Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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TITLE: LOW-SOLIDS FLASH CHEMICAL IONIZING PYROLYSIS
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is anon-provisional of and claims the benefit of and
priority to US Ser.
No. 62/989,303 filed March 13, 2020. All priority documents are herein
incorporated by
reference in their entireties.
BACKGROUND
[0002] My earlier patent, US 10,336,946 B2, discloses a process for upgrading
heavy oil
comprising feeding to a reactor an emulsion of heavy oil, water, and solid
particulates
comprising a mineral support and an oxide or acid addition salt of a Group 3 ¨
16 metal, and
spraying the feed mixture in the reactor at a high temperature and low
pressure.
[0003] My earlier patent, US 10,611,969, discloses flash chemical ionizing
pyrolysis of a
hydrocarbon using a chemical ionizing additive comprising a mineral support
and an oxide
and/or acid addition salt of a Group 3-16 metal, e.g., by emulsifying water
and an oil
component with the additive; introducing the emulsion into a flash chemical
ionizing pyrolysis
(FCIP) reactor maintained at a temperature greater than about 400 C up to
about 600 C and
low pressure to form a chemical ionizing pyrolyzate effluent. Also disclosed
is a process
comprising the further steps of condensing a liquid ionizing pyrolyzate (LIP)
from the effluent;
combining a feedstock oil with the LIP to form a pyrolyzate-feedstock blend;
and thermally
processing the blend at a temperature above about 100 C. In these processes. A
mineral support
such as bentonite is introduced into the reactor system and necessitates the
need for solids
removal steps and equipment.
[0004] There remains a need for more efficient techniques and systems to
refine and process
petroleum and other hydrocarbons with ever higher yields of lighter, higher-
value hydrocarbon
products, while reducing the amount of resid and coke that must be handled. A
solution would
preferably: reduce the amount of solids introduced into the reactor and/or
eliminate or reduce
the size of solids removal equipment; be an upstream process to treat crude
oil; minimize
asphaltene and coke yields; improve saturates and/or aromatics yields; improve
the quality of
the saturates with increased isomerates production; improve lube oil base
stock yields;
minimize end product blending requirements; employ mild pressure conditions
with a short
residence time and high throughput using inexpensive chemical additives;
reduce the need for
feedstock pretreatment or conditioning to remove catalyst poisons; reduce the
need for
dewatering and/or desalting; facilitate crude pre-heating by minimizing
fouling in the pre-
heaters; and/or avoid adding hydrogen.
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SUMMARY
[0005] The present invention discloses improvements to the process applicant
refers to herein
as "flash chemical ionizing pyrolysis" or FCIP, and a liquid ionizing
pyrolyzate or LIP
produced by the process. FCIP can be used as a method to pretreat crude oil,
optionally without
dewatering, to convert asphaltenes from the crude, and form a resulting LIP
with a reduced
sulfide content, increased isomerates content, and other improvements detailed
hereinbelow.
[0006] It has been found, unexpectedly, that when the chemical ionizing
additive is employed
as a system of an iron source material and an alkali or alkaline earth metal
chloride source
material in an emulsion with water, the additive can be used without any
mineral support and
moreover, can achieve even higher conversion rates to liquid oil, a further
reduction of coke
make, and/or a further improved oil quality as reflected in lower density,
lower viscosity, lower
pour point, or the like, and without introducing excessive solids into the
reactor system.
[0007] In one aspect, embodiments according to the present invention provide a
hydrocarbon
conversion process comprising: providing an iron source material (preferably
an unsupported
iron source material); providing an alkali or alkaline earth metal chloride
source material;
providing an aqueous phase; mixing the iron source material, the alkali or
alkaline earth metal
chloride source material, and the aqueous phase with an oil component to form
a feed emulsion
(preferably wherein the feed emulsion comprises less than 1 part by weight of
added
undissolved solids per 100 parts by weight of the oil component); introducing
the feed emulsion
into a flash chemical ionizing pyrolysis (FCIP) reactor maintained at a
temperature greater than
about 400 C up to about 600 C and a pressure from 10 to 50 psia to form a
chemical ionizing
pyrolyzate effluent; and condensing a liquid ionizing pyrolyzate (LIP) from
the effluent.
[0008] In another aspect, embodiments according to the present invention
provide a
hydrocarbon conversion process comprising: reacting iron with a mixture of
hydrochloric acid
and nitric acid in the presence of water (preferably aqua regia) to form an
iron source material;
mixing the iron source material, an alkali or alkaline earth metal chloride
source material, and
an aqueous phase with an oil component to form an emulsion; introducing the
emulsion into a
flash chemical ionizing pyrolysis (FCIP) reactor maintained at a temperature
greater than about
400 C up to about 600 C and a pressure from 10 to 50 psia for a residence time
of from 0.1 to
10 seconds to form a chemical ionizing pyrolyzate effluent; and condensing a
liquid ionizing
pyrolyzate (LIP) from the effluent.
[0009] In a further aspect, embodiments of the present invention provide a
hydrocarbon
refinery process comprising the steps of: preparing a feed emulsion comprising
(i) 100 parts by
weight of an oil component, (ii) from about 1 to 100 parts by weight of water,
(iii) from about
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0.01 to 5 parts by weight of an iron source material, and (iv) from about 0.01
to 5 parts by
weight of an alkali or alkaline earth metal chloride source material; spraying
the feed emulsion
in a flash chemical ionizing pyrolysis reactor at a temperature from about 400
C to about
600 C; collecting an effluent from the flash chemical ionizing pyrolysis
reactor; and recovering
a liquid ionizing pyrolyzate (LIP) from the effluent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 shows a flash chemical ionizing pyrolysis (FCIP) process,
according to
embodiments of the present invention.
[0011] FIG. 2 shows a simplified schematic flow diagram of a method for
preparing an iron
source compound for FCIP, according to embodiments of the present invention.
[0012] FIG. 3 shows a simplified schematic flow diagram of a comparative
method for
preparing an iron source compound for FCIP.
[0013] FIG. 4 shows a schematic flow diagram of a hydrocarbon conversion
process wherein
an LIP is combined with a feedstock oil to form an LIP blend and the LIP blend
is thermally
processed, according to embodiments of the present invention.
[0014] FIG. 5 shows a schematic flow diagram of a hydrocarbon refinery process
wherein LIP
from FCIP is blended with feed oil, desalted, heated, distilled, and
optionally supplied to the
emulsion preparation step for FCIP, according to embodiments of the present
invention.
[0015] FIG. 6 shows a schematic flow diagram of a hydrocarbon refinery process
wherein a
first portion of LIP from FCIP is blended with heavy products from
distillation, supplied to the
emulsion preparation step for FCIP, and a second portion is optionally
supplied to the
distillation step, according to embodiments of the present invention.
[0016] FIG. 7 shows a schematic flow diagram of an FCIP process for making the
LIP,
according to embodiments of the present invention.
[0017] FIG. 8 shows a schematic flow diagram of another FCIP process for
making the LIP,
according to embodiments of the present invention.
[0018] FIG. 9 shows a schematic flow diagram of a further FCIP process for
making the LIP,
according to embodiments of the present invention.
[0019] FIG. 10 shows chromatograms of the non-distilled, residual fraction
(>220 C) from
the LIP-diesel blend of Example 6 according to an embodiment of the present
invention,
compared to the residual fraction from the diesel alone.
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DETAILED DESCRIPTION
DEFINITIONS
[0020] The words and phrases used herein should be understood and interpreted
to have a
meaning consistent with the understanding of those words and phrases by those
skilled in the
relevant art. No special definition of a term or phrase is intended except
where such a special
definition is expressly set forth in the specification. The following
definitions are believed to
be consistent with their understanding by the skilled person, and are provided
for the purpose
of clarification.
[0021] As used in the specification and claims, "near" is inclusive of "at."
The term "and/or"
refers to both the inclusive "and" case and the exclusive "or" case, whereas
the term "and or"
refers to the inclusive "and" case only and such terms are used herein for
brevity. For example,
a component comprising "A and/or B" may comprise A alone, B alone, or both A
and B; and
a component comprising "A and or B" may comprise A alone, or both A and B.
[0022] For purposes herein the term "alkylation" means the transfer of an
alkyl group from
one molecule to another, inclusive of transfer as an alkyl carbocation, a free
radical, a carbanion
or a carbene, or their equivalents.
[0023] For purposes herein, API refers to the American Petroleum Institute
gravity (API
gravity), which is a measure of the density of a petroleum product at 15.6 C
(60 F) compared
to water at 4 C, and is determined according to ASTM D1298 or ASTM D4052,
unless
otherwise specified. The relationship between API gravity and s.g. (specific
gravity) is API
gravity = (141.5/s.g.) -131.5.
[0024] As used herein, the term "aqua regia" refers to any concentrated
mixture of
hydrochloric and nitric acids.
[0025] As used herein, "asphaltenes" refer to compounds which are primarily
composed of
carbon, hydrogen, nitrogen, oxygen, and sulfur, but which may include trace
amounts of
vanadium, nickel, and other metals. Asphaltenes typically have a C:H ratio of
approximately
1:1.1 to about 1:1.5, depending on the source. Asphaltenes are defined
operationally as the n-
heptane (C7H16)-insoluble, toluene (C6H5CH3)-soluble component of a
carbonaceous material
such as crude oil, bitumen, or coal. Asphaltenes typically include a
distribution of molecular
masses in the range of about 400 g/mol to about 50,000 g/mol, inclusive of
aggregates.
[0026] For purposes herein the term "atmospheric distillation" means
distillation where an
uppermost stage is in fluid communication with the atmosphere or with a fluid
near
atmospheric pressure, e.g., less than 5 psig.
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[0027] For purposes herein, the abbreviation AET refers to "atmospheric
equivalent
temperature" of distillation, which is the temperature calculated from an
observed vapor
temperature at a pressure below atmospheric according to the Maxwell and
Bonne11 equations
as described in Annex A9 to ASTM D2892-18a.
[0028] As used herein, "atomization" refers to spraying that forms a fine mist
of droplets or
particles of less than 20 microns.
[0029] For purposes herein the term "blending" means combining two or more
ingredients
regardless of whether any mixing is used.
[0030] For purposes herein the term "calcination" refers to heating a material
in air or oxygen
.. at high temperatures, e.g., at or above about 400 C.
[0031] For purposes herein the term "catalyst" means a substance that
increases the rate of a
chemical reaction usually but not always without itself undergoing any
chemical change. For
example, noble metal catalysts can become slowly poisoned as they contact
deleterious
substances.
[0032] As used herein, "clay" refers to a fine-grained material comprising one
or more clay
minerals, i.e., a mineral from the kaolin group, smectite group (including
montmorillonite),
illite group, or chlorite group, or other clay types having a 2:1 ratio of
tetrahedral silicate sheets
to octahedral hydroxide sheets.
[0033] For purposes herein the term "coking" refers to the thermal cracking of
resid in an oil
refinery processing unit known as a "coker" that converts a heavy oil such as
the residual oil
from a vacuum distillation column into low molecular weight hydrocarbon gases,
naphtha,
light and heavy gas oils, and petroleum coke. Coking is typically effected at
a temperature of
about 480 C.
[0034] For purposes herein the term "cracking" means the process whereby
complex organic
molecules are broken down into simpler molecules by the breaking of carbon-
carbon bonds in
the precursors. "Thermal cracking" refers to the cracking of hydrocarbons by
the application
of temperature, typically but not always 500-700 C and sometimes also
pressure, primarily by
a free radical process, and is characterized by the production of light
hydrocarbon gases, C4 -
C15 olefins in moderate abundance, little aromatization, little or no branched
chain alkanes,
slow double bond isomerization, little or no skeletal isomerization, 13-
scission of
alkylaromatics, and/or slow cracking of naphthenes. "Catalytic cracking"
refers to the cracking
of hydrocarbons in the presence of a catalyst, typically but not always at 475-
530 C that forms
ionic species on catalyst surfaces, and is characterized by the production of
little or no methane
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and/or ethane, little or no olefins larger than C4, some aromatization of
aliphatic hydrocarbons,
rapid skeletal isomerization and branched chain alkanes, rapid olefin
isomerization, a-scission
or dealkylation of alkylaromatics, and/or cracking of naphthenes and n-
paraffins at comparable
rates. "Hydrocracking" refers to cracking in the presence of hydrogen,
typically but not always
at 260-425 C and using a bifunctional catalyst comprising an acid support such
as silica,
alumina, and/or zeolite, and a metal, resulting in hydrogenation or saturation
of aromatic rings
and decyclization.
[0035] For purposes herein the term "crude oil" means an unrefined liquid
mixture of
hydrocarbons that is extracted from certain rock strata.
[0036] For purposes herein the term "desalting" means the removal of salt from
petroleum in
a refinery unit referred to as a "desalter" in which the crude oil is
contacted with water and
separated to remove the salt in a brine.
[0037] For purposes herein the term "distillation" means the process of
separating components
or substances from a liquid mixture by selective boiling and condensation.
[0038] For purposes herein, "distillation temperature" refers to the
distillation at atmospheric
pressure or the AET in the case of vacuum distillation, unless otherwise
indicated.
[0039] For purposes herein the term "emulsion" means a mixture of immiscible
liquids in a
discontinuous dispersed phase and a continuous phase, optionally including
dispersed solids.
[0040] For purposes herein, "essentially free of" means a material is free of
the stated
component or contains such a minor amount of the component that it is
inconsequential to the
essential function of the material, or in any case the component is present in
an amount of less
than 1 percent by weight of the material.
[0041] For purposes herein, "ferrates" refers to a material that can be viewed
as containing
anionic iron complexes, e.g., tetrachloroferrate. Hydrates of FeCl3 generally
feature
tetrachloroferrate ions.
[0042] For purposes herein the term "flash pyrolysis" means thermal reaction
of a material at
a very high heating rate (e.g., >450 C/s, preferably >500 C) with very short
residence time
(e.g., 4 s, preferably <2 s).
[0043] For purposes herein the term "flash chemical ionizing pyrolysis" or
"FCIP" means flash
pyrolysis of a material in the presence of a chemical additive to promote
ionization and/or free
radical formation and is sometimes referred to as "catalytic pyrolysis" as
described in US
10,336,946 B2.
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[0044] For purposes herein "finely divided" refers to particles having a major
dimension of
less than 1 mm, and a minor dimension of less than 1 mm. A particulate "fine"
is defined as a
solid material having a size and a mass which allows the material to become
entrained in a
vapor phase of a thermo-desorption process as disclosed herein, e.g., less
than 250 microns,
preferably less than 4 microns.
[0045] For purposes herein the term "hydrocarbon" means a compound of hydrogen
and
carbon, such as any of those that are the chief components of petroleum and
natural gas. For
purposes herein the term "naphtha" refers to a petroleum distillate with an
approximate boiling
range from 40 C to 195 C, a "kerosene" from greater than 195 C to 235 C, a
"distillate" from
greater than 235 C to 370 C, a "gas oil" from greater than 370 C to 562 C.
[0046] For purposes herein the term "hydrocarbon conversion" means the act or
process of
chemically changing a hydrocarbon compound from one form to another.
[0047] For purposes herein, "incipient wetness loading" refers to loading a
material on a
support by mixing a solution and/or slurry of the material with a dry support
such that the liquid
from the solution and/or slurry enters the pores of the support to carry the
material into the
pores with the slurry, and then the carrier liquid is subsequently evaporated.
Although not
technically "incipient", in the present disclosure and claims "incipient
wetness loading"
specifically includes the use of a volume of the solvent or slurry liquid that
is in excess of the
pore volume of the support material, where the liquid is subsequently
evaporated from the
support material, e.g., by drying.
[0048] For purposes herein, an "ionized" material refers to a material
comprising ions or
capable of dissociating into ions.
[0049] For purposes herein, an "ionizing" material refers to a process in
which an ionized
material is processed or the product from that process.
[0050] For purposes herein, an "iron chloride" generically refers to any
compound comprising
iron and chloride, including ferric chloride, ferrous chloride, iron
oxychloride, and so on.
[0051] For purposes herein, "limited solubility" means that a material mostly
does not dissolve
in water, i.e., not more than 50 wt% of a 5 g sample is digested in 150 ml
distilled water at
95 C in 12 h; and "acid soluble" means that a material mostly dissolves in
aqueous HC1, i.e.,
at least 50 wt% of a 5 g sample is digested in 150 ml of 20 wt% aqueous HC1 at
95 C in 12 h.
[0052] For purposes herein the term "liquid ionizing pyrolyzate" or "LIP"
refers to an FCIP
pyrolyzate that is liquid at room temperature and 1 atm, regardless of
distillation temperature.
In some embodiments, the LIP has blending characteristics indicative of the
presence of ionized
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species and/or stable free radicals that can induce chemical and/or physical
rearrangement of
molecules or "normalization" in the blend components. For example, blending
the LIP with
crude containing asphaltenes results in viscosity changes that are more
significant than would
be predicted from conventional hydrocarbon blending nomographs, which is
consistent with
molecular rearrangement of the asphaltene molecules, including disaggregation.
Such an
unexpected viscosity reduction in turn produces unexpected increases in the
efficiencies of
thermal processes such as distillation, for example, employing the blend.
[0053] In some embodiments, the LIP has blending characteristics such that
when blended with
a specific blend oil, obtains a distillation liquid oil yield (<562 C) that is
greater than a
theoretical liquid oil yield, and/or obtains a total resid yield (>562 C) that
is in an amount less
than a theoretical resid yield, wherein the theoretical yields of the blend
are calculated as a
weighted average of the separate distillation of the LIP and blend oil alone,
wherein yields are
determined by atmospheric distillation in a 15-theoretical plate column at a
reflux ratio of 5:1,
according to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill
method
according to ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
Preferably,
the LIP has one, or preferably more, or more preferably all, of the following
oil blending
characteristics:
1) for a blend of Oil:LIP of 90:10, the liquid hydrocarbon yield, obtained
from distillation of
the blend up to a distillation temperature of 562 C, is equal to or greater
than 1% (preferably
at least 1.5%) more than the theoretical yield, wherein the percentage is
absolute; and/or
2) for a blend of Oil:LIP of 90:10, a resid yield, obtained from the
distillation of the blend that
is decreased in an amount equal to or more than 1.5% (preferably at least
2.5%) of the
theoretical resid yield, wherein the percentage is absolute; and/or
3) for a blend of Oil:LIP of 90:10, amounts of distillation of the blend into
a first fraction
<290 C, a second fraction 291-331 C, a third fraction 332-378 C, a fourth
fraction 379-
440 C, and a fifth fraction 441-531 C, are greater than theoretical amounts of
the respective
fractions, wherein the theoretical amounts of the blend fractions are
calculated as weighted
averages of the separate distillation of the LIP and blend oil alone; and/or
4) for a blend of Oil:LIP of 90:10, densities of fractions distilled into a
first fraction <290 C,
a second fraction 291-331 C, a third fraction 332-378 C, a fourth fraction 379-
440 C, and
a fifth fraction 441-531 C, are less than or equal to the densities in
respective fractions
obtained from distillation of the blend oil alone, preferably wherein the
density in at least
one of the distilled blend oil fractions is less than the density of the
respective blend oil
fraction(s); and/or
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5) for a blend of Oil:LIP of 80:20, the liquid hydrocarbon yield, obtained
from distillation of
the blend up to a distillation temperature of 562 C, is equal to or greater
than 1.5%
(preferably at least 2.5%) more than the theoretical yield, wherein the
percentage is
absolute; and/or
6) for a blend of Oil:LIP of 80:20, a resid yield, obtained from the
distillation of the blend that
is decreased in an amount equal to or more than 2.5% (preferably at least 4%)
of the
theoretical resid yield, wherein the percentage is absolute; and/or
7) for a blend of Oil:LIP of 80:20, amounts of distillation of the blend into
a first fraction
<290 C, a second fraction 291-331 C, a third fraction 332-378 C, a fourth
fraction 379-
440 C, and a fifth fraction 441-531 C, are greater than theoretical amounts of
the respective
fractions, wherein the theoretical amounts of the blend fractions are
calculated as weighted
averages of the separate distillation of the LIP and blend oil alone; and/or
8) for a blend of Oil:LIP of 80:20, densities of fractions distilled into a
first fraction <290 C,
a second fraction 291-331 C, a third fraction 332-378 C, a fourth fraction 379-
440 C, and
a fifth fraction 441-531 C, are less than or equal to the densities in
respective fractions
obtained from distillation of the blend oil alone, preferably wherein the
density in at least
two, or more preferably in at least three, of the blend fractions is less than
the density of
the respective blend oil fraction(s).
9) for a blend of Oil:LIP of 70:30, the liquid hydrocarbon yield, obtained
from distillation of
the blend up to a distillation temperature of 562 C, is equal to or greater
than 2% (preferably
at least 3%) more than the theoretical yield, wherein the percentage is
absolute; and/or
10) for a blend of Oil:LIP of 70:30, a resid yield, obtained from the
distillation of the blend that
is decreased in an amount equal to or more than 3% (preferably at least 5%) of
the
theoretical resid yield, wherein the percentage is absolute; and/or
11) for a blend of Oil:LIP of 70:30, amounts of distillation of the blend into
a first fraction
<290 C, a second fraction 291-331 C, a third fraction 332-378 C, a fourth
fraction 379-
440 C, and a fifth fraction 441-531 C, are greater than theoretical amounts of
the respective
fractions, wherein the theoretical amounts of the blend fractions are
calculated as weighted
averages of the separate distillation of the LIP and blend oil alone; and/or
12) for a blend of Oil:LIP of 70:30, densities of fractions distilled into a
first fraction <290 C,
a second fraction 291-331 C, a third fraction 332-378 C, a fourth fraction 379-
440 C, and
a fifth fraction 441-531 C, are less than or equal to the densities in
respective fractions
obtained from distillation of the blend oil alone, preferably wherein the
density in at least
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two, or more preferably in at least three, of the blend fractions is less than
the density of
the respective blend oil fraction(s).
[0054] As used herein, unless indicated, a "liquid oil" or "liquid product" or
"liquid
hydrocarbon" refers to the fraction(s) of petroleum from distillation that are
normally liquid at
room temperature and 1 atm obtained at distillation temperatures from 29 C to
562 C AET,
including gasoline blending components, naphtha, kerosene, jet fuel,
distillates, diesel, heating
oil, and gas oil; whereas a "resid" or "heavy product" or "heavy hydrocarbon"
refers to the
residual oil remaining after distillation to 562 C AET, including resins,
asphaltenes, and/or
coke.
[0055] For purposes herein the term "oil" means any hydrophobic, lipophilic
chemical
substance that is a liquid at ambient temperatures.
[0056] All percentages are expressed as weight percent (wt%), based on the
total weight of the
particular stream or composition present, unless otherwise noted. All parts by
weight are per
100 parts by weight oil, adjusted for water and/or solids in the oil sample
(net oil), unless
otherwise indicated. Parts of water by weight include water added as well as
water present in
the oil.
[0057] For purposes herein the term "pyrolysis" means decomposition brought
about by high
temperatures.
[0058] For purposes herein the term "ionizing pyrolyzate" means the oil
condensed or
otherwise recovered from the effluent of flash chemical ionizing pyrolysis.
