Extraction method

Abstract

To provide a method and apparatus for extracting rosin and / or terpene fractions from resinous wood. [Solution] The method comprises the steps of: a) providing resinous wood which has been subdivided or desized into wood portions, the wood portions being screened and wood portions having dimensions greater than 1 cm being removed; and b) extracting rosin and / or terpene fractions from the resinous wood by treating or contacting the wood portions of the resinous wood with a terpene-containing agent, wherein the terpenes are present in the agent in an amount of at least 70% by weight, the terpenes in the agent are at least partially recovered, recycled or derived from terpene fractions previously extracted from agents previously used to treat further resinous wood and / or further resinous wood, and the wood portions of the resinous wood are treated in a countercurrent / reverse current manner with the agent.

Description

Technical Field

[0001] Cross - reference to related applications This application claims priority from Australian Provisional Patent Application No. 2020 / 901996, filed on 16 June 2020, the content of which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to methods and apparatus for extracting terpenes and rosin from resinous wood.

Background Art

[0003] There are three recognized commercial sources of rosin (or colophony) and terpenes (or turpentine). These are chemical pulping (i.e., tall oil, and rosin and terpenes derived from CST), manual or semi - manual tapping of live trees (i.e., gum rosin and gum turpentine), and solvent extraction (i.e., wood rosin and wood turpentine).

[0004] Chemical pulping typically uses strong bases and acids to break down wood, and rosin and terpenes are discharged as by - products of this process. By doing so, the rosin and terpenes induced by this process may contain significant levels of contaminants (e.g., sulfides and sulfate compounds) from the pulping process, which then must be removed through various filtration and distillation processes. Thus, the complete removal of trace chemicals or contaminants from such rosin and terpenes is generally not commercially feasible. In addition, the complete recovery of available rosin and terpenes in wood is impossible in the chemical pulping process, for example, due to decomposition into pitch and other compounds therein. Chemical pulping as a means of extracting pine chemicals may further present some environmental adverse effects, such as the discharge of heavy metals and toxic compounds into the environment.

[0005] Gum tapping is carried out using various methods of mechanically cutting, scraping, wounding, or drilling live trees. However, to obtain a commercially viable yield from this process, chemical stimulants are typically used to ensure that the wounds continue to bleed and release their extracts. These stimulants include acids such as etephon and sulfuric acid, as well as hormones. Such chemicals can adversely affect the physical composition of the resulting rosin and terpenes. For example, acids can polymerize terpenes, resulting in higher concentrations of diterpenes and triterpenes than those naturally present in the trees. These terpene polymers are also less desirable than monoterpenes such as α- and β-pinene. Therefore, the gum tapping process typically requires a washing step to remove the added chemicals, and often trace amounts of the chemicals still remain. This washing step also creates a waste stream in which the contaminated water is generally saline.

[0006] Wood rosin and terpenes are generally extracted using tree stumps and solvents. The solvents are typically hexane, methyl ethyl ketone, or other hydrocarbons. The process involves washing the wood in the solvent and then distilling the resulting concentrate into the solvent, rosin, and terpenes. Nevertheless, the wood rosin and terpenes obtained from this solvent extraction process may still contain noticeably trace amounts of solvent and other contaminants. In addition, the wood rosin produced by this process generally requires a further decolorization process, which can negatively impact yield and degrade the rosin.

[0007] Therefore, there is a need for improved methods for extracting rosin and terpenes from resinous wood that may cause less damage to these final products and / or be more environmentally friendly. [Overview of the project] [Means for solving the problem]

[0008] This disclosure is based in part on the remarkable discovery that treating resinous wood with a terpene solvent or a terpene solvent-containing agent can result in more efficient and improved extraction of terpenes and rosin from such wood, as well as reduced levels of unwanted chemical contamination.

[0009] In a first aspect, the Disclosure provides a method for extracting rosin and / or terpene fractions from resinous wood, comprising the step of treating resinous wood with an agent containing, consisting of, or essentially consisting of terpenes, to thereby extract rosin and / or terpene fractions from resinous wood.

[0010] Preferably, the method further includes an initial step of at least partially subdividing the resinous wood, such as by chipping, before treatment with the chemical. In some examples, the time between the initial step of subdividing the resinous wood and the treatment of the resinous wood with the chemical may be about 12 hours or less, about 8 hours or less, about 4 hours or less, about 2 hours or less, or about 1 hour or less.

[0011] Preferably, the method further includes a step of separating the rosin fraction and the terpene fraction extracted from the resinous wood. In some examples, the separation of the rosin fraction and the terpene fraction is carried out at least partially by distillation to produce a distillate containing, essentially consisting of, or comprising the terpene fraction, and a residual filtrate containing, essentially consisting of, or comprising the rosin fraction. In certain specific examples, the method further includes a step of separating or recovering the terpene fraction from the distillate.

[0012] In certain cases, the method includes a subsequent step of heating, for example, steaming, the resinous wood treated with the chemical to at least partially remove any residual chemical and / or terpene fractions therefrom.

[0013] Preferably, the process of treating the resinous wood with a chemical is carried out for a certain period of time under conditions sufficient or suitable for extracting rosin and / or terpene fractions from the resinous wood. In some examples, the process of treating the resinous wood with a chemical is carried out for a time of about 15 minutes to about 120 minutes. In various examples, the process of treating the resinous wood with a chemical is carried out at a temperature of about 75°C to about 155°C. In some examples, the process of treating the resinous wood with a chemical is carried out at a pressure of about 10 psi to about 75 psi.

[0014] Preferably, the resinous wood is contacted or treated with a chemical in a counter-current or counter-flow manner.

[0015] In certain cases, rosin and / or terpene fractions extracted from resinous wood are substantially free of contaminants.

[0016] In certain cases, the agent is at least partially derived from a terpene fraction extracted from resinous wood. In this regard, the method may include a further step of recycling the terpene fraction extracted from resinous wood and / or the agent for use in the processing step.

[0017] In some cases, resinous wood is substantially untreated before chemical treatment.

[0018] In various examples, resinous wood is at least partially derived from, or includes, one or more resinous wood logs and / or stumps.

[0019] In a second aspect, the disclosure provides a terpene fraction produced according to the method of the first aspect.

[0020] In some of the embodiments described above, the terpene fraction comprises at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight of pinene.

[0021] In various examples of the above aspect, the terpene fraction is substantially free of contaminants.

[0022] In certain examples of the above aspect, the terpene fraction contains terpene polymers such as diterpenes and triterpenes that are less than about 25 wt%, less than about 10 wt%, less than about 5 wt%, less than about 2.5 wt%, or less than about 1 wt% of the terpene fraction.

[0023] In certain specific examples of the above aspect, the terpene fraction contains synthetic pine oil that is less than about 10 wt%, less than about 5 wt%, less than about 2.5 wt%, less than about 1 wt%, or less than about 0.5 wt% of the terpene fraction.

[0024] In a third aspect, the present disclosure provides a rosin fraction produced according to the method of the first aspect.

[0025] In certain examples of the above aspect, the rosin fraction has a Gardner color number of about 8 or less, about 5 or less, or about 3 or less.

[0026] In various examples of the above aspect, the rosin fraction is substantially free of contaminants.

[0027] In certain examples of the above aspect, the rosin fraction has an acid value of about 160 to about 175.

[0028] In some examples of the above aspect, the rosin fraction contains an abietic acid content in the range of about 15 wt% to about 35 wt%, about 15 wt% to about 25 wt%, or about 15 wt% to about 20 wt% of the rosin fraction.

[0029] In a fourth aspect, the present disclosure is (a) containing at least about 65 wt%, at least about 70 wt%, at least about 75 wt%, or at least about 80 wt% of pinene of the isolated terpene fraction, (b) substantially free of contaminants, (c) containing less than about 25 wt%, less than about 10 wt%, less than about 5 wt%, less than about 2.5 wt%, or less than about 1 wt% of terpene polymers of the isolated terpene fraction, and (d) Provide an isolated terpene fraction containing one or more of the following: less than 10% by weight, less than 5% by weight, less than 2.5% by weight, less than 1% by weight, or less than 0.5% by weight of synthetic pine oil.

[0030] In the fifth aspect, this disclosure is: (a) Includes a number of Gardner colors of approximately 8 or less, approximately 5 or less, or approximately 3 or less, (b) substantially free of contaminants, (c) Contains acid values ​​of approximately 160 to 175, (d) Provide an isolated rosin fraction containing one or more abietic acid content in the range of about 15% to about 35% by weight, about 15% to about 25% by weight, or about 15% to about 20% by weight of the isolated rosin fraction.

