TWI432580B - Process for the purification of organic acids - Google Patents
Process for the purification of organic acids Download PDFInfo
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Description
本發明有關一種用來生產具有高熱穩定性之有機酸回收及純化方法,特別有關於一種使用膜技術從包含乳酸的發酵液中將具有高熱穩定性之乳酸回收及純化方法。The present invention relates to a method for recovering and purifying organic acids having high heat stability, and more particularly to a method for recovering and purifying lactic acid having high heat stability from a fermentation broth containing lactic acid using a membrane technique.
由於有機酸(諸如乳酸、檸檬酸、抗壞血酸、葡萄糖酸或富馬酸等)在食品、醫藥、洗滌劑或者可生物降解的塑膠工業裡被廣泛使用,使得有機酸的需求逐年在增加。發酵方法使得生產有機酸達到工業規模。取決於使用之細菌菌株的pH值要求,由發酵方法產生的有機酸大致上係為鹽形式。自發酵液回收有機酸是分離專家的一項挑戰。Since organic acids such as lactic acid, citric acid, ascorbic acid, gluconic acid or fumaric acid are widely used in food, pharmaceutical, detergent or biodegradable plastics industries, the demand for organic acids is increasing year by year. The fermentation process allows the production of organic acids to reach an industrial scale. The organic acid produced by the fermentation process is substantially in the form of a salt depending on the pH requirements of the bacterial strain used. The recovery of organic acids from fermentation broths is a challenge for separation experts.
從發酵液將有機酸回收及純化之傳統方法一般上包含一個或數個沉澱階段。舉例言之,在生產乳酸的一已知方法中,通常係將發酵液加熱到大約70℃以殺死細菌,然後用硫酸酸化至pH值1.8。沉澱鹽係以過濾移除,接著,使用活性炭處理將產物液體中的任何色料除去,然後,將澄清液體做離子交換且濃縮到80%。氣味與味道可藉由氧化處理(例如用過氧化氫)來進一步改善。在這個階段所獲得的乳酸通常只是可消耗性的品質,不適用於醫藥等級,尚需要增加幾道純化步驟才能達成醫藥等級的適用。傳統方法最大的缺點在於會有大量的乳酸流失。Conventional methods for recovering and purifying organic acids from fermentation broth generally comprise one or several precipitation stages. For example, in a known method of producing lactic acid, the fermentation broth is usually heated to about 70 ° C to kill the bacteria and then acidified to pH 1.8 with sulfuric acid. The precipitated salt was removed by filtration, and then any colorant in the product liquid was removed using activated carbon treatment, and then the clear liquid was ion-exchanged and concentrated to 80%. The odor and taste can be further improved by oxidation treatment (for example with hydrogen peroxide). The lactic acid obtained at this stage is usually only a consumable quality, not suitable for the pharmaceutical grade, and several additional purification steps are required to achieve the pharmaceutical grade. The biggest drawback of the traditional method is that there is a large amount of lactic acid lost.
為使下游的處理能更加環保,替代的下游處理技術已有進行研究,例如已有提議用電透析膜技術來回收與純化乳酸。然而,已知的電透析膜要求高品質的進料,而且由於快速有機酸輸送需要高電流及在此方法中使用雙極性膜衍生相對較高的操作費用。In order to make the downstream treatment more environmentally friendly, alternative downstream treatment technologies have been studied. For example, it has been proposed to use electrodialysis membrane technology to recover and purify lactic acid. However, known electrodialysis membranes require high quality feeds, and require high currents due to rapid organic acid transport and relatively high operating costs due to the use of bipolar membranes in this process.
另一項已知有機酸純化技術是反應式液對液萃取,其中係利用合適載體將有機酸萃取成為有機相,接著,將有機酸反萃取成為水相。頒給Baniel等人的美國專利US6,472,559號揭示在施加高壓的二氧化碳環境下從水相到富有非水溶性胺有機相之乳酸相轉移萃取的使用。在二氧化碳環境移除之後,乳酸被反萃取成為水相。這種技術的缺點在於要使用大量的有機溶劑。另外,常需要實行進一步的純化步驟來移除雜質。Another known organic acid purification technique is reactive liquid-to-liquid extraction in which an organic acid is extracted into an organic phase using a suitable carrier, followed by back extraction of the organic acid to an aqueous phase. US Patent No. 6,472,559 to Baniel et al. discloses the use of lactic acid phase transfer extraction from an aqueous phase to a water-insoluble amine organic phase in a high pressure carbon dioxide environment. After removal of the carbon dioxide environment, the lactic acid is back extracted into an aqueous phase. The disadvantage of this technique is the large amount of organic solvent used. In addition, it is often necessary to carry out further purification steps to remove impurities.
液體膜分離係另一種用來純化有機酸的技術。已有數種不同材料製成的液體膜,例如液體乳化膜、中空纖維支撐式液體膜、及平板支撐式液體膜。液體膜以包含活性載體的有機相進行該源流的液-液隔離而將有機酸分離,該有機酸被萃取成為有機相,且接著以氣提溶液進行有機相的隔離而將有機酸反萃取成為水相。該支撐式液體膜(SLM)的分離機制與其他膜不同。已知的膜係以尺寸來分離組成份,而支撐式液體膜係透過協助傳送機制的化學手段來萃取想要的組成份。支撐式液體膜的化合基本上是液-液萃取。支撐式液體膜相對於液-液萃取的重要優點在於它需要非常少的有機溶劑。但是,實際工業應用所採用的支撐式液體膜受限於支撐式液體膜的穩定性(使用壽命),這是因為溶劑及/或載體流失到水相。被傳送通過膜層的水在擾動該膜上扮演重要角色。因此,有需要一種使用支撐式液體膜來強化有機酸的純化的改良方法。Liquid membrane separation is another technique used to purify organic acids. There are several liquid membranes made of different materials, such as liquid emulsion membranes, hollow fiber supported liquid membranes, and plate supported liquid membranes. The liquid film is subjected to liquid-liquid isolation of the source stream by an organic phase containing an active carrier to separate the organic acid, the organic acid is extracted into an organic phase, and then the organic phase is separated by a stripping solution to back-extract the organic acid. water box. The separation mechanism of the supported liquid membrane (SLM) is different from that of other membranes. Known membrane systems separate components by size, while supported liquid membranes extract the desired components by chemical means that assist in the delivery mechanism. The combination of the supported liquid membranes is essentially a liquid-liquid extraction. An important advantage of a supported liquid membrane over liquid-liquid extraction is that it requires very little organic solvent. However, the supported liquid membrane employed in practical industrial applications is limited by the stability (lifetime) of the supported liquid membrane because the solvent and/or carrier is lost to the aqueous phase. The water that is transported through the membrane plays an important role in disturbing the membrane. Therefore, there is a need for an improved method of using a supported liquid membrane to enhance the purification of organic acids.
依據本發明的第一觀點,一種從包含有機酸之鹽形式的發酵液中將有機酸回收及純化的方法係包括對發酵液進行超過濾或微過濾以形成第一滲透液,將第一滲透液濃縮以形成濃縮液,將濃縮液導入支撐式液體膜以萃取乳酸來形成包含萃取液的分離流,對萃取液進行活性碳處理以除去顏色,對萃取液進行陽離子交換樹脂處理以脫礦,及對萃取液進行陰離子交換樹脂處理以除去陰離子雜質來形成淡化後的有機酸,過濾此淡化後的有機酸以移除超過預定臨界值的雜質及將此淡化後的有機酸濃縮到所要的濃度。According to a first aspect of the invention, a method for recovering and purifying an organic acid from a fermentation broth comprising a salt form of an organic acid comprises ultrafiltration or microfiltration of the fermentation broth to form a first permeate, the first permeate The liquid is concentrated to form a concentrated liquid, and the concentrated liquid is introduced into a supported liquid membrane to extract lactic acid to form a separated stream containing the extract, the extract is subjected to activated carbon treatment to remove the color, and the extract is subjected to cation exchange resin treatment for demineralization. And subjecting the extract to anion exchange resin treatment to remove anionic impurities to form a degraded organic acid, filtering the diluted organic acid to remove impurities exceeding a predetermined threshold value, and concentrating the diluted organic acid to a desired concentration .
