TWI543809B - Electrodialysis apparatus of purifying bio-succinic acid - Google Patents

Electrodialysis apparatus of purifying bio-succinic acid Download PDF

Info

Publication number
TWI543809B
TWI543809B TW103135049A TW103135049A TWI543809B TW I543809 B TWI543809 B TW I543809B TW 103135049 A TW103135049 A TW 103135049A TW 103135049 A TW103135049 A TW 103135049A TW I543809 B TWI543809 B TW I543809B
Authority
TW
Taiwan
Prior art keywords
chamber
electrodialysis device
aqueous solution
succinic acid
strong acid
Prior art date
Application number
TW103135049A
Other languages
Chinese (zh)
Other versions
TW201613684A (en
Inventor
李文乾
王子賢
林政雄
Original Assignee
國立中正大學
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 國立中正大學 filed Critical 國立中正大學
Priority to TW103135049A priority Critical patent/TWI543809B/en
Publication of TW201613684A publication Critical patent/TW201613684A/en
Application granted granted Critical
Publication of TWI543809B publication Critical patent/TWI543809B/en

Links

Description

用於純化生物丁二酸的電透析裝置 Electrodialysis device for purifying biosuccinic acid

本發明係關於一種電透析裝置,特別係關於一種用於純化生物丁二酸的電透析裝置。 The present invention relates to an electrodialysis device, and more particularly to an electrodialysis device for purifying biosuccinic acid.

丁二酸,是琥珀酸(succinic acid)的學名,廣泛應用於化工原料、醫藥、食品及飼料等。因其用途廣泛,與另外二個四碳二羧酸,即蘋果酸與延胡索酸(fumaric acid)並列為美國國家能源實驗室挑選的十二個最具潛力之生質來源的基礎化學品。丁二酸作可為重要的化工原料及中間體之一,主要用於醫藥工業、食品工業、化學工業、以及分析試劑、配製電鍍藥水與印刷電路板(Printed Circuit Boards,PCB)藥水、清潔劑等。丁二酸亦可作為單體,用於合成生物可分解高分子材料如聚丁二酸丁二醇酯(Poly butylene succinate,PBS)及聚丁二酸乙二醇酯(Poly Ethylene Succinate),PES)。 Succinic acid, the scientific name of succinic acid, is widely used in chemical raw materials, medicine, food and feed. Because of its versatility, it is listed alongside two other four-carbon dicarboxylic acids, malic acid and fumaric acid, as the 12 most promising sources of base chemicals selected by the National Energy Laboratory. Succinic acid is one of the important chemical raw materials and intermediates. It is mainly used in the pharmaceutical industry, food industry, chemical industry, and analytical reagents, electroplating syrup and printed circuit board (PCB) syrup, detergent. Wait. Succinic acid can also be used as a monomer for the synthesis of biodegradable polymer materials such as poly butylene succinate (PBS) and Poly Ethylene Succinate, PES. ).

丁二酸在市場上之需求成長迅速,預計全球市場將從2010年的1.828億美元,於2016年會增加到4.96億美元。由於可生物降解聚酯的新下游應用領域的拓展,值得期待全球丁二酸需求量將呈現兩位數的增長。根據全球行業分析公司(GIA)研究報告顯示,預測到2015年全球丁二酸市場將達到14.47萬噸,因此,近年來Myriant、Bioamber以及Reverdia等公司紛紛想加入這個市場,設計產能約為1萬噸/年,目前僅有Bioamber於2010年1月22日建成世界唯一商業化規模以微生物醱酵生產丁二酸的生物基丁二酸設備,採用小麥來源的葡萄糖為原料,初期生產能力為2000噸/年。因為市場大,各國都有發展空間。目前生物法製造丁二酸在成本上已逐漸可以與石化原料的製程相抗衡。 The demand for succinic acid in the market is growing rapidly. The global market is expected to increase from $182.8 million in 2010 to $496 million in 2016. Due to the expansion of new downstream applications for biodegradable polyesters, it is worthwhile to expect double-digit growth in global demand for succinic acid. According to a global industry analysis company (GIA) research report, it is predicted that the global succinic acid market will reach 144,700 tons by 2015. Therefore, in recent years, companies such as Myriant, Bioamber and Reverdia want to join this market, with a design capacity of about 10,000. Tons/year, only Bioamber has built the world's only commercially available bio-based succinic acid equipment for the production of succinic acid by microbial fermentation on January 22, 2010. The wheat-derived glucose is used as raw material with an initial production capacity of 2000. Tons per year. Because of the large market, countries have room for development. At present, the production of succinic acid by biological methods has gradually been able to compete with the process of petrochemical raw materials.

丁二酸生產方法可分為化學合成以及微生物醱酵法;近年來 綠色化學興起,相較於化學合成,微生物醱酵不僅具有效降低對於環境污染以及解決高耗能問題之優點,且微生物醱酵生產丁二酸時,根據劑量平衡,當以葡萄糖為原料時、需消耗二莫耳二氧化碳(CO2),以生成二莫耳丁二酸。因此以微生物醱酵生產丁二酸還具有利用可再生資源、減少CO2排放之優點,並降低由於石油日益缺少及造成環境污染之問題。有別於石化原料來源的丁二酸,以生質材料(biomass)為原料利用微生物醱酵生產的丁二酸,有時也特別稱為生物丁二酸(Bio-succinic Acid)。 The production process of succinic acid can be divided into chemical synthesis and microbial fermentation; in recent years, green chemistry has arisen. Compared with chemical synthesis, microbial fermentation not only has the effect of reducing environmental pollution and solving high energy consumption problems, but also microbial 酦. When fermenting succinic acid, according to the dose balance, when using glucose as a raw material, it is necessary to consume two moles of carbon dioxide (CO 2 ) to form dimoric succinic acid. Therefore, the production of succinic acid by microbial fermentation also has the advantages of utilizing renewable resources, reducing CO 2 emissions, and reducing the problem of lack of oil and environmental pollution. Unlike succinic acid, a source of petrochemical raw materials, succinic acid produced by microbial fermentation using biomass as a raw material is sometimes called Bio-succinic Acid.

生物丁二酸的製造包括微生物醱酵及產品分離純化兩大部分。微生物醱酵的生產菌種係能代謝葡萄糖或其他碳源,生成高濃度的丁二酸,在醱酵槽中大量培養以製造丁二酸。目前大多數的丁二酸生產菌都是從反芻動物瘤胃中分離出來的微生物,如從牛瘤胃中分離的產琥珀酸放線桿菌(Actinobacillus succinogenes)、產琥珀酸厭氧螺旋菌(Anaerobiospirillum succiniciproducens);產丁二酸菌的種類繁多,尚有曼海姆產琥珀酸菌(Mannheinia succiniciproducens)。大腸桿菌(Escherichia coli)也被視為生產丁二酸菌種之一,藉由移除部分基因,使副產品如醋酸、乳酸、甲酸等生產量下降,突變大腸桿菌菌株的代謝途徑,使其像產琥珀酸放線桿菌與產琥珀酸厭氧螺旋菌一樣可以生產丁二酸。 The production of biological succinic acid includes two parts: microbial fermentation and product separation and purification. The microbial fermentation producing strain can metabolize glucose or other carbon sources to produce a high concentration of succinic acid, which is cultured in large amounts in a fermentation tank to produce succinic acid. At present, most of the succinic acid producing bacteria are microorganisms isolated from the rumen of ruminants, such as Actinobacillus succinogenes isolated from bovine rumen, and Anaerobiospirillum succiniciproducens ; There are many kinds of succinic acid producing bacteria, and there are Mannheinia succiniciproducens . Escherichia coli is also considered to be one of the succinic acid producing strains. By removing part of the gene, the production of by-products such as acetic acid, lactic acid, and formic acid is reduced, and the metabolic pathway of the mutant E. coli strain is made to resemble Producing succinic acid can be produced by Actinobacillus succinogenea as well as anaerobic succinic acid producing succinic acid.

