585902 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（1) 【發明所屬之技術領域】 本發明係關於較以往安全性高之木醋液。 【先行技術】 自以往木醋液（wood vinegar or pyroligneous liquor) (木醋酸或焦油下層水）即銷售作爲園藝用或沐浴用，精 製該木醋液有各種方法。 例如，將木材乾餾或製碳時產生之液體冷卻製成之液 狀物靜置分離製成之木醋液，或進行蒸餾操作製成之木醋 液，使用活性碳過濾製成之木醋液，品質各有差異。 但，推測將木材熱分解時會產生疑似致癌成分，在上 述任一項中之木醋液均殘留木焦油成分，欲消除對木醋液 安全性不安之問題。 【發明所欲解決之課題】 在此本發明欲提供較以往安全性高之木醋液。 【用以解決課題之手段】 爲解決上述課題，本發明木醋液，其特徵在於自含 木焦油成分之原料木醋液除去高沸點之危險成分。 本發明木醋液，因自含木焦油成分之原料木醋液除去 高沸點之危險成分，不含有疑似致癌成分。 高沸點之項:險成分，係除去苯并（a )芘、1 , 2， 5，6 -二苯並蒽、3 -甲基膽蒽、及戴奧辛類。 (請先閱讀背面之注意事項再填寫本頁) • 0ΙΊ n 1— . -裝·585902 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to wood vinegar which is safer than before. [Advanced technology] Since the previous wood vinegar or pyroligneous liquor (wood acetic acid or tar under water) has been sold for gardening or bathing, there are various methods to refine the wood vinegar. For example, the wood vinegar liquid made by liquid cooling the liquid produced during the carbonization of carbon or making carbon is left standing and separated, or the wood vinegar liquid made by distillation operation, and the wood vinegar liquid made by activated carbon filtration , Quality varies. However, it is presumed that a suspected carcinogen may be generated when the wood is thermally decomposed. In any of the above-mentioned wood vinegar solutions, wood tar components remain, and the problem of unsafeness of the wood vinegar solution is to be eliminated. [Problems to be Solved by the Invention] The present invention is intended to provide a wood vinegar solution having higher safety than the conventional ones. [Means for solving the problem] In order to solve the above-mentioned problem, the wood vinegar liquid of the present invention is characterized by removing dangerous components with high boiling points from the wood vinegar liquid containing the raw material of wood tar. The wood vinegar liquid of the present invention removes dangerous components with high boiling points from the wood vinegar liquid containing the raw material of wood tar, and does not contain a suspected carcinogenic component. High boiling point items: dangerous components, which are benzo (a) pyrene, 1,2,5,6-dibenzoanthracene, 3-methylcholanthrene, and dioxin. (Please read the notes on the back before filling out this page) • 0ΙΊ n 1—.
、1T 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇Χ：297公釐） -4- 585902 A7 B7 五、發明説明（2) 在此使用蒸餾鍋蒸餾含木焦油成分原料之木醋液，靜 置已黑I留之木醋液使其分離成輕質油層、水層、沉積焦油 層三層選出上述水層，蒸餾此以回收含木醋液主要成分乙 酸之餾分亦可。 如此進行原料木醋液蒸餾，得將殘留於蒸餾鍋之苯并 (a )芘等高沸點危險成分除去。又靜置上述己蒸餾之木 醋液使其分離成輕質油層、水層、沉積焦油層三層選出水 層，可除去於上層之輕質油層或沉積焦油層中所含較高之 苯并（a )芘等。且經由回收蒸餾上述水層含木醋液主要 成分乙酸之餾分，可除去苯并（a)芘等。 使其分離成輕質油層、水層、沉積焦油層三層選出水 層後，進行該水層之蒸餾以除去低沸點物亦可。 若如此構成，可除去甲醇或丙酮、乙醛類等低沸點物 及可能與此類共沸之苯并（a )芘等。又除去該低沸點物 之蒸餾，例如得將已選出水層放入蒸餾鍋以除去初餾分（ 低沸點物）。 【發明之實施形態】 將含爲原料之木焦油成分之原料木醋液，利用第1鍋 (不銹鋼製蒸餾鍋）於液溫1 0 0 °C以下進行減壓蒸餾。 上述原料木醋液中所含之闻沸點危險成分爲以下之苯 并（a )芘等。苯并（a )芘之沸點常壓下爲49 5 °C， 減壓下（l〇mmHg)爲310〜312艺。1， 2, 5，6 —二苯並蒽常壓下沸點爲5 3 5 °C (融點爲 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) •裝· -訂 經濟部智慧財產局員工消費合作社印製 -5- 585902 A7 B7 五、發明説明（3) 2 6 6 . 6 °C ) 。3 —甲基膽蒽（現今之慣用名爲3 —甲 基膽蒽）常壓下沸點爲2 8 0 °C (融點爲1 8 0 °C )。戴 奧辛類之沸點常壓下爲2 8 4 t〜5 3 7 °C。 於上述蒸餾條件若無法蒸餾此類高沸點之危險成分應 會分別殘留於鍋中，於上述蒸餾後之粗蒸餾液中用於含甲 醇等有機溶液可能共沸進行如下所述進一步之精製。 將上述粗蒸餾液靜置1 0日以上，使其分離成輕質油 層、水層、沉積焦油層三層。因苯并（a )芘爲芳烴極性 低難溶於水，即使含有因易分配於上層之輕質油層或下層 沉積焦油層，含苯并（a )芘可能性低，僅選出乙酸爲主 要成分之水層。 苯并（a)芘與1，2，5, 6 -二苯並蒽，其結構 式及物理性質亦酷似，3 -甲基膽蒽較前二者其沸點稍低 。由此3成分及同於戴奧辛類之有機溶液及可溶於油且難 溶於水之性質，得藉由將上述粗蒸餾液分離成輕質油層、 水層、沉積焦油層三層大致除去危險成分。 接著，將上述選出之水層利用第2蒸餾鍋於液溫 1〇0 °C以下進行常壓蒸餾。此操作，係將上述水層放入 第2黑I留鍋黑態除去初f留分，藉此除去甲醇或丙酮、乙酸 類等低沸點物，可除去可能與此類低沸點物共沸之苯并（ a )芘等。又，例如若如此除去甲醛，事先防範製品化後 殘留於木醋液中甲醛與酚成分反應所形成之樹脂浮於容器 之表層或沉澱於下層，以期木醋液品質穩定化之優點。 