Modeling of the Residence Time Distribution and Application of the Continuous Two Impinging Streams Reactor in Liquid‐Liquid Reactions

The two‐phase monosulfonation of toluene, as an example of liquid‐liquid reactions, has been conducted in a continuous two impinging stream reactor (TISR). The extent of reaction under different operating conditions has been determined. A comparison has been made between the performance capability of the TISR and that of continuous stirred tank reactors (CSTR). Under identical conditions, including mean residence time, temperature, feed compositions and phase ratio, the impinging stream reactor has shown a higher efficiency. Finally, a stochastic model, based on Markov chain processes has been developed for the TISR, which describes the flow pattern and the residence time distribution (RTD) within the reaction system. The RTD model, combined with the kinetic expression, has been applied to calculate the conversion of toluene in the reactor. The predicted values for toluene conversion have been compared with those determined experimentally.     

多级串联等体积全混流反应器与平推流反应器等效性研究——以二级可逆反应为例

在多级串联全混流反应器中,在等温等容条件下给出了二级可逆反应第Ⅳ级反应器的出口浓度表达式.讨论了在相同操作条件下,达到平推流反应器的转化率所需要的等体积串联全混流反应器的级数Ⅳ;主要考察了正反应速率常数k1、平衡常数K、反应物初始浓度之比M、停留时间τ等因素对N的影响,得出了N与正反应速率常数k1、相平衡常数K以及停留...     

泰勒流反应器的流动及反应特性

利用由静态混合器、喷嘴和分气盒组成的新型布气装置在搅拌釜式反应器中诱导生成泰勒流,对反应器流动特性及反应特性进行了实验研究。结果表明,与常规搅拌釜式反应器相比,泰勒流反应器内物料流动更加接近于平推流流型,泰勒流的生成在反应器内构建出局部平推流区域,降低了物料返混程度。反应器反应性能因流动特性改变而得以增强,相同实验条件下,在泰勒流反应器中进行的蔗糖水解反应转化率比在常规搅拌釜式反应器中高出26.7%。在一定操作范围内,局部平推流区域和反应转化率均随搅拌转速或进气量的增加而增大。泰勒流反应器可简化为平推流区和全混流区并联的流动模型,推导出了反应转化率与平推流区域占反应器总体积比率之间的关联关系。     

Residence times,micromixing and conversion in an un-premixed feed reactor — II: Chemical reaction measurements

Conversion measurements for a number of second order chemical reactions have been made at the outlet of an un-premixed feed, confined jet reactor, for which residence time data had been previously determined. A variety of stoichiometric and non-stoichiometric mixtures were used for a range of the dimensionless reaction rate constant k_r$\text{c}$₀τ between 0·1 and 18. A stochastic micro-mixing model, involving a single mixing history parameter and the measured residence time distributions, has been shown to correlate the conversion results for a number of different hydrodynamic conditions, in a manner that suggests that prediction of the outcome of other reactions is possible. The computational and experimental techniques involved are adaptable to the design and operation of industrial reactors where interaction of the hydrodynamics and chemical reaction rates are important in determining overall performance.     

Gas-phase residence time distribution in a falling-film microreactor

Industrial-scale performance of gas-liquid reactors can be difficult to optimise for very rapid or highly exothermic reactions. Microstructured reactors for laboratory measurements offer new opportunities for the study of these reactions by enabling precise heat management and fine control of reactor operating conditions. For accurate experimental study, characterisation of the flow conditions within these new reactor devices is essential.The present study examines experimental residence time distributions for the gas phase through a microstructured falling-film reactor, in order to develop an appropriate flow model for further study of gas-phase mass-transfer characteristics in the system. For the gas-phase residence time distribution experiments, the detection system involves a flow of oxygen containing ozone as a tracer gas with continuous monitoring of the concentration by UV-light absorption. The experimental results are used to model the flow behaviour in the gas volume over the gas-liquid contact zone as a series of continuous stirred tank reactors whose number is a simple function of the gas Reynolds number.The experimental results are compared with computational fluid dynamics calculations of the gas flow within the reactor. The comparison indicates a clear correlation of the flow model behaviour with the appearance of recirculation loops in the reaction chamber and the effect of the gas jet at the entrance of the gas-liquid contact zone.     

