天然气二氧化碳空气和水蒸汽制合成气的热力学研究

采用化学热力学的方法对天然气、二氧化碳、空气和水蒸汽制合成气反应体系进行计算，分别计算了反应温度、原料气组成以及反应压力的影响。计算结果表明：升高反应温度，有利于该反应的进行；原料气各物质的比例不同，可以制备不同C／H比的合成气；升高压力对该反应不利。     

S-1催化环己酮肟气相Beckmann重排反应动力学

目前尼龙6生产中主要采用发烟硫酸催化环己酮肟液相Beckmann重排制己内酰胺,副产大量硫酸铵,而且存在设备腐蚀等问题。采用气相重排法可以克服上述缺点。本工作在以前得到的优化反应条件下,根据实验并采用催化剂失活的Wojciechowski模型获得了S-1催化环己酮肟气相Beckmann重排制己内酰胺反应动力学方程及参数。该模型将催化剂的活性与在线反应时间相关联,进而可以计算任何在线反应时间时催化剂的失活速率,或者根据要求的转化率最低允许值计算催化剂能在线反应的时间。     

呋喃酮的绿色合成工艺的研究

对呋喃酮的绿色合成进行研究。采用丙酮醛为原料的合成方路线。以环己醇为内标物的气相内标法进行分析。得出了本合成路线的最佳反应条件。     

环己烷液相无催化氧化模拟计算及动力学的修正

1 模拟计算1.1 动力学和流动模型模拟计算中采用陈纪忠等建立的动力学模型,其反应网络为:描述该6种组分的生成或消失速率的动力学方程式在文献[1]中已有详细报道。从冷模研究得到:液相流动为全混流;u_g≥7 cm/s 时气相流况可视作平推流。若从各种流动模型的计算结果看,气相即使作为全混流,计算结果差异也甚小。本文采用液相全混、气相平推的流动模型。     

乙炔加氢制乙烯浆态床反应器的CFD模拟

对浆态床反应器中乙炔加氢制乙烯过程进行了模拟研究，采用TFM-PBM耦合方法描述浆态床内气相与浆态相的流动，并耦合乙炔加氢反应动力学建立流动-反应综合模型。通过小试实验对该模型进行验证，并将验证后的模型应用于浆态床中试装置中内构件作用机制与操作条件影响的模拟分析。结果表明，在浆态床反应器放大时，可通过设置竖管内构件，以破碎气泡，抑制气相径向运动，使乙炔加氢过程均匀、充分地进行。乙炔加氢制乙烯过程与气相停留时间和反应温度密切相关，在反应器放大中需严格控制温度，并可通过改变反应器内液位高度实现对气相停留时间的调控，从而可在保证乙炔充分转化的同时获得更高的乙烯选择性。     

离子液体催化合成2-氰基呋喃反应动力学研究

2-氰基呋喃（CF）是一种具有广泛潜在应用的重要生物基衍生物，是合成糠胺、糠酸等产品的关键原料，但目前对于合成2-氰基呋喃的研究甚少。本研究采用离子液体为催化剂，探究了糠醛与离子液体型羟胺盐反应制备2-氰基呋喃的动力学过程。考察了反应温度和反应时间对产物收率的影响，建立了反应动力学模型，对动力学参数进行了有效性验证。实验结果显示：当反应温度为120℃，反应时间为2 h时，糠醛转化率和2-氰基呋喃收率均为100%。通过计算得到了活化能、指前因子及动力学方程，对比了计算值和实验值，发现平均误差为0.34%，从而验证了该反应动力学方程的准确性，为2-氰基呋喃的后续应用提供了理论指导。     

直接酯化法合成BHBT过程主反应动力学研究

以精对苯二甲酸（ＰＴＡ）和１，４ 丁二醇（ＢＤ）为原料，以Ｔｉ（ＳＯ４）２水解物为催化剂，采用直接酯化法合成ＢＨＢＴ，对主反应进行动力学研究，分别按零级、一级反应模型处理，并求得其动力学参数，进行模型的比较和鉴别，得出在本实验范围内，一级反应更为可靠的结论。     

日东京大学开发用于苯直接合成苯酚新催化剂

日本东京大学的研究人员开发了用于苯直接合成苯酚的铼沸石催化剂，制备方法是采用化学气相沉积法将甲基三氧化铼沉积到沸石（HZSM-5）孔道中。研究采用分子氧进行氧化反应，当原料转化率为5．5％时，催化剂的选择性达90%，产物收率达5％。     