[0031] In a sixth aspect, the disclosure provides a method for producing a polymer, comprising the step of processing a rosin fraction and / or terpene fraction produced according to the method of the first aspect to produce a polymer.

[0032] In the seventh aspect, the disclosure relates to a polymer produced according to the method of the sixth aspect.

[0033] In the eighth aspect, the present disclosure provides a method for producing an ester, comprising the step of processing a rosin fraction and / or terpene fraction produced according to the method of the first aspect to produce an ester.

[0034] In the ninth aspect, the present disclosure relates to an ester produced according to the method of the eighth aspect.

[0035] In a tenth aspect, the disclosure provides an apparatus for extracting rosin and / or terpene fractions from resinous wood, comprising a processing chamber for treating the resinous wood with a chemical agent containing, comprising, or essentially comprising terpenes.

[0036] In some examples, the processing chamber is a countercurrent extractor or includes a countercurrent extractor.

[0037] In a particular example, the apparatus further comprises a distillation chamber communicating with the processing chamber, which is used to separate the rosin and terpene fractions extracted from the resinous wood.

[0038] In various examples, the apparatus further comprises a desolvator communicating with the processing chamber, which can heat and treat the resinous wood treated with the chemical, such as with steam or heated oil, to remove at least partially the residual portion of the chemical and / or the terpene fraction therefrom.

[0039] In certain cases, the apparatus further includes a separator, such as a condenser, which is in communication with the distillation chamber, and the separator is for separating the terpene fraction from the distillate produced by the distillation chamber.

[0040] In some examples, the device further includes a scrubbing device.

[0041] Preferably, the apparatus is for use in the method of the first embodiment.

[0042] Throughout this specification, unless otherwise indicated, “comprise,” “comprises,” and “comprising” are used in a non-exclusive and inclusive manner so that the integers or groups of integers described may include one or more other integers or groups of integers not described.

[0043] Conversely, the terms "consist," "consists," and "consisting" are used exclusively to indicate that the integer or group of integers listed is necessary or essential, and no other integers can exist. The phrase "essentially consists of" indicates that the integer or group of integers listed is necessary or essential, but any other element that does not interfere with or contribute to the activity or function of the integer or group of integers listed is optional.

[0044] Furthermore, it should be understood that the indefinite articles "a" and "an" are not read as single indefinite articles, nor as excluding two or more objects from the single object they refer to. For example, "a" protein includes one protein, one or more proteins, or more proteins.

[0045] As used herein, the term “approximately” refers to a variation or tolerance of the stated quantity, concentration, ratio, or percentage. The degree of such tolerances and differences is well understood by those skilled in the art. Typically, such tolerances and differences do not impair the structure, function, and / or implementation of the apparatus and methods described herein. Preferably, “approximately” is defined as being 10%, 5%, 2% or less, or 1% above or below the stated quantity, concentration, ratio, or percentage.

[0046] As merely an example, embodiments of the present disclosure are described in full below with reference to the accompanying drawings. [Brief explanation of the drawing]

[0047] [Figure 1] This is a schematic diagram of an apparatus or system according to a specific embodiment of the present disclosure. [Figure 2] This shows the size distribution of wood chips from logs (A) and tree stumps (B). [Modes for carrying out the invention]

[0048] This disclosure arises, in part, from the identification of novel methods for extracting rosin and terpenes from resinous wood. In particular, these novel methods provide the production of improved rosin and terpene fractions that are free from or contain minimal amounts of contaminants or trace chemicals, and are therefore more suitable for downstream use. In addition, the methods described herein typically have lower capital and operating costs and / or may be more efficient and / or may exhibit improved yields and / or may be more environmentally friendly than those previously described in the art.

[0049] This disclosure provides a non-destructive solvent-based extraction method for the production of rosin and terpenes derived from resinous wood, using self-sustaining and self-generating solvents, i.e., terpenes naturally present in resinous wood. This configuration allows the extraction method to advantageously produce rosin and terpene fractions that are free, or substantially free, of any reagent or trace chemical residues, as typically found in existing methods for producing rosin and terpenes. Solvent extraction by the method of this disclosure can also offer improved efficiency, with extraction of rosin and terpene fractions taking about half the time of other solvent extraction processes known in the art (e.g., only about 30 to 45 minutes). This improved efficiency minimizes any chemical and / or physical changes to the rosin and terpene fractions, such as oxidation and terpene polymerization, which may be detrimental to their value and usefulness. Furthermore, this method can minimize variability between batches, and the rosin and terpene fractions derived by the method of this disclosure typically exhibit the same or less than 1% variability in chemical composition between batches, compared to other prior art methods that may exhibit greater variability of up to 10% or more between batches. The extraction process is also typically simpler than prior art methods, due to a single separation step of the rosin fraction from the terpene fraction, which does not require further solvent removal. In this regard, prior art solvent extraction methods typically involve a two-step process in which the resinous material is removed from the wood by solvent treatment, and then any retaining solvent is recovered from the treated wood by steam treatment (see, e.g., Beglinger, E. (1958), Distillation of Resinous Wood). Waste flow is also minimized, and there is no need to burn hazardous chemicals or discharge contaminated water containing salt.

[0050] In one embodiment, the present disclosure relates to a method for extracting a rosin fraction and / or terpene fraction containing components or derivatives thereof from resinous wood, the method comprising the step of treating the resinous wood with an agent containing, consisting of, or essentially consisting of terpenes, to thereby extract the rosin and / or terpene fraction from the resinous wood.

[0051] As used herein, the term “rosin” broadly refers to resins obtained from different species of resinous trees, such as conifers and softwoods. The composition of rosin can vary to some extent depending on their source, but they typically contain resin acids, such as unsaturated monocarboxylic acids, as the main component, including the component or its derivatives. In this regard, the proportion of different resin acids in rosin can vary depending on the softwood or conifer species from which the rosin was obtained. For example, rosin may contain 85–95% resin acids. Generally, rosin mainly contains abietic acid (e.g., 50–80%), and to lower degrees dihydroabietic acid (e.g., 5–30%) and pimalic acid (e.g., 5–30%). Rosin may also contain isobrominic acid, pulsed phosphoric acid, and neoabietic acid.

[0052] The terms "terpene" and "terpentin" are used interchangeably herein and refer to a wide variety of organic compounds produced by various plants, particularly conifers. As is understood, the main components of terpenes or terpentins are unsaturated hydrocarbon monoterpenes such as α-pinene, β-pinene, and 3-carene.

[0053] In a broad sense, "resinous wood" refers to wood that contains a portion of resin. Resinous wood is generally associated with softwood species such as pine, which secrete resin as a protective mechanism against parasites and diseases, but it may also include resinous hardwood species such as teak, agarwood, and acacia. In some cases, resinous wood contains a terpene fraction. In other cases, resinous wood contains a rosin fraction. In further cases, resinous wood contains both a terpene fraction and a rosin fraction.

[0054] In certain cases, resinous wood may include, consist of, or essentially consist of coniferous wood. Therefore, any reference to “resinous wood” in this specification may be understood to encompass coniferous wood. Accordingly, any description of any aspect, example, embodiment, or feature of this disclosure using the term “resinous wood” should be understood to apply equally to coniferous wood. As commonly used herein, the term “coniferous wood” refers to fibrous masses obtained from coniferous wood, such as, for example, fir, larch, spruce, cedar, cypress, yew, and pine species. Non-limiting examples include Caribbean pine, slash pine, Colorado spruce, balsam fir, Douglas fir, incense pine, Elliott pine, prickly spruce, Banks pine, radiata pine, white swart pine, broad-twisted pine, and redwood.

[0055] Resinous wood may be derived from a single type or species of tree or conifer, or a combination thereof (e.g., types or species such as 1, 2, 3, 4, 5, etc.), and / or may be non-modified and / or modified. Resinous wood may also be transgenic (i.e., genetically modified) and may be derived from any part of a tree or plant, such as branches, logs, roots, and stumps.

[0056] In some cases, resinous wood is substantially derived from logs. As those skilled in the art will understand, the term “log” should be used in a broad sense, typically referring to a harvested unit of tree that may have at least partially stripped bark, or may retain all or substantially all of the bark.