Refolding of proteins in a CSTR

A model to predict refolding of proteins in a continuous stirred tank reactor (CSTR) was developed and compared to a batch refolding process with simple dilution of the protein in a stirred tank reactor. For experimental verification of the model a continuous refolding of a model protein (α-lactalbumin) was performed in a CSTR. The refolding process of denatured and fully reduced α-lactalbumin could be accurately predicted by a set of differential equations assuming a first order reaction rate for folding and a second order reaction rate for aggregation. The system composed of a CSTR with an additional diafiltration circuit for removal of denaturing agents from the feed solution and to maintain constant refolding conditions. Based on the folding kinetic the dynamic behavior of such a continuous refolding reactor was simulated under different operating conditions. It was shown that the refolding efficiency was higher compared to batch dilution under certain conditions, namely high residence times. The yield of refolded protein could further increased by recycling the outlet stream containing unfolded protein to the reactor entrance.     

Optimization of the Continuous Polycondensation Process for Polyethylene Adipate

A continuous polycondensation process for polyethylene adipate in a bubbling reactive distillation tower with six trays allowed achieving high conversion of carboxyl end groups within short residence times. Influences of different operating conditions including residence time, reaction temperature, pressure, etc. on reactor performance were investigated by experimental and simulation analyses. Optimal conditions for polyethylene adipate continuous polycondensation in the bubbling reactive distillation tower reactor were defined and applied to the process.     

叔丁醇体系中化学酶法催化α-蒎烯环氧化

采用叔丁醇作为α-蒎烯环氧化的反应溶剂,使过氧化氢水溶液和其他疏水性反应底物形成均相,构建单相体系以代替传统有机-水“双相”系统。首先在摇瓶中对单相体系进行优化,在α-蒎烯浓度为0.3mol/L时,乙酸乙酯的最适浓度为3.5mol/L,过氧化氢的最适浓度为0.5mol/L,束酸剂为柠檬酸三钠,在40℃下,反应90min,环氧化转化率为92%,收率为88%。此工艺条件下Novozym435重复使用6次后,仍保持64%的相对活力。然后以摇瓶实验为基础,构建了一种连续搅拌釜式反应器（CSTR）,探索反应器的最适运行条件,测试了其长期运行性能,结果表明：当Novozym435酶量为2.0g、过氧化氢浓度为0.5mol/L、停留时间为3h时,釜式反应器的运行效果最好,其转化率可达83%,收率可达79%,在此条件下反应器连续运行十天后依然可以保持70%以上的转化率和55%以上的收率。     

Aspergillus oryzae Lipase-Catalyzed Synthesis of Dioleoyl; Palmitoyl-Rich Triacylglycerols in Two Reactors

Dioleoyl; palmitoyl‐rich triacylglycerols (OPO‐rich TAG) were synthesized through Aspergillus oryzae lipase (AOL)‐catalyzed acidolysis of palm stearin with commercial oleic acid by a one‐step process in a stirred tank reactor and continuous packed bed reactor to evaluate the feasibility of using immobilized AOL. AOL was found to be valuable for the synthesis of OPO‐rich TAG when compared with commercial lipase from Thermomyces lanuginose (Lipozyme^® TL IM; Novozymes A/S, Bagsvaerd, Denmark). The C52 (triglycerides with a carbon number of 52, stands for OPO, OPL, LPL and their isomers) content of AOL was higher (45.65 %), and the intensity of treatment (IOT: lipase amount × reaction time/TAG amount) of AOL was just 6.25 % of that of Lipozyme^® TL IM under similar reaction conditions in the stirred tank reactor. Response surface methodology were used to optimize the reaction conditions of the AOL‐catalyzed acidolysis is reaction in the packed bed reactor. The optimal point for the set of experimental conditions generated were as follows: residence time 3.0 h; temperature 62.09 °C; substrate molar ratio 7.13 mol/mol. The highest C52 content obtained was 48.60 ± 2.36 %, with 57.46 ± 1.72 % total palmitic acid at the sn‐2 position and 74.21 ± 2.45 % oleic acid at the sn‐1,3 positions. The half‐life of AOL was 24 h in the stirred tank reactor and 140 h in the packed bed reactor. The immobilized AOL achieved similar conversion and selectivity to commercial lipases for the catalyzed synthesis of OPO‐rich TAG and may offer a cheaper alternative.     

