New Low-Sulfur Terpene Mix Recovery from Wood Processing

Abstract

The present invention relates to an environmentally friendly liquid wood extract containing terpene compounds. The present invention also relates to cosmetics, toiletries, pharmaceuticals, dietary supplements, antibacterial agents, pesticides or chemical raw material components obtained by using the environmentally friendly liquid wood extract. A method for preparing the environmentally friendly liquid wood extract is also an object of the present invention.

Description

Technical Field

[0001] The present invention relates to the fields of cosmetics, flavorings and industrial raw material components. More particularly, the present invention relates to new valuable natural and solvent-free terpene intermediate mixes for producing fragrances, flavors and / or industrial raw material components.

Background Art

[0002] Wood represents a valuable alternative for the production of chemical building blocks. It is a renewable resource that can potentially be used as a raw material for many products manufactured by the chemical industry. Unfortunately, in the majority of woodworking industries (including pulp, fiberboards such as medium and high density fiberboards (MDF and HDF), plywood, particleboard, oriented strand board (OSB), lumber, laminated strand board, wood-based biofuels such as wood pellets, bioethanol...), most of the residues are collected as waste and not valued. The need to reduce the ecological impact of wood processing creates new opportunities for the wood industry to develop cost-effective and environmentally friendly waste reduction techniques in order to maximize the extraction yield of valuable compounds from wood.

[0003] Examples of valuable wood compounds are not only lignin, cellulose, hemicellulose, but also terpenes. Typically, monoterpenes such as alpha-pinene, beta-pinene and dipentene represent very desirable skeletons that can be used as such or as important intermediates for preparing more complex compounds in different fields such as cosmetics, toiletries, pharmaceuticals and / or agrochemicals. Examples of feedstock components obtained from alpha and beta-pinene and dipentene are synthetic odorants that impart an odor similar to sandalwood oil (e.g., SANDEROL®, EBANOL® or POLYSANTOL® / NIRVANOL®), or woody feedstock components that impart cider and / or amber notes to fragrance and flavor formulations (e.g., SYLVAMBER®), or industrial compounds such as polyterpene resins (e.g., DERCOLYTE® grades A, M, L and S). There is also increasing interest in higher molecular weight compounds such as terpene alcohols used in synthetic fragrances. Typically, cis-pinanol is a terpene alcohol that is pyrolyzed to produce industrial quantities of linalool. Sesquiterpenes are valuable higher molecular weight compounds used as building blocks for biopolymers or as active feedstock components in pharmaceutical compositions. Examples of valuable sesquiterpenes are alpha-cedrene, which is widely used in fragrance formulations and in the synthesis of more valuable aromatic substances such as acetyl cedrene, cedryl ketone, in soaps and detergents, or beta-caryophyllene, which is used as a raw material for synthesizing other fragrances. A final example is longifolene, which is widely used in the fragrance industry, but also as a raw material for synthetic fragrances or in organic synthesis for the preparation of dilongifolylborane and isolongifolene, and finally as a flotation agent for lead-zinc ores.

[0004] Terpenes can be extracted from the tapping industry by first tapping living trees, finally distilling the obtained gum to collect oleoresin, and separating gum turpentine oil (GT) from gum rosin. GT is typically a highly concentrated sulfur-free mixture of non-oxygenated monoterpenes, but the presence of high molecular weight terpene compounds such as terpene alcohols and sesquiterpenes is very low.

[0005] Despite improvements in technology that provide better recovery rates, the collection of oleoresin remains overly labor-intensive, leading to a worldwide decline in this activity. Therefore, there is a need to find new sustainable sources of terpenes.

[0006] Wood extracts, particularly terpene compounds, can be found in heartwood and bark. The extract content of bark is very high compared to wood, but the values reported in the literature can vary widely even for the same species and depend greatly on the extraction method.

[0007] In most cases, in wood, in both softwood and hardwood, most of the extractives are located in the heartwood. Both bark and wood contain carbohydrates and lignin. The composition and content of such carbohydrates and lignin strongly influence the availability of extractives, the stringency of the extraction method, and thus the extraction yield, particularly the composition of the extractives from which valuable compounds (terpenes and other terpene compounds) can be obtained in abundance, and the ease of the preparation or purification steps required before using them as precursors or raw material components.

[0008] Generally, softwood has a higher cellulose content (40 - 45%), a higher lignin content (26 - 34%), and a lower pentosan content (7 - 14%) compared to hardwood (cellulose 38 - 49%, lignin 23 - 30%, and pentosan 19 - 26%).

[0009] Furthermore, lignin consists of a complex array of substituted phenol units that do not have a single repeating unit like cellulose and create a more resistant cross-linked structure to the high temperatures and pressures during pulping. Softwood lignin is slightly different from hardwood lignin, having a methoxyl content of 15 - 16%, while hardwood lignin has a methoxyl content of 21%. However, it has been found that an increase in the methoxyl group content in lignin correlates with a decrease in the softening temperature of wet wood during pulping.

[0010] In the kraft pulp industry, terpene compounds are extracted as a stream from wood pulp and named crude sulfate tall oil (CST). CST is a complex mixture containing monoterpenes, oxygenated monoterpenes, sesquiterpenes, high molecular weight terpene compounds, and aromatic phenolic compounds with significant concentrations of sulfur compounds (typically in the range of 8000 - 40000 ppm). Sulfur compounds are generated by the use of sodium hydroxide and sodium sulfide solutions, so-called white liquor, using wood chips under severe conditions such as typical temperatures up to 180 °C and pressures that can reach 10×10 5 Pa for durations of 60 - 240 minutes. Typical sulfur compounds are methyl mercaptan, dimethyl sulfide, dimethyl disulfide, and thiophene. These compounds are highly flammable and toxic and contribute to the dangerous risks in the production, storage, and transportation of CST.

[0011] High molecular weight terpene compounds are present in CST at fairly significant concentrations. This is due to a combination of two interdependent factors: the wood species used as raw material and the severe kraft pulping operating conditions. The higher the wood lignin concentration, the more severe the operating conditions for pulping the wood. The kraft pulping operating conditions involve partial and / or total vaporization of high molecular weight terpene compounds, which are then also recovered along with non-oxygenated monoterpenes to produce CST. Typical valuable high molecular weight terpene compounds are terpene alcohols such as alpha-terpineol or estragole, and sesquiterpenes such as caryophyllene or longifolene.

[0012] The severe conditions of kraft pulping, which initially aim to remove lignin from carbohydrates, produce high concentrations of lignocellulosic pyrolysis compounds. Typically, decomposition products derived from cellulose, hemicellulose, and lignin are produced, and from these, aromatic phenolic chemicals such as guaiacol, syringol, and para - hydroxyphenol are formed. However, such compounds, and particularly aromatic phenolic chemicals, can only be partially removed from the CST and can increase the complexity of its composition.

[0013] The enrichment of valuable terpene compounds and the removal of all sulfur derivatives are pre - conditions for any use in the production of raw material components in the F&F industry. Thus, the high sulfur content, combined with the complexity of the CST composition (including aromatic phenolic chemicals from lignin decomposition), greatly affects the safety, productivity, and cost of the prior purification methods for isolating valuable monoterpene or sesquiterpene derivatives from the CST for use in the F&F industry. Such industrial separation methods are even more complex and are not economically feasible for high - molecular - weight terpene compounds such as caryophyllene, longifolene, and alpha - terpineol.

[0014] As a result, both the wood species of the wood used and the pretreatment conditions by wood - based industries or forest biorefineries strongly influence not only the quality of the final products, i.e., the main products (paper, fiberboard, particle board...), but also the quality of other extractives that may provide value, such as monoterpenes, or other high - molecular - weight terpene derivatives as sesquiterpenes.

[0015] The extensive use of chemicals, water, and steam not only generates a significant amount of wastewater contaminated with chemicals (such as volatile organic compounds or synthetic chemicals from wood), but also induces the contamination of valuable compounds extracted from wood.

[0016] As the awareness of climate and environmental issues increases and consumption habits change, not only reducing the ecological impact of wood processing but also providing environmentally friendly products to meet consumer needs, new opportunities are opening up for the wood or forest industry to develop cost-effective and functional environmental protection solutions. Typically, the main challenges faced by the wood industry are to reduce the use of chemicals in wood processing and the content of residues released into the environment or contained in the final products, especially terpene compounds.

[0017] Considering the high customer demand for renewable or natural origin compounds and the current situation of industrial tall oil manufacturing, there is a need for a high-quality solvent-free sulfur-free terpene-rich mix that can be used without extensive pretreatment as a raw material for developing biosource raw material components, especially in the F&F industry. As a result, there is an increasing need to develop an environmentally friendly and cost-effective solvent-free method that enables the recovery of such terpene-rich mixes.

