Method for separating and recovering volatile organic compound and method for producing material containing volatile organic compound

Abstract

To provide a method for separating and recovering volatile organic compounds which enables suppression of solvent loss and allows recovery of volatile organic compounds from a wood-based material through a simple operation.SOLUTION: The method for separating and recovering volatile organic compounds comprises the following steps: a mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying treatment of a wood-based material to obtain a mixed liquid; and a distillation step of passing steam through the mixed liquid heated to a predetermined temperature, and cooling the discharged steam to obtain a distillate.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for separating and obtaining volatile organic compounds and a method for producing a volatile organic compound-containing material.

Background Art

[0002] Conventionally, it has been known that volatile organic compounds contained in wood materials have various physiological activities. Specifically, the present inventors have reported that ferruginol, which is a kind of volatile organic compound (diterpene), has antibacterial activity and antioxidant activity at a practical level (Non-Patent Document 1), and also has anti-Alzheimer's disease activity (amyloid-β toxicity-relieving effect) (Patent Document 1).

[0003] In addition, the present inventors have also proposed a method for highly selectively and efficiently separating and obtaining terpenoids such as ferruginol from tar-like substances obtained from sugi wood (Patent Document 2). Specifically, in this method, a mixed solution of water and a high-boiling solvent such as ethylene glycol, diethylene glycol, or triethylene glycol is added to a tar-like substance from sugi wood or sugi wood chips, and distillation (solvent-added distillation) is performed to separate and obtain terpenoids such as ferruginol from the solvent fraction.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0005]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the method of Patent Document 2, since loss of the solvent is inevitable in obtaining the distillate fraction of the solvent, it was considered that it is not always easy to suppress the cost, which is a point to be improved. Further, in the method of Patent Document 2, operations such as removing the solvent from the distillate fraction are necessary, and it was considered that the operation is complicated, which is a point to be improved.

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for separating and obtaining a volatile organic compound that can suppress loss of the solvent and can obtain a volatile organic compound from a woody material by a simple operation, and a method for producing a volatile organic compound-containing material.

Means for Solving the Problems

[0008] In order to solve the above problems, the following method for separating and obtaining a volatile organic compound is provided. [1] A method for separating and obtaining a desired volatile organic compound from a woody material, comprising the following steps: a mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying the woody material to obtain a mixed solution; a distillation step of passing steam through the mixed solution heated to a predetermined temperature, cooling the discharged steam to obtain a distillate containing the target volatile organic compound; including a method for separating and obtaining a volatile organic compound. [2] The method for separating and obtaining a volatile organic compound according to [1], wherein the non-volatile solvent is polyethylene glycol or silicone oil. [3] The method for separating and obtaining a volatile organic compound according to [2], wherein the polyethylene glycol has a molecular weight of 200 to 9300. The method for separating and obtaining a volatile organic compound according to [2]. [4] The method for separating and obtaining a volatile organic compound according to any one of [1] to [3], wherein the volatile organic compound is ferulic alcohol. The method for separating and obtaining a volatile organic compound according to any one of [1] to [3]. [5] The heating temperature of the mixed solution in the distillation step is 100°C to 250°C. The method for separating and obtaining the volatile organic compounds [1] to [4]. [6] The distillation step is repeated two or more times, and the heating temperature of the mixed solution is increased each time the number of distillation steps is repeated. The method for separating and obtaining the volatile organic compounds [1] to [5].

[0009] In order to solve the above problems, the following method for producing a volatile organic compound-containing material is provided. [7] A method for producing a volatile organic compound-containing material using a wood material as a raw material, comprising the following steps: A mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying the wood material to obtain a mixed solution; A distillation step of passing steam through the mixed solution heated to a predetermined temperature, cooling the discharged steam, and obtaining a distillate containing the target volatile organic compound; including A method for producing a volatile organic compound-containing material. [Effect of the Invention]

[0010] According to the method for separating and obtaining a volatile organic compound and the method for producing a volatile organic compound-containing material of the present invention, loss of the solvent can be suppressed, and a volatile organic compound can be obtained from a wood material by a simple operation. [Brief Description of the Drawings]

[0011]

Figure 1

[0012] Hereinafter, an embodiment of the method for separating and obtaining a volatile organic compound and the method for producing a volatile organic compound-containing material of the present invention will be described.

