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`UNITED STATES DEPARTMENT OF COMMERCE
`United States Patent and Trademark Office
`
`December 05, 2013
`
`//
`
`é
`
`
`
`
`
`COOPERATION TREATY.
`
`APPLICATION NUMBER: PCT/US13/36674
`FILING DATE: April 15, 2013
`
`
`
`
`
`
`
`Certifying Officer
`
`By Authority of the
`Under Secretary of Commerce for Intellectual Property
`and Director of the United States Patent and Trademark Office
`
`V
`
`‘
`
`"
`
`J
`
`
`
`P. R. GRANT
`
`
`
`

`

`
`
`_-P
`
`CT/U513/36674
`
`
`
`Application Number:
`
`Confirmation Number:
`
`
`
`
`International Application Number:
`
`
`
` First Named lnventor/Applica nt Name:
`
`
`METHOD AND APPARATUS FOR GENERATING AND/OR HYDROTREATING
`HYDROCARBON FORMATION FLUIDS
`
`Title of Invention:
`
`Marc Va n Dyke
`
`Marc Van Dyke
`
`123 NW. 13th Street, Suite 221
`
`Correspondence Address:
`
`Filer:
`
`Boca Raton
`
`US
`
`5612832070
`
`m@phdpatent.com
`
`Marc Van Dyke
`
`Application Type:
`
`
`
`International Application for filing in the US receiving office
`
`eyment information:
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`Copy provided by USPTO from the IFW Image Database on 11/29/2013
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`genieApril15
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`genieApriI15
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`PCTREQUEST
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`Applicant's or agent's tile reference genieApr1l 1 5
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`Tme 0' Invemm"
`METHOD AND APPARATUS FOR GENERATING AND/
`
`OR HYDROTREATING HYDROCARBON FORMATION
`FLUIDS
`Applicant
`
`
`This person is
`Applicant only
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`Amwnmbr
`All designated States
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`Name
`GENIE IP B . v .
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`“Mm“
`Keizersgracht 62 — 64
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`1015CS Amsterdam
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`Netherlands
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`NL
`State of nationality
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`ThisPersonis
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`Applicant for
`US
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`Name (LAST, First)
`VINEGAR, Harold
`
`
`Address
`4613 Laurel
`
`Bellaire, Texas 77401
`
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`United States of America
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`Us
`State of nationality
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`”-6
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`genieApril15
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`Applicant and inventor
`US
`NGUYEN, SCOtt
`32 3 8 Maroneal
`Houstan, Texas 77025
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`'WEWEWE
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`IV-1-1
`IWVZ Ame
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`
`VAN DYKE, Marc
`123 N.W. 13th Street, Suite 221
`Boca Raton, Florida 33432
`United States of America
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`561-283-2070
`IV-1-3
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`genieApril15
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`

`METHOD AND APPARATUS FOR GENERA TING AND/OR
`HYDROTREATING HYDROCARBON FORMATION FLUIDS
`
`FIELD OF THE INVENTION
`
`Embodiments of the invention relate to techniques for pyrolyzing type IIs kerogen
`compositions derived therefrom, and to related methods of hydrotreating.
`
`BACKGROUND
`
`is declining,
`light crude Oil
`The world’s supply of conventional sweet,
`discoveries and access to new resources for this premium oil are becoming more
`challenging. To supplement this decline and to meet the rising global demand, oils of
`increasing sulfur content are being produced and brought to market. Sources of sulfur—
`rich oil may be found in Canada, Venezuela,
`the United States (California), and the
`Middle East.
`
`Although sulfur—rich oils, such as Maya crude, contribute significantly to the
`world's oil reserves, the economic and environmental costs of refining heavy oils can be
`
`Many sulfur—rich hydrocarbons are sourced from a subset of Type II
`known to be sulfur-rich, called Type II—
`
`8 or 11s. A molecular representation of the type of
`organic matter in Type 118 kerogen is illustrated below:
`
`kerogen
`
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`30
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`
`

