Kinetics and mechanism of N-substituted amide hydrolysis in high-temperature water

N-methylacetamide (NMA) served as a model to investigate the hydrolysis kinetics and mechanism of N-substituted amides in high-temperature water. The major products are acetic acid and methylamine, and the reaction is reversible. The hydrolysis reaction is first order in water and first order in NMA at both subcritical and supercritical conditions. The hydrolysis rate is also pH dependent, and three distinct regions of pH dependence exist. At low and high pH, the conversion increased rapidly with added acid and base, respectively. At near-neutral pH, however, the rate was essentially insensitive to changes in pH. Further investigation revealed that the hydrolysis rate constant was very sensitive to the size of the substituent on the carbonyl carbon atom. An S_N2 mechanism with water as the nucleophile appears to be a likely candidate for the hydrolysis mechanism in high-temperature water at near-neutral conditions.     

分子筛催化葡萄糖水解的宏观动力学

分别采用硅铝比为20~25和30的两种ZRP-5分子筛催化剂研究不同温度下葡萄糖水解动力学。研究结果表明,葡萄糖水解属于一级反应,反应温度显著地影响葡萄糖的转化。在相同反应温度下,前者作用下葡萄糖水解的表观反应速率常数大于后者。前者作用下葡萄糖水解的表观活化能为99.24 kJ/mol,后者作用下葡萄糖水解的表观活化能为108.99 kJ/mol。该反应动力学方程的葡萄糖水解转化率计算值与实验值吻合较好。     

CO_2对高温液态水中苯乙腈水解反应的影响

为探讨添加了CO2的高温液态水中腈类物质的水解规律,考察了不同的CO2添加量对高温液态水中苯乙腈水解的影响,计算了不同CO2添加量和不同温度对高温液态水反应体系pH的影响。结果表明,在473.15 K,0、0.2、0.4 MPa CO2压力下的水解反应速率常数分别为6.2×10-4、4.1×10-4、3.0×10-4 min-1,而相对应的pH分别为5.6、4.1、3.9。对于碱催化机理为主导的苯乙腈水解反应,CO2并不能有效地促进反应进行。     

Noncatalytic Hydrolysis of Iminodiacetonitrile in Near‐Critical Water – A Green Process for the Manufacture of Iminodiacetic Acid

The hydrolysis of iminodiacetonitrile (IDAN) in near‐critical water, without added catalysts, has been successfully conducted with temperature and residence time ranges of 200–260 °C and 10–60 min, respectively. The effects of temperature, pressure, and initial reactant/water ratio on the reaction rate and yield have been investigated. The final reaction products primarily included iminodiacetic acid (IDA) and ammonia associated with other by‐products; gas formation was negligible. The maximum yield of IDA was 92.3 mol.‐% at 210 °C and 10 MPa, with a conversion of almost 100 %.The apparent activation energy and ln A of IDAN hydrolysis were evaluated as 45.77 ± 5.26 kJ/mol and 8.6 ± 0.1 min^–1, respectively, based on the assumption of first‐order reaction. The reaction mechanism and scheme were similar to those of base‐catalyzed reactions of nitriles examined in less severe conditions.     

废尼龙66水解再资源化及其动力学分析

以硫酸为催化剂,对废尼龙66（PA66）水解反应进行了研究,采用红外光谱（FTIR）和核磁共振氢谱（¹H NMR）对产物结构进行了表征研究,并确认为己二酸（AC）和己二胺（HMD）。采用L₉（3⁴）正交实验方法,考察了反应温度、反应时间、催化剂用量及水用量等因素对水解反应结果的影响,并获得较佳的工艺条件：PA66和硫酸的摩尔比1∶2.5;PA66和甲醇的摩尔比1∶30;反应温度为110℃;反应时间为4h。在此工艺条件下,PA66转化率为100%,AC和HMD的摩尔收率分别达到98.06%和97.15%。动力学实验表明,PA66水解为一级反应,活化能为145.31kJ/mol。同时,对PA66在此条件下的水解反应机理进行了初步探讨。     

稀酸催化小麦秸秆分步水解研究

利用农作物秸秆水解产物酿造酒精是发展可再生能源的一条重要途径,促进秸秆组分中半纤维素和纤维素的高效、低成本水解转化是实现这一途径的关键和瓶颈。以小麦秸秆为原料,稀硫酸为催化剂,研究了秸秆组分中半纤维素和纤维素的分步水解工艺,通过正交试验优化了酸浓度、原料固含量、反应时间和反应温度等工艺条件,在优化的分步水解工艺条件下原料转化充分,还原糖得率较高。     

