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WO2015084893A1 - Procédés de production de combustible/carburant - Google Patents

Procédés de production de combustible/carburant Download PDF

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Publication number
WO2015084893A1
WO2015084893A1 PCT/US2014/068238 US2014068238W WO2015084893A1 WO 2015084893 A1 WO2015084893 A1 WO 2015084893A1 US 2014068238 W US2014068238 W US 2014068238W WO 2015084893 A1 WO2015084893 A1 WO 2015084893A1
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Prior art keywords
catalyst
deoxygenation
present
reactor
hydrogen
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Ceased
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PCT/US2014/068238
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English (en)
Inventor
Thien Duyen Thi Nguyen
Krishniah Parimi
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Energia Tech Inc
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Energia Tech Inc
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Filing date
Publication date
Priority claimed from US14/094,487 external-priority patent/US9315736B2/en
Application filed by Energia Tech Inc filed Critical Energia Tech Inc
Publication of WO2015084893A1 publication Critical patent/WO2015084893A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel

Definitions

  • Catalysts are extensively used in a variety of industrial processes. Because of the diversity of the types of processes, there are many types of catalysts. The present inventors have made one or more discoveries pertaining to catalysts, methods of making catalysts, and methods of using catalysts. [0003] An example of one of the areas in which these discoveries may be applicable is the use of renewable feedstocks for producing transportation fuels such as for green energy technologies that seek to use bio-oils to replace petroleum feedstock for fuels. Bio-oils are advantageous raw fuel feedstocks because they are easy to obtain and therefore enable fuel cost stabilization and provide energy autonomy. Bio-oils are a renewable resource with significant environmental benefits.
  • One or more aspects of this invention pertains to catalysts.
  • One aspect of the invention is a catalyst.
  • the catalyst comprises a porous substrate and an electrolessly deposited catalytically effective metal coating having a nanoscale thickness.
  • Another aspect of the invention is a method of making a catalyst.
  • the method comprises providing a porous substrate, providing a solution that comprises a metal for electroless deposition (ELD), mixing the substrate with the solution, controlling the temperature of the mixture of the substrate and the solution, and ramping the temperature while adding a reducing agent incrementally or continuously so as to cause controlled electroless deposition of the metal as a catalytically active stable nanoscale coating of the substrate.
  • ELD electroless deposition
  • Another aspect of the invention is a method of deoxygenation.
  • the method comprises providing a catalyst comprising a porous substrate and an electrolessly deposited catalytically effective nanoscale metal coating on the substrate and contacting the catalyst with the oxygenated hydrocarbons and hydrogen so as to accomplish hydrogenation and deoxygenation wherein the deoxygenation is accomplished preferentially by decarbonylation and decarboxylation over hydrodeoxygenation.
  • the system comprises a deoxygenation stage, the deoxygenation stage comprises at least one deoxygenation reactor chamber and a catalyst, and the catalyst comprises a porous substrate and an electrolessly deposited metal coating having a nanoscale thickness.
  • the system further comprises a hydrocracking and isomerization stage comprising at least one hydrocracking and isomerization reactor and a hydrocracking and isomerization catalyst.
  • the hydrocracking and isomerization stage is configured to receive the liquid hydrocarbons from the deoxygenation stage and hydrogen.
  • the hydrocracking and isomerization stage operates at conditions to convert the liquid hydrocarbons from the deoxygenation stage into gasoline, diesel fuel, and/or aviation/jet fuel.
  • Figure 1 is a magnified image of a catalyst according to one embodiment of the present invention.
  • Figure 1 -1 is a typical Arrhenius plot for one or more embodiments of the present invention.
  • Figure 1 -2 is a graph showing Camelina oil composition.
  • Figure 1 -3 is gas chromatographic data of deoxygenated liquid product according to one or more embodiments of the present invention.
  • Figure 2 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 3 is a flow diagram for an example according to one or more
  • Figure 4 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 5 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 6 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 6-1 is a graph showing measurements of carbon monoxide and carbon dioxide for deoxygenation according to one or more embodiments of the present invention.
  • Figure 6-2 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 7 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 7-1 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 7-2 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 7-3 is a flow diagram according to one or more embodiments of the present invention.
  • Figure 7-4 is a flow diagram according to one or more embodiments of the present invention.
  • the range 10 to 15 includes, but is not limited to, 10, 10.1 , 10.47, 1 1 , 1 1 .75 to 12.2, 12.5, 13 to 13.8, 14, 14.025, and 15.
  • nanoscale is defined as having at least one dimension less than 100 nanometers.
  • porous substrate is defined as a pore structure that results in an equivalent surface area for the porous substrate in the range of 50 - 1500 square meters per gram (m 2 /g) of the porous substrate as measured by a technique such as the Brunauer Emmett Teller (BET) technique or an analogous technique. In other words, the porosity of the substrate is specified by the equivalent surface area for the porous substrate.
  • One aspect of the present invention encompasses a catalyst. Another aspect of the invention encompasses methods of making catalysts. Another aspect of the invention encompasses methods of using catalysts for applications such as, but not limited to, deoxygenation of compounds. Another aspect of the invention encompasses methods of making carbon-based fuels such as, but not limited to, jet fuel, gasoline, and diesel fuel using feedstocks derived from sources such as, but not limited to, plants and other renewable sources.
  • One aspect of the present invention is a catalyst such as for promoting one or more chemical reactions.
  • Catalysts according to one or more embodiments of the present invention comprise a porous substrate and one or more metals dispersed on and/or within the substrate including surfaces forming the pores of the substrate.
  • the metal is or can be made to be catalytically active.
  • the metal is an electrolessly deposited catalytically effective metal coating having a nanoscale thickness. This means that for one or more embodiments of the present invention, the metal is deposited electrochemically by electroless deposition.
  • the porous substrate has a surface area equivalent of 50-1500 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate has a surface area equivalent in the range of 50-100 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate has a surface area equivalent in the range of 100-300 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate has a surface area equivalent in the range of 300-900 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate has a surface area equivalent in the range of 900-1500 m 2 /g.
  • substrates can be used for one or more embodiments of the present invention.
  • suitable substrates for embodiments of the present invention include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica-alumina, silica, zeolites, titania, zirconia, magnesia, chromia, monoliths, or combinations thereof.
  • substrates for one or more embodiments of the present invention may be granular or pelletized.
  • the substrates have low levels of impurities that could interfere with the activity of the catalysts.
  • activated carbon substrates preferably have low metal content and low ash content for some embodiments of the present invention.
  • the impurity levels of some activated carbon can be reduced by an acid wash of the substrate prior to preparation of the catalyst.
  • the substrate has pores 0.2 nm to 10 nm wide. According to another embodiment of the present invention, the substrate has pores 0.2 nm to 10 nm wide and the catalytic metal is present in the pores.
  • the catalyst is substantially stable during the preparation processes, during the activation processes if applicable, and during extended periods of use as a catalyst.
  • the substrates are porous.
  • the catalyst comprises one or more metals such as, but not limited to, palladium (Pd), nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), platinum (Pt), zinc (Zn), silver (Ag), copper (Cu), gold (Au), or mixtures thereof.
  • the catalyst may be configured as a single metal catalyst, as a bi-metallic catalyst, or as a tri-metallic catalyst.
  • the metals may be mixed so that they form an alloy such as palladium and nickel in an alloy.
  • the elements may be present as substantially pure elements.
  • the metal comprises palladium formed as nanoscale palladium deposited on the substrate surfaces including, but not limited to, the surfaces of pores.
  • Metals other than palladium may be used in the catalytic materials for one or more embodiments of the present invention.
  • Substrates for one or more embodiments of the present invention include activated carbon such as coconut activated carbon.
  • the metal is electrolessly deposited using electroless deposition processes so that the metal is substantially free of electroless deposition impurities.
  • metal deposition is electroless deposition accomplished with reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof.
  • reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof.
  • the metal deposition is accomplished with hydrazine incrementally or continuously added during the deposition so that the reducing agent input is distributed.
  • the loading of the metal is less than 15% by weight. According to another embodiment of the present invention, the loading of the metal is less than 5% by weight. According to yet another embodiment of the present invention, the loading of the metal is less than 1 % by weight.
  • the catalyst is catalytically active for deoxygenation of molecules such as oxygenated
  • catalysts are catalytically active for preferential deoxygenation by decarbonylation and
  • decarbonylation and decarboxylation over hydrodeoxygenation is defined as greater than or equal to 60% of oxygen is removed from oxygenated hydrocarbon as carbon dioxide and carbon monoxide and less than or equal to 40% of the oxygen is removed as water at all levels of deoxygenation.
  • the catalyst is catalytically active so as to be capable of preferential deoxygenation by decarbonylation and decarboxylation over hydrodeoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic acids, phenolics, esters, or mixtures thereof by decarbonylation and decarboxylation over hydrodeoxygenation.
  • Catalysts according to one or more embodiments of the present invention are capable of hydrogenation and preferential deoxygenation of triglycerides by decarbonylation and decarboxylation over
  • the metal comprises palladium
  • the substrate has pores 0.2 nm to 1 0 nm wide with the metal present therein
  • the catalyst is active for deoxygenation of triglycerides.
  • the catalyst is catalytically active for hydrogenation and preferential deoxygenation of triglycerides by decarbonylation and decarboxylation over hydrodeoxygenation so that the ratio of odd carbon number molecules to even carbon number molecules in the deoxygenated product is about 6:1 . This ratio is typically less than one for other deoxygenation technologies.
  • Another embodiment of the present invention is a catalyst for deoxygenating bio-oils for fuel production.
  • the catalyst comprises a substrate comprising activated carbon in granular form with size in the range of 0.5 mm to 3 mm.
  • the substrate has pores 0.2 nm to 1 0 nm wide.
  • the catalyst comprises an electrolessly deposited catalytically effective palladium or nickel coating having nanoscale thickness disposed on the surfaces of the pores.
  • the palladium or nickel loading for the catalyst is less than about 2% by weight.
  • the metal comprises palladium grains about 1 5 nanometers wide.
  • One or more embodiments of the present invention comprises a catalyst produced by one or more of the catalyst synthesis processes provided in the present disclosure. More specifically, one or more embodiments of the present invention encompass a product by process. One or more methods of preparing catalysts, according to embodiments of the present invention, produces catalysts having unique properties such as, but not limited to, morphology, particle size, particle distribution, and chemical reactivity. [0045] Catalysts according to one or more embodiments of the present invention can be made using the exemplary processes presented below.
