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WO2012131665A1 - Traitement de la lignocellulose - Google Patents

Traitement de la lignocellulose Download PDF

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Publication number
WO2012131665A1
WO2012131665A1 PCT/IE2012/000014 IE2012000014W WO2012131665A1 WO 2012131665 A1 WO2012131665 A1 WO 2012131665A1 IE 2012000014 W IE2012000014 W IE 2012000014W WO 2012131665 A1 WO2012131665 A1 WO 2012131665A1
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Prior art keywords
reactor
hydrogen peroxide
lignocellulose
mixture
oxygen
Prior art date
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PCT/IE2012/000014
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English (en)
Inventor
Donncha Haverty
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University of Limerick
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University of Limerick
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Priority to BR112013024925A priority Critical patent/BR112013024925A2/pt
Priority to EP12716644.5A priority patent/EP2694723A1/fr
Publication of WO2012131665A1 publication Critical patent/WO2012131665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/08—Pretreatment of the finely-divided materials before digesting with oxygen-generating compounds
    • 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
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D21C3/026—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of O2, e.g. air
    • 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
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • 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
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • 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
    • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
    • D21C3/06—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides sulfur dioxide; sulfurous acid; bisulfites sulfites

Definitions

  • the invention relates to processing of biomass, cellulosic material, natural materials containing biopolymers of largely C5 and or C6 sugars, generally referred to in this specification as "lignocellulose”.
  • Second and third generation bio-refineries are intended to use non-food biomass sources namely lignocellulosic renewable energy crops or wastes such as miscanthus, corn stow over and wood waste for saw mills among others to produce sugars and ultimately compounds that can be employed as fuels, fuel additives and or platform starting materials for the production of valuable chemicals.
  • Typical lignocellulosic materials comprise three substantial biopolymer components, cellulose, hemi-cellulose and lignin.
  • the holo-cellulose, polymers of six and five carbon sugars are hydrolysed, usually under acidic conditions at elevated temperature or through enzymatic fermentation, sequentially to oligomers and sugars.
  • these sugars are converted to either Levulinic Acid (LA) or Furfural (FUR) respectively with a number of other intermediates being formed in the sequence such as Hydroxy-Methyl-Furfural (HMF) while in fermentation the sugars are converted to ethanol and other chemicals such as sussinic acid.
  • LA Levulinic Acid
  • FUR Furfural
  • Second and third generation bio-refineries seek to incorporate multiple operations and strive to utilise all components of the biomass including the lignin such as for example through combined heat and power plants to combust it once separated from the sugar content making use of its higher heating value to supply energy or through gasification and pyro lysis operations to produce bio-oils and or bio-char for use as a soil amender and carbon recycling.
  • Second and third generation bio-refineries seek to incorporate multiple operations and strive to utilise all components of the biomass including the lignin such as for example through combined heat and power plants to combust it once separated from the sugar content making use of its higher heating value to supply energy or through gasification and pyro lysis operations to produce bio-oils and or bio-char for use as a soil amender and carbon recycling.
  • fractionated from the biomass several other lignin uses are under investigation including the production of fuels and polymers therefrom.
  • Physical pretreatments for the conversion of Lignocellulose include ball milling, knife milling and the like, the resulting reduction in the particle size and or the crystallinity of the cellulose content increasing the surface area available for enzymatic or chemical attack in subsequent hydrolysis operations and generally rendering the lignocellulose more amenable to digestion.
  • Studies on various biomasses and indeed pure cellulose compounds have shown that below a particle size of approx 800 micron the rate of cellulose acid hydrolysis is purely kinetic and that mass transfer is not limiting implying that the expenditure of energy in physical processes to reduce the particle size beyond this minimum is wasteful [1].
  • the cost of physical commutation operations is expensive given the capital and operational costs involved and particularly as this mechanical energy input is not readily recovered for reuse.
  • Enzymatic or biological pretreatments involve exposing the lignocellulose to organisms including actinomycetes and other fungi that secrete extracellular enzymes (lignin peroxidases and lactases) that preferentially degrade the lignin content rendering the remaining cellulosic biomass more amenable to hydrolysis.
  • Biological pretreatments are low energy intensive processes they require long residence times of the order of tens of days, are highly susceptible to changes in their environment (conditions of temperature and ph, substrate composition, the presence of components that are toxic to the micro-organisms etc) and consume a fraction of the sugar content to sustain their growth reducing achievable yields of sugars and chemicals derived there from down stream.
  • the microbial or fungal biomass in the resulting mixtures must be separated from the sugar or holo-cellulose containing liquor introducing additional process operations with added operational and capital cost implications.
