201024254 九、發明說明： 【發明所屬之技術領域】 本發明係關於精煉甘油的方法，更特別關於其蒸餾程 序之前的前處理步驟。 【先前技術】 由於化石能源價格波動，以石油為基礎之工業進入「碳 鲁水化合物」時代，朝綠色化學的方向前進。其中開發副產 物應用技術，實現零排放以體現「原子經濟性反應」是綠 色化予的重要課題。在許多工業生產中，甘油常以副產物 形式存在。舉例而言，肥皂生產中，油脂4化產生脂肪酸 鹽（鹼皂）時產生甘油。又例如，在生質柴油量產中，生產】 啼生質柴油約產生謂公斤甘油。另外，在油脂生產中， 如油脂裂解、息化、油脂醇解，除可得到天然脂肪酸、脂 肪酸鹽、脂肪酸甲醋夕卜，也會產生約1〇%左右的甜水。甘 雩油甜水是天然甘油的主要來源，天然甘油產量的9〇%以上 來自油脂產品。 一純淨的甘油是一種無色有甜味的黏狀液體，它是一種 二=醇’因此具有_物質具有之化學性f，可參與許多 =反應’生成各種衍生物’或形成各種化學產品生產的 2例如生產生物分解性塑躁的原料乳酸、生產柴油抗 ’一甘油_及生產聚對苯二甲酸丙KPTT)之原料丙 醇由於甘/由無毒，因此在食品、醫藥、與化工領域皆 201024254 有重要應用，而且隨著生物科技發展，其應用範圍正在不 斷延伸與擴展。 由於甘油黏度高且流動性不佳，為了獲取高纯户 (99.5%以上純度）的甘油’傳統加熱方式將甘油加熱蒸發純 化並不可行，也因此發展出不同甘油純化技術與製程。美 國專利US 2741638提出在甘油中加入易於分離之圓形顆 粒(granular material)以改善加熱法流動性問題。美國專利 US 2615924提出離子交換法純化甘油。美國專利公開號201024254 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of refining glycerol, and more particularly to a pretreatment step prior to its distillation procedure. [Prior Art] Due to fluctuations in fossil energy prices, oil-based industries have entered the era of “carbon-lubricated compounds” and are moving toward green chemistry. Among them, the development of by-product application technology to achieve zero emissions to reflect the "atomic economic response" is an important issue for greening. In many industrial processes, glycerol is often present as a by-product. For example, in the production of soap, glycerin is produced when fats and oils are produced to produce a fatty acid salt (alkali soap). For another example, in the mass production of biodiesel, the production of xenobiotic diesel produces about kilograms of glycerol. In addition, in the production of oils and fats, such as oil cracking, incorporation, and oily alcoholysis, in addition to natural fatty acids, fatty acid salts, and fatty acid methyl vinegar, about 1% of sweet water is produced. Sweet oil is the main source of natural glycerin, and more than 9% of natural glycerin production comes from oil products. A pure glycerin is a colorless and sweet viscous liquid, which is a kind of bis-alcohol. Therefore, it has the chemical nature of the substance, and can participate in many kinds of reactions, 'reacting various derivatives' or forming various chemical products. 2 For example, the raw material lactic acid for producing biodegradable plastic bismuth, the raw material for producing diesel anti- glycerol _ and the production of poly(trimethylene terephthalate) are not toxic, so they are in the fields of food, medicine, and chemical industry. There are important applications, and with the development of biotechnology, its application range is constantly expanding and expanding. Due to the high viscosity of glycerin and poor fluidity, in order to obtain high purity households (99.5% purity) glycerol' traditional heating method is not feasible to heat and purify glycerol, so different glycerol purification techniques and processes have been developed. U.S. Patent No. 2,741,638 teaches the addition of a granular material which is easy to separate into glycerin to improve the flowability of the heating process. U.S. Patent No. 2,615,924 teaches the purification of glycerol by ion exchange. US Patent Publication Number
