富马酸重结晶工艺的改进

针对原富马酸重结晶过程中，漂浮物太多，产品粒度太小，导致重结晶收率低；改进重结晶工艺，使结晶收率达到95％以上，降低劳动强度，节能效果明显，质量明显改善。     

Synthesis and Properties of Fumaric Copolymers as Potential Bitumen Modifiers

New copolymers of dioctyl fumarate (DOF) and styrene (S) were synthetized by radical polymerization and used to modify bitumen. The poly(dioctyl fumarate-co-styrene) copolymers, PFS, were characterized by ¹H-NMR and FTIR spectroscopies and size exclusion chromatography (SEC) in order to determine their monomer composition and weight average molecular weights, respectively. The polymer-bitumen blending conditions were optimized and the samples analyzed by different methodologies. Fluorescence microscopy, rotational viscosity and differential scanning calorimetry (DSC) were used to study the morphological changes of blends during their manufacturing and the rheological and thermal behavior, respectively. All modified bitumen (MB) exhibited higher viscosity than the based bitumen (BB) under studied conditions and this effect was more evident for the MB containing the higher molecular weight polymer. The addition of polymers to BB enhances the bitumen viscosity and thus increased the energy required for the flowing (activation energy calculated by Arrhenius equation). Thermal and morphological analysis showed that all MB exhibited good polymer- bitumen compatibility, which could be consider as a good starting point for a potential applications of this new material in road engineering.     

An Iterative O‐Methyltransferase Catalyzes 1,11‐Dimethylation of Aspergillus fumigatus Fumaric Acid Amides

S‐adenosyl‐l ‐methionine (SAM)‐dependent methyltransfer is a common biosynthetic strategy to modify natural products. We investigated the previously uncharacterized Aspergillus fumigatus methyltransferase FtpM, which is encoded next to the bimodular fumaric acid amide synthetase FtpA. Structure elucidation of two new A. fumigatus natural products, the 1,11‐dimethyl esters of fumaryl‐l ‐tyrosine and fumaryl‐l ‐phenylalanine, together with ftpM gene disruption suggested that FtpM catalyzes iterative methylation. Final evidence that a single enzyme repeatedly acts on fumaric acid amides came from an in vitro biochemical investigation with recombinantly produced FtpM. Size‐exclusion chromatography indicated that this methyltransferase is active as a dimer. As ftpA and ftpM homologues are found clustered in other fungi, we expect our work will help to identify and annotate natural product biosynthesis genes in various species.     

高盐分富马酸废液回收富马酸的工艺研究

针对公司富马酸生产过程中产生废液,其富马酸和COD值高,色泽深,难处理的特点,提出了由公司自产苯酐富余蒸汽提供热源,采用浓缩蒸发-脱色-过滤-结晶-离心-烘干工艺流程回收富马酸,且对产生的污冷凝水进行中水回用,满足循环冷却水使用要求,既实现了废水资源利用,又达到了节能减排、增效的目的。     

Recovery of Fumaric Acid from Industrial Wastewater by Chemical Extraction and Stripping

Abstract

The study on chemical extraction and stripping for the recovery of fumaric acid from low concentration organic acid wastewater has been carried out. The parameters influencing the extraction efficiency were investigated, including extractant concentration, the initial pH, the volume ratio of water to oil (W/O), the extraction temperature, and the concentration of n‐octanol. The heat effect of the extraction process, the formation of acid‐amine complexes, and the corresponding equilibrium constant were determined. In the optimum condition that kerosene/N₇₃₀₁/n‐octanol was 2:2:1, pH was 0.5, W/O was 1:1, and the temperature was 303K, through chemical extraction and stripping, the COD_cr value of fumaric acid wastewater decreased from 71040 mg/l to 8411 mg/l, and the overall COD_cr removal rate reached 88.16%, and the extraction efficiency of fumaric acid was 70.67%. The extractant was regenerated by a stripping process with 2% NaOH, and the stripping rate almost arrived at 100%. The regenerated extractant was cycled seven times without decreasing extraction efficiency and the stripping rate. And fumaric acid was obtained by adjusting the pH of the salt from stripping. After extraction, the fumaric acid wastewater can be further treated by oxidation or biodegradation to environmentally acceptable levels.     

