EP2547822A1 - Process for fibrillating lignocellulosic material, fibres and their use - Google Patents
Process for fibrillating lignocellulosic material, fibres and their useInfo
- Publication number
- EP2547822A1 EP2547822A1 EP11715715A EP11715715A EP2547822A1 EP 2547822 A1 EP2547822 A1 EP 2547822A1 EP 11715715 A EP11715715 A EP 11715715A EP 11715715 A EP11715715 A EP 11715715A EP 2547822 A1 EP2547822 A1 EP 2547822A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ionic liquid
- fibre
- lignocellulosic material
- basically intact
- fibres
- 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.)
- Granted
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/02—Pretreatment of the raw materials by chemical or physical means
-
- 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
- D21C9/001—Modification of pulp properties
- D21C9/007—Modification of pulp properties by mechanical or physical means
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
Definitions
- the invention relates to a process for fibrillating lignocellulosic material wherein the process comprises treating lignocellulosic material with ionic liquid and recovering basically intact fibres of said lignocellulosic material. Typically the process comprises increasing the surface area of said lignocellulosic material.
- Another object of the invention is to provide an activated and/or basically intact fibre wherein the lignocellulosic material is treated with ionic liquid and a basically intact fibre of said lignocellulosic material is recovered.
- the invention further relates to the use of the basically intact fibre of the invention in the production of bio-based materials, preferably bio-plastics, more preferably conductive polymers, stimuli-responsive polymers, bio-based polymer composites, ceramics, fabrics, or elastomers.
- bio-based materials preferably bio-plastics, more preferably conductive polymers, stimuli-responsive polymers, bio-based polymer composites, ceramics, fabrics, or elastomers.
- a process for producing paper, board, pulp or the like from fibers of lignocellulosic material which have been treated with ionic liquid and recovered as basically intact fibres is also enclosed.
- the treating of lignocellulosic material has become even more important due to growing energy demands and environmental concerns.
- Traditional methods of chemical modification employed for treating lignocellulosic materials are fibre modification, pulping, fractionation and depolymerisation.
- the fibre modification method involves enhancement of the fibre properties by additive functionalization, which means adding functionalities that demonstrate enhanced properties of the product.
- a typical example would be fatty acid (hydrophobic functionality) functionalization of wood fibre hydroxyl groups in the production of hydrophobic materials (plastics, hydrophobic coatings, etc).
- TMP thermo mechanical pulp
- CMP chemothermo mechanical pulp
- Fractionation involves separation of the lignocellulosic components. This should be distinct from pulping, as pulping involves depolymerisation of lignin, whereas fractionation should maintain the molecular weight of the lignin.
- Depolymerisation of lignocellulosic material, or fractionated/enriched materials is a method whereby the polymeric structures are degraded to low molecular weight species.
- This may be selective degradation of certain components or structures for the production of commodity chemicals (bioethanol, monosaccharide, disaccharides, oligosaccharides, phenols, catechols, LGO, furanoids, hydroxyalcohols, etc) or indiscriminate degradation of components for the production of mixtures of chemicals, tars and oils, liquid biofuel or wood gas (syngas).
- commodity chemicals bioethanol, monosaccharide, disaccharides, oligosaccharides, phenols, catechols, LGO, furanoids, hydroxyalcohols, etc
- This may involve the catalysed degradation of components in solution (e.g.
- the present invention surprisingly shows that ionic liquids can be used for fibrillating lignocellulosic materials under mild conditions, compared to the conditions used in traditional methods for treating lignocellulosic materials, in order to receive a novel type of fibres.
- Ionic liquids are ambient temperature molten salts. They usually have melting points below 100 °C and are seemingly composed of ions, with no additional molecular solvent present to render the mixture liquid (i.e. as opposed to aqueous salt solutions). Ionic liquids have been described, for example, in US patent application US 20080190321 Al, which discloses the preparation of ionic liquids and a method for dissolving cellulose into a solution comprising an ionic liquid. German patent application DE 102005062608 Al also discloses the preparation of ionic liquids and their use as dissolution systems for celluloses.
- US patent application US 20070215300 Al which relates to a method for the treatment of a lignin-containing material with an ionic liquid to extract lignin there from. The lignin is recovered from the ionic liquid.
- US patent application US 20080185112 Al relates to thermolysis of lignocellulosic materials where ionic liquids are used for pre -treatment of lignocelluloses and US patent application US 20080190013 Al describes a method for converting lignocellulosic material into biofuel. Ionic liquids are used for pre -treatment by dissolution of the lignocellulosic materials in the ionic liquid.
- WO 2008119770 Al relates to a method for modifying the structure of a cellulose material and dissolution of lignocellulosic material is described in WO 2005017001 Al .