  • Catalysts according to one or more embodiments of the present invention are made using electroless deposition processes that include one or more steps such as, but not limited to, improving bath stabilization, distributing the introduction of reducing agent, and ramping the temperature of the plating bath. According to one or more embodiments of the present invention, the distributed introduction of the reducing agent is coupled with the ramping of the temperature.
  • One or more embodiments of the present invention are the first instance of electroless deposition of nanoscale palladium coatings on activated carbon. The catalyst is stable and effective for reactions such as deoxygenation.
  • deoxygenation catalyst is produced with suitable palladium particle size and distribution in the pore structure of the substrate to enable effective deoxygenation of bio-oils at even very low metal loading.
  • Catalysts produced according to one or more embodiments of the present invention have suitable palladium distribution within the pore structure of the substrate to enable high catalytic activities under low metal loading.
  • Deposition of palladium on a substrate according to one or more embodiments of the present invention may be achievable in shorter time as compared to conventional deposition methods such as incipient wetness impregnation.
  • FIG. 1 a magnified image of a catalyst according to one embodiment of the present invention.
  • the surface is magnified 100,000 X.
  • the catalyst comprises a substrate of activated carbon and a coating of electrolessly deposited palladium using an exemplary process presented below.
  • a group of the particles was vacuum encapsulated in epoxy and then sectioned using standard metallographic materials and procedures.
  • the resulting sectioned specimens were then examined, first by conventional scanning electron microscopy (SEM).
  • SEM scanning electron microscopy
  • the first examination suggested that there had been extensive penetration into and deposition of palladium.
  • the second examination Field Emission SEM showed that almost all interior surfaces were coated with palladium.
  • Palladium was present in islands that sometimes coalesce, but are often still discontinuous. The islands vary greatly in size, but appear to consist of grains about 15 nm across. The islands were also present on the deep interior surface of the particles.
  • Catalysts according to one or more embodiments of the present invention were tested.
  • the catalyst had from 0.5% to 5% palladium loading.
  • the catalyst showed very little effect of catalytic metal loading on deoxygenation activity (see Table 1 ).
  • the catalyst was found to be very active for deoxygenation activity with activation energy of about 54 kcal/g-mole for deoxygenation of Camelina oil.
  • the activation energy is typical of active zeolite based hydrocracking catalysts.
  • the specific substrate-active metal combination appears to promote decarbonylation of plant oils in preference to hydrodeoxygenation in removing oxygen from the oil molecule. This is highly advantageous in process design for applications such as converting plant oils to biofuels and is an exceptional and unexpected result.
  • FIG. 1 -2 is a gas chromatograph (GC) trace showing the composition of
  • the method comprises 12 providing a porous substrate and 14 providing a solution that comprises a metal for electroless deposition.
  • the method further comprises 16 mixing the substrate with the solution and 18 controlling the temperature of the mixture of the substrate and the solution.
  • the method comprises 20 ramping up the temperature of the mixture while adding a reducing agent incrementally or continuously so as to cause controlled electroless deposition of the metal as a catalytically active nanoscale coating of the substrate.
  • the controlled deposition includes control of the rate of deposition of the metal and control of the location of the deposited metal.
  • the deposition rate is controlled by the distributed addition of the reducing agent in combination with the controlled ramping up of the temperature so as to allow the rate of mass transfer to allow more thorough distribution of the metal through the porous substrate for the metal deposition.
  • the reducing agent is added continuously or incrementally during most or all of the duration of the electroless deposition of the metal.
  • the method includes using a porous substrate having a surface area equivalent of 50-1500 m 2 /g.
  • the porous substrate has a surface area equivalent in the range of 50-100 m 2 /g.
  • the porous substrate has a surface area equivalent in the range of 100-300 m 2 /g.
  • the porous substrate has a surface area equivalent in the range of 300-900 m 2 /g.
  • the porous substrate has a surface area equivalent in the range of 900-1500 m 2 /g.
  • substrates can be used for methods of making catalysts according to one or more embodiments of the present invention.
  • suitable substrates for embodiments of the present invention include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica, silica-alumina, zeolites, titania, zirconia, magnesia, chromia, monoliths, or combinations thereof.
  • substrates for one or more embodiments of the present invention may be granular or pelletized.
  • the method includes using a substrate having pores 0.2 nm to 10 nm wide. According to another embodiment of the present invention, the method includes depositing metal into substrate pores 0.2 nm to 10 nm wide.
  • the method comprises electrolessly depositing one or more metals such as, but not limited to, palladium, nickel, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, platinum, zinc, silver, copper, gold, or mixtures thereof.
  • the catalyst may be produced as a single metal catalyst, as a bi-metallic catalyst, or as a tri-metallic catalyst.
  • the metals may be mixed so that they form an alloy or the elements may be present as substantially pure elements.
  • the deposition of two or more metals may be done as co-deposition or as sequential deposition of the metals.
  • the method comprises electroless deposition of palladium formed as nanoscale palladium deposited on the substrate surfaces including, but not limited to, the surfaces of pores.
  • the metal is electrolessly deposited using electroless deposition processes so that the metal is substantially free of electroless deposition impurities.
  • the method electrolessly deposited metal using reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof.
  • the method comprises adding hydrazine incrementally or continuously during the deposition so that the reducing agent input is distributed over most or all of the duration of the deposition.
  • the method includes electroless deposition to accomplish a metal loading of less than 1 5% by weight.
  • the method includes electroless deposition to accomplish a metal loading of less than 5% by weight.
  • the method includes electroless deposition to accomplish a metal loading of less than 1 % by weight.
  • the method further comprises sensitizing the substrate prior to electroless deposition such as by, but not limited to, exposing the substrate to a sensitizing solution, exposing the substrate to a solution comprising a dissolved metal, and/or exposing the substrate to a tin chloride solution.
  • the method further comprises activating the substrate prior to electroless deposition such as by, but not limited to, exposing the substrate to an activating solution, exposing the substrate to a solution comprising a dissolved metal, and/or exposing the substrate to a palladium chloride solution.
  • the method further comprises sensitizing the substrate prior to electroless deposition by exposing the substrate to a tin chloride solution followed by activating the substrate by exposing the substrate to a palladium chloride solution.
  • the method uses a substrate that comprises activated carbon, carbon foam, alumina, metal foam, silica-alumina, silica, zeolites, titania, zirconia, magnesia, chromia, monoliths, or combinations thereof and electrolessly deposits metal that comprises chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, platinum, zinc, copper, gold, silver, or mixtures thereof using a reducing agent that comprises hydrazine, aldehydes, carboxylic acids having 1 -6 carbon atoms, or mixtures thereof.
  • the method comprises providing a substrate that comprises granular activated carbon, exposing the substrate to a tin chloride solution so as to sensitize the activated carbon for electroless deposition, and exposing the substrate to a palladium chloride solution so as to activate the activated carbon for electroless deposition.
  • the method also includes providing a solution of palladium for electroless deposition and mixing the substrate with the solution.
  • the method further includes controlling the temperature of the mixture of the substrate and the solution and ramping up the temperature while adding hydrazine incrementally or continuously so as to cause controlled electroless deposition of the palladium as a catalytically active nanoscale coating of the activated carbon.
  • the method comprises providing a substrate that comprises granular activated carbon, exposing the substrate to a tin chloride solution so as to sensitize granular activated carbon for electroless deposition, and exposing the substrate to a palladium chloride solution so as to activate the granular activated carbon for electroless deposition.
  • the method also includes providing a solution of nickel for electroless deposition and mixing the substrate with the solution.
  • the method further includes controlling the temperature of the mixture of the substrate and the solution and ramping up the temperature while adding hydrazine incrementally or continuously so as to cause controlled electroless deposition of the nickel as a catalytically active nanoscale coating of the granular activated carbon.
  • Step 3 shows a flowchart of the steps for preparing the catalysts of the present example.
  • Steps 101 to 104 constitute substrate preparation and are described as follows:
  • Step 101 14 grams of coconut activated carbon (CAC) in granular form with size in the range of 1 .6 mm to 0.8 mm were measured using an analytical balance.
  • Step 102 The CAC was placed in aluminum weighing dish and placed in a vacuum oven. The oven temperature was raised and maintained at 125 °C. The CAC was baked for 12 hours.
  • Step 103 Nitrogen gas was vented into the vacuum oven to reach atmospheric pressure.
  • CAC coconut activated carbon
  • Step 104 The CAC sample was placed in glass beaker with a magnetic stirrer and mixed with 50 ml of 0.2 N HCI acid for 30 minutes. The CAC sample was filtered from the acid solution.
  • Steps 105 to 108 constitute substrate sensitizing and activation and are described as follows: Step 105: In the sensitizing glass beaker, 125 ml of 0.2N HCI was mixed with 0.125 g SnCI 2 until the particles are fully dissolved using the magnetic stirrer. In the activation glass beaker, 125 ml of 0.2 N HCI was mixed with 0.01 125 g PdCI 2 until the particles were fully dissolved using the magnetic stirrer. The CAC sample was put into the sensitizing beaker and mixed for 5 minutes. The CAC sample was filtered from the sensitizing solution. Step 1 06: The CAC sample was mixed in 500 ml of deionized (Dl) H 2 0 for 10 minutes.
  • Dl deionized
  • Step 107 The CAC sample was put into the activation beaker and mixed for 5 minutes. The CAC sample was filtered from the activation solution. Step 108: The CAC sample was mixed in 500 ml of deionized (Dl) H 2 0 for 10 minutes. The CAC sample was filtered from the Dl H 2 0.
  • Dl deionized
  • Steps 109 to 1 12 constitute plating of Pd on an activated carbon substrate and are described as follows: Step 109: In a glass beaker for plating solution, 70 ml of 28% NH 4 OH, 30 ml Dl H 2 0, 0.54 g of PdCI 2 , and 4 g Na 2 EDTA were mixed with a magnetic stirrer until the plating solution was fully dissolved. The temperature of the water bath of the Rotovap was raised to 40° C; 0.1 ml of 35% N 2 H 4 was added to the plating solution and mixed. The plating solution was combined with the CAC sample in a flask attached to the water bath in the Rotovap. The rotation was adjusted to evenly distribute the CAC in the plating solution. [0069] After 10 minutes, one drop of N 2 H 4 was added to the plating solution and the temperature was increased to 45 °C while the plating solution and CAC were
  • Step 1 1 0 The CAC sample was mixed in 500 ml of deionized (Dl) H 2 0 for 30 minutes. The Pd deposited CAC sample was filtered from the Dl H 2 0. The Pd deposited CAC sample was mixed in 500 ml of deionized Dl H 2 0 for 30 minutes. The Pd deposited CAC sample was filtered from the Dl H 2 0. Step 1 1 1 : The Pd deposited CAC was placed in an aluminum weighing dish and placed in a vacuum oven. The vacuum pump was turned on and a vacuum of 25 inches of Hg was maintained in the vacuum oven. The oven temperature was raised and maintained at 1 25 °C.
