`US008668823B2
`
`c12) United States Patent
`Gudde et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 8,668,823 B2
`Mar. 11, 2014
`
`(54) METHODS AND UNITS FOR MITIGATION
`OF CARBON OXIDES DURING
`HYDROTREATING
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`(71) Applicant: BP Corporation North America Inc.,
`Houston, TX (US)
`
`(72)
`
`Inventors: Nicholas J. Gudde, Windlesham (GB);
`John W. Shabaker, Naperville, IL (US)
`
`(73) Assignee: BP Corporation North America Inc.,
`Houston, TX (US)
`
`( *) Notice:
`
`Subject to any disclaimer, the term ofthis
`patent is extended or adjusted under 35
`U.S.C. 154(b) by O days.
`
`(21) Appl. No.: 13/767,906
`
`(22) Filed:
`
`Feb.15,2013
`
`(65)
`
`Prior Publication Data
`
`US 2013/0149210Al
`
`Jun. 13, 2013
`
`Related U.S. Application Data
`
`(62)
`
`Division of application No. 12/564,075, filed on Sep.
`22, 2009, now Pat. No. 8,377,288.
`
`(51)
`
`(52)
`
`(58)
`
`(2006.01)
`
`Int. Cl.
`CJ0G49/22
`U.S. Cl.
`USPC ............ 208/78; 208/80; 208/208 R; 208/213;
`208/216
`R; 585/469; 585/638; 585/639; 585/640;
`585/733; 422/141; 422/143; 422/600; 422/601;
`422/650
`
`Field of Classification Search
`USPC ............ 422/141, 143, 600, 601, 650; 208/78,
`208/80, 208 R-217; 585/302-304, 469,
`585/638-640, 733
`See application file for complete search history.
`
`4,992,605 A
`5,705,722 A
`6,123,835 A
`2008/0156694 Al
`2008/0161614 Al
`2008/0173570 Al
`2009/0019763 Al
`2009/0107033 Al
`2011/0047862 Al *
`2011/0068047 Al
`2011/0219672 Al *
`
`2/ 1991 Craig et al.
`1/1998 Monnier et al.
`9/2000 Ackerson et al.
`7 /2008 Chapus et al.
`7 /2008 Bertoncini et al.
`7/2008 Marchand et al.
`1/2009 Ghonasgi et al.
`4/2009 Gudde et al.
`3/2011 Mayeur et al. .................. 44/307
`3/2011 Gudde et al.
`9/2011 Novak et al. .................... 44/307
`
`FOREIGN PATENT DOCUMENTS
`
`EP
`PL
`WO
`
`3/2004
`1 396 531
`5/1999
`285 073
`11/2003
`WO 03/091363
`(Continued)
`
`OTHER PUBLICATIONS
`
`Baldauf et al., Processing of Vegetable Oil as Fuel in Mineral Oil
`Refinery Processes, VDI Report No. 1126 (1004), pp. 153/168.
`
`(Continued)
`
`Primary Examiner - Brian McCaig
`(74) Attorney, Agent, or Firm - Ekkehard Schoettle; Kelly
`L. Cummings
`
`ABSTRACT
`(57)
`This invention relates to methods and units for mitigation of
`carbon oxides during hydrotreating hydrocarbons including
`mineral oil based streams and biological oil based streams. A
`hydrotreating unit includes a first hydrotreating reactor for
`receiving a mineral oil based hydrocarbon stream and form(cid:173)
`ing a first hydrotreated product stream, and a second
`hydrotreating reactor for receiving a biological oil based
`hydrocarbon stream and forming a second hydrotreated prod(cid:173)
`uct stream.
`
`6 Claims, 12 Drawing Sheets
`
`20
`
`14
`
`32 16
`
`22
`
`26
`
`28
`
`38
`
`32
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`34
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`10
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`I 40
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`
`24
`
`42
`
`36
`
`44
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`1 of 25
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`REFINED TECHNOLOGIES, INC.