- the invention relates to a process for fibrillating lignocellulosic material, such as wood chips, wherein the process comprises treating lignocellulosic material with ionic liquid to produce basically intact fibres of the lignocellulosic material, with minimal degradation.
- the fibrillation may also be combined with mechanical treatment, such as a thermomechanical or chemithermomechanical treatment.
- the process of the invention comprises increasing the surface area of said lignocellulosic material by the fibrillation.
- Another object of the invention is to provide a basically intact fibre which is obtained by treating lignocellulosic material with ionic liquid and by recovering the basically intact fibre.
- the present invention further relates to a process for producing paper, board, pulp and the like from the basically intact fibres of the invention.
- a further object of the present invention is application of the fibrillated material of the invention in the production of bio-based materials such as conductive polymers, stimuli-responsive polymers, bio-based polymer composites, ceramics, fabrics, elastomers and bio-plastics in general from the fibres.
- Another embodiment of the invention provides a refined and efficient lignocellulose functionalization, for the production of novel materials.
- This feature of the treatment in combination with the wide range of chemical or physical modification, allows for tuning of the physiochemical properties to produce high value materials for a given application with increased yields.
- the modification is used to effect changes in hydrophobicity, electrical conductivity/resistance, stimuli response, rheological properties, visual properties, solvent (e.g.
- hydrophobic functionalities such as fatty acid esters derived from rosin acids, tall oil fatty acids (TOFA) or alkyl ketene dimer (AKD) sizing reagents. This can help to "compatibilize” the material for the formation of composite materials with traditional hydrophobic polymers.
- the invention is based on the finding that ionic liquids can be used for fibrillating lignocellulosic materials under mild conditions, compared to the conditions of the traditional methods for treating lignocellulosic materials, in order to receive a novel type of fibers.
- the present invention can further be used as an ionic liquid-mediated fibrillation pre -treatment from where components of the remaining fibrous material are more easily degradated.
- One advantage of the invention is that ionic liquids affords a media which do not contribute to environmentally polluting volatile organic compound (VOC) emissions. This is in part due to the extremely low volatility of most ionic liquid media.
- VOC volatile organic compound
- the ionic liquid technology research is a rapidly expanding area of materials science. Ionic liquids seem to offer potential sustainable technology platforms for some environmentally benign new and alternative processes.
- a further advantage of the invention is that the basically intact fibres are closer to their native structure and molecular weight, than those obtained from traditional pulping, fractionation or extraction processes. During the ionic liquid treatment, the treated fibres maintain their advantageous fibrous properties and yet retain a practically similar mass compared to the mass of the starting lignocellulosic material.
- the present invention is used for pre -treatment of wood, for example before chemical pulping, such as Kraft pulping.
- the ionic liquid treatment allows for milder cooking, for example influences the cooking temperature and time and therefore reduces the energy consumption.
- the process according to the invention also increases the surface area of the lignocellulosic material for the delignification process. Further mild delignification under aqueous basic conditions is achieved, even in the absence of sulphur, yielding a sulphur- free lignin. This is an advantage compared to traditional pulping due to reduced catalyst poisoning during cracking, lower sulphur emissions during combustion or easier reagent recovery.
- small portions of wood components such as polymeric and oligomeric polysaccharides (pectins or hemicelluloses) in particular, are regenerated from the ionic liquid, for example by precipitation with a co-solvent.
- these components are extracted into the ionic liquid mixture during the fibrillation process. Therefore, one benefit of the invention is the increased efficiency of extraction of extractives or particular polysaccharide components, such as pectins or hemicelluloses, from the lignocellulosic material.
- Pectins and hemicelluloses are particularly useful as food additives and their scope is expanding. Extractives may have wide ranging applications as commodity chemicals or as intermediates or drug candidates for agrochemical or pharmaceutical applications.
- One advantage of the invention is the mild deconstruction and optionally reconstruction of the native lignocellulosic material with other bio-based materials. Due to more detailed knowledge of wood structure and the physical and chemical properties of ionic liquids, increased efficiency of the process and an increased quality of product are achieved.
- FIG. 1 A schematic view of one embodiment of the process of the invention.
- the present invention relates to a process for fibrillating lignocellulosic material wherein the process comprises treating lignocellulosic material with ionic liquid and recovering basically intact fibres of said lignocellulosic material.
- the following terms have the meanings defined below.
- fibrillation refers to changes in the fibre structure of the lignocellulosic material, i.e. the fibre walls, whereby a number of fibrils or tracheids are completely or partially separated and the binding between the remaining fibrils or tracheids is weakened, to the state of being reduced to fibres with high aspect ratio.
- the removal of pectins from the lumen by ionic liquid significantly contributes to the fibrillation process, but the fibre structure and aspect ratio are maintained.