從以上揭示及下文對不同較佳實施例的更詳細明,對於熟悉該項技術人士而言,本發明明顯在有機酸純化技術提供重大改良。在此觀點之特別重要者,是本發明能夠提供製造熱穩定有機酸之方法。由以下的詳細說明將可更加了解不同較佳實施例的其他特徵與優點。From the above disclosure and the following more detailed description of the various preferred embodiments, the present invention clearly provides significant improvements in organic acid purification techniques for those skilled in the art. Of particular importance in this regard is the ability of the present invention to provide a method of making a thermally stable organic acid. Other features and advantages of the different preferred embodiments will be apparent from the following detailed description.
請了解所附圖式並無必要依照比例繪製,其係呈現說明本發明基本原理之不同特徵的簡化代表。文中揭示之有機酸純化方法之包含例如在不同階段使用的裝置之具體尺寸之特定設計特徵,其部分將由特定意欲應用與使用環境來決定。圖示實施例之一些特徵係相對其他者有做放大或變形,以便提供清楚的了解。具體而論,例如薄的特徵可以加厚以清楚圖示。所有關於方向與位置的參考,除了另有指明之外,係指在圖式上所示的方向。It is understood that the drawings are not necessarily to scale, The organic acid purification methods disclosed herein include, for example, specific design features of the specific dimensions of the devices used at different stages, some of which will be determined by the particular intended application and use environment. Some of the features of the illustrated embodiments are magnified or modified relative to others to provide a clear understanding. In particular, thin features such as can be thickened for clarity of illustration. All references to direction and position, unless otherwise indicated, refer to the orientation shown on the drawings.
對於熟悉此項技藝人士(亦即在此領域具知識或經驗人士)而言,文中揭示之有機酸純化方法明顯可有多種使用與設計變化。以下對不同替代特徵及實施例的詳細討論將說明本發明關於要用來將乳酸純化的一般原理。在閱讀本文後,對於熟悉技藝人士而言,明顯可有其他適於其他應用之實施例。For those skilled in the art (ie, those with knowledge or experience in this field), the organic acid purification methods disclosed herein are clearly applicable to a variety of uses and design changes. The following detailed discussion of various alternative features and examples will illustrate the general principles of the invention with respect to the purification of lactic acid. After reading this document, it will be apparent to those skilled in the art that other embodiments are suitable for other applications.
本發明揭示一種從發酵液中將有機酸(特別是乳酸)回收及純化方法。在此所述的方法能接受具有任何高於1%乳酸鹽濃度之乳酸發酵液,特別是8%或者更高濃度之乳酸發酵液。參閱圖式,圖1顯示一方法的示意圖,其中發酵液1首先是透過管線2饋入裝置3。該發酵液可以包含例如乳酸之有機酸,且可以是例如乳酸鹽之有機酸的鹽形式。裝置3較佳係例如微過濾膜6或是超過濾膜3的膜,或是二者。該超過濾膜有0.1到0.01微米尺寸的過濾孔,該超過濾膜可以有數種結構型式,例如中空纖維、管式、平板或是螺旋纏繞單元。在一形式中係使用中空纖維膜,其提供優良的表面積對體積比率。本發明的超過濾膜可以由聚合、陶瓷或是金屬材料製成。該超過濾膜做為一個可阻擋懸浮固體、生物量、細菌的屏障形式。配合該超過濾膜的過濾方法可以是橫流法或者端點法。在橫流過濾中,其操作流是與該膜呈平行流動,在端點過濾中,其操作流是與該膜呈垂直流動。與端點過濾法比較,在橫流過濾中只有一部份發酵液穿透過膜。與膜平行之發酵液流動具有足夠的速度來將留住的微粒沖離表面。這連續的橫掃動作可使累積在膜表面上的微粒減到最小,因而延長膜的操作壽命。在這種橫流法中,超過濾膜能從發酵液中取得大約30到99%的所要有機酸回收,特別是60到95%的所要有機酸回收。The invention discloses a method for recovering and purifying an organic acid (particularly lactic acid) from a fermentation broth. The process described herein is capable of accepting a lactic acid fermentation broth having any concentration greater than 1% lactate, particularly a lactic acid fermentation broth having a concentration of 8% or higher. Referring to the drawings, Figure 1 shows a schematic diagram of a process in which fermentation broth 1 is first fed into unit 3 via line 2. The fermentation broth may comprise an organic acid such as lactic acid, and may be in the form of a salt of an organic acid such as lactate. The device 3 is preferably, for example, a membrane of the microfiltration membrane 6 or the ultrafiltration membrane 3, or both. The ultrafiltration membrane has a filter pore size of 0.1 to 0.01 micrometers, and the ultrafiltration membrane may have several structural forms such as a hollow fiber, a tubular, a flat plate or a spiral wound unit. In one form, a hollow fiber membrane is used which provides an excellent surface area to volume ratio. The ultrafiltration membrane of the present invention can be made of a polymeric, ceramic or metallic material. The ultrafiltration membrane acts as a barrier to the suspension of suspended solids, biomass, and bacteria. The filtration method to be combined with the ultrafiltration membrane may be a cross flow method or an end point method. In cross-flow filtration, the operating stream is parallel to the membrane, and in the endpoint filtration, the operating stream flows vertically with the membrane. Compared to the endpoint filtration method, only a portion of the fermentation broth penetrates the membrane in the cross-flow filtration. The fermentation broth flowing parallel to the membrane has sufficient velocity to flush the retained particles away from the surface. This continuous sweeping action minimizes the accumulation of particles on the surface of the film, thereby extending the operational life of the film. In this cross-flow process, the ultrafiltration membrane is capable of recovering about 30 to 99% of the desired organic acid recovery from the fermentation broth, particularly 60 to 95% of the desired organic acid recovery.
為從發酵液中回收更高的有機酸,來自裝置3的濃縮液是通過管線5進入微過濾膜裝置6,該濃縮液中的殘留微粒及/或沈澱物會在該微過濾膜被除去。該微過濾膜具有0.1到1微米尺寸的孔。該裝置6能從發酵液中回收大約50到90%的有機酸,這使發酵液的有機酸的總回收率(超過濾和微過濾二者)增加到大約90至99%。乳酸的進一步回收可藉由微過濾(MF)乳酸發酵液與加水進給來達成。這個方法稱為滲濾。微過濾與滲濾的結合用於提高乳酸的回收。該微過濾膜可以有數種結構型式,例如中空纖維、管式、平板或是螺旋纏繞單元,且包含聚合、陶瓷或者金屬材料。在另一實施例,微過濾-滲濾的結合可直接用來純化該發酵液以取得超過99%的乳酸回收,而不用對該發酵液進行超過濾。第一步驟獲得的是第一滲透液。To recover a higher organic acid from the fermentation broth, the concentrate from unit 3 enters microfiltration membrane unit 6 via line 5, and residual particulates and/or precipitates in the concentrate are removed from the microfiltration membrane. The microfiltration membrane has pores of 0.1 to 1 micron size. The apparatus 6 is capable of recovering about 50 to 90% of the organic acid from the fermentation broth, which increases the total recovery of the organic acid of the fermentation broth (both ultrafiltration and microfiltration) to about 90 to 99%. Further recovery of lactic acid can be achieved by microfiltration (MF) lactic acid fermentation broth with water addition. This method is called percolation. The combination of microfiltration and diafiltration is used to increase the recovery of lactic acid. The microfiltration membrane can be of several structural forms, such as hollow fiber, tubular, flat or spiral wound units, and comprises polymeric, ceramic or metallic materials. In another embodiment, the microfiltration-diafiltration combination can be used directly to purify the fermentation broth to achieve more than 99% lactic acid recovery without ultrafiltration of the fermentation broth. The first step obtained is the first permeate.
