[go: up one dir, main page]

WO2016034727A1 - Extraction sélective et conversion d'une charge cellulosique en éthylène glycol - Google Patents

Extraction sélective et conversion d'une charge cellulosique en éthylène glycol Download PDF

Info

Publication number
WO2016034727A1
WO2016034727A1 PCT/EP2015/070299 EP2015070299W WO2016034727A1 WO 2016034727 A1 WO2016034727 A1 WO 2016034727A1 EP 2015070299 W EP2015070299 W EP 2015070299W WO 2016034727 A1 WO2016034727 A1 WO 2016034727A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
process according
biomass
cellulose
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.)
Ceased
Application number
PCT/EP2015/070299
Other languages
English (en)
Inventor
Adi Aizat RAZALI
Poh Gaik LAW
Azlan Shah HUSSAIN
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.)
Petroliam Nasional Bhd Petronas
Original Assignee
Petroliam Nasional Bhd Petronas
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
Application filed by Petroliam Nasional Bhd Petronas filed Critical Petroliam Nasional Bhd Petronas
Publication of WO2016034727A1 publication Critical patent/WO2016034727A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/003—Pulping cellulose-containing materials with organic compounds

Definitions

  • the present invention relates to a process for treating cellulosic biomass and subsequently converting to ethylene glycol. More specifically, the invention relates to a process for selectively solubilizing and removing lignin and hemi-cellulose components of cellulosic biomass and obtaining a cellulosic feedstock having a higher proportion of cellulose, as compared to the biomass from which it is derived, and having a greater cellulose Crystallinity Index.
  • the cellulosic feedstock obtained by the process of the invention may subsequently be converted to ethylene glycol by catalytic hydrothermal methods.
  • the present invention incorporates the use of specifically selected DES solvents for the treatment of cellulosic biomass, in combination with specifically selected process conditions for the selective hydrogenolysis/hydrogenation of the cellulosic feedstock obtained from the cellulosic biomass treatment to afford ethylene glycol.
  • Ethylene glycol is a useful polyhydric alcohol that is primarily used as a raw material in the manufacture of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) resins. It has also found use in antifreeze, lubricants, plasticizers and surfactants.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • ethylene glycol has been prepared from ethylene, typically derived from the petroleum industry, via the ethylene oxide intermediate. With an increasing focus on the use of renewable feedstocks, such as a biomass, several alternative methods have emerged for each of the stages in the conversion of biomass to ethylene glycol.
  • Biomass more specifically lignocellulosic biomass, is one of the most abundant raw materials on Earth. It is composed principally of cellulose and hemicellulose carbohydrate polymers and lignin, an aromatic polymer, to which the cellulose and hemicellulose components can be tightly bound.
  • lignocellulosic biomass There are generally considered to be three different classes of lignocellulosic biomass: i) virgin biomass; ii) waste biomass; and iii) energy crops.
  • Virgin biomass includes naturally occurring plants and vegetation.
  • Waste biomass corresponds to a low value industrial byproduct, commonly from the agricultural and forestry sectors, examples of which include oil palm frond (OPF), empty fruit bunches (EFB), corn stover, sugarcane bagasse, and straw, as well as saw mill and paper mill discards.
  • OPF oil palm frond
  • EFB empty fruit bunches
  • corn stover corn stover
  • sugarcane bagasse sugarcane bagasse
  • straw as well as saw mill and paper mill
  • Energy crops are known to afford a high yield of lignocellulosic biomass and serve as raw material for production of second generation biofuel, examples of which include switch grass and elephant grass.
  • Methods for converting saccharide-containing materials to ethylene glycol and other polyols include hydrothermal catalytic processes, for example catalytic hydrogenolysis/hydrogenation.
  • US 2010/0255983 discloses a method for converting cellulose, a principal component of biomass, to ethylene glycol through a heterogeneous catalytic reaction under hydrogen atmosphere and hydrothermal conditions.
  • US 4,404,411 discloses a process for the hydrogenolysis of polyols to ethylene glycol where the use of at least 10 mol % of a strong base in non-aqueous solvent is used for increasing the yield of ethylene glycol.
  • US 4,404,411 also indicates that the strongly basic process taught therein is likely to be suitable for saccharides which are reduced to polyols in situ.
  • xylitol and sorbitol are indicated as being preferred polyols as they are readily available from cellulose and hemicellulose, derivable from biomass.
  • US 2013/0252285 exemplifies the use of [Bmim][Ac] and [Emim][Ac] ionic liquids for pretreating biomass in order to provide hydrolysable sources of hemicellulose and cellulose.
  • cellulosic biomass is completely dissolved in a composition comprising [Bmim][Ac] or [Emim][Ac], water and a kosmotrophic anion, the latter facilitating separation of precipitated solids, the aqueous phase and the ionic liquid phase.
  • the solubilized cellulosic content of the biomass is said to be subsequently recovered from the reaction medium by addition of an anti-solvent, such as water, which precipitates the cellulosic material from the ionic liquid phase.
  • an anti-solvent such as water
  • the extraction of cellulose reported in US 2013/0252285 thus corresponds to a two stage regeneration process necessarily requiring the use of an anti-solvent for selectively precipitating dissolved cellulose.
  • the object of the method of US 2013/0252285 is to provide cellulosic material which may be subjected to enzymatic hydrolysis, rather than hydrogenolysis reactions using conventional metallic catalyst systems, at high solids loadings, short residence times and low enzyme concentrations.
  • the aim of the pretreatment in US 2013/0252285 is to increase the surface area of the polysachharides and to decrystallize cellulose, specifically for enhancing depolymerisation thereof by enzymatic hydrolysis. Enzymatic hydrolysis is more effective with substrates having lower cellulose crystallinity.
  • ionic solvents having comparable properties, as well as similar industrial applications, to those of ionic liquids are the deep eutectic solvents (DESs).
  • a DES is an ionic solvent formed of a mixture of two components, which mixture forms a eutectic with a melting point significantly lower than that of either of the individual components of the mixture.
  • DESs are based on quaternary ammonium salts, such as choline chloride, with hydrogen bond donors, such as amides and carboxylic acids. These solvents are generally considered to be more water compatible and less toxic than many ionic liquids.
  • US 2009/0247432 describes the use of DESs as part of a method for solubilizing/removing cellulose, or chemically modified cellulosic polymers, specifically when used in subterranean drilling operations, such as fracturing. In that method, the DES is pumped downhole after fracturing operations to remove cellulosic material used for thickening the fracturing fluid.
  • US 2009/0247432 discloses a number of DES formed from mixtures of (chlor-)choline chloride and various amides and mono- and di- carboxylic acids, including oxalic, malonic and succinic acids.
  • US 2009/0247432 does not disclose the use of the DES for the purpose of selective biomass extraction, nor is there any mention of the modification of the crystallinity of cellulose.
  • WO 2011/155829 discloses a number of DESs based on mixtures of materials of natural origin comprising at least two components.
  • the first component is selected from at least one naturally occurring organic acid or an inorganic compound, such as a salt.
  • the second component is selected from at least one naturally occurring mono- or dimeric sugar, sugar alcohol, amino acid, di- or tri- alkanal or choline derivatives.
  • Extraction of polysaccharides is also generally referred to, although only lentinan, heparin, hyaluronan, alginate, agar, starch and inulin polysaccharides are mentioned specifically.
  • WO 2011/155829 does not mention any form of selective extraction of a particular polysaccharide from a biological product containing multiple polysaccharides.
  • choline-derived solvents which are shown to rapidly dissolve and decrystallize microcrystalline cellulose.
  • the choline-derived solvents are based on choline, either in the chloride, hydroxide or acetate form, together with a quaternary ammonium chloride salt, such as tributylmethylammonium chloride ([TBMA]CI).
  • amorphous cellulose is regenerated by the addition of an anti-solvent (water), and the amorphous cellulose may be subsequently isolated.
  • the choline-derived solvents are considered by Zhang et al to represent valuable alternatives to the traditional imidazolium-based ionic liquids used in solubilizing and decrystallizing cellulose, such as those reported in US 2013/0252285.
  • An extraction performed with the choline-derived solvents reported by Zhang et al would thus also correspond to a two stage regeneration process, necessarily requiring the use of an anti- solvent for selective precipitation of dissolved cellulose, as in US 2013/0252285.
  • the present invention is based on the surprising discovery that a valuable cellulosic feedstock may be obtained following treatment of cellulosic biomass with specifically selected deep eutectic solvents, in particular, those based on a mixture of certain choline derivatives with an alpha-hydroxy carboxylic acid.
  • use of these specific deep eutectic solvents as part of a selective extraction obviates the use of anti-solvents for isolating the cellulose component of the cellulosic biomass by a precipitation process.