- basicically intact fibre refers to the fibres of lignocellulosic material having a basically intact cell structure. Typically the average 2D aspect ratio of the fibres is >5, more preferably >20 and most preferably >50.
- activated refers to fibres of lignocellulosic material which have been activated in the sense that the surface area for reaction is increased, due to fibrillation or swelling of the fibre surface. This affords a material that is more easily subjected to further treatments, such as different kinds of modification, for example chemical functionalization.
- modification in the present specification and claims refers to chemical or physical modification of the fibre material.
- chemical functionalization involving breakage or formation of chemical bonds, comprises adding functionalities which afford enhanced properties of the fibrous material, for example physiochemical properties such as hydrophobicity, electrical conductivity/resistance, rheological properties, visual properties, solvent (e.g. water) adsorbtivity/absorbtivity, swelling properties, elasticity, tensile properties or thermal resistance.
- physiochemical properties such as hydrophobicity, electrical conductivity/resistance, rheological properties, visual properties, solvent (e.g. water) adsorbtivity/absorbtivity, swelling properties, elasticity, tensile properties or thermal resistance.
- modification comprise increasing the molecular weight and fragmentation or depolymerization of the lignocellulosic material. Fragmentation and/or depolymerization is useful in the production of enriched biopolymer preparations, such as lignin, or monomeric and low molecular weight materials to be used as bulk chemicals, commodity chemicals or bio-based fuels.
- Physical modification may involve physical formation or defomation of the material. For example a process of grinding, as is used in the production of TMP, or shearing, as is used for the production of microfibrillar cellulose (MFC), may be used. The modification can take place in the presence of another solid, liquid or gaseous material to affect some chemical, morphological or physical transformation in general.
- wood chips refers to pieces of wood most of which are bigger than 1 cm x 0.5 cm x 0.1 mm, preferably at least 50 % of the wood chips are bigger than 1 cm x 0.5 cm x 0.1 mm, more preferably at least 80 %, most preferably at least 95 %.
- lignocellulosic material in the present specification and claims refers to a natural material comprising cellulose, hemicellulose and lignin that has not been subjected to previous pulping or fibrillation processes.
- the lignocellulosic material may be close to its native (unprocessed) form, or it can be partially processed using typical harvesting and pre -treatment techniques.
- the material may also contain "extractives" which are a range of different low molecular weight compounds and are of value in the forestry product chain. For example carbohydrate polymers (pectins, cellulose and hemicelluloses) are tightly bound to the lignin, by hydrogen and covalent bonds.
- Hemicelluloses are embedded in the cell walls of plants - they bind with pectin and lignin to cellulose to form a network of cross-linked fibres.
- the lignocellulosic material also refers to biomass of different types, such as wood residues (including sawmill and paper mill discards), agricultural residues (including corn stover and sugarcane bagasse), dedicated energy crops (which are mostly composed of fast growing tall, woody grasses), and trees (felled for pulp, construction, materials, chemicals or energy).
- lignocellulosic materials can for example be obtained from vascular plants such as hardwood, softwood, straws, grasses (e.g., rice, esparto, wheat and sabai), canes, reeds (e.g., bagasses or sugar cane), bamboo, bast fibres (e.g., jute, flax, kenaf, linen, ramie, cannabis) and/or leaf fibres (e.g., agaba, minila hemp, sisal).
- the lignocellulosic material is wood, such as softwood or hardwood, for example in the form of wood chips.
- treatment in the present specification and claims refers to treatment of lignocellulosic material with ionic liquid and may involve one or more common treatments such as heating, vacuum, pressure, stirring, vibration, microwave, ultrasound, or other common methods of agitation of mixtures.
- ionic liquid is commonly defined as molten salts, which are comprised of ions and are liquids at certain temperatures.
- ionic liquid refers to molten salts with melting point ranges between -100 °C to 200 °C or even up to 300 °C.
- the ionic liquids comprise one or more anions and one or more cations.
- ionic liquids should be regarded as molten salts at any suitable process conditions.
- the present definition of ionic liquids includes "room temperature ionic liquids" which are molten salts with melting points below room temperature (-17-25 °C in most laboratory settings). Under the present definition of ionic liquids, the fact that the ions may be closely paired or clustered in the solution state (by columbic interaction, hydrogen bonding or weaker interactions), does not exclude them from being classed as ionic liquids.
- phosphate refers to anions of ionic liquids and can mean any homologues of substituted phosphate, phosphonate, sulfate, sulfonate and carboxylate anions respectively.
- methylhydrogenphosphonate can be refered to as a phosphonate.
- Homologues containing alkyl, aryl and partially or perhalogenated substituents are also included under this definition.