圖2顯示該方法的下一步驟,在這裡可藉由濃縮從第一滲透液中將乳酸回收以形成濃縮液來增進回收/萃取率。利用一蒸發器9將第一滲透液濃縮到一濃縮液,特別是在濃縮液裡有20到60%的有機酸含量,且更特別是在30到55%的含量。蒸發處理後獲得的蒸餾物一般包含不到0.5%的乳酸鹽。該蒸餾物幾乎是具有一些揮發性有機碳(VOCs)與微量乳酸的水,其可經由管線10通過一活性碳柱(如圖2中所示的裝置11)而輕易澄清以產生一級品質的水67。或者,蒸餾物可在發酵液中再使用。Figure 2 shows the next step of the process where the recovery/extraction rate can be enhanced by concentrating the lactic acid from the first permeate to form a concentrate. The first permeate is concentrated to a concentrate using an evaporator 9, especially in the concentrate having an organic acid content of 20 to 60%, and more particularly a content of 30 to 55%. The distillate obtained after the evaporation treatment generally contains less than 0.5% of the lactate. The distillate is almost water with some volatile organic carbons (VOCs) and traces of lactic acid, which can be easily clarified via line 10 through an activated carbon column (device 11 as shown in Figure 2) to produce primary quality water. 67. Alternatively, the distillate can be reused in the fermentation broth.
在該發酵液最初pH值比它的酶激活因子(pKa)(例如,乳酸pKa=3.86)高的情況,該濃縮液需要另外的酸化步驟。在本發明中適用的酸化劑14(如圖2中所示)是無機酸,例如鹽酸或者硫酸。因為硫酸不會帶有過多的煙霧與水分,因而使用硫酸不會造成乳酸鹽濃度降低過多。酸化的目的在於轉變發酵液中的有機酸鹽成為有機酸。一般而言,pH值是調整的控制因素。發酵液通常的pH值為5至6.5,並且應該調整到比有機酸的pKa低,對乳酸液特別是1.5至3.8,更好是2至3.6。如果發酵液已經達到低pH值,就不需要進一步酸化來產生酸化液。所需要的酸化劑14數量取決於發酵液的最初pH值。當發酵液在槽13內冷卻時,無機鹽19可能從溶液沉澱,所形成的無機鹽19係取決於用以在發酵期間控制發酵pH值的鹼與酸化劑14。例如,如果使用氫氧化銨控制發酵pH值且使用硫酸來酸化,所形成的無機鹽19將是硫酸銨。硫酸為較佳酸化劑的另一理由是,與其他酸化劑相比較,硫酸鹽一般較容易沈澱。反應式1顯示當引入硫酸到含有乳酸鹽的溶液中時所發生的反應例。Where the initial pH of the fermentation broth is higher than its enzyme activating factor (pKa) (e.g., lactic acid pKa = 3.86), the concentrate requires an additional acidification step. The acidifying agent 14 (shown in Figure 2) suitable for use in the present invention is a mineral acid such as hydrochloric acid or sulfuric acid. Because sulfuric acid does not carry too much smoke and moisture, the use of sulfuric acid does not cause excessive reduction in lactate concentration. The purpose of acidification is to convert the organic acid salt in the fermentation broth into an organic acid. In general, pH is a controlling factor for adjustment. The fermentation broth typically has a pH of from 5 to 6.5 and should be adjusted to a lower pKa than the organic acid, particularly from 1.5 to 3.8, more preferably from 2 to 3.6. If the fermentation broth has reached a low pH, no further acidification is required to produce an acidified liquid. The amount of acidifying agent 14 required depends on the initial pH of the fermentation broth. When the fermentation broth is cooled in the tank 13, the inorganic salt 19 may precipitate from the solution, and the inorganic salt 19 formed depends on the alkali and acidifying agent 14 used to control the pH of the fermentation during the fermentation. For example, if ammonium hydroxide is used to control the fermentation pH and acidified using sulfuric acid, the inorganic salt 19 formed will be ammonium sulfate. Another reason why sulfuric acid is a preferred acidifying agent is that sulfates are generally easier to precipitate than other acidifying agents. The reaction formula 1 shows an example of a reaction which occurs when sulfuric acid is introduced into a solution containing lactate.
反應式1:以硫酸將乳酸鹽酸化成為乳酸Reaction formula 1: Hydrochloric acid is converted into lactic acid by sulfuric acid
2 LacNH4 +H2 SO4 →2 LacH+(NH4 )2 SO4 2 LacNH 4 +H 2 SO 4 →2 LacH+(NH 4 ) 2 SO 4
藉由添加酸產生酸性液的酸化過程是放熱的,因此它生熱且造成溶液溫度增加。在溶液冷卻至大約50℃之後(較佳為25℃),鹽會沉澱析出。在上述實施例中,硫酸銨將開始沉澱析出。當溶液冷卻到室溫(25℃)時,大量的硫酸鹽將結晶析出。在發酵中,乳酸鹽可能是乳酸鈣、乳酸鈉或者乳酸銨。在使用硫酸的酸化期間,將產生相對應的硫酸鹽。如果有任何鹽在這製程期間形成,可使用例如離心機來將它們濾掉。一般而言,如果(i)最初發酵液pH值為5或者更高(在乳酸鈉或乳酸銨中);(ii)用硫酸做為酸化劑;及(iii)在濃縮第一滲透液步驟期間,發酵液的濃度已經增加到超過20%,將會有可觀的鹽形成。透過裝置17能將鹽與發酵液有效分離,該裝置17可以是壓濾機或者是任何其它固體-液體的分離器。該方法的其餘步驟最好是在接近環境條件進行。The acidification process of the acidic liquid by the addition of an acid is exothermic, so it generates heat and causes an increase in the temperature of the solution. After the solution is cooled to about 50 ° C (preferably 25 ° C), the salt precipitates. In the above examples, ammonium sulfate will begin to precipitate. When the solution was cooled to room temperature (25 ° C), a large amount of sulfate precipitated crystals. In fermentation, the lactate may be calcium lactate, sodium lactate or ammonium lactate. During acidification using sulfuric acid, the corresponding sulfate will be produced. If any salts are formed during this process, they can be filtered out using, for example, a centrifuge. In general, if (i) the initial fermentation broth has a pH of 5 or higher (in sodium lactate or ammonium lactate); (ii) sulfuric acid as an acidifying agent; and (iii) during the step of concentrating the first permeate, The concentration of the fermentation broth has increased to more than 20% and there will be considerable salt formation. The salt can be effectively separated from the fermentation broth by means of a device 17, which can be a filter press or any other solid-liquid separator. The remaining steps of the method are preferably carried out in close proximity to environmental conditions.
該(過濾的、酸化的及)濃縮的液體可如上述來進行過濾。濃縮液一般包低水平的懸浮固體。該濃縮液可能是澄清液或者是包含超過20%(特別是20到65%乳酸濃度)乳酸的暗色黏性液體,取決於所要回收乳酸的濃度。該濃縮液被傳送到圖2-4所示的槽21內。當該過濾酸化的發酵液20饋入裝置23時,將進行乳酸回收,如圖3所示。用以從酸化的濃縮液萃取乳酸的裝置23係所稱之支撐式液體膜(SLM)。The (filtered, acidified and) concentrated liquid can be filtered as described above. Concentrates generally contain low levels of suspended solids. The concentrate may be a clear liquid or a dark viscous liquid containing more than 20% (particularly 20 to 65% lactic acid concentration) of lactic acid, depending on the concentration of lactic acid to be recovered. This concentrate is transferred to the tank 21 shown in Figures 2-4. When the filtered acidified fermentation broth 20 is fed into the apparatus 23, lactic acid recovery will be performed as shown in FIG. The means 23 for extracting lactic acid from the acidified concentrate is referred to as a supported liquid membrane (SLM).
