WO2014100303A2 - Tampon recyclable pour le traitement hydrocatalytique hydrothermique de biomasse - Google Patents

Tampon recyclable pour le traitement hydrocatalytique hydrothermique de biomasse Download PDF

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Publication number
WO2014100303A2
WO2014100303A2 PCT/US2013/076325 US2013076325W WO2014100303A2 WO 2014100303 A2 WO2014100303 A2 WO 2014100303A2 US 2013076325 W US2013076325 W US 2013076325W WO 2014100303 A2 WO2014100303 A2 WO 2014100303A2
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WO
WIPO (PCT)
Prior art keywords
ammonia
ammonium
biomass
reaction
source
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PCT/US2013/076325
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English (en)
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WO2014100303A3 (fr
Inventor
Joseph Broun Powell
Glenn Charles Komplin
John Anthony Smegal
Kim Ann JOHNSON
Original Assignee
Shell Oil Company
Shell Internationale Research Maatschappij B.V.
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Application filed by Shell Oil Company, Shell Internationale Research Maatschappij B.V. filed Critical Shell Oil Company
Priority to CN201380066742.8A priority Critical patent/CN104903425B/zh
Priority to EP13818620.0A priority patent/EP2935519A2/fr
Publication of WO2014100303A2 publication Critical patent/WO2014100303A2/fr
Publication of WO2014100303A3 publication Critical patent/WO2014100303A3/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/006—Pulping cellulose-containing materials with compounds not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
    • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
    • C10G3/56—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds suspended in the oil, e.g. slurries, ebullated beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to the hydrothermal hydrocatalytic treatment of biomass in the production of higher hydrocarbons suitable for use in transportation fuels and industrial chemicals from biomass.
  • Biomass is a resource that shows promise as a fossil fuel alternative. As opposed to fossil fuel, biomass is also renewable.
  • Biomass may be useful as a source of renewable fuels.
  • One type of biomass is plant biomass.
  • Plant biomass is the most abundant source of carbohydrate in the world due to the lignocellulosic materials composing the cell walls in higher plants.
  • Plant cell walls are divided into two sections, primary cell walls and secondary cell walls.
  • the primary cell wall provides structure for expanding cells and is composed of three major polysaccharides (cellulose, pectin, and hemicellulose) and one group of glycoproteins.
  • the secondary cell wall which is produced after the cell has finished growing, also contains polysaccharides and is strengthened through polymeric lignin covalently cross-linked to hemicellulose.
  • Hemicellulose and pectin are typically found in abundance, but cellulose is the predominant polysaccharide and the most abundant source of carbohydrates.
  • production of fuel from cellulose poses a difficult technical problem.
  • Some of the factors for this difficulty are the physical density of lignocelluloses (like wood) that can make penetration of the biomass structure of lignocelluloses with chemicals difficult and the chemical complexity of lignocelluloses that lead to difficulty in breaking down the long chain polymeric structure of cellulose into carbohydrates that can be used to produce fuel.
  • Another factor for this difficulty is the nitrogen compounds and sulfur compounds contained in the biomass. The nitrogen and sulfur compounds contained in the biomass can poison catalysts used in subsequent processing.
  • bio-based feedstocks such as biomass provide the only renewable alternative for liquid transportation fuel.
  • biomass resources such as ethanol, methanol, and vegetable oil
  • gaseous fuels such as hydrogen and methane
  • these fuels require either new distribution technologies and/or combustion technologies appropriate for their characteristics.
  • the production of some of these fuels also tends to be expensive and raise questions with respect to their net carbon savings.
  • Processing of biomass as feeds is challenged by the need to directly couple biomass hydrolysis to release sugars, and catalytic hydrogenation/hydrogenolysis/ hydrodeoxygenation of the sugar, to prevent decomposition to heavy ends (caramel, or tars). Further, nitrogen and sulfur compounds from the biomass feed can poison the hydrogenation/hydrogenolysis/ hydrodeoxygenation catalysts, such as Pt/Re catalysts, and reduce the activity of the catalysts.
  • a method comprises: providing lignocellulosic biomass solids in a hydrothermal digestion unit in the presence of a digestive solvent, at least one of ammonia or a source of ammonia, and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a suitable support; heating the lignocellulosic biomass solids and digestive solvent in the presence of hydrogen, supported hydrogenolysis catalyst and the at least one of ammonia or a source of ammonia thereby forming a product solution containing plurality of oxygenated hydrocarbons and ammonia; and recycling at least a portion of the ammonia to the hydrothermal digestion unit.
  • a method comprises: (i) providing a lignocellulosic biomass; (ii) contacting the biomass with a digestive solvent to form a pretreated biomass containing soluble carbohydrates; (iii) contacting, in a reaction mixture, the pretreated biomass with hydrogen at a temperature in the range of 150°C to less than 300°C in the presence of at least one of ammonia or a source of ammonia and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a suitable support, to form a product solution containing plurality of oxygenated hydrocarbons and ammonia; and (iv) recycling at least a portion of the ammonia to the reaction mixture or pretreated biomass.
  • composition comprises:
  • a hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a suitable support;
  • Fig. 1 is a schematically illustrated block flow diagram of an embodiment of a process 100 of this invention.
  • Fig. 2 is a schematically illustrate block flow diagram of another embodiment of a process 200 of this invention.
  • the invention relates to the hydrothermal hydrocatalytic treatment of the biomass with a catalysis system that is tolerant to nitrogen and sulfur and further maintain activity for a prolonged period with minimal loss of active metal in the catalyst such as cobalt or other non-noble metals, during the reaction with the presence of ammonia or a source of ammonia as a pH buffering agent.
  • Ammonia or a source of ammonia can be recycled as ammonia to form ammonium salt buffer in the hydrothermal hydrocatalytic treatment reaction mixture. It has been found that ammonia or a source of ammonia can be an effective buffering agent for the hydrothermal hydrocatalytic treatment of biomass that can be recycled as ammonia.
  • the oxygenated hydrocarbons produced from the process are useful in the production of higher hydrocarbons suitable for use in transportation fuels and industrial chemicals from biomass.
  • the higher hydrocarbons produced are useful in forming transportation fuels, such as synthetic gasoline, diesel fuel, and jet fuel, as well as industrial chemicals.
  • the term "higher hydrocarbons” refers to hydrocarbons having an oxygen to carbon ratio less than the oxygen to carbon ratio of at least one component of the biomass feedstock.
