微乳液体系中脂肪酶催化合成酯反应的动力学研究

不同的微乳液体系中,脂肪酶催化合成酯的反应受脂肪酶浓度、正己酸浓度、正丁醇浓度的影响。结果表明:反应初始速率V0随正己酸的初始浓度的增大而增大,随正丁醇的初始浓度的增大而减小;当十二烷基聚葡糖苷(C12G1.50)量较小,C12G1.5的浓度对反应初始速率V0影响不大;C12G1.5量较大时,反应初始速率V0随C12G1.50浓度增大而增大。固定C12G1.50的浓度不变,当正己酸浓度较低时,反应初始速率V0随正丁醇浓度增大而减小;当正己酸浓度较高时,反应初始速率V0随正丁醇浓度增大而增大。     

聚阴离子纤维素(PAC)与羟丙基甲基纤维素(HPMC)混合体系动态粘弹性研究

考察了溶液浓度对PAC以及PAC/HPMC水溶液动态粘弹性的影响。结果表明,溶液储能模量(G’),耗能模量(G")均随溶液浓度的增大而增大,但储能模量随频率增大的幅度大于耗能模量随频率增大的幅度;溶液的损耗角正切(tanδ)值随浓度增大而逐渐减小;G’~f与G"~f两曲线交点随溶液浓度增大向低频方向移动;由于PAC与HPMC分子间存在氢键作用,因此,与纯PAC溶液相比,相同浓度下PAC/HPMC水溶液的G’~f与G"~f交点对应的频率更高;ω=0相对应的初始tanδ值比同浓度下纯PAC溶液更高。     

超声波/H2O2协同降解水中染料酸性嫩黄的研究

采用US／H2O2协同降解酸性嫩黄染料，考察了超声功率、H2O2用量、染料溶液的初始浓度及初始pH对降解效率的影响，并对降解动力学规律作了初步探讨，结果表明，酸性嫩黄的降解效率随超声波功率的增大而增大，随其初始浓度的增大而降低；当H2O2浓度介于一定范围内，增大H2O2用量可提高酸性嫩黄的降解效率，但H2O2用量过多时，会使降解效率下降；pH〈5时，降解效果较好，且pH越小，降解效率越高；pH≥5时，降解效率较低。在本实验条件下，超声波与双氧水对酸性嫩黄废水的降解存在协同作用，经US／H2O2协同降解120min后，酸性嫩黄的降解效率可迭84．0％。US／H2O2对酸性嫩黄的协同降解符合一级反应动力学规律。     

TiO2/Fe3+催化膜催化H2O2降解水中孔雀石绿

采用溶胶-凝胶共混法制备了一种PVDF/Fe3+-TiO2催化膜,探讨了pH、初始H2O2与孔雀石绿(MG)浓度、反应温度、膜面积等因素对催化反应速率的影响。结果表明:在pH 5.0~9.0内,催化膜具有有效催化H2O2降解MG的能力,且最佳初始H2O2浓度为30 mmol/L;其脱色效果随初始MG浓度的增加而下降;反应速率随着温度的升高明显增大;另外,膜面积的增大明显提高了其对MG的降解效果。反应机理的测试结果表明,反应中的氧化活性物种是·OH、电子空穴和高价铁同时存在。     

异丙醇的O3/H2O2复合氧化动力学研究

采用停流光谱仪研究了异丙醇在T=298K和pH=3～11范围内O3 / H2O2复合氧化的反应动力学.结果表明异丙醇的O3 / H2O2复合氧化反应动力学随反应体系的pH值不同而不同.在酸性和中性条件下,反应相对于O3浓度、异丙醇浓度都为1级;在碱性条件下,异丙醇较容易被O3/H2O2复合氧化降解,总反应级数为2级,相对于O3浓度、异丙醇浓度和H2O2浓度分别为1级、0级和1级,可见异丙醇的降解速率与它的浓度无关.在T=298K,当pH值从9增大到11, 反应速率常数从3486.1(mol·L-1)-1·s-1增大到38239.2(mol·L-1)-1·s-1. 表明在酸性条件下,异丙醇的O3/H2O2复合氧化是O3分子直接攻击异丙醇的反应占主导;在碱性条件下,自由基型反应占主导.     