  • Solvent fractionation pretreatments include the Organosolv process (for example HALLBERG et al WO/2008/144878) in which the lignocellulose material is exposed to organic solvents (usually alcohols) under acidic conditions at temperatures in the range 90-220°C for periods varying from minutes to hours depending on the recalcitrance of the starting biomass.
  • organic solvents usually alcohols
  • the process is intended to produce an insoluble cellulose fraction that is rendered more amenable to digestion by subsequent chemical or enzymatic hydrolysis.
  • the hemi-cellulose, lignin and other extractives are dissolved in the liquid organic phase which can be separated from the cellulosic content for further processing.
  • the process requires the input of heat and the use of expensive solvents which must be recovered and recycled through the construction of additional unit operations.
  • Proportions of the hemicellulose are also converted to furfural analogues as well as oligosaccarides and sugars under the acidic conditions and these compounds are known to be toxic to micro-organisms used in fermentation processes requiring that the furanic components as well as the acid and solvents be removed from the resulting cellulose if intended for subsequent enzymatic hydrolysis to produce ethanol.
  • a fractionation process employing multiple extraction steps with various solvents including mineral acids and organic solvents to produce an amorphous cellulose for subsequent hydrolysis in a fermentor is disclosed by ZHANG, in WO/2007/111605.
  • the process while requiring moderate temperatures requires multiple unit operations to separate components and recover the process chemicals.
  • ionic liquids are ionic compounds usually with organic cations that are liquid at room to moderate temperatures. Depending on the temperature, duration of exposure and the nature of the ionic liquid used these solvents can preferentially dissolve hemi-cellulose and lignin from lignocellulosic biomass facilitating fractionation or dissolve the entire biomass including the cellulose.
  • Ionic liquids of use in the solubilisation of lignocellulose biomass include alkylated imadizaloium chlorides, bromides, fluoro-phosphonates and sulphonates among others.
  • ionic liquids contain anions of halogen compounds that may not be environmentally optimum in the context of an overall biorefining operation where even trace concentrations introduced to pyrolysis or combustion operations is not desirable.
  • Aqueous solutions containing Lewis acids that operate to disrupt the lignocellulose bonding in a similar manner to ionic liquids have also been disclosed (e.g. US20100004437 to Binder et al) as effective pretreatment technologies for fractionation, including the aluminium and chromium salts of chlorine and other halogens. These materials however may be less than environmentally optimal for the same reasons discussed above. Dilute acid hydrolysis
  • Dilute acid hydrolysis has been employed for the preferential hydrolysis of hemicellulose and partial solubilisation of lignin prior to further treatments typically with temperatures in the range 100- 220°C, and mineral acid concentration up to 10% by mass and solid loadings up to 30%.
  • a severity index called the combined severity factor (CSF) has been defined, [2] being representative of the acidic concentration, temperature and duration of exposure to a given set of conditions.
  • CSF combined severity factor
  • the lower severity factor will be chosen to remove the hemicellulose and partially solubilise the lignin by converting it to lower molecular weight lignols, the resulting cellulosic material must be washed of acid, and furanic compounds prior to fermentation.
  • platform chemicals such as FUR and LA
  • prolonged exposure of the lignocellulosic material to acid medium at high temperatures (high CSF) will also result in the hydrolysis of the hemi-cellulose and cellulose to FUR and LA respectively.
  • Fitzpatrick EP 19890905916 discloses a continuous two stage reactor system employing dilute acid hydrolysis for the complete conversion of lingocellulose to FUR and LA comprising subjecting lignocellulose to acid concentrations between 2% and 7% at high temperature >200°C in a first plug flow reactor for less than a minute.
  • a subsequent pressure drop in a flash vessel removes a large portion of the hydrolysed hemicellulose content as FUR in the gas phase, while the liquid phase containing the now more digestible cellulose and lignin is fed to a second reactor operating at lower temperatures and longer residence times where the cellulose is converted to LA.
  • the reduced temperature of the second reactor is expected to favour the conversion of cellulose to glucose and LA as opposed to the condensation products that are known to form from these substrates via undesirable parallel reactions under acidic conditions [1].
  • the short residence times at high temperature needed to reduce the recalcitrance of the starting material is achieved through direct steam injection which facilitates very rapid heating.
  • Dilute acid hydrolysis requires physical commutation to reduce mass transfer dependencies on the reaction rates and in the case of the two stage process of Fitzpatrick the provision of high pressure steam at greater than 30 bar.
  • the combination of high temperature and low pH is severe on process equipment.