放入第2蒸餾鍋之水層經蒸餾約一半後停止蒸餾，將 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） J --------裝-- (請先閱讀背面之注意事項再填寫本頁)、 1T This paper size applies Chinese National Standard (CNS) A4 specification (21〇 ×: 297mm) -4- 585902 A7 B7 V. Description of the invention (2) The wood vinegar containing wood tar ingredients is distilled using a retort Liquid, leaving the wood vinegar liquid that has been left black I to separate it into a light oil layer, a water layer, and a tar layer to select the above water layer, and distill this to recover the fraction containing the main component of the wood vinegar liquid acetic acid. Distillation of the raw wood vinegar liquid in this manner can remove high boiling point hazardous components such as benzo (a) pyrene remaining in the distillation pot. The still-distilled wood vinegar solution was allowed to stand to separate it into a light oil layer, a water layer, and a tar layer. The water layer was selected, and the higher light benzo or tar contained in the deposited tar layer could be removed. (A) 芘 and so on. Furthermore, benzo (a) pyrene and the like can be removed by recovering and distilling the fraction of acetic acid, which is the main component of the woody vinegar solution in the aqueous layer. It is separated into a light oil layer, a water layer, and a tar layer. After the water layer is selected, the water layer may be distilled to remove low-boiling substances. With this structure, low-boiling substances such as methanol, acetone, and acetaldehyde, and benzo (a) pyrene, which may be azeotropic with such substances, can be removed. This low boiling point distillation is removed, for example, the selected water layer can be put into a distillation pot to remove the initial fraction (low boiling point). [Embodiment of the invention] The raw wood vinegar liquid containing the wood tar component as a raw material is distilled under reduced pressure using a first pot (stainless steel still) at a liquid temperature of 100 ° C or lower. The boiling point hazardous components contained in the raw wood vinegar solution are the following benzo (a) pyrene and the like. The benzo (a) pyrene has a boiling point of 49 5 ° C under normal pressure and 310 to 312 cycles under reduced pressure (10 mmHg). 1, 2, 5, 6 —Dibenzoanthracene has a boiling point of 5 3 5 ° C at normal pressure (The melting point is based on the Chinese paper standard (CNS) A4 specification (210X297 mm). Please read the notes on the back first (Please fill in this page again for matters) • Packing ·-Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -5- 585902 A7 B7 V. Description of the invention (3) 2 6 6. 6 ° C). 3-Methylcholanthrene (now commonly known as 3-methylcholanthrene) has a boiling point of 280 ° C (melting point of 180 ° C) at atmospheric pressure. Dioxins have a boiling point of 2 8 4 t to 5 3 7 ° C at normal pressure. If such high boiling point hazardous components cannot be distilled under the above-mentioned distillation conditions, they should be left in the pot separately. The crude distilled liquid after the above distillation may be used for azeotropy of organic solutions containing methanol and the like for further purification as described below. The crude distillate was allowed to stand for more than 10 days, and separated into a light oil layer, a water layer, and a deposited tar layer. Because benzo (a) pyrene is an aromatic hydrocarbon with low polarity and difficult to dissolve in water, even if it contains a light oil layer that is easily distributed in the upper layer or a tar layer deposited in the lower layer, the possibility of containing benzo (a) pyrene is low. Only acetic acid is selected as the main component Water layer. Benzo (a) pyrene and 1,2,5,6-dibenzoanthracene have similar structural formulas and physical