WO2010135804A1 - Derivatives of native lignin - Google Patents
Derivatives of native lignin Download PDFInfo
- Publication number
- WO2010135804A1 WO2010135804A1 PCT/CA2010/000205 CA2010000205W WO2010135804A1 WO 2010135804 A1 WO2010135804 A1 WO 2010135804A1 CA 2010000205 W CA2010000205 W CA 2010000205W WO 2010135804 A1 WO2010135804 A1 WO 2010135804A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lignin
- mmol
- derivative according
- less
- lignin derivative
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/32—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from hydrolysates of wood or straw
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/13—Coniferophyta (gymnosperms)
- A61K36/15—Pinaceae (Pine family), e.g. pine or cedar
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/48—Fabaceae or Leguminosae (Pea or Legume family); Caesalpiniaceae; Mimosaceae; Papilionaceae
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/54—Lauraceae (Laurel family), e.g. cinnamon or sassafras
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
- A61K36/18—Magnoliophyta (angiosperms)
- A61K36/185—Magnoliopsida (dicotyledons)
- A61K36/76—Salicaceae (Willow family), e.g. poplar
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/34—Anti-oxidant compositions; Compositions inhibiting chemical change containing plant or animal materials of unknown composition
-
- 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
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Definitions
- This invention relates to derivatives of native lignin recovered from lignocellulosic feedstocks, and industrial applications thereof. More particularly, this invention relates to derivatives of native lignin having certain chemical properties as well as uses, processes, methods, and compositions thereof.
- Native lignin is a naturally occurring amorphous complex cross-linked organic macromolecule that comprises an integral component of all plant biomass.
- the chemical structure of lignin is irregular in the sense that different structural units (e.g., phenylpropane units) are not linked to each other in any systematic order.
- native lignin comprises pluralities of two monolignol monomers that are methoxylated to various degrees (trans-coniferyl alcohol and trans-sinapyl alcohol) and a third non-methoxylated monolignol (trans-p-coumaryl alcohol).
- Various combinations of these monolignols comprise three building blocks of phenylpropanoid structures i.e. guaiacyl monolignol, syringyl monolignol and p-hydroxyphenyl monolignol, respectively, that are polymerized via specific linkages to form the native lignin macromolecule.
- Extracting native lignin from lignocellulosic biomass during pulping generally results in lignin fragmentation into numerous mixtures of irregular components. Furthermore, the lignin fragments may react with any chemicals employed in the pulping process. Consequently, the generated lignin fractions can be referred to as lignin derivatives and/or technical lignins. As it is difficult to elucidate and characterize such complex mixture of molecules, lignin derivatives are usually described in terms of the lignocellulosic plant material used, and the methods by which they are generated and recovered from lignocellulosic plant material, i.e. hardwood lignins, softwood lignins, and annual fibre lignins.
- Native lignins are partially depolymerized during the pulping processes into lignin fragments which dissolve in the pulping liquors and subsequently separated from the cellulosic pulps.
- Post-pulping liquors containing lignin and polysaccharide fragments, and other extractives are commonly referred to as “black liquors” or “spent liquors", depending on the pulping process.
- black liquors or "spent liquors”
- Such liquors are generally considered a by-product, and it is common practice to combust them to recover some energy value in addition to recovering the cooking chemicals.
- Each type of pulping process used to separate cellulosic pulps from other lignocellulosic components produces lignin derivatives that are very different in their physico-chemical, biochemical, and structural properties.
- lignin derivatives are available from renewable biomass sources there is an interest in using these derivatives in certain industrial applications.
- lignin derivatives obtained via organosolv extraction such as the Alcell® process (Alcell is a registered trademark of Lignol Innovations Ltd., Burnaby, BC, CA)
- Alcell® process Alcell is a registered trademark of Lignol Innovations Ltd., Burnaby, BC, CA
- Alcell is a registered trademark of Lignol Innovations Ltd., Burnaby, BC, CA
- large-scale commercial application of the extracted lignin derivatives particularly those isolated in traditional pulping processes employed in the manufacture of pulp for paper production, has been limited due to, for example, the inconsistency of their chemical and functional properties.
- lignin derivatives are known to have antioxidant properties (e.g. Catignani G.L., Carter M.E., Antioxidant Properties of Lignin, Journal of Food Science, Volume 47, Issue 5, 1982, p. 1745; Pan X. et a/. J. Agric. Food Chem., Vol. 54, No. 16, 2006, pp. 5806-5813) but, to date, these properties have been highly variable making the industrial application of lignin derivatives as an antioxidant problematic.
- antioxidant properties e.g. Catignani G.L., Carter M.E., Antioxidant Properties of Lignin, Journal of Food Science, Volume 47, Issue 5, 1982, p. 1745; Pan X. et a/. J. Agric. Food Chem., Vol. 54, No. 16, 2006, pp. 5806-5813
- thermoplastics and thermosets are used extensively for a wide variety of purposes.
- examples of thermoplastics include classes of polyesters, polycarbonates, polylactates, polyvinyls, polystyrenes, polyamides, polyacetates, polyacrylates, polypropylene, and the like.
- Polyolefins such as polyethylene and polypropylene represent a large market, amounting to more than 100 million metric tons annually.
- processing and use the physical and chemical properties of certain thermoplastics can be adversely affected by various factors such as exposure to heat, UV radiation, light, oxygen, mechanical stress or the presence of impurities. Clearly it is advantageous to mitigate or avoid these problems. In addition, the increase in recycling of material has led to an increased need to address these issues.
- a stabilizer such as an antioxidant, anti-ozonant, or UV block is often included in thermoplastic resins for the purpose of aiding in the production process and extending the useful life of the product.
- stabilizers and antioxidants include amine types, phenolic types, phenol alkanes, phosphites, and the like. These additives often have undesirable or even unacceptable environmental, health and safety, economic, and/or disposal issues associated with their use. Furthermore, certain of these stabilizers/antioxidants can reduce the biodegradability of the product.
- lignin may provide a suitable polymeric natural antioxidant which has an acceptable toxicity, efficacy, and environmental profile. See, for example, A. Gregorova et a/., Radical scavenging capacity of lignin and its effect on processing stabilization of virgin and recycled polypropylene, Journal of Applied Polymer Science 106-3 (2007) pp. 1626- 1631; C. Pouteau et al. Antioxidant Properties of Lignin in Polypropylene, Polymer Degradation and Stability 81 (2003) 9-18.
- lignin for a variety of reasons, it has not been adopted for widespread use as an antioxidant. For instance, it is often problematic to provide lignins that perform consistently in terms of antioxidant activity. Also, the processing of the lignin may introduce substances that are incompatible for use with chemicals such as polyolefins. Additionally, the cost of producing and/or purifying the lignin may make it uneconomic for certain uses.
- the present invention provides derivatives of native lignin having a certain aliphatic hydroxyl content. Surprisingly, it has been found that consistent and predictable antioxidant activity may be provided by selecting for derivatives of native lignin having certain aliphatic hydroxyl contents.
- lignin refers to lignin in its natural state, in plant material.
- lignin derivatives and “derivatives of native lignin” refer to lignin material extracted from lignocellulosic biomass. Usually, such material will be a mixture of chemical compounds that are generated during the extraction process.
- Figure 1 shows the HSQC spectrum of non-acetylated hardwood lignin derivatives (arrows indicate the signals corresponding to the ethoxyl groups).
- Figure 2 shows the quantitative 13 C NMR spectrum of non-acetylated hardwood lignin derivatives.
- Figure 3 shows the quantitative 13 C NMR spectrum of acetylated hardwood lignin derivatives.
- the present invention provides derivatives of native lignin having certain aliphatic hydroxyl contents.
- Lignin derivatives having lower aliphatic hydroxyl contents have been found to score more highly on the Radical Scavenging Index (RSI), a measure of antioxidant activity.
- RSI Radical Scavenging Index
- selecting for derivatives of native lignin having a lower aliphatic hydroxyl content results in a product having a higher and more predictable antioxidant activity.
- derivatives of native lignin having an aliphatic hydroxyl content of about 2.35 mmol/g or less result in a good level of antioxidant activity. For example, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.
- Radical Scavenging Index is a measure of radical scavenging capacity. The assay uses
- DPPH 2,2-diphenyl-l-picrylhydrazyl
- RSI radical scavenging index
- DPPH 2,2-diphenyl-l-picrylhydrazyl
- BHT butylated hydroxytoluene
- the lignin derivative samples 1.0 - 2.0 mg
- Vit. E control samples 1.0-2.0 mg
- BHT control samples 6.0 - 8.0 mg
- the lignin derivative samples 1.0 - 2.0 mg
- Vit. E control samples 1.0-2.0 mg
- BHT control samples 6.0 - 8.0 mg
- An indicating (purple) DPPH stable free radical solution is made by dissolving 3.78 mg DPPH in 100 mL 90% dioxane (95.9 ⁇ M).
- Samples and standards are serially diluted to fill columns of a quarto 96-well plate (8 dilutions).
- the assays are performed by placing aliquots of the sample stock solutions into two rows of wells in a 96-well plate. The first row served as the reference row while the second row received DPPH aliquots. 165 ⁇ L of 90% dioxane was added to each well and mixed. Aliquots of the mixed samples in each row are transferred to the adjacent row which is further diluted with 165 ⁇ L of 90% dioxane in each well.
- the mixing, transferring and dilution are repeated until the last row of wells is prepared. The same volume of aliquots is removed from the last row.
- the 96-well plate also contains a row of wells that received only the 90% dioxane.
- 165 ⁇ L of the DPPH solution is added as quickly as possible to all the control and analytical columns by using an 8-channel auto-pipette and an Eppendorf ® reagent reservoir. As soon as all reagents are added, the plate is placed into a plate-reading spectrophotometer (Spectra Max Plus, Molecular Devices, Sunnyvale, CA, USA), and absorbance measurements are carried out.
- the program for the spectrophotometer (SOFTmax software) consists of a timing sequence of 16 min and a reading of the entire plate at 515 nm.
- RSI is defined as the inverse of the concentration which produces 50% inhibition in DPPH absorbance at 515 nm.
- the results are then 'normalized' by dividing the sample RSI by the RSI value for the BHT control.
- the normalized RSI is represented by this acronym "NRSI".
- the present invention provides derivatives of native lignin recovered during or after pulping of lignocellulosic feedstocks.
- the pulp may be from any suitable lignocellulosic feedstock including hardwoods, softwoods, annual fibres, and combinations thereof.
- Hardwood feedstocks include Acacia; Afzelia; Synsepalum duloificum; Albizia; Alder (e.g. Alnus glutinosa, Alnus rubra); Applewood; Arbutus; Ash (e.g. F. nigra, F. quadrangulata, F. excelsior, F. pennsylvanica lanceolata, F. latifolia, F. profunda, F. ame ⁇ cana); Aspen (e.g. P. grandidentata, P. tremula, P.
- Ironwood e.g. Bangkirai, Carpinus caroliniana, Casua ⁇ na equisetifolia, Cho ⁇ cbangarpia subargentea, Copaifera spp., Eusideroxylon ywageri, Guajacum officinale, Guajacum sanctum, Hopea odorata
- Quercus macrocarpa Quercus alba, Quercus stellata, Quercus bicolor, Quercus mrginiana, Quercus mi ⁇ auxii, Quercus prinus, Quercus muhlenbergii, Quercus chrysolepis, Quercus j I rata, Quercus robur, Quercus petraea, Quercus rubra, Quercus velutina, Quercus laurifolia, Quercus falcata, Quercus nigra, Quercus phellos, Quercus texana); Obeche; Okoume; Oregon Myrtle; California Bay Laurel; Pear; Poplar (e.g.