  • U.S. Patent No. 4,515,816 to Anthony is directed to a process in which lignocellulose is treated with dilute acid in an amount of about 1.5 to 2.5% of the dry weight of lignocellulose.
  • the mixture is the stored at ambient conditions for 5 to 21 days in an air-free environment.
  • Alkaline treatments borrow from the paper industry where alkaline and oxidative media are extensively used to bleach cellulose for paper production.
  • cellulose is not hydrolysed to any great extent when exposed to alkaline conditions provided the pH is not too high or the duration of exposure not too long.
  • lignin is degraded to lower molecular weight lignols soluble in alkaline aqueous solution.
  • WO/1994/003646 to Holtzapple discloses an alkaline pretreatment using calcium hydroxide and oxygen at high pressure in the pH range 8-10.5 resulting in a delignified cellulosic solid phase and a liquid phase containing dissolved lignin and hemicellulose.
  • US4644060 to Chou is directed to the use of super critical ammonia to increase lignocellulose digestibility.
  • US3878304 to Moore is directed to using an amide where urea is reacted with waste carbohydrates in the presence of an acid catalyst.
  • US3, 944,463 to Samuelson et al. is directed to a process for producing cellulose pulp of high brightness.
  • the cellulose is pretreated with an alkaline compound (sodium carbonate, sodium bicarbonate or mixtures thereof) at a temperature of between about 60°C to about 200°C so as to dissolve between 1 and 30% of the dry weight of the material in the pretreatment liquor.
  • an alkaline compound sodium carbonate, sodium bicarbonate or mixtures thereof
  • US4,048,341 to Lagerstrom et al. is directed to a process for increasing the feed value of lignocellulosic material by contacting the material with an alkaline liquid, specifically, sodium hydroxide.
  • US4, 182,780 to Lagerstrom et al. is directed to a process for increasing the feed value of lignocellulosic materials by alkali treatment and subsequent neutralization of the materials with an acid in a closed system under circulation of the treating agents.
  • US4113553 to Samuelson is directed toward a process for pulping hardwood to produce cellulose using sodium sulfide at a pH of about 10.5 to about 13 at temperatures in the range 110° to about 170°C. Hydrogen sulfide is generated in situ by reaction of sodium sulfide with organic acids liberated in the pulping process.
  • Wingerson et al. describe a multi zone reactor system in WO/2002/014598 involving the exposure of lignocellulose to an alkaline wash liquid having a pH between 8 and 13 at pressure and elevated temperature to remove lignin and hemicellulose with a subsequent flash (explosive pressure drop) to produce substantially pure cellulose with low lignin content.
  • the AFEX (Ammonia Fibre Expansion) pretreatment process soaks lignocellulose in liquid ammonia at high pressure and then explosively releases the pressure to increase accessible surface area and reduce cellulose crystallinity. Pre- treatment conditions (30°C - 100°C) are less severe than steam explosion.
  • U.S. Patents 4356196 4600590, 5037663, 5171592, 6416621 and 6176176 among others disclose variations on the AFEX process. Ammonia does not produce by products that are toxic to ethanol producing microbes and is particularly suited to pre-treating biomass intended for fermentation but it is a costly chemical and hazardous to handle. Oxidative pre-treatments
  • Oxidising agents can be used to remove lignin and hemi-cellulose form lignocellulose biomass to produce cellulose that is more amenable to digestion.
  • these oxidants may react selectively with the hemicellulose and or the alkyl and aryl linkages within the lignin breaking the polymer into lignols and dissociating it for the carbohydrate polymers.
  • prolonged exposure of the biomass to the oxidising environment particularly at elevated temperature can result in hemicellulose and cellulose degradation resulting in reduced sugar yields.
  • Oxidants that have been used in the pre-treatment of lignocellulose biomass include air, oxygen, ozone, permanganate, sulphite and hydrogen peroxide.
  • oxidising pretreatments are employed in the paper industry where the oxidation is carried out under alkaline conditions to prevent the degradation of the cellulose.
  • An example of a process that utilises sulphites is the patent of Ingruber et al (US3630832) and an example of a patent utilizing ozone is US4451567 to Ishibasbi.
  • US3939286 to Jelks is directed to oxidizing biomass with high-pressure oxygen under elevated temperature and pressure in the presence of an acid catalyst, and a metal catalyst, to break lignin bonds and to increase digestibility.
  • the catalysts are described as essential to the process and calcium hydroxide is utilized as a neutralizing agent to adjust the resulting pH of the hydrolyzed biomass for use as an animal feed.
  • US4,842,877 to Tyson is directed to a process for the delignification of non-woody biomass ( ⁇ 20% lignin).