® US 2006/0014974以薄膜分離純化甘油。美國專利US 5424467則提出真空蒸顧法純化甘油。當甘油來源係來自 發酵槽時，粗甘油含有烯烴聚合物（olefin linkages)、酮 (acetals)、雙鍵碳化物(carbonyl groups)及其它不飽合有機 污染物質。若使用離子交換法、薄膜分離法、與真空蒸餾 法純化甘油，須先將上述污染物質脫除，才有利於甘油精 煉程序之進行。美國專利US 3198843使用0.2〜5wt.%過氧 ❹化氫與〇.〇1〜〇.5wt.%含氧觸媒將粗甘油進行前處理。美國 專利US 4683347提出利用超臨界高擴散低張力特性，將粗 甘油先進行前處理程序以脫除污染物質，再進行蒸餾純化 程序。另外，當甘油來源係來自生質柴油時，因生質柴油 生產過程中，為提鬲反應轉化率，常加入過量的甲醇及驗 觸媒，這些鹼與甲醇皆溶於副產品甘油。來自生質柴油之 粗甘油含有皂、鹽及酯等物質，若使用真空蒸餾法、薄膜 分離、或離子交換法純化甘油，生產時容易發生甘油聚合 與離子交換粒子失效，甘油純度不穩定，純化效率不高， 6 201024254 且生產、維護、及操作成本高。欲將上述污染物質脫除， 美國專利US 7126032將氮氣分離及製造系統產生之氮 氣，以氮氣流（sparger)方式注入反應槽體，趕出甘油中低 沸點的水及甲醇，改變反應平衡，使甘油中的脂肪酸易於 生成甘油酯（glyceride)，並可於低pH條件下分離出甘油， 最後再進行甘油蒸餾純化程序。 綜上所述，目前仍需較簡易的前處理方法以精煉甘油。 p 【發明内容】 本發明提供一種甘油精煉方法，包括提供粗甘油至第 一分相器；加入醇類及無機酸至粗甘油，形成脂肪酸、第 一甘油、及無機酸鹽，接著以第一分相器分離出第一甘油； 將第一甘油及三氯化鐵加入第二分相器，形成雜質、第二 甘油及鐵皂（通稱脂肪酸鐵鹽），接著以第二分相器分離出 第二甘油；將第二甘油及氳氧化鈉加入靜態混合器，調整 第二甘油之pH值至7.5〜10之間、中合沉澱過量之三氯化 • 鐵、鐵皂及提高第二甘油之純度；以及將第二甘油進行蒸 餾程序，使第二甘油形成精煉甘油。 【實施方式】 本發明針對生質柴油來源產生之甘油，提出一種甘油 純化方法及對應系統。首先，提供粗甘油至第一分相器； 加入醇類及無機酸至粗甘油，形成脂肪酸、第一甘油、及 無機酸鹽，接著以第一分相器分離出第一甘油；將第一甘 油及三氯化鐵加入第二分相器，形成雜質、第二甘油、及 7 201024254 鐵皂，接著以第二分相器分離出第二甘油；將第二甘油及 氫氧化鈉加入靜態混合器，調整第二甘油之pH值至7.5〜10 之間、沉澱過量之三氯化鐵、及提高第二甘油之純度；以 及將第二甘油進行蒸餾程序，使第二甘油形成精煉甘油。 由於在蒸餾程序前，本發明已利用不同助劑，將粗甘油進 行前處理，脫除甘油中脂肪酸、鹽、皂及酯類等物質，再 進行蒸餾純化程序，將甘油精煉至美國藥典規範項目中之 純度等級，此方法或製造程序與習知技藝相較下相對簡 易，適合商業化放大或實施連續大量生產。 第1圖係本發明一實施例中，精煉甘油之設備示意 圖。首先，將粗甘油由泵浦113送入製程，以預熱方式或 使用靜態混合器210將粗甘油與適量的醇類（如甲醇或乙醇) 混合後注入分相器300中。上述稀釋甘油的步驟可改善其 流動性。接著進行酸處理，以泵浦213將無機酸200加入 分相器300内的粗甘油。在本發明一實施例中，無機酸為 硫酸或鹽酸。在本發明一實施例中，無機酸為商用磷酸， 購入濃度85wt%。酸處理可中和粗甘油中之鹼，另一方面 可調整粗甘油的pH值，使粗甘油中的皂或油脂水解為脂 肪酸。在本發明一實施例中，無機酸之添加須控制甘油溶 液之pH值於3.0-5.0之範圍。若當pH值過高時，會大幅 降低甘油純化效能。若pH值過低時，其純度提升並不明 顯且酸根離子易與Fe2+結合形成鐵垢物質如磷酸亞鐵。 在進行酸處理後，將醇類（如曱醇或乙醇）加入分相器 300作為第一階段的助劑。加入醇類的原因在於甘油對無 8 201024254 ㈣分轉度’而醇㈣《鹽有較低 = 文善填酸鹽於分相器中分離效果不佳之 中過诗二、1離之磷酸鹽將進—步於後段過滤器510 醇本發明一實施例中，粗甘油與作為助劑之 重量比例介於！錢至1:2.⑽之間。料類助劑的 ❿ f力县〇董低於上述_，則會減少甘油純辨。增加醇的添 目1奋可增加甘錢化率，但若_助劑的添加比例過高， 則會造錢狀_蒸解_㈣載，增加回收能源投 入值。 由於脂肪酸和甘油互溶性低，可利用分相器300分離 上層月曰肪酸、中層甘油相、及下層部份不溶之無機酸鹽(如 碟酸鹽)及皂化物。分相ϋ 300可為具有擋板及液面控制之 液液分離或液固分離之傾析器，或板式分離器。分離後之 脂肪酸送入脂肪酸儲槽320暫存，中層之甘油相則繼續流 入分相器310。在本發明一實施例中，可採用板式過濾器 φ 或孔隙度小於10微米之濾袋去除無機酸鹽。 由於分相器300之中層甘油相在流入分相器310後， 仍含有殘皂、各種不同分子量的脂肪酸、色素和其他有機 雜質，因此需在分相器310加入三氯化鐵作為第二階段的 助劑’使甘油相中之殘皂及低分子量脂肪酸生成不溶性鐵 息’增加皂化物脫除效率。重視這些皂化物脫除之理由在 於微量的皂化物(<〇·1%)容易造成後段蒸餾塔起泡，蒸餾塔 液位瞬間增加’引起系統操作不穩定情況下，最後可能被 迫停車處理。加入三氯化鐵後，上述之甘油相會分層成三 9 201024254 層。接著以分相器310分離上層黑色雜質、中層甘油相、 及下層部份無機酸鹽類（如磷酸鹽）及皂化物。分相器310 可為具有播板及液面控制之液液分離或液固分離之傾析 器’或板式分離器。在本發明一實施例中，甘油與添加之 三氯化鐵的重量比例介於1:〇 〇〇1至1:0.1之間。若三氯化 鐵助劑的添加量低於上述範圍，則會不利於甘油相中殘皂 之水解及沉殿，此時若同時發生分相器300中脂肪酸脫除 功效不佳，此殘皂將通過分相器31〇並於過濾器510阻塞 鲁 且極易造成蒸餾塔起泡。若三氯化鐵助劑的添加比例過 高’則過量鐵離子可能會於設備内發生結垢現象’降低設 備使用效能。在本發明一實施例中，更包括高速離心機或 過濾器於分相器300及310與靜態混合器410之間以提高 分離及過濾速率或效能。在發明另一實施例中，可進一步 採用板式過濾器或孔隙度小於10微米之濾袋去除無機酸 鹽及/或鐵皂。 經分相器310分離出之甘油，已脫除大部份之皂、脂 肪酸、與無機酸鹽，然因使用三氣化鐵助劑及下述其它理 由’本發明在將甘油相泵入蒸餾程序前，先將分相器310 分離出之甘油以泵浦323注入靜態混合器410，並利用泵 浦403將氫氧化鈉（第三階段助劑）泵入靜態混合器410後 與甘油混合。此步驟利用氫氧化鈉中和無機酸，並利用熱 交換器420控制靜態混合器之反應溫度。一方面，將酯類 轉為皂並成為鈉鹽；另一方面將過量的三氯化鐵水合物轉 變成氫氧化鐵(Fe(OH)3)，使部份未分離之鈉鹽轉為鐵鹽沉 201024254 澱分離，並於後段過濾器510中過濾脫除。脫除鈉鹽之目 地在有效改善後段蒸餾程序塔底之重質物黏度，使得甘由 精顧塔之塔底再沸器設計與操作更加準確容易，亦可降低 設備費用。另外’由於添加氫氧化納作為第三階段助劑， 可使甘油相呈微鹼性’有助於防止後段設備受酸性腐餘， 延長後段蒸顧塔塔組的使用壽命。在本發明一實施例中， 第二甘油與氩氧化鈉之添加量須控制甘油溶液之pH值於 7.5至1〇.〇範圍内。若氫氧化鈉助劑的添加量低於上述範 圍’則鐵皂形成效率不佳’且過低pH值將會使進入甘油 蒸顧塔之脂肪酸含量較高，此時若該塔未有脫除脂肪酸之 設計’例如在進入甘油蒸館塔前再補充適當氫氧化鈉或於 塔中設計脂肪酸分餾系統’則脂肪酸將影響最終甘油產品 之純度’甘油純度無法提高至99.7%以上。若氫氧化納助 劑的添加比例高於上述範圍，則鹼性過強，對設備亦會造 成腐蝕影響。 經上述純化後之甘油則預先注入甘油進料塔5〇〇，暫 存之甘油澄清液以泵浦513注入後段過濾器51〇過濾後， 即可進行甘油純化技術中，較為熟知且常用之蒸館程序。 蒸餾的目的是取得精製甘油，本發明以泵浦523、613、 713、及813配合醇類蒸餾塔600、水份蒸餾塔7〇〇、及甘 油蒸餾塔800進行三道連續蒸餾程序，依序脫除或回收醇 類、水份、及其它雜質’這些雜質可能包括可溶於甘油中 之脂肪酸皂、聚合甘油、水和鹽。