1359805 (1) 九、發明說明 【發明所屬之技術領域】 本發明係自含有含氟醇類與水之混合液，回收含氟醇 類之技術。 【先前技術】 含氟醇類係製造CD—R及DVD— R等資料記錄媒體 時，利用爲記錄層之色素溶媒，係大容量記錄媒體之製造 所不可或缺者。 於上述之記錄媒體之製造步驟中，大量產生含水之含 氟醇類廢液。自此廢液回收含氟醇類，且若可再利用，爲 加強對環境負荷之低減以及製造成本之削減，期待以低成 本自含氟醇類與水之混合液除去水之技術。 然而’因含氟醇類與水之混合液具共沸組成時，非常 難以蒸餾去除水分。例如，2,2,3,3—四氟化丙醇（以下稱 做TFPO)是含氟醇類的一種，其與水之混合液之共沸組成 係TFPO 73質量％，水27%。 於專利文件1揭示了自TFPO與水之混合液在回收 時’以滲透蒸發法將水分離之方法，但期望有更簡便且有 效率之方法。 專利文件1 :特開2001 -1 87756號公報（申請專利範圍 第5項） 【發明內容】1359805 (1) Description of the Invention [Technical Field of the Invention] The present invention is a technique for recovering a fluorine-containing alcohol from a mixed liquid containing a fluorine-containing alcohol and water. [Prior Art] When a fluorine-containing alcohol is used as a data recording medium such as CD-R or DVD-R, it is indispensable for the production of a large-capacity recording medium by using a pigment solvent as a recording layer. In the above-described manufacturing steps of the recording medium, a large amount of aqueous fluoroalcohol-containing waste liquid is produced. In the case where the waste liquid is recovered from the waste liquid, it is expected to reduce the environmental load and reduce the production cost, and it is expected to remove the water from the mixed liquid of the fluorine-containing alcohol and water at a low cost. However, when the mixture of fluorine-containing alcohol and water has an azeotropic composition, it is very difficult to distill off water. For example, 2,2,3,3-tetrafluoropropanol (hereinafter referred to as TFPO) is a type of fluorine-containing alcohol, and its azeotropic composition with water is 73% by mass of TFPO and 27% by water. Patent Document 1 discloses a method of separating water by pervaporation from the mixture of TFPO and water, but a simpler and more efficient method is desired. Patent Document 1: JP-A-2001-1 87756 (Patent Application No. 5) [Summary of the Invention]
-5- (2) 1359805 [發明所欲解決之課題] 本發明係提供自含有含氟醇類與水之混合液將水分 ‘離，簡便地回收含氟醇類的方法爲目的。 [課題解決之手段] 本發明係提供含有含氟醇類以及水之混合液，在回收 含氟醇類時，具有添加酸於前述之混合液中，使其分離爲 φ 二層之步驟爲其特徵之含氟醇類之回收方法。 於本發明，考慮藉由添加酸，使含氟醇類之羥基之解 離（質子自羥基脫離）平衡向非解離側大幅移動，因水之溶 解性低下而引起層分離。此現象係考慮氟原子爲疏水性， 藉由氟原子之效果使羥基變爲易於解離，亦與含氟醇類爲 具有大比重之化合物有關。 因含氟醇類之比重較水爲大，故含有含氟醇類爲主之 層形成於下，含有水爲主之層形成於上。 φ 本發明中之分離爲二層之步驟，可層分離成主要含水 之上層及含主要含氟醇類之下層。依據該層分離，可使下 層中含氟醇類之含有比例爲80質量％以上，特別係可達 90質量％之高濃度。因此，若將該下層藉由蒸餾等進一步 精製，不須與水共沸則可簡便地獲得高純度之含氟醇類 【實施方式】 於本發明之含氟醇類，可舉出全氟-叔-丁醇等具有 全氟烷基之醇類，2,2,3,3,3 —五氟化丙醇，1，1，1，3,3,3 - -6- (3) 1359805 六氟-2 -丙醇，2,2，2 -三氟化乙醇等氟醇類 以及下式1所表示之化合物。 Η -（CRfFCF2)n — CR'R2 - OH···式 1 其中，係氟原子或碳數1〜4之聚氟烷 各爲獨立之氫原子或碳數1〜3之烷基，η爲 數。 式1所表示之化合物，具體可舉出 H(CF2)2CH2OH(TFPO)、H(CF2)4CH2OH、 HCF2CF2CH(CH3)〇H ' HCF2CF2C(CH3)2〇H ' HC(CF3)FCF2CH2OH、HC(CF3)FCF2CH(CH3)OH ' HC(CF3)FCF2C(CH3)2OH。 於本發明中被處理之含有含氟醇類以及水 之水之含有比例以5 0質量％以下爲佳，特別i 以下更佳》前述水之含有比例過大時，除了變 更多的酸之外，於2層分離後之蒸餾步驟中， 間之傾向，進行預先簡單蒸餾等，將水先去除 爲佳。 於本發明所使用之酸以無機酸爲佳，硫酸 酸，氟酸等強酸更佳，其中以硫酸，硝酸，鹽 外，使其2層分離步驟後，所得之下層再進行 步驟時，自不易腐蝕蒸餾裝置觀點看來，特別 爲佳。 ，氟酣類， 基，R1 、 R2 1〜4之整 之混合液中 k 25質量％ 爲必須添加 因有更花時 至某種程度 ，硝酸，鹽 酸爲佳。另 蒸餾之蒸餾 是使用硫酸 (4) 1359805 於本發明，添加之酸量爲相對於含有含氟醇類以及水 之混合液中之水，將質子（H+)換算爲莫耳比係0.10以上 (視酸爲100%解離）之添加量爲佳，0.15以上，或是0.20 • 以上之添加量特佳。前述之莫耳比未滿0.1時，於下層之 水之含有比例變大同時，亦變爲不易層分離。 尙且，通常因過量地添加酸亦無益處，酸之添加量係 引起2層分離，使於下層之含氟醇類之含有比例爲一定之 Φ 最低限量以上爲佳。 添加酸於含有含氟醇類以及水之混合液時，於常溫， 常壓下進行爲佳，一般而言，不需要控制溫度等。爲使所 添加之酸與前述之混合液均勻混合，以攪拌翼等加以混 合。 爲使其2層分離，可將其靜置，亦可使用離心機使其 分離。靜置使其2層分離時，靜置時間依據各層之厚度及 界面面積，以3〜12小時爲佳。 φ 於本發明中2層分離步驟所得之下層中含氟醇類之含 有比例以80質量％以上爲佳，特別是90質量％以上，92 質量％以上更佳。因前述之含氟醇類之含有比例愈大，接 下來的步驟中進行蒸餾時之負擔就愈小。 於本發明中2層分離步驟所得之上層，通常含有10 〜30質量％含氟醇類，針對此上層中之含氟醇類，所得 到之上層，因可於下一批2層分離步驟時使用爲酸之一部 分重複利用而有效地回收。 