WO2014094104A1 - Processes for recovery of derivatives of native lignin - Google Patents
Processes for recovery of derivatives of native lignin Download PDFInfo
- Publication number
- WO2014094104A1 WO2014094104A1 PCT/CA2012/001172 CA2012001172W WO2014094104A1 WO 2014094104 A1 WO2014094104 A1 WO 2014094104A1 CA 2012001172 W CA2012001172 W CA 2012001172W WO 2014094104 A1 WO2014094104 A1 WO 2014094104A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethanol
- temperature
- time
- mmol
- lignin
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
-
- 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
-
- 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
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
Definitions
- TITLE PROCESSES FOR RECOVERY OF DERIVATIVES OF NATIVE LIGNIN
- This disclosure relates to processes for recovery of derivatives of native lignin from lignocellulosic feedstocks, recovered derivatives of native Hgnins, and industrial applications thereof. More particularly, this disclosure relates to processes for recovery of 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 structural 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 Hgnin 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.
- Hgnin derivatives are usuaUy described in terms of the HgnoceUulosic plant material used, and the methods by which they are generated and recovered from HgnoceUulosic plant material, i.e. hardwood Hgnins, softwood Hgnins, and annual fiber Hgnins.
- Native Hgnins are partially depolymerized during chemical pulping processes into Hgnin fragments which are soluble in the pulping Hquors and subsequendy separated from the ceUulosic pulps.
- Post-pulping Hquors containing Hgnin and polysaccharide fragments, and other extractives, are commonly referred to as "black Hquors” or “spent Hquors", depending on the chemical pulping process.
- 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. However, it is also possible to precipitate and/ or recover lignin derivatives from these liquors.
- Each type of chemical 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 processes.
- 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
- large-scale commercial application of the extracted lignin derivatives particularly those isolated in traditional pulping processes employed in the manufacture of pulp and paper, 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 al. 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 al. 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 worldwide.
- 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.
- 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 a low level of toxicity toxicity, efficacy, and environmental profile. See, for example, A. Gregorova et al., Radical scavenging capacity of lignin and its effect on processing stabilization of virgin and recycled polypropylene, Journal of Applied Polymer Science 06-3 (2007) pp. 1626- 1631; C. Pouteau et al. Antioxidant Properties of Lignin in Polypropylene, Polymer Degradation and Stability 81 (2003) 9-18.
- lignin 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.
- Some embodiments of the present disclosure relate to derivatives of native lignin having certain aliphatic hydroxyl contents. Surprisingly, it has been found that stable and predictable antioxidant activity is provided by selecting for derivatives of native lignin having certain aliphatic hydroxyl contents. Some embodiments of the present disclosure relate to processes for organosolv pulping of lignocellulosic biomass feedstocks wherein certain operating parameters are selectively manipulated to recover lignin derivatives having certain aliphatic hydroxyl contents.
- Fig. 1 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from aspen as a function of organic solvent concentration [Ethanol] and pulping temperature [Temperature] at constant pH of 2.47 and pulping time of 68 min;
- Fig. 2 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from acacia as a function of pulping time [time] and acidification of the organic solvent [pH] at constant organic solvent concentration of 60.0% (w/w) and pulping temperature of 185.5°C;
- Fig. 3 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from eucalyptus as a function of acidification of the organic solvent [pH] and pulping temperature pTemperature] at constant organic solvent concentration of 60.0% (w/ w) and pulping time of 68 min;
- Fig. 4 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from hybrid spruce as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 60.5% (w/w) and pulping temperature of 183°C;
- Fig. 5 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from radiata pine as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 60.5% (w/w) and pulping temperature of 183°C;
- Fig. 6 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from loblolly pine as a function of pulping time [Time] and pulping temperature pTemperature, °C] at constant pH of the pulping liquor of 2.43 and organic solvent concentration of 62% w/w ethanol;
- Fig. 7 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from wheat straw as a function of organic solvent concentration [Ethanol] and pulping time [Time] at constant pulping temperature of 185.5°C and organic solvent acidified to a pH of 2.2;
- Fig. 8 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from bagasse as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 55% (w/w) and pulping temperature of 179°C; and
- Fig. 9 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from corn cobs as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 53.5% (w/w) and pulping temperature of 177°C.
- the present disclosure relates to derivatives of native lignin having certain aliphatic hydroxyl contents, and to organosolv pulping processes tailored for recovery of the lignin derivatives from lignocellulosic biomass feedstocks.
- Lignin derivative 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. It has been found that 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 2.00 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 2,2-diphenyl-l-picrylhydrazyl (DPPH), a stable free radical which absorbs light strongly at 515 nm to measure a compound's radical scavenging index (RSI).
- DPPH 2,2-diphenyl-l-picrylhydrazyl
- DPPH* absorbs strongly at 515 nm and has a deep purple colour.
- DPPH gives up its free electron to radical scavengers, it loses its purple colour and its absorbance shifts to 520 nm.
- Vitamin E Vit. E
- BHT butylated hydroxytoluene
- the lignin derivative samples (1.0 - 2.0 mg), Vit. E control samples (1.0-2.0 mg), and BHT control samples (6.0 - 8.0 mg) are prepared for testing by being placed into rnicrocentrifuge tubes after which, each was diluted with 1.0 mL of 90% (v/v) aqueous dioxane, vortexed, transferred to new rnicrocentrifuge tubes and further diluted 50/50 with 90% aqueous dioxane to give stock concentrations of 0.5-1.0 mg/mL for the samples and Vitamin E and 3.0-4.0 mg/mL for BHT.
- An indicating (purple) DPPH stable free radical solution is made by dissolving 3.78 mg DPPH in 100 mL 90% dioxane (95.9 ⁇ ).
- Samples and standards are serially 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 ⁇ , 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 65 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 kL of the DPPH solution is added to all the control and analytical columns by using an 8-channel auto- pipette and an Eppendorf reagent reservoir as quickly as possible. As soon as all reagents are added, the plate is placed into a plate-reading spectrophotometer (Molecular Devices, Sunnyvale, CA, USA, Spectra Max Plus), 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 sample RSI by the RSI value for the BHT control.
