US10703999

US010703999B2
United States Patent ( 10 ) Patent No.: US 10,703,999 B2

Choi et al. (45 ) Date of Patent: Jul. 7 , 2020
(54 ) INTEGRATED SUPERCRITICAL WATER (58 ) Field of Classification Search
AND STEAM CRACKING PROCESS CPC C10G 69/06 ; C10G 51/02; C10G 53/02
See application file for complete search history .
(71) Applicant: Saudi Arabian Oil Company, Dhahran References Cited
(SA ) (56 )
(72 ) Inventors: Ki-Hyouk Choi, Dhahran (SA ); U.S. PATENT DOCUMENTS
Abdullah T. Alabdulhadi, Dhahran 2,733,192 A 1/1956 Sage
(SA ); Gonzalo Feijoo Martinez, 2,880,171 A 3/1959 Flinn et al .
Dhahran (SA ); Ali M. Alsomali, ( Continued )
Dhahran (SA ); Mohammad A.
Alabdullah , Dhahran (SA ); Essam A. FOREIGN PATENT DOCUMENTS
Al-Sayed , Al-Khobar (SA )
CN 1508221 A 6/2004
( 73 ) Assignee : Saudi Arabian Oil Company (SA ) CN 101553553 A 10/2009
(Continued )
( * ) Notice : Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 OTHER PUBLICATIONS
U.S.C. 154(b ) by 200 days .
Cheng al. (Effects of supercritical wat in vacuum residue
(21) Appl. No.: 15 /920,099 upgrading, 2009 , Energy and Fuels, vol. 23, pp . 3178-3183 , see p .
3178 , I. Introduction ). ( Year: 2009 ).*
(22) Filed : Mar. 13 , 2018 (Continued )
(65 ) Prior Publication Data Primary Examiner — Youngsul Jeong
US 2018/0265792 A1 Sep. 20 , 2018 (74 ) Attorney , Agent, or Firm - Bracewell LLP ;
Constance G. Rhebergen
Related U.S. Application Data ( 57 ) ABSTRACT
(60 ) Provisional application No. 62 /471,016 , filed on Mar. A method for producing a supercritical water (SCW ) -treated
14 , 2017 product is provided . The method comprising the steps of
introducing a crude oil stream and a water stream to a
(51) Int. Cl. supercriticalwater process,wherein the crude oil stream can
C10G 69/06 ( 2006.01) undergo conversion reactions to produce the supercritical
C10G 53/02 (2006.01 ) water ( SCW ) -treated product , wherein the SCW -treated
(Continued ) product includes an increased paraffin concentration as
(52 ) U.S. Ci. compared to crude oil stream . The method further includes
??? C10G 69/06 ( 2013.01 ); C10G 9/36
the step of introducing the SCW - treated product to a steam
(2013.01 ); CIOG 31/08 (2013.01); C10G
cracking process , wherein the SCW - treated product can
undergo conversion reactions to produce furnace effluent.
51/023 (2013.01); CIOG 53/02 (2013.01);
C10G 55/04 (2013.01) 19 Claims, 9 Drawing Sheets
Convection
Section
Crude
Supercritical -Furnace
Process
Diluent
Steam Radiation
Section
Stream
US 10,703,999 B2
Page 2
(51) Int. Ci. 6,096,194 A 8/2000 Tsybulevskiy et al.

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* cited by examiner
U.S. Patent Jul. 7 , 2020 Sheet 1 of 9 US 10,703,999 B2
Convecti Section Raditon Section

urnace
1
FIG
1
.
B
C
Diluent Steam
Supercital Proces Water Stream

Crude
w wMW
10 180 285
270
F
170 275
160
260
ww
150
200 250
240 061 140 310

wW*in
3
25
100 230 312 314
*
*
20
130
120 2A
.
FIG
?
215 220 **
105 115
Csoz
205
G
22
205
amine
105
no 2152_130 235
FIG . 2B
300
235 . : 25
312
320 Gemmmmmmmar
314
310
301 20
32
FIG . 3A
230
25
370 30
350 300
270
32
260
170
10
180
275
285
FIG . 3B
230
25
40
WEEK 100 400 300 ( 30
4 6 32
FIG . 4
230
25
2 50 30
100 500 300
4 55 32
FIG . 5
160 260
260 ? 150
5A
.
FIG
250
36
240
140
310
35
312 314
230
210
20
20
130 34
110 120
220 500
105 115 55
205 215
no 2
2
50
230
25
64
2 60 30
100 600 300
4 62 32
FIG . 6
285
OLZ
775
770 180
170
770 275
260
-250 150 705
1240
The 7
.
FIG
230
120 210
-GOZ 2 220
105 115
?
215
G
To 22
U.S. Patent Jul. 7,2020 Sheet 9 of 9 US 10,703,999 B2
270 775
7285
285
:
770 180
170
770 160 275
260 250 ?
150 GOL
FIG
8
.
240 140 310
26
815 312 w.omsr 314
130
120 805
.
205 220
105 15
215
,
G -
r
US 10,703,999 B2
1 2
INTEGRATED SUPERCRITICAL WATER ment, thermal conversion , extraction , and distillation .
AND STEAM CRACKING PROCESS Extraction processes can include a solvent deasphalting
process. However, these processes produce liquid yields of
RELATED APPLICATIONS less than 80 percent by volume, resulting in analogous low
5 product recovery from the steam cracking process . In addi
This application is related and claims priority to U.S. Pat. tion , pre -treatment processes can increase the cost per barrel
App . No. 62/471,016 filed on Mar. 14, 2017. For purposes to the resultant products.
of United States patent practice , this application incorpo
rates the contents of the provisional application by reference 10 SUMMARY
in its entirety.
Disclosed are methods for upgrading petroleum . Specifi
TECHNICAL FIELD cally, disclosed are methods and systems for upgrading
petroleum using an integrated supercriticalwater and steam
Disclosed are methods for upgrading petroleum . Specifi cracking process .
cally, disclosed are methods and systems for upgrading 15 In a first aspect, a method for producing a supercritical
petroleum using an integrated supercriticalwater and steam water (SCW ) -treated product is provided . The method
cracking process . includes the steps of introducing a mixed stream to a
convection section of a furnace to produce a convection
BACKGROUND upgraded stream , where the temperature of the convection
20 upgraded stream is between the critical temperature ofwater
Conventionally, ethane and naphtha (boiling point less and 500 deg C., where conversion reactions occur in the
than 200 degrees Celsius (deg C.)) can be used to produce convection section , introducing the convection upgraded
light olefins, such as ethylene and propylene by a steam stream to a supercritical reactor to produce a reactor effluent,
cracking process . Naphtha , such as straight run naphtha , can where the supercritical reactor is maintained at a tempera
be a paraffin -rich hydrocarbon stream . However , the naphtha 25 ture between 380 deg C. and 450 deg C. and a pressure
fraction in crude oil can be limited to between 10 and 30 between 23 MPa and 35 MPa , wherein one or more con
percent by volume (vol % ). Conventional steam cracking version reactions occur in supercritical reactor, and intro
processes can be used to process gas oil . Gas oil refers to ducing the reactor effluent to a post- reaction stage to pro
hydrocarbons with a boiling point between 200 deg C. and duce the SCW - treated product, wherein the SCW -treated
565 deg C., where light gas oil has a boiling point between 30 producthas an increased paraffin concentration as compared
200 deg C. and 370 deg C., and where vacuum gas oil has to the crude oil stream , wherein the SCW -treated product
a boiling point between 200 deg C. and 565 deg C. Due to include an amount of water .