於本發明中使其2層分離步驟所得之下層，具有再加-5- (2) 1359805 [Problems to be Solved by the Invention] The present invention is directed to a method for easily recovering fluorine-containing alcohol from a mixed liquid containing a fluorine-containing alcohol and water. [Means for Solving the Problem] The present invention provides a mixed liquid containing a fluorine-containing alcohol and water, and when the fluorine-containing alcohol is recovered, a step of adding an acid to the mixed liquid and separating it into two layers of φ is used. A method for recovering fluorine alcohols characterized by a method. In the present invention, it is considered that the dissociation of the hydroxyl group of the fluorine-containing alcohol (the proton is detached from the hydroxyl group) is largely shifted to the non-dissociated side by the addition of the acid, and the layer is separated due to the low solubility of water. This phenomenon is considered to be that the fluorine atom is hydrophobic, and the hydroxyl group is easily dissociated by the effect of the fluorine atom, and is also related to the compound having a large specific gravity of the fluorine-containing alcohol. Since the specific gravity of the fluorine-containing alcohol is larger than that of water, a layer containing a fluorine-containing alcohol as a main layer is formed below, and a layer containing water as a main layer is formed thereon. φ The step of separating into two layers in the present invention, which can be separated into a main aqueous upper layer and a lower fluorine-containing alcohol-containing lower layer. According to the separation of the layer, the content of the fluorine-containing alcohol in the lower layer can be 80% by mass or more, particularly up to 90% by mass. Therefore, when the lower layer is further purified by distillation or the like, a high-purity fluorine-containing alcohol can be easily obtained without azeotropy with water. [Embodiment] The fluorine-containing alcohol of the present invention may be a perfluoro- Alcohols having perfluoroalkyl groups such as tert-butanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3 - -6- (3) 1359805 A fluoroalcohol such as fluoro-2-propanol or 2,2,2-trifluoroacetate or a compound represented by the following formula 1. Η -(CRfFCF2)n - CR'R2 - OH · · · Formula 1 wherein the fluorine atom or the polyfluoroalkane having a carbon number of 1 to 4 is each an independent hydrogen atom or an alkyl group having 1 to 3 carbon atoms, η is number. Specific examples of the compound represented by Formula 1 include H(CF2)2CH2OH(TFPO), H(CF2)4CH2OH, HCF2CF2CH(CH3)〇H 'HCF2CF2C(CH3)2〇H 'HC(CF3)FCF2CH2OH, HC(CF3 ) FCF2CH(CH3)OH 'HC(CF3)FCF2C(CH3)2OH. The content ratio of the water containing the fluorine-containing alcohol and the water to be treated in the present invention is preferably 50% by mass or less, particularly preferably i or less. When the water content ratio is too large, in addition to the more acid. In the distillation step after the separation of the two layers, the tendency is to perform simple distillation in advance, and it is preferred to remove the water first. The acid used in the present invention is preferably an inorganic acid, and a strong acid such as sulfuric acid or hydrofluoric acid is more preferable, and in the case of separating the two layers by sulfuric acid, nitric acid and salt, the lower layer is further difficult to be subjected to the step. The corrosion distillation unit is particularly preferred from the viewpoint of corrosion. In the mixture of fluorinated fluorenes, hydrazines, radicals, R1 and R2 1 to 4, k 25 mass% is necessary. It is preferable to add nitric acid or hydrochloric acid to a certain extent. The other distillation is carried out by using sulfuric acid (4) 1359805 in the present invention, and the amount of acid added is converted to a molar ratio of 0.10 or more with respect to the water in the mixed liquid containing the