`

`Originating from a marine—depositional environment, Type II—s kerogen is rich in
`
`bitumen with high sulfur content. For example, the oil produced in the Iraqi oil fields
`have sulfur content of ~4%.
`
`5
`
`Sulfur—rich oils include both conventional oils as well as unconventional oils. As
`conventional oil becomes less available (e.g. due to the increased cost of producing
`conventional oil from remote locations) and/or unable to meet world demand, it can be
`replaced with production of unconventional oils. Unconventional oils may be derived
`from a number of sources, including but not limited to oil sands, oil shale, coal, biomass,
`and bitumen deposits.
`
`Presently, however, sulfur—rich oils are expensive to develop and bring to market
`for a variety of reasons. Sulfur rich oils must be treated with costly hydrogen gas during
`the refining process
`to lower
`the sulfur content of the oil,
`a process called
`hydrodesulfurization.
`Hydrotreating includes
`the effort
`to hydrodesulfurize and
`hydrodenitrify. Furthermore, sulfur rich oils are typically hydrotreated in sturdy but
`costly vessels due to the high pressures and temperatures required. When the sulfur—rich
`oils include significant quantities of metals,
`the presence of them may poison the
`catalysts, thereby requiring larger quantities of expensive catalyst.
`Embodiments of the present
`invention relate to apparatus, methods and
`compositions associated with oil production from sulfur—rich type 118 kerogen. One
`example of a type IIs kerogen is kerogen of the Ghareb formation of Jordan.
`
`SUMMARY OF THE INVENTION
`
`Embodiments of the present invention relate to a novel technique for pyrolyzing
`sulfur-type IIs kerogen, a novel oil derived therefrom, and novel
`techniques for
`hydrotreating the same at only low-severity conditions.
`
`By slowly pyrolyzing sulfur—rich type IIs kerogen at relatively low temperatures,
`it is possible to obtain an oil which is surprisingly easy to hydrotreat, despite its relatively
`high sulfur content.
`In some embodiments, this ease of hydrotreating relates to one or
`more of the following properties: (i) a relatively high concentration of alkylthiophene
`
`10
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`i
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`relative to multi—rlng sulfur heterocycles such as benzothiophenes or dibenzothiophenes
`and/or (ii) a relatively high concentration of low molecular weight alkylthiophene (i.e.
`C1—C3 alkylthiophenes) relative to higher molecular weight alkylthiophenes.
`
`5
`
`derived from Ghareb formation oil shale indicates that an abundance of C3 thiophenes
`and a substantial lack or complete absence of C4+ thiophenes. Furthermore, analysis of
`these pyrolysis liquids shows that they are both alkylthiophene rich and surprisingly easy
`
`to hydrotreat.
`
`and
`alkylisoquinolines
`alkquuinolines,
`(i.e.
`heterocycles
`basic
`nitrogen
`ring
`relatively rich in alkylpyrroles compared to a concentration of
`alkylacridines); and (ii)
`multi—ring nitrogen neutral heterocycles (i.e. *alkylindoles and alkylcarbazoles).
`Analogously,
`it is believed that low—temperature pyrolysis of type IIs kerogen
`tends to favor formation of lower molecular-weight pyridine and pyrrole species, with
`little or no formation of higher molecular—weight pyridine and pyrrole species.
`Advantageously,
`these
`lower molecular-weight
`single—ring
`heterocyclic
`compounds are significantly easier to hydrotreat than their multi—ring and/or higher—
`molecular weight counterparts. As noted below, it is possible to regulate the pyrolysis
`process so as to favor formation of heterocyclic species which are easier to subsequently
`
`hydrotreat.
`
`Furthermore, experiments conducted on the aforementioned oil blend of
`hydrocarbon pyrolysis liquids derived from Ghareb formation oil shale indicates that this
`oil is surprisingly easy to hydrotreat. In particular, experiments indicate that it is possible
`to produce, from sulfur—rich type 113 kerogen, a light, sweet synthetic crude oil having a
`sulfur content of at most 1% wt/wt and a nitrogen content of at most 0.2% wt/wt without
`relying on external sources of hydrogen gas (e.g. using only hydrogen gas formed by
`pyrolysis of the kerogen) and/or whereby hydrocarbon liquids are subjected to at most
`low— severity hydrotreatment.
`In some embodiments, it is possible to optimize the ease of hydrotreating by
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`10
`
`15
`
`hydrotreat such as thiophenes. This situation is
`in contrast to conventional pyrolysis
`temperatures where smaller quantities of thiophenes are formed, and which favor
`formation of harder to hydrotreat dibenzothiophenes.
`Thus, in some embodiments, a majority or a substantial majority of kerogen of a
`portion (for example, a target portion having length, width and height of at least 20
`meters, or at least least 50 meters, or at least 100 meters, or at least 150 meters) of a
`formation is pyrolyzed in a temperature range between 270 and 290 degrees Celsius.
`Alternatively or additionally,
`in embodiments related to in situ pyrolysis, it is
`possible to regulate a power level of subsurface heaters so as to maximize, within the
`hydrocarbon pyrolysis formation liquids, at
`least one of:
`(i) a fraction of sulfur
`heterocycles that are alkylthiophenes;
`
`possible to regulate a power level of subsurface heaters so as to maximize, within the
`hydrocarbon pyrolysis formation liquids,
`at
`least one of:
`(i) a ratio between a
`concentration of alkylthiophenes and a concentration of alk
`ratio
`between
`
`of
`
`alkylthiophenes
`
`(ii) a
`ylbenzothiophenes;
`and
`a
`concentration of
`
`25
`
`a
`
`concentration
`
`Copy provided by USPTO from the IFW Image Database on 11/29/2013
`
`

