WO2012167252A9 - Production de matières organiques au moyen d'un procédé de dissolution hydrothermique oxydative - Google Patents

Production de matières organiques au moyen d'un procédé de dissolution hydrothermique oxydative Download PDF

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Publication number
WO2012167252A9
WO2012167252A9 PCT/US2012/040746 US2012040746W WO2012167252A9 WO 2012167252 A9 WO2012167252 A9 WO 2012167252A9 US 2012040746 W US2012040746 W US 2012040746W WO 2012167252 A9 WO2012167252 A9 WO 2012167252A9
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WO
WIPO (PCT)
Prior art keywords
composite material
organic
ohd
oxidant
solubilized
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PCT/US2012/040746
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English (en)
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WO2012167252A1 (fr
Inventor
Kenneth B. Anderson
John C. Crelling
William W. Huggett
Derek M. Perry
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Southern Illinois University Carbondale
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Priority to KR1020137031981A priority Critical patent/KR20140090564A/ko
Priority to CA2836738A priority patent/CA2836738A1/fr
Priority to JP2014513791A priority patent/JP2014520104A/ja
Priority to EP12793493.3A priority patent/EP2714855A4/fr
Priority to CN201280026415.5A priority patent/CN103764804A/zh
Priority to BR112013031137A priority patent/BR112013031137A2/pt
Application filed by Southern Illinois University Carbondale filed Critical Southern Illinois University Carbondale
Priority to NZ618723A priority patent/NZ618723B2/en
Priority to RU2013157530/04A priority patent/RU2604726C2/ru
Priority to AU2012261870A priority patent/AU2012261870A1/en
Publication of WO2012167252A1 publication Critical patent/WO2012167252A1/fr
Priority to ZA2013/08767A priority patent/ZA201308767B/en
Publication of WO2012167252A9 publication Critical patent/WO2012167252A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/02—Purification; Separation; Stabilisation; Use of additives by treatment giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D333/40—Thiophene-2-carboxylic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C07H1/08—Separation; Purification from natural products
    • 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
    • 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
    • C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
    • 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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • 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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/047—Hot water or cold water extraction processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • 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
    • 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

  • This document relates to methods of producing organic materials, and in particular to methods of producing petroleum materials and organic compounds such as aromatic acids, phenols, and aliphatic poly-carboxylic acids using an oxidative hydrothermal dissolution (OHD) process.
  • OHT oxidative hydrothermal dissolution
  • bituminous sands also known as oil sands and/or tar sands
  • amounts of oil in place in known bituminous sand deposits may be larger than all remaining worldwide conventional petroleum reserves and is at least of the same order of magnitude as all remaining worldwide conventional petroleum reserves.
  • recovery of these resources is difficult and subject to numerous undesirable environmental consequences.
  • Oxidative hydrothermal dissolution (OHD) technology is an environmentally friendly technology that breaks down macromolecular organic materials using an oxidative bond cleavage process resulting in the generation of organic compounds such as low molecular weight aromatic and aliphatic acids, phenols, and other products.
  • This application describes methods of using OHD technology to break down macromolecular and heterogeneous materials such as bituminous sands, coal, lignocellulosic biomass, and kerogen to produce specific products that are currently used or are potentially useful to the chemical industry, as well as other products.
  • a process for solubilizing an organic solid contained within a composite material including an organic solid and an inorganic matrix may include contacting the composite material with an oxidant in superheated water to form an aqueous mixture comprising at least one solubilized organic solute.
  • the process may further include pulverizing the composite material and combining the pulverized composite material with water to form a slurry prior to contacting the composite material with the oxidant in the superheated water.
  • the oxidant is molecular oxygen (0 2 ), wherein the molecular oxygen is supplied by any known method of supplying, producing, or separating molecular oxygen from any known mixture in any form.
  • methods of obtaining a supply of molecular oxygen include: in situ decomposition of hydrogen peroxide; fractional distillation of liquefied air; electrolysis of water; transfer from a stored oxygen supply; membrane separation from air; and any combination thereof.