`EXHIBIT 2001
`
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`US 8,668,823 B2
`Page 2
`
`(56)
`
`References Cited
`
`FOREIGN PATENT DOCUMENTS
`
`WO
`WO
`WO
`WO
`WO
`WO
`
`WO 2007/138254
`WO 2008/012415
`WO 2008/020048
`WO 2008/040973
`WO 2008/040980
`WO 2008/087279
`
`12/2007
`1/2008
`2/2008
`4/2008
`4/2008
`7/2008
`
`WO
`WO
`WO
`
`WO 2008/119695
`WO 2009/020055
`WO 2009/082366
`
`10/2008
`2/2009
`7/2009
`
`OTHER PUBLICATIONS
`
`Holmgren et al., A New Development in Renewable Fuels: Green
`Diesel, NPRA, Annual Meeting, Mar. 18-20, 2007, San Antoinio, TX
`, pp. 1-2.
`
`* cited by examiner
`
`2 of 25
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`REFINED TECHNOLOGIES, INC.
`EXHIBIT 2001
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`US 8,668,823 B2
`
`1
`METHODS AND UNITS FOR MITIGATION
`OF CARBON OXIDES DURING
`HYDROTREATING
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`This application is a divisional of U.S. patent application
`Ser. No. 12/564,075, filed Sep. 22, 2009, now U.S. Pat. No.
`8,377,288, all of which is hereby incorporated by reference.
`
`BACKGROUND
`
`2
`for receiving a mineral oil based hydrocarbon stream and
`forming a first hydrotreated product stream, and a second
`hydrotreating reactor for receiving a biological oil based
`hydrocarbon stream and forming a second hydrotreated prod-
`5 uct stream.
`According to a third embodiment, the invention includes a
`hydrotreating unit for processing mineral oil based hydrocar(cid:173)
`bon streams, biological oil based hydrocarbon streams, and/
`or the like. The unit includes a hydrotreating reactor for
`10 receiving a feed stream and forming a hydrotreated product
`stream, and a hydrogen recycle system for separating and
`returning unconverted hydrogen to the hydrotreating reactor
`as a hydrogen recycle stream. The unit includes a carbon
`15 oxide removal system for removing at least a portion of car(cid:173)
`bon oxides from the hydrogen recycle stream.
`
`BRIEF DESCRIPTION OF THE DRAWING
`
`1. Technical Field
`This invention relates to methods and units for mitigation
`of carbon oxides during hydrotreating hydrocarbons includ(cid:173)
`ing mineral oil based streams and biological oil based
`streams.
`2. Discussion of Related Art
`Recent air quality issues and production of greenhouse 20
`gases has focused improvement efforts on transportation
`fuels. Efforts to reduce emissions from transportation fuels
`have led to an increase in hydrotreating at refineries, such as
`to reduce sulfur content of the transportation fuels. Other
`efforts focus on renewable sources for transportation fuels, 25
`such as to reduce net carbon footprints for transportation of
`goods, people, and/or services.
`However, even with the above technology in transportation
`fuels, there remains a need and a desire for hydrotreating
`methods and units that consume less hydrogen, have higher
`catalytic activity, suffer less catalyst deactivation, provide
`increased capacity, have reduced capital costs, and can pro(cid:173)
`cess a variety offeedstocks.
`
`The accompanying drawings, which are incorporated in
`and constitute a part of this specification, illustrate embodi(cid:173)
`ments of the invention and, together with the description,
`serve to explain the features, advantages, and principles of the
`invention. In the drawings,
`FIG. 1 schematically shows a hydrotreating unit, according
`to one embodiment;
`FIG. 2 schematically shows a hydrotreating unit, according
`to one embodiment;
`FIG. 3 schematically shows a hydrotreating unit, according
`30 to one embodiment;
`FIG. 4 schematically shows a hydrotreating unit, according
`to one embodiment;
`FIG. 5 schematically shows a carbon oxide removal sys(cid:173)
`tem, according to one embodiment;
`FIG. 6 schematically shows a hydrotreating reactor,
`according to one embodiment; and
`FIG. 7 schematically shows a hydrotreating reactor,
`according to one embodiment;
`FIG. 8 shows a graph of time versus product sulfur level
`40 content, according to one embodiment;
`FIG. 9 shows a graph of time versus product sulfur level
`content, according to one embodiment;
`FIG. 10 shows a graph of time versus product sulfur level
`content, according to one embodiment;
`FIG. 11 shows a graph of time versus a ratio of product
`sulfur level content, according to one embodiment;
`FIG. 12 shows graph of rape seed oil content versus a ratio
`of product sulfur level content, according to one embodiment;
`and
`FIG. 13 shows graph of rape seed oil content versus a ratio
`of product sulfur level content, according to one embodiment.