- the normalized RSI is represented by this acronym "NRSI".
- the present disclosure provides processes for recovery of derivatives of native lignin during or after organosolv 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. americana); Aspen (e.g. P. grandidentata, P. tremula, P.
- Robinia pseudacacia, Gleditsia triacanthos Mahogany; Maple (e.g. Acer saccharum, Acer nigrum, Acer negundo, Acer rubrum, Acer saccharinum, Acer pseudoplatanus); Meranti; Mpingo; Oak (e.g.
- P. balsamifera, P. nigra, Hybrid Poplar (Vopulus 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 regid); Willow (e.g. Salix nigra, Salix alba); Yellow-poplar (Liriodendron tulipifera); bamboo; Palmwood; and combinations/hybrids thereof.
- hardwood feedstocks for the present disclosure may be selected from Acacia, Aspen, Beech, Eucalyptus, Maple, Birch, Gum, Oak, Poplar, and combinations /hybrids thereof.
- the hardwood feedstocks for the present disclosure may be selected from Vopulus spp. (e.g. V. grandidentata, V. tremula, V. tremuloides, V. balsamifera, V. deltoides, V. sargentii, V. heterophylla, V. balsamifera, V. nigra, Vopulus canadensis), Eucaylptus spp. (e.g. E. astrigens, e. clivicola, E.
- dielsii E. forrestiana, E. gardneri, E. globulus, E. nitans, E. occidentalis, E.ornata, E. salubris, E. spathulata), Acacia spp. (e.g. A. albida, A. cavenia, A. dealbata, A. decutrens, A. famesiana, A. meamsii, A. melanoxylon, A. nilotica, A. penninervis, A. pycnatha, A. saligna, and combinations thereof.
- Acacia spp. e.g. A. albida, A. cavenia, A. dealbata, A. decutrens, A. famesiana, A. meamsii, A. melanoxylon, A. nilotica, A. penninervis, A. pycnatha, A. saligna, and combinations thereof.
- the aliphatic hydroxyl content can be measured using quantitative 13 C high resolution NMR spectroscopy of acetylated lignin (using 1,3,5-trioxane as internal reference).
- the spectrometer was coupled with a Bruker QNP cryoprobe (5 mm NMR samples, 13 C direct observe on inner coil, 1H outer coil) that had both coils cooled by helium gas to 20K and all preamplifiers cooled to 77K for maximum sensitivity.
- Sample temperature was maintained at 300 K ⁇ 0.1 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.
- Derivatives of native lignin according to the present disclosure, coming from hardwood feedstocks tend to have a normalized RSI of 30 or greater, 40 or greater, 50 or greater, 60 or greater, 70 or greater.
- Softwood feedstocks include Araucaria (e.g. A. cunninghamii, A. angustifolia, A. araucana); softwood Cedar (e.g. Juniperus virginiana, Thuja plicata, Thuja ocddentalis, Chamaecyparis thyoides Callitropsis nootkatensis); Cypress (e.g. Chamaecyparis, Cupressus Taxodium, Cupressus Taxodium distichum, Chamaecyparis obtusa, Chamaecyparis lawsoniana, Cupressus semperviren); 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 echinatd); Redwood; Rimu; Spruce (e.g. Picea abies, Picea mariana, Picea rubens, Picea sitchensis, Picea glaucd); 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 disclosure may be selected from loblolly pine (P. taedd), radiata pine, jack pine, spruce (e.g., white, interior, black), Douglas fir, black spruce, and combinations/hybrids thereof.
- the softwood feedstocks for the present disclosure may be selected from pine (e.g. Pirns 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 2mmol/g or less, or about 1.75 mmol/g or less.
- Derivatives of native lignin according to the present disclosure, coming from softwood feedstocks tend to have a normalized RSI of 15 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater.
- Annual fibre feedstocks include, for example, flax; cereal straw (wheat, barley, oats, rye); bagasse; corn; hemp, fruit pulp, alfa grass, switchgrass, miscanthus, kenaf, and combinations/hybrids thereof.
- the annual fibre feedstock may be selected from wheat straw, com stover, corn cobs, sugar cane bagasse, and combinations/hybrids thereof.
- Derivatives of native lignin according to the present disclosure, coming from annual fibre feedstocks tend to have a normalized RSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 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. Examples of extractive technologies include (1) solvent extraction of finely ground wood; (2) acidic dioxane extraction (acidolysis) of wood; (3) steam explosion; or (4) acid hydrolysis methods. Furthermore, derivatives of native lignin can be recovered after pulping of lignocellulosic biomass including industrially operated kraft and soda pulping (and their modifications) and sulphite pulping. It should be noted that 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.
- Organosolv extraction tends 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 pulping (aka the "Acetosolv” process).
- Organosolv extraction processes tend to be less aggressive and can be used to separate highly purified lignin and other useful materials from biomass without excessively altering or damaging the lignin. 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 than other industrial methods and thus are generally more complex and expensive.
- the process generally comprises pulping a fibrous biomass feedstock with primarily an ethanol/water solvent solution under conditions that included: (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 ranging from 30 to 120 minutes.
- Derivatives of native lignin are fractionated from the native lignins into the pulping liquor which also receives solubilised hemicelluloses, other saccharides and other extractive 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 extractives released by organosolv pulping significantly acidify of the black liquors to pH levels of about 5.5 and lower.
- the derivatives of native lignin are recovered from the black liquors by depressurization/ flashing followed by dilution 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 solution to a value selected from a range of 60% - 80% ethanol, (b) temperature to a value selected from a range of 120° C to 350° C, (c) pressure to a value selected from a range of 15 aim to 35 atm, and (d) processing time to a duration from a range of 20 minutes to about 2 hours.
- Some modifications to the Alcell ® organosolv process also include the addition of an acid catalyst to the pulping solution to lower its pH to a value from the range of about 1.5-5.5.
