Recovery of new low-sulfur terpene mixtures from wood processing

Abstract

The present invention relates to an eco-friendly liquid wood extract comprising terpene compounds. The invention also relates to fragrances, cosmetics, pharmaceuticals, nutraceuticals, antibacterial agents, agrochemicals or chemical compositions obtained by using said eco-friendly liquid wood extract. A process for preparing an eco-friendly liquid wood extract is also one of the objects of the invention.

Description

Technical Field

[0001] The present invention relates to the fields of perfumery, flavors and industrial ingredients. More specifically, the present invention relates to valuable new natural solvent-free terpene intermediate mixtures for producing perfumery, flavoring and / or industrial ingredients. Background Art

[0002] Wood is an important alternative for the production of chemical building blocks. It is a renewable resource and can be used as a raw material for many products in the chemical industry. Unfortunately, for the vast majority of woodworking industries (pulping, fiberboard including medium-density and high-density fiberboard (MDF and HDF), plywood, particleboard, oriented strand board (OSB), lumber, laminated particleboard, wood-based biofuels such as wood pellets, bioethanol…) most of the residues are collected in the waste and are not utilized. The need to reduce the ecological impact of wood processing creates new opportunities for the wood industry to develop a cost-effective and eco-friendly waste reduction method to maximize the yield of valuable compounds extracted from wood.

[0003] Examples of valuable wood compounds are lignin, cellulose, hemicellulose, and also terpenes. In general, monoterpenes such as α-pinene, β-pinene and dipentene represent very desirable backbones that can be used alone or as key intermediates for the preparation of more complex compounds in different fields (e.g. fragrances, cosmetics, pharmaceuticals and / or agrochemistry). Examples of components obtained from α- and β-pinene and dipentene are synthetic odorants that impart an odor similar to sandalwood oil (e.g. or ), or woody ingredients, which are essential for fragrance and perfume formulations (e.g. ) or industrial compounds such as polyterpene resins (e.g. A, M, L and S grades) impart cedar and / or amber notes. More and more attention is focused on compounds with larger molecular weights, such as terpene alcohols for synthetic fragrances. Typically, cis-pinenol is a terpene alcohol that can be pyrolyzed to produce industrial quantities of linalool. Sesquiterpenes are valuable high molecular weight compounds that can be used as building blocks for biopolymers or as active ingredients in pharmaceutical compositions. Examples of valuable sesquiterpenes are α-cedrene, which is widely used in fragrance blending and in the synthesis of more valuable aromatic substances, such as acetylcedrene and cedrone; β-caryophyllene, which is used in soaps and detergents or as a raw material for the synthesis of other fragrances. A final example is longifolene, which is widely used in the fragrance industry, and is also used as a raw material for synthetic fragrances or in organic synthesis to prepare dilongifole borane and isolongifolene, and finally as a flotation agent for lead-zinc ores.

[0004] Terpenes can be extracted by the tapping industry, which involves first harvesting live trees, collecting the oleoresin, and finally distilling the resulting resin to separate turpentine (GT) from the gum rosin. GT is typically a highly concentrated, sulfur-free mixture of non-oxygenated monoterpenes, but with very low levels of high molecular weight terpene compounds (such as terpene alcohols and sesquiterpenes).

[0005] Although technological advances have provided higher recovery rates, collecting oleoresins remains too labor-intensive, leading to a decline in such activities worldwide. Therefore, there is a need to find new sustainable sources of terpenes.

[0006] Wood extracts, especially terpene compounds, can be found in both heartwood and bark. Compared with wood, bark has a considerably higher extractive content, but the values ​​reported in the literature can vary widely even for the same species and are highly dependent on the extraction method.

[0007] In wood, whether softwood or hardwood, most extractables are located in the heartwood. Both bark and wood contain carbohydrates and lignin. The composition and content of these carbohydrates and lignin have a great influence on the availability of extracts, the severity of the extraction process and the extraction yield, the composition of the obtained extracts, especially the richness of valuable compounds (terpenes and other terpene compounds), and the difficulty of the preparation or purification steps required before use as a precursor or ingredient.

[0008] Generally speaking, softwoods have a higher cellulose content (40-45%), higher lignin (26-34%), and lower pentosan (7-14%) content compared to hardwoods (cellulose 38-49%, lignin 23-30%, and pentosans 19-26%).

[0009] In addition, lignin does not have a single repeating unit like cellulose, but is composed of a complex arrangement of substituted phenolic units, resulting in a cross-linked structure that is more resistant to the high temperatures and pressures during pulping. Softwood lignin is slightly different from hardwood lignin, with a methoxy content of 15-16%, while hardwood lignin has a methoxy content of 21%. However, the study found that an increase in the methoxy content in lignin was associated with a decrease in the softening temperature of wet wood during pulping.

[0010] In the kraft pulping industry, terpene compounds are extracted from wood pulp in the form of a stream and named crude sulfate turpentine (CST). CST is a complex mixture of monoterpenes, oxygenated monoterpenes, sesquiterpenes, high molecular weight terpene compounds, aromatic phenolic compounds and high concentrations of sulfur compounds (usually ranging from 8000 to 40000 ppm). The sulfur compounds are produced by using sodium soda and sodium sulfide solutions (the so-called white liquor) and sawdust under strict conditions, such as temperatures of up to 180 °C and pressures of up to 10×10 5 Pa, with a duration of 60 to 240 minutes. Typical sulfur compounds are methyl mercaptan, dimethyl sulfide, dimethyl disulfide and thiophene. These compounds are highly flammable and toxic, and they pose a dangerous risk to the production, storage and transportation of CST.

[0011] The concentration of high molecular weight terpene compounds in CST is quite high. This is due to a combination of two interdependent factors: the wood species used as raw material and the stringent kraft pulping operating conditions. The higher the wood lignin concentration, the more stringent the pulping operating conditions. Kraft pulping operating conditions involve partial and / or complete evaporation of high molecular weight terpene compounds, which are then also recovered together with non-oxygenated monoterpenes to produce CST. Typical valuable high molecular weight terpene compounds are terpene alcohols, such as in particular α-terpineol or estragole, and sesquiterpenes, such as caryophyllene or longifolene.

[0012] The stringent conditions of kraft pulping are primarily aimed at removing lignin from carbohydrates, resulting in high concentrations of thermal degradation compounds of woody biomass. Typically, cellulose-derived decomposition products, hemicellulose-derived decomposition products, and lignin-derived decomposition products are produced, including aromatic phenolic compounds such as guaiacol, syringol, and p-hydroxyphenol. However, these compounds, especially aromatic phenolic compounds, can only be partially removed from CST and increase the complexity of its composition.

[0013] Enrichment of valuable terpene compounds and removal of all sulfur-containing derivatives are prerequisites for the manufacture of any ingredient for the F&F industry (F&F). Therefore, the high sulfur content coupled with the complexity of the CST composition (especially the aromatic phenolic chemicals produced by lignin degradation) does seriously affect the safety, productivity and cost of previous purification processes used to separate valuable mono- or sesquiterpene derivatives from CST for use in the F&F industry. This industrial separation process is even more complex and economically unviable for higher molecular weight terpene compounds such as caryophyllene, longifolene and α-terpineol.

[0014] Therefore, both the wood species and the wood pretreatment conditions used by the wood industry or forest biorefineries have a strong influence on the quality of the final product, i.e. the main product (paper, fiberboard, particleboard, etc.), but also on other potential extractables such as monoterpenes or other high molecular weight terpene derivatives such as sesquiterpenes.

[0015] The extensive use of chemicals, water and steam not only produces large amounts of wastewater contaminated with chemicals (derived from the wood, such as volatile organic compounds or synthetic chemicals), but also contaminates any valuable compounds extracted from the wood.

[0016] As people's awareness of climate and environmental issues continues to grow and consumer habits change, the wood or forestry industry has new opportunities to develop cost-effective, functional green solutions by reducing the ecological impact of wood processing while providing more environmentally friendly products to meet consumer needs. In general, the main challenges facing the wood industry are to reduce the use of chemicals during wood processing and reduce residues, especially the amount of terpene compounds released into the environment or contained in the final product.

