Study on the enzymatic hydrolysis of racemic methyl ibuprofen ester

The hydrolysis of racemic methyl ibuprofen ester in the presence of lipase from Candida rugosa was investigated in shake flasks. Experiments were performed to study the effect of temperature, pH and shaking speed on the reaction rate. Different hydrophobic co‐solvents were screened for the highest reaction rate and the presence of enzyme inhibition by substrate and products was examined. A kinetic expression was then proposed to describe the reaction. Kinetic parameters were determined for the optimum operating conditions and the proposed model was verified with the experimental results. Next, this reaction was scaled up to a fed batch stirred tank reactor. Batch reactor and fed batch reactor configurations were compared for better conversions. The effects of aqueous phase hold‐up, substrate concentration and feed flow rate on the conversion of the reaction were also studied. Higher conversions were obtained in a fed batch reactor when compared with the batch reactor. In the fed batch reactor, increased conversions were observed with lower feed flowrates and high aqueous phase hold‐up. © 2001 Society of Chemical Industry     

焦炉煤气部分氧化制甲醇合成气研究

应用ChemCAD软件,采用吉布斯反应器模型对转化炉进行模拟,分析了温度、压力、进气量等各工艺条件对反应的影响。模拟结果表明,焦炉煤气部分氧化制取合成气适宜的操作条件为:进气温度500℃,反应压力1.85 MPa,进入转化炉各物流的摩尔流量COG(焦炉煤气):H_2O:O_2:CO_2=1:0.8:0.21:0.095。     

固定化L-天门冬酰胺酶的性质及其填充床反应器的研究

利用海藻酸钙包埋、戊二醛交联的方法对L-天门冬酰胺酶进行固定化。研究了固定化L-天门冬酰胺酶的最适pH、最适温度、米氏常数、半衰期等酶学性质,并考察了影响固定化酶柱式填充床反应器转化率的因素。结果表明:固定化酶最适pH值为8.5,最适温度为67°C,固定化酶的米氏常数Km增大,固定化酶半衰期随着温度的增加而逐渐减小;温度、反应柱内径、底物溶液浓度、流速等因素对填充床反应器转化率均有显著影响。     

双环戊二烯加压连续聚合制备高能量密度燃料

为制备密度大于1 g·ml^-1的高密度燃料母体化合物三环戊二烯（TCPD）,研究了双环戊二烯（DCPD）的加压连续聚合反应。分析了聚合反应产物组成和反应途径,研究了反应条件的影响。与常压间歇反应相比,加压连续反应能极大地提高反应转化率和收率,优化产物组成,TCPD中挂式/桥式（exo/endo）比例大大提高,并生成新的产物exo-DCPD。反应途径分析表明,TCPD中exo/endo比例与exo-DCPD选择性呈线性正相关。研究发现,为维持反应进行压力应不低于1.2 MPa,增加温度能提高反应转化率,而TCPD最高收率出现在160℃,TCPD的exo/endo比例随温度增加而降低,反应转化率和收率随停留时间增加而增加,但转化速率降低,缩短停留时间有利于提高TCPD的exo/endo比例,浓度对反应影响不大。在较优条件下,endo-DCPD转化率达82.2%,TCPD收率达41.7%。     

Manganese oxide dissociation kinetics for the Mn2O3 thermochemical water-splitting cycle. Part 2: CFD model

A detailed CFD model was developed to better understand the kinetics and transport characteristics of Mn₂O₃ dissociation in an aerosol flow reactor (AFR). Radiation was the dominant mode of heat transfer (T=1673–1873 K) and a relation for radiation from the walls and attenuating volume to any volume element in the reactor was developed. Results compared favorably to what was observed experimentally and showed that solid feed concentration into a high temperature AFR has a significant effect on conversion. If the concentration becomes too high, simply increasing the temperature of the reactor wall will not provide enough energy to drive the reaction to a high conversion. Additionally, the model showed that the bulk gas rate does not have that much effect on conversion in the AFR. This is important as a higher gas flow rate provides a faster quench, limiting the possibility of a recombination reaction. Finally, a case study for the diameter of the reactor tube showed that a higher conversion could be achieved by decreasing the size of the reactor tube. Multiple reaction tubes of smaller diameter are likely needed for scale-up.     