[0018] Summary of the Invention The object of the present invention is to provide a high-quality solvent-free, sulfur-free terpene-rich mix and an environmentally friendly and cost-effective wood pretreatment method applicable to various wood-based industries such as the pulp industry, MDF and HDF industries, or biofuel industries.

[0019] In a first aspect, the present invention relates to a) 50 to 95% (by weight) of at least one non-oxygenated monoterpene, and b) 5 to 30% (by weight) of at least one terpene having a higher molecular weight than the non-oxygenated monoterpene, and c) less than 0.1% (by weight) of at least one lignocellulosic biomass pyrolysis compound, and d) a sulfur content of less than 1000 ppm and relates to a liquid wood extract.

[0020] In a second aspect, the present invention is a method for producing a liquid wood extract, comprising a.Providing a wood log mix comprising hardwood and softwood, with more than 50% softwood, typically more than 70% softwood; b.Cutting or chipping or shredding the wood logs into strands or chips; c.Applying a first steam treatment to the wood strands or wood chips such that steam passes over the wood strands or wood chips at a temperature of 50°C to 120°C and a pressure of 0.1×10 5 Pa to 4×10 5 Pa; d.Applying a first compression step to the wood strands or wood chips at a pressure of 7×10 5 Pa to 15×10 5 Pa and adding water to the wood strands or wood chips at a temperature of 10°C to 40°C to obtain pre-softened wood strands or wood chips, and collecting a first compression extract; e.Applying an evaporation step to the first compression extract by evaporating more than 15% of the first compression extract to produce terpene compound-enriched steam; f.Condensing the terpene compound-enriched steam, optionally in combination with steam collected from the first steam treatment process, to obtain a condensed phase; g.Applying a separation phase to the condensed phase by treating the condensed phase by gravimetric decantation and / or centrifugation to obtain a liquid wood extract; relating to a method comprising the above steps.

[0021] Another object of the present invention is a method for obtaining cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical raw material components, comprising the step of obtaining a liquid wood extract according to the method of the present invention.

[0022] Another object of the present invention is to use the liquid wood extract of the present invention as an active compound in cosmetics, toiletries, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical compositions, or to obtain the active compounds of cosmetics, toiletries, pharmaceuticals, dietary supplements, antibacterial agents, pesticides and / or chemical compositions.

BRIEF DESCRIPTION OF THE INVENTION

[0023] A first object of the present invention is a) at least one non-oxygenated monoterpene of 50 to 95% (by weight), preferably 70 to 94%, even more preferably 80 to 93% (by weight) or 80 to 92% (by weight), and b) at least one terpene of higher molecular weight than the non-oxygenated monoterpene of 5 to 30% (by weight), preferably 5 to 20% (by weight), preferably 6 to 20% (by weight), even more preferably 7 to 15% (by weight), and c) less than 0.1% (by weight), preferably less than 0.05% (by weight), more preferably less than 0.001% (by weight) of at least one wood biomass pyrolysis compound, and d) a sulfur content of less than 1000 ppm, preferably less than 200 ppm, or less than 100 ppm, typically less than 80 ppm, even more preferably less than 50 ppm A liquid wood extract comprising.

[0024] The expression "liquid wood extract" refers to a wood-based liquid extract, a liquid composition / mixture extracted from wood or obtained by wood processing or the wood processing industry. In particular, the liquid composition / mixture is a waste stream in the wood industry that performs fiberboard, plywood, particle board, oriented strand board, lumber, laminated strand board or wood-based biofuel industries, especially the waste of the fiberboard industry. The liquid wood extract can be recovered from the liquid waste generated during the conversion of wood materials.

[0025] For clarity, the term "terpene" or "terpene compound" refers to any compound composed of two or more isoprene (C5) units. The term "terpene" includes compounds containing only unmodified isoprene units, as well as compounds containing one or more modified isoprene units (such as oxidation or rearrangement of the carbon skeleton). Such modified terpene compounds may also be referred to as "terpenoids" or "isoprenoids". The number of C atoms present in a terpene is typically evenly divisible by 5 (e.g., C10, C15, C20, C25, C30, and C40). Irregular terpenes have been reported and are also included in the definition of "terpene". Terpenes include, but are not limited to, monoterpenes (C10), sesquiterpenes (C15), diterpenes (C20), sesterterpenes (C25), triterpenes (C30), tetraterpenes (C40), and polyterpenes having longer chains of isoprene units. Terpenes can be linear or cyclic.

[0026] Terpenes or terpene compounds include oxygenated terpenes and non-oxygenated terpenes. Oxygenated terpenes have a terpene skeleton and an oxygen-containing functional group. Non-oxygenated terpenes have a hydrocarbon skeleton without an oxygen functional group. Advantageously, non-oxygenated monoterpenes have a molecular weight of 132 - 140 g / mol. Typically, examples of oxygen functional groups are aldehyde, phenol, carboxylic acid, ketone, epoxide, acid, ether, hydroxy group, and ester.

[0027] Terpenes with a higher molecular weight than non-oxygenated monoterpenes have a molecular weight above 140 g / mol, preferably above 148 g / mol, more preferably between 148 - 600 g / mol, typically between 200 - 400 g / mol. Non-limiting examples of "terpenes with a higher molecular weight than non-oxygenated monoterpenes" are oxygenated monoterpenes, diterpenes, sesquiterpenes, oxygenated sesquiterpenes, sesterterpenes, triterpenes, tetraterpenes, polyterpenes, and are preferably selected from oxygenated monoterpenes, diterpenes, and sesquiterpenes.

[0028] The term "monoterpene" refers to a compound composed of two isoprene units. The term "monoterpene" includes compounds containing only unmodified isoprene units, as well as compounds containing one or more of the above modifications. When a monoterpene contains such a modification, it may also be referred to as a "monoterpenoid". Monoterpenes include oxygenated monoterpenes having a monoterpene skeleton and oxygen-containing functional groups, and non-oxygenated monoterpenes having a monoterpene skeleton without oxygen functional groups.

[0029] Preferably, the monoterpene is acyclic (especially linear), monocyclic or bicyclic.

[0030] According to the present invention, at least one non-oxygenated monoterpene is selected from bicyclic non-oxygenated monoterpenes, monocyclic non-oxygenated monoterpenes, acyclic non-oxygenated monoterpenes and mixtures thereof.

[0031] Non-limiting examples of acyclic non-oxygenated monoterpenes are myrcene, ocimene, allo-ocimene and citronellene.

[0032] Non-limiting examples of monocyclic non-oxygenated monoterpenes are limonene (D-limonene, DL-limonene, dipentene), isolimonene, p-menthane, 1-p-menthene, 3-p-menthene, α-terpinene, γ-terpinene, terpinolene, α-felandrene, β-felandrene, p-cymene, each in the form of any one of their stereoisomers or a mixture thereof.

[0033] For the sake of clarity, in the expression "in the form of any one of their respective stereoisomers or a mixture thereof" or a similar expression, the ordinary meaning understood by those skilled in the art, that is, the compounds cited in the present invention, such as monoterpenes, terpenes or other compounds, typically limonene or α-pinene, can have one or more stereocenters, and thus can be pure enantiomers or diastereomers. In other words, the compounds cited in the present invention may have one or several stereocenters, and each of the stereocenters can have two different stereochemistries (e.g., R or S). The compounds cited in the present invention may be in the form of pure enantiomers or in the form of a mixture of enantiomers or diastereoisomers. The compounds cited in the present invention can be racemates or scalemic forms. Therefore, the compounds cited in the present invention can be in the form of one stereoisomer or in the form of a composition of substances that contain or consist of various stereoisomers.

[0034] Non-limiting examples of bicyclic non-oxygenated monoterpenes are α-pinene, β-pinene, (±)-camphene, delta-3-carene, bornylene, sabinene, thujene, carane, each in the form of any one of their respective stereoisomers or a mixture thereof.

[0035] Preferably, according to the present invention, the preferred non-oxygenated monoterpenes are selected from alpha-pinene, beta-pinene, dipentene and mixtures thereof, more preferably alpha-pinene, beta-pinene, each in the form of any one of their respective stereoisomers or a mixture thereof.