  • Step 1 1 2 Nitrogen gas was vented into the vacuum oven until atmospheric pressure was reached.
  • the Pd deposited CAC sample was taken out of the oven and immediately weighed on the analytical balance to obtain the actual weight of Pd deposited CAC without moisture.
  • the weight difference between step 1 1 2 and step 1 03 represents the quantity of Pd deposited onto 14 grams of coconut activated carbon.
  • Methods of making catalysts according to one or more embodiments of the present invention may comprise using other granular, pelletized, or structured substrates derived from ceramics or metal. Methods according to one or more embodiments of the present invention may comprise using a structured substrate such as monolith or metal foam for various applications.
  • Example 2 Catalyst Preparation - Palladium on Alumina
  • Extrudated gamma-alumina substrate material was crushed using a ceramic mortar and pestle and sifted to obtain particles in the size range of 1 .6 mm to 0.8 mm.
  • An analytical balance was used to measure 14 grams of this gamma alumina substrate.
  • the gamma alumina was baked in a vacuum oven for 12 hours and the dry weight of the gamma alumina substrate was obtained from the analytical balance.
  • the gamma alumina was hydrated by being exposed to steam for 2 hours to minimize gamma alumina decrepitation prior to the sensitizing step.
  • 125 ml of 0.2N HCI was mixed with 0.125 g SnCI 2 until the particles were fully dissolved using a magnetic stirrer.
  • 125 ml of 0.2 N HCI was mixed with 0.01 125 g PdCI 2 until the particles were fully dissolved using a magnetic stirrer.
  • the gamma alumina sample was put into a sensitizing beaker and mixed for 5 minutes. The gamma alumina sample was filtered from the sensitizing solution. The gamma alumina sample was mixed in 500 ml of Dl H 2 0 for 2 minutes. The gamma alumina sample was filtered from the Dl H 2 0. The gamma alumina sample was put into an activation beaker and mixed for 5 minutes. The gamma alumina sample was filtered from the activation solution. The gamma alumina sample was mixed in 500 ml of deionized Dl H 2 0 for 2 minutes. The gamma alumina sample was filtered from the Dl H 2 0.
  • the gamma alumina was put back into the sensitizing beaker and mixed for 5 minutes, filtered, and rinsed in Dl H 2 0 for 2 minutes and filtered.
  • the gamma alumina was put back into the activation beaker and mixed for 5 minutes, filtered, and rinsed in Dl H 2 0 for 2 minutes and the gamma alumina was filtered out.
  • the Pd deposited gamma alumina sample was mixed in 500 ml of deionized (Di) H 2 0 for 10 minutes.
  • Pd deposited gamma alumina sample was filtered from the Dl H 2 0.
  • Pd deposited gamma alumina was placed in aluminum weighing dish and placed in a vacuum oven. The vacuum pump was turned on and a vacuum of 25 inches of Hg was maintained in the vacuum oven. The oven temperature was raised and maintained at 125 °C.
  • the Pd deposited gamma alumina was baked for 12 hours.
  • Nitrogen gas was vented into the vacuum oven to reach atmospheric pressure.
  • the Pd deposited gamma alumina sample was taken out of oven and immediately weighed on the analytical balance to obtain the actual weight of the Pd deposited gamma alumina without moisture.
  • the weight difference before and after Pd plating represents the quantity of Pd deposited onto 14 grams of gamma alumina.
  • the CAC sample was placed in glass beaker with a magnetic stirrer and mixed with 60 ml of 0.2 N HCI acid for 5 minutes. The CAC sample was filtered from the acid solution. The above rinse was repeated 4 more times, each time with a new 60 ml of 0.2 N HCI.
  • 185 ml of 0.2N HCI was mixed with 0.375 g SnCI 2 until the particles were fully dissolved.
  • 185 ml of 0.2 N HCI was mixed with 0.0341 g PdCI 2 until the particles were fully dissolved using a magnetic stirrer.
  • the CAC sample was put into a sensitizing beaker and mixed for 5 minutes. The CAC sample was filtered from the sensitizing solution.
  • the CAC sample was mixed in 500 ml of deionized (Di) H 2 0 for 5 minutes.
  • the CAC sample was filtered from the DI H 2 0.
  • the CAC sample was put into an activation beaker and mixed for 5 minutes.
  • the CAC sample was filtered from the activation solution.
  • the CAC sample was mixed in 500 ml of deionized (DI) H 2 0 for 10 minutes.
  • the CAC sample was filtered from the DI H 2 0.
  • the plating beaker also contained 3 Teflon baffles attached together and oriented 120 degrees apart.
  • the plating solution was poured into a 250 ml beaker containing the CAC sample.
  • the IKA mixer rpm was adjusted in the range of 200-400 in order to evenly distribute the CAC in plating solution.
  • N 2 H 4 was added to the plating solution and the temperature was increased to 70° C while the plating solution and CAC were continually mixed.
  • one drop of N 2 H 4 was added to the plating solution and the temperature was increased to 75° C while the plating solution and CAC were continually mixed.
  • one drop of N 2 H 4 was added to the plating solution and the temperature was increased to 79° C while the plating solution and CAC were continually mixed.
  • one drop of N 2 H 4 was added to the plating solution and the temperature was increased to 79.5° C while the plating solution and CAC were continually mixed.
  • the CAC sample was gently mixed in 100 ml of deionized (Dl) H 2 0 for 5 minutes.
  • the Ni deposited CAC sample was filtered from the Dl H 2 0.
  • a 100 ml water rinse was repeated as many times as necessary until the pH of the rinse solution reached 7.
  • the Ni deposited CAC sample was filtered from the Dl H 2 0.
  • the Ni deposited CAC was placed in aluminum weighing dish and placed in a vacuum oven.
  • the vacuum pump was turned on and a vacuum of 25 inches of Hg was maintained in the vacuum oven.
  • the oven temperature was raised and maintained at 125 °C.
  • the Ni deposited CAC was baked for 12 hours.
  • Nitrogen gas was vented into vacuum oven to reach atmospheric pressure.
  • the Ni deposited CAC sample was taken out of oven and immediately weighed on the analytical balance to obtain the actual weight of Ni deposited CAC without moisture.
  • the weight difference before and after the plating step represents the quantity of Ni deposited onto 22 grams of coconut activated carbon.
  • Another aspect of the invention is a method of deoxygenation.
  • Deoxygenation can occur by three mechanisms, which include hydrodeoxygenation where oxygen is mostly removed as H 2 O, decarbonylation where oxygen is mostly removed as CO, and decarboxylation where oxygen is mostly removed as CO 2 .
  • One or more embodiments of the present invention comprises using one or more catalysts as described above.
  • the selected catalyst is suitable for applications such as, but not limited to, hydrogenation, and deoxygenation of oxygenated
  • the catalysts have properties so that there is low or minimal undesirable by-product formation.
  • one or more embodiments of the present invention comprises using granular catalysts with low metal loading; the catalysts are effective for reactions such as, but not limited to, hydrogenation and deoxygenation of organic materials such as, but not limited to, bio-oils.
  • One or more embodiments of the present invention include using a reactor with the granular catalyst in a packed bed, the reactor and packed bed are arranged to operate in continuous multiphase flow mode.
  • embodiments of the present invention may use upflow mode or may use downflow mode for deoxygenation.
  • the flow in the deoxygenation reactor may be co-current flow or counter current flow.
  • the method comprises providing a catalyst that comprises a porous substrate and an electrolessly deposited catalytically effective nanoscale metal coating on the substrate.
  • the method also includes contacting the catalyst with the oxygenated hydrocarbons and hydrogen so as to accomplish hydrogenation and deoxygenation wherein the deoxygenation is accomplished preferentially by decarbonylation and decarboxylation over hydrodeoxygenation.
  • the method comprises providing a catalyst that comprises a porous substrate and an electrolessly deposited catalytically effective nanoscale metal coating on the substrate.
  • the method also includes contacting the catalyst with the oxygenated hydrocarbons and hydrogen so as to accomplish hydrogenation and deoxygenation wherein the deoxygenation is accomplished preferentially by decarbonylation and decarboxylation over hydrodeoxygenation.
  • the method comprises providing a catalyst that comprises a porous substrate and an electrolessly deposited catalytically effective nanoscale metal coating on the substrate.
  • the method also includes contacting the
  • the method includes generating 6 times more carbon monoxide than carbon dioxide for the deoxygenation.
  • results of the present invention are even more extraordinary because the high production levels of carbon monoxide occur even with the use of palladium as the metal for the catalyst.
  • Palladium is well known to those of ordinary skill in the art as being particularly susceptible to poisoning by carbon monoxide.
  • Experimental results obtained using embodiments of the present invention show that the palladium catalyst maintained its catalytic activity even in the presence of carbon monoxide at partial pressures as high as 0.1 megapascals for tested periods of operation as long as 100 hours.
  • Deoxygenation processes according to methods of the present invention may include the use of variety of substrates for the catalyst.
  • suitable substrates for embodiments of the present invention include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica, silica-alumina, zeolites, titania, zirconia, magnesia, chromia, monoliths, or combinations thereof.
  • substrates for one or more embodiments of the present invention may be granular or pelletized.
  • the deoxygenation process uses a substrate having pores 0.2 nm to 10 nm wide.
  • the substrate has pores 0.2 nm to 10 nm wide and the metal is present in the pores.
  • the catalyst used for the deoxygenation process comprises one or more metals such as, but not limited to, palladium, nickel, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, platinum, zinc, silver, copper, gold, or mixtures thereof.
  • the catalyst may be configured as a single metal catalyst, as a bimetallic catalyst, or as a tri-metallic catalyst.
  • the metals may be mixed so that they form an alloy or the elements may be present as substantially pure elements.
  • the metal comprises palladium formed as nanoscale palladium deposited on the substrate surfaces including, but not limited to, the surfaces of pores.
  • Metals other than palladium may be used in the catalytic materials for one or more embodiments of the present invention.
  • Substrates for one or more embodiments of the present invention include activated carbon such as coconut activated carbon.
  • the metal is electrolessly deposited using electroless deposition processes so that the metal is substantially free of electroless deposition impurities.
  • metal deposition is electroless deposition accomplished with reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof.
  • the metal deposition is accomplished with hydrazine incrementally or continuously added during the deposition so that the reducing agent input is distributed.