the presence of heavier molecules steam cracking of gas oil In certain aspects, the post- reaction stage can be config
results in a reduced yield of ethylene and propylene and ured to adjust the amount of water in the SCW -treated
greater coking rates relative to steam cracking of naptha . 35 product. In certain aspects, the method further includes the
In petroleum - based crude oils , various types ofmolecules step of introducing the SCW -treated product to the convec
are present. Per their chemical structure , molecules can be tion section of the furnace to produce a furnace effluent,
classified as paraffin , olefin , naphthene (a cyclic paraffin ), where the SCW -treated product is subjected to one or more
and aromatic , which can be indicated by an oil composi conversion reactions, where the furnace effluent is with
tion's PONA number. Of the molecules, it is most efficient 40 drawn from a radiation section of the furnace . In certain
to convert paraffins to light olefins, with n -paraffins being aspects, the method further includes the steps of introducing
more effectively converted than iso -paraffins, and for this the SCW -treated product to an intermediate unit to produce
reason n -paraffins can be preferred . Aromatics, such as a product stream , and introducing the product stream to the
benzene and toluene , are stable at high temperatures, have a convection section of the furnace to produce a furnace
low hydrogen to carbon ratio , and are known to be an 45 effluent, where the product stream is subjected to one or
effective precursor for coke formation . The stability of more conversion reactions, where the furnace effluent is
aromatics can be contributed to the carbon - carbon bond withdrawn from a radiation section of the furnace. In certain
energies of the aromatic carbon , as compared to the carbon aspects , the intermediate unit can be selected from the group
carbon bond energies of paraffinic carbons. For these rea consisting of a hydrotreating process, a distillation process,
sons , aromatics are difficult to convert and are not a good 50 and a thermal conversion process. In certain aspects , the
source for producing light olefins. Naphthenes as a source intermediate unit is a hydrotreating process and the product
material are more difficult to convert than paraffins , but stream is a hydrotreating (HTP ) -product. In certain aspects,
easier to convert than aromatics. Olefinic compounds are the crude oil stream includes a concentration of a vacuum
generally cracked in a steam cracker to produce light par residue fraction that is greater than 20 percent by weight ( wt
affins and olefins while aromatics with longer-chained ole- 55 sulfur
fins are formed through cyclization followed by dehydro
% ) and. Ina certain
total sulfur content that is greater than 1.5
1 wt %
aspects, the amount of water in the SCW
genation reactions. Thus, a feedstock for a steam cracking treated product is less than 1,000 parts-per-million by weight
process preferably contains a majority n - paraffins, followed (wtppm ). In certain aspects , themethod further includes the
by iso -paraffins, and naphthenes with little or no olefins or step of introducing hydrogen gas to the hydrotreating pro
aromatics. 60 cess . In certain aspects , the intermediate unit is a distillation
Steam cracking processes cannot effectively process process and the product stream is a distilled product. In
heavy fractions that contain asphaltene. Steam cracking certain aspects, the distillation process is selected from the
asphaltene can produce coke , which can result in plugging group consisting of an atmospheric distillation unit , a
of the process lines . vacuum distillation unit, and a combination thereof. In
Some pre - treatment steps can be taken to make gas oil or 65 certain aspects , the SCW - treated product includes a concen
other heavy oils suitable for use as a steam cracking process tration of the vacuum residue fraction that is greater than 20
feedstock . Pre- treatment approaches can include hydrotreat wt % . In certain aspects , a cut point of distillation of the
US 10,703,999 B2
3 4
distillation process is between 650 degrees Fahrenheit (deg FIG . 5 provides a process diagram of an embodiment of
F.) and 1050 deg F. In certain aspects, the intermediate unit an integrated process .
is a thermal conversion process and the product stream is a FIG . 5A provides a process diagram of an embodiment of
thermal liquid product. In certain aspects, the thermal pro an integrated process .
cess can be selected from the group consisting of a coking 5 FIG . 6 provides a process diagram of an embodiment of
process and a visbreaking process. In certain aspects , the an integrated process .
thermal liquid product includes a concentration of the FIG . 7 provides a process diagram of an embodiment of
vacuum residue fraction of less than 5 wt % . In certain an integrated process .
aspects , the method further includes the steps of pressurizing FIG . 8 provides a process diagram of an embodiment of
a crude oil stream in a feed pump to a pressure at or greater 10 an integrated process .
than the critical pressure of water to produce a pressurized In the accompanying Figures , similar components or
oil, heating the pressurized oil in a feed heater to a tem features, or both , may have a similar reference label.
erature at or less than 150 deg C. to produce a hot oil
stream , pressurizing the water stream in a water pump to a DETAILED DESCRIPTION
pressure at or greater than the critical pressure of water to 15
produce a pressurized water, heating the pressurized water in While the scope of the apparatus and method will be
a water heater to a temperature at or greater than the critical described with several embodiments, it is understood that
temperature ofwater to produce a supercriticalwater stream , one of ordinary skill in the relevant art will appreciate that
and mixing the hot oil stream and the supercritical water many examples, variations and alterations to the apparatus
stream to produce the mixed stream . In certain aspects , the 20 and methods described here are within the scope and spirit
method further includes the steps of pressurizing a crude oil of the embodiments .
stream in a feed pump to a pressure at or greater than the Accordingly, the embodiments described are set forth
critical pressure of water to produce a pressurized oil, without any loss of generality, and without imposing limi
pressurizing the water stream in a water pump to a pressure tations , on the embodiments . Those of skill in the art
at or greater than the critical pressure of water to produce a 25 understand that the scope includes all possible combinations
pressurized water, mixing the pressurized oil and pressur and uses of particular features described in the specification .
ized water to produce the mixed stream , a pressurized mix . Described here are processes and systemsof an integrated
In a second aspect, an apparatus for upgrading a crude oil supercritical water and steam cracking process. The super
stream is provided . The apparatus includes a pre - reaction critical water process can convert crude oil to a feedstock
stage configured to produce a mixed stream from the crude 30 suitable for stream cracking to produce light olefins, such as
oil stream and a water stream , a reaction stage fluidly ethylene and propylene , as well as aromatics such as ben
connected to the pre-reaction stage. The reaction stage zene, toluene, and xylene. The integrated supercriticalwater
includes a convection section of a furnace fluidly connected and steam cracking process leads to synergy improving
to the pre -reaction stage , the convection section configured conversion to olefins .
to subject the mixed stream to conversion reactions to 35 The processes and systems of a supercritical water pro
produce convection upgraded stream and a supercritical cess upstream of a steam cracking process advantageously
reactor fluidly connected to the convection section , the overcomes drawbacks of conventional pre-treating pro
supercritical reactor configured to subject the convection cesses upstream of a steam cracking process. The integrated
upgraded stream to conversion reactions to produce a reactor supercritical water and steam cracking process produces a
effluent. The apparatus further includes a post-reaction stage 40 greater liquid yield than a conventional combination pro
fluidly connected to the reaction stage , the post - reaction cess. The processes and systems of an integrated supercriti
stage configured to separate the reactor effluent to produce cal water and steam cracking process described here can
a supercritical water (SCW ) -treated product, wherein the increase the hydrogen content of the feedstock to the steam
SCW -treated product includes an increased paraffin concen cracking process . An increased hydrogen content in the
tration as compared to crude oil stream , wherein the SCW- 45 feedstock can result in an increased yield of light olefins in
treated product includes an amount of water. the product effluent from the steam cracking process.
The processes and systems of an integrated supercritical
BRIEF DESCRIPTION OF THE DRAWINGS water and steam cracking process described here can
decrease the amount of heavy residue fractions, such as
These and other features, aspects , and advantages of the 50 atmospheric residue and vacuum residue, in the product
scope will become better understood with regard to the stream as compared to the feed stream . Advantageously ,
following descriptions, claims, and accompanying draw decreasing the heavy residue fraction in the feed to a steam
ings . It is to be noted , however, that the drawings illustrate cracker can reduce ormitigate coking; coke can form a layer
only several embodiments and are therefore not to be in the pyrolysis tube of the steam cracking process which
considered limiting of the scope as it can admit to other 55 can inhibit heat transfer , cause physical failure of the pyroly
equally effective embodiments. sis tube , and shorten the run length of a steam cracker
FIG . 1 provides a process diagram of the process. between cleaning and turnaround maintenance .
FIG . 2A provides a process diagram of an embodiment of The processes and systems of an integrated supercritical
an integrated process . water and steam cracking process described here can
FIG . 2B provides a process diagram of an embodiment of 60 decrease the concentration of heteroatoms, such as sulfur
an integrated process . compounds and metal compounds in the product relative to
FIG . 3A provides a process diagram of an embodiment of the feed . Sulfur compounds can suppress carbon monoxide
an integrated process . formation in a steam cracking process by passivating the
FIG . 3B provides a process diagram of an embodiment of inner surface of the pyrolysis tube . The presence of sulfur
an integrated process 65 can form nickel sulfide ,passivating the nickel present in the
FIG . 4 provides a process diagram of an embodiment of pyrolysis tube. Passivated nickel cannot catalyze coke gas
an integrated process. ification , which produces carbon monoxide, so the passiva
US 10,703,999 B2
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tion by the presence of sulfur reduces the amount of carbon As used throughout, “ asphaltene” refers to the fraction of
monoxide produced . At pyrolysis conditions, passivation an oil-containing stream which is not soluble in a n -alkane ,
cannot be reversed , that is at pyrolysis conditions the nickel particularly , n -heptane .
does not return to nickelmetal or oxide by losing sulfur. In As used throughout ,“ heavy fraction” refers to the fraction
certain applications, sulfur can be added to a feedstock for 5 in the petroleum feed having a true boiling point ( TBP ) 10 %
a steam cracking process to maintain a sulfur concentration that is equal to or greater than 650 deg F. (343 deg C.), and
ofbetween 20 parts -per -million by weight (wtppm ) and 400 alternately equal to or greater than 1050 deg F. (566 deg C.).
Examples of a heavy fraction can include the atmospheric
wtppm . Sulfur concentrations greater than 400 wtppm can residue fraction or vacuum residue fraction . The heavy
increase the coking rate in a steam cracking process.
Advantageously , the processes and systems of an inte- 10 fractionwerecannotinclude components from the petroleum feed.
grated supercritical water and steam cracking process that converted in the supercritical water reactor
The heavy fraction can also include hydrocarbons that were
described here can expand the range of crude oils suitable dimerized or oligomerized in the supercritical water reactor
for use to produce light olefins .