產琥珀酸放線桿菌有較高的丁二酸產率,產琥珀酸放線桿菌Actinobacillus succinogenes(BCRC 80310),從牛瘤胃中分離篩選出來(Guettleret al.,Int J SystBacteriol,1999,49:207-216)。A.succinogenes是屬於兼性厭氧菌與革蘭氏陰性菌,該菌還可以利用多種糖類作為碳源製造丁二酸,並且可以耐受葡萄糖和丁二酸的濃度分別高達158g/L和104g/L(Linet al.,J Biochem Eng,2008,41:128-135)。因為該菌可以利用L-阿拉伯糖、纖維二糖、果糖、半乳糖、葡萄糖、乳糖、麥芽糖、甘露醇、甘露糖、蔗糖、和D-木糖等各種糖類進行醱酵,彈性相當大。 Actinobacillus succinogenes has a higher yield of succinic acid, producing Actinobacillus succinogenes (BCRC 80310), which is isolated from the rumen of cattle (Guettleret al., Int J Syst Bacteriol, 1999, 49: 207-216). ). A. succinogenes is a facultative anaerobic and Gram-negative bacterium. It can also use a variety of sugars as a carbon source to produce succinic acid, and can tolerate glucose and succinic acid concentrations up to 158g / L and 104g respectively. /L (Linet al., J Biochem Eng, 2008, 41: 128-135). Because the bacteria can be fermented with various sugars such as L-arabinose, cellobiose, fructose, galactose, glucose, lactose, maltose, mannitol, mannose, sucrose, and D-xylose, the elasticity is quite large.

微生物醱酵之後,接著就是產品的分離純化。大多數的醱酵產物製程中,回收及純化程序佔有主要的花費,以醱酵法生產丁二酸亦然。丁二酸醱酵製程中,由於產物可能同時含數種有機酸(如甲酸、乙酸、乳酸等副產物),分離純化之難度較高。根據美國專利第5,143,834號指出丁二酸 的純化分離占整個生產成本的60%,其原因在於醱酵液中皆含有菌體、鹽類、蛋白及雜酸等物質。菌體可以離心去除,然其它物質則無法去除。本發明技術領域其他分離丁二酸的方法亦如下:(1)利用鈣鹽法分離丁二酸,此法會產生大量的硫酸鈣,導致後續處理程序繁複;(2)利用液-液萃取法分離丁二酸,需使用大量的有機溶劑,若丁二酸產物應用於食品或醫藥的生產時,恐有有機溶劑殘留之疑慮;(3)利用離子交換樹脂吸附法分離丁二酸,但是各種離子交換樹脂對丁二酸吸附的效果不同,其會因到酸鹼條件而影響丁二酸的吸附性;以及(4)利用電透析法分離丁二酸,其操作模式都採批次性(batch),在輸進固定體積的進料之後以較長時間的電透析來達到高的分離效率,但這樣批次操作的缺點是隨著電透析時間增長,丁二酸會析出且沈積在陰離子滲透膜上面,使得丁二酸通道之質傳阻力變大,反而阻礙電透析的進行。因此,需發展出一個有效且低成本之分離純化程序以分離出丁二酸,是確實有其必要性及急迫性。 After the microbial fermentation, the product is then separated and purified. In most fermented product processes, recovery and purification procedures have a major expense, as is the production of succinic acid by fermentation. In the succinic acid fermentation process, since the product may contain several organic acids (such as by-products such as formic acid, acetic acid, lactic acid, etc.), it is difficult to separate and purify. According to U.S. Patent No. 5,143,834, succinic acid is indicated. The purification separation accounts for 60% of the total production cost, because the fermentation broth contains bacteria, salts, proteins and acids. The cells can be removed by centrifugation, but other substances cannot be removed. Other methods for separating succinic acid in the technical field of the present invention are as follows: (1) separation of succinic acid by a calcium salt method, which produces a large amount of calcium sulfate, resulting in complicated subsequent processing procedures; (2) using liquid-liquid extraction method Separation of succinic acid requires the use of a large amount of organic solvent. If the succinic acid product is used in the production of food or medicine, there may be doubts about the residual organic solvent; (3) Separation of succinic acid by ion exchange resin adsorption, but various The effect of ion exchange resin on the adsorption of succinic acid is different, which affects the adsorption of succinic acid due to acid-base conditions; and (4) the separation of succinic acid by electrodialysis, the mode of operation is batch-based ( Batch), after a fixed volume of feed, a long time of electrodialysis to achieve high separation efficiency, but the disadvantage of this batch operation is that as the electrodialysis time increases, succinic acid will precipitate and deposit in the anion Above the permeable membrane, the mass transfer resistance of the succinic acid channel becomes large, which hinders the progress of electrodialysis. Therefore, it is indeed necessary and urgent to develop an effective and low-cost separation and purification procedure to separate succinic acid.

有鑑於此,本發明提供一種用於純化生物丁二酸(Bio-succinic Acid)的電透析裝置,其係包含:一工作槽,含有一陽極側及陰極側;複數個離子滲透膜,位於該工作槽內之該陽極側與陰極側之間;複數個流體室,由該該離子滲透膜依序區隔形成;複數循環輸送管線,用以連接該流體室;一陽極,係設於該陽極側與正電連接;以及一陰極,係設於該陰極側與負電連接;其中該流體室包含有至少一沖洗溶液室、至少一醱酵液室、至少一強酸水溶液室及至少一產品溶液室,且該循環輸送管線分別與該沖洗溶液室、該醱酵液室、該強酸水溶液室及該產品溶液室相連接形成各獨立循環之沖洗溶液、醱酵液、強酸水溶液及產品溶液的循環系統。 In view of the above, the present invention provides an electrodialysis apparatus for purifying bio-succinic acid, which comprises: a working tank containing an anode side and a cathode side; and a plurality of ion permeable membranes located therein Between the anode side and the cathode side in the working tank; a plurality of fluid chambers formed by the ion permeable membranes in sequence; a plurality of circulating transfer lines for connecting the fluid chamber; an anode disposed at the anode a positive electrical connection; and a cathode disposed on the cathode side and negatively coupled; wherein the fluid chamber comprises at least one rinse solution chamber, at least one fermentation liquid chamber, at least one strong acid aqueous solution chamber, and at least one product solution chamber And the circulating conveying pipeline is respectively connected with the rinsing solution chamber, the fermentation broth chamber, the strong acid aqueous solution chamber and the product solution chamber to form a circulation system of the independent circulating rinsing solution, the mashing solution, the strong acid aqueous solution and the product solution. .