[0057] In other examples, resinous wood is substantially derived from stumps. Generally, the term “stump” refers to the remainder of a felled or harvested tree (e.g., the base of the tree) with at least the root portion extending into the ground. Stumps may be substantially debarked or may have some or substantially all of the bark remaining. Similarly, stumps may have some or substantially all of their roots removed before use in the methods of this disclosure.

[0058] For the purposes of this disclosure, resinous wood may be processed by a processor, such as by harvesting trees or removing stumps, before treatment with chemicals.

[0059] This method may further include an initial step of harvesting resinous wood from, for example, a plantation. In specific examples, the period from harvesting the resinous wood to treating it with chemicals is about 12 weeks or less (e.g., about 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 week, or any range therein), about 4 weeks or less, about 2 weeks or less, or about 1 week or less. For this purpose, the inventors have found that this time frame favorably minimizes the loss of the terpene fraction due to evaporation, thereby maximizing the yield and minimizing the effects of oxidation of the rosin fraction in the resinous wood, which can adversely affect its color and reactivity. Preferably, the resinous wood undergoes little or no further processing or treatment after harvesting and before treatment with chemicals (i.e., the resinous wood is essentially in its natural state).

[0060] As used herein, “process” or “treat” may mean, for example, contact, immersion, steam impregnation, spraying, suspension, immersion, saturation, soaking, wetting, rinsing, atmospheric pressure mechanical purification, impregnation, washing, submersion, and / or any modification, and / or combination thereof.

[0061] As those skilled in the art will understand, the process of treating resinous wood may simply involve passing the resinous wood through a bath containing a chemical. In other examples, the process of treating resinous wood may involve passing the resinous wood through a batch tank, which recirculates the chemical.

[0062] In certain cases, resinous wood is brought into contact with or treated with chemicals in a counterflow or counterflow manner. The terms “counterflow” or “counterflow” are understood to mean that the resinous wood being treated in a processing chamber or similar device generally flows or is carried in one direction, while the chemicals and / or terpene / rosin fractions extracted by the processing process flow in the opposite direction. For example, processes for treating resinous wood include passing the resinous wood through rotary extractors, loop extractors, drag chain extractors, and / or continuous belt extractors.

[0063] Preferably, the step of treating the resinous wood with a chemical is carried out for a certain period of time under conditions that are sufficient or suitable for extracting rosin and / or terpene fractions from the resinous wood.

[0064] For this purpose, the processing step is preferably carried out at least in part at a temperature of about 60°C to about 155°C, or any range within that, for example, but not limited to, about 70°C to about 140°C, or about 75°C to about 130°C. Preferably, the processing temperature is higher than the melting point of the rosin fraction at the pressure under which the processing step is performed (e.g., above about 73°C at atmospheric pressure). Similarly, the processing temperature is preferably lower than the boiling point of the terpene fraction (e.g., pinene) at the pressure under which the processing step is performed (e.g., below about 155 to 156°C at atmospheric pressure). In a specific example, the processing steps are approximately 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C The process is carried out at ℃, 113℃, 114℃, 115℃, 116℃, 117℃, 118℃, 119℃, 120℃, 121℃, 122℃, 123℃, 124℃, 125℃, 126℃, 127℃, 128℃, 129℃, 130℃, 131℃, 132℃, 133℃, 134℃, 135℃, 136℃, 137℃, 138℃, 139℃, 140℃, 141℃, 142℃, 143℃, 144℃, 145℃, 146℃, 147℃, 148℃, 149℃, 150℃, 151℃, 152℃, 153℃, 154℃, 155℃, or any range within that range. In certain cases, the processing steps are carried out at temperatures ranging from approximately 75°C to 155°C.

[0065] Furthermore, the processing steps can be performed for approximately 5 minutes to approximately 240 minutes or any range within that range, for example, not limited to, approximately 5 minutes to approximately 100 minutes, or approximately 10 minutes to approximately 90 minutes. In a particular example, the processing steps may be approximately 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 ,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, The process is carried out for 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240 minutes, or any range of time within that period. In a particularly preferred example, the processing step is carried out for approximately 15 to 120 minutes.

[0066] Regarding the processing steps, the agent is preferably present in an amount of about 10% to about 200% by weight of the resinous wood, or any range within that range, for example, not limited to, about 20% to about 150% by weight, about 30% to about 100% by weight, or about 50% to about 70% by weight (i.e., the ratio of the agent to the resinous wood). In certain embodiments, the agent is approximately 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, and 42% by weight of the resinous wood. %, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60% %, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78% , 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt% , 97% by weight, 98% by weight, 99% by weight, 100% by weight, 101% by weight, 102% by weight, 103% by weight, 104% by weight, 105% by weight, 106% by weight, 107% by weight, 108% by weight, 109% by weight, 110% by weight, 111% by weight, 112% by weight , 113% by weight, 114% by weight, 115% by weight, 116% by weight, 117% by weight, 118% by weight, 119% by weight, 120% by weight, 121% by weight, 122% by weight, 123% by weight, 124% by weight, 125% by weight, 126% by weight, 127% by weight, 128 Weight%, 129% by weight, 130% by weight, 131% by weight, 132% by weight, 133% by weight, 134% by weight, 135% by weight, 136% by weight, 137% by weight, 138% by weight, 139% by weight, 140% by weight, 141% by weight, 142% by weight, 143% by weight,144% by weight, 145% by weight, 146% by weight, 147% by weight, 148% by weight, 149% by weight, 150% by weight, 151% by weight, 152% by weight, 153% by weight, 154% by weight, 155% by weight, 156% by weight, 157% by weight, 158% by weight , 159% by weight, 160% by weight, 161% by weight, 162% by weight, 163% by weight, 164% by weight, 165% by weight, 166% by weight, 167% by weight, 168% by weight, 169% by weight, 170% by weight, 171% by weight, 172% by weight, 173% by weight It exists in any range within the following quantities: %, 174% by weight, 175% by weight, 176% by weight, 177% by weight, 178% by weight, 179% by weight, 180% by weight, 181% by weight, 182% by weight, 183% by weight, 184% by weight, 185% by weight, 186% by weight, 187% by weight, 188% by weight, 189% by weight, 190% by weight, 191% by weight, 192% by weight, 193% by weight, 194% by weight, 195% by weight, 196% by weight, 197% by weight, 198% by weight, 199% by weight, 200% by weight, or any range within these quantities.

[0067] Preferably, resinous wood is treated with an agent containing terpenes, consisting of terpenes, or essentially composed of terpenes. In this regard, the agent may be considered a terpene solvent. Terpenes, including those described herein and mixtures thereof, may be present in the agent in an amount of about 50% to about 100% by weight, or any range therein, for example, but not limited to, about 60% to about 80% by weight, about 70% to about 90% by weight, or about 80% to about 100% by weight. In the specific examples of this disclosure, the terpenes make up about 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, and 75% by weight of the drug. terpenes are present in the drug in amounts of 76% by weight, 77% by weight, 78% by weight, 79% by weight, 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 86% by weight, 87% by weight, 88% by weight, 89% by weight, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight, 100% by weight, or any range within these amounts. In a particularly preferred example of this disclosure, terpenes are present in amounts of about 90% by weight to about 100% by weight of the drug.

[0068] In further embodiments, the terpenes of the agent are at least partially recovered, recycled, or derived from terpene fractions previously extracted from resinous wood and / or agents previously used to treat resinous wood. In this regard, the recovered, recycled, or derived terpenes may be partially or completely purified or refined. In this regard, the method may include a further step of recycling terpene fractions extracted from resinous wood and / or agents for use as agents in the treatment process. Thus, the agent may contain terpenes with the same or similar composition as the terpene fraction extracted thereby. In addition, the recovered or recycled terpenes described herein may be subjected to one or more processes, such as purification or filtration, to make them more suitable and / or advantageous for use in the disclosure, without being converted to “high purity” or technical grade / purified (e.g., purity greater than 97%) terpenes or terpentines.

[0069] Preferably, the methods of the present disclosure extract at least partially rosin and / or terpene fractions present in resinous wood. For this purpose, the methods can extract 100% or less of the rosin and / or terpene fractions present in resinous wood. In certain examples, the methods can result in the extraction and / or recovery of about 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, or any range thereof of the rosin and / or terpene fractions present in resinous wood, compared to or relative to the amount of rosin and / or terpene fractions present in resinous wood before treatment with the methods described herein.