As used throughout, “ hydrogen content” refers to the 15 cracking lack of hydrogenation or resistance to thermal
due to either
quantity of the hydrogen atoms bonded to carbon atoms and As used throughout, “ light fraction” refers to the fraction
does not refer to free hydrogen . in the petroleum feed that is not considered the heavy
As used throughout, “ external supply of hydrogen ” refers fraction . For example, when the heavy fraction refers to the
to the addition of hydrogen to the feed to the reactor or to the fraction having a TBP 10 % that is equal to or greater than
reactor itself. For example, a reactor in the absence of an 20 650 deg F. the light fraction has a TBP 90 % that is less than
external supply of hydrogen means that the feed to the 650 deg F. For example, when the heavy fraction refers to
reactor and the reactor are in the absence of added hydrogen , the fraction having a TBP 10 % equal to or greater than 1050
gas ( H ) or liquid , such that no hydrogen (in the form H2) deg F. the light fraction has a TBP 90 % that is less than 1050
is a feed or part of a feed to the reactor. deg F.
As used throughout, " external supply of catalyst” refers to 25 As used throughout, “ light olefins” refers to ethylene ,
the addition of catalyst to the feed to the reactor or the propylene , n -butene , iso -butene, 2 -butenes and combina
presence of a catalyst in the reactor, such as a fixed bed tions of the same. Each of ethylene, propylene, n -butene ,
catalyst in the reactor. For example , a reactor in the absence and iso -butene is a light olefin and together they are light
of an external supply of catalystmeans no catalyst has been olefins.
added to the feed to the reactor and the reactor does not 30 As used throughout, " long chain paraffins ” refers to
contain a catalyst bed in the reactor. paraffins with more than 4 carbons arranged in a line or
As used throughout, " crude oil” refers to petroleum chain .
hydrocarbon streams that can include whole range crude oil , As used throughout, “ favor” means that reaction condi
reduced crude oil, and refinery streams. “ Whole range crude tions are disposed toward the production of certain products
oil ” refers to passivated crude oil which has been processed 35 from the reactant mixture .
by a gas -oil separation plant after being recovered from a As used throughout, “ distillable fraction ” or “ distillate”
production well. “ Reduced crude oil” can also be known as refers to the hydrocarbon fraction lighter than the distillation
“ topped crude oil ” and refers to a crude oil having no light residue from an atmospheric distillation process or a vacuum
fraction , and would include an atmospheric residue stream distillation process.
or a vacuum residue stream . Refinery streams can include 40 As used here, “majority ” means 51 percent ( % ) or more.
" cracked oil ," such as light cycle oil , heavy cycle oil , and As used throughout,“ coke ” refers to the toluene insoluble
streams from a fluid catalytic cracking unit (FCC ), such as material present in petroleum .
slurry oil or decant oil, a heavy stream from hydrocracker As used throughout, “ cracking” refers to the breaking of
with a boiling point greater than 650 deg F. , a deasphalted hydrocarbons into smaller ones containing few carbon atoms
oil (DAO ) stream from a solvent extraction process, and a 45 due to the breaking of carbon -carbon bonds.
mixture of atmospheric residue and hydrocracker bottom As used throughout, “ upgrade” means one or all of
fractions. increasing API gravity, decreasing the amount of impurities,
As used throughout, " heavy oil” refers to hydrocarbons such as sulfur, nitrogen , and metals , decreasing the amount
heavier than gas oil and can include vacuum gas oil , of asphaltene, and increasing the amount of distillate in a
atmospheric residue, vacuum residue , and combinations of 50 process outlet stream relative to the process feed stream .
the same. One of skill in the art understands that upgrade can have a
As used throughout, “ atmospheric residue” or “ atmo relative meaning such that a stream can be upgraded in
spheric residue fraction ” refers to the fraction of oil -con comparison to another stream , but can still contain undesir
taining streamshaving an initial boiling point (IBP) of 650 able components such as impurities .
deg F., such that all of the hydrocarbons have boiling points 55 It is known in the art that hydrocarbon reactions in
greater than 650 deg F. and includes the vacuum residue supercritical water upgrade heavy oil and crude oil contain
fraction . Atmospheric residue can refer to the composition ing sulfur compounds to produce products that have lighter
of an entire stream , such as when the feedstock is from an fractions. Supercritical water has unique properties making
atmospheric distillation unit, or can refer to a fraction of a it suitable for use as a petroleum reaction medium where the
stream , such as when a whole range crude is used . 60 reaction objectives can include upgrading reactions, desul
As used throughout, " vacuum residue ” or “ vacuum resi furization reactions denitrogenation reactions, and demetal
due fraction” refers to the fraction of oil-containing streams lization reactions. Supercritical water is water at a tempera
having an IBP of 1050 deg F. Vacuum residue can refer to ture at or greater than the critical temperature of water and
the composition of an entire stream , such as when the at a pressure at or greater than the critical pressure of water.
feedstock is from a vacuum distillation unit or can refer to 65 The critical temperature ofwater is 373.946 ° C. The critical
a fraction of stream , such as when a whole range crude is pressure of water is 22.06 megapascals (MPa ). Without
used . being bound to a particular theory, it is understood that the
US 10,703,999 B2
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basic reaction mechanism of supercritical water mediated a pressure between 2 bar and 5 bar. The radiation section can
petroleum processes is the same as a free radical reaction be used for severe cracking of hydrocarbons to produce light
mechanism . Thermal energy creates radicals through chemi olefins.
cal bond breakage . Supercritical water creates a " cage As used here , “ supercritical water process” refers to a
effect ” by surrounding the radicals. The radicals surrounded 5 process where crude oil undergoes conversion reactions in
by water molecules cannot react easily with each other, and the presence ofsupercriticalwater at supercritical conditions
thus, intermolecular reactions that contribute to coke for to produce an upgraded hydrocarbon stream . A supercritical
mation are suppressed . The cage effect suppresses coke water process includes a pre -reaction stage , a reaction stage ,
formation by limiting inter- radical reactions compared to and a post -reaction stage. The pre-reaction stage can include
conventional thermal cracking processes , such as delayed 10 units to pressurize, heat and mix the feed streams, such as
coker. Thermal cracking of a paraffin feed can produce pumps, heaters, and mixers. The reaction stage can include
paraffins and olefins having reduced numbers of carbons per at least one supercritical water reactor. The post-reaction
molecule as compared to the paraffin feed . The relative stage can include units to separate the effluent from the
amount of paraffins and olefins and the distribution of carbon reaction stage and can include heat exchangers, pressure
numbers strongly depends on the phase where the thermal 15 letdown devices, and one or more separation vessels.
cracking occurs . In the liquid phase , faster hydrogen transfer Referring to FIG . 1, a general process diagram of an
between molecules occurs due to the high density creating integrated supercritical water and steam cracking process is
closer distances between the molecules which makes hydro provided . Stream A is produced in a supercritical water
gen transfer between molecules easier and faster . Thus , the process from a mixture of a crude oil and a water stream .
liquid phase facilitates the formation of more paraffins than 20 The crude oil and water stream can be pressurized or
gas -phase cracking . Additionally , liquid phase cracking pressurized and heated in the pre -reaction stage of the
shows generally even distribution of the carbon numbers of supercriticalwater process before forming Stream A.Stream
the product while gas phase cracking has more light paraffins A is introduced to the convection section of a furnace of a
and olefins in the product. While , supercritical water facili steam cracking process. The temperature of Stream A is
tates hydrogen transfer between molecules , it is inevitable to 25 increased in the convection section to a temperature between
produce unsaturated hydrocarbons due to a limited amount the critical temperature of water and 500 deg C. and alter
of available hydrogen . Unsaturated carbon -carbon bonds nately between the critical temperature of water and 450 deg
can be distributed through the whole range ofboiling points . C. Conversion reactions involving the components of
Olefins, as a representative unsaturated hydrocarbon , are Stream A begin to occur in the convection section so as to
valuable chemicals, but low stability can cause many prob- 30 produce a partially upgraded stream in Stream B. Stream B
lems such as gum formation when exposed to air. Thus, it is can be introduced to the reaction stage of the supercritical
common practice in the modern refinery to saturate olefins water process to be further upgraded . Stream C is a product
with hydrogen in the presence of catalyst . Advantageously, stream withdrawn from the post-reaction stage of the super
at supercritical conditions water acts as both a hydrogen critical water process and is upgraded relative to the crude
source and a solvent ( diluent) in upgrading reactions, des- 35 oil . The composition of Stream C , including the amount of
ulfurization reactions and demetallization reactions and a water, can be adjusted in the post- reaction stage of the
catalyst is not needed . Hydrogen from the water molecules supercritical water process. Stream C can be combined with
is transferred to the hydrocarbons through direct transfer or a diluent steam and introduced to the convection section of
through indirect transfer, such as the water gas shift reaction . the furnace . The need for diluent steam can be determined
As used here , " conversion reactions” refers to reactions 40 based on a composition of Stream C. In the convection
that can upgrade a hydrocarbon stream including cracking , section , components of Stream C can mix with components
isomerization , alkylation , dimerization , aromatization , cycl of Stream A and can be carried out in Stream B.Components
ization , desulfurization , denitrogenation , deasphalting, and of Stream C can enter the radiation section of the furnace
demetallization. and be carried out in Stream D. Stream D can contain olefins
As used here, “ steam cracking process” refers to a process 45 and other cracked hydrocarbon components .