在本發明之一實施例中,其中該離子滲透膜係由一陽離子滲透膜及一陰離子滲透膜交錯配置,且該離子滲透膜係為雙極性膜(bipolar membrane)。 In an embodiment of the invention, the ion permeable membrane is interlaced by a cation permeable membrane and an anion permeable membrane, and the ion permeable membrane is a bipolar membrane.

在本發明之一實施例中,其中該醱酵液循環系統係包含至少兩個醱酵液室,且兩者之間之連接方式係由該循環輸送管線將一醱酵液室 入口端與另一醱酵液室出口端相連接;或該醱酵液循環系統係包含一個醱酵液室,其係由該循環輸送管線將該醱酵液室入口端與該醱酵液室出口端相連接。 In an embodiment of the invention, the lysing liquor circulation system comprises at least two fermenting liquid chambers, and the connection between the two is a lyophilized liquid chamber by the circulating conveying pipeline. The inlet end is connected to the outlet end of another fermentation chamber; or the fermentation circulatory system comprises a fermentation chamber which is connected to the fermentation chamber by the circulation line The outlet ends are connected.

在本發明之一實施例中,其中該沖洗溶液循環系統係包含至少兩個沖洗溶液室,且兩者之間之連接方式係由該循環輸送管線將一沖洗溶液室入口端與另一沖洗溶液室出口端相連接;或該沖洗溶液循環系統係包含一個沖洗溶液室,其係由該循環輸送管線將該沖洗溶液室入口端與該沖洗溶液室出口端相連接。 In an embodiment of the invention, wherein the rinsing solution circulation system comprises at least two rinsing solution chambers, and the connection between the two is from the circulation conveying line to the inlet end of one rinsing solution chamber and another rinsing solution. The outlet end of the chamber is connected; or the flushing solution circulation system comprises a flushing solution chamber which is connected to the outlet end of the flushing solution chamber by the circulating transfer line.

在本發明之一實施例中,其中該強酸水溶液循環系統係包含至少兩個強酸水溶液室,且兩者之間之連接方式係由該循環輸送管線將一強酸水溶液室入口端與另一沖強酸水溶液室出口端相連接;或該強酸水溶液循環系統係包含一個強酸水溶液室,其係由該循環輸送管線將該強酸水溶液室入口端與該強酸水溶液室出口端相連接。 In an embodiment of the present invention, the strong acid aqueous solution circulation system comprises at least two strong acid aqueous solution chambers, and the connection between the two is connected by the circulating transfer line to a strong acid aqueous solution chamber inlet end and another strong acid. The outlet end of the aqueous solution chamber is connected; or the strong acid aqueous solution circulation system comprises a strong acid aqueous solution chamber which is connected to the outlet end of the strong acid aqueous solution chamber by the circulating transfer line.

在本發明之一實施例中,其中該產品溶液循環系統係包含至少兩個產品溶液室,且兩者之間之連接方式係由該循環輸送管線將一產品溶液室入口端與另一產品溶液室出口端相連接;或該產品溶液循環系統係包含一個產品溶液室,其係由該循環輸送管線將該產品溶液室入口端與該強酸水溶液室出口端相連接。 In an embodiment of the invention, wherein the product solution circulation system comprises at least two product solution chambers, and the connection between the two is from the circulation transfer line to the inlet end of one product solution chamber and another product solution. The outlet end of the chamber is connected; or the product solution circulation system comprises a product solution chamber which is connected to the outlet end of the strong acid aqueous solution chamber by the circulating transfer line.

在本發明之一實施例中,其中該強酸水溶液係為鹽酸或硫酸。 In an embodiment of the invention, the aqueous strong acid solution is hydrochloric acid or sulfuric acid.

在本發明之一實施例中,其中該強酸水溶液室更進一步配置有水分蒸發單元。 In an embodiment of the invention, the strong acid aqueous solution chamber is further configured with a moisture evaporation unit.

在本發明之一實施例中,其中該電透析裝置係為該醱酵液係連續性進入該醱酵液室,且該產品溶液係連續性從該產品溶液室取出的連續式操作模式。 In one embodiment of the invention, the electrodialysis device is a continuous mode of operation in which the fermentation broth is continuously introduced into the fermentation broth and the product solution is continuously removed from the product solution chamber.

在本發明之一實施例中,其中該電透析裝置係為固定電極電性之電透析裝置或正負極與內部可切換之倒極式電透析裝置。 In an embodiment of the invention, the electrodialysis device is a fixed electrode electrical electrodialysis device or a positive and negative electrode and an internally switchable inverted pole electrodialysis device.

本發明係提供一種用於純化生物丁二酸的電透析裝置,該裝置可將醱酵液中的丁二酸與其他成分離,進而獲得高純度的丁二酸。更重 要的是,本發明之電透析裝置具有四個循環系統可連續性地純化較大量之丁二酸,能有助於當於提升醱酵液處理量,且該四個循環系統亦有助於充份利用已分離出丁二酸的醱酵液中的鹽類當電解質,並具有水資源回收及醱酵殘留物再利用的優點,大幅降低生物丁二酸整體純化分離之成本。 The present invention provides an electrodialysis apparatus for purifying biosuccinic acid, which can separate succinic acid from a mash solution with other compounds, thereby obtaining high purity succinic acid. heavier It is desirable that the electrodialysis device of the present invention has four circulation systems for continuously purifying a relatively large amount of succinic acid, which can help to increase the amount of fermentation broth treatment, and the four circulation systems also contribute to The salt in the lysate from which succinic acid has been separated is fully utilized as an electrolyte, and has the advantages of water resource recovery and reutilization of the residue, greatly reducing the cost of the overall purification and separation of the bio-succinic acid.

100‧‧‧電透析裝置 100‧‧‧Electrodialysis unit

101‧‧‧工作槽 101‧‧‧Working trough

102‧‧‧陽極側 102‧‧‧ anode side

103‧‧‧陰極側 103‧‧‧ cathode side

104、105、106‧‧‧陽離子滲透膜 104, 105, 106‧‧‧ cation permeable membrane

107、108‧‧‧陰離子滲透膜 107, 108‧‧‧ anion permeable membrane

109、110‧‧‧沖洗溶液室 109, 110‧‧‧ rinse solution chamber

111、112‧‧‧醱酵液室 111, 112‧‧‧ fermented liquid room

113‧‧‧強酸水溶液室 113‧‧‧ Strong acid aqueous solution room

114‧‧‧產品溶液室 114‧‧‧ Product solution room

115、116、117、118、119、120‧‧‧循環輸送管線 115, 116, 117, 118, 119, 120‧ ‧ Circulating transfer pipeline

121‧‧‧陽極 121‧‧‧Anode

122‧‧‧陰極 122‧‧‧ cathode

第一圖係為本發明用於純化生物丁二酸(Bio-succinic Acid)的電透析裝置之一較佳實施例的示意圖。 The first figure is a schematic representation of one preferred embodiment of an electrodialysis apparatus for purifying bio-succinic acid of the present invention.