  • the composite material may be selected from the group consisting of coal, bituminous sand, carbonaceous shale, and any mixture thereof.
  • the composite material may be contacted with the oxidant in the superheated water within a reactor, wherein the composite material, oxidant, and superheated water are maintained in a non-gaseous phase to inhibit the formation of a head space within the reactor.
  • the process may further include chilling the aqueous mixture to a temperature of about 20° C.
  • FIG. 1 is a schematic of an oxidative hydrothermal dissolution
  • FIG. 2 is a schematic illustration of a semi-continuous micro reactor system used for testing and evaluation of the OHD process
  • FIG. 3 is a schematic illustration of a continuous micro reactor system used for testing and evaluation of the OHD process
  • FIG. 4 is a graph comparing the carbon remaining after the processing of bituminous sand using three methods of carbon removal
  • FIG. 5 are photographs of bituminous sand samples before and after processing using three methods of carbon removal
  • FIG. 6 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and solvent extraction of the OHD liquor using methylene chloride;
  • FIG. 7 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and solvent extraction of the OHD liquor using ethyl acetate;
  • FIG. 8 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and evaporative stripping of water from the OHD liquor;
  • FIG. 9 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using solvent extraction with methylene chloride;
  • FIG. 10 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using pyrolysis
  • FIG. 11 is a total ion chromatogram illustrating the distribution of products observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method
  • FIG. 12 is a multi-ion chromatogram illustrating the distribution of major aliphatic products observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 13 is a multi-ion chromatogram illustrating the distribution of benzoic acid and mono methoxy benzoic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 14 is a single ion chromatogram illustrating the distribution of benzene dicarboxylic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method
  • FIG. 15 is a multi-ion chromatogram illustrating the distribution of thiopene carboxylates and dicarboxylates observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method
  • FIG. 16 is a single ion chromatogram illustrating the distribution of dimethoxy benzenes and dimethoxy benzoic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 17 is a single ion chromatogram illustrating the distribution of benzene tricarboxylic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 18 is a single ion chromatogram illustrating the distribution of dimethoxy benzene dicarboxylic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 19 is a multi-ion chromatogram illustrating the distribution of monomethoxy benzene dicarboxylic acids and unidentified analogs observed by Py- GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 20 is a single ion chromatogram illustrating the distribution of benzene tetra carboxylic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 21 is a multi-ion chromatogram illustrating the distribution of trimethoxy benzenes and furan dicarboxylic acids observed by Py-GC-MS analysis of organic products removed from Illinois coal using an OHD method;
  • FIG. 22 is a total ion chromatogram illustrating the distribution of products observed by Py-GC-MS analysis of organic products removed from soft wood (conifer) lignin using an OHD method;
  • FIG. 23 is a total ion chromatogram illustrating the distribution of products observed by Py-GC-MS analysis of organic products removed from bamboo using an OHD method
  • FIG. 24 is a total ion chromatogram illustrating the distribution of products observed by Py-GC-MS analysis of organic products removed from carbonaceous shale using an OHD method
  • FIG. 25 is a total ion chromatogram illustrating the distribution of products observed by Py-GC-MS analysis of organic products removed from sugar cane bagasse using an OHD method
  • FIG. 26 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and evaporative stripping of water from the OHD liquor;
  • FIG. 27 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and solvent extraction of the OHD liquor using ethyl acetate;
  • FIG. 28 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using pyrolysis
  • FIG. 29 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and evaporative stripping of water from the OHD liquor;
  • FIG. 30 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using an OHD method and solvent extraction of the OHD liquor using ethyl acetate;
  • FIG. 31 is a graph summarizing results of a GC-MS analysis of organic products removed from bituminous sand using pyrolysis.
  • the invention relates generally to methods of producing water- soluble products from organic solids using an oxidative hydrothermal dissolution (OHD) method. Certain aspects of the OHD method are described in detail in PCT Application Number PCT/US10/23886, which is hereby incorporated in its entirety herein.