該支撐式液體膜23包含由合適組成份組成的一有機層,該組成份浸漬在另一膜(基膜)上,例如超過濾(UF)或者微過濾(MF)類型的膜。在一形式中係使用微過濾膜,因為它的孔區域密度高。使用在支撐式液體膜的基膜有疏水性質且可包含例如聚丙烯(PP)、聚乙烯二氟化物(PVDF)及聚乙烯(PE)之疏水性聚合物,或例如聚碸(PSF)、聚醚碸(PES)及聚乙烯亞硫酸鹽(PVS)之兩性聚合物。疏水性聚合物一般上是合適的基膜材料;在最佳的形式中係使用聚丙烯聚合物,因為它的疏水性質高、成本相對較低、優良的機械特性及優良的化學穩定性。The supported liquid film 23 contains an organic layer composed of a suitable component, which is impregnated on another film (base film), such as a membrane of the ultrafiltration (UF) or microfiltration (MF) type. A microfiltration membrane is used in one form because of its high density of pore regions. The base film used in the supported liquid film has hydrophobic properties and may comprise a hydrophobic polymer such as polypropylene (PP), polyethylene difluoride (PVDF), and polyethylene (PE), or, for example, polyfluorene (PSF), An amphoteric polymer of polyether oxime (PES) and polyethylene sulfite (PVS). Hydrophobic polymers are generally suitable base film materials; polypropylene polymers are used in the most preferred form because of their high hydrophobicity, relatively low cost, excellent mechanical properties and excellent chemical stability.
該支撐式液體膜23具有浸漬在基膜內的有機層,該有機層在惡劣的操作期間藉由膜的孔(在此是微孔)的牽制能穩定基膜。該有機層包含4個組成份:一載體、一共同萃取劑、一稀釋劑及一穩定劑。該載體包括不溶於水的胺,特別是第一、第二、第三脂族胺或芳族胺,較佳為包含具有C4 -C24 之至少一烷基鏈的胺。在更佳形式中,該載體是有C8 -C12 之烷基鏈的第三脂族胺。The supported liquid film 23 has an organic layer immersed in the base film, which stabilizes the base film by the pinning of the pores (here, micropores) of the film during the harsh operation. The organic layer comprises four components: a carrier, a co-extractant, a diluent and a stabilizer. The carrier comprises a water-insoluble amine, especially a first, second, third aliphatic or aromatic amine, preferably an amine comprising at least one alkyl chain having from C 4 to C 24 . In a more preferred form, the third carrier is an aliphatic amine alkyl chain of C 8 -C 12.
該共同萃取劑係在該有機酸萃取方法中協助該載體的一液體,該共同萃取劑可包含具有少量水溶性的脂族醇,特別是含C2 -C29 碳鏈的醇,更特別是含C6 -C10 碳鏈的醇。該醇的官能度可以在該碳鏈(正醇)的末端或者在分支。該共同萃取劑可包含例如有C8 -C10 的正鏈醇或者是有C6 -C9 的支鏈醇。The co-extractant assists a liquid of the carrier in the organic acid extraction process, and the co-extractant may comprise an aliphatic alcohol having a small amount of water solubility, particularly an alcohol having a C 2 -C 29 carbon chain, more particularly An alcohol containing a C 6 -C 10 carbon chain. The functionality of the alcohol can be at the end of the carbon chain (n-alcohol) or in the branch. The co-extractant may comprise, for example, a C 8 -C 10 normal chain alcohol or a C 6 -C 9 branched alcohol.
在有機層添加稀釋劑來稀釋載體的濃度,以便增加載體的黏性來幫助萃取速率。一般而言,可使用與基膜相容但與水不相溶的任何有機液體。合適的稀釋劑包括烴、酮,醚或酯。合適的烴可包含例如煤油、甲基異丁基酮、一異丁基酮及醋酸丁酯。在閱讀本文後,對於熟悉技藝人士而言,明顯可有其他合適的稀釋劑。A diluent is added to the organic layer to dilute the concentration of the carrier to increase the viscosity of the carrier to aid in the extraction rate. In general, any organic liquid that is compatible with the base film but not water compatible can be used. Suitable diluents include hydrocarbons, ketones, ethers or esters. Suitable hydrocarbons may include, for example, kerosene, methyl isobutyl ketone, monoisobutyl ketone, and butyl acetate. After reading this document, it will be apparent to those skilled in the art that other suitable diluents are available.
穩定劑幫助有機組成份(即基膜中之萃取劑、共同萃取劑及稀釋劑)穩定。支撐式液體膜的使用壽命取決於有機組成份在其環境即水相裡的損失速率。在習知的支撐式液體膜,損失在幾小時內發生。依據高度需要的特徵,在本文所述的穩定劑是具有非常低水溶解度與低水表面張力的一種非離子性界面活性劑。該穩定劑在該有機組成份中係做為有機相與水相之間的一個屏障,因而降低二相的混合。The stabilizer helps to stabilize the organic component (ie, the extractant, co-extractant, and diluent in the base film). The service life of a supported liquid membrane depends on the rate of loss of the organic component in its environment, ie, the aqueous phase. In conventional supported liquid membranes, losses occur within a few hours. The stabilizers described herein are a nonionic surfactant having very low water solubility and low water surface tension, depending on the highly desirable characteristics. The stabilizer acts as a barrier between the organic phase and the aqueous phase in the organic component, thereby reducing the mixing of the two phases.
適用在本發明中的穩定劑有3個主要基團,它們是:烴基、矽基及碳氟化合物基的穩定劑。非離子界面活性劑是碳氟化合物基。非離子界面活性劑是沒有離子頭部基的界面活性劑形式。該碳氟化合物基界面活性劑的親水基團是非離子羧化物群組,且因此具有非常小的水溶解度。該碳氟化合物基界面活性劑的尾部基團是疏水性且親油性。這確保該穩定劑主要會留在溶劑-水的介面。由碳氟化合物基界面活性劑所創造的邊界將限制膜內之水與有機溶液的混合,因而降低通過膜的水分輸運,因此延長支撐式液體膜的穩定性。該表面活性劑的非離子性質也做為該離子種類一另外的障礙,因此改進膜對於有機酸的選擇性。相較下,界面活性劑對於酸形式中的有機酸較少阻礙,而諸如硫酸與鹽酸的有機酸在水媒介中完全離子化,且因而被限制進入液體膜相(因為水分輸運是有限的),這造成在有機酸與無機酸之間有更好的選擇性。在具有0.01%穩定劑之液體膜組成份的典型實驗裝置中,有機酸相對無機酸的選擇性可能高到數千倍。Stabilizers suitable for use in the present invention have three main groups which are: hydrocarbyl, sulfhydryl and fluorocarbon based stabilizers. The nonionic surfactant is a fluorocarbon based group. Nonionic surfactants are in the form of surfactants without an ionic head group. The hydrophilic group of the fluorocarbon-based surfactant is a group of nonionic carboxylates and therefore has very little water solubility. The tail group of the fluorocarbon-based surfactant is hydrophobic and lipophilic. This ensures that the stabilizer will remain primarily in the solvent-water interface. The boundary created by the fluorocarbon-based surfactant will limit the mixing of the water within the membrane with the organic solution, thereby reducing the moisture transport through the membrane, thus extending the stability of the supported liquid membrane. The nonionic nature of the surfactant also serves as an additional barrier to the ionic species, thus improving the selectivity of the membrane for organic acids. In contrast, surfactants are less obstructive to organic acids in the acid form, while organic acids such as sulfuric acid and hydrochloric acid are completely ionized in aqueous media and are thus restricted from entering the liquid film phase (because moisture transport is limited) ), which results in better selectivity between organic and inorganic acids. In a typical experimental setup with a liquid film composition of 0.01% stabilizer, the selectivity of the organic acid relative to the mineral acid can be as high as several thousand times.
同樣地,水-液體膜相互作用的限制也使葡萄糖穿過膜的輸運減低。包括合適選擇上述萃取劑、共同萃取劑及稀釋劑之本發明的支撐式液體膜之穩定性超過180天。一般而言,可添加從0.001到10%之穩定劑,高量的穩定劑使膜更穩定但是萃取速率低。最佳的穩定劑濃度是從0.005-0.020ppm。該碳氟化合物基的非離子界面活性劑具有Rf CH2 CH2 O(CH2 CH2 O)x H的一般結構,該式子中的x是從0-25的數字,且Rf 是碳氟化合物群組F(CF2 CF2 )y ,該式子中的y是1到20。Likewise, the limitation of water-liquid membrane interaction also reduces the transport of glucose across the membrane. The stability of the supported liquid film of the present invention comprising suitable selection of the above extractant, co-extractant and diluent is over 180 days. In general, from 0.001 to 10% stabilizer can be added, and a high amount of stabilizer makes the film more stable but has a low extraction rate. The optimum stabilizer concentration is from 0.005 to 0.020 ppm. The fluorocarbon-based nonionic surfactant has the general structure of R f CH 2 CH 2 O(CH 2 CH 2 O) x H, where x is a number from 0-25, and R f is The fluorocarbon group F(CF 2 CF 2 ) y , y in the formula is 1 to 20.
