Hydrothermal conversion of carbohydrate biomass to lactic acid

We investigated the hydrothermal conversion of the carbohydrates including glucose, cellulose, and starch to lactic acid using NaOH and Ca(OH)₂ as alkaline catalysts. Both catalysts significantly promoted the lactic acid formation. The highest yield of lactic acid from glucose was 27% with 2.5 M NaOH and 20% with 0.32 M Ca(OH)₂ at 300°C for 60 s. The lactic acid yields from cellulose and starch were comparable with the yield from glucose with 0.32 M Ca(OH)₂ at 300°C, but the reaction time in the case of cellulose was 90 s. The mechanism of lactic acid formation from glucose was discussed by identifying the intermediate products. Lactic acid may be formed via the formation of aldoses of two to four carbons including aldose of three carbons, which are all formed by reverse aldol condensation and double bond rule of hexose. This implies that carbon–carbon cleavage occurs at not only C₃? C₄ but also at C₂? C₃. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Chemicals from biomass: synthesis of lactic acid by alkaline hydrothermal conversion of sorbitol

BACKGROUND: Currently, the ‘green chemistry’ philosophy is being increasingly adopted by the chemical industry and, therefore, new production procedures of valuable chemicals from biomass‐derived raw materials are being sought. In this work, the synthesis of lactic acid from sorbitol under alkaline hydrothermal conditions is investigated by analyzing the influence on conversions and yields of temperature, NaOH/sorbitol molar ratio (MR), initial sorbitol concentration (SC) and reaction time. RESULTS: A 100% sorbitol conversion and a maximum 39.5% yield of lactic acid on a carbon basis are obtained at 280 °C, 50 min, 1.0 mol L^?1 SC and 2.0 MR. Glyceraldehyde was the only identified intermediate while formic acid, acrylic acid, acetic acid, oxalic acid and sodium carbonate were identified as over‐oxidation products, all of them in very low yields with the exception of formic acid (16% yield at a MR of 4 and 280 °C). Several plausible conversion routes of sorbitol involving dehydrations, keto‐enol tautomerisms, reverse aldol condensations, aldol condensations, Cannizzaro reactions and oxidations are proposed. CONCLUSIONS: Considering the high number of parallel conversion routes as a consequence of high functionality of sorbitol, the 39.5% lactic acid yield obtained is a good result. Total carbon mass in all identified products only justifies, at most, 50% of that in sorbitol due to the coexistence of several conversion routes resulting in a large number of products other than lactic acid. Copyright © 2011 Society of Chemical Industry     

Hydrothermal catalytic production of fuels and chemicals from aquatic biomass

One of the promising avenues for biomass processing is the use of water as a reaction medium for wet or aquatic biomass. This review focuses on the hydrothermal catalytic production of fuels and chemicals from aquatic biomass. Two different regimes for conversion of aquatic biomass in hydrothermal conditions are discussed in detail. The first is hydrothermal liquefaction, and the second is hydrothermal gasification. The goals of these processes are to produce liquid‐fuel‐range hydrocarbons and methane or hydrogen, respectively. The catalytic upgrading of biocrude resulting from noncatalytic liquefaction and the stability and degradation of catalysts in high temperature water are also discussed. The review concludes with a brief discussion of the outlook for and opportunities within the field of hydrothermal catalytic valorization of biomass. Copyright © 2012 Society of Chemical Industry     

乳酸的生产技术及其研究进展

综述了绿色平台化合物——乳酸的生产方法及其最新技术研究进展,分析了乳酸生产技术发展的现状。认为关键问题是一方面要进一步完善现有的生产技术,另一方面应开发新的绿色合成技术,实现高效大规模生产,降低生产成本,并对绿色合成技术发展方向进行了分析和探讨。     

模拟自然加快碳循环:水热转化生物质为高附加值产品

综述了作者所在科研组利用水热技术转化生物质成高附加值化工原料的一些最新进展。着重介绍了利用碳水化合物、木质纤维素、纤维素生物质以及生物柴油的副产物甘油产各种有机酸的研究进展,讨论了水热转化的机理和在水热转化中天然碳水化合物各组分之间的相互影响。最后介绍了中试规模连续水热反应系统利用植物源生物质生产乙酸的进展情况。     

Selective conversion of glucose into lactic acid and acetic acid with copper oxide under hydrothermal conditions

Biomass as a source for chemicals production attracts growing attention due to the decreasing storage of fossil fuels and global warming caused by emission of CO₂. In this study, conversion of glucose with copper oxide (CuO) was studied under alkaline hydrothermal conditions using a batch reactor and continuous flow reactor. CuO, as an oxidant, greatly improves the yields of lactic acid (LA) and acetic acid from glucose and was reduced into Cu₂O and Cu. Selective production of LA with the highest yield of 59% and acetic acid with the highest yield of 32% can be achieved by controlling reaction time, temperature, and addition of CuO. A possible mechanism of conversion of glucose with CuO was proposed. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2096–2104, 2013     

生物质转化制备乳酸及其酯类物质研究进展

乳酸是重要的精细化工中间体,在食品、医药、日化及可降解材料等领域具有重要的应用.利用农林废弃物为原料转化制备乳酸,不仅能够充分利用生物质资源,更能缓解乳酸供需矛盾,对推动碳减排及绿色发展具有重要意义.分别从微生物发酵法和化学催化法对生物质转化制备乳酸(酯)的最新研究进展进行了综述,并对当前阶段制约乳酸生产的各方面因素进行了分析总结,最后全面比较了这两种方法的优缺点,展望了生物质转化制备乳酸潜在研究方向、存在的机遇和面临的挑战.     