  • non-woody biomass is treated with a chelating agent, to prevent unnecessary oxidation, and maintained at alkaline, high pH and high temperature in the presence of hydrogen peroxide and pressurized oxygen.
  • Hydrogen peroxide is stated to cause a reaction on the cell walls to allow the hemicellulose and lignin to solubilize and be removed through a subsequent hydrolysis process.
  • Oxygen is added to initiate and accelerate the activation of hydrogen peroxide.
  • Impregnation of the biomass with peroxide and ferric salts in solutions at concentrations up to lOOmmol and 20mmol peroxide and metal salt respectively are claimed to effect a significant improvements in the yields of glucose achievable in a subsequent hydrolysis step.
  • the present invention is directed toward such improvements.
  • a method of transforming a lignocellulose material comprising the steps of:
  • step d continuously removing from the flash vessel a gas stream substantially rich in oxygen and a separate heated liquid stream having suspended or dissolved therein chemically and physically altered components of the lignocellulose including a substantially cellulosic material with reduced recalcitrance relative to the starting lignocellulose material.
  • the hydrogen peroxide concentration is at least 5% by mass.
  • the pressure in the reactor for. step b is at least 35 bar.
  • the pressure change outlet used in step c is a Venturi.
  • the reactor is a plug flow or tubular reactor.
  • the stabiliser includes an acid, a pyrophosphate compound or combinations thereof, and wherein the agent is an enzyme, transition metal salt, an alkaline compound dissolved or suspended in solution, or combinations thereof.
  • the stabiliser includes an acid in combination with a transition metal salt, and wherein the agent includes an alkaline compound dissolved or suspended in solution.
  • the residence time in the reactor is up to 15 min.
  • the compressed oxygen exiting the flash vessel is used to drive motors, for example on pumps, stirrers, conveyors, shakers, vibrators, chippers, grinders, centrifuges and combinations thereof.
  • the oxygen is used for combustion or gasification operations.
  • the lignocellulose biomass is a plant material, a municipal waste, or combinations thereof.
  • physically altered components of the lignocellulose exiting the flash vessel in the liquid stream have a smaller particle size than the starting lignocellulose material. In one embodiment, the physically altered components of the lignocellulose are amenable to acid hydrolysis.
  • the liquid stream containing the physically altered components of the lignocellulose is fed to a second flash vessel or series of flash vessels and subjected to a pressure drop or series of pressure drops.
  • volatile furanic compounds, acids and alcohols contained in the liquid stream are separated into the gas phase in the second flash vessel or series of flash vessels.
  • the liquid stream exiting the second flash vessel or series of flash vessels is fed to a tank reactor, and wherein the cellulosic components, six carbon sugars and hydroxymethylfurfural contained therein is converted to Levulinic acid and formic acid.
  • the temperature in the tank reactor is up to 150°C.
  • cellulose is recovered from the liquid stream exiting the second flash vessel or series of flash vessels through pH adjustment, separation, and washing operations, or combinations thereof.
  • the separation operations include centrifugal separation, filtration, settling and combinations thereof.
  • the invention provides a system for transforming a lignocellulose material, the system comprising:
  • a reactor outlet providing a pressure change and a flash vessel, and means for exiting the mixture of gas, water and solids formed in the reactor through said outlet, into said flash vessel wherein the mixture is separated into a liquid phase containing dissolved or suspended solids and a gas phase substantially rich in oxygen, and
  • lignocellulose means for continusously removing from the flash vessel a gas stream substantially rich in oxygen and a separate heated liquid stream having suspended or dissolved therein chemically and physically altered components of the lignocellulose including a substantially cellulosic material with reduced recalcitrance relative to the starting lignocellulose material.
  • Fig. 1 is a diagram of a reactor of the invention
  • Figs. 2(a) to 2(d) are plots indicating temperature profiles and liquor compositions of pre- treated biomass, as set out in Example 1;
  • Fig. 3 is a set of SEM images for Example 1;
  • Fig. 4 is a plot illustrating glucose release in Example 2.
  • Fig. 5 is a plot illustrating glucose release during cellulose hydrolysis in Example 3. It is well known that hydrogen peroxide undergoes the following exemplary decomposition reactions:
  • This may be circumvented by keeping the exposure time of the biomass to a highly oxygenating environment to a minimum such as in a plug-flow or tubular reactor with a short residence time but this would require a mechanism to trigger the rapid decomposition of the peroxide in a short time period with a facility to remove the partially oxidised biomass from the oxygenating environment quickly thereafter before excessive oxidation could occur.
  • the present invention provides such a system.