該載體、共同萃取劑、稀釋劑及穩定劑在浸漬到基膜的孔內之前,係混合成一均勻相。該基膜是形成中空纖維構造。該裝置23允許一液流(stream)沿著該纖維的內腔流動,而另一液流沿著該纖維的鞘側流動。一更佳的配置是令該源溶液(source solution,即該濃縮液)沿著鞘側流動,而接收溶液(receiving solution,亦稱為氣提溶液)沿著內腔流動。二溶液沿著各自側重新循環:源溶液沿著管線22(如圖3中所示)進入裝置23且沿著管線24將溶液帶回到槽21;該接收溶液沿著管線26輸送進入裝置23且沿著管線27將溶液帶回到支持槽25。藉由酸28透過劑量管線29將源相的pH值保持比該pKa低,例如對乳酸溶液是1.5到3.6。酸28一般與酸化劑14相同。接收溶液可能只是水,或者包含例如鹽酸或者碳酸鈉的化學物。最佳的接收溶液是純水,因為這將使更後階段之淡化(polishing)影響減低。該萃取方法包含:The carrier, co-extractant, diluent and stabilizer are mixed into a homogeneous phase prior to being impregnated into the pores of the base film. The base film is formed into a hollow fiber structure. The device 23 allows a stream to flow along the lumen of the fiber while another stream flows along the sheath side of the fiber. A more preferred configuration is to cause the source solution to flow along the sheath side and a receiving solution (also known as a stripping solution) to flow along the lumen. The two solutions are recirculated along their respective sides: the source solution enters device 23 along line 22 (as shown in Figure 3) and carries the solution back to tank 21 along line 24; the receiving solution is transported along line 26 into device 23 The solution is brought back to the support tank 25 along line 27. The pH of the source phase is maintained below the pKa by the acid 28 through the dose line 29, for example 1.5 to 3.6 for the lactic acid solution. Acid 28 is generally the same as acidifier 14. The receiving solution may be just water or a chemical containing, for example, hydrochloric acid or sodium carbonate. The best receiving solution is pure water as this will reduce the effect of polishing at a later stage. The extraction method comprises:
(I)有機酸與載體的質子化(I) Protonation of organic acids and carriers
[R3 N]org +[LacH]aq [R3 NH+ Lac- ]org [R 3 N] org +[LacH] aq [R 3 NH + Lac - ] org
在質子化期間,有機酸結合在胺上During protonation, the organic acid binds to the amine
(II)乳酸穿過有機層轉移到接收溶液側。(II) Lactic acid is transferred to the receiving solution side through the organic layer.
乳酸胺絡合物從源溶液側輸送穿過有機層到接收溶液側。該輸送機制是絡合物的擴散或者是乳酸鹽分子的躍動:The lactate amine complex is transported from the source solution side through the organic layer to the receiving solution side. The transport mechanism is the diffusion of the complex or the jump of the lactate molecule:
[R3 NH+ Lac- ]org +[R3 N’][R3 N’H+ Lac- ]org +[R3 N][R 3 NH + Lac - ] org +[R 3 N'] [R 3 N'H + Lac - ] org +[R 3 N]
該式子中的N’是接近接收端,及在接收端;及N' in the equation is close to the receiving end and at the receiving end;
(III)胺的去質子化(III) Deprotonation of amines
該乳酸(或者一般有機酸)是從源溶液轉移到接收溶液。The lactic acid (or generally organic acid) is transferred from the source solution to the receiving solution.
源溶液量與接收溶液量的比率較佳從1:1到8:1,且更好是從1:1到4:1。該萃取處理時間有部份是決定在源頭與接收的比率、有機酸濃度及萃取裝置(即該支撐式液體膜)。當源相有機濃度相較於接收相濃度超過20%時,該萃取處理應該停止,因為該萃取速率會太慢。應收集該接收溶液以進一步處理。一新鮮的接收相在系統裡循環以進一步萃取乳酸。在萃取幾次之後,該源溶液當包含少於8%的乳酸,這將不適於萃取,因為萃取速率會變得太慢。在一實施例中,源頭與接收的比率是2:1,且源相乳酸濃度最初是48%;該源溶液乳酸鹽濃度在每3到5小時之6輪萃取之後將降低到7至10%。在接收溶液中的平均乳酸濃度是1到15%。該裝置23的獨特優點是有機酸的高選擇性。通常,該接收溶液中的葡萄糖量不明顯,這是乳酸發酵的原料。因為乳酸已萃取進入乾淨的溶液,所以接收相的顏色相對於該源溶液是低的。與澄清發酵液相比較(在超過濾/微過濾之後),顏色可能化減50到500倍。該支撐式液體膜的高選擇性性質確保該接收相包含最少的離子雜質且實際上與源相離子雜質濃度無關。在包含48%乳酸鹽、PH值3.2、4.0-4.5%銨、10-20%硫酸鹽之最初來源的較佳裝置實施中,接收溶液應包含0.0001-0.05%的銨與0.0001-0.04%的硫酸鹽。The ratio of the amount of the source solution to the amount of the receiving solution is preferably from 1:1 to 8:1, and more preferably from 1:1 to 4:1. Part of the extraction time is determined by the ratio of source to receiver, organic acid concentration, and extraction device (ie, the supported liquid membrane). When the source phase organic concentration is more than 20% compared to the receiving phase concentration, the extraction process should be stopped because the extraction rate will be too slow. The receiving solution should be collected for further processing. A fresh receiving phase is circulated through the system to further extract lactic acid. After several extractions, the source solution contains less than 8% lactic acid, which would be unsuitable for extraction because the extraction rate would become too slow. In one embodiment, the source to receiver ratio is 2:1 and the source phase lactic acid concentration is initially 48%; the source solution lactate concentration is reduced to 7 to 10% after every 3 to 5 hours of 6 rounds of extraction. . The average lactic acid concentration in the receiving solution is 1 to 15%. A unique advantage of this device 23 is the high selectivity of the organic acid. Usually, the amount of glucose in the receiving solution is not significant, which is a raw material for lactic acid fermentation. Because lactic acid has been extracted into a clean solution, the color of the receiving phase is low relative to the source solution. Compared to the clarified fermentation liquid phase (after ultrafiltration/microfiltration), the color may be reduced by 50 to 500 times. The highly selective nature of the supported liquid membrane ensures that the receiving phase contains minimal ionic impurities and is virtually independent of the source phase ionic impurity concentration. In a preferred apparatus implementation comprising an initial source of 48% lactate, pH 3.2, 4.0-4.5% ammonium, 10-20% sulfate, the receiving solution should comprise 0.0001-0.05% ammonium and 0.0001-0.04% sulfuric acid. salt.
為了提升回收率,該濃縮溶液係透過管線30送到另一蒸發器31以進一步濃縮,該裝置31的蒸發容量大約比裝置9小5到8倍,裝置31的排出物可包含15-60%的乳酸,一般約為30-50%。因為該溶液包含的硫酸銨已接近飽和點,在濃縮期間會析出硫酸銨,特別是當濃縮超過40%的時候。該濃縮液係以如前述方法的相同方式來過濾,透過管線33進入一冷卻槽34,且透過管線35進入一濾壓機或任何合適的固液分離裝置36以獲得收集在槽40中的乾淨濃縮液及在38中的硫酸銨結晶或任何碳化的沉澱。在這過濾步驟中,因為該濃縮液已經在低的pH值,沒有必要進一步預酸化。接著使用前述裝置23的相同萃取方法,利用裝置42的支撐式液體膜對槽40中的澄清濃縮液進行乳酸萃取。在將該發酵液溶液導入裝置31以進一步濃縮之前,所形成的溶液可棄置或透過管線49饋入裝置50以進一步進行超過濾。In order to increase the recovery rate, the concentrated solution is sent to another evaporator 31 through line 30 for further concentration. The evaporation capacity of the device 31 is about 5 to 8 times smaller than that of the device 9, and the discharge of the device 31 may include 15-60%. The lactic acid is generally about 30-50%. Since the ammonium sulfate contained in the solution is close to the saturation point, ammonium sulfate is precipitated during concentration, especially when the concentration exceeds 40%. The concentrate is filtered in the same manner as previously described, passed through line 33 into a cooling bath 34, and passed through line 35 to a filter press or any suitable solid-liquid separation device 36 to obtain a clean collection in tank 40. The concentrate and the ammonium sulfate crystals in 38 or any carbonized precipitate. In this filtration step, since the concentrate is already at a low pH, no further pre-acidification is necessary. The clarified concentrate in tank 40 is then subjected to lactic acid extraction using the same extraction method of apparatus 23 described above using a supported liquid membrane of apparatus 42. Before the fermentation broth solution is introduced into the apparatus 31 for further concentration, the formed solution can be disposed of or fed through the line 49 to the apparatus 50 for further ultrafiltration.