- P. balsamifera, P. nigra, Hybrid Poplar Populus X canadensis
- Ramin Red cedar; Rosewood; Sal; Sandalwood; Sassafras; Satinwood; Silky Oak; Silver Wattle; Snakewood; Sourwood; Spanish cedar; American sycamore; Teak; Walnut (e.g. Juglans nigra, Juglans ⁇ gid); Willow (e.g. Salix nigra, Salix alba); Yellow poplar (Uriodendron tulipifer ⁇ ); bamboo; Palmwood; and combinations /hybrids thereof.
- hardwood feedstocks for the present invention may be selected from Acacia,
- the hardwood feedstocks for the present invention may be selected from Populus spp. (e.g. Populus tremuloides), Eucaylptus spp. (e.g. Eucaylptus globulus), ⁇ ca ⁇ a spp. (e.g. ⁇ ca ⁇ a dealbata), and combinations /hybrids thereof.
- Populus spp. e.g. Populus tremuloides
- Eucaylptus spp. e.g. Eucaylptus globulus
- ⁇ ca ⁇ a spp. e.g. ⁇ ca ⁇ a dealbata
- derivatives of native lignin from hardwood feedstocks having an aliphatic hydroxyl content of about 2.35 mmol/g or less have a good level of antioxidant activity. For example, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.
- the aliphatic hydroxyl content can be measured by quantitative 13 C high resolution NMR spectroscopy of acetylated and non-acetylated lignin derivatives, using, for instance, 1,3,5-trioxane and tetramethyl silane (TMS) as internal reference.
- the spectrometer was coupled with a Bruker QNP cryoprobe (5 mm NMR samples, 13 C direct observe on inner coil, 1 H outer coil) that had both coils cooled by helium gas to 2OK and all preamplifiers cooled to 77K for maximum sensitivity.
- Sample temperature was maintained at 300 K ⁇ O.l K using a Bruker BVT 3000 temperature unit and a Bruker BCU05 cooler with ca. 95% nitrogen gas flowing over the sample tube at a rate of 800 L/h.
- the lignin derivatives herein may, for example, have an aliphatic hydroxyl content of 0.001 mmol/g or greater; 0.1 mmol/g or greater; 0.2 mmol/g or greater; 0.4 mmol/g or greater; 0.5 mmol/g or greater.
- Quantification of ethoxyl groups was performed similarly to aliphatic hydroxyls quantification by high resolution 13 C NMR spectroscopy. Identification of ethoxyl groups was confirmed by 2D NMR HSQC spectroscopy. 2D NMR spectra were recorded by a Bruker 700 MHz UltraShield Plus standard bore magnet spectrometer equipped with a sensitive cryogenically cooled 5mm TCI gradient probe with inverse geometry. The acquisition parameters were as follow: standard Bruker pulse program hsqcetgp, temperature of 298 K, a 90° pulse, 1.1 sec pulse delay (dl), and acquisition time of 60 msec.
- Derivatives of native lignin according to the present invention, coming from hardwood feedstocks tend to have a NRSI of 30 or greater, 40 or greater, 50 or greater, 60 or greater, 70 or greater, 80 or greater, 90 or greater, 100 or greater, 110 or greater, 120 or greater.
- Softwood feedstocks include Araucaria (e.g. A. cunninghamii, A. angustifolia, A. araucana); softwood Cedar (e.g. Juniperus virginiana, Thuja plicata, Thuja oc ⁇ dentalis, Chamaecyparis thyoides Callitropsis nootkatensis); Cypress (e.g. Chamaecyparis, Cupressus Taxodium, Cupressus arit ⁇ onica, Taxodium distichum, Chamaecyparis obtusa, Chamaecyparis lawsoniana, Cupressus sempervireri); Rocky Mountain Douglas fir; European Yew; Fir (e.g.
- Pinus nigra Pinus banksiana, Pinus contorta, Pinus radiata, Pinus ponderosa, Pinus resinosa, Pinus sylvestris, Pinus strobus, Pinus monticola, Pinus lambertiana, Pinus taeda, Pinus palustris, Pinus rigida, Pinus echinata); Redwood; Rimu; Spruce (e.g. Picea abies, Picea mariana, Picea rubens, Picea sitchensis, Picea glauca); Sugi; and combinations/hybrids thereof.
- Picea abies Picea mariana, Picea rubens, Picea sitchensis, Picea glauca
- Sugi and combinations/hybrids thereof.
- softwood feedstocks which may be used herein include cedar; fir; pine; spruce; and combinations thereof.
- the softwood feedstocks for the present invention may be selected from loblolly pine ⁇ Pinus taeda), radiata pine, jack pine, spruce (e.g., white, interior, black), Douglas fir, Pinus silvestris, Picea abies, and combinations /hybrids thereof.
- the softwood feedstocks for the present invention may be selected from pine (e.g. Pinus radiata, Pinus taeda); spruce; and combinations/hybrids thereof.
- derivatives of native lignin from softwood feedstocks having an aliphatic hydroxyl content of about 2.35 mmol/g or less have a good level of antioxidant activity. For example, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.
- Derivatives of native lignin according to the present invention, coming from softwood feedstocks tend to have a NRSI 15 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater, 45 or greater, 50 or greater, 55 or greater, 60 or greater.
- Annual fibre feedstocks include biomass derived from annual plants, plants which complete their growth in one growing season and therefore must be planted yearly.
- Examples of annual fibres include: flax, cereal straw (wheat, barley, oats), sugarcane bagasse, rice straw, corn stover, corn cobs, hemp, fruit pulp, alfa grass, switchgrass, and combinations /hybrids thereof.
- Industrial residues like corn cobs, fruit peals, seeds, etc. may also be considered annual fibres since they are commonly derived from annual fibre biomass such as edible crops and fruits.
- the annual fibre feedstock may be selected from wheat straw, corn stover, corn cobs, sugar cane bagasse, and combinations /hybrids thereof.
- Derivatives of native lignin according to the present invention coming from annual fibre feedstocks tend to have a NRSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater, 45 or greater, 50 or greater.
- derivatives of native lignin from annual fibre feedstocks have an aliphatic hydroxyl content of about 3.75 mmol/g or less; 3.5 mmol/g or less; 3.25 mmol/g or less; 3 mmol/g or less; 2.75 mmol/g or less; 2.5 mmol/g or less; 2.35 mmol/g or less; 2.25 mmol/g or less.
- the derivatives of native lignin will vary with the type of process used to separate native lignins from cellulose and other biomass constituents. Preparations very similar to native lignin can be obtained by (1) solvent extraction of finely ground wood (milled-wood lignin, MWL) or by (2) acidic dioxane extraction (acidolysis) of wood. Derivatives of native lignin can be also isolated from biomass pre-treated using (3) steam explosion, (4) dilute acid hydrolysis, (5) ammonia fibre expansion, (6) autohydrolysis methods.
- Derivatives of native lignin can be recovered after pulping of lignocellulosics including industrially operated (3) kraft and (4) soda pulping (and their nucleons) and (5) sulphite pulping.
- lignocellulosics including industrially operated (3) kraft and (4) soda pulping (and their nucleons) and (5) sulphite pulping.
- various pulping methods have been developed but not industrially introduced. Among them four major "organosolv” pulping methods tend to produce highly-purified lignin mixtures.
- the first organosolv method uses ethanol/solvent pulping (aka the Alcell® process); the second organosolv method uses alkaline sulphite anthraquinone methanol pulping (aka the "ASAM” process); the third organosolv process uses methanol pulping followed by methanol, NaOH, and anthraquinone pulping (aka the "Organocell” process); the fourth organosolv process uses acetic acid/hydrochloric acid or formic acid pulping (aka the "Acetosolv” process).
- kraft pulping, sulphite pulping, and ASAM organosolv pulping will generate derivatives of native lignin containing significant amounts of organically-bound sulphur which may make them unsuitable for certain uses. Acid hydrolysis, soda pulping, steam explosion,
- Alcell® pulping, Organocell pulping, and Acetosolv pulping will generate derivatives of native lignin that are sulphur- free or contain low amounts of inorganic sulphur.
- Organosolv processes tend to be less aggressive and can be used to separate highly purified lignin derivatives and other useful materials from biomass without excessively altering or damaging the native lignin building blocks. Such processes can therefore be used to maximize the value from all the components making up the biomass.
- Organosolv extraction processes however typically involve extraction at higher temperatures and pressures with a flammable solvent compared to other industrial processes and thus are generally considered to be more complex and expensive.
- the process generally comprises pulping or pre-treating a fibrous biomass feedstock with primarily an ethanol/water solvent solution under conditions that include: (a) 60% ethanol/40% water, (b) temperature of about 180° C to about 210° C, (c) pressure of about 20 atm to about 35 atm, and (d) a processing time of 5-120 minutes.
- Derivatives of native lignin are fractionated from the native lignins into the pulping liquor which also receives solubilised hemicelluloses, other carbohydrates and other extractives such as resins, organic acids, phenols, and tannins.
- Organosolv pulping liquors comprising the fractionated derivatives of native lignin and other extractives from the fibrous biomass feedstocks, are often called "black liquors".
- the organic acid and extractives released by organosolv pulping significantly acidify the black liquors to pH levels of about 5 and lower.
- the derivatives of native lignin are recovered from the black liquors by depressurization followed by flashing with cold water which will cause the fractionated derivatives of native lignin to precipitate thereby enabling their recovery by standard solids/liquids separation processes.
- WO 2007/129921 describe modifications to the Alcell organosolv process for the purposes of increasing the yields of fractionated derivatives of native lignin recovered from fibrous biomass feedstocks during biorefining.
- Modifications to the Alcell organosolv process conditions included adjusting: (a) ethanol concentration in the pulping liquor to a value selected from a range of 35% - 85% (w/w) ethanol, (b) temperature to a value selected from a range of 100° C to 350° C, (c) pressure to a value selected from a range of 5 atm to 35 atm, and (d) processing time to a duration from a range of 20 minutes to about 2 hours or longer, (e) liquor-to-wood ratio of 3:1 to 15:1 or higher, (f) pH of the cooking liquor from a range of 1 to 6.5 or higher if a basic catalyst is used.
- the present invention provides a process for producing derivatives of native lignin, said process comprising:
- the organic solvent may be selected from short chain primary and secondary alcohols, such as such as methanol, ethanol, propanol, and combinations thereof.
- the solvent may be ethanol.
- the liquor solution may comprise about 20%, by weight, or greater, about 30% or greater, about 50% or greater, about 60% or greater, about 70% or greater, of ethanol.
- Step (a) of the process may be carried out at a temperature of from about 100°C and greater, or about 120°C and greater, or about 140°C and greater, or about 160°C and greater, or about 170°C and greater, or about 18O 0 C and greater.
- the process may be carried out at a temperature of from about 300°C and less, or about 280°C and less, or about 260°C and less, or about 240°C and less, or about 22O 0 C and less, or about 210 0 C and less, or about 205 0 C and less, or about 200°C and less.
- Step (a) of the process may be carried out at a pressure of about 5 atm and greater, or about 10 atm and greater, or about 15 atm and greater, or about 20 atm and greater, or about 25 atm and greater, or about 30 atm and greater.
- the process may be carried out at a pressure of about 150 atm and less, or about 125 atm and less, or about 115 atm and less, or about 100 atm and less, or about 90 atm and less, or about 80 atm and less.
- the fibrous biomass may be treated with the solvent solution of step (a) for about 1 minute or more, about 5 minutes or more, about 10 minutes or more, about 15 minutes or more, about 30 minutes or more.
- the fibrous biomass may be treated with the solvent solution of step (a) at its operating temperature for about 360 minutes or less, about 300 minutes or less, about 240 minutes or less, about 180 minutes or less, about 120 minutes or less.
- the pH of the pulp liquor may, for example, be from about 1 to about 6, or from about 1.5 to about 5.5.
- the weight ratio of liquor to biomass may be any suitable ratio. For example, from about 5:1 to about 15:1, from about 5.5:1 to about 10:1; from about 6:1 to about 8:1.
