EP2736869A2 - Obtention de polyols à partir de saccharides - Google Patents

Obtention de polyols à partir de saccharides

Info

Publication number
EP2736869A2
EP2736869A2 EP12817777.1A EP12817777A EP2736869A2 EP 2736869 A2 EP2736869 A2 EP 2736869A2 EP 12817777 A EP12817777 A EP 12817777A EP 2736869 A2 EP2736869 A2 EP 2736869A2
Authority
EP
European Patent Office
Prior art keywords
group
saccharide
feedstock
catalyst
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12817777.1A
Other languages
German (de)
English (en)
Other versions
EP2736869A4 (fr
Inventor
John Q. Chen
Tom N. Kalnes
Joseph A. Kocal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/192,970 external-priority patent/US8222462B2/en
Priority claimed from US13/192,907 external-priority patent/US20110312487A1/en
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP2736869A2 publication Critical patent/EP2736869A2/fr
Publication of EP2736869A4 publication Critical patent/EP2736869A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8871—Rare earth metals or actinides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a catalyst system and a process for generating at least one polyol from a saccharide containing feedstock using the catalyst system.
  • the process involves, contacting hydrogen, water, and a feedstock comprising saccharide, with a catalyst system to generate an effluent comprising at least one polyol and recovering the polyol from the effluent.
  • the catalyst system comprises both an unsupported catalytic component and a supported catalytic component.
  • Polyols are valuable materials that find use in the manufacture of cold weather fluids, cosmetics, polyesters and many other synthetic products. Generating polyols from saccharides instead of fossil fuel-derived olefins can be a more environmentally friendly and a more economically attractive process. Previously, polyols have been generated from polyhydroxy compounds, see WO 2006/092085 and US 2004/0175806. Recently, catalytic conversion of saccharide into ethylene glycol over supported carbide catalysts was disclosed in Catalysis Today, 147, (2009) 77-85. US 2010/0256424, US
  • WO 2010/060345 teach a method of preparing ethylene glycol from saccharide and a tungsten carbide catalyst to catalyze the reaction.
  • Tungsten carbide catalysts have also been published as successful for batch-mode direct catalytic conversion of saccharide to ethylene glycol in Angew. Chem. Int. Ed 2008, 47, 8510- 8513 and supporting information and Chem. Commun., 2010, 46, 862-864.
  • a small amount of nickel was added to the tungsten carbide catalyst in ChemSusChem 2010, 3, 63-66.
  • the catalyst system comprising at least one unsupported component and at least one supported component for generating at least one polyol from a saccharide containing feedstock described herein addresses this need.
  • One embodiment of the invention is a catalyst system useful for the conversion of at least one saccharide to polyol, the catalyst system comprising an unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, and a supported component comprising an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support.
  • the solid catalyst support is selected from the group consisting of carbon, A1203, Zr02, Si02, MgO, CexZrOy, Ti02, SiC, silica alumina, zeolites, clays and combinations thereof.
  • the mass ratio of the unsupported component to the supported component ranges from 1 : 100 to 100: 1 wherein the supported component comprises from 0.05 to 30 mass percent activated metal.
  • the concentration in the reaction mixture of the unsupported catalyst component ranges from 0.001 to 20 mass % of the reaction mixture, and the
  • the unsupported component of the catalyst system may be selected from the group consisting of tungstic acid, molybedic acid, ammonium metatungstate, heteropoly compounds of tungsten, heteropoly compounds of molybdenum, heteropoly compounds of tungstic acid, heteropoly compounds of molybedic acid, and combinations thereof.
  • One embodiment of the invention is a process for generating at least one polyol from a feedstock comprising saccharide where the process comprises contacting, hydrogen, water, and a feedstock comprising at least one saccharide, with a catalyst system comprising an unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, and a supported component comprising a supported active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a sold catalyst support, to generate an effluent comprising at least one polyol, and recovering the polyol from the effluent.
  • the process may be operated in a batch mode operation or in a continuous mode operation.
  • Another embodiment of the invention is a continuous process for generating at least one polyol from a feedstock comprising at least one saccharide.
  • the process involves, contacting, in a continuous manner, hydrogen, water, and a feedstock comprising at least one saccharide, with a catalyst system to generate an effluent stream comprising at least one polyol and recovering the polyol from the effluent stream.
  • the hydrogen, water, and feedstock are flowed in a continuous manner.
  • the effluent stream is flowed in a continuous manner.
  • the process is a catalytic process employing a catalyst system comprising an unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, and a supported component comprising a supported active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support.
  • the contacting occurs in a reaction zone having at least a first input stream and a second input stream, the first input stream comprising at least the feedstock comprising at least one saccharide and the second input stream comprising hydrogen.