where thermal cracking reactions occur in the presence of The following embodiments , provided with reference to
steam . The steam cracking process can include a furnace . the figures, describe the integrated supercritical water and
The furnace can include a convection section and a radiation steam cracking process in more detail
section . The convection section can be used for preheating An integrated supercritical water and steam cracking
a feedstock stream , a water stream , and other streams. The 50 process is described with reference to FIG . 2A .
convection section can operate at a temperature at or greater In pre -reaction stage 100 , crude oil stream 2 can include
than 650 deg C. The convection section can operate at a crude oil. In at least one embodiment, crude oil stream 2 can
pressure between 2 bar ( 200 kPa) and 5 bar (500 kPa ). Steam include an atmospheric residue fraction of between 20 wt %
can be injected with the hydrocarbon stream in the convec and 95 wt % and a vacuum residue fraction ofbetween 3 wt
tion section . Vaporization of the feed to a steam cracking 55 % and 50 wt % . Crude oil stream 2 can be pressurized in feed
process can increase light olefin production . Vapor-phase pump 115 to a pressure greater than the critical pressure of
cracking of hydrocarbons in the convection section can lead water to produce pressurized oil 215. Pressurized oil 215 can
to formation of light molecules, such as C2 and Cz com be heated in feed heater 120 to produce hot oil stream 220 .
pounds, while liquid -phase cracking can lead to middle Feed heater 120 can be any type of heater capable of
range molecules , such as C , and Cg compounds. Operating 60 increasing the temperature of pressurized oil 215 such as a
conditions to increase vaporization are maintained to avoid gas fired heater or an electric heater. The temperature of hot
the conversion to coke due to non -vaporized hydrocarbons. oil stream 220 can be less than the critical temperature of
Steam , as a diluent, can suppress coke formation. After water, alternately equal to about 150 deg C., and alternately
passing through the convection section , the stream can enter less than 150 deg C.Maintaining the temperature of hot oil
the radiation section where thermal cracking can occur. The 65 stream 220 at less than the critical temperature of water
radiation section can operate at a temperature between 750 reduces the formation of coke in hot oil stream 220 and in
deg C. and 850 deg C. The radiation section can operate at supercritical reactor 140 .
US 10,703,999 B2
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Water stream 4 can be a demineralized water having a conversion reactions in the presence of supercritical water
conductivity less than 1.0 microSiemens per centimeter from mixed stream 230. Convection upgraded stream 25 can
(US /cm ), and alternately less than 0.1 uS /cm . In at least one be at a temperature between the critical temperature ofwater
embodiment, water stream 4 is demineralized water having and 650 deg C., alternately between the critical temperature
a conductivity less than 0.1 uS /cm . Water stream 4 can be 5 of water and 500 deg C., alternately between the critical
pressurized in water pump 105 to a pressure greater than the temperature of water and 450 deg C., and alternately
critical pressure of water to produce pressurized water 205 . between the critical temperature of water and 420 deg C. The
Pressurized water 205 can be heated in water heater 110 to
produce supercritical water stream 210. The temperature of pressure of convection section 312 can be between 2 bar
supercriticalwater stream 210 can be equal to or greater than 10 stream 230andin 5convection
( 200 kPa ) bar (500 kPa). The residence time of mixed
the critical temperature of water , alternately equal to or minutes, and alternately lesssection 312 can be less than 60
greater than 380 deg C., and alternately between 380 deg C. time of mixed stream 230 can beminutes
than 30 . The residence
adjusted to limit the
and 500 deg C.
Feed pump 115 and water pump 105 can be any pumps temperature of convection upgraded stream 25. The flow
capable of increasing the pressure of the respective fluid 15 inpatha downward
of mixed stream 230 in convection section 312 can be
path , and alternately can be in a horizontal
stream to a pressure greater than the critical pressure of
water. In at least one embodiment, feed pump 115 and water path. In at least one embodiment, the flow path of mixed
pump 105 can be diaphragm metering pumps. stream 230 is in the absence of an upflow path .
Feed heater 120 and water heater 110 can be any type of Advantageously , the presence of supercritical water in
exchangers capable of increasing the temperature of the 20 mixed stream 230 can suppress coke formation and forma
respective fluid stream . In at least one embodiment, feed tion of gas compounds compared to processes that use the
heater 120 can be a cross exchanger removing heat from convection section of a steam cracking furnace to preheat a
another portion of the process to increase the temperature of feedstock or to thermal crack a feedstock in the absence of
pressurized oil 215. In at least one embodiment, water heater supercriticalwater. Examples of gas compounds can include
110 can be a cross exchanger removing heat from another 25 methane , ethane , ethylene, propane, propylene, butanes,
portion of the process to increase the temperature of pres butenes, and combinations thereof.
surized water 205. In some embodiments, feed heater 120 In at least one embodiment, convection upgraded stream
and water heater 110 can be fluidly connected on the heat 25 can be introduced to supercritical reactor 140 to produce
transfer medium side. That is the heat transfer medium used reactor effluent 240. The reaction conditions in supercritical
to heat feed heater 120 and water heater 110 can be from the 30 reactor 140 can be maintained such that conversion reactions
same source . occur. The conversion reactions that occur in supercritical
Hot oil stream 220 and supercriticalwater stream 210 can reactor 140 can be the same reactions that occur in convec
be mixed in mixer 130 to produce mixed stream 230. The tion section 312. Reaction conditions can include the tem
ratio of the volumetric flow rate of hot oil stream 220 to perature, pressure, and residence time. The temperature of
supercritical water stream 210 can be between 1:10 and 10 : 1 35 supercritical reactor 140 can be greater than the critical
at standard temperature and pressure (SATP ), and alternately temperature of water, alternately between 380 deg C. and
between 1:5 and 5 :1 at SATP. Mixer 130 can be any mixing 480 deg C., and alternately between 390 deg C. and 450 deg
device suitable for mixing a hydrocarbon stream with a C. The pressure in supercritical reactor 140 can be greater
water stream . Examples of mixer 130 can include an ultra than the critical pressure of water, alternately between 23
sonic device and a tee fitting . Mixed stream 230 can be at a 40 MPa and 35 MPa, and alternately between 24 MPa and 30
pressure at or greater than the critical pressure of water. MPa. Pressure in supercritical reactor 140 can be controlled
Mixed stream 230 can be at a temperature in the range from by depressurizing device 160. Supercritical reactor 140 can
between 200 deg C. to 500 deg C., alternately between 200 be a tubular type reactor. The residence time of supercritical
deg C. to 450 deg C., alternately in the range from between reactor 140 can be between 10 seconds and 120 minutes , and
320 deg C. and 450 deg C. The temperature ofmixed stream 45 alternately between 5 minutes and 30 minutes . In at least one
230 can depend on the temperatures of supercritical water embodiment, the residence time of supercritical reactor 140
stream 210 and hot oil stream 220 . is between 5 minutes and 30 minutes . Supercritical reactor
In at least one embodiment of the integrated supercritical 140 can be in the absence of an external supply ofhydrogen .
water and steam cracking process , mixed stream 230 can be Supercritical reactor 140 can be in the absence of an external
introduced to furnace 310. In at least one embodiment, the 50 supply of catalyst.
entire volume of mixed stream 230 is introduced to convec Reactor effluent 240 can be introduced to post -reaction
tion section 312 of furnace 310. In at least one embodiment, stage 200 to produce SCW -treated product 10 .
a portion of mixed stream 230 is introduced to convection Reactor effluent 240 is introduced to cooling device 150
section 312 of furnace 310 . to reduce the temperature of reactor effluent 240 to produce
Reaction stage 190 includes convection section 312 of 55 cooled effluent 250. Cooling device 150 can be one heat
furnace 310 and supercritical reactor 140. Mixed stream 230 exchanger or a series of heat exchangers. In at least one
can be introduced to convection section 312 of furnace 310 embodiment, cooling device 150 includes a heat exchanger
and can be heated in convection section 312 by hot flue gas that can be used to heat pressurized water 205 by cross
from radiation section 314 to produce convection upgraded exchange with reactor effluent 240. In at least one embodi
stream 25. Convection section 312 can be designed to 60 ment, cooling device 150 can include one or more heat
achieve a Reynolds number of at least 4000 of the streams exchangers capable of removing heat from reactor effluent
in convection section 312. A Reynolds number of at least 240 to produce steam . Cooling device 150 can include any
4000 can ensure development of full turbulence . Full tur type of heat exchanger capable of decreasing the tempera
bulence can increase mixing between the hydrocarbons and ture of reactor effluent 240. In at least one embodiment,
the supercritical water in mixed stream 230. Mixed stream 65 cooling device 150 can be a cross exchanger capable of
230 can undergo conversion reactions in convection section removing heat from reactor effluent 240 to heat another
312, such that hydrocarbons in mixed stream 230 undergo stream .