- the volume of extraction solution is from about 5 to about 10 times the volume of the biomass feedstock.
- the volume of extraction solution may be from about 6 to about 8 times that of the biomass
- the present invention provides a process for producing a lignin derivative having an aliphatic hydroxyl content of about 2.35 mmol/g or less, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less. Said process comprises:
- the pH of the liquor is from about 1 to about 6;
- the present invention provides a process for producing a hardwood lignin derivative having an aliphatic hydroxyl content of about 2.35 mmol/g or less, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less, said process comprises:
- the solution comprises about 30% or greater, by weight, of organic solvent
- the pH of the liquor is from about 1 to about 6;
- the present invention provides a process for producing a softwood lignin derivative having an aliphatic hydroxyl content of about 2.35 mmol/g or less, about 2.25 mmol/g or less, about 2 rnmol/g or less, or about 1.75 mmol/g or less, said process comprises:
- the solution comprises about 30% or greater, by weight, of organic solvent
- the pH of the liquor is from about 1 to about 6;
- the present invention provides a process for producing an annual fibre lignin derivative having an aliphatic hydroxyl content of about 3.75 mmol/g or less; 3.5 mmol/g or less; 3.25 mmol/g or less; 3 mmol/g or less; 2.75 mmol/g or less; 2.5 mmol/g or less; 2.35 mmol/g or less; 2.25 mmol/g or less, said process comprises:
- the solution comprises about 30% or greater, by weight, of organic solvent
- the pH of the liquor is from about 1 to about 6;
- the derivatives of native lignin herein may be incorporated into polymer compositions.
- compositions herein may comprise a lignin derivative according to the present invention and a polymer-forming component.
- the term 'polymer-forming component' means a component that is capable of being polymerized into a polymer as well as a polymer that has already been formed.
- the polymer-forming component may comprise monomer units which are capable of being polymerized.
- the polymer component may comprise oligomer units that are capable of being polymerized.
- the polymer component may comprise a polymer that is already substantially polymerized.
- thermoplastic or thermoset polymers such as epoxy resins, urea- formaldehyde resins, phenol- formaldehyde resins, polyimides, isocyanate resins, and the like.
- polyalkenes such as polyethylene or polypropylene.
- the lignin derivative will comprise from about 0.1%, by weight, or greater, about 0.5% or greater, about 1% or greater, of the composition. Typically, the lignin derivative will comprise from about 80%, by weight, or less, about 60% or less, about 40% or less, about 20% or less, about 10% or less, of the composition.
- compositions comprise lignin derivative and polymer-forming component but may comprise a variety of other optional ingredients such as adhesion promoters; biocides (antibacterials, fungicides, and moldicides), anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppressants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes; plasticizers; processing aids; release agents; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; foaming agents; defoamers; hardeners; odorants; deodorants; antifouling agents; viscosity regulators; waxes; and combinations thereof
- the present invention provides the use of the present derivatives of native lignin as an antioxidant.
- the present use may be as an antioxidant additive for use with thermoplastic polymers such as polyethylene, polypropylene, polyamides, styrene-butadiene, natural rubber, and combinations thereof.
- Other examples include: antioxidant additives for use in the animal health and feed industry, human food and health.
- the present invention provides methods of producing derivatives of native lignin having an aliphatic hydroxyl content of about 2.35 mmol/g or less, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.
- the present invention provides methods of producing hardwood derivatives of native lignin having an aliphatic hydroxyl content of about 2.35 mmol/g or less result, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.
- the present invention provides methods of producing softwood derivatives of native lignin having an aliphatic hydroxyl content of about 2.35 mmol/g or less, about 2.25 mmol/g or less, about 2 mmol/g or less, or about 1.75 mmol/g or less.
- the present invention provides methods of producing annual fibre derivatives of native lignin having an aliphatic hydroxyl content of about 3.75 mmol/g or less; 3.5 mmol/g or less; 3.25 mmol/g or less; 3 mmol/g or less; 2.75 mmol/g or less; 2.5 mmol/g or less; 2.35 mmol/g or less; 2.25 mmol/g or less.
- the present invention provides methods of producing derivatives of native lignin having a NRSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater, 50 or greater, 60 or greater, 70 or greater.
- the present invention provides methods of producing hardwood derivatives of native lignin having a NRSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater, 50 or greater, 60 or greater, 70 or greater.
- the present invention provides methods of producing softwood derivatives of native lignin having a NRSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater.
- the present invention provides methods of producing annual fibre derivatives of native lignin having a NRSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater.
- the present invention provides lignin derivatives comprising alkoxy groups.
- the present lignin derivatives may have an alkoxy content of 2 mmol/g or less; about 1.4 mmol/g or less; about 1.2 mmol/g or less; about 1 mmol/g or less; about 0.8 mmol/g or less; about 0.7 mmol/g or less; about 0.6 mmol/g or less; about 0.5 mmol/g or less; about 0.4 mmol/g or less; about 0.3 mmol/g or less.
- the present lignin derivatives may have an alkoxy content of 0.001 mmol/g or greater, about 0.01 mmol/g of greater, about 0.05 mmol/g or greater, about 0.1 mmol/g or greater.
- the present invention provides lignin derivatives comprising ethoxyl groups.
- the present lignin derivatives may have an ethoxyl content of 2 mmol/g or less; about 1.4 mmol/g or less; about 1.2 mmol/g or less; about 1 mmol/g or less; about 0.8 mmol/g or less; about 0.7 mmol/g or less; about 0.6 mmol/g or less; about 0.5 mmol/g or less; about 0.4 mmol/g or less; about 0.3 mmol/g or less.
- the present lignin derivatives may have an ethoxyl content of 0.001 mmol/g or greater, about 0.01 mmol/g of greater, about 0.05 mmol/g or greater, about 0.1 mmol/g or greater.
- the present lignin derivatives may have any suitable phenolic hydroxyl content such as from about 2 mmol/g to about 8 mmol/g.
- the phenolic hydroxyl content may be from about 2.5 mmol/g to about 7 mmol/g; about 3 mmol/g to about 6 mmol/g.
- the present lignin derivatives may have any suitable number average molecular weight (Mn).
- Mn may be from about 200 g/mol to about 3000 g/mol; about 350 g/mol to about 2000 g/mol; about 500 g/mol to about 1500 g/mol.
- Mw weight average molecular weight
- the Mw may be from about 500 g/mol to about 5000 g/mol; about 750 g/mol to about 4000 g/mol; about 900 g/mol to about 3500 g/mol.
- the present lignin derivatives may have any suitable polydispersity (D).
- D may be from about 1 to about 5; from about 1.2 to about 4; from about 1.3 to about 3.5; from about 1.4 to about 3.
- the present lignin derivatives are preferably hydrophobic. Hydrophobicity may be assessed using contact angle measurements.
- lignins or lignin derivatives may be used in nutritional supplements (e.g. Baurhoo et. a/., Purified Lignin: Nutritional and Health Impacts on Farm Animals - A Review, Animal Feed Science and Technology 144 (2008) 175-184).
- the present derivatives of native lignin may be used in nutritional supplements, nutraceuticals, functional foods, and the like.
- the stable and consistent antioxidant activity may be advantageous when formulating such compositions.
- the present derivatives of native lignin may be used for other purposes such as, for example, laminates, stains, pigments, inks, adhesives, coatings, rubbers, elastomers, plastics, films, paints, carbon fibre composites, panel boards, print-circuit boards, lubricants, surfactants, oils, animal feed, food and beverages, and the like.
- Hardwood feedstock chips were prepared from: (1) aspen (P. tremuloides) grown in British
- Table 1 Pulping conditions for aspen wood chip samples at 6:1 liquor-to- wood ratio.
- Table 2 Pulping conditions for acacia wood chip samples at 6:1 liquor-to-wood ratio.
- Table 3 Pulping conditions for eucalyptus wood chip samples at 6:1 liquor-to-wood ratio.
- the ethanol pulping solvent was prepared to the specified concentration by first, partially diluting the ethanol with water after which, a suitable amount of sulphuric acid was added to achieve the target final acidity. Finally, the ethanol solution was further diluted with water to achieve the target ethanol concentration.
- the vessel was then pressurized and brought up to the target temperature listed in Tables 1-3 (aspen, acacia, eucalyptus, respectively).
- the biomass sample was then "cooked" for the specified period of time, after which, the pulping process was stopped.
- the contents of the pressure vessel were transferred to a hydraulic 20 ton manual shop press (Airco, China).
- the liquor was separated from the solids by first squeezing the pulped materials in the press to express the liquor.
- the expressed liquor was then filtered through a coarse silk screen to separate expressed chip residues from liquor stream. Next, fine particles were separated out from the liquor stream by filtration through fine filter paper (Whatman N° 1).
- the recovered fine particles represent lignin derivatives that were extracted and self-precipitated out from the liquor during cooling of the pulped biomass.
- the particulate lignin is herein referred to as self-precipitated lignin derivatives (Le., "SPL").
- SPL self-precipitated lignin derivatives
- the solubi ⁇ zed lignin derivatives still remaining in the filtered liquor were precipitated from by dilution with cold water.
- the lignin derivatives precipitated by dilution with cold water are referred to as precipitated lignin or "PL".
- each lignin derivative was determined in reference to total native lignin (sum of the acid-insoluble lignin and acid-soluble lignin) value determined for the original biomass sample before pulping.
- the yield of PL lignin derivatives for each sample is shown in Tables 1-3 on a weight % basis relative to their original lignin (acid-insoluble lignin plus acid-soluble lignin values). Characterization of the aliphatic hydroxyl content of lignin derivatives recovered from three hardwood species.
- Functionalized lignin derivatives recovered from hardwood biomass samples as described above were analyzed to determine the content of primary hydroxyl groups mmol/g sample (OH- pr mmol/g) and content of secondary hydroxyl groups mmol/g sample (OH-sec mmol/g). These values were then used to calculate mmol aliphatic hydroxyl groups/g sample (OH-al mmol/g).
- the NMR spectra were Fourier-transformed, phased, calibrated using TMS signals as a reference (0 ppm), and the baseline was corrected by using a polynomial function. The correction of baseline was done using the following interval references to be adjusted to zero: (220-215 ppm)- (185-182 ppm)-(97-92 ppm)-(5-(-20) ppm). No other regions were forced to 0.
- the signals in the quantitative 13 C NMR spectra were assigned on the basis of 2D HSQC spectra ( Figure 1) and a known database. The spectra were integrated then using the area of the internal standard (IS), trioxane, as the reference. Each spectrum was processed (as described) at least twice to ensure good reproducibility of the quantification.
- carboxyl and ester groups resonate in the resonance region of hydroxyl groups (171.5-166.5 ppm) in the spectra of acetylated lignins.
- the amounts of carboxyl and ester groups resonated in the interval of 171.5-166.5 ppm were determined from the spectra of non-acetylated lignins.
- the corrected content of hydroxyl groups was obtained then by deduction of the amounts of the carboxyl and ester groups from the corresponding resonances of hydroxy! groups (Table 4).
- the calculation of the quantity of the specific moieties was done as follows:
- X (mmol/g lignin) I x *m IS /(30m Llg *I IS )*1000
- X (mmol/g lignin) I x *m IS / (3Om L1 ⁇ I 15 - 42*I OHtotal * m IS )*1000
- Figure 1 shows the HSQC spectrum of non-acetylated hardwood lignin derivatives (arrows indicate the signals corresponding to the ethoxyl groups).
- the recorded 13 C NMR spectroscopic data are processed and graphically illustrated as shown in Fig. 2 and 3.
- the aliphatic hydroxyl contents of the PL lignin derivatives from each of the five samples of aspen chips are shown in Table 5. The contents ranged from 0.58 mmol/g in sample 1 to 2.21 mmol/g in sample 5.
- Table 5 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from aspen wood chips.