醇類蒸餾塔可獲得純度 超過99.5%醇類，因此可回收使用；水份蒸餾塔塔底的甘 201024254 油純度已可提高至85%以上，經甘油蒸餾塔，甘油濃度可 進一步蒸餾濃縮。在甘油蒸餾塔之設計上，因考慮常壓下 的甘油沸點是290。(：，但在204〇C便開始分解和發生聚合反 應，因此蒸餾必須在真空度要求在15t〇rr以下條件進^ 使用薄膜紐器作為再㈣，以減少甘油聚合及 =。收集甘油蒸麟㈣之麵料獲 = 油，此甘油之純度分折可撻田4 又又檟煉甘 合併光學分析法確認甘油'密度内差法或 有極微黃色，可通過脫色改d筆若工得的甘油還帶 致色物和離子。 。甘油色澤，進—步移除微量 為使本技藝人士更清每士 之實施例。 楚本發明之特徵’特舉例於下述 t實施例] 實施例1 (醇類助劑之影響） 取100g粗甘油，分別遗姐 稀釋液及助劑，其添加量分:醇、乙醇作為第—階段之 第1表所示），再加入鱗酸中f、100ml、200m1^ 物後，取出甘油層再加M %(pH=7.G)。過濾鹽類及急化 水分。最後倒人分液料，4Γ时除_、雜、及 分析甘油純度(每1個樣品，各 ^隨著甲醇添加量増第2圈所示’ 盯16%至95.87%，此外將甲^油純度也增加，分別由 、甲醇改變為乙醇時，添加量為 201024254 50或100 ml時，甘油純度都較添加曱醇時更為提高，於乙 醇添加量為l〇〇ml，甘油純度為最高約98.25%，但是如再 增加乙醇添加量為200 m卜則甘油純度反而降至90.89%。 經由肉眼觀察，發現添加乙醇所精鍊之甘油其色澤較透 明、清澈，而甲醇或乙醇添加量改變則對甘油色澤變化不 大。 表1.曱醇、乙醇種類及添加量對於甘油純度變化之實驗數據 項次 助劑及用量 甘油積分面積 甘油纯度 A1 甲醇一50ml 2208.4 82.87% 2221.2 83.47% 2215.6 83.12% 平均值 2215.1 83.16% A2 甲醇一100ml 2377.6 93.96% 2374.9 93.53% 2378.5 93.63% 平均值 2377.0 93.71% A3 曱醇一200ml 2686.6 96.25% 2702.6 97.06% 2715.9 9430% 平均值 2701.7 95.87% A4 乙醇~50ml 1952.3 92.25% 1953.9 92.50% 1945.8 92.73% 平均值 1950.7 92.49% A5 乙醇一100ml 3007.9 9835% 2998.8 97.24% 3011.3 99.18% 平均值 3006.0 9825% A6 乙醇一200ml 1949.8 91.38% 1945.9 91.20% 1937.6 90.08% 13 201024254 平均值 平均值 1944.4 90.89% 1 2067 88.01% 2060.1 87.37% 2063 87.09% 206337 87.49% A7 實施例2 (三氯化鐵助劑之影響） 取100mL之實施例1中編號A5步驟純化之甘油及5g 之三氣化鐵混合後，測其皂化值為77.88mg KOH/g。另外 取100mL之實施例1中編號A5步驟純化之甘油，未加三 氯化鐵直接測其皂化值為35.33mg KOH/g。由於三氯化鐵 易吸濕’能生成雙水（FeCl3-2H20)及六水化合物 (FeCl3_6H2〇) ’水溶液呈酸性’有助水解甘油相中殘皂，增 加皂化物脫除效率’並可以與甘油相中之低分子量脂肪酸 結合，使甘油相中油脂平均分子量（又稱皂化當量）增加。® US 2006/0014974 Purifies glycerol by membrane separation. U.S. Patent No. 5,424,467 teaches the purification of glycerol by vacuum evaporation. When the source of glycerol is from a fermenter, the crude glycerol contains olefin linkages, acetals, carbonyl groups, and other unsaturated organic contaminants. If the glycerol is purified by ion exchange, membrane separation, and vacuum distillation, the above pollutants must be removed before the glycerin refining process is facilitated. U.S. Patent No. 3,1988,43 uses a pretreatment of crude glycerol using 0.2 to 5 wt.% peroxygen hydride and 〇.〇1~〇.5 wt.% oxygen-containing catalyst. U.S. Patent No. 4,683,347 teaches the use of supercritical, high-diffusion, low-tension characteristics to pre-treat crude glycerol to remove contaminants and then perform a distillation purification procedure. In addition, when the source of glycerol is derived from biodiesel, in the production process of biodiesel, in order to increase the conversion rate of the reaction, an excess of methanol and a test medium are often added, and these alkalis and methanol are dissolved in by-product glycerin. The crude glycerin from biodiesel contains soap, salt and ester. If glycerol is purified by vacuum distillation, membrane separation or ion exchange, glycerol polymerization and ion exchange particle failure are likely to occur during production. The purity of glycerol is unstable and purified. Inefficient, 6 201024254 and high cost of production, maintenance, and operation. In order to remove the above pollutants, U.S. Patent No. 7,126,032, the nitrogen gas produced by the nitrogen separation and manufacturing system is injected into the reaction tank by a nitrogen gas flow method to drive out the low boiling water