D—3催化剂上糠醛常压气相加氢制糠醇：本证动力学初探

在直流流动积分反应器中,于常压下研究了D—3催化剂上糠醛气相加氢制糠醇反应的本证动力学方程。结果表明加氢对糠醛是0.15级,对氢气是0.61级。     

糠醛液相催化加氢制糠醇金属催化剂的研究进展

糠醛催化加氢是将糠醛转化为生物燃料、医药农药中间体等精细化学品的最常用的反应之一,如糠醇、2-甲基四氢呋喃、内酯、乙酰丙酸盐、环戊酮等皆由糠醛催化加氢制取.当前糠醛催化加氢的过程主要有液相、气相以及催化转移加氢等.综述了近年来糠醛液相催化加氢制备糠醇的不同金属基催化剂的研究进展.从不同过渡金属和贵金属作为催化活性中心制备的单金属及双金属催化剂着手,讨论了部分金属基催化剂用于糠醛液相催化加氢制糠醇反应过程的催化性能.     

糠醛直接合成γ-戊内酯的研究进展

综述近年来由糠醛催化加氢制备γ-戊内酯的研究进展,讨论外部加氢和转移加氢两种催化加氢方式的金属催化剂.外部加氢方面,主要总结了以2-丙醇、2-丁醇为供氢体,采用ZSM-5催化剂、Sn-Al-Beta沸石催化剂、改性β分子筛和负载型β分子筛催化剂催化糠醛转化制备γ-戊内酯;转移加氢方面,主要以MFI分子筛负载硅铝酸盐催化剂、Zr-Al-beta催化剂、ZrPO-X催化剂等为例总结了糠醛直接转换合成γ-戊内酯.糠醛催化加氢直接制备γ-戊内酯的方法,不仅可以充分利用糠醛生产高附加值下游产品,也为γ-戊内酯生产创造一条新路径.     

糠醛和5-羟甲基糠醛双键加氢催化剂及催化作用研究进展

生物质基平台化合物糠醛和5-羟甲基糠醛来源广泛,可从绿色植物中提取得到.糠醛和5-羟甲基糠醛双键加氢制备四氢糠醇和2,5-二羟甲基四氢呋喃具有重要的研究价值.文章综述了近年来糠醛和5-羟甲基糠醛双键加氢反应的研究成果,重点阐述了反应机理的研究进展,讨论了不同催化体系(单金属、合金)对糠醛和5-羟甲基糠醛双键加氢的催化作...     

糠醛气相加氢制糠醇催化剂的研究

详细介绍了一种糠醛气相加氢制糠醇Cu -Zu体系催化剂的研制过程。在固定床反应器中 ,反应温度为 1 2 0～ 1 70℃、液空速为 0 .2h- 1 、H2 与醛物质的量比为 1 0∶1的条件下 ,糠醛转化率和糠醇选择性都在 99%以上。     

糠醛液相化学选择性加氢制糠醇的研究

本文主要介绍了间歇式反应釜中糠醛在Cu-Zn/γAl2O3催化剂条件下在不同温度、时间、糠醛浓度和溶剂体系中的催化加氢制糠醇,从糠醛转化率和糠醇选择性两方面对加氢效果进行比较。通过实验,我们得到了糠醛加氢制糠醇的最佳工艺条件为反应温度为160℃、反应时间为3 h、催化剂用量为糠醛的7wt%、糠醛浓度为5wt%~25wt%、溶剂为甲苯时,糠醛的转化率和糠醇的选择性最好,分别为99%和98%。     

糠醛气相催化加氢制糠醇实验研究

本文研究在铜系催化剂上,糠醛气相加氢条件对糠醛转化率及糠醇收率的影响,提出加氢温度、接触时间、氢气糠醛加料比等优化条件,並以高收率得到糠醇。     

糠醛选择性催化加氢的研究进展

糠醛是种可再生的生物质能源,可从农副产品中萃取得到。糠醛加氢可合成很多高附加值的产物,如糠醇、四氢糠醇、2-甲基呋喃、呋喃、2-甲基四氢呋喃、环戊酮、环戊醇和1,4丁二醇等。糠醛氢化反应除了碳碳双键、呋喃环氢化外,还有其他衍生副反应(脱羰、开环反应、缩合反应、C O键氢化等)。糠醛催化加氢催化剂主要为金属催化剂以及非晶态合金催化剂,单金属催化剂用于反应时的选择性和活性较低,通常采用添加助剂或是另一种金属以提高催化剂的活性和选择性,目前糠醛选择性催化加氢的研究主要集中在催化剂载体和双金属催化剂的研制上。主要阐述糠醛选择性催化加氢催化剂研究进展,指出在研制低成本、高选择性、稳定性、绿色环保的催化剂同时,催化剂的工业化应用研究有待进一步完善,最终以实现糠醛高效高选择性加氢工业应用为目的。     