`

`may be possible to monitor any of the aforementioned ratios, and in response to a
`monitored value or a change therein, increase or decrease a power level of one or more of
`the subsurface heaters.
`
`t0-
`
`As noted above, one advantage of the presently disclosed hydrocarbon pyrolysis
`liquids derived from relatively low temperature and/or slow pyrolysis of type Hs kerogen
`is
`the predominance of easier—to—hydrotreat alkylthiophenes relative to harder—
`hydrotreat alkylbenzothiophenes
`Furthermore, speciation
`and alkyldibenzothiophenes.
`experiments performed on the aforementioned oil blend of hydrocarbon pyrolysis liquids
`derived from Ghareb formation oil shale indicate that the relative concentration of the
`different species of alkylthiophenes follow a definitive pattern. In particular, speciation
`data indicates that
`substantially all
`thiophenes are C2—C3
`thiophenes,
`concentration of Cl thiophenes and even lower concentrations
`as well as C4+ thiophenes.
`
`with low
`
`of both thi0phene C4H4S
`
`10
`
`15
`
`Although C2—
`
`25
`
`30
`
`alkylthlophenes and C4 alkylthiophenes
`alkylpyridines and C4 alkylpyridines;
`alkylpyridines and C3 alkylpyridines;
`alkylpyrroles and C4 alkylpyrroles;
`alkylpyrroles and C3 alkylpyrroles.
`Furthermore, preliminary GC results for the aforementioned blend of hydrocarbon
`pyrolysis liquids indicate that at most small quantities of ethyl-thi0phene are formed by
`
`(11) a ratlo between concentrations of C3
`(iii) a ratio between concentrations of C2
`(iv) a ratio between concentrations of C3
`(v)
`a
`ratio between concentrations of C2
`
`Copy provided by USPTO from the IFW Image Database on 11/29/2013
`
`