  • the first input stream may be pressurized prior to the reaction zone and the second input stream may be pressurized and heated prior to the reaction zone.
  • the first input stream may pressurized and heated to a temperature below the thermal
  • the decomposition temperature of the saccharide prior to the reaction zone and the second input stream may be pressurized and heated prior to the reaction zone.
  • the first input stream and the second input stream further comprise water.
  • the polyol produced is at least ethylene glycol or propylene glycol.
  • Co-products such as alcohols, organic acids, aldehydes, monosaccharides, disaccharides, oligosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, and proteins may also be generated.
  • the feedstock may be treated prior to contacting with the catalyst by a technique such as sizing, drying, grinding, hot water treatment, steam treatment, hydrolysis, pyrolysis, thermal treatment, chemical treatment, biological treatment, catalytic treatment, or combinations thereof.
  • the feedstock may be continuously contacted with at least the supported component of the catalyst system in a reactor system such as an ebullating catalyst bed reactor system, an immobilized catalyst reactor system having catalyst channels, an augured reactor system, and a slurry reactor system.
  • a reactor system such as an ebullating catalyst bed reactor system, an immobilized catalyst reactor system having catalyst channels, an augured reactor system, and a slurry reactor system.
  • operating conditions include temperatures ranging from 100°C to 350°C and hydrogen pressures greater than 150 psig.
  • the temperature in the reactor system may range from 150°C to 350°C, in another embodiment the temperature in the reactor system may range from 200°C to 280°C.
  • the feedstock may be continuously contacted with the catalyst system in the reactor system operated, for example, at a water to feedstock comprising saccharide weight ratio ranging from 1 to 100, a catalyst system (unsupported component plus supported component) to feedstock comprising saccharide weight ratio of greater than 0.005, a pH of less than 10 and a residence time of greater than five minutes.
  • the catalyst to feedstock comprising saccharide weight ratio is greater than 0.01.
  • the hydrogen, water, and feedstock may be contacted with the catalyst in a reaction zone operated at conditions sufficient to maintain at least a portion of the water in the liquid phase.
  • the effluent stream from the reactor system may further comprise the catalyst system, which may be separated from the effluent stream using a technique such as direct filtration, settling followed by filtration, hydrocyclone, fractionation, centrifugation, the use of flocculants, precipitation, liquid extraction, adsorption, evaporation, and combinations thereof.
  • the supported catalyst component, the unsupported catalyst component, or both may be separated from the effluent stream.
  • FIG. 1 is a basic diagram of the flow scheme of one embodiment of the invention. Equipment and processing steps not required to understand the invention are not depicted.
  • FIG. 2 is a basic diagram of the flow scheme of another embodiment of the invention showing an optional pretreatment zone and an optional supported catalyst component separation zone with optional supported catalyst component recycle.
  • the invention involves a catalyst system and a process for generating at least one polyol from a feedstock comprising at least one saccharide.
  • the catalyst system comprises an unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, and a supported component comprising an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support.
  • suitable solid catalyst supports include carbon, AI2O3, Zr0 2 , Si0 2 , MgO, Ce x ZrO y , Ti0 2 , SiC, silica alumina, zeolites, clays and combinations thereof.
  • the process involves contacting, hydrogen, water, and a feedstock comprising at least one saccharide, with the catalyst system comprising an unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof, and a supported component comprising a supported active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support, to generate an effluent comprising at least one polyol, and recovering the polyol from the effluent.
  • the process may be operated in a batch mode operation or in a continuous mode operation.
  • the process involves continuous catalytic conversion of a flowing stream of feedstock comprising saccharide to ethylene glycol or propylene glycol with high yield and high selectivity.
  • the feedstock comprises at least one saccharide which may be any class of monosachharides, disaccharides, oligosachharides, and polysachharides and may be edible, inedible, amorphous or crystalline in nature.
  • the feedstock comprises polysaccharides that consist of one or a number of monosaccharides joined by glycosidic bonds. Examples of polysaccharides include glycogen, cellulose,
  • saccharide as used herein is meant to include all the above described classes of saccharides including polysaccharides.
  • the saccharide is cellulose, hemicellulose, or a combination thereof
  • Hemicellulose is generally understood to be any of several saccharides that are more complex than a sugar and less complex than cellulose. Economic conversion of cellulose and hemicellulose to useful products can be a sustainable process that reduces fossil energy consumption and does not directly compete with the human food supply.
  • Cellulose and hemi cellulose are large renewable resources having a variety of attractive sources, such as residue from agricultural production or waste from forestry or forest products. Since cellulose and hemicellulose cannot be digested by humans, using cellulose and or hemicellulose as a feedstock does not take from our food supply.