- the present disclosure provides a process for producing derivatives of native lignin from lignocellulosic biomass feedstocks wherein the lignin derivatives have certain aliphatic hydroxyl contents selected before pulping is commenced, said process comprising:
- the organic solvent may be selected from short-chain aliphatic alcohols 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.
- the pH of the organic solvent may be adjusted to, for example, from about 1 to about 6, or from about 1.5 to about 5.5.
- 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 180°C and greater.
- the process may be carried out at a temperature of from to 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 220°C and less, or about 210°C and less, or about 205°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) 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 present disclosure 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 2mmol/g or less, or about 1.75 mmol/g or less.
- Said process comprises: a) commingling a fibrous biomass feedstock in a vessel with a selected organic solvent/ water solvent solution having a selectively adjusted pH, wherein: i. the solution comprises about 30% or greater, by weight, of organic solvent; and ii.
- the pH of the organic solvent is adjusted from about 1 to about 5.5; b) heating the commingled fibrous biomass and pH-adjusted organic solvent to a temperature selected from the range of about 100°C to about 300°C; c) raising the pressure in the vessel to about 10 atm or greater; d) mamtaining the elevated temperature and pressure for a period of time selected from the range of about 1 minute to about 360 minutes while continuously commingling fibrous biomass and pH-adjusted organic solvent thereby producing cellulosic pulps and a black liquor, and; e) separating the cellulosic pulps from the pulp liquor f) recovering derivatives of native lignin.
- Liquor-to-biomass ratios can be varied from 2:1 to 15:1 wt:wt
- the present disclosure 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: a) pulping a fibrous biomass feedstock in a vessel with a pH-adjusted organic solvent/water solvent solution to form a liquor, wherein: i. the solution comprises a selected concentration of organic solvent of about 30% or greater; and ii.
- the pH of the organic solvent is selectively adjusted from about 1 to about 5.5; b) heating the liquor to a selected temperature of about 100°C or greater; c) raising the pressure in the vessel to about 10 atm or greater; d) maintaining the elevated temperature and pressure for a selected period of time of 1 minute or longer; e) separating the cellulosic pulps from the pulp liquor f) recovering derivatives of native lignin.
- the present disclosure 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 mmol/g or less, or about 1.75 mmol/g or less, said process comprises: a) corruTiingling a fibrous biomass feedstock in a vessel with a selected organic solvent/water solvent solution having a selectively adjusted pH, wherein: i. the solution comprises about 30% or greater, by weight, of organic solvent; and ii.
- the pH of the organic solvent is adjusted from about 1 to about 5.5; b) heating the commingled fibrous biomass and pH-adjusted organic solvent to a temperature selected from the range of about 100°C to about 300°C; c) raising the pressure in the vessel to about 10 atm or greater; d) mamtaining the elevated temperature and pressure for a period of time selected from the range of about 1 minute to about 360 minutes while continuously commingling fibrous biomass and pH-adjusted organic solvent thereby producing cellulosic pulps and a black liquor, and; e) separating the cellulosic pulps from the pulp liquor
- the present disclosure 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: a) commingling a fibrous biomass feedstock in a vessel with a selected organic solvent/water solvent solution having a selectively adjusted pH, wherein: i. the solution comprises about 30% or greater, by weight, of organic solvent; and ii.
- the pH of the organic solvent is adjusted from about 1 to about 5.5; b) heating the commingled fibrous biomass and pH-adjusted organic solvent to a temperature selected from the range of about 100°C to about 300°C; c) raising the pressure in the vessel to about 10 atm or greater; d) mamtaining the elevated temperature and pressure for a period of time selected from the range of about 1 minute to about 360 minutes while continuously con mingling fibrous biomass and pH-adjusted organic solvent thereby producing cellulosic pulps and a black liquor, and; e) separating the cellulosic pulps from the pulp liquor
- the present disclosure relates to methods for determining suitable operating conditions for organosolv pulping of lignocellulosic biomass feedstocks for production of derivatives of native lignin having certain desirable aliphatic hydroxyl contents.
- Such operating conditions may be determined, for example, by selecting a target operating value for each of at least two process parameters while keeping other process parameters constant.
- Suitable process parameters that can be manipulated by selection of target operating values include: (a) concentration of organic solvent in the pulping liquor, (b) degree of acidification of the organic solvent prior to commencing pulping, (c) temperature at which pulping is conducted, (d) duration of the pulping period, and (e) liquor- to-biomass ratios among others.
- Suitable target operating values can be determined by empirically modelling the performance results collected from a series of preliminary otganosolv pulping runs with subsamples of a selected lignocellulosic feedstock wherein at least one process parameter has been adjusted between each of the runs.
- Exemplary performance results are the aliphatic hydroxyl contents of lignin derivatives recovered from each preliminary organosolv pulping run.
- a suitable number of preliminary pulping runs is about 10, or about 15, or about 20 about 25 or about 30.
- the performance results in combination with the manipulated process parameters can be used for equations for identification of suitable target operating values for one or more organosolv processing conditions for lignocellulosic biomass feedstocks from which lignin derivatives have desirable chemical or structural or functional attributes can be recovered.
- Such equations can be derived from performance results by mathematical tools and software exemplified by Madab ® Version 7.7.0.471 R2008b (Madab is a registered trademark of The Mathworks Inc., Natick, MA, USA) with a Model-Based Calibration Toolbox Version 3.5 supplied by The Mathworks Inc.
- suitable model characteristics include:
- Suitable model terms include:
- Input factors 4 (the process parameters Cooking time [Time], cooking temperature [Temperature], cooking pH [pH], solvent concentration [SOLVENT]
- the maximum and niinimum values used in each model should be those maximum and minimum values observed in the actual performance data points collected for both the input and output variables ("responses").