超声波/H_2O_2协同降解酸性紫红染料的研究

采用超声波/H2O2降解水中酸性紫红染料,考察了超声波/H2O2的协同效应及超声功率、声密度、超声时间、染料初始浓度等因素对酸性紫红染料去除率的影响。结果表明,超声波/H2O2对酸性紫红染料的降解具有明显的协同作用,其去除率比超声波单独作用提高了40%。在一定的条件下,去除率随超声功率的增大而增加,随溶液体积的增加而减少,随超声时间的延长而增大,随染料初始浓度的增加而减少。     

三价铁离子浓度对As(V)-Fe(II)-Fe(III)体系沉淀臭葱石的影响

在常压、95℃、初始pH=1.5的条件下,研究了As(V)–Fe(II)–Fe(III)体系中初始Fe(III)浓度对砷的去除率和臭葱石合成的影响。结果表明,溶液中初始Fe(III)/As(V)摩尔比为0时,沉淀产物为结晶度良好的臭葱石,但砷的去除率仅为24.3%,沉淀浸出砷浓度高于国标规定的浓度限值5 mg/L。溶液中初始Fe(III)/As(V)摩尔比大于0时,在升温过程中生成了无定形砷酸铁,当初始Fe(III)/As(V)摩尔比不超过1.6时,砷酸铁反应8 h后转化为臭葱石;随初始Fe(III)/As(V)摩尔比增大,砷的去除率增大,臭葱石沉淀的结晶度降低、浸出砷浓度降低;其中,初始Fe(III)/As(V)摩尔比为0.8和1.6时,臭葱石沉淀的浸出砷浓度低于5 mg/L,适合安全堆存。当初始Fe(III)/As(V)摩尔比大于1.6时,无定形砷酸铁反应8 h仍不能转化成臭葱石,砷的去除率降低,沉淀浸出砷浓度超标,不适合安全堆存。     

Fe(Ⅲ)-草酸盐络合物/H2O2/UV体系对染料废水的处理研究

研究了活性物质Fe（Ⅲ）--草酸盐络合物和氧化剂H2O2结合起来形成的光催化氧化复合体系对以活性艳红X-3B为代表的七种水溶性染料模拟废水的处理。在250W高压汞灯照射下，复合体系对初始浓度为100mg/L的染料溶液，处理24min后，脱色率均达90%以上，COD去除率为33%～70%。以活性艳红X-3B为对象，研究各种反应条件对其处理效果的影响，结果表明：在pH=3～6范围内，脱色率速率较大；在染料初始浓度为20～200mg/L范围内，脱色速率随浓度增大而降低；Fe（Ⅲ）--草酸盐配比为40/200（mmol/L）时脱色效果最好，H2O2投加量为4～40mg/L时，脱色速率随H2O2投加量的增加而增长较快，在40～100mg/L时，增长很小。     

Fe^3＋/UV/O2光催化降解酸性橙Ⅱ动力学

研究了pH值、UV光强、Fe3＋浓度和染料初始浓度对Fe3＋/UV/O2光催化体系降解染料酸性橙Ⅱ（AOⅡ）动力学的影响。结果表明：Fe3＋/UV/O2光催化降解AOⅡ符合准一级反应动力学,当初始pH值为3时反应速率达到最大;降解速率随着UV光强和Fe3＋浓度的提高逐渐升高,随着染料初始浓度的提高而降低。     

聚丙烯酰胺的O3/H2O2/UV复合氧化动力学研究

采用自制多光源光化学反应器,研究了聚丙烯酰胺在O3/H2O2/UV体系下光化学降解反应的动力学规律,考察了各个因素对HPAM光化学降解速率的影响。结果表明,该反应体系对HPAM有较好的去除率,在任何特定反应条件下,HPAM的降解速率均与HPAM的质量浓度成正比。并且,此体系下优化的降解条件为：紫外灯功率为96 W,初始臭氧浓度为1.50 g/h,初始双氧水浓度为0.83 g/h,初始pH为4,HPAM初始浓度为50 mg/L。在此基础上建立的HPAM降解反应动力学模型对其在光化学氧化体系中降解动力学规律具有良好预测性。     

