WO2016100028A1 - Procédé de production de lévoglucosénone - Google Patents

Procédé de production de lévoglucosénone Download PDF

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Publication number
WO2016100028A1
WO2016100028A1 PCT/US2015/064653 US2015064653W WO2016100028A1 WO 2016100028 A1 WO2016100028 A1 WO 2016100028A1 US 2015064653 W US2015064653 W US 2015064653W WO 2016100028 A1 WO2016100028 A1 WO 2016100028A1
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WIPO (PCT)
Prior art keywords
acid
feedstock
solvent
mixture
levoglucosenone
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PCT/US2015/064653
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English (en)
Inventor
Torren Ryan CARLSON
Joachim C. Ritter
Christina S. Stauffer
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E. I. Du Pont De Nemours And Company
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Publication of WO2016100028A1 publication Critical patent/WO2016100028A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/06—Peri-condensed systems

Definitions

  • Processes for preparing levoglucosenone from carbohydrate feedstocks are provided.
  • the carbohydrate feedstocks can be pretreated with acid and optionally mechanically processed.
  • Levoglucosenone is a highly dehydrated sugar which is useful as a chemical intermediate for the production of pharmaceuticals and industrial chemicals.
  • a reactive ⁇ , ⁇ -unsaturated carbonyl system, protected aldehyde functionality, fixed 1 C 4 conformation, and sterically hindered ⁇ -D-face make levoglucosenone a useful chiral synthon for the synthesis of biologically active compounds.
  • Levoglucosenone can also be used as a feedstock for production of industrial chemicals such as 1 ,6-hexanediol, which is a useful intermediate in the industrial preparation of polyamides such as nylon 66.
  • 1 ,6-Hexanediol can be converted by known methods to 1 ,6-hexamethylene diamine, a starting component in nylon production.
  • renewable sources that is, materials that are produced by a biological activity such as planting, farming, or harvesting. Biomass sources for such materials are becoming more attractive economically versus petroleum-based ones.
  • renewable sources that is, materials that are produced by a biological activity such as planting, farming, or harvesting. Biomass sources for such materials are becoming more attractive economically versus petroleum-based ones.
  • biosourced are used interchangeably.
  • Patent application WO 201 1 /000030 A1 discloses a method of converting particulate lignocellulosic material to produce volatile organic compounds and char; the patent application also discloses a method of converting a lignocellulosic material, such as cellulosic bleached wood pulp, into a mixture of the volatile organic liquids, 1 (S)-6,8- dioxabicyclo[3.2.1 ]oct-2-en-4-one ((-)levoglucosenone, 2-furaldehyde
  • a process for producing levoglucosenone comprising the steps:
  • step c) is performed, and mechanically processing the acid-impregnated feedstock comprises milling, crushing, grinding, shredding, chopping, disc refining, or a combination thereof.
  • the carbohydrate feedstock comprises
  • the carbohydrate feedstock comprises bagasse, switchgrass, corn stover, sorghum, wood, or a mixture thereof.
  • the first solvent comprises diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, acetonitrile, methanol, ethanol, isopropanol, or a mixture thereof.
  • the homogeneous acid comprises a mineral acid.
  • the mineral acid comprises sulfuric acid, hydrochloric acid, phosphoric acid, or a mixture thereof.
  • the homogeneous acid comprises an organic acid.
  • the organic acid comprises a monocarboxylic acid, a dicarboxylic acid, and alkyl sulfonic acid, an aryl sulfonic acid, a halogenated acetic acid, a halogenated alkylsulfonic acid, a halogenated aryl sulfonic acid, or a mixture therein.
  • the homogeneous acid has a concentration in the first solvent between about 1 weight percent and about 20 weight percent, relative to the weight of the feedstock.
  • the first solvent comprises diethyl ether and the homogeneous acid comprises sulfuric acid.
  • the second solvent comprises sulfolane, polyethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol dialkyi ether, polytrimethylene glycol, or mixtures thereof.
  • step d) further comprises adding a second acid. In one embodiment, step d) is performed at a pressure between about 0.25 kPa and about 40 kPa. In one embodiment, step d) is performed in a batch manner. In one embodiment, step d) is performed in a continuous manner. In one embodiment, the process further comprises a step of isolating at least a portion of the levoglucosenone from the product mixture. In one
  • the step of isolating is by distillation.
  • the second temperature is between 200 °C and 250 °C.
  • the product mixture further comprises furfural.
  • compositions, a mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
  • the term "about" modifying the quantity of an ingredient or reactant employed refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through
  • compositions or carry out the methods employed to make the compositions or carry out the methods; and the like.
  • the term "about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a
  • carbohydrate refers to any of a large group of organic compounds having the general formula C m (H 2 0) n , where m and n are integers, and includes C 6 sugars, starch, and cellulose.