`
`SUMMARY
`
`35
`
`This invention relates to methods and units for mitigation
`of carbon oxides while carrying out a hydrotreating process
`with hydrocarbon streams including mineral oil based
`streams and biological oil based streams. This invention
`includes hydrotreating methods and units that consume less
`hydrogen, have higher catalytic activity, suffer less catalyst
`deactivation, provide increased capacity, have reduced capital
`costs, can process a variety offeedstocks, and/or the like.
`According to a first embodiment, the invention includes a 45
`method ofhydrotreating hydrocarbons. The method includes
`a first step of feeding a mineral oil based hydrocarbon stream
`to a hydrotreating unit under hydrotreating conditions in the
`presence of a hydrotreating catalyst to form a hydrotreated
`product stream. The method includes a second step ofmea- 50
`suring a sulfur content of the hydrotreated product stream,
`and a third step of starting co-feed of a biological oil based
`hydrocarbon stream to the hydrotreating unit. The method
`includes a fourth step of measuring the sulfur content of the
`hydrotreated product stream during co-feed, and a fifth step of 55
`stopping co-feed of the biological oil based hydrocarbon
`stream upon the sulfur content of the hydrotreated product
`stream reaching a predetermined value. The method includes
`a sixth step of measuring the sulfur content of the
`hydrotreated product stream after stopping co-feed. The sul- 60
`fur content of the hydrotreated product stream returns to a
`value of close to before the co-feed after the step of stopping
`the co-feed.
`According to a second embodiment, the invention includes
`a hydrotreating unit for processing mineral oil based hydro(cid:173)
`carbon streams, biological oil based hydrocarbon streams,
`and/or the like. The unit includes a first hydrotreating reactor
`
`DETAILED DESCRIPTION
`
`This invention relates to methods and units for mitigation
`of carbon oxides while carrying out a hydrotreating process
`with hydrocarbon streams including mineral oil based
`streams and/or biological oil based streams.
`Triglycerides and other suitable biologically derived feed(cid:173)
`stocks can be converted into transportation fuel components,
`such as biogasoline, biodiesel, and/or biodistillate. Triglyc(cid:173)
`erides can include a range of natural materials formed from
`esterification of fatty acids and/or glycerol, such as vegetable
`oils, animal fats, and/or the like. Coprocessing of natural oils
`65 and/or fats with fractions of crude oil, such as, gas oil in a
`hydrotreater can be a convenient way of converting the natu(cid:173)
`ral oils and/or fats in to a transportation fuel.
`
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`3
`In an oil refinery, hydrotreaters may perform chemical
`conversions and/or reactions, such as hydrodesulfurization,
`hydrodenitrogenation, hydrodearomatization, and/or the like.
`These chemical conversions can be used for production of
`clean and/or low sulfur transportation fuels. A suitable cata(cid:173)
`lyst used for hydrotreating can include cobalt and molybde(cid:173)
`num on an alumina support. During coprocessing of natural
`oils and/or fats, the catalyst can also perform hydrodeoxy(cid:173)
`genation.
`to petroleum
`fats
`Co-feeding natural oils and/or
`hydrotreating processes can result in a loss of activity ( deac(cid:173)
`tivation and/or inhibition) of the catalyst. According to one
`embodiment, the invention relates to recovery of desulfuriza(cid:173)
`tion activity of a hydrodesulfurization catalyst, when used in
`coprocessing mineral oil and/or biological oil (bio-oil) by 15
`periodically turning off the bio-oil feed. The presence of
`bio-oil can cause and/or show the following observable
`effects: an initial increase in sulfur levels of the product
`hydrocarbons followed by a more gradual continuing
`increase in sulfur levels. Once the bio-oil feed ceases, the 20
`original sulfur levels in the product can be restored.