固体超强酸SO4^2-/Fe2O3-CoO催化合成己酸乙酯

以固体超强酸SO4^2-/Fe2O3-CoO为催化剂，通过己酸和乙醇反应合成了己酸乙酯。实验结果表明，固体超强酸SO4^2-/Fe2O3-CoO对酯化具有较高的催化活性，反应的最佳条件为：己酸0．2mol，n（乙醇）：n（己酸）：1．8：1．0，催化剂用量为0．8g（以0．2mol己酸为准），带水剂用量为12mL，反应时间为2h，其酯化率可达97％以上。     

用脂肪酶非水相生物催化合成己酸乙酯的研究

原料为正己烷、己酸、乙醇。最佳反应条件为:在正己烷中加入浓度为0 15mol/L的己酸和0 1mol/L的乙醇,加入质量浓度为0 01kg/L脂肪酶CLL(吸附在聚苯乙烯大孔疏水性树脂上),采用MgCl2控制水分,用反渗析膜隔开,在25℃、100r/min振荡水浴中反应24h条件下,脂肪酶合成己酸乙酯转化率可达99 07%。     

乙酸与丁醇酯化反应和渗透蒸发耦合过程研究

以硫酸锆催化乙酸和丁醇的酯化反应为例对渗透蒸发和酯化反应耦合过程进行研究 ,考察了温度、反应物初始摩尔比、膜面积与反应液体积比和催化剂浓度对耦合过程的影响。     

Characteristics of Crosslinking Polymers Play Major Roles in Improving the Stability and Catalytic Properties of Immobilized Thermomyces lanuginosus Lipase

This study aimed to improve the stability and catalytic properties of Thermomyces lanuginosus lipase (TLL) adsorbed on a hydrophobic support. At the optimized conditions (pH 5 and 25 °C without any additions), the Sips isotherm model effectively fitted the equilibrium adsorption data, indicating a monolayer and the homogenous distribution of immobilized lipase molecules. To preserve the high specific activity of adsorbed lipase, the immobilized lipase (IL) with a moderate loading amount (approximately 40% surface coverage) was selected. Polyethylenimine (PEI) and chitosan (CS) were successfully applied as bridging units to in situ crosslink the immobilized lipase molecules in IL. At the low polymer concentration (0.5%, w/w) and with 1 h incubation, insignificant changes in average pore size were detected. Short-chain PEI and CS (MW ≤ 2 kDa) efficiently improved the lipase stability, i.e., the lipase loss decreased from 40% to <2%. Notably, CS performed much better than PEI in maintaining lipase activity. IL crosslinked with CS-2 kDa showed a two- to three-fold higher rate when hydrolyzing p-nitrophenyl butyrate and a two-fold increase in the catalytic efficiency in the esterification of hexanoic acid with butanol. These in situ crosslinking strategies offer good potential for modulating the catalytic properties of TLL for a specific reaction.     

固体超强酸催化剂S_2O_8~(2-)/ZrO_2-M_xO_y(M=Al,Ti,Cr,Mn,Fe)的研究

以ZrOCl2 ·8H2 O、AlCl3、Ti(SO4 ) 2 、CrCl3、MnSO4 、FeCl3为原料 ,通过NH3·H2 O共沉淀、c〔(NH4 ) 2 S2 O8〕 =0 50mol/L浸渍 ,60 0℃焙烧 3 0h制得S2 O82 - /ZrO2 MxOy(M =Al,Ti,Cr,Mn,Fe)系列固体超强酸催化剂 ,用XRD、EBT、流动Hammett指示剂法和化学分析法测定了其晶型结构、比表面积、酸强度和硫含量 ,用乙酸和正丁醇的酯化反应研究了样品的催化活性。结果表明 :S2 O82 - /ZrO2 MxOy中ZrO2 主要以四方晶相 (tetragonalphase)存在 ,MxOy高度分散 ,样品的比表面积 89 0～ 1 1 4 5m2 / g,酸强度H0 <- 1 4 52 ,w(S) =3 1 6 %～ 5 1 2 %。样品对酯化反应表现出较高的催化活性 ,在反应条件为 :0 1 7mol乙酸、0 33mol正丁醇、1 0g催化剂、8 0mL环己烷 (带水剂 ) ,回流温度反应 2 0h ,乙酸的转化率可达 88 5 %～ 97 1 % ,在同样反应条件下 ,没有催化剂时乙酸的转化率仅为 2 9 6 %。催化剂易回收而且能重复使用 ,具有良好的活性稳定性     