[0036] Typically, at least one oxygenated monoterpene is selected from monoterpene alcohols, monoterpene aldehydes, monoterpene ketones, monoterpene epoxides, monoterpene ethers, and mixtures thereof. Preferably, the oxygenated monoterpene is selected from monoterpene alcohols, monoterpene aldehydes, monoterpene ketones, monoterpene epoxides, and mixtures thereof. Preferably, the oxygenated monoterpene is selected from monoterpene alcohols, monoterpene epoxides, and mixtures thereof.

[0037] Non-limiting examples of acyclic monoterpene alcohols and aldehydes are geraniol, nerol, (+)-citronellol, (-)-citronellol, citral, (+)-citronellal, (-)-citronellal, hydroxycitronellal, linalool, myrcenol, dihydromyrcenol, each in the form of any one of their stereoisomers or mixtures thereof.

[0038] Non-limiting examples of acyclic monoterpene esters are linalyl acetate and any one of their stereoisomers or mixtures thereof.

[0039] Non-limiting examples of monocyclic monoterpene aldehydes are perillyl aldehyde, ferulal, 1,2-dihydroferulal, cumin aldehyde, each in the form of any one of their stereoisomers or mixtures thereof.

[0040] Non-limiting examples of monocyclic monoterpene alcohols are menthol, neomenthol, (+)-isomenthol, isopulegol, α-terpineol, β-terpineol, γ-terpineol, (-)-terpinene-4-ol, thymol, carvacrol, carveol, dihydrocarveol, piperitenol, isopiperitenol, perillyl alcohol, carvomenthol, each in the form of any one of their stereoisomers or mixtures thereof.

[0041] Non-limiting examples of monocyclic monoterpene ethers are any one of thymol methyl ether, carvacrol methyl ether, and their stereoisomers, or mixtures thereof.

[0042] Non-limiting examples of monocyclic monoterpene ketones, more particularly α,β-unsaturated ketones, are carvone, carvotanacetone, α-ionone, β-ionone, and γ-ionone, pipertone, pregeone, piperitenone, isopiperitenone, each in the form of any one of their stereoisomers or mixtures thereof.

[0043] Non-limiting examples of monocyclic monoterpene saturated ketones are dihydrocarvone, mentone, isomentone, each in the form of any one of their stereoisomers or mixtures thereof.

[0044] Non-limiting examples of cyclic monoterpene epoxides are 1,8-cineole, 1,4-cineole, each in the form of any one of their stereoisomers or mixtures thereof.

[0045] Non-limiting examples of bicyclic monoterpene aldehydes are myrtenal, myrtanal, each in the form of any one of their stereoisomers or mixtures thereof.

[0046] Non-limiting examples of bicyclic monoterpene alcohols are myrtenol, myrtanol, pinocarveol, pinan-2,3-diol, isopinocampheol (3-pinanol), borneol, isoborneol, fenchol, verbenol, nopol, each in the form of any one of their stereoisomers or mixtures thereof.

[0047] Non-limiting examples of bicyclic monoterpene esters are fenchyl acetate, each in the form of any one of their stereoisomers or mixtures thereof.

[0048] Non-limiting examples of bicyclic monoterpene ethers are nopyl benzyl ethers, in the form of any one of their stereoisomers or mixtures thereof.

[0049] Non-limiting examples of bicyclic monoterpene ketones, more particularly unsaturated ketones, are verbenone, pinocarvone, in the form of any one of their stereoisomers or mixtures thereof.

[0050] Non-limiting examples of bicyclic monoterpene saturated ketones are camphor, fenchone, alpha-thujone, beta-thujone, 3-pinanone (pinocamphone and isopinocamphone), 2-hydroxy-3-pinanone, in the form of any one of their stereoisomers or mixtures thereof.

[0051] Advantageously, terpenes of higher molecular weight than non-oxygenated monoterpenes are oxygenated monoterpenes, diterpenes, sesquiterpenes and mixtures thereof.

[0052] Preferred oxygenated monoterpenes are selected from monoterpene alcohols, monoterpene aldehydes, monoterpene ketones, monoterpene epoxides and mixtures thereof.

[0053] Preferred oxygenated monoterpenes are terpene alcohols such as terpineol, estragole, anethole, borneol, in the form of any one of their stereoisomers or mixtures thereof.

[0054] Terpineol exists as different positional isomers, all of which are considered terpineol. Terpineol is selected from the group consisting of alpha-terpineol, beta-terpineol, gamma-terpineol, delta-terpineol, 4-terpineol [or (-)-terpinene-4-ol], and is in the form of any one of their stereoisomers or a mixture thereof. More preferably, terpineol is selected from the group consisting of alpha-terpineol, beta-terpineol, gamma-terpineol, delta-terpineol, and is in the form of any one of their stereoisomers or a mixture thereof.

[0055] The term "diterpene" refers to a compound composed of four isoprene units. The term "diterpene" includes compounds containing only unmodified isoprene units, as well as compounds containing one or more of the above modifications. When a monoterpene contains such a modification, this can also be referred to as a "diterpenoid". The liquid wood extract of the present invention preferably contains at least one diterpene, a cyclic diterpene, typically at least one bicyclic diterpene and / or at least one tricyclic diterpene.

[0056] Typically, the diterpene is a non-oxygenated diterpene or an oxygenated diterpene, preferably an oxygenated diterpene.

[0057] Examples of oxygenated diterpenes are diterpenic acids, typically tricyclic diterpenic acids, bicyclic diterpenic acids or mixtures thereof.

[0058] Non-limiting examples of oxygenated diterpenes are tricyclic diterpenic acids selected from abietic acid, dehydroabietic acid, isopimaric acid, levopimaric acid, neoabietic acid, pultrinic acid, pimaric acid, sandaracopimaric acid, and are in the form of any one of their stereoisomers or a mixture thereof.

[0059] Non-limiting examples of oxygenated diterpenes are bicyclic diterpenoid acids selected from agathic acid, isocupreic acid, and trans-communic acid, in the form of any one of their stereoisomers or a mixture thereof.

[0060] According to the present invention, non-limiting examples of diterpenes or diterpenoids are abietane, rosin, rosinane, daphnane, arteane, cassane, podocarboxane, taurane, labdane, and isoabienol, in the form of any one of their stereoisomers or a mixture thereof, preferably abietane rosin, rosinane, isoabienol, and podocarboxane, in the form of any one of their stereoisomers or a mixture thereof.

[0061] Examples of labdane-type diterpenoids are abietadiene, abieta-8(14),13(15)-diene; (Z)-biformene; isoabienol labda-7,14-diene-13-ol, labda-7,13,14-triene; manool, manoyl oxide 13 epi monoyl oxide, in the form of any one of their stereoisomers or a mixture thereof.

[0062] Sesquiterpenes are preferably acyclic sesquiterpenes, cyclic sesquiterpenes, and mixtures thereof.

[0063] Preferably, the acyclic sesquiterpene is farnesene. The cyclic sesquiterpenes are selected from cuparene, curcumene, longifolene, longicyclene, longipinene, caryophyllene, humulene, murulene, α-copaene, β-copaene, and bisabolene, in the form of any one of their stereoisomers or a mixture thereof.

[0064] Preferred sesquiterpenes are selected from farnesene, longifolene, longicyclene, longipinene caryophyllene, humulene, muroene, alpha-muurene, and are in the form of any one of their stereoisomers or a mixture thereof.

[0065] Non-limiting examples of oxygenated sesquiterpenes are any one of caryophyllene oxide and its stereoisomers or a mixture thereof.

[0066] Non-limiting examples of sesterterpenes are any one of ophioderin and its stereoisomers or a mixture thereof. Non-limiting examples of triterpenes are squalane, hopane, sterol, and are in the form of any one of their stereoisomers or a mixture thereof. Non-limiting examples of tetraterpenes are carotane, and are in the form of any one of their stereoisomers or a mixture thereof. A non-limiting example of a polyterpene is natural rubber.

[0067] The "wood biomass pyrolysis compound" should be understood as a compound produced during the exposure of wood biomass, more specifically cellulose, hemicellulose, and lignin, at temperatures exceeding 200°C. Such decomposition compounds, more specifically the decomposition products derived from cellulose, hemicellulose, and lignin, have been extensively studied in the scientific literature (Pyrolysis of Cellulose, Kunio Kato, Agr. BioI. Chern., Vol. 31, No. 6, p. 657~663, 1967; Recent Insights into Lignocellulosic Biomass Pyrolysis: A Critical Review on Pretreatment, Characterization, and Products Upgrading, Z E Zadeh et al; Processes 2020, 8, 799; Hydrothermal liquefaction of wood using a modified multistage shrinking core model, M. Jayathilakea et al; Fuel 280(2020)118616).