  • Lignocellulosic biomass is mixed with hydrogen peroxide and optionally a hydrogen peroxide stabiliser at room temperature.
  • the stabiliser can be a stabiliser in conjunction with a hydrogen peroxide decomposition catalyst present in concentrations or at a pH that favours the overall stabilisation of the mixture at room to moderate temperatures such as for example the presence of a mineral acid (stabiliser) in sufficient concentration to maintain the pH below 3 in combination with ferric ions (decomposition catalyst).
  • Preferred stabilisers include sulphuric acid, nitric acid, phosphoric acid, formic acid and combinations thereof and preferred decomposition catalysts include ferric or ferrous salts and oxides, aluminium salts and oxides, salts and oxides of the alkali metals, alkaline earth and transition metals, supported metal catalysts such as those on siliceous, zirconium or alumna supports, enzymes and combinations thereof.
  • a mixture of up to 60% hydrogen peroxide (Aq) and up to 50% w/w dry lignocellulose biomass with a minimum sulphuric acid concentration of 0.0001 % w/w is relatively stable for sustained periods at room temperature in the presence of ferric sulphate up to concentrations of ferric ion that correspond to a molar ratio of up to 0.5; [Fe 3+ ]/[H + ], preventing excessive rapid decomposition of the peroxide.
  • ferric sulphate up to concentrations of ferric ion that correspond to a molar ratio of up to 0.5; [Fe 3+ ]/[H + ], preventing excessive rapid decomposition of the peroxide.
  • ferric sulphate up to concentrations of ferric ion that correspond to a molar ratio of up to 0.5; [Fe 3+ ]/[H + ], preventing excessive rapid decomposition of the peroxide.
  • ferric sulphate up to concentrations of ferric
  • this moderate activity may facilitate the swelling and softening of the recalcitrant biomass particles to the extent that it can be formed into a suspension that can be pumped more easily than a suspension of the raw biomass in water alone without effecting any significant change in temperature or the significant loss of peroxide or biomass.
  • This process may be carried out at atmospheric pressure.
  • the liquid phase and the sugars and lignols therein dissolved may be separated and recovered separately and fresh solution added on a continuous basis. Exposure times of up to 50 hours may be applied and, depending on the desired throughput a continuously stirred tank reactor ("CSTR") or semi batch reactor, may be sized accordingly to yield the appropriate residence time.
  • CSTR continuously stirred tank reactor
  • the resulting suspension may then be pumped, preferably via a pump that can operate with a high pressure differential across it, to a continuous plug flow or tubular reactor wherein an agent is added to effect the complete, rapid exothermic decomposition of the peroxide.
  • the preferred agent is a base that effects a reduction in the [H + ] concentration proximal to the entrance to the continuous tubular reactor.
  • the base may be a hydroxide or any suitable alkaline solution or suspension, added in sufficient quantity to change the pH of the reacting mixture to between 3 and 10.
  • the residence time in the PFR is up to 15 minutes and the temperature of the reaction mixture may be increased by up to 300°C in the reactor while the pressure may be increased by up to 300 bar.
  • the reaction mixture may then be exited into a first flash vessel preferentially through a Venturi that may be a valve or other suitable cross section having an accompanying pressure drop.
  • a first flash vessel preferentially through a Venturi that may be a valve or other suitable cross section having an accompanying pressure drop.
  • this flash vessel may operate at up to 290 bar, but in any event at a pressure lower than that in the PFR.
  • the explosive effect of the pressure drop may facilitate the further break up of the lignocellulose feed stock.
  • the flash vessel may have an operating temperature of up to 300°C and will have at least two exit streams a first liquid stream containing dissolved or suspended components of the lignocellulose biomass and a second gas stream containing substantially pure oxygen.
  • Those skilled in the art will appreciate how the flash vessel and the exit piping carrying the gas and liquid exiting there from may be sized and controlled through the use of valves that may optionally be actuated.
  • the liquid stream has little or no entrained oxygen and the total pressure in the flash vessel is maintained at a value sufficient to ensure that the vapour pressure of steam and furanic compounds in the gas phase is low.
  • the oxygen gas taken from the first flash vessel being a compressed gas may be utilised to provide the mechanical energy to drive pumps and stirrers such as through the use of air driven motors and optionally in addition captured for use as an oxygen source in combustion and or gasification operations associated with the overall bio-refinery operation.
  • the thermal energy associated with this gas stream will be recovered for reuse through the use of heat exchangers.