Conversion of citric acid to itaconic acid in a novel liquid membrane bioreactor

A novel liquid membrane reactor was designed to carry out the conversion of citric acid to itaconic (methylene succinic) acid by the fungus Aspergillus terreus. This bioreactor contained two supported liquid membranes (SLMs) that divided it into three compartments: (1) the feed chamber containing citric acid; (2) the reaction chamber containing the enzyme A terreus cells; and (3) the product collection chamber containing the counter‐ion. The specificity of SLMs allows the unidirectional flow, of the substrate from the feed to the reaction chamber, and of the product from the reaction to the product chamber in exchange for a counter‐ion, thus maintaining low concentrations of both the product and the substrate, and limiting their inhibitory effects on the conversion process. The yield of itaconic acid in the membrane bioreactor was about two orders of magnitude higher than in the batch process. © 2000 Society of Chemical Industry     

ON THE EFFECTS OF SYNGAS COMPOSITION AND WATER-GAS-SHIFT REACTION RATE ON FT SYNTHESIS OVER IRON BASED CATALYST IN A SLURRY REACTOR

Water gas shift reaction plays an important role in the Fischer-Tropsch synthesis reaction over iron-based catalysts. A slurry reactor model which accounted for the kinetics of both Fischer-Tropsch synthesis and water gas shift reaction was used to investigate the effects of hydrogen to carbon monoxide ratio, water vapor concentration and reactor temperature on synthesis gas conversion. The model was used to determine optimum concentration of water in the feed gas. For a given reactor temperature, the optimum concentration of water in the feed gas was found to increase with decreasing hydrogen to carbon monoxide ratio. The optimum concentration of water in the feed gas was found to decrease with increasing reactor temperature. Increasing the water gas shift reaction rate improved syngas conversion for low reaction temperatures.     

Design strategy and process optimization for reactors with continuous transport of an immobilized enzyme

In order to operate a process which uses immobilized enzymes at constant conversion and constant capacity, the refreshment of the enzyme must be continuous. In this paper, two reactor types with continuous refreshment of the biocatalyst are discussed: the stirred tank and the multistage fluidized bed. A method is presented for dimensioning a reactor in such a way that the costs for the conversion of substrate to product are minimized. These costs are calculated as the sum of the biocatalyst consumption and overall reactor costs.In contrast with the stirred-tank reactor, the multistage fluidized bed can be operated at a non-uniform temperature. For the glucose isomerase process, an optimal temperature gradient results in a small reduction in the biocatalyst consumption (±5%). It is concluded that, in general, a temperature gradient will only favour the economy of processes with relatively expensive biocatalysts.Compared with conventional reactor types, such as the continuous stirred-tank reactor and the fixed-bed reactor, the multistage fluidized-bed reactor can improve the economy of an enzyme-catalysed reaction significantly.     

Optimal temperature profiles in tubular reactors for several catalyst decay laws

Theoretical and experimental work on tubular reactors has shown that a high temperature reaction zone can be induced to move counter to the flow of reactants by conduction and/or radiation through the solid phase. This naturally occurring phenomenon represents a transient mode of operation that can be argued to be preferable to conventional modes of operation. In order to test this hypothesis the complete time and space dependent optimal temperature policy was generated for a tubular reactor subject to several catalyst decay laws. The solutions revealed that a critical parameter is the ratio of the activation energy for the main reaction to that for the catalyst decay reaction. For values of this ratio less than one, the optimum temperature profiles represent a low temperature reaction zone that occupies the entire active bed at all times, essentially a conventional mode of operation. However, for this ratio greater than one the profiles represent a short high temperature reaction zone that propagates with time along the length of the reactor. For a catalyst decay law independent of conversion, propagation in either axial direction was optimal, but for a decay law dependent upon conversion the optimization procedure only generated reverse propagating zones.     

Casson流体层流反应器中连串反应的产品分布

引　言目前化工流体力学涉及的范围已由传统的牛顿流体发展到非牛顿流体 .常见的非牛顿流体包括幂律流体、Bingham流体和Casson流体 .有许多高聚物反应物系和生化反应物系属于非牛顿流体 .特别是某些生化反应系统 ,所处理的物系常由各种天然物质组成 ,因而表现出典型的非牛顿流     

Non‐Isothermal Non‐Adiabatic Dehydrogenation of Cyclohexane in Catalytic Membrane Reactors

Abstract

This study focuses on modeling and analysis of the non‐isothermal, non‐adiabatic, dehydrogenation of cyclohexane in membrane catalytic reactors. The dehydrogenation reaction is endothermic with a low equilibrium conversion of 0.06 at a temperature of 473 K and pressure of 101 kPa. The membrane reactor removes hydrogen from the reaction mixture and results in increase of the reaction conversion. The analysis is made as a function of feed flow rate, feed temperature, feed composition, inert flow rate in the feed stream, flow rate of sweep gas, pressures of the tube side and shell side, permeability constant of hydrogen, and tube diameter. The analysis also includes a study of the co‐current and the counter‐current flow modes. The results show lower conversion for the counter‐current flow mode, because of the decrease in the driving force for permeation. A comparison of model predictions against previous literature studies shows good agreement.     