[0059] Room temperature is 23 C and atmospheric pressure is 101.325 kPa unless
otherwise
noted.
[0060] For purposes herein, SARA refers to the analysis of saturates,
aromatics, resins, and
asphaltenes in an oil sample. SARA can be determined by IP 143 followed by
preparative
HPLC (IP-368) or Clay-Gel (ASTM D-2007), or by IATROSCAN TLC-FID. For the
purposes
of the claims, in the event of a conflict, the results from ASTM D-2007 shall
control.
[0061] For purposes herein, the term "spray" means to atomize or otherwise
disperse in a mass
or jet of droplets, particles, or small pieces.
[0062] For purposes herein, sulfur in crude oil and pyrolyzates is determined
according to
ASTM D-4294. A "high sulfur" oil is one containing more than 0.5 wt% sulfur as
determined
by ASTM D-4294.
[0063] For purposes herein the term "thermal processing" means processing at
an elevated
temperature, e.g., above 100 C.
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[0064] For purposes herein, viscosity is determined at 40 C and 100 s-1,
unless otherwise
stated, or if the viscosity cannot be so determined at 40 C, the viscosity is
measured at higher
temperatures and extrapolated to 40 C using a power law equation.
FLASH CHEMICAL IONIZING PYROLYSIS OF HYDROCARBONS
[0065] Broadly, according to some embodiments of the invention, a hydrocarbon
conversion
process comprises a hydrocarbon conversion process comprising: providing an
iron source
material; providing an alkali or alkaline earth metal chloride source
material; providing an
aqueous phase; mixing the iron source material, the alkali or alkaline earth
metal chloride
source material, and the aqueous phase with an oil component to form an
ionized feed
emulsion; introducing the ionized feed emulsion into a flash chemical ionizing
pyrolysis
(FCIP) reactor maintained at a temperature greater than about 400 C up to
about 600 C and a
pressure from 10 to 50 psia to form a chemical ionizing pyrolyzate effluent;
and condensing a
liquid ionizing pyrolyzate (LIP) from the effluent.
[0066] The iron source material can be any iron compound, e.g., iron oxides,
hydroxides,
oxyhydroxides, hydrates, halides, oxyhalides, hydrochlorides, nitrates,
nitrites, or a mixture
thereof In any embodiment, the iron source material can comprise iron oxide,
iron hydroxide,
iron oxide-hydroxide, iron chloride, or preferably a mixture thereof
Preferably, the iron source
material comprises hematite, magnetite, iron oxide hydroxide (preferably beta-
ferric oxide
hydroxide), or more preferably a mixture thereof, and even more preferably the
iron source
material further comprises chloride. In any embodiment the iron source
material can comprise
beta-ferric oxide hydroxide, and preferably further comprises chloride.
[0067] As an example, the iron source material can be the reaction product of
iron with a
mixture of hydrochloric acid and nitric acid in the presence of water
(preferably aqua regia),
which preferably forms a mixture of hematite, magnetite, and iron oxide
hydroxide (preferably
beta-ferric oxide hydroxide), and more preferably further comprises chloride.
The process can
include, for example, the step of reacting iron with a mixture of hydrochloric
acid and nitric
acid in the presence of water (preferably aqua regia) to form the iron source
material.
[0068] The iron source material can be soluble in the water phase or the oil
phase, or can be
insoluble. Where the iron source material is insoluble, it preferably has a
mean particle size of
10 microns or less, more preferably 4 microns or less, and especially less
than 2 microns.
[0069] In an embodiment the iron source material is unsupported.
[0070] If desired, the process can comprise first mixing the iron source
material, the alkali or
alkaline earth metal chloride source material, and the aqueous phase with a
first portion of the
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oil component to form a pre-mix emulsion, and then mixing the pre-mix emulsion
with a
second portion of the oil component to form the feed emulsion. For example,
the oil component
can be present in the pre-mix emulsion in an amount equal to or less than 20
parts by weight
per 100 parts by weight of the aqueous phase, e.g., from 1 to 10 parts by
weight.
[0071] The iron source material can be present in the feed emulsion in an
amount of from 0.01
up to 5 parts by weight, preferably 0.01 to 1 part by weight, and more
preferably 0.05 to 1 part
by weight, per 100 parts by weight of the oil component.
[0072] The alkali or alkaline earth metal chloride source material can be the
chloride salt of
any alkali metal and/or alkaline earth metal, e.g., NaCl, KC1, LiC1, MgCl2,
CaCl2, BaC12, etc.
The alkali or alkaline earth metal chloride source material is present in the
feed emulsion in an
amount of from 0.01 up to 5 parts by weight, preferably 0.01 to 1 part by
weight, and more
preferably 0.05 to 1 part by weight, per 100 parts by weight of the oil
component. The chloride
salt is preferably added with or in the aqueous phase, i.e., as a brine, or
where a support is used,
the chloride salt can be loaded on the support with (or without) the iron
source material.
[0073] The iron source material can be unsupported or supported on a support
material such
as clay, silica, alumina, zeolite, or the like. In any embodiment, the feed
emulsion can
preferably be essentially free of added solids, e.g., clay solids, or
essentially free of added
mineral solids other than the iron source material and any sediment from the
oil component(s).
In preferred embodiments, the feed emulsion comprises less than 1 part by
weight solids per
100 parts by weight oil, preferably less than 0.5 parts by weight solids per
100 parts by weight
oil.
[0074] In embodiments, the iron source material is unsupported, and the feed
emulsion
comprises less than 1 part by weight of added undissolved solids per 100 parts
by weight of
the oil component.
[0075] In any embodiment, the feed emulsion comprises from 1 to 100 parts by
weight water
per 100 parts by weight total primary and blend oil components, preferably 5
to 50 parts by
weight water, more preferably 5 to 20 parts by weight water.
[0076] In any embodiment, the reactor temperature is preferably from about 425
C to about
600 C, preferably 450 C to 500 C. The reaction pressure is preferably equal
to or greater than
10 psia up to 30 psia, more preferably equal to or less than 25 psia, even
more preferably 1-1.5
atm absolute. Residence time in the flash chemical ionizing pyrolysis reactor
can be from 0.1
up to 10 seconds, preferably from 0.5 to 4 seconds, and especially less than 2
seconds. The
introduction step preferably comprises spraying the ionized feed emulsion in
the flash chemical
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ionizing pyrolysis reactor, more preferably atomizing the ionized feed
emulsion in the flash
chemical ionizing pyrolysis reactor.
[0077] In any embodiment, the oil component can comprise hydrocarbons boiling
at
temperatures both less than and greater than 562 C, wherein the LIP is
enriched in
hydrocarbons boiling at a temperature less than 562 C, as determined by
atmospheric
distillation in a 15-theoretical plate column at a reflux ratio of 5:1,
according to ASTM D2892-
18 up to cutpoint 400 C AET, and by vacuum potstill method according to ASTM
D5236-18a
above the 400 C cutpoint to cutpoint 562 C AET. The oil component can be a
crude oil, gas
oil, resid, or a mixture thereof, preferably a heavy oil.
[0078] The process preferably further comprises combining a feedstock oil with
the LIP to
form a pyrolyzate-feedstock blend and thermally processing the blend at a
temperature above
about 100 C. The thermal processing can include pyrolysis, distillation,
cracking, alkylation,
visbreaking, coking, and so on, including combinations thereof As one example,
the process
can further comprise supplying at least a portion of the pyrolyzate-feedstock
blend as the oil
component to the FCIP feed emulsion preparation step, i.e., the thermal
processing step consists
of or comprises the spraying of the FCIP feed emulsion into the FCIP reactor.
[0079] In embodiments, a hydrocarbon conversion process comprises the steps
of: reacting
iron with a mixture of hydrochloric acid and nitric acid in the presence of
water (preferably
aqua regia) to form an iron source material; mixing the iron source material,
an alkali or
alkaline earth metal chloride source material, and an aqueous phase with an
oil component to
form an emulsion; introducing the emulsion into a flash chemical ionizing
pyrolysis (FCIP)
reactor maintained at a temperature greater than about 400 C up to about 600 C
and a pressure
from 10 to 50 psia for a residence time of from 0.1 to 10 seconds to form a
chemical ionizing
pyrolyzate effluent; condensing a liquid ionizing pyrolyzate (LIP) from the
effluent; and
optionally blending the LIP with a feedstock oil and thermally processing the
blend.
[0080] In embodiments, a hydrocarbon refinery process comprises the steps of:
preparing an
ionized feed emulsion comprising (i) 100 parts by weight of an oil component,
(ii) from about
1 to 100 parts by weight of water, (iii) from about 0.01 to 5 parts by weight
(preferably 0.01 to
less than 1 part by weight) of an iron source material, and (iv) from about
0.01 to 5 parts by
weight of a chloride source material; spraying the ionized feed emulsion in a
flash chemical
ionizing pyrolysis reactor at a temperature from about 400 C to about 600 C;
collecting an
effluent from the flash chemical ionizing pyrolysis reactor; and recovering a
liquid ionizing
pyrolyzate (LIP) from the effluent. The process can also include combining the
recovered LIP
with a feedstock oil comprising crude oil or a petroleum fraction selected
from gas oil, resid,
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or a combination thereof to form a pyrolyzate-feedstock blend; distilling,
cracking,
visbreaking, and/or coking a first portion of the blend; and optionally
supplying a second
portion of the blend as the oil component in the feed emulsion preparation
step. The LIP can
exhibit a SARA analysis having higher saturates and aromatics contents and a
lower
.. asphaltenes content than the feedstock oil.
[0081] In this process, a proportion of the LIP in the oil component in the
flash pyrolysis can
be effective to improve yield of liquid hydrocarbons boiling at a temperature
below 562 C,
relative to separate flash chemical ionizing pyrolysis of the LIP and
feedstock oil, as
determined by atmospheric distillation in a 15-theoretical plate column at a
reflux ratio of 5:1,
according to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill
method
according to ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
[0082] Additionally in this process, a proportion of the LIP in the LIP blend
in the distillation,
cracking, visbreaking, and/or coking step, is effective to improve yield of
liquid hydrocarbons
boiling at a temperature below 562 C, relative to separate distillation,
cracking, visbreaking,
and/or coking of the LIP and feedstock oil, as determined by atmospheric
distillation in a 15-
theoretical plate column at a reflux ratio of 5:1, according to ASTM D2892-18
up to cutpoint
400 C AET, and by vacuum potstill method according to ASTM D5236-18a above the
400 C
cutpoint to cutpoint 562 C AET.
[0083] The feedstock oil may preferably be crude oil, which may be desalted or
preferably un-
desalted, but can also be, for example, gas oil, resid (atmospheric and/or
vacuum), and the like,
including mixtures or combinations. The LIP is present in a sufficient amount
to enhance light
oil enrichment and/or to reduce coke make in the thermal processing, e.g.,
reducing the
Conradson carbon content of the thermal processing products. There is no upper
limit on the
amount of LIP that can be used, but excessive amounts may not be economical.
The pyrolyzate-
.. feedstock blend can comprise the LIP in a weight ratio of about 1:100 to
1:1, preferably from
1:100 to 1:2, more preferably from about 1:20 to 1:3, even more preferably
from about 1:10 to
1:4. Preferably, the percentages of LIP and feedstock oil total 100, i.e., the
blend consists
essentially of or consists of the LIP and the feedstock oil.
[0084] The thermal processing is preferably distillation, e.g., atmospheric
and/or vacuum
distillation, and/or flash chemical ionizing pyrolysis (FCIP), which may
optionally be used to
produce the LIP, but the thermal processing can also be, for example, heating,
cracking
(thermal and/or catalytic), alkylation, visbreaking, coking, and so on,
including combinations
in parallel and/or series.
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[0085] With reference to the embodiment of the invention shown in the
simplified schematic
flow diagram of FIG. 1, broadly, in process 100, a liquid ionizing pyrolyzate
(LIP) 102 is
optionally combined with a feed oil 104 in a blending step (not shown) or
otherwise fed
separately to emulsification in step 106 with iron source material 108,
alkali/alkaline earth
metal chloride source material 110 and water 112. LIP 102 from any source can
be used,
preferably from an FCIP process as described herein. The feed oil 104 can be
any suitable
hydrocarbon liquid, such as, for example, crude oil (including heavy crude
oil), which can be
desalted or un-desalted, petroleum distillation fractions (especially medium
or heavy gas oil)
or residue, waste oil, used lube oil, etc.
[0086] . The emulsion from step 106 is supplied to FCIP instep 114 described
in more detail
hereinafter. One or more effluent(s) are separated in step 116 to obtain
solids 118, water 120,
LIP 102, and noncondensable gas 124.
[0087] When the feed oil 102 is crude oil, it is advantageously un-desalted
since the inorganic
components do not appear to adversely impact FCIP 114 and much of the
inorganics can be
recovered with the solids from FCIP. Since the inorganics are removed in FCIP
process 100,
the load on the desalter associated with treatment of the crude oil for feed
to an atmospheric
distillation can be reduced by the amount fed to the FCIP process 100.
Moreover, the water
content of the crude oil does not impact the FCIP 114 since the feed is in the
form of an
oil/water emulsion. In fact, it is preferred to use the water or brine from
desalting as all or part
of the water 112 for the emulsion preparation, thereby reducing the load on
the desalter and
reducing the amount of water that must be added to the emulsion in step 106.
Further, the salt
may form a eutectic mixture with one or more of the other additive components,
e.g., FeCl3, or
otherwise enhance the catalytic and/or reactive activity of the iron and
chloride source material.
[0088] The LIP 102 may optionally be supplied to the blending and/or emulsion
step 106 along
with or in lieu of another LIP stream from another FCIP source. The remaining
LIP 102 can be
produced as product 125 and/or optionally thermally processed by heating,
distillation,
cracking, visbreaking, coking, alkylation, reforming, etc. and/or directly
supplied as product(s).
If desired, water 120 recovered from the effluent may be recycled to the
supply 112 and/or step
106 for the FCIP feed emulsion.
[0089] Preferably, a portion of the oil component in the FCIP feed emulsion
from step 106
comprises a recycled portion of the product LIP via line 105. If used, the LIP
can be used in
the blend in a weight proportion of LIP 102: feed oil 104 of from 1:100 to
1:1, preferably in an
amount from 1 to 40 wt% based on the total weight of the oil components
supplied to the FCIP
feed emulsion step 106, e.g., 1 to 40 wt% product LIP and 99 to 60 wt% feed
oil, preferably 5
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to 35 wt % product LIP and 95 to 65 wt% feed oil, more preferably 10 to 30 wt%
product LIP
and 90 to 70 wt% feed oil, based on the total weight of the oil component,
preferably where
the percentages of product LIP and feed oil in the LIP blend total 100.
[0090] One advantage of using emulsion from step 106 is that the oil, water,
and iron/chloride
source materials are intimately mixed prior to vaporization of the oil and
water, which are in
close contact with the iron/chloride additives, and the iron/chloride
additives are already well-
dispersed in liquid, promoting fluidization in the gas phase. For example,
iron and/or chloride
ions can associate with charged molecules in the oil component in the feed
emulsion at low
temperature, e.g. hetero atoms in asphaltene constituents, and thereby target
these species for
reaction upon decomposition or catalytic activation of the associated ion at
the high
temperature FCIP conditions.
[0091] Another advantageous feature of the present invention is that in some
embodiments the
emulsion from step 106 can have a viscosity that is lower, preferably an order
of magnitude
lower, than the corresponding oil components, which facilitates preparation,
pumping,
spraying, conversion, yield, etc., and can avoid adding solvent or diluent.
For example, the
feed mixture may be an emulsion having an apparent viscosity at 30 C and 100 s-
lat least 30%
lower than the oil component alone. In embodiments, the emulsion has a
viscosity of less than
or equal to about 50 Pa-s (50,000 cP) at 50 C, or less than or equal to about
20 Pa-s at 50 C,
or less than or equal to about 1 Pa-s (1000 cP) at 50 C, or less than about
500 mPa-s at 50 C.
Accordingly, the emulsion may include heavy oil emulsified with water and the
finely divided
solids to produce a pumpable emulsion which facilitates adequate and uniform
injection of the
feed mixture into the pyrolysis chamber.
[0092] Also, in some embodiments the emulsion from step 106 can have a high
stability that
inhibits separation into oil or water phases and solids precipitation, which
might otherwise
result in a buildup of asphaltenes, wax, mineral particles, etc. The stability
can facilitate
advance preparation and storage of the emulsion 106. For example, the feed
emulsion can have
an electrical stability of equal to or greater than 1600 V, when determined
according to API
13B-2 at 130 C, preferably greater than 1800 V or even greater than 2000 V. If
desired, the
emulsion may further comprise an emulsifying agent such as a surfactant or
surfactant system.
Preferably, the emulsion is substantially free of added surfactant.
[0093] In some embodiments, the process comprises first mixing the feed oil
104 (or blend
with LIP 102) and the iron source material 108, and then mixing in the water
112. The
alkali/alkaline earth metal chloride source material 110 can be present in the
water 112, e.g.,
as a brine, and/or in the feed oil 104, e.g., un-desalted crude, in the iron
source material 108,
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e.g., as a chloride or as a pretreatment in any support material, or it can be
separately added.
Preferably, the process further comprises passing (e.g., pumping) the feed
emulsion through a
line to the reactor 114, as opposed to mixing the oil, water, and/or
chloride/iron source materials
together in the reactor 114, e.g., introducing them separately and/or at a
nozzle used for
spraying the mixture. In embodiments, the heavy oil is combined with the water
and the
chloride/iron source material(s) to form the feed mixture at a temperature of
about 25 C to
about 100 C, e.g., 30 C to 95 C. The emulsion from step 106 may be fed to the
FCIP reactor
114 at a relatively high temperature to minimize viscosity and enhance rapid
heating in the
pyrolysis chamber, but below boiling, e.g., 30 C to 70 C or 40 C to 60 C.
[0094] An exemplary process according to embodiments of the present invention
comprises
the steps of preparing the FCIP feed emulsion 106 comprising (i) 100 parts by
weight of the
oil component which comprises from 1 to 50 wt% of the LIP, preferably 5 to 40
wt% LIP,
based on the total weight of the oil component, (ii) from about 1 to 100 parts
by weight of the
water component 412, (iii) from about 0.01 to 5 parts by weight (preferably
0.01 to 1 part by
weight) iron source material 108 (preferably comprising iron oxide, iron
hydroxide, iron oxide-
hydroxide, iron chloride, or a mixture thereof), and (iv) from about 0.01 to 5
parts by weight
alkali/alkaline earth metal chloride source material 110 comprising alkali or
alkaline earth
metal chloride such as NaCl, KC1, LiC1, MgCl2, CaCl2, BaC12, or a mixture
thereof; spraying
the FCIP feed emulsion from step 108 in a pyrolysis reactor 114 at a
temperature from about
425 C to about 600 C (preferably about 450 C to about 500 C); collecting
effluent(s) 116 from
the pyrolysis reactor 114; recovering a product LIP 102, 125 from the effluent
116; and
optionally supplying a portion 105 of the LIP 102 to the feed emulsion
preparation step 106.
[0095] Higher amounts of water in the emulsion 106, e. g., more than 50 parts
by weight,
particularly when processing paraffins, tend to produce more hydrocarbon
gases, which may
be preferred where olefin production is preferred. On the other hand, when
processing
asphaltenes, higher amounts of water can control cracking, thereby limiting
gas formation and
coke make. Optimally, targets of about 15 parts by weight of water per 100 oil
are used for the
FCIP processing of asphaltene-rich crudes, and about 10 parts by weight of
water per 100 oil
are used for the FCIP processing of paraffinic crudes.
[0096] In embodiments, the absolute pressure in the FCIP reactor 114 is from
below
atmospheric or about atmospheric up to about 5 atm, or preferably up to about
3 atm, or more
preferably up to about 2 atm, or especially up to about 1.5 atm (7-8 psig).
For example, the
pressure in the FCIP reactor 114 can be about 10 to 50 psia, or about 1 to 3
atm, preferably 10
to 30 psia, more preferably 1 to 1.5 atm. The higher pressures are less
preferred since they
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require more expensive equipment to handle them and may inhibit reactions
necessary for
forming the conversion-promoting and/or coke-inhibiting components in the
product LIP 102.
[0097] The FCIP reactor 114 is operated and/or pyrolyzate exits from the
reactor 114
preferably at a temperature between about 425 C and about 600 C, more
preferably between
about 450 C and about 500 C. The lower temperatures tend to favor more liquid
hydrocarbon
products and less gas, but total conversion may also be lower. Conversely, the
higher
temperatures tend to favor more conversion but hydrocarbon gas formation,
including olefins,
is greater and liquid hydrocarbon yield is less. The temperature depends on
the hydrocarbon
products desired: for greater liquid hydrocarbon yields, a temperature of 450
C to 500 C is
preferred, 450 C to 480 C more preferred; for higher olefin and/or other light
hydrocarbon
yields, 500 C to 600 C is preferred.
[0098] In some embodiments, the heating of the reactor 114 and/or emulsion 106
can be direct
by contact with a hot gas such as a combustion effluent or superheated steam,
and/or in indirect
heat exchange relationship with the combustion gas or steam, or by using an
electrical or
induction heating. In direct heating, the flue gas or superheated steam
preferably comprises
less than about 3 vol% molecular oxygen, or less than about 2 vol% molecular
oxygen, or less
than about 1 vol% molecular oxygen.
[0099] In some embodiments, the process comprises injecting the emulsion into
the reactor,
e.g., using an atomizing nozzle, and in some embodiments the injection is into
a stream of
combustion flue gases or other hot gas such as superheated steam in direct
heat exchange to
promote rapid heating and mixing, e.g., countercurrently sprayed upstream
against an
oncoming flow of the steam or combustion gas, for example, spraying the
emulsion
downwardly against an upward flow of the hot gas from below. If desired the
steam,
combustion flue gases or other hot gas can be introduced into a lower end of a
reactor vessel
housing the pyrolysis zone, e.g., through a gas inlet through a side or bottom
wall of the reactor.
Regardless of heating mode, when sprayed downwardly into the reactor, the
residue and solids
can accumulate in the bottom of the reactor, and periodically or continuously
removed from
the reactor, for example, through an outlet for continuous or periodic removal
of the solids,
e.g., using a rotary valve in the outlet.
[0100] In some embodiments, especially where the feedstock oil is a heavy
crude oil or very
heavy crude oil, the pyrolyzate vapor phase preferably comprises a condensate
upon cooling
having an overall API gravity greater than 20 API or greater than 22.3 API
or greater than
26 API. In some embodiments, the process further comprises cooling the
pyrolyzate vapor
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phase to form a condensate, and collecting the condensate, wherein the
condensate has an
overall API gravity greater than 20 or greater than 22.3 .
[0101] In some embodiments, the pyrolyzate vapor phase comprises hydrocarbons
in an
amount recoverable by condensation at 30 C of at least about 70 parts
(preferably 80 parts,
more preferably 90 parts) by weight per 100 parts by weight of the oil in the
feed mixture, and
especially greater than 100 parts by weight liquid hydrocarbons per 100 parts
by weight of the
oil. Liquid hydrocarbon yields in excess of 100% of the feed oil are made
possible by
incorporating hydrogen and/or oxygen (from the water), especially hydrogen,
into the product
oil, and minimizing gas and residue formation. In some embodiments, the
pyrolyzate vapor
phase comprises less than 5 vol% of non-condensable (30 C) hydrocarbon gases
based on the
total volume of hydrocarbons in the pyrolyzate vapor phase (dry basis).