糠醛气相加氢制2—甲基呋喃催化剂初步研究

得到了糠醛气相加氢制 2 -甲基呋喃催化剂的最佳沉淀法制备条件 :沉淀温度 10 0℃ ;Cr、Cu质量比 0 .6 2 ;Ba的质量含量 0 .6 % ;Ca的质量含量 2 .7% ;沉淀溶液 pH值为 6。对催化剂失活原因进行了分析 ,认为失活是由于活性组分铜的重结晶造成的     

糠醛在Pd-Cu膜反应器中催化加氢合成糠醇

以糠醛催化加氢合成糠醇作为模型反应,采用共沉淀法制备的Cu/MgO-K₂O作为催化剂,考察了Pd-Cu膜反应器的加氢性能.膜反应器由双套管组成,采用分别进料的方式操作.即糠醛气化后由载气带入中心膜管的催化床层,而氢气则进入管壳层通过Pd-Cu合金膜渗透到反应区.在不同条件下分别进行糠醛催化加氢反应,考察了糠醛转化率、产品糠醇选择性和收率,并与传统的共进料填充床反应器进行比较.研究结果显示,膜反应器比传统的填充床反应器具有产品收率高、选择性好和副产物少的特点.此外,本文结合催化剂的组成、结构和表面形貌的表征对催化剂的催化活性和失活行为进行了讨论.     

Application of ultramicroelectrodes in studies of homogeneous catalytic reactions—part III. The condition for quasi-first and second order homogeneous catalytic reactions at ultramicrodisk electrodes in the steady state

The conditions for quasi-first and second order homogeneous catalytic reactions and their variation with each other at an ultramicrodisk electrode in the steady state are discussed in this paper. The order of reaction can be controlled by changing the dimension of the ultramicroelectrode: the second order reaction can be changed to quasi-first by decreasing the dimension of the ultramicroelectrode. An example of this is given. The main factor effect on the reaction order is the dimension of the ultramicroelectrode. The K₄Fe(CN)₆-aminopyrine system is selected to confirm the theory, the experiments showing that the system is a second order reaction at a 432 μm microelectrode, and a quasi-first order reaction at a 19 μm ultramicroelectrode. The kinetic constant of the system can be determined by applying the previous theory of homogeneous catalytic reaction.     

羟基氯醋改性聚氨酯预聚体合成反应动力学研究

采用化学分析方法研究了羟基氯醋树脂微粉存在下的聚醚N-220、蓖麻油等聚醚多元醇混合物与甲苯二异氰酸酯（TDI-80）的预聚合反应动力学,获得了聚氨酯预聚体合成反应动力学参数及反应表观速率常数表达式k=0．049exp（-23．95／RT）,并通过反应初期的实验数据对反应级数进行了验证。结果表明,在该体系下的预聚体合成反应中,氨酯化反应的表观速率常数随反应温度的升高而增大,合成反应以氨酯化反应为主,总反应级数为1．74~1．88,为近二级反应。该合成反应机理具有一定的复杂性。实验结果对相关聚氨酯弹性体预聚物合成及改性反应具有一定的理论价值和指导意义。     

基于不同三组分模型解析生物质热解过程

三组分模型（three pseudocomponent model）通常被用来表征生物质热解过程。传统三组分模型中单个模型的反应级数被限定为1或3。在本研究过程中，利用非线性最小二乘法，在不限定反应级数的前提下回归三组分模型动力学参数（活化能、指前因子、反应级数）。通过研究发现，纤维素（cellulose）分解反应级数接近1，与前人结果相一致。木质素（lignin）分解级数与生物质种类有关，接近于1或3。半纤维素（hemicellulose）的分解过程最复杂，其反应级数在1.5～4之间变化。以Ozawa方法计算得到的活化能作为相对标准，对3种三组分模型进行比较，发现反应级数未确定时的模型比其他两种模型更精确地表征生物质热解过程。     

Calculating the Reaction Order and Activation Energy for the Hydrothermal Carbonization of Fructose

The development of accurate kinetic models for hydrothermal carbonization (HTC) faces major difficulties. This is related to the fact that the formation of the solid hydrochar can be regarded as a formation of a second phase from a homogenous solution. The reaction mechanism is not fully understood. From the current state of art, it is obvious that the reaction mechanism is some sort of polymerization reaction, thus, having reaction order higher than one. In order to gain more knowledge about the HTC reaction, fructose is used as a model substance, as it can be regarded as a key intermediate during the hydrothermal processing of carbohydrates. The results indicate that the reaction order is a highly sensitive parameter varying with temperature, reaction time and initial concentration. It can be concluded that the model itself is a strong simplification of the real reaction mechanism, thus more research is necessary to complete the actual knowledge.     

