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WO2023150656A1 - Procédé de production de glycol à partir d'une charge d'alimentation renouvelable - Google Patents

Procédé de production de glycol à partir d'une charge d'alimentation renouvelable Download PDF

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Publication number
WO2023150656A1
WO2023150656A1 PCT/US2023/061899 US2023061899W WO2023150656A1 WO 2023150656 A1 WO2023150656 A1 WO 2023150656A1 US 2023061899 W US2023061899 W US 2023061899W WO 2023150656 A1 WO2023150656 A1 WO 2023150656A1
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catalyst
retro
process according
hydrogenation catalyst
reactor
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Duraisamy Muthusamy
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Shell Internationale Research Maatschappij BV
Shell USA Inc
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Shell Internationale Research Maatschappij BV
Shell USA Inc
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    • 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
    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/04—Regeneration or reactivation
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
    • 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

Definitions

  • This invention relates to a process for producing glycol from renewable feedstock through catalytic hydrogenolysis.
  • glycols such as monoethylene glycol (MEG) and monopropylene glycol (MPG) are useful as heat transfer media, antifreeze and precursors to polymers, such as polyester and polyethylene terephthalate.
  • MEG monoethylene glycol
  • MPG monopropylene glycol
  • MEG is prepared in a two-step process.
  • ethylene is converted to ethylene oxide by reaction with oxygen over a silver oxide catalyst.
  • the ethylene oxide can then be converted into MEG. This may be carried out directly by catalytic or non-catalytic hydrolysis.
  • ethylene oxide is catalytically reacted with carbon dioxide to produce ethylene carbonate.
  • the ethylene carbonate is subsequently hydrolyzed to provide ethylene glycol.
  • certain carbohydrates can be reacted with hydrogen in the presence of a catalyst system to generate polyols and sugar alcohols.
  • Current methods for the conversion of saccharides to glycols revolve around a nickel-promoted tungsten carbide catalytic hydrogenation/retro-aldol process, for example, as described in Ji et al. (“Direct Catalytic Conversion of Cellulose into Ethylene Glycol using Nickel-Promoted Tungsten Carbide Catalysts” Angew. Chem, Int. Ed. 47 : 8510-8513 ; 2008).
  • the hydrogenation catalyst compositions tend to be heterogeneous.
  • the retro-aldol catalysts are generally homogeneous in the reaction mixture. Such catalysts are inherently limited due to solubility constraints.
  • Muthusamy (EP3356314B1, 21 Oct 2020) describes processes for the preparation of glycols such as MEG and MPG using a catalyst system consisting of a catalyst component with retro-aldol catalytic capabilities and a first hydrogenation catalyst comprising an element selected from Groups 8, 9 and 10 of the periodic table.
  • van der Bijl et al. (US2018/0273452A1, 27 Sep 2018) describes a process for producing glycols from saccharide-containing feedstocks under conditions that convert a catalyst precursor into an unsupported hydrogenation catalyst.
  • Singh et al. (US2020/0406237A1, 31 Dec 2020) relates to a process for producing ethylene glycol with a homogeneous catalyst and a heterogeneous catalyst. Spent heterogeneous catalyst is regenerated by removing deposited tungsten and then recycled to the reaction step.
  • a process for the production of glycol from a saccharide-containing feedstock in the presence a catalyst system having a retro-aldol catalyst and a hydrogenation catalyst comprising the steps of: loading the hydrogenation catalyst in a reactor; feeding hydrogen to the reactor; conditioning the hydrogenation catalyst with a treatment solution comprising a conditioning retro-aldol catalyst in the absence of the saccharide-containing feedstock; introducing the saccharide- containing feedstock and a catalytic retro-aldol catalyst to the reactor containing the conditioned hydrogenation catalyst; and producing glycol by hydrogenolysis of the saccharide- containing feedstock.
  • Fig. 1 is a graph showing the results of Comparative Example 1.
  • Fig. 2 is a graph showing the results of Example 2.
  • the present invention provides a process for the production of glycol from a saccharide-containing feedstock in the presence of a catalyst system having a retro-aldo catalyst and a hydrogenation catalyst.
  • Reactions include hydrolysis, retro-aldol condensation, and hydrogenation.
  • the saccharide-containing feedstock comprises cellulose
  • reactions include hydrolysis of cellulose to glucose, C-C cleavage of glucose by retro-aldol condensation to form glycolaldehyde, and hydrogenation of glycolaldehyde to ethylene glycol.
  • glucose may be isomerized to fructose, and fructose is converted to propylene glycol.