- This modelling approach can be used to select and manipulate organosolv process conditions to recover lignin derivatives that have certain targeted ranges of chemical and/or structural attributes, for example, one or more of: non-conjugated carbonyl groups/g lignin derivative in the range of about 0.09 to about 1.62 CO-nc mmol/g; conjugated carbonyl groups/g lignin derivative in the range of about 0.31 to about 1.36 CO-conj mmol/g; total carbonyl groups/g lignin derivative in the range of about 0.51 to about 2.72 CO tot mmol/g;
- total hydroxyl groups/g lignin derivative in the range of about 4.73 to about 10.28 tot-OH mmol/g;
- carboxylic or ester group/g lignin derivative in the range of about 0 to about 4.46 COOR tot mmol/g; methoxyl groups/g lignin derivative in the range of about 3.61 to about 8.46 O-me mmol/g; ethoxyl or other alkoxy groups/g lignin derivative in the range of about 0.28 to about 1.34 O-et mmol/g; syringyl groups/g lignin derivative in the range of about 0 to about 3.60 S mmol/ g; guaiacyl groups /g Hgnin derivative in the range of about 1.33 to about 7.78 G
- Mw weight-average molecular weight
- This modelling approach can be used to select and manipulate organosolv process conditions to recover lignin derivatives that have certain targeted ranges of functional attributes, for example, one or more of: radical scavaging index (RSI) in the range of about 5.44 to about 53.36;
- RSI radical scavaging index
- Tg glass transition temperature
- FI melt flow index
- V viscosity of a phenol-formaldehyde resin containing these lignin derivatives at 40% phenol replacement level in the range of about 50 cP to about 20,000 cP
- normalized shear strength as measured by the automated bonding evaluation system (ABES) of a phenol-formaldehyde resin where 40% of the phenol has been replaced by the lignin derivative about 2,034 MPa*cm 2 /g to about 3796 MPa*cm 2 /g.
- the derivatives of native lignin recovered with the processes described herein may be incorporated into polymer compositions.
- the compositions herein may comprise a lignin derivative according to the present disclosure 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.
- Polymers forming components for use herein may result in thermoplastic polymers such as epoxy resins, urea-formaldehyde resins, polyimides and the like, and thermosets such as phenol- formaldehyde resins, and the like.
- thermoplastic polymers such as epoxy resins, urea-formaldehyde resins, polyimides and the like, and thermosets such as phenol- formaldehyde 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, about 5% 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 disclosure 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, and combinations thereof.
- the present disclosure 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 disclosure provides methods of producing derivatives of native hardwood Kgnin having an aliphatic hydroxyl content of about 2.35 mmol/g or less result, about 2.25 mmol/g or less, about 2mmol/g or less, or about 1.75 mmol/g or less.
- the present disclosure provides methods of producing derivatives of native softwood lignin having an aliphatic hydroxyl content of about 2.35 mmol/g or less, about 2.25 mmol/g or less, about 2mmol/g or less, or about 1.75 mmol/g or less.
- the present disclosure provides methods of producing derivatives of native annual fibre 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 disclosure provides methods of producing derivatives of native lignin having a normalized RSI 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 disclosure provides methods of producing derivatives of native hardwood lignin having a normalized RSI 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 disclosure provides methods of producing derivatives of native softwood lignin having a normalized RSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater, 40 or greater.
- the present disclosure provides methods of producing derivatives of native annual fibre lignin having a normalized RSI of 15 or greater, 20 or greater, 25 or greater, 30 or greater, 35 or greater.
- EXAMPLE 1 Recovery of derivatives of native lignin from hardwood feedstocks, softwood feedstocks, and annual fibre feedstocks.
- the three hardwood feedstocks chips were prepared from: (1) aspen trees grown in British Columbia, Canada, (2) acacia grown in Chile, and (3) eucalyptus grown in Chile. Subsamples of the three hardwood plant species were individually pulped using an autocatalysed ethanol pulping process organosolv process wherein a different set of pulping conditions was used for each subsample. The individual sets of pulping conditions applied to hardwood species are listed in Tables 1(a)— 1(c). Twenty seven different combinations of pulping conditions were tested with each of BC aspen (Table 1(a)), Chilean Acacia dealbata (Table 1(b)), and Chilean Eucalyptus nitens (Table 1(c)).
- the ethanol pulping solvent was prepared as listed in its respective table.
- the ethanol was partially diluted with water after which, a suitable amount of sulphuric acid was added to achieve the target final acidity after which, the ethanol solution was further diluted with water to achieve the target ethanol concentration.
- each fibrous biomass subsample was determined using the Klason lignin determination method. Then, after adding the fibrous biomass subsample to a pressure vessel (100-700g odw chips), the tailored ethanol-based pulping solvent was added to the vessel (6:1 liquor:wood ratio), after which it was pressurized and brought up to the target temperature listed in the table. The biomass subsample was then "cooked" for the specified period of time after which, the pulping process was stopped. After pulping, the derivatives of native lignin were recovered by transferring the contents of the pressure vessel to a press. The solids were then squeezed in a press and filtered through a coarse silk screen which separated the chip residues from the fine particles and the liquids.
- the fine particles were separated from the liquids by filtering the suspension separated from the chip residues, through fine filter paper.
- the fine particles represent derivatives of native lignin that were extracted and which precipitated from solution after cooling and is herein referred to as self-precipitated derivatives of native lignin designated in the tables as "SPL".
- SPL self-precipitated derivatives of native lignin
- the derivatives of native lignin still remaining in the filtered liquid were precipitated from solution by dilution with cold water.
- the derivatives of native lignin precipitated by cold-water dilution are referred to herein as precipitated lignin or "PL".
- each lignin derivative was determined in reference to the total lignin value determined for the biomass sample before pulping.
- the original lignin and carbohydrates content of each fibrous biomass subsample was determined using the methods described in National Renewable Energy Laboratory (NREL) Technical Report entitled 'Determination of Structural Carbohydrates and Lignin in Biomass" - Laboratory Analytical Procedure (TP-510-42618 (25 April 2008)). Ash and extractives content were evaluated according to the standard TAPPI procedures.
- NREL National Renewable Energy Laboratory
- the yields of SPL and PL derivatives of native lignin for each subsample are expressed on a weight % basis relative to the total lignin value in raw biomass, and listed in Tables l(a)-l(c) for the hardwood feedstocks, Tables 3(a)-3(c) for the softwood feedstocks, and Tables 4(a)-4(c) for the annual fibre feedstocks in columns next to the processing conditions used for each subsamples.