  • carbohydrate feedstock refers to any material containing at least one carbohydrate.
  • biomass refers to any cellulosic or lignocellulosic material and includes materials comprising hemicellulose, and optionally further comprising lignin, starch, oligosaccharides and/or monosaccharides.
  • cellulose means a polysaccharide consisting of 1000-3000 or more glucose units in an unbranched, linear chain structure.
  • lignocellulosic means comprising both lignin and cellulose.
  • Lignocellulosic material may also comprise hemicellulose.
  • lignocellulosic material contains glucan and xylan.
  • hemicellulose means a non-cellulosic polysaccharide found in lignocellulosic biomass. Hemicellulose is a branched heteropolymer consisting of different sugar monomers. It typically comprises from 500 to 3000 sugar monomeric units.
  • starch refers to a carbohydrate consisting of a large number of glucose units joined by glycosidic bonds. Starch, also known as amylum, typically contains amylose and amylopectin. Examples of typical starches include corn starch, tapioca, wheat starch, rice starch, and potato starch.
  • sucrose includes monosaccharides, disaccharides, oligosaccharides, and anhydrosugars.
  • Monosaccharides, or “simple sugars,” are aldehyde or ketone derivatives of straight-chain polyhydroxy alcohols containing at least three carbon atoms.
  • a pentose is a monosaccharide having five carbon atoms; examples include xylose, arabinose, lyxose, and ribose.
  • a hexose is a monosaccharide having six carbon atoms; examples include glucose and fructose.
  • Disaccharide molecules consist of two covalently linked monosaccharide units; examples include sucrose, lactose, and maltose.
  • Sucrose is a disaccharide composed of the monosaccharides glucose and fructose with the molecular formula
  • oligosaccharide molecules consist of about 3 to about 20 covalently linked monosaccharide units.
  • Anhydrosugars are molecules with an intramolecular ether formed by the elimination of water from the reaction of two hydroxyl groups of a single monosaccharide;
  • examples include levoglucosenone, levoglucosan, galactosan, and
  • C n sugar includes monosaccharides having n carbon atoms; disaccharides comprising monosaccharide units having n carbon atoms; and oligosaccharides comprising monosaccharide units having n carbon atoms.
  • C& sugar or equivalent includes hexoses, disaccharides comprising hexose units, oligosaccharides
  • LGone refers to levoglucosenone, also known as 1 ,6-anhydro-3,4-dideoxy- -D-pyranosen-2-one.
  • the chemical structure of levoglucosenone is represented by Formula (I).
  • furfural also known as furan-2-carbaldehyde or 2-furaldehyde
  • Formula (II) The chemical structure of furfural, also known as furan-2-carbaldehyde or 2-furaldehyde, is represented by Formula (II).
  • the acid-impregnated feedstock is mechanically processed before contacting with a second solvent. In one embodiment, the acid-impregnated feedstock is not mechanically processed before contacting with a second solvent.
  • the first solvent comprises diethyl ether and the homogeneous acid comprises sulfuric acid.
  • the product mixture further comprises furfural.
  • the carbohydrate feedstock contains at least one carbohydrate, such as glucan, a C & sugar, or an equivalent.
  • the carbohydrate feedstock further contains xylan, a C5 sugar, or an equivalent.
  • Suitable feedstocks comprising lignocellulose, cellulose, C & sugars, starch, or mixtures thereof can be derived from biorenewable resources including biomass.
  • Biomass may be derived from a single source, or biomass can comprise a mixture derived from more than one source; for example, biomass could comprise a mixture of corn cobs and corn stover, or a mixture of wood and leaves.
  • Biomass includes, but is not limited to, bioenergy crops, agricultural residues, municipal solid waste, industrial solid waste, sludge from paper manufacture, yard waste, wood and forestry waste or a
  • biomass examples include, but are not limited to, corn grain, corn cobs, crop residues such as corn husks, corn stover, grasses, wheat, wheat straw, barley, barley straw, hay, rice straw,
  • Biomass that is useful for the present process may include biomass that has a relatively high carbohydrate value, is relatively dense, and/or is relatively easy to collect, transport, store and/or handle.
  • the feedstock is ultimately derived from biomass.
  • the carbohydrate feedstock comprises lignocellulose, cellulose, one or more C & sugars, starch, agricultural residues, forestry waste, paper, wood, or a mixture thereof.
  • the carbohydrate feedstock comprises lignocellulose.
  • the carbohydrate feedstock comprises cellulose.
  • the carbohydrate feedstock comprises starch.
  • the carbohydrate feedstock comprises agricultural residues.