  • hydrocarbon refers to an organic compound comprising primarily hydrogen and carbon atoms, which is also an unsubstituted hydrocarbon.
  • the hydrocarbons of the invention also comprise heteroatoms (i.e., oxygen sulfur, phosphorus, or nitrogen) and thus the term “hydrocarbon” may also include substituted hydrocarbons.
  • heteroatoms i.e., oxygen sulfur, phosphorus, or nitrogen
  • soluble carbohydrates refers to oligosaccharides and monosaccharides that are soluble in the digestive solvent and that can be used as feedstock to the hydro genolysis reaction (e.g., pentoses and hexoses).
  • Nitrogen and sulfur compounds from the biomass feed can poison the hydrogenation/hydrogenolysis/ hydrodeoxygenation catalysts, such as Pt/Re catalysts, and reduce the activity of the catalysts.
  • Reduced or partially reduced nitrogen or sulfur compounds such as those found in proteins and amino acids present in the biomass feed, are potential poisons for transition metal catalysts used to activate molecular hydrogen for reduction reactions. Oxidized forms of nitrogen or sulfur, in the form of nitrates or sulfates may not poison many catalysts used for hydrogen activation and reduction reactions.
  • Biomass hydrolysis starts above 120 °C and continues through 200 °C.
  • Sulfur and nitrogen compounds can be removed by ion exchange resins (acidic) such as discussed in US publication no. US2012/0152836, that are stable to 120 °C, but the base resins required for complete N,S removal cannot be used above 100 °C (weak base), or 60°C for the strong base resins. Cycling of temperature from 60° C ion exchange to reaction temperatures between 120 - 275 °C represents a substantial energy yield loss.
  • Use of a poison tolerant catalyst in the process to enable direct coupling of biomass hydrolysis and catalytic hydrogenation / hydrogenolysis/ hydrodeoxygenation of the resulting sugar is an advantage, for a biomass feed process.
  • the methods and systems of the invention have an advantage of using a poison tolerant catalyst for the direct coupling of biomass hydrolysis and catalytic hydrogenation / hydrogenolysis / hydrodeoxygenation of the resulting sugar and other derived intermediates, with minimal loss of active metal over time.
  • At least a portion of oxygenated hydrocarbons produced in the hydrogenolysis reaction are recycled within the process and system to at least in part from the in situ generated solvent, which is used in the biomass digestion process.
  • This recycle saves costs in provision of a solvent that can be used to extract nitrogen, sulfur, and optionally phosphorus compounds from the biomass feedstock.
  • hydrogenation reactions can be conducted along with the hydrogenolysis reaction at temperatures ranging from 150 °C to 300 °C. As a result, a separate hydrogenation reaction section can optionally be avoided, and the fuel forming potential of the biomass feedstock fed to the process can be increased.
  • This process and reaction scheme described herein also results in a capital cost savings and process operational cost savings. Advantages of specific embodiments will be described in more detail below.
  • a method comprises: providing lignocellulosic biomass solids in a hydrothermal digestion unit in the presence of a digestive solvent, at least one of ammonia or a source of ammonia, and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a suitable support; heating the lignocellulosic biomass solids and digestive solvent in the presence of hydrogen, supported hydrogenolysis catalyst and the at least one of ammonia or a source of ammonia thereby forming a product solution containing plurality of oxygenated hydrocarbons and ammonia; and separating and recycling at least a portion of the ammonia to the hydrothermal digestion unit.
  • the invention provides methods comprising: providing a biomass feedstock, contacting the biomass feedstock with a digestive solvent in a digestion system to form an intermediate stream comprising soluble carbohydrates, contacting the intermediate stream with hydrogen in the presence of a supported hydrogenolysis catalyst containing (a) sulfur and (b) Mo or W and (c) Co and/or Ni and at least one of ammonia or a source of ammonia to form a plurality of oxygenated hydrocarbons (or oxygenated intermediates) and ammonia, wherein a first portion of the oxygenated hydrocarbons are recycled to form the solvent and ammonia is recycled to the reaction mixture or digestion system; and contacting a second portion of the oxygenated hydrocarbons with a catalyst to form a liquid fuel.
  • a method comprises: (i) providing a biomass containing celluloses, hemicelluloses, lignin, nitrogen compounds and sulfur compounds; (ii) contacting the biomass with a digestive solvent to form a pretreated biomass containing carbohydrates; (iii) contacting, in a reaction mixture, the pretreated biomass directly with hydrogen in the presence of at least one of ammonia or a source of ammonia and a supported hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co and/or Ni incorporated into a suitable support to form a plurality of oxygenated hydrocarbons.
  • Ammonia or a source of ammonia may be continuously or semi-continuously or periodically or initially added to the reaction system (or reaction mixture) or generated in the reaction mixture to minimize active metal leaching and maintain catalyst activity.
  • Suitable sources of ammonia may be, for example, ammonium carbonate, ammonium propionate, ammonium glycolate, ammonium levulinate, ammonium acetate, ammonium formate, ammonium butyrate, ammonium chloride, and ammonium sulfate. It is desirable to introduce ammonia or a source of ammonia to the reaction mixture (or via pretreated biomass) in an amount sufficient to maintain the pH of the reaction mixture to a desirable pH.
  • the desirable pH may be in the range of 3 to 10, preferably to 4 to 8, more preferably to 5 to 7. In other embodiments, it may be desirable to run the reaction system under more basic conditions. The amount of ammonia or source of ammonia can be adjusted accordingly.
  • the source of ammonia can be an ammonia salt of a weak acid such as, for example, ammonium acetate or an ammonium salt of a strong acid such as, for example, ammonium sulfate.
  • Ammonia may be generated by adding a strong base such as, for example, KOH or NaOH to the ammonium salt of a strong acid.
  • a strong base such as, for example, KOH or NaOH.
  • Such ammonia derivative (source of ammonia) is a base derivable from ammonia.
  • ammonia (or source of ammonia) in water as solvent neutralizes acetic acid under pressure.
  • lignocellulosic biomass (solids) being continuously or semi- continuously added to the hydrothermal digestion unit may be pressurized before being added to the hydrothermal digestion unit, particularly when the hydrothermal digestion unit is in a pressurized state.
  • Pressurization of the cellulosic biomass solids from atmospheric pressure to a pressurized state may take place in one or more pressurization zones before addition of the cellulosic biomass solids to the hydrothermal digestion unit.