  • OHD oxidative hydrothermal dissolution
  • biomass may include, but not limited to, materials containing cellulose, hemicellulose, lignin, protein and carbohydrates such as starches and sugars, trees, shrubs and grasses, corn, and corn husks, municipal solid waste including materials related to waste that is normally disposed of by occupants of residential dwelling units, commercial establishments and industry, biomass high in starch, including starch, sugar or protein such as corn, grains, fruits and vegetables, branches, bushes, canes, energy crops, forests, fruits, flowers, grains, grasses, herbaceous crops, leaves, bark, needles, logs, roots, saplings, short rotation woody crops, shrubs, switch grasses, trees, vegetables, vines, hard and soft woods, organic waste materials generated from agricultural processes including framing and forestry activities such as forestry wood waste, virgin biomass and/or non-virgin biomass including agricultural biomass, commercial organics, construction and demolition debris, paper, cardboard, scrap wood, saw dust, and plastics.
  • aqueous mixture shall mean a homogeneous mixture of one or more substances (solutes) dispersed molecularly in a sufficient quantity of dissolving medium (solvent).
  • composite material shall mean a combination of two or more constituent materials of different physical or chemical properties which remain separate and distinct in the final structure.
  • the composite material may include an organic solid and an inorganic matrix.
  • the OHD method includes contacting an organic solid with an oxidant in a reactor containing superheated water to form at least one solubilized organic solute.
  • the reaction breaks down the macromolecular structure of the organic solid, which would otherwise not be soluble in water, into lower molecular weight fragments. These lower molecular weight fragments are soluble in water. These water-soluble fragments are referred to as dissolved organic solids, solubilized organics, or solubilized organic solutes.
  • the solubilized fragments can then be used as raw materials for various chemical processes or as liquid fuels.
  • solubilized fragments are dissolved carbohydrates such as low molecular weight sugars or oxidized low molecular weight sugars
  • the dissolved carbohydrates may be fermented to produce alcohols or used in other processes to produce a variety of other products.
  • Non-limiting examples of organic solids suitable for processing using the OHD method include coal, bituminous sand, lignite, kerogen, biomass, and solid organic wastes.
  • Biomass refers to biological material derived from living organisms and includes, for example, plant-based materials such as wood, grasses, and grains.
  • a solid organic waste may be waste plastics.
  • Coal for example, has a complex, high molecular weight macromolecular structure made up of numerous cross-linked aromatic and aliphatic sub-structures. It is believed that coal is insoluble in water primarily because of the extent of cross- linking present between different parts of this structure.
  • Disruption of cross-linking structural elements in organic solids breaks the structure into smaller sub-structural units.
  • coal may be converted into a new product with modified physical properties using OHD methods.
  • the OHD method may be used to convert biomass into soluble organics.
  • biomass containing cellulose, hemicellulose, and/or lignins may be converted into dissolved low molecular weight sugars or oxidized low molecular weight sugars, and other products.
  • the oxidant can be any oxidant capable of oxidizing the organic solid, including but not limited to molecular oxygen (0 2 ).
  • molecular oxygen as an oxidant avoids the use of exotic oxidants, such as permanganates, chromate oxides, or organic peroxides that may be harmful to the environment or expensive.
  • the molecular oxygen may be supplied by any known method of supplying, producing, or separating molecular oxygen from any known mixture in any form.
  • Non-limiting examples of methods of obtaining a supply of molecular oxygen include: in situ decomposition of hydrogen peroxide; fractional distillation of liquefied air; electrolysis of water; transfer from a stored oxygen supply; membrane separation from air; and any combination thereof.
  • suitable stored oxygen supplies include pressurized oxygen tanks. The addition of the oxidant to the superheated water increases the rate of conversion and the overall percent conversion of the organic solid to solubilized products.
  • the reaction media in the OHD method may be superheated water having a temperature from about 100 °C to about 374 °C.
  • the superheated water may have a temperature ranging from about 200 °C to about 350 °C.