[0017] Considering the high customer demand for renewable or natural compounds and the current status of industrial turpentine production, there is a need for a high-quality solvent-free, sulfur-free terpene-rich blend that can be used as a feedstock for the development of bio-sourced ingredients without extensive pretreatment, especially in the flavor and fragrance industry. Therefore, there is an increasing need to develop eco-friendly, cost-effective and solvent-free processes to recover such terpene-rich blends.

[0018] The object of the present invention is to provide a high-quality, solvent-free, sulfur-free terpene-rich blend and an eco-friendly and cost-effective wood pretreatment process suitable for various wood-based industries, such as the pulping industry, the MDF and HDF industry or the biofuel industry. Summary of the invention

[0019] In a first aspect, the present invention relates to a liquid wood extract comprising:

[0020] a) 50 to 95% (wt%) of at least one non-oxygenated monoterpene,

[0021] b) 5% to 30% (wt%) of at least one terpene having a higher molecular weight than the non-oxygenated monoterpene,

[0022] c) less than 0.1% (wt%) of at least one thermally degradable compound of woody biomass,

[0023] d) Sulfur content less than 1000 ppm.

[0024] In a second aspect, the present invention relates to a method for producing a liquid wood extract, comprising:

[0025] a. Provide a mixture of hardwood and softwood logs, of which the softwood content exceeds 50%, usually exceeds 70%,

[0026] b. Cutting, chipping or shredding wood logs into strips or pieces,

[0027] c. The wood strips or wood chips are first steam treated, with steam at a temperature of 50°C to 120°C at 0.1×10 5 Pa to 4×10 5 Pa pressure through the wood strips or wood chips,

[0028] d. In 7×10 5 Pa to 15×10 5 subjecting the wood strips or chips to a first compression step at a pressure of 1.3 Pa and adding water to the wood strips or chips at a temperature of 10 to 40° C. to obtain pre-softened wood strips or chips and collecting a first compressed extract,

[0029] e. applying an evaporation step to the first compressed extract, evaporating more than 15% of the first compressed extract to produce a vapor rich in terpene compounds,

[0030] f. condensing the steam rich in terpene compounds, optionally combining it with the steam collected from the first steam treatment process to obtain a condensed phase,

[0031] g. applying the separating phase to the coacervate phase by treating the coacervate phase, preferably by gravimetric decantation and / or centrifugation, to obtain a liquid wood extract.

[0032] Another object of the present invention is a method for obtaining perfumes, cosmetics, pharmaceuticals, nutraceuticals, antimicrobials, agrochemicals and / or chemical ingredients comprising the step of obtaining a liquid wood extract according to the method of the present invention.

[0033] Another object of the present invention is the use of the liquid wood extract according to the invention as active compound in a perfume, cosmetic, pharmaceutical, nutraceutical, biocide, agrochemical and / or chemical composition or for obtaining an active compound of a perfume, cosmetic, pharmaceutical, nutraceutical, biocide, agrochemical and / or chemical composition. DETAILED DESCRIPTION

[0034] A first object of the present invention is a liquid wood extract comprising:

[0035] a) 50 to 95% (wt%) of at least one non-oxygenated monoterpene, preferably 70 to 94%, even more preferably 80 to 93% (wt%) or 80 to 92% (wt%),

[0036] b) 5 to 30% by weight of at least one terpene having a higher molecular weight than the non-oxygenated monoterpene, preferably 5 to 20% by weight, preferably 6 to 20% by weight, even more preferably 7 to 15% by weight,

[0037] c) less than 0.1% by weight of at least one woody biomass thermal degradation compound, preferably less than 0.05% by weight, more preferably less than 0.001% by weight,

[0038] 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.

[0039] The expression "liquid wood extractives" refers to liquid wood-based extractives, i.e. liquid compositions / mixtures extracted from wood or obtained from wood processing or by the wood processing industry. In particular, the liquid compositions / mixtures are waste streams from the wood industry or from the wood-based biofuel industry for the production of fiberboard, plywood, particleboard, oriented strand board, lumber, laminated particleboard, in particular waste from the fiberboard industry. Liquid wood extractives can be recovered from liquid wastes generated during the conversion of wood materials.

[0040] For the sake of 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 (e.g., 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 terpenes is generally divisible by five (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), dipterpenes (C25), triterpenes (C30), tetraterpenes (C40), and polyterpenes with longer chains of isoprene units. Terpenes may be linear or cyclic.

[0041] Terpenes or terpene compounds include oxygenated terpenes and non-oxygenated terpenes. Oxygenated terpenes have a terpene skeleton and oxygen-containing functional groups. Non-oxygenated terpenes have a hydrocarbon skeleton without oxygen-containing functional groups. Advantageously, the molecular weight of non-oxygenated monoterpenes is 132 to 140 g / mol. Typically, examples of oxygen-containing functional groups are aldehydes, phenols, carboxylic acids, ketones, epoxides, acids, ethers, hydroxyls and esters.

[0042] The molecular weight of the terpenes with a higher molecular weight than the non-oxygenated monoterpenes is greater than 140 g / mol, preferably greater than 148 g / mol, more preferably from 148 to 600 g / mol, typically from 200 to 400 g / mol. Non-limiting examples of "terpenes with a higher molecular weight than the non-oxygenated monoterpenes" are oxygenated monoterpenes, diterpenes, sesquiterpenes, oxygenated sesquiterpenes, diterpenes, triterpenes, tetraterpenes, polyterpenes, preferably selected from oxygenated monoterpenes, diterpenes and sesquiterpenes.

[0043] The term "monoterpene" refers to a compound consisting of two isoprene units. The term "monoterpene" includes compounds containing only unmodified isoprene units, as well as compounds containing one or more modifications as described above. When a monoterpene includes such modifications, it may also be referred to as a "monoterpenoid compound". Monoterpenes include oxygenated monoterpenes having a monoterpene skeleton and oxygen-containing functional groups and non-oxygenated monoterpenes having a monoterpene skeleton but without oxygen functional groups.

[0044] Preferably, the monoterpene is acyclic (especially linear), monocyclic or bicyclic.

[0045] According to the present invention, the at least one non-oxygenated monoterpene is selected from the group consisting of bicyclic non-oxygenated monoterpene, monocyclic non-oxygenated monoterpene, acyclic non-oxygenated monoterpene and mixtures thereof.

[0046] Non-limiting examples of oxygen-free monoterpenes are myrcene, ocimene, alloocimene and citronellene.

[0047] Non-limiting examples of 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-phellandrene, β-phellandrene, p-cymene, each in the form of any one of their stereoisomers or a mixture thereof.

[0048] For the sake of clarity, the expression "each in the form of any one of its stereoisomers or a mixture thereof" or similar expressions refers to the normal meaning understood by a person skilled in the art, i.e., the compounds listed in the present invention, such as monoterpenes, terpenes or other compounds, typically limonene or α-pinene, may have one or more stereocenters and are therefore pure enantiomers or diastereomers. In other words, the compounds listed in the present invention may have one or more stereocenters, and each of the stereocenters may have two different stereochemistries (e.g., R or S). The compounds listed in the present invention may even be in the form of pure enantiomers, or in the form of a mixture of multiple enantiomers or diastereomers. The compounds listed in the present invention may be in racemic form or non-racemic (scalemic) form. Therefore, the compounds listed in the present invention may be in the form of a single stereoisomer, or in the form of a material composition comprising or consisting of various stereoisomers.

[0049] Non-limiting examples of non-oxygenated monoterpenes are α-pinene, β-pinene, (±)-camphene, δ-3-carene, bornene, sabinene, thujene, carane, each in the form of any one of their stereoisomers or a mixture thereof.

[0050] According to the present invention, the preferred non-oxygenated monoterpenes are selected from α-pinene, β-pinene, dipentene and mixtures thereof, more preferably α-pinene, β-pinene, each in the form of any one of their stereoisomers or mixtures thereof.

