WO2015031561A1 - Conversion catalytique d'alcools - Google Patents

Conversion catalytique d'alcools Download PDF

Info

Publication number
WO2015031561A1
WO2015031561A1 PCT/US2014/053053 US2014053053W WO2015031561A1 WO 2015031561 A1 WO2015031561 A1 WO 2015031561A1 US 2014053053 W US2014053053 W US 2014053053W WO 2015031561 A1 WO2015031561 A1 WO 2015031561A1
Authority
WO
WIPO (PCT)
Prior art keywords
butyl
ligand
transition metal
alcohol
halo
Prior art date
Application number
PCT/US2014/053053
Other languages
English (en)
Inventor
Duncan Frank Wass
Original Assignee
Bp Corporation North America Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bp Corporation North America Inc. filed Critical Bp Corporation North America Inc.
Publication of WO2015031561A1 publication Critical patent/WO2015031561A1/fr

Links

Classifications

    • 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
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/825—Osmium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

Definitions

  • This disclosure relates to synthetic processes for converting lower alcohols (e.g., ethanol) to higher alcohols (e.g., butanol) catalyzed by water stable transition metal complexes comprising a Group VIII transition metal and a polydentate nitrogen donor ligand.
  • lower alcohols e.g., ethanol
  • higher alcohols e.g., butanol
  • water stable transition metal complexes comprising a Group VIII transition metal and a polydentate nitrogen donor ligand.
  • Biofuels include fuels which are derived partly or fully from biomass that may be used as a replacement for fossil fuel or that may be utilized as a component blended with fossil fuels, for example in gasoline.
  • Biofuel alternatives or components for gasoline include ethanol and butanol.
  • the latter alcohol is considered to be a more advanced fuel because its fuel performance parameters, such as energy density, are greater than those of ethanol and are much closer to those of conventional gasoline.
  • Butanol can also be blended into conventional gasoline in higher amounts compared with ethanol.
  • This reaction is described in the academic literature as having three stages: (1) dehydrogenation of an alcohol (for example, ethanol) to an aldehyde (for example acetaldehyde); (2) dimerization and dehydration of this aldehyde via an aldol reaction; and (3) re-hydrogenation of the aldol product to a new alcohol (for example, butanol).
  • an alcohol for example, ethanol
  • aldehyde for example acetaldehyde
  • dimerization and dehydration of this aldehyde via an aldol reaction dimerization and dehydration of this aldehyde via an aldol reaction
  • a new alcohol for example, butanol
  • WO/2012/004572 which is hereby incorporated by reference in its entirety, describes a described high selectivity method for the conversion of alcohols to higher alcohols, for example ethanol to butanol.
  • the performance of the catalysts described according to this method can be limited by the amount of water present in the starting alcohol.
  • catalysts, and particularly organometallic catalysts are sensitive to water, which can lead to catalyst poisoning and catalyst deactivation. Because biosynthetically-produced alcohols such as ethanol are typically diluted by large amounts of water, and the separation of water from alcohols such as ethanol is difficult, it is challenging to achieve very low water concentrations in biosynthetically produced alcohols.
  • the disclosure relates to catalytic methods of converting lower molecular weight alcohols (i.e., lower alcohols) to higher molecular weight alcohols (i.e., higher alcohols).
  • the catalysts of the disclosure comprise a Group VIII transition metal complexed to a polydentate nitrogen donor ligand.
  • the catalysts are stable in water and hence, the catalytic conversions can be achieved in the presence of water.
  • the catalytic conversions described herein provide higher order alcohols such as 1 -butanol and hexan-l-ol with high selectivities.
  • a method for converting a first alcohol into a second alcohol comprising the step of contacting the first alcohol with a transition metal catalyst comprising a Group VIII transition metal selected from Ru, Fe and Os complexed to a polydentate nitrogen donor ligand.
  • the first alcohol has a molecular weight that is lower than the second alcohol.
  • the first alcohol is a lower alcohol containing two or three carbon atoms and the second alcohol is a higher alcohol containing between four and ten carbons (e.g. 4, 5, 6, 7, 8, 9, or 10 carbon atoms).
  • the first alcohol is ethanol and the second alcohol is 1 -butanol (also referred to as n-butanol).
  • the first alcohol is ethanol and the second alcohol is hexan-l-ol.
  • the transition metal catalyst is water soluble. In other embodiments, the transition metal catalyst is water stable. In other embodiments, the transition metal catalyst is both water stable and water soluble. [0008]
  • the methods of the disclosure can be carried in the presence of water without significant diminuition of catalyst activity.
  • the catalytic conversions of the disclosure can be carried out in the presence of 5% v/v water or more and still retain catalytic activity.
  • the conversion of ethanol to 1-butanol using a transition metal catalyst of the disclosure can be carried out in the presence of 5% v/v water, 10% v/v water, 15% v/v water, 20% v/v water or 25% v/v water.
  • the catalytic conversions of the disclosure can be carried out in the presence of 5% v/v water, 6% v/v water, 7% v/v water, 8% v/v water, 9% v/v water, 10% v/v water, 1 1% v/v water, 12% v/v water, 13% v/v water, 14% v/v water, 15% v/v water, 16% v/v water, 17% v/v water, 18% v/v water, 19% v/v water, 20% v/v water, 25% v/v water, and still retain catalytic activity.
  • the catalytic conversions of the disclosure can be carried out in the presence of 5% or more v/v water, 6% or more v/v water, 7% or more v/v water, 8% or more v/v water, 9% or more v/v water, 10% or more v/v water, 1 1% or more v/v water, 12% or more v/v water, 13% or more v/v water, 14% or more v/v water, 15% or more v/v water, 16% or more v/v water, 17% or more v/v water, 18% or more v/v water, 19% or more v/v water, 20% or more v/v water, 25% or more v/v water, and still retain catalytic activity. Accordingly, the disclosure provides methods of catalytically converting lower alcohols into higher alcohols in the presence of water.
  • the catalytic methods of the disclosure can be carried out in the presence of a base.
  • the base is selected from potassium i-butoxide (KOtBu), potassium ethoxide (KOEt) and potassium hydroxide (KOH).
  • the transition metal catalysts of the disclosure can be formed by admixing a source of the Group VIII transition metal such as a transition metal complex with a nitrogen donor polydentate ligand under conditions suitable to coordinate the metal comprising the transition metal complex and at least two nitrogen atoms (and possibly other heteroatoms) of the ligand, thereby forming a transition metal catalyst. In the process, at least two atoms of the transition metal complex are displaced.
  • the transition metal catalyst is a salt.
  • the transition metal catalyst contains a non-coordinating counterion such as CI, Br, I, BF 4 , PF 6 or SbF 6 .
  • the polydentate nitrogen donor ligand of the transition metal catalyst can be a bidentate, tridentate or tetradentate ligand with respect to the Group VIII metal.
  • the catalyst can include two or more ligands, which can have the same or different denticity from each other.
  • the catalyst can be in the same phase (i.e., homogeneous catalyst) or in a different phase (i.e., heterogeneous catalyst) than the lower alcohol.
  • the transition metal catalyst is formed in situ in the reaction vessel without isolation.
  • the transition metal can be pre-formed and added to the reaction vessel containing the first alcohol and optionally, a suitable base.
  • the polydentate nitrogen donor ligand has the Formula (I):
  • Qi and Q 2 are each independently a 5- or 6-membered monocyclic aromatic or non- aromatic heterocyclic ring containing at least one nitrogen atom;
  • each (R and (R 2 ) b are independently selected from:
  • the R 1 and R 2 groups form a (C 2 -C 4 )bridge that is either saturated or unsaturated, wherein said bridge is unsubstituted or substituted with 1 , 2, 3, or 4 substitutents selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t- butyl, sec -butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl;
  • (iii) a is an integer selected from 0, 1 , 2 and 3;
  • (iv) b is an integer selected from 0, 1 , 2 and 3;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl.
  • the polydentate nitrogen donor ligand is 1,10-phenantroline or a substituted 1,10-phenanthroline.
  • the 1 ,10-phenantroline derivative has one of the following chemical structures:
  • the transition metal catalyst is selected from [Ru(r
  • the transition metal catalyst has one of the following chemical structures:
  • FIG. 1 shows the percent of ethanol conversion as a function of catalyst loading (mol%) after the reaction was run for 4 hours at 150°C in the presence of 5 mol% potassium hydroxide (KOH).
  • FIG. 2 shows the effect of different transition metal catalysts on the conversion of ethanol to 1-butanol.
  • FIG. 3 shows the effect of different 1-10-phenanthroline derived ligands on the conversion of ethanol to 1-butanol.
  • FIG. 4 shows the catalytic conversion of ethanol to 1-butanol as a function of increasing initial water volume after 4 hours reaction of ethanol in the presence of 0.1 mol% of the transition metal catalyst [Ru(r
  • FIG. 5 shows selectivity as a function of catalyst loading (mol%) after the reaction was run for 4 hours at 150 ° C in the presence of 5 mol% potassium hydroxide (KOH). [Ru(r
  • FIG. 6 shows a schematic depiction of an integrated process including production of a lower alcohol followed by conversion of the lower alcohol to a higher alcohol.
  • a catalytic method for converting a first alcohol into a second alcohol there is provided a catalytic method for converting a first alcohol into a second alcohol.
  • the first alcohol is a lower molecular weight alcohol such as ethanol or propanol and the second alcohol has a molecular weight that is greater than the first alcohol.
  • the lower alcohol is ethanol.
  • the lower alcohol is propanol. Accordingly, the disclosure provides catalytic methods of converting lower alcohols into higher alcohols.
  • the second alcohol is one of the isomers of butanol, such as 1 -butanol.
  • the term includes isobutanol (or 2-methyl 1 -propanol), 1 -butanol and/or 2-butanol.
  • the second alcohol is hexan-l-ol.
  • the first alcohol is ethanol and the second alcohol is 1 -butanol.
  • the first alcohol is ethanol and the second alcohol is hexan-l-ol.
  • the second (higher alcohol) can represent the final product; in other examples, the second alcohol can be subject to further conversion, to the product, for example to an alkene.
  • 1 -butanol can be converted to 1-butene or hexan-l -ol can be converted to 1-hexene.
  • the further conversion can be effected using the same or additional conversion catalyst, which can be present in combination with the catalyst, or can be physically separate.
  • the starting composition can be a pre-cursor to an alcohol in some examples, for example an acetaldehyde or an alkene (e.g., ethylene).
  • the method can be selective to the production of one or more types of butanol.
  • the butanol produced can be substantially all 1 -butanol.
  • substantially all the butanol can be 2-butanol.
  • the conversion products include less than 10% by weight of 2-ethylbutanol and hexan-l-ol e.g. less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2% or less than 1 % by weight.
  • the first alcohol (lower alcohol) can be pretreated prior to conversion in order to achieve the preferred conditions for reaction, which will vary according to the alcohol which is to be converted. Pretreatment can include the removal of trace contaminants deleterious to the process, and/or heating/cooling to preferred reaction conditions (phase, temperature and pressure).
  • the reactant (i.e., lower alcohol) alcohol can be purified prior to reaction to remove unwanted minor components such as the fusel alcohols.
  • fusel alcohols are not removed from the lower alcohol prior to conversion to the higher alcohol.
  • the fusel alcohols can react to give minor product components. These minor product components can be subsequently separated from the main product if desired.
  • a single lower alcohol can be converted to a single higher alcohol.
  • a mixture of lower alcohols can be converted to a mixture of higher alcohol products.
  • Additional products can be formed from the 1-butanol produced in by methods of the disclosure.
  • 2-ethylhexanol can be produced from 1-butanol manufactured in accordance with methods of the disclosure.
  • the 2-ethylhexanol can be used to produce plasticizers such as 2-ethylhextl phthalate.
  • the 1-butanol produced in accordance with methods of the disclosure can be used to produce 1-butyylacetate, ethyl acetate, hexan-l-ol, 2- ethylbutan-l-ol, 1-octanol or 2-ethylhexan-l-ol.
  • the alcohol to be converted comprises ethanol.
  • the ethanol used in the reaction can be produced synthetically through the hydration of ethylene or acetylene.
  • the ethanol can be produced from biosynthetic conversion (fermentation) of biomass.
  • the method can be used to convert bio-ethanol, for example ethanol which is derived from biomass or ethanol produced by the fermentation of sugars.
  • ethanol derived from biomass or from fermentation contains a certain percentage of water (e.g., about 5% or more water by volume).
  • the amount of water in the ethanol can be reduced using techniques known in the art, such as azeotropic distillation or through the use of adsorption.
  • the methods of the disclosure can be carried out readily in the presence of water without significantly compromising yield or selectivity (see, e.g., FIG. 4).
  • the ethanol is not subjected to additional purification (e.g., azeotropic distillation) prior to reaction.
  • the fermentation of sugars to ethanol can be carried out by one or more appropriate fermenting microorganisms in single or multistep fermentations.
  • Fermenting microorganisms can be wild type microorganisms or recombinant microorganisms, and include Escherichia, Zymomonas, Saccharomyces, Candida, Pichia, Streptomyces, Bacillus, Lactobacillus, and Clostridium.
  • Particularly suitable species of fermenting microorganisms include Escherichia coli, Zymomonas mobilis, Bacillus stearothermophilus, Saccharomyces cerevisiae, Clostridia thermocellum, kluveromyces, Thermoanaerobacterium saccharolyticum, and Pichia stipitis. Genetically modified strains of E. coli or Zymomonas mobilis can be used for ethanol production (see, e.g., Underwood et al, 2002, Appl. Environ. Microbiol. 68:6263-6272 and US 2003/0162271 Al).
  • the fermentation can be carried out in a minimal media with or without additional nutrients such as vitamins and corn steep liquor (CSL).
  • CSL corn steep liquor
  • the fermentation can be carried out in any suitable fermentation vessel known in the art.
  • fermentation can be carried out in an Erlenmeyer flask, Fleaker, DasGip fedbatch-pro (DasGip technology), 2L BioFlo fermenter or 10L fermenter (B. Braun Biotech) or a commercial size fermenter.
  • the fermentation process can be performed as a batch, fed-batch or as a continuous process.
  • Typical fermentable sugars for production of ethanol include glucose, mannose, fructose, sucrose, galactose, xylose, arabinose and cellobiose.
  • Fermentation products can be recovered using various methods known in the art. Products can be separated from other fermentation components by centrifugation, filtration, microfiltration, and nanofiltration. Products can be extracted by ion exchange, solvent extraction, or electrodialysis. Flocculating agents can be used to aid in product separation.
  • bioproduced ethanol can be isolated from the fermentation medium using methods known in the art for ABE fermentations (see for example, Durre, 1998, Appl. Microbiol. Biotechnol. 49:639-648; Groot et al., 1992, Process. Biochem. 27:61 -75; and references therein).
  • solids can be removed from the fermentation medium by centrifugation, filtration, decantation, or the like.
  • the ethanol can be separated from the fermentation broth by any of the many conventional techniques known to separate ethanol from aqueous solutions. These methods include evaporation, distillation, azeotropic distillation, solvent extraction, liquid-liquid extraction, membrane separation, membrane evaporation, adsorption, gas stripping, pervaporation, and the like.
  • biomass refers to any composition comprising cellulose (optionally also hemicellulose and/or lignin).
  • hydrolyzed biomass i.e., hydro lysate
  • hydrolyzed biomass can be detoxified prior to fermentation.
  • biomasses which can be hydrolyzed or detoxified according to the methods of the disclosure can include biomasses obtained from agricultural crops such as, e.g., containing grains; corn stover, grass, bagasse, straw, e.g., from rice, wheat, rye, oat, barley, rape, sorghum; tubers, e.g. , beet and potato.
  • the biomass is preferably lignocellulosic.
  • the lignocellulosic biomass is suitably from the grass family.
  • the proper name is the family known as Poaceae or Gramineae in the class Liliopsida (the monocots) of the flowering plants. Plants of this family are usually called grasses, and include bamboo. There are about 600 genera and some 9,000-10,000 or more species of grasses (Kew Index of World Grass Species).
  • Poaceae includes the staple food grains and cereal crops grown around the world, lawn and forage grasses, and bamboo.
  • Grasses can be either annual or perennial.
  • Examples of annual cool season are wheat, rye, annual bluegrass (annual meadowgrass, Poa annua and oat).
  • Examples of perennial cool season are orchardgrass (cocksfoot, Dactylis glomerata), fescue (Festuca spp.), Kentucky bluegrass and perennial ryegrass ⁇ Lolium perenne).