色谱相对外标法定量聚合级丙烯中烃类杂质

本方法参照ＧＢ３３９２－８２标准，采用气相色谱相对外标法定量聚合级丙烯中烃类杂质。该方法在实际生产中应用，操作简单，计算方便。     

SO4^2-／MxOy固体超强酸催化合成1，4-二氧六环

以乙二醇为原料,采用颗粒型SO4^2-／MxOy固体超强酸倦化剂，在常压、气相条件下,固定床催化合成了1。4-二氧六环；同时考察了不同反应温度、原料配比、进料速度等条件对催化反应的影响．并对上述影响因素进行了探讨。产品经气相色谱，红外光谱及质谱分析。结果表明。原料在260℃温度条件下，以进料流速为0．12mL／min为最佳反应条件。在该实验条件下，1。4-二氧六环的生成产率达到60％-70％左右。该合成工艺应用固体超强酸催化剂具有较高的催化活性、化学稳定性好、无环境污染。是工业生产1，4-二氧六环较理想方法，具有良好的工业生产前景。     

Kinetics of the photocatalytic total oxidation of different alkanes and alkenes on TiO2 powder

Although photocatalyzed total oxidation reaction of hydrocarbon species has been discussed in the literature, most of these studies were performed to obtain an appropriate reaction mechanism. Studies on the kinetics of this type of reaction are rare. Using titanium dioxide as the photo catalyst, the kinetics of the total oxidation of methane, ethane, ethene, as well as propene, have been investigated using a continuous‐stirred tank reactor. In the experiments, the hydrocarbon concentrations, the oxygen concentration, and the irradiation intensity were varied. The results obtained are evaluated on the basis of a kinetic model to derive rate equations which can be used for reactor design.     

4-氨基苯磺酰胺的合成工艺改进

研究了由乙酰苯胺经过氯磺化、胺化、水解反应制备4-氨基苯磺酰胺（简称磺胺）的合成工艺改进。其中包括在氯磺化过程中吸收氯化氢气体配制成30%盐酸,该盐酸将作为副产品出售;将氯磺化产物分解过程中产生的部分废酸用于水解反应之后调节反应混合液pH值,剩余废酸全部用于本公司二羟基萘生产的酸化工艺中;采取浓缩磺胺母液的方式提高产品收率,将最终磺胺母液用于氯磺化产物分解反应;磺胺母液浓缩过程产生的无机盐大部分为氯化钠,将作为冷冻盐水使用;磺胺母液浓缩过程收集的冷凝水,将用于对乙酰胺基苯磺酰氯（ASC）洗涤。原有工艺改进后,磺胺收率由工业生产的69.0%提高到72.5%,成本降低,三废排放很少。     

管式反应器中苯乙烯连续本体热聚合过程模型化和数值模拟

建立了管式层流反应器中苯乙烯本体热聚合过程的模型。数值模拟了反应介质流速和温度沿反应器的轴向和径向的分布,考察了反应器的几何尺寸、壁温、反应介质入口温度和流量对反应器出口转化率和产物相对分子质量的影响。结果表明,反应器的几何尺寸和反应器壁温及进料质量流量对单体转化率影响较大,而入口温度影响不大。     

Kinetic studies of alkyl formate hydrolysis using formic acid as a catalyst

BACKGROUND: The hydrolysis of methyl formate is the major industrial process for the production of formic acid. The aim of the work is to determine the reaction kinetics quantitatively in the presence of formic acid catalyst, develop a mathematical model for the reaction system and estimate the kinetic parameters for the purpose of optimization. RESULTS: Liquid phase hydrolysis kinetics of alkyl formates (ethyl and methyl formate) was studied in an isothermal batch reactor at 80–110 °C and 20 bar nitrogen pressure. The catalyst of choice was formic acid. The reaction rate was enhanced but the formic acid product yield was slightly suppressed relative to the uncatalysed system. A kinetic model comprising mass balances and rate equations was developed and the kinetic and equilibrium parameters included in the rate equations were estimated from the experimental data with non‐linear regression analysis. CONCLUSION: The model was able to predict the experimental results successfully. The results obtained were compared quantitatively with an earlier model involving alkyl formate hydrolysis in a neutral aqueous solution. Copyright © 2011 Society of Chemical Industry     

Recursive data-based prediction and control of product quality for a PMMA batch process

In many batch processes, frequent process/feedstock disturbances and unavailability of direct on-line quality measurements make it very difficult to achieve tight control of product quality. Motivated by this, we present a simple data-based method in which measurements of other process variables are related to end product quality using a historical data base. The developed correlation model is used to make on-line predictions of end quality, which can serve as a basis for adjusting the batch condition/time so that desired product quality may be achieved. This strategy is applied to a methyl methacrylate (MMA) polymerization process. Important end quality variables, the weight average molecular weight and the polydispersity, are predicted recursively based on the measurements of reactor cooling rate. Subsequently, a shrinking-horizon model predictive control approach is used to manipulate the reaction temperature. The results in this study show promise for the proposed inferential control method.     