  • the loading of the metal is less than 15% by weight. According to another embodiment of the present invention, the loading of the metal is less than 5% by weight. According to yet another embodiment of the present invention, the loading of the metal is less than 1 % by weight.
  • the catalyst is catalytically active for deoxygenation of molecules such as oxygenated
  • catalyst is catalytically active for preferential deoxygenation by decarbonylation and decarboxylation over hydrodeoxygenation. Preferential deoxygenation by decarbonylation and
  • decarboxylation over hydrodeoxygenation is defined as greater than or equal to 60% of oxygen is removed from oxygenated hydrocarbon as carbon dioxide and carbon monoxide and less than or equal to 40% of the oxygen is removed as water.
  • the catalyst is catalytically active so as to be capable of preferential deoxygenation by decarbonylation and decarboxylation over hydrodeoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic acids, phenolics, esters, or mixtures thereof by decarbonylation and decarboxylation over hydrodeoxygenation.
  • Catalysts are capable of hydrogenation and preferential deoxygenation of triglycerides by decarbonylation and decarboxylation over
  • the activation energy for deoxygenation is about 54 kcal/g-mole for Camelina oil.
  • the metal comprises palladium
  • the substrate has pores 0.2 nm to 10 nm wide with the metal present therein
  • the catalyst is active for deoxygenation of triglycerides.
  • the catalyst is catalytically active for hydrogenation and preferential deoxygenation of triglycerides by decarbonylation and decarboxylation over hydrodeoxygenation so that the ratio of odd carbon number molecules to even carbon number molecules in the deoxygenated product is about 6:1 .
  • Another embodiment of the present invention is a catalyst for deoxygenating bio-oils for fuel production.
  • the catalyst comprises a substrate comprising activated carbon in granular form with size in the range of 0.5 mm to 3 mm.
  • the substrate has pores 0.2 nm to 10 nm wide.
  • the catalyst comprises an electrolessly deposited catalytically effective palladium or nickel coating having nanoscale thickness disposed on the surfaces of the pores.
  • the palladium or nickel loading for the catalyst is less than about 2% by weight.
  • the metal comprises palladium grains about 15 nanometers wide.
  • the metal coating of the catalyst is palladium and the method of deoxygenation is performed with the catalyst exposed to carbon monoxide partial pressure up to about 0.1 megapascals.
  • the oxygenated hydrocarbons comprise triglycerides
  • the substrate is activated carbon
  • the metal comprises palladium.
  • the method further includes contacting the catalyst with the oxygenated hydrocarbons and hydrogen so as to preferentially accomplish
  • the hydrocarbons comprise triglycerides
  • the substrate comprises activated carbon, carbon foam, alumina, metal foam, silica-alumina, silica, zeolites, titania, zirconia, magnesia, chromia, monoliths, or combinations thereof.
  • the metal is selected from the group consisting of chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, nickel, rhodium, iridium, palladium, platinum, zinc, gold, silver, copper, or mixtures thereof, and contacting the catalyst with the oxygenated hydrocarbons and hydrogen so as to preferentially accomplish deoxygenation by decarbonylation and decarboxylation over hydrodeoxygenation is accomplished at temperatures in the range 300 °C to 400 °C and pressures in the range 1 .5 megapascals to 15 megapascals.
  • the catalyst has a metal loading of less than or equal to about 2% with deoxygenation efficiency greater than about 90% or the catalyst has a metal loading of less than or equal to about 1 % with deoxygenation efficiency greater than about 90%.
  • the method includes using a weight hourly space velocity of 0.2 to 2.5. The weight hourly space velocity is calculated as the mass flow rate of the feed divided by the mass of catalyst.
  • Example 4 Deoxygenation Using Palladium on Activated Carbon
  • catalysts were made with different Pd metal loading on coconut activated carbon.
  • the catalysts were placed in a packed bed reactor with the same operating parameters processing Camelina oil in continuous multiphase flow mode.
  • the results that were obtained were exceptional and unexpected with respect to the low metal loading and high percentage of deoxygenation.
  • Table 1 shows that high deoxygenation can be achieved at low metal loading.
  • catalysts with average metal loading of 5 weight % was made and loaded into a packed bed reactor to process Camelina oil in continuous operation for 100 operating hours. Sustained deoxygenation activity was observed over the duration of the continuous operation.
  • Palladium catalyst prepared according to one or more embodiments of the present invention may have significant cost advantages that can be gained by using lower metal loading to carry out deoxygenation of bio-oils.
  • Catalysts according to one or more embodiments of the present invention when used to carry out deoxygenation reaction, did not show any plugging or coking issues throughout a 500-hour continuous run in a packed bed reactor.
  • Catalysts according to one or more embodiments of the present invention achieve deoxygenation primarily through decarbonylation chemistry as evident by CO content in reactor gas outlet composition.
  • WHSV Weight Hourly Space Velocity
  • Methods of deoxygenation comprise using palladium catalyst material finely dispersed on activated carbon which may be prepared as described above.
  • the method uses the fine pore structure of the activated carbon. The method uses relatively higher temperatures to effectively hydrogenate and split feed molecules so that the fragments have easy access to the fine pore structure of the substrate.
  • the inventors have also used one or more embodiments of the present invention in test for 100 hours of continuous flow operation for deoxygenation of Camelina oil and showed that sustained catalyst activity was achieved under smooth reactor operation with no evidence of plugging or coking.
  • other embodiments of the present invention in test for 100 hours of continuous flow operation for deoxygenation of Camelina oil and showed that sustained catalyst activity was achieved under smooth reactor operation with no evidence of plugging or coking.
  • the method of preparing the catalysts allows penetration of nanocrystalline palladium into micropores of 0.4 to 2 nanometers. Small pore volume offers the most surface area for reactions. Methods according to one or more embodiments of the present invention have shown that large concentration of palladium is not needed in the catalysts, which is a result that is unexpected and exceptional and may be the result of having deposited the palladium perhaps substantially as a nanoscale coating.
  • the specific substrate-active metal combination appears to promote decarbonylation of oils, such as plant oils, in preference to hydrodeoxygenation in removing oxygen from the oil molecule. This is highly advantageous in process design for applications such as converting plant oils to biofuels and is an exceptional and unexpected result.
  • Figure 1 -3 is a gas chromatograph trace showing the composition of deoxygenated product produced according to one or more embodiments of the present invention. As the gas chromatograph shows, odd number carbon atoms dominate to the extent the ratio of odd and even number atoms is about 6 to 1 . In contrast to the results obtained using embodiments of the present invention, data reported for other processes show that the ratio of odd to even number carbon species is in the range from 0 to 1 .
  • One or more embodiments of the present invention result in about 60-65% of oxygen removed as oxides of carbon with only about one third going to make water. This is an unexpected and extraordinary result for one or more embodiments of the present invention.
  • One or more embodiments of the present invention comprises using a reactor space velocity that may be higher than in a typical hydroprocessing unit commonly used in petroleum refining. Processes according to one or more embodiments of the present invention use modest temperatures and modest hydrogen pressure. According to one embodiment of the present invention, the process includes using a conventional downflow fixed bed reactor. The option to use a fixed bed reactor makes the process easy to scale-up. Preferred embodiments of the present invention do not use a solvent during deoxygenation processes.
  • Example 5 Deoxygenation Using Palladium on Alumina Catalyst
  • Refined Camelina oil was the feedstock used in a deoxygenation reactor according to one or more embodiments of the present invention. Deoxygenation experiments were carried out in a continuous down-flow multiphase packed bed reactor. In this example, 6.1 grams of 0.5 wt% Pd on gamma alumina catalyst according to one or more embodiments of the present invention was loaded into a stainless steel reactor. The reactor was 0.305 inches in internal diameter and 10 inches in length with pre-heat and post-heat zones. The reactor volume was 12 cc. Heat for the reactor was supplied by a 3-zone temperature controlled furnace with heat equalizing blocks. Camelina oil feed was pumped at a 0.1 cc/min rate into the reactor. Liquid and gaseous products exiting the reactor were collected in a separator.
  • Backpressure regulators maintained operating system pressure at 500 psig.
  • the Pd on gamma alumina catalyst was reduced under hydrogen at 250 °C for 2 hours to activate the catalyst.
  • Reactor temperature was raised from 250 °C to 350 °C within 60 minutes.
  • Liquid Camelina oil feed was then pumped into the reactor at a 0.1 cc/min rate.
  • Hydrogen gas feed rate into the reactor was 70 cc/min.
  • the reactor temperature was maintained at 350 °C and the reactor was run for 10 hours.
  • the reactor gas product was analyzed using a gas chromatograph.
  • the major reactant gaseous product observed other than H 2 was CO.
  • Paraffinic wax product was separated from water by gravity. Elemental analysis was performed on the paraffinic wax product to determine the oxygen content of deoxygenated product. Oxygen elemental analysis showed approximately 96% of oxygen had been removed from the original Camelina oil feed.
  • Example 6 Deoxygenation Using Nickel on Activated Carbon Catalyst
  • Refined Camelina oil was the feedstock used in deoxygenation micro unit according to one or more embodiments of the present invention.
  • Deoxygenation experiments were carried out in a continuous down-flow multiphase packed bed reactor.
  • 6.1 grams of 0.9 wt% Ni on activated carbon catalyst according to one or more embodiments of the present invention was loaded into a stainless steel reactor.
  • the reactor was 0.305 inches in internal diameter and 10 inches in length with pre-heat and post-heat zones.
  • the reactor volume was 12 cc.
  • Heat for the reactor was supplied by a three-zone temperature controlled furnace with heat equalizing blocks. Liquid and gaseous products exiting the reactor were collected in a separator. Backpressure regulators maintained operating system pressure at 1000 psig.
  • the Ni on the activated carbon catalyst was reduced under hydrogen at 250 °C for 2 hours to activate the catalyst.
  • the Ni catalyst was used in bare metal form instead of as a sulfide form that is typical for the hyproprocessing industry.
  • Oxygen elemental analysis showed approximately 87% of oxygen had been removed from the original Camelina oil feed.
  • Catalysts according to one or more embodiments of the present invention promote decarbonylation and decarboxylation rather than hydrodeoxygenation.
  • the process consumes considerably less hydrogen for one or more possible benefits such as, but not limited to, favorable process economics, use of existing refinery
  • one or more processes according to embodiments of the present invention comprises a high yield of distillate fuels with low or minimal production of undesired by-products.
  • Deoxygenation reactors according to embodiments of the present invention comprise one or more of multiphase downflow packed bed configuration, continuous flow operation capability, and the absence of extraneous or process derived solvents or diluents.
  • a part of the process of producing synthetic biofuels from biosources is deoxygenation.