  • Examples of annual warm season are corn, sudangrass and pearl millet.
  • Examples of Perennial Warm Season are big bluestem, indiangrass, bermudagrass and switchgrass.
  • anomochlooideae a small lineage of broad-leaved grasses that includes two genera (Anomochloa, Streptochaeta); 2) Pharoideae (aka Poaceae), a small lineage of grasses that includes three genera, including Pharus and Leptaspis; 3) Puelioideae a small lineage that includes the African genus Puelia; 4) Pooideae which includes wheat, barley, oats, brome-grass (Bromus) and reed-grasses (Calamagrostis); 5) Bambusoideae which includes bamboo; 6) Ehrhartoideae, which includes rice, and wild rice; 7) Arundinoideae, which includes the giant reed and common reed 8) Centothecoideae, a small subfamily of 1 1 genera that is sometimes included in Panico
  • Agricultural grasses grown for their edible seeds are called cereals. Three common cereals are rice, wheat and maize (corn). Of all crops, 70% are grasses. [0043] Therefore a preferred biomass is selected from the group consisting of the energy crops. In a further preferred embodiment, the energy crops are grasses. Preferred grasses include Napier Grass or Kenya Grass, such as Pennisetum purpureum; or, Miscanthus; such as Miscanthus giganteus and other varieties of the genus miscanthus, or Indian grass, such as Sorghastrum nutans; or, switchgrass, e.g.
  • the biomass is sugarcane, which refers to any species of tall perennial grasses of the genus Saccharum.
  • biomass include seeds, grains, tuber ⁇ e.g., potatoes and beets), plant waste or byproducts of food processing or industrial processing ⁇ e.g., stalks), corn and corn byproducts (including, e.g. , corn husks, corn cobs, corn fiber, corn stover, and the like), wood and wood byproducts (including, e.g. , processing waste, deciduous wood, coniferous wood, wood chips ⁇ e.g., deciduous or coniferous wood chips), sawdust ⁇ e.g., deciduous or coniferous sawdust)), paper and paper byproducts ⁇ e.g.
  • leaves sunflower stems, seedless sunflower heads, sunflower hulls, and sunflower residue
  • Arundo nut shells, deciduous leaves, cotton fiber, manure, coastal Bermuda grass, clover, Johnsongrass, flax, straw ⁇ e.g. , barley straw, buckwheat straw, oat straw, millet straw, rye straw amaranth straw, spelt straw), amaranth and amaranth products ⁇ e.g., amaranth stems, amaranth leaves, and amaranth residue), alfalfa, and bamboo.
  • Such hardwood and softwood include, but are not limited to, the following: pine trees, such as loblolly pine, jack pine, Caribbean pine, lodgepole pine, shortleaf pine, slash pine, Honduran pine, Masson's pine, Sumatran pine, western white pine, egg-cone pine, longleaf pine, patula pine, maritime pine, ponderosa pine, Monterey pine, red pine, eastern white pine, Scots pine, araucaria tress; fir trees, such as Douglas fir; and hemlock trees, plus hybrids of any of the foregoing.
  • pine trees such as loblolly pine, jack pine, Caribbean pine, lodgepole pine, shortleaf pine, slash pine, Honduran pine, Masson's pine, Sumatran pine, western white pine, egg-cone pine, longleaf pine, patula pine, maritime pine, ponderosa pine, Monterey pine, red pine, eastern white pine, Scots pine, araucaria tress
  • Additional examples include, but are not limited to, the following: eucalyptus trees, such as Dunn's white gum, Georgian blue gum, rose gum, Sydney blue gum, Timor white gum, and the E. urograndis hybrid; populus trees, such as eastern cottonwood, bigtooth aspen, quaking aspen, and black cottonwood; and other hardwood trees, such as red alder, Sweetgum, tulip tree, Oregon ash, green ash, and willow, plus hybrids of any of the foregoing.
  • eucalyptus trees such as Dunn's white gum, Jamaican blue gum, rose gum, Sydney blue gum, Timor white gum, and the E. urograndis hybrid
  • populus trees such as eastern cottonwood, bigtooth aspen, quaking aspen, and black cottonwood
  • other hardwood trees such as red alder, Sweetgum, tulip tree, Oregon ash, green ash, and willow, plus hybrids of any of the foregoing.
  • Any hydrolysis process can be used to prepare lignocellulosic hydrolysates, including acid hydrolysis and base hydrolysis.
  • Acid hydrolysis is a cheap and fast method and can suitably be used.
  • a concentrated acid hydrolysis is preferably operated at temperatures from 20°C to 100°C, and an acid strength in the range of 10% to 45%.
  • Dilute acid hydrolysis is a simpler process, but is optimal at higher temperatures (100°C to 230°C) and pressure.
  • Suitable acids including nitric acid, sulfurous acid, nitrous acid, phosphoric acid, acetic acid, hydrochloric acid and sulfuric acid can be used in the hydrolysis step. Depending on the acid concentration, and the temperature and pressure under which the acid hydrolysis step is carried out, corrosion resistant equipment and/or pressure tolerant equipment may be needed.
  • the hydrolysis can be carried out by subjecting the biomass material to a two step process.
  • the first (chemical) hydrolysis step is carried out in an aqueous medium at a temperature and a pressure chosen to effectuate primarily depolymerization of hemicellulose without achieving significant depolymerization of cellulose into glucose.
  • This step yields slurry in which the liquid aqueous phase contains dissolved monosaccharides and soluble and insoluble oligomers of hemicellulose resulting from depolymerization of hemicellulose, and a solid phase containing cellulose and lignin. See, e.g., U.S.
  • sulfuric acid is utilized to affect the first hydrolysis step. After the sugars are separated from the first-stage hydrolysis process, the second hydrolysis step is run under harsher condition to hydrolyze the more resistant cellulose fractions.
  • the hydrolysis method entails subjecting biomass material to a catalyst comprising a dilute solution of a strong acid and a metal salt in a reactor.
  • the biomass material can, e.g., be a raw material or a dried material.
  • This type of hydrolysis may lower the activation energy, or the temperature, of cellulose hydrolysis, ultimately allowing higher yields of fermentable sugars. See, e.g., U.S. Patent Nos. 6,660,506; 6,423,145.
  • a further exemplary method involves processing a biomass material by one or more stages of dilute acid hydrolysis using about 0.4% to about 2% of an acid; followed by treating the unreacted solid lignocellulosic component of the acid hydrolyzed material with alkaline delignification. See, e.g., U.S. Patent No. 6,409,841.
  • Another exemplary hydrolysis method comprises prehydrolyzing biomass (e.g., lignocellulosic materials) in a prehydro lysis reactor; adding an acidic liquid to the solid lignocellulosic material to make a mixture; heating the mixture to reaction temperature; maintaining reaction temperature for a period of time sufficient to fractionate the lignocellulosic material into a solubilized portion containing at least about 20% of the lignin from the lignocellulosic material, and a solid fraction containing cellulose; separating the solubilized portion from the solid fraction, and removing the solubilized portion while at or near reaction temperature; and recovering the solubilized portion.
  • biomass e.g., lignocellulosic materials
  • Hydrolysis can also comprise contacting a biomass material with stoichiometric amounts of sodium hydroxide and ammonium hydroxide at a very low concentration. See Teixeira et al , 1999, Appl. Biochem. and Biotech. 77-79: 19-34. Hydrolysis can also comprise contacting a lignocellulose with a chemical ⁇ e.g. , a base, such as sodium carbonate or potassium hydroxide) at a pH of about 9 to about 14 at moderate temperature, pressure, and pH. See PCT Publication WO 2004/081185.
  • a chemical ⁇ e.g. , a base such as sodium carbonate or potassium hydroxide
  • Ammonia hydrolysis can also be used.
  • Such a hydrolysis method comprises subjecting a biomass material to low ammonia concentration under conditions of high solids. See, e.g., U.S. Patent Publication No. 20070031918 and PCT publication WO 2006/1 10901.
  • biomass hydrolysis can be carried out in the presence of one or more hydrolyzing proteins.
  • Hydrolyzing proteins include cellulases, hemicellulases (including but not limited to xylanases, mannanases, beta-xylosidases), carbohydrate esterases (including but not limited to acetyl xylan esterases and ferulic acid esterases), laccases (which are believed to act on lignin), and non-enzymatic proteins such as swollenins (which are thought to swell the cellulose (non-catalytically and make it more accessible to cellulases).
  • hydrolyzing proteins refers to a single protein, preferably an enzyme (yet more preferably a cellulase or hemicellulase) or a cocktail of different proteins, including one or more enzymes (preferably a cellulase and/ or hemicellulase) and optionally one or more non-enzymatic proteins such as swollenins.
  • the hydrolyzing proteins can have naturally occurring or engineered polypeptide sequences.