气液喷射式磺化反应器的应用研究

用喷射式磺化反应器分别对脂肪酸甲酯、烷基苯、重烷基苯、脂肪醇、脂肪醇聚氧乙烯醚和α 烯烃等原料进行了SO3气相磺化/硫酸化反应,研究了反应器主要结构参数对产品质量的影响,并与膜式反应器作了比较。结果表明:喷射磺化反应器制备的烷基苯磺酸、脂肪酸甲酯磺酸的产品质量与膜式磺化反应器相当,制备的重烷基苯磺酸盐产品质量稳定,降低原油/水界面张力的能力优于膜式磺化器制备的产品,但在磺化α 烯烃、硫酸化脂肪醇和脂肪醇聚氧乙烯醚时转化率低于90%,产品质量明显不及膜式反应器。从两种反应器的传质、传热机理及效率,不同有机原料的SO3磺化机理及反应速度等方面对以上现象进行了分析和讨论,认为喷射式磺化反应器适用于脂肪酸甲酯、烷基苯、重烷基苯的磺化,目前的结构参数不适用于α 烯烃、脂肪醇和脂肪醇聚氧乙烯醚的磺化/硫酸化反应,需要进一步调整,改善传质效率。     

乙炔加氢反应器的先进控制(Ⅱ)--软测量仪表及工程实践

在深入理解乙炔加氢反应器工艺特点的基础上，推导基于动态机理数学模型的反应器催化床层活性、选择性及出口组成软仪表公式。软仪表工业实施效果良好。     

反应器网络综合三分布参数通用模型

提出了一种应用于反应器网络综合的三分布参数通用模型 .3个分布参数分别是侧线进料、侧线循环和侧线采出参数 ,这些参数能影响反应器网络内部的浓度和停留时间分布 ,所以由它们构成的通用模型具有简捷有效的特点 .基于此模型可将反应器网络集成转化成一个优化问题 ,通过有限元正交配置将原来含有微分方程的优化模型转化为非线性优化问题 ,优化计算后得到最优分布参数 .从案例研究可以看出 ,侧线进料、循环和采出策略能较全面地反映在不同动力学和优化目标函数下的最优反应器网络特征 ,并进而简化为工业可行的反应器网络     

EXPERIMENTAL EVALUATION OF SELECTIVITY IN SLOW AROMATIC CHLORINATIONS

A dispersion plug flow reactor model (DPFR) has been derived and experimentally verified to predict product distribution and selectivity for commercial aromatic halogenation reactions. From the model recommendations for process modifications to reduce the amounts of undesirable byproducts arising from similar reactions can be obtained. The selectivity of the monochlorinated product is shown to depend on kinetic and hydrodynamic parameters, mixing in the reactor and chlorine solubility. The pertinent variables are arranged in five dimensionless groups which include the kinetic and hydrodynamic Damkohler Numbers, the Peclet Number, ratio of the rate constants and the ratio of chlorine solubility to the inlet aromatic concentration.

A micro pilot plant which duplicates industrial conditions for benzene and toluene chlorination was constructed to test the DPFR model. Chlorination studies were performed under a range of conditions. Hydrodynamic parameters required for the model were obtained from published correlations. The model prediction of selectivity agreed within 8% for all the experimental results, and actually better than 5% for most runs.

A graphical technique which provides recommendations for reducing the dichlorinated products is presented along with examples for both the design of a reactor, and troubleshooting of an existing reactor system.     

A KINETIC MODEL FOR THE PRODUCTION OF LIQUIDS FROM THE FLASH PYROLYSIS OF BIOMASS

A kinetically based prediction model for the production of organic liquids from the flash pyrolysis of biomass is proposed. Wood or other biomass is assumed to be decomposed according to two parallel reactions yielding liquid tar and ( gas + char) The tar is then assumed to further react by secondary homogeneous reactions to form mainly gas as a product

The model provides a very good agreement with the experimental results obtained using a pilot plant fluidized bed pyrolysis reactor

The proposed model is shown to be able to predict the organic liquid yield as a function of the operating parameters of the process, within the optimal conditions for maximizing the tar yields, and the reaction rate constants compare reasonably well with those reported in the literature