %
to 1.0 wt. %, from 0.1 wt. % to 0.8 wt. %, from 0.1 wt. % to 0.6
wt. %, from 0.1 wt. % to 0.4 wt. %, from 0.1 wt. % to 0.2 wt. %,
from 0.2 wt. % to 6 wt. %, from 0.2 wt. % to 5 wt. %, from 0.2 wt.
% to 4.7 wt. %, from 0.2 wt. % to 4.0 wt. %, from 0.2 wt. % to 3.0
wt. %, from 0.2 wt. % to 2.5 wt. %, from 0.2 wt. % to 2.0 wt. %,
from 0.2 wt. % to 1.8 wt. %, from 0.2 wt. % to 1.6 wt. %, from 0.2
wt. % to 1.0 wt. %, from 0.2 wt. % to 0.8 wt. %, from 0.2 wt. % to
0.6 wt. %, from 0.2 wt. % to 0.4 wt. %, from 0.4 wt. % to 6 wt. %,
from 0.4 wt. % to 5 wt. %, from 0.4 wt. % to 4.7 wt. %, from 0.4
wt. % to 4.0 wt. %, from 0.4 wt. % to 3.0 wt. %, from 0.4 wt. % to
2.5 wt. %, from 0.4 wt. % to 2.0 wt. %, from 0.4 wt. % to 1.8 wt.
%, from 0.4 wt. % to 1.6 wt. %, from 0.4 wt. % to 1.0 wt. %, from
0.4 wt. % to 0.8 wt. %, from 0.4 wt. % to 0.6 wt. %, from 0.6 wt. %
to 6 wt. %, from 0.6 wt. % to 5 wt. %, from 0.6 wt. % to 4.7 wt. %,
from 0.6 wt. % to 4.0 wt. %, from 0.6 wt. % to 3.0 wt. %, from 0.6
wt. % to 2.5 wt. %, from 0.6 wt. % to 2.0 wt. %, from 0.6 wt. % to
1.8 wt. %, from 0.6 wt. % to 1.6 wt. %, from 0.6 wt. % to 1.0 wt.
%, from 0.6 wt. % to 0.8 wt. %, from 0.8 wt. % to 6 wt. %, from 0.8
wt. % to 5 wt. %, from 0.8 wt. % to 4.7 wt. %, from 0.8 wt. % to
4.0 wt. %, from 0.8 wt. % to 3.0 wt. %, from 0.8 wt. % to 2.5 wt.
%, from 0.8 wt. % to 2.0 wt. %, from 0.8 wt. % to 1.8 wt. %, from
0.8 wt. % to 1.6 wt. %, from 0.8 wt. % to 1.0 wt. %, from 1.0 wt. %
to 6 wt. %, from 1.0 wt. % to 5 wt. %, from 1.0 wt. % to 4.7 wt. %,
from 1.0 wt. % to 4.0 wt. %, from 1.0 wt. % to 3.0 wt. %, from 1.0
wt. % to 2.5 wt. %, from 1.0 wt. % to 2.0 wt. %, from 1.0 wt. % to
1.8 wt. %, from 1.0 wt. % to 1.6 wt. %, from 1.6 wt. % to 6 wt. %,
from 1.6 wt. % to 5 wt. %, from 1.6 wt. % to 4.7 wt. %, from 1.6
wt. % to 4.0 wt. %, from 1.6 wt. % to 3.0 wt. %, from 1.6 wt. % to
2.5 wt. %, from 1.6 wt. % to 2.0 wt. %, from 1.6 wt. % to 1.8 wt.
%, from 1.8 wt. % to 6 wt. %, from 1.8 wt. % to 5 wt. %, from 1.8
wt. % to 4.7 wt. %, from 1.8 wt. % to 4.0 wt. %, from 1.8 wt. % to
3.0 wt. %, from 1.8 wt. % to 2.5 wt. %, from 1.8 wt. % to 2.0 wt.
%, from 2.0 wt. % to 6 wt. %, from 2.0 wt. % to 5 wt. %, from 2.0
wt. % to 4.7 wt. %, from 2.0 wt. % to 4.0 wt. %, from 2.0 wt. % to
3.0 wt. %, from 2.0 wt. % to 2.5 wt. %, from 2.5 wt. % to 6 wt. %,
from 2.5 wt. % to 5 wt. %, from 2.5 wt. % to 4.7 wt. %, from 2.5
wt. % to 4.0 wt. %, from 2.5 wt. % to 3.0 wt. %, from 3.0 wt. % to
6 wt. %, from 3.0 wt. % to 5 wt. %, from 3.0 wt. % to 4.7 wt. %,
from 3.0 wt. % to 4.0 wt. %, from 4.0 wt. % to 6 wt. %, from 4.0
wt. % to 5 wt. %, or approximately 1.7 wt. % asphaltene
(heptane-insoluble) by weight of the upgraded product
152. The upgraded product 152 may include less than 83 parts per
million (ppm) metals. In embodiments, the metals may be vanadium,
nickel, or both. In embodiments, the upgraded product 152 may
include from 1 ppm to 100 ppm, from 1 ppm to 82 ppm, from 1 ppm to
50 ppm, from 1 ppm to 25 ppm, from 1 ppm to 15 ppm, from 1 ppm to
10 ppm, from 1 ppm to 8 ppm, from 1 ppm to 5 ppm, from 1 ppm to 3
ppm, from 3 ppm to 100 ppm, from 3 ppm to 82 ppm, from 3 ppm to 50
ppm, from 3 ppm to 25 ppm, from 3 ppm to 15 ppm, from 3 ppm to 10
ppm, from 3 ppm to 8 ppm, from 3 ppm to 5 ppm, from 5 ppm to 100
ppm, from 5 ppm to 82 ppm, from 5 ppm to 50 ppm, from 5 ppm to 25
ppm, from 5 ppm to 15 ppm, from 5 ppm to 10 ppm, from 5 ppm to 8
ppm, from 8 ppm to 100 ppm, from 8 ppm to 82 ppm, from 8 ppm to 50
ppm, from 8 ppm to 25 ppm, from 8 ppm to 15 ppm, from 8 ppm to 10
ppm, from 10 ppm to 100 ppm, from 10 ppm to 82 ppm, from 10 ppm to
50 ppm, from 10 ppm to 25 ppm, from 10 ppm to 15 ppm, from 15 ppm
to 100 ppm, from 15 ppm to 82 ppm, from 15 ppm to 50 ppm, from 15
ppm to 25 ppm, or approximately 9 ppm metals. The upgraded product
152 may have a viscosity at 50.degree. C. of less than 640
centiStokes (cSt). In embodiments, the upgraded product 152 may
have a viscosity at 50.degree. C. from 10 to 639 cSt, from 10 cSt
to 600 cSt, from 10 cSt to 400 cSt, from 10 cSt to 200 cSt, from 10
cSt to 150 cSt, from 10 cSt to 100 cSt, from 10 cSt to 90 cSt, from
10 cSt to 88 cSt, from 10 cSt to 70 cSt, from 10 cSt to 50 cSt,
from 10 cSt to 35 cSt, from 10 cSt to 28 cSt, from 10 cSt to 26
cSt, from 10 cSt to 20 cSt, from 20 cSt to 639 cSt, from 20 cSt to
600 cSt, from 20 cSt to 400 cSt, from 20 cSt to 200 cSt, from 20
cSt to 150 cSt, from 20 cSt to 100 cSt, from 20 cSt to 90 cSt, from
20 cSt to 88 cSt, from 20 cSt to 70 cSt, from 20 cSt to 50 cSt,
from 20 cSt to 35 cSt, from 20 cSt to 28 cSt, from 20 cSt to 26
cSt, from 26 cSt to 639 cSt, from 26 cSt to 600 cSt, from 26 cSt to
400 cSt, from 26 cSt to 200 cSt, from 26 cSt to 150 cSt, from 26
cSt to 100 cSt, from 26 cSt to 90 cSt, from 26 cSt to 88 cSt, from
26 cSt to 70 cSt, from 26 cSt to 50 cSt, from 26 cSt to 35 cSt,
from 26 cSt to 28 cSt, from 28 cSt to 639 cSt, from 28 cSt to 600
cSt, from 28 cSt to 400 cSt, from 28 cSt to 200 cSt, from 28 cSt to
150 cSt, from 28 cSt to 100 cSt, from 28 cSt to 90 cSt, from 28 cSt
to 88 cSt, from 28 cSt to 70 cSt, from 28 cSt to 50 cSt, from 28
cSt to 35 cSt, from 35 cSt to 639 cSt, from 35 cSt to 600 cSt, from
35 cSt to 400 cSt, from 35 cSt to 200 cSt, from 35 cSt to 150 cSt,
from 35 cSt to 100 cSt, from 35 cSt to 90 cSt, from 35 cSt to 88
cSt, from 35 cSt to 70 cSt, from 35 cSt to 50 cSt, from 50 cSt to
639 cSt, from 50 cSt to 600 cSt, from 50 cSt to 400 cSt, from 50
cSt to 200 cSt, from 50 cSt to 150 cSt, from 50 cSt to 100 cSt,
from 50 cSt to 90 cSt, from 50 cSt to 88 cSt, from 50 cSt to 70
cSt, from 70 cSt to 639 cSt, from 70 cSt to 600 cSt, from 70 cSt to
400 cSt, from 70 cSt to 200 cSt, from 70 cSt to 150 cSt, from 70
cSt to 100 cSt, from 70 cSt to 90 cSt, from 70 cSt to 88 cSt, from
88 cSt to 639 cSt, from 88 cSt to 600 cSt, from 88 cSt to 400 cSt,
from 88 cSt to 200 cSt, from 88 cSt to 150 cSt, from 88 cSt to 100
cSt, from 88 cSt to 90 cSt, or approximately 89 cSt.
[0053] The upgraded product 152 may then be cooled by cooler 154 to
a temperature from 150.degree. C. to 250.degree. C., from
150.degree. C. to 225.degree. C., from 150.degree. C. to
200.degree. C., from 150.degree. C. to 175.degree. C., from
175.degree. C. to 250.degree. C., from 175.degree. C. to
225.degree. C., from 175.degree. C. to 200.degree. C., from
200.degree. C. to 250.degree. C., from 200.degree. C. to
225.degree. C., or from 225.degree. C. to 250.degree. C. to form a
cooled, upgraded product 156. Various cooling devices are
contemplated for the cooler 154, such as a heat exchanger.