  • the hydrogenation catalyst also tends to produce sorbitol and/or mannitol, as undesirable by-products. Accordingly, in conventional processes, there is an initial ramping up of glycol production while sorbitol production decreases. This ramp-up period can last several days, for example, 300 hours.
  • the present inventor has surprisingly discovered that, by conditioning the hydrogenation catalyst with a conditioning retro-aldol catalyst before introducing the saccharide-containing feedstock to the reactor, the ramp-up period can be significantly reduced.
  • a conditioning retro-aldol catalyst before introducing the saccharide-containing feedstock to the reactor, the ramp-up period can be significantly reduced.
  • an equilibnum amount of metal from the conditioning retro-aldol catalyst is deposited on the surface of the hydrogenation catalyst. This deposit provides a portion of the conditioning retro-aldol activity, supplemental to the normally available activity of the catalytic retro-aldol catalyst. To compensate for the lower specific activity of the hydrogenation catalyst thus treated, the volumetric concentration of the catalyst may be increased. The total retro-aldol activity available for the reaction is thus higher than possible without the conditioning of the hydrogenation catalyst.
  • the glycol is selected from the group consisting of ethylene and propylene glycols. More preferably, the glycol is selected from monoethylene glycol (MEG), monopropylene glycol (MPG), and combinations thereof.
  • the saccharide-containing feedstock for the process of the present invention is selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides.
  • the saccharide-containing feedstock comprises saccharides selected from glucose, sucrose, starch, maltose, cellobiose, com syrup, cellulose, hemicellulose, glycogen, chitin, and combinations thereof. More preferably, the saccharide-containing feedstock comprises saccharides selected from glucose, sucrose, starch, and combinations thereof. Most preferably, the saccharide- containing feedstock comprises glucose.
  • the saccharide-containing feedstock includes, or is derived from, oligosaccharides or polysaccharides
  • the oligosaccharides and polysaccharides are preferably subjected to pre-treatment before being used in the process of the present invention.
  • Suitable pre-treatment methods are known in the art and one or more may be selected from the group including, but not limited to, sizing, drying, milling, hot water treatment, steam treatment, hydrolysis, pyrolysis, thermal treatment, chemical treatment, biological treatment, saccharification, fermentation, and solid removal.
  • the starting material still comprises mainly monomeric and/or oligomeric saccharides.
  • the saccharides are, preferably, soluble in the reaction solvent.
  • the saccharide-containing feedstock after any pre-treatment, comprises saccharides selected from glucose, starch and/or hydrolysed starch.
  • Hydrolysed starch comprises glucose, sucrose, maltose, and oligomeric forms of glucose.
  • the saccharides are suitably present as a solution, a suspension, or a slurry in a solvent.
  • the treated feedstock stream is suitably converted into a solution, a suspension, or a slurry in a solvent.
  • the solvent may be water, or a Cl to C6 alcohol or poly alcohol, or mixtures thereof including 50:50 mixtures of water and Cl to C6 alcohol or polyalcohol.
  • Suitable Cl to C6 alcohols include methanol, ethanol, 1 -propanol, and isopropanol.
  • Suitable polyalcohols include glycols, particularly products of the hydrogenation reaction, glycerol, erythritol, threitol, sorbitol, 1, 2-hexanediol, and mixtures thereof.
  • the polyalcohol may be glycerol or 1, 2-hexanediol.
  • Further solvent may also be added to a reactor vessel or reactor vessels in a separate feed stream or may be added to the treated feedstock stream before it enters the reactor.
  • the concentration of the saccharide-containing feedstock as a solution in the solvent supplied to the reactor vessel is at most at 80 wt.%, preferably at most 60 wt.%, more preferably, at most 45 wt.%.
  • the concentration of the saccharide-containing feedstock as a solution in the solvent supplied to the reactor vessel is at least 5 wt.%, preferably at least 20 wt.%, more preferably at least 35 wt.%.
  • the catalyst system used in the process of the present invention is comprised of a hydrogenation catalyst and a retro-aldol catalyst.
  • the hydrogenation catalyst comprises a transition metal having catalytic hydrogenation capabilities selected from Groups 8, 9 and 10 of the periodic table.
  • the hydrogenation catalyst comprises a metal selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, and combinations thereof.
  • the metal or metals may be present in elemental form or as compounds. It is also suitable that this component is present in chemical combination with one or more other ingredients in the hydrogenation catalytic composition.
  • the hydrogenation catalytic composition comprises metals supported on a solid support.
  • the solid supports may be in the form of a powder or in the form of regular or irregular shapes such as spheres, extrudates, pills, pellets, tablets, monolithic structures.