  • cellulosic feedstock obtained from the treatment with the above deep eutectic solvent has been found to give desirable yields of ethylene glycol in subsequent catalytic hydrogenolysis/hydrogenation reactions, as well as desirable selectivity for ethylene glycol over other polyols, such as 1 ,2-propylene glycol.
  • the present invention provides a process for preparing a cellulosic feedstock comprising the steps of: i) contacting cellulosic biomass with a deep eutectic solvent (DES) formed from a mixture of a) a choline derivative selected from choline chloride, chlorocholine chloride, choline acetate, acetylcholine chloride or phosphatidyl choline; and b) an alpha-hydroxy carboxylic acid; and ii) obtaining a cellulosic feedstock which has a higher proportion of cellulose component, as compared with the cellulosic biomass from step;
  • DES deep eutectic solvent
  • step ii) wherein the majority of the cellulosic feedstock obtained in step ii) is obtained without regenerating cellulose by precipitation.
  • Treatment of cellulosic biomass with a deep eutectic solvent according to the process of the present invention has been found to selectively solubilize and remove amorphous components of cellulosic biomass, such as lignin and hemicellulose, over cellulose.
  • the cellulosic feedstock obtainable by the process of the present invention has surprisingly been found to exhibit increased cellulose crystallinity compared with its level of crystallinity whilst entrained in untreated biomass.
  • the present invention also provides a process for selectively solubilizing and removing lignin and hemi-cellulose components of a cellulosic biomass comprising the steps of: i) contacting cellulosic biomass with a deep eutectic solvent (DES) formed from a mixture of a) a choline derivative selected from choline chloride, chlorocholine chloride, choline acetate, acetylcholine chloride or phosphatidyl choline; and b) an alpha-hydroxy carboxylic acid; and ii) obtaining a cellulosic feedstock which has a higher proportion of a cellulose component, as compared with the cellulosic biomass from step i); wherein the majority of the cellul
  • DES deep eutectic solvent
  • the present invention also provides a use of a deep eutectic solvent formed from a mixture of a) a choline derivative selected from choline chloride, chlorocholine chloride, choline acetate, acetylcholine chloride or phosphatidyl choline; and b) an alpha-hydroxy carboxylic acid for selectively solubilizing and removing lignin and hemi-cellulose components of a cellulosic biomass and/or for increasing the cellulose Crystallinity Index of the cellulose component of cellulosic biomass.
  • a deep eutectic solvent formed from a mixture of a) a choline derivative selected from choline chloride, chlorocholine chloride, choline acetate, acetylcholine chloride or phosphatidyl choline; and b) an alpha-hydroxy carboxylic acid for selectively solubilizing and removing lignin and hemi-cellulose components of a cellulosic
  • the deep eutectic solvent as described herein is used to increase the cellulose Crystallinity Index value of the cellulose component of cellulosic biomass to a value of 42.5 % or above, as measured using CP/MAS.
  • Cellulosic biomass used herein refers to all forms of lignocellulosic biomass. Examples of biomass include oil palm biomass, for example oil palm frond (OPF) and empty fruit bunches (EFB), corn stover, sugarcane bagasse, straw, energy crops, for example switch grass and Elephant grass, as well as saw mill and paper mill discards.
  • the biomass is oil palm biomass, more preferably empty fruit bunches (EFB).
  • Biomass in accordance with the present invention comprises the three principal components of cellulose, hemicellulose and lignin, at varying levels.
  • the biomass may also contain other polysacharides, such as glycogen, starch and chitin.
  • the biomass may also contain monosacharides, disaccharides and oligosaccharides. Examples of monosacharides include glucose, fructose, galactose, xylose, arabinose and mannose.
  • biomass used herein is intended to cover “raw biomass” or “crude biomass” which has not been subjected to any form of refinement, or only physical refining such as by shredding/chipping and/or dewatering.
  • a further form of biomass includes "chemically treated biomass” or “pretreated biomass”, where raw or crude biomass has undergone some form of treatment either to partially remove lignin and/or hemicellulose, or to partially depolymerize any of its polymeric components.
  • pretreatments include hot water treatment, steam treatment, chemical treatment, biological treatment, catalytic treatment, thermal treatment, hydrolysis, and/or pyrolysis.
  • this form of biomass may be used in conjunction with the present invention, it will be appreciated that a benefit of the present invention is that it is unnecessary to pretreat biomass prior to use in the process. As such, it is preferred that the biomass used in the present invention is raw or crude biomass, or biomass which has only undergone physical refining.
  • cellulosic feedstock refers to the material obtained as a result of the treatment of cellulosic biomass with a deep eutectic solvent according to the invention and which contains a higher proportion of cellulose component than the cellulosic biomass from which it is derived.
  • the cellulose contained within the cellulosic feedstock exhibits greater cellulose Crystallinity Index (CI), as compared with its level of crystallinity whilst entrained in untreated biomass.
  • CI cellulose Crystallinity Index
  • deep eutectic solvent used herein is intended to refer to an ionic solvent formed from a eutectic mixture of two components.
  • the term “deep eutectic solvent (DES)” includes mixtures having both high melting points and compounds having low melting points, e.g. at or below room temperature. Thus, many DESs have melting points below 200°C, particularly below 100°C, around room temperature (15 to 30°C), or even below 0°C.
  • the deep eutectic solvent used with the process of the present invention comprises a mixture of a) a choline derivative selected from choline chloride, chlorocholine chloride, choline acetate, acetylcholine chloride or phosphatidyl choline and b) an alpha-hydroxy carboxylic acid.
  • the alpha-hydroxy carboxylic acid component of the deep eutectic solvent is selected from naturally occurring acids, such as glycolic acid, lactic acid, tartaric acid, citric acid, mandelic acid, and malic acid. Synthetic versions of these acids, which may exist in different stereoisomeric forms, may of course also be used in accordance with the present invention, however. More preferably, the alpha-hydroxy carboxylic acid is selected from malic acid and lactic acid. Most preferably, the alpha-hydroxy carboxylic acid is selected from malic acid.
  • the choline derivative of the deep eutectic solvent is selected from choline chloride, chlorocholine chloride, or acetylcholine chloride. Most preferably, the choline derivative is selected from choline chloride.
  • the specific deep eutectic solvents used in the process of the present invention have been found to be particularly suitable for dissolution, and selective removal, of amorphous components of biomass, such as lignin and hemicellulose.
  • amorphous components of biomass such as lignin and hemicellulose.
  • the preferential dissolution of hemicellulose over cellulose is particularly notable in the context of the present invention.
  • a cellulosic material having a higher proportion of cellulose component than that of the untreated biomass may be obtained following pretreatment with the specific deep eutectic solvents described hereinbefore.
  • the cellulosic material obtained by the process of the present invention has been found to exhibit increased crystallinity, as compared with its crystallinity in the untreated biomass. This is the opposite of what would be expected based on known prior art biomass pretreatments using ionic liquids or alternative deep eutectic solvents. For example, treatment of biomass with [Bmim][Ac] or [Emim][Ac] completely dissolves biomass and the cellulose component, once regenerated, is substantially decrystallized. This has been verified by the present inventors who have found that cellulose Crystallinity Index of biomass treated with [Bmim][Ac] is significantly lower than that of untreated biomass (which findings are reported hereinbelow).
  • TBMA tributylmethylammonium chloride
  • the cellulosic feedstock obtained from the process of the invention has also been found to be particularly suitable for converting to ethylene glycol, in good yield and with high selectivity over 1 ,2-propylene glycol, by catalytic hydrogenolysis/hydrogenation methods.
  • the DESs described hereinbefore are readily prepared from commodity chemicals by processes well known to the person of skill in the art.
  • the skilled person is able to prepare a deep eutectic solvent for use with the present invention by mixing the choline derivative together with the alpha-hydroxy carboxylic acid under heating (for example, at about 80 °C), until a homogeneous, clear liquid has been formed.
  • the choline derivative and alpha-hydroxy carboxylic acid may both be dissolved in water solvent before the water component of the resulting mixture is removed at low temperature (for example, at about 70 °C) using, for instance, a rotary evaporator to leave a eutectic mixture.
  • a suitable molar ratio of the two components which leads to a eutectic mixture may be readily ascertained by the skilled person.
  • a DES For a DES, often the components are present in the mixture in equimolar ratio, although other ratios are known. Generally, however, the molar ratio of the components can be expressed as integers, typically varying from 1 :1 to 4:1 . Illustrative ratios of preferred DESs according to the present invention are provided in Table 1 below. J. Am. Chem. Soc, 2004, 126 (29), pp 9142-9147, also describes the formation of deep eutectic solvents between choline chloride and various carboxylic acids.