  • cellulose and hemicellulose can be a low cost waste type feedstock material which is converted herein to high value products like polyols such as ethylene glycol and propylene glycol.
  • the feedstock comprising saccharide of the process may be derived from sources such as agricultural crops, forest biomass, waste material, recycled material. Examples include short rotation forestry, industrial wood waste, forest residue, agricultural residue, energy crops, industrial wastewater, municipal wastewater, paper, cardboard, fabrics, pulp derived from biomass, corn starch, sugarcane, grain, sugar beet, glycogen and other molecules comprising the molecular unit structure of C m (H20) n , and combinations thereof. Multiple materials may be used a co-feedstocks.
  • the feedstock may be whole biomass including cellulose, lignin and hemicellulose or treated biomass where the polysaccharide is at least partially depolymerized, or where the lignin, hemicellullose or both have been at least partially removed from the whole biomass.
  • the process of the invention maybe operated in a batch mode operation, or may be operated in a continuous mode operation. In a batch mode operation, the necessary reactants and catalyst system are combined and allowed to react. After a period of time, the reaction mixture is removed from the reactor and separated to recover products. Autoclave reactions are common examples of batch reactions. While the process may be operated in the batch mode, there are advantages to operating in the continuous mode, especially in larger scale operations. The following description will focus on a continuous mode operation, although the focus of the following description does not limit the scope of the invention.
  • the feedstock is continually being introduced into the reaction zone as a flowing stream and a product comprising a polyol is being continuously withdrawn.
  • Materials must be capable of being transported from a low pressure source into the reaction zone, and products must be capable of being transported from the reaction zone to the product recovery zone.
  • a challenge in processing a feedstock comprising saccharide in a pressurized hydrogen environment is that the feedstock may be an insoluble solid. Therefore, pretreatment of the feedstock may be performed in order to facilitate the continuous transporting of the feedstock. Suitable pretreatment operations may include sizing, drying, grinding, hot water treatment, steam treatment, hydrolysis, pyrolysis, thermal treatment, chemical treatment, biological treatment, catalytic treatment, and combinations thereof. Sizing, grinding or drying may result in solid particles of a size that may be flowed or moved through a continuous process using a liquid or gas flow, or mechanical means.
  • An example of a chemical treatment is mild acid hydrolysis of polysaccharide.
  • catalytic treatments are catalytic hydrolysis of polysaccharide, catalytic hydrogenation of polysaccharide, or both, and an example of biological treatment is enzymatic hydrolysis.
  • Hot water treatment, steam treatment, thermal treatment, chemical treatment, biological treatment, or catalytic treatment may result in lower molecular weight saccharides and depolymerized lignins that are more easily transported as compared to the untreated saccharide.
  • Suitable pretreatment techniques are found in "Catalytic Hydrogenation of Corn Stalk to Ethylene Glycol and 1,2-Propylene Glycol" Jifeng Pang, Mingyuan Zheng, Aiqin Wang, and Tao Zhang Ind. Eng. Chem. Res. DOI: 10.1021/iel02505y, Publication Date (Web): April 20, 2011. See also, US 2002/0059991.
  • the saccharide is thermally sensitive. Exposure to excessive heating prior to contacting with the catalyst may result in undesired thermal reactions of the saccharide such as charring of the saccharide.
  • the feedstock comprising saccharide is provided to the reaction zone containing the catalyst in a separate input stream from the primary hydrogen stream.
  • the reaction zone has at least two input streams.
  • the first input stream comprises at least the feedstock comprising saccharide
  • the second input stream comprises at least hydrogen. Water may be present in the first input stream, the second input stream or in both input streams. Some hydrogen may also be present in the first input stream with the feedstock comprising saccharide.
  • the hydrogen stream may be heated in excess of the reaction temperature without also heating the feedstock comprising saccharide to reaction temperature.
  • the temperature of first input stream comprising at least the feedstock comprising saccharide may be controlled not to exceed the temperature of unwanted thermal side reactions.
  • the temperature of first input stream comprising at least the feedstock comprising saccharide may be controlled not to exceed the
  • the first input stream, the second input stream, or both may be pressurized to reaction pressure before being introduced to the reaction zone.
  • the feedstock comprising saccharide is continuously introduced to a catalytic reaction zone as a flowing stream.
  • Water and hydrogen both reactants, are present in the reaction zone.
  • at least a portion of the hydrogen may be introduced separately and independent from the feedstock comprising saccharide, or any combination of reactants, including feedstock comprising saccharide, may be combined and introduced to the reaction zone together.