  • the fermentable sugars used to produce ethanol can also be produced through hydrolysis of starch from starchy cereal crops such as maize, sorghum or wheat or from the extraction of sucrose from sucrose based crops such as sugarcane or sugar beet.
  • starchy cereal crops such as maize, sorghum or wheat
  • sucrose from sucrose based crops
  • sugarcane or sugar beet examples of enzymes used for the hydrolysis of starch include a-amylase, ⁇ -amylase, saccharifying a-amylase , Glucoamylase and Pillulanase. These enzymes are produced by various sources of bacteria or fungi including B.
  • the hydrolyzed product typically comprises a mixture of acid or base, partially degraded biomass and fermentable sugars, particularly where acid or ammonia hydrolysis methods are used.
  • the acid or base Prior to further processing, the acid or base can be removed from the mixture by applying a vacuum. The mixture can also be neutralized prior to detoxification. 6.2 Transition Metal Catalysts
  • the methods of the disclosure are carried out in the presence of a transition metal catalyst comprising a Group VIII transition metal and a polydentate nitrogen donor ligand.
  • the transition metal catalysts are prepared using a source of a Group VIII metal (see Section 5.2.1) and a polydentate nitrogen donor ligand (see Section 5.2.2).
  • the transition metal catalysts described herein are capable of catalyzing the conversion of lower alcohols to higher alcohols.
  • the transition metal catalyst can be formed in situ without isolation or can be pre- formed prior to the conversion of the lower alcohol to the higher alcohol.
  • the catalytic conversions of lower alcohols to higher alcohols can be performed in the presence of a base.
  • the molar ratio between the source of the Group VIII transition metal and the polydentate nitrogen donor ligand is typically between 1 : 10 and 10: 1, and more typically is between 1 : 2 and 1 : 1.
  • the source of the Group VIII transition metal catalyst is typically added or present in an amount of 0.005 mol% to about 1 mol % relative to the first alcohol, or about 0.01 mol% to about 0.5 mol% relative to the first alcohol, or about 0.05 mol% to about 0.25 mol% relative to the first alcohol.
  • the molar ratio between the source of a Group VIII metal and the base is typically between 1 : 1 and 1 : 1000, and more typically between 1 : 1 and 1 : 100.
  • the source of the Group VIII transition metal, polydentate nitrogen donor ligand and base can be added in any order, separately or together in the process reactor.
  • the transition metal catalyst can be pre-formed and isolated prior to conversion of the lower alcohol to the higher alcohol.
  • the method can include the step of reacting the source of the Group VIII transition metal (Section 5.2.1) and polydentate nitrogen donor ligand (Section 5.2.2) to form a catalyst complex prior to conversion of the alcohol.
  • the source of a Group VIII transition metal can be reacted with the polydentate nitrogen donor ligand in a suitable solvent.
  • the transition metal catalyst is in salt form.
  • the transition metal catalysts contain a non-coordinating counterion such as CI, Br, I, BF 4 , PF 6 or SbF 6 .
  • This pre-formed Group VIII transition metal - nitrogen donor ligand complex ⁇ i.e., transition metal catalyst
  • the source of a Group VIII transition metal and/or nitrogen donor ligand or pre-formed Group VIII transition metal— nitrogen donor ligand complex can be pre-reacted with the base and then added to the process reactor.
  • the addition can be at the beginning of the reaction or can be periodic during the reaction or can be continuous throughout the reaction.
  • the catalyst can be added at a constant rate or the rate can be varied.
  • the rate of catalyst addition can be used to control reaction rate and/or to modify reaction selectivity.
  • the rate of catalyst addition can be used to control reaction rate.
  • the rate of catalyst addition can be used to modify reaction selectivity.
  • the rate of catalyst addition can be used to control reaction rate and to modify reaction selectivity.
  • the pre-formed catalyst is typically added in or present in an amount of 0.005 mol% to about 1 mol % relative to the first alcohol, or about 0.01 mol% to about 0.5 mol% relative to the first alcohol, or about 0.05 mol% to about 0.25 mol% relative to the first alcohol, or about 0.05 mol% to about 0.25 mol% relative to the first alcohol; or about 0.10 mol% to about 0.20 mol% relative to the first alcohol.
  • the pre-formed transition metal catalyst is added at about 0.1 mol% relative to the first alcohol.
  • the molar ratio between the pre-formed transition metal catalyst and the base is typically between 1 : 1 and 1 : 1000, and more typically between 1 : 1 and 1 : 100.
  • the base can be added in an amount between about 1 mol% to about 10 mol% relative to the first alcohol.
  • the base can be added in an amount between about 3 mol% to about 7 mol% relative to the first alcohol.
  • the base can be added in an amount of about 5 mol% relative to the first alcohol.
  • FIG. 1 shows the percent of ethanol conversion as a function of catalyst loading (mol%) after the reaction was run at 4 hours at a 150 ° C in the presence of 5 mol% potassium hydroxide (KOH). [ ⁇ ⁇ ( ⁇ 5 - € 5 ⁇ 5 )( phen)Cl] (see Section 5.2.2.1) was used as the transition metal catalyst. The optimum conversion of ethanol was achieved at a loading of approximately 0.05% transition metal catalyst.
  • the transition metal catalysts of the disclosure typically have a turnover number (TON) exceeding 100 and a turnover frequency (TOF) exceeding 25/hour.
  • TON refers to the total number of moles of ethanol converted to product per mole of catalyst.
  • TOF is TON per hour. In some embodiments, the TON is 200 or greater and the TOF is 50/hour or greater.
  • FIGS. 2 and 3 provide TONs and TOFs for the conversion of ethanol to 1 -butanol using 5 mol% of specific transition metal catalysts of the disclosure after four hours reaction time.
  • the Group VIII transition metal is selected from one or more of Ru, Fe, and Os.
  • the Group VIII transition metal comprises Ru.
  • the source of a group VIII metal can be the metal itself in some embodiments.
  • the metal can for example be dispersed on a support material such as carbon, silica or alumina, silica alumina and combinations thereof.
  • the Group VIII metal can comprise a compound of the metal.
  • the transition metal catalyst can be formed by admixing a transition metal complex with the nitrogen donor polydentate ligand under conditions suitable to coordinate the metal comprising the transition metal complex and at least two nitrogen atoms) and possibly other heteroatoms) of the ligand.
  • the transition metal complex used to prepare the transition metal catalyst can comprise a component of a complex comprising a species of formula [M(L) n ] m :
  • n is an integer from 1 to 8
  • the transition metal complex can be charged.
  • M of the complex is one or more of Ru and Fe.
  • M of the complex is one or more of Ru and Os.
  • M of the complex is one or more of Fe and Os.
  • M of the complex is Fe.
  • M of the complex is Os.
  • M of the complex is Ru.
  • M is Ru.
  • the L groups from [M(L) n ] m can be the same or different and are ligands, for example chloride, bromide, iodide, hydride, alkoxide, amide, acetate, acetylacetonate, alkyl (for example methyl, ethyl, butyl), amine, ether, a hydrocarbon or substituted hydrocarbon ligand (for example ⁇ 3 - allyl, r
  • ligands for example chloride, bromide, iodide,
  • L groups can also be solid state materials that act as ligands and produce a supported metal species, for example silica, alumina, zeolites or poly(vinyl pyridine).
  • Particular ligands include chloride, bromide, iodide, hydride, acetate, acetylacetonate, a hydrocarbon or substituted hydrocarbon ligand (for example r
  • one or more L groups of the transition metal complex can be displaced.
  • n can be an integer from 1 to 8. In certain embodiments, n is an integer from 2 to 6. In other embodiments, n is an integer from 3 to 5.
  • the Group VIII metal of the transition metal complex can comprise a component of a complex comprising a species of formula [M(L) n ] m
  • m is an integer representing the nuclearity of the complex.
  • L is selected to achieve suitable stability of the complex.
  • a single source of a Group VIII transition metal or a mixture of two or more sources can be used. Suitable sources for Fe and Os metal are known in the art.
  • single sources of a Group VIII transition metal can be used.
  • Suitable sources for Ru metal include, for example, one of the following transition metal complexes:
  • the transition metal complex used to form the transition metal catalysts of the disclosure is [Ru(cymene)Cl 2 ] 2 , which has the following chemical structure:
  • the polydentate nitrogen donor ligand comprises at least two nitrogen atoms that are capable of binding to the Group VIII metal of the transition metal catalysts.
  • Ligands in which only the two nitrogen atoms bind to the Group VIII metal are bidentate ligands.