- the aliphatic hydroxyl contents of the PL lignin derivatives from each of the four samples of acacia chips are shown in Table 6. The contents ranged from 0.76 mmol/g in sample 1 to 2.31 mmol/g in sample 4.
- Table 6 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from acacia wood chips.
- Table 7 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from E.nitens wood chips.
- the lignin derivatives samples produced above were assessed for their normalized radical scavenging index (NRSI).
- the potential antioxidant activity of each PL lignin derivative was determined by measuring its radical savaging capacity.
- the assay used 2,2-diphenyl-l-picrylhydrazyl (DPPH), a stabile free radical which absorbs light strongly at 515 nm to measure a compound's radical scavenging index (RSI).
- DPPH* absorbs strongly at 515 nm and has a deep purple colour. As DPPH gives up its free electron to radical scavengers, it loses its purple colour and its absorbance shifts to 520 nm.
- E control samples 1.0 - 2.0 mg
- BHT control samples 6.0 - 8.0 mg
- E control samples 1.0 - 2.0 mg
- BHT control samples 6.0 - 8.0 mg
- E control samples 1.0 - 2.0 mg
- BHT control samples 6.0 - 8.0 mg
- An indicating (purple) DPPH stable free radical solution is made by dissolving 3.78 mg DPPH in 100 mL 90% dioxane (95.9 ⁇ M).
- Samples and standards are serial diluted to fill columns of a quartz 96-well plate (8 dilutions).
- the assays were performed by placing aliquots of the sample stock solutions into two rows of wells in a 96-well plate. The first row served as the reference row while the second row received DPPH aliquots. 165 ⁇ L of 90% dioxane was added to each well and mixed. Aliquots of the mixed samples in each row were transferred to the adjacent row and further diluted with 165 ⁇ L of 90% dioxane in each well. The mixing, transferring and dilution were repeated until the last row of wells is prepared. The same volume of aliquots was removed from the last row.
- the 96-well plate also contained a row of wells that received only the 90% dioxane.
- 165 ⁇ L of the DPPH solution was added to all the control and analytical columns by using an 8-channel auto-pipette and an Eppendorf ® reagent reservoir as quickly as possible.
- the plate is placed into a plate-reading spectrophotometer (Molecular Devices, Sunnyvale, CA, USA, Spectra Max Plus), and absorbance measurements are commenced.
- the program for the spectrophotometer (SOFTmax software) consisted of a timing sequence of 16 min and a reading of the entire plate at 515 nm.
- RSI radical scavenging index
- the NRSI values for lignin derivatives recovered from aspen wood chips are shown in Table 5.
- the NRSI values for lignin derivatives recovered from acacia wood chips are shown in Table 6.
- the NRSI values for lignin derivatives recovered from eucalyptus wood chips are shown in Table 7.
- Softwood feedstock chips were prepared from: (1) hybrid spruce trees grown in British
- Table 8 Pulping conditions for hybrid spruce wood chip samples at 6:1 liquor-to-wood ratio.
- Table 9 Pulping conditions for radiata pine wood chip samples at 6:1 liquor- to-wood ratio.
- Table 10 Pulping conditions for loblolly pine wood chip samples at 6:1 liquor-to-wood ratio.
- the ethanol pulping solvent was prepared to the specified concentration by first, partially diluting the ethanol with water after which, a suitable amount of sulphuric acid was added to achieve the target final acidity. Finally, the ethanol solution was further diluted with water to achieve the target ethanol concentration.
- the lignin content of each original fibrous biomass subsample was determined using the
- NREL method (NREL/TP-510-42618 (April 2008)). Then, after adding the fibrous biomass sample to a pressure vessel (2L or 7 L Parr reactor (Parr Instrument Company, Moline, IL, USA) (100-700 g odw chips), the pH-adjusted ethanol-based pulping solvent was added to the vessel at a 6:1 liquorwood ratio & the pH recorded. The vessel was then pressurized and brought up to the target temperature listed in Tables 8-10 (spruce, radiata pine, loblolly pine, respectively). The biomass sample was then "cooked" for the specified period of time, after which, the pulping process was stopped. After pulping, the contents of pressure vessel were transferred to a hydraulic 20 ton manual shop press (Airco, China).
- the liquor was separated from the solids by first squeezing the pulped materials in the press to express the liquor.
- the expressed liquor was then filtered through a coarse silk screen to separate expressed chip residues from liquor stream.
- fine particles were separated out from the liquor stream by filtration through fine filter paper (Whatman N° 1).
- the recovered fine particles represent lignin derivatives that were extracted and self-precipitated out from the liquor during cooling of the pulped biomass.
- the particulate lignin is herein referred to as self-precipitated lignin derivatives (i.e., "SPL").
- SPL self-precipitated lignin derivatives
- the lignin derivatives precipitated by dilution with cold water are referred to as precipitated lignin or "PL".
- PL precipitated lignin
- the relative yield of each lignin derivative was determined in reference to the total lignin content (acid-insoluble plus the acid-soluble lignin) determined for the original biomass sample before pulping.
- the yield of PL lignin derivatives for each sample is shown in Tables 8-10 on a weight % basis relative to total lignin in the original biomass.
- Functionalized lignin derivatives recovered from hardwood biomass samples as described above were analyzed using the procedures described in Example 1 to determine the weights of primary hydroxyl groups mmol/g sample (OH-pr mmol/g) and weights of secondary hydroxyl groups mmol /g sample (OH-sec mmol/g). These values were then used to calculate the total mmol aliphatic hydroxyl groups/g sample (OH-al mmol/g).
- the aliphatic contents of the PL lignin derivatives from each of the three samples of hybrid spruce chips are shown in Table 11. The contents ranged from 1.72 mmol/g in sample 1 to 2.24 mmol/g in sample 3.
- the aliphatic contents of the PL lignin derivatives from each of the three samples of radiata pine chips are shown in Table 12. The contents ranged from 2.18 mmol/g in sample 1 to 2.26 mmol/g in sample 3.
- the aliphatic contents of the PL lignin derivatives from each of the three samples of loblolly pine chips are shown in Table 13. The contents ranged from 1.35 mmol/g in sample 1 to 1.87 mmol/g in sample 3.
- Table 11 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from hybrid spruce wood chips.
- Table 12 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from radiata pine wood chips.
- Table 13 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from loblolly pine wood chips.
- NRSI normalized radical scavenging index
- Two sets of annual fibre feedstock materials were prepared from: (1) bagasse produced from sugarcane grown and processed in Brazil, and (2) corn cobs produced in Europe.
- Four samples of the sugarcane bagasse were individually pulped using an acid-catalyzed ethanol pulping process based wherein a different set of pulping conditions was used for each sample (Table 14).
- Table 14 Pulping conditions for sugarcane bagasse samples at 6:1 liquor-to-wood ratio.
- Table 15 Pulping conditions for corn cob samples at 6:1 liquor-to-wood ratio.
- the ethanol pulping solvent was prepared to the specified concentration by first, partially diluting the ethanol with water after which, a suitable amount of sulphuric acid was added to achieve the target final acidity. Finally, the ethanol solution was further diluted with water to achieve the target ethanol concentration.
- NREL method (NREL/TP-510-42618 (April 2008)). Then, after adding the fibrous biomass sample to a pressure vessel (2L or 7L Parr reactor (Parr Instrument Company, Moline, IL, USA) (100-700 g odw chips), the pH-adjusted ethanol-based pulping solvent was added to the vessel at a 6:1 liquor:biomass ratio & the pH recorded. The vessel was then pressurized and brought up to the target temperature listed in Tables 14-15 (bagasse, corncobs, respectively). The biomass sample was then "cooked" for the specified period of time, after which, the pulping process was stopped. After pulping, the contents of pressure vessel were transferred to a hydraulic 20 ton manual shop press (Aicro, China).
- the liquor was separated from the solids by first squeezing the pulped materials in the press to express the liquor.
- the expressed liquor was then filtered through a coarse silk screen to separate expressed chip residues from liquor stream.
- fine particles were separated out from the liquor stream by filtration through fine filter paper (Whatman N° 1).
- the recovered fine particles represent lignin derivatives that were extracted and self-precipitated out from the liquor during cooling of the pulped biomass.
- the particulate lignin is herein referred to as self-precipitated lignin derivatives (Le., "SPL").
- the solubilized lignin derivatives still remaining in the filtered liquor were precipitated from by dilution with cold water.
- the lignin derivatives precipitated by dilution with cold water are referred to as precipitated lignin or "PL".
- PL precipitated lignin
- the relative yield of each lignin derivative was determined in reference to the total lignin (sum of acid-insoluble lignin plus acid- soluble lignin) value determined for the original biomass sample before pulping.
- the yield of PL lignin derivatives for each sample is shown in Tables 14-15 on a weight % basis relative to their original total lignin values.
- Functionalized lignin derivatives recovered from annual fibre biomass samples as described above were analyzed using the procedures described in Example 1 to determine the primary hydroxyl groups mmol/g per sample (OH-pr mmol/g) and the secondary hydroxyl groups mmol /g sample (OH-sec mmol/g). These values were then used to calculate total mmol aliphatic hydroxyl groups /g sample (OH-al mmol/g).
- the aliphatic content of the PL lignin derivatives from each of the four samples of sugarcane bagasse biomass are shown in Table 16. The content ranged from 1.74 mmol/g in sample 1 to 2.34 mmol/g in sample 4.
- the aliphatic content of the PL lignin derivatives from each of the three samples of shredded corn cobs are shown in Table 17. The content ranged from 2.18 mmol/g in sample 1 to 2.26 mmol/g in sample 4.
- NRSI normalized radical scavenging index
- Table 16 Aliphatic hydroxyl content and normalized radical scavenging index of PL lignins recovered from sugarcane bagasse biomass.