Esterification in a structured catalytic reactor with counter-current water removal

In this research the liquid phase esterification of hexanoic acid and 1-octanol was studied. Very high activities were obtained for zeolite BEA and Nafion/silica composite with 13% of Nafion. The advantage of water removal in this system was demonstrated. In a closed system an equilibrium conversion of 35% was reached, while in a system with water removal all the reactants were converted in a shorter period. The initial reaction rate decreases when increasing the initial water concentration, following a Langmuir–Hinshelwood type of rate expression. An active zeolite coated structured monolithic reactor configuration was prepared. Enhancement by the counter-current water stripping of the performance of the structured catalysts was demonstrated.     

Enzymatic Synthesis of Diacylglycerols Enriched with Conjugated Linoleic Acid by a Novel Lipase from <Emphasis Type="Italic">Malassezia globosa</Emphasis>

Diacylglycerols (DAG) of conjugated linoleic acid (CLA) were prepared by esterification of glycerol with fatty acids enriched with CLA (FFA–CLA, >95%) in the presence of a novel lipase from Malassezia globosa (SMG1). Lipase SMG1 is strictly specific to mono- and diacylglycerols but not triacylglycerols, which is similar to the properties of lipase from Penicillium camembertii (lipase G 50), but lipase SMG1 showed preference on the production of DAG with the reaction proceeding. Low temperature was beneficial for the conversion of FFA–CLA into acylglycerols, the degree of esterification reached 93.0% when the temperature was 5 °C. The maximum DAG content (53.4%) was achieved at 25 °C. The rate of DAG synthesis increased as the enzyme loading increased. However, at lipase amounts above 240 U/g mixtures, no significant increases in DAG concentration were observed. The molar ratio of FFA–CLA to glycerol and initial water content were optimized to be 1:3 (mol/mol) and 3%. Lipase SMG1 showed no regioselectivity because the contents of 1,3-DAG and 1,2-DAG were 43.1% and 21.2% based on total content of acylglycerols. By calculating the ratio of 9c, 11t-CLA to 10t, 12c-CLA, it was indicated that lipase SMG1 showed a little preference to 10t, 12c-CLA at the sn-1(3) position of monoacylglycerols (MAG), while no selectivity for 9c, 11t-CLA at the sn-2 position of DAG was obviously found.     

S2O82-/ZrO2-TiO2 固体超强酸催化剂的制备及其酯化性能

利用共沉淀和低温陈化法制备S₂O₈^2-/ZrO₂-TiO₂ 固体超强酸作为合成硬脂酸正丁酯的催化剂。通过XRD、FT-IR和SEM对催化剂进行表征, 考察n(Zr)∶n(Ti)、焙烧温度、浸渍液浓度和浸渍时间对催化剂催化活性的影响,以酯化合成硬脂酸正丁酯实验为探针,同时考察反应温度和n(硬脂酸)∶n(正丁醇)对酯化率的影响。结果表明,在n(Zr)∶n(Ti)=2∶2、浸渍液(NH₄)₂ S₂O₈浓度0.5 mol·L^-1、浸渍时间6 h、焙烧温度500 ℃、n(硬脂酸)∶n(正丁醇)=1∶3、催化剂用量0.2 g、反应温度120 ℃和反应时间3 h条件下,酯化率可达98.69%。     

Regioselective acylation of flavonoids catalyzed by lipase in low toxicity media

Flavonoid fatty esters were prepared by acylation of flavonoids (rutin and naringin) by fatty acids (C8, C10, C12), catalyzed by immobilized lipase from Candida antarctica in various solvent systems. The reaction parameters affecting the conversion of the enzymatic process, such as the nature of the organic solvent and acyl donor used, the water activity (a_w) of the system, as well as the acyl donor concentration have been investigated. At optimum reaction conditions, the conversion of flavonoids was 50—60% in tert‐butanol at a_w less than 0.11. In all cases studied, only flavonoid monoester was identified, which indicates that this lipase‐catalyzed esterification is regioselective.