  • suitable reactor systems include ebullating catalyst bed reactor systems, immobilized catalyst reactor systems having catalyst channels, augured reactor systems, fluidized bed reactor systems, mechanically mixed reactor systems and slurry reactor systems, also known as a three phase bubble column reactor systems.
  • metallurgy of the reactor system is selected to be compatible with the reactants and the desired products within the range of operating conditions.
  • suitable metallurgy for the reactor system include titanium, zirconium, stainless steel, carbon steel having hydrogen embrittlement resistant coating, carbon steel having corrosion resistant coating.
  • the metallurgy of the reaction system includes zirconium either coated or clad carbon steel.
  • the reactants proceed through catalytic conversion reactions to produce at least one polyol.
  • Desired polyols include ethylene glycol and propylene glycol.
  • Co-products may also be produced and include compounds such as alcohols, organic acids, aldehydes, monosaccharides, saccharides, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, carbohydrates, and proteins.
  • the co-products may have value and may be recovered in addition to the product polyols.
  • the reactions may proceed to completion, or some reactants and intermediates may remain in a mixture with the products.
  • Intermediates which are included herein as part of the co-products, may include compounds such as depolymerized cellulose, lignin, and hemicellulose. Unreacted hydrogen, water, and saccharide may also be present in the reaction zone effluent along with products and co- products. Unreacted material and or intermediates may be recovered and recycled to the reaction zone.
  • the reactions are catalytic reactions and the reaction zone comprises at least one catalyst system.
  • the catalyst system for conversion of saccharide to at least one polyol comprises an unsupported component comprising a compound selected from the group consisting of a tungsten compound, a molybdenum compound, and any combination thereof; and a supported component comprising an active metal component selected from the group consisting of Pt, Pd, Ru, Rh, Ni, Ir, and combinations thereof on a solid catalyst support. Multiple active metals may be present on the solid catalyst support.
  • unsupported components examples include tungstic acid, molybedic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group I or II element, metatungstate compounds comprising at least one Group I or II element, paratungstate compounds comprising at least one Group I or II element, heteropoly compounds of tungsten, heteropoly compounds of molybdenum, tungsten oxides, molybdenum oxides, and combinations thereof.
  • One or more unsupported catalyst components may be used with one or more supported catalyst components.
  • the catalyst system may also be considered a multi-component catalyst, and the terms are used herein interchangeably.
  • the supported catalyst component of the catalyst system requires a solid catalyst support.
  • the support may be in the shape of a powder, or specific shapes such as spheres, extrudates, pills, pellets, tablets, irregularly shaped particles, monolithic structures, catalytically coated tubes, or catalytically coated heat exchanger surfaces.
  • the active metal may be incorporated onto the catalytic support in any suitable manner known in the art, such as by coprecipitation, coextrusion with the support, or
  • the active metal may be in the reduced form.
  • Refractory oxide catalyst supports and others may be used. Examples of the refractory inorganic oxide supports include but are not limited to silica, aluminas, silica-alumina, titania, zirconia, magnesia, clays, zeolites, molecular sieves, etc. It should be pointed out that silica-alumina is not a mixture of silica and alumina but means an acidic and amorphous material that has been cogelled or coprecipitated. Carbon and activated carbon may also be employed as supports.
  • the active metal may comprise from 0.05 to 30 mass % of the supported catalyst component. In another embodiment of the invention the active metal may comprise from 0.3 to 15 mass % of the supported catalyst component, and in another embodiment of the invention the active metal may comprise from 0.5 to 7 mass % of the supported catalyst component.
  • the amount of the catalyst system used in the process may range from 0.005 to 0.4 mass % of the feedstock comprising saccharide. In other embodiment, the amount of the catalyst system used in the process may range from 0.01 to 0.25 mass % of the feedstock comprising saccharide. In still other embodiment, the amount of the catalyst system used in the process may range from 0.02 to 0.15 mass % of the feedstock comprising saccharide.
  • the reactions occurring are multi-step reactions and different amounts of the catalyst system, or relative amounts of the components of the catalyst system, can be used to control the rates of the different reactions. Individual applications may have differing requirements as to the amounts of the catalyst system, or relative amounts of the components of the catalyst system used.
  • the concentration of the unsupported catalyst component in the reaction mixture ranges from 0.001 to 20 mass % and the concentration of the supported catalyst component in the reaction mixture ranges from 0.001 to 20 mass %.
  • the mass ratio of unsupported component to supported component ranges from 1 : 100 to 100: 1 as measured by ICP or other common wet chemical methods. In another embodiment, the mass ratio of unsupported component to supported component ranges from 1 :20 to 50: 1 and the mass ratio of unsupported component to supported component ranges from 1 : 10 to 10: 1.