來自支撐式液體膜製程的全部接收萃取液(收集在槽25及44中)是結合成一液流,該液流包含一些會使萃取液有顏色的化合物。該結合流被饋入活性碳塔裝置54(如圖7中所示),在此藉由將活性碳引入萃取液來減弱溶液顏色。活性碳與有色化合物結合,從萃取液中將他們移除。All of the received extract from the supported liquid membrane process (collected in tanks 25 and 44) is combined into a liquid stream containing some of the compounds that will color the extract. The combined stream is fed to an activated carbon column unit 54 (as shown in Figure 7) where the color of the solution is attenuated by introducing activated carbon into the extract. Activated carbon is combined with the colored compounds and removed from the extract.
如圖7所示,來自該裝置54的脫色萃取液能夠透過管線68導入裝置69以供濃縮。一般而言,裝置69可以是任何能夠從發酵液溶液中除去水來濃縮有機酸的裝置,特別是將進給溶液從低到0.05%的濃度濃縮到高達50%的濃度,在較佳的實施例中,從1-8%的進給濃度濃縮到高達8-10%的輸出濃度。在該較佳的實施例中,裝置69是高分子膜,在它的操作模式下,只允許萃取液中的水流過該膜。裝置69的水容許性可以是壓力驅動、真空驅動及/或熱驅動。在最佳的實施例中,在裝置69中使用逆滲透(RO)膜(一種壓力驅動膜),裝置69的使用可以用比傳統蒸發裝置低的能源成本將萃取液濃縮到較高的濃度。裝置69的預濃縮有效地降低了後續步驟中裝置所需要處理的體積。由裝置69除去的水能夠導入裝置25及44用為發酵液的源頭或者其它需要的地方。或者,濃縮步驟可在脫色步驟之前進行。As shown in Figure 7, the decolorized extract from the apparatus 54 can be introduced into the apparatus 69 through line 68 for concentration. In general, the apparatus 69 can be any apparatus capable of concentrating the organic acid from the fermentation broth solution, particularly concentrating the feed solution from as low as 0.05% to a concentration of up to 50%, preferably in a preferred embodiment. In the example, the concentration is concentrated from a feed concentration of 1-8% to an output concentration of up to 8-10%. In the preferred embodiment, device 69 is a polymeric membrane that, in its mode of operation, only allows water in the extract to flow through the membrane. The water tolerance of device 69 can be pressure driven, vacuum driven, and/or thermally driven. In the preferred embodiment, a reverse osmosis (RO) membrane (a pressure driven membrane) is used in apparatus 69, and the use of apparatus 69 can concentrate the extract to a higher concentration with lower energy costs than conventional evaporation apparatus. Preconcentration of device 69 effectively reduces the volume that the device needs to handle in subsequent steps. The water removed by the device 69 can be introduced into the devices 25 and 44 as the source of the fermentation broth or other desired location. Alternatively, the concentration step can be carried out prior to the decolorization step.
不論是否從裝置69進行進一步濃縮,萃取液之後都可被導入一系列柱中進行淡化(polishing)以提高質量。該系列的淡化柱可包含例如i)用於除去陽離子雜質的陽離子交換塔(去礦物質);ii)用於除去陰離子雜質的陰離子交換塔;iii)用於脫色的淡化脫色樹脂或活性碳塔。儘管在較佳實施例中,陽離子交換塔較佳係在陰離子交換塔之間,而脫色或活性碳塔可設在陽離子交換塔與陰離子交換塔之前、之後或之間,這三種塔能夠以任意順序進行操作。Whether or not further concentration is performed from device 69, the extract can then be introduced into a series of columns for polishing to improve quality. The series of desalination columns may comprise, for example, i) a cation exchange column (demineralization) for removing cationic impurities; ii) an anion exchange column for removing anionic impurities; iii) a desalinated decolorizing resin or activated carbon column for decolorization . Although in a preferred embodiment, the cation exchange column is preferably between the anion exchange columns, and the decolorizing or activated carbon column can be placed before, after or between the cation exchange column and the anion exchange column, the three columns can be optionally Operate in sequence.
來自裝置69的預濃縮液與來自裝置54的脫色發酵液透過管線70或管線55導入陽離子交換塔裝置56以個別移除任何微量陽離子雜質。一般而言,在裝置56中可使用任何強陽離子交換樹脂,大孔類型的陽離子交換樹脂是一種選項。除了移除陽離子雜質以外,陽離子交換塔56也進一步將發酵液的一些或所有顏色除去。接著以陰離子交換裝置58透過管線57進一步處理該脫礦乳酸溶液。在該陰離子交換裝置58裡將全部陰離子雜質除去。在裝置58中需要弱陰離子交換樹脂,在一實施例中係使用大孔類型的樹脂。The pre-concentrate from unit 69 and the decolorized fermentation broth from unit 54 are introduced into cation exchange column unit 56 via line 70 or line 55 to individually remove any traces of cationic impurities. In general, any strong cation exchange resin can be used in unit 56, and a macroporous type of cation exchange resin is an option. In addition to removing cationic impurities, the cation exchange column 56 further removes some or all of the color of the fermentation broth. The demineralized lactic acid solution is then further treated by anion exchange unit 58 through line 57. All anion impurities are removed in the anion exchange unit 58. A weak anion exchange resin is required in device 58, and in one embodiment a macroporous type of resin is used.
如果必要,去除顏色的步驟可以重複進行。此外,陽離子交換、陰離子交換及顏色去除後也可重覆進行濃縮步驟。例如,儘管自陰離子交換裝置58排出的萃取液通常沒有顏色,但在任意方法中萃取液經過陰離子交換之後,低水平的顏色仍繼續存在,來自陰離子交換塔的排出物可進一步透過包含例如淡化脫色樹脂或活性碳的裝置60來脫色。根據起始的濃度,產物萃取液一般包含7-12%的乳酸。如果要求溶液產物的濃度低於10%,使該溶液經過另一濃縮裝置62是有利的。裝置62可以類似裝置69的任何具體設備,在一較佳實施例中,另一RO膜可用在裝置62中,裝置62能夠將溶液濃縮成11-15%的乳酸。根據起始的濃度與產物的濃度,由裝置62所去除的水63可包含0.1-6%的乳酸。產物萃取液包含11-15%的有機酸,然後將其透過裝置72進行純化。裝置72是一種基於分子量截流的分離裝置,它會去除可能已經通過所有先前過程的預定臨界值以上的大分子量雜質。裝置72較佳是具有100-300道爾頓的截流分子量(MWCO)的奈米過濾膜,更佳是具有100-150道爾頓的MWCO以純化乳酸。裝置72允許乳酸通過該膜,同時保留下分子量高於其MWCO的大部分雜質,當進一步將其濃縮到超過75%的更高濃度時,它改善了乳酸溶液的色值。The step of removing the color can be repeated if necessary. In addition, the concentration step can be repeated after cation exchange, anion exchange, and color removal. For example, although the extract from the anion exchange unit 58 is generally colorless, after any anion exchange in the process, the low level of color continues to exist and the effluent from the anion exchange column can be further permeable, for example, by desalination. A device 60 of resin or activated carbon is used for decolorization. Depending on the initial concentration, the product extract typically contains 7-12% lactic acid. If the concentration of the solution product is required to be less than 10%, it is advantageous to pass the solution through another concentration device 62. Device 62 can be similar to any particular device of device 69. In a preferred embodiment, another RO membrane can be used in device 62, which is capable of concentrating the solution to 11-15% lactic acid. Depending on the initial concentration and the concentration of the product, the water 63 removed by the device 62 may comprise from 0.1 to 6% lactic acid. The product extract contains 11-15% organic acid which is then purified by means of apparatus 72. Device 72 is a molecular weight cut-off separation device that removes large molecular weight impurities that may have passed above a predetermined threshold of all previous processes. Device 72 is preferably a nanofiltration membrane having a cutoff molecular weight (MWCO) of from 100 to 300 Daltons, more preferably having a MWCO of from 100 to 150 Daltons to purify the lactic acid. Device 72 allows lactic acid to pass through the membrane while retaining most of the impurities having a molecular weight above its MWCO, which improves the color value of the lactic acid solution when further concentrated to a higher concentration of more than 75%.