[0051] 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.

[0052] 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 a mixture thereof.

[0053] Non-limiting examples of acyclic monoterpene esters are linalyl acetate and any of their stereoisomers or mixtures thereof.

[0054] Non-limiting examples of monocyclic monoterpene aldehydes are perillaldehyde, phelaldehyde, 1,2-dihydrophelaldehyde, cuminaldehyde, each in the form of any one of their stereoisomers or a mixture thereof.

[0055] Non-limiting examples of monocyclic monoterpene alcohols are menthol, neomenthol, (+)-isomenthol, isopulegol, α-terpineol, β-terpineol, γ-terpineol, (-)-terpinen-4-ol, thymol, carvacrol, carveol, dihydrocarveol, piperitenol, isopiperitenol, perillyl alcohol, carvementhol and any one of their stereoisomers or in the form of a mixture thereof.

[0056] Non-limiting examples of monocyclic monoterpene ethers are thymol methyl ether, carvacrol methyl ether and any one of their stereoisomers or mixtures thereof.

[0057] Non-limiting examples of monocyclic monoterpene ketones, more particularly α,β-unsaturated ketones, are carvone, carvotanacetone, α-ionone (α-violet ketone), β-ionone and γ-ionone, piperitone, pulegone, piperitenone, isopiperitone, each in the form of any one of their stereoisomers or a mixture thereof.

[0058] Non-limiting examples of monocyclic monoterpene saturated ketones are dihydrocarvone, menthone, isomenthone, each in the form of any one of their stereoisomers or mixtures thereof.

[0059] 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.

[0060] Non-limiting examples of bicyclic monoterpene aldehydes are myrtenal, myrtal, each in the form of any one of their stereoisomers or mixtures thereof.

[0061] Non-limiting examples of bicyclic monoterpene alcohols are myrtenol, myrtanol, pinaceous carveol, pinane-2,3-diol, isopintopineol (3-pinenol), borneol, isoborneol, fenchol, verbenol, nopol, each in the form of any one of their stereoisomers or a mixture thereof.

[0062] A non-limiting example of a bicyclic monoterpene ester is fenchyl acetate, each in the form of any one of its stereoisomers or a mixture thereof.

[0063] A non-limiting example of a bicyclic monoterpene ether is nopol benzyl ether, each in the form of any one of its stereoisomers or a mixture thereof.

[0064] Non-limiting examples of bicyclic monoterpene ketones, more particularly unsaturated ketones, are verbenone, carvone, each in the form of any one of their stereoisomers or mixtures thereof.

[0065] Non-limiting examples of bicyclic monoterpene saturated ketones are camphor, fenchone, α-thujone, β-thujone, 3-pinene (pinene and isopinone), 2-hydroxy-3-pinene, each in the form of any one of their stereoisomers or mixtures thereof.

[0066] Advantageously, the terpenes having a higher molecular weight than non-oxygenated monoterpenes are oxygenated monoterpenes, diterpenes, sesquiterpenes and mixtures thereof.

[0067] Preferred oxygen-containing monoterpenes are selected from monoterpene alcohols, monoterpene aldehydes, monoterpene ketones, monoterpene epoxides and mixtures thereof.

[0068] Preferred oxygenated monoterpenes are terpene alcohols, such as terpineol, estragole, anethole, borneol, each in the form of any one of their stereoisomers or a mixture thereof.

[0069] Terpineol exists in different regioisomers, all of which are considered terpineol. Terpineol is selected from α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, 4-terpineol [or (-)-terpinene-4-ol], each in the form of any one of its stereoisomers or a mixture thereof. More preferably, terpineol is selected from α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, each in the form of any one of its stereoisomers or a mixture thereof.

[0070] The term "diterpene" refers to a compound consisting of four isoprene units. The term "diterpene" includes compounds comprising only unmodified isoprene units, as well as compounds comprising one or more modifications as described above. When a monoterpene comprises such modifications, it may also be referred to as a "diterpene". The liquid wood extract of the present invention advantageously comprises at least one diterpene, a cyclic diterpene, typically at least one dicyclic diterpene and / or at least one tricyclic diterpene.

[0071] Typically, the diterpene is a non-oxygenated diterpene or an oxygenated diterpene, preferably an oxygenated diterpene.

[0072] Examples of oxygenated diterpenes are diterpene acids, typically tricyclic diterpene acids, bicyclic diterpene acids or mixtures thereof.

[0073] Non-limiting examples of oxygenated diterpenes are tricyclic diterpene acids selected from abietic acid, dehydroabietic acid, isopimaric acid, levopimaric acid, neoabietic acid, palustric acid, pimaric acid, sandaracopimaric acid, each in the form of any one of their stereoisomers or a mixture thereof.

[0074] Non-limiting examples of oxygenated diterpenes are bicyclic diterpene acids selected from agathic acid, isocupressic acid, trans-communic acid, each in the form of any one of their stereoisomers or a mixture thereof.

[0075] According to the present invention, non-limiting examples of diterpenes or diterpenoids are abietane, rosin, rosinane, daphnane, arteane, cassane, podocarboxane, taurane, labdane, isoabienol, each in the form of any one of their stereoisomers or a mixture thereof, preferably abietane, rosin, rosinane, isoabienol, podocarboxane, each in the form of any one of their stereoisomers or a mixture thereof.

[0076] Examples of hemipentane-type diterpenoids are abietadiene, abiet-8(14),13(15)-diene; (Z)-biformene; isoborol, hemipentane-7,14-diene-13-ol, hemipentane-7,13,14-triene; manool, manoyl oxide, and epimonoyl oxide, each in the form of any one of their stereoisomers or a mixture thereof.

[0077] The sesquiterpenes are preferably acyclic sesquiterpenes, cyclic sesquiterpenes and mixtures thereof.

[0078] Preferably, the acyclic sesquiterpene is farnesene, and the cyclic sesquiterpene is selected from cuparene, curcumene, longifolene, longifolene, longifolene, caryophyllene, humulene, murolene / muurolene, α-copaene, β-copaene, and bisabolene, each in the form of any one of its stereoisomers or a mixture thereof.

[0079] Preferred sesquiterpenes are selected from farnesene, longifolene, longifolene, longifolene, caryophyllene, humulene, ylang-ylang-olene, α-ylang-ylang-olene; each in the form of any one of its stereoisomers or a mixture thereof.

[0080] A non-limiting example of an oxygenated sesquiterpene is caryophyllene oxide and any one of its stereoisomers or mixtures thereof.

[0081] A non-limiting example of a diterpene is ophioboline and any of its stereoisomers or mixtures thereof. A non-limiting example of a triterpene is squalane, hopane, sterols, each in the form of any of its stereoisomers or mixtures thereof. A non-limiting example of a tetraterpene is carotane, each in the form of any of its stereoisomers or mixtures thereof. A non-limiting example of a polyterpene is natural rubber.

[0082] By “thermal degradation compounds of woody biomass” it is understood compounds produced during exposure of woody biomass, more specifically cellulose, hemicellulose and lignin, to temperatures exceeding 200° C. Such degradation compounds, more specifically cellulose-derived decomposition products, hemicellulose-derived decomposition products and lignin-derived decomposition products, have been extensively studied in the scientific literature (Pyrolysis of Cellulose, Kunio Katō, 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, ZE 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).

[0083] The cellulose derived decomposition products are hydroxymethylfurfural, levoglucosan, cellobiose, anhydroglucose derivatives, acetaldehyde, methanol, glyoxal, acrolein, each in the form of any one of their stereoisomers or a mixture thereof.

[0084] The hemicellulose-derived decomposition product is furan or a furan derivative, in particular any one of furan, furfuraldehyde (also known as furfural), and furfuryl alcohol.