[0102] In embodiments, the feed oil 104 can be a crude oil, including heavy
crude oil, extra
heavy crude oil, tar, sludge, tank bottoms, spent lubrication oils, used motor
crankcase oil, oil
recovered from oil based drill cuttings, etc., including combinations and
mixtures thereof In
embodiments, the feed oil has an API gravity of less than 22.3 API or less
than 20 API or less
than 10 API. In embodiments, the heavy oil has a viscosity at 50 C greater
than 10,000 cP, or
greater than 50,000 cP, or greater than 100,000 cP, or greater than 300,000
cP, whereas the LIP
422 can have a viscosity at 50 C less than 1000 cP, or less than 100 cP, or
less than 30 cP.
[0103] As mentioned above, the feed oil need not be dewatered or desalted and
can be used
with various levels of aqueous and/or inorganic contaminants. Any water that
is present, for
example, means that less water needs to be added to form the emulsion 106 to
obtain the desired
water:oil ratio. The salts and minerals that may be present in crude oil do
not appear to
adversely affect results, and may provide an alkali/alkaline earth metal
chloride source material
in addition to or in lieu of the added alkali/alkaline earth metal chloride
source material 110.
These embodiments are particularly advantageous in being able to process waste
emulsions or
emulsions such as rag interface that is often difficult to break. Considering
that the industry
goes to great lengths to break emulsions into clean oil and water phases,
feeding such emulsions
in the feed mixture herein to the reactor can avoid the need to break such
emulsions altogether,
or at least reduce the volume of emulsion that must be separated. For example,
the rag layer
that often forms at the interface between the oil and water, that is often
quite difficult to
separate, can be used as a blend component in the feed emulsion step 106.
[0104] In some embodiments of the present invention, a hydrocarbon refinery
process
comprises the steps of: (a) combining an LIP with a feedstock oil to form an
LIP blend
comprising from 1 to 50 wt% LIP and 99 to 50 wt% feedstock oil, preferably 5
to 35 wt % LIP
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and 95 to 65 wt% feedstock oil, more preferably 10 to 30 wt% LIP and 90 to 70
wt% feedstock
oil, based on the total weight of the oil component, preferably where the
percentages of LIP
and feedstock oil total 100; (b) preparing an FCIP feed emulsion comprising
(i) 100 parts by
weight of a first portion of the LIP blend, (ii) from about 1 to 100 parts by
weight of a water
component, (iii) from about 0.01 to 5 parts by weight (or 0.01 to 1 part by
weight) iron source
material 108 (preferably comprising iron oxide, iron hydroxide, iron oxide-
hydroxide, iron
chloride, or a mixture thereof, more preferably where the iron source material
is unsupported),
and (iv) from about 0.01 to 5 parts by weight chloride source material 110
comprising alkali or
alkaline earth metal chloride such as NaCl, KC1, LiC1, MgCl2, CaCl2, BaC12, or
a mixture
thereof; (c) spraying the FCIP feed emulsion in a flash pyrolysis reactor at a
temperature from
about 425 C to about 600 C, preferably 450 C to 500 C; (d) collecting an
effluent from the
flash pyrolysis reactor; (e) recovering a product LIP from the effluent; (0
incorporating at least
a portion of the product LIP into the LIP blend; and (g) distilling a second
portion of the LIP
blend. The feedstock oil preferably comprises crude oil, more preferably un-
desalted crude oil,
e.g., the process may further comprise water washing to desalt the second
portion of the LIP
blend, and distilling the desalted second portion of the LIP blend in step
(g).
[0105] In some embodiments of the present invention, a hydrocarbon refinery
process
comprises the steps of: (a) preparing an FCIP feed emulsion comprising (i) 100
parts by weight
of an oil component, (ii) from about 5 to 100 parts by weight of a water
component, (iii) from
about 0.01 to 5 parts by weight iron source material 108 (preferably
comprising iron oxide,
iron hydroxide, iron oxide-hydroxide, iron chloride, or a mixture thereof,
more preferably
where the iron source material is unsupported) and (iv) from about 0.01 to 5
parts by weight
alkali/alkaline earth metal chloride source material 110 comprising alkali or
alkaline earth
metal chloride such as NaCl, KC1, LiC1, MgCl2, CaCl2, BaC12, or a mixture
thereof; (b)
spraying the FCIP feed emulsion in a pyrolysis reactor at a temperature from
about 425 C to
about 600 C, preferably 450 C to 500 C; (c) collecting an effluent from the
pyrolysis reactor;
(d) recovering LIP from the effluent; (e) combining the recovered LIP with a
feedstock oil
comprising a petroleum fraction selected from medium weight gas oil, heavy gas
oil, resid, or
a combination thereof to form an LIP blend; and (0 distilling, cracking,
visbreaking, and/or
coking the LIP blend. Preferably, the oil component in the feed emulsion from
the preparation
step (a) comprises the petroleum fraction used in step (d), e.g., the feed
emulsion from step (a)
may comprise the LIP blend from the combining step (e).
[0106] The LIP 102 is thus produced from a flash chemical ionizing pyrolysis
(FCIP) process
114 (see FIGs. 7-9 discussed below), e.g., the process referred to as
catalytic pyrolysis in US
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10,336,946 B2. In any embodiment, the FCIP preferably comprises the steps of
preparing an
FCIP feed emulsion comprising (i) an oil component, (ii) a water component,
and (iii) finely
divided solids comprising a mineral support and the iron source material
(preferably
comprising iron oxide, iron hydroxide, iron oxide-hydroxide, iron chloride, or
a mixture
thereof), preferably 100 parts by weight of the oil component, from about 1 to
100 parts by
weight of the water component, and from about 1 to 20 parts by weight of the
finely divided
solids; spraying the FCIP feed emulsion in a pyrolysis reactor, preferably at
a temperature from
about 425 C to about 600 C, preferably 450 C to 500 C; collecting an effluent
from the
pyrolysis reactor; and recovering a product LIP from the effluent.
[0107] In any embodiment, the FCIP preferably comprises the steps of preparing
an FCIP feed
emulsion comprising (i) an oil component, (ii) a water component, (iii)
unsupported iron source
material, and (iv) an alkali or alkaline earth metal chloride source material,
wherein the feed
emulsion comprises less than 1 part by weight added solids per 100 parts oil;
spraying the FCIP
feed emulsion in a pyrolysis reactor, preferably at a temperature from about
425 C to about
600 C, preferably 450 C to 500 C; collecting an effluent from the pyrolysis
reactor; and
recovering a product LIP from the effluent.
[0108] In any embodiment, the FCIP feed emulsion may preferably comprise from
about 20 to
about 50 parts by weight of the water, and/or from about 0.01 to about 1 part
by weight of each
of the iron and alkali/alkaline earth metal chloride source materials, per 100
parts by weight
LIP-feedstock blend or other feed oil.
[0109] In embodiments, the iron/chloride source materials may preferably
comprise or be
prepared as the finely divided solids and/or any of those catalysts disclosed
in my earlier patent,
US 10,336,946 B2, which is hereby incorporated herein by reference in
jurisdictions where
permitted. For example, the iron/chloride source materials can comprise the
finely divided
solids comprising clay and/or a derivative from a clay, such as
montmorillonite, for example,
bentonite. The mineral support can be any other mineral disclosed in the '946
patent, including
processed drill cuttings, albite, and so on. The metal can comprise a Group 3
¨ 16 metal, e.g.,
iron, lead, zinc, or a combination thereof, preferably a Group 8 ¨ 10 metal,
e.g., iron, cobalt,
nickel or the like. In any embodiment, the finely divided solids may comprise
an oxide and/or
acid addition salt of a Group 8 ¨ 10 metal supported on clay, preferably iron
oxide, iron
hydroxide, iron oxide-hydroxide, iron chloride, or a mixture thereof
[0110] Preferably, the iron source material comprises iron oxide, iron
hydroxide, iron oxide-
hydroxide, iron chloride, or a mixture thereof, more preferably where the iron
source material
is unsupported, and a source of a chloride salt. When present, the
montmorillonite or other
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support is preferably a non-swelling clay such as calcium bentonite. The
iron/chloride source
materials are preferably the product of the method comprising the steps of:
(a) treating iron
with an aqueous mixture of hydrochloric and nitric acids to form a solids
mixture of iron oxide,
iron hydroxide, iron oxide-hydroxide, and iron chloride, preferably wherein
the mixture has
limited solubility in water and is acid soluble, (b) treating montmorillonite,
preferably calcium
bentonite, with an alkali or alkaline earth metal chloride brine, preferably
NaCl brine and
drying the treated montmorillonite; (c) combining the solids mixture with the
treated
montmorillonite to load the iron oxide, iron hydroxide, iron oxide-hydroxide,
iron chloride
mixture on the montmorillonite, preferably by incipient wetness or by adding
an aqueous slurry
of the solids mixture to the essentially dry montmorillonite; and (d) heat
treating the loaded
montmorillonite at a temperature above 400 C up to the FCIP temperature,
preferably 400 C
to 425 C (see FIGs. 5-6 discussed below).
[0111] Preferably, the iron and alkali metal/alkaline earth metal chloride
source materials
comprise iron compound derived from the treatment of iron with an aqueous
mixture of
hydrochloric and nitric acids to form a solids mixture of mixed valences of
iron and iron oxides,
iron hydroxides, iron oxide-hydroxides, and iron chlorides. The admixture of
one part by
weight iron and 1-2 parts by weight aqua regia (HC1:H20:HNO3 at 3:2:1 by
weight) forms
hematite, magnetite, beta-iron oxide hydroxide, and chlorides, which is
consistent with the
reddish black coloration of the solids that is observed. The aqua regia is
preferably slowly
added to the iron, or may be added in several aliquots, to avoid excessive
heat formation and
reactant vaporization since the reaction is very exothermic. The proportion of
iron may be
increased somewhat, but too much iron may form insufficient ferric material as
indicated by a
generally brown or rust color. Greater proportions of aqua regia do not yield
much if any benefit
and thus may lead to lower yields of the solids mixture and/or excessive
reagent costs. The
admixture of solids can also contain elemental iron, since the iron may be
present in excess.
Also, other iron chlorides, nitrates, nitrites, oxides, oxychlorides,
hydrochlorides, hydroxides,
hydrates or combinations and/or mixtures of these may also be present. For
example, treatment
of iron with aqua regia may in theory form ferrates such as tetrachloroferrate
(III),
hexachloroferrate (VI) and so on. Further, since water is present, these
compounds may be
hydrated to varying degrees, e.g., especially upon slurrying with water, or
decomposed by the
water.
[0112] The iron source materials preferably have limited solubility, e.g.,
less than 50 wt% will
dissolve in hot water when mixed at a ratio of 1 g solids to 30 ml distilled
water, preferably
less than 40 wt%; and the iron source material is preferably acid soluble,
e.g., more than 50
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wt% will dissolve in 20 wt% aqueous HC1 when mixed at a ratio of 1 g solids to
30 ml aqueous
HC1, preferably at least about 65 wt%. The solids mixture may be dried, e.g.,
in an oven at a
temperature above 100 C, for example, 100 C to 150 C, and ground as needed.
When the iron
source materials is slurried in water and partially dissolved, the aqueous
solution phase may
comprise an excess of chloride ions, e.g., a molar ratio of chloride to total
dissolved iron that
is greater than 3:1, such as between 4 and 5 moles chloride per mole of
solubilized iron. The
aqueous phase of the slurry may also contain nitrite and/or nitrate in lesser
amounts, e.g., 0.04-
0.8 mole nitrite per mole of dissolved iron and/or 0.01-0.2 mole nitrate per
mole of iron.
[0113] FIG. 2 shows the preparation of the iron source compound in exemplary
embodiments
according to method 200. In the summarized method 200, iron 202 is treated
with acid 204,
which may be an aqueous mixture of HC1 and HNO3, in iron source material
preparation step
206. In step 206, finely-divided elemental iron 202, e.g., 100 mesh carbon
steel or high purity
iron shavings, are admixed with aqua regia 204, preferably an excess where the
total moles of
HC1 and HNO3 are at least 3-6 times greater than the moles of iron, e.g., at a
weight ratio of
.. 1:1-2 (Fe: aqua regia) where the aqua regia has a weight ratio of nitric
acid:hydrochloric
acid:water of about 1:3:2. The aqua regia is preferably added in multiple
aliquots while stirring,
and the temperature may increase, e.g., to about 95 C or greater, forming.
[0114] The solid iron compound can be recovered from the aqueous phase, e.g.,
by filtration,
water washing, and drying, for example in an oven as shown in step 208. In
step 210, the
recovered solids can be ground, e.g., to pass a 100 mesh screen, preferably a
325 mesh or 400
mesh screen.
[0115] The aqua-regia-treated Fe solids ("AR-Fe") at this point can comprise a
complex
mixture of iron oxide, iron hydroxide, iron oxide-hydroxide, iron chloride, or
a mixture thereof,
with the iron in various valence states, e.g., Fe(0), Fe(II), Fe(III), and so
on. Primarily, solids
comprise hematite, magnetite, and beta-ferric oxide hydroxide. The AR-Fe
unexpectedly has a
low fractional solubility in water so that no more than 40 wt%, preferably no
more than about
wt% or 30 wt%, dissolves and/or digests in an aqueous mixture of 1 g AR-Fe in
30 ml total
mixture (33.33 g/L) at 100 C, but has a high fractional solubility in 20 wt%
aqueous
hydrochloric acid such that at least 90 wt%, preferably at least about 95 wt %
or 98 wt%,
30 dissolves and/or digests in an aqueous mixture of 1 g AR-Fe in 30 ml
total mixture (33.33 g/L)
at 100 C.
[0116] The method 300 seen in FIG. 3 shows the alternative preparation of a
supported
iron/chloride source compound. Brine 302, preferably 1M sodium chloride, is
admixed in step
304 with calcium bentonite 306, preferably passing through a 100 mesh screen.
Preferably, the
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weight ratio of Ca-bentonite to brine is 1:2. The mixture can be stirred,
e.g., for 1 h, and allowed
to stand, e.g., for 16-24 h. In step 308, the excess brine is discarded, e.g.,
by decantation and/or
filtration, and in step 310 the solids are dried, e.g., dried in an oven at
120-130 C for 4-6 h.
When the NaCl-bentonite is dry, it can be optionally ground in step 312, e.g.,
to pass through
an 80 mesh screen. Separately the iron compound is prepared. In step 320,
finely-divided
elemental iron 322 is admixed with aqua regia 324. In step 326, the solid iron
compound can
be recovered and dried. In step 328, the recovered solids can be ground as
desired. In step 330
the solids are slurried in water, e.g., at 4 weight percent solids. Then, in
step 332 the slurry
from step 330 is admixed with the dry, ground NaCl-bentonite from step 312,
e.g., at a weight
ratio of 2:3 (slurry: NaCl-bentonite) to load the AR-Fe on the NaCl-bentonite
by incipient
wetness. The mixture from step 332 is then dried and calcined, e.g., at 400 C
for 2 h in step
334, cooled and ground in step 336, e.g., to pass an 80 mesh screen, and
recovered as the
supported iron-based solids 338.
[0117] While not wishing to be bound by theory, as mentioned above one
advantage of using
a feed emulsion is that iron and/or chloride ions can pre-associate with
heteroatoms in the
asphaltene molecules and thereby target these species for reaction upon
decomposition and/or
catalytic activation of the associated ions at the high temperature FCIP
conditions. The ionized
species present in the emulsion presents a level of molecular-scale pre-mixing
of oil, water,
catalysts and other reactants that cannot occur where the reactants and
catalysts are supplied
separately to the reactor.
[0118] While not wishing to be bound by theory, it is believed that hydrogen
radicals and/or
molecular hydrogen are generated in situ during flash pyrolysis by reaction
and/or catalysis of
one or more iron compound(s) at the pyrolysis conditions, e.g., at 450 ¨ 500
C. For example,
hydrogen may be formed by the decomposition of ferric chloride in the presence
of steam,
according to the following reactions, e.g.:
FeCl3 c*. FeCl2(s) + Cl+
Cl + + 2H20 c*. HC10 + H+
Here, the formation of hydrogen may be favored due to an excess of water
(steam).
[0119] Ferric chloride can be formed by the decomposition of iron chloride
compounds in the
iron source material, e.g., Fe0C1 may decompose into FeCl3, according to the
equation:
3Fe0C1 c*. Fe2O3 + FeCl3.
[0120] Ferric chloride can also be formed by the decomposition of the chloride
source material
to form HC1, which then reacts with iron oxides, e.g., according to the
reactions:
NaCl + H20 (Superheated steam) c*. HC1 + NaOH
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Fe2O3 + 6HCL c*. 2FeC13 + 3H20
[0121] In turn, organic carboxylic acids can be decarboxylated according to
the reactions:
R-COOH + NaOH <=> R-COONa + HOH
R-COONa + NaOH <=> RH + Na2CO3(s)
where R is a hydrocarbyl.
[0122] In addition to the chemical production of hydrogen radicals by
decomposition, FeCl3
per se and bentonite (if present) can function as Lewis and/or Bronsted acids,
and thus in theory
can initiate ionic cracking reactions to form liquid ionizing pyrolyzate.
Another possibility in
theory is that iron compound(s) having higher oxidation states relative to
Fe(III) may be formed
during the preparation of the iron compounds with aqua regia and/or during
heat treatment,
e.g., hexachloroferrate ion (Fe(VI)C13)3- which might also help form ions
and/or free radicals
to propagate thermal and/or catalytic cracking reactions.
[0123] Furthermore, iron compounds such as magnetite, hematite, iron oxide
hydroxide, iron
oxychloride, ferrates, and the like, can act as catalysts per se in various
hydrocarbon reactions.
[0124] While not wishing to be bound by theory, it is believed that FCIP using
the Fe/C1 system
at low pressure and a specific range of temperatures achieves extensive
conversion of heavy
hydrocarbons such as asphaltenes and/or resins to lighter hydrocarbons, and
removal of
heteroatoms such as nitrogen, sulfur, metals, etc., by reactions normally seen
in high pressure
catalytic cracking and hydrocracking, e.g., isomerization, cracking,
dealkylation, aromatic
saturation, decyclization, etc. For example, there is evidence that sulfur is
both reduced,
presumably by hydrogen radicals, and oxidized, presumably by reaction with
HC10 that is
formed, as indicated above, by the reaction between the chlorine radical
liberated from the iron
chloride decomposition and the water that is present in the emulsion. The LIP
product is
unexpectedly characterized by low noncondensable gas yield, e.g., only small
quantities of
methane may be formed; the light products may be primarily C1-C6 hydrocarbons;
small
quantities of or no C4+ olefins may be seen; and there may be significant
formation of branched
chain alkanes, isomerates, dealkylated aromatics, and naphthene cracking
products. At the
same time, the yield of coke can be minimized.
[0125] The montmorillonite support, if present, is preferably a non-swellable
bentonite such
as calcium bentonite. The bentonite is preferably treated with a chloride
brine to replace
calcium ions with the cation, e.g., by treating the bentonite with 1 molar
NaCl or other chloride
brine. The treated bentonite may then be dried, e.g., in an oven at a
temperature above 100 C,
for example, 100 C to 150 C, and ground as needed to prepare it for loading
with the
iron/chloride source materials slurry by incipient wetness. The loading is
thus achieved by
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mixing the iron/chloride source materials slurry with the dried chloride brine-
treated bentonite,
which may form a paste. In this mixture, Na ions in the bentonite may
theoretically be displaced
with iron and/or iron complex cations to form, e.g., possible species such as
Fe(II)X-(0-Si-
bentonite) and/or Fe(III)X2(-0-Si-bentonite), where X is an anion. The mix of
iron compound
and dried, chloride brine-treated bentonite is then preferably heat treated or
calcined. Heat
treating the finely divided solids involves heating at a temperature above 200
C, such as from
about 300 C up to 600 C, for a period of time from less than 1 minute up to 24
hours or more,
e.g., 1 to 16 hours. Heating at a temperature above 400 C for a period of 4 to
6 hours is
preferred. High temperatures above 400 C are preferred to activate the
iron/chloride source
materials, and may result in isolated Lewis and/or Bronsted acid sites in the
bentonite being
formed and/or other hydrate compounds, e.g., iron compound hydrates, may be
dehydrated.
Lower temperatures may result in insufficient activation or require longer
periods of heating.
Substantially higher temperatures may cause undesirable reaction,
volatilization, and/or
deactivation of the chemical species in the solids. Preferably, the heat
treatment is at a
temperature lower than the FCIP temperature, which may avoid premature
reaction and/or
deactivation of the solids material prior to FCIP, more preferably the heat
treating is at a
temperature of equal to or greater than 400 C up to a temperature equal to or
less than 425 C.
[0126] Although not wishing to be bound by theory, it is believed salts or
ions present in the
iron/chloride source materials can form a eutectic mixture with one or more
metal compounds
or reaction products thereof, especially where the metal compound melts or
boils at the heat
treatment temperature and the eutectic mixture is non-volatile. For example,
where the iron
compound includes or forms FeCl3, which has a normal boiling point of 315 C
and is thus
normally quite volatile at 400 -425 C, the presence of NaCl or another salt
may form a eutectic
mixture of FeCl3-NaCl with substantially lower volatility. This allows the
FeCl3 to remain on
the support during heat treatment at 400 -425 C and to be available as a
reactant and/or catalyst
at a higher pyrolysis temperature. Other iron compounds such as nitrates
and/or nitrites may or
may not decompose during the heat treatment step, e.g., to form iron oxides.
In theory, similar
eutectic systems such as FeCl3-Na-bentonite may also form. Also, the iron
compound resulting
from the aqua regia treated iron has unexpectedly limited solubility in water
suggesting that
other complexes may be formed which could also limit volatility during heat
pretreatment. As
an example, the aqua regia-treated iron compounds might form covalent bonds
with the
bentonite, e.g., Fe(III)C12(-0-Si-bentonite), to limit premature volatility.
When used, the solids
mixture of iron compounds or other iron source may be loaded on the bentonite
in an amount
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from 1 mg/kg to 10 wt%, for example, from about 1000 mg/kg to 5 wt%,
preferably 2-4 wt%,
based on the total weight of the finely divided solids.
[0127] Liquid ionizing pyrolyzate (LIP) products obtained when a feedstock oil
is processed
by FCIP according to embodiments disclosed herein, especially when an oil with
high contents
of asphaltenes and/or resins is processed, include various medium-length
hydrocarbon
fractions having from about 12 to about 30 carbons, and various light oil
fractions having from
about 6 to 12 carbons. The LIP is thus enriched in hydrocarbons similar to
those seen in
catalytic and/or hydrocracking products.