  • the liquid phase exiting the first flash vessel may contain soluble components of the biomass including oligosaccharides of 5 and 6 carbon sugars, sugars, furanic compounds, acids including levulinic acid and formic acid in conjunction with lignols and the un-hydrolysed remaining solid components of the biomass. These solids may be present in the form of physically commuted fibres having a smaller particle size and more homogenous size distribution with a higher cellulose fraction than the starting raw lignocellulose material.
  • the liquid stream may additionally contain inorganic salts derived from the partial neutralisation reactions that occurred in the PFR.
  • the liquid exit stream from the first flash vessel may be fed to a second flash vessel wherein a further pressure drop is applied to the reaction mixture separating it into two further streams, one gas, one substantially liquid, that exit the second flash vessel.
  • a further pressure drop is applied to the reaction mixture separating it into two further streams, one gas, one substantially liquid, that exit the second flash vessel.
  • This gas phase containing substantially the hydrolysis products of 5 carbon sugars (furanic compounds) in conjunction with steam and lower molecular weight alcohols and acids may be exited from the second flash vessel for product recovery and heat transfer operations.
  • a series of second flash vessels may be required to effect the removal of substantially all the 5 carbon sugar hydrolysis products form the reaction mixture depending on the nature of the starting biomass and the operating conditions of the reactor configuration.
  • the liquid phase exiting the second flash vessel or series of second flash vessels may contain substantially soluble, saccharides, sugars, lignols, acids, alcohols and heavier furanic compounds such as HMF in combination with un-hydrolysed biomass solids comprised largely of insoluble lignin and cellulose.
  • desired products of the biorefining operation are glucose
  • LA and FA this liquid stream may be fed to a continuous stirred tank reactor CSTR wherein the temperature is maintained in the range of between 70 and 190°C with a residence time of up to 8 hrs, such conditions favouring the conversion of the cellulose to glucose and LA as opposed to the condensation products known to form at higher temperatures.
  • Such streams may be added as required to adjust pH and the solids to liquid ratio as required.
  • the resulting mixture may be subjected to settling or filtration operations such as through the use of settling tanks, centrifugal separators or mechanical filters to separate a largely aqueous solution containing glucose, LA and formic acid from a largely solid fraction containing lignin and potentially inorganic solids.
  • the liquid stream exiting the second flash vessel or series of second flash vessels may be cooled and subjected to ph adjustments, washing, drying and mechanical operations to separate cellulose from the lignin.
  • exemplary combinations of stabilisers and agents that may be used in the present invention are presented in Table 1 and include the stabilisers often present in commercial hydrogen peroxide solutions such as pyrophosphates.
  • stabilised peroxide enzymes such as catalyse could be used to decompose the mixture on entry to the PFR provided that the pH is simultaneously adjusted to between 3.5 and 9.5. In the case of catalyse the enzyme may be provided from a natural source such as an animal or plant waste stream.
  • the use of the peroxide composition to swell the initial biomass may reduce the mechanical energy inputs to the process associated with pre-process physical commutation operations.
  • the peroxide decomposition provides the heat for the process without the requirement for additional heat from an external source
  • the oxidative action of the peroxide reduces the recalcitrance of the biomass through partial hydrolysis and oxidation of the halo-cellulose and lignin components respectively.
  • the severity of high acid concentration in combination with high temperature may be avoided due to the partial neutralisation occurring in the PFR increasing the life of the reactor and reducing capital costs as well as the requirement for neutralisation in subsequent steps.
  • the rapid throughput in the reactor and flash vessels may require that only a small part of the overall process configuration needs to be capable of withstanding high pressure/temperature conditions, thus reducing capital costs
  • the potential energy of the compressed gas may be used to drive flow through the process reducing operational costs
  • Yields may be increased through the hydrolysis of a more homogenous material with reduced particle size and recalcitrance
  • a batch reactor with a large head volume was used to illustrate the efficacy of the invention on a lab scale using the combination of peroxide with Formic Acid and a mixture of Ferric sulphate and sodium hydroxide as the decomposing agent.
  • Miscanthus 300 g was mixed with liquor (2700 g) and sealed in an 8L Parr reactor, with a maximum operating pressure of 130 bar, and modified with additional ports.
  • the liquor was made up such that the total mass (liquor and biomass) was 2.5, 5 and 7.5 w/w % with respect to peroxide, using the requisite amount of 30% aqueous peroxide in each case (stabilised with ppm levels of Sodium Pyrophosphate), and adjusting the formic acid weight fraction accordingly.
  • the reactor was equipped with a stirrer which operated at 1500 rpm.
  • NaOH solution 125 ml, 4 M, containing 100 mg/L Fe 2 (S0 4 )3 in a charging vessel fixed to the reactor was injected to the liquor at time zero by means of nitrogen back pressure.