乙烯基硅氧烷改性丙烯酸酯乳液聚合的动力学及成核机理分析

用种子乳液聚合法研究了硅氧烷改性丙烯酸酯的乳液聚合,对影响种子乳液聚合动力学的因素进行讨论,并分析了乳液聚合的成核机理.实验结果表明：反应温度、引发剂浓度、乳化剂浓度和有机硅氧烷用量对有机硅改性丙烯酸酯乳液聚合动力学有较大的影响.反应温度越高,引发剂浓度越高、乳化剂浓度越高、有机硅氧烷用量相对较小,乳液聚合反应的转化率越高;此外,体系的pH值在6～8之间时也有利于反应的进行.种子乳液聚合中R_P∝［E］^0.72,R_P∝［I］^0.56,表观活化能E_a为143.92 kJ•mol^-1.种子乳液聚合初期,反应主要是单体液滴成核;进入壳层反应时,反应成核主要是以胶束成核为主.     

Parameter optimization for the enzymatic hydrolysis of sunflower oil in high-pressure reactors

This study is concerned with the hydrolysis of sunflower oil in the presence of lipase preparation Lipolase 100T (Aspergillus niger lipase). Supercritical carbon dioxide was used as a solvent for this reaction. In a high-pressure stirred tank reactor operated in a batch mode, the effects of various process parameters (temperature, pressure, enzyme/substrate ratio, pH, and oil/buffer ratio) were investigated to determine the optimal reaction rate and conversion for the hydrolysis process. The optimal concentration of lipase was 0.0714 g/mL of CO₂-free reaction mixture, and the highest conversions of oleic acid (0.193 g/g of oil phase) and linoleic acid (0.586 g/g of oil phase) were obtained at 50°C, 200 bar, pH=7, and an oil/buffer ratio of 1∶1 (w/w).     

Acidic and basic hydrolysis of poly(N‐vinylformamide)

Poly(N‐vinylformamide) (PNVF) was synthesized and hydrolyzed to poly(vinylamine) (PVAm) in both HCl and NaOH solutions. The hydrolysis kinetics and the equilibrium hydrolysis were examined experimentally at different temperatures, polymer concentrations, and acid‐ or base‐to‐amide molar ratios. The hydrolysis kinetics strongly depended on temperature, polymer, and HCl or NaOH concentrations, but showed little dependence on PNVF molecular weight. The acid hydrolysis of PNVF exhibited limited conversions because of the electrostatic repulsion among the cationic amine groups generated during hydrolysis and proton hydrates. In the basic hydrolysis, complete amide conversions were observed when the NaOH/amide molar ratios were greater than unity. The effects of temperature and PNVF concentration on the equilibrium amide conversion appeared to be negligible in both acidic and basic hydrolysis. The equilibrium conversions of base hydrolysis were higher than those of acidic hydrolysis under the same reaction conditions. At NaOH/amide ratios of less than unity, the equilibrium hydrolysis experiments revealed that one base molecule could induce the hydrolysis of more than one amide group. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3412–3419, 2002     

Kinetics of Formation of an Iron-Zircon Pink Color

The kinetics of formation of an iron-zircon pink color were studied by X-ray diffraction. The iron reacts with the zirconia at a temperature below the reaction temperature. The initial reaction is nucleation-growth-controlled. At higher percent conversion a change in mechanism occurs, probably becoming diffusion-controlled. At any given reaction temperature, there is an apparent limiting percent conversion.     

Hydrolysis of a disperse reactive dye for application to wool fibres

The synthesis of a reactive dye in the anhydride form is described, and its kinetics of hydrolysis investigated at various pH values. Two different hydrolysis products were identified. The experimental rate constants were determined by nonlinear approximation. It was found that the experimental rate constant depends on pH, with the maximum between pH 5 and 6. The best wool dyeing conditions were obtained by dyeing for 60 min at 100d?C and pH 7.     