  • the solid supports may be present as surface coatings, for example on the surfaces of tubes or heat exchangers.
  • Suitable supports for the hydrogenation catalyst are those known to the skilled person and include, without limitation, alumina, silica, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, carbon, activated carbon, zeolite, clay, silica alumina and combinations thereof.
  • the hydrogenation catalyst is a Raney-metal type catalyst, suitably a Raney -nickel (Raney-Ni) catalyst.
  • Raney-Ni is provided in a pelletised form.
  • the first catalyst is a supported hydrogenation catalyst, such as ruthenium supported on activated carbon.
  • the conditioning retro-aldol catalyst and the catalytic retro-aldol catalyst each independently preferably comprise a transition metal compound, complex or elemental material comprising tungsten, molybdenum, lanthanum, tin, vanadium, niobium, chromium, titanium, zirconium, and combinations thereof.
  • the retro-aldol catalyst composition comprises one or more material selected from the group consisting of tungstic acid, molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group I or II element, such as sodium tungstate; metatungstate compounds comprising at least one Group I or II element, such as sodium metatungstate, paratungstate compounds comprising at least one Group I or II element, such as sodium paratungstate, heteropoly compounds of tungsten, heteropoly compounds of molybdenum, tungsten oxides, molybdenum oxides, vanadium oxides, metavanadates, chromium oxides, chromium sulfate, titanium ethoxide, zirconium acetate, zirconium carbonate, zirconium hydroxide, niobium oxides, niobium ethoxide, and combinations thereof.
  • the retro-aldol catalyst composition comprises one or more compound, complex or elemental material selected from those containing tungsten or alternatively those containing molybdenum.
  • the conditioning retro-aldol catalyst and the catalytic retro-aldol catalyst may be the same or different.
  • the hydrogenation catalyst is loaded in a reactor.
  • the hydrogenation catalyst is a heterogenous catalyst and is retained or supported within the reactor vessel.
  • the amount of hydrogenation catalyst loaded to the reactor is selected to provide the desired weight ratio of the hydrogenation catalyst composition (based on the amount of metal in said composition) to the potential saccharide-containing feedstock.
  • the amount of hydrogenation catalyst is provided to reach a catalystfeed weight ratio in a range of from 10: 1 to 1 : 100.
  • the hydrogenation catalyst is loaded to achieve an operating catalyst: feed weight ratio in the producing step of 1: 1.8 to 10: 1.8.
  • Hydrogen is fed to the reactor to displace a majority of air and/or oxygen-containing gas. Hydrogen may be fed continuously during the conditioning step or halted until the feedstock is introduced and/or until the producing step.
  • the catalyst is then conditioned by adding a treatment solution comprising a conditioning retro-aldol catalyst in the absence of the saccharide-containing feedstock.
  • the ratio of conditioning retro-aldol catalyst to hydrogenation catalyst is in a range from 100: 1 to 1: 100 (w/w). 1 wt.% conditioning retro- aldol catalyst (based on weight of hydrogenation catalyst) has a conditioning effect.
  • An excess of conditioning retro-aldol catalyst beyond a threshold concentration required for a monolayer coverage on the hydrogenation catalyst surface is not expected to have additional benefit.
  • the treatment solution may further comprise a glycol reaction product, suitably selected from the group consisting of ethylene glycol, propylene glycol, 1,2- butanediol, glycerol, erythritol, threitol, sorbitol, 1,2-hexanediol, and combinations thereof.
  • a glycol reaction product suitably selected from the group consisting of ethylene glycol, propylene glycol, 1,2- butanediol, glycerol, erythritol, threitol, sorbitol, 1,2-hexanediol, and combinations thereof.
  • the treatment solution comprises sorbitol.
  • the pH of the conditioning step is preferably controlled by adding an acidic component, for example by adding glycolic acid, lactic acid, acetic acid, and/or phosphoric acid.
  • the volumetric concentration of the catalyst is increased.
  • the volumetric catalyst concentration may be increased, for example, by 50 - 100%.
  • the deposited retro-aldo catalyst provides additional retro-aldol catalytic activity supplemental to the retro-aldol activity when the catalytic retro-aldol catalyst is later fed to the reactor with the saccharide-containing feedstock.
  • the total retro-aldol activity available for the reaction is thus higher than is possible without first conditioning the hydrogenation catalyst.
  • the hydrogenation catalyst is a Raney- Ni catalyst that is treated with tungstic acid, as the retro-aldol catalyst.
  • an equilibrium amount of tungstate is deposited on the surface of the Raney-Ni.