[0054] Referring again to FIG. 1, upon exiting the cooler 154, the
pressure of the cooled, upgraded product 156 may be reduced MPa to
create a depressurized, upgraded product 159, which may have a
pressure from 0.01 MPa to 1.0 MPa, from 0.01 MPa to 0.8 MPa, from
0.01 MPa to 0.5 MPa, from 0.01 MPa to 0.3 MPa, from 0.01 MPa to 0.1
MPa, from 0.01 MPa to 0.08 MPa, from 0.01 MPa to 0.05 MPa, from
0.01 MPa to 0.03 MPa, from 0.03 MPa to 1.0 MPa, from 0.03 MPa to
0.8 MPa, from 0.03 MPa to 0.5 MPa, from 0.03 MPa to 0.3 MPa, from
0.03 MPa to 0.1 MPa, from 0.03 MPa to 0.08 MPa, from 0.03 MPa to
0.05 MPa, from 0.05 MPa to 1.0 MPa, from 0.05 MPa to 0.8 MPa, from
0.05 MPa to 0.5 MPa, from 0.05 MPa to 0.3 MPa, from 0.05 MPa to 0.1
MPa, from 0.05 MPa to 0.08 MPa, from 0.08 MPa to 1.0 MPa, from 0.08
MPa to 0.8 MPa, from 0.08 MPa to 0.5 MPa, from 0.08 MPa to 0.3 MPa,
from 0.08 MPa to 0.1 MPa, from 0.1 MPa to 1.0 MPa, from 0.1 MPa to
0.8 MPa, from 0.1 MPa to 0.5 MPa, from 0.1 MPa to 0.3 MPa, from 0.3
MPa to 1.0 MPa, from 0.3 MPa to 0.8 MPa, from 0.3 MPa to 0.5 MPa,
from 0.5 MPa to 1.0 MPa, from 0.5 MPa to 0.8 MPa, or from 0.8 MPa
to 1.0 MPa. The depressurizing can be achieved by many devices, for
example, a valve 158 as shown in FIGS. 1 and 2.
[0055] The depressurized, upgraded product 159 may then be passed
to a gas/oil/water separator 160. The gas/water separator 160 may
separate the depressurized, upgraded product 159 into a first gas
fraction 164, a liquid oil fraction 162, and a first water fraction
166. The gas/water separator 160 may be any separator known in the
industry. While the gas/oil/water separator 160 may separate the
depressurized, upgraded product 159 into at least a first gas
fraction 164 comprising CO, CO.sub.2, NH.sub.3, H.sub.2, H.sub.2S,
C.sub.1, C.sub.2, C.sub.3, C.sub.4, C.sub.5, C.sub.6, or
combinations thereof; a liquid oil fraction 162; and a first water
fraction 166, it should be appreciated that additional fractions
may also be produced. In embodiments, the first gas fraction 164
may include from 0.5 wt. % to 3 wt. %, from 0.5 wt. % to 2 wt. %,
from 0.5 wt. % to 1.5 wt. %, 0.5 wt. % to 1.2 wt. %, from 0.8 wt. %
to 3 wt. %, from 0.8 wt. % to 2 wt. %, from 0.8 wt. % to 1.5 wt. %,
from 0.8 wt. % to 1.2 wt. %, or approximately 1 wt. % H.sub.2 by
weight of the first gas fraction 164. In embodiments, the first gas
fraction 164 may include from 2 wt. % to 50 wt. %, from 2 wt. % to
25 wt. %, from 5 wt. % to 50 wt. %, from 5 wt. % to 25 wt. %, from
5 wt. % to 15 wt. %, from 5 wt. % to 13 wt. %, from 8 wt. % to 50
wt. %, from 8 wt. % to 25 wt. %, from 8 wt. % to 15 wt. %, from 8
wt. % to 13 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 25
wt. %, from 10 wt. % to 15 wt. %, from 10 wt. % to 13 wt. %, from
11 wt. % to 50 wt. %, from 11 wt. % to 25 wt. %, from 11 wt. % to
15 wt. %, from 11 wt. % to 13 wt. %, or approximately 12 wt. %
C.sub.1 by weight of the first gas fraction 164. In embodiments,
the first gas fraction 164 may include from 2 wt. % to 50 wt. %,
from from 2 wt. % to 25 wt. %, from 5 wt. % to 50 wt. %, from 5 wt.
% to 25 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %,
from 8 wt. % to 15 wt. %, from 8 wt. % to 12 wt. %, from 10 wt. %
to 15 wt. %, from 10 wt. % to 12 wt. %, or approximately 11 wt. %
C.sub.2 by weight of the first gas fraction 164. In embodiments,
the first gas fraction 164 may include from 2 wt. % to 50 wt. %,
from 2 wt. % to 25 wt. %, from 2 wt. % to 15 wt. %, from 5 wt. % to
50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 15 wt. %, from
5 wt. % to 13 wt. %, from 5 wt. % to 11 wt. %, from 7 wt. % to 15
wt. %, from 7 wt. % to 13 wt. %, from 7 wt. % to 11 wt. %, from 9
wt. % to 15 wt. %, from 9 wt. % to 13 wt. %, from 9 wt. % to 11 wt.
%, or approximately 10 wt. % C.sub.3 by weight of the first gas
fraction 164. In embodiments, the first gas fraction 164 may
include from 1 wt. % to 50 wt. %, from 1 wt. % to 25 wt. %, from 3
wt. % to 15 wt. %, from 3 wt. % to 12 wt. %, from 3 wt. % to 10 wt.
%, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %, from 5 wt. %
to 10 wt. %, from 8 wt. % to 15 wt. %, from 8 wt. % to 12 wt. %,
from 8 wt. % to 10 wt. %, or approximately 9 wt. % C.sub.4 by
weight of the first gas fraction 164. In embodiments, the first gas
fraction 164 may include from 0 wt. % to 50 wt. %, from 0 wt. % to
25 wt. %, from 0 wt. % to 10 wt. %, from 0 wt. % to 5 wt. %, from 0
wt. % to 1 wt. %, from 1 wt. % to 15 wt. %, from 1 wt. % to 10 wt.
%, from 1 wt. % to 8 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. %
to 8 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 12 wt. %,
from 5 wt. % to 10 wt. %, from 5 wt. % to 8 wt. %, from 6 wt. % to
10 wt. %, from 6 wt. % to 8 wt. %, or approximately 7 wt. % C.sub.5
by weight of the first gas fraction 164. The first gas fraction 164
may include from 0 wt. % to 25 wt. %, from 0 wt. % to 10 wt. %,
from 0 wt. % to 1 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to
10 wt. %, from 1 wt. % to 7 wt. %, from 1 wt. % to 5 wt. %, from 2
wt. % to 10 wt. %, from 2 wt. % to 7 wt. %, from 2 wt. % to 5 wt.
%, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt. %, from 3 wt. %
to 5 wt. %, or approximately 4 wt. % C.sub.6 by weight of the first
gas fraction 164. In embodiments, the first gas fraction 164 may
include from 0 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1
wt. % to 5 wt. %, from 1 wt. % to 3 wt. %, or approximately 2 wt. %
CO by weight of the first gas fraction 164. In embodiments, the
first gas fraction 164 may include from 0 wt. % to 25 wt. %, from 0
wt. % to 10 wt. %, from 0 wt. % to 1 wt. %, from 1 wt. % to 25 wt.
%, from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, from 1 wt. %
to 5 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 7 wt. %, from
2 wt. % to 5 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt.
%, from 3 wt. % to 5 wt. %, or approximately 4 wt. % CO.sub.2 by
weight of the first gas fraction 164. In embodiments, the first gas
fraction 164 may include from 1 wt. % to 50 wt. %, from 1 wt. % to
35 wt. %, from 1 wt. % to 30 wt. %, from 1 wt. % to 26 wt. %, from
10 wt. % to 50 wt. %, from 10 wt. % to 35 wt. %, from 10 wt. % to
30 wt. %, from 10 wt. % to 26 wt. %, from 15 wt. % to 50 wt. %,
from 15 wt. % to 35 wt. %, from 15 wt. % to 30 wt. %, from 15 wt. %
to 26 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. % to 35 wt. %,
from 20 wt. % to 30 wt. %, from 20 wt. % to 26 wt. %, from 23 wt. %
to 50 wt. %, from 23 wt. % to 35 wt. %, from 23 wt. % to 30 wt. %,
from 23 wt. % to 26 wt. %, from 25 wt. % to 50 wt. %, from 25 wt. %
to 35 wt. %, from 25 wt. % to 30 wt. %, from 25 wt. % to 26 wt. %,
or approximately 25.6 wt. % H.sub.2S by weight of the first gas
fraction 164. In embodiments, the first gas fraction 164 may
include from 1 wt. % to 50 wt. %, from 1 wt. % to 25 wt. %, from 1
wt. % to 20 wt. %, from 1 wt. % to 15 wt. %, from 5 wt. % to 50 wt.
%, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. %
to 15 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 25 wt. %,
from 10 wt. % to 20 wt. %, from 10 wt. % to 15 wt. %, from 12 wt. %
to 50 wt. %, from 12 wt. % to 25 wt. %, from 12 wt. % to 20 wt. %,
from 12 wt. % to 15 wt. %, from 14 wt. % to 50 wt. %, from 14 wt. %
to 25 wt. %, from 14 wt. % to 20 wt. %, from 14 wt. % to 15 wt. %,
or approximately 14.6 wt. % NH.sub.3 by weight of the first gas
fraction 164. In embodiments, the first gas fraction 164 may
include no C.sub.5 or C.sub.6 components. In embodiments, the
liquid oil fraction 162 may have a T.sub.5 true boiling point (TBP)
of less than 500.degree. C., of less than 400.degree. C., of less
than 350.degree. C., of less than 325.degree. C., of less than
300.degree. C., of less than 275.degree. C., or of less than
260.degree. C. In embodiments, the liquid oil fraction 162 may have
a T.sub.5 TBP of from 25.degree. C. to 350.degree. C., from
25.degree. C. to 325.degree. C., from 25.degree. C. to 300.degree.
C., from 25.degree. C. to 275.degree. C., from 25.degree. C. to
250.degree. C., from 25.degree. C. to 225.degree. C., from
25.degree. C. to 200.degree. C., from 25.degree. C. to 175.degree.
C., from 25.degree. C. to 150.degree. C., from 25.degree. C. to
125.degree. C., from 25.degree. C. to 100.degree. C., from
25.degree. C. to 75.degree. C., from 25.degree. C. to 50.degree.
C., from 50.degree. C. to 350.degree. C., from 50.degree. C. to
325.degree. C., from 50.degree. C. to 300.degree. C., from
50.degree. C. to 275.degree. C., from 50.degree. C. to 250.degree.
C., from 50.degree. C. to 225.degree. C., from 50.degree. C. to
200.degree. C., from 50.degree. C. to 175.degree. C., from
50.degree. C. to 150.degree. C., from 50.degree. C. to 125.degree.
C., from 50.degree. C. to 100.degree. C., from 50.degree. C. to
75.degree. C., from 75.degree. C. to 350.degree. C., from
75.degree. C. to 325.degree. C., from 75.degree. C. to 300.degree.