[0085] The lignin-derived decomposition products contain phenols, generally phenol, cresol, catechol, eugenol, methyl eugenol, guaiacol, 4-propylphenol, 4-ethyl guaiacol, methyl eugenol, syringol, p-hydroxyphenol, hydroxymethoxytoluene, hydroxymethoxyethylbenzene, hydroxymethoxyvinylbenzene, hydroxymethoxypropylbenzene, dimethoxyphenol, hydroxydimethoxytoluene, hydroxydimethoxyethylbenzene, hydroxydimethoxypropylbenzene, pyrocatechol, benzofuran, dibenzofuran and vanillin. Among these phenols, phenol and cresol are particularly important compounds in industry. The lignin-derived decomposition products to be obtained here contain at least phenol or cresol.

[0086] Typically, the content of at least one woody biomass thermal degradation compound in the liquid wood extract of the present invention is from 0.0000001 to 0.1%, or from 0.0000001 to 0.05%, or from 0.0000001 to 0.1%, or from 0.0000001 to 0.001% (wt%).

[0087] The sulfur content refers to the total sulfur content of the extract. Typically, the sulfur content is assessed by fluorescent UV on a sulfur analyzer Antek Multitek NT-HS according to ASTM D 5453 standard. Advantageously, the sulfur content is from 1000 ppm to 0.01 ppm, preferably from 200 ppm to 0.1 ppm, or from 100 ppm to 1 ppm, typically from 80 ppm to 2 ppm, even more preferably less than 50 ppm. In particular, the liquid wood extract contains no sulfur compounds.

[0088] A second object of the present invention is to provide a method for producing a liquid wood extract, comprising:

[0089] a. Provide a mixture of hardwood and softwood logs, of which the softwood content exceeds 50%, usually exceeds 70%,

[0090] b. cutting, chopping or tearing wood logs into strips or pieces,

[0091] c. The wood strips or wood chips are first steam treated, with steam at a temperature of 50°C to 120°C at 0.1×10 5 Pa to 4×10 5 Pa pressure through the wood strips or wood chips,

[0092] d. In 7×10 5 Pa to 15×105 subjecting the wood strips or wood chips to a first compression step at a pressure of 1.5 Pa and adding water to the wood strips or wood chips at a temperature of 10 to 40° C. to obtain pre-softened wood strips or wood chips, collecting a first compression extract,

[0093] e. applying an evaporation step to the first compressed extract, evaporating more than 15% of the first compressed extract, preferably evaporating 20% ​​to 80% of the first compressed extract, even more preferably evaporating 22% to 40% of the first compressed extract, typically evaporating 25% to 35% of the first compressed extract, to produce a vapor rich in terpene compounds,

[0094] f. condensing the steam rich in terpene compounds, optionally combining it with the steam collected from the first steam treatment process to obtain a condensed phase,

[0095] g. applying the separating phase to the coacervate phase by treating the coacervate phase by gravimetric decantation and / or centrifugation to obtain a liquid wood extract.

[0096] According to the present invention, the wood log mix of hardwood and softwood comprises about 70% to 100% softwood, preferably 75% to 98%, 80% to 95% or 85% to 90% softwood.

[0097] "Softwood" is understood to be wood produced by angiosperms or conifers. Non-limiting examples of softwoods are Araucaria; cedar (Cedrus); cypress (Chamaecyparis, Cupressus, Taxodium); Rocky Mountain Douglas fir (Pseudotsugamenziesii var. glauca); European yew (Taxus baccata); fir (Abies); hemlock (Tsuga): Eastern hemlock (Tsuga canadensis), Mountain hemlock (Tsugamertensiana), Western hemlock (Tsuga heterophylla); Kauri (Agathis australis); Japanese torreya (Torreya nucifera; larch (Larix); pine (Pinus); spruce (Picea); white and yellow cedar (Nootka Cypress, Callithopsis nootkatensis, formerly Chamaecyparis nootkatensis); red cedar; redwood (Sequoiasempervirens) and New Zealand cedar (Dacrydium cupressinum).

[0098] Typically, the cypress (Chamaecyparis, Cupressus, Taxodium) is selected from the group consisting of Cupressus arizonica, Taxodium distichum, Chamaecyparis obtusa, Chamaecyparis lawsoniana, and Cupressus sempervirens.

[0099] Typically, the hemlock (Tsuga) is selected from the group consisting of eastern hemlock (Tsuga canadensis), mountain hemlock (Tsuga mertensiana), and western hemlock (Tsuga heterophylla).

[0100] Typically, the larch (genus Larix) is selected from the group consisting of European larch (Larix decidua), Japanese larch (Larix kaempferi), American larch or Tamarack (Larix laricina), Western larch (Larix occidentalis).

[0101] Typically, the pine (Pinus) is selected from the group consisting of: Corsican pine (Pinus nigra), jack pine (Pinus banksiana), twisted pine (Pinus contorta subsp latifolia), Mondar pine (Pinus radiata), ponderosa pine (Pinus ponderosa), red pine (North America) (Pinus resinosa), Scots pine, red pine (UK), redwood (UK), redwood (UK, old name) (Pinus sylvestris), white pine (Pinus ponderosa or Pinewood, Eastern white pine (Pinus strobus), Western white pine (Pinus monticola), sugar pine (Pinus lambertiana), southern yellow pine (Pinus taeda), longleaf pine (Pinus palustris), pitch pine (Pinus rigida), shortleaf pine (Pinus sproutingii), echinata), maritime pine (Pinus Pinaster), slash pine (Pinus Elliottii), masson pine (Pinus Massoniana), Aleppo pine (Pinus Halepensis), Sumatran pine (Pinus Merkusii), and Mondar pine and radiata pine (Pinus Radiata).

[0102] Softwoods of particular interest are more particularly the maritime pine (Pinus Pinaster), the slash pine (Pinus Elliottii), the masson pine (Pinus Massoniana), the Aleppo pine (Pinus Halepensis) and the Mondari pine, the radiata pine (Pinus Radiata).

[0103] Typically, the spruce (genus Picea) is selected from the group consisting of 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).

[0104] Typically, the white cedar is selected from the group consisting of northern white cedar (Thuja occidentalis) and southern white cedar (Chamaecyparis thyoides).

[0105] Typically, the cedar is selected from the group consisting of eastern red cedar (Juniperus virginiana), western red cedar (Thuja plicata).

[0106] Typically, the genus Araucaria is selected from the group consisting of Hoop Pine (Araucaria cunninghamii); Parana Pine (Araucaria angustifolia); Chilean Pine (or Pehuén, Araucariaaraucana);

[0107] Typically, the cypress (Chamaecyparis, Cupressus, Taxodium) is selected from the group consisting of Cupressus arizonica, Taxodium distichum, Chamaecyparis obtusa, Chamaecyparis lawsoniana, and Cupressus sempervirens.

[0108] According to the present invention, the wood log mix comprises 0 to 30%, preferably 2 to 25%, even more preferably 5 to 20% of hardwood logs.

[0109] For the sake of clarity, "hardwood" refers to wood produced by angiosperm trees that have broad leaves and produce flowers. Hardwoods have broad leaves and enclosed nuts or seeds, such as acorns. They grow in subtropical regions such as Africa, but also in Europe and other regions such as Asia. The main difference between hardwood and softwood is the presence or absence of pores or vessels.

[0110] Non-limiting examples of hardwoods are Afzelia; Synsepalum duloificum; Albizia; Alder (Alnus); Applewood or Wild Apple (Malus); Ash (Fraxinus); Populus; Distemonanthus benthamianus; Balsa (Ochroma pyramidale); Basswood (Tilia americana); Beech (Fagus); Birch (Betula); Black Bean (Castanospermum australe); Blackwood; Ragwood (Cordia alliodora); Boxwood or Box (Buxus sempervirens); Brazilwood (Caesalpinia echinata); Guibourtia; Horse Chestnut (Aesculus); Juglans regia cinerea; Andiroba, Carap, Crappo, Crabwood and Santa Maria (Carapa guianensis); Catalpa; Cherry (Prunus); Chestnut (Castanea dentata); Hornwood (Ceratopetalum apetalum); Dalbergia (Dalbergia retusa); Corkwood (Leitneria floridana); Eastern Cottonwood (Populus deltoides); Dogwood (Cornus spp.); Ebony (Diospyros); Elm; Eucalyptus; Greenheart (Guyana) (Chlorocardium rodiei); Mpingo (Dalbergia melanoxylon); Gum; Carya; Carpinus species; Eastern Carpinus (Ostrya virginiana); Iroko (Milicia excelsa, syn. Chlorophora excelsa).

