己内酰胺水解聚合过程数学模型化与优化研究进展

综述了己内酰胺水解聚合反应动力学模型，并系统论述了ＰＡ６工业聚合反应器包括高压间歇釜反应器（ＢＳＴＲ）、活塞流反应器（ＰＦＲ）、连续搅拌釜反应器（ＣＳＴＲ）和ＣＳＴＲ与ＰＦＲ组合反应器模型化与优化研究，对数值计算方法也作了简要评价，同时就ＰＡ６聚合过程有待进一步研究的问题提出了几点建议。     

反应器操作方式对酶动力学拆分立体选择性的影响

描述了在批式反应器和连续流搅拌反应器（ＣＳＴＲ）中酶动力学拆分对映异构体的不同之处，从宏观反应器平衡角度，推导出了在ＣＳＴＲ反应器中不同于在批式反应器中的一定酶立体选择性（Ｅ）下，底物或产物的对映体过量值与反应的转化率之间关系的定量关系式。并通过商品脂肪酶及芽胞杆菌Ｅ－５３脂肪酶催化的萘普生甲酯的不对称水解反应得到了证实。分别在批式反应器和ＣＳＴＲ反应器中进行萘普生的酶法拆分，在一定转化率下，批式     

浸没循环撞击流反应器极具应用潜力的液相和液固相反应装置

理论分析和实验研究结果表明, 浸没循环撞击流反应器（ＳＣＩＳＲ） 与传统的搅拌槽反应器（ＳＴＲ） 相比,虽然在可测量尺度上的混合特性并不占优;但由于撞击区中流体元间剪切速率更高,因而微观混合更强烈。这对于在分子尺度上进行的化学反应具有重要意义。制取“超细”白炭黑研究的结果佐证了ＳＣＩＳＲ强化微观混合的特性。除此以外, ＳＣＩＳＲ在结构方面还具有多项胜过ＳＴＲ的优点, 极具开发应用的潜力。     

浸没循环撞击流反应器——极具应用潜力的液相和液固相反应装置

理论分析和实验研究结果表明,浸没循环撞击流反应器（ＳＣＩＳＲ）与传统的搅拌槽反应器（ＳＴＲ）相比,虽然在可测量尺度上的混合特性并不占优;但由于撞击区中流体元间剪切速率更高,因而微观混合更强烈。这对于在分子尺度上进行的化学反应具有重要意义。制取“超细”白炭黑研究的结果佐证了ＳＣＩＳＲ强化微观混合的特性。除此以外,ＳＣＩＳＲ在结构方面还具有多项胜过ＳＴＲ的优点,极具开发应用的潜力。     

声化学反应器设计研究进展

论述声化学反应器的研究进展及设计的基本原理,包括反应器采用的超声换能器的端面面积、输出声强、ＣＳＴＲ和ＰＦＴ模型下两种反应器中物料衡算方程,增加声化学反应器中声化学产额的空化效应动力学途径以及换能器与反应溶液之间的电 声耦合关系     

丙烯聚合反应动态模拟

从聚合反应动力学出发,根据反应系统内物料平衡和能量平衡原理,建立环管式丙烯聚合反应器动态数学模型,并采用机理模型与经验模型相结合的方法给出聚丙烯熔融指数推理模型。使用建立的数学模型,对反应器进行仿真试验,考察操作条件的变化对反应温度、浆液密度和产品熔融指数等产生的影响。采用该数学模型,可以准确地预测出操作条件的变化对产品质量的影响,对实际生产过程中产品质量的调整与控制具有指导意义。     

分子筛催化下苯与长直链烯烃的烷基化反应研究

在全混釜批式反应器（ＣＳＴＲ）中研究了Ｙ型分子筛催化剂作用下苯与长直链烯烃的烷基化反应，探讨了投料比对烯烃转化率以及温度对产物选择性的影响。在所设计的新型液固循环反应－再生流化床反应系统中，用工业原料验证了在分子筛催化剂作用下采用该反应系统连续合成长直链基苯的工业可行性     

基于催化剂颗粒停留时间分布的双峰聚乙烯牌号切换优化

针对环管-流化床串联的Borstar双峰聚乙烯工艺,建立了包括催化剂切换在内的双反应器串联牌号切换模型,使产品牌号的切换时间最短、过渡料数量最少。同时,推导了双反应器串联工艺中,存在催化剂切换时各反应器内聚合物的瞬时与累积性能指标（熔融指数与密度）的模型。研究表明,对于涉及催化剂切换的牌号切换,最优策略是采用催化剂分步进料方式,综合考虑新旧催化剂对操作参数的不同要求及各反应器内残留原催化剂比重对最终产品性能的影响,从而达到明显缩短切换时间、有效抑制操作变量急剧变化、平缓产品性质变化轨迹的优化目的。     

硬脂酸钴催化剂中钴的测定

硬脂酸钴催化剂中钴的测定秦黎薇，丁长福ＤＥＴＥＲＭＩＮＡＴＩＯＮＯＦＣＯＢＡＬＴＩＮＣＯＢＡＬＴＳＴＥＡＲＡＴＥＣＡＴＡＬＹＳＴ１前言测定钴的方法主要有经典α─亚硝基β─萘酚重量法、比色法和极谱法。重量法适用范围广准确度高，但耗时长。比色法和极谱法适...     