Optimal temperature policies for catalytic transport reactors under periodic operation

The influence of inlet gas concentration cycling on the optimal temperature policy of catalytic transport reactors is studied theoretically. The model considered is based on plug flow of gas and catalyst particles with negligible interand intra-particle diffusional resistances and concentration dependent deactivation kinetics. To utilise the concentration of the reactant and the activity of the deactivating catalyst fully a proper temperature sequence along the reactor is needed. Thus, a general optimal temperature policy using the continuous minimum principle is derived for the reactor under periodic operation. The model equations are solved analytically for gas concentration, activity and temperature profiles. Resonance behaviour (maximum in conversion with pulse width) is obtained using the optimal temperature policy for certain sets of parameters. The effects of activation energy groups, reaction and deactivation constant groups and inlet temperature on the optimal temperature policy under periodic operation are evaluated. In all cases an improvement in conversion with the optimal temperature policy under periodic operation over that with an isothermal policy under periodic operation is obtained. A suboptimal policy, comprising constant temperature over different reactor sections, which is useful for implementation purposes is also discussed.     

连续相变的加氢反应器

引　言加氢反应是一类强放热反应 ,在采用滴流床反应器的情况下 ,经常遇到由于液体分布不均而导致的催化剂不完全润湿的现象[1] 。当液体反应物中含有挥发性组分时 ,在一定条件下 ,液相反应物可能会蒸发 ,伴随着反应速度的突然增加[2 ] ,使催化剂局部过热而失活 .另外 ,由于液体在催化剂床层中的不均匀分布而使床层出现未被润湿的干区 ,在强放热反应中 ,会经常观察到出现热点 ,床层的轴向温度出现振荡[3] .两相并流向上的固定床反应器 ,由于床层内的持液量较高 ,液体分布均匀 ,催化剂能很好地润湿 ,因此有可能避免出现热点[4 ] .这种操作形…     

Design and simulation of a solar chemical reactor for the thermal reduction of metal oxides: Case study of zinc oxide dissociation

A laboratory-scale solar reactor was designed and simulated for the thermal reduction of metal oxides involved in water-splitting thermochemical cycles for hydrogen production. This reactor features a cavity-receiver directly heated by concentrated solar energy, in which solid particles are continuously injected. A computational model was developed by coupling the fluid flow, heat and mass transfer, and the chemical reaction. The reactive particle-laden flow was simulated, accounting for a multiphase model (solid-gas flow). A discrete phase model based on a Lagrangian approach was developed. The kinetics of the chemical reaction was considered in the specific case of zinc oxide dissociation for which reliable data are available. The complete model predicts temperature and gas velocity distributions, species concentration profiles inside the reactor, particle trajectories and fates, and conversion rate assessing the reaction degree of completion. The reaction extent is highly dependent on temperature of the radiation-absorbing particles. Initial diameter of injected particles is also a key parameter because it determines the available surface area for a given particle mass feed rate. The higher the particle surface area, the higher the conversion rate. As a result, reaction completion can be achieved when particle temperature exceeds 2200 K for a initial particle diameter.     

反胶团酶反应过程开发研究进展

反胶团酶反应具有水相与有机相酶反应的共同优点 ,因而受到人们的重视。制约其实际应用的重要原因在于如何解决酶的重复利用问题。最初人们采用水溶液萃取法回收酶 ,但由于条件苛刻 ,酶活回收率较低。相变法利用温度的改变使体系分相以实现酶的回收 ,操作简便 ,但仍有较大的酶活损失。连续流两相离心反应器可以实现反胶团酶反应的连续操作且酶的损失很小 ,但该反应器传质速率较低因而转化率不高。膜反应器是反胶团酶反应中研究最多也最有应用前途的一种反应器形式。文中介绍了反胶团酶反应中酶重复利用的方法 ,对其过程开发的最新进展进行了综述。     