  • step i) of the process of the invention cellulosic biomass is contacted with the DES.
  • Contacting step i) may be carried out by contacting the cellulosic biomass with the DES in a vessel wherein the resulting mixture is stirred using, for example, a mechanical stirrer, an ultrasonic stirrer, an electromagnetic stirrer or by bubbling an inert gas through the mixture.
  • Step i) may be conducted at ambient temperature up to temperatures lower than which polysachharide decomposition occurs.
  • Step i) is suitably conducted at a temperature of from 25°C to 110°C, preferably from 30°C to 100°C.
  • the mass ratio of cellulosic biomass to deep eutectic solvent in contacting step i) is from 1 :1 to 1 :300, preferably in a mass ratio of from 1 :20 to 1 :100.
  • Mixing of the cellulosic biomass with the deep eutectic solvent as part of contacting step i) may suitably last from from 1 hour to 48 hours, preferably 2 hours to 24 hours, more preferably 6 to 20 hours, and most preferably 10 to 18 hours, for example 16 hours.
  • contacting step i) may be conducted in the presence of a co-solvent which is compatible with the deep eutectic solvent and the components of cellulosic biomass.
  • a co-solvent may be appropriate where it is desired to modify the viscosity of the DES; provide a medium to ensure sufficient mixing of components; and/or to enhance dissolution effects of the DES.
  • Suitable co-solvents include, for example, water and/or an organic co-solvent.
  • the reaction medium comprises a co-solvent selected from water, methanol, ethanol, propanols, butanols, ethylene glycol, glycerol, or a combination thereof.
  • the reaction medium comprises an aqueous co-solvent.
  • co-solvent is present in an amount of no more than 15 wt% based on the total weight of the reaction mixture. In a further embodiment of the invention, co-solvent is present in an amount no more than 10 wt% based on the total weight of the reaction mixture.
  • contacting step i) is conducted substantially in the absence of a co-solvent (i.e. less than 5 wt%, for example 2 wt% or 1 wt% based on the total weight of the reaction mixture).
  • contacting step i) of the process of the invention consists essentially of contacting cellulosic biomass with a deep eutectic solvent as described hereinbefore.
  • step ii) of the process of the invention a cellulosic feedstock is obtained, wherein the majority of the cellulosic feedstock is obtained without regeneration of cellulose by precipitation. Separation of the feedstock from the reaction mixture in step ii) may be carried out by simple filtration methods.
  • the deep eutectic solvents used in conjunction with the present invention may selectively dissolve the amorphous components of the biomass, such as lignin and hemicellulose, and can therefore leave a solid cellulosic material, typically in a fibrous form.
  • the majority of the cellulosic feedstock obtained it is intended to refer to over 50 wt.% of the total amount of cellulose feedstock obtained.
  • at least 60 wt.% of the total amount of cellulose feedstock obtained is obtained without regeneration of cellulose by precipitation, more preferably at least 70 wt.%, at least 80.wt%, at least 90 wt.% or even at least 95 wt.% of the total amount of cellulose feedstock is obtained without regeneration of cellulose by precipitation.
  • none of the cellulose feedstock is obtained by regeneration of cellulose by precipitation.
  • One of the notable advantages of the present invention is that the particular deep eutectic solvents are able to selectively solubilise hemicellulose and lignin components over cellulose, thus obviating regeneration steps involving precipitation of dissolved cellulose by means of anti-solvents, which are relied upon as part of cellulose extraction processes employed in the prior art.
  • an anti-solvent preferably water
  • an anti-solvent such as water, acetone, dichloromethane and/or acetonitrile, in order to isolate the cellulosic feedstock product.
  • the cellulosic material may occupy a co-solvent phase which is distinct from the deep eutectic phase which contains the substantial content of lignin and hemicellulose components, and may be separated on this basis.
  • Such phases may also be separated using, for example, a decanter, a hydrocyclone, electrostatic coalescer or a centrifuge. Step i) followed by step ii) may be repeated several times, until a desired level of extraction of the biomass has occurred.
  • Steps i) and ii) may also be carried out together in a centrifugal contact separator, for example, a centrifugal contact separator as described in US 4,959,158, US 5,571 ,070, US 5,591 ,340, US 5,762,800, WO 99/12650, and WO 00/29120.
  • a centrifugal contact separator for example, a centrifugal contact separator as described in US 4,959,158, US 5,571 ,070, US 5,591 ,340, US 5,762,800, WO 99/12650, and WO 00/29120.
  • Suitable centrifugal contact separators include those supplied by Costner Industries Nevada, Inc.
  • the deep eutectic solvent and optional co-solvent/biomass mixture may be introduced into an annular mixing zone of the centrifugal contact separator.
  • the DES, any optional co-solvent and biomass are introduced as separate feed streams into the annular mixing zone.
  • the deep eutectic solvent any optional co-solvent and biomass are rapidly mixed in the annular mixing zone such that at least a portion of amorphous components of the biomass are extracted into the deep eutectic solvent.
  • the resulting mixture is then passed to a separation zone wherein a centrifugal force is applied to the mixture to produce a clean separation of any optional co-solvent phase, deep eutectic solvent extract phase and solid biomass derivative.
  • the deep eutectic solvent phase which has been used in the process of the present invention may be recycled after use.
  • a precipitating solvent antioxidant
  • the precipitating solvent may then by separated from the deep eutectic solvent by, for instance, driving off the solvent at reduced pressure.
  • Normal solvents which are immiscible with the deep eutectic solvent may also be used for extracting by-products dissolved in the deep eutectic solvent which may then be phase-separated as described hereinbefore.
  • Crystalline cellulose is known to exist in the form of four different crystallographic allomorphs (I through IV), and it is also known that one allomorph may be converted to another by chemical (e.g. ammonia) and/or heat treatment. As the skilled person will be aware, cellulose crystallinity is commonly reported by reference to the Crystallinity Index (CI) parameter.
  • CI Crystallinity Index
  • the cellulosic feedstock obtained from the process of the invention has been found to be particularly suitable for converting to ethylene glycol, in good yield and with high selectivity over 1 ,2-propylene glycol, by catalytic hydrogenolysis/hydrogenation methods.
  • the present invention provides a process for preparing ethylene glycol from cellulosic biomass comprising the steps of: i) contacting cellulosic biomass with a deep eutectic solvent formed from a mixture of a) a choline derivative selected from choline chloride, chlorocholine chloride, choline acetate, acetylcholine chloride or phosphatidyl choline; and b) an alpha-hydroxy carboxylic acid; ii) obtaining a cellulosic feedstock which has a higher proportion of cellulose, as compared with the cellulosic biomass from step i), and wherein the majority of the cellulosic feedstock is obtained without regenerating cellulose by precipitation;
  • the heterogenous catalyst system for use with step iii) of the process of the invention will have at least two components which are suitable for catalysing the hydrogenolysis and hydrogenation reactions respectively.
  • the heterogeneous catalyst system comprises:
  • component 1 ) of the catalyst system comprises molybdenum in elemental form or in the form of molybedic acid.
  • component 1 ) of the preferred heterogeneous catalyst comprises tungsten in elemental form or in the form of a compound selected from sodium tungstate, tungsten nitride, tungsten carbide, tungsten phosphide, tungsten oxide, tungsten sulfide, tungsten chloride, tungsten hydroxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate (for example, ammonium metatungstate), paratungstic acid, paratungstate, peroxotungstic acid, peroxotungstate, heteropoly tungstic acid or combinations thereof.
  • component 1 of the heterogeneous catalyst system comprises tungsten in the form of a compound selected from sodium tungstate, tungsten carbide, tungsten bronze, tungstic acid or a combination thereof. Even more preferably, the heterogeneous catalyst system comprises tungsten in the form of a compound selected from sodium tungstate, tungstic acid or a combination thereof.
  • component 2) of the preferred heterogeneous catalyst system comprises a metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum or a combination thereof.
  • component 2) of the heterogeneous catalyst system comprises a metal selected from nickel, ruthenium, platinum or a combination thereof. More preferably, component 2) of the catalyst system comprises nickel.
  • the amount of the catalyst system used in the process of the present invention may range from 0.1 to 10 wt. %, preferably 0.3 to 7 wt.%, based on the weight of cellulosic feedstock and the catalytic system measured on the basis of elemental tungsten or molybdenum.
  • the ratio of active metals in catalyst components 1 ) and 2) respectively is preferably 1 :100 to 100:1 , more preferably 1 : 10 to 10:1 , measured on an elemental basis.
  • Step iii) of the process is conducted at a temperature and pressure which is suitable for the catalytic reaction to occur and which avoids thermal decomposition of the cellulosic material.