  • the unsupported catalyst component may be a solid that is soluble in the reaction mixture, or at least partially soluble in the reaction mixture which includes at least water and the feedstock at reaction conditions.
  • An effective amount of the unsupported catalyst should be soluble in the reaction mixture. Different applications and different unsupported catalyst components will result in differing effective amounts of unsupported catalyst component needed to be in solution in the reaction mixture.
  • the unsupported catalyst component is a liquid which is miscible or at least partially miscible with the reaction mixture. As with the solid unsupported catalyst component, an effective amount of the liquid unsupported catalyst should be miscible in the reaction mixture.
  • the amount of unsupported catalyst component miscible in water is in the range of 1 to 100 %, in another embodiment, from 10 to 100 %, and in still another embodiment, from 20 to 100 %.
  • the multicomponent catalyst of the present invention may provide several advantages over a more traditional single component catalyst. For example, the manufacture costs of the catalyst may be reduced since fewer active components need to be incorporated onto a solid catalyst support. Operational costs may be reduced since it is envisioned that less catalyst make-up will be required and more selective processing steps can be used for recovery and recycle of catalyst. Other advantages include improved catalyst stability which leads to lower catalyst consumption and lower cost per unit of polyol product, and the potential for improved selectivity to ethylene glycol and propylene glycol with reduced production of co-boiling impurities such as butane diols.
  • the catalyst system may be contained within the reaction zone, and in other embodiments the catalyst may continuously or intermittently pass through the reaction zone, and in still other embodiments, the catalyst system may do both, with at least one catalyst system component residing in a reaction zone while the other catalyst system component continuously or intermittently passes through the reaction zone.
  • Suitable reactor systems include an ebullating catalyst bed reactor system, an immobilized catalyst reactor system having catalyst channels, an augured reactor system, a fluidized bed reactor system, a mechanically mixed reactor systems and a slurry reactor system, also known as a three phase bubble column reactor system and combinations thereof.
  • Examples of operating conditions in the rector system include temperatures ranging from 100°C to 350°C and hydrogen pressures greater than 150 psig.
  • the temperature in the reactor system may range from 150°C to 350°C, in another embodiment the temperature in the reactor system may range from 200°C to 280°C.
  • the feedstock which comprises at least one saccharide, may be continuously contacted with the catalyst system in the reactor system at a water to feedstock weight ratio ranging from 1 to 100, a catalyst (unsupported component + supported component) to feedstock weight ratio of greater than 0.005, a pH of less than 10 and a residence time of greater than 5 minutes.
  • the water to feedstock weight ratio ranges from 1 to 20 and the catalyst to feedstock weight ratio is greater than 0.01.
  • the water to feedstock weight ratio ranges from 1 to 5 and the catalyst to feedstock weight ratio is greater than 0.1.
  • the catalytic reaction system employs a slurry reactor.
  • Slurry reactors are also known as three phase bubble column reactors.
  • Slurry reactor systems are known in the art and an example of a slurry reactor system is described in US 5,616,304 and in Topical Report, Slurry Reactor Design Studies, DOE Project No. DE-AC22-89PC89867, Reactor Cost Comparisons, which may be found at http://www.fischer-tropsch.0rg/DOE/DOE_reports/91005752/de91005752_toc.htm.
  • the catalyst system may be mixed with the water and feedstock comprising saccharide to form a slurry which is conducted to the slurry reactor.
  • the reactions occur within the slurry reactor and the catalyst is transported with the effluent stream out of the reactor system.
  • the slurry reactor system may be operated at conditions listed above.
  • the catalytic reaction system employs an ebullating bed reactor. Ebullating bed reactor systems are known in the art and an example of an ebullating bed reactor system is described in US 6,436,279.
  • the effluent stream from the reaction zone contains at least the product polyol(s) and may also contain unreacted water, hydrogen, saccharide, byproducts such as phenolic compounds and glycerol, and intermediates such as depolymerized polysaccharides and lignins.
  • the effluent stream may also contain at least a portion of the catalyst system.
  • the effluent stream may contain a portion of the catalyst system that is in the liquid phase, or a portion of the catalyst system that is in the solid phase. In some embodiments it may be advantageous to remove solid phase catalyst components from the effluent stream, either before or after and desired products or by-products are recovered.
  • Solid phase catalyst components may be removed from the effluent stream using one or more techniques such as direct filtration, settling followed by filtration, hydrocyclone, fractionation, centrifugation, the use of flocculants, precipitation, extraction, evaporation, or combinations thereof.
  • separated catalyst may be recycled to the reaction zone.
  • the catalyst system, water, and feedstock comprising saccharide are conducted via stream 122 to reaction zone 124.
  • the mixture in stream 122 has, for example, a water to feedstock comprising saccharide weight ratio of 5 and a catalyst system to feedstock comprising saccharide weight ratio of 0.05.