[0070] Preferably, the resinous wood is in a subdivided or fragmented form for processing by the method described herein. For this purpose, the resinous wood may include chips, flakes, strands, pellets, etc. Thus, the method of this embodiment further includes a step prior to or preceding the desizing, subdividing, fragmenting, or reducing (e.g., chipping, grinding, flaking, shredding, crushing) of the resinous wood after harvesting, although this step is prior to the chemical treatment. In this regard, solid wood such as logs and stumps is preferably subdivided into smaller pieces or fragments, such as strands, fibers, flakes, and / or chips, before their processing to facilitate the extraction of rosin and / or terpene fractions from them. In some examples, the resinous wood is subjected to a desizing step to achieve a target particle size, such as those described herein. Thus, the resinous wood preferably includes wood chips or flakes derived from one or more resinous trees, such as those described above. It is further assumed that the wood may be subdivided by any suitable means known in the art, preferably by a conventional wood chipper and / or hammer mill.

[0071] Considering the above, resinous wood is approximately 0.01 cm 3 ~about 1cm 3 (For example, approximately 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1cm) 3 It may include a wooden portion having a volume of , or any range thereof.

[0072] Furthermore, resinous wood treated with chemicals is approximately 0.03 cm thick. 2 ~about 0.5cm 2 (For example, approximately 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5 cm) 2It may include a wooden portion having a surface area of ​​, or any range thereof.

[0073] Furthermore, resinous wood may include wood portions having dimensions such as length, width, or diameter ranging from approximately 0.01 cm to approximately 1 cm (for example, approximately 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1 cm, or any range within that range). In some examples, the dimensions of the wood portions are approximately 0.1 to approximately 0.35 cm.

[0074] Based on the above, the method of this embodiment may further include a step of screening the resinous wood before chemical treatment to ensure an appropriate size and / or surface area. The portions of resinous wood removed or selected by this screening step may then be subjected to further subdivision steps until an appropriate size or surface area is achieved for chemical treatment. Thus, resinous wood may be screened before treatment to remove wood portions having a volume, surface area, and / or dimensions greater than any of these above values. In some examples, resinous wood is screened before treatment to remove wood portions having dimensions such as length, width, or diameter greater than about 0.15 cm, about 0.20 cm, about 0.25 cm, about 0.30 cm, about 0.35 cm, about 0.40 cm, about 0.45 cm, or about 0.50 cm.

[0075] Generally, the time between the initial step of subdividing the resinous wood and the treatment of the resinous wood with chemicals may be about 12 hours or less (e.g., 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.25, 0.1 hours, or any range thereof), about 8 hours or less, about 4 hours or less, about 2 hours or less, about 1 hour or less, about 30 minutes or less, about 15 minutes or less, or about 5 minutes or less. In this regard, those skilled in the art will understand that the step of treating the resinous wood may occur almost immediately after the subdivision step. Again, this ensures that the terpene and rosin fractions are retained in the log or wood core for as long as possible without loss of terpene due to evaporation and / or adverse effects on the quality of the rosin fraction due to oxidation.

[0076] Preferably, the method of this embodiment further includes the step of separating a rosin fraction from a terpene fraction extracted from resinous wood. As used herein, the term “separating a rosin fraction from a terpene fraction” means separating a mixture of molecules containing rosin and terpenes into a first fraction of molecules having a higher concentration of rosin or substantially containing rosin, and a second fraction of molecules having a higher concentration of terpenes or substantially containing terpenes, including terpenes from the drug. In this regard, it will be understood that the terpene fraction can be separated from the rosin fraction together with the drug, since the drug also contains terpenes and is preferably derived from a terpene fraction previously extracted from resinous wood, as described herein. It is assumed that such separation can be carried out by any method or means known in the art, such as distillation, fractionation, chromatographic separation, crystallization, or extraction.

[0077] In some cases, the respective rosin and terpene fractions are separated, at least partially, by distillation. The term “distillation” refers to the process of physically separating chemical components into a vapor phase or vapor stream and a liquid phase or liquid stream based on the boiling points of each component and the difference in vapor pressure at a particular temperature and pressure. Distillation is typically carried out in a distillation column or chamber, which usually includes a series of vertically spaced plates. The feed stream enters the distillation column at an intermediate point, dividing the column into two sections. The upper section may be called the rectifying section, and the lower section may be called the stripping section. Condensation and vaporization occur at each plate, with lower boiling point components, such as the terpene fraction, rising to the top of the distillation column, and higher boiling point components, such as the rosin fraction, descending to the bottom. A reboiler is located at the base of the distillation column to add thermal energy. As those skilled in the art will understand, energy recovery and process flow recycling can be applied to improve plant efficiency. For the purposes of this disclosure, the “bottom” product or liquid flow containing, consisting of, or essentially derived from the rosin fraction may then be removed directly from the base of the distillation column. A reflux pump is generally used to maintain the flow in the rectifying section of the distillation column by pumping a portion of the distillate back into the distillation column.

[0078] A condenser is typically located above a distillation column and operably connected to it to condense the vapor or gaseous stream emanating from the top of the distillation column to produce a distillate. The associated condenser and liquid separation vessel that may be used with the distillation column may be of any conventional design. In this disclosure, the distillate preferably includes a terpene fraction, an agent used to extract the terpene fraction, and optionally a water fraction, if vapor is used in the distillation process. Thus, the method may further include a step of separating the terpene fraction and / or agent from the distillate, in particular, if the distillate includes, for example, a water fraction.

[0079] Preferably, the distillation conditions, such as the feed rate, feed pressure, feed temperature, column pressure, column temperature, reflux rate, and distillation time, are suitable for the efficient separation of rosin and terpene fractions (including pharmaceuticals) within the distillation column.

[0080] In certain cases, during the distillation process, the mixture of terpene fraction, rosin fraction, and pharmaceutical is heated to approximately 150°C to 250°C.

[0081] As will be understood by those skilled in the art, one or more steps, or parts thereof, of the methods of this embodiment may be carried out under pressure or under vacuum. For example, one or more steps, or parts thereof, of the methods of the present disclosure may be carried out at a pressure of about 0 psi to about 120 psi, or any range within that range, for example, but not limited to, about 25 psi to about 75 psi, or about 40 psi to about 60 psi. In certain examples of this disclosure, one or more steps of the method, or parts thereof, are approximately 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 6 The process is carried out at pressures of 4, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120 psi, or any range within that range. In some examples, the process of treating resinous wood with chemicals, or a part thereof, is carried out at pressures of approximately 10 psi to approximately 75 psi. In various examples, the process of separating the terpene fraction and the rosin fraction, or part thereof, is carried out at a pressure of approximately 25 psi to 120 psi.

[0082] Preferably, the method of this embodiment further includes a subsequent step of heating or heat-treating the resinous wood treated with the chemical to at least partially remove any residual portions of the chemical and / or terpene fractions therefrom. Such heating is expected to be carried out by any method or means known in the art to thermally evaporate any residual portions of the chemical and terpene fractions from the treated resinous wood. In a particular example, the treated resinous wood is heat-treated at a temperature of about 150°C to about 300°C (e.g., about 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300°C, or any range therein). This heat treatment process can also be carried out for a time of approximately 5 to 30 minutes (for example, approximately 5, 10, 15, 20, 25, 30 minutes, or any range within that range).

[0083] In certain cases, resinous wood, after being treated with a chemical, is steam-treated in a desolvator or desolvator-toaster to generate a further gaseous flow. This further gaseous flow may come into contact with further separators, such as further condensers, to facilitate the separation of further portions of the chemical and terpene fractions from the water fraction derived from the steam. Considering the density difference between the chemical / terpene fraction and the water fraction, gravity separation may be used for separation, with the less dense chemical / terpene fraction floating above the denser water fraction. The remaining portions of the chemical and terpene fractions can then be removed from the further separators or condensers and transferred to a central storage container as needed.

[0084] It will be understood that resinous wood may have downstream uses following treatment by the methods described herein. For example, treated resinous wood may be used as mulch, animal bedding (due to being sterilized in the process), a purified or concentrated source of lignin and / or cellulose for further chemical production, and as a raw material for wood pellets or biofuels, but is not limited to these uses. In some examples, treated resinous wood may be further treated by methods known in the art (e.g., kraft pulping, see also PCT / AU2015 / 050389) to produce cellulose materials suitable for paper, cardboard, and textile production. In other examples, treated resinous wood may be further treated by methods known in the art (e.g., PCT / AU2015 / 050390) to produce partially hydrolyzed lignocellulose materials suitable for downstream fermentable sugar and biofuel production.