第二圖係為本發明之電透析裝置搭配醱酵槽及結晶等步驟可建立個連續生產與純化生物丁二酸的流程的示意圖。 The second figure is a schematic diagram of a process for continuously producing and purifying bio-succinic acid by the steps of the electrodialysis device of the present invention in combination with a fermentation tank and crystallization.

第三圖係為本發明利用Actinobacillas succinogenes突變株醱酵葡萄糖代謝(g/L)、光密度(OD 660nm)、生成丁二酸(g/L)以及生成醋酸(g/L)的曲線圖。 The third figure is a graph showing the fermentation of glucose metabolism (g/L), optical density (OD 660 nm), production of succinic acid (g/L), and production of acetic acid (g/L) by the Actinobacillas succinogenes mutant strain.

第四圖係為本發明用於純化生物丁二酸(Bio-succinic Acid)的電透析裝置之一較佳實施例的醱酵液中丁二酸濃度(g/L)及產品溶液中丁二酸濃度(g/L)變化曲線圖。 The fourth figure is the concentration of succinic acid (g/L) in the fermentation broth of a preferred embodiment of the electrodialysis device for purifying bio-succinic acid of the present invention and the product solution Acid concentration (g/L) curve.

本發明之用於純化生物丁二酸(Bio-succinic Acid)的電透析裝置,其係藉由四個循環系統以及陽離子與陰離子滲透膜,除去醱酵液中的鹽類和離子,最後讓丁二酸根與氫離子結合以形成丁二酸。該電透析裝置在電場的作用下,陰陽離子受到電極磁場吸引,並使用陰陽離子滲透膜的選擇通透性達到分離之作用,即陽離子只能通過陽離子滲透膜、陰離子只能通過陰離子滲透膜;而中性分子如殘糖等則因無法通透陰陽離子滲透膜,故而一直留在醱酵液中,最後分別將醱酵液中的丁二酸根和氫離子分離出來,後續混合形成之溶液再經由濃縮、結晶得到高純度丁二酸晶體。 The electrodialysis device for purifying bio-succinic acid of the present invention removes salts and ions in the fermentation broth by four circulation systems and cation and anion permeable membranes, and finally The diacid is combined with hydrogen ions to form succinic acid. Under the action of an electric field, the anion and cation are attracted by the magnetic field of the electrode, and the selective permeability of the anion-cation permeable membrane is used for separation, that is, the cation can only pass through the cation permeable membrane, and the anion can only pass through the anion permeable membrane; Neutral molecules, such as residual sugar, are unable to penetrate the anion and cation membrane, so they remain in the mash. Finally, the succinate and hydrogen ions in the broth are separated, and the solution is formed by subsequent mixing. High purity succinic acid crystals are obtained by concentration and crystallization.

本發明之用於純化生物丁二酸的電透析裝置係如第一圖所示,該電透析裝置100係包含:一含有陽極側102及陰極側103的工作槽101;位於該工作槽101內之陽極側102與陰極側103之間的陽離子滲透膜104105106以及陰離子滲透膜107108;由複數個離子滲透膜區隔形成的沖洗溶液室109110、醱酵液室111112、強酸水溶液室113及 產品溶液室114;用以連接複數個流體室複數循環輸送管線115116117118119120;一設於陽極側102與正電連接的陽極121;以及一設於陰極側103與負電連接的陰極122The electrodialysis apparatus for purifying biosuccinic acid of the present invention is as shown in the first figure. The electrodialysis apparatus 100 comprises: a working tank 101 containing an anode side 102 and a cathode side 103 ; and is located in the working tank 101 . The cation permeable membranes 104 , 105 and 106 and the anion permeable membranes 107 and 108 between the anode side 102 and the cathode side 103 ; the rinsing solution chambers 109 and 110 formed by the plurality of ion permeable membranes, the fermentation broth chamber 111 and 112 , a strong acid aqueous solution chamber 113 and a product solution chamber 114 ; for connecting a plurality of fluid chambers, a plurality of circulating transfer lines 115 , 116 , 117 , 118 , 119 and 120 ; an anode 121 disposed on the anode side 102 and positively connected; A cathode 122 is provided on the cathode side 103 and negatively electrically connected.

本發明之用於純化生物丁二酸(Bio-succinic Acid)的電透析裝置,其係包含四個循環系統,其中,該循環輸送管線115與該沖洗溶液室109入口端與該沖洗溶液室110出口端相連接;該循環輸送管線116與該沖洗溶液室110入口端與該沖洗溶液室109出口端相連接,以形成沖洗溶液循環系統;該循環輸送管線117與該醱酵液室111入口端與該醱酵液室112出口端相連接;該循環輸送管線118與該醱酵液室112入口端與醱酵液室111出口端相連接,以形成醱酵液循環系統;該循環輸送管線119分別與該強酸水溶液室113入口端與出口端相連接,以形成強酸水溶液循環系統;以及該循環輸送管線120與該產品溶液室114入口端與出口端相連接,以形成產品溶液循環系統。 The electrodialysis device for purifying bio-succinic acid of the present invention comprises four circulation systems, wherein the circulation delivery line 115 and the inlet end of the rinse solution chamber 109 and the rinse solution chamber 110 The outlet end is connected; the circulation transfer line 116 is connected to the outlet end of the rinse solution chamber 110 and the outlet end of the rinse solution chamber 109 to form a rinse solution circulation system; the circulation transfer line 117 and the inlet end of the fermentation solution chamber 111 112 is connected to the outlet end of the fermentation broth Po chamber; transfer line 118 of the loop 111 is connected to the outlet end of the fermentation broth Po chamber 112 and the inlet end of the fermentation liquid chamber Po, Po fermentation to form a liquid circulating system; the cycle transfer line 119 The inlet and outlet ends of the strong acid aqueous solution chamber 113 are respectively connected to form a strong acid aqueous solution circulation system; and the circulation transfer line 120 is connected to the inlet and outlet ends of the product solution chamber 114 to form a product solution circulation system.

此外,在本發明之電透析裝置具有四個循環系統中,強酸水溶液從循環輸送管線119之一分岔口流入,醱酵液從循環輸送管線118之一分岔口流入以及循環輸送管線117之一分岔口流出,產品溶液從循環輸送管線120之一分岔口流出,以形成可連續性地純化較大量之丁二酸之電透析裝置。 Further, in the electrodialysis apparatus of the present invention having four circulation systems, the aqueous solution of strong acid flows in from the branching port of one of the circulation conveying lines 119 , and the fermentation liquid flows in from the branching port of one of the circulating conveying lines 118 and one of the circulating conveying lines 117 . The mouthpiece flows out and the product solution flows out of the split port of the circulation line 120 to form an electrodialysis unit that can continuously purify a larger amount of succinic acid.

