WO2011115781A1 - Conversion d'oxygénats en carburants hydrocarbonés par désoxygénation - Google Patents

Conversion d'oxygénats en carburants hydrocarbonés par désoxygénation Download PDF

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WO2011115781A1
WO2011115781A1 PCT/US2011/027557 US2011027557W WO2011115781A1 WO 2011115781 A1 WO2011115781 A1 WO 2011115781A1 US 2011027557 W US2011027557 W US 2011027557W WO 2011115781 A1 WO2011115781 A1 WO 2011115781A1
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starting material
kpa
hydroxyl
propanol
propanal
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Enrique Iglesia
Maria Eugenia Sad
De Chen
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The Regents Of The University Of California
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G45/22—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 with hydrogen dissolved or suspended in the oil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/52—Gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the search for new sources of energy, and particularly renewable energy sources includes the generation of fuels from biomass, i.e., organic material derived from plants and animals.
  • biomass i.e., organic material derived from plants and animals.
  • the typical molecules derived from biomass particularly oxygenates such as carbohydrates and polyols, contain significant amounts of oxygen that must be removed before the molecules are converted to useful fuels and other chemicals.
  • Light (C]-C 4 ) alkanes, branched C 6 -C 12 alkanes, and linear or singly branched C 7 -Q 2 alkanes can be obtained from biomass by a series of catalytic processes, as disclosed by Chheda, J.N., et al., "An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass- derived carbohydrates," Catalysis Today 123 (2007), 59-70. Included among the reactions are hydrogenolysis, hydrogenation, and dehydrogenation, which are typically performed on supported metal catalysts. Nevertheless, the conversion of biomass-derived feedstocks to liquid fuels remains a challenge.
  • a mild and inexpensive oxygen removal process is sought that combines C-C coupling with hydrogenation to achieve the higher molecular weight alkanes needed for gasoline, diesel, and jet fuel and that will make the resulting biofuels economically competitive with fossil fuels.
  • One means of C-C coupling is acid- or base-catalyzed aldol condensation, followed by dehydration of the resulting ⁇ -hydroxycarbonyl compound and hydrogenation of the dehydrated intermediate.
  • the removal of oxygen and the formation of C-C bonds when done separately, however, result in energy loss due to the need for a supply of hydrogen gas, and in high capital costs due to the need for separate reactors.
  • biomass-derived oxygenates and generally organic moieties that contain at least one hydroxyl substitution on a chain containing two or more carbon atoms, biomass-derived or otherwise, can be converted to longer-chain hydrocarbons with a lower proportion of oxygen atoms than the starting oxygenates, and in some cases no oxygen atoms, in a single reaction vessel by contacting the oxygenates in gaseous form with a solid catalyst at an elevated temperature.
  • a solid catalyst at an elevated temperature.
  • reaction route leading to the aldehyde and alcohol that combine in the aldol condensation, as well as the composition of the final product, including the number of oxygen atoms remaining in the product vary with the choice of metal and with the presence or absence of additional reactants in the feed stream to the reactor.
  • oxygen removal without chain extension is achieved as well, resulting in a product mixture that contains oxygen-free
  • the conversions herein are achieved through either of two principal reaction routes.
  • the first is through an aldehyde intermediate and the second through an alcohol intermediate.
  • 1,3-propanediol as a prototype for the hydroxyl-substituted starting material
  • the first route entails dehydrogenation and dehydration to produce acrolein followed by rehydrogenation to propanal and a partial further hydrogenation to achieve a propanal/propanol mixture, which then undergoes an aldol condensation to 2-methylpentanal which, depending on the choice of catalyst, may then be converted to 3-pentanone.
  • the aldol condensation is then followed by further hydrogenations, condensations, and dehydrations for further oxygen removal and chain lengthening.
  • the second reaction route again using 1,3-propanediol as a prototype of the starting material, entails dehydration to allyl alcohol followed first by tautomerization to propanal and then by hydrogenation to propanol.
  • Chain extension can be achieved by an aldol condensation between the propanal and propanol, the latter obtained by hydrogenation of propanal. Both can occur simultaneously, yielding a mixture of chain-extended and non- extended products, or one can be favored over the other, depending on the presence or absence of carbon monoxide, the partial pressure of hydrogen gas, and other system variables.
  • the hydrogen used for propanal hydrogenation in this route can be generated in situ by supplying water with the carbon monoxide to produce a water-gas shift reaction to occur in the reactor, or be externally supplied (“on-purpose") hydrogen. Hydroxyl-substituted organic moieties other than 1,3-propanediol can likewise be converted to similar effects. Recovery of the desired products from the product mixture can be achieved by conventional means.
  • FIG. 1 is a plot of the conversion of the propanol/propanal pool in accordance with the invention as a function of time on stream under different reactant mixtures and partial pressures.
  • FIG. 2 is a plot of the selectivity of the propanol/propanal pool toward different products in accordance with the invention as a function of conversion.
  • FIG. 3 is a diagram of a reaction scheme in accordance with the invention.
  • FIG. 4 is a plot of the termination probability vs. Au crystal diameter.
  • FIG. 5A is a plot of aldol condensation reaction rate vs. propanal partial pressure and FIG. 5B is a plot of hydrocarbon/oxygenate ratios vs. hydrogen partial pressure.
  • FIG. 6 is a plot of carbon number selectivity vs. ethanol/acetaldehyde pool conversion.