fluorine-containing alcohol and water (H+) ( The addition amount of acid is 100% dissociation), preferably 0.15 or more, or 0.20 • or more. When the molar ratio described above is less than 0.1, the proportion of water in the lower layer becomes large, and the layer separation is also difficult. Further, it is usually not advantageous to add an acid excessively, and the amount of the acid added causes separation of two layers, so that the content of the fluorine-containing alcohol in the lower layer is preferably a certain amount of Φ or more. When the acid is added to the mixed solution containing the fluorine-containing alcohol and water, it is preferably carried out at normal temperature and normal pressure. Generally, it is not necessary to control the temperature. In order to uniformly mix the added acid with the above-mentioned mixture, it is mixed by a stirring blade or the like. In order to separate the two layers, it may be allowed to stand, or may be separated using a centrifuge. When standing still to separate the two layers, the standing time is preferably from 3 to 12 hours depending on the thickness of each layer and the interface area. φ is preferably 80% by mass or more, particularly preferably 90% by mass or more, and more preferably 92% by mass or more, in the lower layer obtained by the two-layer separation step in the present invention. The higher the content ratio of the above-mentioned fluorine-containing alcohols, the smaller the burden when the distillation is carried out in the subsequent steps. In the present invention, the upper layer obtained by the two-layer separation step usually contains 10 to 30% by mass of a fluorine-containing alcohol, and the upper layer obtained for the fluorine-containing alcohol in the upper layer is available in the next batch of the two-layer separation step. It is effectively recycled as part of the acid reuse. In the present invention, the lower layer obtained by the two-layer separation step has the addition
-8- (5) 1359805 以蒸餾之蒸餾步驟爲佳。藉此可再將下層之水分去除，可 得水分濃度小之含氟醇類》 蒸餾條件並無特別之限定，以普通之多級蒸餾可除去 水分。於本發明以2層分離步驟所得之下層因水之含有比 例小，此蒸餾步驟可以短時間完成。 於蒸餾步驟，藉由蒸餾前述之下層部分等，以得到水 分濃度爲1000ppm以下之含氟醇類爲佳。此乃因將含氟 醇類用作資料記憶媒體所用之色素溶媒時，水分濃度低者 爲佳。特別是水分濃度爲5 00ppm以下，更進一步使水分 濃度爲200 ppm以下爲佳。爲達成前述之水分濃度，於本 發明中，於蒸餾步驟後亦可設計有使用沸石等乾燥劑，除 去含氟醇類中之水分之步驟。 實施例 以下，參照實施例（例1〜3)說明本發明。 [例1]-8- (5) 1359805 The distillation step of distillation is preferred. Thereby, the water of the lower layer can be removed, and the fluorine-containing alcohol having a small water concentration can be obtained. The distillation conditions are not particularly limited, and the water can be removed by ordinary multi-stage distillation. In the present invention, the lower layer obtained by the two-layer separation step is smaller in water content ratio, and the distillation step can be completed in a short time. In the distillation step, it is preferred to obtain a fluorine-containing alcohol having a water concentration of 1000 ppm or less by distillation of the lower layer portion or the like. This is because when a fluoroalcohol is used as a pigment solvent for a data memory medium, the water concentration is preferably low. In particular, the water concentration is preferably 500 ppm or less, and further preferably the water concentration is 200 ppm or less. In order to achieve the above-described water concentration, in the present invention, a step of removing the moisture in the fluorine-containing alcohol may be employed after the distillation step using a desiccant such as zeolite. EXAMPLES Hereinafter, the present invention will be described with reference to examples (Examples 1 to 3). [example 1]