C., from 75.degree. C. to 275.degree. C., from 75.degree. C. to
250.degree. C., from 75.degree. C. to 225.degree. C., from
75.degree. C. to 200.degree. C., from 75.degree. C. to 175.degree.
C., from 75.degree. C. to 150.degree. C., from 75.degree. C. to
125.degree. C., from 75.degree. C. to 100.degree. C., from
100.degree. C. to 350.degree. C., from 100.degree. C. to
325.degree. C., from 100.degree. C. to 300.degree. C., from
100.degree. C. to 275.degree. C., from 100.degree. C. to
250.degree. C., from 100.degree. C. to 225.degree. C., from
100.degree. C. to 200.degree. C., from 100.degree. C. to
175.degree. C., from 100.degree. C. to 150.degree. C., from
100.degree. C. to 125.degree. C., from 125.degree. C. to
350.degree. C., from 125.degree. C. to 325.degree. C., from
125.degree. C. to 300.degree. C., from 125.degree. C. to
275.degree. C., from 125.degree. C. to 250.degree. C., from
125.degree. C. to 225.degree. C., from 125.degree. C. to
200.degree. C., from 125.degree. C. to 175.degree. C., from
125.degree. C. to 150.degree. C., from 150.degree. C. to
350.degree. C., from 150.degree. C. to 325.degree. C., from
150.degree. C. to 300.degree. C., from 150.degree. C. to
275.degree. C., from 150.degree. C. to 250.degree. C., from
150.degree. C. to 225.degree. C., from 150.degree. C. to
200.degree. C., from 150.degree. C. to 175.degree. C., from
175.degree. C. to 350.degree. C., from 175.degree. C. to
325.degree. C., from 175.degree. C. to 300.degree. C., from
175.degree. C. to 275.degree. C., from 175.degree. C. to
250.degree. C., from 175.degree. C. to 225.degree. C., from
175.degree. C. to 200.degree. C., from 200.degree. C. to
350.degree. C., from 200.degree. C. to 325.degree. C., from
200.degree. C. to 300.degree. C., from 200.degree. C. to
275.degree. C., from 200.degree. C. to 250.degree. C., from
200.degree. C. to 225.degree. C., from 225.degree. C. to
350.degree. C., from 225.degree. C. to 325.degree. C., from
225.degree. C. to 300.degree. C., from 225.degree. C. to
275.degree. C., from 225.degree. C. to 250.degree. C., from
250.degree. C. to 350.degree. C., from 250.degree. C. to
325.degree. C., from 250.degree. C. to 300.degree. C., from
250.degree. C. to 275.degree. C., from 275.degree. C. to
350.degree. C., from 275.degree. C. to 325.degree. C., from
275.degree. C. to 300.degree. C., from 300.degree. C. to
350.degree. C., from 300.degree. C. to 325.degree. C., or from
325.degree. C. to 350.degree. C. The liquid oil fraction 162 may
have a T.sub.90 TBP of less than or equal to 650.degree. C., less
than or equal to 600.degree. C., less than or equal to 575.degree.
C., or less than or equal to 550.degree. C. In embodiments, the
liquid oil fraction 162 may have a T.sub.90 TBP from 200.degree. C.
to 650.degree. C., from 200.degree. C. to 600.degree. C., from
200.degree. C. to 575.degree. C., from 200.degree. C. to
550.degree. C., from 200.degree. C. to 540.degree. C., from
200.degree. C. to 530.degree. C., from 200.degree. C. to
525.degree. C., from 200.degree. C. to 500.degree. C., from
200.degree. C. to 450.degree. C., from 200.degree. C. to
400.degree. C., from 200.degree. C. to 300.degree. C., from
300.degree. C. to 650.degree. C., from 300.degree. C. to
600.degree. C., from 300.degree. C. to 575.degree. C., from
300.degree. C. to 550.degree. C., from 300.degree. C. to
540.degree. C., from 300.degree. C. to 530.degree. C., from
300.degree. C. to 525.degree. C., from 300.degree. C. to
500.degree. C., from 300.degree. C. to 450.degree. C., from
300.degree. C. to 400.degree. C., from 400.degree. C. to
650.degree. C., from 400.degree. C. to 600.degree. C., from
400.degree. C. to 575.degree. C., from 400.degree. C. to
550.degree. C., from 400.degree. C. to 540.degree. C., from
400.degree. C. to 530.degree. C., from 400.degree. C. to
525.degree. C., from 400.degree. C. to 500.degree. C., from
450.degree. C. to 650.degree. C., from 450.degree. C. to
600.degree. C., from 450.degree. C. to 575.degree. C., from
450.degree. C. to 550.degree. C., from 450.degree. C. to
540.degree. C., from 450.degree. C. to 530.degree. C., from
450.degree. C. to 525.degree. C., from 450.degree. C. to
500.degree. C., from 500.degree. C. to 650.degree. C., from
500.degree. C. to 600.degree. C., from 500.degree. C. to
575.degree. C., from 500.degree. C. to 550.degree. C., from
500.degree. C. to 540.degree. C., from 500.degree. C. to
530.degree. C., from 500.degree. C. to 525.degree. C., from
525.degree. C. to 650.degree. C., from 525.degree. C. to
600.degree. C., from 525.degree. C. to 575.degree. C., from
525.degree. C. to 550.degree. C., from 525.degree. C. to
540.degree. C., from 525.degree. C. to 530.degree. C., from
530.degree. C. to 650.degree. C., from 530.degree. C. to
600.degree. C., from 530.degree. C. to 575.degree. C., from
530.degree. C. to 550.degree. C., from 530.degree. C. to
540.degree. C., from 540.degree. C. to 650.degree. C., from
540.degree. C. to 600.degree. C., from 540.degree. C. to
575.degree. C., from 540.degree. C. to 550.degree. C., from
550.degree. C. to 650.degree. C., from 550.degree. C. to
600.degree. C., from 550.degree. C. to 575.degree. C., from
575.degree. C. to 650.degree. C., from 575.degree. C. to
600.degree. C., or from 600.degree. C. to 650.degree. C., where the
T.sub.90 TBP is greater than the T.sub.5 TBP previously described.
The liquid oil fraction 162 may have an API gravity from 12.degree.
to 45.degree., from 12.degree. to 35.degree., from 12.degree. to
30.degree., from 12.degree. to 27.degree., from 12.degree. to
25.degree., from 15.degree. to 45.degree., from 15.degree. to
35.degree., from 15.degree. to 30.degree., from 15.degree. to
27.degree., from 15.degree. to 25.degree., from 18.degree. to
45.degree., from 18.degree. to 35.degree., from 18.degree. to
30.degree., from 18.degree. to 27.degree., from 18.degree. to
25.degree., from 20.degree. to 45.degree., from 20.degree. to
35.degree., from 20.degree. to 30.degree., from 20.degree. to
27.degree., from 20.degree. to 25.degree., from 21.degree. to
45.degree., from 21.degree. to 35.degree., from 21.degree. to
30.degree., from 21.degree. to 27.degree., from 21.degree. to
25.degree., from 23.degree. to 45.degree., from 23.degree. to
35.degree., from 23.degree. to 30.degree., from 23.degree. to
27.degree., from 23.degree. to 25.degree., or approximately
24.degree.. The liquid oil fraction 162 may include less than 3.4
wt. % or less than 2.7 wt. % total sulfur content by weight of the
liquid oil fraction 162. In embodiments, the liquid oil fraction
162 may include from 0.1 wt. % to 5 wt. %, from 0.1 wt. % to 4 wt.
%, from 0.1 wt. % to 3.3 wt. %, from 0.1 wt. % to 3.0 wt. %, from
0.1 wt. % to 2.8 wt. %, from 0.1 wt. % to 2.6 wt. %, from 0.1 wt. %
to 2.3 wt. %, from 0.1 wt. % to 2.0 wt. %, from 0.1 wt. % to 1.8
wt. %, from 0.1 wt. % to 1.6 wt. %, from 0.1 wt. % to 1.3 wt. %,
from 0.1 wt. % to 1.0 wt. %, from 0.1 wt. % to 0.5 wt. %, from 0.5
wt. % to 5 wt. %, from 0.5 wt. % to 4 wt. %, from 0.5 wt. % to 3.3
wt. %, from 0.5 wt. % to 3.0 wt. %, from 0.5 wt. % to 2.8 wt. %,
from 0.5 wt. % to 2.6 wt. %, from 0.5 wt. % to 2.3 wt. %, from 0.5
wt. % to 2.0 wt. %, from 0.5 wt. % to 1.8 wt. %, from 0.5 wt. % to
1.6 wt. %, from 0.5 wt. % to 1.3 wt. %, from 0.5 wt. % to 1.0 wt.
%, from 1.0 wt. % to 5 wt. %, from 1.0 wt. % to 4 wt. %, from 1.0
wt. % to 3.3 wt. %, from 1.0 wt. % to 3.0 wt. %, from 1.0 wt. % to
2.8 wt. %, from 1.0 wt. % to 2.6 wt. %, from 1.0 wt. % to 2.3 wt.
%, from 1.0 wt. % to 2.0 wt. %, from 1.0 wt. % to 1.8 wt. %, from
1.0 wt. % to 1.6 wt. %, from 1.0 wt. % to 1.3 wt. %, from 1.3 wt. %
to 5 wt. %, from 1.3 wt. % to 4 wt. %, from 1.3 wt. % to 3.3 wt. %,
from 1.3 wt. % to 3.0 wt. %, from 1.3 wt. % to 2.8 wt. %, from 1.3
wt. % to 2.6 wt. %, from 1.3 wt. % to 2.3 wt. %, from 1.3 wt. % to
2.0 wt. %, from 1.3 wt. % to 1.8 wt. %, from 1.3 wt. % to 1.6 wt.
%, from 1.6 wt. % to 5 wt. %, from 1.6 wt. % to 4 wt. %, from 1.6
wt. % to 3.3 wt. %, from 1.6 wt. % to 3.0 wt. %, from 1.6 wt. % to
2.8 wt. %, from 1.6 wt. % to 2.6 wt. %, from 1.6 wt. % to 2.3 wt.