  • FIG. 7 is a plot of C 2+ formation rates vs. aldehyde pressure.
  • FIG. 8 is a plot of hydrocarbon/oxygenate ratio vs. ethanol/acetaldehyde pool conversion.
  • FIG. 9 is a plot of hydrocarbon/oxygenate ratio vs. hydrogen partial pressure.
  • FIG. 10 is a diagram of further reaction schemes in accordance with the invention.
  • FIG. 11 is a diagram of chain growth pathways in accordance with the invention.
  • FIG. 12 is a plot of hydrocarbon/oxygenate ratio vs. ethanol/acetaldehyde pool conversion.
  • FIG. 13 is a plot of total termination probability vs. ethanol/acetaldehyde pool conversion.
  • FIG. 14 is a plot of the propanol/propanal mole ratio vs. hydrogen partial pressure for different reaction media in accordance with the invention.
  • FIG. 15 is a diagram of a further reaction scheme in accordance with the invention.
  • FIG. 16 is a plot of various product yields and conversion times vs. reactor residence time (space time) in accordance with the invention.
  • FIG. 17 is a plot of selectivity for various products and of ⁇ values in accordance with the invention.
  • FIG. 18 is a diagram of further possible reaction schemes in accordance with the invention.
  • FIG. 19 is a plot of initial formation rates for aldol condensation reactions and esterification reactions as a function of propanal pressure in accordance with the invention.
  • FIGS. 20A, 20B, and 20C are plots of propanol/propanal pool turnover rates vs. Cu dispersion for aldol condensation (FIG. 20A), and esterification (FIG. 20B), and the formation of light hydrocarbons (20C), in accordance with the invention.
  • FIG. 21 is a plot of aldol/ester ratio as a function on Cu dispersion at different H 2 pressures in accordance with the invention.
  • the catalyst can be a fluidized bed or a fixed catalyst such as a packed bed, a grid, a solid surface of a wall, a baffle, or a reactor insert.
  • the preferred form of the catalyst is a packed bed.
  • the active component of the catalyst is gold, copper, or a combination of gold and copper, preferably as metallic deposits on solid supports. As will be seen below, the
  • the copper: gold weight ratio in preferred embodiments will range from about 0.3 to about 5.0, and most preferably from about 0.5 to about 2.0.
  • the hydrogenation is preferably supplied from an external source as a co-reactant, i.e., it is fed to the reactor together with the hydroxyl-substituted starting material.
  • the partial pressure of the hydrogen in the incoming gas, i.e., the feed stream to the reactor can vary, and effective results can be obtained with the partial pressure in a range whose upper limit as high as 100 MPa or higher, or as high as 75 MPa, 50 MPa, 30 MPa, or 20 MPa, and a lower limit as low as 5 kPa.
  • Effective results are also obtained at more moderate hydrogen partial pressures, such as those within the range of about 5 kPa to about 100 kPa, or about 5 kPa to about 75 kPa, or about 5 kPa to about 30 kPa.
  • the mole ratios of the reactant gases can vary as well. In preferred processes, the mole ratio of hydrogen gas to the hydroxyl-substituted starting material is within the range of about 5: 1 to about 330: 1 (H 2 :hydrocarbon), most preferably from about 5: 1 to about 150: 1.
  • the preferred catalyst is a combination of gold and copper.
  • hydrogen gas is again needed to form the saturated alcohol, and can likewise be fed to the reactor as part of the feed stream, at the partial pressures cited above.
  • a portion or all of the hydrogen gas can be generated by a water-gas shift reaction by including carbon monoxide and water in the feed stream to the reactor.
  • the partial pressure of carbon monoxide, when included in the feed stream, can vary, and effective results can be obtained with a partial pressure in a range whose upper limit as high as 100 MPa or higher, or as high as 75 MPa, 50 MPa, 30 MPa, or 20 MPa, and a lower limit as low as 5 kPa. Effective results are also obtained at more moderate partial pressures, such as those within the range of about 5 kPa to about 75 kPa, or about 10 kPa to about 50 kPa.
  • the partial pressure of water vapor, when included in the feed stream can vary, and effective results can be obtained with the same partial pressure ranges as those for carbon monoxide. Effective results can also be obtained with water vapor partial pressures within the range of about 10 kPa to about 100 kPa, and the range of about 20 kPa to about 80 kPa.
  • the mole ratios of the reactant gases can vary as well.
  • the mole ratio of carbon monoxide to the hydroxyl-substituted starting material is within the range of about 5: 1 to about 330: 1 (CO:hydrocarbon), most preferably from about 5: 1 to about 150: 1.
  • the mole ratio of water vapor to carbon monoxide is within the range of about 1 : 1 to about 30: 1 (H 2 0:CO), most preferably from about 2: 1 to about 10: 1.
  • the present invention is applicable to the treatment of any hydroxyl-substituted biomass-derived organic material that can release oxygen by dehydration.
  • the invention is of particular interest in the treatment of organic compounds that contain at least one hydroxyl substitution on a chain containing two or more carbon atoms.
  • the term "containing” herein is intended to mean “including, but not limited to,” and thus the chains in these compounds can contain atoms other than carbon atoms, notably oxygen atoms, and can be saturated or unsaturated.
  • the starting materials are polyhydroxyl-substituted hydrocarbons, where "polyhydroxyl-substituted" denotes two or more hydroxyl substitutions.