- Table 17 Aliphatic hydroxyl content and radical scavenging index of PL lignins recovered from corn cobs biomass.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080029603.4A CN102459426B (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin |
EP10779947.0A EP2435453B1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin |
BRPI1014400-5A BRPI1014400B1 (en) | 2009-05-28 | 2010-02-15 | LIGNIN AND COMPOSITION DERIVATIVE |
CA2798158A CA2798158C (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18204409P | 2009-05-28 | 2009-05-28 | |
US61/182,044 | 2009-05-28 | ||
US23334509P | 2009-08-12 | 2009-08-12 | |
US61/233,345 | 2009-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2010135804A1 true WO2010135804A1 (en) | 2010-12-02 |
Family
ID=43220959
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2010/000209 WO2010135805A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin from annual fibre feedstocks |
PCT/CA2010/000210 WO2010135806A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin from softwood feedstocks |
PCT/CA2010/000211 WO2010135807A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin from hardwood feedstocks |
PCT/CA2010/000205 WO2010135804A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin |
PCT/CA2010/000801 WO2010135833A1 (en) | 2009-05-28 | 2010-05-27 | Derivatives of native lignin, lignin-wax compositions, their preparation, and uses thereof |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2010/000209 WO2010135805A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin from annual fibre feedstocks |
PCT/CA2010/000210 WO2010135806A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin from softwood feedstocks |
PCT/CA2010/000211 WO2010135807A1 (en) | 2009-05-28 | 2010-02-15 | Derivatives of native lignin from hardwood feedstocks |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2010/000801 WO2010135833A1 (en) | 2009-05-28 | 2010-05-27 | Derivatives of native lignin, lignin-wax compositions, their preparation, and uses thereof |
Country Status (6)
Country | Link |
---|---|
US (14) | US8431635B2 (en) |
EP (5) | EP2435454B1 (en) |
CN (4) | CN102459426B (en) |
BR (4) | BRPI1014395A8 (en) |
CA (6) | CA2798256C (en) |
WO (5) | WO2010135805A1 (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8404355B2 (en) | 2010-12-09 | 2013-03-26 | Virdia Ltd | Methods and systems for processing lignocellulosic materials and related compositions |
WO2014094104A1 (en) * | 2012-12-18 | 2014-06-26 | Lignol Innovations Ltd. | Processes for recovery of derivatives of native lignin |
US9115467B2 (en) | 2010-08-01 | 2015-08-25 | Virdia, Inc. | Methods and systems for solvent purification |
US9260609B2 (en) | 2009-05-28 | 2016-02-16 | Fibria Innovations Inc. | Derivatives of native lignin |
US9410216B2 (en) | 2010-06-26 | 2016-08-09 | Virdia, Inc. | Sugar mixtures and methods for production and use thereof |
US9476106B2 (en) | 2010-06-28 | 2016-10-25 | Virdia, Inc. | Methods and systems for processing a sucrose crop and sugar mixtures |
US9512495B2 (en) | 2011-04-07 | 2016-12-06 | Virdia, Inc. | Lignocellulose conversion processes and products |
EP3108938A1 (en) * | 2015-06-24 | 2016-12-28 | Procter & Gamble International Operations SA | Consumer goods product comprising lignin oligomer |
US9617608B2 (en) | 2011-10-10 | 2017-04-11 | Virdia, Inc. | Sugar compositions |
US9663836B2 (en) | 2010-09-02 | 2017-05-30 | Virdia, Inc. | Methods and systems for processing sugar mixtures and resultant compositions |
US9840621B2 (en) | 2011-03-24 | 2017-12-12 | Fibria Innovations Inc. | Compositions comprising lignocellulosic biomass and organic solvent |
US9895445B2 (en) | 2015-06-24 | 2018-02-20 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9902812B2 (en) | 2015-06-24 | 2018-02-27 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9901526B2 (en) | 2015-06-24 | 2018-02-27 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9907742B2 (en) | 2015-06-24 | 2018-03-06 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9982174B2 (en) | 2010-02-15 | 2018-05-29 | Fibria Innovations Inc. | Binder compositions comprising lignin derivatives |
US10533030B2 (en) | 2010-02-15 | 2020-01-14 | Suzano Canada Inc. | Carbon fibre compositions comprising lignin derivatives |
US11078548B2 (en) | 2015-01-07 | 2021-08-03 | Virdia, Llc | Method for producing xylitol by fermentation |
Families Citing this family (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20120012035A1 (en) * | 2009-03-20 | 2012-01-19 | Sika Technology Ag | Method for producing chemically modified lignin decomposition products |
US8378020B1 (en) | 2009-05-28 | 2013-02-19 | Lignol Innovations Ltd. | Processes for recovery of derivatives of native lignin |
CN107022089A (en) | 2009-05-28 | 2017-08-08 | 菲布里亚创新有限公司 | Resin combination comprising modified lignin |
US8569465B2 (en) * | 2009-07-06 | 2013-10-29 | Wisconsin Alumni Research Foundation | Method for modifying lignin structure using monolignol ferulate conjugates |
CA2769746C (en) | 2010-01-19 | 2013-10-15 | Renmatix, Inc. | Production of fermentable sugars and lignin from biomass using supercritical fluids |
CA2801384A1 (en) * | 2010-06-03 | 2011-12-08 | Lignol Innovations Ltd. | Environmental remediation using lignin |
EP2596104B1 (en) | 2010-07-23 | 2016-11-09 | Board Of Trustees Of Michigan State University | FERULOYL-CoA:MONOLIGNOL TRANSFERASE |
AT510812A1 (en) * | 2010-10-29 | 2012-06-15 | Annikki Gmbh | METHOD OF OBTAINING LIGNIN |
SG194724A1 (en) * | 2011-05-04 | 2013-12-30 | Renmatix Inc | Lignin production from lignocellulosic biomass |
EP2764096B1 (en) | 2011-10-06 | 2018-04-04 | Board Of Trustees Of Michigan State University | Hibiscus cannabinus feruloyl-coa:monolignol transferase |
EP2597100A1 (en) * | 2011-11-28 | 2013-05-29 | Annikki GmbH | Method for extracting low-molecular lignin (LML) |
ES2924876T3 (en) * | 2011-12-09 | 2022-10-11 | Upm Kymmene Corp | Method for preparing a lignin component, lignin component and its use and product |
WO2013090814A2 (en) | 2011-12-16 | 2013-06-20 | Board Of Trustees Of Michigan State University | p-Coumaroyl-CoA:Monolignol Transferase |
US8759498B2 (en) * | 2011-12-30 | 2014-06-24 | Renmatix, Inc. | Compositions comprising lignin |
CA3060976C (en) | 2012-05-03 | 2022-08-23 | Virdia, Inc. | Methods for treating lignocellulosic materials |
US9447326B2 (en) | 2012-06-22 | 2016-09-20 | Sundrop Fuels, Inc. | Pretreatment of biomass using steam explosion methods before gasification |
US9657146B2 (en) | 2013-03-14 | 2017-05-23 | Virdia, Inc. | Methods for treating lignocellulosic materials |
WO2014178911A1 (en) | 2013-05-03 | 2014-11-06 | Virdia, Inc. | Methods for treating lignocellulosic materials |
JP2016512285A (en) * | 2013-03-15 | 2016-04-25 | レンマティックス, インコーポレイテッドRenmatix, Inc. | High-purity lignin, lignin composition, and higher-order lignin |
KR20160007537A (en) | 2013-05-03 | 2016-01-20 | 버디아, 인크. | Methods for preparing thermally stable lignin fractions |
US20150045543A1 (en) | 2013-08-12 | 2015-02-12 | Melvin Mitchell | Isolation method for water insoluble components of a biomass and products provided therefrom |
US20150044306A1 (en) | 2013-08-12 | 2015-02-12 | Melvin Mitchell | Process for fractionation and extraction of herbal plant material to isolate extractives for pharmaceuticals and nutraceuticals |
US9421477B2 (en) | 2013-08-12 | 2016-08-23 | Green Extraction Technologies | Biomass fractionation and extraction apparatus |
US20160273010A1 (en) * | 2013-10-31 | 2016-09-22 | Virginia Tech Intellectual Properties, Inc. | Melt compounding and fractionation of lignocellulosic biomass and products produced therefrom |
FI126737B (en) | 2013-11-26 | 2017-04-28 | Upm Kymmene Corp | A process for treating lignin and preparing a binder composition |
EP3083653A4 (en) * | 2013-12-16 | 2017-08-23 | Ren Fuel K2B AB | Composition comprising esters of lignin and organic solvent |
CN103910766A (en) * | 2014-02-25 | 2014-07-09 | 北京林业大学 | Preparation method for poplar acetic acid lignin through separation and purification |
EP2918640A1 (en) * | 2014-03-13 | 2015-09-16 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Bitumen composition |
US10767308B2 (en) | 2014-07-09 | 2020-09-08 | Virdia, Inc. | Methods for separating and refining lignin from black liquor and compositions thereof |
US9458884B2 (en) * | 2014-08-18 | 2016-10-04 | Robert Alan Shortridge, SR. | Bearing surface coating |
JP6413522B2 (en) * | 2014-09-09 | 2018-10-31 | セイコーエプソン株式会社 | Sheet manufacturing apparatus, sheet manufacturing method, sheet manufactured by these, composite used for these, and container for the same |
SG11201701742RA (en) | 2014-09-26 | 2017-04-27 | Renmatix Inc | Adhesive compositions comprising type-ii cellulose |
KR20180026716A (en) | 2015-07-07 | 2018-03-13 | 솔레니스 테크놀러지스, 엘.피. | Methods for inhibiting the deposition of organic contaminants in pulp and paper making systems |
CN105304469B (en) * | 2015-09-25 | 2018-03-27 | 京东方科技集团股份有限公司 | A kind of polyimide substrate, its preparation method and flexible display |
JP6834140B2 (en) * | 2016-02-17 | 2021-02-24 | 富士通株式会社 | Information distribution system, information distribution program, information distribution method and information distribution device |
CN106189325A (en) * | 2016-08-04 | 2016-12-07 | 南京工业大学 | A kind of lignin enhancement mode Wood-plastic material and preparation method thereof |
BR102016019278A2 (en) * | 2016-08-19 | 2018-03-06 | Suzano Papel E Celulose S.A. | OLEFINIC POLYMERIC COMPOSITION, USE OF LIGNIN AND OBJECT |
CN106432909B (en) * | 2016-09-28 | 2019-03-29 | 武汉纺织大学 | A kind of lignin-base antioxidant and preparation method and application for polyolefin |
WO2018102378A1 (en) | 2016-12-02 | 2018-06-07 | The Willamette Valley Company Llc | Wax-organic extender emulsion and method for manufacture thereof |
AT519535A1 (en) * | 2016-12-23 | 2018-07-15 | Univ Wien Tech | PRODUCTION METHOD |
EP3615644B1 (en) | 2017-04-24 | 2023-08-23 | Cargill, Incorporated | Wax compositions and dissipation factor |
EP3615645A4 (en) * | 2017-04-26 | 2021-01-27 | Cargill, Incorporated | Wax compositions and surface tension |
JP2020533436A (en) * | 2017-09-07 | 2020-11-19 | レンマティックス, インコーポレイテッドRenmatix, Inc. | Polymer antioxidant stabilizer |
PT115562B (en) * | 2019-06-03 | 2021-12-24 | Raiz Instituto De Investig Da Floresta E Papel | EUCALYPTUS GLOBULUS PEEL PULP AND ITS PRODUCTION PROCESS FOR TISSUE PAPER PRODUCTS |
FR3097849B1 (en) * | 2019-06-27 | 2021-07-30 | Univ De Pau Et Du Pays De Ladour | Food packaging material and preparation process |
CA3091213A1 (en) | 2019-08-26 | 2021-02-26 | Walker Industries Holdings Limited | Aqueous wax emulsions and dispersions and uses thereof |