[0128] Additionally, the LIP from the FCIP disclosed herein has an
unexpectedly low viscosity
for its density, compared to other hydrocarbons, suggesting the presence of
relatively high
levels of isomerates. Moreover, blends of the LIP with other crude oils, heavy
oils, resids, and
the like also have an unexpectedly low viscosity compared to conventional
crude oil blends.
Applicant is not bound by theory, but believes there may be ionized species in
the LIP such as
stable radicals that can inhibit asphaltene aggregation and/or decyclize
asphaltenes, which is
reflected in a significant reduction in coking tendency. The asphaltenes and
other hydrocarbon
molecules subjected to FCIP can form relatively stable free radical species,
and can also form
hydrogen donor species such as hydroaryl compounds. Some rearrangement of
molecules
appears to occur at ambient temperatures upon blending, whereas at moderate
thermal
processing temperatures, e.g., 100-250 C, the free radicals and hydrogen
donors can facilitate
conversion to saturates, aromatics, and lube oil base stock molecules, and
reducing the amount
of Conradson carbon residue and coke make.
[0129] In any case, when a feedstock oil is blended with the LIP, the
viscosity reduction and
reduced tendency to form coke results in unexpected improvements in thermal
processing. For
example, a crude-LIP blend can be heated more rapidly, e.g., during preheating
for feed to the
distillation column, since fouling from coke formation and deposition is
markedly reduced.
Distillation of a crude-LIP or resid-LIP blend results in liquid oil yields
that are substantially
and synergistically higher, and resid yields that are substantially and
synergistically lower, than
could be obtained by separate distillation of the LIP and crude or resid.
Flash pyrolysis of a
crude-LIP or resid-LIP blend, by FCIP as described herein, or otherwise,
likewise results in
similarly increased yields of liquid oil products and decreased yields of coke
and also
noncondensable gases. Unexpectedly, the resid from thermal processing of such
LIP-modified
blends exhibits a remarkably low viscosity, suggesting it contains an
unusually high proportion
of lube oil base stock. Moreover, the production of olefins by FCIP can be
controlled by the
selection of appropriate operational parameters, e.g., increasing the water
content in the
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emulsion feed to the pyrolysis reactor and/or increasing the pyrolysis
temperature can produce
relatively larger amounts of olefins such as ethylene and propylene.
[0130] With reference to the embodiment of the invention shown in the
simplified schematic
flow diagram of FIG. 4, in FCIP process 400, feed oil 402 and liquid ionizing
pyrolyzate (LIP)
from stream 404 are optionally blended in step 406 or otherwise fed separately
to
emulsification in step 408 with chloride source 409, iron source 410 and water
412. The
emulsion from step 408 is supplied to FCIP step 414. One or more effluents are
separated in
step 416 to obtain solids 418, water 420, LIP 422, and noncondensable gas 424.
[0131] With reference to the embodiment of the invention shown in the
simplified schematic
.. flow diagram of FIG. 5, a hydrocarbon refinery process 500 comprises
combining a liquid
ionizing pyrolyzate (LIP) 502 from FCIP 504 with a feed oil 506 in step 508 to
form an LIP
blend comprising the LIP. A first portion 520 of the LIP blend from 508 is
supplied for FCIP
504, and a second portion 509 for distillation 514.
[0132] The LIP can be used in the blend in a weight proportion of LIP 502:
feed oil 502 of
from 1:100 to 1:1, e.g., or from 1:20 to 1:2, preferably in an amount from 1
or 5 to 35 wt%,
e.g., about 10 to 30 wt%, based on the total weight of the feed oil 506 and
LIP 502 supplied to
the blending step 508. Lesser amounts of the LIP have diminishing improvement
of the blend,
whereas higher amounts may not be economically attractive.
[0133] Surprisingly, it has been found that a blend of the LIP and crude oil
can have a
.. substantially lower viscosity than would be expected from traditional API
viscosity prediction
methods for blends.
[0134] The first LIP blend portion 520 can be pyrolyzed in FCIP 504. In step
522, there is
prepared an FCIP feed emulsion comprising (i) 100 parts by weight of the first
portion 520 of
the LIP blend, (ii) from about 1 to 100 parts by weight water 528, (iii) from
about 0.01 to 5
parts by weight of the iron source material 526, and (iv) from about 0.01 to 5
parts by weight
of the chloride source material 525, e.g., from about 5 to about 50 parts by
weight of the water
528, and from about 0.05 to about 1 parts by weight each of the iron/chloride
source materials
525, 526, per 100 parts by weight of the LIP blend from step 508. In step 504,
the FCIP feed
emulsion from 522 is injected, preferably sprayed, in a pyrolysis reactor at a
temperature from
about 425 C to about 600 C. An effluent 530 is collected from the pyrolysis
reactor, a product
LIP 502 is recovered from the effluent, and at least a portion is incorporated
into the LIP blend
in step 508 as mentioned above.
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[0135] Feed oil 524, which can be the same feed oil as 506 or another oil
source can optionally
be supplied to the emulsion step 522 along with or in lieu of stream 520.
Where blend stream
520 and feed oil 524 are both used, they can optionally be blended together in
a vessel or line
(not shown) before the emulsion step 522. Preferably, the blend stream 520 is
the exclusive oil
source for the emulsion 522 fed to FCIP 504, i.e., feed oil 524 is not
supplied to the emulsion
522, thereby avoiding a duplication of oil blending equipment.
[0136] The emulsion step 522 emulsifies the blend stream 520 and/or feed oil
524 with chloride
source material 525, iron source material 526, and water 528. The emulsion is
pyrolyzed in
FCIP step 504, and separated in step 530 to obtain solids 532, water 534, LIP
502, and
noncondensable gas 536. Use of the blend stream 520 in this manner can
facilitate pyrolysis
by reducing fluid viscosities, improving emulsion stability, enhancing
atomization, improving
conversion, improving liquid yield of LIP 502, and improving the isomerization
and/or
alkylation promoting qualities of the product LIP 502, relative to the feed
oil 506 and/or feed
oil 524.
[0137] The second portion 509 of the LIP blend from 508 is fractionated in
distillation 514. In
any embodiment, the feed oil 506 may be a crude oil, preferably un-desalted
crude oil,
preferably where the process further comprises water washing in step 510 to
desalt the second
portion 509 of the LIP blend, preheating the crude in step 512, and distilling
in step 514 to
obtain light and heavy products 516, 518. In practice, the crude is often
partially preheated to
reduce viscosity, desalted, and then preheated to the distillation feed
temperature. The
distillation step 514 can include atmospheric and/or vacuum distillation, with
which the skilled
person is familiar.
[0138] Desalting 510 of the LIP blend portion 509 is facilitated due to lower
salt and water
content, synergistically lower viscosity and lower density, relative to the
feed oil 506 by itself,
and can thus be separated from water or brine more readily than the crude.
Because some of
the inorganic contaminants are removed by FCIP 504 from the first portion 520,
the load on
the desalter 510 is likewise reduced. If desired, the water 536 for the
desalting 510 may come
from the FCIP water 534, and/or the brine 538 may be supplied to water 528 for
preparing the
emulsion in 522.
[0139] Heating 512 can likewise be improved by less tendency to form coke or
otherwise foul
the heat transfer surfaces, allowing a higher differential temperature to be
applied. To avoid
this, refineries often use a series of heaters, e.g., more than a dozen, to
incrementally raise the
crude to the desired temperature. The LIP blend may reduce the number of
heaters required.
Also, the LIP blend has an unexpectedly lower viscosity and may provide higher
heat transfer
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coefficients. Finally, distillation 514 is improved by providing a higher
yield of light products
516, a lower yield of heavy products 518, and improved quality of both the
light and heavy
products 516, 518. For example, the lighter products 516 tend to have an
unexpectedly high
proportion of the type of hydrocarbons normally obtained by isomerization
and/or alkylation,
which can be reflected in a lower density, lower viscosity, higher viscosity
index, etc.
[0140] With reference to the embodiment according to the present invention
shown in the
simplified schematic flow diagram of FIG. 6, a hydrocarbon refinery process
600 is shown in
which (i) a blend of the heavy products 610 from distillation 612 and a
portion 602 of the
product LIP 604 is treated in FCIP 606 for improved conversion, liquid yield,
and LIP quality,
and a reduction in the amount of coke that is formed, relative to treatment of
the heavy products
610 alone and especially relative to conventional processing of the heavy
products 610, e.g., in
a delayed coker; and/or (ii) a portion 616 of the product LIP 604 is supplied
to distillation 612
for improved yield and quality of distillates, and a reduction in the yield of
the heavy products
610 and/or the amount of coke that is formed, relative to distillation of the
feed oil 618 alone.
[0141] Optionally, the feed oil 618 used for distillation 612 can be processed
for feed to the
distillation 602 in the manner as shown in FIG. 5 for the feed oil 506 in
process 500 that is fed
to distillation 514. In this arrangement, FIG. 5 can be seen as the front end
or pretreatment of
the crude supplied in a blend with the LIP to the distillation 514, 612, and
FIG. 6 as a
downstream processing of the heavy products 518, 610 from distillation 514,
612. In other
words, processes 500 and 600 can be integrated where distillation 514 and 612
are equivalent,
light products 516 and 620 are equivalent, and heavy products 518 and 610 are
equivalent. The
feed oil 618 is preferably a washed, preheated crude oil, e.g., the oil from
heating step 512 in
FIG. S.
[0142] A first portion 602 of LIP 604 from FCIP 606 can be blended in step 608
with heavy
products 610 from distillation 612. The blend, iron source material 613a, and
chloride source
material 613b are supplied with water 615 to the emulsion preparation step 614
for the FCIP
606.
[0143] A second portion 616 of the LIP 604 is optionally collected as a
product stream and/or
supplied to the distillation 612 for improved conversion of the feed oil 618
to light products
620 from the distillation, improved yield and quality of light products 620,
and decreased yield
of heavy products 610 and/or a reduced flow rate to resid processing 622. If
desired, the LIP in
stream 616 may be blended in step 508 with the feed oil 618 (corresponding to
feed oil 506 in
FIG. 5) upstream from the desalting 510, heating 512, and so on. When the LIP
604 derived
from the heavy product 610 in FIG. 6 is supplied to the blending 508 in FIG.
5, the treatment
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loop through line 520 to FCIP 504 and return from LIP 502 may or may not be
used, and if
used, the processing rate through FCIP 504 may be reduced in size relative to
the flow scheme
of FIG. 3 alone.
[0144] Effluent 624 from FCIP 606 is separated to recover LIP 604,
noncondensable gas 626,
water 628, and solids 630. Recovered water 628 may optionally be supplied for
re-use as the
water 615 fed to the emulsion step 614 and/or water 528 (see FIG. 5).
[0145] With reference to FIG. 7, an apparatus 700 that may be used to prepare
the feed mixture
in accordance with some embodiments of the present invention comprises a
mixing tank 702A
equipped with an agitator 704A, which may be driven by motor 706A. If desired,
redundant
.. pumps 708A, 710A can be provided with valved lines for selective
recirculation and transfer
to an optional holdup tank 712 and/or directly to reactor 714. If desired, an
optional second
mixing train 716, including mixing tank 702B, agitator 704B, motor 706B, and
pumps 708B,
710B, can be provided to facilitate batch, semi-batch or continuous feed
mixture preparation.
[0146] In batch operation, feed oil 718, water 720, chloride source material
721, and iron
.. source material 722 are charged to the mixing tank 702A (or 702B) in any
order, preferably by
transferring the feed oil into the mixing tank, then any solids, and then the
water while
maintaining agitation via agitator 704A (or 704B) and/or providing agitation
before and/or after
each addition. Alternatively, the solids can be dispersed and/or dissolved in
the water, e.g., in
the mixing tank, and then the oil added, e.g., as a first portion to form a
pre-mix emulsion to
aid dispersion of the iron source material, and then as a second portion
comprising the
remainder of the oil. One of the pumps 708A, 710A (708B, 710B) can recirculate
the mixture
via valved line 711A (711B) while agitating to facilitate mixing. Once the
mixture has been
prepared, the pumps 708A, 710A (708B, 710B) can transfer the mixture to
holding tank 712
via valved line 724A (724B), or directly to FCIP reactor 714 via valved lines
726A (726B) and
728.
[0147] If desired, the feed oil 718 may be heated or mixed with a hydrocarbon
diluent to reduce
viscosity and facilitate pumping and mixing. The water 720 may also be
optionally heated to
facilitate mixing. Also, if desired, the tanks 702A, 702B, 712 and the
associated lines and
pumps may also be heated to keep the viscosity of the mixture low; however,
the mixture in
.. some embodiments has a lower viscosity than the feed oil 718, so it may be
possible to maintain
a lower temperature for the mixture or to avoid heating altogether.
Furthermore, the mixing
operation may be exothermic providing a source of heat in situ for the
mixture. Moreover, the
emulsion of the feed mixture is stable in some embodiments and so it may be
prepared in
advance, e.g., up to several days or more, and stored until use without phase
separation, before
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transfer to the tank 712 and/or reactor 714. The emulsion can also be prepared
off-site and
pumped or trucked to the pyrolysis site. The feed mixture preparation
apparatus shown in FIG.
7 may be used in or with any of the embodiments of the invention as shown in
the other figures.
[0148] In some embodiments, the feed mixture may be mixed using an in-line
mixer(s) and/or
produced in-situ within the FCIP reactor 714 by adding at least one of the
feed oil, water and/or
the finely divided solids directly into the FCIP reactor 714 and/or by the
addition of water
and/or addition of solids directly to the pyrolysis chamber, depending on the
composition of
the feed oil and the end use of the product LIP.
[0149] In some embodiments, the pyrolyzate vapor phase is condensable to form
an oil phase
lighter than the feed oil. In some embodiments the pressure in the FCIP
reactor 714 is
sufficiently low and the temperature sufficiently high such that the
pyrolyzate exits the reactor
in the vapor phase or primarily in the vapor phase, e.g. with at least 70 wt%
of the recovered
hydrocarbons, preferably at least 80 wt%, or at least 90 wt%, or at least 95
wt%, or at least 98
wt%, or at least 99 wt% or at least 99.9 wt%, or 100 wt% of the recovered
hydrocarbon exit
the reactor 146 in the vapor phase, based on the total weight of the recovered
hydrocarbons. In
general, the pyrolyzate effluent 148 is primarily or mostly gas phase,
comprised of
hydrocarbons, steam, and in the case of direct heating, additional steam or
flue gases such as
carbon dioxide or monoxide, nitrogen, additional steam, etc., but may entrain
relatively minor
amounts of liquid droplets and/or small-particle solids (fines) that may be
removed by
filtration, cyclonic separation and/or condensation with the recovered
hydrocarbons when they
are subsequently condensed to produce the catalytic pyrolysis oil product.
[0150] In an embodiment, the absolute pressure in the reactor 714 is from
about 10 to 50 psia,
e.g. from about 10 to 30 psia, or from about 1 atm to about 1.5 atm, or to
about 1.1 atm, and
the pyrolyzate vapor 148 exits from the reactor at a temperature above 425 C,
e.g., above
450 C, up to about 480 C, up to about 500 C, or up to about 600 C, e.g., 450 C-
500 C, 450 C-
480 C, or 500 C-600 C.
[0151] The feed mixture from line 728 may be heated in the pyrolysis chamber
by hot gas 730,
e.g., steam, combustion effluent or another gas at a temperature from about
300 C or 600 C
up to about 1200 C, either in direct heat exchange relation via line 732 or
indirect heat
exchange relation via line 734. In practice only one arrangement is present in
the apparatus
700, either direct or indirect heating. In embodiments the hot gas 730
comprises steam, or
combustion gas from a fuel-rich combustion, e.g., comprising less than about 1
vol% molecular
oxygen, or another effluent having a sufficiently low oxygen content to
inhibit combustion in
the reactor 714. In direct heating, the hot gas 730 may have a temperature
from about 300 C
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to about 1200 C, and is contacted or mixed directly with the feed mixture or
reaction products
thereof, and the hot gas exits the FCIP reactor 714 with the pyrolyzate in
effluent stream 736.
In indirect heating, the hot gas 730, preferably supplied at an inlet
temperature from about
600 C to about 1200 C, enters a heat exchanger 737 within the FCIP reactor 714
and cooled
gas 738 is collected from an outlet of the heat exchanger. Solids 740
accumulating in the reactor
714 may be periodically or continuously removed for disposal or for recycling
in the process
(re-used as the finely divided solids and/or its preparation), with or without
regeneration.
[0152] In embodiments, the effluent 736 with the product LIP exits the FCIP
reactor 714 at a
temperature greater than about 425 C, or greater than about 450 C. In
embodiments, the
effluent 736 exits the FCIP reactor 714 at a temperature of about 600 C or
below, or below
about 500 C. The effluent 736 from the reactor 714 can be processed as
desired, e.g., in
separator 742 to remove entrained fines 744 and/or in separator 746 to recover
water 748 and
one or more oil fractions, e.g., LIP 750, and to exhaust non-condensable gases
752. The
separator 742 can comprise a cyclone separator, a filter such as a baghouse,
an electric
precipitator, etc. Separator 746 can comprise condensers to recover condensate
and gravity
separation devices, e.g., a centrifuge or oil-water separator tank, to phase
separate condensate
comprising oil and water mixtures. Separator 746 can if desired optionally
further include
recovery of light hydrocarbons, e.g., hydrogen, methane, ethane, ethylene,
propane, propylene,
fuel gas, or the like, using a cryogenic process, membrane separators, and so
on.
[0153] In embodiments, the FCIP reactor 714 comprises a turbulent environment,
and may
contain a bed of particulate inert solids (see FIG. 9), which may comprise
silica, alumina, sand,
or a combination thereof, and/or may include nonvolatile residues from
previously treated
mixtures such as ash, coke, and/or heavy hydrocarbons (i.e., having 40 carbons
or more). These
residues may collect and/or may be continuously or periodically removed from
the FCIP
reactor 714. In embodiments, the feed mixture in line 728 is fed to FCIP
reactor 714 at a point
below a bed, thus fluidizing the bed, and/or the feed mixture may enter just
over the bed, e.g.,
downwardly directed such as onto the bed or on an impingement plate (fixed or
partially
fluidized bed) from which the more volatile compounds rise immediately and the
less volatile
compounds are converted to more volatile compounds in the bed.
[0154] In embodiments, the combustion gases utilized as the hot gas 730 in any
of the
processes disclosed herein, especially in the direct heating embodiments, are
sub-
stoichiometric with respect to oxygen (oxygen lean/fuel rich) such that the
concentration of
molecular oxygen 02 in the reactor is less than about 1 vol%, or less than 0.1
vol%, or the
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combustion gas is essentially free of molecular oxygen. Accordingly, in
embodiments, the
pyrolysis reactor 714 comprises a reducing atmosphere.
[0155] With reference to FIG. 8, a process 800 according to some embodiments
of the present
invention comprises a mixer and/or mixing tank 802 to combine feed oil 804,
water 806,
chloride source 807, and iron source 808 into an emulsion as described herein
(cf discussion
of FIG. 7). The emulsion is transferred via pump 810 to FCIP reactor 812. An
oxygen source
814 such as air, oxygen or oxygen-enriched air is combined with fuel 816 in
combustion burner
818 to supply combustion effluent in line 820 to the reactor 812, as described
herein (cf.
discussion of FIG. 7). Control system 821 is provided to control the operating
conditions of the
FCIP reactor 812, e.g., by manipulation or adjustment of the feed rate(s)
and/or combustion
rates to maintain the pyrolysis zone at a temperature, pressure and residence
time to form an
LIP vapor phase. In the case of indirect heating, cold gas 822 is recovered;
otherwise the
combustion gases are mixed with the steam and LIP vapors and recovered in
effluent line 824.
Solids 826 may be recovered from the reactor 812 continuously or periodically.
[0156] The effluent from line 824 is optionally processed in fines removal
unit 828, to separate
fines 830, optionally including any liquid droplets or other solids, and the
remaining vapor can
optionally be supplied directly to an oil or heavy oil reservoir recovery
process (see Fig. 11 of
US 2016/0160131 Al), or after conditioning to remove any undesirable
components,
supplement any additional components needed, compress to injection pressure,
heat to the
desired injection temperature, and/or cool to recover waste heat. Where the
iron source material
is unsupported, the fines removal can be eliminated or designed for
substantially reduced fines
content.
[0157] The remaining vapor can be cooled in exchanger 834 and hydrocarbon
condensate (LIP
I) 836 recovered from separator 838. The process temperature in the exchanger
834 and
separator 838 is preferably above the water dew point so that the condensate
836 is essentially
free of water, e.g., less than 1 wt%. The vapors from separator 838 are then
cooled in exchanger
840 and condensate 842 recovered from separator 844. The process temperature
in the
exchanger 840 and separator 844 is preferably below the water dew point so
that the condensate
842 is a mixture of water and oil, which can be further separated in separator
846, which can
be a centrifuge or gravity settling tank, for example, to obtain oil product
(LIP II) 848 and water
850. The overhead vapor from the separator 844 can be exhausted and/or used as
a fuel gas, or
it can optionally be further processed in exchanger 852 for cooling and
separated in separator
854 into non-condensable gases 856 and or product 858 comprised of one or more
streams of
hydrogen, methane, ethane, ethylene, propane, propylene, carbon dioxide, fuel
gas, including
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combinations thereof The separator 854 can be any one or suitable combination
of a cryogenic
separator, membrane separator, fractionator, solvent extraction, pressure
swing absorption, or
the like.
[0158] With reference to FIG. 9, a process 900 comprises a reactor 902 that is
directly heated
by combustion gases or steam supplied from burner 904 and combustion chamber
or boi1er906
through duct 908, which can direct the combustion effluent/steam through
distributor 908a
located to fluidize the solids 909. Feed mixture 910 can be prepared, for
example, as described
above (cf discussion of FIGs. 7-8). The feed mixture 910 is supplied to nozzle
912 and forms
a preferably conical spray pattern 914 in the reactor 902.
[0159] The nozzle 912 is directed downwardly and can be positioned near the
upper end of the
reactor, e.g., 1/3 of the way down from the top of the reactor toward the
bottom. The nozzle
912 is preferably designed and positioned so that the spray pattern 914 avoids
excessive
impingement on the inside surfaces of the reactor 902 that can lead to caking
and/or buildup of
solids on the walls. For example, the nozzle 912 can provide a conical spray
pattern. The feed
mixture 910 is thus introduced countercurrently with respect to the flue gas
or steam from
combustion chamber or boiler 906 to promote mixing and rapid heating to
facilitate the
conversion and volatilization of hydrocarbons.
[0160] The pyrolyzate vapor phase exits the reactor 902 together with the
combustion gas and
steam from the feed mixture water into duct 916. The upward flow rate of the
gases in the
reactor 902 in some embodiments is sufficiently low to avoid excessive
entrainment of solid
particulates. The solid particulates can thus fall to the bottom of the
reactor 902 and can be
periodically and/or continuously withdrawn, e.g., via rotary valve 918, for
disposal and/or
regeneration and recycle to the slurry preparation. Regeneration can be
effected in some
embodiments by contacting the solids with an oxygen containing gas at high
temperature to
promote combustion of hydrocarbon residue and coke from the particles. In any
embodiment,
regeneration can be in situ in reactor 902, e.g., by supplying oxidant gas
into the solids bed 909
for combustion of coke.