  • Suitable pressurization zones that may be used for pressurizing and introducing lignocellulosic biomass to a pressurized hydrothermal digestion unit are described in more detail in commonly owned United States Patent Application Publications 20130152457 and 20130152458.
  • Suitable pressurization zones described therein may include, for example, pressure vessels, pressurized screw feeders, and the like. In some embodiments, multiple pressurization zones may be connected in series to increase the pressure of the cellulosic biomass solids in a stepwise manner.
  • digestion unit 6 that may have one or more units, containing a supported hydrogenolysis catalyst containing (a) sulfur and (b) Mo or W and (c) Co and/or Ni or mixtures thereof, and a digestive solvent 10 (that may be recycled from the process), and at least one of ammonia or ammonia precursor, whereby when heated with molecular hydrogen 21 produces oxygenated hydrocarbons.
  • the effluent product stream from the digestion unit 28 contains oxygenated hydrocarbons and at least one of ammonia or ammonia precursor.
  • Ammonia may be separated from the product stream 30 by separation, that can be facilitated by heating or reducing pressure in a separation unit 36 (as an example as an overhead stream 25) that is recycled to the digestion unit 6.
  • the digester-reactor may be configured as disclosed in a co-pending US application no. 61/720757 filed October 31, 2012 which disclosure is hereby ed by reference.
  • biomass 102 is provided to digestion zone 106 that may have one or more digester(s), whereby the biomass is contacted with a digestive solvent 110.
  • the treated biomass pulp 120 contains soluble carbohydrates and other intermediates containing sulfur compounds and nitrogen compounds from the biomass. The sulfur and nitrogen content may vary depending on the biomass source 102.
  • At least a portion of the treated biomass 120 is catalytically reacted with hydrogen 121, in the hydrothermal hydrocatalytic treatment zone 126, in the presence of a supported hydrogenolysis catalyst containing (a) sulfur and (b) Mo or W and (c) Co and/or Ni and at least one of ammonia or a source of ammonia supplied through a stream containing ammonium hydroxide precursor to produce a product stream 128 containing plurality of oxygenated hydrocarbons and ammonia and/or a source of ammonia; separating ammonia from the product stream (that may be an overhead distillate containing ammonia 125) and a product stream 130.
  • a supported hydrogenolysis catalyst containing (a) sulfur and (b) Mo or W and (c) Co and/or Ni and at least one of ammonia or a source of ammonia supplied through a stream containing ammonium hydroxide precursor to produce a product stream 128 containing plurality of oxygenated hydrocarbons and ammonia and/or a source
  • At least a portion of the ammonia containing stream is recycled to the reaction mixture in 126 (as in figure 2) or to pretreated biomass via stream 120 (not shown). At least a portion of the oxygenated intermediates may be processed further to produce higher hydrocarbons to form a liquid fuel.
  • the digestion zone 106 and the hydrothermal hydrocatalytic treatment zone 126 may be conducted in the same reactor or in a separate reactor.
  • the treated biomass 120 may be optionally washed prior to contacting in the hydrogenolysis zone (or hydrothermal hydrocatalytic treatment zone) 126. If washed, water is most typically used as wash solvent.
  • the ammonium hydroxide or an ammonium hydroxide precursor may be introduced with the digestive solvent, with the biomass, with the catalyst, or separately, so long as the ammonium hydroxide or an ammonium hydroxide precursor is present with the supported hydrogenolysis catalyst in the hydrogenolysis zone.
  • lignocellulosic biomass can be, for example, selected from, but not limited to, forestry residues, agricultural residues, herbaceous material, municipal solid wastes, waste and recycled paper, pulp and paper mill residues, and combinations thereof.
  • the biomass can comprise, for example, corn stover, straw, bagasse, miscanthus, sorghum residue, switch grass, bamboo, water hyacinth, hardwood, hardwood chips, hardwood pulp, softwood, softwood chips, softwood pulp, and/or combination of these feedstocks.
  • the biomass can be chosen based upon a consideration such as, but not limited to, cellulose and/or hemicelluloses content, lignin content, growing time/season, growing location/transportation cost, growing costs, harvesting costs and the like.
  • the untreated biomass Prior to treatment with the digestive solvent, the untreated biomass can be washed and/or reduced in size (e.g., chopping, crushing or debarking) to a convenient size and certain quality that aids in moving the biomass or mixing and impregnating the chemicals from digestive solvent.
  • providing biomass can comprise harvesting a lignocelluloses-containing plant such as, for example, a hardwood or softwood tree. The tree can be subjected to debarking, chopping to wood chips of desirable thickness, and washing to remove any residual soil, dirt and the like.
  • washing with water prior to treatment with digestive solvent is desired, to rinse and remove simple salts such as nitrate, sulfate, and phosphate salts which otherwise may be present, and contribute to measured concentrations of nitrogen, sulfur, and phosphorus compounds present.
  • This wash is accomplished at a temperature of less than 60 degrees Celsius, and where hydrolysis reactions comprising digestion do not occur to a significant extent.
  • Other nitrogen, sulfur, and phosphorus compounds are bound to the biomass and are more difficult to remove, and requiring digestion and reaction of the biomass, to effect removal.
  • These compounds may be derived from proteins, amino acids, phospholipids, and other structures within the biomass, and may be potent catalyst poisons.
  • the poison tolerant catalyst described herein allows some of these more difficult to remove nitrogen and sulfur compounds to be present in subsequent processing.
  • the size-reduced biomass is contacted with the digestive solvent where the digestion reaction takes place.
  • the digestive solvent must be effective to digest lignins.
  • the digestive solvent maybe a Kraft-like digestive solvent that contains (i) at least 0.5 wt%, preferably at least 4 wt%, to at most 20 wt%, more preferably to 10 wt%, based on the digestive solvent, of at least one alkali selected from the group consisting of sodium hydroxide, sodium carbonate, sodium sulfide, potassium hydroxide, potassium carbonate, ammonium hydroxide, and mixtures thereof, (ii) optionally, 0 to 3%, based on the digestive solvent, of anthraquinone, sodium borate and/or polysulfides; and (iii) water (as remainder of the digestive solvent).
  • alkali selected from the group consisting of sodium hydroxide, sodium carbonate, sodium sulfide, potassium hydroxide, potassium carbonate, ammonium hydroxide, and mixtures thereof
  • optionally, 0 to 3% based on the digestive solvent, of anthraquinone, sodium borate and/or polysulfides
  • the digestive solvent may have an active alkali of between 0.5% to 25%, more preferably between 10 to 20%.