  • Deoxygenation can occur by three mechanisms, which include hydrodeoxygenation where oxygen is mostly removed as H 2 O, decarbonylation to where oxygen is mostly removed as CO, and decarboxylation where oxygen is mostly removed as CO 2 .
  • the processing of bio-oils which have a different chemistry than conventional petroleum oils have one or more problems that are overcome by one or more embodiments of the present invention.
  • embodiments of the present invention can efficiently convert any type of bio-oils and/or other suitable feedstocks
  • one or more of the following examples provide data for deoxygenation of non-edible bio-oils.
  • nonedible bio-oils include Tung, Jojoba, Jatropha, Camelina sativa, Tall, Crambe, Castor, Industrial Rapeseed, Cuphea, Lesquerella, and others.
  • Advancements in genetics engineering offer the possibilities for bio-oils to be extracted from oil seed crops that are hardy, drought tolerant, pest resistant, and can be grown on marginal soil to provide high oil weight content.
  • bio-oils can also be extracted from algae and other genetically engineered biological systems. Estimated bio-oil content from these sources can range from 25 wt% to 50 wt%.
  • System 300 comprises a deoxygenation stage 31 0 which comprises at least one deoxygenation reactor chamber 31 5 and a catalyst 320 contained in the deoxygenation reactor chamber 315.
  • Catalyst 320 comprises a porous substrate and an electrolessly deposited metal coating having a nanoscale thickness.
  • Catalyst 320 according to one or more embodiments of the present invention is essentially the same as catalysts described earlier in the present disclosure.
  • at least one deoxygenation reactor chamber 31 5 and the catalyst 320 are configured as a packed bed reactor to operate in continuous multiphase flow mode with hydrogen as a reactant.
  • the porous substrate of catalyst 320 has a surface area equivalent of 50-1 500 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate of catalyst 320 has a surface area equivalent in the range of 50-1 00 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate of catalyst 320 has a surface area equivalent in the range of 1 00-300 m 2 /g. According to one or more other embodiments of the present invention, the porous substrate of catalyst 320 has a surface area equivalent in the range of 300-900 m 2 /g.
  • the porous substrate of catalyst 320 has a surface area equivalent in the range of 900-1500 m 2 /g.
  • a variety of substrates can be used for catalyst 320.
  • suitable substrates for catalyst 320 include, but are not limited to, activated carbon, carbon foam, alumina, metal foam, silica, silica-alumina, zeolites, titania, zirconia, magnesia, chromia, monoliths, or combinations thereof.
  • substrates catalysts 320 may be granular or pelletized.
  • the substrate of catalyst 320 has pores 0.2 nm to 10 nm wide. According to another embodiment of the present invention, the substrate of catalyst 320 has pores 0.2 nm to 10 nm wide and the metal is present in the pores.
  • catalyst 320 comprises one or more metals such as, but not limited to, palladium (Pd), nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), platinum (Pt), zinc (Zn), silver (Ag), copper (Cu), gold (Au), or mixtures thereof.
  • metals such as, but not limited to, palladium (Pd), nickel (Ni), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), platinum (Pt), zinc (Zn), silver (Ag), copper (Cu), gold (Au), or mixtures thereof.
  • catalyst 320 may be configured as
  • the metal comprises palladium formed as nanoscale palladium deposited on the substrate surfaces including, but not limited to, the surfaces of pores.
  • Metals other than palladium may be used in the catalytic materials for one or more embodiments of the present invention.
  • Substrates for one or more embodiments of the present invention include activated carbon such as coconut activated carbon.
  • the metal is electrolessly deposited using electroless deposition processes so that the metal is substantially free of electroless deposition impurities.
  • metal deposition is electroless deposition accomplished with reducing agents such as, but not limited to, hydrazine, aldehydes, carboxylic acids with up to 6 carbon atoms, or mixtures thereof.
  • the metal deposition is accomplished with hydrazine incrementally or continuously added during the deposition so that the reducing agent input is distributed.
  • the loading of the metal is less than 15% by weight. According to another embodiment of the present invention, the loading of the metal is less than 5% by weight. According to yet another embodiment of the present invention, the loading of the metal is less than 1 % by weight.
  • catalyst 320 is catalytically active for deoxygenation of molecules such as oxygenated
  • catalyst 320 is catalytically active for preferential deoxygenation by decarbonylation and decarboxylation over hydrodeoxygenation. Preferential deoxygenation by decarbonylation and
  • decarboxylation over hydrodeoxygenation is defined as greater than or equal to 60% of oxygen is removed from oxygenated hydrocarbon as carbon dioxide and carbon monoxide and less than or equal to 40% of the oxygen is removed as water.
  • catalyst 320 is catalytically active so as to be capable of preferential deoxygenation by decarbonylation and decarboxylation over hydrodeoxygenation of alcohols, ethers, aldehydes, ketones, carboxylic acids, phenolics, esters, or mixtures thereof by decarbonylation and decarboxylation over hydrodeoxygenation.
  • Catalyst 320 according to one or more embodiments of the present invention is capable of hydrogenation and preferential deoxygenation of triglycerides by decarbonylation and decarboxylation over
  • the activation energy for deoxygenation is about 54 kcal/g-mole for Camelina oil when using catalysts 320.
  • the metal of catalyst 320 comprises palladium
  • the substrate has pores 0.2 nm to 10 nm wide with the metal present therein
  • the catalyst is active for deoxygenation of triglycerides.
  • catalyst 320 is catalytically active for hydrogenation and preferential deoxygenation of triglycerides by decarbonylation and decarboxylation over hydrodeoxygenation so that the ratio of odd carbon number molecules to even carbon number molecules in the deoxygenated product is about 6:1 .
  • Catalyst 320 comprises a substrate comprising activated carbon in granular form with size in the range of 0.5 mm to 3 mm.
  • the substrate has pores 0.2 nm to 10 nm wide.
  • Catalyst 320 comprises an electrolessly deposited catalytically effective palladium or nickel coating having nanoscale thickness disposed on the surfaces of the pores.
  • the palladium or nickel loading for catalyst 320 is less than about 2% by weight.
  • catalyst 320 comprises palladium grains about 15 nanometers wide.
  • system 300 further comprises a three-phase separator configured to receive effluent from deoxygenation stage 310 and to separate water, liquid hydrocarbons, and gases from the effluent into separate streams.
  • system 300 further comprises a hydrocracking and isomerization stage 350 comprising at least one hydrocracking and isomerization reactor 355 and a hydrocracking and isomerization catalyst 360.
  • Hydrocracking and isomerization stage 350 is configured to receive the liquid hydrocarbons from deoxygenation stage 310 and hydrogen.
  • Hydrocracking and isomerization stage 350 operates at conditions to convert the liquid hydrocarbons from deoxygenation stage 310 into gasoline, diesel fuel, and/or aviation/jet fuel. More specifically, hydrocracking and isomerization stage 350 is configured to operate at temperatures and pressures to accomplish converting the hydrocarbons into the fuels.
  • Hydrocracking and isomerization catalyst 360 may be one or more commercially available catalyst for hydrocracking and isomerization.
  • deoxygenation stage 310 comprises two or more deoxygenation reactor chambers 315 each containing catalyst 320.
  • the two or more deoxygenation reactor chambers 315 are connected in series (not shown in Figure 4).
  • deoxygenation stage 310 comprises two or more deoxygenation reactor chambers 315 each containing catalyst 320 or a mixture of catalysts.
  • the two or more deoxygenation reactor chambers 315 are connected in series and system 300 further comprises a separator system to remove carbon monoxide, light gases, carbon dioxide, and water from the effluent stream connecting the two or more deoxygenation reactor chambers 315 between the two or more deoxygenation reaction chambers (additional reaction chambers and separator not shown in Figure 4).
  • system 300 further comprises a product separation stage 370 configured to receive products from hydrocracking and isomerization stage 350 and separate the products into diesel fuel, gasoline, and/or aviation/jet fuel.
  • System 300 further comprises a separator 375 comprising more than one separation stage to separate hydrogen from hydrocracking isomerization stage 350 effluent for recycle back to hydrocracking isomerization stage 350.
  • System 400 for producing fuel from feedstocks such as renewable feedstocks such as, but not limited to, bio-oils and other oxygenated hydrocarbons.
  • System 400 comprises a
  • System 400 further comprises a separator 410 configured to receive the gases from three phase separator 335 and to separate hydrogen from carbon monoxide, carbon dioxide, and light gases. Separator 41 0 is connected to provide hydrogen to deoxygenation stage 31 0 or to hydrocracking stage 350.
  • System 400 further comprises a steam reformer and water gas shift stage 420 connected so as to receive carbon monoxide, C0 2 , and light gases from separator 41 0 and light gases from product separation stage 370.
  • Steam reformer and water gas shift stage 420 produces hydrogen from the gases that it receives using water gas shift reactions and/or reformer and provides the hydrogen to deoxygenation stage 31 0 and/or hydrocracking and isomerization stage 350.
  • system 400 comprises a three-phase separator 335 configured to receive effluent from the deoxygenation stage and to separate water, liquid hydrocarbons, and gases from the effluent into separate streams; and a second separator 41 0 and reformer/shift stage 420 to produce hydrogen from the carbon monoxide and the light gases.
  • the deoxygenation stage comprises two or more deoxygenation reactor chambers connected in series and a separator to remove carbon monoxide, carbon dioxide, water, and light gases from the stream between the two or more deoxygenation reaction chambers.
  • Another separator is used to separate hydrogen from the carbon monoxide, the carbon dioxide, and light gases.
  • a reformer/shift reactor is included to produce hydrogen from the carbon monoxide and the light gases.
  • a basic process is to deoxygenate the naturally occurring, nonedible bio-oils or algae oil to produce corresponding alkanes and further treat them to produce specification biofuels.
  • the treatment process involves hydrocracking and isomerization.
  • One or more embodiments of the present invention include a two-stage process wherein the first process involves deoxygenating the oil using catalysts and operating conditions according to one or more embodiments of the present invention to suppress water formation.
  • the second stage of the process comprises hydroprocessing of the first stage product in a second stage reactor.
  • the total gas and liquid mixture from the first stage reactor is cooled and flashed to remove the gases and light liquid products, if any.
  • the three-phase separator also removes any water produced in the first stage deoxygenation reactor to avoid degradation of the second stage catalyst.
  • the hydrogen feed gas in the first-stage reactor is operated in once-through mode.
  • the gas mixture from the three-phase separator will contain large amounts of CO and hydrogen besides CO 2 and other light hydrocarbon product gases.