Performance characteristics of a cstr containing immobilised enzyme particles

The effects of internal and external substrate diffusion resistances on the performance of a continuous stirred tank reactor are analysed in this work. Both immobilised enzymatic reactions with and without substrate inhibitions are considered. The substrate conversion for the reaction without substrate inhibition is dependent on four dimensionless parameters: the Thiele modulus, the dimensionless Michaelis constant, the mass transfer Nusselt number and β, which represents a combination of particle hold-up, maximum reaction rate, input substrate concentration and substrate residence time in the continuous stirred tank reactor. For the corresponding reaction with substrate inhibition, the effect of the additional dimensionless inhibition constant on the substrate conversion is also very significant. The substrate conversion generally decreases with decrease in dimensionless parameter β, increase in Thiele modulus and decrease in mass transfer Nusselt number. For the reaction with small Thiele modulus, β and strong substrate diffusion resistances, a multireactor system may be needed if a certain desired substrate conversion is required. The single CSTR model can be extended to describe the multireactor system and the effect of the number of reactors on the substrate conversion for a two- or more reactor system is also examined.     

Continuous free-radical polymerization of styrene in the stirred tank reactor. Effect of inhibitors

The influence of inhibitors (p-benzoquinone) on the conversion and the molecular weight distribution (MWD) during free radical polymerization (AIBN) of styrene was examined. A continuous stirred tank reactor (CSTR) was used for the experiments. The concentration of the inhibitor and initiator, the mean residence time and the reaction temperature were modified. The measurement of the residence time distribution (macroscopic mixing) and the estimation of the segregation number showed an ideal mixing behaviour (HCSTR). The conversion and the MWD were calculated. As the results show, it is possible to calculate the reaction in a HCSTR by only using the kinetic constants measured in discontinuous runs.     

Le rendement de deux réservoirs agités en série avec alimentation séparée,basé sur la cinétique de monod

The performance of a bioreactor composed of two chemostats in series can be affected significantly by the split of feed into two, one for each chemostat, for reactions following Monod kinetics. Under certain operating conditions, split of feed can be greatly beneficial to the reactor performance. Optimization of performance is discussed; a general criterion is presented, applicable to either the maximization of overall conversion for a given total residence time or the minimization of total residence time for a given overall conversion. The maximization of overall conversion has also been studied with respect to the feed-split ratio. The dimensionless Michaelis-Menten constant is a very important parameter in the selection of optimal operating conditions.     

Dehydration of ortho-boric acid in a three-phase bubble column reactor operating at low pressure

This study investigates the applicability of the bubble column as a reactor to perform the dehydration of ortho-boric acid efficiently and economically. The effects of operating conditions such as reaction time, temperature, gas flow rate, particle size and solid content in the slurry phase on the fractional conversion of the reaction have been determined, and the performance of the three-phase bubble column reactor operating at low pressure (92 kPa) has been discussed. It can be noted from this study that the reaction time has been reduced and the particle size and solid content which are required in the slurry phase for favourable fractional conversion have been increased in the bubble column reactor in comparison with those in the continuous stirred tank reactor. The reaction could be described by means of a fluid–solid heterogeneous reaction model.     

Micromixing effects on a parallel reaction in flow reactors

Using the micromixing concepts of Danckwerts and Zwietering, the Peclet number Pe has been correlated mathematically to the degree of segregation J for the axial dispersion model. The results were applied to compare the micromixing effects on a model, mixed-order parallel reaction system in continuous flow reactors. Axial dispersion model, and Ng and Rippin's two-environment model were used to find the micromixing effects in tubular and stirred tank reactors, respectively. The performance of these reactors, with varying geometries, has been evaluated in terms of overall conversion, selectivity, and yield under identical operating and reaction conditions. The overall conversion increases in a tubular reactor with the increase in J, irrespective of the kinetic orders. However, in a stirred tank reactor, the conversion is found to be micromixing-sensitive, depending on the order of reaction. For m = 1 and n = 2 (case 1), the conversion is fairly insensitive to micromixing effects while it decreases for m = 0.5 and n = 1 (case 2) with increasing J. For the same extent of micromixing, a tubular reactor gives, in both cases, a higher conversion than a stirred tank reactor. The selectivity, in either case, decreases in both reactors with increasing segregation effects. However, in each case, the selectivity of a tubular reactor was fairly close to that of a stirred tank reactor at the same value of J. As far as the yield is concerned, both reactors achieve nearly the same value, without significant micromixing effects.     