本發明之用於純化生物丁二酸(Bio-succinic Acid)的電透析裝置,開始進行電透析時,在陽離子滲透膜104與陰離子滲透膜107之間的醱酵液室111,而該沖洗水溶液室109110在起始時是純水,其中醱酵液室111中陽離子(H+、K+、Mg2+、Na+等)會穿過陽離子滲透膜104到沖洗水溶液室109中;陰離子(丁二酸根、醋酸根等)會穿過陰離子滲透膜107到產品溶液室114中。在陽極側102與陽離子滲透膜106之間的醱酵液室112,其中之陽離子(H+、K+、Mg2+、Na+等)則穿過陽離子滲透膜106到沖洗水溶液室110之中;陰離子(丁二酸根、醋酸根等)會循環到醱酵液室111時,穿過陰離子滲透膜107到產品溶液室114中。在陽離子滲透膜105與陰離子滲透膜108之間的強酸水溶液室113,其中之陰離子(OH-、Cl-等)會穿過陰離子滲透膜108到沖洗水溶液室110之中;氫離子則穿過陽離子滲透105 進入產品溶液室114與穿過陰離子滲透膜107的丁二酸根與醋酸根結合,形成丁二酸與醋酸。 The electrodialysis apparatus for purifying bio-succinic acid of the present invention starts the electrolysis dialysis, and the lysate chamber 111 between the cation permeable membrane 104 and the anion permeable membrane 107 , and the rinsing aqueous solution The chambers 109 and 110 are initially pure water, wherein the cation (H + , K + , Mg 2+ , Na + , etc.) in the fermentation broth 111 passes through the cation permeable membrane 104 into the rinsing aqueous solution chamber 109 ; (Succinate, acetate, etc.) will pass through the anion permeable membrane 107 into the product solution chamber 114 . The fermentation chamber 112 between the anode side 102 and the cation permeable membrane 106 , wherein the cations (H + , K + , Mg 2+ , Na + , etc.) pass through the cation permeable membrane 106 into the rinsing aqueous solution chamber 110 An anion (succinate, acetate, etc.) will circulate through the anion permeable membrane 107 into the product solution chamber 114 as it circulates to the fermentation broth 111 . In the strong acid aqueous solution chamber 113 between the cation permeable membrane 105 and the anion permeable membrane 108 , the anions (OH - , Cl - etc.) pass through the anion permeable membrane 108 into the rinsing aqueous solution chamber 110 ; the hydrogen ions pass through the cation The permeate 105 enters the product solution chamber 114 and combines with the succinate through the anion permeable membrane 107 to form succinic acid and acetic acid.

本發明之電透析裝置可達到從醱酵液中純化出丁二酸的目的,產品溶液中含有丁二酸及醋酸,可藉由電透析條件的改變讓醋酸含量降低,比較有效的是利用後續濃縮與結晶步驟,因丁二酸與醋酸沸點與溶解度的不同,可以完全分離,得到高純度的丁二酸。 The electrodialysis device of the invention can achieve the purpose of purifying succinic acid from the broth, and the product solution contains succinic acid and acetic acid, and the acetic acid content can be reduced by changing the electrodialysis conditions, and it is effective to use the follow-up The concentration and crystallization steps can be completely separated due to the difference in boiling point and solubility of succinic acid and acetic acid to obtain high-purity succinic acid.

基於上述,相較於一般批式(batch)電透析純化的裝置,本發明之電透析裝置具有四個循環系統可連續性地純化較大量之丁二酸,該四個循環系統能有助於當於提升醱酵液處理量,以達到降低整體純化分離之成本,其中各循環系統之優點如下: Based on the above, the electrodialysis device of the present invention has four circulation systems for continuously purifying a larger amount of succinic acid than the conventional batch dialysis purification device, and the four circulation systems can contribute to When the amount of the fermentation broth is increased to reduce the cost of the overall purification separation, the advantages of each circulatory system are as follows:

1.沖洗水溶液循環系統:進行電透析前,沖洗水溶液室內是純水,進行電透析時不斷從醱酵液室中取得電解質做為電解液,因此本發明在電透析過程不需補充電解質,也不需持續提供水源。相較於一般批式電透析純化的裝置,在電透析後會有大量之廢鹽生成,其導致在連續操作時會有過量之鹽類析出在滲透膜上造成分離效果降低;而本發明以循環水流設計之電透析裝置,因具有沖洗水溶液循環系統可避免降低鹽類析出同時可以此當作電解液。同時,鹽類可經回收後再當作鹼液用以調控醱酵槽之pH值。 1. Flushing the aqueous solution circulation system: Before performing electrodialysis, the rinse aqueous solution chamber is pure water, and the electrolyte is continuously taken from the fermentation liquid chamber as the electrolyte during the electrodialysis, so the invention does not need to be supplemented with electrolyte in the electrodialysis process. There is no need to provide continuous water supply. Compared with the conventional batch electrodialysis purification device, a large amount of waste salt is formed after electrodialysis, which results in excessive salt precipitation on the permeable membrane during continuous operation, resulting in a decrease in separation effect; The electrodialysis device designed for circulating water flow can avoid the precipitation of salts and can be used as an electrolyte because of the flushing aqueous circulation system. At the same time, the salt can be recovered and used as an alkali solution to regulate the pH of the fermentation tank.

2.強酸水溶液循環系統:本發明之強酸水溶液循環系統可以不斷供給氫離子,但不會導致供給過高濃度之氫離子,故本發明可將所有丁二酸鹽生成丁二酸,且不使丁二酸的濃度過高,使得不因過高濃度之酸造成陰陽離子滲透膜損毀及裝置損毀。再者,雖然隨著電透析的進行,強酸的濃度會逐漸降低,但可以透過水分蒸發的設備讓強酸的濃度提升再利用,節省強酸用量。 2. Strong acid aqueous solution circulation system: the strong acid aqueous solution circulation system of the present invention can continuously supply hydrogen ions, but does not cause supply of excessively high concentration of hydrogen ions, so the present invention can generate all succinate from succinic acid without causing The concentration of succinic acid is too high, so that the anion and cation membrane are not damaged and the device is damaged due to excessive concentration of acid. Furthermore, although the concentration of strong acid will gradually decrease with the progress of electrodialysis, the concentration of strong acid can be increased and reused by means of evaporation of water, thereby saving the amount of strong acid.

3.產品溶液循環系統:可維持低雜質汙染的優點,並隨著電透析時間增加,產品濃度提高,這項優點是無產品循環的電透析裝置所無法達到的。此外,因在連續操作時,會累積大量丁二酸生成,當丁二酸達到一定濃度時,則可能造成析出而導致分離效果降低,因此循環水流有助於避免丁二酸析出。 3. Product solution circulation system: It can maintain the advantages of low impurity pollution, and as the electrodialysis time increases, the product concentration increases. This advantage cannot be achieved by an electrodialysis device without product circulation. In addition, since a large amount of succinic acid is accumulated during continuous operation, when the succinic acid reaches a certain concentration, precipitation may occur and the separation effect is lowered, so that the circulating water flow helps to prevent the precipitation of succinic acid.