and methanol in the glycerin to change the reaction balance. Fatty acids in glycerol tend to form glycerides, and glycerol can be separated under low pH conditions, and finally a glycerol distillation purification procedure. In summary, there is still a need for a simple pre-treatment method to refine glycerol. [Invention] The present invention provides a glycerin refining method comprising providing crude glycerol to a first phase separator; adding an alcohol and a mineral acid to crude glycerol to form a fatty acid, a first glycerin, and a mineral acid salt, followed by a first The phase separator separates the first glycerin; the first glycerin and the ferric chloride are added to the second phase separator to form impurities, the second glycerin and the iron soap (commonly referred to as fatty acid iron salt), and then separated by the second phase separator The second glycerin; the second glycerin and sodium strontium oxide are added to the static mixer, the pH of the second glycerin is adjusted to between 7.5 and 10, and the excessive precipitation of trichlorinated iron, iron, iron soap and the second glycerin are adjusted. Purity; and the second glycerol is subjected to a distillation procedure to form the second glycerol to form refined glycerol. [Embodiment] The present invention relates to a glycerin-purifying method and a corresponding system for glycerol produced from a raw diesel fuel source. First, providing crude glycerol to the first phase separator; adding an alcohol and a mineral acid to the crude glycerin to form a fatty acid, a first glycerin, and a mineral acid salt, and then separating the first glycerin by a first phase separator; Glycerin and ferric chloride are added to the second phase separator to form impurities, second glycerin, and 7 201024254 iron soap, and then the second glycerin is separated by a second phase separator; the second glycerin and sodium hydroxide are added to the static mixture And adjusting the pH of the second glycerin to between 7.5 and 10, precipitating an excess of ferric chloride, and increasing the purity of the second glycerin; and subjecting the second glycerin to a distillation procedure to form the second glycerol to form refined glycerol. Since the present invention has used different auxiliaries before the distillation process, the crude glycerin is pretreated to remove fatty acids, salts, soaps and esters from glycerol, and then subjected to a distillation purification procedure to refine the glycerin to the US Pharmacopoeia specification project. In terms of purity grade, this method or manufacturing procedure is relatively simple compared to conventional techniques and is suitable for commercial scale-up or continuous mass production. Fig. 1 is a schematic view showing the apparatus for refining glycerin in an embodiment of the present invention. First, crude glycerin is fed from the pump 113 to the process, and the crude glycerin is mixed into an appropriate amount of an alcohol such as methanol or ethanol in a preheating manner or using a static mixer 210, and then injected into the phase separator 300. The above step of diluting glycerin can improve its fluidity. Next, an acid treatment is carried out to pump the inorganic acid 200 to the crude glycerin in the phase separator 