Gas–liquid mass transfer in periodically operated trickle-bed reactors: Influence of the liquid-phase physical properties and flow modulation

The influence of periodic operation on trickle-bed reactor (TBR) hydrodynamics and gas–liquid mass transfer was investigated. Two-phase pressure drop, dynamic liquid hold-up and gas–liquid mass transfer coefficient (k_La) were determined at various liquid flow rates and for different modes of liquid flow variation (increasing and decreasing liquid flow rate). The results reveal the considerable influence of type of liquid flow rate modulation on k_La values (deviations of up to 80% in k_La). Simulation studies on gas-limited reaction in a periodically operated TBR indicate that an enhancement in conversion of about 14% can be expected from an appropriate selection of the operating mode, thus clearly demonstrating the quantitative process intensification feasible through increased gas–liquid mass transfer.     

微管内环己烷氧化反应研究进展

介绍了微管反应器和微管内环己烷氧化反应的特点;详述了微管内环己烷无催化氧化的反应工艺、微管内气液流动情况、反应机理以及微管内壁负载催化剂的环己烷催化氧化反应工艺;指出无催化及内壁涂覆催化剂的微管内环己烷氧化反应在改善反应的安全性、强化气液传质效果和提高催化性能等方面具有较大优势,微管内壁负载纳米金催化剂的反应器形式在环己烷氧化反应中前景看好。     

Interfacial area and mass transfer in carbon dioxide absorption in TEA aqueous solutions in a bubble column reactor

The hydrodynamic behaviour and mass transfer of carbon dioxide removal process by aqueous solutions of triethanolamine (TEA) are analysed. The experiments were made in a bubble column reactor (BCR) as gas–liquid contactor. The interfacial area and mass transfer coefficient were calculated by using a photographic method based on the bubble diameter determination. The influence of operation conditions, liquid phase nature and chemical reaction on the mass transfer coefficient and gas–liquid interfacial area has been also analysed.     

Effects of surface active agents on hydrodynamics and mass transfer characteristics in a split-cylinder airlift bioreactor with packed bed

The effects of three types of surface active agents (containing SDS, HCTBr and Tween 40) with various concentrations (0–5 ppm) on the hydrodynamic and oxygen mass transfer characteristics in a split-cylinder airlift bioreactor with and without packing were investigated. It was observed that in the surfactant solutions, surface tension of the liquid decreased and smaller bubbles were produced in comparison with pure water. So, surfactants presence strongly enhanced mixing time and gas hold-up although oxygen mass transfer coefficient and the liquid circulation velocity reduced. Furthermore, the packing installation enhanced the overall gas–liquid volumetric mass transfer coefficient by increasing flow turbulency and Reynolds number compared to an unpacked column. The packing increased gas hold-up and decreased bubbles size and liquid circulation velocity.     

Mathematical modeling and simulation for gas–liquid reactors

Gas–liquid reactors are widely used in many industrial processes such as oxidation, hydroformylation, chlorination, etc. The paper develops comprehensive model for reactors using the mixing cell approach. It incorporates heat and mass transfer effects in the film and uses a boundary element method to solve the film model equations. The fluxes obtained at the interface are then directly used as the link to the reactor model. Simple isothermal and non-isothermal reactions were numerically tested. Application to two industrially important case studies, chlorination of butanoic acid and oxidation of cyclohexane are briefly illustrated. For the autocatalytic chlorination of butanoic acid, the yield of desired product, monochlorobutanoic acid, is favored by the high degree of mixing in the liquid phase. Therefore, this reaction should be carried out in a CSTR. A series of five bubble tanks with parallel gas reactant feed for cyclohexane oxidation was also simulated. It was found that the cyclohexane conversion is low while the oxygen conversion is relatively high and almost constant in each tank. Due to the complex multistep nature of this reaction scheme, oxygen is consumed in many steps of oxidation and selectivity of main products (which are intermediate products in the reaction scheme) depends on the critical control of over-oxidation in the kinetic mechanism.     