  • the pressure in the reactor may be specified to be sufficient to maintain the water in a liquid state (without water loss into a gas phase).
  • the pressure may range from about 100 kPa (kiloPascal) to about 22 MPa (megaPascal) in one embodiment. In other embodiments, the pressure may range from about 1 .5 MPa to about 17 MPa, and from about 12 MPa to about 16 MPa.
  • hydrophilmal water and “superheated water” may be used interchangeably throughout the specification.
  • the oxidation reaction is a surface reaction of the oxidant and the organic solid surface. Therefore, maintaining a sufficiently high surface-area-to-volume ratio of the organic solid may enhance the rate of the reaction.
  • the organic solid may have a small particle size to provide greater surface area per volume for the reaction. However, the organic solid may be any size without impeding the progression of the reaction. The reaction may begin at the surface of the organic solid and etches away the surface until the solid is dissolved or until the reaction is halted.
  • the OHD method may also include the addition of other
  • components to the reaction including but not limited to pH modifiers, catalysts, additional solvents, and any combination thereof. It is contemplated that these additives may promote the formation of particular desired products or minimize the formation of undesired products.
  • the process may optionally further include chilling the solubilized organic solute.
  • chilling the solubilized organic solute may be to prevent further oxidation of the solubilized organic solute.
  • the solubilized organic solute may be chilled to room temperature or approximately 20 °C.
  • further processing such as distillation, evaporation, or further reaction of the dissolved organics, may not require cooling, and chilling may not be desirable.
  • FIG. 1 is a schematic diagram of the OHD process 100.
  • An organic solid may be loaded into a reactor 200.
  • the reactor 200 may be an up-flow reactor with no gaseous head space to enhance the efficiency of the OHD method.
  • Superheated water may be introduced into the reactor 200 through a port 102 until equilibration is reached.
  • An oxidant for example, molecular oxygen
  • molecular oxygen may be introduced into the reactor 200 through a port 104.
  • Molecular oxygen may be supplied directly from a storage tank, separated from the surrounding air, or molecular oxygen may be generated by a chemical process such as the thermal decomposition of hydrogen peroxide prior to addition to the reactor 200.
  • a port 106 may be used to introduce any other components added to the reaction, including, but not limited to, pH modifiers, catalysts, or organic solvents.
  • the solubilized organic solute resulting from the organic solid exits the reactor 200 from a port 108 and may optionally enter a chiller 300.
  • the cooled effluent from a port 110 may be monitored for the presence of solubilized organic solute or may be collected for further processing or analysis.
  • suitable analysis techniques for the cooled effluent include photodiode array detection (PDA), GC-MS, and any combination thereof.
  • PDA photodiode array detection
  • GC-MS GC-MS
  • OHD process may be conducted as a batch, semi- continuous, or continuous process.
  • the raw product (OHD liquor) derived from the processing of organic matter using OHD methods may be an aqueous solution of dissolved organic products.
  • the OHD liquor may be a clear solution and does not contain suspended colloidal solids.
  • the OHD liquor may include suspended particles.
  • suspended particles include inorganic particles such as inorganic matrix, unreacted organic solids, and any combination thereof.
  • the OHD liquor may include suspended particles of unreacted organic solid; in this example, the OHD process may include too low of an oxidant concentration and/or too brief of a reaction time.
  • the formation of the OHD liquor product is not the result of simple hydrolysis. Based on previous observations (not shown herein) production of the dissolved product is directly related to the delivery of 0 2 and the response of the reactor to delivery of the oxidant is rapid.
  • the OHD methods may be applied to a wide range of organic materials, including, but not limited to, coal, carbonaceous shales, organic-rich carbonate rocks, bituminous sands, lignocellulosic and other biomass as described herein above, lignite, bituminous coal, anthracite and wood charcoal. Complete conversion of organic materials to soluble products may be readily achieved using the OHD method, although rates of reaction may vary considerably.