  • the temperature and pressure of the contents were monitored and logged to a PC.
  • the reactor was fitted with a liquid sampling port through which aliquots (20 mL) were removed at regular intervals to determine the temporal composition of the liquor.
  • the solids content at the end of each run was filtered and washed with Formic Acid and water and subjected to further analysis.
  • the results of the example can be summarised as follows:
  • the enthalpy derived from the catalytic decomposition of the peroxide is sufficient to heat the reaction system above 70°C while at low concentrations of peroxide (2.5%) it is not.
  • the hydrogen peroxide concentration is at least 3% by mass, and preferably at least 5%.
  • the temperature curve is characterised by a rapid increase in temperature followed by a plateau at or about the boiling point of the FA/water azeotrope (107°C).
  • the reactor system was not insulated, but the duration of the plateau at 7.5% ⁇ 2 0 2 as compared with 5.0 % is consistent, with more heat being released for the 7.5% concentration.
  • the pressure profiles for both concentrations are consistent with the calculated pressures arising from the expected amount of oxygen released from the decomposition of hydrogen peroxide.
  • Fig. 2 also shows the temporal evolution of the lignin and sugar concentrations in the liquor. Approximately 20% of the initial lignin present in the biomass was solubilised in 25 hrs in the 2.5% peroxide medium, because the system did not become peroxide, and by extension oxidising peroxy radical species, were present for extended periods in the liquor, and consequently solubilised lignin is oxidised further to lignols and lower molecular weight fragments.
  • ⁇ ⁇ and T ⁇ X for the 7.5% liquor is shown in Fig. 2d. While the present example relates to a batch reactor with the consequence that the decomposition commenced from a standing cold start, it should be noted that once the temperature reaches 40°C the decomposition reaction rate becomes essentially exponential. In a continuous high pressure reactor (plug flow reactor) operating at steady state the required residence time in a high pressure environment could be reduced to as little as 5 min ( Figure 2d).
  • Hemicellulose removal from the pulp increases from 13 to 68 to 89 % respectively for the 2.5, 5.0, and 7.5 % initial peroxide concentrations. This is attributed to the increased oxidising potential of the liquor and to the greater amount of heat released by the higher initial concentrations of peroxide. In this way the reaction mixture is maintained at the elevated temperature for longer periods.
  • the mass distribution of the hemicellulose sugars at the end of each experiment across the liquor and pulp indicates that the amount of hemicellulose recoverable from the liquor as sugars increases significantly with increasing initial peroxide concentration.
  • Fig. 3 shows SEM and laser con-focal microscopy images of the raw material and pulps recovered after treatment with the different initial peroxide concentrations. At the higher concentrations sufficient oxidising potential and heat is released to de- lignify the biomass and break down the secondary structure of the plant. This is evidenced by the morphologies of the cellulose recovered from the 5.0 arid 7.5 % treatments. In these, the remaining cellulose is in the form of fibres some hundreds of microns in length and, crucially, all with an approximate diameter of 10 microns.
  • Example 2 Enhanced enzymatic digestibility of the pre-treated material in subsequent enzymatic hydrolysis
  • Fig. 4 shows the rate of glucose release from the pre-treated materials demonstrating a 20- fold increase in the digestibility of the pre-treated material as compared with the starting raw material.
  • Example 3 Enhanced Glucose release from the pretreated materials in subsequent acid hydrolysis
  • the pre-treated material and the raw Miscanthus were hydrolysed at 150 C in 1% Aq H 2 S0 4 at the same initial mass loading (10%w/w).
  • the rates of glucose release (cellulose hydrolysis) are shown in both cases in Fig. 5.
  • Maximum glucose concentration (lOOmmol) in the pre-treated material is achieved in approximately 125 min under the mild hydrolysis conditions used as compared with the untreated material wherein maximum glucose concentration has still not been achieved after 400 min.
  • the invention may be varied in construction and design depending on the particular lignocellulose materials being processed. Accordingly, the invention is not limited to the embodiments described but may be varied in construction and detail but directed to a process that utilises Hydrogen peroxide as a means to chemically and physically alter lignocellulose materials while simultaneously supplying the thermal energy (derived from the enthalpy of its decomposition) necessary to effect its hydrolysis.
  • lignocellulose is used this could be replaced with the term biomass, cellulosic material, natural materials containing biopolymers of largely C5 and or C6 sugars.
  • a Venturi any other inlet which allows flow through an orifice with an accompanying pressure drop could be used.