將TFPO 5〇g以及去離子水15g置入分液漏斗中，搖 晃使二者完全混合，變爲均勻之液體。再緩慢滴下96質 量％之濃硫酸1 1.5g，搖晃並靜置3小時後之混合液分離 爲2層。且前述之濃硫酸之添加量爲相對於混合液中之 水，將質子（H+ )之莫耳比換算後爲0.27。分別取出分層 後之上層與下層，得到上層爲24.6g，下層爲49.8g。將 上層以及下層之TFPO濃度以NMR定量後，上層之TFPO -9- (6) 1359805 濃度爲24.5質量％，下層之TFP0濃度舄93.7質量％ β N MR之測定條件如以下所示。 \ <NMR測定條件〉 測定裝置：日本電子社製 ECP-400 測定核： 測定法：單脈衝法 測定溶媒：無（僅採取試料至試驗管） φ 測定溫度：室溫 試料管外徑：5mm [例2] 除96質量％之濃硫酸之滴下量爲9g，其餘均與例i 相同，進行TFPO與去離子水之混合 '分離。且前述之濃 硫酸之添加量爲相對於混合液中之水，將質子（H+)之莫耳 比換算後爲0.2 1。靜置後混合液分離爲2層，得到上層爲 23.0g’下層爲50_7g。上層之TFPO濃度爲18.3質量％， 下層之TFPO濃度爲93.4質量％。 [例3] 除96質量％之濃硫酸之滴下量爲4.5g，其餘均與例 1相同，進行TFPO與去離子水之混合、分離。且前述之 濃硫酸之添加量爲相對於混合液中之水，將質子（H+)之莫 耳比換算後爲〇. 1 1。靜置後混合液分離爲2層，得到上層 爲I5.7g，下層爲53.7g。上層之TFPO濃度爲15.5質量 -10- 1359805 - (7) %，下層之TFPO濃度爲 " 本發明之含氟醇類的 ’ 造 CD— R 及 DVD— R 而 -且再利用之方法。 且，此處引用2005 4 申請200 5 -3 78 8 8號之說 要之全部內容，取用爲本 90.0質量％。 回收方法，係適合作爲自因爲製 產生之廢液中，將含氟醇類回收 F 2月1 5日申請專利之日本專利 明書、申請專利範圍、圖面及摘 發明之說明書之揭示。TFPO 5〇g and 15g of deionized water were placed in a separatory funnel, and the two were thoroughly mixed to form a uniform liquid. Further, 1 1.5 g of 96% by mass concentrated sulfuric acid was slowly dropped, and the mixture was shaken and allowed to stand for 3 hours, and the mixture was separated into 2 layers. Further, the amount of the concentrated sulfuric acid added was 0.27 based on the molar ratio of the proton (H+) to the water in the mixed solution. The upper layer and the lower layer after separation were respectively taken out to obtain 24.6 g of the upper layer and 49.8 g of the lower layer. The TFPO concentration of the upper layer and the lower layer was quantified by NMR, and the concentration of the upper layer of TFPO-9-(6) 1359805 was 24.5% by mass, and the lower layer of TFP0 concentration was 93.7 mass%. The measurement conditions of β N MR were as follows. \ <NMR measurement conditions> Measurement apparatus: ECP-400 manufactured by JEOL Ltd. Measurement core: Measurement method: Single pulse method for measuring solvent: None (sample only to test tube) φ Measurement temperature: room temperature Sample tube outer diameter: 5 mm [Example 2] The amount of concentrated sulfuric acid of 96% by mass was 9 g, and the others were the same as in Example i, and the mixture of TFPO and deionized water was separated. Further, the amount of the concentrated sulfuric acid added was 0.2 1 based on the molar ratio of the proton (H+) to the water in the mixed solution. After standing, the mixed liquid was separated into 2 layers to obtain an upper layer of 23.0 g' and a lower layer of 50-7 g. The TFPO concentration of the upper layer was 18.3% by mass, and the concentration of TFPO of the lower layer was 93.4% by mass. [Example 3] The amount of concentrated sulfuric acid of 96% by mass was 4.5 g, and the rest was the same as in Example 1, and mixing and separation of TFPO and deionized water were carried out. Further, the amount of the concentrated sulfuric acid added is 〇.1 1 with respect to the water in the mixed solution, the molar ratio of the proton (H+) is converted. After standing, the mixture was separated into 2 layers to give an upper layer of 5.7 g and a lower layer of 53.7 g. The TFPO concentration of the upper layer is 15.5 mass -10- 1359805 - (7) %, and the TFPO concentration of the lower layer is " the method of making the CD-R and DVD-R of the fluorine-containing alcohol of the present invention - and recycling. Moreover, the entire contents of the 2005 4 application No. 200 5 -3 78 8 8 are cited herein, and the usage is 90.0% by mass. The recovery method is suitable for the recovery of the fluorine-containing alcohol from the waste liquid produced by the system. The Japanese patent application filed on February 15th, the patent application scope, the drawings and the description of the invention are disclosed.
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