[0068] The decomposition products derived from cellulose are any one of hydroxymethylfurfural, levoglucosan, cellobiose, anhydroglucose derivatives, acetaldehyde, methanol, glyoxal, acrolein, and are in the form of any one of their stereoisomers or a mixture thereof.

[0069] The decomposition products derived from hemicellulose are any one of furan or furan derivatives, particularly furan, furfuraldehyde (also called furfural), furfuryl alcohol.

[0070] The decomposition products derived from lignin contain phenols, typically phenol, cresol, catechol, eugenol, methyleugenol, guaiacol, 4-propylphenol, 4-ethylguaiacol, methyleugenol, syringol, p-hydroxyphenol, hydroxymethoxytoluene, hydroxymethoxyethylbenzene, hydroxymethoxyvinylbenzene, hydroxymethoxypropylbenzene, dimethoxyphenol, hydroxydimethoxytoluene, hydroxydimethoxyethylbenzene, hydroxydimethoxypropylbenzene, pyrocatechol, benzofuran, dibenzofuran and vanillin. Among these phenols, phenol and cresol are industrially particularly important compounds. The decomposition products derived from lignin obtained here contain at least phenol or cresol.

[0071] Typically, the content of at least one lignocellulosic pyrolysis compound in the liquid wood extract of the present invention is 0.0000001 to 0.1%, or 0.0000001 to 0.05%, or 0.0000001 to 0.1%, or 0.0000001 to 0.001% (by weight).

[0072] The sulfur content means the total sulfur content of the extract. Typically, the sulfur content is evaluated by fluorescence UV of a Sulfur Analyser Antek Multitek NT-HS according to the standard ASTM D 5453. Advantageously, the sulfur content is 1000 ppm to 0.01 ppm, preferably 200 ppm to 0.1 ppm, or 100 ppm to 1 ppm, typically 80 ppm to 2 ppm, and even more preferably less than 50 ppm. In particular, the liquid wood extract does not contain sulfur compounds.

[0073] A second object of the present invention is a method for producing a liquid wood extract, a. providing a wood log mix containing hardwood and softwood, with more than 50% softwood, typically more than 70% softwood; b. cutting or chipping or shredding the wood logs into strands or chips; c. At a temperature of 50°C to 120°C and a pressure of 0.1×10 5 Pa to 4×10 5 Pa, apply a first steam treatment to the wood strands or wood chips such that steam passes over the wood strands or wood chips, and d. Apply a first compression step to the wood strands or wood chips at a pressure of 7×10 5 Pa to 15×10 5 Pa, and add water to the wood strands or wood chips at a temperature of 10°C to 40°C to obtain pre-softened wood strands or wood chips, and collect the first compression extract, and e. Apply an evaporation step to the first compression extract by evaporating more than 15% of the first compression extract, preferably more than 20 - 80% of the first compression extract, even more preferably 22 - 40%, typically 25 - 35% to produce terpene compound-enriched steam, and f. Optionally combine the terpene compound-enriched steam with the steam collected from the first steam treatment process, and condense it to obtain a condensed phase, and g. Apply a separation phase to the condensed phase by treating the condensed phase by gravimetric decantation and / or centrifugation to obtain a liquid wood extract and relates to a method.

[0074] According to the present invention, the hardwood and softwood wood log mix contains about 70 - 100% softwood, preferably 75 - 98%, 80 - 95% or 85 - 90% softwood.

[0075] "Softwood" should be understood as wood produced by angiosperms or conifers. Non-limiting examples of softwood are Araucaria; Himalayan cedar (Cedrus); false cypress (Chamaecyparis), Cupressus, Taxodium; Rocky Mountain Douglas fir (Pseudotsuga menziesii var. glauca); European yew (Taxus baccata); fir (Abies); hemlock (Tsuga): Eastern hemlock (Tsuga canadensis), mountain hemlock (Tsuga mertensiana), Western hemlock (Tsuga heterophylla); kauri (New Zealand) (Agathis, Australia); kaya (Torreya nucifera); larch (Larix); pine (Pinus); spruce (Picea); white cedar and yellow cedar (Nootka Cypress Callitropsis nootkatensis, formerly Chamaecyparis nootkatensis); red cedar; redwood (Sequoia sempervirens) and rimu (New Zealand) (Dacrydium cupressinum).

[0076] Typically, false cypress (Chamaecyparis, Cupressus, Taxodium) is selected from Arizona cypress (Cupressus arizonica), pond cypress or southern false cypress (Taxodium distichum), hinoki cypress (Chamaecyparis obtusa), Lawson cypress (Chamaecyparis lawsoniana) and Italian cypress (Cupressus sempervirens).

[0077] Typically, hemlock (Tsuga) is selected from eastern hemlock (Tsuga canadensis), mountain hemlock (Tsuga mertensiana) and western hemlock (Tsuga heterophylla).

[0078] Typically, larch (Larix) is selected from European larch (Larix decidua), Japanese larch (Larix kaempferi), tamarack larch or tamarack (Larix laricina), western larch (Larix occidentalis).

[0079] Typically, pine (Pinus) is selected from Corsican pine (Pinus nigra), jack pine (Pinus banksiana), lodgepole pine (Pinus contorta subsp latifolia), Monterey pine (Pinus radiata), ponderosa pine (Pinus ponderosa), red pine (North America) (Pinus resinosa), Scots pine, red pine (UK), red deal (UK), redwood (UK, old style) (Pinus sylvestris), white pine (yellow pine or weymouth pine, eastern white pine (Pinus strobus), western white pine (Pinus monticola), sugar pine (Pinus lambertiana), southern yellow pine (loblolly pine (Pinus taeda)), longleaf pine (Pinus palustris), pitch pine (Pinus rigida), shortleaf pine (Pinus echinata), maritime pine (Pinus pinaster), Pinus elliottii - slash pine (Pinus elliottii), masson pine (Pinus massoniana), Aleppo pine (Pinus halepensis), Sumatra pine (Pinus merkusii), Monterey pine, radiata pine (Pinus radiata).

[0080] Softwoods of particular interest are, more specifically, maritime pine (Pinus Pinaster), slash pine (Pinus Elliottii), Masson pine (Pinus Massoniana), Aleppo pine (Pinus Halepensis) and Monterey pine, radiata pine (Pinus Radiata).

[0081] Typically, spruces are selected from Norway spruce (Picea abies), black spruce (Picea mariana), red spruce (Picea rubens), Sitka spruce (Picea sitchensis), white spruce (Picea glauca) and Japanese cedar (Cryptomeria japonica).

[0082] Typically, white cedars are selected from northern white cedar (Thuja occidentalis), southern white cedar (Chamaecyparis thyoides).

[0083] Typically, red cedars are selected from eastern red cedar (Juniperus virginiana), western red cedar (Thuja plicata).

[0084] Typically, the araucaria is selected from hoop pine (Araucaria cunninghamii), Paraná pine (Araucaria angustifolia); Pehuen or Chile pine (Araucaria araucana).

[0085] Typically, the false cypress (Chamaecyparis, Cupressus, Taxodium) is selected from Arizona cypress (Cupressus arizonica), swamp cypress or southern false cypress (Taxodium distichum), hinoki cypress (Chamaecyparis obtusa), Lawson cypress (Chamaecyparis lawsoniana) and Italian cypress (Cupressus sempervirens).

[0086] According to the present invention, the wood log mix contains 0 to 30%, preferably 2 to 25%, more preferably 5 to 20% of hardwood logs.

[0087] For the sake of clarity, "hardwood" means wood produced by angiosperm trees having broad leaves and reproducing flowers. Hardwoods have broad leaves and seeds such as closed nuts or acorns. These grow in subtropical regions such as Africa, as well as in other regions such as Europe and Asia. The main feature that differentiates hardwoods from softwoods is the presence of pores or conduits.

[0088] Non-limiting examples of hardwoods are afzelia (Afzelia); agba yun (Synsepalum duloificum); albizia (Albizia); alder (Alnus); apple or wild apple (Malus); ash (Fraxinus); aspen (Populus); ayang (Distemonanthus benthamianus); balsa (Ochroma pyramidale); basswood (Tilia americana); beech (Fagus); birch (Betula); blackbean (Castanospermum australe); blackwood; bocote (Cordia alliodora); boxwood or box (Buxus sempervirens); Brazilian rosewood (Caesalpinia echinata); bubinga (Guibourtia); buckeye (Aesculus); butternut (Juglans cinerea); carapa (or andiroba, carap, crappo, clubwood and Santa Maria) (Carapa guianensis); catalpa (Catalpa); cherry (Prunus); chestnut (Castanea dentata); coachwood (Ceratopetalum apetalum); cocobolo (Dalbergia retusa); corkwood (Leitneria floridana); cottonwood, eastern (Populus deltoides); dogwood (Cornus species);Ebony (Diospyros); Beech; Eucalyptus (Eucalyptus); Greenheart (Guyana) (Chlorocardium rodiei); Granadilla (Mpingo) (Dalbergia melanoxylon); Gum; Hickory (Carya); Hornbeam (Carpinus species); Hop Hornbeam, Eastern (Ostrya virginiana); Ipe or Pau (Tabebuia); Iroko (Milicia excelsa, synonym Chlorophora excelsa).;

[0089] Typically, beech (Fagus) is selected from European beech (Fagus sylvatica), American beech (Fagus grandifolia).