  • Combinations of these materials and mixtures of these materials with other biomass-derived substances such as more volatile gases, including saturated compounds and those with shorter chain lengths, can also be passed through the reactor.
  • Polyhydroxyl- substituted C 2 -C 6 hydrocarbons, and particularly polyhydroxyl-substituted C 2 -C 6 saturated hydrocarbons and mixtures of monohydroxyl-substituted and polyhydroxyl-substituted C 2 -C 6 hydrocarbons, are subsets of further interest. Further subsets are polyhydroxyl-substituted C 3 -C 6 hydrocarbons, and saturated forms of these hydrocarbons. Still further subsets of interest are dihydroxyl-substituted C 3 -C 6 saturated hydrocarbons. 1,3-Propanediol and propanol, notably 1- propanol, are illustrative. Also illustrative are ethanol and glycerol.
  • the starting material is supplied to the reactor as a gas in a gaseous feed stream, optionally in combination with an inert diluent gas.
  • the partial pressure of the starting material in the feed stream can vary, and like the other reactant gases, effective results can be obtained with the partial pressure in a range whose upper limit is 100 MPa or even higher, or as high as 75 MPa, 50 MPa, 30 MPa, or 20 MPa, and a lower limit as low as 5 kPa. Effective results are also obtained at more moderate partial pressures, such as those within the ranges of about 0.1 kPa to about 2.0 kPa, or from about 0.25 kPa to about 1.0 kPa.
  • Volatilization of otherwise liquid starting materials can be achieved by heating, either directly or by mixing the materials with a preheated inert carrier or diluent gas. Examples of such gases are helium, argon, and nitrogen.
  • the reaction temperature can vary, but is generally contemplated to be within the range of about 400 K to about 600 K, with a preferred temperature range of about 450 K to about 550 K.
  • the reactions can be performed in a batchwise mode, a continuous mode, or a combination of batchwise and continuous modes. Continuous operation, i.e., performance of the reaction in a continuous-flow reactor, is preferred.
  • the space time in the reactor defined as the weight of catalyst in grams (g ca t) divided by the molar flow rate of the starting material in moles per kilosecond, can vary to the extent that the other reaction conditions, such as temperature and pressure, remain controllable and the conversion levels remain practical.
  • the optimal space time in any run will vary with temperature and other system parameters, it is presently contemplated that the space time will range from about 30 g c a f ks-mol "1 to about 3,000
  • gca f ks-mol "1 and preferably from about 500 g c a f ks-mol "1 to about 2,000 gca f ks-mol "1 .
  • a gold catalyst support on titania (Au/Ti0 2 , 1.56 weight percent, 3.3 ⁇ 0.7 nm), prepared by deposition-precipitation, was obtained from the World Gold Council.
  • a copper catalyst over a silica support (Cu/Si0 2 , 5 weight percent) was prepared by incipient wetness impregnation of silica (CAB-O-SIL HS-5, 31 1 m 2 /g) with Cu(N0 3 )-2.5 H 2 0.
  • the Cu-impregnated silica was treated in ambient air at 383 K, followed by flowing dry air (0.83 cm 3 g " 1 s “1 ) at 73 K (0.083 K s “1 ) for 5 hours, and finally in 10% H 2 /He (Praxair, 99.999%) at 503 K (0.167 K s "1 ) for two hours.
  • the catalyst was then passivated in 1% 0 2 /He (Praxair, 0.83 cm 3 g "1 s "1 ) at ambient temperature for one hour prior to exposure to atmosphere.
  • the dispersion of Cu i.e., the ratio of the number of exposed Cu metal atoms to the total number of Cu atoms in each sample, was determined to be 5% by surface titration of N0 2 .
  • the reactants (1,3 -propanediol: Aldrich, 99.6%; propanol: Sigma- Aldrich, 99.7%; or propanal: Acros, >99%) were introduced using a syringe pump (Cole Parmer, 74900 series) by vaporization into a helium (Praxair, UHP) stream at 363 K (for propanol and propanal) or 433 K (for 1,3-propanediol) using transfer lines kept at 473 K. Helium and hydrogen were adjusted to vary the H 2 partial pressure.
  • K eq is the equilibrium constant for the hydrogenation of propanal to propanol.
  • ⁇ at equilibrium is one.
  • EXAMPLE 2 Conversion of 1,3-Propanediol on Mixture of Au/Ti0 2 and Cu/Si0 2
  • Example 1 The reactions of Example 1 were repeated at the same conditions except that the catalyst was a combination of Au/Ti0 2 and Cu/Si0 2 at a weight ratio of 3: 1.
  • the reaction rates of the various products and the values for ⁇ are listed in Table II.
  • the rate of formation of C 6 products increased from 536 jimol-Cgca t -ks) "1 on Au/Ti0 2 to 719 ujtnol-(g ca rks) "1 on the mixed catalyst, while the C 9 /Q ratio increased from 0.17 to 0.22.
  • the reaction scheme shows that oxygen removal and C-C bond formation will occur using only the hydrogen atoms that are indigenous to the oxygenate reactants by coupling the reactions together on metal catalysts, but the reaction stops at the aldol condensation products. Hydrogenation of the aldol condensation products requires additional hydrogen.
  • Table III shows that both Au and Cu catalysts can catalyze C-C bond formation via aldol condensation reactions, but that Au is much more active than Cu.