`Desirably, a balance between sulfur levels in a product and
`the ability to coprocess biological oil in existing refinery
`hydrotreatment equipment can be achieved by operating the
`process in a campaign-type mode, where addition ofbio-oil 25
`only occurs periodically, intermittently, and/or cyclically.
`Generally during processing bio-oil, increased hydrotreat(cid:173)
`ing process effluent sulfur content can be observed for cobalt
`molybdenum containing catalysts (generally low pressure
`hydrodesulfurization service), but sulfur content may be at 30
`least relatively stable with nickel molybdenum containing
`catalysts (generally high pressure hydrodesulfurization ser(cid:173)
`vice). The methods and techniques of the invention can be
`applied to any suitable catalyst at any suitable conditions.
`Addition of octanol (CS alcohol) as opposed to fatty acid 35
`biological oils may not cause a reduced loss of desulfuriza(cid:173)
`tion activity. According to one embodiment, bio-oil can be
`converted to a linear alcohol, such as before hydrotreating.
`According to one embodiment, the invention relates to
`recovery of desulfurization activity of a cobalt molybdenum 40
`based hydrodesulfurization catalyst, when used in coprocess(cid:173)
`ing mineral oil and bio-oil by periodically turning off and/or
`terminating a bio-oil feed. Operating strategies and/or tech(cid:173)
`niques based on this phenomenon may be used and/or prac(cid:173)
`ticed to lengthen a lifetime of hydrodesulfurization catalyst 45
`used in bio-oil coprocessing applications and/or increase a
`hydrotreating unit capacity.
`According to one embodiment, the invention can include a
`single stage hydrotreater with bio-oil co-feed. The bio-oils
`can be more reactive than mineral based gas-oil. Bio-oils can 50
`have a higher hydrogen consumption; and an increased gas
`yield, such as more methane, ethane, ethylene, propane, pro(cid:173)
`pylene, and/or the like. For example, replacement of about 5
`weight percent of gas-oil with vegetable based oil (veg-oil) at
`the same total feed-rate can cause (a) a higher hydrogen 55
`make-up rate and increased purge rate to maintain a same
`recycle purity of a hydrogen recycle stream, and (b) an
`increased exotherm in the reactor, such as from the deoxy(cid:173)
`genation of the veg-oil.
`According to one embodiment, a hydrotreating unit may 60
`include a preheater designed to minimize veg-oil degrada(cid:173)
`tion. The hydrotreating unit may include a high hydrogen
`consumption along with an associated exotherm when pro(cid:173)
`cessing veg-oil versus when not processing veg-oil. The
`hydrotreating unit may include a temperature control device 65
`and/or scheme, such as a high pressure liquid quench, and/or
`the like. The hydrotreating unit can also include a gas circu-
`
`4
`lation rate with relatively high flow rates (Cl-C3 compounds,
`hydrogen, and/or the like) and the hydrotreating unit can
`handle more water, such as formed from processing the veg(cid:173)
`oil. The hydrotreating unit can include catalyst to handle
`5 carbon oxides and may include carbon dioxide hydrogenation
`(such as to form methane and water) and/or carbon dioxide
`scrubbing. The hydrotreating unit may have reduced capital
`costs compared to another unit, such as effectively diluting
`the veg-oil to maintain the exotherm under control can allow
`10 lower alloy and/or milder steel vessel construction and/or
`fabrication.
`According to one embodiment, the invention can include a
`single stage gas oil hydrotreating unit (main reactor) with a
`side-stream veg-oil hydrotreater ( second reactor). The second
`reactor can be used in a same gas circuit as the main reactor,
`such as with the same compressors and high pressure sepa(cid:173)
`rator. Both reactors can operate at nominally the same pres(cid:173)
`sure and/or circulation (treat) gas composition. Catalyst used
`in the second reactor can be the same or different than catalyst
`used in the main reactor. Desirably, the catalyst for the second
`reactor can be somewhat sulfur tolerant. The second reactor
`can be any suitable size. A ratio of the main reactor volume to
`the second reactor volume can be between about 100: 1 to
`about 1: 100, between about 20: 1 to about 1:20, about 1: 1,
`and/or the like. Any suitable amount of the hydrotreating
`process effluent (product) can be based on co-feeding veg-oil,
`such as between about O weight percent and about 100 weight
`percent, between about 5 weight percent and about 25 weight
`percent, and/or the like of a total feed to a hydrotreating zone
`and/or unit.