300 by pumping 213. In an embodiment of the invention, the mineral acid is sulfuric acid or hydrochloric acid. In one embodiment of the invention, the mineral acid is commercial phosphoric acid and is purchased at a concentration of 85 wt%. The acid treatment neutralizes the base in the crude glycerin, and on the other hand, adjusts the pH of the crude glycerin to hydrolyze the soap or fat in the crude glycerin to a fatty acid. In one embodiment of the invention, the addition of the mineral acid is controlled to control the pH of the glycerol solution in the range of from 3.0 to 5.0. If the pH is too high, the glycerol purification efficiency will be greatly reduced. If the pH is too low, the purity increase is not obvious and the acid ions are easily combined with Fe2+ to form an iron scale substance such as ferrous phosphate. After the acid treatment, an alcohol such as decyl alcohol or ethanol is added to the phase separator 300 as a first stage auxiliary. The reason for adding alcohol is that glycerin is not 8 201024254 (four) degree of rotation 'and alcohol (four) "salt is lower = wenshan acid salt in the phase separator is not good in the separation of poetry 2, 1 away from the phosphate will Further Steps in the Rear Section Filter 510 Alcohol In one embodiment of the invention, the weight ratio of crude glycerin to the additive is between! Money is between 1:2. (10). The auxiliaries of the auxiliaries are lower than the above _, which will reduce the pure identification of glycerol. Increasing the amount of alcohol added can increase the rate of sweetening, but if the proportion of auxiliaries is too high, it will be _ _ _ _ _ (four) load, increase the value of recycled energy. Since the mutual solubility of the fatty acid and the glycerin is low, the phase separator 300 can be used to separate the upper layer of the fatty acid, the middle glycerin phase, and the lower partially insoluble inorganic acid salt (e.g., the acid salt) and the saponified product. The phase separation unit 300 can be a decanter having a liquid-liquid separation or a liquid-solid separation of the baffle and the liquid level control, or a plate separator. The separated fatty acid is sent to the fatty acid storage tank 320 for temporary storage, and the middle glycerin phase continues to flow to the phase separator 310. In one embodiment of the invention, the mineral acid salt may be removed using a plate filter φ or a filter bag having a porosity of less than 10 microns. Since the layer glycerin phase in the phase separator 300 still contains residual soap, various fatty acids, pigments and other organic impurities after flowing into the phase separator 310, it is necessary to add ferric chloride as the second stage in the phase separator 310. The additive 'increases the insoluble iron in the residual glycerin phase and the low molecular weight fatty acid' to increase the saponification removal efficiency. The reason for paying attention to the removal of these saponifications is that a small amount of saponification (<1%) is likely to cause foaming in the latter distillation column, and the liquid level in the distillation column is instantaneously increased, causing unstable operation of the system, and may eventually be forced to stop. . After the addition