  • active alkali is a percentage of alkali compounds combined, expressed as sodium oxide based on weight of the biomass less water content (dry solid biomass).
  • the digestion is carried out typically at a cooking-liquor to biomass ratio in the range of 2 to 6, preferably 3 to 5.
  • the digestion reaction is carried out at a temperature within the range of from 60 °C, preferably 100 °C, to 270 °C, and a residence time within 0.25 h to 24h.
  • the reaction is carried out under conditions effective to provide a pretreated biomass stream containing pretreated biomass having a lignin content that is less than 20% of the amount in the untreated biomass feed, and a chemical liquor stream containing alkali compounds and dissolved lignin and hemicellulose material.
  • the digestion can be carried out in a suitable vessel, for example, a pressure vessel of carbon steel or stainless steel or similar alloy.
  • the digestion zone can be carried out in the same vessel or in a separate vessel.
  • the cooking can be done in continuous or batch mode.
  • Suitable pressure vessels include, but are not limited to the "PANDIATM Digester” (Voest-Alpine Industrienlagenbau GmbH, Linz, Austria), the “DEFIBRATOR Digester” (Sunds Defibrator AB Corporation, Sweden), M&D (Messing & Durkee) digester (Bauer Brothers Company, Springfield, Ohio, USA) and the KAMYR Digester (Andritz Inc., Glens Falls, New York, USA).
  • the digestive solvent has a pH from 10 to 14, preferably around 12 to 13 depending on the concentration of active alkali AA.
  • the contents can be kept at a temperature within the range of from 100 °C to 230 °C for a period of time, more preferably within the range from 130 °C to 180 °C.
  • the period of time can be from 0.25 to 24.0 hours, preferably from 0.5 to 2 hours, after which the pretreated contents of the digester are discharged.
  • a sufficient volume of liquor is required to ensure that all the biomass surfaces are wetted.
  • Sufficient liquor is supplied to provide the specified digestive solvent to biomass ratio. The effect of greater dilution is to decrease the concentration of active chemical and thereby reduce the reaction rate.
  • the chemical liquor may be regenerated in a similar manger to a Kraft pulp and paper chemical regeneration process.
  • an at least partially water miscible organic solvent that has partial solubility in water, preferably greater than 2 weight percent in water, may be used as digestive solvent to aid in digestion of lignin, and the nitrogen, and sulfur compounds.
  • the digestive solvent is a water- organic solvent mixture with optional inorganic acid promoters such as HC1 or sulfuric acid. Oxygenated solvents exhibiting full or partial water solubility are preferred digestive solvents.
  • the organic digestive solvent mixture can be, for example, methanol, ethanol, acetone, ethylene glycol, propylene glycol, triethylene glycol and tetrahydrofurfuryl alcohol.
  • Organic acids such as acetic, oxalic, acetylsalicylic and salicylic acids can also be used as catalysts (as acid promoter) in the at least partially miscible organic solvent process.
  • Temperatures for the digestion may range from 130 to 270 °C, preferably from 140 to 220 °C , and contact times from 0.25 to 24 hours, preferably from one to 4 hours.
  • a pressure from 2 to 100 bar, and most typically from 5 to 50 bar, is maintained on the system to avoid boiling or flashing away of the solvent.
  • the pretreated biomass stream can be washed prior to hydrogenolysis zone depending on the embodiment.
  • the pretreated biomass stream can be washed to remove one or more of non-cellulosic material, and non-fibrous cellulosic material prior to hydrogenolysis.
  • the pretreated biomass stream is optionally washed with a water stream under conditions to remove at least a portion of lignin, hemicellulosic material, and salts in the pretreated biomass stream.
  • the pretreated biomass stream can be washed with water to remove dissolved substances, including degraded, but non-processable cellulose compounds, solubilized lignin, and/or any remaining alkaline chemicals such as sodium compounds that were used for cooking or produced during the cooking (or pretreatment).
  • the washed pretreated biomass stream may contain higher solids content by further processing such as mechanical dewatering as described below.
  • the pretreated biomass stream is washed counter- currently.
  • the wash can be at least partially carried out within the digester and/or externally with separate washers.
  • the wash system contains more than one wash steps, for example, first washing, second washing, third washing, etc. that produces washed pretreated biomass stream from first washing, washed pretreated biomass stream from second washing, etc. operated in a counter current flow with the water, that is then sent to subsequent processes as washed pretreated biomass stream.
  • the water is recycled through first recycled wash stream and second recycled wash stream and then to third recycled wash stream. Water recovered from the chemical liquor stream by the concentration system can be recycled as wash water to wash system.
  • the washed steps can be conducted with any number of steps to obtain the desired washed pretreated biomass stream. Additionally, the washing may adjust the pH for subsequent steps to the desired pH for the hydrothermal hydrocatalytic treatment.
  • the ammonium hydroxide or an ammonium hydroxide precursor may be optionally added at this step to adjust the pH to the desired pH for the hydrothermal hydrocatalytic treatment.
  • biomass 102 is provided to digestion zone 106 that may have one or more digestion zones and/or digesting vessels, whereby the biomass is contacted with a digestive solvent.
  • the digestive solvent is optionally at least a portion recycled from the hydrogenolysis reaction as a recycle stream.
  • the hydrogenolysis recycle stream can comprise a number of components including in situ generated solvents, which may be useful as digestive solvent at least in part or in entirety.
  • in situ refers to a component that is produced within the overall process; it is not limited to a particular reactor for production or use and is therefore synonymous with an in-process generated component.
  • the in situ generated solvents may comprise oxygenated intermediates.
  • the digestive process to remove nitrogen, and sulfur compounds may vary within the reaction media so that a temperature gradient exists within the reaction media, allowing for nitrogen, and sulfur compounds to be extracted at a lower temperature than cellulose.
  • the reaction sequence may comprise an increasing temperature gradient from the biomass feedstock 102.
  • the non-extractable solids may be removed from the reaction as an outlet stream.
  • the treated biomass stream 120 is an intermediate stream that may comprise the treated biomass at least in part in the form of carbohydrates.
  • the composition of the treated biomass stream 120 may vary and may comprise a number of different compounds.
  • the contained carbohydrates will have 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
  • the carbohydrates may also have an oxygen to carbon ratio from 0.5: 1 to 1: 1.2.