[0013] The method for separating and obtaining volatile organic compounds of the present invention is a method for separating and obtaining a desired volatile organic compound from a woody material, and includes the following steps: A mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying the woody material to obtain a mixed solution; and, A distillation step of passing steam through the mixed solution heated to a predetermined temperature, cooling the discharged steam, and obtaining a distillate containing the target volatile organic compound is included.

[0014] Hereinafter, each step of the method for separating and obtaining volatile organic compounds (solvent-added steam distillation) of the present invention will be described.

[0015] (Mixing step) In the mixing step, a non-volatile solvent is added to a tar-like substance obtained by drying the woody material to obtain a mixed solution.

[0016] The woody material is not particularly limited, and a material containing a desired volatile organic compound can be appropriately selected. The volatile organic compound is typically diterpenes, and specifically, examples thereof include ferruginol, abietadiene, abietatriene, sandaracopimarinal, and cembrene. For example, when the target volatile organic compound is ferruginol, abietadiene, abietatriene, or sandaracopimarinal, the woody material is preferably cedar wood. Further, for example, when the target volatile organic compound is cembrene, the woody material is preferably Japanese red pine.

[0017] As described above, for example, in the drying process of cedar wood, generally, heated steam of about 120 to 200 ° C is used for cedar wood such as lumber, veneer, and chips, and the steam discharged after the drying process is cooled and recovered to produce a tar-like substance that is a sticky precipitate. This tar-like substance contains useful volatile organic compounds such as ferruginol. In the method for separating and obtaining volatile organic compounds of the present invention, a non-volatile solvent is added to such a tar-like substance to obtain a mixed solution.

[0018] The non-volatile solvent is preferably polyethylene glycol or silicone oil. The boiling point of polyethylene glycol or silicone oil is preferably 250 °C or higher.

[0019] The polyethylene glycol preferably has a molecular weight of 200 to 9300, more preferably 3100 to 9300. When the molecular weight of the polyethylene glycol is within this range, loss of the solvent (polyethylene glycol) can be suppressed, and volatile organic compounds can be obtained from the woody material by a simple operation.

[0020] The silicone oil is not particularly limited, and examples thereof include dimethyl silicone oil, methylphenyl silicone oil, alkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, and fatty acid ester-modified silicone oil.

[0021] The addition amount of the non-volatile solvent (polyethylene glycol or silicone oil) to the tar-like substance can be set as appropriate. For example, it is preferably in the range of 200 to 2000 parts by mass with respect to 100 parts by mass of the tar-like substance.

[0022] (Distillation step) In the distillation step, steam is passed through the mixed solution heated to a predetermined temperature, and the discharged steam is cooled to obtain a distillate.

[0023] The means for heating the mixed solution is not particularly limited, and known means can be appropriately selected. Also, the means for cooling the steam is not particularly limited, and known means can be appropriately selected.

[0024] The heating temperature of the mixed solution in the distillation step is preferably, for example, 60 °C to 300 °C, more preferably 100 °C to 250 °C.

[0025] The distillation process is preferably repeated two or more times. In this case, it is preferable to increase the heating temperature of the mixed solution each time the number of distillation processes is increased. As a result, components having a boiling point lower than that of the target volatile organic compound can be recovered as the distillate of the previous-stage distillation, so that the target volatile organic compound can be selectively obtained as the distillate by the subsequent-stage distillation.

[0026] Hereinafter, a form in which the distillation process is performed three times will be described as an example (first to third distillation processes).

[0027] In the first distillation process, steam is passed through a mixed solution heated to 100°C to 120°C (first temperature), and the discharged steam is cooled to obtain a first distillate. The first temperature can be appropriately set within the above range according to the type of the target volatile organic compound and the like. For example, when a tar-like substance of cedar wood is used as a raw material, if the first temperature is within this range, steam containing essential oil components such as sesquiterpenes is discharged and cooled. Therefore, in this case, the first distillate contains essential oil components such as sesquiterpenes. In the first distillation process, the time for passing steam through the mixed solution is not particularly limited, but can be appropriately set, for example, in the range of about 30 minutes to 48 hours.