[0111] Typically, the beech (Fagus) is selected from European beech (Fagus sylvatica) and American beech (Fagusgrandifolia).

[0112] Typically, the birch (Betula) is selected from the group consisting of gray birch (Betula populifolia), paper birch (Betula papyrifera), sweet birch (Betula lenta), yellow birch (B. alleghaniensis syn Betulalutea), silver birch (Betula pendula), white birch (Betula pubescens).

[0113] Typically, the alder (genus Alnus) is selected from the group consisting of black alder (Alnus glutinosa), red alder (Alnus rubra).

[0114] Typically, the genus Fraxinus is selected from the group consisting of Fraxinus nigra, Fraxinus quadrangulata, Fraxinus excelsior, Fraxinus pennsylvanica lanceolata, Fraxinus americana.

[0115] Typically, the genus Populus is selected from the group consisting of Populus tremuloides, Populus grandidentata, and Populus tremula.

[0116] Typically, the blackwood is selected from Australian blackwood also known as Tasmanian blackwood (Acacia melanoxylon), African blackwood or Mpingo (Dalbergia melanoxylon).

[0117] Typically, the horse chestnut (Aesculus) is selected from common horse chestnut (Aesculus hippocastanum), yellow horse chestnut (Aesculus flava).

[0118] Typically, the cherry wood (Prunus) is selected from black cherry wood (Prunus serotina), red cherry wood (Prunus pennsylvanica), wild cherry wood (Prunus avium Prunus serotina), and Brazilian cherry wood.

[0119] Typically, the chestnut wood (Castanea dentata) is selected from Cape chestnut wood (Calodendrum capense).

[0120] Typically, the ebony (Diospyros) is selected from the group consisting of Andaman marble wood (India) (Diospyros kurzii), ebony (Mauritius, East Africa) (Diospyros melanida), Gabon ebony, black ebony, African ebony (Diospyros crassiflora).

[0121] Typically, the elm is selected from the group consisting of American elm (Ulmus americana), English elm (Ulmus procera), rock elm (Ulmus thomasii), slippery elm (Ulmus rubra), European mountain elm (Ulmus glabra).

[0122] Typically, the eucalyptus is selected from Lyptus, Karri (Western Australia) (Eucalyptus diversicolor), Bigleaf (New South Wales) (Eucalyptus), Ironbark (Eucalyptus sideroxylon), Jarrah or Western Australian Eucalyptus (Eucalyptus marginate), Tasmanian Oak or Rowan (Eucalyptus regnans, Eucalyptus obliqua, Eucalyptus delegatensis), River Red Gum, Blue Gum (Eucalyptus saligna).

[0123] Typically, the gum is selected from black gum (Nyssa sylvatica), blue gum (Eucalyptus globulus), redgum or Sweetgum (Liquidambarstyraciflua), Tupelo gum (Nyssa aquatica).

[0124] Typically, the pecan tree (Carya) is selected from the group consisting of Carya alba, Carya glabra, Carya ovata, and Carya laciniosa.

[0125] Hardwood is particularly advantageous in terms of processing, firstly because of its high cellulose and lignin content and secondly because it contains valuable heavier terpene compounds. Unfortunately, due to the low content of non-oxygenated monoterpenes of interest, hardwood logs containing more than 30% are not particularly advantageous for extracting the target monoterpene mixture and further purifying it by an economically viable process.

[0126] In fact, these softwood species are particularly advantageous due to their typical turpentine chemistry, showing large amounts of alpha-pinene and / or beta-pinene and / or dipentene.

[0127] According to the method of the invention, the wood logs are cut, chopped or shredded into strips or chips. In general, the size of the wood strips or chips has been shown to improve the extraction process. It has been shown to be particularly advantageous to cut, chop or shred the wood into a length in the range of 50 to 200 mm, preferably 70 to 180 mm, particularly preferably 90 to 150 mm.

[0128] The term "wood log" refers to the heartwood and / or bark [i.e. the outermost layer of the stems and roots of woody plants].

[0129] According to an alternative embodiment, the wood strips or chips are pretreated with hot water at a temperature of 50° C. to 100° C., and the pretreatment extract is collected or, optionally, recycled for one or more batches of wood strips or chips before collection. Pretreatment has been shown to increase the extraction of monoterpenes. Typically, such pretreatment can be applied to part or all of the wood batch. Advantageously, the pretreatment is carried out for 10 to 60 minutes, preferably 15 to 45 minutes, particularly preferably 20 to 30 minutes.

[0130] According to another alternative embodiment of the invention, the wood strands or wood chips are not cleaned before the first steam treatment.

[0131] According to the invention, the first steam treatment is preferably carried out at 50° C. to 120° C., in particular at 50° C. to 100° C. This temperature range is particularly advantageous since the evaporation temperature of the monoterpenes of interest is 150° C. to 170° C.

[0132] Typically, the wood strands or chips are first steam treated by passing steam through the wood strands or chips to obtain a temperature of 60 to 110°C, preferably 70 to 100°C, in particular typically about 80 to 90°C.

[0133] Typically, the first steam treatment of wood strands or chips is carried out by subjecting the wood strands or chips to a steam pressure of 1×10 5 Pa to 4×10 5 Pa, especially 1×10 5 Pa to 3×10 5 Pa, more particularly 1.5 × 10 5Pa to 3×10 5 Pa, preferably about 2×10 5 Pa pressure through the wood strips or wood chips.

[0134] Advantageously, the combination of pressure and temperature during the first steam treatment begins to soften the lignin, and therefore the wood strands or chips, which then allows the start of the release of low molecular weight volatile compounds, such as non-oxygenated monoterpenes.

[0135] Typically, the first steam treatment of the strands or chips is carried out for 10 to 60 minutes, preferably 15 to 45 minutes, in particular 20 minutes.

[0136] The amount of steam applied during the first steam treatment is 0.05 to 0.2 kg steam / kg wood strands or wood chips.

[0137] Preferably, the steam is live steam and / or recycle steam from downstream steps.

[0138] According to the invention, the first compression step of the wood strips or chips is preferably carried out at 8×10 5 Pa to 14×10 5 Pa, preferably 10×10 5 Pa to 13×10 5 Pa pressure.

[0139] Advantageously, in the first compression step, the water is introduced at a temperature of 12 to 38°C, typically 15 to 35°C, 18 to 30°C, and preferably around room temperature. Introducing the water at such a temperature is particularly interesting because it prevents overheating of the wood. The water also serves to transport foreign matter and liquids (typically terpene compounds and water) out of the system. The first compressed extract collected in this step is the first fluid from which the bulk of the terpene compounds have been removed.

[0140] According to any embodiment of the invention, the wood strands or chips are not cleaned after the first steam treatment and before the first compression step.

[0141] According to any of the above embodiments of the present invention, the method comprises a second steam treatment applied to the pre-softened wood strands or chips by passing steam through the pre-softened wood strands or chips at a temperature of 150°C to 220°C.

[0142] According to any of the above embodiments of the present invention, in the second steam treatment process, the steam is heated at 7×10 5 Pa to 17×10 5 Pa pressure is applied to the pre-softened wood strips or wood chips.

[0143] Keeping the temperature below 220° C. is particularly advantageous in limiting thermal degradation of the wood and thus the formation of thermal degradation products of the wood.

[0144] Typically, this combination of pressure and temperature will continue to soften the wood strands or chips, thereby allowing for increased release of volatile compounds. The second steam treatment is desirably conducted at a temperature of 155°C to 210°C, more specifically 160°C to 190°C. Advantageously, the second steam treatment is desirably conducted at 8×10 5 Pa to 15×10 5 Pa, particularly preferably 9×10 5 Pa to 14×10 5 Any combination of the above temperature and pressure ranges is conceivable.