  • the carbohydrate feedstock comprises forestry waste. In some embodiments, the feedstock comprises wood. In some embodiments, the carbohydrate feedstock comprises paper. In some embodiments, the carbohydrate feedstock comprises a C & sugar. In some embodiments, the carbohydrate feedstock is a C & sugar comprising glucose, levoglucosan, sucrose, fructose, or mixtures thereof. In some embodiments, the
  • carbohydrate feedstock comprises glucose. In some embodiments, the carbohydrate feedstock comprises levoglucosan. In some embodiments, the carbohydrate feedstock comprises sucrose.
  • the feedstock may be used directly as obtained from the source or may be dried to reduce the amount of moisture contained therein.
  • the feedstock has a moisture content of less than about 15 weight percent, for example less than about 10 weight percent, or for example less than about 5 weight percent.
  • the carbohydrate feedstock is contacted with a first solvent and a homogeneous acid at a first temperature between about 20 °C and about 35 °C for a first reaction time.
  • the first solvent, or first solvent mixture may serve to reduce the viscosity of the system to improve fluidity of the mixture of the feedstock, the solvent, and the acid in the reaction vessel, and / or to remove the heat of reaction and improve the performance of the process.
  • Suitable first solvents typically have relatively low boiling points and are substantially inert under the reaction conditions of the first contacting step. Examples of suitable first solvents include low boiling ethers, low boiling ketones, low boiling nitriles, and low boiling alcohols.
  • the first solvent comprises an ether.
  • Ethers useful as the first solvent in the processes disclosed herein may be linear or branched, cyclic or acyclic, and may contain from two to 12 carbon atoms.
  • useful ethers include tetrahydrofuran, tetrahydropyran, tetrahydro-2H-pyran-2-methanol, 1 ,4-dioxane, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, and dihexyl ether.
  • the first solvent comprises a ketone.
  • Ketones useful as the first solvent in the processes disclosed herein may be linear or branched and may contain from two to eight carbon atoms. Examples of useful ketones include acetone and methyl ethyl ketone.
  • the first solvent comprises a nitrile.
  • Nitriles useful as the first solvent in the processes disclosed herein may be linear or branched and may contain from two to eight carbon atoms. Examples of useful nitriles include acetonitrile, and propionitrile.
  • the first solvent comprises an alcohol.
  • Alcohols useful as the first solvent in the processes disclosed herein may be linear or branched and may contain from one to eight carbon atoms. Examples of useful alcohols include methanol, ethanol, n-propanol, iso-propanol, and 2- methylpropanol.
  • the first solvent comprises diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, acetone, acetonitrile, methanol, ethanol, isopropanol, or a mixture thereof.
  • the first solvent comprises diethyl ether.
  • the first solvent comprises tetrahydrofuran.
  • the first solvent comprises 2- methyltetrahydrofuran.
  • the first solvent comprises acetone.
  • the first solvent comprises acetonitrile.
  • the first solvent comprises methanol.
  • the first solvent comprises ethanol.
  • the first solvent comprises isopropanol.
  • Suitable first solvents are typically available commercially from various sources, such as Sigma-Aldrich (St. Louis, MO), in various grades, many of which may be suitable for use in the processes disclosed herein.
  • Technical grades of a solvent can contain a mixture of compounds, including the desired component and higher and lower molecular weight components or isomers.
  • the amount of first solvent used in the first contacting step of the process can vary, depending for example on the viscosity of the mixture of feedstock, first solvent, and acid.
  • the solvent may be present in the first contacting step in an amount ranging from about 75 weight percent to about 98 weight percent, based on the weight of the feedstock, catalyst, and solvent.
  • the solvent may comprise from about 80 weight percent to about 98 weight percent, or from about 85 weight percent to about 98 weight percent, or from about 90 weight percent to about 98 weight percent, of the total weight.
  • the amount of solvent may be adjusted to obtain the desired viscosity.
  • the homogeneous acid may comprise a mineral acid, an organic acid, or a mixture thereof.
  • the homogeneous acid is a mineral acid, and the mineral acid comprises sulfuric acid, hydrochloric acid, phosphoric acid, or a mixture thereof.
  • the homogeneous acid comprises sulfuric acid.
  • the homogeneous acid comprises hydrochloric acid.
  • the homogeneous acid comprises phosphoric acid.
  • phosphoric acid refers to orthophosphoric acid, H 3 P0 4 , and can include, unless otherwise specified, polyphosphoric acids derived from condensation of orthophosphoric acid molecules and having the general formula HO(P0 2 OH) x H, where x is the number of phosphoric units in the molecule.
  • the homogeneous acid is an organic acid
  • the organic acid comprises a monocarboxylic acid, a dicarboxylic acid, and alkyl sulfonic acid, an aryl sulfonic acid, a halogenated acetic acid, a halogenated alkylsulfonic acid, a halogenated aryl sulfonic acid, or a mixture therein.