[0028] In the second distillation process, the mixed solution after the first distillation process is heated to a temperature higher than the first temperature (second temperature), steam is passed through this mixed solution, and the discharged steam is cooled to obtain a second distillate.

[0029] The second temperature can be appropriately set according to the type of the target volatile organic compound and the like, and for example, the range of 170°C to 180°C can be exemplified. For example, when a tar-like substance of cedar wood is used as a raw material, if the second temperature is within this range, the second distillate contains, for example, abietatriene, abietadiene, and the like. In the second distillation process, the time for passing steam through the mixed solution can also be appropriately set in the same manner as in the first distillation process.

[0030] In the third distillation step, the mixed solution after the second distillation step is heated to a temperature higher than the second temperature (the third temperature), steam is passed through this mixed solution, and the discharged steam is cooled to obtain a third distillate.

[0031] The third temperature can be appropriately set according to the type of the target volatile organic compound and the like. For example, a range of 240°C to 250°C can be exemplified. For example, when a tar-like substance of cedar wood is used as a raw material, the third distillate contains, for example, sandaracopimarinal, ferruginol, and the like. Regarding ferruginol, 90% or more of the total amount initially contained in the raw tar-like substance can be contained in the third distillate.

[0032] In the method for separating and obtaining a volatile organic compound of the present invention, since the non-volatile solvent is used as a heat medium without boiling, the loss of the solvent is suppressed, and the cost can be suppressed. Further, in the method for separating and obtaining a volatile organic compound of the present invention, since the target volatile organic compound is distilled and recovered together with steam, operations such as removing the solvent are unnecessary, and the volatile organic compound can be obtained by a simple operation.

[0033] Furthermore, in the method for separating and obtaining a volatile organic compound of the present invention, a purification step using a known purification method (liquid-liquid extraction, column chromatography, etc.) may be included according to the type and content of the target volatile organic compound. Thereby, for example, terpenes in the distillate can be separated into individual types.

[0034] Specifically, as an embodiment of the method for separating and obtaining a volatile organic compound of the present invention, for example, when separating ferruginol from the distillate obtained in the distillation step, a form in which normal-phase medium-pressure column chromatography and reverse-phase column chromatography are performed stepwise on the distillate can be exemplified. In these purifications, for example, toluene, n-hexane, methanol, diethyl ether, ethyl acetate, etc. can be used as the eluent.

[0035] In addition, the method for producing a volatile organic compound-containing material of the present invention has the same characteristics as the method for separating and obtaining the volatile organic compound described above.

[0036] That is, the method for producing a volatile organic compound-containing material of the present invention is a method for producing a volatile organic compound-containing material using a woody material as a raw material, and includes the following steps: A mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying the woody material to obtain a mixed solution; A distillation step of passing steam through the mixed solution heated to a predetermined temperature, cooling the discharged steam, and obtaining a distillate containing the target volatile organic compound; including.

[0037] The method for separating and obtaining a volatile organic compound and the method for producing a volatile organic compound-containing material of the present invention are not limited to the above embodiments.

Example

[0038] Hereinafter, the present invention will be described together with examples, but the method for separating and obtaining a volatile organic compound and the method for producing a volatile organic compound-containing material of the present invention are not limited to the following examples at all.

[0039] Note that the following example is a method for separating and obtaining ferulic alcohol as a volatile organic compound from a tar-like substance of sugi wood.

[0040] <Experimental method> (1) Solvent-aided steam distillation 500 g of polyethylene glycol 6000 (PEG 6000 manufactured by Fujifilm Wako Pure Chemical Corporation, molecular weight 7300 - 9300) was added to 250 g of a tar-like substance obtained from sugi wood (191.2 g of organic matter and 58.8 g of water) to obtain a mixture (mixing step). When the viscosity of the tar-like substance is high, polyethylene glycol 4000 (PEG4000: molecular weight 2700 - 3300) manufactured by the same company can also be used. While maintaining this mixture at 100 °C, steam was passed through for 8 hours. The steam containing the discharged volatile components was cooled to recover the distillate (the first distillation step). Further, while heating the solvent, steam was passed through to perform distillation operations at 175 °C for 16 hours and at 250 °C for 16 hours, respectively obtaining distillates (the second distillation step, the third distillation step). The distillates under each temperature condition were separated and dissolved in toluene. (2) Purification of Feruginol The 250 °C distillate fraction obtained by the above-mentioned solvent-aided steam distillation method was added to a medium-pressure column (BUCHI Sepacore Silica) for fractionation. Feruginol was eluted using toluene as the eluent. Subsequently, the final purification of feruginol was performed using reverse-phase HPLC (column: GL Sciences Inc. Inertsil ODS-3 20×250 mm, eluent: methanol). (3) Component Analysis Feruginol and other volatile components were analyzed by gas chromatography (GC). Based on the peak areas of the chromatograms obtained by GC analysis, the content of each component was determined by the internal standard method. Heptadecane was used as the internal standard (I.S.). The GC analysis conditions were as follows: using a GC-1700 type analyzer (detector: FID) manufactured by Shimadzu Corporation equipped with HP-5 (0.25 mm × 30 m, manufactured by Hewlett Packard), the initial temperature was 60 °C, and the temperature was raised to 240 °C at a rate of 3 °C / min.