环己烷液相氧化工艺研究进展

介绍了近年来环己烷液相空气均相和非均相催化氧化、光诱导催化氧化、无催化氧化、纯氧氧化等的研究进展 ,并对今后的研究发展方向进行了分析。     

环己烷富氧氧化反应器内液相空间危险性分析

通过冷模实验对环己烷富氧氧化反应器内液相空间危险性进行分析,测试了液相空间气泡危险性。结果表明:环己烷富氧氧化(氧气体积分数大于30.0%)反应时,液相气泡的危险性比空气氧化的危险性大;在空气氧化和富氧氧化(氧气体积分数小于50.4%)工艺条件下,均未观察到气泡经点火后引起反应器体系内压力升高的现象,液相气体内反应均无燃爆危险。     

Tuning millisecond chemical reactors for the catalytic partial oxidation of cyclohexane

It is demonstrated that millisecond partial oxidation of cyclohexane can be tuned by varying the catalyst and operating conditions to generate product distributions that favor (1) oxygenates, (2) olefins, or (3) syngas (H₂ and CO). High selectivities to parent oxygenates require low conversions using low-temperature catalysts, such as Ag or Co. Olefins are favored by Pt or Pt-Sn and H₂ addition eliminates the production of CO and CO₂, thereby increasing olefin selectivities. For syngas, Rh is the catalyst of choice. Finally, a Pt-10% Rh single gauze gives high selectivities to both oxygenates and olefins.Conventional methods for the partial oxidation of cyclohexane are liquid-phase processes that are plagued by poor conversions, high recycle costs, long residence times (minutes to hours), and expensive catalysts. In contrast, with a cyclohexane–oxygen feed at C₆H₁₂/O₂=2, a Pt-10% Rh single gauze catalyst can give total selectivities exceeding 80% to oxygenates and olefins at 25% cyclohexane conversion and complete oxygen conversion. The products consist of nearly 60% selectivity to the C₆ products, cyclohexene and 5-hexenal. The temperature profile attained in the single-gauze reactor allows the preservation of these highly non-equilibrium products.Alternative catalysts for cyclohexane oxidation to oxygenates and olefins include α-alumina monoliths coated with Pt, Rh, Pt-Rh, Pt-Sn, Co, Mo or Ag. The Co, Mo and Ag catalysts give very high selectivities to C₆ oxygenates but are hindered by poor conversions (<5%) of both cyclohexane and oxygen at these millisecond contact times. H₂ addition to cyclohexane oxidation feed mixtures over Pt and Pt-Sn is shown to significantly increase the selectivities to C₆ olefins while reducing the formation of CO and CO₂.Cyclohexane oxidation in air over Rh monoliths enables the production of high yields (>95%) of syngas. This process could find applications in the automotive industry as the production of hydrogen from liquid fuels becomes important.     

Tomographic measurement of liquid hold up and effective interfacial area distributions in a column packed with high performance structured packings

In this paper, we report on the use of a high energy and high resolution X-ray tomograph to visualize and quantify the distribution of liquid hold up and of gas–liquid interfacial area in a 0.1 m diameter column filled with MellapakPlus 752.Y packing elements. A standard air–water system at room temperature and atmospheric pressure were used. Tomographic measurements have been carried out in a large number of packing cross sections situated at different heights between the top and the bottom of the packed column, giving access to the evolution of axial profiles of liquid hold up and of gas–liquid interfacial area as a function of the operating conditions. Gas–liquid interfacial area values were also measured by a chemical method (CO₂ absorption from air into a caustic solution). For the first time, a whole set of gas–liquid interfacial area values evaluated from tomographic images are interestingly compared with values measured by a chemical method. A comparison is also presented with literature models.     

Transient gas–liquid mass transfer model for thin liquid films on structured solid packings

This paper describes a model for gas–liquid mass transfer through thin liquid films present on structured packings for gas–liquid operations under dispersed gas flow regime. The model has been derived for two cases: the absorption (or desorption) of a gaseous component into the liquid film and the transfer of the gaseous component through the liquid film to the packing surface where an infinitely fast reaction takes place. These cases have been solved for three bubble geometries: rectangular, cylindrical, and spherical. For Fourier numbers below 0.3, the model corresponds to Higbie’s penetration theory for both cases. The Sherwood numbers for cylindrical and spherical bubbles are 20% and 35% higher, respectively, than for rectangular bubbles. In case of absorption and Fourier numbers exceeding 3, the effect of bubble geometry becomes more pronounced. The Sherwood numbers for cylindrical and spherical bubbles now are 55% and 100% higher, respectively, than for rectangular bubbles. In case of an infinitely fast reaction at the packing surface, the Sherwood number corresponds to Whitman’s film theory (Sh=1$Sh=1$) for all bubble geometries. In this paper also practical approximations to the derived Sherwood numbers are presented. The approximations for both cases and all bubble geometries describe all the model data within an error of 4%. The application of the model has been demonstrated for three examples: (1) gas–liquid mass transfer for a structured packing; (2) gas–liquid mass transfer in a microchannel operated with annular flow; (3) gas–liquid mass transfer in a microchannel with Taylor flow.     