[0090] Typically, birch (Betula) is selected from gray birch (Betula populifolia), paper birch (Betula papyrifera), sweet birch (Betula lenta), yellow birch (B. alleghaniensis, synonym Betula lutea), silver birch (Betula pendula), downy birch (Betula pubescens).

[0091] Typically, alder (Alnus) is selected from black alder (Alnus glutinosa), red alder (Alnus rubra).

[0092] Typically, ash (Fraxinus) is selected from black ash (Fraxinus nigra), blue ash (Fraxinus quadrangulata), common ash (Fraxinus excelsior), green ash (Fraxinus pennsylvanica lanceolata), white ash (Fraxinus americana).

[0093] Typically, aspen (Populus) is selected from American aspen (Populus tremuloides), bigtooth aspen (Populus grandidentata), European aspen (Populus tremula).

[0094] Typically, blackwood is also selected from Australian blackwood, Tasmanian blackwood (Acacia melanoxylon), African blackwood or mpingo (Dalbergia melanoxylon).

[0095] Typically, buckeye (Aesculus) is selected from horse chestnut (Aesculus hippocastanum), yellow buckeye (Aesculus flava).

[0096] Typically, sakura (Prunus) is selected from black cherry (Prunus serotina), red cherry (Prunus pennsylvanica), sweet cherry (Prunus avium Prunus serotina), and Brazilian cherry.

[0097] Typically, chestnut (Castanea dentata) is selected from Cape chestnut (Calodendrum capense).

[0098] Typically, ebony (Diospyros) is selected from Andaman marblewood (India) (Diospyros kurzii), ebony marble (Mauritius, East Africa) (Diospyros melanida), Gabon ebony, black ebony, African ebony (Diospyros crassiflora).

[0099] Typically, elm is selected from American elm (Ulmus americana), English elm (Ulmus procera), rock elm (Ulmus thomasii), slippery elm (Ulmus rubra), and wych elm (Ulmus glabra).

[0100] Typically, eucalyptus (Eucalyptus) is selected from Eucalyptus, karri (Western Australia) (Eucalyptus diversicolor), mahogany eucalyptus (New South Wales) (Eucalyptus), ironbark (Eucalyptus sideroxylon), jarrah or Western Australian eucalyptus (Eucalyptus marginata), Tasmanian oak or mountain ash (Eucalyptus regnans, Eucalyptus obliqua, Eucalyptus delegatensis), river red gum, blue gum (Eucalyptus saligna).

[0101] Typically, gum is selected from black gum (Nyssa sylvatica), blue gum (Eucalyptus globulus), red gum or sweet gum (Liquidambar styraciflua), tupelo gum (Nyssa aquatica).

[0102] Typically, hickory (Carya) is selected from mockernut hickory (Carya alba), pignut hickory (Carya glabra), shagbark hickory (Carya ovata), shellbark hickory (Carya laciniosa).

[0103] Hardwoods are particularly advantageous methodologically, firstly due to the presence of a high content of cellulose and lignin, and secondly due to the presence of more valuable heavy terpene compounds. Unfortunately, due to the low presence of the target non-oxygenated monoterpenes, a content of hardwood logs exceeding 30% is not particularly advantageous for the extraction of the target monoterpene mix to be further purified by an economically viable method.

[0104] In fact, these species of softwoods are particularly advantageous due to their typical turpentine oil chemical composition showing a high presence of alpha-pinene and / or beta-pinene and / or dipentene.

[0105] According to the method of the invention, the wood logs are cut into strands or chips, chipped, or shredded. Typically, the size of the wood strands or wood chips has been demonstrated to improve the extraction method. It has been shown to be particularly advantageous to cut into chips or shred the wood having a length in the range of 50 - 200 mm, preferably 70 - 180 mm, particularly preferably 90 - 150 mm.

[0106] The term "wood log" refers to pieces of heartwood and / or bark [i.e., the outermost layer of the woody stem and roots].

[0107] According to an optional embodiment, the wood strands or wood chips are pretreated with hot water at a temperature of 50°C - 100°C, and the pretreatment extract is collected or optionally recycled for one or more batches of the wood strands or wood chips before collection. The pretreatment has been shown to increase the extraction of monoterpenes. Typically, such a pretreatment can be applied to part or all of the wood batch. Advantageously, the pretreatment is applied for 10 - 60 minutes, preferably 15 - 45 minutes, particularly preferably 20 - 30 minutes.

[0108] According to another optional embodiment of the invention, the wood strands or wood chips are not washed before the first steam treatment.

[0109] According to the present invention, the first steam treatment is preferably carried out at 50°C to 120°C, particularly 50°C to 100°C. This temperature range is particularly advantageous in that the vaporization temperature of the target monoterpene is 150°C to 170°C.

[0110] Typically, the first steam treatment is applied to the wood strands or wood chips such that the steam passes over the wood strands or wood chips to obtain a temperature of 60°C to 110°C, preferably 70°C to 100°C, particularly typically about 80°C to 90°C.

[0111] Typically, the first steam treatment is 1×10 5 Pa to 4×10 5 Pa, particularly 1×10 5 Pa to 3×10 5 Pa, more particularly 1.5×10 5 Pa to 3×10 5 Pa, preferably about 2×10 5 Pa, and is applied to the wood strands or wood chips such that the steam passes over the wood strands or wood chips.

[0112] Advantageously, the combination of pressure and temperature during the first steam treatment initiates the softening of lignin, resulting in the softening of the wood strands or wood chips, and then enables the release of low molecular weight volatile compounds such as non-oxygenated monoterpenes.

[0113] Typically, the first steam treatment of the wood strands or wood chips is carried out over a period of 10 to 60 minutes, preferably 15 to 45 minutes, particularly 20 minutes.

[0114] The amount of steam applied during the first steam treatment is 0.05 to 0.2 kg steam / kg wood strands or wood chips.

[0115] Preferably, the steam is fresh steam and / or recycled steam from a downstream step.

[0116] According to the present invention, the first compression step of the wood strands or wood chips is preferably 8×10 5 Pa to 14×10 5 Pa, preferably 10×10 5 Pa to 13×10 5 Pa is applied.

[0117] Advantageously, during the first compression step, water is introduced at 12 to 38°C, typically 15 to 35°C, 18 to 30°C, preferably at approximately room temperature. Introducing water at such temperatures has proven particularly interesting as it prevents the wood from overheating. Water is also used to carry out foreign matter and available liquids in the system, typically terpene compounds and aqueous substances. The first compression extract collected during this step is the first stream that removes substantial terpene compounds.

[0118] According to any embodiment of the present invention, the wood strands or wood chips are not purified after the first steam treatment and before the first compression step.

[0119] According to any one of the above embodiments of the present invention, the method includes a second steam treatment applied to the pre-softened wood strands or wood chips such that the steam passes over the pre-softened wood strands or wood chips at a temperature of 150°C to 220°C.

[0120] According to any one of the above embodiments of the present invention, during the second steam treatment, the steam is applied to the pre-softened wood strands or wood chips at a pressure of 7×10 5 Pa to 17×10 5 Pa.

[0121] In order to limit the thermal decomposition of the wood that results in the formation of wood pyrolysis products, it is particularly advantageous to maintain the temperature below 220°C.

[0122] Typically, this combination of pressure and temperature continues to soften the wood strands or wood chips, allowing for an increase in the release of volatile compounds. The second steam treatment is preferably carried out at a temperature of 155°C to 210°C, more specifically 160°C to 190°C. Advantageously, the second steam treatment is preferably carried out at a pressure of 8×10 5 Pa to 15×10 5 Pa, particularly preferably 9×10 5 Pa to 14×10 5 Pa. Any combination within the above temperature and pressure ranges is conceivable.

[0123] The steam can be either fresh steam and / or recycled steam from any downstream step.