%, from 1.6 wt. % to 2.0 wt. %, from 1.6 wt. % to 1.8 wt. %, or
approximately 1.7 wt. % total sulfur content by weight of the
liquid oil fraction
162. The liquid oil fraction 162 may include less than 1.2 wt. % or
less than 0.9 wt. % total nitrogen content by weight of the liquid
oil fraction 162. In embodiments, the liquid oil fraction 162 may
include from 0.01 wt. % to 2 wt. %, from 0.01 wt. % to 1.1 wt. %,
from 0.01 wt. % to 1.0 wt. %, from 0.01 wt. % to 0.8 wt. %, from
0.01 wt. % to 0.6 wt. %, from 0.01 wt. % to 0.4 wt. %, from 0.01
wt. % to 0.2 wt. %, from 0.01 wt. % to 0.1 wt. %, from 0.1 wt. % to
2 wt. %, from 0.1 wt. % to 1.1 wt. %, from 0.1 wt. % to 1.0 wt. %,
from 0.1 wt. % to 0.8 wt. %, from 0.1 wt. % to 0.6 wt. %, from 0.1
wt. % to 0.4 wt. %, from 0.1 wt. % to 0.2 wt. %, from 0.2 wt. % to
2 wt. %, from 0.2 wt. % to 1.1 wt. %, from 0.2 wt. % to 1.0 wt. %,
from 0.2 wt. % to 0.8 wt. %, from 0.2 wt. % to 0.6 wt. %, from 0.2
wt. % to 0.4 wt. %, from 0.4 wt. % to 2 wt. %, from 0.4 wt. % to
1.1 wt. %, from 0.4 wt. % to 1.0 wt. %, from 0.4 wt. % to 0.8 wt.
%, from 0.4 wt. % to 0.6 wt. %, or approximately 0.3 wt. % total
nitrogen content by weight of the liquid oil fraction 162. The
liquid oil fraction 162 may include less than 4.8 wt. % or less
than 1.7 wt. % asphaltene (heptane-insoluble) by weight of the
liquid oil fraction 162. In embodiments, the liquid oil fraction
162 may include from 0.01 wt. % to 6 wt. %, from 0.01 wt. % to 5
wt. %, from 0.01 wt. % to 4.7 wt. %, from 0.01 wt. % to 4.0 wt. %,
from 0.01 wt. % to 3.0 wt. %, from 0.01 wt. % to 2.5 wt. %, from
0.01 wt. % to 2.0 wt. %, from 0.01 wt. % to 1.8 wt. %, from 0.01
wt. % to 1.6 wt. %, from 0.01 wt. % to 1.0 wt. %, from 0.01 wt. %
to 0.8 wt. %, from 0.01 wt. % to 0.6 wt. %, from 0.01 wt. % to 0.4
wt. %, from 0.01 wt. % to 0.2 wt. %, from 0.01 wt. % to 0.1 wt. %,
from 0.1 wt. % to 6 wt. %, from 0.1 wt. % to 5 wt. %, from 0.1 wt.
% to 4.7 wt. %, from 0.1 wt. % to 4.0 wt. %, from 0.1 wt. % to 3.0
wt. %, from 0.1 wt. % to 2.5 wt. %, from 0.1 wt. % to 2.0 wt. %,
from 0.1 wt. % to 1.8 wt. %, from 0.1 wt. % to 1.6 wt. %, from 0.1
wt. % to 1.0 wt. %, from 0.1 wt. % to 0.8 wt. %, from 0.1 wt. % to
0.6 wt. %, from 0.1 wt. % to 0.4 wt. %, from 0.1 wt. % to 0.2 wt.
%, from 0.2 wt. % to 6 wt. %, from 0.2 wt. % to 5 wt. %, from 0.2
wt. % to 4.7 wt. %, from 0.2 wt. % to 4.0 wt. %, from 0.2 wt. % to
3.0 wt. %, from 0.2 wt. % to 2.5 wt. %, from 0.2 wt. % to 2.0 wt.
%, from 0.2 wt. % to 1.8 wt. %, from 0.2 wt. % to 1.6 wt. %, from
0.2 wt. % to 1.0 wt. %, from 0.2 wt. % to 0.8 wt. %, from 0.2 wt. %
to 0.6 wt. %, from 0.2 wt. % to 0.4 wt. %, from 0.4 wt. % to 6 wt.
%, from 0.4 wt. % to 5 wt. %, from 0.4 wt. % to 4.7 wt. %, from 0.4
wt. % to 4.0 wt. %, from 0.4 wt. % to 3.0 wt. %, from 0.4 wt. % to
2.5 wt. %, from 0.4 wt. % to 2.0 wt. %, from 0.4 wt. % to 1.8 wt.
%, from 0.4 wt. % to 1.6 wt. %, from 0.4 wt. % to 1.0 wt. %, from
0.4 wt. % to 0.8 wt. %, from 0.4 wt. % to 0.6 wt. %, or
approximately 0.3 wt. % asphaltene (heptane-insoluble) by weight of
the liquid oil fraction 162. The upgraded product stream 152 may
include less than 83 parts per million (ppm) or less than 9 ppm
metals. In embodiments, the metals may be vanadium, nickel, or
both. In embodiments, the upgraded product stream 152 may include
from 1 ppm to 100 ppm, from 1 ppm to 82 ppm, from 1 ppm to 50 ppm,
from 1 ppm to 25 ppm, from 1 ppm to 15 ppm, from 1 ppm to 10 ppm,
from 1 ppm to 8 ppm, from 1 ppm to 5 ppm, from 1 ppm to 3 ppm, from
3 ppm to 100 ppm, from 3 ppm to 82 ppm, from 3 ppm to 50 ppm, from
3 ppm to 25 ppm, from 3 ppm to 15 ppm, from 3 ppm to 10 ppm, from 3
ppm to 8 ppm, from 3 ppm to 5 ppm, or approximately 4 ppm metals.
The liquid oil fraction 162 may have a viscosity at 50.degree. C.
of less than 640 centiStokes (cSt) or less than 89 cSt. In
embodiments, the liquid oil fraction 162 may have a viscosity at
50.degree. C. from 10 cSt to 639 cSt, from 10 cSt to 600 cSt, from
10 cSt to 400 cSt, from 10 cSt to 200 cSt, from 10 cSt to 150 cSt,
from 10 cSt to 100 cSt, from 10 cSt to 90 cSt, from 10 cSt to 88
cSt, from 10 cSt to 70 cSt, from 10 cSt to 50 cSt, from 10 cSt to
35 cSt, from 10 cSt to 28 cSt, from 10 cSt to 26 cSt, from 10 cSt
to 20 cSt, from 20 cSt to 639 cSt, from 20 cSt to 600 cSt, from 20
cSt to 400 cSt, from 20 cSt to 200 cSt, from 20 cSt to 150 cSt,
from 20 cSt to 100 cSt, from 20 cSt to 90 cSt, from 20 cSt to 88
cSt, from 20 cSt to 70 cSt, from 20 cSt to 50 cSt, from 20 cSt to
35 cSt, from 20 cSt to 28 cSt, from 20 cSt to 26 cSt, from 26 cSt
to 639 cSt, from 26 cSt to 600 cSt, from 26 cSt to 400 cSt, from 26
cSt to 200 cSt, from 26 cSt to 150 cSt, from 26 cSt to 100 cSt,
from 26 cSt to 90 cSt, from 26 cSt to 88 cSt, from 26 cSt to 70
cSt, from 26 cSt to 50 cSt, from 26 cSt to 35 cSt, from 26 cSt to
28 cSt, or approximately 27 cSt.
[0056] As shown in FIG. 1, the first gas fraction 164 may be passed
to a gas storage tank 165, the liquid oil fraction 162 may be
passed to an oil storage tank 163, and the first water fraction 166
may be passed to a water storage tank 167.
[0057] FIG. 2 schematically depicts a process 200 for treating a
disulfide oil composition 205, according to embodiments described.
For the reference numbers and descriptions of the process 200 that
correlate with previous reference numbers and descriptions for
process 100, it is intended that all previous description for
process 100 relevant to the reference numbers used in process 200
should be incorporated. For example, and not by way of limitation,
water stream 110 in process 200 is meant to correspond and
incorporate all previous description of water stream 110 in process
100.
[0058] The disulfide oil composition 205 may refer to any disulfide
composition. In embodiments, it is contemplated that the disulfide
oil composition 205 may be the product of a naphtha and LPG
mercaptan oxidation unit 203, which is a refining technology that
selectively removes mercaptans sulfur by caustic extraction and
generates disulfide oil (RSSR), by oxidizing sulfur rich caustic
solution, as byproduct. In embodiments, the disulfide composition
205 may include dimethyl disulfide, methyl ethyl disulfide, methyl
isopropyl disulfide, diethyl disulfide, methyl n-propyl disulfide,
ethyl isopropyl disulfide, ethyl n-propyl disulfide, di-isopropyl
disulfide, ethyl n-butyl disulfide, dipropyl disulfide, dimethyl
trisulfide, diethyl trisulfide, methyl propyl trisulfide,
di-isopropyl trisulfide, or combinations thereof. It is noted that
different components may have different names but the same chemical
formula.
[0059] The disulfide oil composition 205 may include from 5 wt. %
to 50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 20 wt. %,
from 5 wt. % to 18 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to
13 wt. %, from 5 wt. % to 10 wt. %, from 5 wt. % to 8 wt. %, from 8
wt. % to 50 wt. %, from 8 wt. % to 25 wt. %, from 8 wt. % to 20 wt.
%, from 8 wt. % to 18 wt. %, from 8 wt. % to 15 wt. %, from 8 wt. %
to 13 wt. %, from 8 wt. % to 10 wt. %, from 10 wt. % to 50 wt. %,
from 10 wt. % to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. %
to 18 wt. %, from 10 wt. % to 15 wt. %, from 10 wt. % to 13 wt. %,
from 13 wt. % to 50 wt. %, from 13 wt. % to 25 wt. %, from 13 wt. %
to 20 wt. %, from 13 wt. % to 18 wt. %, from 13 wt. % to 15 wt. %,
from 15 wt. % to 50 wt. %, from 15 wt. % to 25 wt. %, from 15 wt. %
to 20 wt. %, from 15 wt. % to 18 wt. %, from 18 wt. % to 50 wt. %,
from 18 wt. % to 25 wt. %, from 18 wt. % to 20 wt. %, from 20 wt. %
to 50 wt. %, from 20 wt. % to 25 wt. %, from 25 wt. % to 50 wt. %,
or approximately 14 wt. % C.sub.2H.sub.6S.sub.2 by weight of the
disulfide oil composition 205. In embodiments,
C.sub.2H.sub.6S.sub.2 may include dimethyl disulfide.