  • the conditioning step is conducted in the reactor in the presence of hydrogen that was fed to the reactor with a treatment solution comprising a conditioning retro-aldol catalyst in the absence of the saccharide-containing feedstock to produce a conditioned hydrogenation catalyst.
  • the conditioning step is conducted at a temperature in a range of from 150°C to 280°C, preferably in a range of from 160°C to 270°C, more preferably in a range of from 180°C to 250°C.
  • the conditioning step is conducted at an acidic pH.
  • the pH is in a range from 2 to 8, more preferably from 3 to 6, as measured in the reactor effluent at room temperature.
  • the conditioning step can be carried out over a time period of up to 48 hours, typically not less than 24 hours, suitably not less than 12 hours, more suitably not less than 6 hours.
  • an optional testing step may be conducted by introducing a first portion of the saccharide-containing feedstock to the reactor containing the conditioned hydrogenation catalyst.
  • the first portion of the saccharide-containing feedstock is preferably diluted before introduction to the reactor.
  • the testing step is used to determine the amount of feedstock converted to product glycol and/or by-products and intermediates.
  • the testing step is preferably conducted at a temperature in a range of from 50°C to 120°C, depending, for example, on the feed rate.
  • the saccharide-containing feedstock and the catalytic retro-aldol catalyst are introduced to the reactor.
  • the feedstock and catalytic retro-aldol catalyst may be combined prior to introducing to the reactor.
  • the saccharide-containing feedstock and the catalytic retro-aldol catalyst are fed separately to the reactor.
  • the weight ratio of the catalytic retro-aldol catalyst to saccharide is suitably in the range of from 1 : 1 to 1 : 1000, preferably 1 : 50 to 1 : 100, based on the metal content of the catalytic retro-aldol catalyst.
  • Glycol is produced by hydrogenolysis of the saccharide-containing feedstock.
  • the temperature in the reactor is suitably at least 80°C, preferably at least 130°C, more preferably at least 160°C, most preferably at least 190°C.
  • the temperature in the reactor is suitably at most 300°C, preferably at most 280°C, more preferably at most 250°C, most preferably at most 230°C.
  • Operating at higher temperatures has the potential disadvantage of increased amounts of side-reactions, leading to lower yield, and operating at a low temperature might result in suppression or inactivation of the retro-aldol activity.
  • the production step is conducted at a temperature in a range of from 180°C to 250°C, more preferably in a range of from 210°C to 250°C.
  • the pressure in the reactor is suitably at least 1 MPa, preferably at least 2 MPa, more preferably at least 3 MPa.
  • the pressure in the reactor is suitably at most 25 MPa, preferably at most 20 MPa, more preferably at most 18 MPa.
  • the production step is conducted at a pressure in a range of from 3 MPa to 14 MPa.
  • the reactor is pressurised to a pressure within these limits by addition of hydrogen before the introducing step and is maintained at such a pressure as the reaction proceeds through on-going addition of hydrogen.
  • the residence time in the reactor during the glycol production step is suitably at least 1 minute, preferably at least 2 minutes, more preferably at least 5 minutes.
  • the residence time in the reactor is no more than 5 hours, preferably no more than 2 hours, more preferably no more than 1 hour.
  • reaction parameters may be adjusted as needed over time to achieve a steady state concentration of product in the reactor.
  • the parameters that may be adjusted include, without limitation, feed rate, residence time, saccharide concentration in the feed, temperature and/or pressure. A corresponding amount of reactor effluent is removed continuously from the reactor.
  • the spent conditioned hydrogenation catalyst is removed from the reactor and mixed with powdered aluminum metal.
  • the mixture is melted to form a Ni-W-Al alloy catalyst that may be used for producing glycol from a further saccharide-containing feedstock.
  • the Ni-W-Al alloy is preferably crushed and leached with a concentrated NaOH solution to produce an active hydrogenation catalyst.
  • the Ni-W-Al alloy is crushed and leached with an acid under high-pressure hydrogen conditions to produce an active hydrogenation catalyst.
  • the spent conditioned hydrogenation catalyst is removed from the reactor and treated with a solution of ammonium salt to form a fresh hydrogenation catalyst and a solution comprising oxidized soluble tungstate.
  • the fresh hydrogenation catalyst may be recycled to the loading step of the present invention.
  • the solution comprising oxidized soluble tungstate may be recycled to the conditioning step and/or the introducing step of the present invention
  • the solution of ammonium salt is preferably a dilute solution containing ammonium nitrate and/or ammonium carbonate.