- Table 2 shows the chemical composition of the raw lignocellulosic biomass samples used in this disclosure. The chip residues remaining after the first filtering step were pressed, dried and weighed. The yield of de-lignified residues, "pulp", (referred to in Tables 1 , 3, 4 as "PBY”) is expressed on a % basis relative to the dry weight of the pre-pulping biomass subsample.
- Derivatives of native lignin recovered from hardwood feedstocks were analyzed to determine mmol of primary hydroxyl groups/g sample (OH-pr mmol/g) and mmol of secondary hydroxyl groups/g sample (OH-sec mmol/g). These data were then used to calculate mmol aliphatic hydroxyl groups/g sample (OH-al mmol/g).
- hydroxyl contents were determined by analyses of NMR spectra recorded on a Bruker 700 MHz spectrometer equipped with Cryoprobe at 300 K using ca 30% solutions of sample in DMSO- ⁇ - Chemical shifts were referenced to TMS (0.0 ppm). To ensure more accurate baseline, especially in the carbonyl region (215-185 ppm), the spectra were recorded over the interval 240-(-40) ppm. The following conditions were provided for the quantitative ,3 C-NMR:
- 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 for adjustment to zero: (220-215ppm)-(l 85-182ppm)-(97-92ppm)-(5-(-20)ppm). No other regions were forced to 0.
- the signals in the quantitative 13 C NMR spectra were assigned on the base of 2D HSQC NMR and a known database. After the baseline correction the spectra were integrated using the area of internal standard (IS), trioxane, as the reference. Each spectrum was processed (as described) at least twice to ensure good reproducibility of the quantification. The calculation of the quantity of specific moieties was done as follows:
- X (mmol/g lignin) I x *m IS /(30m Lig *I ls - 42*I OHtotal * m IS )*1000
- the aliphatic hydroxyl content of the PL Ugnin derivatives from each of the twenty seven samples of aspen chips are shown in Table 1(a). The contents ranged from 0.70 mmol/g in run 1 to 5.52 mmol/g in run 27.
- each of the lignin derivative subsamples produced above was assessed for its radical scavenging index (RSI).
- 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 ⁇ ).
- 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 of 90% dioxane was added to each well and mixed. Aliquots of the mixed samples in each row are transferred to the adjacent row with 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 was prepared. The same volume of aliquots was removed from the last row.
- the 96-well plate also contains a row of wells that received only the 90% dioxane.
- 165 ⁇ of the DPPH solution is 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 program for the spectrophotometer (SOFTmax software) consists of a timing sequence of 16 rnin and a reading of the entire plate at 515 nm.
- RSI radical scavenging index
- the NRSI values for lignin derivatives recovered from BC aspen are shown in Table 1(a).
- the NRSI values for lignin derivatives recovered from Chilean acacia biomass are shown in Table 1(b).
- the NRSI values for lignin derivatives recovered from Chilean eucalyptus biomass are shown in Table 1(c).
- EXAMPLE 2 Recovery of derivatives of native Iignin from softwood feedstocks.
- Three softwood feedstocks chips were prepared from: (1) hybrid spruce (Picea engelmannii x Picea glauca) trees grown in British Columbia, (1) radiata pine grown in Chile, and (2) loblolly pine (Pinus taedd) grown in the southeast USA. Subsamples of the three plant species were individually pulped using an autocatalysed ethanol pulping process wherein a different set of pulping conditions was used for each subsample.
- the ethanol pulping solvent was prepared as listed in its respective table.
- the ethanol was partially diluted with water after which, a suitable amount of sulphuric acid was added to achieve the target final acidity after which, the ethanol solution was further diluted with water to achieve the target ethanol concentration.
- the raw Hgnin content of each fibrous biomass subsample was determined using the methods described in National Renewable Energy Laboratory (NREL) Technical Report entitled “Determination of Structural Carbohydrates and Lignin in Biomass” - Laboratory Analytical Procedure (TP-510-42618 (25 April 2008)). Then, after adding the fibrous biomass subsample to a pressure vessel (100-700 g odw chips), the tailored ethanol-based pulping solvent was added to the vessel (6:1 liquor:wood ratio) after which it was brought up to the target temperature and pressure listed in the table. The biomass subsample was then "cooked" for the specified period of time, after which, the pulping process was stopped.
- NREL National Renewable Energy Laboratory
- TP-510-42618 25 April 2008
- the derivatives of native lignin were recovered by transferring the contents of pressure vessel to a press. The solids were then squeezed in a press and filtered through a coarse silk screen which separated the chip residues from the fine particles and the liquids. Next, the fine particles were separated from the liquids by filtering the suspension separated from the chip residues, through fine filter paper. The fine particles represent derivatives of native lignin that were extracted and which precipitated from solution after cooling and is herein referred to as self-precipitated derivatives of native lignin designated in the tables as "SPL". Finally, the derivatives of native Hgnin still remaining in the filtered liquid were precipitated from solution by dilution with cold water.
- the derivatives of native lignin precipitated by cold-water dilution are referred to herein as precipitated lignin or "PL".
- PL precipitated lignin
- the yields of SPL and PL derivatives of native lignin for each subsample are expressed on a weight % basis relative to its total lignin value, and listed in Tables 4(a) -4(c) for the softwood feedstocks in columns next to the processing conditions used for each subsamples.
- the chip residues remaining after the first filtering step were pressed, dried and weighed.
- the yield of de-lignified residues, "pulp” referred to in Tables 4(a)-4(c) as "PBY” are expressed on a % yield basis relative to the dry weight of the pre-pulping biomass subsample.
- Derivatives of native lignin recovered from softwood feedstocks were analyzed as discussed above to determine mmol primary hydroxyl groups/g sample (OH-pr mmol/g) and mmol secondary hydroxyl groups/g sample (OH-sec mmol/g). These data were then used to calculate mmol aliphatic hydroxyl groups/g sample (OH-al mmol/g).