  • the ratio of CO to CO 2 from the first-stage product gas mixture is significantly higher than reported in literature by others.
  • this gas mixture can be used as a source for hydrogen generation or used to produce the needed process heat.
  • the product gas from the first stage after removal of water and other heavy condensable can be further processed to separate hydrogen from CO, CO 2 , and light hydrocarbons.
  • the recovered hydrogen can then be returned to the reactor.
  • the stream containing some hydrogen, CO, CO 2 , and light hydrocarbon gases can be made to go through steam reforming and water-gas-shift reactions to produce hydrogen which can be used as make-up to both the first and the second stage reactors.
  • the light hydrocarbon gas stream can be supplemented by addition of some light liquid products from the process so as to meet the total requirement of make-up hydrogen for the process.
  • Another option would be to use the separated CO, CO 2 , and light hydrocarbon gas stream for combustion in a furnace to provide the necessary process heat to the unit. In this mode of operation, a single recycle gas stream and one recycled gas compressor can be used for both stages for further simplification of the overall flow scheme.
  • the liquid product from the first-stage deoxygenation reactor will be primarily be a mixture of straight chain normal paraffins with a low melting point. These are mixed with a fresh stream of recycle hydrogen and passed through another fixed bed reactor to conduct isomerization and mild hydrocracking reactions.
  • Product from the second-stage reactor will have hydrocarbon components that boil in the gasoline, jet, and diesel range temperatures.
  • a suitable commercially available hydroprocessing catalyst that provides these functions is housed in the second-stage reactor.
  • the first- stage deoxygenation reactor used deoxygenation catalyst according to one or more embodiments of the present invention made by processes according to one or more embodiments of the present invention.
  • the deoxygenation process uses process conditions according to one or more embodiments of the present invention.
  • Liquid product from the first-stage conversion was analyzed using GC/MS and a trace for the liquid product from deoxygenation of Camelina oil is shown in Figure 1 -3.
  • the GC trace showed that the paraffinic product primarily contained paraffins with chain length that is one carbon less than the original fatty acid composition when compared with Figure 1 - 2.
  • the results indicate that liquid product is primarily paraffinic product and also indicate that deoxygenation is mostly achieved through production of CO and CO 2 rather than water.
  • the ratio of odd to even number carbon species in the liquid product from the first stage is an indicator of the predominant mechanism for deoxygenation:
  • decarbonylation, decarboxylation, or hydrodeoxygenation The higher ratio indicates that the more predominant mechanism is the decarbonylation or decarboxylation mechanism (producing oxides of carbon rather than water).
  • Experimental results for embodiments of the present invention show this ratio is about 6 in the liquid product; however, in other deoxygenation technologies, the ratio is typically less than 1 .
  • a low ratio is an indication that large quantities of water are produced by hydrodeoxygenation and the process consumes large quantities of hydrogen.
  • the ratio of CO to CO 2 obtained using deoxygenation catalyst and processes according to one or more embodiments of the present invention is approximately 6, which indicates that deoxygenation for embodiments of the present invention is primarily as decarbonylation.
  • the ratio of CO to C0 2 is from 0 to 2.
  • the higher CO content in the gas product mixture has advantages for use as fuel and for hydrogen generation.
  • Hydroprocessing units and associated catalysts are unique at least in part because of their capability to selectively convert different types of bio-oils into aviation and other transportation fuels with performance characteristics comparable to conventional petroleum based products.
  • Long chain alkanes resulting from deoxygenation of oils can be cracked in the presence of hydrogen and catalysts to produce bio-jet fuel (boiling temperature range 1 18-314 °C) and bio-diesel fuel (boiling temperature range 262-407 °C).
  • the alkane chain can be isomerized to produce branched hydrocarbons.
  • the product can be customized by controlling the degree of cracking and isomerization to produce "designer" bio-jet and bio-diesel fuels with specific desirable properties.
  • One embodiment of the present invention is a process to produce diesel and aviation fuels from renewable bio-feedstocks.
  • the specific bio-feedstocks are vegetable oils and cellulose-derived bio-oils. Pyrolysis, liquefaction, or microbial means can be used to produce bio-oils from cellulosic materials like wood chips, farm residues, or municipal waste.
  • the oil should pass though a pre-treating step to rid it of contaminants and potential catalyst poisons.
  • the pre-treating step may only consist of acid washing steps and treatment with an ion exchange material.
  • extensive pre-treatment steps are needed to improve their processibility. They should undergo significant upgrading to remove contaminants and to improve stability.
  • These oils whether derived from crop oils or cellulosic bio-oils, consist of oxygen in significant amounts in addition to carbon and hydrogen in their constituent molecule. The process described here consists of steps to remove this oxygen.
  • the resultant molecule is a straight-chain paraffin.
  • the paraffin is further subjected to additional processing steps to yield a bio-fuel to meet all the specifications of transportation fuels.
  • the process to convert renewable feedstocks like crop oils therefore, consists of two process steps: oxygen removal and isomerization/mild cracking to produce the final biofuel product.
  • the first step consists of breaking the triglyride backbone, hydrogenating to saturate the molecule, and removing oxygen (deoxygenation) from the oil molecule.
  • the deoxygenation is a catalytic reaction in the presence of a catalyst and hydrogen.
  • Hydrogen is a reactant.
  • the catalyst is loaded into a continuous flow fixed bed reactor. Hydrogen gas and the bio-oil feedstock are mixed together ahead of the reactor, heated to reaction temperature in a feed furnace, and reacted in the continuous flow fixed bed reactor.
  • a catalyst such as that according to one or more embodiments of the present invention, is loaded into the reactor and preferentially removes oxygen by
  • decarbonylation and decarboxylation rather than hydrodeoxygenation.
  • Decarbonylation produces carbon monoxide
  • decarboxylation produces carbon dioxide
  • Cold hydrogen gas is used to quench the reaction/product mixture between catalyst beds in a multi-bed reactor. Higher water generation in the reactor also can cause damage to the integrity and mechanical strength of the catalyst under certain situations.
  • the total gas and liquid mixture from the reactor is cooled and flashed to remove the gases and light liquid products, if any.
  • the liquid product will be primarily a mixture of straight chain normal paraffins with a low melting point. These are mixed with a fresh stream of recycle hydrogen and passed through another fixed bed reactor to conduct isomerization and mild hydrocracking reactions.
  • a suitable catalyst that provides these functions is housed in this reactor. Product from this reactor will have hydrocarbon components that boil in the gasoline, jet, and diesel range temperatures.
  • the liquid stream separated from the gas stream is distilled to yield the required jet and diesel fuel in addition to other light liquid and gases which are disposed of or used as in any conventional refinery.
  • the light liquid products can be light paraffins that result from mild hydrocracking that occurs in the second-stage reactor.
  • the recycle hydrogen gas from the first stage can be operated in once- through mode.
  • the once-through recycle hydrogen gas will contain large amounts of CO and hydrogen besides CO 2 and other light hydrocarbon product gases.
  • This gas mixture can be a good source for hydrogen generation or to produce the needed process heat.
  • the unit can be operated in recycle gas mode by continuously removing CO, CO 2 , and some light gases from a separation unit downstream of the three-phase separator.
  • the CO and the light gases can be used to produce the necessary hydrogen for the process through steam reforming and water gas shift reactions.
  • bio-feedstocks like cellulose (wood chips, corn stover, farm residues, etc.) can be used to produce hydrogen. These bio-feedstocks are steam reformed in a separate unit to produce hydrogen. Steam reforming (gasification) produces production gas which consists of mostly hydrogen and oxides of carbon besides many contaminants. The gas has to be cleaned before it can undergo water- gas shift reaction to produce hydrogen which can then be used in the process to convert crop oils and other bio-oils to specification biofuels.
  • One or more embodiments of the present invention comprise using at least one crop oil such as, but not limited to, algae or microbial oil, canola oil, corn oil, jatropha oil, camelina oil, rapeseed oil, pall oil, and combinations thereof.
  • One or more embodiments of the present invention further include the options of co-feeding or mixing with a component derived from fossil fuels,
  • One or more embodiments of the present invention further include generating a gas stream that can be used to generate the process heat necessary in a
  • Example 7 Jet/Aviation Fuel Synthesis from Bio-Oils Using Nanocoated Palladium on Activated Carbon Deoxygenation Catalyst
  • Refined Camelina oil was the feedstock used in a deoxygenation reactor according to one or more embodiments of the present invention. Deoxygenation experiments were carried out in a continuous down-flow multiphase packed bed.
  • the reactor was 0.305 inches in internal diameter and 18 inches long with pre-heat and post-heat zones.
  • the reactor volume was 22 cubic centimeters.
  • Heat for the reactor was supplied by a three-zone controlled furnace with heat equalizing blocks.
  • the Camelina oil feed rate into the reactor was 0.1 cc/min. Liquid and gaseous products exiting the reactor were collected in a separator. Backpressure regulators maintained the operating system pressure at 1000 psig.
  • the catalyst was reduced under hydrogen at 250 °C for 2 hours first.
  • Reactor temperature was raised from 250 °C to 360 °C within 60 minutes.
  • Liquid Camelina oil was pumped into the reactor at a rate of 0.1 cc/min.
  • Hydrogen gas feed rate into the reactor was 135 cc/min.
  • Reactor temperature was maintained at 360 °C and the reactor was run for 24 hours.
  • Reactor gas product was analyzed using a GC. The major reactant gaseous product observed other than H 2 was CO. Paraffinic wax product was collected and separated from water by gravity.
  • the isomerization and hydrocracking reactor used a commercially available standard catalyst.
  • the paraffinic wax feed line was maintained at 40 °C to ensure that wax was properly pumped into the isomerization/cracking reactor.
  • the isomerization/cracking experiment was carried out in a continuous down- flow multiphase packed bed reactor.
  • Commercially available isomerization catalyst totaling 3.8 grams was loaded into the stainless steel reactor.
  • the reactor was a 0.305 inch internal diameter and 5 inch long reactor with pre-heat and post-heat zones.
  • the reactor volume was 6 cc.
  • Heat for the reactor was supplied by a three-zone controlled furnace with heat equalizing blocks.
  • a pump was used to pump the paraffinic wax feed at 0.1 cc/min rate into the reactor. Liquid and gaseous products exiting the reactor were collected in a separator. Backpressure regulators maintained operating system pressure at 1000 psig.
  • the isomerization and hydrocracking reactor used a commercially available standard catalyst.