The effects of modes of hydrogen input and reactor configuration on reaction rate and H2 efficiency in the catalytic hydrogenation of alkynol to alkenol

Hydrogenation often involves three phases where hydrogen-on-demand is the typical mode of operation in industrial scale reactors. In research labs and publications, however, continuous hydrogen flow has been used. This paper investigates the effect of such modes of operation on reaction rate using a selective hydrogenation of 3-butyn-2-ol over Pd/Al₂O₃ to obtain 3-buten-2-ol as the model reaction. The two modes of operation were first tested in a commercial PARR stirred tank reactor and then repeated in an oscillatory baffled reactor (OBR) in order to validate the experimental results. Our investigation demonstrates that an enhanced reaction performance and 10 times better H₂ efficiency were obtained when the pressure was maintained constant during the reaction by feeding gas as required, ie hydrogen-on-demand mode. The method of a continuous flow of hydrogen in hydrogenation means that excess hydrogen is vented out when operating at ambient pressures or builds up at elevated pressures. Our work also enables a comparison of reactor designs on reactor performance, and three times higher H₂ efficiency and 2.3 times shorter residence time were achieved when using the OBR instead of the PARR due to its enhanced and uniform mixing, regardless of the mode of operation.     

撞击流气化炉内颗粒停留时间分布的随机模拟

根据多喷嘴对置式气化炉流场测试,将气化炉划分为若干区域,运用时间离散、状态离散的马尔可夫链随机模型,模拟了气化炉内颗粒相的停留时间分布(RTD)。当颗粒在撞击区和射流区间的回流比为0.5,向下撞击流股区和管流区为平推流模型,其他区域按全混流模型处理时,模拟值与实验值吻合较好。随着进料流量的增大,平均停留时间减小,量纲1方差减小;随着回流比的增加,平均停留时间增大;气固两相平均停留时间接近,但RTD存在一定差异。     

Facile and Rapid Synthesis of Neopentyl Glycol in a Continuous-Flow Microreactor

Neopentyl glycol (NPG) synthesis by condensation disproportionation of formaldehyde and isobutyraldehyde (IBD) with sodium hydroxide as catalyst was studied in a continuous-flow microreactor under various experimental conditions, such as reaction temperature, residence time, and the molar ratio of reactants. All the conditions were determined by Box-Behnken experimental design and the response surface method based on the preferred range selected by single-factor experiments. For comparison, NPG was synthesized by condensation disproportionation of the same reactants in a batch reactor. The results showed that higher NPG yield and shorter residence time were achieved in a continuous-flow microreactor than in a batch reactor when the other experimental conditions were similar.     

Glycerolysis of Fatty Acid Methyl Esters: 2. Simulation and Experiments in Continuous Reactors

The glycerolysis of methyl ester was investigated in flow reactors. This reaction represents a liquid two-phase reaction with changing reaction rates in a batch reactor. A semi-empirical model tested earlier with batch reactor data was used to simulate different continuous processes for this reaction. Among the processes simulated, a single continuous-flow stirred tank reactor (CSTR) without recycling was considered most appropriate for experimental implementation, although simulations showed that a faster reaction rate is possible with the application of a CSTR followed by a tubular reactor with certain associated residence times. The CSTR simulations were verified experimentally. A good agreement was found between the experimental data and simulation results.     

凹凸棒石镍基催化剂对污泥气化焦油催化裂解的特性分析

以凹凸棒石为催化剂载体,采用等体积浸渍法制备了多种镍基催化剂,并对催化剂进行了XRD、SEM、BET、EDS等特性分析。在固定床反应器中对催化剂催化裂解污泥气化焦油模型化合物的特性进行了实验研究。考察了反应温度、水碳比（S/C）、气相停留时间、助剂等因素对模型化合物催化裂解特性的影响。结果表明,提高反应温度、增加S/C、延长停留时间、添加助剂均能提高催化剂的催化活性,模型化合物转化率明显增加。但是助剂含量过高反而导致催化剂催化裂解的能力减弱,模型化合物转化率下降。对比Fe、Ce、Cu、Ca 4种助剂发现,在实验范围内,增加Fe的含量,模型化合物转化率上升。当Ce、Cu、Ca助剂质量分数达到3%及以上时,转化率下降明显,甚至低于未添加助剂时的转化率。     

管式搅拌反应器中流动特性实验及模型研究

为进一步研究带机械搅拌装置的新型管式反应器内流动特性,采用刺激-响应技术,测定流体在不同操作条件下的停留时间分布(RTD)曲线并与无搅拌停留时间分布曲线作对比,计算了平均停留时间分布的统计特征值。用混合时间表征混合特性,用Peclet操作准数表征轴向扩散特性。结果表明,适当增大转速、流量或降低水位,都有利于反应器内流体的均匀混合。大体上随流量的减少和液位的升高停留时间有延长的趋势,转速变化对停留时间的影响不显著。在搅拌转速不超过400 r/min时,混合时间随着搅拌转速的增大而缩短。在实验范围内,反应器相当于3个串联全混槽反应器。