[0124] Advantageously, the second steam treatment of the pre-softened wood strands or wood chips having the above temperature and pressure ranges is carried out over a period of 1 to 30 minutes, preferably 5 to 10 minutes. The amount of steam is 0.05 to 0.2 kg steam / kg wood strands or wood chips. The released vapors in which the monoterpenes are present can then be recycled to the first steam treatment step and / or sent directly to a condenser (see below).

[0125] Advantageously, the steam released from the steam treatment step is recycled to the first steam treatment. This recycling is particularly advantageous for energy savings but also for further concentrating the terpene compounds in the steam.

[0126] According to the above embodiment of the present invention, the second compression step is applied at a pressure of 7×10 5 Pa to 15×10 5 Pa after the second steam treatment to obtain softened wood strands or wood chips, and a second compression extract is collected.

[0127] Advantageously, the second compression step is 9×10 5 Pa to 14×10 5Pa, and more preferably 10×10 5 Pa to 13×10 5 Pa is applied at a pressure of.

[0128] According to any one of the above embodiments of the present invention, the second compression step is applied at a temperature of 130°C to 220°C after the second steam treatment to obtain softened wood strands or wood chips, and the second compression extract is collected at a temperature of particularly 140°C to 200°C, particularly 140°C to 180°C, and more particularly 150°C to 170°C.

[0129] According to any one of the above embodiments of the present invention, subsequent steam treatment and compression steps are applied to the softened wood strands or wood chips to obtain deeply softened wood strands or wood chips, and subsequent compression extracts are collected. Advantageously, the steam released from one or more subsequent steam treatments is recycled to the first steam treatment and / or the second steam treatment.

[0130] According to any one of the above embodiments of the present invention, the method includes a refining step applied by passing steam over pre-softened wood strands or wood chips, or softened wood strands or wood chips, or deeply softened wood strands or wood chips at a temperature of 150°C to 220°C, typically at a pressure of 7×10 5 Pa to 15×10 5 Pa, preferably for less than 3 minutes, typically for less than 2 minutes.

[0131] The term "refining" refers to a mechanical process of treating lignocellulose-containing solids in order to beat, strike, cut, and / or fibrillate the fibers in the lignocellulose-containing solids. Refining refers to both the rough separation (defibration) of the fibers and the processing of the fibers (refining in the true sense). Thus, refining can be used to reduce the size of lignocellulose-containing solids and provide materials including bundles of cellulose-based fibers, separate cellulose-based fibers, fragments of cellulose-based fibers, and combinations thereof. Such mechanical processing is preferably carried out at a temperature of 140 °C to 210 °C, more specifically 160 °C to 190 °C, at a pressure of 6 × 10 5 Pa to 14 × 10 5 Pa, particularly preferably 9 × 10 5 Pa to 13 × 10 5 Pa. Steam is typically applied for less than 2 minutes, preferably less than 1 minute. The duration of the refining step should be less than 3 minutes in order to limit thermal wood decomposition as described above.

[0132] Advantageously, the steam released from the refining step is recycled to the first steam treatment and / or the second steam treatment.

[0133] According to any one of the above embodiments of the present invention, the evaporation step is applied to a mixture of the first compressed extract and / or the second compressed extract, and / or one or more subsequent compressed extracts by evaporating more than 15%, preferably 20% to 80%, even more preferably 22% to 40%, typically 25% to 35% of the mixture of the compressed extracts.

[0134] Advantageously, the first compressed extract or the mixture of compressed extracts is centrifuged before the evaporation step. This centrifugation is particularly advantageous for removing solid materials released by the wood strands or wood chips.

[0135] Typically, the pressure applied during the evaporation step is 0.2 × 10 5 Pa to 1 × 10 5Pa, preferably 0.5×10 5 Pa to 1×10 5 Pa (i.e., under medium vacuum) or atmospheric pressure. The temperature of the mixture is typically maintained above the boiling point of water due to the presence of the dissolved compound. The water boiling temperature is 0.2×10 5 Pa to 1×10 5 Pa evaporation pressure, 65°C to 105°C temperature; 0.5×10 5 to 1×10 5 Pa evaporation pressure, the temperature corresponding to 85°C to 105°C temperature respectively.

[0136] Preferably, the terpene compound-enriched steam optionally combined with the steam collected from the first steam treatment and / or the second steam treatment and / or the refining step is condensed to obtain a condensed phase.

[0137] The condensation step is carried out by any type of condenser capable of completely condensing the vapor stream and resulting in a two-phase liquid.

[0138] Advantageously, the off-gas steam from the first steam treatment and / or the second steam treatment step and / or the refining step is independently processed by the control system of the condenser to obtain a subsequent condensed phase.

[0139] The condensed phase and / or the subsequent condensed phase are further processed by a separation phase by density difference (gravitational decantation) or assisted gravity (centrifugation) to obtain the liquid wood extract of the present invention.

[0140] This process is particularly advantageous in that it makes it possible to remove terpenes from the aqueous stream that is usually sent to a wastewater treatment unit, and as a result, enables a more efficient and environmentally friendly water treatment process.

[0141] According to any embodiment of the method of the present invention, the method of the present invention is carried out in the absence of an organic solvent, an additive, a synthetic or natural extractant and / or compressed air. Only water and steam are used during the method of the present invention.

[0142] The liquid wood extract of the present invention, and the liquid wood extract obtained by the method of the present invention, can be converted into cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical raw material components. Those skilled in the art are fully aware of the method of converting the liquid wood extract of the present invention into cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical raw material components. In particular, the liquid wood extract of the present invention can be converted into the raw material components without a desulfurization step.

[0143] This method is particularly advantageous in that it enables the preparation of a liquid wood extract containing less than 0.1% (by weight) of at least one pyrolysis compound of lignocellulosic biomass and having a sulfur content of less than 1000 ppm. The method of the present invention makes it possible to avoid a purification step. In other words, the liquid wood extract can be used as it is.

[0144] A third object of the present invention is a method for obtaining cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical raw material components, comprising the step of obtaining a liquid wood extract according to the method of the present invention.

[0145] A fourth object of the present invention is to use the liquid wood extract of the present invention as an active compound in cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical compositions, or to obtain an active compound in cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial agents, pesticides and / or chemical compositions.

[0146] Another object of the present invention is a method for preparing cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial agents, pesticides and / or chemical compositions or articles, comprising adding an effective amount of the liquid wood extract of the present invention as an active compound to the composition or article.

[0147] Another object of the present invention is a method for obtaining cosmetics, makeup products, pharmaceuticals, dietary supplements, antibacterial pesticides and / or chemical compositions or articles, a) Obtaining a liquid wood extract according to the method of the present invention; b) Adding the liquid wood extract of step a) to a cosmetic, a toiletry, a pharmaceutical, a dietary supplement, an antibacterial pesticide and / or a chemical composition or article; The method includes the above steps.

[0148] According to a specific embodiment of the present invention, the liquid wood extract of step a) is directly added to a cosmetic, a toiletry, a pharmaceutical, a dietary supplement, an antibacterial pesticide and / or a chemical composition or article. In other words, the method of the present invention does not include a purification step between step a) and step b).

[0149] According to another specific embodiment of the present invention, the liquid wood extract of step a) is purified by a method known to those skilled in the art, such as distillation or rectification.

[0150] Another object of the present invention is a method for preparing an active compound for a cosmetic, a toiletry, a pharmaceutical, a dietary supplement, an antibacterial agent, a pesticide and / or a chemical substance, the method including one or more steps for converting the liquid wood extract of the present invention into the active compound.

[0151] Another object of the present invention is a method for preparing an active compound for a cosmetic, a toiletry, a pharmaceutical, a dietary supplement, an antibacterial agent, a pesticide and / or a chemical composition, a) Obtaining a liquid wood extract according to the method of the present invention; b) Converting the liquid wood extract of step a) into an active compound for a cosmetic, a toiletry, a pharmaceutical, a dietary supplement, an antibacterial pesticide and / or a chemical composition; The method includes the above steps.

[0152] According to any embodiment of the present invention, the liquid wood extract of step a) is directly converted into a cosmetic, a toiletry, a pharmaceutical, a dietary supplement, an antibacterial pesticide and / or a chemical composition or article. In other words, the method of the present invention does not include a purification step between step a) and step b).

[0153] In particular, the "active compound" is selected from the group consisting of fragrance raw material components, flavor raw material components, dietary supplement raw material components, malodor control raw material components, antibacterial raw material components, cosmetic raw material components, insect repellent or insect attractant raw material components, chemical raw material components and / or pesticide raw material components.

