CN101898945B - 盐析萃取发酵液中丙酮和丁醇的方法 - Google Patents
盐析萃取发酵液中丙酮和丁醇的方法 Download PDFInfo
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- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于生物工程技术领域，涉及到微生物发酵液的分离技术，特别涉及到盐析萃取发酵液中丙酮和丁醇的方法。其特征是向丙酮丁醇发酵液中添加一种或两种以上盐，以及一种或两种以上萃取剂；加盐后发酵液中盐的饱和度达到10％～100％，含盐发酵液与萃取剂的体积比为1∶0.1～1∶5；静置至分相，上相即为富含丙酮和丁醇的溶剂相或萃取相，下相为富盐相或萃余相。本发明的效果和益处是解决了目前从微生物发酵液中提取分离丙酮丁醇工艺存在的诸多弊端，工艺得以简化、分离时间短、成本低、经济可行，是一种具有工业应用前景的丙酮丁醇分离方法。
Description
技术领域
本发明属于生物工程技术领域，涉及到微生物发酵液的分离技术，特别涉及一种盐析萃取发酵液中丙酮和丁醇的方法。
背景技术
丙酮和丁醇是优良的有机溶剂和重要的化工原料。其中丁醇可用作油漆和表面涂料的溶剂以及各种塑料、橡胶制品的生产，还可以生产醋酸丁酯、丙烯酸丁酯、丁醛、丁酸、丁胺和乳酸丁酯等化工产品，是继乙醇后的一种极具发展前景的新一代液体燃料。丙酮主要用作制造醋酸纤维素胶片薄膜、塑料和涂料的溶剂，溶剂之外的主要用途是生产甲基丙烯酸甲酯(MMA)、双酚A、醇醛缩合物等化工产品。丙酮丁醇发酵是一项传统的大宗发酵，曾是仅次于酒精发酵的世界第二大发酵过程。我国从建国初期开始利用玉米粉进行丙酮丁醇发酵的工业化生产，形成了稳定的发酵工艺。由于石化工业的发展，丙酮丁醇发酵逐渐衰退。但是随着石化资源的耗竭和温室效应等环境问题的日益突出，利用可再生资源生产化工原料和能源物质受到高度重视。丙酮丁醇发酵重新显示出竞争优势，然而目前丙酮丁醇发酵过程所得溶剂的总浓度较低，一般发酵后总溶剂(丙酮、丁醇和乙醇)的质量浓度在15-20g/L左右，致使溶剂的提取分离成本占总成本比例大，限制了丙酮和丁醇的应用，丙酮丁醇发酵生产受到制约。自从发酵法生产丙酮丁醇成为可能以来，科研工作者一直努力探索一条既省事又可降低成本的有效的分离方法。
丙酮丁醇传统的提纯方法是使发酵液首先经过粗分离塔蒸馏提浓，去掉发酵液中的固形物和部分水，得到含乙醇4％、丙酮10％、正丁醇26％和水60％的物料，然后继续用蒸馏法分离得到乙醇、丙酮和正丁醇，能耗很大。工业上每生产1t溶剂，约需18t蒸汽(陈騊声，化学工业出版社，1991)，其中分离阶段约消耗10吨蒸汽，约占60％。目前从微生物发酵液中提取分离丙酮丁醇的主要技术包括吸附、气提、液液萃取、渗透汽化、排斥萃取(盐析)等。吸附法主要集中在使用硅藻土、活性炭、聚乙烯吡咯烷酮作为吸附剂。Meagher等(US，5755967[P]，1998)利用硅藻土吸附丙酮丁醇发酵液，发现硅藻土对丁醇和丙酮具有较高的吸附能力，遗憾的是缺乏解吸的报道。相对于其他方法，吸附法成本较高、操作复杂、选择性差且易受发酵液污染，能耗较高(BiotechnologyAdvances，2000，18(7)：581-599)。气提与丙酮丁醇发酵耦合分离能够提高发酵产率及底物的利用率，但该工艺受到载气回收速率、泡大小、消泡剂等众多因素的影响，操作相对困难。液液萃取目前研究较多的萃取剂有油醇(CurrentOpinion in Biotechnology，2007，18：220-227)、苯甲酸苄酯、邻苯二甲酸二丁酯(Journal of Fermentation and Bioengineering，1995，2(80)：185-189)、生物柴油(生物加工过程，2007，5(1)：27-33)等，上述过程存在分配系数偏低，回收率不高，存在乳化现象等缺点。