  • the C 9 and C 12 compounds were most likely formed by chain growth through aldol condensation with C 3 as the building block, but the data show that the C 6 formation rate on the Au catalyst in terms of grams of catalyst was almost ten times as high, and in terms of atoms of the metal about fifty times as high, than that achieved on the Cu catalyst.
  • the amount of Cu/Si0 2 used in the mixed catalyst in the reactions Table II was only 30% of the amount used in the reactions of Table III, the two tables together show that the aldol condensation reactions occur primarily on the Au surfaces in the mixed catalysts.
  • FIG. 1 is a plot of conversions of a propanal/propanol pool as a function of time on stream at 503 K and 540 gca t -ks-mol "1 over Au/Ti0 2 , at varying reaction conditions. These reactions were also performed in the presence of CO over Au/Ti0 2 . An initial decrease in conversion was observed at a hydrogen partial pressure of 50 kPa, followed by a leveling off.
  • FIG. 2 is a plot of pool selectivity as a function of pool conversion over Au/Ti0 2 in the absence of added hydrogen.
  • open diamonds represent C compounds
  • filled circles represent C 9 compounds
  • open triangles represent Q 2 compounds.
  • C 3+ hydrocarbons and oxygenates were the predominant products, with small amounts of methane, ethane, and ethene, and only trace amounts of propane and propene, detected.
  • the decrease in C 6 selectivity and the increase in C 9 and C 12 selectivity with increasing pool conversion are due to chain growth.
  • the ratio of C 9 to C compounds in the product stream increased with pool conversion, with higher rates of increase occurring at lower conversions.
  • the C 6 compounds are the products of self aldol condensation between C 3 reactants, while the C 9 compounds are the products of cross aldol condensation between C 3 reactants and C 6 self aldol condensation products.
  • the data Table IV indicate that the formation rates of C 6 , C 9 , and Q 2 increased with decreasing propanol to propanal ratio, except for a slightly lower rate at 0 kPa H 2 (absence of on- purpose hydrogen) than at 10 kPa hydrogen pressure.
  • the lower rate in the absence of on- purpose hydrogen may be the result of deactivation and a low hydrogenation of the unsaturated dehydrated aldol condensation product.
  • the higher rates or formation of C 3+ that were generally obtained at higher propanal pressures clearly indicate the importance of the propanal-mediated reactions in the formation of C 3+ oxygenates and hydrocarbons. These results clearly indicate chain growth due to successive aldol condensations.
  • Au catalysts were prepared by standard impregnation of the Ti0 2 support (5 g,
  • Au metal dispersions were determined by HRTEM and X-ray diffraction (XRD). High- resolution transmission electron microscope (HRTEM) was performed with a field emission gun (FEM) (JEOL JEM 201 OF). The sample used for TEM was crushed to a powder in a crucible before it was dissolved in an ethanol solution for 10 min with the help of an ultrasonic bath. One drop of this suspension was deposited onto a copper grid covered by a holey carbon membrane.
  • Table V shows that aldol condensation reaction rates increase with decreasing Au average crystallite diameter at propanal pressures of 0.04, 0.062, 0.19, and 0.32 kPa. This clearly suggests that the aldol condensation occurs mainly on Au surfaces. Smaller Au nanoparticles are more active for the aldol condensation reaction. Moreover, the hydrocarbon- to-oxygenate (H/O) ratios in the product increased with average crystallite diameter of Au clusters at different hydrogen pressures, from 0 to 80 kPa. This indicates that the relative rate of hydrogenation/dehydrogenation of the aldol condensation product, which results in the hydrocarbon with the same carbon number as the aldol condensation product, is higher on larger Au crystals.
  • H/O hydrocarbon- to-oxygenate
  • the total chain termination probability is larger on larger Au crystals, especially for C 6 and C 9 products, as shown in FIG. 4, which shows the effect of the average crystal diameter on the total termination probability ⁇ 3 , ⁇ 6 , ⁇ 9 for C 3 , C 6 and C 9 , respectively.
  • the difference between H/O ratios becomes larger at high hydrogen pressures because the dehydration/hydrogenation reaction requires kinetically and stoichiometrically more hydrogen than the aldol condensation reaction.
  • EXAMPLE 6 Conversion of Propanol on Au/Ti0 2 - Effect of Catalyst Support
  • Au/Fe 2 0 3 (5 wt%, 3.6 nm) and Au/Ti0 2 ( 1.56 wt , 3.3 ⁇ 0.7 nm) were provided by World Gold Council.
  • Au/Al 2 0 3 , Au/Si0 2 and Au/pCNF catalysts were prepared by standard impregnation of the alumina, silica and the platelet carbon nanofibers (obtained by chemical vapor decomposition of the CO/H 2 mixture on Fe catalysts) with HAuCl 4 (Aldrich) solutions.
  • Au supported on Ti0 2 and A1 2 0 3 are more active for aldol condensation reaction, which are 10 times higher than on Si0 2 and carbon support. Au particle sizes on these supports were similar, except for Si0 2 where the particle size was 2.0 nm. These data demonstrate that the catalyst support has a large effect on the aldol condensation reaction.
  • the catalyst support also has an effect on the hydrocarbon to oxygenate ratio, as shown in FIGS. 5 A and 5B.
  • the acid sites on A1 2 0 3 which catalyze hydrogenation/dehydration reactions, lead to higher hydrocarbons instead of oxygenates.