- the present invention relates to a process for fibrillating lignocellulosic material wherein the process comprises treating lignocellulosic material with ionic liquid and recovering basically intact fibres of said lignocellulosic material.
- the treatment involves heating (by standard methods), vacuum, pressure, stirring, vibration, microwave, ultrasound, or other common methods of agitation of mixtures to enhance the fibrillation.
- the heating typically involves using process temperatures between 20 °C and 150 °C, preferably between 50 °C and 120 °C, more preferably between 75 °C and 120 °C.
- Microwaves and ultrasound have in the prior art been found to aid dissolution of cellulose with ionic liquids.
- the use of microwaves and/or ultrasound to enhance fibrillation requires appropriate control of the fibrillation conditions, not to dissolve material.
- the treatment to facilitate fibrillation involves heating in combination with mechanical treatment.
- Such a treatment is for example used in the production of thermomechanical pulp or chemothermomechanical pulp.
- the basically intact fibre fibrillated according to the process of the invention has an average 2D aspect ratio at least 5, more preferably at least 20 and most preferably at least 50.
- the average 2D aspect ratio of the basically intact fibre of the invention is at least 10, at least 15, at least 25, at least 30, at least 35, at least 40, at least 45 or at least 55.
- the basically intact fibre is activated during the treatment of the lignocellulosic material and/or modified after the recovery of the basically intact fibres.
- a modification of the basically intact fibre is preferably made by chemical or physical modification or upgrading of the fibres.
- chemical modifications are esterification, redox reactions, etherifications, carbamate formations, carbonate formation, crosslinking and/or other reactions where covalent linkages are formed.
- physical modification are grinding, as is used in the production of TMP or CTMP, or shearing, as is used for the production of MFC.
- the fibrillated lignocellulosic material can be modified after recovery from the ionic liquid media but according to another aspect of the invention the fibrillated lignocellulosic material is modified in the ionic liquid media before recovery.
- the fibres, which are present in the ionic liquid or which have been recovered from the ionic liquid are in an activated state.
- the basically intact fibre of the invention is chemically modified by additive chemical functionalization. Such functionalization involves modification of functional groups on the surface or through the fibre in order to produce a fibrous material with enhanced properties.
- One example of this embodiment is fatty acid functionalization of the surface hydroxyl groups of the basically intact fibre to form a bio-based plastic material.
- the invention also relates to a process for recovery of the fibrillated lignocellulosic material, components dissolved from the lignocellulosic material and purified ionic liquid.
- separation of the solid material from the liquid material is done at any stage of the process by filtration, centrifugation and other common solid/liquid separation techniques.
- small amounts of molecular solvent are added to the reaction mixture to increase the efficiency of separation, yet still avoiding precipitation of the dissolved components.
- dissolved compounds, such as pectins are recovered by addition of a further molecular solvent, allowing for solid/liquid separation, or by membrane filtration.
- the ionic liquid is recovered after precipitation of dissolved components and/or removal of solid material by evaporation of the solvent used for precipitating.
- One or more of the components are optionally recycled.
- a range of molecular solvents is used to remove traces of ionic liquid remaining on the fibre by heating.
- Another object of the invention is to provide a basically intact fibre which is obtained by treating lignocellulosic material with ionic liquid and recovering basically intact fibres of said lignocellulosic material.
- ionic liquid treatment increases the surface area of the fibres.
- the basically intact fibre of the invention typically has an average 2D aspect ratio of at least 5, more preferably at least 20 and most preferably at least 50. According to other preferred embodiments the 2D aspect ratio values of the basically intact fibre of the invention is at least 10, at least 15, at least 25, at least 30, at least 35, at least 40, at least 45 or at least 55.
- the basically intact fibre is activated during treatment of the lignocellulosic material and/or thereafter modified either in the ionic liquid or after the recovery of the basically intact fibres.
- a modification of the basically intact fibre is preferably made by chemical or physical modification.
- the basically intact fibre is dissolved in an ionic liquid after being recovered from the ionic liquid used for treating the lignocellulosic material.
- a further object of the invention is the use of the basically intact fibre of the process of the invention in the production of bio-based materials, preferably bio-plastics, more preferably conductive polymers, stimuli-responsive polymers, bio-based polymer composites, ceramics, fabrics, or elastomers.
- a still other object of the invention is to provide a process for producing paper, board, pulp or the like from fibers of lignocellulosic material which have been treated in ionic liquid and recovered as basically intact fibres of said lignocellulosic material.
- the ionic liquid of the invention typically comprises at least one anionic portion and at least one cationic portion.
- the choice of one or more cationic portions and anionic portions depends first of all on the lignocellulosic material and thereto on the treatment and the conditions chosen.