GC-MS测定环己烷氧化液中有机酸和酯的含量

采用气相色谱-质谱联用法(GC-MS)测定环己烷氧化液中的有机酸和有机酯的含量。在GC-MS分析条件下环己烷氧化液直接进样,通过毛细管柱DB-1701,60 m×0.15 mm×0.25μm分离,由电子轰击源选择离子监测模式下进行检测。结果表明:有机酸和有机酯的标准曲线相关系数大于0.98,相对标准偏差均小于7.0%,回收率为94.9%～98.6%。     

Gas–liquid and liquid–liquid mass transfer in microstructured reactors

This article is a comprehensive overview of gas–liquid and liquid–liquid mass transfer in microstructured reactors (MSR). MSR are known to offer high heat and mass transfer rates for two phase systems due to high surface to volume ratio as compared to conventional reactors. The reactions with fast kinetics controlled by mass transfer have been successfully intensified using MSR. The first part of the review deals with the methods of mass transfer characterization. Further, different dimensionless parameters used to analyze mass transfer in MSR are discussed. The literature data with different flow regimes and proposed empirical correlations for both gas–liquid and liquid–liquid systems is also presented. The conventional mass transfer models such as penetration and film theory are analyzed. Finally, the important issues of mass transfer in MSR are summed up.     

Kinetic Modeling of Liquid Phase Oxidation of Cyclohexane

A kinetic model for the liquid phase oxidation (LPO) of cyclohexane has been derived using a reaction network based on a consistent free radical mechanism. It was demonstrated that on embedding this rate model within the overall model of a semi‐batch gas‐liquid reactor (SBR) one can predict the time variation of the dissolved oxygen concentration and the rate of oxygen absorption which compare fairly closely with some well regarded published experimental data. The model is distinguished by easy extendibility and modularity whereby it could be tailored to predict, in the context of a SBR, cyclohexane conversion and ketone‐alcohol (K‐A) product selectivity levels as observed in commercial plants and in the published data on pilot plant experimentation. The model is expected to be of use in the design and scale‐up of LPO reactors.     

Room temperature photocatalytic oxidation of liquid cyclohexane into cyclohexanone over neat and modified TiO2

The oxidation of liquid cyclohexane by O₂ over UV-illuminated TiO₂ at room temperature has been studied in a static slurry reactor. From the effects of the mass of catalyst, the temperature, the radiant flux, the concentration of C₆H₁₂ (using acetonitrile as a solvent), it is concluded that the reaction is photocatalytic. Using mainly the 365 nm-ray of a mercury-lamp, an initial quantum yield of 0.1 is found for pure cyclohexane and radiant fluxes < ca.5mWcm^–2 (6×10¹⁵ photons s^–1 cm^–2). A high selectivity to cyclohexanone is observed (83%), the other products being cyclohexanol (5%) and CO₂ (12%). The low amount of cyclohexanol is explained by the higher rate of oxidation of this alcohol compared to that of cyclohexane. Smaller oxidation rates are observed when TiO₂ is loaded with 0.5 to 10 wt%Pt and the cyclohexanone/cyclohexanol ratio decreases to ca. 4. Finally, the C₆H₁₂ oxidation has been employed as a test reaction to confirm the detrimental effect of the doping with several tri or pentavalent cations upon the photocatalytic activity of TiO₂.     

Investigations on hydrodynamics and mass transfer in gas–liquid stirred reactor using computational fluid dynamics

In this work, the hydrodynamics and mass transfer in a gas–liquid dual turbine stirred tank reactor are investigated using multiphase computational fluid dynamics coupled with population balance method (CFD–PBM). A steady state method of multiple frame of reference (MFR) approach is used to model the impeller and tank regions. The population balance for bubbles is considered using both homogeneous and inhomogeneous polydispersed flow (MUSIG) equations to account for bubble size distribution due to breakup and coalescence of bubbles. The gas–liquid mass transfer is implemented simultaneously along with the hydrodynamic simulation and the mass transfer coefficient is obtained theoretically using the equation based on the various approaches like penetration theory, slip velocity, eddy cell model and rigid based model. The CFD model predictions of local hydrodynamic parameters such as gas holdup, Sauter mean bubble diameter and interfacial area as well as averaged quantities of hydrodynamic and mass transfer parameters for different mass transfer theoretical models are compared with the reported experimental data of [Alves et al., 2002a] and [Alves et al., 2002b] . The predicted hydrodynamic and mass transfer parameters are in reasonable agreement with the experimental data.     