[0145] The steam may be live steam and / or recovered steam from any downstream steps.

[0146] Advantageously, the second steam treatment of the pre-softened wood strands or wood chips is carried out within the above-mentioned temperature and pressure range for a period of 1 to 30 minutes, preferably 5 to 10 minutes. The steam quantity is 0.05 to 0.2 kg steam / kg wood strands or wood chips. The released steam containing monoterpenes can then be recycled to the first steam treatment step and / or sent directly to a condenser (see below).

[0147] Advantageously, the steam released in the steam treatment step is recycled to the first steam treatment. Such recycling is particularly advantageous for saving energy and can also further concentrate the terpene compounds in the steam.

[0148] According to the above embodiment of the present invention, after the second steam treatment, at 7×10 5 Pa to 15×10 5 A second compression step is performed at a pressure of 1.3 Pa to obtain softened wood strips or wood chips, and a second compressed extract is collected.

[0149] Advantageously, the second compression step is performed at 9×10 5 Pa to 14×10 5 Pa, more preferably 10×10 5 Pa to 13×10 5 Pa pressure.

[0150] According to any of the above embodiments of the present invention, after the second steam treatment, a second compression step is carried out at a temperature of 130°C to 220°C to obtain softened wood strips or wood chips, and a second compressed extract is collected, particularly at a temperature of 140°C to 200°C, particularly at a temperature of 140°C to 180°C, and even more particularly at a temperature of 150°C to 170°C.

[0151] According to any of the above embodiments of the present invention, the softened wood strips or chips are subjected to a subsequent steam treatment and compression step to obtain deeply softened wood strips or chips, and a subsequent compressed extract is collected. Advantageously, the steam released from the subsequent steam treatment is recycled to the first steam treatment and / or the second steam treatment.

[0152] According to any of the above embodiments of the present invention, the method comprises a refining step, wherein the refining step is to make steam at a temperature of 150°C to 220°C, usually at 7×10 5 Pa to 15×10 5 Pa, preferably in less than 3 minutes, typically less than 2 minutes, through pre-softened wood strips or chips, or through softened wood strips or chips, or through deeply softened wood strips or chips.

[0153] The term "refining" refers to a mechanical process of treating lignocellulose-containing solids to beat, bruise, cut and / or fibrillate the fibers therein. Refining refers to both the coarse separation of fibers (fiber separation) and the processing of fibers (the real refining). Thus, refining can be used to reduce the size of lignocellulose-containing solids and provide a material comprising cellulose fiber bundles, individual cellulose fibers, cellulose fiber fragments and combinations thereof. This mechanical processing is preferably carried out at a temperature of 140° C. to 210° C., more particularly 160° C. to 190° C., at 6×10 5 Pa to 14×10 5 Pa, particularly preferably 9×10 5 Pa to 13×10 5 The steam is usually applied for a period of less than 2 minutes, preferably less than 1 minute. The duration of the refining step should be less than 3 minutes to limit any thermal degradation of the wood, as previously described.

[0154] Advantageously, the steam released from the refining step is recirculated to the first steam treatment and / or the second steam treatment.

[0155] According to any of the above embodiments of the present invention, an evaporation step is applied to the compressed extract mixture comprising the first compressed extract and / or the second compressed extract, and / or to the subsequent compressed extract, in which step more than 15% of the compressed extract mixture is evaporated, preferably 20% to 80%, even more preferably 22% to 40%, typically 25% to 35% of the compressed extract mixture.

[0156] Advantageously, the first compressed extract or the compressed extract mixture is centrifuged before the evaporation step. Such centrifugation is particularly advantageous for removing solid matter released by the wood strands or chips.

[0157] Typically, the pressure applied during the evaporation step is 0.2 × 10 5 Pa to 1×10 5 Pa, preferably 0.5×10 5 Pa to 1×10 5 Pa (i.e., under moderate vacuum) or at atmospheric pressure. The temperature of the mixture is kept above the boiling point of water, which is usually due to the presence of dissolved compounds. The boiling point of water is at an evaporation pressure of 0.2×10 5 Pa to 1×10 5 Pa, respectively, the temperature is 65°C to 105°C; at the evaporation pressure of 0.5×10 5 to 1×10 5 Pa is a temperature of 85°C to 105°C.

[0158] Preferably, the steam enriched in terpene compounds (optionally combined with steam collected from the first steam treatment and / or the second steam treatment and / or refining step) is condensed to obtain a condensed phase.

[0159] The condensation step is accomplished by any type of condenser capable of completely condensing the vapor stream and producing a two-phase liquid.

[0160] Advantageously, the steam released from the first steam treatment and / or the second steam treatment step and / or the refining step is treated independently by the control system of the condenser to obtain a subsequent condensed phase.

[0161] The coacervate phase and / or subsequent coacervate phases are further processed from the separated phases by density difference (gravity decantation) or assisted gravity (centrifugation) to obtain the liquid wood extract of the present invention.

[0162] A particular advantage of the process is that it is able to remove terpenes from water streams that are typically sent to wastewater treatment units, resulting in a more efficient and eco-friendly water treatment process.

[0163] According to any embodiment of the process according to the invention, the process according to the invention is carried out without any organic solvents, additives, synthetic or natural extractants and / or compressed air. Only water and steam are used in the process according to the invention.

[0164] The liquid wood extract of the present invention can be converted into fragrances, cosmetics, medicines, nutrients, antimicrobials, agricultural chemicals and / or chemical ingredients by the method of the present invention. The method of converting the liquid wood extract of the present invention into fragrances, cosmetics, medicines, nutrients, antimicrobials, agricultural chemicals and / or chemical ingredients is well known to those skilled in the art. In particular, the liquid wood extract of the present invention can be converted into the ingredients without a desulfurization step.

[0165] The process is particularly advantageous in that it allows the preparation of a liquid wood extractive comprising less than 0.1% (wt%) of at least one woody biomass thermal degradation compound and a sulfur content of less than 1000 ppm. The process of the invention allows the avoidance of purification steps. In other words, the liquid wood extractive can be used as is.

[0166] A third object of the present invention is a method for obtaining fragrances, cosmetics, pharmaceuticals, nutraceuticals, antimicrobial agents, agrochemicals and / or chemical ingredients, comprising the step of obtaining a liquid wood extract according to the method of the present invention.

[0167] A fourth object of the present invention is the use of the liquid wood extract of the present invention as an active compound in a perfume, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agrochemical and / or chemical composition, or for obtaining an active compound in a perfume, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agrochemical and / or chemical composition.

[0168] Another object of the present invention is to provide a method for preparing a perfume, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agricultural chemical and / or chemical composition or article, which comprises adding an effective amount of the liquid wood extract of the present invention as an active compound to the composition or article.

[0169] Another object of the present invention is a process for obtaining a fragrance, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agrochemical and / or chemical composition or article comprising the following steps:

[0170] a) obtaining a liquid wood extract according to the method of the present invention; and

[0171] b) adding the liquid wood extract of step a) to a fragrance, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agrochemical and / or chemical composition or article.

[0172] According to a particular embodiment of the present invention, the liquid wood extract in step a) is directly added to a fragrance, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agrochemical and / or chemical composition or article. In other words, the method of the present invention does not include a purification step between steps a) and b).

[0173] According to another particular embodiment of the present invention, the liquid wood extract in step a) is purified by methods known to those skilled in the art, such as distillation or rectification.

[0174] Another object of the present invention is a process for the preparation of active compounds for use in fragrances, cosmetics, pharmaceuticals, nutraceuticals, biocides, agrochemicals and / or chemicals, comprising one or more steps to convert the liquid wood extract of the present invention into an active compound.

[0175] Another object of the present invention is a process for preparing an active compound for use in fragrances, cosmetics, pharmaceuticals, nutraceuticals, antimicrobials, agrochemicals and / or chemical compositions comprising the following steps:

[0176] a) obtaining a liquid wood extract according to the method of the present invention; and

[0177] b) converting the liquid wood extract of step a) into active compounds for use in fragrances, cosmetics, pharmaceuticals, nutraceuticals, biocides, agrochemicals and / or chemical compositions.