- the cationic portion of the ionic liquid according to the invention can depending on the lignocellulosic material and the treatment and conditions chosen comprise one or more organic cations prepared by derivatizing one or more of imidazole, pyrazole, thiazole, isothiazole, azathiazole, oxothiazole, oxazine, oxazoline, oxazaborole, dithiazole, triazole, selenazole, oxaphosphole, pyrrole, borole, furan, thiophene, phosphole, pentazole, indole, induline, oxazole, isoxazole, isotetrazole, tetrazole, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, thiadiazole, pyridine, pyrimidine, pyrazine, pyridazine, piperazine, piperd
- the substituents may also be aromatic substituents, such as substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, or a variety of heterocyclc aromatics having one, two or three heteroatoms in the ring portion thereof, said heterocyclics being substituted or unsubstituted.
- the substituents may include additional terminal functionalities such as disubstituted chalcogens (ethers, thioethers etc.), carboxylic acids, carboxylic esters, thioacids, thioesters, carbonates, carbamates, nitriles, imines, amides, aldehydes, ketones or other heteroatom-containing functionalities.
- the basic cation structure can be singly substituted, multiply substituted, unsubstituted or covalently linked to one or more cations to give dicationic, tricationic or polymeric cationic species.
- the ionic liquid of the invention comprises a cationic portion, which comprises a cation of imidazolium type of Formula I
- Another preferred ionic liquid of the invention comprises a cationic portion, which comprises a cation of pyridinium type of Formula II
- R 1 , R 2 , R 3 and R 4 independently of each other are H or Ci-Ce, preferably H or C 1 -C 2 , and R 5 and R 6 independently of each other are H or Q-Cg.
- the side chain functionalities of the compounds of Formula I or II are cyclic or acyclic and the imidazolium is preferably di- or tri- substituted.
- the pyridinium is prefereably mono- or di-substituted.
- the cation structures are drawn as the canonical resonance hybrid structures and are assumed to encompass the contributing canonical resonance structures.
- Imidazole based ionic liquids are one preferred type of ionic liquids that can be used according to the present invention.
- the imidazole is replaced with a pyridinium cation, as a low cost heterocycle.
- Examples of ionic liquid cations according to the invention which depending on the lignocellulosic material and the treatment and conditions used are preferred, comprise l-butyl-3- methylimidazolium ([bmim] + ), l-allyl-3-methylimidazolium ([amim] + ), l-ethyl-3- methylimidazolium ([emim] + ), 1,3-dimethylimidazolium ([mmim] + ), l-hydrogen-3- methylimidazolium ([hmim] + ), l-benzyl-3-methylimidazolium ([bnmim] + ), l-(2-hydroxyethyl)-3- methylimidazolium ([hemim] + ), l-propyl-3-methylimidazolium ([prmim] + ), l-isopropyl-3- methylimidazolium (['prmim] + ), 1,2,
- the anionic portion of ionic liquids typically comprises one or more inorganic moieties, one or more organic moieties, or combinations thereof.
- the anionic portion of the ionic liquid according to the invention can depending on the lignocellulosic material and the treatmentand conditions chosen comprise one or more portions selected from halogens, phosphates, alkylphosphates, arylphosphates, alkylphosphonates, arylphosphonates, partially halogenated or perhalogenated alkylphosphates, such as (CF3CF2C 2PO2 " or (CF 3 CF20)(CH3CH 2 0)P02 " , partially halogenated or perhalogenated alkylphosphonates, such as CF 3 CF 2 HPO 3 " or CF 3 CF 2 FPO 3 " , partially halogenated or perhalogenated alkylsulfates, such as CF
- carboxylates such as formate, acetate, propionate, butyrate, valerate, pivalate, hexanoate, heptanoate, octanoate, maleate, fumarate, oxalate, lactate, pyruvate, tartarate and their isomers.
- the anionic portion of the invention is chosen from a list consisting of phosphate, diphosphate, phosphonate, carboxylate, halides, sulphonate, sulphate or perfluorinated alkylphosphate or combinations thereof.
- ionic liquid anions which depending on the lignocellulosic material and the treatment and conditions used may be used according to the invention, include chloride (CI ), bromide (Br ), iodide ( ⁇ ), formate (HCOO ), acetate (AcO ), propanoate (C 2 H 5 COO ), butyrate (C 3 H 7 COO ⁇ ), pivalate (Me 3 CCOO ⁇ ), valerate (C 4 H 9 COO ⁇ ), hexanoate (C 5 H u COO ), benzoate (PhCOO ), methylsulfate (MeS0 4 ⁇ ), ethylsulfate (EtS0 4 ⁇ ), propylsulfate (PrS0 4 ⁇ ), isopropylsulfate ('PrSCV), butylsulfate (BuS0 4 ⁇ ), phenyl sulfate (PhS0 4 ),
- ionic liquids can be prepared and used according to the present invention by combining one or more cations with one or more anions to form ionic liquid.