US 10,703,999 B2
11 12
Cooled effluent 250 can be depressurized in depressuriz has a decreased concentration of heteroatoms, such as sulfur
ing device 160 to produce depressurized effluent 260 . compounds, nitrogen compounds, and metal compounds as
Depressurizing device 160 can be any device capable of compared to crude oil stream 2 .
reducing the pressure of cooled effluent 250. In at least one SCW - treated product 10 can be introduced to convection
embodiment, depressurizing device 160 can be a back 5 section 312 of furnace 310. The components of SCW -treated
pressure regulator. In at least one embodiment, depressur product 10 can mix with the diluent components from mixed
izing device 160 can be a pressure control valve . stream 230 after it enters convection section 312. Compo
Depressurized effluent 260 is introduced to gas -liquid nents of SCW - treated product 10 can mix with the diluent
separator 170 to produce gas stream 270 and liquid stream components in radiation section 314 to produce furnace
275. Gas stream 270 can contain hydrogen , hydrogen sul- 10 effluent 20. Furnace effluent 20 can include olefins.
fide, methane, ethane , propane, ethylene , carbon monoxide , The reactions in furnace 310 can include radical-mediated
carbon dioxide, and combinations of the same. Liquid reactions that occur in the radiation section of furnace 310 .
stream 275 is introduced to oil -water separator 180 to At temperatures between 750 deg C. and 875 deg C.,
produce SCW - treated product 10 and produced water 285 . hydrocarbon molecules can be cracked to generate a radical.
Produced water 285 can contain an amount of hydrocar- 15 Through propagation of radicals , new molecules and radi
bons. The amount of hydrocarbons in produced water 285 cals can be generated . In steam cracking, the low operating
can be measured as total organic carbon (TOC ). Hydrocar pressure and presence of steam as a diluent favor the
bons in produced water 285 means a loss of oil from production of light olefins.
SCW - treated product 10 , therefore the TOC of produced Advantageously, SCW -treated product 10 is a water-in -oil
water 285 can be less than 5 grams of organic carbon in 100 20 emulsion , with the amount ofwater controlled by separation .
grams of water (0.5 wt % ), alternately less than 0.1 wt % , Advantageously , the presence of emulsified water in SCW
and alternately less than 0.02 wt % . In at least one embodi treated product 10 can assist vaporization ofhydrocarbons in
ment, the TOC in produced water 285 is less than 0.02 wt % . furnace 310 because the emulsified water has a boiling point
The operating conditions of depressurizing device 160 , greater than 100 deg C. A boiling point greater than 100 deg
gas - liquid separator 170 , and oil-water separator 180 can be 25 C. of the emulsified water can be due to the pressure in
adjusted to control an amount of water in SCW - treated furnace 310 , the emulsified state of the water or both . The
product 10. In at least one embodiment, the residence times emulsified water stays in emulsion for longer resulting in
in gas - liquid separator 170 and oil-water separator 180 can thermal cracking of the hydrocarbons and suppression of
control the amount of water in SCW -treated product 10. In coke formation .
at least one embodiment, shorter residence times in gas- 30 Referring to FIG . 2B with reference to FIG . 2A , an
liquid separator 170 and oil-water separator 180 can increase alternate embodiment of the integrated supercritical water
the amount ofwater in SCW -treated product 10. In at least and steam cracking process is provided . Pressurized oil 215
one embodime adding a demulsifier to liquid stream 275 and pressurized water 205 can be mixed in mixer 130 to
can enhance the separation in oil-water separator 180 and produced pressurized mix 235 , a mixed stream . Pressurized
can control the amount ofwater in SCW -treated product 10. 35 mix 235 can be introduced to convection section 312 to
In at least one embodiment, demulsifier can be added to produce convection upgraded stream 25 .
liquid stream 275 in the range from 0.01 wt % to 0.1 wt % Referring to FIG . 3A with reference to FIG . 2A , a process
(weight of demulsifier to weight of liquid stream 275 ). In at flow diagram of a steam cracking process 300 is provided .
least one embodiment, SCW -treated product 10 can contain Furnace 310 is a unit of steam cracking process 300. Furnace
an amount of water . The amount of water in SCW - treated 40 310 produces furnace effluent 20 , which can be introduced
product 10 can be less than 1 percent by weight (wt % ) to cracker downstream unit 320. Furnace effluent 20 can
water, alternately less than 0.1 wt % of water ( 1,000 wt contain a greater amount of light olefins , methane, acety
ppm ), alternately less than 0.05 wt % (500 wt ppm ), alter lene, benzene , toluene , xylene, pyrolysis gasoline , pyrolysis
nately less than 0.01 wt % ( 100 wt ppm ), alternately between fuel oil and other products as compared to crude oil stream
0.03 wt % (300 ppm ) and 0.1 wt % of water, and alternately 45 2. Other products can include coke .
between 0.03 wt % (300 ppm ) and 1 wt % of water. Cracker downstream unit 320 can include operational
SCW - treated product 10 contains an upgraded oil . SCW units to further process furnace effluent 20 , including further
treated product 10 can include a distillable fraction , an cracking units , heat recovery units, depressurization units,
atmospheric residue fraction , and a vacuum residue fraction . and separation units. Cracker downstream unit 320 can
SCW -treated product 10 can have a paraffin concentration . 50 produce cracked product 30 and fuel oil 32. Cracked product
SCW - treated product 10 can have an increased paraffin 30 can include light olefins,methane, and ethane . Cracked
concentration by weight in the distillable fraction as com product 30 has a greater amount of lightolefins as compared
pared to crude oil stream 2. In at least one embodiment, to a product from a steam cracking process in the absence of
SCW - treated product 10 can have a reduced concentration of being integrated with a supercritical water process. Fuel oil
an atmospheric residue fraction as compared to the concen- 55 32 can include pyrolysis fuel oil with a boiling point greater
tration of the atmospheric residue fraction in crude oil than 200 deg C., which can be an unstable and low quality
stream 2. In at least one embodiment, SCW - treated product hydrocarbon stream that is useful as a fuel oil . Fuel oil 32
10 can have a reduced concentration of a vacuum residue can have a yield that is less than 30 wt % of the feed to steam
fraction as compared to the concentration of the vacuum cracking process 300. In at least one embodiment, fuel oil 32
residue fraction in crude oil stream 2. In at least one 60 can have a yield that is less than 30 wt % of SCW -treated
embodiment, SCW - treated product 10 can include n -paraf product 10 .
fins and a -olefins in the distillable fraction due to the In at least one embodiment, as shown in FIG . 3B , gas
cracking of alkyl-substituted aromatic compounds in con stream 270 can be introduced to sweetening process 350 to
vection section 312 and supercritical water reactor 140, remove hydrogen sulfide from the stream to produced sweet
where the alkyl-substituted aromatic compounds have alkyl 65 ened gas stream 370. Sweetening process 350 can be any
groups with long chain paraffins attached to the aromatic type of unit capable of sweetening a gas phase stream by
cores. In at least one embodiment, SCW -treated product 10 removing sulfur compounds. Examples of sweetening units
US 10,703,999 B2
13 14
can include the use of an alkaline solution . Sweetened gas greater than 20 wt % and the total sulfur content of crude oil
stream 370 can be transferred to steam cracking process 300 stream 2 is greater than 1.5 wt % of sulfur. In at least one
as a feed or a fuel gas . Advantageously , sweetening process embodiment, the concentration of water in SCW -treated
350 enables use of the by -product gases from the supercriti product 10 is less than 1,000 wt ppm , and alternately less
cal water process for steam cracking . Sulfur compounds can 5 than 100 wt ppm prior to being introduced to hydrotreating
reduce coke formation in steam cracker through passivation process 400. Advantageously, a concentration of water in
of the inner wall of the cracking coil. However, sulfur SCW - treated product 10 of less than 1,000 wt ppm can limit
compounds also cause severe corrosion in the steam crack deactivation of a hydrotreating catalyst by water.
ing zone as well as in downstream units, such as quenching Hydrogen gas stream 6 is introduced to hydrotreating
process. Therefore, sweetening process 350 enables use of 10 process 400. Hydrogen gas stream 6 can be from any source
gas stream 270 in steam cracking process 300 . of hydrogen gas. In at least one embodiment, hydrogen gas
The composition of the crude oil stream can impact the stream 6 can be recycled from steam cracking process 300,
composition of the SCW - treated product. The composition where hydrogen gas can be generated . The ratio of the flow
of the SCW -treated product can impact whether the SCW rate of hydrogen gas stream 6 to the flow rate of SCW
product is suitable for treatment in the steam cracking 15 treated product 10 can be between 100 cubic nanometers per
process. In embodiments , where the composition of the kiloliter (nm >/kL ) and 800 nm3/kL , and alternately between
SCW -treated product is not suitable for treatment in the 200 nm ? /kL and 500 nm3/kL .