  • step iii) of the process is conducted at a temperature of at least 150°C, more preferably at a temperature of from 200 to 300°C, for example at a temperature of 245°C.
  • step iii) of the process of the invention is conducted at a pressure of 0.1 to 15 MPa, more preferably at a pressure of 1 to 7 MPa, for example at a pressure of 2 MPa.
  • Step iii) of the process is conducted in the presence of a reaction medium which is compatible with the catalytic reaction and typically comprises water and/or an organic solvent.
  • the reaction medium comprises a solvent selected from water, methanol, ethanol, propanols, butanols, ethylene glycol, glycerol, or a combination thereof.
  • the reaction medium comprises an aqueous solvent.
  • the amount of reaction medium present is such that the feedstock represents between 1 and 30 wt.%, based on the combined weight of reaction medium and feedstock. More preferably, the amount of reaction medium present is such that the feedstock represents between 5 and 15 wt.%, based on the combined weight of reaction medium and feedstock.
  • the hydrogenolysis/hydrogenation reactions of step iii) of the process are preferably conducted under acidic conditions.
  • it has been found to be advantageous to conduct the hydrogenolysis/hydrogenation reactions preferably at a pH of from 2.0 to 6.5, preferably at a pH of from 2.25 to 5, more preferably at a pH from 2.5 to 4, most preferably at a pH of from 2.75 to 3.25, for example a pH of 3.
  • Particularly high levels of cellulosic feedstock conversion and yield of ethylene glycol have been found to be achievable with this range of pH.
  • ethylene glycol is a preferred precursor for several commercial processes, for instance in the preparation of PET, and has wider application than the other polyols which may be prepared from the hydrogenolysis/hydrogenation of biomass derived feedstock.
  • Step iii) of the process of the above further aspect of the invention is preferably conducted in the presence of an organic or inorganic acid.
  • step iii) of the process is conducted in the presence of an inorganic acid selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, preferably selected from hydrochloric acid and sulfuric acid.
  • step iii) is conducted in the presence of an organic acid selected from acetic acid, maleic acid, butyric acid, benzenesulfonic acid, terephthalic acid, benzoic acid, phthalic acid and salicylic acid, preferably selected from benzenesulfonic acid.
  • the acid may be in an amount of from 0.0001 to 2.0 wt.%, preferably 0.001 to 0.1 wt.%, based on the total weight of the reaction mixture, or in an amount of 1 ppm to 20,000 ppm, preferably 10 ppm to 1000 ppm.
  • the cellulosic feedstock obtained in step ii) may be used directly or may be further processed before being reacted in step iii) of the process.
  • Step iii) typically comprises mixing cellulosic feedstock, reaction medium and heterogeneous catalyst system in a sealed reaction vessel, optionally adjusting the pH of the reaction mixture, introducing hydrogen and stirring the resulting mixture using, for example, a mechanical stirrer, an ultrasonic stirrer or an electromagnetic stirrer. Thereafter, the reaction mixture is left for a suitable period of time to allow the catalytic reaction to proceed.
  • An adequate residence time is no less than 5 minutes.
  • the residence time for step c) of the process is from 30 minutes to 3 hours, for example, 2 hours.
  • the heterogeneous catalyst system utilized in the process of the present invention may be either partially or fully supported or in unsupported form.
  • component 1 ) and/or 2) of the preferred catalyst system may be supported or unsupported. Where a component of the preferred catalyst system is utilized in supported form, it is preferred that component 2) of the preferred catalyst system is supported.
  • Suitable supports include carbon, activated carbon, silica, zirconia, alumina, alumina-silica, silicon carbide, zeolites, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, clays and combinations thereof.
  • the support is selected from silica, titanium oxide and activated carbon. Any method of which the person skilled in the art is aware for generating supported metallic catalysts may be used for generating a supported catalyst component.
  • a supported catalyst may be prepared by dissolving the chosen catalyst component in a suitable solvent, such as water, ethers, alcohols, carboxylic acids, ketones and aldehydes, preferably water or alcohols. The mixture may then be added to the chosen support or, alternatively, the support is immersed in the mixture.
  • a suitable solvent such as water, ethers, alcohols, carboxylic acids, ketones and aldehydes, preferably water or alcohols.
  • An impregnated support may then be recovered using any conventional separation technique, including, for example, decantation and/or filtration. Once recovered, the impregnated support may be dried, preferably by placing the support in an oven at elevated temperature. Alternatively, or additionally, a desiccator may be employed. For the purposes of the present invention, one or two of the at least two components of the heterogeneous catalyst system may be adsorbed onto the support such that the active component(s) is present in an amount of 0.05-50wt.%, based on the weight of the supported catalyst component.
  • Steps iii) and/or v) of the further aspect of the invention may be conducted via a batch or continuous mode of operation.
  • a batch mode operation the cellulosic feedstock, reaction medium and catalyst are typically combined in the presence of hydrogen, stirred and allowed to react for a suitable amount of time.
  • An adequate contact time for the catalytic reaction to proceed sufficiently is at least 5 minutes.
  • the reaction mixture is removed from the reaction vessel and the constituents separated and product ethylene glycol recovered.
  • a cellulosic feedstock containing stream is continuously fed into a reaction zone, whilst an ethylene glycol product/effluent stream is continuously being withdrawn.
  • the reaction zone may include separate feed streams for feedstock and hydrogen.
  • the feed stream for the feedstock may also comprise reaction medium, optionally any acidic species for modifying pH of the reaction, as well as components of the catalyst system, or alternatively these may be fed to the reaction zone separately.
  • One or more components of the catalyst system may be immobilized in the reaction zone, for instance, as part of a catalyst bed reactor system.
  • contacting step iii) may include passing the cellulosic feedstock and reaction medium through a column packed with the supported catalyst system component(s) (i.e. a packed bed arrangement).
  • the cellulosic feedstock may be passed through a column containing the supported catalyst system component(s).
  • the cellulosic feedstock will thus undergo catalytic reaction in the presence of the at least partially supported catalyst and hydrogen, following which an effluent stream may be removed from the column comprising ethylene glycol.
  • a fixed-bed arrangement having a plurality of plates and/or trays may be used.
  • the reaction mixture removed from the reaction vessel / effluent stream may comprise by-product polyols, such as 1 ,2-propylene glycol and glycerol, other alcohols, aldehydes, unreacted saccharides, phenolic compounds and any acidic species used for modifying the pH of the reaction mixture.
  • Solid components of the reaction mixture, in particular components of the catalyst system may be separated by, for instance, by filtration, centrifugation, hydrocyclone, fractionation, extraction, evaporation, or combinations thereof. In this way, it is possible to isolate components of the catalyst system such that they may be recycled.
  • the process of the invention further comprises a step of recycling one or more of the catalyst system components.
  • the present invention also provides a use of a cellulosic feedstock obtained by the process described hereinbefore for preparing ethylene glycol.
  • a cellulosic feedstock obtained by the process described hereinbefore for preparing ethylene glycol.
  • Deep eutectic solvents based on mixtures of malic acid or lactic acid with choline chloride ((ChCI)(Mal) and (ChCI(Lac) respectively) were chosen for the pretreatment of empty fruit bunches (EFB), a form of oil palm biomass.
  • the DESs were each prepared by adding one of the alpha-hydroxy acids and choline chloride at a molar ratio of 1.2:1 to water solvent. The aqueous mixture was then heated to 60 °C and stirred for approximately 16 hours before the water component of the mixture was removed by slow rotary evaporation (3 kPa) for 3 hours at 70 °C, after which a eutectic mixture was obtained.
  • EFB biomass was contacted in a reaction vessel with deep eutectic solvent at a temperature and for a time period indicated below.
  • a cellulosic material was subsequently obtained from the reaction mixture.
  • the Crystallinity Index of the cellulose was measured using nuclear magnetic resonance ( 13 C NMR) with "cross polarization and magic angle spinning" (CP/MAS).
  • CP/MAS nuclear magnetic resonance
  • a sample of the cellulosic material was hydrolysed in order to assess its sugar monomer composition. The assessment was made according to the NREL Laboratory Analytical Procedure (LAP) (version 07-08-2011 ) entitled "Determination of Structural Carbohydrates and Lignin in Biomass".
  • LAP NREL Laboratory Analytical Procedure
  • a sample is hydrolysed in a two-step hydrolysis, whereupon the cellulosic material is converted into its monomeric form, before quantifying with HPLC with refractive index detector.
  • Comparative Example 4 The process of Comparative Example 2 was repeated, except that 1 wt.% sulfuric acid solution was added until a reaction mixture was formed having a pH of 6. Results are presented in Table 4 below. Comparative Example 4