`The hydrotreating unit with the main reactor and the sec(cid:173)
`ond reactor (in series configurations and/or parallel configu(cid:173)
`rations) may minimize and/or reduce an impact of co-feed on
`the main reactor. The combined product of the reactors can
`reduce and/or simplify handling of high cloud-point veg-oil
`based product. The combined unit with two reactors can have
`reduced capital costs compared to separate units, such as by
`utilizing a common gas separator, a common gas compressor,
`other recycle equipment, and/or the like. The second reactor
`can be optimized for veg-oil treatment, such as by selecting
`appropriate catalysts, reactor temperatures, and/or the like.
`The second reactor may use a more acidic catalyst designed to
`perform isomerization and/or cracking, such as to improve
`cold-flow properties of the product, for example.
`According to one embodiment, the invention can include a
`single stage gas oil hydrotreater (main reactor) with veg-oil
`hydrotreater (second reactor) in a hydrogen make-up circuit.
`A hydrogen make-up rate to the unit can provide enough flow
`of hydrogen (treat) gas for the main reactor and second reac(cid:173)
`tor. In this configuration, the second reactor essentially can
`operate on once through hydrogen. An optional make-up
`supply can be connected to the main reactor. This configura(cid:173)
`tion can allow the second reactor to be fully optimized in
`terms of catalyst choice and/or reaction conditions, such as
`temperature and/or pressure. This configuration can offer
`more options for veg-oil product upgrade because the veg-oil
`reactor does not contact a sulfur containing feedstock (paral(cid:173)
`lel hydrotreaters). This configuration can allow hydrodes(cid:173)
`ulfurization to occur without competition of the hydrodeoxy(cid:173)
`genation and associated inhibiting byproducts ( carbon oxides
`and/or water). The second reactor may use a precious metal
`catalyst and may be easier to construct than side-stream reac(cid:173)
`tor, such as by simplifying piping in the hydrogen recycle
`system.
`Principle components ofbio-oils can include triglycerides,
`pyrolysis oils, other suitable compounds, derivatives of other
`biologically based components, and/or the like. Triglycerides
`
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`EXHIBIT 2001
`
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`
`US 8,668,823 B2
`
`5
`can be formed from three fatty acids (branches) attached to a
`glycerol backbone (3 carbon atoms). The fatty acids may have
`a carbon chain length of any suitable number, such as between
`about 12 and about 24 carbon atoms. The bio-oils can be fully
`saturated and/or have one or more unsaturated double bonds 5
`in the hydrocarbon chain and/or branch. Generally, bio-oils
`can be low in sulfur content, but may have oxygen and/or
`nitrogen heteroatoms.
`Triglycerides can be upgraded to biodiesel products by
`using various processes which can include esterification, 10
`hydrogenation, decarboxylation, and/or the like.
`Hydrogenation can consume a large amount of hydrogen
`with a portion forming the reaction product water. Increased
`hydrogen consumption can be expensive due to capital and/or
`operating costs of hydrogen supply. Decarboxylation can
`form methane as carbon dioxide hydrogenates. Hydrotreater
`operations can seek to minimize carbon dioxide formation,
`such as may reduce hydrogen consumption, reduce potential
`corrosion problems, reduce potential metallurgical issues,
`and/or the like. Carbon dioxide levels can be controlled with
`a purge stream. The purge stream can include hydrogen fur(cid:173)
`ther increasing hydrogen consumption. The purge stream can
`be burned as fuel gas, flared, recovered in a hydrogen recov(cid:173)
`ery unit ( cryogenic, adsorption, absorption, membrane, and/
`or the like), sent to a sulfur recovery unit (Claus unit and/or
`the like), returned to a hydrogen plant front end for clean up
`(before and/or after a reformer, for example), and/or the like.