- Table 4(c) The aliphatic hydroxyl contents of the PL lignin derivatives from each of the thirty samples of loblolly pine chips are shown in Table 4(c). The contents ranged from 1.35 mmol/g in run 1 to 4.39 mmol/g in run 30.
- Each of the lignin derivative subsamples produced above were assessed for its radical scavenging index (RSI).
- the potential antioxidant activity of each PL lignin derivative was determined as described above.
- the NRSI values for lignin derivatives recovered from hybrid spruce biomass are shown in Table 4(a).
- the NRSI values for lignin derivatives recovered from radiate pine biomass are shown in Table 4(b).
- the NRSI values for lignin derivatives recovered from loblolly pine biomass are shown in Table 4(c).
- EXAMPLE 3 Recovery of derivatives of native lignin from three annual fibre feedstocks.
- Three annual fibre feedstocks were prepared from : (1) wheat straw from Alberta Canada, (2) sugarcane bagasse from Brazil, and (3) corn cobs from crops produced in Europe. Subsamples of the three plant species were individually pulped using an autocatalysed ethanol pulping process based on the Alcell ® organosolv process wherein a different set of pulping conditions was used for each subsample.
- the ethanol pulping solvent was prepared as listed in its respective table.
- the ethanol was partially diluted with water after which, a suitable amount of sulphuric acid was added to achieve the target final acidity after which, the ethanol solution was further diluted with water to achieve the target ethanol concentration.
- the raw lignin content of each fibrous biomass subsample was determined using the Klason lignin determination method. Then, after adding the fibrous biomass subsample to a pressure vessel (100-700 g odw chips), the tailored ethanol-based pulping solvent was added to the vessel (6:1 liquorwood ratio) after which it was brought up to the target temperature and pressure listed in the table. The biomass subsample was then "cooked" for the specified period of time after which, the pulping process was stopped. After pulping, the derivatives of native lignin were recovered by transferring the contents of pressure vessel to a press. The solids were then squeezed in a press and filtered through a coarse silk screen which separated the chip residues from the fine particles and the liquids.
- the fine particles were separated from the liquids by filtering the suspension separated from the chip residues, through fine filter paper.
- the fine particles represent derivatives of native lignin that were extracted and which precipitated from solution after cooling and is herein referred to as self-precipitated derivatives of native Ugnin designated in the tables as "SPL".
- SPL self-precipitated derivatives of native Ugnin designated in the tables as "SPL”.
- the derivatives of native lignin still remaining in the filtered liquid were precipitated from solution by dilution with cold water.
- the derivatives of native lignin precipitated by cold-water dilution are referred to herein as precipitated lignin or "PL".
- the relative yield of each Hgnin derivative was determined in reference to the Klason lignin value determined for the biomass sample before pulping.
- the yields of SPL and PL derivatives of native lignin for each subsample are expressed on a weight % basis relative to its total lignin value, and listed in Tables 5(a)-5(c) for the annual fibre feedstocks in columns next to the processing conditions used for each subsamples.
- the chip residues remaining after the first filtering step were pressed, dried and weighed.
- the yield of de-lignified residues referred to in Tables 5(a)-5(c) as "PBY" are expressed on a % yield basis relative to the dry weight of the pre- pulping biomass subsample.
- the aliphatic hydroxyl contents of the PL lignin derivatives from each of the twenty seven samples of wheat straw biomass are shown in Table 5(a). The contents ranged from 2.03 mmol/g in 2.03 run 1 to 3.59 mmol/g in run 27.
- the aliphatic hydroxyl contents of the PL lignin derivatives from each of the twenty six samples of sugarcane bagasse biomass are shown in Table 5(b). The contents ranged from 1.72 mmol/g in run 1 to 3.70 mmol/g in run 26.
- each of the lignin derivative subsamples produced above was assessed for its radical scavenging index (RSI).
- the potential antioxidant activity of each PL lignin derivative was determined by measuring its radical savaging capacity as described above.
- the NRSI values for lignin derivatives recovered from wheat straw biomass are shown in Table 5(a).
- the NRSI values for lignin derivatives recovered from sugarcane bagasse biomass are shown in Table 5(b).
- the NRSI values for lignin derivatives recovered from corn cob biomass are shown in Table 5(c).
- EXAMPLE 4 Predictive equations for selective recovery of lignin derivatives having targeted aliphatic hydroxyl contents, from organosolv pulping of hardwood biomass feedstocks
- Fig. 1 shows aliphatic hydroxyl contents of lignin derivatives recovered from aspen as a function of organic solvent concentration [Ethanol] and pulping temperature [Temperature] at constant pH of 2.47 and pulping time of 68 min., and shows process conditions suitable for producing lignin derivatives of the present disclosures have either decreased or increased aliphatic hydroxyl contents.
- Fig. 2 shows aliphatic hydroxyl contents of lignin derivatives recovered from acacia as a function of pulping time [time] and acidification of the organic solvent [pH] at constant organic solvent concentration of 60.0% (w/w) and pulping temperature of 185.5°C, and shows process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents.
- FIG. 3 shows aliphatic hydroxyl contents of lignin derivatives recovered from eucalyptus as a function of acidification of the organic solvent (pH] and pulping temperature [Temperature] at constant organic solvent concentration of 60.0% (w/w) and pulping time of 68 min, and shows process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents.
- EXAMPLE 5 Predictive equations for selective recovery of lignin derivatives having targeted aliphatic hydroxyl contents, from organosolv pulping of softwood biomass feedstocks
- Fig. 4 shows aliphatic hydroxyl contents of lignin derivatives recovered from hybrid spruce as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 60.5% (w/w) and pulping temperature of 183°C, and shows process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents.
- Fig. 5 shows aliphatic hydroxyl contents of lignin derivatives recovered from radiata pine as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 60.5% (w/w) and pulping temperature of 183°C, and shows process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents.