[0085] In some examples, the method further includes a final scrubbing step of the residual gas stream. In this regard, the residual gas stream from one or more separators or condensers may be brought into contact with a scrubbing device, such as a wet scrubber or other scrubbing devices known in the art, to remove any further residual terpene fractions and / or agents therefrom. These further residual terpene fractions and / or agents may then be separated by yet another separator or condenser or decanting and transferred to a central storage container for the terpene fractions and agents.

[0086] Preferably, the rosin and / or terpene fractions extracted from resinous wood by the method of this embodiment are free from or substantially free from contaminants that may be present with other solvents or tapping extraction methods known in the art (e.g., hexane, methyl ethyl ketone, hydrocarbons, petrochemicals, sulfides, sulfates, heavy metals, acids, growth hormones, etc.) (e.g., having about 0.5% by weight, 0.2% by weight, 0.1% by weight, or 0.05% by weight or less of contaminants in the fraction).

[0087] In some examples, the terpene fraction contains approximately 50% to 100% by weight of pinene (e.g., approximately 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100% by weight, or any range within that range). As used herein, the term "pinene" refers to the bicyclic monoterpene chemical compound of the formula (1S,5S)-2,6,6-trimethylbicyclo[3.1.1]hept-2-ene. Two structural isomers of pinene exist in nature: α-pinene and β-pinene, both of which are chiral. As used herein, pinene may be α-pinene, β-pinene, or a mixture thereof, for example, a 50-50 mixture. As will be understood by those skilled in the art, the components of the terpene fraction and / or the percentage of pinene may vary, for example, with the type, species, and age of the resinous wood.

[0088] The terpene fraction extracted from resinous wood preferably contains less than about 25% by weight of terpene polymers such as diterpenes and triterpenes (e.g., less than about 25% by weight, 24% by weight, 23% by weight, 22% by weight, 21% by weight, 20% by weight, 19% by weight, 18% by weight, 17% by weight, 16% by weight, 15% by weight, 14% by weight, 13% by weight, 12% by weight, 11% by weight, 10% by weight, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.5% by weight, 1% by weight, 0.5% by weight, 0.4% by weight, 0.3% by weight, 0.2% by weight, 0.1% by weight, or any range thereof). In this regard, the terpene fraction may be considered to contain or substantially contain no terpene polymers. The term "terpene polymer" is used herein to refer to oligomers or polymers containing one or more structural repeating units derived from terpenes. These may include, for example, homopolymers and copolymers.

[0089] The terpene fraction extracted from resinous wood preferably contains less than about 15% by weight of synthetic pine oil, such as terpene alcohols, of the terpene fraction (e.g., about 15% by weight, 14% by weight, 13% by weight, 12% by weight, 11% by weight, 10% by weight, 9% by weight, 8% by weight, 7% by weight, 6% by weight, 5% by weight, 4.5% by weight, 4% by weight, 3.5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.5% by weight, 1% by weight, 0.5% by weight, 0.4% by weight, 0.3% by weight, 0.2% by weight, less than 0.1% by weight, or any range within that range). In this regard, the terpene fraction may be considered to contain or substantially contain no synthetic pine oil. For this purpose, the absence of acid in this extraction method advantageously prevents or minimizes the conversion of α- and β-pinene to synthetic pine oil.

[0090] Preferably, the rosin fraction extracted from resinous wood is nearly colorless or very pale. In certain cases, the rosin fraction has a Gardner color number of about 8 or less (e.g., about 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.5, 1, and any range therein). In certain cases, the rosin fraction has a Gardner color number of about 5 or less. In other cases, the rosin fraction has a Gardner color number of about 3 or less. In this regard, the present method advantageously facilitates the production of rosin fractions with little to no color, which is a known drawback of prior art solvent extraction methods (see, for example, US4,906,733).

[0091] As used herein, the term “Gardner color” refers to a visual scale originally developed to describe the colors of commercially available chemical products such as rosin. A smaller value on the Gardner scale indicates a lighter color of the chemical product. The coloration of the rosin fraction may be determined by any means known in the art, such as comparison with a Lovibond disc. Those skilled in the art will further understand that color charts defining colors, such as those defining rosin color from M, N, WG, WW, X, and XA, may be used to estimate the color of the rosin fraction or as an alternative to the Gardner scale (e.g., X or WW is 5 on the Gardner scale). In certain examples, the rosin fractions described herein have not been subjected to any further decolorization steps known in the art (e.g., contact with a decolorizing agent) (see, for example, US 4,906,733).

[0092] In certain cases, the rosin fraction has an acid value of approximately 160 to approximately 175 (e.g., approximately 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, and any range within that range). In certain cases, the rosin fraction has an acid value of approximately 162 to approximately 170. In one example, the rosin fraction has an acid value of approximately 165. Those skilled in the art will understand that the acid value is the mass of milligrams of potassium hydroxide (KOH) required to neutralize one gram of the chemical, or in this case, rosin or a rosin derivative. For this purpose, the acid value is a measure of the amount of carboxylic acid groups present in the rosin fraction. The acid value of the rosin fraction can be determined by any method known in the art, such as titration using KOH of a solution of rosin in a suitable solvent, or by using an indicator to determine the endpoint (as described, for example, in ASTM Method D 465-05 (2010)).

[0093] Preferably, the rosin fraction contains an abietic acid content or concentration in the range of about 15% to about 35% by weight of the rosin fraction (e.g., about 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35% by weight, or any range thereof). In some specific examples, the abietic acid content of the rosin fraction is about 15% to about 25% by weight or about 15% to about 20% by weight of the rosin fraction. In one particular example, the abietic acid content of the rosin fraction is about 20%. Those skilled in the art will understand that abietic acid is the main component of rosin and is an abietanediterpenoid, which is abieta-7,13-diene substituted with a carboxyl group at position 18.

[0094] In a further embodiment, the disclosure provides terpene fractions produced according to the above method.

[0095] Therefore, the terpene fraction may be as described above.

[0096] In some examples, the terpene fraction contains at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight of pinene (e.g., about 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, Includes 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100% by weight, or any range within those amounts.

[0097] In various cases, the terpene fraction is substantially free of contaminants.

[0098] In certain cases, the terpene fraction contains terpene polymers such as diterpenes and triterpenes in amounts of less than 20% by weight, less than 10% by weight, less than 5% by weight, less than 2.5% by weight, or less than 1% by weight of the terpene fraction.

[0099] In certain cases, the terpene fraction contains less than approximately 15% by weight, less than approximately 10% by weight, less than approximately 5% by weight, less than approximately 2.5% by weight, less than approximately 1% by weight, or less than approximately 0.5% by weight of synthetic pine oil.

[0100] In relevant embodiments, this disclosure has the following characteristics: (a) comprising at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight of pinene in the isolated terpene fraction, (b) substantially free of contaminants, (c) The isolated terpene fraction contains less than about 25% by weight, less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, or less than 1% by weight of terpene polymers, and (d) Provide an isolated terpene fraction comprising one or more of the following: less than about 15% by weight, less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, less than about 1% by weight, or less than about 0.5% by weight of synthetic pine oil.

[0101] In certain examples, the isolated terpene fraction contains at least about 75% by weight of pinene, is substantially free of contaminants, contains less than about 2.5% by weight of terpene polymers, and contains less than about 2.5% by weight of synthetic pine oil.

[0102] For the purposes of this disclosure, “isolated” means material that has been removed from its natural state or otherwise subjected to artificial manipulation. An isolated material may substantially or essentially not contain the components normally associated with it in its natural state, or it may be manipulated to be in an artificial state with the components normally associated with it in its natural state. Preferably, the isolated substance is in its natural or nearly natural form.

[0103] In another aspect, the disclosure relates to a rosin fraction produced according to the method of the first aspect mentioned.

[0104] Therefore, the rosin fraction may be as described above.

[0105] In certain cases, the rosin fraction has a Gardner color number of approximately 8 or less.

[0106] In various cases, the rosin fraction is substantially free of contaminants.

[0107] In certain cases, the rosin fraction has an acid value of approximately 160 to 175.

[0108] In another related aspect, this disclosure has the following characteristics: (a) Includes a number of Gardner colors of approximately 8 or less, approximately 5 or less, or approximately 3 or less, (b) Free from or substantially free from contaminants (c) containing acid values ​​of approximately 160 to approximately 175 (for example, approximately 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, and any range within that range), (d) Provide an isolated rosin fraction containing one or more of the following abietic acid content: about 15% to about 35% by weight of the isolated rosin fraction (e.g., about 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, and any range thereof), about 15% to about 25% by weight, or about 15% to about 20% by weight.