  • Reaction rate may depend on particle size, reaction temperature, oxidant loading and flow rate/contact time, as well as varying the choice of organic material used as the initial substrate. Typically, the reaction proceeds in a matter of minutes for the complete dissolution of bituminous coal particles having a particle size ranging from about 60 mesh to 20 mesh. In general, low rank materials react faster than high rank materials, (presumably due to the more polycondensed nature of the high rank materials), and macerals react in order of structure (fastest to slowest): liptinite>vitrinite> inertinite.
  • the OHD method likely works by oxidative cleavage of labile structures, resulting in the disruption of the overall macromolecular structure.
  • reaction medium water
  • the dissolved organics are separated from residual solid, thereby exposing fresh substrate surface for subsequent reaction with additional oxidant. Rapid removal of the water and separation of the produced organic solute or quenching prevents over-oxidation of the dissolved organic compounds in the OHD liquor product.
  • Characterization of the solubilized products indicates that the OHD liquor product typically consists of moderately complex mixtures of low molecular weight organics. For bituminous coal, these consist predominantly of: (i) aliphatic carboxylic acids and diacids from C1 to about C20; and (ii) mono-aromatic carboxylic acids, polyacids and phenols, including methoxylated analogs. In many cases acetic acid is the single most abundant product obtained and may account for up to about 5% of the raw product, depending on the initial feedstock processed using the OHD method. In an embodiment, one or more specific organic compounds may be isolated or purified from the OHD liquor product using any known method of refining such as fractional distilling and others.
  • OHD products derived from biomass tend to be simpler mixtures of organic compounds compared to OHD products derived from coals.
  • Non-limiting examples of OHD products derived from biomass include mixtures of low molecular weight sugars including glucose, fructose, galactose, sucrose, maltose, lactose, oxidized low molecular weight sugars, and any combination thereof.
  • Non-limiting examples of oxidized low molecular weight sugars include keto, aldo, and carboxy derivatives of any of the low molecular weight sugars described herein above.
  • cellulose, hemicellulose, and other macromolecular carbohydrates may be broken down by the OHD process via hydrolysis and oxidative cleavage to produce these.
  • Other specific mixtures of organic compounds contained in the OHD liquor products derived from various organic materials in other aspects are illustrated herein below in the Examples.
  • FIG. 2 An embodiment of a semi-continuous flow OHD device is illustrated schematically in FIG. 2.
  • An organic solid may be loaded into a reactor 6 and superheated water and an oxidant may be introduced into the reactor 6 by pumps 1 and 2. If the oxidant is derived from hydrogen peroxide, hydrogen peroxide may be decomposed in a heater 3, and the resulting molecular oxygen and superheated water may enter the reactor via ports 4 and 5 respectively. Additional components or water may be introduced into the reactor 6 via a port 7.
  • a reaction between the organic solid and the oxidant takes place in the reactor 6 and generates a solubilized organic solute, which leaves the reactor 6 and optionally enters a chiller 8. Effluent may collected in a vessel 9, and data are collected by a detector 10.
  • FIG. 3 An embodiment of a continuous flow OHD device is illustrated schematically in FIG. 3.
  • An organic solid such as coal, bituminous sand, or carbonaceous shale, in which the inorganic component of the shale may comprise minerals including but not limited to silicates or carbonates, may be used as a feedstock to the OHD device.
  • the feedstock may be pulverized in a mill 302 and combined with water to form a slurry in a slurry generator 304.
  • the mill 302 and the slurry generator 304 may be combined into a single operation by a process such as wet milling.
  • the slurry may then be pumped into a reactor 306 by a slurry pump 308.
  • the slurry may be heated before entering the reactor 306 using a preheater 320.
  • An oxidant such as molecular oxygen, and superheated water may be introduced into the reactor 306 by a pump 310. If the molecular oxygen is derived from hydrogen peroxide, the hydrogen peroxide may be decomposed in a heater 312 and molecular oxygen and superheated water may then enter the reactor 306.
  • a reaction between the organic solid and the oxidant may take place in the reactor 306 and generate a solubilized organic solute.