US11155683B2 (en) | 2019-09-13 | 2021-10-26 | Nanophase Technologies Corporation | Lipophillically dispersed phenolic polymer particles |
WO2022016117A1 (en) | 2020-07-16 | 2022-01-20 | Nanophase Technologies Corporation | Particulates of polyphenolics and dispersions thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4764596A (en) | 1985-11-05 | 1988-08-16 | Repap Technologies Inc. | Recovery of lignin |
WO2007129921A1 (en) | 2006-05-08 | 2007-11-15 | Biojoule Ltd. | Process for the production of biofuel from plant materials |
US7465791B1 (en) | 2007-05-31 | 2008-12-16 | Lignol Innovations Ltd. | Continuous counter-current organosolv processing of lignocellulosic feedstocks |
Family Cites Families (130)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US789366A (en) * | 1903-11-18 | 1905-05-09 | Hart & Hegeman Mfg Co | Electric switch. |
US1358164A (en) | 1919-11-11 | 1920-11-09 | Victor A Kottinger | Lathe-center |
US2508735A (en) * | 1947-06-18 | 1950-05-23 | Socony Vacuum Oil Co Inc | Glazing compositions |
US2934531A (en) | 1957-12-02 | 1960-04-26 | Int Paper Canada | Manufacture of lignin derivatives |
US2977352A (en) | 1958-07-25 | 1961-03-28 | Int Paper Canada | Process for obtaining infusible products of high carbon contents from lignin sulphonates |
US3461082A (en) | 1964-10-10 | 1969-08-12 | Nippon Kayaku Kk | Method for producing carbonized lignin fiber |
US3546199A (en) | 1967-02-06 | 1970-12-08 | Kaiser Aluminium Chem Corp | Process for producing polyoxyalkylene ether-polyols from lignin |
US3585104A (en) * | 1968-07-29 | 1971-06-15 | Theodor N Kleinert | Organosolv pulping and recovery process |
CA1079008A (en) | 1975-10-24 | 1980-06-10 | Cp Associates Limited | Solvent pulping process |
CA1100266A (en) | 1977-08-31 | 1981-05-05 | Laszlo Paszner | Organosolv delignification and saccharification process for lignocellulosic plant materials |
US4594130A (en) | 1978-11-27 | 1986-06-10 | Chang Pei Ching | Pulping of lignocellulose with aqueous alcohol and alkaline earth metal salt catalyst |
AU531852B2 (en) | 1979-10-17 | 1983-09-08 | Hayes, F.W. | Production of ethanol from sugar cane |
US4279788A (en) | 1980-04-18 | 1981-07-21 | Boise Cascade Corporation | Aqueous polyisocyanate-lignin adhesive |
US4308033A (en) * | 1980-10-23 | 1981-12-29 | Gunnerman Rudolf W | Fuel pellet and process for making it by shaping under pressure an organic fibrous material |
US4612017A (en) * | 1981-02-18 | 1986-09-16 | Georgia-Pacific Corporation | Pelletizing wood |
CA1201115A (en) | 1981-03-26 | 1986-02-25 | Laszlo Paszner | High efficiency organosolv saccharification process |
US4470851A (en) | 1981-03-26 | 1984-09-11 | Laszlo Paszner | High efficiency organosolv saccharification process |
US4486557A (en) | 1981-11-11 | 1984-12-04 | Atlantic Richfield Company | Organic polyisocyanate-liquid aromatic epoxide-lignin adhesive binder compositions |
EP0105937B1 (en) | 1982-10-04 | 1987-11-19 | Baron Howard Steven Strouth | Method of manufacturing alcohol from ligno-cellulose material |
HU197774B (en) | 1983-02-16 | 1989-05-29 | Laszlo Paszner | Organic solvent process for the hydrolytic saccharification of vegetable materials of starch type |
GB8526723D0 (en) | 1985-10-30 | 1985-12-04 | Rca Corp | Spacecraft structure |
US5788812A (en) * | 1985-11-05 | 1998-08-04 | Agar; Richard C. | Method of recovering furfural from organic pulping liquor |
CA1267648A (en) * | 1985-11-05 | 1990-04-10 | Raphael Katzen | Process for lignin recovery |
CA1278294C (en) * | 1987-09-17 | 1990-12-27 | George S. Ritchie | Method for fractionation of lignins from steam exploded lignocellulosics to provide fractions with different, but reproducible properties,and some methods for their interconversions and the products so produced |
US4918167A (en) | 1988-04-19 | 1990-04-17 | Center For Innovative Technology | Method of producing prepolymers from hydroxyalkyl lignin derivatives |
US4897497A (en) | 1988-04-26 | 1990-01-30 | Biofine Incorporated | Lignocellulose degradation to furfural and levulinic acid |
US5344921A (en) | 1988-06-06 | 1994-09-06 | Forestry And Forest Products Research Institute, Ministry Of Agriculture, Forestry And Fisheries | Method for manufacturing lignin for carbon fiber spinning |
US5223601A (en) | 1988-12-29 | 1993-06-29 | Midwest Research Institute Ventures, Inc. | Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils |
US4968771A (en) | 1989-10-17 | 1990-11-06 | Georgia-Pacific Resins, Inc. | Wood adhesives modified with surface active agents |
US5196460A (en) | 1990-05-29 | 1993-03-23 | Repap Technologies Inc. | Rubber compositions containing high purity lignin derivatives |
EP0472820B1 (en) * | 1990-08-17 | 1997-10-29 | Alcell Technologies Inc. | Continuous solvent pulping process |
EP0485150A1 (en) | 1990-11-06 | 1992-05-13 | Biodyne Chemical Inc. | Pulping processes, extraction of lignin and composition of matter for use in such processes |
US5173527A (en) | 1991-05-15 | 1992-12-22 | Forintek Canada Corp. | Fast cure and pre-cure resistant cross-linked phenol-formaldehyde adhesives and methods of making same |
US5411594A (en) | 1991-07-08 | 1995-05-02 | Brelsford; Donald L. | Bei hydrolysis process system an improved process for the continuous hydrolysis saccharification of ligno-cellulosics in a two-stage plug-flow-reactor system |
US5202403A (en) | 1992-01-15 | 1993-04-13 | Georgia-Pacific Resins, Inc. | Lignin modified phenol-formaldehyde resins |
CA2116544A1 (en) * | 1992-01-29 | 1993-08-05 | Jairo H. Lora | Pulping of fibrous plant materials and recovery of resultant by-products |
DE4241513A1 (en) | 1992-12-10 | 1994-06-16 | Ruetgerswerke Ag | Binder mixture |
US5424417A (en) | 1993-09-24 | 1995-06-13 | Midwest Research Institute | Prehydrolysis of lignocellulose |
ZA957645B (en) | 1994-09-13 | 1996-10-14 | Innoval Management Ltd | A method for production of ethyl alcohol |
US5730837A (en) | 1994-12-02 | 1998-03-24 | Midwest Research Institute | Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars |
US5756098A (en) | 1995-12-12 | 1998-05-26 | The University Of Montana | Methods for the extraction of phytochemicals from fibrous plants in the absence of solvent |
KR19980702567A (en) | 1995-12-29 | 1998-07-15 | 케네쓰 알. 커플 | Lignin-Base Polyol |
SE506458C2 (en) | 1996-02-09 | 1997-12-15 | Kvaerner Pulping Tech | Continuous boiling of cellulosic material with heat exchange between boiler extraction and circulating boiling liquid |
BR9600672A (en) | 1996-03-08 | 1997-12-30 | Dedini S A Administracao E Par | Acid hydrolysis process of lignocellulosic material and hydrolysis reactor |
EP0923651B1 (en) | 1996-05-20 | 2003-10-01 | Bundaberg Foundry Engineers Ltd. | Apparatus and method for crushing sugar cane |
DE19632623A1 (en) * | 1996-08-13 | 1998-02-19 | Consortium Elektrochem Ind | Multi-component system for changing, breaking down or bleaching lignin, lignin-containing materials or similar substances as well as methods for their use |
US6228177B1 (en) | 1996-09-30 | 2001-05-08 | Midwest Research Institute | Aqueous fractionation of biomass based on novel carbohydrate hydrolysis kinetics |
US6022419A (en) | 1996-09-30 | 2000-02-08 | Midwest Research Institute | Hydrolysis and fractionation of lignocellulosic biomass |
US5911276A (en) | 1997-05-27 | 1999-06-15 | Texaco Inc | Use of unmodified kraft lignin, an amine and a water-soluble sulfonate composition in enhanced oil recovery |
US5916780A (en) | 1997-06-09 | 1999-06-29 | Iogen Corporation | Pretreatment process for conversion of cellulose to fuel ethanol |
DE69735372T2 (en) | 1997-09-12 | 2006-10-19 | Kabushiki Kaisha Maruto, Yokkaichi | LIGNINE DERIVATIVES, DERIVATIVE MOLDED PARTS AND METHOD OF PREPARING THEM |
CN1211394C (en) * | 1997-09-12 | 2005-07-20 | 船冈正光 | Novel lignin derivative, moldings produced by using the derivative, and process for the preparation thereof |
US6342378B1 (en) | 1998-08-07 | 2002-01-29 | The Regents Of The University Of California | Biogasification of solid waste with an anaerobic-phased solids-digester system |
US6172272B1 (en) | 1998-08-21 | 2001-01-09 | The University Of Utah | Process for conversion of lignin to reformulated, partially oxygenated gasoline |
US6172204B1 (en) | 1999-06-04 | 2001-01-09 | Regents Of The University Of Minnesota | Compositions based on lignin derivatives |
US6281328B1 (en) | 1999-08-06 | 2001-08-28 | Exxonmobil Research And Engineering Company | Process for extraction of naphthenic acids from crudes |
DE19952563A1 (en) * | 1999-11-01 | 2001-05-03 | Romonta Gmbh | Wax compound |
US6258175B1 (en) | 1999-11-03 | 2001-07-10 | Gene E. Lightner | Method to produce fermentable sugars from a lignocellulose material |
WO2001060752A1 (en) * | 2000-02-17 | 2001-08-23 | Forskningscenter Risø | A method for processing lignocellulosic material |
US20020069987A1 (en) | 2000-08-08 | 2002-06-13 | Pye Edward Kendall | Integrated processing of biomass and liquid effluents |
US6423145B1 (en) | 2000-08-09 | 2002-07-23 | Midwest Research Institute | Dilute acid/metal salt hydrolysis of lignocellulosics |
US6852234B2 (en) | 2000-11-09 | 2005-02-08 | The Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Apparatus and method for in situ burning of oil spills |
US6464827B1 (en) * | 2000-11-28 | 2002-10-15 | Praxair Technology, Inc. | Method of digesting wood with an alkaline liquor by adding an acidic agent to precipitate dissociated lignin |
JP4632166B2 (en) | 2001-01-31 | 2011-02-16 | 日本ポリウレタン工業株式会社 | Adhesive composition for lignocellulosic hot-press molded body and method for producing hot-press molded body using the same |
US6632286B2 (en) | 2001-03-19 | 2003-10-14 | Trustees Of Dartmouth College | Cross-flow process for the production of decomposable soluble products from a slurry of solids |
WO2003071025A2 (en) | 2002-02-22 | 2003-08-28 | Gilles Gervais | Process of treating lignocellulosic material to produce bio-ethanol |
CN1421423A (en) * | 2003-01-08 | 2003-06-04 | 中国科学院生态环境研究中心 | Organic-inorganic composite fertilizer with lignin |
US8877992B2 (en) | 2003-03-28 | 2014-11-04 | Ab-Cwt Llc | Methods and apparatus for converting waste materials into fuels and other useful products |
GB0402469D0 (en) | 2004-02-04 | 2004-03-10 | Ciba Spec Chem Water Treat Ltd | Production of a fermentation product |
US7081159B2 (en) * | 2004-03-19 | 2006-07-25 | The University Of Southern Mississippi | Soy protein based adhesive and particleboard |
SI3219806T1 (en) | 2004-03-25 | 2020-08-31 | Novoyzmes, Inc. | Methods for degrading or converting plant cell wall polysaccharides |