[0178] According to any embodiment of the present invention, the liquid wood extract in step a) is directly converted into a fragrance, cosmetic, pharmaceutical, nutraceutical, antimicrobial, agrochemical and / or chemical composition or article. In other words, the method of the present invention does not include a purification step between steps a) and b).

[0179] In particular, the "active compound" is selected from the group consisting of perfuming ingredients, flavoring ingredients, nutritional ingredients, malodor counteracting ingredients, antimicrobial ingredients, cosmetic ingredients, insect repellent ingredients or insect attractant ingredients, chemical and / or agrochemical ingredients.

[0180] Thus, to be considered an "active compound", the compound must possess at least one property that enables it to be used as a perfuming ingredient, as a malodor counteracting ingredient, as a flavoring ingredient, as a cosmetic ingredient, as a nutritional ingredient, as an antimicrobial ingredient, as an insect repellent or attractant ingredient, and / or as a chemical ingredient.

[0181] The term "perfuming ingredient" is understood as a compound that is used as an active ingredient in a perfuming preparation or composition to impart a hedonic effect. In other words, to be considered a perfuming ingredient, the compound must be recognized by a technician in the field of perfumery as being able to impart or modify the smell of the composition in an active or pleasant manner, rather than just having a smell. In addition to modifying or imparting smell, perfuming ingredients can impart additional benefits, such as persistence, burst, malodor offset, antimicrobial effect, antiviral effect, microbial stability, pest control. The term "flavoring ingredient" is understood as being able to impart a taste sensation to the pallet of the taster. The term "malodor offsetting ingredient" is understood as being able to reduce the sensation of malodor (i.e., an unpleasant or offensive odor to a person's nose). The term "antimicrobial ingredient" is understood as being able to kill microorganisms or reduce or prevent their growth and / or accumulation, and includes antibacterial, antibiotic, antifungal, antiviral and antiparasitic ingredients. The term "attractant or repellent" should be understood as a compound that has a positive or negative impact on insects. Examples of attractant or repellent ingredients may be found in the literature or other works of a similar nature, for example: AMEl-Sayed, The Pherobase 2005, http: / / www.pherobase.net.

[0182] The term "chemical ingredient" is understood to mean a chemical compound which is used as an active ingredient in chemical processes, as a starting material in chemical syntheses or as a molecular building block.

[0183] Generally, adhesives, the liquid wood extracts of the present invention can be used as active compounds in chewing gum, ink, tire, asphalt compositions or for obtaining them.

[0184] By definition, a "nutrient" is a component of food or other ingestible form that has been determined to provide a beneficial effect on the human body, either to prevent or treat one or more diseases or to improve physiological function. Essential nutrients are considered nutrients if they provide a benefit beyond their basic role in normal growth or maintenance of the human body.

[0185] Unless otherwise indicated, percentages (%) refer to weight percent (wt %) of the composition.

[0186] Typical ways of carrying out the process of the invention are reported in the examples hereinafter.

[0187] Example

[0188] The present invention will now be described in further detail by the following examples.

[0189] Example 1

[0190] In order to illustrate the wood terpene extracts of the above invention, three wood terpene extracts of different properties were collected and compared. These wood terpene extracts come from the same softwood source. The selected softwood source, Pinus pinaster, is the most commonly used wood in the woodworking industry in southern Europe. The first wood terpene extract sample was obtained by the Kraft pulping process, hereinafter referred to as crude sulfate turpentine (abbreviated CST), the second wood terpene extract sample was obtained by the tapping process, hereinafter referred to as turpentine (abbreviated GT) (both processes are well known to those skilled in the art), and the third wood terpene extract was hereinafter referred to as LST (low sulfur turpentine), which was obtained by the method of the present invention, that is, the liquid wood extract obtained from the woodworking industry was partially evaporated, continuously and completely condensed, and finally separated from water by simple decantation to obtain a terpene oil mixture called LST.

[0191] The three terpene extracts were analyzed by gas chromatography (GCFID) on an Agilent 8890 equipped with a polar column such as CPWAX 57CB (25 m / 0.25 mm / 0.20 μm).

[0192] The total sulfur content of the wood terpene extracts from the rubber tapping process and the above-mentioned inventive method was determined using the fluorescent UV method on the sulfur analyzer Antek Multitek NT-HS (compliant with ASTM D 5453). The total sulfur content of the wood terpene extracts from the kraft pulping process was determined using the fluorescent X-ray method on the Horiba SLFA 6800 (compliant with ASTM D 4294).

[0193] Flash point was measured using an Eraflash instrument according to ASTM D 3828.

[0194] Identification of terpenes is performed using a mass spectrometer equipped with a non-polar column (such as DB5ms) and quantification is performed using a GCFID equipped with a polar column (such as ZBwax or CPWax 57CB). This orthogonal LRI procedure is used by comparing experimental values ​​with theoretical values ​​and with standards if available.

[0195] The results are shown in Table 1 below.

[0196] Table 1:

[0197]

[0198] The three extracts listed in Table 1 showed very high concentrations of non-oxygenated monoterpenes, 85.9% for CST, 91.5% for LST, and 96.2% for GT. Considering the same wood origin of these wood terpene extracts, α-pinene, β-pinene, and dipinene were the three most common terpenes. Nevertheless, the relative percentage of α-pinene to the whole non-oxygenated monoterpenes was similar in CST (70.0%) and LST (69.8%), and higher in GT (72.6%). In addition, the relative percentage of β-pinene was similar in CST (19.0%) and GT (19.3%), but higher in LST (21.5%).

[0199] GT and LST showed the highest concentrations of non-oxygenated monoterpenes. In fact, GT was the most interesting extract for the recovery of only non-oxygenated monoterpenes (96.2%) due to the low content of other chemicals (3.8%).

[0200] The main components of the “other chemicals” mentioned in Table 1 are higher molecular weight terpene compounds, such as oxygenated monoterpenes, sesquiterpenes, diterpenes, but also some woody biomass thermal degradation compounds, such as aromatic phenolic compounds if the extraction conditions are strict; for example, 4-propylphenol, 4-ethylguaiacol, methyleugenol. Woody biomass thermal degradation compounds were found to be present in higher concentrations in CST. By comparing the three extracts, GT showed very low concentrations of other chemicals. Such low contents do not allow to isolate and / or concentrate the valuable higher molecular weight terpene compounds in an economical way to use them as industrial raw materials.

[0201] In contrast, CST showed a higher content of higher molecular weight terpene compounds. However, in CST extracts, the compounds found in the “other chemicals” were also enriched in a mixture of sulfur compounds. This high concentration of sulfur compounds is due to the use of sodium carbonate and sodium sulfide in the kraft pulping process to produce sodium sulfide (Na2S). The sulfur compounds identified for CST were mainly methyl mercaptan and dimethyl sulfide, dimethyl disulfide, 1-(methylthio)ethanethiol, thiophene, formylmethylthiophene and propionylthiophene.

[0202] In addition, in order to reduce the flash point and ensure safety, the high concentration (12400 ppm) of sulfur-containing compounds in CST requires a specific purification stage, i.e., a desulfurization step, such as distillation and chemical reactions, such as oxidation with peracetic acid (see Environmental technology and Innovation 18 (21), 100628, 2020), oxidation with hypochlorite (see Bioresources 16 (4), 8098-8110, 2021) or treatment with modified activated carbon (CN104449395). All of these well-known methods significantly affect the total cost of the obtained α-pinene, β-pinene extracts, and caryophyllene, longifolene and humulene extracts. Similar observations were made for the extraction and purification of terpene alcohols.

[0203] Therefore, the potential application of CST to extract α-pinene and β-pinene, terpene alcohols (e.g., terpineol), or sesquiterpenes (e.g., caryophyllene, longifolene, and humulene) as raw materials for further chemical synthesis is not an economical route for industrial use.