  • the solubilized organic solute may exit the reactor 306 and may optionally enter a chiller 314.
  • Back pressure may be controlled by a backpressure regulator 316. Effluent may be collected in a vessel 318. Wiring and control details have been omitted, but are implicit in the design of the reactor system. This system may be operated continuously, and the temperature and flow rate of reactants may be controlled automatically by a computer 322 or other data processing device.
  • the OHD methods described above herein may be used to recover petroleum materials from bituminous sands or oil shales in other embodiments.
  • the particular device, operating systems, and reactants used to recover the petroleum materials in this embodiment may vary depending on the nature and location of the deposit in which the bituminous sands or oil shales occur and desired petroleum materials to be extracted.
  • the OHD methods described above herein may be used to produce useful raw materials and other organic compounds for the chemical industry, including but not limited to aromatic acids, phenols, and aliphatic acids.
  • the particular device, operating systems, and reactants used to produce the raw materials and other organic compounds may vary depending on the particular organic solid materials from which the feedstocks to the OHD device are produced, as well as the desired organic compound products to be produced using the OHD method.
  • Non-limiting examples of organic matter suitable for use as a feedstock in the OHD method in this embodiment include coal, carbonaceous shales, organic-rich carbonate rocks, bituminous sands, lignocellulosic biomass, lignite, bituminous coal, anthracite, wood charcoal, and kerogen.
  • "Kerogen" refers to a mixture of organic chemical compounds that make up a portion of the organic matter in sedimentary rocks, including but not limited to oil shale.
  • Table 1 is a listing of non-limiting examples of organic compounds that may be produced using the OHD method described herein above.
  • Ri H or OH or OCH 3
  • R 2 H or OH, or OCH 3
  • R 3 H or CH 3
  • n is an integer between 1 and about 30 or more.
  • the organic compounds obtained from the OHD methods may be recoverable in high yield.
  • OHD processing may be measured by assessing the removal of organics from an inorganic matrix, especially in those cases in which bituminous sand is processed using the OHD method.
  • the yield of OHD processing may be measured as the residual carbon retained in the inorganic phase after OHD processing or as the overall mass loss resulting from high- temperature ashing or combustion after OHD processing.
  • Low amounts of residual carbon remaining in the inorganic matrix may be desirable, because this indicates that most or all of the bituminous material has been removed from the inorganic matrix resulting in "cleaner" sand or other inorganic matrix that may be returned to the environment.
  • potentially more of the bituminous product may be recovered for refining into organic compounds.
  • Another method of assessing the yield of organic compounds after OHD processing may include measuring the amount of carbon contained within the aqueous phase or OHD liquor resulting from the processing of the organic matter in the reactor in an OHD process.
  • the yield may be quantified as the % of the initial carbon contained in the organic matter that is recovered as dissolved product in the aqueous phase or OHD liquor.
  • High yields of carbon in the dissolved product may be desirable, because this indicates that the aqueous phase contains a large proportion of the original bituminous material that may be recovered and refined into organic compounds.
  • Carbon not recovered and not retained in the inorganic residue may be lost as gaseous products.
  • the gaseous products may include CO with some C0 2 . CO may be recovered as a useful by-product, but typically minimal gas production is desirable.
  • a bituminous sand sample of Athabasca oil sand was processed using the OHD method described herein above.
  • OHD O-dimethyl methacrylate
  • the raw sand was compared with products produced by hot water extraction (to approximately simulate current extraction technologies, exhaustive laboratory extraction with organic solvents, and OHD. Both soluble and insoluble products were recovered after processing by each method and analyzed. Insoluble products were analyzed for carbon content and high
  • FIG. 4 is a bar graph summarizing the percentage of carbon remaining in the bituminous sand samples after treatment with the various methods to remove the bituminous materials from the inorganic sand matrix. These data illustrate that about 86% of the carbon initially present in the bituminous sand was removed by OHD processing, compared with 23% removed with superheated water alone and 69% removed by exhaustive laboratory extraction with organic solvent (CH 2 CI 2 ).