steam cracking process, the SCW -treated product can be Hydrotreating process 400 can contain a hydrotreating
introduced to an intermediate unit to produce a product catalyst. The hydrotreating catalyst can be a cobalt-molyb
stream and the product stream can be introduced to the steam 20 denum (Como), nickel -molybdenum (NiMo), or any other
cracking process. The composition of the SCW - treated prod catalyst known in the art. In hydrotreating process 400,
uct is suitable for treatment in the steam cracking process hydrotreating reactions can occur such as hydrogenation ,
when the concentration of the vacuum residue fraction in the hydrodesulfurization , and hydronitrogenation . Hydrogena
SCW - treated product is less than 5 wt % and alternately less tion reactions can hydrogenate unsaturated bonds, including
than 3 wt % . The concentration of the vacuum residue 25 of olefins. Hydrodesulfurization and hydronitrogenation
fraction can bemeasured using simulated distillation (SIM reactions with hydrotreating catalyst can remove sulfur from
DIS ) , a common method described in ASTM D 7169. When compounds upgraded by the supercritical water process. The
the concentration of the vacuum residue fraction is greater supercritical water process can convert large sulfur mol
than 5 wt % , severe coking can occur in a steam cracking ecules into lighter sulfur molecules such as alkyl thiophenes
process which can cause pressure drop throughout the steam 30 and thiols . Lighter sulfur molecules can exhibit increased
cracking tubes and can inhibit heat transfer between the heat reactivity of sulfur compounds, such that sulfur can be
source, such as a flame, and the fluid in the steam cracking removed more easily from lighter sulfur molecules .
tubes . A buildup of coke on the steam cracking tubes can act Hydrotreating process 400 can include a hydrotreating
as an insulator which disrupts the heat transfer process . reactor. The operating temperature of the hydrotreating
The combination of convection section 312 and super- 35 reactor can be between 300 deg C. and 480 deg C. and
critical reactor 140 can convert 80 wt % of the vacuum alternately between 320 deg C. and 400 deg C. In the
residue fraction in crude oil stream 2 to light fraction hydrotreating reactor, in the presence of the hydrotreating
components , alternately 75 wt % of the vacuum residue catalyst, unsaturated bonds of the hydrocarbons present in
fraction in crude oil stream 2 to light fraction components , SCW - treated product 10 can be hydrogenated by hydrotreat
and alternately at least 70 wt % of the vacuum residue 40 ing. The olefin saturation reaction is exothermic and the
fraction in crude oil stream 2 to light fraction components . operating temperature should be kept as low as possible. The
In at least one embodiment, crude oil stream 2 contains a operating pressure of the hydrotreating reactor can be
concentration of vacuum residue fraction of less than 20 wt between 3 MPa and 25 MPa, and alternately between 5 MPa
% and the combination of convection section 312 and and 15 MPa. The liquid hourly space velocity of the
supercritical reactor 140 converts 75 wt % of the vacuum 45 hydrotreating reactor can be between 0.1 per hour (/hr) and
residue fraction in crude oil stream 2 to light fraction 2 /hr, and alternately between 0.2/hr and 1/hr.
components resulting in SCW -treated product 10 containing HTP - treated product 40 can be introduced to the furnace
less than 5 wt % vacuum residue fraction . of steam cracking process 300. HTP -treated product 40 can
In embodiments where the composition of the SCW be used a feedstock to the furnace for steam cracking .
treated product contains a concentration of the vacuum 50 HTP - treated product 40 can have a boiling point range that
residue fraction of greater than 5 wt % , an intermediate unit is less than the boiling point range of SCW -treated product
can process the SCW -treated product to produce a product 10 due to hydrogenative and catalytic upgrading in
stream suitable for use in the steam cracking process . hydrotreating process 400. The amountof heavy fractions in
Examples of the intermediate unit can include a hydrotreat HTP - treated product 40 is less than the amount in SCW
ing process , a distillation process, and a thermal conversion 55 treated product 10. The amount of impurities such as sulfur,
process. Advantageously , the intermediate unit can remove nitrogen and metals in HTP -treated product 40 is less than
a portion of the vacuum residue fraction present in the the amount in SCW -treated product 10. The operating con
SCW -treated product. ditions , such as temperature and pressure , of HTP -treated
Referring to FIG . 4 , with reference to FIG . 2A , an product 40 can be adjusted based on the operating conditions
embodiment of an integrated supercritical water and steam 60 of steam cracking process 300. In at least one embodiment,
cracking process with an intermediate unit is provided . the temperature of HTP - treated product 40 can be in the
SCW -treated product 10 is introduced to hydrotreating pro range from about 10 deg C. to about 400 deg C. when
cess 400. Hydrotreating process 400 can treat SCW -treated entering steam cracking process 300. In at least one embodi
product 10 to produce hydrotreating process (HTP ) -product ment, the pressure of HTP - treated product 40 can be in the
40. Hydrotreating process 400 advantageously can be used 65 range from about 0.01 MPa to about 5 MPa when entering
to process SCW -treated product 10 when the concentration steam cracking process 300. In at least one embodiment,
of the vacuum residue fraction of crude oil stream 2 is HTP - treated product 40 is reduce to a temperature between
US 10,703,999 B2
15 16
30 deg C. and 90 deg C.and reduced to a pressure of ambient process 300. As used here , “ cut point” refers to the final
pressure . In at least one embodiment, a diluent stream is boiling point of distillates. The cut point of distillation of
mixed with HTP - treated product 40 prior to being intro distillation process 500 can be between 650 deg F. and 1050
duced to the furnace of steam cracking process 300. The deg F., alternately between 850 deg F. and 1050 deg F. In at
diluent stream can be steam . Hydrotreating process 400 can 5 least one embodiment, the cut point of distillation of distil
include heat exchangers, depressurizing valves, and other lation process 500 can be designed to remove or eliminate
process units that can adjust operating conditions down the vacuum residue fraction from distilled product 50. In at
stream of the hydrotreating reactor . least one embodiment, the cut point of distillation process
Advantageously , the integrated supercritical water and 500 is between 850 deg F. and 1050 deg F. The greater the
steam cracking process can remove metallic compounds 10 cut point of distillation , the greater the volume of distilled
from crude oil stream 2 , where the metallic compounds can product 50 that can be directed toward steam cracking
be separated from the upgraded oil into the water. As result, process 300 ; however, coke formation can be increased due
SCW - treated product 10 contains a reduced metallic content to a shorter run length . Increased coke formation can lead to
as compared to crude oil stream 2. The reduced metallic a requirement for decoking. The cut point of distillation can
content of SCW -treated product 10 results in a longer life for 15 be determined in consideration of steam cracking process
the hydrotreating catalyst in hydrotreating process 400 as 300 and available decoking processes .
compared to a conventional hydrotreating process treating Distilled residue 55 can contain the fraction separated by
crude oil. the cut point. In at leastone embodiment, distilled residue 55
Advantageously , the integrated supercritical water and can be recycled to the front end of the integrated supercriti
steam cracking process can convert asphaltene to maltene 20 cal water and steam cracking process and can be mixed with
without generating coke . Therefore, SCW -treated product crude oil 2. In at least one embodiment, distilled residue 55
10 can have a reduced asphaltene concentration as compared can be combined with fuel oil 32. In at least one embodi
to crude oil stream 2. Asphaltene is a known precursor for ment, fuel oil 32 can have a yield that is less than 30 wt %
coke formation on a hydrotreating catalyst. Therefore, the of distilled product 50 .
reduced asphaltene results in a longer life for the hydrotreat- 25 Referring to FIG . 5A , with reference to FIG . 2A , an
ing catalyst in hydrotreating process 400 as compared to a embodiment of an integrated supercritical water and steam
conventional hydrotreating process treating crude oil. cracking process with distillation process 500 is provided .
Advantageously, treatment of crude oil by the integrated Depressurized effluent 260 can be introduced to convection
supercritical water and steam cracking process can relieve section 312. Depressurized effluent 260 can be at a pressure
load to hydrotreating process 400 thus allowing for milder 30 between 1 pounds per square inch (psig ) and 200 psig .
conditions in hydrotreating process 400 than would other Depressurized effluent 260 can be at a temperature of less
wise be expected in a hydrotreating process. As used here, than the critical temperature of water. Cooling of depres
“ relieve load” means a reduced operating pressure in surized effluent 260 can be due pressure letdown without
hydrotreating process, a reduced operating temperature in additional temperature reducing device. Depressurized
hydrotreating process, a shorter residence time in 35 effluent 260 is an emulsion and can be heated by passing
hydrotreating process , a longer catalyst life time in through convection section 312 to produce heated emulsion
hydrotreating process, less production of lightgases, such as 34. Heated emulsion 34 can be at the same pressure as
methane and ethane in hydrotreating process, and reduced depressurized effluent 260. Heated emulsion 34 can be at a
operating cost in hydrotreating process . temperature between 350 deg C. and 600 deg C. The
In at least one embodiment, fuel oil 32 can have a yield 40 temperature of heated emulsion 34 can be adjusted based on
that is less than 30 wt % ofHTP -treated product 40 . the cut point of distillation in distillation process 500.
Referring to FIG . 5 , with reference to FIG . 2A , an Heated emulsion 34 can be introduced to distillation process
embodiment of an integrated supercritical water and steam 500 to produce distilled product 50 and distilled residue 55 .
cracking process with an intermediate unit is provided . Distilled residue 55 can contain dirty water . The dirty
SCW - treated product 10 is introduced to distillation process 45 water can include water and metal compounds .