[0109] In certain cases, the isolated rosin fraction contains a Gardner color number in the range of approximately 3 to approximately 5, is free of or substantially free of contaminants, has an acid value of approximately 163 to approximately 170, and contains an abietic acid content in the range of approximately 17% to approximately 22%.

[0110] In a particular example, the isolated rosin fraction contains a Gardner color number of approximately 3, is free of or substantially free of contaminants, has an acid value between approximately 165, and contains approximately 20% abietic acid.

[0111] In another embodiment, the Disclosure provides a method for producing a polymer, comprising the step of processing a rosin fraction and / or terpene fraction produced according to a method described herein, such as by chemical treatment, to produce a polymer. In some examples, the method relates to the production of a rosin polymer, and the method comprises the step of processing a rosin fraction produced according to a method described herein to produce a rosin polymer. In other examples, the method relates to the production of a terpene polymer, and the method comprises the step of processing a terpene fraction produced according to a method described herein to produce a terpene polymer.

[0112] In related embodiments, this disclosure relates to polymers produced in accordance with the above embodiments.

[0113] The term "polymer" refers to compounds prepared by polymerizing monomer units, such as terpene and rosin monomer units, whether of the same or different types. Therefore, the general term polymer encompasses the terms homopolymer (i.e., polymers prepared from only one type of monomer) and interpolymer (i.e., polymers prepared by polymerizing at least two different types of monomers).

[0114] Polymerized rosin compounds typically possess high levels of pigment dispersion, miscibility, cohesiveness, adhesion, and other properties, and are therefore advantageously used as binders or additives in a wide range of applications, including printing inks, paints, pressure-sensitive adhesives or glues, and fluxes. Terpene polymers can also be used as bioplastics and biofuels.

[0115] Various methods are used to produce polymerized rosin compounds and polymerized terpene compounds. These may include, for example, the use of solvents (e.g., organic solvents such as toluene or xylene), and / or catalysts such as acid catalysts (e.g., aliphatic sulfonic acids, formic acid, p-toluenesulfonic acid, methanesulfonic acid), metal catalysts, and Friedel-Crafts catalysts.

[0116] In another embodiment, the present disclosure provides a method for producing an ester, comprising the step of treating a rosin fraction and / or terpene fraction produced according to a method described herein to produce an ester. This method may include esterifying the rosin fraction and / or terpene fraction with an esterifying agent such as an alcohol.

[0117] In some examples, the method relates to the production of rosin esters, and the method includes the step of processing a rosin fraction produced according to the method described herein to produce a rosin ester.

[0118] In another example, the present method relates to the production of terpene esters, and the method includes the step of processing a terpene fraction produced according to the method described herein to produce terpene esters.

[0119] The term "ester" broadly defines a chemical compound derived from an acid (e.g., organic or inorganic) in which at least one -OH (i.e., hydroxyl) group is substituted by an -O-alkyl (i.e., alkoxy) group.

[0120] The carboxylic acid groups in the rosin fraction can be converted to rosin esters through reactions with one or more alcohols, such as glycerol, pentaerythritol, methanol, and tri-ethylene glycol. In some examples, the ester or rosin ester is either a glycerol ester of rosin or contains a glycerol ester of rosin. For example, the rosin fraction may be reacted or treated with glycerin, such as food-grade glycerin, to produce a glycerol ester. Glycerol esters of rosin represent oil-soluble food additives also known as glyceryl abaitate or ester gum. Glycerol esters of rosin function as stabilizers and / or thickeners in some foods and beverages. They are food-grade materials used in foods, beverages, and cosmetics to keep oils suspended in water. Exemplary foods and beverages containing glycerol esters of rosin include fruit and citrus flavored sodas, lemonades, vitamin-fortified waters, sports drinks, chewing gums, fruit coatings, and confectionery inks.

[0121] In a relevant aspect, this disclosure relates to esters produced according to the methods of the prior aspects.

[0122] In the final embodiment, the Disclosure provides an apparatus or system for extracting rosin and / or terpene fractions from resinous wood, comprising a processing chamber for treating the resinous wood with a chemical agent containing, comprising, or essentially comprising terpenes.

[0123] In some examples, the processing chamber is a countercurrent extractor, such as those described above, or comprises a countercurrent extractor.

[0124] In a particular example, the apparatus further comprises a distillation chamber communicating with the processing chamber, which is used to separate the rosin and terpene fractions extracted from the resinous wood.

[0125] In various examples, the apparatus further comprises a desolvator communicating with the processing chamber, which can remove at least partially the residual portion of the chemical and / or terpene fraction from the chemically treated resinous wood by heating, such as by steam treatment.

[0126] In certain cases, the apparatus further includes a separator, such as a condenser, which is in communication with the distillation chamber, and the separator is for separating the terpene fraction from the distillate produced by the distillation chamber.

[0127] In some examples, the apparatus further includes a scrubbing device such as a wet scrubber.

[0128] In some examples, the device is configured to operate in a continuous or semi-continuous manner.

[0129] Preferably, the apparatus is for use in the method of the first embodiment.

[0130] A specific embodiment of the apparatus or system 10 is shown in Figure 1. Referring to Figure 1, the apparatus 10 includes a first shredder 15 for shredding the resin wood before it enters the processing chamber 20. Once the resin wood has been shredded by the first shredder, it is transferred to a screen 16 to remove any excessively large and / or excessively small pieces of the resin wood. These excessive pieces can then be transferred to a second shredder (not shown) or returned to the first shredder 15 to reduce them to a size suitable for processing.

[0131] Following the screening process, appropriately sized portions of resinous wood are transferred to storage bins 17, which are in communication with the processing chamber 20. The storage bins 17 function to level the resinous wood stored within them and to control the amount of resinous wood entering the processing chamber 20, which is equipped with an inlet for receiving the resinous wood to be treated with a terpene-containing agent, as previously described.

[0132] The processing chamber 20 is designed to process resinous wood in a backflow manner with a chemical at a temperature and / or pressure specified by the user, such as those provided above. Preferably, there is little or no agitation of the resinous wood while it is in the processing chamber 20. In the provided embodiments, the processing chamber 20 is a rotary extractor, such as a rotocellent extractor, or includes a rotary extractor, which generally comprises a cylindrical chamber containing a plurality of separated processing cells (not shown) for receiving resinous wood. The cylindrical chamber 21 rotates around a central shaft at a desired speed, while the chemical is applied as a spray to the separated processing cells. In this regard, the processing chamber 20 may include a plurality of nozzles or sprayers (not shown) for spraying the chemical onto the resinous wood.

[0133] As the resinous wood moves through the processing chamber 20, it is progressively treated within the processing cell by a spray applicator. The spray applicator delivers the chemical onto the resinous wood, and the chemical, terpene fraction and / or rosin fraction are then discharged therefrom and collected in their respective collection trays by gravity or vacuum. "Fresh" chemical (i.e., chemical that does not contain rosin fraction or contains only low concentrations) is provided by the spray applicator at or near the end of the processing cycle and then enters the final or distal collection tray, flowing against the movement of the resinous wood through the processing chamber 20.

[0134] In this regard, the chemicals collected in the collection trays are then pumped back to their respective sprayers through pipes or conduits. In this manner, the processing chamber 20 allows for continuous or semi-continuous countercurrent processing of the resinous wood chemicals or contact with the resinous wood chemicals to partially or completely remove rosin and terpene fractions from it with minimal chemical use. The chemicals collected in the most proximal collection trays typically contain the highest concentrations of terpene and rosin fractions extracted from the resinous wood and are then transferred by pipe to the distillation column 25. Thus, the cleanest or freshest chemicals come into contact with the "cleanest" resinous wood, and the chemicals with the highest concentrations of rosin come into contact with the resinous wood as soon as they enter the processing chamber 20.

[0135] In an alternative example, it will be understood that the rotary extractor may be replaced by a conveyor, such as a belt conveyor, to facilitate the movement of the resinous wood through the processing chamber 20.