[0161] The gases from the reactor 902 in some embodiments are optionally
passed into cyclone
920 for removal of fines. Where an unsupported iron source material is used,
for example, the
cyclone 920 may not be needed and/or can be designed for removal of
substantially reduced
fines content. Fines, when present, can be periodically and/or continuously
withdrawn from
the cyclone 920, e.g., via rotary valve 926. The solids-lean gases in some
embodiments are
then passed through condensers 922 and 924. The first condenser 922 preferably
condenses
hydrocarbons, which have a relatively higher boiling point than water, at a
temperature above
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the water dew point so that the oil 928 (LIP I) has a low water content, e.g.,
essentially free of
water so that water separation is not needed. The second condenser 924
preferably condenses
the hydrocarbons and water which may be processed, if desired, in separator
932 to separate
an oil phase 934 (LIP II) from a water phase 936, e.g., by gravity settling,
centrifuge, or the
like. The recovered water in this and any of the other embodiments illustrated
herein can, if
desired, be recycled for preparation of the feed mixture to the FCIP reactor
(cf. FIGs. 1, 4-8),
the desalting 510 (FIG. 5), and so on. Non-condensed exhaust gases 938 are
recovered
overhead from the condenser 924.
EMBODIMENTS
[0162] The present invention provides, among others, the following preferred
embodiments:
1. A hydrocarbon refinery process comprising the steps of:
(a) combining a liquid ionizing pyrolyzate (LIP) with crude oil to form an LIP-
crude blend
comprising the pyrolyzate in an amount from 10 to 20 wt% based on the total
weight of the
HP-crude blend;
(b) combining a first portion of the LIP-crude blend, water, an iron source
material, and an
alkali or alkaline earth metal chloride brine, to obtain a feed emulsion
comprising (i) 100
parts by weight of an oil phase, (ii) 5-20 parts by weight of an aqueous
phase, (iii) 0.01 to
5 parts by weight of an iron source material, (iv) 0.01 to 5 parts by weight
of an alkali or
alkaline earth metal chloride, wherein the feed emulsion comprises less than 1
part by
weight solids;
(c) spraying the feed emulsion in a vapor phase of a flash chemical ionizing
pyrolysis reactor
at a temperature of 450-500 C;
(d) collecting an effluent from the flash chemical ionizing pyrolysis reactor;
(e) recovering a liquid pyrolyzate from the effluent;
(f) supplying the liquid pyrolyzate from step (e) as the hydrocarbon
pyrolyzate in step (a);
(g) desalting a second portion of the LIP-crude blend from step (a);
(h) supplying brine recovered from step (g) as the water in step (b);
(i) preheating the desalted LIP-crude blend from step (g);
(j) atmospherically distilling the preheated LIP-crude blend from step (i) to
separate an
atmospheric resid from lower boiling hydrocarbon fractions; and
(k) vacuum distilling the atmospheric resid to separate a vacuum resid from
gas oil.
2. A hydrocarbon refinery process comprising the steps of:
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(a) combining a liquid ionizing pyrolyzate (LIP) with resid to form an LIP-
resid blend
comprising the pyrolyzate in an amount from 10 to 20 wt% based on the total
weight of the
LIP-resid blend;
(b) combining a first portion of the LIP-resid blend, water, an iron source
material, and an
alkali or alkaline earth metal chloride source material, to obtain an emulsion
comprising (i)
100 parts by weight of an oil phase, (ii) 5-20 parts by weight of an aqueous
phase, (iii) 0.01
to 5 parts by weight of an iron source material, (iv) 0.01 to 5 parts by
weight of an alkali or
alkaline earth metal chloride, wherein the feed emulsion comprises less than 1
part by
weight solids;
.. (c) spraying the feed emulsion in a vapor phase of a flash chemical
ionizing pyrolysis reactor
at a temperature of 450-500 C;
(d) collecting an effluent from the flash chemical ionizing pyrolysis reactor;
(e) recovering a liquid ionizing pyrolyzate product from the effluent;
(0 supplying the liquid ionizing pyrolyzate product from step (e) as the
liquid ionizing
pyrolyzate in step (a);
(g) distilling a second portion of the LIP-resid blend from step (a) to
separate resid from lower
boiling hydrocarbon fractions;
(h) supplying a first portion of the resid from step (g) to the LIP-resid
blend in step (a); and
(i) optionally coking a second portion of the resid from step (g) to obtain
coker gas oil.
Al. A hydrocarbon conversion process, comprising the steps of:
emulsifying water and an oil component with an iron source material
(preferably hematite,
magnetite, iron oxide hydroxide, or a mixture thereof optionally comprising
chloride)
and an alkali or alkaline earth metal chloride source material, wherein the
emulsion
comprises less than 1 part by weight solids per 100 parts by weight oil;
.. introducing the emulsion into a flash chemical ionizing pyrolysis (FCIP)
reactor maintained at
a temperature greater than about 400 C up to about 600 C and a pressure up to
about
1.5 atm to form an ionized pyrolyzate effluent;
condensing the ionized pyrolyzate from the effluent to recover a liquid
ionized pyrolyzate
(LIP);
combining a feedstock oil with the LIP to form a pyrolyzate-feedstock blend;
and
thermally processing the blend at a temperature above about 100 C.
A2. The process of embodiment Al, wherein the emulsion comprises less than
0.5 parts by
weight solids per 100 parts oil component.
A3. The process of embodiment Al, wherein the iron source material is
unsupported.
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A4. The process of embodiment A3, comprising preparing the iron source
material by a
method comprising contacting iron with an aqueous mixture of hydrochloric and
nitric acids to
form a mixture of hematite, magnetite, and iron oxide hydroxide comprising
chlorides.
AS. The process of any of embodiments Al to A4, further comprising the
steps of:
wherein the emulsion comprises (i) 100 parts by weight of the oil component,
preferably
wherein the oil component comprises the pyrolyzate-feedstock blend; (ii) from
about
1 to 100 parts by weight of water, (iii) from about 0.01 to 5 parts by weight
(preferably 0.01 to less than 1 part by weight) of the iron source material,
and (iv)
from about 0.01 to 5 parts by weight of the alkali or alkaline earth metal
chloride
source material; and
spraying the emulsion into the reactor, wherein the reactor temperature is
from about 425 C
to about 600 C, preferably 450 C to 500 C.
A6. The process of embodiment AS, wherein the emulsion comprises less
than 1 part by
weight solids per 100 parts oil component.
A7. The process of any of embodiments Al to A6, wherein the feedstock oil
comprises
hydrocarbons boiling at a temperature equal to or greater than 562 C, and
further comprising
the step of recovering a hydrocarbon product from the thermally processed
blend, the
hydrocarbon product having an enriched yield of liquid hydrocarbons boiling at
a temperature
below 562 C, relative to separate thermal processing of the LIP and feedstock
oil, as
determined by atmospheric distillation in a 15-theoretical plate column at a
reflux ratio of 5:1,
according to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill
method
according to ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
A8. The process of embodiment A7 wherein the feedstock oil is crude oil,
gas oil, resid, or
a mixture thereof
A9. The process of any of embodiments Al to A8 wherein the thermal processing
comprises pyrolysis, distillation, cracking, alkylation, visbreaking, coking,
and combinations
thereof
A10. The process of any of embodiments Al to A9, further comprising supplying
at least a
portion of the pyrolyzate-feedstock blend as the oil component to the FCIP
feed emulsion
preparation step wherein the thermal processing step consists of or comprises
the spraying of
the FCIP feed emulsion into the flash pyrolysis reactor.
All. A flash chemical ionizing pyrolysis (FCIP) process comprising the steps
of:
preparing a feed emulsion comprising (i) 100 parts by weight of an oil
component comprising
a liquid ionizing pyrolyzate (LIP) and a feedstock oil at a weight ratio of
from 1:100
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to 1:1, (ii) from about 1 to 100 parts by weight of water, (iii) from about
0.01 to 5
parts by weight (preferably 0.01 to less than 1 part by weight) of an iron
source
material, and (iv) from about 0.01 to 5 parts by weight of an alkali or
alkaline earth
metal chloride source material, wherein the emulsion comprises less than 1
part by
weight total solids;
spraying the feed emulsion in a flash pyrolysis reactor at a temperature from
about 425 C to
about 600 C;
collecting an effluent from the reactor;
recovering a product oil from the effluent; and
supplying a portion of the product oil as the LIP to the feed emulsion
preparation step.
Al2. A hydrocarbon refinery process comprising the steps of:
combining a liquid ionizing pyrolyzate (LIP) blend component with a feedstock
oil at a weight
ratio from about 1:100 to about 1:1 to form an LIP blend;
preparing an emulsion comprising (i) a first portion of the LIP blend, (ii)
water, (iii) an iron
source material, and (iv) an alkali or alkaline earth metal chloride source
material,
wherein the emulsion comprises less than 1 part by weight total solids;
spraying the emulsion in a flash pyrolysis reactor at a temperature from about
425 C to about
600 C and a pressure from about 1 to about 1.5 atm;
collecting an effluent from the reactor;
recovering a product LIP from the effluent;
incorporating the product LIP as the LIP blend component in the LIP blend; and
distilling a second portion of the LIP blend.
A13. The process of embodiment Al2, wherein the feedstock oil comprises crude
oil.
A14. The process of embodiment A13, wherein the feedstock oil comprises un-
desalted
.. crude oil wherein the process further comprises water washing to desalt the
second portion of
the LIP blend, and distilling the desalted second portion of the LIP blend.
A15. The process of embodiment A9 wherein the feedstock oil comprises crude
oil and
further comprising washing the LIP blend with wash water, recovering a solute-
enriched
spent water from the water washing step, recovering a desalted LIP blend, and
heating the
desalted LIP blend in advance of distillation of the LIP blend.
A16. A hydrocarbon refinery process comprising the steps of:
preparing a feed emulsion comprising (i) 100 parts by weight of an oil
component, (ii) from
about 1 to 100 parts by weight of water, (iii) an iron source material, and
(iv) an alkali
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or alkaline earth metal chloride source material (preferably wherein the
emulsion
comprises less than 1 part by weight total solids);
spraying the feed emulsion in a flash pyrolysis reactor at a temperature from
about 425 C to
about 600 C;
collecting an effluent from the flash pyrolysis reactor;
recovering a liquid ionizing pyrolyzate (LIP) from the effluent;
combining the recovered LIP with a feedstock oil comprising crude oil or a
petroleum fraction
selected from gas oil, resid, or a combination thereof to form a pyrolyzate-
feedstock
blend;
distilling, cracking, visbreaking, and/or coking a first portion of the LIP
blend; and
supplying a second portion of the LIP blend as the oil component in the feed
emulsion
preparation step.
A17. The process of embodiment A16, wherein the LIP exhibits a SARA analysis
having
higher saturates and aromatics contents and a lower asphaltenes content than
the feedstock
oil.
A18. The process of embodiment A16 or A17 wherein a proportion of the LIP in
the oil
component in the flash pyrolysis is effective to improve yield of liquid
hydrocarbons boiling
at a temperature below 562 C, relative to separate flash chemical ionizing
pyrolysis of the LIP
and feedstock oil, as determined by atmospheric distillation in a 15-
theoretical plate column at
a reflux ratio of 5:1, according to ASTM D2892-18 up to cutpoint 400 C AET,
and by vacuum
potstill method according to ASTM D5236-18a above the 400 C cutpoint to
cutpoint 562 C
AET.
A19. The process of any of embodiments Al 6 to Al 8 wherein a proportion of
the LIP in the
LIP blend in the distillation, cracking, visbreaking, and/or coking step, is
effective to improve
yield of liquid hydrocarbons boiling at a temperature below 562 C, relative to
separate
distillation, cracking, visbreaking, and/or coking of the LIP and feedstock
oil, as determined
by atmospheric distillation in a 15-theoretical plate column at a reflux ratio
of 5:1, according
to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
A20. A crude oil upgrading process, comprising:
blending a liquid ionizing pyrolyzate (LIP) with a heavy oil; and
thermally processing the blend at a temperature above about 100 C.
A21. The process of any of embodiments Al to A19 wherein the oil component
and/or the
feedstock oil comprise crude oil.
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A22. The process of any of embodiments Al to A19 wherein the oil component
and/or the
feedstock oil comprise heavy crude oil.
A23. The process of any of embodiments Al to A19 wherein the oil component
and/or the
feedstock oil comprise diesel.
A24. The process of any of embodiments Al to A19 wherein the oil component
and/or the
feedstock oil comprise atmospheric resid.
A25. The process of any of embodiments Al to A19 wherein the oil component
and/or the
feedstock oil comprise vacuum resid.
A26. The process of any of embodiments Al to A25 wherein the emulsion further
comprises
finely divided solids in an amount of from 1 to 20 parts by weight per 100
parts by
weight oil.
A27. The process of any of embodiments Al to A25 wherein the emulsion
comprises less
than 1 part by weight total solids per 100 parts by weight oil.
B I . A hydrocarbon conversion process, comprising the steps of:
combining a feedstock oil with a liquid ionizing pyrolyzate (LIP) to form an
LIP blend;
thermally processing the LIP blend; and
recovering a hydrocarbon product having an enriched yield of liquid
hydrocarbons boiling at a
temperature below 562 C, relative to separate thermal processing of the LIP
and
feedstock oil, as determined by atmospheric distillation in a 15-theoretical
plate column
at a reflux ratio of 5:1, according to ASTM D2892-18 up to cutpoint 400 C AET,
and
by vacuum potstill method according to ASTM D5236-18a above the 400 C cutpoint
to cutpoint 562 C AET.
B2. The process of embodiment B1 wherein the feedstock oil is crude oil,
gas oil, resid, or
a mixture thereof
B3. The process of embodiment B1 or embodiment B2 wherein the thermal
processing
comprises emulsion flash chemical ionizing pyrolysis (FCIP), distillation,
cracking,
alkylation, visbreaking, coking, and combinations thereof, preferably FCIP
and/or
distillation.
B4. The process of embodiment B3 wherein the liquid ionizing pyrolyzate
(LIP) is
produced from emulsion flash chemical ionizing pyrolysis (FCIP) comprising the
steps
of:
preparing an FCIP feed emulsion comprising (i) 100 parts by weight of an oil
component,
preferably wherein the oil component comprises the LIP blend; (ii) from about
5 to 100
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parts by weight of a water component, (iii) from about 0.01 to 5 parts by
weight
(preferably 0.01 to less than 1 part by weight) of the iron source material,
and (iv) from
about 0.01 to 5 parts by weight of the alkali or alkaline earth metal chloride
source
material, wherein the emulsion comprises less than 1 part by weight total
solids per 100
parts by weight oil;
spraying the FICP feed emulsion in a pyrolysis reactor at a temperature from
about 425 C to
about 600 C, preferably 450 C to 500 C;
collecting an effluent from the pyrolysis reactor; and
recovering a product LIP from the effluent for use in the combining step to
form the LIP blend.
B5. The process of embodiment B4 wherein the emulsion comprises finely
divided solids,
wherein the finely divided solids comprise the iron source material and the
alkali or
alkaline earth metal chloride source material, preferably wherein the finely
divided
solids comprise:
(i) a mixture of hematite, magnetite, and iron oxide hydroxide recovered from
the treatment of
iron with an aqueous mixture of hydrochloric and nitric acids, the mixture
supported on
a brine-treated montmorillonite, preferably NaCl brine-treated calcium
bentonite,
and/or
(ii) the product of the method comprising the steps of:
treating iron with an aqueous mixture of hydrochloric and nitric acids to form
a solids mixture,
preferably wherein the solids mixture has limited solubility;
treating montmorillonite, preferably calcium bentonite, with brine, preferably
NaCl brine;
combining a slurry of the solids mixture with the dried, treated
montmorillonite to load the
mixture on the montmorillonite; and
heat treating the loaded montmorillonite at a temperature above 400 C,
preferably 400 C to
425 C.
B6. An emulsion flash chemical ionizing pyrolysis (FCIP) process
comprising the steps of:
preparing an FCIP feed emulsion comprising 100 parts by weight of an oil
component, from
about 5 to 100 parts by weight of a water component, from about 0.01 to 5
parts by
weight (preferably 0.01 to less than 1 part by weight) of the iron source
material, and
from about 0.01 to 5 parts by weight of the alkali or alkaline earth metal
chloride source
material, wherein the emulsion comprises less than 1 part by weight total
solids per 100
parts by weight oil;
spraying the FICP feed emulsion in a flash pyrolysis reactor at a temperature
from about 425 C
to about 600 C;
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collecting an effluent from the pyrolysis reactor;
recovering a product liquid ionizing pyrolyzate (LIP) from the effluent;
combining at least a portion of the product LIP with a feedstock oil to form
an LIP blend
comprising from 1 to 33.33 wt% of the product LIP; and
thermally processing the LIP blend to form a hydrocarbon product having an
enriched yield of
liquid hydrocarbons boiling at a temperature below 562 C, relative to separate
thermal
processing of the LIP and feedstock oil, relative to separate thermal
processing of the
LIP and feedstock oil, as determined by atmospheric distillation in a 15-
theoretical plate
column at a reflux ratio of 5:1, according to ASTM D2892-18 up to cutpoint 400
C
AET, and by vacuum potstill method according to ASTM D5236-18a above the 400 C
cutpoint to cutpoint 562 C AET.
B7. The process of embodiment B6, further comprising supplying at least a
portion of the
LIP blend as the oil component to the FCIP feed emulsion preparation step
wherein the thermal
processing step consists of or comprises the spraying of the FCIP feed
emulsion into the flash
.. pyrolysis reactor.
B8. An emulsion flash chemical ionizing pyrolysis (FCIP) process comprising
the steps of:
preparing an FCIP feed emulsion comprising (i) 100 parts by weight of an oil
component
comprising a feedstock oil and from 1 to 33.33 wt% of a liquid hydrocarbon
pyrolyzate
(LIP), based on the total weight of the oil component, (ii) from about 5 to
100 parts by
weight of a water component, (iii) from about 0.01 to 5 parts by weight
(preferably 0.01
to less than 1 part by weight) of the iron source material, and (iv) from
about 0.01 to 5
parts by weight of the alkali or alkaline earth metal chloride source
material, wherein
the emulsion comprises less than 1 part by weight total solids per 100 parts
by weight
oil;
spraying the FCIP feed emulsion in a pyrolysis reactor at a temperature from
about 425 C to
about 600 C;
collecting an effluent from the pyrolysis reactor;
recovering a product LIP from the effluent; and
optionally supplying a portion of the product LIP to the feed emulsion
preparation step.
B9. A hydrocarbon refinery process comprising the steps of:
combining a liquid ionizing pyrolyzate (LIP) with a feedstock oil to form an
LIP blend
comprising the LIP in an amount from 1 to 33.33 wt% based on the total weight
of the
LIP blend;
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preparing an FCIP feed emulsion comprising (i) 100 parts by weight of a first
portion of the
LIP blend, (ii) from about 5 to 100 parts by weight of a water component,
(iii) from
about 0.01 to 5 parts by weight (preferably 0.01 to less than 1 part by
weight) of the
iron source material, and (iv) from about 0.01 to 5 parts by weight of the
alkali or
alkaline earth metal chloride source material, wherein the emulsion comprises
less than
1 part by weight total solids per 100 parts by weight oil;
spraying the FCIP feed emulsion in an emulsion flash chemical ionizing
pyrolysis reactor at a
temperature from about 425 C to about 600 C;
collecting an effluent from the flash pyrolysis reactor;
recovering a product LIP from the effluent;
incorporating at least a portion of the product LIP into the LIP blend; and
distilling a second portion of the LIP blend.
B10. The process of embodiment B9, wherein the feedstock oil comprises crude
oil,
preferably un-desalted crude oil wherein the process further comprises water
washing to desalt
the second portion of the LIP blend, and distilling the desalted second
portion of the LIP blend.
B11. The process of embodiment B9 wherein the feedstock oil comprises crude
oil and
further comprising washing the LIP blend with wash water, recovering a solute-
enriched spent
water from the water washing step, recovering a desalted LIP blend, and
heating the desalted
LIP blend, preferably in advance of distillation of the LIP blend.
B12. A hydrocarbon refinery process comprising the steps of:
preparing a feed emulsion comprising (i) 100 parts by weight of an oil
component, (ii) from
about 5 to 100 parts by weight of a water component, (iii) from about 0.01 to
5 parts by
weight (preferably 0.01 to less than 1 part by weight) of the iron source
material, and
(iv) from about 0.01 to 5 parts by weight of the alkali or alkaline earth
metal chloride
source material, wherein the emulsion comprises less than 1 part by weight
total solids
per 100 parts by weight oil;
spraying the feed emulsion in a flash pyrolysis reactor at a temperature from
about 425 C to
about 600 C;
collecting an effluent from the flash pyrolysis reactor;
.. recovering a liquid ionizing pyrolyzate (LIP) from the effluent;
combining the recovered LIP with a feedstock oil comprising a petroleum
fraction selected
from gas oil, resid, or a combination thereof to form an LIP blend; and
distilling, cracking, visbreaking, and/or coking the LIP blend.
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B13. The process of embodiment B12 wherein the oil component in the feed
emulsion from
the preparation step comprises the petroleum fraction, preferably the LIP
blend from the
combining step.
B14. The process of any of embodiments B6 to B13 wherein the pressure in the
pyrolysis
reactor is from about 10 to 50 psia, preferably 1 to 1.5 atm.
B15. The process of any of embodiments B6 to B13 wherein the LIP blend
comprises the
feedstock oil and a proportion of the LIP effective to improve conversion in
the pyrolysis
reactor of the oil component to the LIP at an enriched yield of liquid
hydrocarbons boiling at a
temperature below 562 C, and/or an enriched yield of distillates, relative to
separate FCIP of
the LIP and feedstock oil, relative to separate thermal processing of the LIP
and feedstock oil,
as determined by atmospheric distillation in a 15-theoretical plate column at
a reflux ratio of
5:1, according to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum
potstill method
according to ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
B16. The process of any of embodiments B6 to B13 wherein the LIP blend
comprises the
LIP in an amount from 1 to 33.33 percent and the feedstock oil in an amount
from 99 to 66.67
percent, by weight of the LIP blend, preferably from 5 to 25 percent LIP and
from 95 to 75
percent feedstock oil, more preferably from 10 to 20 percent LIP and from 90
to 80 percent
feedstock oil.
B17. The process of any of embodiments B6 to B13 wherein the mineral support
comprises
montmorillonite, preferably bentonite, more preferably wherein the process
comprises treating
calcium bentonite with a sodium chloride brine and/or heat treating the
bentonite, preferably
to a temperature of 400 C to 425 C.
B18. The process of embodiment B17 wherein the iron source material comprises
an iron
oxide, an iron hydroxide, an iron oxide hydroxide, an iron chloride, or a
mixture thereof.
B19. The process of embodiment B17, wherein the iron source material comprises
the
reaction product of elemental iron with an aqueous mixture of hydrochloric
acid and nitric acid,
preferably wherein a molar ratio of the iron to the total hydrochloric and
nitric acids is from
1:2 to 2:1, a molar ratio of the iron to water is from 1:2 to 2:1, and/or a
molar ratio of
hydrochloric acid to nitric acid is from 1:1 to 10:1, more preferably the
reaction product of 1-
2 parts by weight of the iron and aqua regia wherein the aqua regia comprises
3 parts by weight
hydrochloric acid, 2 parts by weight water, and 1 part by weight nitric acid.