Unstructured mathematical model for biomass,lactic acid and bacteriocin production by lactic acid bacteria in batch fermentation

BACKGROUND: A simple macroscopical model was proposed to describe the fermentation kinetics of growth, bacteriocins and lactic acid production by Lactococcus lactis and Pediococcus acidilactici in a batch system. The equations used were: the logistic reparametrized for growth, the Luedeking–Piret model for bacteriocin production, the maintenance energy model for glucose consumption; and the homofermentative balance equation for lactic acid formation. RESULTS: In all the cultures, the mathematical models, consistents and robusts, adjusted, perfectly, the experimental kinetic profiles. Also, the corresponding kinetic parameters were significant, so much biological as statistically. CONCLUSIONS: The group of integrated equations used, besides showing high accuracy in predicting the studied bioproductions, established a useful tool for the control of lactic acid bacteria kinetics in bioreactors in terms of its statistical consistency. Copyright © 2007 Society of Chemical Industry     

乳酸催化制备丙烯酸反应液中乳酸和丙烯酸含量的联合测定

以正丁醇为内标,氢火焰离子化检测器测定,建立了气相色谱法直接进样测定乳酸催化制备丙烯酸反应液中乳酸和丙烯酸含量的方法。在载气（N2）流速为30mL·min^-1,氢气流速为88mL·min^-1,空气流速为300mL·min^-1,进样器和离子室温度为160℃,柱温为150℃的10％PEG-20M（3m×3mml填充柱上能实现很好的分离。乳酸和丙烯酸测定方法的线性相关系数分别为0．9994和0．9996,相对标准偏差分别为O．74％和0．56％,平均回收率分别为97．35％-1197．60％,检出限分别为8．62mg·L^-1和1．21mg·L^-1方法简便、快速、准确。     

CLA production from ricinoleic acid by lactic acid bacteria

The ability to produce CLA from ricinoleic acid is widely distributed in lactic acid bacteria. Washed cells of Lactobacillus plantarum JCM 1551 were selected as a potential catalyst for CLA production from ricinoleic acid. Cells cultivated in medium supplemented with a mixture of α-linolenic acid and linoleic acid showed enhanced CLA productivity. Under optimal reaction conditions, with the free acid form of ricinoleic acid as the substrate and washed cells of L. plantarum as the catalyst, 2.4 mg/mL CLA was produced from 3.4 mg/mL ricinoleic acid in 90 h, with a molar yield with respect to ricinoleic acid of 71%. The CLA produced, which was obtained in the FFA form, consisted of a mixture of two CLA isomers, cis-9,trans-11-octadecadienoic acid (21% of total CLA) and trans-9,trans-11-octadecadienoic acid (79% of total CLA), and accounted for 72% of the total FA obtained.     

Potential and assessment of lactic acid production and isolation – a review

The majority of commodity plastics is made from petroleum‐based chemicals. Lactic acid serves as a monomer for the production of the biodegradable polymer polylactic acid (PLA). This paper provides a review on the state of the art production and isolation process for lactic acid. Problems in production and isolation have been identified, the relevant results in optimized production are presented in the first part of the paper. In the second part, a decision matrix is used as a guideline for the discussion on the state of research in the isolation and purification of lactic acid. Mechanical unit operations, mass transfer unit operations, reactive separation techniques, and process combinations are reported in the literature. At the end, an economic evaluation of isolation processes such as conventional precipitation, reactive membrane separation, and reactive distillation are presented. © 2017 Society of Chemical Industry     

Telechelic poly(L‐lactic acid) for dilactide production and prepolymer applications

The suitability of different types of telechelic poly(lactic acid) (PLA) copolymers for dilactide production and prepolymer products was evaluated. L ‐lactic acid (L ‐LA) was copolymerized with 1,4‐butanediol, pentaerythritol, adipic acid, or 1,2,3,4‐butanetetracarboxylic acid (1,2,3,4‐BTCA). The influence of branching, the choice of catalyst, and the type of terminal groups on the properties and the thermal stability of the end product was determined. Carboxyl‐termination of PLA was shown to lead to higher molar masses than hydroxyl‐termination. The observed differences in the molar masses were explained by the lower thermal stability of the hydroxyl‐terminated PLA, as evidenced by the faster depolymerization rate of the hydroxyl‐terminated polymers and their higher tendency to undergo racemization. Sn(Oct)₂ was found to be a more effective copolymerization catalyst than Fe(OAc)₂ in terms of the final molar masses obtained. It was additionally found that the amount of chains not attached to the comonomers decreased toward longer polymerization times and was typically higher for the hydroxyl‐terminated copolymers. The results suggest that predominant carboxyl‐termination would increase the thermal stability of PLA polymers, whereas hydroxyl‐termination could be utilized to increase the production speed and efficiency of dilactide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