用多孔金属—SiO2复合膜反应器进行CO水蒸汽变换反应

用自制的多孔金属－ＳｉＯ２复合膜组装成一种新颖的膜反应器，利用ＣＯ变换反应考察该膜反应器的性能实验系统地考察了反应温度，空速、水／气比和只发气流量对ＣＯ转化率的影响。结果表明，在相同的反应条件下，膜反应器的转化率比固定床反应器的转化率提高４－１１％左右，最高可达２０％。     

列管固定床反应器内CO氧化偶联制草酸二甲酯反应模拟及优化

针对列管式固定床反应器中的单根反应管,采用在接近工业条件下获得的CO氧化偶联制草酸二甲酯动力学方程,建立了一维、二维拟均相模型,并与单管实验结果进行了对比,结果表明一维拟均相反应器模型更能准确描述单管反应器内的CO偶联反应。进一步利用一维拟均相模型模拟计算了操作参数对床层热点温度、反应转化率、产物选择性及床层压降的影响,分析了反应器热点温度对操作参数的敏感性。计算结果表明：冷却介质温度对反应管热点温度、亚硝酸甲酯转化率有较大影响,是需要严格控制的工艺指标;较低的空速容易引起反应器飞温;反应器进口压力、原料气进料温度和反应物组成在计算范围内对反应器热点温度影响相对较小。为了提高偶联反应器的负荷和强化床层内的传热效果,可以将进料空速提高至4000 h^-1,同时,可以通过将反应器进口压力增大至500 kPa来降低压缩机能耗。研究结果可为现有列管式CO氧化偶联反应器的改进和工艺优化提供参考。     

A heterogeneous chemical reactor analysis and design laboratory: The kinetics of ammonia decomposition

A laboratory module for senior-level reaction engineering/reactor design students is described. Students use low-conversion experimental data to explore and characterize the kinetics of ammonia decomposition over various supported catalysts at atmospheric pressure in a packed-bed reactor. Each student team is assigned one of four catalyst types, a reactor temperature, and a series of feed flow rates and compositions. Aggregate data from all student groups is then summarily analyzed per catalyst type. In each experimental trial, the reactor conversion is determined by a thermal conductivity measurement applied to the feed (reactor bypass) and reactor effluent gases. An analysis of the reaction rate across a range of temperatures and varying feed gas partial pressures allows students to test various reaction mechanisms, to suggest rate-determining steps, and to statistically determine rate law parameters. Students typically use the Langmuir–Hinshelwood–Hougen–Watson (LHHW) approach to derive rate law expressions, and determine rate constants through application of the Arrhenius equation. High student numbers (ca. 140) are accommodated through the availability of four experimental stations — each sharing a common source of feed gas and equipped with independent flow controllers and gas analyzers.     

The optimization of reactors with decaying catalyst: The effect of macromixing

The following general problem is considered: in a catalytic reactor with uniform temperature and a particular residence-time distribution (RTD), given the kinetics of the reaction and the kinetics of decay of the catalyst activity, how should the temperature be varied with time so that the total conversion over a fixed period of time is maximized? The solution to this problem is presented for reactors with various RTD's, and the effect of macromixing on the optimal policy is discussed. For reactors in segregated flow, with decay rate independent of conversion and a single irreversible reaction, the policy for any RTD is formed from three components: a stationary arc of constant conversion and two constrained arcs at the lower and upper temperature limits. In all but exceptional cases, the policy must end on the upper limit of temperature. By comparing the optimal average conversion in a single CSTR with that obtained by applying the optimal plug-flow policy to the CSTR one can find the maximum loss in conversion to be suffered by using the optimal plug-flow policy in a reactor of arbitrary, perhaps unknown, RTD. This loss was found in a numerical example to be negligible, which suggests that a reactor may be operated almost optimally without knowing its RTD.     

Optimization by distributed control of reactors with decaying catalyst Part I: Non-linear catalyst deactivation

The quasi-steady state optimization of a single tubular fixed bed reactor with a slowly decaying catalyst is considered. The optimal choice of temperature T(z, t) distributed in both the space of the reactor and in chronological time is sought so as to maximize the total amount of reaction in a fixed given period of time. A single irreversible reaction is considered with a rate expressible as a product of separate functions of temperature, activity and conversion. The rate of catalyst decay is also a product of separate functions of temperature and activity but independent of conversion. Upper and lower bounds are placed on the permitted temperature. Theoretical characterization of the optimal policy is obtained using Sirazetdinov and Degtyarev's maximum principle derived for first-order partial differential equations and the influence of the ratio of reaction activation energy to catalyst deactivation energy on the derived optimal policy is indicated. Numerical calculations are presented to illustrate the optimal policies.