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de solubilisation et d'élimination sélectif des composants de lignine et d'hémicellulose d'une biomasse cellulosique et l'obtention d'une charge cellulosique ayant une proportion plus élevée de cellulose, comparativement à la biomasse à partir de laquelle elle est dérivée, et ayant un indice de cristallinité cellulosique plus élevé. En particulier, le procédé comprend : i) la mise en contact de la biomasse cellulosique avec un solvant eutectique profond (DES) formé à partir d'un mélange de a) un dérivé de choline choisi parmi le chlorure de choline, le chlorure de chlorocholine, l'acétate de choline, le chlorure d'acétylcholine ou la phosphatidylcholine ; et b) un acide alpha-hydroxy carboxylique ; et ii) l'obtention d'une charge cellulosique solide ayant une proportion plus élevée de composant de cellulose, comparativement à la biomasse cellulosique de l'étape i), la majorité de la charge cellulosique obtenu à l'étape ii) étant obtenue sans régénérer la cellulose par précipitation.
PCT/EP2015/070299 2014-09-05 2015-09-04 Extraction sélective et conversion d'une charge cellulosique en éthylène glycol Ceased WO2016034727A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2014002585 2014-09-05
MYPI2014002585A MY182605A (en) 2014-09-05 2014-09-05 Selective extraction and conversion of a cellulosic feedstock to ethylene glycol