B20. The process of embodiment B19, wherein the iron source material comprises
chloride.
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B21. The process of any of embodiments B6 to B13, further comprising
preparation of the
iron source material and alkali or alkaline earth metal chloride source
material according to a
procedure comprising the steps of:
(a) reacting elemental iron with an aqueous mixture of hydrochloric acid
and nitric acid,
preferably wherein a molar ratio of the iron to the total hydrochloric and
nitric acids is
from 1:2 to 2:1, a molar ratio of the iron to water is from 1:2 to 2:1, and/or
a molar ratio
of hydrochloric acid to nitric acid is from 1:1 to 10:1, more preferably the
reaction
product of equal weights of the iron and aqua regia wherein the aqua regia
comprises 3
parts by weight hydrochloric acid, 2 parts by weight water, and 1 part by
weight nitric
acid;
(b) treating calcium bentonite with a chloride brine;
(c) loading the reaction product from (a) on the treated bentonite from
(b), preferably by
incipient wetness, more preferably by drying the treated bentonite from (b),
slurrying
the reaction product from (a), and contacting the dried bentonite with the
slurry;
(d) heat treating the bentonite loaded with the reaction product,
preferably by heating to a
temperature from 400 C to 425 C; and
(e) grinding the heat treated sodium bentonite, preferably to a size
passing a 60 mesh
screen.
B22. The process of any of embodiments B1 to B21 wherein the oil component (if
present)
and/or the feedstock oil comprise crude oil.
B23. The process of any of embodiments B1 to B21 wherein the oil component (if
present)
and/or the feedstock oil comprise heavy crude oil.
B24. The process of any of embodiments B1 to B21 wherein the oil component (if
present)
and/or the feedstock oil comprise diesel.
B25. The process of any of embodiments B1 to B21 wherein the oil component (if
present)
and/or the feedstock oil comprise atmospheric resid.
B26. The process of any of embodiments B1 to B21 wherein the oil component (if
present)
and/or the feedstock oil comprise vacuum resid.
B27. The process of any of embodiments B4 to B26, wherein the FCIP comprises
contacting
the emulsion with superheated steam.
Cl. A hydrocarbon desulfurization process, comprising the steps of:
emulsifying water and a high sulfur oil component comprising a feedstock oil
with an iron
source material and an alkali or alkaline earth metal chloride source
material, wherein
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the emulsion comprises less than 1 part by weight total solids per 100 parts
by weight
oil;
introducing the emulsion into a flash chemical ionizing pyrolysis (FCIP)
reactor maintained at
a temperature greater than about 400 C up to about 600 C and a pressure up to
about
1.5 atm to form an ionized pyrolyzate effluent;
condensing the ionized pyrolyzate from the effluent to recover a liquid
ionized pyrolyzate (LIP)
having a reduced sulfur content relative to the high sulfur oil component.
C2. The process of embodiment Cl, wherein the emulsion comprises a brine
of the alkali
or alkaline earth metal chloride.
C3. The process of embodiment C2, wherein the iron source material
comprises an iron
oxide, an iron hydroxide, an iron oxide hydroxide, an iron chloride, or a
mixture thereof
C4. The process of embodiment C3, comprising preparing the iron source
material by a
method comprising contacting iron with an aqueous mixture of hydrochloric and
nitric acids to
form a mixture of hematite, magnetite, and iron oxide hydroxide.
C5. The process of any of embodiments Cl to C4, further comprising:
wherein the emulsion comprises (i) 100 parts by weight of the oil component,
preferably
wherein the oil component comprises the pyrolyzate-feedstock blend; (ii) from
about
1 to 100 parts by weight of water, (iii) from about 0.01 to 5 parts by weight
(preferably 0.01 to less than 1 part by weight) of the iron source material,
and (iv)
from about 0.01 to 5 parts by weight of the alkali or alkaline earth metal
chloride
source material (preferably wherein the emulsion comprises less than 0.5 parts
by
weight total solids per 100 parts by weight oil); and
spraying the emulsion into the reactor, wherein the reactor temperature is
from about 425 C
to about 600 C, preferably 450 C to 550 C.
C6. The process of embodiment C5 wherein the iron source material further
comprises
chloride.
C7. The process of any of embodiments Cl to C6, further comprising
combining the
feedstock oil with the LIP from the condensation step to form the oil
component for the
emulsifying step (preferably at weight ratio of 5-35 wt% LIP and 95-65 wt%
feedstock oil).
C8. The process of embodiment Cl, further comprising:
combining the feedstock oil with the LIP from the condensation step to form a
pyrolyzate-
feedstock blend; and
thermally processing the blend at a temperature above about 100 C.
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C9. The process of embodiment C8, wherein the feedstock oil comprises
hydrocarbons
boiling at a temperature equal to or greater than 562 C, and further
comprising the step of
recovering a hydrocarbon product from the thermally processed blend, the
hydrocarbon
product having an enriched yield of liquid hydrocarbons boiling at a
temperature below 562 C,
.. relative to separate thermal processing of the LIP and feedstock oil, as
determined by
atmospheric distillation in a 15-theoretical plate column at a reflux ratio of
5:1, according to
ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
C10. The process of embodiment C9 wherein the feedstock oil is crude oil, gas
oil, resid, or
a mixture thereof
C 1 1. The process of any of embodiments C8 to C10 wherein the thermal
processing
comprises pyrolysis, distillation, cracking, alkylation, visbreaking, coking,
and combinations
thereof
C12. The process of any of embodiments C8 to C11, further comprising supplying
at least a
.. portion of the pyrolyzate-feedstock blend as the oil component to the FCIP
feed emulsion
preparation step wherein the thermal processing step consists of or comprises
the spraying of
the FCIP feed emulsion into the flash pyrolysis reactor.
C13. A flash chemical ionizing pyrolysis (FCIP) process comprising the steps
of:
preparing a feed emulsion comprising (i) 100 parts by weight of an oil
component comprising
a liquid ionizing pyrolyzate (LIP) and a high sulfur feedstock oil at a weight
ratio of
from 1:100 to 1:1, (ii) from about 1 to 100 parts by weight of water, (iii)
from about
0.01 to 5 parts by weight (preferably 0.01 to less than 1 part by weight) of
the iron
source material, and (iv) from about 0.01 to 5 parts by weight of the alkali
or alkaline
earth metal chloride source material, wherein the emulsion comprises less than
1 part
by weight total solids per 100 parts by weight oil;
spraying the feed emulsion in a flash pyrolysis reactor at a temperature from
about 425 C to
about 600 C;
collecting an effluent from the reactor;
recovering a product oil from the effluent, wherein the product oil has a
sulfur content lower
than sulfur content of the oil component; and
supplying a portion of the product oil as the LIP to the feed emulsion
preparation step.
C14. A hydrocarbon refinery process comprising the steps of:
combining a liquid ionizing pyrolyzate (LIP) blend component with a high
sulfur feedstock oil
at a weight ratio from about 1:100 to about 1:1 to form an LIP blend;
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preparing an emulsion comprising (i) a first portion of the LIP blend, (ii)
water, (iii) from about
0.01 to 5 parts by weight (preferably 0.01 to less than 1 part by weight) of
the iron
source material, and (iv) from about 0.01 to 5 parts by weight of the alkali
or alkaline
earth metal chloride source material, wherein the emulsion comprises less than
1 part
by weight total solids per 100 parts by weight oil;
spraying the emulsion in a flash pyrolysis reactor at a temperature from about
425 C to about
600 C and a pressure from about 1 to about 1.5 atm;
collecting an effluent from the reactor;
recovering a product LIP from the effluent;
incorporating the product LIP as the LIP blend component in the LIP blend; and
distilling a second portion of the LIP blend.
C15. The process of embodiment C14, wherein the feedstock oil comprises crude
oil.
C16. The process of embodiment C15, wherein the feedstock oil comprises un-
desalted crude
oil wherein the process further comprises water washing to desalt the second
portion of the LIP
blend, and distilling the desalted second portion of the LIP blend.
C17. The process of embodiment C11 wherein the feedstock oil comprises high
sulfur
crude oil and further comprising washing the LIP blend with wash water,
recovering a solute-
enriched spent water from the water washing step, recovering a desalted LIP
blend, and
heating the desalted LIP blend in advance of distillation of the LIP blend.
C18. A hydrocarbon refinery process comprising the steps of:
preparing a feed emulsion comprising (i) 100 parts by weight of an oil
component, (ii) from
about 1 to 100 parts by weight of water, (iii) from about 0.01 to 5 parts by
weight
(preferably 0.01 to less than 1 part by weight) of the iron source material,
and (iv) from
about 0.01 to 5 parts by weight of the alkali or alkaline earth metal chloride
source
material, wherein the emulsion comprises less than 1 part by weight total
solids per 100
parts by weight oil;
spraying the feed emulsion in a flash pyrolysis reactor at a temperature from
about 425 C to
about 600 C;
collecting an effluent from the flash pyrolysis reactor;
recovering a liquid ionizing pyrolyzate (LIP) from the effluent;
combining the recovered LIP with a high sulfur feedstock oil comprising crude
oil or a
petroleum fraction selected from gas oil, resid, or a combination thereof to
form a
pyrolyzate-feedstock blend;
distilling, cracking, visbreaking, and/or coking a first portion of the LIP
blend; and
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supplying a second portion of the LIP blend as the oil component in the feed
emulsion
preparation step.
C19. The process of embodiment C18, wherein the LIP exhibits a SARA analysis
having
higher saturates and aromatics contents and a lower asphaltenes content than
the feedstock oil.
C20. The process of embodiment C18 or C19 wherein a proportion of the LIP in
the oil
component in the flash pyrolysis is effective to improve yield of liquid
hydrocarbons boiling
at a temperature below 562 C, relative to separate flash chemical ionizing
pyrolysis of the LIP
and feedstock oil, as determined by atmospheric distillation in a 15-
theoretical plate column at
a reflux ratio of 5:1, according to ASTM D2892-18 up to cutpoint 400 C AET,
and by vacuum
potstill method according to ASTM D5236-18a above the 400 C cutpoint to
cutpoint 562 C
AET.
C21. The process of any of embodiments C18 to C20 wherein a proportion of the
LIP in the
LIP blend in the distillation, cracking, visbreaking, and/or coking step, is
effective to improve
yield of liquid hydrocarbons boiling at a temperature below 562 C, relative to
separate
distillation, cracking, visbreaking, and/or coking of the LIP and feedstock
oil, as determined
by atmospheric distillation in a 15-theoretical plate column at a reflux ratio
of 5:1, according
to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
C22. The process of any of embodiments Cl to C21, wherein the FCIP comprises
contacting
the emulsion with superheated steam.
Dl. A hydrocarbon conversion process, comprising the steps of:
providing an iron source material;
providing an alkali or alkaline earth metal chloride source material;
providing an aqueous phase;
mixing the iron source material, the alkali or alkaline earth metal chloride
source
material, and the aqueous phase with an oil component to form a feed emulsion
comprising less than 1 part by weight of total solids per 100 parts by weight
of
the oil component;
introducing the feed emulsion into a flash chemical ionizing pyrolysis (FCIP)
reactor
maintained at a temperature greater than about 400 C up to about 600 C and a
pressure from 10 to 50 psia to form a chemical ionizing pyrolyzate effluent;
and
condensing a liquid ionizing pyrolyzate (LIP) from the effluent.
D2. The
process of embodiment D1, wherein the iron source material comprises an iron
oxide, an iron hydroxide, an iron oxide hydroxide, an iron chloride, or a
mixture thereof
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D3. The process of embodiment D1, wherein the iron source material
comprises hematite,
magnetite, iron oxide hydroxide, or a mixture thereof
D4. The process of any of embodiments D1 to D3, wherein the iron source
material
comprises a mixture of hematite, magnetite, and iron oxide hydroxide.
D5. The process of any of embodiments D1 to D4, wherein the iron source
material
comprises beta-ferric oxide hydroxide and optionally comprises chloride.
D6. The process of any of embodiments D1 to D5, wherein the iron source
material further
comprises chloride.
D7. The process of any of embodiments D1 to D6, wherein the iron source
material
comprises the reaction product of iron with a mixture of hydrochloric acid and
nitric acid in
the presence of water (preferably aqua regia), preferably to form a mixture of
hematite,
magnetite, and iron oxide hydroxide.
D8. The process of embodiment D7, further comprising reacting iron with a
mixture of
hydrochloric acid and nitric acid in the presence of water (preferably aqua
regia) to form the
iron source material.
D9. The process of any of embodiments D1 to D8, wherein the iron source
material
comprises solid particulates, preferably particles having a major dimension
equal to or less than
4 microns.
D10. The process of any of embodiments D1 to D9, further comprising first
mixing the iron
source material, the alkali or alkaline earth metal chloride source material,
and the aqueous
phase with a first portion of the oil component to form a pre-mix emulsion,
and then mixing
the pre-mix emulsion with a second portion of the oil component.
D11. The process of embodiment D10, wherein the oil component is present in
the pre-mix
emulsion in an amount equal to or less than 20 parts by weight per 100 parts
by weight of the
aqueous phase.
D12. The process of any of embodiments D1 to D11, wherein the iron source
material is
present in the ionized feed emulsion in an amount of from 0.01 to 5 parts by
weight, per 100
parts by weight of the primary oil component, preferably 0.05 to 1 part by
weight.
D13. The process of any of embodiments D1 to D12, wherein the alkali or
alkaline earth
metal chloride source material comprises NaCl, KC1, LiC1, MgCl2, CaCl2, BaC12,
or a mixture
thereof
D14. The process of any of embodiments D1 to D13, wherein the alkali or
alkaline earth
metal chloride source material is present in the ionized feed emulsion in an
amount of from
0.01 to 5 parts by weight, per 100 parts by weight of the primary oil
component, preferably
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0.05 to 1 part by weight.
D15. The process of any of embodiments D1 to D14, wherein the iron source
material is
unsupported, preferably wherein the feed emulsion is essentially free of added
clay solids.
D16. The process of any of embodiments D1 to D15, wherein the feed emulsion
comprises
.. less than 1 part by weight undissolved solids per 100 parts by weight of
the oil component,
more preferably less than 0.5 parts by weight undissolved solids per 100 parts
by weight of the
oil component.
D17. The process of any of embodiments D1 to D16, wherein the feed emulsion is
essentially
free of added solids other than the iron source material and any sediment from
the oil
component.
D18. The process of any of embodiments D1 to D17, wherein the feed emulsion
comprises
from 1 to 100 parts by weight water per 100 parts by weight of the oil
component, preferably
5 to 50 parts by weight water, more preferably 5 to 20 parts by weight water.
D19. The process of any of embodiments D1 to D18, wherein the reactor
temperature is from
about 425 C to about 600 C, preferably 450 C to 500 C.
D20. The process of any of embodiments D1 to D19, wherein the reaction
pressure is equal
to or greater than 10 psia up to 30 psia, preferably equal to or less than 25
psia, more preferably
1-1.5 atm.
D21. The process of any of embodiments D1 to D20, comprising a residence time
in the flash
chemical ionizing pyrolysis reactor from 0.1 up to 10 seconds, preferably from
0.5 to 4 seconds.
D22. The process of any of embodiments D1 to D21, wherein the introduction
step comprises
spraying the feed emulsion in the flash chemical ionizing pyrolysis reactor,
preferably
atomizing the feed emulsion in the flash chemical ionizing pyrolysis reactor.
D23. The process of any of embodiments D1 to D22, wherein the iron source
material
comprises the product of treating iron with an aqueous mixture of hydrochloric
and nitric
acids to form a product mixture of hematite, magnetite, and beta-ferric oxide
hydroxide,
preferably wherein the product mixture further comprises chloride.
D24. The process of any of embodiments D1 to D23, wherein the oil component
comprises
hydrocarbons boiling at temperatures less than and greater than 562 C, and
wherein the LIP
is enriched in hydrocarbons boiling at a temperature less than 562 C, as
determined by
atmospheric distillation in a 15-theoretical plate column at a reflux ratio of
5:1, according to
ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
D25. The process of any of embodiments D1 to D24, wherein the oil component is
crude
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oil, gas oil, resid, or a mixture thereof, preferably a heavy oil.
D26. The process of any of embodiments D1 to D25, further comprising the steps
of:
combining a feedstock oil with the LIP to form a pyrolyzate-feedstock blend;
and
thermally processing the blend at a temperature above about 100 C.
D27. The process of embodiment D26, wherein the thermal processing comprises
pyrolysis,
distillation, cracking, alkylation, visbreaking, coking, and combinations
thereof
D28. The process of embodiment D26 or D27, further comprising supplying at
least a
portion of the pyrolyzate-feedstock blend as the oil component to the FCIP
feed emulsion
preparation step wherein the thermal processing step consists of or comprises
the spraying of
the FCIP feed emulsion into the flash chemical ionizing pyrolysis reactor.
D29. A hydrocarbon conversion process, comprising the steps of:
reacting iron with a mixture of hydrochloric acid and nitric acid in the
presence of water
(preferably aqua regia) to form an iron source material;
mixing the iron source material, an alkali or alkaline earth metal chloride
source
material, and an aqueous phase with an oil component to form a feed emulsion
essentially free of added mineral support;
introducing the feed emulsion into a flash chemical ionizing pyrolysis (FCIP)
reactor
maintained at a temperature greater than about 400 C up to about 600 C and a
pressure from 10 to 50 psia for a residence time of from 0.1 to 10 seconds to
form a chemical ionizing pyrolyzate effluent; and
condensing a liquid ionizing pyrolyzate (LIP) from the effluent;
optionally blending the LIP with a feedstock oil and thermally processing the
blend.
D30. A hydrocarbon refinery process comprising the steps of:
preparing a feed emulsion comprising (i) 100 parts by weight of an oil
component, (ii)
from about 1 to 100 parts by weight of water, (iii) from about 0.01 to 5 parts
by weight of an iron source material, and (iv) from about 0.01 to 5 parts by
weight of an alkali or alkaline earth metal chloride source material, wherein
the
feed emulsion is free of added mineral solids other than the added iron source
material and sediment in the oil component;
spraying the ionized feed emulsion in a flash chemical ionizing pyrolysis
reactor at a
temperature from about 400 C to about 600 C;
collecting an effluent from the flash chemical ionizing pyrolysis reactor; and
recovering a liquid ionizing pyrolyzate (LIP) from the effluent.
D31. The method of embodiment D30, further comprising:
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combining the recovered LIP with a feedstock oil comprising crude oil or a
petroleum
fraction selected from gas oil, resid, or a combination thereof to form a
pyrolyzate-feedstock blend;
distilling, cracking, visbreaking, and/or coking a first portion of the blend;
and
optionally supplying a second portion of the blend as the oil component in the
ionized
feed emulsion preparation step.
D32. The process of embodiment D31, wherein the LIP exhibits a SARA analysis
having
higher saturates and aromatics contents and a lower asphaltenes content than
the feedstock
oil.
D33. The process of embodiment D31 or D32, wherein a proportion of the LIP in
the oil
component in the flash chemical ionizing pyrolysis is effective to improve
yield of liquid
hydrocarbons boiling at a temperature below 562 C, relative to separate flash
chemical
ionizing pyrolysis of the LIP and feedstock oil, as determined by atmospheric
distillation in a
15-theoretical plate column at a reflux ratio of 5:1, according to ASTM D2892-
18 up to
cutpoint 400 C AET, and by vacuum potstill method according to ASTM D5236-18a
above
the 400 C cutpoint to cutpoint 562 C AET.
D34. The process of any of embodiments D31 to D33, wherein a proportion of the
LIP in the
LIP blend in the distillation, cracking, visbreaking, and/or coking step, is
effective to improve
yield of liquid hydrocarbons boiling at a temperature below 562 C, relative to
separate
distillation, cracking, visbreaking, and/or coking of the LIP and feedstock
oil, as determined
by atmospheric distillation in a 15-theoretical plate column at a reflux ratio
of 5:1, according
to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
D35. The process of any of embodiments D1 to D34, wherein the feed emulsion
comprises
less than 1 part solids per 100 parts oil.
D36. The process of any of embodiments D1 to D35, wherein the FCIP comprises
contacting
the emulsion with superheated steam.
El. A hydrocarbon conversion process, comprising the steps of:
providing an unsupported iron source material;
providing an alkali or alkaline earth metal chloride source material;
providing an aqueous phase;
mixing the iron source material, the alkali or alkaline earth metal chloride
source
material, and the aqueous phase with an oil component to form a feed emulsion,
wherein the feed emulsion comprises less than 1 part by weight of added
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undissolved solids per 100 parts by weight of the oil component;
introducing the feed emulsion into a flash chemical ionizing pyrolysis (FCIP)
reactor
maintained at a temperature greater than about 400 C up to about 600 C and a
pressure from 10 to 50 psia to form a chemical ionizing pyrolyzate effluent;
and
condensing a liquid ionizing pyrolyzate (LIP) from the effluent.
E2. The process of embodiment El, wherein the iron source material
comprises an iron
oxide, an iron hydroxide, an iron oxide hydroxide, an iron chloride, or a
mixture thereof,
preferably hematite, magnetite, iron oxide hydroxide, or a mixture thereof
E3. The process of embodiment El, wherein the iron source material
comprises the reaction
product of iron with a mixture of hydrochloric acid and nitric acid in the
presence of water
(preferably aqua regia), preferably to form a mixture of hematite, magnetite,
and iron oxide
hydroxide.
E4. The process of any of embodiments El to E3, further comprising reacting
iron with a
mixture of hydrochloric acid and nitric acid in the presence of water
(preferably aqua regia) to
form the iron source material.
E5. The process of any of embodiments El to E4, wherein the iron source
material
comprises hematite, magnetite, iron oxide hydroxide, and chloride.
E6. The process of any of embodiments El to E5, wherein the iron source
material
comprises solid particulates, preferably particles having a major dimension
equal to or less than
4 microns.
E7. The process of any of embodiments El to E6, further comprising first
mixing the iron
source material, the alkali or alkaline earth metal chloride source material,
and the aqueous
phase with a first portion of the oil component to form a pre-mix emulsion,
and then mixing
the pre-mix emulsion with a second portion of the oil component.
E8. The process of embodiment E7, wherein the oil component is present in
the pre-mix
emulsion in an amount equal to or less than 20 parts by weight per 100 parts
by weight of the
aqueous phase.
E9. The process of any of embodiments El to E8, wherein the iron source
material is present
in the ionized feed emulsion in an amount of from 0.01 to 5 parts by weight,
per 100 parts by
weight of the oil component, preferably 0.05 to less than 1 part by weight.
E10. The process of any of embodiments El to E9, wherein the alkali or
alkaline earth metal
chloride source material comprises NaCl, KC1, LiC1, MgCl2, CaCl2, BaC12, or a
mixture
thereof
El 1. The process of any of embodiments El to El 0, wherein the alkali or
alkaline earth metal
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chloride source material is present in the ionized feed emulsion in an amount
of from 0.01 to 5
parts by weight, per 100 parts by weight of the primary oil component,
preferably 0.05 to 1
part by weight.