  • FIG. 5 is a series of photographs of the bituminous sand samples before and after treatment with the various methods to remove the bituminous materials from the inorganic sand matrix samples.
  • the residue derived from OHD processing is free-flowing, clean sand.
  • bituminous product obtained from Athabasca bituminous sand was recovered and analyzed by GC-MS analysis using pyrolytic injection and in-situ methylation with tetramethyl ammonium hydroxide. These data were compared with data for the raw tar sand, from which the organic matter was simply distilled by flash pyrolysis.
  • FIG. 10 Data for the raw tar sands, shown in FIG. 10 are typical for this type of analysis of heavy oil and bitumen.
  • the three OHD products, shown in FIGS. 6-8 indicate that the carbon content of the OHD liquor samples is comparable regardless of the method of extraction. Further, the carbon content of all OHD liquor samples (FIGS. 6-8) are consistent with the distillate of the raw tar sands, shown in FIG. 9, except that the OHD products contain discrete series of carboxylic acids and diacids that are much less apparent in the product from the distillate of the raw tar sands. This is expected due to the oxidative nature of the OHD process and does not significantly affect the usefulness of the derived "oil".
  • a bituminous sand sample of Athabasca oil sand was processed using the OHD method described herein above.
  • the soluble products were recovered and analyzed using methods similar to those described in Example 1 .
  • FIGS. 26-28 The results of the GC-MS analysis of the recovered organic products are summarized in FIGS. 26-28.
  • the gas chromatographic mass spectrometric analysis of the raw bituminous sand are presented in FIG. 28 as the content of volatiles generated by flash distillation (i.e. Py-GC-MS) and OHD derived oils isolated by evaporative water removal (FIG. 26) and extraction of OHD liquor with ethyl acetate (FIG. 27).
  • FIGS. 29-31 The results of the GC-MS analysis of the recovered organic products are summarized in FIGS. 29-31 .
  • the gas chromatographic mass spectrometric analysis of the raw bituminous sand are presented in FIG. 31 as the content of volatiles generated by flash distillation (i.e. Py-GC-MS) and OHD derived oils isolated by evaporative water removal (FIG. 29) and extraction of OHD liquor with ethyl acetate (FIG. 30).
  • a sample of Illinois coal was processed using the OHD method described herein above.
  • the soluble products were recovered and analyzed using methods similar to those described in Example 1 .
  • a total ion chromatogram summarizing the results of the GC-MS analysis of OHD liquor derived from the Illinois coal is provided in FIG. 11.
  • the OHD liquor was pyrolyzed at a temperature of about 480° for about 10 seconds.
  • Tetramethyl ammonium hydroxide was added to the OHD liquor for in situ derivatization of acidic oxygen-containing functional groups (phenol + carboxylate).
  • Table 3 A key listing the specific compounds associated with specific peaks is shown in Table 3:
  • FIGS. 12-21 are single and multi-ion chromatograms extracted from the total ion chromatogram of FIG. 11 , illustrating the observed distributions of products of specific structural families.
  • FIG. 12 is a multi-ion chromatogram
  • FIG. 14 is a single ion chromatogram
  • a sample of soft wood (conifer) lignin was processed using the OHD method described herein above.
  • a second sample of lignin-rich grass was processed using the OHD method described herein above.
  • a sample of sugar cane bagasse was processed using the OHD method described herein above.
  • the soluble products were recovered and analyzed using methods similar to those described in Example 1 .
  • a total ion chromatogram summarizing the results of the GC-MS analysis of OHD liquor derived from the sugar cane bagasse is provided in FIG. 25.
  • Tetramethyl ammonium hydroxide was added to the OHD liquor for in situ derivatization of acidic oxygen-containing functional groups (phenol + carboxylate).