4.醱酵液循環系統:除了持續讓醱酵液室中的鹽類當電解質來源之 外,最後醱酵液室中可得到高濃度的蛋白質及核酸等,固液分離之後可回收水資源,固體殘留物可做為飼料或肥料之用途。而且,當以循環水流時,則可以不斷供給丁二酸鹽使其達到分離純化之目的,以降低丁二酸分離的時間,相較於一般批式電透析純化的條件下,僅能得到一定濃度之丁二酸,故本發明可大幅降低整體分離成本。 4. Fermentation circulatory system: in addition to continuing to let the salt in the lysate chamber be the source of electrolyte In addition, a high concentration of protein and nucleic acid can be obtained in the final fermentation broth chamber. After solid-liquid separation, water resources can be recovered, and solid residues can be used as feed or fertilizer. Moreover, when circulating water, the succinate can be continuously supplied for separation and purification, so as to reduce the time of succinic acid separation, which can only be obtained under the conditions of general batch electrodialysis purification. The concentration of succinic acid can greatly reduce the overall separation cost.

實施例1 建立個連續生產與純化生物丁二酸的流程Example 1 Establishing a process for continuous production and purification of bio-succinic acid

如第二圖所示,本發明之電透析裝置搭配醱酵槽100及結晶等步驟可建立個連續生產與純化生物丁二酸的流程,因為可以連續式(continuous)操作,工業化遠比批次操作具有優勢。 As shown in the second figure, the electrodialysis apparatus of the present invention can be combined with the fermentation tank 100 and crystallization to establish a process for continuously producing and purifying the bio-succinic acid, because the continuous operation can be carried out, and the industrialization is much more than the batch. Operation has an advantage.

本發明所使用的生物丁二酸製造流程,其包含:經由微生物醱酵法生產丁二酸醱酵液,經由離心將醱酵液中的蛋白質、菌絲、多醣等物質返回醱酵槽中重複利用,離心後的上清液利用本發明的電透析裝置100純化生物丁二酸,所得產品溶液加熱濃縮之後利用活性炭脫色純化,之後以再結晶方式使丁二酸析出。 The biosuccinic acid production process used in the present invention comprises: producing a succinic acid mash solution by a microbial fermentation method, and returning the protein, hyphae, polysaccharide and the like in the broth to the fermentation tank by centrifugation. The supernatant after centrifugation is purified by using the electrodialysis apparatus 100 of the present invention, and the obtained product solution is heated and concentrated, and then decolorized and purified by using activated carbon, followed by precipitation of succinic acid by recrystallization.

實施例2 醱酵液製備Example 2 Preparation of broth

醱酵使用菌株為產琥珀酸放線桿菌Actinobacillas succinogenes(BCRC 80310)。菌株培養及醱酵方法如下:取10μL菌液接種於5mL胰蛋白大豆蛋白(tryptic soy broth,TSB)培養基並培養24小時,再取2mL菌液接種至80mL中間培養基培養24小時(達初始靜置期),將80mL菌液接種至5L醱酵槽體積為800mL之醱酵培養基,總體積共880mL;每4至5小時取樣一次,並分析其OD值、葡萄糖或甘油、丁二酸、乳酸、醋酸隨時間之變化量,培養基成分如表一所示。醱酵時之攪拌轉速控制為200rpm,通二氧化碳量通氣量0.5vvm,pH值控制於6.7,前7小時以2N氫氧化鈉(NaOH)調控pH值,之後則改以氫氧化鎂(Mg(OH)2)調控pH值,其用意為NaOH用以提供生長,以Mg(OH)2除可避免因添加過量NaOH導致菌體代謝生長能力下降還可提升丁二酸生產能力。 The strain used in the fermentation was Actinobacillas succinogenes (BCRC 80310). The strain culture and fermentation methods were as follows: 10 μL of the bacterial solution was inoculated into 5 mL tryptic soy broth (TSB) medium and cultured for 24 hours, and then 2 mL of the bacterial solution was inoculated to 80 mL of the intermediate medium for 24 hours (up to initial rest). Period), inoculate 80 mL of bacterial solution into a 5 L fermentation tank with a volume of 800 mL of fermentation medium, total volume of 880 mL; sample every 4 to 5 hours, and analyze its OD value, glucose or glycerin, succinic acid, lactic acid, The amount of acetic acid changed with time, and the composition of the medium is shown in Table 1. The stirring speed of the fermentation was controlled at 200 rpm, the carbon dioxide ventilation was 0.5 vvm, the pH was controlled at 6.7, and the pH was adjusted with 2N sodium hydroxide (NaOH) for the first 7 hours, followed by magnesium hydroxide (Mg (OH). 2 ) The pH value is adjusted, which means that NaOH is used to provide growth, and the removal of Mg(OH) 2 can avoid the lactic acid production capacity can be improved by the decrease of the metabolic growth ability of the bacteria caused by the addition of excess NaOH.

表一、各培養基之組成 Table 1, the composition of each medium

醱酵結束後,醱酵液中的葡萄糖全部耗用完畢,產品為丁二酸,濃度介於50至100g/L之間,視原料純度、二氧化碳供應及醱酵條件而定,且伴隨有少量的醋酸生成,醋酸量約為丁二酸的1/8。第三圖為利用產琥珀酸放線桿菌Actinobacillas succinogenes(BCRC 80310)醱酵葡萄糖代謝、光密度(OD 660nm)、生成丁二酸以及生成醋酸的時程曲線,其結果顯示當葡萄糖經產琥珀酸放線桿菌(BCRC 80310)消耗後,丁二酸開始以倍數增加,同時光密度及醋酸都有提升,證實丁二酸在醱酵液中生成。 After the fermentation, the glucose in the fermentation broth is completely consumed. The product is succinic acid, and the concentration is between 50 and 100 g/L, depending on the purity of the raw materials, the supply of carbon dioxide and the fermentation conditions, accompanied by a small amount. The acetic acid is formed in an amount of about 1/8 of that of succinic acid. The third picture shows the time course of fermentation of glucose metabolism, optical density (OD 660nm), succinic acid production and acetic acid production by Actinobacillas succinogenes (BCRC 80310). The results show that when glucose is produced by succinic acid release line After consumption by Bacillus (BCRC 80310), succinic acid began to increase in multiples, while both optical density and acetic acid increased, confirming that succinic acid was produced in the mash.

實施例3 丁二酸分離純化Example 3 Separation and purification of succinic acid

醱酵完成後經離心(去除菌體)所得醱酵上清液作為透析液進行電透析分離純化。電透析所提供材料及設定如下:1M鹽酸水溶液、醱酵液(丁二酸55g/L,醋酸7.7g/L)、逆滲透(Reverse Osmosis,RO)水,電源供應設定條件為電壓3V、電流100mA。 After the completion of the fermentation, the fermentation supernatant obtained by centrifugation (removing the cells) is used as a dialysate for electrodialysis separation and purification. The materials and settings provided by electrodialysis are as follows: 1M hydrochloric acid aqueous solution, mash (55g/L succinic acid, 7.7g/L acetic acid), reverse Osmosis (RO) water, power supply setting conditions are voltage 3V, current 100mA.