E12. The process of any of embodiments El to Ell, wherein the ionized feed
emulsion is
essentially free of added clay solids.
E13. The process of any of embodiments El to E12, wherein the ionized feed
emulsion
comprises less than 1 part by weight undissolved solids per 100 parts by
weight of the oil
component, more preferably less than 0.5 parts by weight undissolved solids
per 100 parts by
weight of the oil component.
E14. The process of claim any of embodiments El to E13, wherein the ionized
feed emulsion
is essentially free of added solids other than the iron source material and
any sediment from
the oil component.
E15. The process of any of embodiments El to E14, wherein the ionized feed
emulsion
comprises from 1 to 100 parts by weight water per 100 parts by weight of the
oil component,
preferably 5 to 50 parts by weight water, more preferably 5 to 20 parts by
weight water.
E16. The process of any of embodiments El to EIS, wherein the reactor
temperature is from
about 425 C to about 600 C, preferably 450 C to 500 C.
E17. The process of any of embodiments El to E16, wherein the reaction
pressure is equal
to or greater than 10 psia up to 30 psia, preferably equal to or less than 25
psia, more preferably
1-1.5 atm.
E18. The process of any of embodiments El to E17, comprising a residence time
in the flash
chemical ionizing pyrolysis reactor from 0.1 up to 10 seconds, preferably from
0.5 to 4 seconds.
E19. The process of any of embodiments El to E18, wherein the introduction
step comprises
spraying the ionized feed emulsion in the flash chemical ionizing pyrolysis
reactor, preferably
atomizing the ionized feed emulsion in the flash chemical ionizing pyrolysis
reactor.
E20. The process of any of embodiments El to E19, wherein the iron source
material and
the alkali or alkaline earth metal chloride source material comprise the
product of the method
comprising the steps of:
treating iron with an aqueous mixture of hydrochloric and nitric acids to form
a product
mixture of two or more of hematite, magnetite, ferric oxide hydroxide, and
chloride;
treating a support material, preferably montmorillonite, silica, alumina,
and/or zeolite, with
NaCl brine and drying the treated support material;
combining a slurry of the product mixture with the treated montmorillonite to
load the
product mixture on the support material; and
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heat treating the loaded support material, preferably at a temperature above
400 C.
E21. The process of any of embodiments El to E20, wherein the oil component
comprises
hydrocarbons boiling at temperatures less than and greater than 562 C, and
wherein the LIP
is enriched in hydrocarbons boiling at a temperature less than 562 C, as
determined by
.. atmospheric distillation in a 15-theoretical plate column at a reflux ratio
of 5:1, according to
ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
E22. The process of any of embodiments El to E21, wherein the oil component is
crude
oil, gas oil, resid, or a mixture thereof, preferably a heavy oil.
E23. The process of any of embodiments El to E22, further comprising the steps
of:
combining a feedstock oil with the LIP to form a pyrolyzate-feedstock blend;
and
thermally processing the blend at a temperature above about 100 C.
E24. The process of embodiment E23, wherein the thermal processing comprises
pyrolysis,
distillation, cracking, alkylation, visbreaking, coking, and combinations
thereof
E25. The process of embodiment E23 or E24, further comprising supplying at
least a
portion of the pyrolyzate-feedstock blend as the oil component to the FCIP
feed emulsion
preparation step wherein the thermal processing step consists of or comprises
the spraying of
the FCIP feed emulsion into the flash chemical ionizing pyrolysis reactor.
E26. A hydrocarbon conversion process, comprising the steps of:
reacting iron with a mixture of hydrochloric acid and nitric acid in the
presence of water
(preferably aqua regia) to form an unsupported iron source material;
mixing the unsupported iron source material, an alkali or alkaline earth metal
chloride
source material, and an aqueous phase with an oil component to form an ionized
feed emulsion, wherein the ionized feed emulsion comprises less than 1 part by
weight of added undissolved solids per 100 parts by weight of the oil
component;
introducing the ionized feed emulsion into a flash chemical ionizing pyrolysis
(FCIP)
reactor maintained at a temperature greater than about 400 C up to about 600 C
and a pressure from 10 to 50 psia for a residence time of from 0.1 to 10
seconds
to form a chemical ionizing pyrolyzate effluent;
condensing a liquid ionizing pyrolyzate (LIP) from the effluent; and
optionally blending the LIP with a feedstock oil and thermally processing the
blend.
E27. A hydrocarbon refinery process comprising the steps of:
preparing an ionized feed emulsion comprising (i) 100 parts by weight of an
oil
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component, (ii) from about 1 to 100 parts by weight of water, (iii) from about
0.01 to 5 parts by weight of an unsupported iron source material, and (iv)
from
about 0.01 to 5 parts by weight of an alkali or alkaline earth metal chloride
source material, wherein the ionized feed emulsion comprises less than 1 part
by weight of added undissolved solids per 100 parts by weight of the oil
component;
spraying the ionized feed emulsion in a flash chemical ionizing pyrolysis
reactor at a
temperature from about 400 C to about 600 C;
collecting an effluent from the flash chemical ionizing pyrolysis reactor; and
recovering a liquid ionizing pyrolyzate (LIP) from the effluent.
E28. The method of embodiment E27, further comprising:
combining the recovered LIP with a feedstock oil comprising crude oil or a
petroleum
fraction selected from gas oil, resid, or a combination thereof to form a
pyrolyzate-feedstock blend;
distilling, cracking, visbreaking, and/or coking a first portion of the blend;
and
optionally supplying a second portion of the blend as the oil component in the
ionized
feed emulsion preparation step.
E29. The process of embodiment E28, wherein the LIP exhibits a SARA analysis
having
higher saturates and aromatics contents and a lower asphaltenes content than
the feedstock
oil.
E30. The process of embodiment E28 or E29, wherein a proportion of the LIP in
the oil
component in the flash chemical ionizing pyrolysis is effective to improve
yield of liquid
hydrocarbons boiling at a temperature below 562 C, relative to separate flash
chemical
ionizing pyrolysis of the LIP and feedstock oil, as determined by atmospheric
distillation in a
15-theoretical plate column at a reflux ratio of 5:1, according to ASTM D2892-
18 up to
cutpoint 400 C AET, and by vacuum potstill method according to ASTM D5236-18a
above
the 400 C cutpoint to cutpoint 562 C AET.
E31. The process of any of embodiments E28 to E30, wherein a proportion of the
LIP in the
LIP blend in the distillation, cracking, visbreaking, and/or coking step, is
effective to improve
yield of liquid hydrocarbons boiling at a temperature below 562 C, relative to
separate
distillation, cracking, visbreaking, and/or coking of the LIP and feedstock
oil, as determined
by atmospheric distillation in a 15-theoretical plate column at a reflux ratio
of 5:1, according
to ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
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E32. The process of any of embodiments El to E31, wherein the FCIP comprises
contacting
the emulsion with superheated steam.
Fl. A hydrocarbon conversion process, comprising the steps of:
mixing an aqueous phase and catalyst particulates comprising iron and chloride
with an oil
component to form a feed emulsion;
introducing the feed emulsion into a pyrolysis reactor maintained at a
temperature greater than
about 400 C up to about 600 C and a pressure from about 1 to about 1.5 atm
absolute to form
a pyrolyzate effluent; and
condensing a liquid pyrolyzate (LP) from the effluent.
F2. The process of embodiment Fl, wherein the catalyst particulates
comprise an iron
oxide, an iron hydroxide, an iron oxide hydroxide, an iron chloride, or a
mixture thereof
F3. The process of embodiment Fl or embodiment F2, wherein the catalyst
particulates
comprise hematite, magnetite, iron oxide hydroxide, or a mixture thereof
F4. The process of embodiment F3 wherein the catalyst particulates comprise
a mixture of
hematite, magnetite, and iron oxide hydroxide.
F5. The process of embodiment F3, wherein the catalyst particulates
comprise beta-ferric
oxide hydroxide.
F6. The process of any of embodiments Fl ¨ F5, wherein the catalyst
particulates comprise
the reaction product of iron with a mixture of hydrochloric acid and nitric
acid in the presence
of water.
F7. The process of embodiment F6, wherein the mixture of hydrochloric acid
and nitric
acid comprises aqua regia.
F8. The process of embodiment F6, wherein the catalyst particulates
comprise a mixture of
hematite, magnetite, and iron oxide hydroxide.
F9. The process of any of embodiments Fl ¨ F8, further comprising reacting
iron with a
mixture of hydrochloric acid and nitric acid in the presence of water to form
the catalyst
particulates.
F10. The process of any of embodiments Fl ¨ F9, wherein the catalyst
particulates comprise
solid particulates having a major dimension equal to or less than 4 microns.
F11. The process of any of embodiments Fl ¨ F8, wherein the feed emulsion
further
comprises an alkali or alkaline earth metal chloride source material.
F12. The process of embodiment F11, further comprising first mixing the
catalyst
particulates, the alkali or alkaline earth metal chloride source material, and
the aqueous phase
with a first portion of the oil component to form a pre-mix emulsion, and then
mixing the pre-
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mix emulsion with a second portion of the oil component to form the feed
emulsion.
F13. The process of embodiment F12, wherein the oil component is present in
the pre-mix
emulsion in an amount equal to or less than 20 parts by weight per 100 parts
by weight of the
aqueous phase.
F14. The process of any of embodiments Fl ¨ F13, wherein the catalyst
particulates are
present in the feed emulsion in an amount of from 0.01 to 5 parts by weight,
per 100 parts by
weight of the oil component, preferably 0.05 to 1 part by weight.
F15. The process of any of embodiments Fll ¨ F14, wherein the alkali or
alkaline earth
metal chloride source material comprises NaCl, KC1, LiC1, MgCl2, CaCl2, BaC12,
or a mixture
thereof, preferably NaCl.
F16. The process of any of embodiments Fll ¨ F15, wherein the alkali or
alkaline earth
metal chloride source material is present in the feed emulsion in an amount of
from 0.01 to 5
parts by weight, per 100 parts by weight of the primary oil component,
preferably 0.05 to 1
part by weight.
F17. The process of any of embodiments Fl ¨ F16, wherein the catalyst
particles are
unsupported, wherein the feed emulsion is essentially free of added clay
solids.
F18. The process of any of embodiments Fl ¨ F17, wherein the feed emulsion
comprises
less than 1 part by weight undissolved solids per 100 parts by weight of the
oil component,
preferably less than 0.5 parts by weight undissolved solids per 100 parts by
weight of the oil
component.
F19. The process of any of embodiments Fl ¨ F18, wherein the feed emulsion is
essentially
free of added solids other than the catalyst particulates and any sediment
from the oil
component.
F20. The process of any of embodiments Fl ¨ F16, wherein the catalyst
particulates further
comprise clay.
F21. The process of any of embodiments Fl ¨ F20, wherein the feed emulsion
comprises
from 1 to 100 parts by weight water per 100 parts by weight of the oil
component, preferably
5 to 50 parts by weight water, more preferably 5 to 20 parts by weight water.
F22. The process of any of embodiments Fl ¨ F21, wherein the reactor
temperature is from
about 425 C to about 600 C, preferably 450 C to 500 C.
F23. The process of any of embodiments Fl ¨ F22, wherein the pyrolysis reactor
comprises
a flash chemical ionizing pyrolysis (FCIP) reactor comprising a residence time
from 0.1 up to
10 seconds, preferably from 0.5 to 4 seconds.
F24. The process of any of embodiments Fl ¨ F23, wherein the introduction step
comprises
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spraying the feed emulsion in the FCIP reactor.
F25. The process of any of embodiments Fl ¨ F24, wherein the catalyst
particulates
comprise the product of the method comprising the steps of:
treating iron with an aqueous mixture of hydrochloric and nitric acids to form
a product mixture
of hematite, magnetite, and beta-ferric oxide hydroxide, wherein the product
mixture further
comprises chloride;
treating a support material with a chloride brine and drying the treated
support material;
combining a slurry of the product mixture with the treated support material to
load the product
mixture on the support material; and
heat treating the loaded support material.
F26. The process of any of embodiments Fl ¨ F25, wherein the oil component
comprises
hydrocarbons boiling at temperatures less than and greater than 562 C, and
wherein the LP is
enriched in hydrocarbons boiling at a temperature less than 562 C, as
determined by
atmospheric distillation in a 15-theoretical plate column at a reflux ratio of
5:1, according to
ASTM D2892-18 up to cutpoint 400 C AET, and by vacuum potstill method
according to
ASTM D5236-18a above the 400 C cutpoint to cutpoint 562 C AET.
F27. The process of any of embodiments Fl ¨ F26, wherein the oil component
comprises a
heavy oil comprising crude oil, gas oil, resid, or a mixture thereof
F28. The process of any of embodiments Fl ¨ F27, further comprising the steps
of:
combining a feedstock oil with the LP to form a pyrolyzate-feedstock blend;
and
thermally processing the blend at a temperature above about 100 C.
F29. The process of embodiment F28, wherein the thermal processing comprises
pyrolysis,
distillation, cracking, alkylation, visbreaking, coking, or a combination
thereof
F30. The process of embodiment F28 or embodiment F29, further comprising
supplying at
least a portion of the pyrolyzate-feedstock blend as the oil component to the
feed emulsion
preparation step wherein the thermal processing step consists of or comprises
the spraying of
the feed emulsion into the pyrolysis reactor.
F31. The process of any of embodiments Fl to F30, wherein the FCIP comprises
contacting
the emulsion with superheated steam.
Gl. Any preceding embodiment wherein the iron source material comprises
hematite.
G2. Any preceding embodiment wherein the iron source material comprises
magnetite.
G3. Any preceding embodiment wherein the iron source material comprises
beta ferric
oxide hydroxide.
G4. Any preceding embodiment wherein the iron source material comprises
chloride.
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G5. Any preceding embodiment wherein the iron source material comprises
hematite and
magnetite.
G6. Any preceding embodiment wherein the iron source material comprises
hematite and
beta ferric oxide hydroxide.
G7. Any preceding embodiment wherein the iron source material comprises
hematite and
chloride.
G8. Any preceding embodiment wherein the iron source material comprises
magnetite and
beta ferric oxide hydroxide.
G9. Any preceding embodiment wherein the iron source material comprises
magnetite and
chloride.
G10. Any preceding embodiment wherein the iron source material comprises beta
ferric
oxide hydroxide and chloride.
G11. Any preceding embodiment wherein the iron source material comprises
hematite,
magnetite and beta ferric oxide hydroxide.
G12. Any preceding embodiment wherein the iron source material comprises
hematite,
magnetite and chloride.
G13. Any preceding embodiment wherein the iron source material comprises
hematite,
magnetite, beta ferric oxide hydroxide, and chloride.
EXAMPLES
[0163] Example 1A: Preparation of iron solids: Preferred finely divided solids
according to
the present invention were prepared by mixing with constant stirring 1 part by
weight 100 mesh
hydrogen reduced iron shavings with 1 part by weight aqua regia (1 part by
weight nitric acid,
3 parts by weight hydrochloric acid, 2 parts by weight water). The aqua regia
was added in
three aliquots (1 part each, i.e., 1/3, 1/3, 1/3), and the temperature
increased to 95 C. The
material dried considerably, leaving wet solids. The oxidized iron solids were
dried in an oven
at 130 C, and ground to pass a 100 mesh screen. The oxidized iron solids had a
reddish black
or dark violet color.
[0164] The oxidized iron solids were analyzed by wet chemistry by sequential
digestion in hot
water, followed by digestion of the water-insoluble solids in 20 wt% HC1(aq),
and recovery of
the insoluble material which was not further analyzed. Initially, a 5 g sample
of the oxidized
iron solids was placed in 150 ml of 100 C water, and the water-insoluble
solids remaining were
recovered and weighed. The amount digested in the water was surprisingly only
1.4488 g, or
28.98 wt%. The filtrate was diluted to 1 L and the solute was found by
spectrophotometry to
contain 11.32 wt% total Fe consisting of 3.24 wt% Fe(II) and 8.08 wt% Fe(III),
32.79 wt%
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chloride, 3.52 wt% nitrite, and 1.17 wt% nitrate. The water-soluble fraction
was thus
determined to be mostly chloride and nitrite salts with some nitrate salts.
[0165] The water-insoluble fraction was then digested in 150 ml of 20% HC1 in
water, and
3.478 g went into solution, or 69.56 wt% of the initial oxidized iron sample.
The acid soluble
fraction was found to contain 62.23 wt% total Fe consisting of 7.04 wt% Fe(II)
and 55.19
Fe(III), 51.18 wt% nitrate, and 0.2587 wt% nitrite. The acid soluble fraction
was thus found to
contain mostly ferric oxides and/or nitrates, with some ferrous iron and a
small amount of
nitrite. From a relatively small proportion of ferrous iron seen in the acid
soluble fraction, it
was inferred that little or no elemental iron was present. The acid insoluble
fraction was just
1.46 wt% of the original sample, and appeared from its red color to be Fe(III)
oxide, hematite.
The wet chemistry data are summarized in Table 1.
TABLE 1. WET CHEMISTRY ANALYSIS OF IRON OXIDIZED BY AQUA REGIA
Total
Nitrate Nitrite
Iron, Fe(II), Fe(III), Chloride, (NO3-), (NO2),
Sample Mass, g wt% wt% wt% wt%
Original Sample 5
Water Solubles 1.449 11.32 3.24 8.08 32.79
1.17 3.52
Acid Solubles 3.478 62.23 7.04 55.19 nd
51.18 0.2587
Acid Insolubles 0.073 nd nd nd nd nd
nd
nd = not determined
[0166] Example 1B: Preparation of iron solids with 2X aqua regia: The finely
divided solids
were prepared as in Example 1A except 1 part by weight 100 mesh hydrogen
reduced iron
shavings was mixed with 2 parts by weight aqua regia comprising 1 parts by
weight nitric acid,
3 parts by weight hydrochloric acid, and 2 parts by weight water. Following
the reaction
between 25 kg of the iron and 50 kg of the aqua regia, the reaction mass
weighed 58.5 kg. After
drying at 130 C, the acidified iron product weighed 36 kg and had a reddish
black color. XRD
analysis showed the presence of hematite, magnetite, and beta-ferric oxide
hydroxide. SEM
analysis showed 65.5 wt% Fe; 23.0 wt% 0; 8.08 wt% Cl; 1.97 wt% Cu; and less
than 1 wt%
of Cr, Si, Al, and Sr. The acidified iron product or one similar to it was
used in the following
examples 2A-3B.
[0167] Example 2A: Flash Chemical Ionizing Pyrolysis Tests on Texistepec Crude
Oil-LIP
Blend in a Lab Reactor with High-Chloride Iron Additive: These flash chemical
ionizing
pyrolysis (FCIP) tests used an externally heated lab scale reactor equipped
with a condenser
and a bag for non-condensable gases. The feed emulsion was pulsed into the
reactor using a
spray nozzle at a rate to keep the reactor within a range of about +/- 10 C
of the average, 460
C.
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[0168] Texistepec crude oil was pretreated by heating to a temperature of 150
C for 1 h to
remove water and sediment that settled out. The pretreated crude oil (s.g.
1.221 g/cm3, viscosity
5,676,000 cP at 50 C, Flash point 200 C, boiling point 280 C, Conradson
carbon 18.2%)
was blended at 70 C with an LIP obtained from previous FCIP at a weight ratio
of crude:LIP
of 90:10 to obtain a blend having s.g. of 1.1 g/cm3, viscosity 57,900 cP at 50
C, and Conradson
carbon 14.4%. The blend contained 9.96 wt% soluble inorganics.
[0169] The feed emulsion was prepared by first mixing the high-chloride iron
additive of
Example 1B (168 g per 100 kg oil) with 1 M NaCl (876 g NaCl per 100 kg oil)
and water (total
water 15 kg/100 kg oil) using a high speed blender at ambient temperature, and
then mixing
the water-NaCl-Fe additive mixture with the oil blend at 70 C. The
resulting feed emulsion
had density of 1.1 g/cm3 and viscosity at 50 C of 34,980 cP. The feed
emulsion had the
composition shown in Table 2:
TABLE 2. FCIP FEED EMULSION, EXAMPLE 2A
Component Wt%
Hydrocarbons 78.60
Soluble inorganics 8.80
Total crude oil 87.40
Water 11.77
Fe compound (Example 2B) 0.143
NaCl 0.689
Total additives 12.60
Total 100.00
[0170] FCIP of the feed emulsion yielded two immiscible oil layers, a light
oil layer (67.5 wt%,
hydrocarbons basis) and a heavy oil layer (17.5 wt%, hydrocarbons basis), non-
condensable
gas (12.8 wt%, hydrocarbons basis), and coke (2.2 wt%, hydrocarbons basis).
These surprising
results indicate that 97.8 wt% of the Texistepec crude can be recovered as
high quality oil and
light hydrocarbons. Also recovered were 82.6 wt% of the water (feed basis) and
69.5 wt% of
the inorganic solids (total feed basis). The product mix is listed in Table 3:
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TABLE 3. FCIP PRODUCT MIX, EXAMPLE 2A
Component Wt%
LIP #1, light oil phase yield' 67.5
LIP #2, heavier oil phase yield' 17.5
Total oil yield' 85.0
Gas yield' 12.8
Coke yield' 2.2
Total hydrocarbon yield' 100.0
Water yield2 82.6
Solid inorganics yield3 69.5
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based on water
in feed emulsion; 3 ¨ based on total feed soluble inorganics, NaCl, and
Fe compound
[0171] The recovered oils were markedly improved with lower density, lower
viscosities,
lower flash points, lower boiling points, and lower pour points. A comparison
of properties
with the pretreated Texistepec crude oil and the LIP blend is listed in Table
4:
TABLE 4. OIL PROPERTIES, EXAMPLE 2A
Property Units TXPC
TXPC/LIP LIP-1 LIP-2
Blend
(90/10)
Density API <0 <0 28 21
Density g/cm3 1.221 1.1 0.89 0.93
Viscosity @ 50 C cP 5.68x106 57.9x103 5.6 34.7
Viscosity A 50 C mm2/s 12.8 6.6 41.1
Viscosity @ 50 C SUS 2.2 30.3 189.4
Flash point C 200 29 64
Boiling point C 280 75 102
Pour point C >30 -55 -35
Conradson carbon wt% 18.2 14.4 2.7 4.5
[0172] It is seen from Tables 3 and 4 that the LIP-1 and LIP-2 are recovered
from the FPIC of
the Texistepec crude oil in surprisingly high yield. Moreover, LIP-1 and LIP-2
have
unexpectedly improved properties indicative of astonishingly high quality as
reflected in low
densities, low viscosities, low flash points, low boiling points, low pour
points and low
Conradson carbon contents. The low conversion to coke in the FCIP and the low
Conradson
carbon contents in the LIP products indicate that thermal processing, e.g.,
distillation, will
result in very little coke make.