[0060] The disulfide oil composition 205 may include include from
10 wt. % to 50 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to
35 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 28 wt. %,
from 10 wt. % to 25 wt. %, from 10 wt. % to 23 wt. %, from 10 wt. %
to 20 wt. %, from 10 wt. % to 15 wt. %, from 15 wt. % to 50 wt. %,
from 15 wt. % to 40 wt. %, from 15 wt. % to 35 wt. %, from 15 wt. %
to 30 wt. %, from 15 wt. % to 28 wt. %, from 15 wt. % to 25 wt. %,
from 15 wt. % to 23 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. %
to 50 wt. %, from 20 wt. % to 40 wt. %, from 20 wt. % to 35 wt. %,
from 20 wt. % to 30 wt. %, from 20 wt. % to 28 wt. %, from 20 wt. %
to 25 wt. %, from 20 wt. % to 23 wt. %, from 23 wt. % to 50 wt. %,
from 23 wt. % to 40 wt. %, from 23 wt. % to 35 wt. %, from 23 wt. %
to 30 wt. %, from 23 wt. % to 28 wt. %, from 23 wt. % to 25 wt. %,
from 25 wt. % to 50 wt. %, from 25 wt. % to 40 wt. %, from 25 wt. %
to 35 wt. %, from 25 wt. % to 30 wt. %, from 25 wt. % to 28 wt. %,
from 28 wt. % to 50 wt. %, from 28 wt. % to 40 wt. %, from 28 wt. %
to 35 wt. %, from 28 wt. % to 30 wt. %, from 30 wt. % to 50 wt. %,
from 30 wt. % to 40 wt. %, from 30 wt. % to 35 wt. %, from 35 wt. %
to 50 wt. %, from 35 wt. % to 40 wt. %, from 40 to 50 wt. %, or
approximately 24 wt. % C.sub.3H.sub.8S.sub.2 by weight of the
disulfide oil composition 205. In embodiments,
C.sub.3H.sub.8S.sub.2 may include methyl ethyl disulfide.
[0061] The disulfide oil composition 205 may include from 10 wt. %
to 50 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to 35 wt. %,
from 10 wt. % to 30 wt. %, from 10 wt. % to 28 wt. %, from 10 wt. %
to 26 wt. %, from 10 wt. % to 23 wt. %, from 10 wt. % to 20 wt. %,
from 10 wt. % to 15 wt. %, from 15 wt. % to 50 wt. %, from 15 wt. %
to 40 wt. %, from 15 wt. % to 35 wt. %, from 15 wt. % to 30 wt. %,
from 15 wt. % to 28 wt. %, from 15 wt. % to 26 wt. %, from 15 wt. %
to 23 wt. %, from 15 wt. % to 20 wt. %, from 20 wt. % to 50 wt. %,
from 20 wt. % to 40 wt. %, from 20 wt. % to 35 wt. %, from 20 wt. %
to 30 wt. %, from 20 wt. % to 28 wt. %, from 20 wt. % to 26 wt. %,
from 20 wt. % to 23 wt. %, from 23 wt. % to 50 wt. %, from 23 wt. %
to 40 wt. %, from 23 wt. % to 35 wt. %, from 23 wt. % to 30 wt. %,
from 23 wt. % to 28 wt. %, from 23 wt. % to 26 wt. %, from 26 wt. %
to 50 wt. %, from 26 wt. % to 40 wt. %, from 26 wt. % to 35 wt. %,
from 26 wt. % to 30 wt. %, from 26 wt. % to 28 wt. %, from 28 wt. %
to 50 wt. %, from 28 wt. % to 40 wt. %, from 28 wt. % to 35 wt. %,
from 28 wt. % to 30 wt. %, from 30 wt. % to 50 wt. %, from 30 wt. %
to 40 wt. %, from 30 wt. % to 35 wt. %, from 35 wt. % to 50 wt. %,
from 35 wt. % to 40 wt. %, from 40 to 50 wt. %, or approximately 27
wt. % C.sub.4H.sub.10S.sub.2 by weight of the disulfide oil
composition 205. In embodiments, C.sub.4H.sub.10S.sub.2 may include
methyl isopropyl disulfide, diethyl disulfide, methyl n-propyl
disulfide, or combinations thereof.
[0062] The disulfide oil composition 205 may include from 5 wt. %
to 50 wt. %, from 5 wt. % to 25 wt. %, from 5 wt. % to 23 wt. %,
from 5 wt. % to 20 wt. %, from 5 wt. % to 18 wt. %, from 5 wt. % to
16 wt. %, from 5 wt. % to 14 wt. %, from 5 wt. % to 12 wt. %, from
5 wt. % to 10 wt. %, from 10 wt. % to 50 wt. %, from 10 wt. % to 25
wt. %, from 10 wt. % to 23 wt. %, from 10 wt. % to 20 wt. %, from
10 wt. % to 18 wt. %, from 10 wt. % to 16 wt. %, from 10 wt. % to
14 wt. %, from 10 wt. % to 12 wt. %, from 12 wt. % to 50 wt. %,
from 12 wt. % to 25 wt. %, from 12 wt. % to 23 wt. %, from 12 wt. %
to 20 wt. %, from 12 wt. % to 18 wt. %, from 12 wt. % to 16 wt. %,
from 12 wt. % to 14 wt. %, from 14 wt. % to 50 wt. %, from 14 wt. %
to 25 wt. %, from 14 wt. % to 23 wt. %, from 14 wt. % to 20 wt. %,
from 14 wt. % to 18 wt. %, from 14 wt. % to 16 wt. %, from 16 wt. %
to 50 wt. %, from 16 wt. % to 25 wt. %, from 16 wt. % to 23 wt. %,
from 16 wt. % to 20 wt. %, from 16 wt. % to 18 wt. %, from 18 wt. %
to 50 wt. %, from 18 wt. % to 25 wt. %, from 18 wt. % to 23 wt. %,
from 18 wt. % to 20 wt. %, from 20 wt. % to 50 wt. %, from 20 wt. %
to 25 wt. %, from 20 wt. % to 23 wt. %, from 23 wt. % to 50 wt. %,
from 23 wt. % to 25 wt. %, from 25 wt. % wt. % to 50 wt. %, or
approximately 15 wt. % C.sub.5H.sub.12S.sub.2 by weight of the
disulfide oil composition 205 by weight of the disulfide oil
composition 205. In embodiments, C.sub.5H.sub.12S.sub.2 may include
ethyl n-propyl disulfide, ethyl isopropyl disulfide, or both.
[0063] The disulfide oil composition 205 may include from 1 wt. %
to 20 wt. %, from 1 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %,
from 1 wt. % to 8 wt. %, from 1 wt. % to 6 wt. %, from 1 wt. % to 4
wt. %, from 1 wt. % to 2 wt. %, from 2 wt. % to 20 wt. %, from 2
wt. % to 15 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 8 wt.
%, from 2 wt. % to 6 wt. %, from 2 wt. % to 4 wt. %, from 4 wt. %
to 20 wt. %, from 4 wt. % to 15 wt. %, from 4 wt. % to 10 wt. %,
from 4 wt. % to 8 wt. %, from 4 wt. % to 6 wt. %, from 6 wt. % to
20 wt. %, from 6 wt. % to 15 wt. %, from 6 wt. % to 10 wt. %, from
6 wt. % to 8 wt. %, from 8 wt. % to 20 wt. %, from 8 wt. % to 15
wt. %, from 8 wt. % to 10 wt. %, from 10 wt. % to 20 wt. %, from 10
wt. % to 15 wt. %, from 15 wt. % to 20 wt. %, or approximately 5
wt. % C.sub.6H.sub.14S.sub.2 by weight of the disulfide oil
composition 205. In embodiments, C.sub.6H.sub.14S.sub.2 may include
di-isopropyl disulfide, di-propyl disulfide, ethyl n-butyl
disulfide, or combinations thereof.
[0064] The disulfide oil composition 205 may include from 1 wt. %
to 30 wt. %, from 1 wt. % to 25 wt. %, from 1 wt. % to 20 wt. %,
from 1 wt. % to 18 wt. %, from 1 wt. % to 16 wt. %, from 1 wt. % to
14 wt. %, from 1 wt. % to 12 wt. %, from 1 wt. % to 10 wt. %, from
1 wt. % to 5 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 25
wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 18 wt. %, from 5
wt. % to 16 wt. %, from 5 wt. % to 14 wt. %, from 5 wt. % to 12 wt.
%, from 5 wt. % to 10 wt. %, from 10 wt. % to 30 wt. %, from 10 wt.
% to 25 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 18 wt.
%, from 10 wt. % to 16 wt. %, from 10 wt. % to 14 wt. %, from 10
wt. % to 12 wt. %, from 12 wt. % to 30 wt. %, from 12 wt. % to 25
wt. %, from 12 wt. % to 20 wt. %, from 12 wt. % to 18 wt. %, from
12 wt. % to 16 wt. %, from 12 wt. % to 14 wt. %, from 14 wt. % to
30 wt. %, from 14 wt. % to 25 wt. %, from 14 wt. % to 20 wt. %,
from 14 wt. % to 18 wt. %, from 14 wt. % to 16 wt. %, from 16 wt. %
to 30 wt. %, from 16 wt. % to 25 wt. %, from 16 wt. % to 20 wt. %,
from 16 wt. % to 18 wt. %, from 18 wt. % to 30 wt. %, from 18 wt. %
to 25 wt. %, from 18 wt. % to 20 wt. %, from 20 wt. % to 30 wt. %,
from 20 wt. % to 25 wt. %, from 25 wt. % wt. % to 30 wt. %, or
approximately 15 wt. % NaOH and water combined by weight of the
disulfide oil composition 205.
[0065] As shown in FIG. 2, the disulfide oil composition 205 may be
pressurized in disulfide pump 212 to create pressurized disulfide
oil composition 216. The pressure of pressurized disulfide oil
composition 216 may be at least 22.1 megapascals (MPa), which is
approximately the critical pressure of water. Alternatively, the
pressure of the pressurized disulfide oil composition 216 may be
between 23 MPa and 35 MPa, or between 24 MPa and 30 MPa. For
instance, the pressure of the pressurized disulfide oil composition
216 may be between 25 MPa and 29 MPa, 26 MPa and 28 MPa, 25 MPa and
30 MPa, 26 MPa and 29 MPa, or 24 MPa and 28 MPa.
[0066] The pressurized disulfide oil composition 216 may then be
heated in one or more disulfide pre-heaters 220 to form
pressurized, heated disulfide oil composition 224. In one
embodiment, the pressurized, heated disulfide oil composition 224
has a pressure greater than the critical pressure of water and a
temperature greater than 75.degree. C. The temperature of the
pressurized, heated disulfide oil composition 224 may be between
10.degree. C. and 300.degree. C., or between 50.degree. C. and
250.degree. C., or between 75.degree. C. and 225.degree. C., or
between 100.degree. C. and 200.degree. C., or between 140.degree.