  • Suitable monocarboxylic acids include formic acid and acetic acid.
  • Suitable dicarboxylic acids include oxalic acid, malonic acid, and citric acid.
  • An example of a suitable alkyl sulfonic acid is methane sulfonic acid.
  • An example of a suitable aryl sulfonic acid is toluenesulfonic acid.
  • An example of a suitable halogenated acetic acid is trifluoroacetic acid.
  • An example of a suitable halogenated alkylsulfonic acid is trifluoromethane sulfonic acid.
  • An example of a suitable halogenated aryl sulfonic acid is fluorobenzenesulfonic acid.
  • the carbohydrate feedstock is impregnated with the homogeneous acid.
  • concentration of the homogeneous acid in the first solvent may be selected to provide acceptable rates of
  • the homogenous acid has a concentration in the first solvent between about 1 weight percent and about 20 weight percent, relative to the weight of the feedstock.
  • the acid catalyst concentration in the reaction mixture is between and optionally includes any two of the following values: 1 wt%, 1 .5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 1 1 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, and 20 wt%.
  • concentration of homogenous acid employed may depend on conditions such as temperature, the specific acid used, and the feedstock. The acid may be obtained from commercial sources.
  • Impregnating the carbohydrate feedstock with a homogeneous acid may be performed at a first temperature between about 20 °C and about 35 °C, or for example between about 20 °C and about 30 °C. In some
  • the first temperature is between and optionally includes any two of the following values: 20 °C, 21 °C, 22 °C, 23 °C, 24 °C, 25 °C, 26 °C, 27 °C, 28 °C, 29 °C, 30 °C, 31 °C, 32 °C, 33 °C, 34 °C, and 35 °C.
  • the temperature may be kept constant or varied. Higher contacting temperatures may lead to reaction of the glucan and xylan contained in the feedstock and may be undesirable at this step in the process. Lower temperatures can also be used.
  • first reaction time between about 0.1 hours (h) and about 12 h, for example between about 0.1 h and about 8 h.
  • the first reaction time is between and optionally includes any two of the following values: 0.1 h, 0.2 h, 0.3 h, 0.4 h, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h, 1 .5, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 1 1 h, 1 1 .5 h, and 12 hours.
  • the choice of first reaction time may be related to the temperature of the contacting step, the concentration of the homogeneous
  • Contacting the carbohydrate feedstock with the first solvent and a homogeneous acid may be performed in any suitable reactor.
  • the reactor may be equipped with a means, such as impellers, for agitating the feedstock, first solvent, and homogeneous acid.
  • the contacting may be performed in a batch or continuous manner, and in a single reactor or in a series of reactors.
  • Suitable reactor types may include, for example, continuous stirred-tank reactors.
  • the first solvent is removed to obtain an acid- impregnated feedstock.
  • the first solvent may be removed under reduced pressure or by filtration.
  • the acid-impregnated feedstock can be dried before performing the next step in the process. Drying may be by air drying at room or at elevated temperature, or by heating in an oven or vacuum oven.
  • the dry acid-impregnated feedstock may contain from about 1 to about 20 weight percent acid, for example from about 5 weight percent to about 15 weight percent, or from about 7 weight percent to about 12 weight percent, based on the weight of the feedstock.
  • the acid-impregnated feedstock may be mechanically processed by applying energy to the feedstock, for example to reduce the size, increase the exposed surface area, and/or increase the availability of C6 sugars or equivalents present in the acid-impregnated feedstock for the next process step.
  • Energy means useful for mechanically processing the acid- impregnated feedstock include, but are not limited to, milling, crushing, grinding, shredding, chopping, disc refining, ultrasound, and microwave.
  • the feedstock can have an average particle size below about 5 mm, for example below about 2 mm, before mechanical processing, and an average particle size below about 2 mm, for example below about 1 mm, after mechanical processing.
  • the mechanical processing step may optionally be performed under an inert atmosphere, for example under nitrogen.
  • the acid-impregnated feedstock is contacted with a second solvent.
  • Suitable second solvents typically have boiling points in the range of 150°C to 500°C, for example in the range of 150 °C to 300 °C, and are substantially inert under the reaction conditions of this contacting step.
  • the second solvent comprises an aprotic polar solvent, a polar polymeric material, or mixtures thereof.
  • the second solvent comprises an aprotic solvent.
  • suitable aprotic polar solvents include sulfolane,
  • the aprotic solvent comprises sulfolane. Sulfolane is also referred to as tetrahydrothiophene 1 , 1 -dioxide, or as 2,3,4,5- tetrahydrothiophene-1 , 1 -dioxide.