Effective interfacial area for mass transfer in the liquid–liquid slug flow capillary microreactors

Liquid–liquid biphasic reactions play an important role in the chemical and pharmaceutical industries. The liquid–liquid slug flow capillary microreactor offers considerable potential benefits over the conventional liquid–liquid contactors. Though the hydrodynamics and mass transfer have been investigated for this reactor concept, so far the effective interfacial area available for mass transfer has not been experimentally quantified. Despite the well-defined flow patterns arising in the capillary microreactor, the wetting behaviour of the liquids at the capillary wall is inadequately integrated into the models and thus, the true interfacial area being used for mass transfer is uncertain.     

Uncatalyzed selective oxidation of liquid cyclohexane with air in a microcapillary reactor

The uncatalyzed selective oxidation of cyclohexane with air was performed at high-p,T-conditions in a microcapillary reactor. Operation pressures were between 2.0 and 8.0 MPa and operating temperatures between 453 and 533 K. The measured space-time-yield showed only a slight dependence on the pressure, but a strong dependence on temperature. At 533 K, a space-time-yield of about 6.000 kg/(m³ h) was reached, which corresponds to a size of 2 m×2 m×2 m (8 m³) of the microstructured reactor assuming a capacity of 100.000 t/a compared to 500 m³ total reactor volume realized with a cascade of bubble columns of each about 100 m³. Unfortunately, selectivity drops at this temperature below 80% which is significantly lower than the selectivity in the conventional process. Passivating the capillary walls with silicon allowed an increase in selectivity. By fitting a simple mass transfer/reaction model for molecular oxygen, the mass transfer coefficient could be determined for T=453 K and a 0.75 mm capillary as k_L=3.04×10^?3 m/s. With the help of the Hatta number, mass transfer limitations can be excluded for the microcapillary reactor, whereas the bubble column reactor is weakly limited by the gas/liquid mass transfer of the molecular oxygen. Thus, process intensification by enhancing mass transfer using a microstructured reactor for cyclohexane oxidation with air is quite low.     

Hydrodynamics and mass transfer study of aliphatic alcohols in airlift reactors

Gas holdup and gas–liquid mass transfer coefficient were considered in an external airlift reactor. Air was sparged through some aliphatic alcohols (methanol, ethanol, n-propanol, and n-butanol) with different concentrations (0–1%, v/v). It was observed that gas holdup and mass transfer coefficient increased with increasing the number of carbons in alcohols. Furthermore, an increment in alcohols concentration increased gas holdup and mass transfer coefficient. The same behavior was observed in external and internal loop airlift reactors although gas holdup and mass transfer coefficient values were less than those of internal airlift reactor. According to the experiments, two correlations for gas holdup and mass transfer were developed.     

Liquid-phase oxidation of cyclohexane using Co-P-MCM-41 catalyst

Co-P-MCM-41 catalyst was prepared by introduction of cobalt nitrate and phosphoric acid during gel-preparation for the synthesis of MCM-41. The catalyst, which was found to have very high surface area (995 m²/g), was tested for the one step liquid oxidation of cyclohexane to adipic acid using a semi-batch autoclave reactor (without addition of any promoter and solvent) at 115°C and in a flow of 5 bar of oxygen. The effect of the amount of catalyst on the induction time, catalytic conversion of cyclohexane, and selectivity to adipic acid was investigated. Depending on the amount of catalysts used in the reaction (from 0.1 to 3.0 g), an induction period from about 100 min to less than 10 min, cyclohexane conversion from 30 to 99%, and a selectivity to adipic acid from 15 to 40 %, could be achieved using Co-P-MCM-41 as the catalyst.     

环己烷仿生催化氧化产物及杂质浅析

对环己烷仿生催化氧化产物与无催化氧化产物进行了分析,对氧化液中各组分的比例和烷四釜中各杂质的含量进行了对比。结果表明:与环己烷无催化氧化相比,仿生催化氧化环己烷转化率高,产物中醇、酮、酸、酯含量高,过氧化物含量降低;烷四釜中杂质种类相同,各组分的含量不同,其杂质总量约为无催化氧化的1．5倍,杂质可在精馏过程中分离。