500. Distillation process 500 can be any distillation process Distilled product 50 can contain the majority of water
capable of separating streams. Examples of distillation pro present in heated emulsion 34. Distilled product 50 can be
cess 500 include an atmospheric distillation unit , vacuum introduced to convection section 312 of furnace 310. Diluent
distillation unit, or a combination thereof. In at least one stream 36 can be mixed with distilled product 50 before
embodiment, distillation process 500 can include a distilla- 50 being added to convection section 312. Diluent stream 36
tion unit. Distillation process 500 can distill SCW -treated can include water at a temperature and pressure such that the
product 10 to produce distilled product 50 and distilled water is present in diluent stream 36 as steam . The steam to
residue 55. Distilled product 50 can be introduced to the oil ratio for furnace 310 can be between 0.4 kilogram -steam
furnace of steam cracking process 300 . per kilogram -oil (kg -steam /kg-oil) and 1.0 kg -steam /kg-oil .
Distillation process 500 advantageously can be used to 55 In general the heavier the feed , the greater the volume of
process SCW - treated product 10 when the concentration of steam to be included in furnace 310. In at least one embodi
the vacuum residue fraction of crude oil stream 2 is greater ment, the water concentration in distilled product 50 can be
than 20 wt % or the concentration of the vacuum residue measured and the volume of diluent stream 36 can be
fraction of SCW -treated product 10 is greater than 5 wt % . adjusted based on the measured amount ofwater in distilled
Distillation process 500 can use steam as an energy carrier 60 product 50. Advantageously, introducing depressurized
and diluent in the distillation unit. In at least one embodi effluent 260 to convection section 312 and using distillation
ment, the concentration of water in SCW -treated product 10 process 500 to separate distilled product 50, can reduce the
can be less than 1 pound per barrel ( lb /barrel). In at least one amount of diluent stream 36 used in convection section 312 .
embodiment, the concentration of water in SCW -treated Referring to FIG . 6 , an embodiment of an integrated
product 10 can be less than 0.3 wt % . 65 supercritical water and steam cracking process with an
The cut point of distillation of distillation process 500 can intermediate unit is provided . SCW -treated product 10 is
be selected based on the specifications of steam cracking introduced to thermal conversion process 600. Thermal
US 10,703,999 B2
17 18
conversion process 600 can include a coking process and a product from a delayed coker has a lesser hydrogen to
visbreaking process. Coking processes can include a delayed carbon ratio than a liquid product from a supercriticalwater
coker process and a fluid coker process . A visbreaking process. In addition , a supercritical water process can pro
process can operate at a temperature between 450 deg C. and duce less coke than a delayed coker.
500 deg C., a pressure between 1 MPa and 2.5 MPa, and a 5
residence time between 1 minute and 20 minutes. A delayed EXAMPLES
coker process can operate at a temperature between 410 deg
C. and 470 deg C., a pressure between 0.04 MPa and 0.17 Example 1
MPa, and a residence timebetween 5 hours and 20 hours . A
fluid coker process can operate at a temperature between 480 10 Example 1 Contains Aspen HYSYS® Simulations from
deg C. and 560 deg C., a pressure at ambient pressure, and Aspen Technology, Inc. Bedford ,Mass. illustrating the inte
a residence time between 5 seconds and 20 seconds . gration of the convection section of the furnace to the
Thermal conversion process 600 converts the upgraded supercritical water process. In a first simulation , with refer
oil in SCW -treated product 10 to produce thermal liquid ence to FIG . 7 and FIG . 2A , water stream 4 was simulated
product 60 , coke 62, and thermal gas product 64. In at least 15 as a demineralized water with a conductivity of less than 0.1
one embodiment, thermal conversion process 600 can be a uS/ cm . The composition of crude oil stream 2 is shown in
delayed coker. Thermal liquid product60 contains less than Table 1. Pressurized water 205 is pre -heated by cross
5 wt % vacuum residue fraction . Coke 62 can contain solid exchange with cooling device 150 to produce pre -heated
coke, pitch , heavy molecules such as asphaltenes, and com water 705. Pre -heated water 705 is heated in water heater
binations of the same. Thermal gas product 64 can include 20 110 to produce supercritical water stream 210 .
methane, ethane , ethylene , propane, propylene , hydrogen Mixed stream 230 is introduced to supercritical reactor
sulfide, other lightmolecules, and combinations of the same. 140. Reactions occur in supercritical reactor 140 with a
Thermal liquid product 60 can be introduced to steam residence time of less than 15 minutes .
cracking process 300 . Supercritical reactor 140 was simulated as a tubular-type
Thermal conversion process 600 advantageously can be 25 reactor to give residence time to the mixed stream of at least
used to process SCW - treated product 10 when the vacuum 15 minute . Depressurized effluent 260 is introduced to
residue fraction of crude oil stream 2 is greater than 20 wt gas-liquid separator 170 , which produced vapor stream 770
% or the vacuum residue fraction of SCW - treated product 10 and liquid stream 275. Vapor stream 770 is introduced to
is greater than 5 wt % . In at least one embodiment, the vapor separator 700 , which produced gas stream 270 and
concentration of water in SCW - treated product 10 can be 30 separated liquid 775. Liquid stream 275 and separated liquid
less than 20 wt % prior to entering thermal conversion 775 are introduced to oil-water separator 180 to produce
process 600. The amount of water in SCW -treated product SCW -treated product 10 and produced water 285 .
10 can be adjusted based on the process design of thermal The properties of SCW - treated product 10 are in Table 1.
conversion process 600, the energy demands, and the Operating conditions of the streams are in Table 2 .
desired product composition . The amount of water in SCW- 35 Table 1 provides the properties of the streams.
treated product 10 can reduce coke generation , by generating
hydrogen through reforming and due to the water - gas shift TABLE 1
reaction . The amount of water in SCW - treated product 10 Stream properties for Example 1 .
can increase liquid product yield in thermal conversion
process 600 . 40 Properties Stream 2 Stream 10
In certain embodiments , when thermal liquid product 60 28.2 34.2
contains a concentration of vacuum residue fraction of Specific Gravity (API)
TBP 5 % (deg C.) 41 35
greater than 5 wt % , thermal liquid product 60 can be TBP 10 % (deg C.) 92 98
processed in another unit such as a distillation or fraction TBP 30 % ( deg C.) 234 215
ation unit to remove the vacuum residue fraction and there- 45 TBP 50 % (deg C.) 363 337
fore reduce the concentration of vacuum residue fraction to TBP 70 % (deg C.) 524 453
less than 5 wt % prior to being introduced to steam cracking TBP 90 % (deg C.) 745 596
process 300 . TBP 95 % (deg C.) 819 634
Sulfur Content (wt % ) 2.9 2.7
Thermal gas product 64 can be introduced to steam Nitrogen Content (wt ppm ) 1536 925
cracking process 300 (not shown ) as a feed or as a fuel. 50 Kinematic Viscosity at 100 deg F. 16.7 1.5
While the embodiments here have been described with (centistokes (cSt))
reference to the integrated supercritical water and steam
cracking process described with reference to FIG . 2A , it is
understood that the embodiments of a supercritical water TABLE 2
and steam cracking process with an intermediate unit could 55 Operating Conditions of the Simulation according to FIG . 7
also be employed with reference to the integrated supercriti
cal water and steam cracking process described with refer Mass Flow Liquid
ence to FIG . 2B . Temperature Pressure (kilograms per Volume Flow
Embodiments of an integrated supercritical water and Stream ( deg C.) (psig ) hour (kg/h )) (barrel/day )
steam cracking process are in the absence of a delayed coker. 60 Stream 4 20 661.1 100.00
A delayed coker can produce large amounts of solid coke Stream 205 22 3901 661.1 100.00
which is problematic for a steam cracking process. In Stream 705 337 3901 661.1 100.00
addition , a delayed coker can produce a large amount of Stream Stream 210
2
400
20
3901
1
661.1
600.0
100.00
100.00
gases such as methane and ethane , which can include Stream 215 21 3901 600.0 100.00
hydrogen . A supercritical water process can produce less gas 65 Stream 220 150 3901 600.0 100.00
than a delayed coker thus keeping more hydrogen in the Stream 230 368 3901 1261.1 200.00
liquid hydrocarbon product. This means that the liquid
US 10,703,999 B2
19 20
TABLE 2 - continued temperatures increases the amount of hydrocarbons that
undergo conversion reactions, resulting in more light frac
Operating Conditions ofthe Simulation according to FIG . 7 tions.
Mass Flow Liquid Although the present invention has been described in
Temperature Pressure (kilograms per Volume Flow 5 detail , it should be understood that various changes , substi
Stream (deg C.) (psig ) hour (kg/h )) (barrel/day) tutions , and alterations can be made hereupon without
Stream 240 450 3901 1261.1 206.3 departing from the principle and scope of the invention .