  • the ligands can contain other heteroatoms in addition to the two nitrogen atoms that are capable of binding to the Group VIII metal of the transition metal catalyst.
  • three heteroatoms of the polydentate nitrogen donor ligand can bind to the Group VIII metal, thereby forming a tridentate ligand.
  • four heteroatoms of the polydentate nitrogen donor ligand can bind to the Group VIII metal, thereby forming a tetradentate ligand.
  • the polydentate ligand is comprised of two 5- or 6- membered nitrogen-containing heterocyclic rings which can be bonded together or linked through a linking group.
  • Such ligands are represented by the Formula (I):
  • Qi and (3 ⁇ 4 are each independently a 5- or 6-membered monocyclic aromatic or non- aromatic heterocyclic ring containing at least one nitrogen atom;
  • each (R 1 ⁇ and (R 2 ) b are independently selected from:
  • the R 1 and R 2 groups form a (C 2 -C 4 )bridge that is either saturated or unsaturated, wherein said bridge is unsubstituted or substituted with 1 , 2, 3, or 4 substitutents selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t- butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl;
  • (iii) a is an integer selected from 0, 1 , 2 and 3;
  • (iv) b is an integer selected from 0, 1 , 2 and 3;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl, and phenyl.
  • Qi and Q 2 are independently selected from pyridinyl, pyrazinyl, pyrimidinyl, triazinyl, piperidinyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, isoxazolidinyl, oxazolidinyl, dihydropyrrolyl, dihydropyrazolyl, dihydroimidazolyl, dihydroisoxazolyl, dihydrooxazolyl, dihydrothiazolyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl and isoindoledionyl.
  • Qi and (3 ⁇ 4 are pyridinyl. In another embodiment, Qi is pyridinyl and (3 ⁇ 4 is dihydroisoxazolyl. In another embodiment, Qi is pyridinyl and (3 ⁇ 4 is dihydrothiazolyl. In another embodiment, Qi and Q 2 are pyrimidinyl.
  • the -(5- or 6-membered)heterocycles Qi and (3 ⁇ 4 can be attached to linking group X of Formula (I) via a nitrogen or carbon atom.
  • the -(5- or 6-membered)heterocycles Qi and (3 ⁇ 4 can be covalently bonded to each other via two carbon atoms on the respective rings.
  • the ligand can be a 2,2-bipyridine or 2,2-bipyrimidine of Formula IA:
  • Z is -CH- or -N- a nndd ((RR''))a a aanndd ((RR 2 )b aarree ddeeffined as above.
  • 2,2- bipyridine ligands include:
  • the ligand can have the Formula (IB)
  • X in Formula (I) is present as a heterocyclic group that links rings Qi and Q 2.
  • X is 1 ,3-phenylene, 1 ,4-phenylene, 1 ,2-phenylene, 2,5-pyridylene, 2,5-pyridylene, 3,6-pyridylene or 2,5- pyrimidylene or 2,5- pyrimidylene.
  • X is a phenylene group selected from 1 ,2-phenylene, 1 ,4-phenylene and 1,3-phenylene.
  • Particular examples of such ligands include:
  • the R 1 and R 2 groups of Formula (I) can form a (C 2 -C 4 )bridge that either saturated or unsaturated.
  • R 1 and R 2 can form an ethylene bridg
  • the ligand can be a 1,10-phenantroline compound the Formula (IC):
  • R4 is selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl, and c is 0, 1 or 2.
  • 1,10-phenanthroline ligands of Formula (IC) include:
  • Examples of pre- formed complexes in which 1,10- phenanthroline (phen) is used as an exemplar polydentate nitrogen donor ligand include: [Ru(r
  • other ligands described herein could be substituted for the phen ligand.
  • the pre- formed transition metal catalyst has one of the following chemical structures:
  • the polydentate ligand is comprised of a 5- or 6- membered nitrogen- containing heterocyclic ring which is bonded directly or through a linker to an amine donor or imine- type donor.
  • Such ligands are represented by the Formula (II):
  • Qi is a 5- or 6-membered aromatic or non-aromatic heterocyclic ring containing at least one nitrogen atom
  • (ii) is selected from halo, cyano, hydroxyl, nitro, amino, methyl, ethyl, isopropyl, n- propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl, phenyl, ortho-tolyl, meta-tolyl, para-tolyl, isopropylphenyl, dimethylphenyl, mesityl, naphthyl, -(C 2 -C 6 )alkenyl, -(C 2 -C 6 )alkynyl, and -(Ci-C 6 )alkoxy;
  • each R 5 is independently selected from:
  • dihydropyrazolyl dihydroimidazolyl, dihydroisoxazolyl, dihydrooxazolyl, dihydrothiazolyl, pyrazolyl, imidazolyl, and isoindoledionyl, which can be substituted with one or more R 3 groups;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl, and phenyl; (vi) a is 0, 1 or 2; and
  • the value of y determines the unsaturation of the nitrogen on the polydentate nitrogen donor ligand.
  • the nitrogen is a fully saturated amine donor, for example dimethylamino if both R 1 groups are methyl.
  • the polydentate nitrogen donor ligand can have the Formula (IIA):
  • the polydentate nitrogen donor ligand can have the Formula ( ⁇ ):
  • the polydentate ligand is a ligand of Formula (III):
  • each R 5 is independently selected from:
  • dihydropyrazolyl dihydroimidazolyl, dihydroisoxazolyl, dihydrooxazolyl, dihydrothiazolyl, pyrazolyl, imidazolyl, and isoindoledionyl, which can be substituted with one or more R 3 groups;
  • G is -CH 2 -, -CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -CH-, -CH 2 CH 2 -, -CH 2 CH-, -CH(R 5 )CH(R 5 )-, CH 2 N(R 5 )CH 2 -, -CH 2 CH 2 N(R 5 )CH 2 CH 2 -, 1 ,3-phenylene, 1 ,4-phenylene, 1,2- phenylene, 2,5-pyridylene, 2,5-pyridylene, 3,6-pyridylene or 2,5- pyrimidylene and 2,5- pyrimidylene;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl; and
  • the value of y determines the unsaturation of the nitrogen on the polydentate nitrogen donor ligand.
  • the nitrogen is a fully saturated amine donor, for example dimethylamino if both R 1 groups are methyl.
  • ligands of Formula (III) include:
  • ligands of Formula (III) include ethylenediamine,
  • di ethyl enetriamine 1 ,2-diphenylethylenediamine, and N-p-Tosyl-l,2-diphenylethylenediamine.
  • the base's conjugate acid has a pKa greater than 5.
  • the base can comprise any compound with a conjugate acid having a pKa preferably greater than 5.
  • Suitable bases include metal alkoxides (such as NaOMe, KOMe, NaOEt, NaOBu), metal hydroxides, amines and metal carbonates, or basic solid-state materials.
  • the base is a metal alkoxide or hydroxide.
  • the base can be potassium hydroxide, potassium methoxide, potassium ethoxide and potassium butoxide. These can also be formed in the reaction media by reaction of sodium or potassium metal with an alcohol or water.
  • the Group VIII metal and/or polydentate ligand may fulfill the role of the base.
  • the polydentate ligand may contain a basic functionality within its structure (such as an amine) which has a conjugate acid with a pKa greater than 5.
  • the catalytic conversions of the disclosure can be can be run as batch, semi -batch or continuous processes.
  • the feed alcohol (lower alcohol) and the prepared catalyst can be fed to a reactor.
  • base is added, the addition can be made once during a reaction or periodically or continually.
  • the rate of base addition can be used to control reaction rate and/or reaction selectivity.
  • the rate of base addition can be used to control reaction rate.
  • the rate of base addition can be used to control reaction selectivity.
  • the rate of base addition can be used to control reaction rate and selectivity.
  • More than one base can be added.
  • the base can be added as a solution in a suitable solvent, for example dissolved in the reactant or in an inert solvent.
  • the base can also be added as a solid.
  • the reaction can be configured so that the process stream containing the catalyst first passes over a solid base in a first zone and subsequently enters a reaction zone where the conversion of the first alcohol to the second alcohol occurs.
  • a dissolved base can be mixed with the reactant in a first zone and this is then passed over an immobilized form of the catalyst in a subsequent reaction zone.
  • the catalytic conversions of the disclosure can be carried in the presence of water without significant attenuation of catalyst activity.
  • the catalytic conversions of the disclosure can be carried out in the presence of 5% v/v water or more and still retain catalytic activity.
  • the conversion of ethanol to 1-butanol using a transition metal catalyst of the disclosure can be carried out in the presence of 5% v/v water, 10% v/v water, 15% v/v water, 20% v/v water or 25% v/v water.
  • the amount of water can be bounded by any of the two foregoing embodiments, e.g., between 5% v/v water and 25% v/v water, between 5% v/v water and 20% v/v water, between 5% v/v water and 10% v/v water, between 10% v/v water and 20% v/v water, and so on, and so forth.
  • FIG. 4 shows the catalytic conversion of ethanol to 1-butanol as a function of increasing initial water volume after 4 hours reaction of ethanol with 0.1 mol% of the transition metal catalyst [Ru ⁇ 5 -C 5 H 5 )( phen)Cl] and 5 mol% of the base sodium ethoxide (NaOEt) at a temperature of 150°C (see diamond shapes). While the yield of 1-butanol decreases with increasing water volume, the catalysts are still highly active in water. In contrast, diphosphine ligand catalyst (square shapes) described in WO/2012/004572 show a significant reduction of catalytic activity when the reaction is conducted under otherwise identical conditions.