of ferric chloride, the above glycerin phase will be layered into three 9 201024254 layers. Next, the upper layer black impurity, the middle layer glycerin phase, and the lower portion of the inorganic acid salt (such as phosphate) and the saponified product are separated by a phase separator 310. The phase separator 310 can be a decanter or a plate separator having liquid-liquid separation or liquid-solid separation of the seeding and liquid level control. In one embodiment of the invention, the weight ratio of glycerin to added ferric chloride is between 1: 〇〇 至 1 and 1: 0.1. If the addition amount of the ferric chloride auxiliary agent is lower than the above range, the hydrolysis and the sinking of the residual soap in the glycerin phase are disadvantageous, and if the fatty acid removal effect in the phase separator 300 occurs at the same time, the residual soap is not good. It will pass through the phase separator 31 and block at the filter 510, and it will easily cause the distillation tower to foam. If the proportion of the addition of ferric chloride auxiliaries is too high, then excessive iron ions may cause fouling in the equipment to reduce the efficiency of the equipment. In one embodiment of the invention, a high speed centrifuge or filter is further included between phase splitters 300 and 310 and static mixer 410 to increase separation and filtration rates or performance. In another embodiment of the invention, the inorganic acid salt and/or iron soap may be further removed using a plate filter or a filter bag having a porosity of less than 10 microns. The glycerol separated by the phase separator 310 has removed most of the soap, fatty acid, and inorganic acid salt, but because of the use of the three-iron iron auxiliary agent and other reasons described below, the present invention pumps the glycerin phase into the distillation. Prior to the procedure, the glycerol separated from the phase separator 310 is first injected into the static mixer 410 by the pump 323, and the sodium hydroxide (third stage auxiliary) is pumped into the static mixer 410 by the pump 403 to be mixed with the glycerin. This step neutralizes the mineral acid with sodium hydroxide and controls the reaction temperature of the static mixer using heat exchanger 420. In one aspect, the ester is converted to a soap and becomes a sodium salt; on the other hand, an excess of ferric chloride hydrate is converted to iron hydroxide (Fe(OH)3), and a portion of the unseparated sodium salt is converted to iron. The salt was separated by 201024254 and removed by filtration in the back filter 510. The purpose of removing the sodium salt is to effectively improve the viscosity of the heavy material at the bottom of the distillation step, so that the design and operation of the bottom reboiler of the tower can be more accurate and easy, and the equipment cost can also be reduced. In addition, due to the addition of sodium hydroxide as the third-stage additive, the glycerin phase can be made slightly alkaline, which helps to prevent the acidity of the latter equipment from being affected, and prolongs the service life of the steaming tower in the latter stage. In one embodiment of the invention, the second glycerol and sodium arsenide are added in an amount to control