Nitration of nitrobenzene at high‐concentrations of sulfuric acid: Mass transfer and kinetic aspects

This article reports studies on mass transfer and kinetics of nitration of nitrobenzene at high concentrations of sulfuric acid in a batch reactor at different temperatures. The effects of concentration of sulfuric acid, speed of stirring, and temperature on mass transfer coefficient were investigated. The kinetics of nitration under homogenized conditions was studied at different sulfuric acid concentrations at these temperatures. The reaction rate constants were determined. The variation of rate constant with sulfuric acid concentration was explained by the M_c function. The activation energies of the reactions were determined from the Arrhenius plots. The regimes of the reactions were determined using the values of the mass transfer coefficients and the reaction rate constants. A model was developed for simultaneous mass transfer and chemical reaction in the aqueous phase. The yields of the three isomers of dinitrobenzene were determined, and the variation of isomer distribution with sulfuric acid concentration and temperature was analyzed. This work demonstrates that more than 90% conversion of nitrobenzene is possible at high‐sulfuric acid concentrations resulting in high yield of the product even at moderate temperatures and at low speeds of stirring. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

椰壳酸水解制备木糖的反应动力学

本文研究了椰壳经酸水解制备木糖的反应温度、反应时间和酸浓度对水解液中木糖浓度的影响,探讨了椰壳酸水解反应的机理,建立了木聚糖降解与木糖分解的均相不可逆连串水解反应动力学模型,求出了反应活化能Ea,木糖生成与分解反应速率常数k_1、k₂,建立了k₁ 与酸浓度C和反应温度T的关系式,分析了提高k₁与k₁/k₂比值的酸水解条件,其规律可供实现工业化生产借鉴。     

磷酸氧钛负载钌双功能催化剂催化纤维素转化制山梨醇

山梨醇是纤维素催化加氢转化中重要的平台化合物之一。制备了固体酸磷酸氧钛TiOPO₄及磷酸氧钛负载钌Ru/TiOPO₄双功能催化剂,首先对磷酸氧钛催化纤维素水解反应进行研究,以葡萄糖收率为目标,考察了反应时间、氢压、温度的影响,得到了最适宜水解反应条件。在此基础上,以磷酸氧钛负载钌为催化剂,对其催化纤维素制山梨醇的催化性能进行研究,结果表明,水解加氢反应中,在反应温度（453 K）稍低于最适宜水解温度（463 K）,反应时间（150 min）略短于最适宜水解时间（180 min）的反应条件下进行反应可得到更好的效果,最高山梨醇收率为77.6%,纤维素转化率99.3%。改变不同催化剂与底物之比,研究水解反应与水解加氢反应的转化率、产物分布,结果表明,双功能催化剂Ru/TPO可以使葡萄糖快速进行加氢反应,减少葡萄糖进一步降解的发生,液相中碳回收率显著提高,可达80%以上。     

杨木废弃物稀酸水解预处理条件的响应面优化

以聚糖类转化率为考核指标,探讨了杨木废弃物稀酸水解预处理物料的适宜颗粒尺寸范围,并用响应面实验设计优化了稀酸水解条件.结果表明,稀酸水解预处理物料的适宜颗粒尺寸为0.075~0.096 mm,稀硫酸水解的优化工艺条件为:固液比1:10,温度158 ℃,时间5 min,硫酸质量分数2.5%.在此优化条件下,聚糖类转化率为59.23%.稀酸水解液的高效液相色谱分析表明,水解液主要成分为木糖(29.897 g/L),占总糖量的64.8%,其次为葡萄糖(8.748 g/L),占总糖量的18.9%,稀酸水解单糖继续降解较少.SEM形貌和XRD分析表明,水解残渣的纤维结构破坏明显,其结晶度由原料的57.45%降低到47.37%,该稀酸水解残渣存在通过酶解和发酵制备生物乙醇的可能性.     

The kinetics of epoxidation of trimethylolpropane ester

Kinetics pertaining epoxidation reaction of a palm oil‐based synthetic lubricant trimethylolpropane (TMP) ester were investigated. The epoxidation reaction of TMP ester was carried out utilizing peracetic acid generated by an in situ technique. The analysis of the reaction kinetics was performed within the low temperature (30, 50, and 60°C) and high temperature (70, 80, and 90°C) regions, owing to the nature of the reactions. The maximum conversion of the unsaturated carbon to oxirane ring was achieved in 1 h at high temperature region, while epoxidation of TMP esters took more than 4 h to reach the maximum conversion at the low temperature region. From the experimental data, the kinetics of epoxidation of TMP esters fitted well with both the second‐order and pseudo first‐order models. The rate constants for pseudo first‐order model increased from 0.0009 to 0.0055 by increasing temperature at the low temperature region, and from 0.0129 to 0.0209 within the high temperature region. The values of activation energies at low temperature and high temperature regions were found to be 69.4 and 53.3 kJ/mol, respectively.     