  • a key listing the specific compounds associated with specific peaks is shown in Table 5:

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Abstract

L'invention concerne des procédés de production de matières organiques telles que des matières pétrolières et des acides aromatiques, des phénols et des acides polycarboxyliques aliphatiques, au moyen d'un procédé de dissolution hydrothermique oxydative (OHO). Le procédé OHD comprend la mise en contact d'une matière solide organique avec un oxydant, dans un réacteur contenant de l'eau surchauffée pour former au moins un soluté organique solubilisé. La réaction brise la structure macromoléculaire de la matière solide organique en fragments de poids moléculaire inférieur. Ces fragments de poids moléculaire inférieur sont solubles dans l'eau. Lesdits fragments solubles dans l'eau sont appelés matières solides organiques dissoutes, matières organiques solubilisées ou solutés organiques solubilisés. Les fragments solubilisés peuvent ensuite être utilisés comme matières premières dans divers procédés chimiques ou comme combustibles liquides. Si les fragments solubilisés sont des hydrates de carbone dissous tels que des sucres de faible poids moléculaire ou des sucres oxydés de faible poids moléculaire, ils peuvent être fermentés afin de produire des alcools ou être utilisés dans d'autres procédés pour produire divers autres produits.
PCT/US2012/040746 2011-06-03 2012-06-04 Production de matières organiques au moyen d'un procédé de dissolution hydrothermique oxydative WO2012167252A1 (fr)

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CA2836738A CA2836738A1 (fr) 2011-06-03 2012-06-04 Production de matieres organiques au moyen d'un procede de dissolution hydrothermique oxydative
JP2014513791A JP2014520104A (ja) 2011-06-03 2012-06-04 酸化的熱水溶解法を用いた有機材料の製造
EP12793493.3A EP2714855A4 (fr) 2011-06-03 2012-06-04 Production de matières organiques au moyen d'un procédé de dissolution hydrothermique oxydative
CN201280026415.5A CN103764804A (zh) 2011-06-03 2012-06-04 使用氧化热液溶蚀方法生产有机材料
BR112013031137A BR112013031137A2 (pt) 2011-06-03 2012-06-04 produção de materiais orgânicos usando um método de dissoluçao hidrotérmica oxidativa
KR1020137031981A KR20140090564A (ko) 2011-06-03 2012-06-04 산화적 수열 용해 방법을 이용한 유기 물질의 제조
NZ618723A NZ618723B2 (en) 2011-06-03 2012-06-04 Production of organic materials using an oxidative hydrothermal dissolution method
RU2013157530/04A RU2604726C2 (ru) 2011-06-03 2012-06-04 Производство органических материалов с использованием способа окислительного гидротермического растворения
AU2012261870A AU2012261870A1 (en) 2011-06-03 2012-06-04 Production of organic materials using an oxidative hydrothermal dissolution method
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WO1981000854A1 (fr) * 1979-09-27 1981-04-02 Modar Inc Traitement de materiaux organiques dans de i'eau supercritique
US5560823A (en) * 1994-12-21 1996-10-01 Abitibi-Price, Inc. Reversible flow supercritical reactor and method for operating same
US6576145B2 (en) * 1997-02-27 2003-06-10 Continuum Environmental, Llc Method of separating hydrocarbons from mineral substrates
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US7179379B2 (en) * 2003-03-28 2007-02-20 Ab-Cwt, Llc Apparatus for separating particulates from a suspension, and uses thereof
US7692050B2 (en) * 2003-03-28 2010-04-06 Ab-Cwt, Llc Apparatus and process for separation of organic materials from attached insoluble solids, and conversion into useful products
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EP2714855A1 (fr) 2014-04-09
WO2012167252A1 (fr) 2012-12-06
KR20140090564A (ko) 2014-07-17
BR112013031137A2 (pt) 2017-06-27
CN103764804A (zh) 2014-04-30
EP2714855A4 (fr) 2014-11-12
RU2604726C2 (ru) 2016-12-10
NZ618723A (en) 2015-12-24
RU2013157530A (ru) 2015-07-20
CA2836738A1 (fr) 2012-12-06

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