  • At least hydrogen is conducted via stream 125 to reaction zone 124.
  • Reaction zone 124 is operated, for example, at a temperature of 250°C a hydrogen pressure of 1200 psig, a pH of 7 and a residence time of 8 minutes.
  • reaction zone 124 Prior to introduction into reaction zone 124, the catalyst, water, and feedstock comprising saccharide in stream 122 and the hydrogen in stream 125 are brought to a pressure of 1800 psig to be at the same pressure as reaction zone 124. However, only stream 125 comprising at least hydrogen is raised to at least 250°C to be at a temperature greater than or equal to the temperature in reaction zone 124.
  • the mixture in stream 122 which contains at least the saccharide is temperature controlled to remain at a temperature lower than the decomposition or charring temperature of the saccharide.
  • the saccharide is catalytically converted into at least ethylene glycol or propylene glycol.
  • Reaction zone effluent 126 contains at least the product ethylene glycol or propylene glycol. Reaction zone effluent 126 may also contain alcohols, organic acids, aldehydes, monosaccharides,
  • Reaction zone effluent 126 is conducted to product recovery zone 134 where the desired glycol products are separated and recovered in steam 136. Remaining
  • reaction zone effluent 126 components of reaction zone effluent 126 are removed from product recovery zone 134 in stream 138.
  • water and feedstock comprising polysaccharide 210 is introduced to pretreatment unit 220 where the saccharide is ground to a particle size that is small enough to be pumped as a slurry with the water using conventional equipment.
  • the pretreated feedstock is combined with water in line 219 and catalyst system in line 223 and combined stream 227 is conducted to reaction zone 224.
  • the combined stream 227 has, for example, a water to feedstock comprising saccharide weight ratio of 20 and a catalyst system to saccharide weight ratio of 0.1.
  • At least hydrogen is conducted via stream 225 to reaction zone 224. Some hydrogen may be combined with stream 227 prior to reaction zone 224 as shown by optional dotted line 221.
  • Reaction zone 224 is operated, for example, at a temperature of 280°C a hydrogen pressure of 200 psig, a pH of 7 and a residence time of 8 minutes.
  • the catalyst system, water, and pretreated feedstock comprising saccharide in stream 227 and the hydrogen in stream 225 Prior to introduction into reaction zone 224, the catalyst system, water, and pretreated feedstock comprising saccharide in stream 227 and the hydrogen in stream 225 are brought to a pressure of 1800 psig to be at the same temperature as reaction zone 224. However, only stream 225 comprising at least hydrogen is raised to at least 250°C to be at a temperature greater than or equal to the temperature of reaction zone 224.
  • the mixture in stream 227 which contains at least the saccharide is temperature controlled to remain at a temperature lower than the
  • reaction zone 224 the saccharide is catalytically converted into at least ethylene glycol or polyethylene glycol.
  • Reaction zone effluent 226 contains at least the product ethylene glycol or propylene glycol and catalyst. Reaction zone effluent 226 may also contain alcohols, organic acids, aldehydes, monosaccharides, polysaccharides, phenolic compounds, hydrocarbons, glycerol, depolymerized lignin, and proteins. Reaction zone effluent 226 is conducted to optional catalyst system recovery zone 228 where catalyst components are separated from reaction zone effluent 226 and removed in line 232. Catalyst components in line 232 may optionally be recycled to combine with line 223 or to reaction zone 224 as shown by optional dotted line 229. The catalyst component-depleted reaction zone effluent 230 is conducted to product recovery zone 234 where the desired glycol products are separated and recovered in steam 236. Remaining components of effluent 230 are removed from product recovery zone 234 in stream 238.
  • Ni on orit CA-1 catalyst was prepared by impregnating various amounts of Ni using Ni nitrate in water onto activated carbon support Norit-CAl using incipient wetness technique. The impregnated support was then dried at 40°C overnight in an oven with nitrogen purge and reduced in H2 at 750°C for 1 hrs. 5%Pd/C and %Pt/C were purchased from Johnson Matthey.
  • Ethylene glycol and propylene glycol yields were measured as mass of ethylene glycol or propylene glycol produced divided by the mass of feedstock used and multiplied by 100.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Saccharide Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention porte sur un procédé d'obtention d'au moins un polyol, à partir d'une charge de départ comportant un saccharide, effectué d'une manière continue ou discontinue. Le procédé comprend la mise en contact d'hydrogène, d'eau et d'une charge de départ comportant un saccharide avec un système catalyseur pour produire un courant d'effluent comportant au moins un polyol et la récupération du polyol dans le courant d'effluent. Le système catalyseur comporte au moins un constituant non supporté et au moins un constituant supporté.
EP12817777.1A 2011-07-28 2012-07-03 Obtention de polyols à partir de saccharides Withdrawn EP2736869A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US13/192,970 US8222462B2 (en) 2011-07-28 2011-07-28 Process for generation of polyols from saccharides
US13/192,907 US20110312487A1 (en) 2011-07-28 2011-07-28 Catalyst system for generation of polyols from saccharides
PCT/US2012/045343 WO2013015955A2 (fr) 2011-07-28 2012-07-03 Obtention de polyols à partir de saccharides