生物质生产乙酰丙酸研究进展

乙酰丙酸具有高反应活性和广泛的用途,是重要的平台化合物,可由生物质转化而来。本文综述了生物质生产乙酰丙酸的研究进展,包括催化方法和纯化方法。     

发酵粗甘油产乳酸的戊糖乳杆菌代谢进化

以生物柴油产业的副产物粗甘油为底物,可降低乳酸发酵的生产成本。但是,粗甘油发酵生产乳酸存在菌体生长缓慢、菌浓较低、产酸速率和终产物浓度偏低等问题。以实验室筛选的一株戊糖乳杆菌 (Lactobacillus pentosus R3-8)为出发菌株进行代谢进化。通过在培养基中添加高浓度的粗甘油和乳酸,分别进行菌株耐底物和产物抑制的代谢进化。用粗甘油驯化的第60代菌株,可耐受130 g·L^-1的粗甘油,与出发菌株相比,生长速率提高, 且生物量是原始菌株的1.23倍。用乳酸驯化的第50代菌株可耐受20 g·L^-1的乳酸,生物量比初始菌株提升了18%。驯化菌株的5 L发酵罐分批发酵结果显示,以粗甘油驯化至 60 代的菌株的批次发酵水平相对较好,乳酸产量、甘油转化率以及生产强度分别为 45.0 g·L^-1、0.989 g·g^-1和 0.47 g·L^-1·h^-1。以粗甘油驯化至 60 代的菌株进行补料分批发酵,乳酸终浓度为83.8 g·L^-1,比分批发酵提高了近1倍。     

乳酸连续化发酵进展

对一些新型的乳酸连续化发酵装置,包括恒浊器、两级恒化器、两级固定床、两级膜细胞循环反应器、三相流化床-电渗析、塑料支持生物膜反应器及相应的发酵条件进行了综述;讨论了连续化发酵的控制(无反馈控制、反馈控制)、数学模型、最优化方法;并分析了不同连续化发酵装置的优缺点及前景.     

乳酸菌发酵甘蔗糖蜜产乳酸的培养条件优化

乳酸是有广泛应用的有机酸,廉价原料是降低乳酸生产成本的重要因素。以实验室前期筛选的植物乳杆菌sy4为出发菌株研究了利用甘蔗糖蜜生产乳酸的培养条件。在确定发酵温度和初始pH后,通过Plackett-Burman实验和中心复合实验优化乳酸发酵条件。结果表明：植物乳杆菌sy4乳酸发酵的最适条件为温度32℃、60h、初始pH 6.5;Plackett-Burman实验表明酵母提取物、糖蜜和碳酸钙是影响乳酸产量的主要因素;中心复合实验得到三因素的最优组合为：酵母提取物13.19g/L、糖蜜476.63g/L和碳酸钙134.82g/L,确定了最适发酵培养基。在此条件下乳酸产量为（145.53±1.24） g/L,与模型预测值147.23g/L接近。本研究为以甘蔗糖蜜为原料生产乳酸提供了技术支持。     

Conjugated linoleic acid production from linoleic acid by lactic acid bacteria

After screening 14 genera of lactic acid bacteria, Lactobacillus plantarum AKU 1009a was selected as a potential strain for CLA production from linoleic acid. Washed cells of L. plantarum with high levels of CLA production were obtained by cultivation in a nutrient medium with 0.06% (wt/vol) linoleic acid (cis-9,cis-12-octadecadienoic acid). Under the optimal reaction conditions with the free form of linoleic acid as the substrate, washed cells of L. plantarum produced 40 mg CLA/mL reaction mixture (33% molar yield) from 12% (wt/vol) linoleic acid in 108 h. The resulting CLA was a mixture of two CLA isomers, cis-9,trans-11 (or trans-9,cis-11)-octadecadienoic acid (CLA1, 38% of total CLA) and trans-9,trans-11-octadecadienoic acid (CLA2, 62% of total CLA), and accounted for 50% of the total FA obtained. A higher yield (80% molar yield to linoleic acid) was attained with 2.6% (wt/vol) linoleic acid as the substrate in 96 h, resulting in CLA production of 20 mg/mL reaction mixture [consisting of CLA1 (2%) and CLA2 (98%)] and accounting for 80% of total FA obtained. Most of the CLA produced was associated with the cells (ca. 380 mg CLA/g dry cells), mainly as FFA.