罗建泉等采用渗透汽化膜分离技术(化学工程，2010，38(2)：43-46)对丙酮丁醇体系进行了分离研究，分离对象为模拟发酵液。结果表明，渗透汽化法能实现对丁醇的高效分离浓缩，对丙酮的分离效果不明显。该工艺受到膜材料本身性质的影响比较大，分离性能和通量很大程度上取决于膜本身特性，膜寿命较短，在一定程度上限制了其应用范围(Appl.Microbiol.Biotechnol.，1998，49：639-648)。胡柏玲等人采用排斥萃取分离方法研究了各种盐类对丙酮丁醇模拟发酵液的分离效果。结果表明复合盐萃取剂可以增大丁醇和丙酮在两相的分配系数和选择系数，在一定程度上可以达到分离提浓丁醇和丙酮的目的(华南理工大学学报，2003，31：58-62)。
近几年一些研究者在进行溶剂析出结晶研究时发现，在适当温度条件下，如果体系中无机盐、有机溶剂和水的浓度适当，这类体系中的盐可能不会析晶，而是出现液液分相现象。如果所用有机溶剂是亲水的低分子物质，如甲醇、乙醇、丙酮等，就可以形成一种新型的双水相萃取体系。与传统的高分子聚合物双水相体系相比，这种新型的双水相体系分相更清晰，成本更低，萃取相不含黏度大、难处理的聚合物。尽管这方面研究在国内外刚刚起步，但已表现出良好的分离性能，如Louwrier用磷酸氢二钾/乙醇体系萃取牛血清蛋白、α-酪蛋白、核糖核酸酶等生物质大分子(Biotechnology Techniques，1998，12(5)：363-365)，李全民、高云涛等人用丙酮/氯化钠体系萃取金属络合物或金属离子(应用化学，2001，18(3)：241-243；分析测试学报，2002，21(3)：75-77)均得到相当满意的结果。本研究团队采用新型的双水相体系分离提取发酵液中的1，3-丙二醇和2，3-丁二醇，有效地实现了目标产物和发酵液的分离，分离效果明显(过程工程学报，2008，8(5)：888-900；Process Biochemistry，2009，44，112-117；Biotechnol.Lett，2009，31(3)：371-376；Separation and Purification Technology，2009，66：472-478)。实际上，盐析效应既对亲水性有机溶剂的萃取有明显效果，对传统的有机萃取也有显著的改善效果，盐析与萃取结合形成新型的盐析萃取技术，而新型双水相萃取是盐析萃取的一种形式。到目前为止，盐析萃取体系对丙酮-丁醇-水体系的分离尚未见文献报道。与传统的有机溶剂萃取相比，盐析萃取技术具有分配系数高、收率高、溶剂用量少等特点；与传统的盐析或排斥萃取相比，盐析萃取技术盐用量小，对设备的腐蚀性弱，所用无机盐和有机盐可回收，进行多级盐析萃取。与传统的PEG/无机盐双水相体系相比，它具有分配系数高、分相快、溶剂和产物易回收、廉价等特点；与其他分离方法相比，它具有操作简单、能耗低、效率高等优势，而且可以直接从发酵液中提取丙酮和丁醇，节省了固液分离步骤。
发明内容
本发明提供了一种盐析萃取技术从发酵液中分离丙酮和丁醇的方法，克服了目前从发酵液中分离丙酮/丁醇存在的分离工艺复杂、分离能力小、总体收率低和能耗高等问题。
本发明采用的技术方案：
丙酮丁醇发酵液可以用絮凝、过滤、微滤或离心的方法进行预处理，除去菌体得到清液，也可以是未经预处理的发酵原液，或者是经过浓缩的原液或清液，其中丙酮丁醇的浓度范围为4-500g/L。向上述发酵液或清液中添加一种或两种以上盐，所加盐为固体或浓盐溶液，加盐后发酵液中盐的饱和度达到10％～100％；然后加入一种或两种以上萃取剂，含盐发酵液和萃取剂的体积比为1∶0.1～1∶5。
无机盐可以是碳酸钠、碳酸钾、氯化钠、氯化锂、硫酸铵、硫酸钠、磷酸氢二钾、磷酸氢二钠、磷酸钾、磷酸钠、磷酸二氢钾或磷酸二氢钠等；
有机盐可以是醋酸钠、醋酸钾、柠檬酸钠、柠檬酸钾、草酸钠或草酸钾等。
萃取剂可以是甲醇、乙醇、丙酮、正丙醇、异丙醇、正丁醇、异丁醇、乙二醇、乙醚、乙酸甲酯或乙酸乙酯等。