Publications (2)

Publication Number Publication Date
EP2736869A2 true EP2736869A2 (fr) 2014-06-04
EP2736869A4 EP2736869A4 (fr) 2015-01-07

Family

ID=47601711

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12817777.1A Withdrawn EP2736869A4 (fr) 2011-07-28 2012-07-03 Obtention de polyols à partir de saccharides

Country Status (6)

Country Link
EP (1) EP2736869A4 (fr)
CN (1) CN103608320A (fr)
BR (1) BR112013026705A2 (fr)
CA (1) CA2832741A1 (fr)
TW (1) TWI539994B (fr)
WO (1) WO2013015955A2 (fr)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014161852A1 (fr) 2013-04-05 2014-10-09 Shell Internationale Research Maatschappij B.V. Procédé pour la préparation de glycols
CN105073693B (zh) 2013-04-05 2017-05-03 国际壳牌研究有限公司 用于含糖原料转化的方法
BR112015019100A2 (pt) 2013-04-26 2017-07-18 Shell Int Research processo para a preparação de monoetileno glicol a partir de sacarose, e, processo para a conversão de sacarose em frutose e/ou derivados de frutose
BR112016003939B1 (pt) * 2013-08-26 2021-02-23 Shell Internationale Research Maatschappij B.V. processo para a preparação de um composto
US9656933B2 (en) 2013-08-30 2017-05-23 Shell Oil Company Process for the conversion of saccharide-containing feedstock
WO2015154258A1 (fr) * 2014-04-09 2015-10-15 Petroliam Nasional Berhad (Petronas) Conversion sélective de charge d'alimentation contenant des saccharides en éthylène glycol
CN111606781B (zh) 2014-09-28 2023-11-28 长春美禾科技发展有限公司 一种制备二元醇的方法
CN107428642B (zh) * 2015-01-13 2020-11-27 阿凡田知识中心有限公司 从碳水化合物源制备乙二醇的工艺
AU2016207242B2 (en) 2015-01-13 2018-09-13 Avantium Knowledge Centre B.V. Continuous process for preparing ethylene glycol from a carbohydrate source
CN107406359A (zh) 2015-01-13 2017-11-28 阿凡田知识中心有限公司 从碳水化合物制备乙二醇的工艺
EP3245183B1 (fr) 2015-01-13 2019-10-23 Avantium Knowledge Centre B.v. Procédé de préparation d'éthylène glycol à partir d'une source de glucides
CA2989506C (fr) * 2015-06-30 2023-10-10 Evert Van Der Heide Procede de preparation de glycols
EP3347499B1 (fr) * 2015-09-07 2019-12-11 Shell International Research Maatschappij B.V. Procédé de récupération de métaux
CN108348898A (zh) * 2015-11-19 2018-07-31 国际壳牌研究有限公司 用于制造二醇的催化剂体系和方法
WO2017085219A1 (fr) 2015-11-19 2017-05-26 Shell Internationale Research Maatschappij B.V. Système catalytique et procédé pour la production de glycols
CA3002894C (fr) * 2015-11-19 2023-10-03 Shell Internationale Research Maatschappij B.V. Systeme de catalyseur et procede pour la production de glycols
BR112018010230A2 (pt) * 2015-11-19 2018-11-27 Shell Int Research sistema catalisador e processo para a produção de glicóis
US10294181B2 (en) 2015-12-09 2019-05-21 Shell Oil Company Process for the preparation of glycols
BR112018016284A2 (pt) 2016-02-09 2018-12-18 Shell Int Research processo para a produção de alquileno glicóis
CA3014386C (fr) * 2016-03-07 2024-01-30 Shell Internationale Research Maatschappij B.V. Procede de recuperation d'un composant metallique
CN109641191B (zh) * 2016-06-03 2023-04-04 爱荷华谷类推广协会 将产生己醛糖的碳水化合物高度选择性地转化为乙二醇的连续方法
CA3031857A1 (fr) 2016-08-04 2018-02-08 Shell Internationale Research Maatschappij B.V. Procede de production de glycols
US10752567B2 (en) * 2016-09-29 2020-08-25 Shell Oil Company Method for acid treatment conditioning of a catalyst in the production of glycols
CN109843840B (zh) * 2016-10-28 2022-06-03 国际壳牌研究有限公司 二醇的制造方法
WO2020055796A1 (fr) 2018-09-13 2020-03-19 Shell Oil Company Procédé d'arrêt pour la production de glycols
US11485693B2 (en) 2018-09-13 2022-11-01 Shell Usa, Inc. Start-up process for the production of glycols
WO2020212542A1 (fr) 2019-04-17 2020-10-22 Shell Internationale Research Maatschappij B.V. Processus de mélange par injection agitée
WO2023083948A1 (fr) 2021-11-12 2023-05-19 Shell Internationale Research Maatschappij B.V. Procédé de séparation de glycol à partir de diols
WO2023150656A1 (fr) 2022-02-04 2023-08-10 Shell Usa, Inc. Procédé de production de glycol à partir d'une charge d'alimentation renouvelable