[0154] Therefore, in order to be regarded as an "active compound", the compound must have at least one property that makes the compound useful as a fragrance raw material component, a malodor control raw material component, a flavor raw material component, a cosmetic raw material component, a dietary supplement raw material component, an antibacterial raw material component, an insect repellent or insect attractant raw material component and / or a chemical raw material component.

[0155] The term "fragrance raw material component" is understood as a compound used as an active raw material component in a fragrance preparation or composition to impart a pleasant effect. In other words, a compound regarded as a fragrance raw material component must be recognized by those skilled in the art of cosmetics as not only having an odor, but also being able to impart or modify the odor of the composition to be positive or pleasant. The fragrance raw material component may impart additional benefits beyond modifying or imparting an odor, such as persistence, blooming, malodor control, antibacterial effect, antiviral effect, microbial stability or pest control. The term "flavor raw material component" is understood as something that can impart a taste to the palate of a taster. The term "malodor control raw material component" is understood as something that can reduce the perception of a malodor, i.e., an unpleasant or offensive odor to the human nose. The term "antibacterial raw material component" is understood as something that can kill microorganisms or reduce or prevent their growth and / or accumulation, and includes antibacterial, antibiotic, antifungal, antiviral and antiparasitic raw material components. The term "insect attractant or repellent" is understood as a compound having a positive or negative effect on insects. Examples of insect attractant or insect repellent raw material components can be found in reference works or other studies of a similar nature, such as A.M. El-Sayed, The Pherobase 2005, http: / / www.pherobase.net.

[0156] The term "chemical raw material component" is understood as a compound used as a raw material, as a building block for chemical synthesis, or as an active raw material component in a chemical process.

[0157] Typically, the adhesive, the liquid wood extract of the present invention, can be used as an active compound in chewing gum, ink, tires, bitumen compositions, or to obtain them.

[0158] By definition, "nutritional supplement raw material component" refers to a component of a food or other ingestible form that has been determined to be beneficial to the human body in the prevention or treatment of one or more diseases or the improvement of physiological performance. Essential nutrients can be considered nutritional supplements if they provide benefits beyond their essential role in the normal growth or maintenance of the human body.

[0159] Unless otherwise specified, percentages (%) are meant to indicate weight percentages (wt%) of the composition.

[0160] A typical manner for carrying out the method of the present invention is reported below in the examples.

Examples

[0161] The present invention will be described in more detail by the following examples.

[0162] Example 1 To exemplify the wood terpene extract of the above invention, three different types of wood terpene extracts were collected and compared together. These wood terpene extracts were obtained from the same softwood origin. The selected softwood origin, Pinus Pinaster, is the most common wood used in the woodworking industry in southern Europe. The first sample of the wood terpene extract was obtained by the kraft pulping process, which is hereinafter referred to as crude sulfate turpentine oil, CST. The second sample of the wood terpene extract was obtained by the tapping process, which is hereinafter referred to as gum turpentine oil, GT (both processes are well-known to those skilled in the art). The third wood terpene extract, hereinafter referred to as LST (low sulfur turpentine oil), was obtained by the method according to the present invention, i.e., by partially evaporating the liquid wood extract obtained from the woodworking industry, then completely condensing it, and finally separating it from water by simple decantation to obtain a terpene oil mixture called LST.

[0163] The three terpene extracts were analyzed by gas chromatography (GCFID) using an Agilent 8890 equipped with a polar column such as CPWAX 57CB (25m / 0.25mm / 0.20μm).

[0164] For the wood terpene extracts from the tapping process and the method of the present invention described above, the total sulfur content was obtained by fluorescence UV with a Sulfur Analyser Antek Multitek NT-HS (in accordance with ASTM D 5453). The total sulfur content of the wood extract terpenes from the kraft pulping process was obtained by fluorescence X with a Horiba SLFA 6800 (in accordance with ASTM D 4294).

[0165] The flash point was measured with an Eraflash device in accordance with ASTM D 3828.

[0166] The identification of terpenes was performed by using a mass spectrometer equipped with a non-polar column (such as DB5ms), and the quantification was performed by GCFID equipped with a polar column (such as ZBwax or CPWax 57CB). This orthogonal LRI procedure was used by comparing the experimental values with the theoretical values compared to the standard when available.

[0167] The results obtained are shown in Table 1 below.

[0168]

Table 1

[0169] The three extracts shown in Table 1 show very high concentrations of non-oxygenated monoterpenes, 85.9% in CST, 91.5% in LST, and 96.2% in GT. Alpha-pinene, beta-pinene, and diterpene are the three most present terpenes considering the same wood origin of these wood terpene extracts. Nevertheless, the relative proportion of alpha-pinene to the total non-oxygenated monoterpenes is similar in CST (70.0%) and LST (69.8%), and higher in GT (72.6%). Furthermore, the relative proportion of beta-pinene is similar in CST (19.0%) and GT (19.3%), but higher in LST (21.5%).

[0170] GT and LST show the highest concentrations in non-oxygenated monoterpenes. In fact, GT is the most interesting extract for recovering only non-oxygenated monoterpenes (96.2%) because of the low content of other chemicals (3.8%).

[0171] The main components of the "other chemical substances" listed in Table 1 are not only high-molecular-weight terpene compounds such as oxygenated monoterpenes, sesquiterpenes, and diterpenes, but also, when the extraction conditions are severe, some pyrolysis compounds of lignocellulosic biomass such as aromatic phenol compounds, for example, 4-propylphenol, 4-ethylguaiacol, and methyleugenol. The pyrolysis compounds of lignocellulosic biomass are found at higher concentrations in CST. When the three extracts were compared, GT showed a very low concentration of other chemical substances. Such low content does not allow for an economical route to separate and / or concentrate the more valuable terpene compounds of higher molecular weight for use as raw materials at the industrial level.

[0172] In contrast, CST shows a higher content of higher-molecular-weight terpene compounds. Nevertheless, in the CST extract, the compounds found in the "other chemical substances" are also abundant in the mixture of sulfur compounds. This high concentration of sulfur compounds is due to the use of sodium hydroxide and sodium sulfide, which produce sodium sulfide (Na2S) during the kraft pulping process. The sulfur compounds identified in CST are mainly methyl mercaptan and dimethyl sulfide, dimethyl disulfide, 1-(methylthio)ethanethiol, thiophene, formyl-methylthiophene, and propionylthiophene.

[0173] Furthermore, to reduce concerns about flash point and safety, the presence of such high concentrations (12400 ppm) of sulfur compounds in CST requires specific purification steps, namely, desulfurization steps; for example, distillation and chemical reactions, such as oxidation by peracetic acid (see Environmental technology and Innovation 18(21), 100628, 2020), hypochlorite (see Bioresources 16(4), 8098 - 8110, 2021), or treatment with modified activated carbon (CN104449395). All of these well-known methods significantly affect the overall cost of the resulting alpha-pinene, beta-pinene extracts, as well as the resulting caryophyllene, longifolene, and humulene extracts. Similar observations were made for the extraction and purification of terpene alcohols.

[0174] As a result, the use of CST to extract alpha-pinene and beta-pinene, terpene alcohols such as terpineol, or sesquiterpenes such as caryophyllene, longifolene, and humulene for potential use as raw materials for further chemical synthesis does not enable an economic route for industrial use.

[0175] LST exhibits a very favorable composition with respect to the recovery of non-oxygenated monoterpenes (close to 91.5%) and also with respect to other chemicals such as sesquiterpenes (8.5%). The latter represents more than twice the level found in GT.

[0176] During the method according to the present invention, no chemical substances are used, and very low concentrations of sulfur compounds less than 10 ppm were found. As a result, the LST flash point is higher than the CST and is similar to the GT, enabling safer operating conditions for manufacturing, storage, and transportation. Furthermore, these sulfur compounds can be easily removed within the normal turpentine oil refining process. As a result, the LST extract is rich in non-oxygenated monoterpenes and contains a significant amount of high molecular weight terpene compounds, and the purification of all these compounds is easily possible for their use as building blocks as such or in subsequent chemical syntheses.

[0177] Example 2 Additional research was conducted to better identify other chemical substances found in the GT and LST of Example 1, and the results obtained are shown in Table 2.

[0178] The identification of the compounds was carried out by using a mass spectrometer equipped with a non-polar column (such as DB5ms), and the quantification was carried out by GCFID equipped with a polar column (such as ZBwax or CPWax 57CB). This orthogonal LRI procedure was used by comparing the experimental values with the theoretical values compared to the standards when available.

[0179] Table 2 shows the compounds identified in the LST and GT extracts from the fraction above "other chemical substances".