乙炔前加氢催化剂活性分析方法研究

乙炔加氢催化剂活性对反应器入口CO浓度变化非常敏感,量化CO浓度对催化剂活性的影响程度并预测催化剂活性与反应器入口温度的对应关系十分必要。通过反余切三角函数建立催化剂活性随CO浓度变化的模型,定量描述CO浓度对催化剂活性的影响,并结合反应器入口温度、入口原料气总质量、入口与出口各物质的含量等实际生产数据,优化动力学参数和失活模型参数,定性和定量描述催化剂活性变化后反应器入口温度的调整方法,利用此模型结合相关数据考察反应器入口温度对催化剂活性的影响。     

Deposit Growth on Chemical Reactor Walls and the Associated Heat and Mass Transfer

A mathematical model is formulated for the crystallization of the product of a bimolecular reaction in a laminar flow of a viscous solution containing foreign solid particles that serve as crystallization centers. A model is reported for the layerwise formation of a deposit consisting of the reaction product crystals and the foreign solid particles on the walls of a continuous flow reactor. A classification of the deposits is suggested, and the formation rate of the deposits of some types is calculated in the framework of the formulated model. The role of the reactor design in deposit formation is disclosed. The hydrodynamic interaction between the crystals formed in a reactor and those deposited on its walls is studied.     

Low-temperature methanol synthesis in a circulating slurry bubble reactor

A circulating slurry bubble reactor was developed to synthesise methanol via methyl formate from the gas mixture of carbon monoxide and hydrogen at low temperature. The strategy for designing and scaling up the bubble reactor involved a preliminary understanding of fluid dynamics in a cold model, continuous operations under industrial conditions and a parallel experiment in an autoclave. Per-pass syngas conversion was investigated during 100-h operations. The axial profile of solid catalyst concentration was measured just before the shutdown and the composition of liquid product was analysed after the shutdown. These results show that the circulating slurry bubble column will become a potential reactor for the commercial process of low-temperature methanol synthesis after the catalyst system has been improved.     

PET固相缩聚反应器动态模型

PET固相缩聚过程涉及反应固体颗粒和反应器床层两个空间尺度的传质,是一个复杂的多维多相对象。以反应过程控制为目标,在已有的反应动力学模型基础上,同时考虑可逆化学反应和小分子产物内外扩散两个控制因素,并借用固定床拟均相模型的建模思想,将小分子产物在颗粒内外扩散形成的浓度梯度用一个有效系数来表示,从而建立了简化的PET固相缩聚反应器一维动态模型。在相关文献的实验条件下求解分布参数模型的数值解,并进行启动过程仿真和过程动态分析,计算反应器出口质量指标,与文献曲线和数据对照,验证了模型的正确性。     

Heterogeneous numerical modelling for the auto thermal reforming of crude glycerol in a fixed bed reactor

A mathematical model for the catalytic autothermal reforming (ATR) reaction of synthetic crude glycerol to hydrogen in a fixed bed tubular reactor (FBTR) and over an in-house developed metal oxide catalyst is presented in this work. The heterogeneous model equations account for a two-phase system of solid catalyst and bulk feed gas. Also, the ATR of crude glycerol reaction scheme and intrinsic kinetic rate model over an active, selective, and stable nickel-based catalyst were integrated in the developed model. Also, the model was validated using experimental data generated in our labs for the ATR of synthetic crude glycerol. The modelling results adequately described the detailed gas product composition and distribution, temperature profiles, and conversion propagation in the axial direction of the fixed bed reactor over a wide range of reaction temperature (773-923 K) and mass-time (12.71-158.23 g cat·min·(mol C)^-1). The crude glycerol conversion predicted with the model showing a close resemblance to those obtained experimentally with an average absolute deviation (AAD) of less than 8%. The maximum crude glycerol conversion and hydrogen yield were found to be 92% and 3 mol hydrogen/mol crude glycerol, respectively. Also, the gas product concentration profile in the reactor was adequately described (90%) accuracy with a hydrogen concentration of 39% (volume).     

SOLID ADSORBENTS IN BATCH FERMENTATIONS

The addition of a non-specific solid adsorbent reduces the liquid-phase substrate concentration at the start of a batch fermentation. Then, as product is generated, it displaces the substrate from the adsorbent, reducing liquid-phase product concentration. So both substrate and product inhibition can be reduced and the productivity of the fermentation increased. A mathematical model for this process is developed including a modified Langmuir bi-solute adsorption isotherm, and both growth- and non-growth-associated product formation. The model agrees well with experimental data on the effect of Linde JXC activated carbon on the fermentation of glucose to ethanol by S. cerevisiae. Only product inhibition is considered and NH₃ is the sole nitrogen source to avoid complications arising from the adsorption of organic nitrogen compounds. Since ethanol is very hydrophilic and high concentrations of activated carbon are apparently toxic to yeast, there is little increase in volumetric productivity for this fermentation, the gains from reduced inhibition being cancelled by the additional reactor volume needed for the carbon. However, a significant increase is predicted for fermentations where the product and/or substrate is more inhibitory and adsorbs more readily.     