[0204] LST showed a very favorable composition for the recovery of non-oxygenated monoterpenes (nearly 91.5%), as well as other chemicals such as sesquiterpenes (8.5%). The latter recovery was more than double the levels found in GT.

[0205] Since no chemicals are used in the process of the present invention, the concentration of sulfur compounds is found to be very low, less than 10 ppm. Therefore, the flash point of LST is higher than that of CST and similar to that of GT, thereby providing safer operating conditions for production, storage and transportation. In addition, these sulfur compounds can be easily removed during the usual turpentine purification process. Therefore, not only is the LST extract rich in non-oxygenated monoterpenes and contains a large amount of high molecular weight terpene compounds, but all of these compounds are easily purified so as to be used as is or as molecular building blocks for subsequent chemical synthesis.

[0206] Example 2

[0207] To better identify the other chemicals found in the GT and LST of Example 1, additional studies were performed and the results are listed in Table 2.

[0208] Identification of the compounds is performed using a mass spectrometer equipped with a non-polar column (such as DB5ms) and quantification is performed using a GCFID equipped with a polar column (such as ZBwax or CPWax 57CB). This orthogonal LRI procedure is used by comparing the experimental values ​​with the theoretical values ​​and with standards if available.

[0209] Table 2 shows the compounds identified from the LST and GT extracts in the section above “Other chemicals”.

[0210] Table 2:

[0211]

[0212] As shown in Table 2 , the main high molecular weight terpene compounds in GT and LST are terpene alcohols and sesquiterpenes.

[0213] The main terpene alcohols include α-terpineol, fenchol, borneol and terpinene-4-ol; the sesquiterpenes include longifolene, caryophyllene, longifole pinene, longifole ringene, humulene and α-ylang-ylang oilseed.

[0214] It is noteworthy that, in contrast to CST extracts, no lignin thermal degradation compounds were detected in GT and LST. This confirms that the conditions provided by the method of the present invention reduce the degradation of lignocellulosic biomass to such an extent that the LST extracts are comparable to GT.

[0215] The absence of such degradation compounds reduces the complexity of any upstream processes before using the terpene extract as a feedstock.

[0216] In contrast, the terpene alcohol content in LST is 20% higher than that in GT. In addition, the content of alpha-terpineol (the most valuable terpene alcohol) in LST is actually 20% higher than that in GT.

[0217] Likewise, the content of higher molecular weight terpenes in LST was more than 200% higher than that in GT. Among them, longifolene and caryophyllene, the most interesting sesquiterpenes, were actually more than 200% higher in LRT than in GT.

[0218] Thus, the expected very significant concentration of non-oxygenated monoterpenes combined with the unexpectedly quite significant concentration of high molecular weight terpene compounds, especially sesquiterpenes, gives LST a unique and valuable chemical composition profile.

[0219] Thus, in contrast to CST and GT, LST extracts can be used as eco-friendly chemical-free, easy to handle [non-flammable and non-toxic], easily accessible (purified / enriched), bio-sourced molecular building blocks / raw materials for the flavors and fragrances industry (F&F) for non-oxygenated monoterpenes, notably α-pinene, β-pinene and dipentene, for oxygenated monoterpenes more specifically terpene alcohols such as pinolene, and for sesquiterpenes, typically caryophyllene, longifolene, humulene.

Claims

1. A liquid wood extract, comprising: a) 50 to 95% (wt%) of at least one non-oxygenated monoterpene, b) 5% to 30% (wt%) 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 thermally degradable compound of woody biomass, d) Sulfur content less than 1000 ppm.

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

3. The liquid wood extract according to any one of the preceding claims, wherein the at least one terpene having a higher molecular weight than a non-oxygenated monoterpene is at least one oxidized 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. The liquid wood extract according to any one of the preceding claims, wherein the at least one terpene having a higher molecular weight than non-oxygenated monoterpenes is at least one sesquiterpene selected from acyclic sesquiterpenes, cyclic sesquiterpenes and mixtures thereof, preferably selected from farnesene, longifolene, longifolene, longifolene, caryophyllene, humulene, ylangolene, each in the form of any one of their stereoisomers or a mixture thereof.

5. The liquid wood extract according to any one of the preceding claims, wherein the at least one non-oxygenated monoterpene is a bicyclic non-oxygenated monoterpene, a monocyclic non-oxygenated monoterpene, an acyclic non-oxygenated monoterpene and mixtures thereof.

6. The liquid wood extract according to any one of the preceding claims, wherein the at least one non-oxygenated monoterpene is - at least one bicyclic non-oxygenated monoterpene selected from α-pinene, β-pinene, camphene, δ-3-carene, bornene, sabinene, thujacene, 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, alloocimene, 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.

7. The liquid wood extract according to any one of the preceding claims, wherein the at least one woody biomass thermal degradation compound is any one of: - at least one cellulose-derived decomposition 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 decomposition product selected from furans or furan derivatives, such as furfural, furfuryl alcohol, and / or - at least one lignin-derived decomposition product selected from phenol or phenol derivatives, such as cresol, catechol, eugenol, methyleugenol, guaiacol, 4-propylphenol, 4-ethylguaiacol, eugenol, 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 - A mixture thereof.

8. A liquid wood extract according to any one of the preceding claims, comprising: - less than 0.05% (wt%) of at least one woody biomass thermal degradation compound and / or - less than 200 ppm of sulfur and / or - 5 to 20% (wt%) of at least one terpene having a higher molecular weight than the non-oxygenated monoterpene.

9. The liquid wood extract according to any one of the preceding claims, wherein the at least one oxygen-containing 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. A method for producing a liquid wood extract, include: a. Provide a mixture of hardwood and softwood logs, of which the softwood content exceeds 50%, usually exceeds 70%, b. cutting, chopping or tearing wood logs into strips or fragments, c. The wood strips or wood chips are first steam treated, with steam at a temperature of 50°C to 120°C at 0.1×10 5 Pa to 4×10 5 Pa pressure through the wood strips or wood chips, d. In 7×10 5 Pa to 15×10 5 subjecting the wood strips or chips to a first compression step at a pressure of 1.3 Pa and adding water to the wood strips or chips at a temperature of 10 to 40° C. to obtain pre-softened wood strips or chips and collecting a first compressed extract, e. applying an evaporation step to the first compressed extract, evaporating more than 15% of the first compressed extract to produce a vapor rich in terpene compounds, f. condensing the steam rich in terpene compounds, optionally combining it with the steam collected from the first steam treatment process to obtain a condensed phase, g. applying the separating phase to the coacervate phase by treating the coacervate phase, preferably by gravimetric decantation and / or centrifugation, to obtain a liquid wood extract.

11. The method according to claim 10, wherein the method include: - The pre-softened wood strips or chips are subjected to a second steam treatment, wherein the steam is heated at a temperature of 150°C to 220°C at 7×10 5 Pa to 17×10 5 Pa pressure through the pre-softened wood strips or wood chips, - After the second steam treatment at 7×10 5 Pa to 15×10 5 Pa to obtain softened wood strips or chips and collect a second compressed extract.

12. The method according to claim 10 or 11, wherein the method comprises a refining step by subjecting the refining step to steam at a temperature of 150°C to 220°C at 7×10 5 Pa to 17×10 5 The softening is carried out under a pressure of Pa through pre-softened wood strips or wood chips or softened wood strips or wood chips.

13. A method according to claim 11 or 12, wherein the condensed phase further comprises steam collected from a second steam treatment and / or refining step.

14. A method for obtaining fragrances, cosmetics, pharmaceuticals, nutraceuticals, antimicrobial agents, agrochemicals and / or chemical ingredients, comprising the step of obtaining a liquid wood extract according to the method of claims 10 to 13.

15. Use of liquid wood extracts according to claims 1 to 9 as active compounds in fragrances, cosmetics, pharmaceuticals, nutraceuticals, biocides, agrochemicals and / or chemical compositions or for obtaining active compounds of fragrances, cosmetics, pharmaceuticals, nutraceuticals, biocides, agrochemicals or chemical compositions.

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