`

`low~temperature pyrolysis of type IIs kerogen. This indicates that a substantial majority,
`or substantially all C2 alkylthiophenes are di-methyl
`thiophenes rather than ethyl-
`thiophenes. The present
`inventors propose a pyrolysis mechanism related to slow
`pyrolysis of kerogen comprising sulfur cross-linked chlorophyll chains at low pyrolysis
`temperature (e.g. in the range between 270 and 290 degrees Celsius).
`According to this proposed mechanism, at temperatures between 270 and 290
`degrees Celsius, the weakest sulfur—sulfur bonds are the first to be broken. In a Type IIs
`kerogen, S-S bonds crosslink the chlorophyll chains compriseing a backbone of about 20
`carbon atoms. . After the 8-8 bond is thermally cleaved, the backbone 'folds around' and
`forms an alkylated thiophene having one or more CN alkyl groups where N is a 'large
`number (e.g. typically about 20 carbons in naturally—occurring high sulfur oils derived
`from Type IIs kerogen) ). However, unlike the naturally-occurring oils, when
`the
`kerogen is maintained at the low pyrolysis temperatures between 270 and 290 degrees C
`for a relatively flong' period of time, the kinetics favor breaking the long carbon chains at
`their weakest point,
`leaving only relatively stable methyl groups attached to the
`
`thiophene or di—methyl-thiophene or tri—methyl—thiophene or tetra—methyl—thiophene.
`Thus, when kerogen is exposed to these low-temperature pyrolysis temperatures
`for a relatively long period of time, significant quantities of alkylated thiophenes may be
`yielded, where the thiophene ring is alkylated only by one or more methyl group(s).
`Not wishing to be bound by theory,
`it is believed that this is in contrast to
`
`CN alkyl thiophenes where N is relatively 'large,' being equal to at least 5 or at least 10 or
`
`at least 20.
`
`5
`
`10
`
`15
`
`20
`
`25
`
`Not wishing to be bound by theory, it is believed that this is also in contrast to
`pyrolysis liquids generated from conventional high—temperature,
`'fast-heating' surface
`retorts
`, which are known to generate mostly high—molecular weight species, including
`sulfur—bearing compounds. These higher molecular weight species comprise high
`concentrations of multi-ring aromatic compounds, including dibenzothiphenes and alkyl
`
`I 30
`
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`
`

`

`dibenzothiophenes, which are much more difficult to hydrotreat than the methylated
`
`thiophenes.
`
`Embodiments of the present invention relate to techniques for producing, from
`sulfur-rich type IIs kerogen, a light,
`
`5 most 1% wt/wt and a nitrogen content of at most 0 2% wt/wt In a manner that IS self-
`suff1c1ent With respect to hydrogen gas and/or whereby hydrocarbon liqulds are subjected
`to at most low-severity hydrotreatment.
`
`10
`
`15
`
`20
`
`By pyrolyzmg the type Hs kerogen at relative low temperatures which are
`sustalned for a relatlvely long period of time, 1t 1s poss1ble to generate hydrocarbon
`
`indicates that these formation fluids are rich in easier-to-hydrotreat heterocyclic species,
`in contrast to hydrocarbon formation fluids obtained from similar kerogen under higher
`temperature and/or 'fast-heating' conditions.
`
`Experimental data
`
`'low severity' hydrotreating conditions are
`the present disclosure,
`For
`characterlzed by (1) a max1mum temperature of at most 350 degrees Cels1us or at most
`340 degrees Cels1us or at most 330 degrees Cels1us, and (11) a max1mum pressure of at
`most 120 atmospheres (atm) or at most 110 atm or at most 100 atm or at most 90 atm or
`at most 80 atm or at most 70 atm.
`
`For the present disclosure, the statement “hydrotreating is sustained only by the
`hydrogen gas component of the pyrolysis gases” includes only H2 gas formed as a
`reaction product of the pyrolysis itself, and does not include hydrogen gas derived from
`steam methane reforming of the pyrolysis gases.
`
`For the present disclosure, a process that
`is 'self—
`sufficient with respect
`to
`hydrogen gas” consumes only the H2 gas formed as a reaction product of the pyrolysis
`
`Copy provided by USPTO from the IFW Image Database on 11/29/2013
`
`