[0180] [Table 2]

[0181] As shown in Table 2, the main high molecular weight terpene compounds between GT and LST are terpene alcohols and sesquiterpenes.

[0182] The main terpene alcohols are alpha-terpineol, fenchol, borneol and terpinene-4-ol. The sesquiterpenes are longifolene, caryophyllene, longipinene, longicyclene, humulene and alpha-muurolene.

[0183] It should be noted that, in contrast to the CST extract, no wood pyrolysis compounds were detected in the GT and LST. This confirms that the conditions provided under the method of the present invention reduce the degradation of lignocellulosic biomass and make the LST extract fully comparable to the GT to this extent.

[0184] The absence of such degradation compounds reduces the complexity of the upstream process before using the terpene extract as a raw material.

[0185] In comparison, LST contains more than 20% terpene alcohol than GT. Furthermore, the amount of alpha-terpineol (the most valuable terpene alcohol) is effectively 20% more in LST than in GT.

[0186] Similarly, high molecular weight terpene compounds are present in LST more than 200% more than in GT. Among these, longifolene and caryophyllene are the most interesting sesquiterpenes, but are effectively present in LRT more than 200% more than in GT.

[0187] As a result, the combination of a very significant concentration of non-oxygenated monoterpenes that is expected and a very significant concentration of high molecular weight terpene compounds, especially sesquiterpenes, that is not expected, enables the LST to have a unique and valuable chemical composition profile.

[0188] Thus, in contrast to CST and GT, the LST extract can be used as an environmentally friendly, chemical-free, easy-to-handle (neither flammable nor toxic), readily available (purified / enriched) source of building blocks / raw materials for the F&F industry with respect to non-oxygenated monoterpenes, especially alpha-pinene, beta-pinene and dipentene, oxygenated monoterpenes, more specifically terpene alcohols such as terpineol, and sesquiterpenes, typically caryophyllene, longifolene, humulene.

Claims

1. a) 50 to 95% (by weight) of at least one non-oxygenated monoterpene; b) 5 to 30% (by weight) of at least one terpene having a higher molecular weight than the non-oxygenated monoterpene; c) less than 0.1% (wt%) of at least one woody biomass pyrolysis compound; d) a sulfur content of less than 1000 ppm; Liquid wood extract, including

2. 2. The liquid wood extract of claim 1, wherein the at least one terpene having a higher molecular weight than the non-oxygenated monoterpene has a molecular weight greater than 140 g / mol and / or is selected from oxygenated monoterpenes, diterpenes, sesquiterpenes and mixtures thereof.

3. 2. The liquid wood extract of claim 1, wherein the at least one terpene having a higher molecular weight than the non-oxygenated monoterpene is at least one oxygenated monoterpene selected from monoterpene alcohols, monoterpene epoxides, and mixtures thereof, and / or at least one diterpene selected from bicyclic diterpenes, tricyclic diterpenes, and mixtures thereof.

4. 2. The liquid wood extract of claim 1, wherein the at least one terpene having a higher molecular weight than the non-oxygenated monoterpene is at least one sesquiterpene selected from acyclic sesquiterpenes, cyclic sesquiterpenes and mixtures thereof, preferably selected from farnesene, longifolene, longicyclen, longipinene, caryophyllene, humulene, muurolene, each in the form of any one of their stereoisomers or mixtures thereof.

5. 2. The liquid wood extract of claim 1, wherein the at least one non-oxygenated monoterpene is a bicyclic non-oxygenated monoterpene, a monocyclic non-oxygenated monoterpene, an acyclic non-oxygenated monoterpene, or a mixture thereof.

6. the at least one non-oxygenated monoterpene at least one bicyclic non-oxygenated monoterpene selected from α-pinene, β-pinene, camphene, delta-3-carene, bornylene, sabinene, thujene, and carene, each in the form of any one of their stereoisomers or a mixture thereof; and / or at least one acyclic non-oxygenated monoterpene selected from myrcene, ocimene, allo-ocimene, citronellene, each in the form of any one of their stereoisomers or a mixture thereof; and / or at least one monocyclic non-oxygenated monoterpene selected from limonene, dipentene, isolimonene, p-menthane, 1-p-menthene, 3-p-menthene, α-terpinene, γ-terpinene, terpinolene, α-phellandrene, β-phellandrene, and p-cymene, each in the form of any one of their stereoisomers or a mixture thereof; 2. The liquid wood extract of claim 1.

7. The at least one woody biomass pyrolysis compound is one of the following: at least one cellulose-derived degradation product selected from hydroxymethylfurfural, levoglucosan, cellobiose, anhydroglucose derivatives, acetaldehyde, methanol, glyoxal, acrolein, each in the form of any one of their stereoisomers or a mixture thereof; and / or at least one hemicellulose-derived degradation product selected from furfuraldehyde, furan or a furan derivative, such as furfuryl alcohol; and / or at least one lignin-derived degradation product selected from phenol or phenol derivatives, such as cresol, catechol, eugenol, methyleugenol, guaiacol, 4-propylphenol, 4-ethylguaiacol, syringol, p-hydroxyphenol, hydroxymethoxytoluene, hydroxymethoxyethylbenzene, hydroxymethoxyvinylbenzene, hydroxymethoxypropylbenzene, dimethoxyphenol, hydroxydimethoxytoluene, hydroxydimethoxyethylbenzene, hydroxydimethoxypropylbenzene, pyrocatechol, benzofuran, dibenzofuran, vanillin, each in the form of any one of their stereoisomers or a mixture thereof; and / or It is a mixture of them, 2. The liquid wood extract of claim 1.

8. less than 0.05% (by weight) of at least one woody biomass pyrolysis compound, and / or a sulfur content of less than 200 ppm, and / or 5-20% (by weight) of at least one terpene with a higher molecular weight than the non-oxygenated monoterpenes 2. The liquid wood extract of claim 1, comprising:

9. 3. The liquid wood extract according to claim 2, wherein the at least one oxygenated monoterpene is at least one monocyclic monoterpene alcohol, preferably terpineol, estragole, anethole, borneol, each in the form of any one of their stereoisomers or a mixture thereof.

10. 1. A method for producing a liquid wood extract, comprising: a. providing a wood log mix comprising hardwood and softwood, the wood log mix comprising greater than 50% softwood, typically greater than 70% softwood; b. cutting or chipping or shredding the wood log mix into wood strands or wood chips; c. Temperature of 50°C to 120°C and 0.1 x 10 ５ Pa ~ 4 x 10 ５ applying a first steam treatment to the wood strands or wood chips such that steam is passed over the wood strands or wood chips at a pressure of 100 Pa; d. 7 x 10 ５ Pa ~ 15 x 10 ５ applying a first compression step to said wood strands or wood chips at a pressure of 100 Pa and adding water to said wood strands or wood chips at a temperature of 10°C to 40°C to obtain pre-softened wood strands or wood chips, and collecting a first compression extract; e. subjecting said first pressed extract to an evaporation step by evaporating more than 15% of said first pressed extract to produce steam enriched in terpene compounds; f. condensing the terpene compound-enriched steam, optionally in combination with steam collected from the first steaming process, to obtain a condensed phase; g. Applying a separation phase to the condensed phase, preferably by gravimetric decantation and / or centrifugation, to obtain a liquid wood extract; A method comprising:

11. The steam is heated to a temperature between 150°C and 220°C, ５ Pa ~ 17 x 10 ５ a second steam treatment applied to the pre-softened wood strands or wood chips so as to pass over the pre-softened wood strands or wood chips at a pressure of 100 Pa; After the second steam treatment, ５ Pa ~ 15 x 10 ５ a second compression step, in which a pressure of 1000 Pa is applied to obtain softened wood strands or wood chips and to collect a second compressed extract; The method of claim 10, comprising:

12. Temperature: 150°C to 220°C, 7 x 10 ５ Pa ~ 15 x 10 ５ 11. The method of claim 10, comprising a scouring step applied by passing steam over the pre-softened wood strands or wood chips or over the softened wood strands or chips at a pressure of 100 Pa.

13. 12. The method of claim 11, wherein the condensed phase also comprises steam collected from the second steaming and / or the refining step.

14. 14. A method for obtaining a cosmetic, cosmetic product, pharmaceutical product, dietary supplement, antimicrobial pesticide and / or chemical raw material ingredient, comprising the step of obtaining a liquid wood extract according to the method of any one of claims 10 to 13.

15. 10. Use of the liquid wood extract according to any one of claims 1 to 9 as an active compound in or for obtaining an active compound for a cosmetic, cosmetic, pharmaceutical, nutraceutical, antibacterial, pesticide or chemical composition.