  • Oligomeric carbohydrates containing more than 12 carbon atoms may also be present.
  • at least a portion of the digested pulp is contacted with hydrogen in the presence of the supported hydrogenolysis catalyst containing (a) sulfur and (b) molybdenum and/or tungsten and (c) cobalt and/or nickel in the presence of at least one of ammonia or a source or ammonia to produce a plurality of oxygenated hydrocarbons.
  • lignocellulosic biomass is contacted with hydrogen in the presence of digestive solvent and the supported hydrogenolysis catalyst containing (a) sulfur and (b) molybdenum and/or tungsten and (c) cobalt and/or nickel in the presence of at least one of ammonia or a source or ammonia to produce a plurality of oxygenated hydrocarbons.
  • Ammonia or source of ammonia present in the product stream along with the oxygenated hydrocarbons can be separated in a separation zone or unit 136 or 36 to produce an oxygenated hydrocarbon stream and ammonia that can be recycled to 126 or 6 (or oxygenated intermediate stream).
  • a first portion of the oxygenated hydrocarbon (or oxygenated intermediate stream) from product stream 130 or 30 can be recycled to digestion zone 106 or hydrothermal digestion unit 6, respectively.
  • a second portion of the oxygenated hydrocarbon (or oxygenated intermediates stream) is processed to produce higher hydrocarbons to form a liquid fuel.
  • step (ii) and (iii) allows conditions to be optimized for digestion and hydrogenation or hydrogenolysis of the digested biomass components, independent from optimization of the conversion of oxygenated intermediates to monooxygenates, before feeding to step (iv) to make higher hydrocarbon fuels.
  • a lower reaction temperature in step (iii) may be advantageous to minimize heavy ends byproduct formation, by conducting the hydrogenation and hydrogenolysis steps initially at a low temperature. This has been observed to result in an intermediates stream which is rich in diols and polyols, but essentially free of non-hydro genated monosaccharides which otherwise would serve as heavy ends precursors.
  • organic acids e.g., carboxylic acids
  • Some lignin can be solubilized before hemicellulose, while other lignin may persist to higher temperatures.
  • Organic in situ generated solvents which may comprise a portion of the oxygenated intermediates, including, but not limited to, light alcohols and polyols, can assist in solubilization and extraction of lignin and other components.
  • carbohydrates can degrade through a series of complex self-condensation reactions to form caramelans, which are considered degradation products that are difficult to convert to fuel products.
  • some degradation reactions can be expected with aqueous reaction conditions upon application of temperature, given that water will not completely suppress oligomerization and polymerization reactions.
  • the hydrolysis reaction can occur at a temperature between 20 °C and 270 °C and a pressure between 1 atm and 100 atm.
  • An enzyme may be used for hydrolysis at low temperature and pressure.
  • the hydrolysis reaction can occur at temperatures as low as ambient temperature and pressure between 1 bar (100 kPa) and 100 bar (10,100 kPa).
  • the hydrolysis reaction may comprise a hydrolysis catalyst (e.g., a metal or acid catalyst) to aid in the hydrolysis reaction.
  • the catalyst can be any catalyst capable of effecting a hydrolysis reaction.
  • suitable catalysts can include, but are not limited to, acid catalysts, base catalysts, metal catalysts, and any combination thereof.
  • Acid catalysts can include organic acids such as acetic, formic, levulinic acid, and any combination thereof.
  • the acid catalyst may be generated in the hydrogenolysis reaction and comprise a component of the oxygenated intermediate stream.
  • the digestive solvent may contain an in situ generated solvent.
  • the in situ generated solvent generally comprises at least one alcohol, ketone, or polyol capable of solvating some of the sulfur compounds, and nitrogen compounds of the biomass feedstock.
  • an alcohol may be useful for solvating nitrogen, sulfur, and optionally phosphorus compounds, and in solvating lignin from a biomass feedstock for use within the process.
  • the in situ generated solvent may also include one or more organic acids.
  • the organic acid can act as a catalyst in the removal of nitrogen and sulfur compounds by some hydrolysis of the biomass feedstock.
  • Each in situ generated solvent component may be supplied by an external source, generated within the process, and recycled to the hydrolysis zone, or any combination thereof.
  • a portion of the oxygenated intermediates produced in the hydrogenolysis reaction may be separated in the separator stage for use as the in situ generated solvent in the hydrolysis reaction.
  • the in situ generated solvent can be separated, stored, and selectively injected into the recycle stream so as to maintain a desired concentration in the recycle stream.
  • Each reactor vessel preferably includes an inlet and an outlet adapted to remove the product stream from the vessel or reactor.
  • the vessel in which at least some digestion occurs may include additional outlets to allow for the removal of portions of the reactant stream.
  • the vessel in which at least some digestion occurs may include additional inlets to allow for additional solvents or additives.
  • the digestion may occur in any contactor suitable for solid-liquid contacting.
  • the digestion may for example be conducted in a single or multiple vessels, with biomass solids either fully immersed in liquid digestive solvent, or contacted with solvent in a trickle bed or pile digestion mode.
  • the digestion step may occur in a continuous multizone contactor as described in US Patent No. 7285179 (Snekkenes et al., "Continuous Digester for Cellulose Pulp including Method and Recirculation System for such Digester").
  • the digestion may occur in a fluidized bed or stirred contactor, with suspended solids.
  • the digestion may be conducted batch wise, in the same vessel used for pre-wash, post wash, and/or subsequent reaction steps.
  • the relative composition of the various carbohydrate components in the treated biomass stream affects the formation of undesirable by-products such as tars or heavy ends in the hydrogenolysis reaction.
  • undesirable by-products such as tars or heavy ends in the hydrogenolysis reaction.
  • a low concentration of carbohydrates present as reducing sugars, or containing free aldehyde groups, in the treated biomass stream can minimize the formation of unwanted by-products.
  • oxygenated intermediates e.g., mono-oxygenates, diols, and/or polyols
  • lignin is removed with solvent from digesting step.
  • the remaining lignin if present, can be removed upon cooling or partial separation of oxygenates from hydrogenolysis product stream, to comprise a precipitated solids stream.
  • the precipitated solids stream containing lignin may be formed by cooling the digested solids stream prior to hydrogenolysis reaction.
  • the lignin which is not removed with digestion solvent is passed into step (iv), where it may be precipitated upon vaporization or separation of hydrogenolysis product stream, during processing to produce a higher hydrocarbon stream.