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007326849A (ja) * 2006-05-09 2007-12-20 Kao Corp 多価アルコールの水素化分解物の製造方法
EP2017250A1 (fr) * 2006-05-09 2009-01-21 Kao Corporation Procede de production d'un produit d'hydrogenolyse d'alcool polyhydrique
CN101768050A (zh) * 2009-12-25 2010-07-07 北京大学 一种生产乙二醇和1，2-丙二醇的方法
US20100256424A1 (en) * 2008-10-24 2010-10-07 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method of preparing ethylene glycol cellulose
WO2011050691A1 (fr) * 2009-10-27 2011-05-05 中国科学院大连化学物理研究所 Catalyseur au carbure de tungstène supporté sur du carbone mésoporeux, sa préparation et ses applications
EP2548858A1 (fr) * 2010-03-17 2013-01-23 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Procédé de préparation d'éthylène glycol à partir de composés polyhydroxylés
WO2013015990A2 (fr) * 2011-07-28 2013-01-31 Uop Llc Procédé catalytique pour la génération de polyols en continu

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4642394A (en) * 1985-07-16 1987-02-10 Celanese Corporation Production of propanediols
MY159308A (en) * 2009-12-30 2016-12-30 Virent Inc Catalysts for hydrodeoxygenation of polyols

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007326849A (ja) * 2006-05-09 2007-12-20 Kao Corp 多価アルコールの水素化分解物の製造方法
EP2017250A1 (fr) * 2006-05-09 2009-01-21 Kao Corporation Procede de production d'un produit d'hydrogenolyse d'alcool polyhydrique
US20100256424A1 (en) * 2008-10-24 2010-10-07 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method of preparing ethylene glycol cellulose
WO2011050691A1 (fr) * 2009-10-27 2011-05-05 中国科学院大连化学物理研究所 Catalyseur au carbure de tungstène supporté sur du carbone mésoporeux, sa préparation et ses applications
CN101768050A (zh) * 2009-12-25 2010-07-07 北京大学 一种生产乙二醇和1，2-丙二醇的方法
EP2548858A1 (fr) * 2010-03-17 2013-01-23 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Procédé de préparation d'éthylène glycol à partir de composés polyhydroxylés
WO2013015990A2 (fr) * 2011-07-28 2013-01-31 Uop Llc Procédé catalytique pour la génération de polyols en continu

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHAMINAND J ET AL: "Glycerol hydrogenolysis on heterogeneous catalysts", GREEN CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, CAMBRIDGE, GB, vol. 6, 1 January 2004 (2004-01-01), pages 359-361, XP003016972, ISSN: 1463-9262, DOI: 10.1039/B407378A *
MING-YUAN ZHENG ET AL: "Transition Metal-Tungsten Bimetallic Catalysts for the Conversion of Cellulose into Ethylene Glycol", CHEMSUSCHEM, vol. 3, no. 1, 25 January 2010 (2010-01-25), pages 63-66, XP055003506, ISSN: 1864-5631, DOI: 10.1002/cssc.200900197 *
See also references of WO2013015955A2 *

Also Published As

Publication number Publication date
TW201315540A (zh) 2013-04-16
TWI539994B (zh) 2016-07-01
CA2832741A1 (fr) 2013-01-31
CN103608320A (zh) 2014-02-26
WO2013015955A2 (fr) 2013-01-31
BR112013026705A2 (pt) 2016-12-27
WO2013015955A3 (fr) 2013-03-21
EP2736869A4 (fr) 2015-01-07

Similar Documents

Publication Publication Date Title
US8222462B2 (en) Process for generation of polyols from saccharides
US8222463B2 (en) Process for generation of polyols from saccharide containing feedstock
TWI539994B (zh) 自醣類生產多元醇及用於其之觸媒系統
US20110312487A1 (en) Catalyst system for generation of polyols from saccharides
US8222465B2 (en) Catalytic process for continuously generating polyols
US20110312488A1 (en) Catalyst system for generation of polyols from saccharide containing feedstock
US8323937B2 (en) Continuous catalytic generation of polyols from cellulose
US8410319B2 (en) Continuous catalytic generation of polyols from cellulose with recycle
US8222464B2 (en) Catalytic process for continuously generating polyols
EP3039002B1 (fr) Procédé de conversion de produit de départ comprenant un saccharide
US20160145178A1 (en) Methods and apparatuses for generating a polyol from whole biomass
EP3191436B1 (fr) Procédé de conversion de charge d'alimentation contenant de la saccharide
TWI477481B (zh) 由包含醣類之原料生產多元醇
US20160168061A1 (en) Methods and apparatuses for generating a polyol from biomass using multiple reaction zones and catalysts
EP2981516B1 (fr) Procédé de conversion de charge d'alimentation contenant de la saccharide

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140114

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20141208

RIC1 Information provided on ipc code assigned before grant

Ipc: C07C 31/26 20060101ALI20141202BHEP

Ipc: B01J 23/40 20060101ALI20141202BHEP

Ipc: C07C 29/157 20060101AFI20141202BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20150718