Publications (1)

Publication Number Publication Date
WO2016034727A1 true WO2016034727A1 (fr) 2016-03-10

Family

ID=54185932

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/070299 Ceased WO2016034727A1 (fr) 2014-09-05 2015-09-04 Extraction sélective et conversion d'une charge cellulosique en éthylène glycol

Country Status (2)

Country Link
MY (1) MY182605A (fr)
WO (1) WO2016034727A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106755189A (zh) * 2016-10-31 2017-05-31 广东工业大学 一种利用两种深度共熔溶剂分步预处理以提高水稻秸秆中纤维素酶解效率的绿色方法
CN107760739A (zh) * 2017-09-30 2018-03-06 江南大学 一种新型双氢键低共熔溶剂及结合碳酸钠预处理水稻秸秆的方法
CN107904266A (zh) * 2017-12-18 2018-04-13 湘潭大学 一种高效绿色提高木质纤维素酶解糖化效率的预处理方法及应用
CN108441530A (zh) * 2018-03-13 2018-08-24 北京化工大学 一种利用碱性低共熔溶剂预处理木质纤维素的方法
CN109824912A (zh) * 2019-01-16 2019-05-31 中国科学院广州能源研究所 一种木质纤维生物质水解联产丁烯二酸和木质素的方法
WO2019140245A1 (fr) * 2018-01-12 2019-07-18 Tyton Biosciences, Llc Procédés de recyclage de fibres de coton et de polyester à partir de déchets textiles
CN110694618A (zh) * 2019-10-12 2020-01-17 华南理工大学 一种钌基催化剂在深度低共熔溶剂条件下对木质素进行加氢脱氧的方法
CN110947421A (zh) * 2019-11-19 2020-04-03 华侨大学 一种功能化木质素负载低共熔溶剂异相催化剂的制备方法及其在二氧化碳化学转化中的应用
WO2020229732A1 (fr) * 2019-05-15 2020-11-19 Lappeenrannan-Lahden Teknillinen Yliopisto Lut Procédé de fractionnement d'une matière lignocellulosique et produits obtenus selon ledit procédé
CN111979280A (zh) * 2020-09-11 2020-11-24 东北林业大学 一种多氢键缔合溶剂及利用木质纤维制备葡萄糖的方法
WO2020234761A1 (fr) * 2019-05-23 2020-11-26 Politecnico Di Milano Procédé de traitement de biomasse
CN112144309A (zh) * 2020-10-13 2020-12-29 北京林业大学 一种木质纤维主要组分清洁分离的方法
CN112411235A (zh) * 2020-11-24 2021-02-26 陕西科技大学 一种豆渣纳米纤维素的清洁高效尺寸可控制备方法
CN112411230A (zh) * 2020-11-24 2021-02-26 陕西科技大学 一种超疏水豆渣纳米纤维素薄膜及清洁制备该薄膜的方法
CN112458121A (zh) * 2020-11-27 2021-03-09 江南大学 一种水葫芦的预处理和糖化方法
CN112501458A (zh) * 2020-11-12 2021-03-16 浙江大学 利用苄基季铵盐低共熔溶剂选择性萃取分离废催化剂浸出液中钼的方法
CN113149023A (zh) * 2021-03-11 2021-07-23 昆明理工大学 一种介孔二氧化硅纳米颗粒经皮递送低共熔体系制备方法
CN114351493A (zh) * 2021-12-08 2022-04-15 华南理工大学 一种去除胞间层木质素的方法
CN114514216A (zh) * 2019-09-25 2022-05-17 国际壳牌研究有限公司 用于产生二醇的木质纤维素进料的预处理
WO2023096956A1 (fr) * 2021-11-23 2023-06-01 Energy Solutions (US) LLC Suspensions polymères aqueuses sans danger pour l'environnement
US12331157B2 (en) 2021-09-16 2025-06-17 Circ, LLC Method of forming a polyester from a regenerated diacid formed from depolymerization of a waste material