`

`itself, and does not include hydrogen gas derived from external hydrogen sources or
`
`steam methane reforming of the pyrolysis gases.
`
`"Sulfur-rich" type IIs kerogen refers to type IIs kerogen having an average sulfur
`
`content of at least 8% wt/wt (in some embodiments, at least 10% wat or at least 12%
`
`wt/wt) and an average nitrogen content of at least 1.5% wt/wt (in some embodiments, at
`
`least 1.75% wt/wt or at least 2% wt/wt).
`
`Type IIs kerogen is pyrolyzed to form hydrocarbon pyrolysis fluids, which are
`
`hydrotreated only at low—severity conditions and/or without relying on external sources of
`
`hydrogen gas. In some examples, the pyrolysis is performed primarily at relatively low
`temperatures
`and/or
`in a manner
`that maximizes
`a
`ratio between respective
`
`10
`
`concentrations of alkylthiophenes and alkyldibenzothiophenes within the resulting
`pyrolysis liquids. In some embodiments, the pyrolysis is performed in a manner that
`
`maximizes a fraction of alkylthiophenes that are either (i) unalkylated or (ii) alkylated
`
`only by one or more methyl groups. In some embodiments, the pyrolysis is performed in
`
`15
`
`a manner that maxlmizes a fractlon of alkylthiophenes that are (1) unalkylated or (11) C1-
`
`C3 alkylthiophenes.
`
`In some embodiments, the pyrolys1s 1s performed in a manner that
`
`maximizes a fraction of alkylthiophenes that are (i) unalkylated or
`
`(ii)
`
`C2—C3
`
`alkylthiophenes.
`
`It is believed that the pyrolysis primarily at low temperature is conducive for
`
`20
`
`formation of relatively high concentrations lower—molecular—weight and single-ring
`heterocyclic species that are easier to hydrotreat
`than their multi—ring or higher—
`molecular-weight counterparts.
`
`Copy provided by USPTO from the IFW Image Database on 11/29/2013
`
`

`

`Although low—temperature pyrolysis may be significantly slower than pyrolysis at
`
`higher temperatures for well—studied kerogens such as Green River Type I kerogen,
`
`experiments commissioned by the presentinventors indicate that type IIs kerogen, such
`
`as
`
`that
`
`in Ghareb formations, pyrolyzes at a surprisingly fast
`
`rate even at
`
`low
`
`5
`
`temperatures of less than 290 degrees Celsius, where the pyrolysis liquids are relatively
`
`rich in easier-to-hydrotreat species.
`
`In order to maintain the type IIs kerogen within a desired low—temperature
`
`pyrolysis range for sufficient time, it may be desirable to quickly ramp up to a desired
`
`low temperature pyrolysis temperature, and then to control heater power (e.g. reducing
`
`10
`
`heater power) in a manner so as to prolong an amount of time the kerogen is maintained
`
`at 'low' range of pyrolysis temperatures below 290 degrees Celsius.
`
`Copy provided by USPTO lrom the IFW Image Database on 11/29/2013
`
`

`

`DESCRIPTION OF EMBODIMENTS
`
`10
`
`For convenience,
`
`in the context of the description herein, various terms are
`
`presented here. To the extent that definitions are provided, explicitly or implicitly, here or
`
`5
`
`elsewhere in this application, such definitions are understood to be consistent With the
`
`usage of the defined terms by those of skill in the pertinent art(s). Furthermore, such
`
`definitions are to be construed in the broadest possible sense consistent with such usage.
`
`For convenience,
`
`in the context of the description herein, various terms are
`
`presented here. To the extent that definitions are provided, explicitly or implicitly, here or
`elsewhere in this application, such definitions are understood to be consistent with the
`
`10
`
`15
`
`20
`
`25
`
`usage of the defined terms by those of skill in the pertinent art(s). Furthermore, such
`definitions are to be construed in the broadest possible sense consistent with such usage.
`If two numbers A and B are "on the same order of magnitude", then ratio between
`(i) a larger of A and B and (ii) a smaller of A and B is at most 15 or at most 10 or at most
`5.
`
`Unless specified otherwise, a 'substantial majority' refers to at least 75%. Unless
`
`least 90%. In some embodiments
`'substantially all' refers to at
`specified otherwise,
`'substantially all' refers to at least 95% or at least 99%.
`
`Embodiments of the present invention relate to compositions (e.g. oils) containing
`one or more types of heterocyclic compounds including (i)
`sulfur heterocyclic
`compounds
`such
`as
`the
`single—ring
`alkylthiophenes,
`or
`the multi—ringed
`alkylbenzothiophenes or alkyldibenzothiophenes
`and (ii)
`nitrogen
`heterocyclic
`compounds such as the single—ringed alkylpyridines or alkylpyrroles, or the multi—ringed
`alkquuinolines, alkylisoquinolines, alkylacridines, and alkylindoles, and alkylcarbazoles.
`The term 'alkylthiophenes'
`includes
`thiophene C4H48 as well as alkylated
`thiophenes.
`'Alkylated thiophenes' are thiophenes where an alykl group is bonded to one
`or more locations on the thiophene ring. Thiophene C4H48 is an 'alkylthiophene' but is
`not an 'alkylated thiophene.’ Examples of alkylated thiophenes include but are not limited
`to methyl thiophenes, di-methyl thiophenes, ethyl thiophenes, ethyl methyl-thiophenes,
`
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`
`

