有机酸对甜高粱渣亚临界水解产物的影响

半纤维素的高效转化是提高甜高粱渣原料全组分利用的关键技术之一。采用亚临界水热预处理方法,并将强度因子R₀引入研究过程,考察了不同温度（160~200℃）和反应时间（10~60 min）对甜高粱渣水解反应的影响。在这基础上,进一步考察了多种有机酸（乳酸、醋酸及乳酸+醋酸）对亚临界水解效果的影响。实验表明,当强度因子lgR₀=3.96（180℃,40 min）时,采用不外加酸的亚临界水热预处理工艺得到的最大木糖浓度为4.79 g·L^-1;有机酸的加入可强化水解反应,提高木糖浓度;与单一乳酸或醋酸处理方法相比,加入同浓度的乳酸+醋酸既可以促进半纤维素水解,又可以抑制副产物生成;在温度180℃,时间40 min,乳酸+醋酸（乳酸：醋酸=6：4）的浓度1%（质量）的条件下,木糖浓度为7.92 g·L^-1。     

Enzymatic esterification of lactic acid,utilizing the basicity of particular polar organic solvents to suppress the acidity of lactic acid

BACKGROUND: Lipase‐catalyzed esterification of lactic acid with ethanol was investigated; however, some difficulties exist with such a system. Because of its high polarity, lactic acid is immiscible with non‐polar organic solvents, which have generally been used for non‐aqueous enzyme reactions. In addition, the strong acidity of lactic acid causes acid inactivation of enzymes and acid‐catalyzed, non‐enzymatic esterification. RESULT: In the present study, particular polar organic solvents, such as 1,4‐dioxane, were found to suppress the enzyme inactivation and non‐enzymatic esterification caused by the acidity. The magnitude of this effect varied with solvents and strongly correlated with the Kamlet‐Taft parameter β, which indicates the basicity of the solvents in non‐aqueous systems. An immobilized lipase from Candida antarctica was found to be the most active and stable enzyme for the reaction. Based on the findings, lipase‐catalyzed esterification of lactic acid (1.0 mol L^?1) could be continued for up to 4 weeks without any loss of enzyme activity. CONCLUSION: In addition to miscibility with lactic acid, the effect of these polar solvents, which is to suppress the acidity of lactic acid and is presumably due to the basicity, appears to play a very important role in the efficient enzymatic reaction of lactic acid. Copyright © 2008 Society of Chemical Industry     

微波有机合成及反应器的新进展

简述了微波促进有机合成反应的机理 ,讨论了微波密闭合成反应技术、微波常压合成反应技术、微波连续合成反应技术及微波干法合成反应技术在近年来的进展情况。分析了家用微波炉的缺点 ,对目前国内外实验用微波反应器在有机合成应用中的不足之处进行了评价 ,结合本教研室所做的工作 ,介绍了有机合成专用微波炉。展望了微波有机合成的发展前景。     

乳酸还原浸出低品位软锰矿

用乳酸还原浸出低品位软锰矿,采用单因素实验考察乳酸用量、反应时间、温度、硫酸用量等因素对锰浸出率的影响,用响应面法对反应条件进行了优化,用高效液相色谱测定了反应中的有机物,对还原浸出产物进行了研究. 结果表明,在锰矿粉加入量10.0 g、乳酸用量1.2 mL、反应时间3.47 h、温度90℃、硫酸用量12%、搅拌速率200 r/min、液固比10 mL/g条件下,锰的浸出率可达93.99%. 还原产物为丙烯酸、甲酸和乙酸;还原浸出60 min后乳酸反应基本完全,210 min内丙烯酸含量降低不明显,甲酸和乙酸含量缓慢增加.     