  • Au/Ti0 2 is more selective to oxygenate and is preferential to the chain growth reaction.
  • Ethanol reactions were carried out on Au/Ti0 2 at 503 K using gaseous ethanol and with and without H 2 in the inlet stream as a function of residence time. Metal-free supports and diluents did not lead to detectable products at these conditions. At all conditions tested, ethanol and acetaldehyde reached thermodynamic equilibrium at the prevalent H 2 pressure. Ethanol and acetaldehyde are therefore treated herein as a single chemical reactant pool and all reported conversions and selectivities are based on the molecules that leave the ethanol/acetaldehyde reactant pool.
  • the products formed from these equilibrated ethanol-acetaldehyde mixtures include molecules with 4, 6, and 8 carbon atoms, such as butyraldehyde, 2-ethyl-butyraldehyde, n-hexanal, 4-ethyl hexanal, 2-ethyl hexanal, n-octanal, small amounts of some of the
  • FIG. 6 shows the carbon number selectivity (carbon basis) as a function of ethanol/acetaldehyde pool conversion on Au/Ti0 2 without added H 2 .
  • the squares represent selectivity of C 2 , the circles C 4 , the upward-pointing triangles C 4 , the downward-pointing triangles C 6 , and the left-pointing triangles C 8 .
  • Pool conversion changed from 23 to 93 % as a consequence of changes in ethanol space velocity from 180 to 860 g cat 'ks-mol " 1 .
  • the selectivity to chain growth products was >95 at all conversions, and methane, ethane and ethylene were present in trace amounts.
  • C 4 selectivity decreased and C 6 and C 8 selectivity concurrently increased with increasing conversion, consistent with sequential condensation reactions.
  • Rates of formation of C 4 , C 6 , C 8 and C 10 molecules are shown in Table VI, as a function of H 2 pressure, which concurrently changes ethanol/propanol ratios to reflect thermodynamic equilibrium.
  • [a] C 2 refer to ethylene and ethane.
  • FIG. 7 which shows the monotonic effects of acetaldehyde (but not ethanol) pressure on C 2+ formation rates, whether this pressure was varied through changes in residence time, H 2 pressure, or inlet ethanol pressure.
  • the squares represent the reaction rate of the ethanol/acetaldehyde reactant pool conversion
  • the triangles represent the ratio of reaction rates of R 2 /Ri
  • the circles represent the ratio of reaction rates of R 3 /R 2 as a function of the mean pressure of acetaldehyde on Au Ti0 2 , at 503 K, 0.38 kPa ethanol, 180 to 860 gcat-ks-mol- 1, 10 to 80 kPa H 2 and 1-3 kPa ethanol, balance He.
  • the C 4 fraction contained not only butyraldehyde, the expected product of acetaldehyde condensation and hydrogenation of aldol intermediates, but also smaller amounts of butanone (via condensation and intramolecular hydride shift before dehydration), n-butanol, and 2-butanol (formed by hydrogenation of the respective oxygenates), and hydrocarbons, predominantly n- butene (via n-butanol dehydration) and n-butane.
  • FIG. 8 shows the hydrocarbon to oxygenate ratios in product fractions as a function of ethanol/acetaldehyde reactant pool conversion. The squares represent C 4 product fractions, the circles represent C 6 product fractions, and the triangles represent C 8 product fractions.
  • Ketones are also formed in a trace amount ( ⁇ 3 %) via intramolecular hydride shift before dehydrogenation of aldol intermediates.
  • thermodynamic equilibrium constants of 1-hexanal to n-hexanol and 2-ethyl-butyraldehyde to 2- ethyl-l-butanol are 22 and 26, respectively, indicating that hydrogenations of C 6 aldehydes to corresponding alkanols are also thermodynamically favorable.
  • the hydrocarbon-to oxygenate ratios in the C 4 , C , and C 8 products increased with increasing H 2 pressure at similar reactant pool conversions (30-33 %), as shown in FIG. 9, where the squares represent C 4 , the circles C 6 , and the triangles Q. This is consistent with H 2 -mediated paths for the hydrogenation of aldehydes to alkanols and subsequent dehydrations to hydrocarbons.
  • Table VII shows that ethanol reaction rates increased with increasing temperature (503- 573 K), as a result of the combined effects on rate constants and in the prevalent pressure of acetaldehyde, which is formed from ethanol in endothermic reactions favored at high
  • Table VII also shows that increasing H 2 pressures led to shorter chains and higher hydrocarbon contents in the products as a result of a concomitant decrease in the concentration of acetaldehyde monomers at both 503 and 573 K.
  • the H 2 effects are two-fold: high H 2 pressure decreased the acetaldehyde concentration through an equilibration between ethanol and acetaldehyde and thus decreased the chain growth rate via aldol-type condensation reactions; and the higher H 2 pressure increased the hydrogenation and dehydration rate, which terminated the chain growth, as shown in FIG. 11.
  • FIG. 11 shows that increasing H 2 pressures led to shorter chains and higher hydrocarbon contents in the products as a result of a concomitant decrease in the concentration of acetaldehyde monomers at both 503 and 573 K.
  • the H 2 effects are two-fold: high H 2 pressure decreased the acetaldehyde concentration through an equilibration between ethanol and acetaldehyde and thus decreased the chain growth rate via
  • [C 2 H 4 0] and [H 2 ] represent the concentrations of acetaldehyde and hydrogen, respectively.