  • the aprotic solvent comprises dimethylformamide.
  • the aprotic solvent comprises N-methyl-2-pyrrolidone.
  • the aprotic solvent comprises dimethyl sulfoxide.
  • the second solvent comprises a polar polymeric material.
  • suitable polar polymer materials include polyethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol dialkyl ether, polytrimethylene glycol, and mixtures thereof.
  • the second solvent comprises polyethylene glycol.
  • the second solvent comprises polyethylene glycol alkyl ether, wherein the alkyl groups are selected from methyl or ethyl.
  • the second solvent comprises polyethylene glycol monomethyl ether. In one
  • the second solvent comprises polyethylene glycol monoethyl ether. In one embodiment, the second solvent comprises polyethylene glycol dialkyl ether, wherein the alkyl groups are selected from methyl or ethyl. In one embodiment, the second solvent comprises polyethylene glycol dimethyl ether. In one embodiment, the second solvent comprises polyethylene glycol diethyl ether. In one embodiment, the second solvent comprises
  • Suitable polyethylene glycols, polyethylene glycol alkyl ethers, polyethylene glycol dialkyl ethers, and polytrimethylene glycols have molecular weights between about 300 daltons and 10,000 daltons.
  • the number average molecular weight of the polyethylene glycols, the polyethylene glycol alkyl ethers, the polyethylene glycol dialkyl ethers, and/or the polytrimethylene glycols is between and optionally includes any two of the following values: 300 daltons, 500 daltons, 1000 daltons, 1500 daltons, 2000 daltons, 2500 daltons, 3000 daltons, 3500 daltons, 4000 daltons, 5000 daltons, 6000 daltons, 7000 daltons, 8000 daltons, 9000 daltons, and 10,000 daltons.
  • the molecular weight is between 300 daltons and 1500 daltons. In some embodiments, the molecular weight is between1000 and 10,000 daltons. In some embodiments, the molecular weight is between 500 daltons and 5000 daltons.
  • the second solvent has a water content of about 5 weight percent or less. In some embodiments, the second solvent has a water content of about 2 weight percent or less, for example about 1 weight percent or less. In some embodiments, the second solvent is anhydrous.
  • the amount of second solvent used can vary, depending for example on the viscosity of the mixture of acid-impregnated feedstock and second solvent.
  • the second solvent may be present in this contacting step in an amount ranging from about 75 weight percent to about 98 weight percent, based on the weight of the feedstock and solvent.
  • the solvent may comprise from about 80 weight percent to about 98 weight percent, or from about 85 weight percent to about 98 weight percent, or from about 90 weight percent to about 98 weight percent, of the total weight.
  • the amount of solvent may be adjusted to obtain the desired viscosity.
  • an acid-impregnated feedstock is contacted with a second solvent at a second temperature between about 150 °C and about 250 °C for a second reaction time sufficient to form a product mixture comprising levoglucosenone.
  • the acid impregnated in the feedstock catalyzes conversion of the cellulose, C& sugar, starch, or mixtures thereof in the feedstock to levoglucosenone. If the feedstock also contains xylan or C5 sugars, the product mixture further comprises furfural.
  • a second acid may be added to the acid-impregnated feedstock, or to the second solvent.
  • the second acid may be the same or different from the homogeneous acid used to impregnate the feedstock.
  • the amount of the second catalyst used can be between about 1 weight percent and bout 20 weight percent (wt%), based on the weight of the feedstock.
  • the amount of the second catalyst used is between and optionally includes any two of the following values: 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 1 1 swt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, and 20 wt%, based on the weight of the acid-impregnated feedstock.
  • the second acid may be obtained from commercial sources.
  • a second acid may be added to increase the rate of levoglucosenone and/or furfural production.
  • process economics may be improved by using a sufficient amount of homogenous acid in the step of impregnating the feedstock, so that addition of a second acid later in the process is
  • Contacting the acid-impregnated feedstock with a second solvent may be performed at a temperature between about 150 °C and about 250 °C.
  • the second temperature is between and optionally includes any two of the following values: 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C, 195 °C, 200 °C, 205 °C, 210 °C, 215 °C, 220 °C, 225 °C, 230 °C, 235 °C, 240 °C, 245 °C, and 250 °C.
  • the second temperature is between about 100 °C and about 300 °C. In some embodiments, the second temperature is between about 200 °C and about 250 °C. In some embodiments, the second temperature is between about 150 °C and about 250 °C. In some embodiments, the second temperature is between about 180 °C and about 220 °C. During the contacting step, the second temperature may be kept constant or varied.
  • Contacting the acid-impregnated feedstock with the second solvent may be performed below atmospheric pressure, at atmospheric pressure, or above atmospheric pressure.