微波法合成醇胺类离子液体及其吸收SO_2研究

采用水浴微波法合成并表征了一系列由乙醇胺、二乙醇胺、三乙醇胺、N,N-二甲基乙醇胺提供阳离子,乳酸、乙酸、甲酸提供阴离子的醇胺类离子液体。通过正交实验对乙醇胺乳酸盐离子液体(HEL)的水浴微波合成条件进行了优化,当反应时间为30 min,反应温度为65℃,微波功率为300 W,乙醇胺和乳酸的摩尔比为1∶1.1时,能够得到较高的产率(92.74%)。发现HEL对SO2有较好的吸收选择性,且有较宽的温度适应范围,同时微波辅助能加快解吸速率,大大缩短解吸时间;此外,添加溶剂后的离子液体也显示出良好的吸收效果。这为离子液体的进一步工业化应用奠定了一定的基础。     

Microwave-assisted synthesis of anion-exchange resins for sorption of noble metals: how to boost sorption capacity using a proper reaction environment

In the present studies a series of anion-exchange resins was synthesized in a microwave field. The 1,6-diaminohexane functionalized resins were obtained in presence of selected organic solvents, N,N-dimethyl formamide, dimethyl sulfoxide and 1-methyl-2-pyrrolidone. The resins were employed in batch and dynamic processes of Au(III), Pt(IV) and Pd(II) sorption from tricomponent systems in 0.1 M HCl. The experiment was designed in a way that allowed to determine the use of a specific solvent in the microwave field and how it impacts on properties of the anion exchangers. An influence of a reaction environment was discussed taking into account i.e., dielectric characteristics of the specific solvent, efficiency of the syntheses processes as well as the maximum sorption capacity of the resins. Ultimately the application of a specific reaction environment was set together with sorption of noble metals ability and evaluated using infrared spectroscopy. The proceeded analyzes allowed to determine which organic solvent from the selected ones is the most suitable for microwave-assisted synthesis of the anion-exchange resins.     

Structure,transport properties,and dielectric properties of lactic acid/pyruvic acid aqueous solution in a biofuel cell: A molecular simulation study

Molecular dynamics (MD) simulation of lactic acid (L‐acid) and pyruvic acid (P‐acid) in a physiological salt solution has been performed, which is used as the electrolyte in a sort of biofuel cell working on a human skin. The structure, frequency distribution of molecules, dielectric properties, rotational correlation functions, and diffusion coefficients have been calculated. The anomalous behavior of dielectric constants for the lower concentration of L‐acid and P‐acid has been obtained from MD. The anomalous dielectric constant is discussed in relation with the various physical properties of the solution including the life time of the interaction in the solution. MD results suggest that the anomalous behavior is supposed to be attributed to the difference of interactions between ions in the lower and higher concentration region. POLYM. ENG. SCI., 59:2474–2478, 2019. © 2019 Society of Plastics Engineers     

微波辅助合成聚羧酸减水剂及其性能研究

利用微波技术具有操作简便、清洁、高效、安全及靶向性等特性,分别采用微波辅助合成和常规水浴法,以甲基烯基聚氧乙烯醚(TPEG)、丙烯酸(AA)为单体合成梳状聚羧酸减水剂.通过实验,研究了微波加热对减水剂表征及性能的影响,结果表明,微波辅助合成的方法有效提高了聚合反应的转化率,可更好地控制反应进程,并对新拌浆体絮凝结构拥有更好的吸附-分散性能.     

乳酸/聚乙二醇嵌段共聚物的合成与表征

利用直接缩聚法制备了乳酸与聚乙二醇的嵌段共聚物(PLEG)。采用正交试验法考察了乳酸与聚乙二醇质量比、催化剂种类、催化剂含量、反应温度和反应时间对PLEG性能的影响。结果显示优化的反应条件:乳酸与聚乙二醇质量比为8.5∶1.5,采用自制的复合催化剂,催化剂质量分数0.6%,聚合温度160℃,聚合时间5h。另外还考察了扩链剂对PLEG性能的影响,结果表明扩链剂能够显著提高PLEG的相对分子质量。对合成的PLEG通过红外光谱、核磁共振、热分析进行了表征。     

Effect of solvent and impurity on synthesis of ethyl lactate from fermentation-derived ammonium lactate