  • the lower alcohol to be converted is intimately contacted with the catalyst of the disclosure, which can be in solid or liquid form. Additional chemicals can be added to promote or moderate the reaction, along with hydrogen and/ or other gas to maintain the required pressure.
  • the reactor design will be appropriate to the form of the catalyst, the phase of the reaction and the need to add or remove heat. Lower alcohols may prefer vapor phase operation or require higher pressure to remain in liquid phase at reaction temperature, while higher alcohols may prefer liquid phase operation or require lower pressure operation to enable vaporization at reaction temperature. Intimate contacting of the reactant and catalyst may be effected naturally (as with the flow of vapor phase reactant through a solid catalyst bed), mechanically by use of an agitator or hydraulically by liquid or vapor jet mixing.
  • the catalyst can be placed in an immobilized form within a distillation column and the reactant allowed to distil through the catalyst bed.
  • a reactive distillation takes place where more volatile reactant passes up the distillation column and reacts. Unreacted alcohol can be removed above the reaction zone and returned lower in the column for further reactive distillation. Product alcohol with lower vapor pressure passes down the distillation column and can be removed lower in the column.
  • This configuration allows for a continuous reaction with high conversion.
  • reactant and other materials such as base are mixed in solution and introduced to a reactor. The stream is allowed to react and then leaves the reactor where the reaction is then terminated by cooling or quenching by for example reducing the pH of the stream or by separating reactant from the catalyst.
  • the material leaving the reactor can undergo a primary separation in a primary separator to separate the desired product(s) from unreacted feed materials which can then be recycled to the reactor.
  • This primary separation can take a number of forms, including flash separation, distillation, liquid liquid extraction, size selective absorption or adsorption, pressure swing adsorption, membranes or a combination of suitable techniques.
  • Primary separation can also be combined with reaction in a reactive distillation system. Any unreacted feed materials in gas or vapor phase leaving the primary separation can be treated to remove trace contaminants deleterious to the process and/or heated/cooled and/or compressed/pumped to the appropriate conditions for recycle to the reactor.
  • any dissolved solids such as catalyst or base are fully or partially separated from the stream to give a liquid mixture of product and unreacted feed material which are then separated from each other in a subsequent step.
  • a higher boiling solvent can be added prior to the reaction, during it or subsequently, which can then be used to maintain the catalyst system and/or base in solution whist fully or substantially removing the reactant alcohol(s) and the product alcohol(s)
  • a product stream comprising reactant alcohol(s) and product alcohol(s) is separated from the dissolved solids and gases but is then not further separated.
  • This mixture can be used directly, for example as a fuel composition or can be used as a reactant mixture.
  • the transition metal catalyst can be in the same phase as the lower alcohol (for example a homogeneous reaction in the liquid phase) or in a different phase (for example a solid catalyst and liquid or gaseous ethanol).
  • the amount of catalyst in the process reactor (based on molar ratio ethanol to the Group VIII transition metal) will vary depending on the specific reactor configuration used but will typically be between 10 8 and 100 to 1.
  • the higher alcohol product can also act as a diluent, or an additional diluent solvent can be added.
  • Suitable diluents include alkanes (such as butane, pentane, hexane, cyclohexane), arenes (such as benzene, toluene, xylene), alcohols (such as methanol, ethanol, propanol, butanol), ethers (such as diethyl ether, dibutyl ether, tetrahydrofuran), carboxylic acids and carboxylic acid derivatives (such as acetic acid, ethyl acetate), water, or mixture thereof.
  • alkanes such as butane, pentane, hexane, cyclohexane
  • arenes such as benzene, toluene, xylene
  • alcohols such as methanol, ethanol, propanol, butanol
  • ethers such as diethyl ether, dibutyl ether, tetrahydrofuran
  • the catalyst system can optionally be used in dissolved form during the reaction period but then recovered in solid form outside the reaction zone and re-solubilized for subsequent use.
  • the catalyst can be recovered in its dissolved form by leaving it in contact with a suitable solvent throughout which can be the reactant the product or another solvent.
  • the catalyst can be recovered in dissolved form by extracting it from the reaction mixture with a solvent. Process variables such as pH or temperature can be varied to modify catalyst solubility to effect such separations.
  • Certain diluents can also be used as entrainers in a reactive distillation configuration so as to be able to remove water from the reactive distillation whilst leaving the reactant alcohol in the distillation column.
  • Cyclohexane for example would be a suitable diluent and entrainer to use with ethanol allowing water to be removed at the top of the reactive distillation column. Removing water in this way can improve reaction rate.
  • a diluent can be chosen so that following reaction it then assists in the subsequent separation by breaking azeotropes either with water or between reactants and products.
  • a diluent which is the same as a subsequent article of commerce to be produced from the product alcohol or which can be produced from the reactant alcohol in order to obviate the need to then separate the diluent from the reactant or the product.
  • Examples of this approach include using 2-ethylhexyl alcohol as diluent when making 1 -butanol and subsequently using this product to produce 2-ethylhexanol.
  • butyl acetate could be used and the 1 -butanol product used to make butyl acetate.
  • Ethyl acetate could be used and the residual ethanol be used to produce ethyl acetate.
  • the steady state reaction temperature can be between 0 °C and 500 °C, and more typically between 70 °C and 200 °C or between 130 °C and 170 °C.
  • the reaction is performed at a temperature between about 131 °C and 170°C; 132°C and 170°C; 133°C and 170°C; 134°C and 170°C; 135°C and 170°C; 140°C and 170°C; 145°C and 170°C; 145°C and 170°C; 150°C and 170°C; 165°C and 170°C; 160°C and 170°C; 165°C and 170°C; 131 °C and 165°C; 132°C and 165°C; 133°C and 165°C; 134°C and 165°C; 135°C and 165°C; 140°C and 165°C; 145°C and 165°C; 145°C and 165°C
  • the catalytic methods of the disclosure are carried out at a temperature between about 145°C and 155°C; 146°C and 154°C; 147°C and 153°; C148°C and 152°C; 149°C and 151 °C.
  • the method is carried out at a temperature of about 150°C.
  • the method of the disclosure can be performed under an inert atmosphere, typically argon or hydrogen.
  • the process reaction can be performed under a pressure of hydrogen.
  • the process reaction is carried out under a pressure of hydrogen e.g.
  • the methods of the disclosure can further include the step of separating the higher alcohol product from the reaction composition.
  • the separation can be carried out by any appropriate method, for example by passing the reaction product to a membrane separator.
  • the alcohol product e.g., 1-butanol
  • the alcohol product is sufficiently pure that it can be used at least for some applications without further purity being required.
  • the process optionally includes a subsequent separation step designed to maximize the recovery of the transition metal catalyst from the process effluent streams.
  • Techniques such as distillation, precipitation, membrane separation, electrolysis, ion exchange and liquid extraction can be used.
  • FIG. 6 It can be beneficial to integrate the production of the lower alcohol and the catalytic conversion to a higher alcohol into a single integrated process.
  • a lower alcohol e.g., ethanol
  • the lower alcohol is then fed into a reactor along with a transition metal catalyst of the disclosure and a suitable base.
  • the stream leaving the reactor is comprised of a mixture of reactants, impurities and the higher alcohol product.
  • the higher alcohol product can be isolated by using an appropriate separation technique such as flash separation, distillation, or liquid liquid extraction.