  • the ratio of C 2 H 4 0/H 2 can be regarded as a chemical potential for the chain growth in the aldol-type condensation reactions.
  • the chain growth is favored at higher concentrations of acetaldehyde and lower concentrations of hydrogen.
  • FIG. 12 shows the effect of pool conversion and carbon number on the oxygenate-to-hydrocarbon ratio.
  • the squares in FIG. 12 represent C 4 , the circles C 6 , and the triangles C 8 .
  • the figure shows that with the increase in pool conversion (varied by residence time from 3.7 to 37 g-ks-mol "1 ), more oxygenates are produced, which would continue coupling with acetaldehyde to form larger carbon chains or undergo hydrogenation /dehydration to form hydrocarbons.
  • C 4 oxygenates tend to continue cross coupling with acetaldehyde, while C 6 and C 8 oxygenates tend to undergo a hydrogenation-dehydration reaction.
  • the hydrocarbon-to-oxygenate ratio in C 4 remains stable and barely increases.
  • the hydrocarbon-to- oxygenate ratio in C 6 , and especially in C 8 increases, greatly with the pool conversion. For C 8+ products, most oxygenates are converted to hydrocarbons and almost no oxygenates are found.
  • FIG. 13 shows the effects of pool conversion and carbon number on the total chain termination probability of ⁇ 2 (squares), ⁇ 4 (circles), and ⁇ 6 (triangles), for C 2 , C , and C 6 respectively.
  • the chain termination probability is very low for C 2 under whole conversion regime, which means C 2 aldehyde will grow to a longer carbon chain instead of terminating to hydrocarbon.
  • the chain termination probability increases with the carbon number.
  • the probability of termination of C 4 is relatively high but decreases with increase in the pool conversion. This indicates that a large proportion of C 4 oxygenates are converted to the hydrocarbons at large pool conversions. For C 6 oxygenates, the termination probability is significantly high and increases with increases in the pool conversion.
  • a copper catalyst on zinc oxide and alumina (Cu/ZnO/Al 2 0 3) was prepared by co- precipitation from aqueous solutions of Cu(NO 3 ) « 2.5H 2 0 (Aldrich, 99.99%), ⁇ ( ⁇ 3 ) ⁇ 6 ⁇ 2 0 (Sigma-Aldrich, 98%) and ⁇ 1( ⁇ 3 ) 3 ⁇ 9 ⁇ 2 0 (Sigma-Aldrich, 98%) with anhydrous Na 2 C0 3 (EMD Chemicals Inc. GR ACS) at 333 K in a stirred batch reactor. Mixed Cu, Zn and Al nitrate solutions were added dropwise to a stirred Na 2 C0 3 solution (800 rpm).
  • the resulting colloidal suspension was aged by stirring for 2 hours at 333 K.
  • the solids were separated by filtration and rinsed with deionized water at 330 K (0.5 L/g solid) and then treated in ambient air at 373 K overnight.
  • These precursors were decomposed in flowing dry He (Praxair, 99.99%, 0.8 cm3 g "1 s "1 ) by heating to 673 K (0.03 K s "1 ) and holding for 8 hours.
  • X-ray diffractograms showed that the hydrotalcite structure of the precipitated precursors disappeared upon thermal treatment and was replaced by CuO and ZnO phases.
  • Copper catalysts over carbon (Cu/carbon) and silica (Cu/Si0 2 ) were prepared by incipient wetness impregnation of Si0 2 (CAB-O-SIL HS-5, 311 m 2 /g) or carbon (HSAG 300, TEVIREX, 230 m /g), respectively, with a Cu(N0 3 ) » 2.5H 2 0 solution.
  • the impregnated catalyst samples were treated in ambient air at 383 K, then in flowing dry air (0.83 cm3 g "1 s “1 ) by heating to 773 K (at 0.083 K s “1 ) and holding for 5 hours, cooling to ambient temperature, and finally by treating the samples in flowing 10 % H 2 /He (Praxair, 99.999%), heating from 298 K to 503 K (at 0.167 K s "1 ) and holding for 2 hours. All catalyst samples were passivated in 1% 0 2 /He (Praxair, 0.83 cm3 g "1 s "1 ) at ambient temperature for 1 hour before exposing them to ambient conditions.
  • catalyst samples (0.3 g) were treated with 20% H 2 /Ar (Praxair, 99.999%, 5.56 cm 3 g "1 s “1 ) by heating to 553 K (at 0.167 K s “1 ) and holding for 1 hour. Catalysts were then purged with Ar (Praxair, 99.999%, 5.56 cm 3 g "1 s "1 ) at 553 K for 0.5 hour and cooled to the adsorption temperature (313 K). Finally, the samples were contacted with a 0.5% N 2 0/Ar (Praxair, 99.999%, 5.56 cm 3 g "1 s "1 ) stream.
  • the intensity of the N 2 0 parent ion (44 amu) was measured by mass spectrometry (Inficon, Transpector series), and differences between the inlet and outlet streams were used to measure the amount of chemisorbed oxygen.
  • Cu dispersions were estimated from a 0/Cu s stoichiometry of 0.5. Mean crystallite diameters were calculated from dispersion values by assuming hemispherical clusters and Cu surface densities for bulk Cu metal ( 1.47 x 1019 Cu atoms/m 2 ) .