C. and 200.degree. C., or between 160.degree. C. and 200.degree. C.
The temperature of the pressurized, heated disulfide oil
composition 224 may be from 100.degree. C. to 300.degree. C., from
100.degree. C. to 250.degree. C., from 100.degree. C. to
200.degree. C., from 100.degree. C. to 190.degree. C., from
100.degree. C. to 180.degree. C., from 100.degree. C. to
170.degree. C., from 100.degree. C. to 160.degree. C., from
100.degree. C. to 150.degree. C., from 150.degree. C. to
300.degree. C., from 150.degree. C. to 250.degree. C., from
150.degree. C. to 200.degree. C., from 150.degree. C. to
190.degree. C., from 150.degree. C. to 180.degree. C., from
150.degree. C. to 170.degree. C., from 150.degree. C. to
160.degree. C., from 160.degree. C. to 300.degree. C., from
160.degree. C. to 250.degree. C., from 160.degree. C. to
200.degree. C., from 160.degree. C. to 190.degree. C., from
160.degree. C. to 180.degree. C., from 160.degree. C. to
170.degree. C., from 170.degree. C. to 300.degree. C., from
170.degree. C. to 250.degree. C., from 170.degree. C. to
200.degree. C., from 170.degree. C. to 190.degree. C., from
170.degree. C. to 180.degree. C., from 180.degree. C. to
300.degree. C., from 180.degree. C. to 250.degree. C., from
180.degree. C. to 200.degree. C., from 180.degree. C. to
190.degree. C., from 190.degree. C. to 300.degree. C., from
190.degree. C. to 250.degree. C., from 190.degree. C. to
200.degree. C., from 200.degree. C. to 300.degree. C., from
200.degree. C. to 250.degree. C., or from 250.degree. C. to
300.degree. C. Without intending to be bound by theory, the
disulfide oil is a light material and does not require high heat to
be mixed with water; therefore, it may be desirable to heat it at
or below 180.degree. C. Heating above 180.degree. C. may consume
unnecessary energy and may cause undesirable evaporation of the
disulfide oil before it is mixed with water and cause operation
difficulties. It is contemplated that it may be important to keep
the oil and water in liquid phase for better mixing. Heating below
100.degree. C. may result in difficult mixing and induce oil and
water phase separation. It is important to heat up the combined
feedstock stream 232 after the mixer 130 close to water critical
temperature (374.degree. C.) by heat exchanger, or an electric
heater or any type of heater (not shown in the FIG. 2) to avoid
quenching the inlet of the supercritical water hydrogenation
reactor 150 and to assure that the reactions inside the reactor 150
are taking place at water supercritical conditions.
[0067] Similar to water pre-heater 122 and hydrogen pre-heaters
128, suitable disulfide pre-heaters 220 may include a natural gas
fired heater, a heat exchanger, and an electric heater. The
disulfide pre-heater 220 may be a unit separate and independent
from the water pre-heater 122 and the hydrogen pre-heater 128.
[0068] The heated water stream 126, the heated hydrogen stream 129,
and the pressurized, heated disulfide oil composition 224 may then
be mixed in feed mixer 130 to produce a combined disulfide feed
stream 232. The feed mixer 130 can be any type of mixing device
capable of mixing the heated water stream 126 and the pressurized,
heated disulfide oil composition 224. In one embodiment, the feed
mixer 130 may be a mixing tee. The feed mixer 130 may be an
ultrasonic device, a small continuous stir tank reactor (CSTR), or
any suitable mixer. The volumetric flow ratio of each component fed
to the feed mixer 130 may vary. In embodiments, the volumetric flow
ratio of the heated disulfide oil composition 224 to the heated
water stream 126 may be from 1:10 to 1:1, from 1:10 to 1:5, from
1:10 to 1:2, from 1:5 to 1:1, from 1:5 to 1:2, or from 1:2 to 1:1
at standard ambient temperature and ambient pressure (SATP). In
embodiments, the hydrogen to oil volumetric flow can be from 10 to
5000 cubic feet of heated hydrogen stream 129 to one barrel of
heated disulfide oil composition 224, at SATP.
[0069] The combined disulfide feed stream 232 may then be
introduced to the supercritical water hydrogenation reactor 150
configured to upgrade the combined feed stream 232. The
supercritical water hydrogenation reactor 150 may be substantially
similar to the supercritical water hydrogenation reactor 150 as
previously described. In the supercritical water hydrogenation
reactor 150 the disulfide oil and hydrogen are dissolved in the
supercritical water where C--S, H--H, and S--S bonds are broken and
the generated hydrocarbon and heteroatoms radicals are
saturated.
[0070] Referring to FIG. 2, upon exiting the supercritical water
hydrogenation reactor 150, the upgraded disulfide product 252 may
be cooled by cooler 154 to a temperature from 20.degree. C. to
50.degree. C., from 20.degree. C. to 40.degree. C., from 20.degree.
C. to 30.degree. C., from 30.degree. C. to 50.degree. C., from
30.degree. C. to 40.degree. C., or from 40.degree. C. to 50.degree.
C. to form a cooled, upgraded disulfide product 256.
[0071] Upon exiting the cooler 154, the pressure of the cooled,
upgraded disulfide product 256 may be reduced to create a
depressurized, upgraded disulfide product 259, which may have a
pressure from 0.01 MPa to 1.0 MPa, from 0.01 MPa to 0.8 MPa, from
0.01 MPa to 0.5 MPa, from 0.01 MPa to 0.3 MPa, from 0.01 MPa to 0.1
MPa, from 0.01 MPa to 0.08 MPa, from 0.01 MPa to 0.05 MPa, from
0.01 MPa to 0.03 MPa, from 0.03 MPa to 1.0 MPa, from 0.03 MPa to
0.8 MPa, from 0.03 MPa to 0.5 MPa, from 0.03 MPa to 0.3 MPa, from
0.03 MPa to 0.1 MPa, from 0.03 MPa to 0.08 MPa, from 0.03 MPa to
0.05 MPa, from 0.05 MPa to 1.0 MPa, from 0.05 MPa to 0.8 MPa, from
0.05 MPa to 0.5 MPa, from 0.05 MPa to 0.3 MPa, from 0.05 MPa to 0.1
MPa, from 0.05 MPa to 0.08 MPa, from 0.08 MPa to 1.0 MPa, from 0.08
MPa to 0.8 MPa, from 0.08 MPa to 0.5 MPa, from 0.08 MPa to 0.3 MPa,
from 0.08 MPa to 0.1 MPa, from 0.1 MPa to 1.0 MPa, from 0.1 MPa to
0.8 MPa, from 0.1 MPa to 0.5 MPa, from 0.1 MPa to 0.3 MPa, from 0.3
MPa to 1.0 MPa, from 0.3 MPa to 0.8 MPa, from 0.3 MPa to 0.5 MPa,
from 0.5 MPa to 1.0 MPa, from 0.5 MPa to 0.8 MPa, or from 0.8 MPa
to 1.0 MPa. The depressurizing can be achieved by many devices, for
example, a valve 158 as shown in FIGS. 1 and 2.
[0072] The depressurized, upgraded disulfide product 259 may then
be passed to a gas/water separator 160. The gas/water separator 160
may separate the depressurized, upgraded disulfide product 259 into
a second gas fraction 264 and a second water fraction 266. The
gas/water separator 160 may be any separator known in the industry.
While the gas/water separator 160 may separate the depressurized,
upgraded disulfide product 259 into at least a second gas fraction
264 and a second water fraction 266, it should be appreciated that
additional fractions may also be produced. The second gas fraction
264 may be passed to the gas storage tank 165 and the second water
fraction 266 may be passed to the water storage tank 167. In
embodiments, the percent conversion of the disulfide oil
composition 205 may be from 50% to 99%, from 50% to 95%, from 50%
to 90%, from 50% to 85%, from 50% to 82%, from 60% to 99%, from 60%
to 95%, from 60% to 90%, from 60% to 85%, from 60% to 82%, from 70%
to 99%, from 70% to 95%, from 70% to 90%, from 70% to 85%, from 70%
to 82%, from 75% to 99%, from 75% to 95%, from 75% to 90%, from 75%
to 85%, from 75% to 82%, from 78% to 99%, from 78% to 95%, from 78%
to 90%, from 78% to 85%, from 78% to 82%, or approximately 80%.
[0073] In embodiments, the second gas fraction 264 may include
H.sub.2, C.sub.2H.sub.6, C.sub.3H.sub.8, C.sub.4H.sub.10,
C.sub.5H.sub.12, C.sub.6H.sub.14, CH.sub.3SH, C.sub.2H.sub.5SH,
C.sub.4H.sub.9SH, C.sub.5H.sub.11SH, H.sub.2S,
C.sub.2H.sub.6S.sub.2, C.sub.3H.sub.8S.sub.2,
C.sub.4H.sub.10S.sub.2, C.sub.5H.sub.12S.sub.2,
C.sub.6H.sub.14S.sub.2, or combinations thereof.
[0074] The second gas fraction 264 may include from 0.1 wt. % to
0.5 wt. %, from 0.1 wt. % to 0.4 wt. %, from 0.1 wt. % to 0.3 wt.
%, from 0.1 wt. % to 0.2 wt. %, from 0.2 wt. % to 0.5 wt. %, from
0.2 wt. % to 0.4 wt. %, from 0.2 wt. % to 0.3 wt. %, from 0.3 wt. %
to 0.5 wt. %, from 0.3 wt. % to 0.4 wt. %, from 0.4 wt. % to 0.5
wt. %, or approximately 0.3 wt. % H.sub.2 by weight of the second
gas fraction 264.
[0075] The second gas fraction 264 may include from 1 wt. % to 13
wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 7 wt. %, from 1
wt. % to 5 wt. %, from 1 wt. % to 3 wt. %, from 1 wt. % to 2 wt. %,
from 2 wt. % to 13 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to
7 wt. %, from 2 wt. % to 5 wt. %, from 2 wt. % to 3 wt. %, from 3
wt. % to 13 wt. %, from 3 wt. % to 10 wt. %, from 3 wt. % to 7 wt.
%, from 3 wt. % to 5 wt. %, from 5 wt. % to 13 wt. %, from 5 wt. %
to 10 wt. %, from 5 wt. % to 7 wt. %, from 7 wt. % to 13 wt. %,
from 7 wt. % to 10 wt. %, from 10 wt. % to 13 wt. %, or
approximately 4 wt. % C.sub.2H.sub.6 by weight of the second gas
fraction 264.
[0076] The second gas fraction 264 may include from 5 wt. % to 20
wt. %, from 5 wt. % to 18 wt. %, from 5 wt. % to 15 wt. %, from 5
wt. % to 13 wt. %, from 5 wt. % to 11 wt. %, from 5 wt. % to 8 wt.
%, from 8 wt. % to 20 wt. %, from 8 wt. % to 18 wt. %, from 8 wt. %
to 15 wt. %, from 8 wt. % to 13 wt. %, from 8 wt. % to 11 wt. %,
from 11 wt. % to 20 wt. %, from 11 wt. % to 18 wt. %, from 11 wt. %
to 15 wt. %, from 11 wt. % to 13 wt. %, from 13 wt. % to 20 wt. %,
from 13 wt. % to 18 wt. %, from 13 wt. % to 15 wt. %, from 15 wt. %
to 20 wt. %, from 15 wt. % to 18 wt. %, from 18 wt. % to 20 wt. %,
or approximately 12 wt. % C.sub.3H.sub.8 by weight of the second
gas fraction 264.