  • the reactor pressure is between about 0.25 kPa and about 40 kPa, and optionally includes any two of the following values: 0.25 kPa, 0.5 kPa, 1 kPa, 2 kPa, 3 kPa, 4 kPa, 5 kPa, 6 kPa, 7 kPa, 8 kPa, 9 kPa, 10 kPa, 15 kPa, 20 kPa , 25 kPa, 30 kPa, 35 kPa, and 40 kPa.
  • the pressure is between about 1 kPa and about 40 kPa, for example between about 10 kPa and about 40 kPa, or between about 20 kPa and about 40 kPa. In some embodiments, the pressure is between about 1 kPa and about 20 kPa.
  • the contacting is done under autogenous pressure.
  • the contacting may be performed under an inert gas such as nitrogen or argon. The choice of operating pressure may be related to the temperature of the contacting step and is often influenced by economic considerations and/or ease of operation.
  • any water formed in this contacting step can be removed in a vapor stream. Removing the water reduces its concentration in the product mixture and thus may minimize furfural formation.
  • the step of contacting the acid-impregnated feedstock with a second solvent to form a product mixture comprising levoglucosenone is performed as a reactive distillation, wherein at least a portion of the water and at least a portion of the levoglucosenone are removed from the product mixture under reduced pressure.
  • the water content of the product mixture comprising levoglucosenone is less than about 15 weight percent.
  • the acid-impregnated feedstock is contacted with the second solvent for a second reaction time sufficient to form a product mixture comprising levoglucosenone.
  • the second reaction time may be between about 1 minute and about 30 min, for example between about 5 min and about 25 min.
  • the choice of the second reaction time may be related to the
  • the product mixture formed during the step of contacting an acid- impregnated feedstock with a second solvent comprises levoglucosenone, and optionally furfural.
  • the product mixture further comprises solvent and homogeneous acid.
  • the product mixture may contain from about 0.1 weight percent to about 8 weight percent levoglucosenone, for example from about 0.1 weight percent to about 6 weight percent, or from about 0.1 weight percent to about 5 weight percent, or from about 0.1 weight percent to about 3 weight percent levoglucosenone, based on the total weight of the product mixture.
  • the product mixture may further contain from about 0.01 to about 8 weight percent furfural, for example from about 0.1 to about 5 weight percent, or from about 0.2 to about 2 weight percent, based on the total weight of the product mixture.
  • the product mixture may further comprise one or more of levoglucosan, 1 ,6-anhydro-beta-D-glucofuranose, hydroxymethylfurfural, or formaldehyde.
  • the processes disclosed herein may further comprise a step of isolating at least a portion of the levoglucosenone from the product mixture.
  • the processes disclosed herein may further comprise a step of isolating at least a portion of the furfural from the product mixture.
  • the isolating steps may be performed using techniques known in the art, for example by distillation or liquid-liquid extraction.
  • Contacting the acid-impregnated feedstock with a second solvent can be performed in any suitable reactor.
  • the reactor may be equipped with a means, such as impellers, for agitating the acid-impregnated feedstock and second solvent.
  • the contacting may be performed in a batch, continuous, or semi-continuous manner.
  • the contacting step may be performed in one reactor, or in a series of reactors.
  • Suitable reactor types may include, for example, continuous stirred-tank reactors, plug flow tubular flow reactors, and slurry bubble column reactors. Reactor design is well- known and is disclosed in engineering handbooks.
  • Impregnating the carbohydrate feedstock with acid, and optionally mechanically processing the impregnated material can provide higher yield of levoglucosenone, relative to the yield obtained from untreated carbohydrate feedstock.
  • contacting the acid-impregnated feedstock with a solvent at a temperature between about 150 °C and about 250 °C can help to control unwanted secondary reactions, minimize char formation, and minimize polymerization of reactive compounds.
  • the continuous removal of water via distillation under reduced pressure can limit the water-catalyzed degradation of levoglucosenone to furfural and provide higher yields of levoglucosenone.
  • LGone means levoglucosenone
  • FF means furfural
  • DMSO means dimethylsulfoxide
  • °C means degrees Celsius
  • wt% means weight percent
  • g means gram(s);
  • mg means milligram(s),
  • mmol means millimole(s),
  • mol% means mole percent
  • M means molar
  • mg/g means milligram(s) per gram,
  • h means hour(s),
  • min means minute(s);
  • % means percent
  • wt%” means weight percent;
  • ml_ means milliliter(s);
  • ⁇ means microliter(s),
  • pm means micrometer(s),
  • mm means millimeter(s),
  • m means meter(s),
  • GC means gas chromatography;
  • HPLC means high pressure liquid
  • Wood 60% Aspen/40% Maple, Banton Milled ⁇ 1 .0 mm
  • Table 1 provides the composition and moisture content of each feedstock after drying. Table 1 .