SE527646C2 (en) | 2004-09-24 | 2006-05-02 | Skandinavisk Kemiinformation A | Production of engine fuel or hydrogen for fuel cells from lignocellulosic material, comprises disolving lignin, hydrolysis, fermentation and pyrolysis or gasification steps |
CN100365068C (en) | 2004-10-25 | 2008-01-30 | 罗学刚 | Environment friendly lignin resin of high water absorbence and its preparation method |
DK176774B1 (en) | 2004-12-22 | 2009-08-03 | Danish Plant Fibre Technologie | Modified sorbent lignocellulosic fibrous material, process for its preparation, method of removing contaminants from fluid and aqueous media, and application of the material |
US7842731B2 (en) * | 2005-05-20 | 2010-11-30 | Henry Company | Wax emulsion for manufacture of composite boards |
US20070034345A1 (en) | 2005-06-15 | 2007-02-15 | Leonardus Petrus | Process for organosolv pulping and use of a gamma lactone in a solvent for organosolv pulping |
US20070036873A1 (en) | 2005-07-27 | 2007-02-15 | Shibnath Ghosal | Method of treatment or management of stress |
BRPI0505212A (en) * | 2005-11-01 | 2007-08-07 | Dedini Sa Ind De Base | improvements in fast acid hydrolysis process of lignocellulosic material and hydrolysis reactor |
US7604743B2 (en) | 2005-12-19 | 2009-10-20 | Stanley Consultants, Inc. | Process for producing ethanol and for energy recovery |
JP4963616B2 (en) | 2006-03-23 | 2012-06-27 | Jx日鉱日石エネルギー株式会社 | Adsorbent for removing trace components in hydrocarbon oil and method for producing the same |
US20080021155A1 (en) | 2006-04-21 | 2008-01-24 | Bono Pierre J | Methods for Producing Modified Aromatic Renewable Materials and Compositions Thereof |
US20090062516A1 (en) * | 2006-05-08 | 2009-03-05 | Biojoule Limited | Lignin and other products isolated from plant material, methods for isolation and use, and compositions containing lignin and other plant-derived products |
JP4958166B2 (en) | 2006-05-31 | 2012-06-20 | 独立行政法人産業技術総合研究所 | Treatment of plant biomass with alcohol in the presence of oxygen |
GB2439135A (en) | 2006-06-13 | 2007-12-19 | Ecopulpa Limitada | Pulp process |
WO2008008793A2 (en) | 2006-07-10 | 2008-01-17 | Dyadic International Inc. | Methods and compositions for degradation of lignocellulosic material |
WO2008033812A2 (en) | 2006-09-11 | 2008-03-20 | Purdue Research Foundation | System and process for producing synthetic liquid hydrocarbon |
WO2008033709A2 (en) | 2006-09-12 | 2008-03-20 | Soane Energy Llc | Tunable surfactants for oil recovery applications |
US7959765B2 (en) | 2007-02-06 | 2011-06-14 | North Carolina State Universtiy | Product preparation and recovery from thermolysis of lignocellulosics in ionic liquids |
US8329436B2 (en) | 2007-02-09 | 2012-12-11 | Zeachem, Inc. | Method of making propanol and ethanol from plant material by biological conversion and gasification |
CA2597135C (en) | 2007-04-27 | 2011-07-26 | Lignol Energy Corporation | Continuous counter-current organosolv processing of lignocellulosic feedstocks |
CA2685177A1 (en) | 2007-05-02 | 2008-11-13 | Mascoma Corporation | Two-stage method for pretreatment of lignocellulosic biomass |
AR060847A1 (en) | 2007-05-03 | 2008-07-16 | Spannagel Lucia Antonia | FORMULATION BASED ON CALENDULA, ALOE AND CENTELLA. |
NZ580751A (en) | 2007-05-31 | 2012-08-31 | Lignol Innovations Ltd | Continuous counter-current organosolv processing of lignocellulosic feedstocks |
US8193324B2 (en) | 2007-05-31 | 2012-06-05 | Lignol Innovations Ltd. | Continuous counter-current organosolv processing of lignocellulosic feedstocks |
WO2008144903A1 (en) | 2007-05-31 | 2008-12-04 | Lignol Innovations Ltd. | Concurrent anaerobic digestion and fermentation of lignocellulosic feedstocks |
US7678358B2 (en) | 2007-06-25 | 2010-03-16 | Weyerhaeuser Nr Company | Carbon fibers from kraft softwood lignin |
US8058041B2 (en) | 2007-07-04 | 2011-11-15 | Alex Berlin | Concurrent saccharification and fermentation of fibrous biomass |
EP2025735A1 (en) | 2007-08-14 | 2009-02-18 | Bergen Teknologioverforing AS | One-step conversion of solid lignin to liquid products |
CA2697469A1 (en) * | 2007-08-31 | 2009-03-05 | Biojoule Ltd. | Lignin and other products isolated from plant material, and methods and compositions therefor |
ES2326455B2 (en) | 2007-11-27 | 2010-02-26 | Universidad De Sevilla | PROCEDURE FOR THE MANUFACTURING IN AMBIENT TEMPERATURE OF MICRO AND NANOFIBERS OF LIGNINA AND OTHER RESINOSUS COMPOUNDS. |
DE202008001703U1 (en) * | 2008-02-07 | 2008-04-10 | Spalt Trauerwaren Gmbh | coffin fittings |
US7960325B2 (en) * | 2008-02-15 | 2011-06-14 | Renewable Densified Fuels, Llc | Densified fuel pellets |
JP5461799B2 (en) * | 2008-07-30 | 2014-04-02 | 株式会社ニューフレアテクノロジー | Charged particle beam drawing apparatus and method for diagnosing DAC amplifier unit in charged particle beam drawing apparatus |
US7947182B2 (en) | 2008-08-29 | 2011-05-24 | Conocophillips Company | Naphthenic acid removal process |
US20100071829A1 (en) | 2008-09-25 | 2010-03-25 | Jay Tanzer | Accelerated Curing Adhesive For Wood Composites |
US8278070B2 (en) | 2008-12-19 | 2012-10-02 | E I Du Pont De Nemours And Company | Organic solvent pretreatment of biomass to enhance enzymatic saccharification |
US20100159522A1 (en) | 2008-12-19 | 2010-06-24 | E.I. De Pont De Nemours And Company | Organosolv and ozone treatment of biomass to enhance enzymatic saccharification |
BRPI1007047A2 (en) | 2009-01-16 | 2015-08-18 | Lignol Innovations Ltd | Whole sugarcane biorrefino irganosolv. |
PL2421911T3 (en) | 2009-04-23 | 2015-04-30 | Greenfield Ethanol Inc | Separation of reactive cellulose from lignocellulosic biomass with high lignin content |
US8431635B2 (en) | 2009-05-28 | 2013-04-30 | Lignol Innovations Ltd. | Derivatives of native lignin from softwood feedstocks |
US8378020B1 (en) | 2009-05-28 | 2013-02-19 | Lignol Innovations Ltd. | Processes for recovery of derivatives of native lignin |
CN107022089A (en) | 2009-05-28 | 2017-08-08 | 菲布里亚创新有限公司 | Resin combination comprising modified lignin |
US9335043B2 (en) | 2009-08-24 | 2016-05-10 | Abengoa Bioenergy New Technologies, Inc. | Method for producing ethanol and co-products from cellulosic biomass |
US20120202260A1 (en) | 2009-09-04 | 2012-08-09 | Lignol Innovations Ltd. | Hybrid biorefining and gasification of lignocellulosic feedstocks |
US8821733B2 (en) | 2009-09-29 | 2014-09-02 | Soane Mining, Llc | Systems and methods for recovering fine particles from fluid suspensions for combustion |
US20110091711A1 (en) | 2009-10-20 | 2011-04-21 | University Of Maine System Board Of Trustees | Carbon nanostructures from organic polymers |
EP2536780A4 (en) | 2010-02-15 | 2013-11-13 | Lignol Innovations Ltd | Carbon fibre compositions comprising lignin derivatives |
CA2827023A1 (en) | 2010-02-15 | 2011-08-18 | Lignol Innovations Ltd. | Organosolv process |
CN102959033B (en) | 2010-02-15 | 2016-10-12 | 丽格诺新创有限公司 | Adhesive composition containing modified lignin |
CA2695083A1 (en) | 2010-03-01 | 2011-09-01 | Lignol Innovations Ltd. | Multiple batch organosolv extraction system |
WO2011140306A1 (en) | 2010-05-05 | 2011-11-10 | Soane Energy, Llc | Systems and methods for removing oil from fluid streams |
CA2801384A1 (en) | 2010-06-03 | 2011-12-08 | Lignol Innovations Ltd. | Environmental remediation using lignin |
CA2803177C (en) | 2010-06-30 | 2018-07-24 | Lignol Innovations Ltd. | Organosolv process |
EP2614108A2 (en) | 2010-09-07 | 2013-07-17 | Lignol Innovations Ltd. | Biomass extraction process |
CA2812346A1 (en) | 2010-09-24 | 2012-03-29 | Lignol Innovations Ltd. | Remediation of naphthenic acid contamination |
EP2688959A4 (en) | 2011-03-24 | 2014-09-10 | Lignol Innovations Ltd | Compositions comprising lignocellulosic biomass and organic solvent |
WO2012129652A1 (en) | 2011-03-29 | 2012-10-04 | Lignol Innovations Ltd. | Flocculants for enzyme recovery and recycling |
US8399688B2 (en) | 2011-05-25 | 2013-03-19 | Wisconsin Alumni Research Foundation | Production of levulinic acid, furfural, and gamma valerolactone from C5 and C6 carbohydrates in mono- and biphasic systems using gamma-valerolactone as a solvent |
US9174909B2 (en) | 2012-02-02 | 2015-11-03 | Wisconsin Alumni Research Foundation | Two-stage, acid-catalyzed conversion of carbohydrates into levulinic acid |
CA2895215A1 (en) | 2012-12-18 | 2014-06-26 | Fibria Innovations Inc. | Processes for recovery of derivatives of native lignin |
-
2010
- 2010-02-15 US US12/705,938 patent/US8431635B2/en active Active
- 2010-02-15 BR BRPI1014395A patent/BRPI1014395A8/en not_active Application Discontinuation
- 2010-02-15 WO PCT/CA2010/000209 patent/WO2010135805A1/en active Application Filing
- 2010-02-15 WO PCT/CA2010/000210 patent/WO2010135806A1/en active Application Filing
- 2010-02-15 BR BRPI1012286A patent/BRPI1012286A2/en not_active Application Discontinuation
- 2010-02-15 US US12/705,939 patent/US8426502B2/en active Active
- 2010-02-15 CA CA2798256A patent/CA2798256C/en active Active
- 2010-02-15 CN CN201080029603.4A patent/CN102459426B/en active Active
- 2010-02-15 CA CA2798161A patent/CA2798161C/en active Active
- 2010-02-15 CA CA2798160A patent/CA2798160A1/en not_active Abandoned
- 2010-02-15 WO PCT/CA2010/000211 patent/WO2010135807A1/en active Application Filing
- 2010-02-15 WO PCT/CA2010/000205 patent/WO2010135804A1/en active Application Filing
- 2010-02-15 CA CA2798158A patent/CA2798158C/en active Active
- 2010-02-15 CN CN201080029015.0A patent/CN102459424B/en active Active
- 2010-02-15 CN CN201080029026.9A patent/CN102803281B/en active Active
- 2010-02-15 BR BRPI1014694-6A patent/BRPI1014694A2/en not_active Application Discontinuation
- 2010-02-15 EP EP10779948.8A patent/EP2435454B1/en active Active
- 2010-02-15 US US12/705,934 patent/US8445562B2/en active Active
- 2010-02-15 CA CA2989498A patent/CA2989498C/en active Active
- 2010-02-15 CN CN201080029348.3A patent/CN102459425B/en active Active
- 2010-02-15 EP EP10779949.6A patent/EP2435455B1/en active Active
- 2010-02-15 BR BRPI1014400-5A patent/BRPI1014400B1/en active IP Right Grant
- 2010-02-15 EP EP10779947.0A patent/EP2435453B1/en active Active
- 2010-02-15 EP EP10779950A patent/EP2435456A4/en not_active Withdrawn
- 2010-02-15 US US12/705,944 patent/US8288460B2/en active Active
- 2010-05-27 US US13/322,907 patent/US20120247617A1/en not_active Abandoned
- 2010-05-27 CA CA2798196A patent/CA2798196C/en active Active
- 2010-05-27 EP EP10779976A patent/EP2435458A4/en not_active Withdrawn
- 2010-05-27 WO PCT/CA2010/000801 patent/WO2010135833A1/en active Application Filing
-
2013
- 2013-03-14 US US13/829,608 patent/US8696865B2/en active Active
- 2013-03-14 US US13/826,817 patent/US8912257B2/en active Active
- 2013-05-16 US US13/896,254 patent/US8765846B2/en active Active
-
2014
- 2014-02-24 US US14/188,495 patent/US9150729B2/en active Active