[0077] The second gas fraction 264 may include from 5 wt. % to 30
wt. %, from 5 wt. % to 23 wt. %, from 5 wt. % to 20 wt. %, from 5
wt. % to 18 wt. %, from 5 wt. % to 16 wt. %, from 5 wt. % to 14 wt.
%, from 5 wt. % to 12 wt. %, from 5 wt. % to 10 wt. %, from 10 wt.
% to 30 wt. %, from 10 wt. % to 23 wt. %, from 10 wt. % to 20 wt.
%, from 10 wt. % to 18 wt. %, from 10 wt. % to 16 wt. %, from 10
wt. % to 14 wt. %, from 10 wt. % to 12 wt. %, from 12 wt. % to 30
wt. %, from 12 wt. % to 23 wt. %, from 12 wt. % to 20 wt. %, from
12 wt. % to 18 wt. %, from 12 wt. % to 16 wt. %, from 12 wt. % to
14 wt. %, from 14 wt. % to 30 wt. %, from 14 wt. % to 23 wt. %,
from 14 wt. % to 20 wt. %, from 14 wt. % to 18 wt. %, from 14 wt. %
to 16 wt. %, from 16 wt. % to 30 wt. %, from 16 wt. % to 23 wt. %,
from 16 wt. % to 20 wt. %, from 16 wt. % to 18 wt. %, from 18 wt. %
to 30 wt. %, from 18 wt. % to 23 wt. %, from 18 wt. % to 20 wt. %,
from 20 wt. % to 30 wt. %, from 20 wt. % to 23 wt. %, from 23 wt. %
to 30 wt. %, or approximately 15 wt. % C.sub.4H.sub.10 by weight of
the second gas fraction 264.
[0078] The second gas fraction 264 may include from 1 wt. % to 20
wt. %, from 1 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1
wt. % to 8 wt. %, from 1 wt. % to 6 wt. %, from 1 wt. % to 4 wt. %,
from 1 wt. % to 2 wt. %, from 2 wt. % to 20 wt. %, from 2 wt. % to
15 wt. %, from 2 wt. % to 10 wt. %, from 2 wt. % to 8 wt. %, from 2
wt. % to 6 wt. %, from 2 wt. % to 4 wt. %, from 4 wt. % to 20 wt.
%, from 4 wt. % to 15 wt. %, from 4 wt. % to 10 wt. %, from 4 wt. %
to 8 wt. %, from 4 wt. % to 6 wt. %, from 6 wt. % to 20 wt. %, from
6 wt. % to 15 wt. %, from 6 wt. % to 10 wt. %, from 6 wt. % to 8
wt. %, from 8 wt. % to 20 wt. %, from 8 wt. % to 15 wt. %, from 8
wt. % to 10 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 15
wt. %, from 15 wt. % to 20 wt. %, or approximately 5 wt. %
C.sub.5H.sub.12 by weight of the second gas fraction 264.
[0079] The second gas fraction 264 may include from 0.5 wt. % to 5
wt. %, from 0.5 wt. % to 3.5 wt. %, from 0.5 wt. % to 3.0 wt. %,
from 0.5 wt. % to 2.5 wt. %, from 0.5 wt. % to 2.2 wt. %, from 0.5
wt. %, to 1.8 wt. %, from 0.5 wt. % to 1.5 wt. %, from 0.5 wt. % to
1.0 wt. %, from 1.0 wt. % to 5 wt. %, from 1.0 wt. % to 3.5 wt. %,
from 1.0 wt. % to 3.0 wt. %, from 1.0 wt. % to 2.5 wt. %, from 1.0
wt. % to 2.2 wt. %, from 1.0 wt. %, to 1.8 wt. %, from 1.0 wt. % to
1.5 wt. %, from 1.5 wt. % to 5 wt. %, from 1.5 wt. % to 3.5 wt. %,
from 1.5 wt. % to 3.0 wt. %, from 1.5 wt. % to 2.5 wt. %, from 1.5
wt. % to 2.2 wt. %, from 1.5 wt. %, to 1.8 wt. %, from 1.8 wt. % to
5 wt. %, from 1.8 wt. % to 3.5 wt. %, from 1.8 wt. % to 3.0 wt. %,
from 1.8 wt. % to 2.5 wt. %, from 1.8 wt. % to 2.2 wt. %, from 2.2
wt. % to 5 wt. %, from 2.2 wt. % to 3.5 wt. %, from 2.2 wt. % to
3.0 wt. %, from 2.2 wt. % to 2.5 wt. %, from 2.5 wt. % to 5 wt. %,
from 2.5 wt. % to 3.5 wt. %, from 2.5 wt. % to 3.0 wt. %, from 3.0
wt. % to 5 wt. %, from 3.0 to 3.5 wt. %, from 3.5 to 5 wt. %, or
approximately 2 wt. % C.sub.6H.sub.14 by weight of the second gas
fraction 264.
[0080] The second gas fraction 264 may include from 8 to 58 wt. %,
from 8 to 50 wt. %, from 8 to 40 wt. %, from 8 to 30 wt. %, from 8
to 20 wt. %, from 8 to 15 wt. %, from 8 to 10 wt. %, from 10 to 58
wt. %, from 10 to 50 wt. %, from 10 to 40 wt. %, from 10 to 30 wt.
%, from 10 to 20 wt. %, from 10 to 15 wt. %, from 15 to 58 wt. %,
from 15 to 50 wt. %, from 15 to 40 wt. %, from 15 to 30 wt. %, from
15 to 20 wt. %, from 20 to 58 wt. %, from 20 to 50 wt. %, from 20
to 40 wt. %, from 20 to 30 wt. %, from 30 to 58 wt. %, from 30 to
50 wt. %, from 30 to 40 wt. %, from 40 to 58 wt. %, from 40 to 50
wt. %, from 50 to 58 wt. %, or approximately 35 wt. % H.sub.2S by
weight of the second gas fraction 264.
[0081] The second gas fraction 264 may include from 1 wt. % to 5
wt. %, from 1 wt. % to 4 wt. %, from 1 wt. % to 3.5 wt. %, from 2
wt. % to 5 wt. %, from 2 wt. % to 4 wt. %, from 2 wt. % to 3.5 wt.
%, from 2.5 wt. % to 5 wt. %, from 2.5 wt. % to 4 wt. %, from 2.5
wt. % to 3.5 wt. %, or approximately 3 wt. % CH.sub.3SH by weight
of the second gas fraction 264.
[0082] The second gas fraction 264 may include from 0.5 wt. % to 4
wt. %, from 0.5 wt. % to 3 wt. %, from 0.5 wt. % to 2.5 wt. %, from
1 wt. % to 4 wt. %, from 1 wt. % to 3 wt. %, from 1 wt. % to 2.5
wt. %, from 1.5 wt. % to 4 wt. %, from 1.5 wt. % to 3 wt. %, from
1.5 wt. % to 2.5 wt. %, or approximately 2 wt. % C.sub.2H.sub.5SH
by weight of the second gas fraction 264.
[0083] The second gas fraction 264 may include from 0.25 wt. % to 2
wt. %, from 0.25 wt. % to 1.5 wt. %, from 0.25 wt. % to 1.25 wt. %,
from 0.5 wt. % to 2 wt. %, from 0.5 wt. % to 1.5 wt. %, from 0.5
wt. % to 1.25 wt. %, from 0.75 wt. % to 2 wt. %, from 0.75 wt. % to
1.5 wt. %, from 0.75 wt. % to 1.25 wt. %, or approximately 1 wt. %
C.sub.4H.sub.9SH by weight of the second gas fraction 264.
[0084] The second gas fraction 264 may include from 0.25 wt. % to 2
wt. %, from 0.25 wt. % to 1.5 wt. %, from 0.25 wt. % to 1.25 wt. %,
from 0.5 wt. % to 2 wt. %, from 0.5 wt. % to 1.5 wt. %, from 0.5
wt. % to 1.25 wt. %, from 0.75 wt. % to 2 wt. %, from 0.75 wt. % to
1.5 wt. %, from 0.75 wt. % to 1.25 wt. %, or approximately 1 wt. %
C.sub.5H.sub.11SH by weight of the second gas fraction 264.
[0085] The second gas fraction 264 may include from 1 wt. % to 5
wt. %, from 1 wt. % to 4 wt. %, from 1 wt. % to 3.5 wt. %, from 2
wt. % to 5 wt. %, from 2 wt. % to 4 wt. %, from 2 wt. % to 3.5 wt.
%, from 2.5 wt. % to 5 wt. %, from 2.5 wt. % to 4 wt. %, from 2.5
wt. % to 3.5 wt. %, or approximately 3 wt. % C.sub.2H.sub.6S.sub.2
by weight of the second gas fraction 264.
[0086] The second gas fraction 264 may include from 1 wt. % to 10
wt. %, from 1 wt. % to 8 wt. %, from 1 wt. % to 7 wt. %, from 3 wt.
% to 10 wt. %, from 3 wt. % to 8 wt. %, from 3 wt. % to 7 wt. %,
from 5 wt. % to 10 wt. %, from 5 wt. % to 8 wt. %, from 5 wt. % to
7 wt. %, or approximately 6 wt. % C.sub.3H.sub.8S.sub.2 by weight
of the second gas fraction 264.
[0087] The second gas fraction 264 may include from 1 wt. % to 10
wt. %, from 1 wt. % to 8 wt. %, from 1 wt. % to 7 wt. %, from 3 wt.
% to 10 wt. %, from 3 wt. % to 8 wt. %, from 3 wt. % to 7 wt. %,
from 5 wt. % to 10 wt. %, from 5 wt. % to 8 wt. %, from 5 wt. % to
7 wt. %, or approximately 6 wt. % C.sub.4H.sub.10S.sub.2 by weight
of the second gas fraction 264.
[0088] The second gas fraction 264 may include from 1 wt. % to 5
wt. %, from 1 wt. % to 4 wt. %, from 1 wt. % to 3.5 wt. %, from 2
wt. % to 5 wt. %, from 2 wt. % to 4 wt. %, from 2 wt. % to 3.5 wt.
%, from 2.5 wt. % to 5 wt. %, from 2.5 wt. % to 4 wt. %, from 2.5
wt. % to 3.5 wt. %, or approximately 3 wt. % C.sub.5H.sub.12S.sub.2
by weight of the second gas fraction 264.
[0089] The second gas fraction 264 may include from 0.25 wt. % to 2
wt. %, from 0.25 wt. % to 1.5 wt. %, from 0.25 wt. % to 1.25 wt. %,
from 0.5 wt. % to 2 wt. %, from 0.5 wt. % to 1.5 wt. %, from 0.5
wt. % to 1.25 wt. %, from 0.75 wt. % to 2 wt. %, from 0.75 wt. % to
1.5 wt. %, from 0.75 wt. % to 1.25 wt. %, or approximately 1 wt. %
C.sub.6H.sub.14S.sub.2 by weight of the second gas fraction
264.