`

`ll
`
`5
`
`10
`
`15
`
`propyl thiophenes, etc. Analogous definitions (i.e. analogous to 'alkylthiophenes') apply
`to the multi—ring
`sulfur heterocyclic compounds
`(i.e.
`alkylbenzothiophenes and
`alkyldibenzothiophenes)
`to the
`single-ring nitrogen heterocyclic compounds
`(i.e.
`alkylpyridines and alkylpyrroles) and to the multi-ring nitrogen heterocyclic compounds
`(i.e.
`alkquuinolines,
`alkylisoquinolines
`alkylacridines,
`and
`alkylindoles
`and
`alkylcarbazoles).
`
`By way of example, methyl thiophenes are a 'Cl alkylthiophene' because the total
`number of carbon atoms of alkyl groups bonded to a member of the thiophene ring is
`exactly 1. Both di—methyl thiophenes and ethyl thiophenes are 'C2 alkylthiophenes'
`because the total number of carbon atoms of bonded—alkyl group(s) bounded to a member
`of thiophene ring is exactly 2. C3 alkylthiophenes are molecules where the total number
`of carbon atoms of bonded—alkyl group(s) bounded to a member of thiophene ring is
`exactly 3 ---
`thus, C3 alkylthiophenes include tri—methyl
`thiophenes, methyl ethyl
`thiophenes
`and propyl
`thiophenes. Analogous
`defmitions
`(i.e.
`analogous
`to
`'alkylthiophenes')
`apply to the multi—ring
`sulfur heterocyclic
`compounds
`(i.e.
`alkylbenzothiophenes
`and
`alkyldibenzothiophenes)
`to
`the
`single-ring
`nitrogen
`heterocyclic compounds (i.e. alkylpyridines and alkylpyrroles) and to the multi—ring
`nitrogen heterocyclic compounds (i.e. alkquuinolines, alkylisoquinolines alkylacridines,
`and alkylindoles and alkylcarbazoles).
`
`20
`
`25
`
`30
`
`For a positive integer N, the terms 'CN alkylthiophenes' and 'CN thiophenes' are
`used synonymously and refer to alkylthiophenes (which also happen to be 'alkylated
`thiophenes') where the total number of carbon atoms of bonded-alkyl group(s) bounded
`to a member of thiophene ring is exactly N. Analogous definitions (i.e. analogous to
`'alkylthiophenes')
`apply to
`the multi—ring
`sulfur heterocyclic
`compounds
`(i.e.
`alkylbenzothiophenes
`and
`alkyldibenzothiophenes)
`to
`the
`single—ring
`nitrogen
`heterocyclic compounds (i.e. alkylpyridines and alkylpyrroles) and to the multi-ring
`nitrogen heterocyclic compounds (i.e. alkquuinolines, alkylisoquinolines alkylacridines,
`and alkylindoles and alkylcarbazoles).
`
`For a positive integer N, the terms 'CN+ alkylthiophenes' and 'CN+ thiophenes' are
`used synonymously and refer to alkylthiophenes (which also happen to be 'alkylated
`thiophenes') where the total number of carbon atoms of bonded—alkyl group(s) bounded
`
`Copy provided by USPTO from the IFW Image Database on 11/29/2013
`
`