放线菌酮对米根霉积累L-苹果酸代谢途径的调控作用

实验考察了富马酸酶活抑制剂放线菌酮对米根霉发酵产L-苹果酸和富马酸的影响. 结果表明,发酵16 h加入浓度15 mg/L的放线菌酮使米根霉富马酸酶胞质同功酶比活力峰值降低48.7%,而苹果酸脱氢酶胞质同功酶活力却未有明显改变,生成的富马酸比对照样减少37.1%,而L-苹果酸积累量提高54.6%,达到21.7 g/L. 表明通过对米根霉富马酸酶胞质同功酶的抑制作用能减弱米根霉积累富马酸代谢途径中由L-苹果酸向富马酸的转化,从而促进米根霉积累L-苹果酸.     

富马酸与三种环糊精在水溶液中包合作用的研究

本实验分别探讨了α-环糊精、β-环糊精、羟丙基-β-环糊精在水溶液中对富马酸的包合作用.实验采用紫外吸收光谱法和相溶解度法研究三种环糊精在水溶液中对富马酸的包合和增溶作用,以及包合过程中热力学参数的变化情况.结果表明,富马酸与三种环糊精在水溶液中均可自发形成了1:1(物质的量比)可溶性包合物,从而增加了其溶解度.同时,富马酸与三种环糊精在包合过程中的吉布斯自由能变化(△G)、焓变(△H)和熵变(△S)均为负值,所有过程均为焓驱动过程,且为放热过程(△H＜0)和熵减过程(△S＜0).     

富马海松酸环氧树脂的制备及漆膜性能

通过松香(RA)与富马酸(FA)高温下的Diels-Alder反应合成了富马海松酸(FPA),并利用碳谱(13CNMR)、电喷雾质谱(ESI-MS)、红外光谱(IR)对其进行了表征;通过FPA与丁二醇二缩水甘油醚(BDGE)、己二醇二缩水甘油醚(HDGE)的酯化反应合成了松香基环氧树脂预聚体(FB、FH),测试了预聚体与固化剂不同配比下固化物的漆膜性能;结果表明,当n(活性氢)/n(环氧基)在1.0、1.2时,漆膜的硬度大于HB,附着力小于2级,T-弯实验小于2 T,耐冲击强度大于9.8 J,耐化学性能良好。     

高效防霉剂富马酸单甲酯的合成与抑菌活性研究

以TiSiW12O40/TiO2为催化剂，用富马酸与甲醇直接酯化合成了防霉剂富马酸单甲酯（MMF），通过正交试验确定了醇酸物质的量比、催化剂用量、反应温度和反应时间对反应产率的影响。得到最佳工艺条件为：n（富马酸）：n（甲醇）=1、0：1、0，催化剂用量为w（TiSiW12O40/TiO2）=2％（占富马酸的质量分数），反应温度为60℃，反应时间为3h，MMF的产率可达91．6％。抑菌活性试验和防腐保鲜试验结果表明，MMF对多种霉菌具有良好的抑制作用，尤其对黄曲霉菌、黑根霉菌和棒柬青霉菌的抑制作用更好，MMF的防霉和防腐保鲜效果优于DMF、丙酸钙。     

100L罐中深层发酵生产L-苹果酸的研究

报道了温特曲霉 (AspergilluswentiiF- 891)发酵L- 苹果酸的工艺特点 ,在 10 0L罐上研究了通风量、温度、pH值及发酵培养基中富马酸浓度等因素对深层发酵富马酸生产L -苹果酸的影响。确定了最佳发酵条件 ,其中富马酸浓度 11% ,通风量 1∶1 0 5 (发酵前期 )～ 1∶1 2 8v/v/m(发酵中后期 ) ,温度 30℃ (发酵前期 )～ 2 5℃(中后期 ) ,初始pH值 6. 0～ 6 . 2 ;发酵周期 10 8h左右 ,富马酸平均转化率 83. 5 2 % ,平均产L 苹果酸 10 . 2 3%。