Stream 250 150 3901 1261.1 206.3 Accordingly , the scope of the present invention should be
Stream 260 153 100 120.0 206.3 determined by the following claims and their appropriate
Stream
Stream
270
285
50
50
1 0.6
661.0
0.1 10 legal equivalents .
100.0 There various elements described can be used in combi
Stream 10 50 599.5 106.2
nation with all other elements described here unless other
wise indicated .
In a second simulation , with reference to FIG . 2A , FIG . 7 , The singular forms “ a ” , “ an ” and “ the” include plural
and FIG . 8 , pre-heated water 705 is introduced to convection 15 referents, unless the context clearly dictates otherwise .
section 312 of furnace 310 to produce heated water 805 . Optional or optionally means that the subsequently
Therefore , the embodiment of the process as shown in FIG . described event or circumstances may or may not occur. The
8 is in the absence ofwater heater 110. Heated water 805 is description includes instances where the event or circum
mixed with hot oil 220 in mixer 130 to produce mixed feed stance occurs and instances where it does not occur .
815. Mixed feed 815 can have the same operating conditions 20 Ranges may be expressed here as from about one par
as described with reference to mixed stream 230. Mixed feed ticular value to about another particular value and are
815 is introduced to convection section 312 of furnace 310 inclusive unless otherwise indicated . When such a range is
where the hydrocarbons present in mixed feed 815 undergo expressed , it is to be understood that another embodiment is
conversion reactions in the presence of supercriticalwater in 25 from the one particular value to the other particular value ,
along with all combinations within said range.
convection section 312. Convection section 312 is simulated Throughout this application , where patents or publica
to provide a Reynolds number of 4000 in convection section tions are referenced , the disclosures of these references in
312. Table 3 contains those streams that are not already their entireties are intended to be incorporated by reference
disclosed in Table 2 .
into this application , in order to more fully describe the state
TABLE 3
30 of the art to which the invention pertains, exceptwhen these
references contradict the statements made here .
Operating Conditions of the Simulation according to FIG . 8 As used here and in the appended claims, the words
" comprise," " has,” and “ include ” and all grammatical varia
Mass Flow
Temperature Pressure (kilograms per
Liquid
Volume Flow
tions thereof are each intended to have an open , non -limiting
Stream (deg C.) (psig ) hour (kg/h )) (barrel/day) 35 meaning that does not exclude additional elements or steps.
That which is claimed is :
Stream 15 364 3901 1261.1 200.0 1. A method for producing a supercritical water (SCW )
Stream 25
Stream 240
416
450
3901
3901
1261.1
1261.1
200.0
206.3
treated product, the method comprising the steps of:
Stream 250 150 3901 1261.1 206.3 introducing a mixed stream comprising hot oil and super
Stream 260 153 100 1261.1 206.3 40 critical water to a convection section of a furnace ,
Stream 270 50 1 0.6 0.1 where conversion reactions occur in the convection
Stream 285 50 1 661.0 100.0 section , wherein the furnace comprises a convection
Stream 10 50
1 599.5 106.2 section and a radiation section ;
upgrading the mixed stream in the convection section of
45 the furnace to produce a convection upgraded stream at
TABLE 4 a temperature of between the critical temperature of
water and 500 ° C .;
Stream properties for Example 1.
introducing the convection upgraded stream to a super
FIG . 7 FIG . 8 critical reactor, where the supercritical reactor is main
Properties Stream 10 Stream 10 50 tained at a temperature between 380º C. and 450 ° C.
Specific Gravity (API) 34.2 34.4
and a pressure between 23 MPa and 35 MPa, wherein
TBP 5 % (deg C.) 35 35 one or more conversion reactions occur in the super
TBP 10 % (deg C.) 98 99 critical reactor;
TBP 30 %
TBP 50 %
(deg C.)
(deg C.)
215
337
184
262
upgrading the convection upgraded stream in the super
TBP 70 % (deg C.) 453 418
55 critical reactor to produce a reactor effluent;
TBP 90 % (deg C.) 596 543 introducing the reactor effluent to a post -reaction stage to
TBP 95 % (deg C.) 634 611 produce the SCW -treated product, wherein the SCW
Sulfur Content (wt % ) 2.7 2.6 treated product comprises an increased paraffin con
Nitrogen Content (wt ppm ) 925 895
centration as compared to a crude oil stream , wherein
Kinematic Viscosity at 100 F. (cSt) 1.5 1.4
the SCW -treated product comprises an amount of
60
water ;
The results in Table 4 show that passing the mixed feed introducing the SCW -treated product to the convection
through the convection section of a furnace produces a section of the furnace ;
SCW -treated product (FIG . 8 stream 10 ) that is of better mixing a first fraction of components of the SCW -treated
quality than the SCW - treated product from a supercritical 65 product with the mixed stream such that some compo
water process that does not integrate a steam cracker ( FIG . nents of the SCW -treated product are in the convection
7 stream 10 ). The longer exposure of the stream to hot upgraded stream ;
US 10,703,999 B2
21 22
flowing a second fraction of components of the SCW 11. The method of claim 9, wherein the crude oil stream
treated product to the radiation section of the furnace ; comprises a vacuum residue fraction that is greater than 20
mixing the second fraction of components of the SCW wt % .
treated product that flow to the radiation section of the 12. The method of claim 9 , wherein the SCW -treated
furnace;with diluents in the radiation section of the
furnace 5 product comprises a concentration of a vacuum residue
upgrading the second fraction of components of the fraction that is greater than 20 wt % .
SCW -treated product in the radiation section of the 13. The method of claim 9, wherein a cut point of
furnace to produce a furnace effluent, where the second distillation of the distillation process is between 650 ° F. and
fraction of components of the SCW - treated product are 1050 ° F.
10
subjected to radical-mediated reactions; and 14. The method of claim 3 , wherein the intermediate unit
withdrawing the furnace effluent from the radiation sec is a thermal conversion process, further wherein the product
tion of the furnace . stream is a thermal liquid product.
2. Themethod of claim 1 , wherein the post -reaction stage 15. The method of claim 14 , wherein the thermal con
is configured to adjust the amount of water in the SCW 15 version process is selected from the group consisting of a
treated product.
3. The method of claim 1, further comprising the steps of: coking process and a visbreaking process .
introducing the SCW - treated product to an intermediate comprises method
16. The of claim 14 , wherein the crude oil stream
a concentration of a vacuum residue fraction that
unit to produce a product stream ; and
introducing the product stream to the convection section is greater
17. The
than 20 wt % .
method of claim 14 , wherein the thermal liquid
of the furnace, where the product stream is subjected to 20
one or more conversion reactions, where components product comprises a concentration of a vacuum residue
fraction that is less than 5 wt % .
of theproduct stream flow to the radiation section of the 18. The method of claim 1, further comprising the steps
furnace and mix with the diluents in the radiation of:
section of the furnace to produce the furnace effluent, pressurizing a crude oil stream in a feed pump to a
where the furnace effluent is withdrawn from the radia- 25 pressure at or greater than the critical pressure ofwater
tion section of the furnace . to produce a pressurized oil ;
4. The method of claim 3 , wherein the intermediate unit heating the pressurized oil in a feed heater to a tempera
is selected from the group consisting of hydrotreating ture at or less than 150 deg C. to produce a hot oil
process, a distillation process , and a thermal conversion 30 stream ;
process .
5. The method of claim 3 , wherein the intermediate unit pressurizing a water stream in a water pump to a pressure
is a hydrotreating process, and wherein the product stream at or greater than the critical pressure of water to
is a hydrotreating process product. produce a pressurized water;
6. The method of claim 5 , wherein the crude oil stream heating the pressurized water in a water heater to a
comprises a concentration of a vacuum residue fraction that 35 temperature at or greater than the critical temperature
is greater than 20 wt % , wherein the crude oil stream of water to produce a supercritical water stream ; and
comprises a total sulfur content that is greater than 1.5 wt % mixing the hot oil stream and the supercritical water
sulfur . stream to produce the mixed stream .
7. The method of claim 5 , wherein the amount of water in 19. The method of claim 1 , further comprising the steps
40 of:
the SCW -treated product is less than 1,000 wt ppm . pressurizing a crude oil stream in a feed pump to a
8. The method of claim 5 , further comprising a step of pressure at or greater than the critical pressure ofwater
introducing hydrogen gas to the hydrotreating process. to produce a pressurized oil ;
9. The method of claim 3 , wherein the intermediate unit
is a distillation process, further wherein the product stream pressurizing a water stream in a water pump to a pressure
is a distilled product. 45 at or greater than the critical pressure of water to
10. The method of claim 9 , wherein the distillation produce a pressurized water; and
process is selected from the group consisting of an atmo mixing the pressurized oil and the pressurized water to
spheric distillation unit, a vacuum distillation unit, and a produce the mixed stream .
combination thereof.

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United States Patent ( 10 ) Patent No.: US 10,703,999 B2

(51) Int. Ci. 6,096,194 A 8/2000 Tsybulevskiy et al.

( 56 ) References Cited Kniel, “ Ethylene : Keystone to the Petrochemical Industry ” , Marcel

Convecti Section Raditon Section

Supercital Proces Water Stream

240 061 140 310

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