Fermentation-derived ammonium lactate was converted into ethyl lactate by decomposition in various organic solvents followed by esterification with ethanol over Amberlyst catalyst. The ammonium lactate was decomposed more efficiently in an organic solvent with high boiling point, where the produced lactic acid was stabilized well as a monomer without oligomerization. However, only the nonreactive phosphate-type solvent such as triethyl phosphate and tributyl phosphate showed a notable ethyl lactate yield in the subsequent esterification reaction compared with dimethyl sulfoxide and N-methyl pyrolidine. The lactic acid yield in ammonium lactate decomposition and the subsequent ethyl lactate yield were also highly dependent on solvent ratio to ammonium lactate, temperature and pressure in ammonium lactate decomposition reaction. The amino acid impurity contained in the fermented ammonium lactate as well as the unreacted ammonium lactate reduced the acid strength of Amberlyst-36, which resulted in the final ethyl lactate yield.     

微波辅助下固体酸催化剂对稻壳热解油的催化加氢

微波辅助下,以甲醇为溶剂的固体酸催化剂对稻壳热解油的催化加氢,采用Gc/MS分析稻壳热解油催化前后正己烷萃取物.结果表明:稻壳生物油中的化合物十分复杂,主要成分为酮、酚、醛、酸和酯等含氧化合物;在固体酸催化下,酮和酚的含量大大降低;同时,稻壳热解油催化后正己烷的萃取物中的化合物种类也有所增加;微波辅助下,固体酸催化剂对...     

可降解聚乳酸复合材料研究进展

对聚乳酸（PLA）复合材料的生物降解性能进行综述,总结PLA与有机物（如木质素、纤维素等）、无机物（如碳酸钙、纳米银颗粒等）复合后力学性能、热性能、生物相容性、抗菌性的变化及在不同环境条件下生物降解速率的变化,梳理了PLA复合材料结构、组成与降解性能的相互关系,对降解性能可控的PLA复合材料应用前景进行了展望。     

Design and control of reactive distillation for hydrolysis of methyl lactate

Esterification of raw lactic acid from fermentation broth and then hydrolysis of lactate ester in reactive distillation column is an effective process for purification of lactic acid. Reactive distillation for hydrolysis of methyl lactate is studied. First, the thermodynamic properties and reaction kinetics are analyzed; then the reactive distillation column is designed based on the objective function total annual cost. The effects of tray number of rectifying section, tray number of reactive section, and feed location on the total annual cost are investigated. And a dual-temperature control structure is proposed for the optimal reactive distillation column, and the results show that it works quite well for this hydrolysis system.     

几种金属材料在乳酸中的腐蚀性能研究

采用失重法对316L不锈钢、Ti、Ni 3种材料在不同条件下的耐乳酸腐蚀行为进行了研究,详细考察了反应温度和反应时间对316L腐蚀的影响。结果表明,316L在L-乳酸中腐蚀速率随反应温度的升高而增大,在反应时间36 h,反应温度90℃和120℃下,腐蚀速率分别为0.382 mm/a和0.801 3 mm/a,属尚耐腐蚀;150℃和180℃下腐蚀速率分别为3.85 mm/a和6.01 mm/a,属不耐腐蚀。金相显微镜分析表明,316L不锈钢表面在较低温度的乳酸中以点蚀为主。现场挂片腐蚀实验结果表明,当温度低于120℃,316L可以作为乳酸生产设备的选材。     

Use of 1‐hexyl‐3‐methylimidazolium bromide ionic liquid in the recovery of lactic acid from wine