`According to one embodiment, the invention can include a
`fixed bed hydrotreater with a co-feed of bio-oil with feed of
`mineral oil. The hydrotreater reactor system can operate at a
`relatively low hydrogen pressure, such as less than about 30
`bars. The hydrotreater can operate at a high bio-oil content,
`such as greater than about 30 weight percent of fresh feed.
`The hydrotreater can use a cobalt and molybdenum catalyst
`on an alumina support. The hydrotreater can include a carbon
`dioxide scrubbing device in a recycle gas system. The carbon
`dioxide scrubber can include an amine and/or a promoted
`amine, such as monoethanolamine, diethanolamine, and/or
`the like. The carbon dioxide scrubber can include a mem(cid:173)
`brane to separate carbon dioxide from hydrogen, such as a
`polymeric membrane, a ceramic membrane, a metal film
`membrane, and/or the like. The carbon dioxide scrubber can
`include a solid adsorbent, such as a zeolite, a molecular sieve,
`an activated carbon, an amorphous silica-aluminate, and/or
`the like. The carbon dioxide scrubber can include a basic
`oxide formed from an alkali metal (Li, Na, K, Cs, and/or the
`like), an alkaline earth metal (Mg, Ca, Sr, Ba, and/ or the like),
`a rare-earth metal (La, Ce, and/or the like), and/or the like.
`The adsorbent could be regenerated thermally at a suitable
`temperature and/or with a suitable medium and/or carrier gas.
`The carbon dioxide may be suitable for industrial applica(cid:173)
`tions, food applications, beverage applications, medical
`applications, liquefaction, solidification, sequestration, and/
`or the like.
`According to one embodiment, the invention can include a
`hydrotreater with an interbed purge. A multiple bed reactor
`can include interbed removal of process gas, such as hydro(cid:173)
`gen, carbon dioxide (inhibiting byproduct), other light gases,
`and/or the like. The reactor can include injection of fresh
`hydrogen (make-up and/or recycle following a carbon oxide
`removal system) to each bed. Any suitable amount of flow
`through the bed can be used for the interbed purge, such as
`between about O volume percent to about 100 volume percent,
`between about 5 volume percent and about 50 volume per(cid:173)
`cent, between about 10 volume percent and about 30 volume
`percent, and/or the like.
`
`6
`According to one embodiment, the invention can include a
`fluidized bed hydrotreater, an ebullated bed hydrotreater, and/
`or the like. The catalyst may include any suitable particle size.
`A portion of the catalyst can be withdrawn from the reactor on
`a continuous basis and/or an intermittent basis (batch) to be
`regenerated. Catalyst regeneration can occur in a main reac-
`tion zone, a separate zone, a separate vessel, and/or the like.
`Regeneration can be done with hydrogen, water, steam, oxy(cid:173)
`gen, and/or the like.
`Some potential benefits of the hydrotreater units of the
`invention can include reduced hydrogen consumption, pro(cid:173)
`duction of concentrated carbon dioxide streams, improved
`environmental performance by lower greenhouse gas emis(cid:173)
`sions, and/or the like. According to one embodiment, the
`15 invention includes adding a carbon dioxide removal step and/
`or system in combination with low operating pressures. The
`carbon dioxide removal system may also remove hydrogen
`sulfide, nitrogen oxides, and/or the like from the recycle gas.
`According to one embodiment, the invention can include a
`20 process for the production of hydrocarbons. The process can
`include the step of (a) feeding hydrogen and a first feedstock
`including one or more hydrocarbons to a first reactor to pro(cid:173)
`duce a first hydrogenated product stream including hydrocar(cid:173)
`bons present in or derived from the first feedstock, and the
`25 step of (b) feeding hydrogen and a second feedstock (bio-oil),
`such as including a carboxylic acid, a phenol, a ketone, an
`alcohol, derivatives thereof, and/or the like, to a second reac(cid:173)
`tor to produce a second hydrogenated product stream includ(cid:173)
`ing hydrocarbons derived from the bio-oil. The process can
`30 also include the step of ( c) feeding the first hydrogenated
`product stream and second hydrogenated product stream to a
`separator, and the step of ( d) removing from the separator a
`liquid hydrocarbon phase including hydrocarbons from the
`first hydrogenated product stream and from the second hydro-
`35 genated product stream, and a vapor phase including unre(cid:173)
`acted hydrogen and volatile components present in the first
`and second feedstocks, and produced in the hydrogenation
`reactions in the first and second reactors.