  • Tests to determine reaction rates and selectivities were performed by feeding gas phase reactants at 503 K through a fixed-bed continuous-flow tubular reactor.
  • Reduced and passivated catalyst samples (125-180 ⁇ , 0.05-0.4 g) were diluted with 125-180 ⁇ Si0 2 aggregates (Fluka, purum. P.a.), treated at ambient temperature with concentrated nitric acid, washed with dionized water, filtered and finally treated in dry air at 673 K, at 0.167 K s "1 , and held for 2 hours.
  • the samples were then treated in situ with a mixture of 5% H 2 in He (Praxair, 99.999%) at 503 K (0.0833 K s "1 ) for 1 hour before use.
  • Liquid reactants (1,3-propanediol: Aldrich, 99.6%; propanol, Sigma-Aldrich, 99.7%; propanal: Acros, >99% and deionized water) were introduced through a syringe pump (Cole Parmer, 74900 series) by vaporization into a He (Praxair, UHP) stream at 363 K (for propanol and propanal), 378 K (for water) or 433 K (for 1,3 propanediol). Transfer lines were heated to prevent condensation. Carbon monoxide (Praxair, 99.999%) and hydrogen gas (Praxair, 99.999%) were also used as reactants.
  • EXAMPLE 9 Reactions of 1,3-Propanediol With H 2 , H 2 -CO, and CO-H 2 0
  • Table VIII shows that the catalyst gave nearly complete 1,3-propanediol conversions, even without co-reactants, and produced mixtures of propanal and propanol with a molar ratio corresponding to thermodynamic equilibrium at the H 2 pressures present at the reactor exit (FIG. 14, where open squares represent the diol-H 2 reaction, open circles represent the diol-H 2 -CO reaction, and filled triangles represent the diol-CO-H 2 0 reaction). Small amounts of propene, propane, propanol, allyl alcohol and acrolein were also formed depending on the co-reactant used.
  • FIG. 16 shows 1,3-propanediol conversions and product yields (defined as moles of product per mole of 1,3-propanediol fed) as a function of residence time when 10 kPa of H 2 was included as co-reactant. Propanal and propanol are considered to be kinetically indistinguishable because they are in equilibrium at these experimental conditions.
  • the non-zero initial slopes for propanal/propanol and acrolein yields indicate that they are primary products or secondary products involving reactive or unstable intermediates, such as allyl alcohol, that are below detection limits.
  • the acrolein yield curve increased with residence time, reached a maximum, and then decreased, indicating that this product is transformed into other molecules at higher residence times.
  • the propene yield curve has an initial zero slope, indicating that this is a secondary product.
  • Table VIII also shows the effects of H 2 formed in situ by water-gas shift reactions of CO-H 2 0 mixtures on 1,3-propanediol reaction rates and selectivities.
  • Water-gas shift reaction rates on the catalyst were first measured in the absence of the diol. The CO conversion deceased on stream from 24% or 60 % (initially) to 4% or 15 % (after 10.8 ks), for reactions using 8 kPa CO and 21 or 80 kPa H 2 0, respectively. Since CO-H 2 0 reactants led to gradual deactivation, H 2 (30 kPa) was added to stabilize the rates, evidenced by a lack of detectable deactivation for about 40 hours.
  • Table VIII lists the diol conversions and product selectivities using diol-CO-H 2 0 mixtures as well as those obtained with diol-CO-H 2 0-H 2 mixtures. Diol conversions were greater than 95% in these experiments and the propanol/propanal ratios corresponded to equilibrium values at effluent H 2 pressures.
  • EXAMPLE 10 Effects of Catalyst Support on 1,3-Propanediol Conversion
  • the question of whether the catalyst support was in part responsible for the conversion of 1,3-propanediol was investigated by using a Cu-free Zn0-Al 2 0 3 sample in place of the Cu/ZnO/Al 2 0 3 catalyst of the preceding examples.
  • the Cu-free ZnO-Al 2 0 3 sample was prepared by the procedure described above for the Cu/ZnO/Al 2 0 3 catalyst, with the same Zn Al ratio of 60/40 and BET surface area of 65 m 2 /g.
  • Table IX The results for l,3-propanediol-H 2 and 1,3- propanediol-He reactant mixtures are shown in Table IX.
  • Integral rate calculated by dividing the 1,3-propanediol conversion by the residence time
  • H 2 did improve the total products formation rate.
  • the rate of formation of propanal on the Cu-free support with added H 2 was more than five times the rate obtained without added H 2 , whereas the acrolein formation rate decreased to 22%.
  • the improvement in the total formation rate when H 2 is co-fed with 1,3-propanediol is thus attributable to an increase in the amount of acrolein formed from 1,3-propanediol due to a consecutive conversion of acrolein to propanal (a reaction that consumes H 2 ).
  • Copper is therefore essential for both the activation of 1,3-propanediol and the interconversion of the activation products with H 2 , regardless of whether the H 2 is generated in situ in an alkanol-gas shift reaction or added as part of the feed stream.
  • EXAMPLE 11 Primary and Secondary Products in PropanoI-PropanaI-H 2 Reactions on Cu Catalysts
  • propylpropionate, 2-methylpentanal, 2-methyl-3-pentanone, 3-pentanone and propene are the primary products and propane is a secondary product.
  • the Figure also shows the value of ⁇ (open circles), representing the approach to equilibrium, for propanol/propanal reactions at different space velocities.