- Some preferred ionic liquids are for example: l-allyl-3- methylimidazolium dimethylphosphate 1,3-dimethylimidazolium dimethylphosphate; l-ethyl-3- methylimidazolium dimethylphosphate, l-allyl-3 -methylimidazolium methylhydrogenphosphonate 1 ,3 -dimethylimidazolium methylhydrogenphosphonate; 1 -ethyl-3 -methylimidazolium methylhydrogenphosphonate, l-allyl-3-methylimidazolium formate 1,3-dimethylimidazolium formate; l-ethyl-3-methylimidazolium formate, l-allyl-3-methylimidazolium acetate 1,3- dimethylimidazolium acetate; l-ethyl-3-methylimidazolium acetate, l-allyl-3-methylimidazolium propionate 1,3-
- the ionic liquid(s) of the invention comprises the use of various ionic liquids incorporating acetates, phosphates and phosphonates as the anionic portion and dialkylimidazoliums as the cationic portion.
- the ionic liquids useful according to the invention encompass pyridinium halides, pyridinium carboxylates, pyridinium phosphates or pyridinium phosphonates.
- Examples of specific preferred examples of the present invention are l-ethyl-3-methylimidazolium dimethylphosphate l-ethyl-3-methylimidazolium methylphosphonate ([emimJMeHPOs) and l-ethyl-3-methylimidazo Hum acetate ([emimJOAc).
- ionic liquids for the ionic liquid treatment according to the invention by combining one or more cations with one or more anions to form a ionic liquid.
- Multiple heterocyclic or acyclic ionic liquids could be used as well.
- dicationic materials exhibit increased thermal stability and are thus useful in embodiments, where it is desirable to carry out the treatment of the lignocellulosic materials at increased temperatures.
- Dicationic ionic liquids can be prepared using any combination of cations and anions, such as those described above.
- imidazoles and pyridines could be used in preparing dicationic ionic liquids in a similar manner as described for ionic liquids having only a single cationic moiety.
- Ionic liquids are typically relatively easy to prepare by known syntheses.
- the Kunststoffutkin reaction amine quaternization
- a substituted imidazole is reacted with a trialkylphosphate or dialkylhydrogenphosphonate (dialkylphosphite) or trialkylphosphonate
- amine quaternization amine quaternization
- Related compounds can be prepared by transesterification of phosphites, phosphates or phosphonates starting with alcohols, such as, partially fluorinated or perfluorinated alcohols, allyl alcohol, propargyl alcohol, phenol or higher chain homologues with differing degrees of unsaturation.
- alcohols such as, partially fluorinated or perfluorinated alcohols, allyl alcohol, propargyl alcohol, phenol or higher chain homologues with differing degrees of unsaturation.
- substitution may be accessed, by employing the Michaelis-Arbuzov reaction (shown below), by starting from easily accessible trialkylphosphite esters:
- Phosphate and phosphonate based ionic liquids typically have lower viscosities compared to halide -based ionic liquids, which makes them particularly easy to use without the need for excessive heating.
- ionic liquids comprises derivatization which involves functionalization of some existing molecular heterocyclic or acyclic compound with a substituent or it involves anion metathesis where an existing anion of an ionic liquid is replaced or reacted with a reagent leaving another anion in its place. This may give a completely new pure ionic liquid, or an ionic liquid, which contains a mixture of anions and cations.
- a further preferred method of ionic liquid preparation involves direct mixing of two pure salts to give a molten salt or ionic liquid mixture.
- Yet another method of ionic liquid preparation involves direct mixing of a pure salt with a non-ionic (molecular) compound, to afford an ionic liquid or eutectic mixture with high ionic character.
- a pure salt with a non-ionic (molecular) compound
- Such compounds are not typically thought of as ionic liquids, but are herein referred to as ionic liquids.
- the invention further relates to the use of various mixtures of ionic liquids.
- ionic liquid mixtures can be useful for providing mixtures having customized physiochemical properties, such as viscosity or ability to process different materials, according to the present invention.
- l-benzyl-3-methylimidazolium dimethylphosphate is a relatively viscous ionic liquid, however, its viscosity can be significantly reduced by mixing it with another ionic liquid such as [emim]MeHP0 3 .
- the viscosity of the ionic liquid mixture can thus be adjusted by varying the ratio between the more viscous component and the less viscous component.
- various pure ionic liquids or ionic liquid mixtures are mixed with additives, such as molecular solvents, preferably inorganic or organic solvents and/or an organic acid or base.
- additives such as molecular solvents, preferably inorganic or organic solvents and/or an organic acid or base.