[0090] In embodiments, the second gas fraction 264 may have a
similar composition to liquefied petroleum gas (LPG), due to the
presence of butane and propane. In embodiments, the second gas
fraction 264 may have a composition similar to LPG+, meaning that
the second gas fraction 264 includes components present in LPG
(butane and propane) along with additional liquid components, such
as a pentane and hexane. Therefore, the process 200 as shown in
FIG. 2 may be used to convert hazardous waste, such as disulfide
oil, into desirable products, such as H.sub.2, C.sub.2 to C.sub.6
hydrocarbons, H.sub.2S, or combinations thereof.
EXAMPLES
Example 1
[0091] An example process for upgrading a hydrocarbon-based
composition 105 according to embodiments described herein was run.
The hydrocarbon-based composition 105 had the properties shown in
Table 2.
TABLE-US-00002 TABLE 2 Properties of Feed and Product Hydrocarbon-
based Upgraded Liquid Oil composition Product Fraction Properties
(105) (152) (162) Mass Flow (kg/hr) 49 48.1 45.6 API.degree. 11
19.8 24 Hydrogen Flow (kg/hr) 0.4 0.0 0.0 Distillation(TBP) 5% 367
297 256 10% 395 337 300 30% 465 420 374 50% 526 464 415 70% 587 519
461 90% 647 592 538 95% 671 632 568 Total Sulfur Content 3.4 2.7
1.7 (wt. %) Total Nitrogen Content 1.2 0.9 0.3 (wt. %) Viscosity
(cSt) at 50.degree. C. 640 89 27 Asphaltene (Heptane- 4.8 1.7 0.3
insoluble) (wt. %) Metals (V and Ni) (wt ppm) 83 9 4 Water (wt. %)
0 0.2 0 kg/hr Sulfur in Feed = 1.7 Nitrogen in Feed = 0.6 Sulfur in
Liquid Product = 0.8 Nitrogen in Liquid Product = 0.1
[0092] A water stream 110 included demineralized water having a
conductivity of less than 0.1 .mu.S/cm.sup.2. The hydrocarbon-based
composition 105, the water stream 110, and a hydrogen stream 127
were fed at rates of 50 L/hr, 100 L/hr, and 157 ft.sup.3/hr,
respectively, at a process pressure of 3,600 psig.
[0093] As shown in FIG. 1, the hydrocarbon-based composition 105
and the water stream 110 are fed to pumps 112 and 114,
respectively, to increase their pressure to 3600 psig. The
pressurized hydrocarbon-based composition 116, pressurized water
stream 118, and hydrogen stream 127 are heated to about 350.degree.
C. by heaters 120, 122, and 128, respectively. The pressurized,
heated hydrocarbon-based composition 124, the heated water stream
126, and the heated hydrogen stream 129 exiting the heaters were
routed to a static mixer 130, where the hydrogen, oil, and water
are mixed vigorously to generate combined feed stream 132. The
combined feed stream 132 is then routed to to the supercritical
water hydrogenation reactor 150 that is configured to upgrade the
combined feed stream 132 that is maintained at 440.degree. C. and
3600 psig. The upgraded product 152 has the properties shown in
Table 2 was routed to cooler 154 to form a cooled, upgraded product
156. The cooled, upgraded product 156 was depressurized by valve
158 to reduce the mixture pressure to 1 atm to form a
depressurized, upgraded product 159. The depressurized, upgraded
product 159 was then sent to a gas/oil/water separator 160 to
separate the depressurized, upgraded product 159 into a first gas
fraction 164, a liquid oil fraction 162, and a first water fraction
166. The liquid oil fraction 162 had the properties shown in Table
2. The liquid oil fraction 162 was then collected in an oil storage
tank 163. The composition of the first gas fraction 164 is shown in
Table 3:
TABLE-US-00003 TABLE 3 First Gas Fraction 164 First Gas Fraction
164 Concentration MW Species (wt. %) (kg/kmol) kg/hr kmol/hr
H.sub.2 1.0 2.0 0.04 0.02 CH.sub.4 11.9 16.0 0.45 0.03
C.sub.2H.sub.6 10.9 30.1 0.41 0.01 C.sub.3H.sub.8 10.0 44.1 0.38
0.01 C.sub.4H.sub.10 9.0 58.1 0.34 0.01 C.sub.5H.sub.12 7.0 72.2
0.26 0.00 C.sub.6H.sub.14 4.0 86.2 0.15 0.00 CO 2.0 28.0 0.08 0.00
CO.sub.2 4.0 44.0 0.15 0.00 H.sub.2S 25.6 34.1 0.97 0.03 NH.sub.3
14.6 17.0 0.55 0.03 kg/hr Sulfur in Gas Product = 0.9 Nitrogen in
Gas Product = 0.5
Example 2
[0094] An example process for treating disulfide oil according to
embodiments described herein was run. A disulfide oil stream of 180
kg/hr exiting LPG Merox is hydrotreated in supercritical water to
remove the sulfur in the form of H.sub.2S. The disulfide oil
composition 205 had the composition shown in Table 4:
TABLE-US-00004 TABLE 4 Disulfide Oil Composition 205 MW
Concentration (kg/ kmol/ Species (wt. %) kg/hr kmol) hr
C.sub.2H.sub.6S.sub.2 14 23 94 0.24 C.sub.3H.sub.8S.sub.2 24 39 108
0.36 C.sub.4H.sub.10S.sub.2 27 44 122 0.36 C.sub.5H.sub.12S.sub.2
15 24 136 0.18 C.sub.6H.sub.14S.sub.2 5 8 150 0.05 NaOH + water 15
24 Total 100 162 Total Feed (Excluding NaOH + water) (kg/hr) =
139
[0095] The disulfide oil composition 205 included 2.4 kilomoles per
hour (kmol/hr) of sulfur. The flow rate of the total feed excluding
NaOH and water was 139 kilograms per hour (kg/hr). The water stream
110 was demineralized water having a conductivity lower than 0.1
.mu.S/cm.sup.2. The disulfide oil composition 205 and the water
stream 110 were fed to pumps 212 and 114, respectively, to increase
their pressure to a pressure of 3600 psi to form pressurized
disulfide composition 216 and pressurized water stream 118,
respectively. The pressurized disulfide oil composition 216, the
pressurized water stream 118, and the hydrogen stream 127 were fed
to the process at rates of 162 kg/hr, 360 L/hr, and 500
ft.sup.3/hr, respectively. The pressurized disulfide oil
composition 216, the pressurized water stream 118, and the hydrogen
stream 127 were preheated by heaters 220, 122, and 128,
respectively, to a temperature of 180.degree. C., to form
pressurized, heated disulfide oil composition 224, heated water
stream 126, and heated hydrogen stream 129. The heated water stream
126, the heated hydrogen stream 129, and the pressurized, heated
disulfide oil composition 224 were then mixed in a static mixer 130
to produce a combined disulfide feed stream 232. The combined
disulfide feed stream 232 was then introduced to the supercritical
water hydrogenation reactor 150. The disulfide oil was then
hydrotreated in the supercritical water hydrogenation reactor 150
at 450.degree. C. and 3600 psig (24.8 MPa) to form upgraded
disulfide product 252. Upon exiting the supercritical water
hydrogenation reactor 150, the upgraded disulfide product 252 was
cooled by water cooler 154 to 35.degree. C. to form cooled,
upgraded disulfide product 256. The cooled, upgraded disulfide
product 256 was then depressurized to 1 atm by back pressure
regulator valve 158 to form depressurized, upgraded disulfide
product 259. The depressurized, upgraded disulfide product 259 was
then sent to the gas/water separator 160 to separate the
depressurized, upgraded disulfide product 259 into the second water
fraction 266 and the second gas fraction 264. The gas/water
separator 160 was operated at 1 atmosphere and a maximum of
90.degree. C. The percent conversion of disulfide oil was 80%. The
second gas fraction 264 collected in the gas storage tank 165 was a
mixture of light paraffins, thiols, un-converted disulfide oil and
hydrogen, and hydrogen sulfide. The composition of the second gas
fraction 264 is shown in Table 5:
TABLE-US-00005 TABLE 5 Properties of the second gas fraction 264
Second gas fraction 264 Sulfur Concen- in tration MW kmol/ Product
Species (wt. %) kg/hr (kg/kmol) hr kmol/hr H.sub.2 0.3 0.3 2 0.17
0.6 C.sub.2H.sub.6 4 4.5 30 0.15 C.sub.3H.sub.8 12 13.4 44 0.30
C.sub.4H.sub.10 15 16.7 58 0.29 C.sub.5H.sub.12 5 5.6 72 0.08
C.sub.6H.sub.14 2 2.2 86 0.03 CH.sub.3SH 3 3.3 48 0.07
C.sub.2H.sub.5SH 2 2.2 62 0.04 C.sub.4H.sub.9SH 1 1.1 90 0.01
C.sub.2H.sub.11SH 1 1.1 104 0.01 H.sub.2S 35 60.6 34 1.78
C.sub.2H.sub.6S.sub.2 3 4.5 94 0.05 C.sub.3H.sub.8S.sub.2 6 7.8 108
0.07 C.sub.4H.sub.10S.sub.2 6 8.8 122 0.07 C.sub.5H.sub.12S.sub.2 3
4.9 136 0.04 C.sub.6H.sub.14S.sub.2 1 1.6 150 0.01 Total 100 139
Total Sulfur Out (kg/hr) = 76
[0096] It should be apparent to those skilled in the art that
various modifications and variations may be made to the embodiments
described within without departing from the spirit and scope of the
claimed subject matter. Thus, it is intended that the specification
cover the modifications and variations of the various embodiments
described within provided such modification and variations come
within the scope of the appended claims and their equivalents.
[0097] As used throughout the disclosure, the singular forms "a,"
"an" and "the" include plural referents unless the context clearly
dictates otherwise. Thus, for example, reference to "a" component
includes aspects having two or more such components, unless the
context clearly indicates otherwise.
[0098] Having described the subject matter of the present
disclosure in detail and by reference to specific embodiments
thereof, it is noted that the various details disclosed within
should not be taken to imply that these details relate to elements
that are essential components of the various embodiments described
within, even in cases where a particular element is illustrated in
each of the drawings that accompany the present description.
Further, it should be apparent that modifications and variations
are possible without departing from the scope of the present
disclosure, including, but not limited to, embodiments defined in
the appended claims. More specifically, although some aspects of
the present disclosure are identified as particularly advantageous,
it is contemplated that the present disclosure is not necessarily
limited to these aspects.
* * * * *