  • the main products were C 5 and C 6 compounds obtained by the formation of new C-C and C-O bonds, and that propane and propene were formed in low proportions even at large residence times when only H 2 and propanol were fed. This suggests that the reaction scheme is that shown in FIG. 18, in which aldol
  • condensation products (mainly 2-methyl-3-pentanone) and propylpropionate were the main reaction products during propanol-propanal-H 2 reactions on Cu-based catalysts involving the formation of new C-C and/or C-O bonds. While the reaction scheme of FIG. 18 does not include the formation of acrolein, acrolein may indeed be formed as an intermediate, although one that is difficult to detect due to the high activity of the Cu catalyst.
  • This example provides further support for the reaction scheme shown in FIG. 18 by showing the results of kinetic studies of propanol-propanal-H 2 reactions using 10 weight % Cu/Si0 2 (5.5% dispersion) at 503 K.
  • FIG. 19 shows the rate of esterification and aldol condensation reactions (10 ⁇ 6 moles-g ⁇ -Cu-s "1 ) as functions of propanal pressure on 10 weight % Cu/Si0 2 .
  • the squares represent the formation rates for esterification and the circles represent the formation rates for the aldol condensation reactions, from propanol- propanal-H 2 mixtures on 10 % wt.
  • Kf equilibrium constant for: propanol dissociative adsorption (K/), dehydrogenation to form adsorbed propanal (-3 ⁇ 4') > molecular adsorption of propanal hydrogen dissociative adsorption (A3 ⁇ 4 and propanal hydrogenation to propanol (K 5 )
  • Each point in FIG. 19 corresponds to the extrapolation to zero residence time for a given propanal pressure to avoid any conversion effects on rates or selectivities as a function of propanal (bottom X-axis) or propanol pressure » (H 2 pressure*] ⁇ 1 ) 1 (top X-axis).
  • the curves are nearly identical, thereby showing the equilibrated nature of propanal hydrogenation to propanol.
  • the effects of propanal (or propanol) pressure on esterification and condensation reactions indicate that these reactions proceed via intermediates that can form from either hydrogenation of the aldehyde or dehydrogenation of the alkanol during propanol-propanal equilibration. This indicates that propanal and propanol interconvert on a Cu surface and form intermediates with different H contents depending on the H* coverage on the surface which depends on the H 2 pressure and also sets the propanol/propanal ratios.
  • Supported catalysts containing 5 to 20 weight % of Cu at different dispersions (2 to 17%) and different cluster sizes (5 to 55 nm) were prepared by incipient wetness impregnation using Cu(NO 3 )-2.5H 2 0 and varying the temperature of thermal treatment or using
  • Table XI and FIGS. 20A, 20B, and 20C show the effects of Cu dispersion on propanol/propanal pool turnover rates (expressed as mol/(mol of surface Cu-s), where the number of moles of surface Cu was determined by N 2 0 decomposition) for three H 2 pressures.
  • Table XI Effect of Cu dispersion and average crystallite diameter on propanol/propanal pool turnover rates in the presence of H 2
  • FIGS. 20A, 20B, and 20C The effect of metal dispersion on individual reaction paths is shown in FIGS. 20A, 20B, and 20C.
  • Aldol condensation (FIG. 20A) and esterification reactions (FIG. 20B) are sensitive to structure, which could be a result of the complex chemical nature of the molecules involved and the type of bond activation required.
  • the formation of light hydrocarbons is not structurally sensitive (FIG. 20C).
  • the aldol/ester ratio as a function on Cu dispersion at different H 2 pressures is presented in FIG. 21, using 10% wt. Cu/Si0 2 , at 503 K and 0.64 kPa propanol, balance He.
  • the triangles represent 30 kPa, the circles represent 20 kPa, and the squares represent 10 kPa.
  • the aldol/ester ratio was higher than 1 in all cases, except for the smallest cluster. This suggests that the intermediate with the C-H bond activated at the -position is probably the most thermodynamically favored and thus the more stable.
  • EXAMPLE 15 Conversion of C 2 -C 5 Oxygenates on Mixture of Au/Ti0 2 and Cu/Si0 2 Catalysts
  • the main products obtained from acetone as the reactant were C 6 hydrocarbons and oxygenates, a result similar to that obtained with 1 -propanol with the same carbon number.
  • the main products from C 4 and C 5 alkanols as reactants were C 8 and Qo hydrocarbons and oxygenates.
  • the reaction rates were related to the carbon number of the reactant, and were much higher for the smaller alkanols such as ethanol, similar for alkanols with same carbon number (acetone and 1-propanol) and lower for larger alkanols (n-butanol and 3- pentanone) .

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Abstract

Selon la présente invention, des oxygénats issus de la biomasse, en particulier des hydrocarbures en C2 et plus, substitués par un hydroxyle, sont traités pour l'élimination d'une partie ou de la totalité de leurs atomes d'oxygène et pour l'allongement de chaîne par couplage carbone-carbone dans un milieu réactionnel unique dans la phase gazeuse sur un catalyseur solide.
PCT/US2011/027557 2010-03-17 2011-03-08 Conversion d'oxygénats en carburants hydrocarbonés par désoxygénation WO2011115781A1 (fr)

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EP3297985A4 (fr) * 2015-05-18 2019-01-02 Rhodia Operations Procédé d'oxydation d'alcools à l'aide de gaz contenant de l'oxygène

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