[0173] Example 2B: Flash Chemical Ionizing Pyrolysis Tests on Texistepec Crude
Oil-LIP
Blend in a Lab Reactor with Supported Iron Additive: These flash chemical
ionizing pyrolysis
(FCIP) tests used an externally heated lab scale reactor equipped with a
condenser and a bag
for non-condensable gases as in Example 2A. The feed emulsion was pulsed into
the reactor
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using a spray nozzle at a rate to keep the reactor within a range of about +/-
10 C of the
average, 470 C, similar to Example 2A.
[0174] As in Example 2A, Texistepec crude oil was pretreated by heating to a
temperature of
150 C for 1 h to remove water and sediment that settled out. The pretreated
crude oil (s.g. 1.221
g/cm3, viscosity 5,676,000 cP at 50 C, Flash point 200 C, boiling point 280
C, Conradson
carbon 18.2%) was blended at 70 C with an LIP obtained from previous FCIP, at
a weight
ratio of crude:LIP of 90:10 to obtain a blend having s.g. of 1.1 g/cm3,
viscosity 57,900 cP at 50
C, and Conradson carbon 14.4%. The blend contained 10.1 wt% soluble
inorganics.
[0175] The feed emulsion was prepared by first mixing the supported iron
additive of Example
1C (5 kg per 100 kg oil, 5.4 wt% acidified iron, 4.5 wt% NaCl) with the oil
blend at 70 C
using a high speed blender, and then adding the water (15 kg per 100 kg oil).
The resulting feed
emulsion had density of 1.1 g/cm3 and viscosity at 50 C of 32,000 cP. The
feed emulsion had
the composition shown in Table 5:
TABLE 5. FCIP FEED EMULSION, EXAMPLE 2B
Component Wt%
Hydrocarbons 76.52
Soluble inorganics 8.58
Total crude oil 85.1
Water 11.50
Fe compound (Example 1C) 3.4
Total additives 14.9
Total 100.00
[0176] FCIP of the feed emulsion yielded two immiscible oil layers, a light
oil layer (61.9 wt%,
hydrocarbons feed basis) and a heavy oil layer (27.7 wt%, hydrocarbons feed
basis), non-
condensable gas (5.1 wt%, hydrocarbons basis), and coke (5.3 wt%, hydrocarbons
basis).
These results indicate that 94.7 wt% of the Texistepec crude can be recovered
as high quality
oil and light hydrocarbons. Also recovered were 93 wt% of the water (feed
basis) and 100.2
wt% of the inorganic solids (total feed basis). Compared to Example 2A,
Example 2B using
the supported catalyst produced less LIP-3 and more coke. The product mix is
listed in Table
6:
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TABLE 6. FCIP PRODUCT MIX, EXAMPLE 2B
Component Wt%
LIP-3, light oil phase yield' 61.9
LIP-4, heavier oil phase yield' 27.7
Total oil yield' 89.6
Gas yield' 5.1
Coke yield' 5.3
Total hydrocarbon yield' 100.0
Water yield2 93.0
Solid inorganics yield3 100.2
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based on water
in feed emulsion; 3 ¨ based on total feed soluble inorganics, NaCl, and
Fe compound
[0177] It is thus seen that the coke make is greater and the LIP-3 yield is
lower when the
bentonite was present. Moreover, the solid inorganics yield included spent
bentonite, which
would require solids removal equipment.
[0178] The recovered oils were markedly improved with lower density, lower
viscosities,
lower flash points, lower boiling points, and lower pour points. However, the
values for the
LIP-3 were not as good compared to the LIP-1 obtained from Example 2A which
was run
bentonite-free. A comparison of properties with the pretreated Texistepec
crude oil and the LIP
blend is listed in Table 7:
TABLE 7. OIL PROPERTIES, EXAMPLE 2B
Property Units TXPC TXPC/LIP Emulsion LIP-3 LIP-4
Blend to FCIP
(90/10)
Density API <0 <0 <0 24 21
Density g/cm3 1.221 1.1 1.1 0.91
0.93
Viscosity @ 50 C cP 5.68x106 57.9x103 32x103 13
21
Viscosity @50 C mm2/s 12.8 16 23
Viscosity @ 50 C SUS 2.2 74 106
Flash point C 200 80 85
Boiling point C 280 56 90
Pour point C >30 -40 -35
Conradson carbon wt% 18.2 14.4 1.8 2.2
[0179] It is seen from Tables 6 and 7 that the LIP-3 and LIP-4 are recovered
from the FCIP of
the Texistepec crude oil in surprisingly high yield using the bentonite-loaded
iron compound
and NaCl. Moreover, LIP-3 and LIP-4 have unexpectedly improved properties
indicative of
high quality as reflected in low densities, low viscosities, low flash points,
low boiling points,
low pour points and low Conradson carbon contents. The low conversion to coke
in the FCIP
and the low Conradson carbon contents in the LIP products indicate that
thermal processing,
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e.g., distillation, will result in very little coke make. It is further seen
from a comparison of the
properties that the LIP-1 of Example 2A prepared without bentonite has a
higher proportion of
lower molecular weight hydrocarbons than the LIP-3 prepared using bentonite,
indicating a
higher degree of conversion, as reflected in the lower pour point of LIP-1. It
is further seen that
the LIP-4 prepared with bentonite has a higher proportion of light fractions
and higher quality
compared to LIP-3 if the goal is to produce gasoline ranges of hydrocarbons.
[0180] Example 3A: Flash Chemical Ionizing Pyrolysis on Maya Crude Oil in a
Lab Reactor
with High-Chloride Iron Additive: These flash chemical ionizing pyrolysis
(FCIP) tests used
the same lab scale reactor as Example 2A. The feed emulsion was pulsed into
the reactor using
a spray nozzle at a rate to keep the reactor within a range of about +/- 10 C
of the average,
500 C.
[0181] A 22 API Maya crude oil was used having s.g. 0.92 g/cm3, viscosity 450
cP at 50 C,
flash point 133 C, boiling point 155 C, Conradson carbon 12%, and 1 wt%
inorganic solids
content. The feed emulsion was prepared by first mixing the high-chloride iron
additive of
Example 1B (168 g per 100 kg crude) with 0.25 M NaCl (219 g NaCl per 100 kg
crude) and
water (total water 15 kg/100 kg crude) using a high speed blender at ambient
temperature, and
then mixing the water-NaCl-Fe additive mixture with the crude oil. The feed
emulsion had the
composition shown in Table 8:
TABLE 8. FCIP FEED EMULSION, EXAMPLE 3A
Component Wt%
Hydrocarbons 85.81
Soluble inorganics 0.87
Total crude oil 86.68
Water 13.00
Fe compound (Example 2B) 0.144
NaCl 0.173
Total additives 13.32
Total 100.00
[0182] FCIP of the feed emulsion yielded LIP (89.9 wt%, hydrocarbons basis),
non-
condensable gas (9.4 wt%, hydrocarbons basis), and coke (0.7 wt%, hydrocarbons
basis).
These surprising results indicate that 99.3 wt% of the Maya crude can be
recovered as high
quality oil and light hydrocarbons. Also recovered were 81.8 wt% of the water
(feed basis) and
97.0 wt% of the inorganic solids (total feed basis). The product mix is listed
in Table 9:
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TABLE 9. FCIP PRODUCT MIX, EXAMPLE 3A
Component Wt%
LIP-5 yield' 89.9
Gas yield' 9.4
Coke yield' 0.7
Total hydrocarbon yield' 100.0
Water yield2 81.8
Solid inorganics yield3 97.0
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based
on water in feed emulsion; 3 ¨ based on total feed soluble
inorganics, NaCl, and Fe compound
[0183] The recovered oil LIP-5 was markedly improved with lower density, lower
viscosity,
lower flash point, lower boiling point, and lower pour point. A comparison of
properties with
the Maya crude oil and the feed emulsion is listed in Table 10:
TABLE 10. OIL PROPERTIES, EXAMPLE 3A
Property Units Maya Feed LIP-5
Crude Emulsion
Density API 22 34
Density g/cm3 0.92 0.86
Viscosity @ 50 C cP 450 7.5
Viscosity co, 50 C mm2/s
Viscosity @ 50 C SUS
Flash point C 133 58
Boiling point C 155 70
Pour point C -57
Conradson carbon wt% 12 1.5
[0184] It is seen from Tables 9 and 10 that the LIP-5 was recovered from the
FPIC of the Maya
crude oil in surprisingly high yield. Moreover, the LIP-5 had unexpectedly
improved properties
indicative of astonishingly high quality as reflected in low density, low
viscosity, low flash
point, low boiling point, low pour point and low Conradson carbon content. The
low conversion
to coke in the FCIP and the low Conradson carbon content in the LIP-5 product
indicate that
thermal processing, e.g., FCIP and distillation, will result in very little
coke make.
[0185] Example 3B: Flash Chemical Ionizing Pyrolysis on Maya Crude Oil in a
Lab Reactor
with Supported Iron Additive: These flash chemical ionizing pyrolysis (FCIP)
tests used the
same lab scale reactor and Maya crude oil as Example 3A. The feed emulsion was
pulsed into
the reactor using a spray nozzle at a rate to keep the reactor within a range
of about +/- 10 C
of the average, 510 C.
[0186] The feed emulsion was prepared by first mixing the supported iron
additive of Example
1C (5 kg per 100 kg oil, 5.4 wt% acidified iron, 4.5 wt% NaCl) with the oil
blend at 70 C
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using a high speed blender, and then adding the water (15 kg per 100 kg oil).
The resulting feed
emulsion had density of 0.96 g/cm3 and viscosity at 50 C of 270 cP. The feed
emulsion had
the composition shown in Table 11:
TABLE 11. FCIP FEED EMULSION, EXAMPLE 3B
Component Wt%
Hydrocarbons 82.54
Soluble inorganics 0.83
Total crude oil 83.37
Water 12.50
Additive particulates (Example 1C)* 4.13
Total additives 16.63
Total 100.00
* - Supplying 270 g iron compound and 225 g NaCl per 100 kg crude oil
[0187] FCIP of the feed emulsion yielded LIP-6 (93.0 wt%, hydrocarbons basis),
non-
condensable gas (5.0 wt%, hydrocarbons basis), and coke (2.0 wt%, hydrocarbons
basis).
These surprising results indicate that 98 wt% of the Maya crude can be
recovered as high
quality oil and light hydrocarbons. Also recovered were 84.2 wt% of the water
(feed basis) and
99.7 wt% of the inorganic solids (total feed basis). The product mix is listed
in Table 12:
TABLE 12. FCIP PRODUCT MIX, EXAMPLE 3B
Component Wt%
LIP-6 yield' 93.0
Gas yield' 5.0
Coke yield' 2.0
Total hydrocarbon yield' 100.0
Water yield2 84.2
Solid inorganics yield3 99.7
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based
on water in feed emulsion; 3 ¨ based on total feed soluble
inorganics, NaCl, and Fe compound
[0188] The recovered oil LIP-6 was markedly improved with lower density, lower
viscosity,
lower flash point, lower boiling point, and lower pour point. A comparison of
properties with
the Maya crude oil is listed in Table 13:
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TABLE 13. OIL PROPERTIES, EXAMPLE 3B
Property Units Maya Feed LIP-6
Crude Emulsion
Density API 22 28
Density g/cm3 0.92 0.96 0.89
Viscosity A 50 C cP 450 270 4.7
Viscosity @ 50 C mm2/s 7.6
Viscosity @ 50 C SUS 35
Flash point C 133 54
Boiling point C 155 68
Pour point C -35
Conradson carbon wt% 12 2
[0189] It is seen from Tables 12 and 13 that the LIP-6 was recovered from FPIC
of the Maya
crude oil in surprisingly high yield. Moreover, the LIP-6 had unexpectedly
improved properties
indicative of high quality as reflected in low density, low viscosity, low
flash point, low boiling
point, low pour point and low Conradson carbon content. The low conversion to
coke in the
FCIP and the low Conradson carbon content in the LIP-6 product indicate that
thermal
processing, e.g., FCIP and distillation, will result in very little coke make.
[0190] It is further seen that the LIP-5 of Example 3A prepared without
bentonite is even better
than the LIP-6 of Example 3B prepared with bentonite in that the LIP-5 has a
lower density
and comparable Conradson carbon content. There appear to be no untoward
effects from
eliminating the bentonite but using the same or similar amounts of the iron
compound and
NaCl.
[0191] Example 4A: Flash Chemical Ionizing Pyrolysis on Texistepec Crude Oil
in a Lab
Reactor with Mixed Iron Additive: This flash chemical ionizing pyrolysis
(FCIP) test used
commercially obtained iron compounds hematite (Fe2O3, industrial grade),
magnetite (Fe304,
industrial grade), and prepared (3-Fe0OH, and Fe0C1.
[0192] (3-Fe0OH was prepared by adding 100 mL of a 5.4 M NaOH solution (20.147
g
NaOH/100 mL of distilled water) dropwise over an equal volume of a solution of
FeC13.6H20
(53.8 g in 100 mL of distilled water) at a temperature of 40 C 2 C and
with constant
agitation. The mixture was then placed in an oven at 100 C for 6 hours. After
this time the
reaction was stopped by rapid cooling in cold water. The product (15.45 g) was
collected by
filtration, washed with distilled water, dried at room temperature and crushed
to obtain a fine
powder.
[0193] Fe0C1 was prepared in a 500 mL ball flask to which was added 7.00 g of
Fe2O3 and
8.20 g of FeCl3 = 6H20. The flask was purged with argon and heated to 370 C
for 30 minutes
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to carry out the reaction. After cooling, the product (11.16 g) was crushed to
obtain a fine
powder.
[0194] The iron compounds were screened to remove +100 mesh particles, using
only the fines
that passed through the sieve. The iron compound used in this example was a
mixture of equal
parts by weight of Fe2O3, Fe304, (3-Fe0OH, and Fe0C1.
[0195] Texistepec crude oil was pretreated by heating to a temperature of 150
C for 1 h to
remove water and sediment that settled out. The pretreated crude oil had s.g.
1.2 g/cm3,
viscosity 833,800 cP at 50 C, Flash point 228 C, boiling point 314 C,
Conradson carbon
15%. The feed emulsion was prepared by first mixing the blended iron additive
(240 g per 100
kg oil) with 1 M NaCl (220 g NaCl per 100 kg oil) and water (total water 15
kg/100 kg oil)
using a high speed blender at ambient temperature, and then mixing the water-
NaCl-Fe additive
mixture with the pretreated Texistepec crude at 70 C. The resulting feed
emulsion had density
of 1.2 g/cm3 and viscosity at 50 C of 199,400 cP. The flash chemical ionizing
pyrolysis (FCIP)
used the same lab scale reactor as Example 2A. The feed emulsion was pulsed
into the reactor
using a spray nozzle at a rate to keep the reactor within a range of about +/-
5 C of the average,
530 C.
[0196] FCIP of the feed emulsion yielded liquid oil (85.8 wt%, hydrocarbons
basis), non-
condensable gas (1.6 wt%, hydrocarbons basis), and coke (12.7 wt%,
hydrocarbons basis).
These surprising results indicate that 97.8 wt% of the Texistepec crude can be
recovered as
high quality oil and light hydrocarbons. Also recovered were 75.2 wt% of the
water (feed basis)
and 95.6 wt% of the inorganic solids (total feed basis). The product mix is
listed in Table 14:
TABLE 14. FCIP PRODUCT MIX, EXAMPLE 4A
Component Wt%
LIP #7, light oil phase yield' 85.8
Gas yield' 1.6
Coke yield' 12.7
Total hydrocarbon yield' 100.0
Water yield2 75.2
Solid inorganics yield3 95.6
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based on water
in feed emulsion; 3 ¨ based on total feed soluble inorganics, NaCl, and
Fe additive
[0197] The recovered oil (LIP-7) was markedly improved with lower density,
lower viscosity,
lower flash point, lower boiling point, and lower pour point. A comparison of
properties with
the pretreated Texistepec crude oil and the LIP blend is listed in Table 15:
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TABLE 15. OIL PROPERTIES, EXAMPLE 4A
Property Units TXPC LIP-7
Density API 25
Density g/cm3 1.221 0.91
Viscosity A 50 C cP 8.34x105 15.58
Viscosity @ 50 C mm2/s 12.8 14.77
Viscosity A 50 C SUS 2.2 68.04
Flash point C 228 80
Boiling point C 314 115
Pour point C >30 -28
Conradson carbon wt% 15 4.61
[0198] It is seen from Tables 14 and 15 that the LIP-7 was recovered from the
FCIP of the
Texistepec crude oil in surprisingly high yield. Moreover, LIP-7 has
unexpectedly improved
properties indicative of astonishingly high quality as reflected in low
density, low viscosity,
low flash point, low boiling point, low pour point and low Conradson carbon
content. These
would be further improved by using the Texistepec in a blend with the LIP-7 in
the feed
emulsion.
[0199] Example 4B: Flash Chemical Ionizing Pyrolysis on Texistepec Crude Oil
in a Lab
Reactor with Mixed Iron Additives (sans Fe30 4): This flash chemical ionizing
pyrolysis (FCIP)
test used commercially obtained hematite (3 parts by weight), and prepared (3-
Fe0OH (3 parts
by weight), and Fe0C1 (2 parts by weight) as in Example 4A. The feed emulsion
was prepared
by first mixing the blended iron additive (240 g per 100 kg oil) with 1 M NaCl
(220 g NaCl
per 100 kg oil) and water (total water 15 kg/100 kg oil) using a high speed
blender at ambient
temperature, and then mixing the water-NaCl-Fe additive mixture with the
pretreated
Texistepec crude at 70 C. The resulting feed emulsion had density of 1.16
g/cm3 and viscosity
at 50 C of 137,300 cP. The flash chemical ionizing pyrolysis (FCIP) used the
same lab scale
reactor as Examples 2A/4A. The feed emulsion was pulsed into the reactor using
a spray nozzle
at a rate to keep the reactor within a range of about +/- 5 C of the average,
514 C.
[0200] FCIP of the feed emulsion yielded liquid oil (81 wt%, hydrocarbons
basis), non-
condensable gas (1 wt%, hydrocarbons basis), and coke (18 wt%, hydrocarbons
basis). These
surprising results indicate that 82 wt% of the Texistepec crude can be
recovered as high quality
oil and light hydrocarbons. Also recovered were 70.7 wt% of the water (feed
basis) and 99.9
wt% of the inorganic solids (total feed basis). The product mix is listed in
Table 16:
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TABLE 16. FCIP PRODUCT MIX, EXAMPLE 4B
Component Wt%
LIP #8, oil yield' 81
Gas yield' 1
Coke yield' 18
Total hydrocarbon yield' 100.0
Water yield2 70.7
Solid inorganics yield3 99.9
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based on water
in feed emulsion; 3 ¨ based on total feed soluble inorganics, NaCl, and
Fe additive
[0201] The recovered oil (LIP-8) was markedly improved with lower density,
lower viscosity,
lower flash point, lower boiling point, and lower pour point. A comparison of
properties with
the pretreated Texistepec crude oil is listed in Table 17:
TABLE 17. OIL PROPERTIES, EXAMPLE 4B
Property Units TXPC LIP-8
Density API 30
Density g/cm3 1.221 0.878
Viscosity A 50 C cP 8.34x105 10.19
Viscosity @ 50 C mm2/s 12.8 11.03
Viscosity @ 50 C SUS 2.2 50.79
Flash point C 228 76
Boiling point C 314 120
Pour point C >30 -41
Conradson carbon wt% 15 1.3
[0202] It is seen from Tables 16 and 17 that the LIP-8 was recovered from the
FCIP of the
Texistepec crude oil in surprisingly high yield. Moreover, LIP-8 has
unexpectedly improved
properties indicative of high quality as reflected in low density, low
viscosity, low flash point,
low boiling point, low pour point and low Conradson carbon content. These
would be further
improved by using the Texistepec in a blend with the LIP in the feed emulsion.
[0203] Example 4C: Flash Chemical Ionizing Pyrolysis on Texistepec Crude Oil
in a Lab
Reactor with Mixed Iron Additives (sans Fe 20 3): This flash chemical ionizing
pyrolysis (FCIP)
test used commercially obtained magnetite (3 parts by weight), and prepared (3-
Fe0OH (3 parts
by weight), and Fe0C1 (2 parts by weight) as in Example 4A. The feed emulsion
was prepared
by first mixing the blended iron additive (240 g per 100 kg oil) with 1 M NaCl
(220 g NaCl
per 100 kg oil) and water (total water 15 kg/100 kg oil) using a high speed
blender at ambient
temperature, and then mixing the water-NaCl-Fe additive mixture with the
pretreated
Texistepec crude at 70 C. The resulting feed emulsion had density of 1.14
g/cm3 and viscosity
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at 50 C of 137,300 cP. The flash chemical ionizing pyrolysis (FCIP) used the
same lab scale
reactor as Examples 2A/4A. The feed emulsion was pulsed into the reactor using
a spray nozzle
at a rate to keep the reactor within a range of about +/- 5 C of the average,
517 C.
[0204] FCIP of the feed emulsion yielded liquid oil (81 wt%, hydrocarbons
basis), non-
condensable gas (1 wt%, hydrocarbons basis), and coke (18 wt%, hydrocarbons
basis). These
surprising results indicate that 82 wt% of the Texistepec crude can be
recovered as high quality
oil and light hydrocarbons. Also recovered were 70.7 wt% of the water (feed
basis) and 99.9
wt% of the inorganic solids (total feed basis). The product mix is listed in
Table 18:
TABLE 18. FCIP PRODUCT MIX, EXAMPLE 4B
Component Wt%
LIP #9, oil yield' 81
Gas yield' 1
Coke yield' 18
Total hydrocarbon yield' 100.0
Water yield2 70.7
Solid inorganics yield' 99.9
Notes: 1 ¨ based on hydrocarbons in feed emulsion; 2 ¨ based on water
in feed emulsion; 3 ¨ based on total feed soluble inorganics, NaCl, and
Fe additive
[0205] The recovered oil (LIP-8) was markedly improved with lower density,
lower viscosity,
lower flash point, lower boiling point, and lower pour point. A comparison of
properties with
the pretreated Texistepec crude oil is listed in Table 19:
TABLE 19. OIL PROPERTIES, EXAMPLE 4C
Property Units TXPC LIP-8
Density API 27
Density g/cm3 1.221 0.893
Viscosity @ 50 C cP 8.34x105 8.15
Viscosity (0, 50 C mm2/s 12.8 12.44
Viscosity @ 50 C SUS 2.2 57.31
Flash point C 228 70
Boiling point C 314 140
Pour point C >30 -40
Conradson carbon wt% 15 1.5
[0206] It is seen from Tables 18 and 19 that the LIP-9 was recovered from the
FCIP of the
Texistepec crude oil in surprisingly high yield. Moreover, LIP-9 has
unexpectedly improved
properties indicative of high quality as reflected in low density, low
viscosity, low flash point,
low boiling point, low pour point and low Conradson carbon content. These
would be further
improved by using the Texistepec in a blend with the LIP in the feed emulsion.
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CA 03179191 2022-10-01
WO 2021/183155 PCT/US2020/026950
[0207] The invention has been described above with reference to numerous
embodiments and
specific examples. Many variations will suggest themselves to those skilled in
this art in light
of the above detailed description. All such obvious variations are within the
full intended scope
of the appended claims.
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