- Typical solvents are polar aprotic solvents such as dimethylsulfoxide (DMSO) in small quantities ( ⁇ 20 %).
- DMSO dimethylsulfoxide
- DMSO dimethylsulfoxide
- FIG. 1 shows one embodiment of the process according to the invention.
- the lignocellulosic material is a typical pulpwood feedstock, and the process involves chipping debarked wood (1) to give wood chips (2) of the appropriate size.
- the chips may also be extracted with a solvent, such as acetone, to further dry the sample or remove extractives.
- the wood chips (2) are fibrillated in ionic liquid media with heating and mechanical treatment to give the fibres in ionic liquid media (3).
- This material is diluted with the appropriate amount of solvent, such as methanol, and filtered to give the "wet" fibres (4).
- the filtrate solution which can be a mixture of ionic liquid, polysaccharides (pectins and/or hemicelluloses) and extractives (7), is retained.
- the "wet" fibres may be further treated with a solvent at elevated temperatures to remove any remaining traces of ionic liquid from the fibres.
- the mixture is again filtered and dried to give dried fibres (5), the yield of which will be typically 90-95 %.
- the filtrate from the second filtration step is combined with the solution of ionic liquids, polysaccharides (pectins and/or hemicelluloses) and extractives. Any polysaccharides or extractives (9) may be recovered in 5-10 % yield by a suitable method such as filtration and/or membrane filtration.
- the remaining ionic liquid and solvent (8) is treated by evaporation and/or pervaporation as a final step in recycling the ionic liquid and molecular solvents.
- the dried fibre (5) product of Fig. 1 may be treated further (6).
- the further treatment involves for example a sequence of chemical modification steps, such as one or more of bleaching, mild pulping, esterification, etherification or further extraction using additional solvents such as supercritical-C0 2 extraction (SC-CO 2 ), pressurized hot water extraction (PHWE), traditional molecular solvent extraction or additional ionic liquid extraction.
- SC-CO 2 supercritical-C0 2 extraction
- PHWE pressurized hot water extraction
- additional ionic liquid extraction additional solvents
- the isolated polysaccharides and extractives (9) are optionally further separated (10) using techniques such as solvent and chemical extraction, membrane filtration (nanofiltration, ultrafiltration) or selective precipitation.
- Fibrillation capability was assessed for a series of ionic liquids and wood species.
- Some specific examples of ionic liquids, capable of efficiently fibrillating lignocellulose, are chosen from a series of ionic liquids that were screened in a methodical manner. Screening involved varying both the cation and anion structures of the ionic liquids. Screening was also assessed against a selection of hardwoods, such as birch, aspen and oak, and softwoods, such as such as pine and spruce. The results are presented in Table 1.
- the fibrillation experiments were performed in one of the following ways: Pine, spruce (softwood) ,birch or aspen (hardwood) chips (ca. 2.5 cm x 1 cm x 0.2 mm) were soaked for 2 days at room temperature in acetone, in order to remove extractives and partially dry the material. The chips were then dried in an oven at 105 °C. Extracted and dried wood chips (2 g) in ionic liquid (20 ml) were heated without agitation between 95 - 110 °C for 18 - 66 hr in ionic liquid. Hardwoods required higher temperatures. Methanol (40 ml) was added to the mixture and the fibres were filtered.
- [mPyr]MeHP0 3 - methylpyridinium methylhydrogenphosphonate It was determined that [emim]MeHP0 3 was the most preferred ionic liquid tested for fibrillating softwoods such as pine and spruce, while [emimJOAc was also capable of fibrillating hardwoods such as Birch, Aspen and Oak (at 95 °C over 18 hr). The combination of [emim]MeHP0 3 with softwoods under milder conditions (110 °C over 18 hr) was able to produce fibres with no significant darkening, characteristic of dehydration and lignin oxidation, in comparison to the starting wood material.
- Ionic liquids such as [emim]Me 2 P0 4 and [mmim]Me 2 P0 4 fibrillated softwood under harsher conditions (110 °C up to 3 days) and yielded fibres that were more colourized than the [emim]MeHP0 3 fibrillated samples.
- lignocellulosic material the specific softwood or hardwood species
- ionic liquid and treatment conditions did not lead to fibrillation, also these ionic liquids are believed to fibrillate other lignocellulosic materials according to the process of the invention.
- Example 40 Total sugar analysis of fibrillated pine wood chips, after treatment with [mmim]Me 2 P0 .