  • the W-oxides are oxidized into soluble tungstates, and removed from the surfaces, providing a cleaner surface on the hydrogenation catalyst.
  • the ammonium-salt wash solution is suitable for the recovery of the active form retro-aldol catalyst.
  • an effluent is removed from the reactor after the producing step.
  • Product glycol is separated from a heavy-end stream comprising conditioned hydrogenation catalyst and retro-aldol catalyst.
  • the heavy-end stream is then passed to a treatment reactor for converting organic acids to alcohols and/or for converting polyols to glycols.
  • a stream comprising the conditioned hydrogenation catalyst is separated from the effluent of the treatment reactor and can be recycled to the reactor.
  • the feed composition was changed to 10 wt.% glucose in water and introduced at a feed rate of 5 ml/min over a period of 12 hours to test the yield/activity of the hydrogenation catalyst. Partial conversion of glucose to sorbitol was observed at a sorbitol yield of 47.7 wt.%, which translates to a reaction rate of 2.94 x IO’ 4 mol sorbitol/min/ g Raney -Ni)/glucose concentration (mol/1).
  • the reactor temperature was increased to 230°C over a period of 4 hours, after which the feed composition was changed to 20 wt.% glucose, 0.043 wt.% glycolic acid and 0.527 wt.% Na2WO4.2H2O.
  • the pH was controlled at 3.75, as measured in the reactor effluent, by feeding additional trace amounts of glycolic acid.
  • the conversion of glucose was virtually complete and after 26 hours a yield of 44.5 wt.% MEG, 7.8 wt.% MPG, 1.6 wt.% 1,2-butanediol and 20.6 wt.% sorbitol was observed. Glycol yield increases and sorbitol yield decreases over time.
  • a feed solution of 2.5 wt.% sorbitol, 0.56 wt.% Na2WOr.2H2O and 0.48 wt.% glycolic acid was introduced to the reactor at a feed rate of 3 ml/min and the temperature was kept constant at 230 °C over a period of 24 hours. The temperature was reduced to 70 °C over a period of 3 hours. As noted above, this step of reducing temperature was done for purposes of the optional testing step wherein a first portion of the saccharide-containing feedstock is introduced to the reactor for determining the amount of feedstock converted to product glycol and/or by-products and intermediates.
  • the feed composition was changed to 10 wt.% glucose in water and introduced at a feed rate of 5 ml/min over a period of 14 hours to test the yield/activity of the conditioned hydrogenation catalyst. Partial conversion of glucose to sorbitol was observed at a sorbitol yield of 35.6 wt.%, which translates to a reaction rate of 1.80 x 1 O' 4 mol sorbitol/min/(g Raney -Ni)/glucose concentration (mol/1). The reaction rate for hydrogenation has been reduced by 38.7%, due to treatment with the tungstate containing feed, relative to the reaction rate observed after catalyst treatment in the absence of tungstate (see Comparative Example 1).
  • the reactor temperature was increased to 230°C over a period of 4 hours, after which the feed composition was changed to 20 wt.% glucose, 0.043 wt.% glycolic acid and 0.527 wt.% Na2WO4.2H2O.
  • the pH was controlled at 3.75, as measured in the reactor effluent, by feeding additional trace amounts of glycolic acid.
  • the conversion of glucose was virtually complete and, after 26 hours, a yield of 51.6wt.% MEG, 6.3 wt.% MPG, 1.5 wt.% 1 ,2-butanediol and 17.2 wt.% sorbitol was observed.

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

Abstract

La présente invention concerne un procédé de production de glycol à partir d'une charge d'alimentation contenant des saccharides, en présence d'un système catalytique comprenant un catalyseur de réaction de rétro-aldolisation et un catalyseur d'hydrogénation, qui comprend une étape de conditionnement pour le catalyseur d'hydrogénation. Le catalyseur d'hydrogénation est conditionné avec une solution de traitement comprenant un catalyseur de réaction de rétro-aldolisation de conditionnement en l'absence de la charge d'alimentation contenant des saccharides. Ensuite, la charge d'alimentation contenant des saccharides et un catalyseur de réaction de rétro-aldolisation catalytique sont introduits dans le réacteur contenant le catalyseur d'hydrogénation conditionné, et du glycol est produit par hydrogénolyse de la charge d'alimentation contenant des saccharides.
PCT/US2023/061899 2022-02-04 2023-02-03 Procédé de production de glycol à partir d'une charge d'alimentation renouvelable Ceased WO2023150656A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118084612A (zh) * 2024-02-26 2024-05-28 浙江大学 一种葡萄糖加氢制备山梨醇的方法

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