the pH of the glycerin solution in the range of 7.5 to 1 Torr. If the addition amount of the sodium hydroxide auxiliary agent is lower than the above range 'the iron soap formation efficiency is poor' and the too low pH value will make the fatty acid content into the glycerin steaming tower higher, at this time, if the tower is not removed The design of the fatty acid 'for example, adding the appropriate sodium hydroxide before entering the glycerin steaming tower or designing the fatty acid fractionation system in the tower' will affect the purity of the final glycerin product - the purity of glycerol cannot be increased to more than 99.7%. If the addition ratio of the sodium hydroxide assisting agent is higher than the above range, the alkalinity is too strong, which may cause corrosion to the equipment. The glycerin purified by the above is pre-injected into the glycerin feed tower 5〇〇, and the temporarily stored glycerin clarification liquid is pumped into the post-stage filter 51〇 by the pump 513, and then the glycerin purification technology can be carried out, and the steam is more well-known and commonly used. Library program. The purpose of the distillation is to obtain purified glycerin. The present invention performs three continuous distillation procedures by pumping 523, 613, 713, and 813 with an alcohol distillation column 600, a water distillation column 7〇〇, and a glycerin distillation column 800, in order. Removal or recovery of alcohols, moisture, and other impurities. These impurities may include fatty acid soaps, polymeric glycerol, water, and salts that are soluble in glycerin. The alcohol distillation column can obtain more than 99.5% alcohol, so it can be recycled. The purity of the oil in the bottom of the water distillation tower can be increased to more than 85%. The glycerol distillation column can further distill and concentrate the glycerol concentration. In the design of the glycerin distillation column, the boiling point of glycerol under normal pressure is 290. (:, but at 204〇C, it begins to decompose and polymerize. Therefore, the distillation must be carried out under the conditions of vacuum requirement of 15t〇rr to use the membrane as the re-(four) to reduce the polymerization of glycerol and =. (4) The fabric obtained = oil, the purity of this glycerin can be divided into 挞田4 and 槚 槚 合并 and combined with optical analysis to confirm the glycerol 'density difference method or has a very slight yellow, can be changed by decolorization Coloring matter and ions. Glycerin color, and further removal of trace amounts are examples for making the skilled person clearer of the present invention. The characteristics of the invention are described in the following t examples. Example 1 (Alcohol Effect of the auxiliary agent) Take 100g of crude glycerin, respectively, the diluent and auxiliary agent of the elder sister, the addition amount is: alcohol, ethanol as the first stage of the first stage), and then add squaric acid f, 100ml, 200m1 After the object, the glycerin layer was taken out and added with M% (pH = 7.G). Filter salts and sharpen moisture. Finally, the liquid material is poured, and the purity of glycerol is removed at 4 ( (for each sample, each ^ is shown as the second lap of the methanol addition), which is 16% to 95.87%, and the oil will be added. The purity also increased. When methanol was changed to ethanol, the purity of glycerol was higher than that of adding sterol when the amount was increased to 201024254 50 or 100 ml. The amount of ethanol added was l〇〇ml, and the purity of glycerol was the highest. 