SOLID ADSORBENTS IN BATCH FERMENTATIONS

The addition of a non-specific solid adsorbent reduces the liquid-phase substrate concentration at the start of a batch fermentation. Then, as product is generated, it displaces the substrate from the adsorbent, reducing liquid-phase product concentration. So both substrate and product inhibition can be reduced and the productivity of the fermentation increased. A mathematical model for this process is developed including a modified Langmuir bi-solute adsorption isotherm, and both growth- and non-growth-associated product formation. The model agrees well with experimental data on the effect of Linde JXC activated carbon on the fermentation of glucose to ethanol by S. cerevisiae. Only product inhibition is considered and NH₃ is the sole nitrogen source to avoid complications arising from the adsorption of organic nitrogen compounds. Since ethanol is very hydrophilic and high concentrations of activated carbon are apparently toxic to yeast, there is little increase in volumetric productivity for this fermentation, the gains from reduced inhibition being cancelled by the additional reactor volume needed for the carbon. However, a significant increase is predicted for fermentations where the product and/or substrate is more inhibitory and adsorbs more readily.     

CFD modelling of the hydrodynamics and kinetic reactions in a fluidised-bed MTO reactor

This study presents a computational investigation of the hydrodynamics and kinetic reactions in a fluidised-bed MTO reactor. By integrating a kinetic model of methanol conversion with a two-fluid flow model, a gas–solid flow and reaction model was established. CFD analyses were performed, and the influences of various operating parameters were evaluated. The results indicate that the velocity, volume fraction and species concentration were considerably non-uniform in the axial and radial directions of the MTO reactor. Methanol conversion rate and product yields were more sensitive to the reaction temperature and pressure than to the initial methanol content in the feedstock. A gas velocity of 2.5–3.0 m/s and a catalyst circulation rate of 100–120 kg/(m² s) were found to be ideal for the current reactor. Coke deposition significantly affected the methanol conversion rate, product distribution and species selectivity. The ethylene-to-propylene ratio could be adjusted by varying the amount of coke on the catalyst.     

The influences of the gas rate dissolution and mass-transfer limitation at the interfaces on selectivity of gas–liquid processes in stirred reactors with a suspended catalyst

A complex mathematical model accounting for the hydrogen dissolution process in suspensions and mass-transfer steps at the liquid–solid interface for the gas and liquid components is given. The calculated data according to the model for the reaction A→B→C shows, that the yield of an intermediate product B is very much affected by the relation of the gas component mass-transfer coefficient on the gas–liquid interface to that on the liquid–solid one. The hydrogenation of chlornitroaromatic compounds was analysed. The kinetics of the catalytic reduction of p-chlornitrobenzene to p-chloraniline via corresponding arylhydroxilamine on the Ir/C catalyst experimentally in a batch reactor has been studied. In this process the first reactions depend on the hydrogen concentration but the second ones are not dependent — this is a disproportion of the intermediate product to the final product — amine.     

Inlet effect on the coal pyrolysis to acetylene in a hydrogen plasma downer reactor

Coal pyrolysis to acetylene in hydrogen plasma is a clean process for the coal utilization. A gas–solid downer reactor was employed to facilitate the high temperature reactions of coal pyrolysis in milliseconds. The effect of the inlet design on the coal injection was studied using CFD simulations, which were qualitatively compared with the cold model experiments in the prototype of a 2 MW hydrogen plasma reactor. The results revealed that the distribution of the coal particles near the inlet nozzles was significantly influenced by the layout of the flat‐shaped nozzles and the operating conditions. Accordingly the heating efficiency of the particles by the hot gas showed strong dependence on the inlet design. The hot model tests demonstrated that the reactor performance characterized by the concentration of acetylene in the product gas increased from ～7.6 to 9.6% by optimizing the nozzle design, which indicated the critical role of the nozzle design in the coal pyrolysis process.     

大颗粒三相环隙气升式环流反应器流体力学行为

研究了大颗粒体系气升式环流反应器的流体力学行为,考察了表观气速和颗粒质量分数对床层膨胀高度、循环液速和固含率分布的影响。实验结果表明,按颗粒的运动状态不同可以将反应器内的流动分为3个区域,即固定床区域、膨胀床区域和循环床区域,各流动区域内的流动行为存在显著差异。随着颗粒质量浓度的增大,起始流化气速和最小循环气速均显著增大。基于三相流化床的流化模型和环流反应器的特点建立了相应的数学模型,对大颗粒三相气升式环流反应器的起始流化气速和最小循环气速进行了预测,模型预测值与实验测量值吻合良好。