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4404411A (en) 1982-02-01 1983-09-13 E. I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol in nonaqueous solvents
US4959158A (en) 1989-03-30 1990-09-25 The United States Of America As Represented By The Unitd States Department Of Energy Method for separating disparate components in a fluid stream
US5571070A (en) 1996-01-16 1996-11-05 Costner Industries Nevada, Inc. Rotor sleeve for a centrifugal separator
US5591340A (en) 1995-09-01 1997-01-07 Costner Industries Nevada, Inc. Centrifugal separator
WO1999012650A1 (fr) 1997-09-11 1999-03-18 Costner Industries Nevada, Inc. Rotor autonettoyant pour separateur centrifuge
WO2000029120A1 (fr) 1998-11-16 2000-05-25 Costner Industries Nevada, Inc. Ensemble rotor pour separateur centrifuge
US20090247432A1 (en) 2008-03-26 2009-10-01 Shrieve Chemical Products, Inc. Deep eutectic solvents and applications
US20100255983A1 (en) 2008-08-14 2010-10-07 Tao Zhang Tungsten carbide catalysts, their preparation and application in synthesis of ethylene glycol from cellulose
WO2011155829A1 (fr) 2010-06-07 2011-12-15 Universiteit Leiden Procédés d'extraction de matériaux à partir d'un matériau biologique
CN102731254A (zh) 2011-12-20 2012-10-17 中国科学院大连化学物理研究所 一种以玉米秸秆和/或高粱秸秆为原料制备乙二醇的方法
WO2013102911A1 (fr) * 2012-01-03 2013-07-11 Council Of Scientific & Industrial Research Procédé de conversion chimique de la cellulose extraite d'une biomasse aromatique en hydroxyméthyl furfural
US20130252285A1 (en) 2010-09-22 2013-09-26 The Regents Of The University Of California Ionic liquid pretreatment of cellulosic biomass: enzymatic hydrolysis and ionic liquid recycle
WO2013153203A1 (fr) * 2012-04-12 2013-10-17 Technische Universiteit Eindhoven Prétraitement de biomasse lignocellulosique et récupération de substituants au moyen de mélanges naturels de solvants eutectiques profonds (des)/composés présentant des températures de transition basses
WO2015128550A1 (fr) * 2014-02-28 2015-09-03 Teknologian Tutkimuskeskus Vtt Oy Solvants de type mélanges eutectiques profonds et leur utilisation

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4404411A (en) 1982-02-01 1983-09-13 E. I. Du Pont De Nemours And Company Hydrogenolysis of polyols to ethylene glycol in nonaqueous solvents
US4959158A (en) 1989-03-30 1990-09-25 The United States Of America As Represented By The Unitd States Department Of Energy Method for separating disparate components in a fluid stream
US5591340A (en) 1995-09-01 1997-01-07 Costner Industries Nevada, Inc. Centrifugal separator
US5762800A (en) 1995-09-01 1998-06-09 Costner Industries Nevada, Inc. Centrifugal separator
US5571070A (en) 1996-01-16 1996-11-05 Costner Industries Nevada, Inc. Rotor sleeve for a centrifugal separator
WO1999012650A1 (fr) 1997-09-11 1999-03-18 Costner Industries Nevada, Inc. Rotor autonettoyant pour separateur centrifuge
WO2000029120A1 (fr) 1998-11-16 2000-05-25 Costner Industries Nevada, Inc. Ensemble rotor pour separateur centrifuge
US20090247432A1 (en) 2008-03-26 2009-10-01 Shrieve Chemical Products, Inc. Deep eutectic solvents and applications
US20100255983A1 (en) 2008-08-14 2010-10-07 Tao Zhang Tungsten carbide catalysts, their preparation and application in synthesis of ethylene glycol from cellulose
WO2011155829A1 (fr) 2010-06-07 2011-12-15 Universiteit Leiden Procédés d'extraction de matériaux à partir d'un matériau biologique
US20130252285A1 (en) 2010-09-22 2013-09-26 The Regents Of The University Of California Ionic liquid pretreatment of cellulosic biomass: enzymatic hydrolysis and ionic liquid recycle
CN102731254A (zh) 2011-12-20 2012-10-17 中国科学院大连化学物理研究所 一种以玉米秸秆和/或高粱秸秆为原料制备乙二醇的方法
WO2013102911A1 (fr) * 2012-01-03 2013-07-11 Council Of Scientific & Industrial Research Procédé de conversion chimique de la cellulose extraite d'une biomasse aromatique en hydroxyméthyl furfural
WO2013153203A1 (fr) * 2012-04-12 2013-10-17 Technische Universiteit Eindhoven Prétraitement de biomasse lignocellulosique et récupération de substituants au moyen de mélanges naturels de solvants eutectiques profonds (des)/composés présentant des températures de transition basses
WO2015128550A1 (fr) * 2014-02-28 2015-09-03 Teknologian Tutkimuskeskus Vtt Oy Solvants de type mélanges eutectiques profonds et leur utilisation

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
J. AM. CHEM. SOC., vol. 126, no. 29, 2004, pages 9142 - 9147
PARK ET AL., BIOTECHNOLOGY FOR BIOFUELS. CELLULOSE CRYSTALLINITY INDEX: MEASUREMENT TECHNIQUES AND THEIR IMPACT ON INTERPRETING CELLULOSE PERFORMANCE, vol. 3, 2010, pages 10
ZHANG ET AL.: "Green and Inexpensive Choline-Derived Solvents for Cellulose Decrystallization", CHEMISTRY - A EUROPEAN JOURNAL, vol. 18, 2012, pages 1043 - 1046