Monitoring the reaction progress of a high‐performance phenylethynyl‐terminated poly(etherimide). Part I: Cure kinetics modeling

The cure kinetics of a phenylethynyl‐terminated poly(etherimide) are examined via differential scanning calorimetry (DSC) measurements. Isothermal holds at temperatures ranging from 325°C to 360°C provided the necessary information to develop reaction kinetics models using both first‐order reaction kinetics and combination reaction kinetics. The first‐order reaction kinetics model works well for quick estimates of degree of cure versus time over the experimental temperature range. However, significantly more accurate predictions of degree of cure versus time were provided by the combination reaction kinetics model. The lack of accuracy in the first order model is due to the fact that the reaction cannot be described by a simple order. The experimental procedures followed to obtain the cure kinetics data and the construction of the models from this data are described; the predictions of these models are compared with the experimental results.     

固定床反应器进行n级反应的飞温判据

本文以一级反应系统参数敏感性理论为依据，给出ｎ级反应系统以ε为扰动参数的临界热点温度表达式，内插得到该系统的飞温判据。结果表明：反应级数越大，系统抵抗外部环境干扰的能力越强，安全操作区域越大，参数敏感区域越小。     

Hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols: II. Kinetics and mechanism of the reaction using Cu and Cd oleates as catalysts

The kinetics and mechanism of the Cu and Cd-soap-catalyzed hydrogenation of oleic acid have been studied. The reaction is first order in Cd and H₂, and also first order in Cu if the double bond is completely preserved during reduction of the carboxyl group to the hydroxyl group. It will deviate from this order if the selectivity is lower owing to an increased Cu concentration. The reaction rate-determining step is independent of the Cd concentration. Its activation energy, of 13.4 kcal/mole, corresponds to that of the chemisorption of hydrogen on Cu. Unsaturated and saturated fatty acids of the same chain length have the same reaction rate. A decrease of the chain length causes a decrease in the reaction rate and in the final degree of conversion. Water and low molecular weight acids have an inhibitory effect on the reaction. A reaction mechanism is proposed which is based on the assumption that cadmium oleate plays a double role: it stabilizes the copper sol and is intermediate for the hydrogenation.     

Application of ultramicroelectrodes in studies of homogeneous catalytic reactions—part II. A theory of quasi-first and second-order homogeneous catalytic reactions

The analytical expressions of quasi-first and second order homogeneous catalytic reactions with different diffusion coefficients at ultramicrodisk electrodes under steady state conditions are obtained by using the reaction layer concept. The method of treatment is simple and its physical meaning is clear. The relationship between the diffusion layer, reaction layer, the electrode dimension and the kinetic rate constant at an ultramicroelectrode is discussed and the factor effect on the reaction order is described. The order of a catalytic reaction at an ultramicroelectrode under steady state conditions is related not only to C^*_z/C^*_o but also to the kinetic rate constant and the dimension of the ultramicroelectrode; thus the order of reaction can be controlled by the dimension of the ultramicroelectrode. The steady state voltammetry of the ultramicroelectrode is one of the most simple methods available to study the kinetics of fast catalytic reactions.     

Kinetics of heterogeneous oxidation of ammonium sulphite

The heterogeneous oxidation of ammonium sulphite was investigated with cobalt sulphate catalyst at 30°C. For a wide range of concentrations the reaction was found to be nearly first order in oxygen and zero order in sulphite. These kinetics contrast with the results of homogeneous experiments which indicate that the reaction is zero order in oxygen and three-halves order in sulphite. The catalytic effect of cobalt ions was found to be proportional to the square root of the total concentration of cobalt. The apparent activation energy for the overall oxidation was calculated to be 13 kcal/g mol. It is concluded that the kinetics in the heterogeneous system are determined by the catalyst regeneration reaction which is diffusion controlled.     

Factors affecting the kinetics of the heterogeneous oxidation of ammonium sulfite

Absorption of oxygen into 0.09 – 0.7 M solutions of ammonium sulfite was measured by utilizing a stirred cell. The concentration ranges of the cobalt sulfate catalyst was 5.5 × 10^?5 – 4.7 × 10^?3 M and that of oxygen in the gas phase 21 – 100%. The theory of absorption with fast pseudo-nth order reaction was used to find the order of intrinsic rate of reaction with respect to reactants and the catalyst. Above a critical sulfite concentration the order in sulfite is zero, in O₂ is 0.4 – 1, and in CoSO₄ is 1. Under those conditions a proposed reaction mechanism yields orders of zero, 1, and 1, respectively. Below the critical point the order in sulfite is 2, indicating that another reaction mechanism is applicable. Although an increase of the ionic strength enhances the reaction rate slightly, an increase of pH from 7.6 to 8.5 causes a 1.4 fold increase. Under oxidative conditions deactivation of the catalyst and insoluble precipitate formation is observed.