络合萃取法分离发酵液中的3-羟基丙酸
发布时间:2018-03-12 21:06
本文选题:络合萃取 切入点:3-羟基丙酸 出处:《中国科学院大学(中国科学院过程工程研究所)》2017年硕士论文 论文类型:学位论文
【摘要】:3-羟基丙酸(3-HP)是一种重要的平台化合物,可用于合成多种工业产品。利用发酵法替代化学合成法生产3-羟基丙酸日益受到关注,但相应的分离技术的缺乏制约着3-羟基丙酸的大规模生产。络合萃取法具有高效、处理量大、操作简单、易于放大等优点,在高度亲水性有机物稀溶液的萃取分离中显示了良好的应用前景。本学位论文以有机胺类为萃取剂,开展了 3-羟基丙酸络合萃取的研究。论文首先以三辛胺(TOA)、三癸胺和三正十二胺三种叔胺为萃取剂,比较了它们对水溶液中3-羟基丙酸的萃取能力。进一步选取萃取能力较好的TOA为萃取剂,考察了稀释剂种类、溶液的pH、温度、油水相比和有机相中萃取剂体积分数等关键因素对3-羟基丙酸萃取效率和分配系数的影响。在萃取温度为293 K,相比为1:1,有机相中TOA体积分数为30%,3-轻基丙酸初始浓度为0.330 mol/L的条件,3-羟基丙酸的萃取率达到81.6%。通过采用红外谱光谱分析及质量作用定律,探讨了络合萃取过程中的3-羟基丙酸萃取机理。结果表明,3-羟基丙酸可以与TOA以离子缔合或氢键缔合的形式结合。萃取平衡后的有机相中存在1:1和2:1型的酸胺萃合物,且1:1型的酸胺萃合物占主导地位。论文还考察了二辛胺、二癸胺和双正十二烷基胺三种仲胺对水溶液中3-羟基丙酸的萃取效果。研究发现,仲胺类萃取剂萃取3-羟基丙酸的能力强于烷基链长度相同的叔胺萃取剂。随后探讨了不同种类稀释剂、温度、溶液的PH、油水相比和萃取剂浓度对二癸胺萃取效率和分配系数的影响。以二癸胺和正辛醇分别为萃取剂和稀释剂,在相比为1:1,萃取温度为303 K的条件下,对3-羟基丙酸的分配系数为77.6,萃取率为98.8%。通过采用红外谱光谱分析及质量作用定律,探讨了络合萃取过程中的3-羟基丙酸萃取机理。结果表明,二癸胺通过离子缔合与3-羟基丙酸结合。萃取后的有机相中,主要存在1:1和2:1两种类型的酸胺萃合物。在研究发酵液的性质的基础上,首先采用加热和加酸调pH相结合的方式对发酵液进行预处理,可以高效去除其中易于产生乳化的蛋白质。在此基础上,将上述两种萃取剂应用于发酵液中3-羟基丙酸的萃取分离。研究结果表明,稀释剂对两种萃取剂萃取3-羟基丙酸的能力具有显著的影响。而对于同一种稀释剂,三辛胺对于发酵液中3-羟基丙酸的萃取能力略优于二癸胺。利用三辛胺和正丁醇为萃取体系,通过四级萃取,3-羟基丙酸的回收率可达96.7%。
[Abstract]:3- hydroxy propionic acid (3-HP) is an important platform for the synthesis of compounds, a variety of industrial products. By fermentation method instead of chemical synthesis of 3- hydroxy propionic acid production has been paid more and more attention, but the lack of corresponding separation technology restricts the large-scale production of 3- hydroxy propionic acid. The complexation extraction method has the advantages of high efficiency, large capacity, operation simple, easy to enlarge the advantages of highly hydrophilic organic compounds in dilute solution extraction shows a good application prospect. In this thesis, using organic amine as extractant, studied 3- hydroxypropionic acid complexation extraction. The first three octylamine (TOA), three and twelve amines decylamine tri three kinds of tertiary amine as extractant, them in aqueous solution 3- hydroxypropionic acid extraction ability. Further select the better extraction capacity TOA as extraction agent, effects of diluent, solution pH, temperature, oil and water as compared to organic The key factors affecting the phase extractant volume fraction of 3- hydroxy propionic acid extraction efficiency and distribution coefficient. The extraction temperature was 293 K, compared to 1:1, TOA in the organic phase volume fraction is 30%, 3- light acid initial concentration of 0.330 mol/L, the rate of extraction of 3- hydroxy propionic acid to 81.6%. by using infrared spectrum the spectral analysis and the law of mass action, discussed 3- hydroxypropionic acid extraction mechanism of complexation extraction process. The results showed that 3- and TOA can 3-hydroxypropionic to ion association or hydrogen bond association in the form of combination. The extraction equilibrium after the organic phase of 1:1 and 2:1 type acid amine complex, and 1:1 acid amine extraction complexes dominate. The paper also studied two octylamine, decylamine extraction effect of two and twelve are double alkyl amine three secondary amines in aqueous solution of 3- hydroxy propionic acid. The study found that secondary amine extractant 3- hydroxy propionic acid in the ability Is the same as the length of alkyl chain tertiary amine extractant. Then it discusses the different types of diluent, temperature, solution PH, compared with the effect of oil-water extractant concentration of two decylamine extraction efficiency and distribution coefficient. By two decylamine and n-octanol as extractant and diluent respectively, in comparison to 1:1, extraction temperature conditions 303 K, the distribution coefficient of 3- hydroxy propionic acid was 77.6, the extraction rate of 98.8%. by using infrared spectra analysis and mass action law, discusses 3- hydroxypropionic acid extraction mechanism of complexation extraction process. The results showed that two decylamine by ion association with 3- hydroxy propionic acid in organic phase after extraction. The presence of 1:1 and 2:1, the main two types of acid amine complex. Based on the properties of fermentation liquid on the first use of heating and adding acid to adjust pH combination of the fermentation broth was pretreated, which can efficiently remove the easy to produce Emulsified protein. On this basis, the above two kinds of extractants used in fermentation broth of 3- hydroxy propionic acid extraction. The results show that the significant effect of diluents on the extraction of two kinds of 3- 3-hydroxypropionic ability. For the same kind of diluent, three octyl amine in fermentation solution of 3- hydroxy propionic acid extraction capacity slightly better than the two. Three using decylamine octylamine and n-butanol extraction system, through four stage extraction, 3- hydroxy propionic acid recovery rate can reach 96.7%.
【学位授予单位】:中国科学院大学(中国科学院过程工程研究所)
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:TQ028.32;TQ921.7
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