  • the peroxide concentration could be different from that described, such as at least 2%, and the pressure in the PFR could be at least 15 bar.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
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Abstract

L'invention concerne un procédé de transformation d'un matériau de lignocellulose qui comprend les étapes de : a. combinaison d'un matériau de lignocellulose avec une solution contenant du peroxyde d'hydrogène et un stabilisant de peroxyde d'hydrogène pour produire un mélange qui a au moins 3% en masse de peroxyde d'hydrogène, b. alimentation dudit mélange à l'entrée d'un réacteur continu concomitante avec la fourniture d'un agent qui facilite la décomposition rapide du peroxyde d'hydrogène dans la solution proximale à l'entrée du réacteur de manière à provoquer une décomposition exothermique explosive du peroxyde d'hydrogène en oxygène et eau en formant ainsi un mélange de gaz, liquide et solides et en augmentant la pression et la température dans le réacteur à au moins 15 bars, et 70°C respectivement, sans addition de chaleur provenant d'une source externe, c. faire sortir le mélange de gaz, d'eau et de solides formé dans le réacteur par une sortie avec un changement de pression, dans un récipient de détente dans lequel le mélange est séparé en une phase liquide contenant des solides dissous ou en suspension et une phase gazeuse substantiellement riche en oxygène, et d. enlèvement en continu à partir du récipient de détente d'un courant de gaz substantiellement riche en oxygène et d'un courant de liquide chauffé séparé avec les composants altérés chimiquement et physiquement de la lignocellulose en suspension ou dissous, y compris un matériau substantiellement cellulosique avec une résistance réduite par rapport au matériau de départ de lignocellulose.
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WO2014087016A1 (fr) * 2012-12-07 2014-06-12 Dsm Ip Assets B.V. Procédé pour la production d'un hydrolysat de biomasse
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FR3016359A1 (fr) * 2014-01-10 2015-07-17 Arkema France Compositions de peroxyde d'hydrogene pour la delignification de matiere vegetale et leurs utilisations
US9663807B2 (en) 2011-01-18 2017-05-30 Poet Research, Inc. Systems and methods for hydrolysis of biomass
US9982317B2 (en) 2011-07-07 2018-05-29 Poet Research, Inc. Systems and methods for acid recycle
US10533203B2 (en) 2010-03-19 2020-01-14 Poet Research, Inc. System for the treatment of biomass
CN111530413A (zh) * 2020-04-15 2020-08-14 广东省微生物研究所（广东省微生物分析检测中心） 一种增强土壤自修复的生物炭及其制备方法与应用
CN113906122A (zh) * 2019-03-21 2022-01-07 埃文·普劳特 提高纤维素废物的热值
US20220153680A1 (en) * 2016-03-24 2022-05-19 Les Exploitations J.Y.B. Papineau Inc. Catalytic Conversion of Lignocellulosic Biomass Into Industrial Biochemicals

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US9034620B2 (en) 2010-03-19 2015-05-19 Poet Research, Inc. System for the treatment of biomass to facilitate the production of ethanol
US10533203B2 (en) 2010-03-19 2020-01-14 Poet Research, Inc. System for the treatment of biomass
US9663807B2 (en) 2011-01-18 2017-05-30 Poet Research, Inc. Systems and methods for hydrolysis of biomass
US9982317B2 (en) 2011-07-07 2018-05-29 Poet Research, Inc. Systems and methods for acid recycle
US10731229B2 (en) 2011-07-07 2020-08-04 Poet Research, Inc. Systems and methods for acid recycle
WO2014087016A1 (fr) * 2012-12-07 2014-06-12 Dsm Ip Assets B.V. Procédé pour la production d'un hydrolysat de biomasse
FR3016359A1 (fr) * 2014-01-10 2015-07-17 Arkema France Compositions de peroxyde d'hydrogene pour la delignification de matiere vegetale et leurs utilisations
EP3092196A1 (fr) * 2014-01-10 2016-11-16 Arkema France Compositions de peroxyde d'hydrogène pour la délignification de matière végétale et leurs utilisations
US20220153680A1 (en) * 2016-03-24 2022-05-19 Les Exploitations J.Y.B. Papineau Inc. Catalytic Conversion of Lignocellulosic Biomass Into Industrial Biochemicals
US11780797B2 (en) * 2016-03-24 2023-10-10 11127012 Canada Inc. Catalytic conversion of lignocellulosic biomass into industrial biochemicals
CN113906122A (zh) * 2019-03-21 2022-01-07 埃文·普劳特 提高纤维素废物的热值
CN111530413A (zh) * 2020-04-15 2020-08-14 广东省微生物研究所（广东省微生物分析检测中心） 一种增强土壤自修复的生物炭及其制备方法与应用

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