[0041] <Results> As a result of applying solvent-aided steam distillation to the tar-like substance, 172.2 g of distillate was obtained from 191.2 g of raw material (yield 90.1%). The breakdown by distillation temperature was 8.8 g (yield 4.6%) of the fraction distilled at 100 °C, 92.1 g (yield 48.2%) of the fraction distilled at 175 °C, and 71.3 g (yield 37.3%) of the fraction distilled at 250 °C. As a result of GC analysis of each fraction, essential oil components mainly composed of sesquiterpenes were obtained as the distillate selectively at 100 °C, abietatriene and abietadiene at 175 °C, and sandaracopimarinal and ferruginol at 250 °C. Among these, for ferruginol, more than 90% of the total amount initially contained in the raw material was separated and recovered as the fraction distilled at 250 °C.

[0042] The fraction at 250 °C obtained by solvent-aided steam distillation was added to a normal-phase medium-pressure column and eluted using toluene and ethanol. Of these, 42% was eluted and recovered in the toluene fraction, and 55% was recovered in the ethanol fraction. As a result of GC analysis, the toluene fraction contained ferruginol and the ethanol fraction contained sandaracopimarinal. The ferruginol content (purity) in the toluene fraction was 58.2%. Subsequently, peak fractionation by reversed-phase HPLC was performed for final purification, and high-purity ferruginol showing a single peak in GC analysis was obtained at a yield of 6.9% from the raw material (58.0% based on the initial amount of ferruginol). The GC analysis data at each stage until the purified ferruginol product was obtained from the tar-like substance as the raw material are shown in Fig. 1, and the yields and the like are shown in Table 1.

[0043]

Table 1

[0044] According to the method described above, it was confirmed that ferruginol can be purified at a lower cost and more simply than the conventional method because there is no loss of solvent and there is no need for a step to remove the solvent.

Claims

1. A method for separating and obtaining a desired volatile organic compound from a woody material, comprising the following steps: A mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying the woody material to obtain a mixed solution; and A distillation step of passing steam through the mixed solution heated to a predetermined temperature, cooling the discharged steam to obtain a distillate containing the target volatile organic compound including A method for separating and obtaining a volatile organic compound.

2. The non-volatile solvent is polyethylene glycol or silicone oil, The method for separating and obtaining a volatile organic compound according to Claim 1.

3. The molecular weight of the polyethylene glycol is 200 to 9300, The method for separating and obtaining a volatile organic compound according to Claim 2.

4. The volatile organic compound is ferulic alcohol, The method for separating and obtaining a volatile organic compound according to Claim 1.

5. The heating temperature of the mixed solution in the distillation step is 100°C to 250°C, The method for separating and obtaining a volatile organic compound according to Claim 1.

6. The distillation step is repeated two or more times, and the heating temperature of the mixed solution is increased each time the number of times of the distillation step is repeated, The method for separating and obtaining a volatile organic compound according to Claim 1.

7. A method for producing a volatile organic compound-containing material using a woody material as a raw material, comprising the following steps: A mixing step of adding a non-volatile solvent to a tar-like substance obtained by drying the woody material to obtain a mixed solution; and A distillation step of passing steam through the mixed solution heated to a predetermined temperature, cooling the discharged steam to obtain a distillate containing the target volatile organic compound including A method for producing a volatile organic compound-containing material.

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