静置至分相，上相即为富含丙酮和丁醇的溶剂相或萃取相，下相为富盐相或萃余相。含有菌体的发酵液经盐析萃取后在两相之间形成固相层，由细胞、蛋白、核酸、多糖等组成。用蒸馏或精馏法从溶剂相或萃取相中回收溶剂，并得到丙酮和丁醇粗品和固体盐；富盐相或萃余相经蒸馏浓缩得到的浓盐液可以循环使用，也可以加入回收的有机溶剂使盐结晶析出。对于碱性盐来说，可以将发酵和分离过程排出的CO2废气通入萃取后的富盐相，CO2与碱性盐反应生成溶解度较低的酸式盐，以沉淀的方式析出，或经过滤、离心回收，或加入有机溶剂溶析结晶。所生成的酸式盐可以为碳酸氢钠、碳酸氢钾、碳酸氢铵、磷酸二氢钾、磷酸二氢钠等。所生成的酸式盐可作为副产物加以利用，也可以通过加热分解的方式回收高浓度的CO2，并回收碱性无机盐，实现发酵法生产丙酮丁醇的节能减排。
盐析萃取的操作方式可以是间歇的或连续的，对于分配系数较小的体系可采用多级萃取方式。
本发明的效果和益处克服了目前从微生物发酵液中提取分离丙酮丁醇工艺存在的诸多弊端，使工艺得以简化，分离时间短，成本降低，经济可行。具体表现在：①由单一或复合萃取剂和无机盐/有机盐组成的盐析萃取体系对丙酮和丁醇有较好的萃取效果，解决了传统萃取剂萃取效率较低的难题；萃取剂可以选用丙酮、丁醇、乙醇或它们的混合物，有利于降低生产成本；②该盐析萃取体系可以直接处理发酵液，免除了菌体分离步骤，并且可以将发酵液中大量的核酸、蛋白、多糖除掉，解决了超滤除杂动力消耗较大、且需要对膜进行清洗、菌体浓缩液中残留较多的丙酮丁醇无法回收等问题；③CO2回收减排：利用富盐相吸收生产过程中产生的二氧化碳既可以有效地回收无机盐，又可以回收大部分的二氧化碳，解决了盐析萃取体系中盐回收困难和生产过程中CO2大量排放的问题。
具体实施方式
以下结合技术方案详细叙述本发明的具体实施例。
发酵模拟液是将分析级的丁醇、丙酮和乙醇溶入水中获得，其最终浓度分别为21.08g/L、10.17g/L和3.82g/L。
发酵液是采用丙酮丁醇梭菌Clostridium acetobutylicum L7批式流加葡萄糖发酵得到的，其中丁醇、丙酮和乙醇的浓度分别为13.51g/L、6.47g/L和2.15g/L。
实施例1
磷酸氢二钾/丙酮盐析萃取发酵模拟液中的丁醇和乙醇
取5g发酵模拟液，加入2.5g磷酸氢二钾，待盐溶解后再加入2.5g的丙酮，混合、静置，体系分为两相。上相体积为4.2mL，其中丁醇、丙酮和乙醇含量较高；下相中盐浓度较高，体积为4.3mL。丁醇、丙酮、乙醇的分配系数分别为：391.84、58.90、16.07；丁醇和乙醇回收率分别为99.74％和94.01％。
实施例2
磷酸氢二钾/乙醇盐析萃取发酵模拟液中的丙酮和丁醇
取5g发酵模拟液，加入2.5g磷酸氢二钾，待盐溶解后再加入2.5g的95％乙醇，混合、静置，体系分为两相。上相体积为4.9mL，其中丁醇、丙酮和乙醇含量较高；下相中盐浓度较高，体积为4mL。丁醇、丙酮、乙醇的分配系数分别为：25.03、71.29、14.76；丁醇和丙酮回收率分别为96.84％和98.87％。
实施例3
碳酸钠/丙酮盐析萃取发酵模拟液中的丁醇和乙醇
取6g发酵模拟液，加入1.5g碳酸钠，待盐溶解后再加入2.5g的丙酮，混合、静置，体系分为两相。上相体积为4.9mL，其中丁醇、丙酮和乙醇含量较高；下相中盐浓度较高，体积为4.5mL。丁醇、丙酮、乙醇的分配系数分别为：55.70、30.34、8.56；丁醇和乙醇回收率分别为98.38％和90.31％。
实施例4
碳酸钠/乙醇盐析萃取发酵模拟液中的丙酮和丁醇
取6g发酵模拟液，加入1.5g碳酸钠，待盐溶解后再加入2.5g的95％乙醇，混合、静置，体系分为两相。上相体积为5.1mL，其中丁醇、丙酮和乙醇含量较高；下相中盐浓度较高，体积为3.9mL。丁醇、丙酮、乙醇的分配系数分别为：35.06、65.96、13.82；丁醇和丙酮回收率分别为97.87％和98.85％。
实施例5
磷酸氢二钾/丙酮盐析萃取发酵液中的丁醇和乙醇