  • the integration can be made by adding the catalytic reactor into the rectification stage of the fermentation process distillation as a reactive distillation zone where solid material is kept in the base of the distillation column and the transition metal catalyst is separated from the solids by a portion of column containing substantially liquid or vapor components.
  • the catalytic reactor is integrated subsequent to the distillation stage so as to be fed with a substantially solids free process stream.
  • the temperature of the catalytic reaction can be significantly higher than the process temperatures of a fermentation process. In one embodiment, this temperature difference can be used to provide heat integration for the ethanol distillation section. In the case of a lignocellulosic ethanol process it can be used to provide heat integration to the pretreatment stage. In a corn or wheat ethanol process it can be used to provide heat integration to the starch liquefaction stage, evaporation and/or the ethanol distillation stage. In a sugarcane ethanol process it can be used to provide heat integration to the evaporation and/or ethanol distillation stage. [0107] Because the lower to higher alcohol process includes its own product separation stage, the integrated process allows a lower separation efficiency in the separation of ethanol from the fermentation broth.
  • water need not be so completely removed as in a non integrated ethanol process.
  • Fusel alcohols need not be so completely removed.
  • Other organic components such as furans produced in a lignocellulosic ethanol process need not be so fully removed. These materials can all be subsequently separated in the higher alcohol separation stage.
  • the purity of the second alcohol generated as a product of the catalyzed reaction of the disclosure can reach high levels, for example greater than 80% or 90%.
  • the reaction products are such that substantially no further reaction and/ or separation of the second alcohol from other reaction products is required.
  • the conversion is highly selective giving a high yield of the second alcohol relative to other products, particularly alcohol byproducts. While it is envisaged that the product including the second alcohol can include a mixture of two or more different alcohols, preferably the second alcohol is present as the dominant alcohol product.
  • the term "selectivity" refers to the percentage by weight of the second alcohol in the final product based on the weight of all alcohols (excluding the first alcohol) in the conversion products. If the catalytic conversions of the disclosure are run as a batch process, the selectivity may gradually decrease with the extent of conversion as products are formed in the reaction chamber. If the catalytic conversions are performed in a continuous process, the liquid fractions containing the product are continuously removed and hence, selectivity does not vary significantly with extent of conversion.
  • other alcohol byproducts may form, including 2-ethoxybutanol, hexan-l-ol and 2-ethylhexanol.
  • a selectivity of 90% 1-butanol indicates that 90% of the total alcohol products in 1-butanol.
  • the remaining 10% often comprises a mixture of 2-ethoxybutanol, hexan-l-ol and 2-ethylhexanol.
  • selectivity of at least 80% of the second alcohol can be achieved at a conversion of 20% or greater of the first alcohol.
  • selectivity of at least 85% of the second alcohol can be achieved at a conversion of 20% or greater of the first alcohol.
  • selectivity of at least 90% can be achieved at a conversion of 20% or greater of the first alcohol.
  • the selectivity of the second alcohol produced by methods in accordance with the disclosure can be 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100% at a conversion of 20% or greater of the first alcohol.
  • the selectivity of the second alcohol can be bounded by any of the two foregoing embodiments, e.g., a selectivity of between 90% and 95%, a selectivity between 90% and 97%, a selectivity of between 92% and 95%, a selectivity of between 92% and 97%, a selectivity of between 92% and 99%, a selectivity of between 93% and 97%, a selectivity of between 95% and 98%, at a conversion of 20% or greater of the first alcohol.
  • FIGS. 2 and 3 show selectivities for the conversion of ethanol to 1-butanol using 5 mol% of specific transition metal catalysts of the disclosure after four hours reaction time.
  • FIG. 1 shows the percent of ethanol conversion as a function of catalyst loading (mol%) after the reaction was run at 4 hours at a 150°C in the presence of 5 mol% potassium hydroxide (KOH).
  • KOH potassium hydroxide
  • FIG. 5 shows the product distribution (i.e., selectivity) at the various catalyst loadings. As shown in FIG. 5, high selectivities were achieved at all levels of catalyst loading, with the optimal selectivities achieved at catalyst loading between about 0.05 mol% and about 0.1 mol%.
  • Example 21 Essentially the same procedure as Example 21 was followed, only with varying amounts of added water (see FIG. 4). In all cases selectivity was higher than 90% and conversion to 1-butanol is indicated in the graph.
  • a method for converting a lower alcohol to a higher alcohol comprising the step of contacting said lower alcohol with a transition metal catalyst comprising a Group VIII transition metal complexed to a polydentate nitrogen donor ligand for a time sufficient to form said higher alcohol.
  • transition metal is Ru, Fe or Os.
  • Qi and (3 ⁇ 4 are each independently a 5- or 6-membered monocyclic aromatic or non- aromatic heterocyclic ring containing at least one nitrogen atom;
  • each (R 1 ⁇ and (R 2 ) b are independently selected from:
  • the R 1 and R 2 groups form a (C 2 -C 4 )bridge that is either saturated or unsaturated, wherein said bridge is unsubstituted or substituted with 1, 2, 3, or 4 substitutents selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t- butyl, sec -butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl;
  • (iii) a is an integer selected from 0, 1, 2 and 3;
  • (iv) b is an integer selected from 0, 1, 2 and 3;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl, and phenyl.
  • R 4 is selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl and c is an integer selected from 0, 1 and 2.
  • Z is -CH- or -N-.
  • Z is -CH- or -N- and T is or -0-, -S-, or -NH-
  • Qi is a 5- or 6-membered monocyclic heterocyclic ring containing at least one nitrogen atom which is either saturated non-aromatic, unsaturated non-aromatic or aromatic;
  • (ii) (R') a is selected from halo, cyano, hydroxyl, nitro, amino, methyl, ethyl, isopropyl, n- propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl, phenyl, ortho-tolyl, meta-tolyl, para-tolyl, isopropylphenyl, dimethylphenyl, mesityl, naphthyl, -(C 2 -C 6 )alkenyl, -(C 2 -C 6 )alkynyl, and -(Ci-C 6 )alkoxy;
  • G is selected from:
  • each R 5 is independently selected from:
  • dihydropyrazolyl dihydroimidazolyl, dihydroisoxazolyl, dihydrooxazolyl, dihydrothiazolyl, pyrazolyl, imidazolyl, and isoindoledionyl, which can be substituted with one or more R 3 groups;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl, and phenyl;
  • each R 5 is independently selected from:
  • dihydropyrazolyl dihydroimidazolyl, dihydroisoxazolyl, dihydrooxazolyl, dihydrothiazolyl, pyrazolyl, imidazolyl, and isoindoledionyl, which can be substituted with one or more R 3 groups;
  • G is -CH 2 -, -CH 2 OCH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -CH-, -CH 2 CH 2 -, -CH 2 CH-, -CH(R 5 )CH(R 5 )-, CH 2 N(R 5 )CH 2 -, -CH 2 CH 2 N(R 5 )CH 2 CH 2 -, 1 ,3-phenylene, 1 ,4-phenylene, 1,2- phenylene, 2,5-pyridylene, 2,5-pyridylene, 3,6-pyridylene or 2,5- pyrimidylene and 2,5- pyrimidylene;
  • each R 3 is independently selected from halo, cyano, hydroxyl, nitro, amino, aminoalkyl, methyl, ethyl, isopropyl, n-propyl, t-butyl, sec-butyl, isobutyl, n-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, benzyl and phenyl; and (iv) y is 1 or 2.
  • transition metal catalyst is formed in situ by admixing a source of the Group VIII transition metal with the polydentate nitrogen donor ligand in the presence of the lower alcohol.
  • reaction mixture comprises at least 10% water by volume.
  • biosynthetic process comprises fermenting one or more fermentable sugars.
  • lignocellulosic biomass comprises one or more of Napier grass, energy cane, sorghum, giant reed, sugar beet, switchgrass, bagasse, rice straw, miscanthus, switchgrass, wheat straw, wood, wood waste, paper, paper waste, agricultural waste, municipal waste, birchwood, oat spelt, corn stover, eucalyptus, willow, hybrid poplar, short-rotation woody crop, conifer softwood, crop residue.
  • a transition metal catalyst comprising a Group VIII transition metal complexed to a polydentate nitrogen donor ligand in a method for producing a higher alcohol from a lower alcohol, wherein the reaction mixture comprises at least 5% water by volume.
  • reaction mixture comprises at least 10% water by volume.
  • reaction mixture comprises at least 15% water by volume.
  • reaction mixture comprises at least 20% water by volume.
  • reaction mixture comprises at least 25% water by volume.