[0136] As can be seen in Figure 1, the apparatus 10 further includes a distillation column 25 in fluid or gas communication with the processing chamber 20, the distillation column being configured to facilitate the separation of the terpene fraction and the pharmaceutical from the rosin fraction. In this embodiment, the distillation column 25 is a continuous vapor distillation column, and vapor distillation may be carried out by conventional vapor distillation methods as known in the art. The distillation chamber 25 comprises a series of vertically spaced plates 26, a reboiler 27 located at its base, and a first condenser 30 connected to and in fluid communication with the upper part thereof. A feed stream from the processing chamber 20 containing the pharmaceutical, terpene fraction and rosin fraction enters the distillation column 25 at or toward its midpoint via an inlet (not shown), contacts the plates, thereby resulting in the generation of a gaseous stream containing the pharmaceutical, terpene fraction and water fraction from added vapor, and a liquid stream containing the rosin fraction. The liquid stream containing the rosin fraction collects at the base of the distillation column 25 and can then be removed directly from the distillation column 25 for storage in the storage container 35.

[0137] The gas flow rises within the distillation chamber 25 and collects in the first condenser 30, where it cools the terpene fraction, pharmaceutical, and water fraction of the components to form a distillate. Based on their respective densities, the terpene fraction and pharmaceutical are separated from the water fraction by gravity, then decanted and transferred to the central storage chamber 40.

[0138] Referring to Figure 1, the apparatus 10 further comprises a desolvator 50, to which the resinous wood may be transferred after treatment with the chemicals. The desolvator 50 is designed to heat-treat the resinous wood treated with superheated steam. The desolvator 50 comprises a chamber with a floor, on which a series of permeable trays are positioned for receiving the resinous wood. The trays are heated by steam (and / or other heating medium such as oil), and the resinous wood may be heated and permeated by passing through the steam. Thus, a further gaseous stream containing steam, as well as a mixture of vaporized residual portions of the chemicals and terpene fractions, flows upward within the desolvator 50 to a second condenser 60 operably connected thereto. Similar to the first condenser 30, the second condenser 60 is designed to separate the residual portions of the chemicals and terpene fractions from the water fraction derived from the superheated steam. Once separated, the residual portions of the chemicals and terpene fractions may be transferred to a central storage chamber 40.

[0139] As shown in Figure 1, the apparatus further comprises a wet scrubber 70. Those skilled in the art will understand that the wet scrubber 70 is designed to protect the apparatus or system 10 from high pressure or overpressure by having, each condenser 30, 60 have a waste gas or volatile gas vent (not shown), are sealed and connected to the wet scrubber 70 by pipes. The wet scrubber 70 works by spraying water onto the gas streams originating from the first and second condensers 30, 60, and frothing the gas streams through a certain level of oil to further capture any non-condensable gases, such as terpene-containing gases. This process may be controlled by a vacuum pump 80 positioned to ensure a good vapor or gas stream through the condensers 30, 60 and to generate a slight vacuum to reach the atmosphere for any non-condensable gases. Any terpene fractions extracted by the wet scrubber 70 may be further transferred to a central storage chamber 40.

[0140] Specific aspects of this disclosure are described in the following numbered descriptions illustrating exemplary uses of the disclosure for coniferous timber. It will be understood that this disclosure is not limited to these exemplary uses for coniferous timber.

[0141] 1. A method for extracting rosin and / or terpene fractions containing components or derivatives thereof from coniferous wood, comprising the step of treating / contacting coniferous wood with an agent containing terpenes, consisting of terpenes, or essentially composed of terpenes, thereby extracting rosin and / or terpene fractions from coniferous wood.

[0142] 2. The method according to description 1, further comprising an initial step of subdividing coniferous timber.

[0143] 3. The method according to description 2, wherein the period between the initial step of subdividing the coniferous wood and the treatment of the coniferous wood with chemicals is approximately 8 weeks or less, approximately 4 weeks or less, or approximately 2 weeks or less.

[0144] 4. The method according to any one of the prior descriptions, further comprising the step of separating a rosin fraction and a terpene fraction extracted from coniferous wood.

[0145] 5. The method according to Description 4, wherein the separation of the rosin fraction and the terpene fraction is carried out at least partially by distillation to produce a distillate containing, essentially consisting of, or comprising the terpene fraction, and a residual rozin fraction containing, essentially consisting of, or comprising the rosin fraction.

[0146] 6. The method according to description 5, further comprising the step of separating the terpene fraction from the distillate.

[0147] 7. The method according to any one of the preceding descriptions, further comprising a subsequent step of heating coniferous wood treated with a chemical to remove at least partially any residual portion of the chemical and / or terpene fraction.

[0148] 8. The method according to any one of the preceding descriptions, wherein the process of treating coniferous wood with a chemical is performed for a period of time of approximately 15 minutes to approximately 120 minutes.

[0149] 9. The method according to any one of the preceding descriptions, wherein the process of treating coniferous wood with a chemical is carried out at a temperature of 75°C to approximately 135°C.

[0150] 10. The method according to any one of the preceding descriptions, wherein the process of treating coniferous wood with a chemical is carried out at a pressure of approximately 10 psi to approximately 75 psi.

[0151] 11. The method according to any one of the preceding descriptions, wherein coniferous wood is treated in a countercurrent / reverse flow manner using chemicals.

[0152] 12. The method according to any one of the preceding descriptions, wherein the rosin and / or terpene fraction extracted from coniferous wood is substantially free of contaminants.

[0153] 13. A terpene fraction produced according to the method described in any one of descriptions 1 to 12.

[0154] 14. The terpene fraction described in description 13, comprising at least about 65%, at least about 70%, at least about 75%, or at least about 80% pinene.

[0155] 15. The terpene fraction described in description 13 or 14, wherein the terpene fraction is substantially free of contaminants.

[0156] 16. A terpene fraction according to any one of descriptions 13 to 15, comprising terpene polymers such as diterpenes and triterpenes in amounts of less than approximately 20%, less than approximately 10%, less than approximately 5%, less than approximately 2.5%, or less than approximately 1%.

[0157] 17. Rosin fraction produced according to the method described in any one of descriptions 1 to 12.

[0158] 18. The rosin fraction described in description 17, having approximately 8 or fewer Gardner colors.

[0159] 19. The rosin fraction described in description 17 or 18, wherein the rosin fraction is substantially free of contaminants.

[0160] 20. A rosin fraction having an acid value of approximately 160 to 175, as described in any one of descriptions 17 to 19.

[0161] 21. Apparatus for extracting rosin and / or terpene fractions from coniferous wood, comprising a processing chamber for treating the coniferous wood with a chemical agent containing, consisting of, or essentially composed of terpenes.

[0162] 22. The apparatus according to description 21, wherein the processing chamber is a countercurrent extractor or comprises a countercurrent extractor.

[0163] 23. The apparatus according to description 21 or 22, further comprising a distillation chamber in communication with the processing chamber, the distillation chamber being for separating rosin and terpene fractions extracted from coniferous wood.

[0164] 24. The apparatus according to any one of descriptions 21 to 23, further comprising a desolvator communicating with a processing chamber, the desolvator for heating coniferous wood treated with a chemical therefrom to remove at least partially any residual portions of the chemical and / or terpene fraction.

[0165] 25. The apparatus according to any one of descriptions 21 to 24, further comprising a separator in communication with a distillation chamber, the separator being for at least partially separating a terpene fraction from the distillate produced by the distillation chamber.

[0166] 25. The apparatus according to any one of descriptions 21 to 25, further comprising a scrubbing device.

[0167] 26. The apparatus described in any one of descriptions 21 to 25 for use in the method described in any one of descriptions 1 to 12.

[0168] To facilitate understanding and practical application of the present invention, certain preferred embodiments are described by the following non-limiting examples. [Examples]

[0169] Example 1 This embodiment relates to the desizing and size distribution of resinous wood treated by the method described herein.

[0170] wood processing Several tons of resinous pine stumps and logs are passed at high speed through a Vermeer grinder in the feed setting to create large chips that are then fed to a hammer mill. The chips are fed into a bin feed hopper to regulate the flow rate into the processing process. The bin feed flows on a conveyor to direct the flow of wood chips towards the hammer mill.

[0171] In this embodiment, the objective was to reduce the chip size to dimensions of 1 / 8 inch to 1 / 2 inch (3.175 mm to 12.7 mm) and minimize deviation from this range. Fine chips smaller than 3 mm can pass through the sieve and enter the extractor without issue.

[0172] The size distribution data for wood chips is shown in Figures 2A and 2B. As these figures show, the majority of the desized resinous wood is a suitable size for subsequent processing in the extractor or processing chamber.

[0173] [Table 1]

[0174] bulk density ● Bulk density of wood chips from logs that have passed through a chipper and hammer mill: 312.65 kg / m³ 3 ● Bulk density of wood chips from tree stumps that have passed through a Vermeer grinder and hammer mill: 266.9 kg / m³ 3

[0175] Example 2 This embodiment provides one example of plant operating conditions for terpene and rosin extraction based on the method described herein.