`This configuration can include and/or produce two sepa-
`40 rate hydrogenation reactions, hydrogenation of a first hydro(cid:173)
`carbon-containing feedstock takes place in a first reactor, and
`hydrogenation of a second feedstock including a bio-oil takes
`place in a second reactor. Two reactors can be operated con(cid:173)
`currently, although separate batch processing may be used. A
`45 product stream from the first reactor (the first hydrogenated
`product stream) can include hydrocarbons that are present in
`and/or derived from the hydrocarbon-containing oil (min(cid:173)
`eral). A product stream from the second reactor (the second
`hydrogenated product stream) can include hydrocarbons pro-
`50 duced from the reaction between hydrogen and the bio-oil.
`The process can be used in the production ofliquid hydro(cid:173)
`carbon fuels, for example gasoline, diesel, aviation gasoline,
`jet fuel, kerosene, fuel oil, bunker oil, and/or the like. Light
`hydrocarbons can also be produced by the process, for
`55 example one or more Cl to C4 hydrocarbons which may be
`paraffinic in nature. The light hydrocarbons can be used in the
`production of gaseous hydrocarbon fuels, LPG (liquefied
`petroleum gas), and/or the like. According to one embodi(cid:173)
`ment, the hydrocarbon fuels can be used directly and/or for
`60 blend stocks in products meeting and/or complying with
`industry standards and/or regulations.
`According to one embodiment and in the first reactor, a first
`feedstock including one or more hydrocarbons contacts with
`hydrogen to produce a first hydrogenated product stream. The
`65 hydrocarbons in the first hydrocarbon-containing feedstock
`may be predominantly paraffinic hydrocarbons, but can also
`include other hydrocarbons. Other hydrocarbons may include
`
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`REFINED TECHNOLOGIES, INC.
`EXHIBIT 2001
`
`
`
`US 8,668,823 B2
`
`5
`
`7
`unsaturated hydrocarbons, olefins, aromatics, heteroatom
`containing organic compounds, organonitrogen compounds,
`organosulfur compounds, and/or the like.
`The first feedstock may be derived from gas, coal, biomass,
`other suitable raw materials, and/or the like. The raw materi-
`als may be converted to syngas (synthesis gas) through pro(cid:173)
`cesses, such as steam reforming, partial oxidation, gasifica(cid:173)
`tion, and/or the like. The syngas can be subsequently
`converted to hydrocarbons through Fischer-Tropsch synthe(cid:173)
`sis, other suitable gas to liquids processes, and/or the like.
`According to one embodiment, the one or more hydrocar(cid:173)
`bons in the first feedstock can be derived from crude oil.
`Crude-oil derived hydrocarbon compositions can be higher in
`heteroatom-containing organic compounds compared to Fis(cid:173)
`cher Tropsch-derived oils. The first feedstock can include 15
`hydrocarbons derived from one or more process streams asso(cid:173)
`ciated with crude oil refining, for example straight-run frac(cid:173)
`tions, naphtha, kerosene, light gas oil, heavy gas oil, vacuum
`gas oil, light cycle oil, heavy cycle oil, coker naphtha, vis bro(cid:173)
`ken naphtha, coker gas oil, visbroken gas oil, and/or the like. 20
`Additionally and/or alternatively, it may be derived from or
`include hydrocarbons produced by one or more other refinery
`processes, such as cracking, catalytic cracking, hydrocrack(cid:173)
`ing, reforming, coking, dearomatization, isomerization, alky(cid:173)
`lation, and/or the like.
`Sulfur compounds may include carbonyl sulfide, hydrogen
`sulfide, mercaptans, sulfides, disulfides, cyclic thioethers,
`polycyclic thioethers, aromatic thioethers, thiophenes, ben(cid:173)
`zot