`

`12
`
`to a member of thiophene ring is greater than or equal to N. Analogous definitions (i.e.
`analogous to 'alkylthiophenes') apply to the multi—ring sulfur heterocyclic compounds
`(i.e. alkylbenzothiophenes and alkyldibenzothiophenes)
`to the single—ring nitrogen
`heterocyclic compounds (i.e. alkylpyridines and alkylpyrroles) and to the multi-ring
`nitrogen heterocyclic compounds (i.e. alkquuinolines, alkylisoquinolines alkylacridines,
`and alkylindoles and alkylcarbazoles).
`
`For positive integers M M (M>N), the terms 'CN—CM alkylthiophenes' and 'CN+
`thiophenes' are used synonymously and refer to alkylthiophenes (which also happen to be
`'alkylated thiophenes') where the total number of carbon atoms of bonded—alkyl group(s)
`bounded to a member of thiophene ring is either (i) exactly N; or (ii) exactly M or (iii)
`greater than N and less than M. Analogous definitions (i.e. analogous to 'alkylthiophenes')
`apply to the multi-ring sulfur heterocyclic compounds (i.e. alkylbenzothiophenes and
`alkyldibenzothiophenes)
`to the single-ring nitrogen heterocyclic compounds
`(i.e.
`alkylpyridines and alkylpyrroles) and to the multi-ring nitrogen heterocyclic compounds
`(i.e.
`alkquuinolines,
`alkylisoquinolines,
`alkylacridines,
`and
`alkylindoles
`and
`alkylcarbazoles).
`
`analogy,
`by
`(or,
`alkylthiophenes
`of
`concentration
`determining
`When
`alkylbenzothiophenes or alkyldibenzothiophenes or alkylpyridines and alkylpyrroles or
`alkquuinolines,
`or
`alkylisoquinolines
`or
`alkylacridines
`or
`alkylindoles
`or
`alkylcarbazoles), the location to which alkyl group(s) are attached is immaterial.
`For the present invention, an 'alkylthiophene-rich oil' is an oil where a majority (or
`a substantial majority) of the sulfur compounds are alkylthiophenes and/or an oil that is at
`least 10% or at least 20% by volume alkylthiophene. For the present invention, an
`'alkylpyridine and/or alkylpyrrole rich oil' is an oil where a majority (or a substantial
`majority) of the nitrogen compounds are alkylpyridines or alkylpyrroles and/or an oil that
`is at least 10% or at least by volume either alkylpyridines or alkylpyrroles.
`For the present disclosure, 3 'sulfur—rich feedstock' or a 'sulfur—rich pyrolysis
`liquid' is at least 3% wt/wt or at least 4% wt/wt sulfur.
`
`5
`
`10
`
`15
`
`20
`
`25
`
`For the present disclosure, sulfur—rich type 113 kerogen is at least 6% wt/wt or at
`least 7% wt/wt or at least 8% WM sulfur.
`
`30
`
`Copy provided by USPTO from the IFW Image Database on 11/29/2013
`
`

`

`13
`
`'low temperature pyrolysis' is pyrolysis that occurs at
`For the present disclosure,
`temperatures of at most 290 degrees Celsius. In some embodiment,
`'low temperature
`pyrolysis' occurs between 270 degrees Celsius and 290 degrees Celsius.
`to
`For the present disclosure, a process that
`is 'self—sufficient with respect
`hydrogen gas” consumes only H2 gas formed as a reaction product of the pyrolysis itself,
`and does not
`include hydrogen gas derived from steam methane reforming of the
`pyrolysis gases.
`
`are
`conditions
`'low severity’ hydrotreating
`disclosure,
`the present
`For
`characterized by (i) a maximum temperature of at most 350 degrees Celsius or at most
`340 degrees Celsius or at most 330 degrees Celsius; and (ii) a maximum pressure is at
`most 120 atmospheres (atm) or at most 110 atm or at most 100 atm or at most 90 atm or
`at most 80 atm or at most 70 atm.
`
`For the present disclosure, unless otherwise specified, when a feature related to a
`portion or a fraction of a composition (e.g. of an oil) is disclosed, this refers is by weight
`(e.g. wt/wt%) and not by mole or by volume. For the present disclosure, unless otherwise
`specified concentrations and ratios therebetween are by weight (e.g. wt/wt%) and not by
`mole or by volume.
`
`invention relate to a multi—stage technique for
`Embodiments of the present
`producing a light, sweet synthetic crude oil having a sulfur content of at most 1% wt/wt
`and a nitrogen content of at most 0.2% wt/wt
`from sulfur-rich type IIs kerogen without
`relying on external sources of hydrogen gas. Experiments conducted by the present
`inventors indicated th