- 2014-06-05 US US14/297,360 patent/US9260609B2/en active Active
- 2014-12-15 US US14/570,815 patent/US9447280B2/en active Active
-
2015
- 2015-08-13 US US14/826,147 patent/US9347177B2/en active Active
-
2016
- 2016-01-05 US US14/988,515 patent/US9708490B2/en active Active
-
2017
- 2017-04-27 US US15/499,585 patent/US10435562B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4764596A (en) | 1985-11-05 | 1988-08-16 | Repap Technologies Inc. | Recovery of lignin |
WO2007129921A1 (en) | 2006-05-08 | 2007-11-15 | Biojoule Ltd. | Process for the production of biofuel from plant materials |
US7465791B1 (en) | 2007-05-31 | 2008-12-16 | Lignol Innovations Ltd. | Continuous counter-current organosolv processing of lignocellulosic feedstocks |
Non-Patent Citations (29)
Title |
---|
ASGARI, F ET AL.: "Fundamentals of oxygen delignification. Part II. Functional group formation/elimination in residual ln-kraft lignin", CAN. J. CHEM., vol. 76, 1998, pages 1606 - 1615, XP008149424 * |
BAURHOO: "Purified Lignin: Nutritional and Health Impacts on Farm Animals - A Review", ANIMAL FEED SCIENCE AND TECHNOLOGY, vol. 144, 2008, pages 175 - 184, XP022765342, DOI: 10.1016/j.anifeedsci.2007.10.016 |
C. POUTEAU ET AL.: "Antioxidant Properties of Lignin in Polypropylene", POLYMER DEGRADATION AND STABILITY, vol. 81, 2003, pages 9 - 18, XP004425568, DOI: 10.1016/S0141-3910(03)00057-0 |
CATETO, CA ET AL.: "Lignins as Macromonomers for Polyurethane Snthesis: A Comparative Study on Hydroxyl Group Determination", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 109, 2008, pages 3008 - 3017, XP008149420 * |
CATIGNANI G.L.CARTER M.E.: "Antioxidant Properties of Lignin", JOURNAL OF FOOD SCIENCE, vol. 47, 1982, pages 1745, XP008149296, DOI: 10.1111/j.1365-2621.1982.tb05029.x |
CATIGNANI, GL ET AL.: "Antioxidant Properties of Lignin", JOURNAL OF FOOD SCIENCE, 1982, XP008149296 * |
CHAKAR, FS ET AL.: "Biobleaching chemistry of laccase-mediator systems on high-lignin-content kraft pulps", CAN. J. CHEM., vol. 82, 2004, pages 344 - 352, XP008149423 * |
CHAKAR, FS ET AL.: "Laccase-Lignin Reactions", IPST TECHNICAL PAPER SERIES NUMBER 876, August 2000 (2000-08-01), XP008149432 * |
COLODETTE, JL ET AL.: "Influence of pulping conditions on eucalyptus kraft pulp yield, quality, and bleachability", TAPPI JOURNAL, 2002, pages 14 - 20, XP008148500 * |
DIZHBITE, T ET AL.: "Characterization of the radical scavenging activity of lignins - natural antioxidants", BIORESOURCE TECHNOLOGY, vol. 95, 2004, pages 309 - 317, XP008149292 * |
DIZHBITE, T. ET AL.: "Characterization of the radical scavenging activity of lignins - natural antioxidants", BIORESOURCE TECHNOLOGY, vol. 95, 2004, pages 309 - 317, XP008149292, DOI: 10.1016/j.biortech.2004.02.024 |
FROASS, PM ET AL.: "Nuclear Magnetic Resonance Studies. 4. Analysis of Residual Lignin after Kraft Pulping", IND. ENG. CHEM. RES., vol. 37, 1998, pages 3388 - 3394, XP008149421 * |
GELLERSTEDT, G ET AL.: "Chemical Structures Present in Biofuel Obtained from Lignin", ENERGY & FUELS, vol. 22, 2008, pages 4240 - 4244, XP008149425 * |
GREGOROVA ET AL.: "Radical scavenging capacity of lignin and its effect on processing stabilization of virgin and recycled polypropylene", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 106-3, 2007, pages 1626 - 1631, XP055676539, DOI: 10.1002/app.26687 |
GREGOROVA, A ET AL.: "Stabilization effect of lignin in polypropylene and recycled propylene", POLYMER DEGRADATION AND STABILITY, vol. 89, 2005, pages 553 - 558, XP025279152 * |
KASPRZYCKA-GUTTMAN, T ET AL.: "Antioxidant properties of lignin and its fractions", THERMOCHIMICA ACTA, vol. 231, 1994, pages 161 - 168, XP026579269 * |
KOSIKOVA, B ET AL.: "Lignin-stimulated protection of polypropylene films and DNA in cells of mice against oxidation damage", BIORESOURCES, vol. 4, no. 2, May 2009 (2009-05-01), pages 805 - 815, XP008149286 * |
LUCIA, LA ET AL.: "Comparative Evaluation of Oxygen Delignification Processes for Low- and High-Lignin-Content Softwood Kraft Pulps", IND. ENG. CHEM. RES., vol. 41, 2002, pages 5171 - 5180, XP008149422 * |
MEGIATTO, JD ET AL.: "Sisal Fibers: Surface Chemical Modifications Using Reagent Obtained from a Renewable Source; Characterization of Hemicellulose and Lignin as Model Study", J. AGRIC. FOOD CHEM., vol. 55, 2007, pages 8576 - 8584, XP008149435 * |
NIEMINEN, MOJ ET AL.: "Determination of Hydroxyl Groups in Kraft Pine Lignin by Silicon-29 NMR Spectroscopy", HOLZFORSCHUNG, vol. 43, no. 5, 1989, pages 303 - 307, XP008149433 * |
PAN X. ET AL., J. AGRIC. FOOD CHEM., vol. 54, no. 16, 2006, pages 5806 - 5813 |
PU, Y ET AL.: "Investigation of the photo-oxidative chemistry of acetylated softwood lignnin", JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A: CHEMISTRY, vol. 163, 2004, pages 215 - 221, XP008149219 * |
PU, Y ET AL.: "Structural analysis of acetylated hardwood lignins and their photoyellowing properties", CAN. J. CHEM., vol. 83, 2005, pages 2132 - 2139, XP008149427 * |
SEALEY, J ET AL.: "Residual Lignin Studies of Laccase Delignified Kraft Pulps", IPST TECHNICAL PAPER SERIES NUMBER 621, August 1996 (1996-08-01), XP008149431 * |
See also references of EP2435453A4 |
TOHMURA, S ET AL.: "Determination of Arylglycerol-beta-aryl Ethers and Other Linkages in Lgnins Using DFRC/31 P NMR", J. AGRIC. FOOD CHEM., vol. 49, 2001, pages 536 - 542, XP008149297 * |
VINARDELL, MP ET AL.: "Potential applications of antioxidant lignins from different sources", INDUSTRIAL CROPS AND PRODUCTS, 2008, pages 220 - 223, XP022398510 * |
X. PAN ET AL.: "Organosolv Ethanol Lignin From Hybrid Poplar as a Radical Scavenger: Relationship Between Lignin Structure", EXTRACTION CONDITIONS, AND ANTIOXIDANT ACTIVITY, vol. 54, no. 16, 2006, pages 5806 - 5813, XP008148495, DOI: 10.1021/jf0605392 |
YANG, R ET AL.: "Oxygen Degradation and Spectroscopic Characterization of Hardwood Kraft Lignin", IND. ENG. CHEM. RES., vol. 41, 2002, pages 5941 - 5948, XP008149426 * |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10435562B2 (en) | 2009-05-28 | 2019-10-08 | Fibria Innovations Inc. | Derivatives of native lignin, lignin-wax compositions, their preparation, and uses thereof |
US9260609B2 (en) | 2009-05-28 | 2016-02-16 | Fibria Innovations Inc. | Derivatives of native lignin |
US9708490B2 (en) | 2009-05-28 | 2017-07-18 | Fibria Innovations Inc. | Derivatives of native lignin |
US9982174B2 (en) | 2010-02-15 | 2018-05-29 | Fibria Innovations Inc. | Binder compositions comprising lignin derivatives |
US10533030B2 (en) | 2010-02-15 | 2020-01-14 | Suzano Canada Inc. | Carbon fibre compositions comprising lignin derivatives |
US9963673B2 (en) | 2010-06-26 | 2018-05-08 | Virdia, Inc. | Sugar mixtures and methods for production and use thereof |
US9410216B2 (en) | 2010-06-26 | 2016-08-09 | Virdia, Inc. | Sugar mixtures and methods for production and use thereof |
US10752878B2 (en) | 2010-06-26 | 2020-08-25 | Virdia, Inc. | Sugar mixtures and methods for production and use thereof |
US9476106B2 (en) | 2010-06-28 | 2016-10-25 | Virdia, Inc. | Methods and systems for processing a sucrose crop and sugar mixtures |
US10760138B2 (en) | 2010-06-28 | 2020-09-01 | Virdia, Inc. | Methods and systems for processing a sucrose crop and sugar mixtures |
US9115467B2 (en) | 2010-08-01 | 2015-08-25 | Virdia, Inc. | Methods and systems for solvent purification |
US11242650B2 (en) | 2010-08-01 | 2022-02-08 | Virdia, Llc | Methods and systems for solvent purification |
US10240217B2 (en) | 2010-09-02 | 2019-03-26 | Virdia, Inc. | Methods and systems for processing sugar mixtures and resultant compositions |
US9663836B2 (en) | 2010-09-02 | 2017-05-30 | Virdia, Inc. | Methods and systems for processing sugar mixtures and resultant compositions |
US8404355B2 (en) | 2010-12-09 | 2013-03-26 | Virdia Ltd | Methods and systems for processing lignocellulosic materials and related compositions |
US9840621B2 (en) | 2011-03-24 | 2017-12-12 | Fibria Innovations Inc. | Compositions comprising lignocellulosic biomass and organic solvent |
US10876178B2 (en) | 2011-04-07 | 2020-12-29 | Virdia, Inc. | Lignocellulosic conversion processes and products |
US11667981B2 (en) | 2011-04-07 | 2023-06-06 | Virdia, Llc | Lignocellulosic conversion processes and products |
US9512495B2 (en) | 2011-04-07 | 2016-12-06 | Virdia, Inc. | Lignocellulose conversion processes and products |
US9845514B2 (en) | 2011-10-10 | 2017-12-19 | Virdia, Inc. | Sugar compositions |
US9617608B2 (en) | 2011-10-10 | 2017-04-11 | Virdia, Inc. | Sugar compositions |
US9976194B2 (en) | 2011-10-10 | 2018-05-22 | Virdia, Inc. | Sugar compositions |
US10041138B1 (en) | 2011-10-10 | 2018-08-07 | Virdia, Inc. | Sugar compositions |
WO2014094104A1 (en) * | 2012-12-18 | 2014-06-26 | Lignol Innovations Ltd. | Processes for recovery of derivatives of native lignin |
US11078548B2 (en) | 2015-01-07 | 2021-08-03 | Virdia, Llc | Method for producing xylitol by fermentation |
WO2016207807A1 (en) * | 2015-06-24 | 2016-12-29 | Procter & Gamble Inernational Operations Sa | Consumer goods product comprising lignin oligomer |
US9907742B2 (en) | 2015-06-24 | 2018-03-06 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9907744B2 (en) | 2015-06-24 | 2018-03-06 | The Procter & Gamble Company | Consumer goods product comprising lignin oligomer |
US9901526B2 (en) | 2015-06-24 | 2018-02-27 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9902812B2 (en) | 2015-06-24 | 2018-02-27 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
US9895445B2 (en) | 2015-06-24 | 2018-02-20 | The Procter & Gamble Company | Consumer goods product comprising functionalised lignin oligomer |
EP3108938A1 (en) * | 2015-06-24 | 2016-12-28 | Procter & Gamble International Operations SA | Consumer goods product comprising lignin oligomer |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9708490B2 (en) | Derivatives of native lignin | |
US8796380B2 (en) | Processes for recovery of derivatives of native lignin | |
US9267027B2 (en) | Resin compositions comprising lignin derivatives | |
WO2014094104A1 (en) | Processes for recovery of derivatives of native lignin |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080029603.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10779947 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10260/DELNP/2011 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010779947 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2798158 Country of ref document: CA |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: PI1014400 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: PI1014400 Country of ref document: BR Kind code of ref document: A2 Effective date: 20111128 |