  • the treated biomass stream 120 may comprise C5 and C6 carbohydrates that can be reacted in the hydrogenolysis reaction.
  • oxygenated intermediates such as sugar alcohols, sugar polyols, carboxylic acids, ketones, and/or furans can be converted to fuels in a further processing reaction.
  • the hydrogenolysis reaction comprises hydrogen and a hydrogenolysis catalyst to aid in the reactions taking place.
  • the various reactions can result in the formation of one or more oxygenated hydrocarbon (or oxygenated intermediate streams) 130.
  • One suitable method for performing hydrogenolysis of carbohydrate-containing biomass includes contacting a carbohydrate or stable hydroxyl intermediate with hydrogen or hydrogen mixed with a suitable gas and a hydrogenolysis catalyst in a hydrogenolysis reaction under conditions effective to form a reaction product comprising smaller molecules or polyols.
  • hydrogen is dissolved in the liquid mixture of carbohydrate, which is in contact with the catalyst under conditions to provide catalytic reaction.
  • At least a portion of the carbohydrate feed is contacted directly with hydrogen in the presence of the hydrogenolysis catalyst.
  • directly the reaction is carried out on at least a portion of the carbohydrate without necessary stepwise first converting all of the carbohydrates into a stable hydroxyl intermediate.
  • the term "smaller molecules or polyols" includes any molecule that has a lower molecular weight, which can include a smaller number of carbon atoms or oxygen atoms than the starting carbohydrate.
  • the reaction products include smaller molecules that include polyols and alcohols. This aspect of hydrogenolysis entails breaking of carbon-carbon bonds, where hydrogen is supplied to satisfy bonding requirements for the resulting smaller molecules, as shown for the example:
  • R and R' are any organic moieties.
  • a carbohydrate e.g., a 5 and/or 6 carbon carbohydrate molecule
  • a hydrogenolysis reaction in the presence of a hydrogenolysis catalyst.
  • the hydrogenolysis catalyst may include a support material that has incorporated therein or is loaded with a metal component, which is or can be converted to a metal compound that has activity towards the catalytic hydrogenolysis of soluble carbohydrates.
  • the support material can comprise any suitable inorganic oxide material that is typically used to carry catalytically active metal components. Examples of possible useful inorganic oxide materials include alumina, silica, silica- alumina, magnesia, zirconia, boria, titania and mixtures of any two or more of such inorganic oxides.
  • the preferred inorganic oxides for use in the formation of the support material are alumina, silica, silica- alumina and mixtures thereof. Most preferred, however, is alumina.
  • the metal component of the catalyst composition may be incorporated into the support material by any suitable method or means that provides the support material that is loaded with an active metal precursor, thus, the composition includes the support material and a metal component.
  • One method of incorporating the metal component into the support material includes, for example, co- mulling the support material with the active metal or metal precursor to yield a co-mulled mixture of the two components.
  • another method includes the co-precipitation of the support material and metal component to form a co-precipitated mixture of the support material and metal component.
  • the support material is impregnated with the metal component using any of the known impregnation methods such as incipient wetness to incorporate the metal component into the support material.
  • the support material When using the impregnation method to incorporate the metal component into the support material, it is preferred for the support material to be formed into a shaped particle comprising an inorganic oxide material and thereafter loaded with an active metal precursor, preferably, by the impregnation of the shaped particle with an aqueous solution of a metal salt to give the support material containing a metal of a metal salt solution.
  • the inorganic oxide material which preferably is in powder form, is mixed with water and, if desired or needed, a peptizing agent and/or a binder to form a mixture that can be shaped into an agglomerate.
  • the mixture is desirable for the mixture to be in the form of an extrudable paste suitable for extrusion into extrudate particles, which may be of various shapes such as cylinders, trilobes, etc. and nominal sizes such as 1/16", 1/8", 3/16", etc.
  • the support material of the inventive composition thus, preferably, is a shaped particle comprising an inorganic oxide material.
  • the calcined shaped particle can have a surface area (determined by the BET method employing N 2 , ASTM test method D 3037) that is in the range of from 1 m /g to 500 m 2 /g.
  • the calcined shaped particle is impregnated in one or more impregnation steps with a metal component using one or more aqueous solutions containing at least one metal salt wherein the metal compound of the metal salt solution is an active metal or active metal precursor.
  • the metal elements are (a) molybdenum (Mo) and (b) cobalt (Co) and/or nickel (Ni). Phosphorus (P) can also be a desired component.
  • the metal salts include metal acetates, formates, citrates, oxides, hydroxides, carbonates, nitrates, sulfates, and two or more thereof.
  • the preferred metal salts are metal nitrates, for example, such as nitrates of nickel or cobalt, or both.
  • the metal salts include metal oxides or sulfides.
  • Preferred are salts containing the Mo and ammonium ion, such as ammonium heptamolybdate and ammonium dimolybdate.
  • Phosphorus is an additive that may be incorporated in these catalysts. Phosphorus may be added to increase the solubility of the molybdenum and to allow stable solutions of cobalt and/or nickel with the molybdenum to be formed for impregnation. Without wishing to be bound by theory, it is thought that phosphorus may also promote hydrogenation and hydrodenitrogenation (HDN).
  • HDN hydrodenitrogenation
  • the ability to promote HDN is an important one since nitrogen compounds are known inhibitors of the HDS reaction.
  • the addition of phosphorus to these catalysts may increase the HDN activity and therefore increases the HDS activity as a result of removal of the nitrogen inhibitors from the reaction medium.
  • the ability of phosphorus to also promote hydrogenation is also advantageous for HDS since some of the difficult, sterically hindered sulfur molecules are mainly desulfurized via an indirect mechanistic pathway that goes through an initial hydrogenation of the aromatic rings in these molecules.
  • the promotion of the hydrogenation activity of these catalysts by phosphorus increases the desulfurization of these types of sulfur containing molecules.
  • the phosphorus content of the finished catalyst is typically in a range from 0.1 to 5.0 wt .
  • the concentration of the metal compounds in the impregnation solution is selected so as to provide the desired metal content in the final composition of the hydrogenolysis catalyst taking into consideration the pore volume of the support material into which the aqueous solution is to be impregnated.
  • concentration of metal compound in the impregnation solution is in the range of from 0.01 to 100 moles per liter.