電透析過程醱酵液與產品溶液中,丁二酸濃度隨時間的變化,如第四圖所示,其結果顯示醱酵液中的丁二酸逐漸減少,產品溶液中的丁二酸濃度逐漸增加,證實本發明之電透析裝置可純化出丁二酸。 During the electrodialysis process, the concentration of succinic acid in the lysate and product solution changes with time, as shown in the fourth figure. The results show that the succinic acid in the mash is gradually reduced, and the concentration of succinic acid in the product solution gradually decreases. In addition, it was confirmed that the electrodialysis apparatus of the present invention can purify succinic acid.

實施例4 丁二酸濃縮與再結晶Example 4 Concentration and Recrystallization of Succinic Acid

電透析所得產品溶液為純的有機酸溶液,除丁二酸之外尚有少量醋酸,可直接以加熱濃縮回收丁二酸。因醋酸沸點遠低於水,故當升至100℃時此時醋酸與水皆揮發,故可得高純度之丁二酸。所得丁二酸產品純度98.8%。 The product solution obtained by electrodialysis is a pure organic acid solution, and a small amount of acetic acid is added in addition to succinic acid, and succinic acid can be directly concentrated by heating. Since the boiling point of acetic acid is much lower than that of water, when it is raised to 100 ° C, both acetic acid and water are volatilized, so that high-purity succinic acid can be obtained. The obtained succinic acid product had a purity of 98.8%.

除上述方法外,電透析所得產品溶液加熱濃縮之後,亦可利 用活性炭脫色,之後以再結晶方式使丁二酸析出,最終產品中丁二酸的純度可達99.9%,結果顯示脫色後再結晶可使產品純度提高。 In addition to the above methods, after the product solution obtained by electrodialysis is heated and concentrated, it may also be advantageous. Decolorization with activated carbon, followed by precipitation of succinic acid by recrystallization, the purity of the succinic acid in the final product can reach 99.9%, and the results show that the recrystallization after decolorization can improve the purity of the product.

綜上所述,本發明之用於純化生物丁二酸的電透析裝置因具有四個循環系統,並產生不會有丁二酸產物在膜上沈積,因而降低電透析的效率的問題,同時處理的進料體積相對提升很多,更佳的是丁二酸產物可以持續移出,進料可持續補充,達到連續生產丁二酸的效果,此為傳統電透析設計無法達到的優點。再者,除了可純化醱酵液中的丁二酸之外,可以充份利用醱酵液中的鹽類當電解質,同時具有水資源回收及醱酵殘留物再利用的優點,有利於工業上大量生產。 In summary, the electrodialysis apparatus for purifying biosuccinic acid of the present invention has four circulation systems and produces a problem that no succinic acid product is deposited on the membrane, thereby reducing the efficiency of electrodialysis. The feed volume of the treatment is relatively increased. More preferably, the succinic acid product can be continuously removed, and the feed can be continuously replenished to achieve the continuous production of succinic acid, which is an advantage that cannot be attained by the conventional electrodialysis design. Furthermore, in addition to purifying the succinic acid in the mash, the salt in the mash can be fully utilized as an electrolyte, and the advantages of water recovery and fermentation residue reuse are beneficial to the industry. Mass production.

100‧‧‧電透析裝置 100‧‧‧Electrodialysis unit

101‧‧‧工作槽 101‧‧‧Working trough

102‧‧‧陽極側 102‧‧‧ anode side

103‧‧‧陰極側 103‧‧‧ cathode side

104、105、106‧‧‧陽離子滲透膜 104, 105, 106‧‧‧ cation permeable membrane

107、108‧‧‧陰離子滲透膜 107, 108‧‧‧ anion permeable membrane

109、110‧‧‧沖洗溶液室 109, 110‧‧‧ rinse solution chamber

111、112‧‧‧醱酵液室 111, 112‧‧‧ fermented liquid room

113‧‧‧強酸水溶液室 113‧‧‧ Strong acid aqueous solution room

114‧‧‧產品溶液室 114‧‧‧ Product solution room

115、116、117、118、119、120‧‧‧循環輸送管線 115, 116, 117, 118, 119, 120‧ ‧ Circulating transfer pipeline

121‧‧‧陽極 121‧‧‧Anode

122‧‧‧陰極 122‧‧‧ cathode

Claims (14)