  • the solid to be analyzed was either air dried or dried in a vacuum oven at 80 ° C until the moisture content was less than 20 wt%.
  • the biomass was milled in a knife mill until it passed through a >20 mesh screen.
  • the percent solid for each biomass was determined by drying with a halogen moisture analyzer to 105 C (Mettler Toledo), and then 300 mg (dry weight basis) of the biomass was weighed into a 100 mL glass pressure vessel (Chemglass, CG- 1880-05). 3.0 mL of 72 wt % H 2 SO 4 in water was added to the solid and the mixture was mixed using a 1 /4" diameter polytetrafluoroethylene (PTFE) rod to ensure complete coverage of acid on the solid particles.
  • PTFE polytetrafluoroethylene
  • the mixture was submerged in a stirred 30 ° C water bath for 30 min. It was then briefly mixed again by vortexing the tubes between 8-10 seconds and returned to the water bath for an additional 30 min. To avoid losses, the PTFE rod remained in the mixture for this first hour. After this initial incubation period, deionized water (84 g) was added to the vessel and it was thoroughly mixed. The PTFE rod remained in the solution.
  • a sugar recovery standard was prepared by weighing glucose, xylose, arabinose, and DMSO (internal standard) into a bottle along with 200 g of water. 84 g of this solution was added to each of two 100 mL pressure tubes. 3 mL of 72 wt % H 2 S0 4 was added to each pressure tube. A sample of each acidic SRS solution was removed before and after heating for HPLC analysis. After heating, the HPLC areas were less than before heating due to sugar degradation during the acid hydrolysis. The area ratios of each sugar were recorded and were used to calculate a unique degradation correction factor for the glucose, xylose and arabinose sugars. The correction factor was applied to the sugars detected in the unknown biomass samples being analyzed during the same experiment in an attempt to adjust for degraded sugars during the procedure.
  • SRS sugar recovery standard
  • the pressure vessels were put into an autoclave.
  • the autoclave was rapidly heated to a temperature of 121 -126 ° C and held there for 60 min, after which time it cooled slowly.
  • the samples were pulled from the autoclave after 1 .5 h.
  • the temperature of the autoclave cooled to approximately 80 ° C at this time.
  • the vessels were then further cooled on ice.
  • a weighed amount of internal standard typically DMSO, but sometimes DMF; about 0.8000 g or 0.1000 for the smaller scale analysis
  • the mixture was filtered to remove any remaining undissolved solids using a tared polypropylene filter funnel with a 10 micron polyethylene fritted disc (Chemglass, OP-6602).
  • the PTFE rod was removed from the pressure tube during the filtering step.
  • the PTFE rod was thoroughly washed over the filter.
  • a portion of the filtrate was collected and analyzed by HPLC.
  • the undissolved solid collected on the fritted disc was washed with copious amounts of water and was dried in a vacuum oven at 80 ° C.
  • the weight of the washed and dried acid insoluble material was recorded and expressed as wt% lignin.
  • the mole amounts of monomeric carbohydrates solubilized by the compositional analysis process and detected by the HPLC analysis were determined.
  • the mole amounts of each were converted to weights using the molecular weights of the polymer bound sugars (i.e. 132 g / mole for xylose and arabinose as monomeric units in hemicellulose or 162 g / mole for glucose as the monomeric unit in
  • Levoglucosenone and furfural amounts were determined as follows.
  • the injector was maintained at 250 °C and the injection volume was 1 ⁇ with a split ratio of 20: 1 .
  • the carrier gas was helium at 1 mL/min and a FID detector at 250 °C was used. Concentrations of levoglucosenone and furfural were determined from a standard calibration curve developed for each of the analytes with diethylene glycol diethyl ether.
  • LGone yields were calculated based on the glucan content of each feedstock. FF yields were based on the xylan content of each feedstock to simplify calculations, although small amounts of FF were also produced from the glucan content of the biomass. Typically less than about 5% FF was observed using cellulose as feedstock under similar conditions.
  • Moisture analysis was performed using a halogen moisture analyzer (Mettler-Toledo).
  • a 4-necked round-bottom flask (250 ml_) was equipped with each of the following items attached to one of the necks: a short path distillation apparatus, a glass solid addition tube, a glass dip-tube filled with mineral oil for internal temperature monitoring, and an adapter containing a metal tube used for nitrogen purge.
  • a round-bottom flask was attached as a distillation receiver to the end of the condenser of the short path distillation unit to collect any volatiles that distilled over; the distillation receiver was cooled with a dry ice/acetone bath. Vacuum was introduced to the system using a diaphragm vacuum pump. House nitrogen supply was used as the nitrogen source. The vacuum and nitrogen flow were controlled with Swagelok® needle valves.