  • Example 8 Diesel Fuel Synthesis from Bio-Oils Using Nanocoated
  • Refined Camelina oil was the feedstock used in a deoxygenation reactor according to one or more embodiments of the present invention. Deoxygenation experiments were carried out in a continuous down-flow multiphase packed bed reactor. Eleven grams of 1 .72 wt% nanocoated Pd on activated carbon catalyst according to one or more embodiments of the present invention was loaded into a stainless steel reactor. The reactor was a 0.305 inch internal diameter and 18 inch long reactor with pre-heat and post-heat zones. The reactor volume was 22 cc. Heat for the reactor was supplied by a three-zone controlled furnace with heat equalizing blocks. A pump was used to pump the Camelina oil feed at 0.1 cc/min into the reactor. Liquid and gaseous products exiting the reactor were collected in a separator. Backpressure regulators maintained operating system pressure at 1000 psig.
  • the paraffinic wax feed line was maintained at 40 °C to ensure that wax was properly pumped into the isomerization/cracking reactor.
  • the isomerization/cracking experiment was carried out in a continuous down-flow
  • the reactor was 0.305 inches in internal diameter and 5 inches long with preheat and post-heat zones.
  • the reactor volume was 6 cc.
  • Heat for the reactor was supplied by a three-zone controlled furnace with heat equalizing blocks.
  • a pump was used to pump the paraffinic wax feed at 0.1 cc/min into the reactor.
  • Liquid and gaseous products exiting the reactor were collected in a separator.
  • Backpressure regulators maintained operating system pressure at 1000 psig.
  • the isomerization/cracking catalyst was reduced under hydrogen at 260 °C for 2 hours. Reactor temperature was lowered to 232 °C.
  • Methods according to one or more embodiments of the present invention may also comprise depositing palladium to make palladium membranes for hydrogen separation.
  • Methods according to one or more embodiments of the present invention may also comprise depositing palladium and/or other metals nanoscale coatings on zeolites, alumina, or silica-alumina substrates to make catalyst for hydrocracking applications of hydrocarbon fuels.
  • System 500 comprises a deoxygenation stage 510 which comprises at least one deoxygenation reactor chamber 515 and a catalyst 320 contained in the deoxygenation reactor chamber 515.
  • Catalyst 320 comprises a porous substrate and an electrolessly deposited metal coating having a nanoscale thickness.
  • Catalyst 320 according to one or more embodiments of the present invention is essentially the same as catalysts described earlier in the present disclosure such as for the description of Figure 4.
  • At least one deoxygenation reactor chamber 515 and the catalyst 320 are configured as a packed bed reactor to operate in continuous multiphase upflow mode with hydrogen and oxygenated hydrocarbons as feeds. More specifically, the embodiment shown in Figure 6 shows the hydrogen and the oxygenated hydrocarbons entering at or near the bottom of deoxygenation reactor chamber 515 then flow upward through catalyst 320.
  • system 500 further comprises a three-phase separator 335 configured to receive effluent from deoxygenation stage 510 and to separate water, liquid hydrocarbons, and gases from the effluent into separate streams.
  • system 500 further comprises a hydrocracking and isomerization stage 350 comprising at least one hydrocracking and isomerization reactor 355 and a hydrocracking and isomerization catalyst 360.
  • Hydrocracking and isomerization stage 350 is configured to receive the liquid hydrocarbons from deoxygenation stage 510 and hydrogen.
  • Hydrocracking and isomerization stage 350 operates at conditions to convert the liquid hydrocarbons from deoxygenation stage 510 into gasoline, diesel fuel, and/or aviation/jet fuel. More specifically, hydrocracking and isomerization stage 350 is configured to operate at temperatures and pressures to accomplish converting the hydrocarbons into the fuels.
  • Hydrocracking and isomerization catalyst 360 may be one or more commercially available catalyst for hydrocracking and isomerization.
  • deoxygenation stage 510 comprises two or more deoxygenation reactor chambers 515, each containing catalyst 320.
  • the two or more deoxygenation reactor chambers 515 are connected in series (not shown in Figure 6).
  • deoxygenation stage 510 comprises two or more deoxygenation reactor chambers 515 each containing catalyst 320 or a mixture of catalysts.
  • the two or more deoxygenation reactor chambers 515 are connected in series and system 500 further comprises a separator system to remove carbon monoxide, light gases, carbon dioxide, and water from the effluent stream connecting the two or more deoxygenation reactor chambers 515 and from between the two or more deoxygenation reaction chambers (additional reaction chambers and separator not shown in Figure 6).
  • System 500 further comprises a product separation stage 370 configured to receive products from hydrocracking and isomerization stage 350 and separate the products into diesel fuel, gasoline, and/or aviation/jet fuel.
  • System 500 further comprises a separator 375 comprising more than one separation stage to separate hydrogen from hydrocracking isomerization stage 350 effluent for recycle back to hydrocracking isomerization stage 350.
  • Another embodiment of the present invention includes a method of producing fuel from oxygenated hydrocarbons.
  • the method comprises providing in a packed bed a catalyst 320 comprising a porous substrate and an electrolessly deposited
  • the method also includes contacting catalyst 320 with an upflow of the oxygenated hydrocarbons and hydrogen through the packed bed to accomplish hydrogenation and deoxygenation.
  • the deoxygenation is accomplished preferentially by decarbonylation and
  • the method includes isomerizing and/or hydrocracking the paraffinic wax product to produce the fuel.
  • the fuel comprises diesel fuel, jet fuel, and/or gasoline.
  • the contacting catalyst 320 with the oxygenated hydrocarbons and hydrogen is accomplished in continuous co-current multiphase upflow mode.
  • the method can be performed using a system substantially as diagrammed in Figure 6.
  • the oxygenated hydrocarbons and hydrogen are combined and continuously fed into the packed bed reactor inlet so that the flow direction is opposite the direction of gravity.
  • an upflow packed bed reactor having an internal diameter of 0.305 inch with a length of 24 inches was used.
  • the catalyst in the packed bed was a catalyst substantially as described in Examples 1 -8 above.
  • the reactor contained in the following order: a stainless steel mesh at the inlet, glass wool, 4.57 grams of 4.19 wt% palladium on activated carbon catalyst, 6.2 grams of 1 wt% palladium on activated carbon catalyst, glass wool, 20 glass balls with 2 mm diameter, 20 glass balls with 3 mm diameter, 98 glass balls with 4 mm diameter, and a stainless steel mesh at the reactor outlet.
  • a backpressure regulator maintained operating system pressure at 1000 psig.
  • Heat for the reactor was supplied by a 3-zone temperature controlled furnace with heat equalizing blocks.
  • the palladium on activated carbon catalysts were reduced under hydrogen at 250 °C for 2 hours at hydrogen rate of 430 cc/min.
  • the reactor temperature was raised from 250 °C to 380 °C within 60 minutes.
  • Liquid Camelina oil feed was then pumped into the reactor inlet at a rate of 0.1 cc/min.
  • Hydrogen gas feed rate to the reactor inlet was 160 cc/min.
  • the Camelina oil and hydrogen were fed into the reactor with a flow direction that is opposite to the direction of gravity.
  • the reactor temperature was maintained at 380°C and the reactor was run for over 100 hours continuously.
  • the reactor gas product was analyzed using a gas chromatograph.
  • the major deoxygenated products observed were CO and CO 2 as shown in Figure 6-1 .
  • the data in Figure 6-1 also show stable operation of the reactor and stable production of oxides of carbon for the deoxygenation.
  • the paraffinic wax product was separated from water by gravity. An elemental oxygen balance between the Camelina oil feed and the paraffinic wax product showed that approximately 95% of the oxygen had been removed from the Camelina oil feed.
  • the experimental data clearly shows that selective deoxygenation was achieved in upflow packed bed reactor operation.
  • Figure 6-1 shows that the concentration of carbon dioxide is about 0.6%, whereas the concentration of carbon monoxide is about 3%.
  • System 505 for producing fuel from feedstocks such as renewable feedstocks such as, but not limited to, bio-oils and other oxygenated hydrocarbons.
  • System 505 comprises a
  • System 505 further comprises a separator 410 configured to receive the gases from three phase separator 335 and to separate hydrogen from carbon monoxide, carbon dioxide, and light gases. Separator 410 is connected to provide hydrogen to deoxygenation stage 510 or to hydrocracking stage 350.
  • System 505 further comprises a steam reformer and/or water gas shift stage 420 connected so as to receive carbon monoxide, C0 2 , and light gases from separator 410 and light gases from product separation stage 370. Steam reformer and/or water gas shift stage 420 produces hydrogen from the gases that it receives using water gas shift reactions and/or reformer reactions and provides the hydrogen to deoxygenation stage 510 and/or hydrocracking and isomerization stage 350.
  • system 505 comprises a three-phase separator 335 configured to receive effluent from the deoxygenation stage and to separate water, liquid hydrocarbons, and gases from the effluent into separate streams; and a second separator 410 and reformer and/or shift stage 420 to produce hydrogen from the carbon monoxide and the light gases.
  • carbon monoxide produced from the deoxygenation reaction is used as fuel to produce process heat.
  • System 600 comprises a deoxygenation stage 610 which comprises at least one deoxygenation reactor chamber 615 and a catalyst 320 contained in the deoxygenation reactor chamber 615.
  • Catalyst 320 comprises a porous substrate and an electrolessly deposited metal coating having a nanoscale thickness.
  • Catalyst 320 according to one or more embodiments of the present invention is essentially the same as catalysts described earlier in the present disclosure such as for the description of Figure 4.
  • at least one deoxygenation reactor chamber 615 and the catalyst 320 are configured as a packed bed reactor to operate in continuous multiphase flow mode for hydrogen and oxygenated hydrocarbons as feeds and a recycle stream.
  • the multiphase flow mode may be downflow mode or it may be upflow mode.
  • the embodiment shown in Figure 7 provides hydrogen, oxygenated hydrocarbons, and the recycle stream at or near the top of deoxygenation reactor chamber 615, which flow downward through catalyst 320.
  • system 600 further comprises a three-phase separator configured to receive effluent from deoxygenation stage 610 and to separate water, paraffinic wax product, and gases from the effluent into separate streams.
  • system 600 further comprises a hydrocracking and isomerization stage 350 comprising at least one hydrocracking and isomerization reactor 355 and a hydrocracking and isomerization catalyst 360.
  • Hydrocracking and isomerization stage 350 is configured to receive the paraffinic wax product from deoxygenation stage 610 and hydrogen.
  • Hydrocracking and isomerization stage 350 operates at conditions to convert the paraffinic wax product from deoxygenation stage 610 into gasoline, diesel fuel, and/or aviation/jet fuel. More specifically, hydrocracking and isomerization stage 350 is configured to operate at temperatures and pressures to accomplish converting the paraffinic wax product into the fuels.