- Fig. 6 is a chart showing aliphatic hydroxyl contents of lignin derivatives of the present disclosure recovered from loblolly pine as a function of pulping time [Time] and pulping temperature [Temperature, °C] at constant pH of the pulping liquor of 2.43 and organic solvent concentration of 62% w/w ethanol, and process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents;
- EXAMPLE 6 Predictive equations for selective recovery of lignin derivatives having targeted aliphatic hydroxyl contents, from organosolv pulping of annual fibre biomass feedstocks
- Fig. 7 shows aliphatic hydroxyl contents of lignin derivatives recovered from wheat straw as a function of organic solvent concentration [Ethanol] and pulping time [Time] at constant pulping temperature of 85.5°C and organic solvent acidified to a pH of 2.2, and shows process conditions suitable for producing lignin derivatives of the present disclosures that have either decreased or increased aliphatic hydroxyl contents.
- Fig. 8 shows aliphatic hydroxyl contents of lignin derivatives recovered from bagasse as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 55% (w/w) and pulping temperature of 179°C, and shows process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents.
- Fig. 9 shows aliphatic hydroxyl contents of lignin derivatives recovered from corn cobs as a function of acidification of the organic solvent [pH] and pulping time [Time] at constant organic solvent concentration of 53.5% (w/w) and pulping temperature of 177°C, and shows process conditions suitable for producing lignin derivatives of the present disclosures having either decreased or increased aliphatic hydroxyl contents.
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112015014630A BR112015014630A2 (en) | 2012-12-18 | 2012-12-18 | process for recovering a lignin derivative, lignin derivative and its use, composition |
EP12890314.3A EP2935298A4 (en) | 2012-12-18 | 2012-12-18 | Processes for recovery of derivatives of native lignin |
CN201280078222.4A CN105283462A (en) | 2012-12-18 | 2012-12-18 | Processes for recovery of derivatives of native lignin |
PCT/CA2012/001172 WO2014094104A1 (en) | 2012-12-18 | 2012-12-18 | Processes for recovery of derivatives of native lignin |
CA2895215A CA2895215A1 (en) | 2012-12-18 | 2012-12-18 | Processes for recovery of derivatives of native lignin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CA2012/001172 WO2014094104A1 (en) | 2012-12-18 | 2012-12-18 | Processes for recovery of derivatives of native lignin |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014094104A1 true WO2014094104A1 (en) | 2014-06-26 |
Family
ID=50977443
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2012/001172 WO2014094104A1 (en) | 2012-12-18 | 2012-12-18 | Processes for recovery of derivatives of native lignin |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP2935298A4 (en) |
CN (1) | CN105283462A (en) |
BR (1) | BR112015014630A2 (en) |
CA (1) | CA2895215A1 (en) |
WO (1) | WO2014094104A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104911939A (en) * | 2015-06-15 | 2015-09-16 | 华南理工大学 | Low-liquor ratio bamboo material neutral sulfite cooking method |
US9708490B2 (en) | 2009-05-28 | 2017-07-18 | Fibria Innovations Inc. | Derivatives of native lignin |
US9840621B2 (en) | 2011-03-24 | 2017-12-12 | Fibria Innovations Inc. | Compositions comprising lignocellulosic biomass and organic solvent |
EP3137553A4 (en) * | 2014-05-01 | 2018-01-17 | Renmatix Inc. | Upgrading lignin from lignin-containing residues through reactive extraction |
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 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110541320B (en) * | 2019-09-12 | 2021-12-17 | 武汉轻工大学 | Method for separating lignin and cellulose from lignocellulose raw material |
CN113667207A (en) * | 2021-09-13 | 2021-11-19 | 浦江盛茂新材料有限公司 | Preparation method of Polyethylene (PE) composite material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010135805A1 (en) * | 2009-05-28 | 2010-12-02 | Lignol Innovations Ltd. | Derivatives of native lignin from annual fibre feedstocks |
CA2798268A1 (en) * | 2010-02-15 | 2011-08-18 | Lignol Innovations Ltd. | Carbon fibre compositions comprising lignin derivatives |
CA2803177A1 (en) * | 2010-06-30 | 2012-01-05 | Lignol Innovations Ltd. | Organosolv process |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4764596A (en) * | 1985-11-05 | 1988-08-16 | Repap Technologies Inc. | Recovery of lignin |
US6172204B1 (en) * | 1999-06-04 | 2001-01-09 | Regents Of The University Of Minnesota | Compositions based on lignin derivatives |
US20080295980A1 (en) * | 2007-05-31 | 2008-12-04 | Lignol Innovations Ltd. | Continuous counter-current organosolv processing of lignocellulosic feedstocks |
US9267027B2 (en) * | 2009-05-28 | 2016-02-23 | Fibria Innovations Inc. | Resin compositions comprising lignin derivatives |
CA2827023A1 (en) * | 2010-02-15 | 2011-08-18 | Lignol Innovations Ltd. | Organosolv process |
WO2012126099A1 (en) * | 2011-03-24 | 2012-09-27 | Lignol Innovations Ltd. | Compositions comprising lignocellulosic biomass and organic solvent |
-
2012
- 2012-12-18 WO PCT/CA2012/001172 patent/WO2014094104A1/en active Application Filing
- 2012-12-18 CA CA2895215A patent/CA2895215A1/en not_active Abandoned
- 2012-12-18 EP EP12890314.3A patent/EP2935298A4/en not_active Withdrawn
- 2012-12-18 CN CN201280078222.4A patent/CN105283462A/en active Pending
- 2012-12-18 BR BR112015014630A patent/BR112015014630A2/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010135805A1 (en) * | 2009-05-28 | 2010-12-02 | Lignol Innovations Ltd. | Derivatives of native lignin from annual fibre feedstocks |