properties, and 3-methylcholanthrene has a slightly lower boiling point than the previous two. From this, the three components and the same organic solution as dioxin and oil-soluble and hardly water-soluble properties can be roughly removed by separating the above crude distillate into a light oil layer, a water layer, and a tar layer. ingredient. Next, the selected water layer was subjected to atmospheric distillation using a second distillation pot at a liquid temperature of 100 ° C or lower. In this operation, the above water layer is placed in the black state of the second black I retention pot to remove the initial f fraction, thereby removing low boiling points such as methanol, acetone, and acetic acid, and removing azeotropes that may be azeotropic with such low boiling points. Benzo (a) pyrene and the like. For example, if the formaldehyde is removed in this way, the resin formed by the reaction between formaldehyde and phenol components remaining in the wood vinegar solution after the production is prevented in advance from floating on the surface layer of the container or deposited on the lower layer, in order to stabilize the quality of the wood vinegar solution. Put about half of the water layer into the second retort and stop the distillation. The paper size shall be in accordance with the Chinese National Standard (CNS) A4 specification (210 × 297 mm). J -------- install-(please (Read the notes on the back before filling out this page)
、1T 線 經濟部智慧財產局員工消骨合作社印製 -6 - 585902 A7 _B7 五、發明説明（4) (請先閱讀背面之注意事項再填寫本頁彳) 鍋中剩餘一半之殘留液移至第3蒸餾鍋。又，經蒸餾一半 之水層放回第2蒸餾鍋再次蒸餾，在此將剩餘之殘留鍋移 至第3蒸餾鍋。藉此可再次確實除去低沸點物及可能與此 類共沸之苯并（a )芘等。 除去低沸點物後，將自被移至第3蒸餾鍋之水層之殘 留液以液溫約1 0 0〜1 2 0 °C常壓蒸餾，有效地回收含 木醋液主要成分乙酸之餾分，製成高純度蒸餾精製木醋液 〇 如上述製成之木醋液，用氣體色譜法/質量分析計（ G C /M S )分析。其結果，自該木醋液完全檢測不出苯 并（a )芘、1，2 , 5 , 6 -二苯並蒽、3 —甲基膽蒽 、戴奧辛類。 因如上述可反覆除去苯并（a )芘等，可提供較以往 安全性極高之木醋液。 【發明之效果】 經濟部智慧財產局員工消費合作社印製 本發明係如上述所構成，因不含疑似致癌成分，可提 供較以往安全性高，供園藝用或沐浴用之木醋液° 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）Printed by the bone-eliminating cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T line -6-585902 A7 _B7 V. Description of the invention (4) (Please read the precautions on the back before filling this page 彳) The remaining half of the remaining liquid in the pot was moved The third retort. Furthermore, the half of the distilled water layer was returned to the second distillation pot and distilled again, and the remaining residual pot was transferred to the third distillation pot. This will surely remove low-boiling substances and benzo (a) pyrene, which may be azeotropic with them. After removing the low boiling point, the residual liquid from the water layer moved to the third distillation pot was distilled at a liquid temperature of about 100 to 120 ° C under normal pressure to effectively recover the acetic acid fraction containing the main component of the wood vinegar solution. A high-purity distilled and refined wood vinegar solution was prepared. The wood vinegar solution prepared as described above was analyzed with a gas chromatography / mass spectrometer (GC / MS). As a result, benzo (a) pyrene, 1,2,5,6-dibenzoanthracene, 3-methylcholanthrene, and dioxin were not completely detected from the wood vinegar solution. Because benzo (a) pyrene can be removed repeatedly as described above, it is possible to provide a wood vinegar solution which is extremely safer than before. [Effects of the invention] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, this invention is composed as described above, and because it does not contain suspected carcinogens, it can provide wood vinegar liquid for gardening or bathing with higher safety than before. Paper size applies to Chinese National Standard (CNS) A4 (210X297 mm)