然後可用產物蒸發器(即如圖8所示的裝置75)將來自裝置72的滲透液進行進一步濃縮。裝置75的濃縮係數可以為20-40倍,通常是25-35倍。來自裝置75的濃縮液76可導向產品包裝部。來自裝置72的濃縮液74可透過裝置9或者31來蒸發,或者回到裝置54中以增加乳酸的回收率,如圖12所示。該淡化後的有機酸可用例如過氧化氫的氧化劑進行處理以製造出熱穩定的有機酸,也就是說在高溫下耐脫色的酸。The permeate from unit 72 can then be further concentrated using a product evaporator (i.e., apparatus 75 as shown in Figure 8). The concentration factor of device 75 can be 20-40 times, typically 25-35 times. Concentrate 76 from device 75 can be directed to the product packaging. Concentrate 74 from device 72 can be vaporized through device 9 or 31 or returned to device 54 to increase the recovery of lactic acid, as shown in FIG. The desalted organic acid can be treated with an oxidizing agent such as hydrogen peroxide to produce a thermally stable organic acid, that is, an acid that is resistant to decolorization at high temperatures.
圖9顯示可用裝置11將來自裝置14、28及75的蒸餾物加以處理以除去揮發性有機碳(VOCs)及微量乳酸以生產一級品質的水67。水67的數量一般而言足夠補充對包括設備沖洗之整個方法需求的70-90%。或者,來自裝置14及28的蒸餾物可直接用於製備發酵液,而來自裝置75的蒸餾物能用做支撐式液體膜的接收溶液。Figure 9 shows that the available equipment 11 treats the distillates from units 14, 28 and 75 to remove volatile organic carbons (VOCs) and traces of lactic acid to produce primary quality water 67. The amount of water 67 is generally sufficient to supplement 70-90% of the overall process requirements including equipment flushing. Alternatively, the distillate from units 14 and 28 can be used directly to prepare the fermentation broth, while the distillate from unit 75 can be used as a receiving solution for the supported liquid membrane.
本發明將以下列例子做進一步說明,但無論如何這些例子不應解釋為對本發明的範圍做限制。The invention is further illustrated by the following examples, but these examples should not be construed as limiting the scope of the invention in any way.
例1-超過濾Example 1 - Ultrafiltration
253公升的發酵液在有2巴進料壓力之超過濾膜系統裡循環,該超過濾膜是聚醚碸基的中空纖維膜,其具有3.5 m2 的有效面積。進料溶液被饋入並且在該纖維的腔室內流動。排料壓力控制在1.6巴壓力,跨膜壓力為1.8巴。最初滲透液流動速率是1.9公升/分,且在3個小時回收86%之後下降到0.5公升/分。平均流通量19.5 LMH。在原發酵液中及在第一滲透液中的懸浮固體分別為3.88克/公升和0.005克/公升,該液的濃縮物中有懸浮固體49.78克/公升。The 253 liter fermentation broth was circulated in an ultrafiltration membrane system having a feed pressure of 2 bar, which is a polyether fluorene-based hollow fiber membrane having an effective area of 3.5 m 2 . The feed solution is fed into and flows within the chamber of the fiber. The discharge pressure is controlled at a pressure of 1.6 bar and the transmembrane pressure is 1.8 bar. The initial permeate flow rate was 1.9 liters/min and dropped to 0.5 liters/min after 86% recovery over 3 hours. The average liquidity is 19.5 LMH. The suspended solids in the original fermentation broth and in the first permeate were 3.88 g/liter and 0.005 g/liter, respectively, and the concentrate of the liquid had a suspended solid of 49.78 g/liter.
例2-微過濾Example 2 - Microfiltration
16公升的超過濾(UF)濃縮液(即微過濾(MF)進料)在不鏽鋼微過濾膜內循環,該微過濾膜有二氧化鈦塗層。該膜孔徑為0.1微米,該微過濾進料有49.78克/公升的懸浮固體,該微過濾在3巴跨膜壓力下操作,平均流通量80 LMH。A 16 liter ultrafiltration (UF) concentrate (i.e., a microfiltration (MF) feed) is circulated through a stainless steel microfiltration membrane having a titanium dioxide coating. The membrane had a pore size of 0.1 micron and the microfiltration feed had 49.78 grams per liter of suspended solids which was operated at a 3 bar transmembrane pressure with an average throughput of 80 LMH.
例3-第一滲透液從11%濃縮到48%Example 3 - The first permeate is concentrated from 11% to 48%
100公升的第一滲透液從11%濃縮到48%。回收的濃縮液數量為22.9公升,而77.1公升以蒸餾物收集。100 liters of the first permeate was concentrated from 11% to 48%. The amount of concentrated concentrate recovered was 22.9 liters, while 77.1 liters were collected as distillate.
例4-酸化及硫酸銨的結晶Example 4 - Acidification and crystallization of ammonium sulfate
以13.8公斤的硫酸將包含48.6%乳酸鹽之77.2公升的濃縮溶液從pH值5.6酸化至3.2。在酸化及將溶液冷卻到25℃之後,析出6.1公斤(濕重)的硫酸銨結晶。在濾掉硫酸銨結晶之後,回收82.2公升酸化液。乳酸鹽回收達到99.5%。A 77.2 liter concentrated solution containing 48.6% lactate was acidified to pH 3.2 from pH 5.6 with 13.8 kg of sulfuric acid. After acidification and cooling of the solution to 25 ° C, 6.1 kg (wet weight) of ammonium sulfate crystals were precipitated. After filtering off the ammonium sulfate crystals, 82.2 liters of the acidified liquid was recovered. The lactate recovery reached 99.5%.
例5-以支撐式液體膜萃取乳酸Example 5 - Extraction of Lactic Acid with a Supported Liquid Membrane
以具有70m2 膜面積之中空纖維支撐式液體膜(SLM)將具有40-48%乳酸鹽濃度之濃縮乳酸液萃取。浸漬在膜內的有機層包含0.001-10%的載體、99.9-90.0%的共同萃取劑及稀釋劑。以水作為接收液。接收液的使用量是每次萃取之起始源溶液的一半,萃取持續3到5個小時。相同的方法按比例放大到具有300 m2 有效膜面積之工業尺寸模組上。A concentrated lactic acid liquid having a concentration of 40-48% lactate was extracted with a hollow fiber supported liquid membrane (SLM) having a membrane area of 70 m 2 . The organic layer impregnated in the film contains 0.001 to 10% of a carrier, 99.9 to 90.0% of a co-extractant, and a diluent. Use water as the receiving liquid. The amount of the receiving liquid used is half of the starting source solution for each extraction, and the extraction is continued for 3 to 5 hours. The same method was scaled up to an industrial size module with an effective membrane area of 300 m 2 .
例6-以活性碳來脫色Example 6 - Decolorization with activated carbon
以長度1米、塔直徑1.5英吋、有重0.8公斤碳的活性碳塔處理來自支撐式液體膜程序之共77.2公升的萃取液。A total of 77.2 liters of extract from the supported liquid membrane procedure was treated with an activated carbon column having a length of 1 m, a column diameter of 1.5 inches, and a weight of 0.8 kg of carbon.