  • the internal pot temperature and the short path distillation head temperature were monitored using digital Fluke 5211 thermocouples.
  • the 4-necked round- bottom flask and its contents were heated with an oil bath, and aluminum foil was used to insulate the exposed sections of the apparatus which were not immersed in the oil bath.
  • the system was placed under a vacuum of about 13.3 kPa ( ⁇ 99.6 Torr). Subsurface nitrogen purging ( ⁇ 327 mL/min) was initiated once the vacuum had stabilized. Heating was begun once both the nitrogen and vacuum pressure were equilibrated. The internal temperature of the flask contents was monitored and upon reaching ⁇ 200 °C, the dry feedstock in the solid addition tube was dispensed into the sulfolane over about 3 minutes. The reaction mixture was subsequently heated at ⁇ 200-210 °C for a reaction time between about 5 and 25 minutes. After the desired reaction time, the product mixture was allowed to cool to room temperature.
  • Comparative Examples A through M demonstrated the yield of levoglucosenone and furfural obtained from various carbohydrate feedstocks which had not undergone a chemical pretreatment step before contacting with sulfolane solvent in the presence of an acid catalyst and heat.
  • the untreated feedstock was subjected to the General Procedure as disclosed herein above for the reaction time indicated.
  • the reaction time shown included the time for addition of the feedstock to the sulfolane solvent and for heating at ⁇ 200- 210 °C.
  • Selected carbohydrate feedstocks were pretreated before contacting with sulfolane solvent and heat.
  • the pretreatment consisted of an acid- impregnation step followed by a mechanical processing step.
  • the acid- impregnation step was performed by placing the carbohydrate feedstock in diethyl ether solvent containing 9 wt% H 2 S0 4 (relative to the feedstock), and stirring the mixture at room temperature for 1 hour. The diethyl ether was then removed under reduced pressure.
  • the acid-impregnated feedstock was allowed to air dry, then subjected to ball milling using 20 mm stainless steel balls as grinding media for 2 hours.
  • the acid-impregnated, mechanically processed feedstock was then contacted with sulfolane and heated for 10 minutes following the general procedure disclosed herein above, except that no additional sulfuric acid was added to the sulfolane. Results are presented in Table 3.
  • switchgrass was ground using a ball mill for 2 hours (20 mm stainless steel balls), then contacted with sulfolane, about 9 wt% H 2 S0 4 relative to feedstock, and heated according to the General Procedure, .
  • switchgrass was impregnated with 10 wt% H 2 S0 4 , relative to feedstock then contacted with sulfolane and heated according to the General Procedure, but with no additional acid in the sulfolane.
  • switchgrass was impregnated with 9 wt% H 2 S0 4 relative to the feedstock and then ball milled before contacting with sulfolane and heat according to the General Procedure, but with no additional acid in the sulfolane.
  • Comparative Examples C and D were performed according to the General Procedure using untreated switchgrass and 4.6 wt% H 2 S0 4 relative to feedstock in the sulfolane contacting step.

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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des procédés de production de lévoglucosénone. Dans un mode de réalisation, une charge de départ de glucides est mise en contact avec un premier solvant et un acide homogène à une première température entre environ 20°C et environ 35°C et pendant un premier temps de réaction; le solvant est ensuite éliminé en vue d'obtenir une charge de départ imprégnée d'acide, qui peut éventuellement être traitée mécaniquement; et la charge de départ imprégnée d'acide est ensuite mise en contact avec un deuxième solvant à une deuxième température entre environ 150°C et environ 250°C pendant un deuxième temps de réaction suffisant pour former un mélange de produits comprenant de la lévoglucosénone.
PCT/US2015/064653 2014-12-16 2015-12-09 Procédé de production de lévoglucosénone WO2016100028A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011000030A1 (fr) 2009-07-01 2011-01-06 Circa Group Pty Ltd Procédé de conversion de matériaux lignocellulosiques en substances chimiques utiles

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011000030A1 (fr) 2009-07-01 2011-01-06 Circa Group Pty Ltd Procédé de conversion de matériaux lignocellulosiques en substances chimiques utiles

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KAWAMOTO ET AL., J. WOOD SCI, vol. 53, 2007, pages 127 - 133
KAWAMOTO ET AL.: "Catalytic pyrolysis of cellulose in sulfolane with some acidic catalysts", J. WOOD SCI, vol. 53, April 2007 (2007-04-01), pages 127 - 133, XP055218769, DOI: 10.1007/s10086-006-0835-y *
SHAFIZADEH ET AL., CARBOHYDRATE RESEARCH, vol. 71, 1979, pages 169 - 191

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