  • Cobalt, nickel, or combination thereof can be present in the support material having a metal component incorporated therein in an amount in the range of from 0.5 wt. % to 20 wt. , preferably from 1 wt. % to 15 wt. , and, most preferably, from 1 wt. % to 12 wt. , based on metals components (b) and (c) as metal oxide form; and the molybdenum can be present in the support material having a metal component incorporated therein in an amount in the range of from 1 wt. % to 50 wt. , preferably from 2 wt. % to 40 wt. , and, most preferably, from 2 wt. % to 30 wt.
  • metals components (b) and (c) based on metals components (b) and (c) as metal oxide form.
  • the above-referenced weight percents for the metal components are based on the dry support material and the metal component as the element (change "element” to "metal oxide form") regardless of the actual form of the metal component.
  • the metal loaded catalyst may be sulfided prior to its loading into a reactor vessel or system for its use as hydrogenolysis catalyst or may be sulfided, in situ, in a gas phase or liquid phase activation procedure.
  • the liquid soluble carbohydrate feedstock can be contacted with a sulfur-containing compound, which can be hydrogen sulfide or a compound that is decomposable into hydrogen sulfide, under the contacting conditions of the invention.
  • decomposable compounds include mercaptans, CS 2 , thiophenes, dimethyl sulfide (DMS), dimethyl sulfoxide (DMSO), sodium hydrogen sulfide, and dimethyl disulfide (DMDS).
  • the sulfiding is accomplished by contacting the hydrogen treated composition, under suitable sulfurization treatment conditions, with a suitable feed source that contains a concentration of a sulfur compound.
  • the sulfur compound of the hydrocarbon feedstock can be an organic sulfur compound, particularly, one that is derived from the biomass feedstock or other sulfur containing amino-acids such as cysteine.
  • Suitable sulfurization treatment conditions are those which provide for the conversion of the active metal components of the precursor hydrogenolysis catalyst to their sulfided form.
  • the sulfiding temperature at which the precursor hydrogenolysis catalyst is contacted with the sulfur compound is in the range of from 150 °C to 450 °C, preferably, from 175 °C to 425 °C, and, most preferably, from 200 °C to 400 °C.
  • the sulfurization conditions can be the same as the process conditions under which the hydrogenolysis is performed.
  • the sulfiding pressure generally can be in the range of from 1 bar to 70 bar, preferably, from 1.5 bar to 55 bar, and, most preferably, from 2 bar to 35 bar.
  • the resulting active catalyst typically has incorporated therein sulfur content in an amount in the range of from 0.1 wt. % to 40 wt. , preferably from 1 wt. % to 30 wt. , and, most preferably, from 3 wt. % to 24 wt. , based on metals components (b) and (c) as metal oxide form .
  • the conditions for which to carry out the hydrogenolysis reaction will vary based on the type of biomass starting material and the desired products (e.g. gasoline or diesel).
  • the desired products e.g. gasoline or diesel.
  • the hydrogenolysis reaction is conducted at temperatures in the range of 110 °C to 300 °C, and preferably of 170 °C to less than 300 °C, and most preferably of 180 °C to 290 °C.
  • the hydrogenolysis reaction is conducted at pressures in a range of 0.2 to 200 bar (20 to 20,000 kPa), and preferably in a range of 20 to 140 bar (2000 kPa to 14000 kPa), and even more preferably in the range of 50 and 110 bar (5000 to 11000 kPa).
  • the hydrogen used in the hydrogenolysis reaction of the current invention can include external hydrogen, recycled hydrogen, in situ generated hydrogen, and any combination thereof.
  • the use of a hydrogenolysis reaction may produce less carbon dioxide and a greater amount of polyols than a reaction that results in reforming of the reactants.
  • reforming can be illustrated by formation of isopropanol (i.e., IPA, or 2-propanol) from sorbitol:
  • polyols and mono-oxygenates such as IPA can be formed by hydrogenolysis, where hydrogen is consumed rather than produced:
  • the products of the hydrogenolysis reaction may comprise greater than 25% by mole, or alternatively, greater than 30% by mole of polyols, which may result in a greater conversion in a subsequent processing reaction.
  • the use of a hydrolysis reaction rather than a reaction running at reforming conditions may result in less than 20% by mole, or alternatively less than 30% by mole carbon dioxide production.
  • oxygenated intermediates generically refers to hydrocarbon compounds having one or more carbon atoms and between one and three oxygen atoms (referred to herein as 0+01-3 hydrocarbons), such as polyols and smaller molecules (e.g., one or more polyols, alcohols, ketones, or any other hydrocarbon having at least one oxygen atom).
  • hydrogenolysis is conducted under neutral or acidic conditions, as needed to accelerate hydrolysis reactions in addition to the hydrogenolysis.
  • Hydrolysis of oligomeric carbohydrates may be combined with hydrogenation to produce sugar alcohols, which can undergo hydrogenolysis.
  • a second aspect of hydrogenolysis entails the breaking of -OH bonds such as:
  • This reaction is also called “hydrodeoxygenation”, and may occur in parallel with C-C bond breaking hydrogenolysis.
  • Diols may be converted to mono-oxygenates via this reaction.
  • concentration of polyols and diols relative to mono-oxygenates will diminish, as a result of this reaction.
  • Selectivity for C-C vs. C-OH bond hydrogenolysis will vary with catalyst type and formulation.
  • Full de- oxygenation to alkanes can also occur, but is generally undesirable if the intent is to produce monoxygenates or diols and polyols which can be condensed or oligomerized to higher molecular weight fuels, in a subsequent processing step.
  • reaction mixture may contain:
  • a hydrogenolysis catalyst containing (a) sulfur, (b) Mo or W, and (c) Co, Ni or mixture thereof, incorporated into a suitable support;
  • composition may further comprise (v) digestive organic solvent.
  • catalyst may further comprise (d) phosphorus.
  • the pretreated biomass containing carbohydrates may be converted into an stable hydroxyl intermediate comprising the corresponding alcohol derivative through a hydrogenolysis reaction in addition to an optional hydrogenation reaction in a suitable reaction vessel (such as hydrogenation reaction as described in co-pending patent application publication nos. US20110154721 and US20110282115).
  • the oxygenated intermediate stream 130 may then pass from the hydrogenolysis system to a further processing stage.
  • optional separation stage includes elements that allow for the separation of the oxygenated hydrocarbons into different components.
  • the separation stage can receive the oxygenated intermediate stream 130 from the hydrogenolysis reaction and separate the various components into two or more streams.