Abstract

La présente invention concerne des procédés de conversion d'un alcool court (<i />par exemple l'éthanol) en un alcool long (<i />par exemple le butanol) en présence d'un catalyseur à base de métal de transition stable dans l'eau comprenant un métal de transition du Groupe VIII et un ligand donneur azoté polydentate. Les procédés décrits dans la présente invention peuvent être mis en œuvre en présence d'eau et atteindre des puretés élevées en alcools longs.
PCT/US2014/053053 2013-08-30 2014-08-28 Conversion catalytique d'alcools WO2015031561A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361872079P 2013-08-30 2013-08-30
US61/872,079 2013-08-30

Publications (1)

Publication Number Publication Date
WO2015031561A1 true WO2015031561A1 (fr) 2015-03-05

Family

ID=51541318

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/053053 WO2015031561A1 (fr) 2013-08-30 2014-08-28 Conversion catalytique d'alcools

Country Status (1)

Country Link
WO (1) WO2015031561A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109896923A (zh) * 2017-12-07 2019-06-18 中国科学院大连化学物理研究所 一种双组分催化剂上乙醇转化制备高碳伯醇的方法
IT201800004226A1 (it) * 2018-04-05 2019-10-05 Procedimento migliorato per la trasformazione di alcoli alifatici primari in alcoli alifatici superiori
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536325A (en) 1979-03-23 1996-07-16 Brink; David L. Method of treating biomass material
US6409841B1 (en) 1999-11-02 2002-06-25 Waste Energy Integrated Systems, Llc. Process for the production of organic products from diverse biomass sources
US6423145B1 (en) 2000-08-09 2002-07-23 Midwest Research Institute Dilute acid/metal salt hydrolysis of lignocellulosics
US20030162271A1 (en) 2000-05-01 2003-08-28 Min Zhang Zymomonas pentose-sugar fermenting strains and uses thereof
WO2004081185A2 (fr) 2003-03-07 2004-09-23 Athenix Corporation Procede permettant d'ameliorer l'activite d'enzymes de degradation de la lignocellulose
WO2006110901A2 (fr) 2005-04-12 2006-10-19 E. I. Du Pont De Nemours And Company Traitement de biomasse en vue d'obtenir des sucres fermentescibles
JP2008266267A (ja) * 2007-04-25 2008-11-06 Mitsubishi Chemicals Corp アルコールの製造方法
JP2008303160A (ja) * 2007-06-06 2008-12-18 Mitsubishi Chemicals Corp アルコールの製造方法
EP2221289A1 (fr) * 2007-12-20 2010-08-25 Mitsubishi Chemical Corporation Procédé de production d'un alcool
WO2012004572A1 (fr) 2010-07-09 2012-01-12 BP Biofuels UK Limited Conversion d'alcools

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5536325A (en) 1979-03-23 1996-07-16 Brink; David L. Method of treating biomass material
US6409841B1 (en) 1999-11-02 2002-06-25 Waste Energy Integrated Systems, Llc. Process for the production of organic products from diverse biomass sources
US20030162271A1 (en) 2000-05-01 2003-08-28 Min Zhang Zymomonas pentose-sugar fermenting strains and uses thereof
US6423145B1 (en) 2000-08-09 2002-07-23 Midwest Research Institute Dilute acid/metal salt hydrolysis of lignocellulosics
US6660506B2 (en) 2000-08-09 2003-12-09 Midwest Research Institute Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics
WO2004081185A2 (fr) 2003-03-07 2004-09-23 Athenix Corporation Procede permettant d'ameliorer l'activite d'enzymes de degradation de la lignocellulose
WO2006110901A2 (fr) 2005-04-12 2006-10-19 E. I. Du Pont De Nemours And Company Traitement de biomasse en vue d'obtenir des sucres fermentescibles
US20070031918A1 (en) 2005-04-12 2007-02-08 Dunson James B Jr Treatment of biomass to obtain fermentable sugars
JP2008266267A (ja) * 2007-04-25 2008-11-06 Mitsubishi Chemicals Corp アルコールの製造方法
JP2008303160A (ja) * 2007-06-06 2008-12-18 Mitsubishi Chemicals Corp アルコールの製造方法
EP2221289A1 (fr) * 2007-12-20 2010-08-25 Mitsubishi Chemical Corporation Procédé de production d'un alcool
WO2012004572A1 (fr) 2010-07-09 2012-01-12 BP Biofuels UK Limited Conversion d'alcools

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
CARLINI ET AL., JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 200, 2003, pages 137 - 146
DURRE, APPL. MICROBIOL. BIOTECHNOL., vol. 49, 1998, pages 639 - 648
GEORGE R. M. DOWSON ET AL: "Catalytic Conversion of Ethanol into an Advanced Biofuel: Unprecedented Selectivity for n -Butanol", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 52, no. 34, 19 August 2013 (2013-08-19), pages 9005 - 9008, XP055144914, ISSN: 1433-7851, DOI: 10.1002/anie.201303723 *
GROOT ET AL., PROCESS. BIOCHEM., vol. 27, 1992, pages 61 - 75
KODA ET AL., CHEMISTRY LETTERS, vol. 38, 2009, pages 838
NIXON ET AL., DALTON TRANSACTION, 2009, pages 753 - 762
TEIXEIRA ET AL., APPL. BIOCHEM. AND BIOTECH., vol. 77-79, 1999, pages 19 - 34
UNDERWOOD ET AL., APPL. ENVIRON. MICROBIOL., vol. 68, 2002, pages 6263 - 6272

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109896923A (zh) * 2017-12-07 2019-06-18 中国科学院大连化学物理研究所 一种双组分催化剂上乙醇转化制备高碳伯醇的方法
CN109896923B (zh) * 2017-12-07 2022-10-21 中国科学院大连化学物理研究所 一种双组分催化剂上乙醇转化制备高碳伯醇的方法
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors
IT201800004226A1 (it) * 2018-04-05 2019-10-05 Procedimento migliorato per la trasformazione di alcoli alifatici primari in alcoli alifatici superiori
WO2019193079A1 (fr) 2018-04-05 2019-10-10 Alma Mater Studiorum - Universita' Di Bologna Procédé amélioré pour la transformation d'alcools aliphatiques primaires en alcools aliphatiques supérieurs
US11932592B2 (en) 2018-04-05 2024-03-19 Alma Mater Studiorum—Universita' di Bologna Process for the transformation of primary aliphatic alcohols into higher aliphatic alcohols
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors

Similar Documents

Publication Publication Date Title
EP2635712B1 (fr) Traitement de biomasse pour produire des matières utiles pour des biocarburants
EP2513080B1 (fr) Procédé de production de furfural à partir d&#39;un matériau biomassique lignocellulosique
EP2847344B1 (fr) Procédé continu ou semi-continu de traitement d&#39;une biomasse
López-Linares et al. Bioethanol production from rapeseed straw at high solids loading with different process configurations
Sannigrahi et al. Fundamentals of biomass pretreatment by fractionation
US10087160B2 (en) Process for the manufacture of furural and furfural derivatives
US20160312249A1 (en) Process comprising sulfur dioxide and/or sulfurous acid pretreatment and enzymatic hydrolysis
US20170073365A1 (en) Preparation of lignin
EP2825519B1 (fr) Procédé de production d&#39;acide lévulique à partir de biomasse lignocellulosique
US20140024093A1 (en) Process for the production of digested biomass useful for chemicals and biofuels
RU2010116359A (ru) Двухстадийный способ ферментативного гидролиза для обработки лигноцеллюлозных материалов
WO2015031561A1 (fr) Conversion catalytique d&#39;alcools
WO2009092749A1 (fr) Procédé pour prétraiter un matériau lignocellulosique en vue de produire du bioéthanol, et procédé de production de bioéthanol
US11299850B2 (en) Converting lignocellulosic biomass to glucose using a low temperature sulfur dioxide pretreatment
Wang et al. Organosolv fractionation process with various catalysts for improving bioconversion of triploid poplar
KR20140002804A (ko) 바이오매스 성분을 분리하기 위한 일 단계 방법
US20150307952A1 (en) Liquid co-extraction process for production of sucrose, xylo-oligosaccharides and xylose from feedstock
WO2015160887A1 (fr) Procédés de production de produits de fermentation
CN108753870A (zh) 一种生物质处理方法
Russ et al. Effect of steam explosion temperature on wheat straw enzymatic hydrolysis
Oliva-Taravilla et al. Optimization of the laccase detoxification step in hybrid hydrolysis and fermentation processes from wheat straw by K. marxianus CECT 10875
KR101663110B1 (ko) 효과적인 불순물제거와 당 분리를 통한 바이오매스로부터 셀룰로오스 당을 제조하는 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14766289

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14766289

Country of ref document: EP

Kind code of ref document: A1