微型流化床中焦油热裂解和水蒸气重整的反应特性及动力学对比

采用微型流化床反应分析仪(MFBRA)考察了不同温度(T,750~950℃)和水蒸气分压(SP,10%~30%)下生物质焦油水蒸气重整过程中的气体生成、气体产物中总碳转化和焦油转化等反应特性,求算反应动力学,并与焦油热裂解特性进行比较。在热裂解过程中,随温度增加,各气体(H₂、CH₄、CO、CO₂)产率和气体产物中的总碳转化率增加,反应时间缩短。而在焦油水蒸气重整过程中,等温下的反应时间明显延长,且H₂、CH₄、CO产率和气体产物中的总碳转化率显著提升,而CO₂产率在850℃时有最大值。在焦油水蒸气重整过程中,不仅有焦油裂解,还有裂解产物与水蒸气的反应,促进碳转化。在950℃、SP=30%条件下,气体产物中的总碳转化率达到92.34%。水蒸气作用下,气体组分的产率和气体产物中的总碳转化率增加,而等温条件下的反应速率下降。水蒸气分压对各气体组分的影响具有差异性。随分压增加,CO、CH₄的生成速率和气体产物中的总碳转化的反应速率增加;H₂生成速率逐渐下降,速率稳定段扩大;CO₂生成速率在850℃时有最大值。采用均相模型求取焦油水蒸气重整反应过程中的活化能,气体产物的生成活化能(H₂、CO、CO₂和CH₄)、气体产物中的总碳转化及焦油转化的活化能明显偏低,分别为90.10、42.01、58.56、64.92、61.44和63.26 kJ/mol,对应数值明显小于焦油热裂解,说明水蒸气对焦油重整反应的促进作用。最后,将焦油热裂解动力学数据与文献数据对比,验证了MFBRA对焦油水蒸气重整反应测试的可行性和分析结果的准确性。     

聚3-羟基丁酸酯降解技术研究进展

综述了目前聚3-羟基丁酸酯（poly-3-hydroxybutyrate,PHB）的几种主要降解技术,包括热裂解、水解、溶剂降解和酶解等。重点介绍了各种降解技术的产物分布和反应机理,并对影响PHB热稳定性的主要因素进行了总结和讨论。各种技术的所需反应温度总体趋势为：热裂解>水解≥溶剂降解>酶解。PHB热解工艺简单,通常情况下PHB主要降解为巴豆酸和其低聚物,过高反应温度（>500℃）则使PHB分解为二氧化碳和丙烯。水解和溶剂降解都是以针对性地断开PHB酯键为出发点,以获得高产率的PHB单体（3-羟基丁酸、巴豆酸）或其酯类化合物（如巴豆酸甲酯）。与热解、水解和溶剂降解技术相比,酶解法限制因素较多且工艺成本高,需要新的技术突破。提出了两个需进一步重点研究的方向：①PHB催化热解脱羧制备高品位液体燃料;②直接转化富含PHB的微生物为高价值化学品。     

磺酸功能化离子液体催化不饱和脂肪酸甲酯的环氧化研究

The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.     

Properties and catalytic mechanism of -glutamyltranspeptidase from NX-2

Since ?-glutamyltranspeptidase (GGT) especially catalyses the transfer of the ?-glutamyl moiety to a variety of amino acids and short peptides, GGT has important practical value for enzymatic synthesis of ?-glutamyl compounds. In this paper, the GGT produced from Bacillus subtilis NX-2 was purified by a combination of ammonium sulfate fractionation and ion exchange chromatography, and the properties of purified GGT were investigated. At the conditions of pH 10.0, D-glutamine (D-Gln)/L-tryptophan (L-Trp) with a molar ratio of 5 : 7, a temperature 40°C and a reaction time of 4 h, a higher conversion rate of 42% was obtained. According to the time course, the catalytic mechanism of enzymatic synthesis of ?-D-glutamyl-L-tryptophan (?-D-Gln-L-Trp) was discussed. It was demonstrated that the GGT can catalyze not only the reaction of transpeptidation, but also the irreversible hydrolysis of the products which results in the decrease of the yield of the products. The affinity parameter of GGT to D-Gln (Km) was 5.08 mmol·L^-1 and the maximum reaction rate of transpeptidation (r_max) was determined as 0.034 mmol·min^-1·L^-1, while the affinity parameter of GGT to ?-D-Gln-L-Trp (K’_m) was 2.267 mmol·L^-1, and the maximum reaction rate of hydrolysis (r’_max) was 0.012 mmol·min^-1·L^-1.