BACKGROUND: Lactic acid has many different applications in a variety of industries including the food, cosmetics, packaging, leather and chemical industries. Current methodologies for lactic acid production are lengthy and complicated and more efficient methods are being sought. Some organic wastes contain lactic acid and our work investigates the use of ionic liquids (ILs) in the efficient and selective extraction of lactic acid from organic waste using wine as a model system. The ionic liquid was chosen based on its ability to selectively solvate and separate lactic acid from the remaining bulk waste material. RESULTS: Several ILs including 1‐hexyl‐3‐methylimidazolium chloride (hmimCl), 1‐hexyl‐3‐methylimidazolium bromide (hmimBr), 1‐hexyl‐3‐methylimidazolium iodide (hmimI) and N‐hexylpyridinium iodide (hpyrI) have been synthesized in high yield (68‐95%) using microwave technology. Lactic acid is soluble in each of the ILs synthesized with optimum results achieved with hmimBr where lactic acid is miscible in all proportions. HmimBr has been used to successfully separate and extract lactic acid from wine as confirmed by FTIR spectroscopy. Furthermore, it has been possible to recover the IL for recycle in subsequent extraction cycles where the efficiency for the extraction process increases with each recycle. CONCLUSION: HmimBr has been used for the first time in a novel process for the separation and recovery of lactic acid from wine, as confirmed by FTIR spectroscopy. This work demonstrates a novel process which can be applied to the recovery of lactic acid from organic waste. Copyright © 2012 Society of Chemical Industry     

Microwave-assisted solvent extraction of castor oil from castor seeds

This study was aimed at evaluating the physicochemical properties and oxidation stability of castor oil using microwave-assisted solvent extraction (MAE). MAE was performed using 5% ethanol in hexane as solvent at different extraction times, power intensities and solvent-to-feed (S/F, ml of solvent to gram of feed) ratios. The process parameters were optimized by statistical approach using historical data design of response surface method (RSM). The oils were characterized for yield, physicochemical properties, dielectric properties and oxidation stability, and comparison was also made with oil extracted using Soxhlet method. Results show that the maximum oil yield of 37% was obtained at 20 min with microwave power intensity of 330 W and S/F ratio of 20. The main fatty acid composition of castor oil is ricinoleic acid. The density, refractive index, dielectric properties and oxidation stability of oils are not affected by the extraction methods and extraction parameters of MAE. However, the MAE-extracted oil is more viscous compared to that by Soxhlet method. With extra caution on oil oxidation, MAE could be a promising solvent extraction method with an 86% less in processing time and a higher yield.     

脱水法合成乳酸乙酯

以乳酸和乙醇为原料 ,在对甲苯磺酸的催化下以氧化钙或 3A分子筛或MgSO3 为脱水剂 ,采用自制的索氏提取器进行回流脱水合成乳酸乙酯。对影响乳酸乙酯产率的诸因素进行了考察。实验结果表明 :加入脱水剂和带水剂可以显著提高乳酸乙酯的产率 ,酯的产率随催化剂用量的增加、醇酸物质的量比的增大、反应时间的延长先增加到最高点后略有降低。当乳酸 0 1mol、乙醇 0 3mol、对甲苯磺酸 1 0g、带水剂环己烷 5 0mL、脱水剂CaO 18 7g和反应 2h时 ,乳酸乙酯的产率达 84 5 %。     

乳酸的乳化液膜萃取与有机溶剂萃取的比较

在乳酸发酵与分离耦合过程中,可以采用乳化液膜萃取法或有机溶剂萃取法提取发酵液中的乳酸。本文比较了这两种方法的传质机理和操作过程,并实验分别研究了它们的最佳工艺条件,提出：在最佳操作条件下,提取相同量的乳酸,有机溶剂萃取有机相的消耗量为乳化液膜法的３－４倍,乳化液膜法萃取率高,而且能得到浓缩的乳酸。     

微波有机合成及反应器研究新进展

综述了近年来微波辐射技术在有机合成应用中的新进展。针对微波有机合成反应技术及专用微波反应器作了重点介绍。     

发酵液中乳酸的盐析萃取

研究了一种利用盐析萃取法分离发酵液中乳酸的新方法. 通过系统考察乳酸在不同盐析萃取体系中的分配规律,发现K2HPO4-甲醇和K2HPO4-乙醇体系适合分离发酵液中的乳酸. 发酵液中乳酸浓度为167 g/L时,采用25%(w) K2HPO4-26%(w)甲醇盐析萃取体系,乳酸的分配系数和回收率分别为4.01和86.0%;采用14%(w) K2HPO4-30%(w)乙醇盐析萃取体系,乳酸的分配系数和回收率分别为3.23和90.6%. 此时上相中残余葡萄糖、菌体和可溶性蛋白的去除率分别达67.3%, 100%和85.9%.