[0176] feeding speed Considering the volume of the processing chamber or extractor, and the current bulk density of the wood chips being processed, this system can handle approximately 125 tons per day for stumps or 150 tons per day for logs.

[0177] Extractor conditions / solvent supply ●Full rotation of wood chips takes 1.5 hours - holding time in the extractor ○ Washing time using extractants: Approximately 45 to 60 minutes (for example, approximately 53 minutes) ○The ratio of solvent to wood in the extractor (i.e., the ratio of solid to liquid) is approximately 0.50 to 0.60 (ranging from approximately 0.3 to 1.5 depending on the flow of wood chips and solvent). ○Place the six solvent sprayers after the first half of the rotation and apply the extractant to the wood chips. ○The remaining time inside the extractor (approximately 40-50 minutes) is for the discharge of wood chips before the exit chute and for the exit process itself. ●The temperature of the wood chips used as solvent / chemical detergent is approximately 90-100°C. Heaters are present on each recirculation line to maintain the temperature inside the extractor. ● Solvent / chemical supply rate to the extractor at 50 L / min, 90°C

[0178] desolvator Next, the solvent / chemical-treated wood chips from the extractor are supplied to the desolvator. The solvent / chemical-treated wood chips are approximately 25% solvent-saturated (dry wood chip weight + 25% terpene). The time required for the wood chips to move from stages 1-5 was 1 minute 30 seconds, and the final holding time for the 5 stages with raw steam injection was approximately 9 minutes.

[0179] Distillation chamber Each rosin and terpene fraction can be separated from each other in the distillation chamber, as described above.

[0180] result Terpenes: ●Currently observed yields: Average = approximately 1.1% for logs, approximately 4.3% for stumps, range = 1-5% (depending on the composition of the initial raw materials of resinous wood) ●Color: Straw yellow to pale yellow Rosin: ●Color of the rosin produced: translucent reddish-brown ● Acid value: Observation range = 160~175 ● Dropping point: Observation range = 69~75℃ ●Yield: Average = approximately 8%, range is approximately 5-20% (depending on the composition of the initial raw materials of the resinous wood)

[0181] Tables 2 and 3 provide examples of the physicochemical properties of rosin and terpene fractions extracted by the methods described herein.

[0182] [Table 2]

[0183] [Table 3]

[0184] Throughout this specification, the aim has been to describe preferred embodiments of the disclosure without limiting it to any one embodiment or particular set of features. Therefore, it will be understood by those skilled in the art that various modifications and changes can be made to the specific embodiments described without departing from the scope of the disclosure.

[0185] All computer programs, algorithms, patents, and scientific literature referenced herein are incorporated herein by reference.

Claims

1. A method for extracting rosin and / or terpene fractions from resinous wood, comprising the steps of treating the resinous wood with an agent containing terpenes, consisting of terpenes, or essentially composed of terpenes, or contacting the resinous wood with the agent to thereby extract the rosin and / or terpene fractions from the resinous wood.

2. The method according to claim 1, further comprising an initial step of subdividing or desizing the resinous wood at least partially.

3. The method according to claim 2, wherein the period between the initial step of subdividing the resinous wood and the treatment of the resinous wood with the chemical agent is approximately 8 weeks or less, approximately 4 weeks or less, or approximately 2 weeks or less.

4. The method according to any one of the prior claims, further comprising the step of separating the rosin fraction and the terpene fraction extracted from the resinous wood.

5. The method according to claim 4, wherein the separation of the rosin fraction and the terpene fraction is carried out at least partially by distillation to produce a distillate containing, essentially consisting of, or comprising the terpene fraction, and a residual filtrate containing, essentially consisting of, or comprising the rosin fraction.

6. The method according to claim 5, further comprising the step of separating the terpene fraction from the distillate.

7. The method according to any one of the prior claims, further comprising the subsequent step of heating the resinous wood treated with the agent, thereby removing at least partially any residual portion of the agent and / or the terpene fraction.

8. The method according to any one of the prior claims, wherein the step of treating the resinous wood with the chemical is performed for a time of about 15 minutes to about 120 minutes.

9. The method according to any one of the prior claims, wherein the step of treating the resinous wood with the chemical agent is carried out at a temperature of 75°C to about 155°C.

10. The method according to any one of the prior claims, wherein the step of treating the resinous wood with the chemical is performed at a pressure of about 10 psi to about 75 psi.

11. The method according to any one of the prior claims, wherein the resinous wood is treated in a countercurrent / reverse current manner using the chemical agent.

12. The method according to any one of the prior claims, wherein the rosin and / or terpene fraction extracted from the resinous wood is substantially free of contaminants.

13. The method according to any one of the prior claims, wherein the terpene fraction comprises at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight of pinene.

14. The method according to any one of the prior claims, wherein the terpene fraction is substantially free of contaminants.

15. The method according to any one of the prior claims, wherein the terpene fraction comprises less than about 20% by weight, less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, or less than 1% by weight of a terpene polymer.

16. The method according to any one of the prior claims, wherein the terpene fraction comprises less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, less than about 1% by weight, or less than about 0.5% by weight of synthetic pine oil.

17. The method according to any one of the prior claims, wherein the rosin fraction has a Gardner color number of about 8 or less.

18. The method according to any one of the prior claims, wherein the rosin fraction is substantially free of contaminants.

19. The method according to any one of the prior claims, wherein the rosin fraction has an acid value of about 160 to about 175.

20. The method according to any one of the prior claims, wherein the rosin fraction contains an abietic acid content in the range of about 15% to about 35% by weight, about 15% to about 25% by weight, or about 15% to about 20% by weight.

21. A terpene fraction produced according to the method of any one of claims 1 to 20.

22. Isolated terpene fraction, (a) comprising at least about 65% by weight, at least about 70% by weight, at least about 75% by weight, or at least about 80% by weight of pinene in the isolated terpene fraction, (b) Substantially free of contaminants, (c) comprising less than about 25% by weight, less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, or less than 1% by weight of terpene polymers from the isolated terpene fraction, and (d) One or more isolated terpene fractions comprising less than about 10% by weight, less than about 5% by weight, less than about 2.5% by weight, less than about 1% by weight, or less than about 0.5% by weight of synthetic pine oil.

23. A rosin fraction produced according to the method of any one of claims 1 to 20.

24. Isolated rosin fraction, (a) Includes a number of Gardner colors of approximately 8 or less, approximately 5 or less, or approximately 3 or less, (b) Substantially free of contaminants, (c) containing an acid value of approximately 160 to approximately 175, (d) an isolated rosin fraction comprising one or more of the following abietic acid content: about 15% to about 35% by weight, about 15% to about 25% by weight, or about 15% to about 20% by weight of the isolated rosin fraction.

25. A method for producing a polymer, comprising the step of processing a rosin fraction according to claim 23 or 24 and / or a terpene fraction according to claim 21 or 22 to produce the polymer.

26. A polymer produced according to the method of claim 25.

27. A method for producing an ester, comprising the step of processing a rosin fraction according to claim 23 or 24 and / or a terpene fraction according to claim 21 or 22 to produce the ester.

28. An ester produced according to the method of claim 27.

29. Apparatus for extracting rosin and / or terpene fractions from resinous wood, comprising a processing chamber for treating the resinous wood with a chemical agent containing, consisting of, or essentially composed of terpenes.

30. The apparatus according to claim 29, wherein the processing chamber is a countercurrent extractor or comprises a countercurrent extractor.

31. The apparatus according to claim 29 or 30, further comprising a distillation chamber communicating with the processing chamber, wherein the distillation chamber is for separating the rosin and terpene fractions extracted from the resinous wood.

32. The apparatus according to any one of claims 29 to 31, further comprising a desolvator communicating with the processing chamber, wherein the desolvator heats the resinous wood treated with the agent and therefrom removes at least partially any residual portion of the agent and / or the terpene fraction.

33. The apparatus according to any one of claims 29 to 32, further comprising a separator in communication with the distillation chamber, the separator for at least partially separating the terpene fraction from the distillate produced by the distillation chamber.

34. The apparatus according to any one of claims 29 to 33, further comprising a scrubbing device.

35. The apparatus according to any one of claims 29 to 34, wherein the processing chamber contains the agent comprising, consisting of, or essentially comprising a terpene.

36. The apparatus according to any one of claims 29 to 35 for use in the method according to any one of claims 1 to 20.

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