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106755189B (zh) * 2016-10-31 2021-01-05 广东工业大学 一种利用两种深度共熔溶剂分步预处理以提高水稻秸秆中纤维素酶解效率的绿色方法
CN106755189A (zh) * 2016-10-31 2017-05-31 广东工业大学 一种利用两种深度共熔溶剂分步预处理以提高水稻秸秆中纤维素酶解效率的绿色方法
CN107760739A (zh) * 2017-09-30 2018-03-06 江南大学 一种新型双氢键低共熔溶剂及结合碳酸钠预处理水稻秸秆的方法
CN107904266A (zh) * 2017-12-18 2018-04-13 湘潭大学 一种高效绿色提高木质纤维素酶解糖化效率的预处理方法及应用
US12006403B2 (en) 2018-01-12 2024-06-11 Circ, LLC Methods for recycling cotton and polyester fibers from waste textiles
US11370895B2 (en) 2018-01-12 2022-06-28 Circ, LLC Methods for recycling cotton and polyester fibers from waste textiles
US10501599B2 (en) 2018-01-12 2019-12-10 Tyton Biosciences, Llc Methods for recycling cotton and polyester fibers from waste textiles
US11180629B2 (en) 2018-01-12 2021-11-23 Circ, LLC Methods for recycling cotton and polyester fibers from waste textiles
WO2019140245A1 (fr) * 2018-01-12 2019-07-18 Tyton Biosciences, Llc Procédés de recyclage de fibres de coton et de polyester à partir de déchets textiles
CN108441530B (zh) * 2018-03-13 2021-10-08 北京化工大学 一种利用碱性低共熔溶剂预处理木质纤维素的方法
CN108441530A (zh) * 2018-03-13 2018-08-24 北京化工大学 一种利用碱性低共熔溶剂预处理木质纤维素的方法
CN109824912B (zh) * 2019-01-16 2020-12-18 中国科学院广州能源研究所 一种木质纤维生物质水解联产丁烯二酸和木质素的方法
CN109824912A (zh) * 2019-01-16 2019-05-31 中国科学院广州能源研究所 一种木质纤维生物质水解联产丁烯二酸和木质素的方法
WO2020229732A1 (fr) * 2019-05-15 2020-11-19 Lappeenrannan-Lahden Teknillinen Yliopisto Lut Procédé de fractionnement d'une matière lignocellulosique et produits obtenus selon ledit procédé
WO2020234761A1 (fr) * 2019-05-23 2020-11-26 Politecnico Di Milano Procédé de traitement de biomasse
US20220213276A1 (en) * 2019-05-23 2022-07-07 Politecnico Di Milano Processes for biomass treatments
CN114514216B (zh) * 2019-09-25 2023-12-15 国际壳牌研究有限公司 用于产生二醇的木质纤维素进料的预处理
CN114514216A (zh) * 2019-09-25 2022-05-17 国际壳牌研究有限公司 用于产生二醇的木质纤维素进料的预处理
CN110694618B (zh) * 2019-10-12 2021-09-21 华南理工大学 一种钌基催化剂在深度低共熔溶剂条件下对木质素进行加氢脱氧的方法
CN110694618A (zh) * 2019-10-12 2020-01-17 华南理工大学 一种钌基催化剂在深度低共熔溶剂条件下对木质素进行加氢脱氧的方法
CN110947421B (zh) * 2019-11-19 2022-06-07 华侨大学 一种功能化木质素负载低共熔溶剂异相催化剂的制备方法及其在二氧化碳化学转化中的应用
CN110947421A (zh) * 2019-11-19 2020-04-03 华侨大学 一种功能化木质素负载低共熔溶剂异相催化剂的制备方法及其在二氧化碳化学转化中的应用
CN111979280B (zh) * 2020-09-11 2022-04-15 东北林业大学 一种多氢键缔合溶剂及利用木质纤维制备葡萄糖的方法
CN111979280A (zh) * 2020-09-11 2020-11-24 东北林业大学 一种多氢键缔合溶剂及利用木质纤维制备葡萄糖的方法
CN112144309B (zh) * 2020-10-13 2022-03-11 北京林业大学 一种木质纤维主要组分清洁分离的方法
CN112144309A (zh) * 2020-10-13 2020-12-29 北京林业大学 一种木质纤维主要组分清洁分离的方法
CN112501458A (zh) * 2020-11-12 2021-03-16 浙江大学 利用苄基季铵盐低共熔溶剂选择性萃取分离废催化剂浸出液中钼的方法
CN112411230A (zh) * 2020-11-24 2021-02-26 陕西科技大学 一种超疏水豆渣纳米纤维素薄膜及清洁制备该薄膜的方法
CN112411235A (zh) * 2020-11-24 2021-02-26 陕西科技大学 一种豆渣纳米纤维素的清洁高效尺寸可控制备方法
CN112458121A (zh) * 2020-11-27 2021-03-09 江南大学 一种水葫芦的预处理和糖化方法
CN113149023A (zh) * 2021-03-11 2021-07-23 昆明理工大学 一种介孔二氧化硅纳米颗粒经皮递送低共熔体系制备方法
CN113149023B (zh) * 2021-03-11 2023-05-02 昆明理工大学 一种介孔二氧化硅纳米颗粒经皮递送低共熔体系制备方法
US12331157B2 (en) 2021-09-16 2025-06-17 Circ, LLC Method of forming a polyester from a regenerated diacid formed from depolymerization of a waste material
WO2023096956A1 (fr) * 2021-11-23 2023-06-01 Energy Solutions (US) LLC Suspensions polymères aqueuses sans danger pour l'environnement
CN114351493A (zh) * 2021-12-08 2022-04-15 华南理工大学 一种去除胞间层木质素的方法

Also Published As

Publication number Publication date
MY182605A (en) 2021-01-26

Similar Documents

Publication Publication Date Title
WO2016034727A1 (fr) Extraction sélective et conversion d'une charge cellulosique en éthylène glycol
TWI735409B (zh) 令包含醣類之原料變爲乙二醇之選擇性轉化
Cheng et al. A high-solid DES pretreatment using never-dried biomass as the starting material: towards high-quality lignin fractionation
Vom Stein et al. From biomass to feedstock: one-step fractionation of lignocellulose components by the selective organic acid-catalyzed depolymerization of hemicellulose in a biphasic system
EP2807175B1 (fr) Procédé destiné à la récupération de saccharides à partir d'un mélange réactionnel d'hydrolyse de cellulose
EP2513080B1 (fr) Procédé de production de furfural à partir d'un matériau biomassique lignocellulosique
Krishania et al. Integrated approach for extraction of xylose, cellulose, lignin and silica from rice straw
US10532990B2 (en) Methods for converting cellulose to furanic products
CN112574009B (zh) 一种提高生物质的木质素分级分离和解聚的方法及其应用
CN104395478A (zh) 处理生物质以生产可用于生物燃料的材料的连续或半连续方法
WO2012064701A1 (fr) Procédé de fabrication de combustibles hydrocarbures liquides directement à partir d'une biomasse lignocellulosique
US10253009B2 (en) One-step production of furfural from biomass
EP3129346B1 (fr) Procédé de traitement de biomasse
He et al. Fractionation of poplar wood using a bifunctional aromatic acid under mild conditions
WO2013102911A1 (fr) Procédé de conversion chimique de la cellulose extraite d'une biomasse aromatique en hydroxyméthyl furfural
Win et al. Investigation of organosolv and hot-compressed water pretreatments of rice straw
Hu et al. Integrated strategies for furfural production and lignocellulose fractionation in aqueous deep eutectic solvents
Fúnez-Núñez et al. Recovery of pentoses-containing olive stones for their conversion into furfural in the presence of solid acid catalysts
Sunar et al. Green approach on pretreatment of rice straw using deep eutectic solvent for lignin recovery and efficient hydrolysis
US20240199565A1 (en) Process for producing furfural and catalyst for use in same
JP6882175B2 (ja) 混合溶媒を使用したフルフラールの調製
Yang et al. Upgrading straw for lignin separation and levulinic acid production using lactic acid DES and HSO3-based ionic liquids
Ravindra et al. Pure hydrolyzable cellulose from rice straw, wheat straw and sugarcane bagasse by a simple scalable two-step treatment
Yang et al. One-pot lignocellulose fractionation towards efficient whole sugar conversion and aromatic monomer production using a mild alkaline oxidation system
Pérez-Merchán et al. An integrated biorefinery approach based on spent coffee grounds valorization

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15767439

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC

122 Ep: pct application non-entry in european phase

Ref document number: 15767439

Country of ref document: EP

Kind code of ref document: A1