取5g发酵液，加入3g磷酸氢二钾，待盐溶解后再加入2g的丙酮，混合、静置，体系分为三相。上相体积为3.5mL，其中丁醇、丙酮和乙醇含量较高；中间相主要为菌体和蛋白，体积为0.7mL；下相中盐浓度较高，体积为5mL。蛋白和菌体的去除率分别为：91.21％、99.86％；丙酮、乙醇的分配系数分别为：67.58、24.51；乙醇回收率为94.49％。下相未检测到丁醇的存在，几乎全部存在于上相。
实施例6
碳酸钠/丙酮盐析萃取发酵液中的丁醇和乙醇
取6g发酵模拟液，加入1.8g碳酸钠，待盐溶解后再加入2g的丙酮，混合、静置，体系分为两相。上相体积为3.8mL，其中丁醇、丙酮和乙醇含量较高；中间相主要为菌体和蛋白，体积为0.7mL；下相中盐浓度较高，体积为5.1mL。蛋白和菌体的去除率为：87.13％、99.92％；丁醇、丙酮、乙醇的分配系数分别为：32.17、35.79、2.59；丁醇和乙醇回收率分别为95.99％和91.21％。
Claims (3)
1.一种盐析萃取发酵液中丙酮和丁醇的方法，其特征是向丙酮丁醇发酵液中添加盐和萃取剂；盐是碳酸钠、碳酸钾、氯化钠、氯化锂、硫酸铵、硫酸钠、磷酸氢二钾、磷酸氢二钠、磷酸钾、磷酸钠、磷酸二氢钾、磷酸二氢钠、醋酸钠、醋酸钾、柠檬酸钠、柠檬酸钾、草酸钠或草酸钾；萃取剂是甲醇、乙醇、丙酮、正丙醇、异丙醇、正丁醇、异丁醇、乙二醇、乙醚、乙酸甲酯或乙酸乙酯；加盐后发酵液中盐的饱和度达到10%～100%，含盐发酵液与萃取剂的体积比为1:0.1～1:5。
2.根据权利要求1所述的盐析萃取发酵液中丙酮和丁醇的方法，其特征是其中的发酵液是未经预处理含有菌体的发酵液、未经预处理含有菌体的浓缩液、去除菌体的清液或去除菌体的浓缩液，发酵液中丙酮和丁醇的浓度为4-500 g/L。
3.根据权利要求1所述的盐析萃取发酵液中丙酮和丁醇的方法，其特征是盐析萃取的操作方式是间歇的或连续的。
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| CN101012152A (zh) * | 2007-01-24 | 2007-08-08 | 大连理工大学 | 一种从发酵液中分离2,3－丁二醇的双水相萃取方法 |
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| US5755967A (en) | 1996-05-22 | 1998-05-26 | Meagher; Michael M. | Silicalite membrane and method for the selective recovery and concentration of acetone and butanol from model ABE solutions and fermentation broth |
| CN101898945B (zh) | 2010-07-27 | 2013-05-08 | 大连理工大学 | 盐析萃取发酵液中丙酮和丁醇的方法 |
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| 用排斥萃取分离正丁醇-丙酮-水体系;胡柏玲等;《华南理工大学学报(自然科学版)》;20031231;第31卷(第12期);58-62 * |
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| CN101898945A (zh) | 2010-12-01 |
| WO2012013004A1 (zh) | 2012-02-02 |
| US20130190536A1 (en) | 2013-07-25 |
| US8779209B2 (en) | 2014-07-15 |
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