  • a suitable separator may include, but is not limited to, a phase separator, stripping column, extractor, filter, or distillation column.
  • a separator is installed prior to a processing reaction to favor production of higher hydrocarbons by separating the higher polyols from the oxygenated intermediates.
  • the higher polyols can be recycled back through to the hydrogenolysis reaction, while the other oxygenated intermediates are passed to the processing reaction.
  • an outlet stream from the separation stage containing a portion of the oxygenated intermediates may act as in situ generated digestive solvent when recycled to the digester 106.
  • the separation stage can also be used to remove some or all of the lignin from the oxygenated intermediate stream.
  • the lignin may be passed out of the separation stage as a separate stream, for example as output stream.
  • the processing reaction may comprise a condensation reaction to produce a fuel blend.
  • the higher hydrocarbons may be part of a fuel blend for use as a transportation fuel.
  • condensation of the oxygenated intermediates occurs in the presence of a catalyst capable of forming higher hydrocarbons. While not intending to be limited by theory, it is believed that the production of higher hydrocarbons proceeds through a stepwise addition reaction including the formation of carbon-carbon bond.
  • the resulting reaction products include any number of compounds, as described in more detail below.
  • an outlet stream 130 containing at least a portion of the oxygenated intermediates can pass to a processing reaction or processing reactions.
  • Suitable processing reactions may comprise a variety of catalysts for condensing one or more oxygenated intermediates to higher hydrocarbons, defined as hydrocarbons containing more carbons than the oxygenated intermediate precursors.
  • the higher hydrocarbons may comprise a fuel product.
  • the fuel products produced by the processing reactions represent the product stream from the overall process at higher hydrocarbon stream.
  • the oxygen to carbon ratio of the higher hydrocarbons produced through the processing reactions is less than 0.5, alternatively less than 0.4, or preferably less than 0.3.
  • the oxygenated intermediates can be processed to produce a fuel blend in one or more processing reactions.
  • a condensation reaction can be used along with other reactions to generate a fuel blend and may be catalyzed by a catalyst comprising acid or basic functional sites, or both.
  • the basic condensation reactions generally consist of a series of steps involving: (1) an optional dehydrogenation reaction; (2) an optional dehydration reaction that may be acid catalyzed; (3) an aldol condensation reaction; (4) an optional ketonization reaction; (5) an optional furanic ring opening reaction; (6) hydrogenation of the resulting condensation products to form a C4+ hydrocarbon; and (7) any combination thereof.
  • Acid catalyzed condensations may similarly entail optional hydrogenation or dehydrogenation reactions, dehydration, and oligomerization reactions. Additional polishing reactions may also be used to conform the product to a specific fuel standard, including reactions conducted in the presence of hydrogen and a hydrogenation catalyst to remove functional groups from final fuel product.
  • a catalyst comprising a basic functional site, both an acid and a basic functional site, and optionally comprising a metal function, may be used to effect the condensation reaction.
  • the aldol condensation reaction may be used to produce a fuel blend meeting the requirements for a diesel fuel or jet fuel.
  • the fuel yield of the current process may be greater than other bio-based feedstock conversion processes. Without wishing to be limited by theory, it is believed that the presence of the ammonium hydroxide or an ammonium hydroxide precursor with the nitrogen and sulfur tolerant catalyst used in process prolongs such catalyst life by preventing the leaching of active metal such as cobalt.
  • a 75-milliliter Parr5000 reactor was charged with 30.21 grams of 50 wt% glycerol in deionized water, 0.202 grams of ammonium carbonate buffer, and 0.304 grams of the catalyst (DC-2534, containing 1-10% cobalt oxide and molybdenum trioxide (up to 30 wt%) on alumina, and less than 2% nickel), obtained from Criterion Catalyst & Technologies L.P., and sulfided by the method described in US2010/0236988 Example 5.
  • DC-2534 containing 1-10% cobalt oxide and molybdenum trioxide (up to 30 wt%) on alumina, and less than 2% nickel
  • the reactor was pressured to 53 bar with hydrogen and heated to 250 °C for 5 hours. A final pH of 5.6 was obtained, indicating effective buffering of acetic and other acids formed as a byproduct of reaction
  • Reactor product was analyzed by gas chromatography using a 60-m x 0.32 mm ID DB-5 column of 1 ⁇ thickness, with 50: 1 split ratio, 2 ml/min helium flow, and column oven at 40 °C for 8 minutes, followed by ramp to 285 °C at 10°C/min, and a hold time of 53.5 minutes.
  • the injector temperature was set at 250 °C, and the detector temperature was set at 300 °C.
  • GC analysis indicated 26% conversion of glycerol, with 1,2-propylene glycol the dominant product formed, along with a few weight percent of ethanol and propanol.
  • Example 1 The reactor contents from Example 1 were distilled in a short path still at atmospheric pressure, under a blanket of nitrogen. The distillation was continued at a bottoms temperature from 142.5 to 245 °C, to yield 50.1% of the initial charge as an overhead product. The pH of the distillate averaged to 7.5, while a pH of 8.6 was obtained for the final distillate sample comprising 8% of the initial charge. The pH of the remaining bottoms fraction was 6.6.
  • This example demonstrates the ability to distill the ammonia buffer overhead as base, which can be recycled to neutralize acidity in a subsequent reaction cycle.

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Abstract

L'invention concerne un procédé de traitement hydrocatalytique hydrothermique de biomasse. Des matières solides de biomasse lignocellulosique sont introduites dans une unité de digestion hydrothermique en présence d'un solvant de digestion, au moins l'un parmi l'ammoniaque ou une source d'ammoniaque, et un catalyseur d'hydrogénolyse supporté contenant (a) du soufre, (b) Mo ou W et (c) Co, Ni ou un mélange de ceux-ci, incorporé dans un support approprié. Les matières solides de biomasse lignocellulosique et le solvant de digestion sont chauffés en présence d'hydrogène, du catalyseur d'hydrogénolyse supporté et dudit un parmi l'ammoniaque ou une source d'ammoniaque formant une solution de produit contenant une pluralité d'hydrocarbures oxygénés et de l'ammoniaque. Au moins une partie de l'ammoniaque est séparée et recyclée vers l'unité de digestion hydrothermique.
PCT/US2013/076325 2012-12-19 2013-12-19 Tampon recyclable pour le traitement hydrocatalytique hydrothermique de biomasse WO2014100303A2 (fr)

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EP2935519A2 (fr) 2015-10-28

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