98.25%, but if the amount of ethanol added is 200 m, the purity of glycerol will drop to 90.89%. It is found by visual observation that the glycerin refined by adding ethanol is more transparent and clear, while the amount of methanol or ethanol is changed. The color change of glycerol is not big. Table 1. The type and amount of sterol, ethanol and the amount of glycerol purity change experimental data sub-auxiliaries and dosage glycerol integral area glycerin purity A1 methanol-50ml 2208.4 82.87% 2221.2 83.47% 2215.6 83.12% average 2215.1 83.16% A2 methanol-100ml 2377.6 93.96% 2374.9 93.53% 2378.5 93.63% average 2377.0 93.71% A3 sterol-200ml 2686.6 96.25% 2702.6 97.06% 2715.9 9430% Mean 2701.7 95.87% A4 Ethanol~50ml 1952.3 92.25% 1953.9 92.50% 1945.8 92.73% Average 1950.7 92.49% A5 Ethanol-100ml 3007.9 9835% 2998.8 97.24% 3011.3 99.18% Average 3006.0 9825% A6 Ethanol-200ml 1949.8 91.38% 1945.9 91.20% 1937.6 90.08% 13 201024254 Average value 1944.4 90.89% 1 2067 88.01% 2060.1 87.37% 2063 87.09% 206337 87.49% A7 Example 2 (Impact of ferric chloride auxiliary) Take 100 mL of the purification step No. A5 in Example 1 After mixing glycerin and 5 g of three iron-iron, the saponification value was 77.88 mg KOH/g, and 100 mL of the glycerin purified in the step A5 of Example 1 was used, and the saponification value was directly measured without adding ferric chloride. 35.33mg KOH/g. Because ferric chloride is hygroscopic, it can produce double water (FeCl3-2H20) and hexahydrate (FeCl3_6H2〇). 'The aqueous solution is acidic' helps to hydrolyze the residual soap in the glycerin phase and increase the saponification. In addition to the efficiency' and can be combined with the low molecular weight fatty acids in the glycerin phase, the average molecular weight (also known as saponification equivalent) of the fat in the glycerin phase is increased.
雖然本發明已以實施例揭露如上，然其並非用以限定 本發明，任何所屬技術領域中具有通常知識者，在不脫離 本發明之精神和範圍内，當可作任意之更動與潤飾，因此 本發明之保護範圍當視後附之申請專利範圍所界定者為 準。 201024254 【圖式簡單說明】 第1圖係本發明一實施例中，精煉甘油之設備示意 圖；以及 第2圖係本發明一實施例中，不同添加量之醇類助劑 與精煉甘油純度的對應曲線。 【主要元件符號說明】 113、213、323、403、513、523、613、713、813〜泵 浦； 200〜無機酸； 210、410〜靜態混合器； 300、310〜分相器； 320〜脂肪酸儲槽； 420〜熱交換器； 5 00〜甘油進料塔； 510〜後段過濾器； 600〜醇類蒸餾塔； 700〜水份蒸餾塔； 800〜甘油蒸鶴塔。 15Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any person skilled in the art can make any changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of an apparatus for refining glycerin according to an embodiment of the present invention; and FIG. 2 is a diagram showing the purity of alcohol additives of different amounts and refined glycerin in an embodiment of the present invention. curve. [Description of main component symbols] 113, 213, 323, 403, 513, 523, 613, 713, 813~pump; 200~ inorganic acid; 210, 410~ static mixer; 300, 310~ phase splitter; 320~ Fatty acid storage tank; 420~ heat exchanger; 5 00~ glycerin feed tower; 510~ rear stage filter; 600~ alcohol distillation tower; 700~ water distillation tower; 800~ glycerin steamed crane tower. 15