WO2010135804A1 (en) * | 2009-05-28 | 2010-12-02 | Lignol Innovations Ltd. | Derivatives of native lignin |
WO2010135806A1 (en) * | 2009-05-28 | 2010-12-02 | Lignol Innovations Ltd. | Derivatives of native lignin from softwood feedstocks |
CA2798268A1 (en) * | 2010-02-15 | 2011-08-18 | Lignol Innovations Ltd. | Carbon fibre compositions comprising lignin derivatives |
CA2803177A1 (en) * | 2010-06-30 | 2012-01-05 | Lignol Innovations Ltd. | Organosolv process |
Non-Patent Citations (14)
Title |
---|
BROSSE, N ET AL.: "Dilute Sulphuric acid and ethanol Organosolv Pretreatment of Miscanthus x Giganteus", CELLUOSE CHEMISTRY AND TECHNOLOGY, vol. 44, 1 January 2010 (2010-01-01), pages 71 - 78, XP055262327 * |
BROSSE, N ET AL.: "Pretreatment of Miscanthus giganteus Using the Ethanol Organolsolv Process for Ethanol Production''.", IND. ENG. CHEM. RES, vol. 48, no. 18, 16 September 2009 (2009-09-16), pages 8328 - 8334, XP055262324, DOI: 10.1021/IE9006672 * |
EL HAGE, R ET AL.: "Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus", POLYMER DEGRADATION AND STABILITY, vol. 94, 1 October 2009 (2009-10-01), pages 1632 - 1638, XP026719420, DOI: 10.1016/J.POLYMDEGRADSTAB.2009.07.007 * |
EL HAGE, R ET AL.: "Effect of the Pre-Treatment Severity on the Antioxidant Properties of Ethanol Organosolv Miscanthus x giganteus lignin", NATURAL RESOURCES, vol. 3, no. 2, June 2012 (2012-06-01), pages 29 - 34, XP055265926 * |
EL HAGE, R ET AL.: "Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin''.", POLYMER DEGRADATION AND STABILITY, vol. 95, no. 6, 2010, pages 997 - 1003, XP027035677 * |
GLOSSELINK, RJA.: "Lignin as a reneweable aromatic resource for the chemical industry", THESIS FOR THE DEGREE OF DOCTOR AT WAGENINGEN UNIVERSITY.., 6 December 2011 (2011-12-06), pages 1 - 26, XP055271803 * |
HU, G ET AL.: "Structuial Characterization of Switchgrass Lignin after Ethanol Organosolv Pretreatment''.", ENERGY FUELS, vol. 26, no. 1, 19 January 2012 (2012-01-19), pages 740 - 745, XP055262320, DOI: 10.1021/EF201477P * |
PAN, X ET AL.: "Biorefining of Softwoods Using Ethanol Organosolv Pulping: Preliminary Evaluation of Process Streams for Manufacture of Fuel-Grade Ethanol and Co-Products", BIOTECHNOLOGY AND BIOENGINEERING, vol. 90, no. 4, 20 May 2005 (2005-05-20), pages 473 - 481, XP008128416, DOI: 10.1002/BIT.20453 * |
PAN, X ET AL.: "Organosolv Ethanol Lignin from Hybrid Poplar as a Radial Scavenger: Relationship between Lignin Structure, Extraction Conditions, and Antioxidant Activity''.", J. AGRIC, FOOD CHEM, vol. 54, no. 16, 9 August 2006 (2006-08-09), pages 5806 - 5813, XP008148495, DOI: 10.1021/JF0605392 * |
PAN, X ET AL.: "The Bioconversion of Mountain Pine Beetle-Killed Lodgepole Pine to Fuel Ethanol Using the Organolsolv Process''.", BIOTECHNOLOGY AND BIOENGINEERING, vol. 101, no. 1, 1 September 2008 (2008-09-01), pages 39 - 48, XP002542737, DOI: 10.1002/BIT.21883 * |
SANNIGRAHI, P ET AL.: "Lignin Structural Modifications Resulting from Ethanol Organosolv Treatment of Loblollv Pine''.", ENERGY FUELS, vol. 24, no. 1, 21 January 2010 (2010-01-21), pages 683 - 689, XP055262330, DOI: 10.1021/EF900845T * |
See also references of EP2935298A4 * |
XU, F ET AL.: "Comparative study of organosolv lignins from wheat straw''.", INDUSTRIAL CROPS AND PRODUCTS, vol. 23, no. 2, 1 March 2006 (2006-03-01), pages 180 - 193, XP028001284, DOI: 10.1016/J.INDCROP.2005.05.008 * |
XUE, B-L ET AL.: "Polyols Production by Chemical Modification of Autocatalyzed Ethanol-Water lignin from Betula Ainoides''.", PAPER PS-79. PROCEEDINGS OF THE 55TH INTERNATIONAL CONVENTION OF SOCIETY OF WOOD SCIENCE AND TECHNOLOGY, 27 August 2012 (2012-08-27), BEIJING, CHINA, pages 434 - 442, XP055262290, DOI: 10.1002/APP.38610 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9708490B2 (en) | 2009-05-28 | 2017-07-18 | Fibria Innovations Inc. | Derivatives of native lignin |
US10435562B2 (en) | 2009-05-28 | 2019-10-08 | Fibria Innovations Inc. | Derivatives of native lignin, lignin-wax compositions, their preparation, and uses thereof |
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 |
US9840621B2 (en) | 2011-03-24 | 2017-12-12 | Fibria Innovations Inc. | Compositions comprising lignocellulosic biomass and organic solvent |
EP3137553A4 (en) * | 2014-05-01 | 2018-01-17 | Renmatix Inc. | Upgrading lignin from lignin-containing residues through reactive extraction |
US10240006B2 (en) | 2014-05-01 | 2019-03-26 | Renmatix, Inc. | Upgrading lignin from lignin-containing residues through reactive extraction |
CN104911939A (en) * | 2015-06-15 | 2015-09-16 | 华南理工大学 | Low-liquor ratio bamboo material neutral sulfite cooking method |
Also Published As
Publication number | Publication date |
---|---|
CN105283462A (en) | 2016-01-27 |
EP2935298A1 (en) | 2015-10-28 |
CA2895215A1 (en) | 2014-06-26 |
EP2935298A4 (en) | 2016-09-07 |
BR112015014630A2 (en) | 2017-07-11 |
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: 201280078222.4 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12890314 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2895215 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: IDP00201504427 Country of ref document: ID |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012890314 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015014630 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112015014630 Country of ref document: BR Kind code of ref document: A2 Effective date: 20150618 |