  • Hydrocracking and isomerization catalyst 360 may be one or more
  • System 600 further comprises a product separation stage 370 configured to receive products from hydrocracking and isomerization stage 350 and separate the products into diesel fuel, gasoline, and/or aviation/jet fuel.
  • System 600 further comprises a separator 375 comprising more than one separation stage to separate hydrogen from hydrocracking isomerization stage 350 effluent for recycle back to hydrocracking isomerization stage 350.
  • fresh feed oxygenated hydrocarbons is mixed with recycled paraffinic wax product and with hydrogen; they are continuously fed into deoxygenation reactor chamber 615 so as to flow through catalyst 320.
  • Example 10 Selective Deoxygenation Using Recycle Operating Mode In Downflow Packed Bed Reactor Configuration
  • a downflow packed bed reactor having an internal diameter of 0.305 inch with a length of 25.59 inches was used.
  • the catalyst in the packed bed was a catalyst substantially as described in Examples 1 -8 above.
  • the reactor contained in the following order from the outlet: a stainless steel mesh, glass wool, 68 glass balls with 4 mm diameter, 20 glass balls with 3 mm diameter, 20 glass balls with 2 mm diameter, glass wool, 13.37 grams of 1 wt% palladium on activated carbon catalyst, and a stainless steel mesh at the reactor inlet.
  • a backpressure regulator maintained operating system pressure at 1000 psig.
  • Heat for the reactor was supplied by a 3-zone temperature controlled furnace with heat equalizing blocks.
  • the palladium on activated carbon catalysts were reduced under hydrogen at 250 °C for 2 hours at hydrogen rate of 430 cc/min.
  • the reactor temperature was raised from 250°C to 380°C within 60 minutes.
  • the initial reactor feed consisted of a well-mixed blend of 50 volume percent of fresh liquid Camelina oil and 50 volume percent of paraffinic wax product.
  • the blend maintained at 40 °C was pumped into the reactor inlet at a rate of 0.1 cc/min.
  • Hydrogen gas feed rate to the reactor inlet was 160 cc/min.
  • the reactor temperature was maintained at 380 °C.
  • One or more embodiments of the present invention may use sources other than that used for the embodiment shown in Figure 7 for the recycle stream to the deoxygenation stage.
  • a system 601 for producing fuels such as gasoline, diesel fuel, and jet fuel from oxygenated hydrocarbons.
  • System 601 is essentially the same as system 600 shown in Figure 7 with the exception that the recycle stream in system 601 includes paraffinic wax product split from the paraffinic wax product flow from three phase separator 335 and separation product from separation stage 370.
  • the separation product from separation stage 370 is the bottom product such as for a distillation system.
  • the bottom product may comprise paraffinic wax which may also contain some un-separated diesel fuel.
  • FIG. 7-2 where there is shown a system 602 for producing fuels such as gasoline, diesel fuel, and jet fuel from oxygenated hydrocarbons.
  • System 602 is essentially the same as system 600 shown in Figure 7 with the exception that the recycle stream in system 602 includes separation product from separation stage 370.
  • the separation product from separation stage 370 may be the bottom product such as for a distillation system and/or a portion of diesel fuel from product separation stage 370.
  • the bottom product may comprise paraffinic wax which may also contain some un- separated diesel fuel.
  • FIG. 7-3 where there is shown a system 603 for producing fuels such as gasoline, diesel fuel, and jet fuel from oxygenated hydrocarbons.
  • System 603 is essentially the same as system 600 shown in Figure 7 with the exception that the recycle stream in system 603 includes separation product from separation stage 370.
  • separation product from separation stage 370 may be a portion of diesel fuel from product separation stage 370.
  • Another embodiment of the present invention includes a method of producing fuel from oxygenated hydrocarbons.
  • the method comprises providing a catalyst in a deoxygenation reactor.
  • the catalyst comprises a porous substrate and an electrolessly deposited catalytically effective nanoscale metal coating on the substrate.
  • the method further comprises providing a feed of oxygenated hydrocarbons, a feed of hydrogen, and a recycle stream to the deoxygenation reactor so as to accomplish hydrogenation and deoxygenation wherein the deoxygenation is accomplished preferentially by decarbonylation and decarboxylation over hydrodeoxygenation to convert the oxygenated hydrocarbons into a paraffinic wax product.
  • the method also comprises isomerizing and/or hydrocracking the paraffinic wax product to produce the fuel.
  • the recycle stream comprises at least a portion of the paraffinic wax product formed in the deoxygenation reactor. More specifically, the paraffinic wax product exits the
  • the paraffinic wax product is separated from one or more other components of the effluent stream.
  • the method further comprises distilling the fuel to separate diesel fuel, jet fuel, and/or gasoline from un-reacted paraffinic wax product and feeding the un-reacted paraffinic wax product as at least a portion of the recycle stream to the deoxygenation reactor.
  • the method further comprises distilling the fuel to separate diesel fuel, jet fuel, and/or gasoline from un-reacted paraffinic wax product and feeding_at least a portion of the diesel fuel as at least a portion of the recycle stream to the deoxygenation reactor.
  • the method according to one or more embodiments of the present invention comprises contacting the catalyst with the feed of oxygenated hydrocarbons, the feed of hydrogen, and the recycle stream is accomplished in a packed bed reactor operating in continuous multiphase flow mode.
  • the method may use upflow mode or it may use downflow mode.
  • the flow in the deoxygenation reactor may be co-current flow or counter current flow.
  • the method according to one or more embodiments of the present invention uses volume ratios of the feed of liquid recycle stream to the feed of oxygenated hydrocarbons in the range of 0.1 :1 to 8:1 .
  • the liquid recycle stream may include, but is not limited to, paraffinic wax product, diesel fuel, other liquid hydrocarbons, and combinations thereof.
  • the method according to one or more embodiments of the present invention uses volume ratios of the feed of liquid recycle stream to the feed of oxygenated hydrocarbons in the range of 0.1 :1 to 4:1 .
  • the volume ratio of the feed of liquid recycle stream to the feed of oxygenated hydrocarbons is 1 :1 .
  • one or more embodiments of the present invention as illustrated by the flow diagrams in Figures 7, 7-1 , 7-2, or 7-3 may further include using the carbon monoxide generated in the deoxygenation reactor as feed for a water gas shift reaction to produce hydrogen.
  • the carbon monoxide generated in the deoxygenation reactor may further include using the carbon monoxide generated in the deoxygenation reactor as feed for a water gas shift reaction to produce hydrogen.
  • deoxygenation reactor may be used as fuel to produce process heat.
  • the carbon monoxide may be separated from other components prior to use in the water gas shift reaction or prior to use as fuel for producing process heat.
  • System 605 is essentially the same as system 601 shown in Figure 7-1 with the exception that system 605 further comprises a separator 410 configured to receive the gases from three phase separator 335 and to separate hydrogen from carbon monoxide, carbon dioxide, and light gases. Separator 410 is connected to provide hydrogen to deoxygenation stage 610 or to hydrocracking stage 350. System 605 further comprises a steam reformer and/or water gas shift stage 420 connected so as to receive carbon monoxide, carbon dioxide, and light gases from separator 410 and light gases from product separation stage 370.
  • a separator 410 configured to receive the gases from three phase separator 335 and to separate hydrogen from carbon monoxide, carbon dioxide, and light gases.
  • Separator 410 is connected to provide hydrogen to deoxygenation stage 610 or to hydrocracking stage 350.
  • System 605 further comprises a steam reformer and/or water gas shift stage 420 connected so as to receive carbon monoxide, carbon dioxide, and light gases from separator 410 and light gases from product separation stage 370.
  • Steam reformer and/or water gas shift stage 420 produces hydrogen from the gases that it receives using water gas shift reactions and/or reformer reactions and provides the hydrogen to deoxygenation stage 610 and/or hydrocracking and isomerization stage 350.
  • the carbon monoxide produced from the deoxygenation reaction is used as fuel to produce process heat.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “at least one of,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited only to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • "or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un ou plusieurs aspects et/ou un ou plusieurs modes de réalisation de catalyseurs, des procédés de préparation de catalyseur, des procédés de désoxygénation et des procédés de production de combustible/carburant.
PCT/US2014/068238 2013-12-02 2014-12-02 Procédés de production de combustible/carburant Ceased WO2015084893A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14/094,487 2013-12-02
US14/094,487 US9315736B2 (en) 2010-12-16 2013-12-02 Methods of fuel production

Publications (1)

Publication Number Publication Date
WO2015084893A1 true WO2015084893A1 (fr) 2015-06-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108671912A (zh) * 2018-04-16 2018-10-19 昆明理工大学 一种多孔孔壁多孔铝负载纳米Ag催化材料的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830880A (en) * 1986-04-22 1989-05-16 Nissan Chemical Industries Ltd. Formation of catalytic metal nuclei for electroless plating
US6207128B1 (en) * 1997-05-05 2001-03-27 Akzo Nobel N.V. Method of producing a catalyst
US20060161032A1 (en) * 2005-01-14 2006-07-20 Fortum Oyj Method for the manufacture of hydrocarbons
US20080308458A1 (en) * 2007-06-15 2008-12-18 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
US20090229173A1 (en) * 2008-03-17 2009-09-17 Gosling Christopher D Production of Diesel Fuel and Aviation Fuel from Renewable Feedstocks
US20100113848A1 (en) * 2008-11-04 2010-05-06 Energy & Environment Research Center Process for the conversion of renewable oils to liquid transportation fuels

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830880A (en) * 1986-04-22 1989-05-16 Nissan Chemical Industries Ltd. Formation of catalytic metal nuclei for electroless plating
US6207128B1 (en) * 1997-05-05 2001-03-27 Akzo Nobel N.V. Method of producing a catalyst
US20060161032A1 (en) * 2005-01-14 2006-07-20 Fortum Oyj Method for the manufacture of hydrocarbons
US20080308458A1 (en) * 2007-06-15 2008-12-18 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
US20090229173A1 (en) * 2008-03-17 2009-09-17 Gosling Christopher D Production of Diesel Fuel and Aviation Fuel from Renewable Feedstocks
US20100113848A1 (en) * 2008-11-04 2010-05-06 Energy & Environment Research Center Process for the conversion of renewable oils to liquid transportation fuels

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108671912A (zh) * 2018-04-16 2018-10-19 昆明理工大学 一种多孔孔壁多孔铝负载纳米Ag催化材料的制备方法
CN108671912B (zh) * 2018-04-16 2020-11-17 昆明理工大学 一种多孔孔壁多孔铝负载纳米Ag催化材料的制备方法

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