一種純化生物丁二酸(Bio-succinic Acid)的電透析裝置,其係包含:一工作槽,具有一陽極側及一陰極側;複數個離子滲透膜,設於該工作槽內之該陽極側與陰極側之間,將該工作槽內區隔成複數個流體室;複數個循環輸送管線,用以連接該些流體室;一正電,電連接於該陽極側;以及一負電,電連接於該陰極側;其中,該流體室包含有至少一沖洗溶液室、至少一醱酵液室、至少一強酸水溶液室及至少一產品溶液室,且該循環輸送管線分別與該沖洗溶液室、該醱酵液室、該強酸水溶液室及該產品溶液室相連接形成各獨立循環之沖洗溶液、醱酵液、強酸水溶液及產品溶液的循環系統。 An electrodialysis device for purifying bio-succinic acid, comprising: a working tank having an anode side and a cathode side; and a plurality of ion permeable membranes disposed on the anode side of the working tank Between the cathode side and the cathode side, the working tank is partitioned into a plurality of fluid chambers; a plurality of circulating conveying lines are connected to the fluid chambers; a positive electric current is electrically connected to the anode side; and a negative electric connection On the cathode side; wherein the fluid chamber comprises at least one rinse solution chamber, at least one fermentation liquid chamber, at least one strong acid aqueous solution chamber, and at least one product solution chamber, and the circulation transfer line and the rinse solution chamber respectively The fermentation broth chamber, the strong acid aqueous solution chamber and the product solution chamber are connected to form a circulation system of the independent circulation washing solution, the mashing solution, the strong acid aqueous solution and the product solution. 如申請專利範圍第1項所述之電透析裝置,其中該離子滲透膜係由一陽離子滲透膜及一陰離子滲透膜交錯配置。 The electrodialysis device according to claim 1, wherein the ion permeable membrane is alternately arranged by a cation permeable membrane and an anion permeable membrane. 如申請專利範圍第1項所述之電透析裝置,其中該離子滲透膜係為雙極性膜(bipolar membrane)。 The electrodialysis device according to claim 1, wherein the ion permeable membrane is a bipolar membrane. 如申請專利範圍第1項所述之電透析裝置,其中該醱酵液循環系統係包含至少兩個醱酵液室,且兩者之間之連接方式係由該循環輸送管線將一醱酵液室入口端與另一醱酵液室出口端相連接。 The electrodialysis device according to claim 1, wherein the fermentation circulatory system comprises at least two fermenting liquid chambers, and the connection between the two is a fermentation broth by the circulating transport line. The inlet end of the chamber is connected to the outlet end of another fermentation chamber. 如申請專利範圍第1項所述之電透析裝置,其中該醱酵液循環系統係包含一個醱酵液室,其係由該循環輸送管線將該醱酵液室入口端與該醱酵液室出口端相連接。 The electrodialysis device according to claim 1, wherein the lysate circulation system comprises a fermentation broth chamber, wherein the fermentation solution chamber inlet end and the fermentation broth chamber are arranged by the circulation transfer line The outlet ends are connected. 如申請專利範圍第1項所述之電透析裝置,其中該沖洗溶液循環系統係包含至少兩個沖洗溶液室,且兩者之間之連接方式係由該循環輸送管線將一沖洗溶液室入口端與另一沖洗溶液室出口端相連接。 The electrodialysis device according to claim 1, wherein the rinsing solution circulation system comprises at least two rinsing solution chambers, and the connection between the two is from the circulatory delivery line to the inlet end of the rinsing solution chamber. Connected to the outlet end of another rinse solution chamber. 如申請專利範圍第1項所述之電透析裝置,其中該沖洗溶液循環系統係包含一個沖洗溶液室,其係由該循環輸送管線將該沖洗溶液室入口端與該沖洗溶液室出口端相連接。 The electrodialysis device according to claim 1, wherein the rinsing solution circulation system comprises a rinsing solution chamber, wherein the rinsing solution chamber inlet end is connected to the rinsing solution chamber outlet end . 如申請專利範圍第1項所述之電透析裝置,其中該強酸水溶液循環系統 係包含至少兩個強酸水溶液室,且兩者之間之連接方式係由該循環輸送管線將一強酸水溶液室入口端與另一強酸水溶液室出口端相連接。 The electrodialysis device according to claim 1, wherein the strong acid aqueous solution circulation system The system comprises at least two strong acid aqueous solution chambers, and the connection between the two is connected by the circulating transfer line to the inlet end of the strong acid aqueous solution chamber to the outlet end of the other strong acid aqueous solution chamber. 如申請專利範圍第1項所述之電透析裝置,其中該強酸水溶液循環系統係包含一個強酸水溶液室,其係由該循環輸送管線將該強酸水溶液室入口端與該強酸水溶液室出口端相連接。 The electrodialysis device according to claim 1, wherein the strong acid aqueous solution circulation system comprises a strong acid aqueous solution chamber, wherein the inlet end of the strong acid aqueous solution chamber is connected to the outlet end of the strong acid aqueous solution chamber by the circulating transfer line. . 如申請專利範圍第1項所述之電透析裝置,其中該產品溶液循環系統係包含至少兩個產品溶液室,且兩者之間之連接方式係由該循環輸送管線將一產品溶液室入口端與另一產品溶液室出口端相連接。 The electrodialysis device according to claim 1, wherein the product solution circulation system comprises at least two product solution chambers, and the connection between the two is from the circulation delivery line to the inlet end of a product solution chamber. Connected to the outlet end of another product solution chamber. 如申請專利範圍第1項所述之電透析裝置,其中該強酸水溶液係為鹽酸或硫酸。 The electrodialysis device according to claim 1, wherein the strong acid aqueous solution is hydrochloric acid or sulfuric acid. 如申請專利範圍第1項所述之電透析裝置,其中該強酸水溶液室更進一步配置有水分蒸發單元。 The electrodialysis device according to claim 1, wherein the strong acid aqueous solution chamber is further configured with a moisture evaporation unit. 如申請專利範圍第1項所述之電透析裝置,其中該電透析裝置係為該醱酵液係連續性進入該醱酵液室,且該產品溶液係連續性從該產品溶液室取出的連續式操作模式。 The electrodialysis device according to claim 1, wherein the electrodialysis device is that the fermentation liquid system continuously enters the fermentation liquid chamber, and the product solution is continuously continuous from the product solution chamber. Mode of operation. 如申請專利範圍第1項所述之電透析裝置,其中該電透析裝置係為固定電極電性之電透析裝置或正負極與內部可切換之倒極式電透析裝置。 The electrodialysis device according to claim 1, wherein the electrodialysis device is an electric dialysis device with a fixed electrode or a positive and negative electrode and an internally switchable inverted electrode electrodialysis device.
TW103135049A 2014-10-08 2014-10-08 Electrodialysis apparatus of purifying bio-succinic acid TWI543809B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
TW103135049A TWI543809B (en) 2014-10-08 2014-10-08 Electrodialysis apparatus of purifying bio-succinic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
TW103135049A TWI543809B (en) 2014-10-08 2014-10-08 Electrodialysis apparatus of purifying bio-succinic acid

Publications (2)

Publication Number Publication Date
TW201613684A TW201613684A (en) 2016-04-16
TWI543809B true TWI543809B (en) 2016-08-01

Family

ID=56361082

Family Applications (1)

Application Number Title Priority Date Filing Date
TW103135049A TWI543809B (en) 2014-10-08 2014-10-08 Electrodialysis apparatus of purifying bio-succinic acid

Country Status (1)

Country Link
TW (1) TWI543809B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10688438B2 (en) 2017-03-31 2020-06-23 Industrial Technology Research Institute Electrodialysis module and electrodialysis system

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10688438B2 (en) 2017-03-31 2020-06-23 Industrial Technology Research Institute Electrodialysis module and electrodialysis system

Also Published As

Publication number Publication date
TW201613684A (en) 2016-04-16

Similar Documents

Publication Publication Date Title
US10882880B2 (en) Process for efficient purification of neutral human milk oligosaccharides (HMOs) from microbial fermentation
Wang et al. In-situ combination of fermentation and electrodialysis with bipolar membranes for the production of lactic acid: continuous operation
CN103865792B (en) A kind of circulating fermentable reaction and feed liquid isolation integral equipment
CN107055712B (en) Method for recovering ammonia nitrogen, phosphorus and volatile fatty acid in livestock and poultry excrement hydrolysate by using two-stage bipolar membrane electrodialysis
US20080272001A1 (en) Production line treatment for organic product
CN101234961A (en) Method for preparing lactic acid by applying double pole film electrodialysis technique
CN102492782B (en) Desalting method for syrup and production method for glucose syrup
CN105771663B (en) A kind of electrodialysis plant and method for starch sugar hydrolyzate desalination
CN106631854B (en) A method of inorganic salts in removal l-Alanine fermented feed liquid
TWI543809B (en) Electrodialysis apparatus of purifying bio-succinic acid
Antczak et al. An environment-friendly multi-step membrane-based system for succinic acid recovery from the fermentation broth
CN108285912B (en) Method for preparing and extracting pharmaceutical grade valine by fermentation
CN108285913B (en) Process for preparing and extracting L-glutamine
CN203820791U (en) Integrated circulating-type microbial fermentation reaction and feed liquid separation device
CN104195590A (en) Treatment method of gluconate crystallization mother liquor
CN101818216B (en) Method for refining corncob acid hydrolysis solution
Hoffmann et al. Recent advances in application of electrodialysis with bipolar membranes for organic acid recovery from fermentation broth
CN106117012B (en) A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination
CN105837460A (en) Clean production process for separating and extracting glutamic acid from molasses fermented glutamic acid fermentation liquid
CN106040001B (en) A kind of methionine salt saponification liquor decarburization acid salt technique
CN112778149A (en) Method for extracting and separating beta-alanine from fermentation liquor
Rózsenberszki et al. Bipolar membrane electrodialysis integration into the biotechnological production of itaconic acid: a proof-of-concept study
CN111592454A (en) Method for producing diamine salt, diamine salt solution, diamine salt and polymer
CN110548465A (en) ionic membrane reactor device and method for preparing sodium glutamate
CN105964146A (en) Method of separating nucleotide acid from enzymolytic liquid