例7-以強陽離子交換樹脂來脫礦Example 7 - Demineralization with strong cation exchange resin
以長度1米、直徑1.5英吋且有重0.7公斤樹脂的大孔強陽離子交換樹脂塔處理已經被用活性碳處理之共82.2公升的萃取乳酸溶液。A total of 82.2 liters of the extracted lactic acid solution which had been treated with activated carbon was treated with a macroporous strong cation exchange resin column having a length of 1 m, a diameter of 1.5 inches and a weight of 0.7 kg of resin.
例8-以弱陰離子交換樹脂除去陰離子雜質Example 8 - Removal of anionic impurities by weak anion exchange resin
以長度1米、直徑1.5英吋且有重0.6公斤樹脂的大孔弱陰離子交換樹脂處理共84.29公升的脫礦萃取乳酸溶液。A total of 84.29 liters of demineralized lactic acid solution was treated with a macroporous weak anion exchange resin having a length of 1 m, a diameter of 1.5 inches and a weight of 0.6 kg of resin.
例9-奈米過濾膜Example 9 - Nanofiltration membrane
由裝置62(RO膜)獲得的萃取乳酸溶液經過兩種不同的處理路徑:i)經由裝置75直接濃縮到88±5%;ii)用裝置72(蒸發器)處理,隨後用裝置75(蒸發器)濃縮來自裝置72(NF膜)的滲透液。The extracted lactic acid solution obtained from unit 62 (RO membrane) was passed through two different treatment routes: i) directly concentrated to 88 ± 5% via unit 75; ii) treated with apparatus 72 (evaporator), followed by apparatus 75 (evaporation) The permeate from device 72 (NF membrane) is concentrated.
例10-產品濃度Example 10 - Product Concentration
將88公升稀釋淨化的淡化後乳酸溶液濃縮到88%的乳酸濃度。The 88 liter diluted and purified desalted lactic acid solution was concentrated to a concentration of 88% lactic acid.
穩定劑在支撐式液體膜裡的影響Effect of stabilizers in supported liquid membranes
液體膜的穩定性與水穿過膜的輸運有高度相關,較高的水輸運將導致低穩定性。在實驗情況下,水一般係從接收液轉移到源溶液。使用以同批次之高分子基材纖維製造的二新液體膜模組。除了一個具有0.001-0.02%的非離子界面活性劑,浸漬在微孔纖維裡的有機層具有相同的組成份。在這些試驗上係使用相同之L-乳酸發酵液來源。The stability of the liquid film is highly correlated with the transport of water through the membrane, and higher water transport will result in low stability. In the experimental case, water is generally transferred from the receiving liquid to the source solution. A two-new liquid membrane module made of the same batch of polymer substrate fibers was used. The organic layer impregnated in the microporous fibers has the same composition except for a nonionic surfactant having 0.001 to 0.02%. The same L-lactic acid fermentation broth source was used in these experiments.
過氧化氫的影響Effect of hydrogen peroxide
由裝置72(NF膜)獲得的萃取液經過i)過氧化氫處理;ii)無過氧化氫處理,隨後濃縮成88±3%wt/wt的乳酸濃縮液。The extract obtained from unit 72 (NF membrane) was subjected to i) hydrogen peroxide treatment; ii) without hydrogen peroxide treatment, followed by concentration to 88 ± 3% wt/wt lactic acid concentrate.
熱穩定性試驗Thermal stability test
對由上述方法的實施例之一獲得的濃縮88%的淡化後的乳酸溶液(45MT)於195±5℃在不同時間下進行熱穩定試驗。測量最終溶液的顏色。The 88% concentrated desalted lactic acid solution (45 MT) obtained by one of the above methods was subjected to a heat stability test at 195 ± 5 ° C at different times. The color of the final solution was measured.
從以上揭示及幾個實施例之詳細描述,在不脫離本發明之真實範圍與精神之下,明顯可有各種的修改、附加及其他替代實施例。所討論的實施例係選擇及描述以提供本發明原理與實際應用的最佳說明,因而使得熟悉此項技術人士可運用本發明在不同的實施例與適合個別預期使用的各種修改上。當後附申請專利範圍係公平地、依法地及衡平地依據最大範圍解釋時,全部的變化與修改仍屬本發明之範圍內。Various modifications, additions, and other alternative embodiments are apparent to those skilled in the art. The embodiments discussed are chosen and described in order to provide a description of the embodiments of the present invention All changes and modifications are still within the scope of the invention when the scope of the appended claims is interpreted in a fair, legal, and equitable manner.
1...發酵液1. . . Fermentation liquid
2...管線2. . . Pipeline
3...裝置3. . . Device
5...管線5. . . Pipeline
6...裝置6. . . Device
9...蒸發器9. . . Evaporator
10...管線10. . . Pipeline
11...裝置11. . . Device
13...槽13. . . groove
14...酸化劑14. . . Acidifier
17...裝置17. . . Device
19...無機鹽19. . . Inorganic salt
21...槽twenty one. . . groove
22...管線twenty two. . . Pipeline
23...裝置twenty three. . . Device
24...管線twenty four. . . Pipeline
25...槽25. . . groove
26...管線26. . . Pipeline
27...管線27. . . Pipeline
28...酸28. . . acid
29...劑量管線29. . . Dose line
30...管線30. . . Pipeline
31...裝置31. . . Device
33...管線33. . . Pipeline
34...冷卻槽34. . . Cooling tank
35...管線35. . . Pipeline
36...壓濾機36. . . Filter press
40...槽40. . . groove
42...裝置42. . . Device
44...槽44. . . groove
49...管線49. . . Pipeline
50...裝置50. . . Device
54...裝置54. . . Device
55...管線55. . . Pipeline
56...裝置56. . . Device
57...管線57. . . Pipeline
58...裝置58. . . Device
60...裝置60. . . Device
62...裝置62. . . Device
63...水63. . . water
67...水67. . . water
68...管線68. . . Pipeline
69...裝置69. . . Device
70...管線70. . . Pipeline
72...裝置72. . . Device
74...濃縮液74. . . Concentrate
75...裝置75. . . Device
76...濃縮液76. . . Concentrate
圖1顯示依據一實施例之原發酵液過濾方法的示意圖。1 shows a schematic diagram of a method of filtering a raw fermentation broth according to an embodiment.
圖2顯示一主要方法流體濃縮階段的示意圖。Figure 2 shows a schematic of a major process fluid concentration stage.
圖3顯示一主要支撐式液體膜階段的示意圖。Figure 3 shows a schematic of a primary supported liquid membrane stage.
圖4顯示一支撐方法流體濃縮階段的示意圖。Figure 4 shows a schematic of a support process fluid concentration stage.
圖5顯示一輔助支撐式液體膜階段的示意圖。Figure 5 shows a schematic of an auxiliary supported liquid film stage.
圖6顯示一輔助超濾階段的示意圖。Figure 6 shows a schematic of an auxiliary ultrafiltration stage.
圖7顯示一淡化階段的示意圖。Figure 7 shows a schematic of a fade phase.
圖8顯示具有微奈米過濾淡化階段之產品蒸發階段的示意圖。Figure 8 shows a schematic of the product evaporation stage with a micro-nanofiltration desalination stage.
圖9顯示水回收階段的示意圖。Figure 9 shows a schematic of the water recovery stage.
圖10顯示支撐式液體膜的流動設計的示意圖。Figure 10 shows a schematic of the flow design of a supported liquid membrane.
圖11顯示支撐式液體膜的萃取方法的示意圖。Figure 11 shows a schematic diagram of an extraction method of a supported liquid membrane.
圖12顯示更高回收率之有機酸的循環步驟的示意圖。Figure 12 shows a schematic of the recycling step of a higher recovery organic acid.
1...發酵液1. . . Fermentation liquid
2...管線2. . . Pipeline
3...裝置3. . . Device
5...管線5. . . Pipeline
6...裝置6. . . Device
9...蒸發器9. . . Evaporator
Claims (21)
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SG201003464-3A SG168460A1 (en) | 2009-07-28 | 2010-05-18 | Process for the purification of organic acids |
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