Abstract
Description
Claims
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FI20105272A FI20105272A (en) | 2010-03-18 | 2010-03-18 | Method for fibrillation of lignocellulosic material, fibers and their use |
PCT/FI2011/050234 WO2011114004A1 (en) | 2010-03-18 | 2011-03-18 | Process for fibrillating lignocellulosic material, fibres and their use |
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US (1) | US20130056165A1 (en) |
EP (1) | EP2547822B1 (en) |
JP (1) | JP2013522411A (en) |
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JP2011254727A (en) * | 2010-06-07 | 2011-12-22 | Toyota Motor Corp | Method of treating plant biomass |
US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
FR2983111B1 (en) | 2011-11-30 | 2014-08-22 | Faurecia Interieur Ind | PROCESS FOR PRODUCING A COMPOSITE MATERIAL COMPRISING LIGNOCELLULOSIC FIBERS IN A PLASTIC MATRIX |
US20140048221A1 (en) | 2012-08-20 | 2014-02-20 | Celanese International Corporation | Methods for extracting hemicellulose from a cellulosic material |
FI127682B (en) | 2013-01-04 | 2018-12-14 | Stora Enso Oyj | A method of producing microfibrillated cellulose |
US10240259B2 (en) * | 2013-04-04 | 2019-03-26 | Aalto University Foundation Sr | Process for the production of shaped cellulose articles |
CN105592992B (en) | 2013-05-24 | 2019-07-16 | 斯托拉恩索公司 | The protection of timber |
FI20135773L (en) | 2013-07-16 | 2015-01-17 | Stora Enso Oyj | |
JP6295495B2 (en) * | 2013-07-17 | 2018-03-20 | 福井県 | Method for synthesizing ammonium salt and composition containing polysaccharide in synthesized ammonium salt |
CN103388272B (en) * | 2013-07-31 | 2015-10-28 | 东北林业大学 | A kind of preparation method of ionic liquid plasticizing lignocellulosic material |
US10011931B2 (en) | 2014-10-06 | 2018-07-03 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing dyed and welded substrates |
US10982381B2 (en) * | 2014-10-06 | 2021-04-20 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing welded substrates |
KR20180027430A (en) * | 2015-07-10 | 2018-03-14 | 이데미쓰 고산 가부시키가이샤 | Organic electroluminescent devices and electronic devices |
CN105167174A (en) * | 2015-07-16 | 2015-12-23 | 华南理工大学 | Leaching liquor capable of effectively reducing lignin content in tobacco waste as well as preparation method and application of leaching liquor |
FI3331939T3 (en) * | 2015-08-04 | 2023-06-16 | Granbio Intellectual Property Holdings Llc | Processes for producing high-viscosity compounds as rheology modifiers, and compositions produced therefrom |
CN105220552B (en) * | 2015-09-09 | 2017-03-29 | 郑州轻工业学院 | Using the method for the asymmetric Gemini ionic liquid extracts cellulose of imidazoles |
JP7421861B2 (en) | 2016-03-25 | 2024-01-25 | ナチュラル ファイバー ウェルディング インコーポレーテッド | Methods, processes, and apparatus for producing welded substrates |
CN113930874B (en) | 2016-05-03 | 2022-11-01 | 天然纤维焊接股份有限公司 | Method, process and apparatus for producing dyed weld matrix |
SE539950C2 (en) * | 2016-05-20 | 2018-02-06 | Stora Enso Oyj | An uv blocking film comprising microfibrillated cellulose, amethod for producing said film and use of a composition hav ing uv blocking properties |
CN106087411B (en) * | 2016-06-06 | 2018-06-12 | 深圳市新纶科技股份有限公司 | A kind of modifying aramid fiber pulp and preparation method thereof and the brake block manufactured with it |
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WO2019143802A1 (en) * | 2018-01-17 | 2019-07-25 | Texas Tech University System | Dissolution of cellulose in ionic liquids |
CN110130094B (en) * | 2019-04-25 | 2020-12-22 | 东华大学 | Activated plant fiber, preparation method thereof and application thereof in polylactic acid composite material |
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DE102005017715A1 (en) | 2005-04-15 | 2006-10-19 | Basf Ag | Solution, useful for physical or chemical treatment of cellulose, comprises cellulose and an ionic liquid containing anions and cations as solvent, where the cation exhibits nitrogen, oxygen, sulfur and phosphorus atoms in protonated form |
DK1966284T3 (en) * | 2005-12-23 | 2013-07-08 | Basf Se | Solution system based on molten ionic liquids, preparation and use thereof for the production of regenerated carbohydrates |
DE102005062608A1 (en) * | 2005-12-23 | 2007-07-05 | Basf Ag | Solution system based on molten ionic liquid e.g. imidazolium salt for dissolving carbohydrate e.g. starch, cellulose or derivative and regeneration e.g. for fiber production also contains water and/or other protic solvent |
EP1860201A1 (en) * | 2006-05-25 | 2007-11-28 | BP p.l.c. | Conversion method |
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