Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

Operation of Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl wire mesh honeycomb catalytic modules in diesel steam and autothermal reforming

The Rh/Ce_0·75Zr_0·25O_2–δ-ƞ-Al₂O₃/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h⁻¹. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h⁻¹), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h⁻¹. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h⁻¹. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H₂, CO, CO₂), the reaction should be carried out at GHSV = 20,000 h⁻¹. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.     

A tool for mass transfer evaluation in packed-bed columns for chemical engineering students

This paper presents a Microsoft Excel tool to calculate liquid-gas mass transfer coefficients in packed towers to support numerical design activities in the courses of Unit Operations for Industrial Process and Sustainable Process Design for the Master’s degree in Chemical Engineering of the University of Naples Federico II (Italy).The Mass Transfer Solver Tool (MT Solver Tool) uses several available models to estimate, separately, the values of liquid and gas mass-transfer coefficients and the wet surface area for 144 random and structured packings of interest for absorption/stripping and distillation processes. In addition, a separate spreadsheet can be used in a user-defined mode, to evaluate the mass transfer coefficients with new packing types or to interpret experimental data when the geometrical and physical characteristics of the packing are known. Eventually, the tool is supplied with a data library, where packing geometry and model fitting parameters can be retrieved.The software is aimed to support students and educators in the Unit Operations for Industrial Process and Sustainable Process Design courses. In particular, this is meant to be an example on how the accuracy of design algorithms adopted in unit operation processes is affected by the use of the underpinning correlations for mass transfer rate or pressure drops. Besides, this is aimed to encourage comparison of different correlations when exact field data are not available. Besides, chemical engineers and researchers interested in packed columns design and modelling data may also benefit from the utilization of the software. The MT Solver Tool was introduced to students in a dedicated tutorial lesson after lecturers on packed column design algorithms for distillation, absorption and stripping. Most of the students of the course participated to a group training aimed to simulate the design of an absorption column supported by the MT Solver Tool providing feedback on its application.After the training, an anonymous survey was proposed to the students to monitor the approval rating of the proposed activity and the use of the MT Solver Tool software to support numerical calculations.     

基于结构化遮挡编码和极限学习机的局部遮挡人脸识别

提出使用结构化遮挡编码（SOC）结合极限学习机（ELM）的算法来处理人脸识别中的遮挡问题。首先，使用SOC去除图像上的遮挡物，将遮挡物体与人脸分离开；同时，通过局部性约束字典（LCD）来估计遮挡物的位置，建立遮挡字典和人脸字典。然后，将建立好的人脸字典矩阵进行归一化处理，并利用ELM对归一化的数据进行分类识别。最后，在AR人脸库上进行的仿真实验结果表明，所提方法对不同遮挡物和不同区域遮挡的图像具有较好的识别率和鲁棒性。     

Determining most effective structural form of nickel-cobalt catalysts for dry reforming of methane

In this study, catalytic activity of carbon dioxide reforming of methane was investigated over nickel-cobalt catalysts in various structural forms. Catalytic activity tests were performed at the temperatures of 600–800 °C in a micro-flow quartz reactor. SEM-EDX, XRD and XPS studies were also performed to understand the surface morphology of the catalysts. The results showed that 8 wt%Ni-2wt.%Co on wash-coated MgO over monolithic structure led to highest catalytic performances with CH₄ and CO₂ conversions of 83% and 89% respectively as well as H₂/CO ratio of 0.95 at 750 °C. SEM-EDX and XPS results of catalyst spent at 750 °C also showed considerable amount of coke formation; however, the use of 3% oxygen in the feed suppressed the coke formation significantly. The catalyst was stable for 48 h in the presence of O₂ (3%) added feed at the temperature of 750 °C.     

Critical state model for structured soil

Structure is an evident determinant for macroscopic behaviors of soils. However, this is not taken into account in most constitutive models, as structure is a rather complex issue in models. For this, it is important to develop and implement simple models that can reflect this important aspect of soil behavior. This paper tried to model structured soils based on well-established concepts, such as critical state and sub-loading. Critical state is the core of the classic Cam Clay model. The sub-loading concept implies adoption of an inner (sub-loading) yield surface, according to specific hardening rules for some internal strain-like state variables. Nakai and co-workers proposed such internal variables for controlling density (ρ) and structure (ω), using a modified stress space, called t_ij. Herein, similar variables are used in the context of the better-known invariants (p and q) of the Cam Clay model. This change requires explicit adoption of a non-associated flow rule for the sub-loading surface. This is accomplished by modifying the dilatancy ratio of the Cam Clay model, as a function of the new internal variables. These modifications are described and implemented under three-dimensional (3D) conditions. The model is then applied to simulating laboratory tests under different stress paths and the results are compared to experiments reported for different types of structured soils. The good agreements show the capacity and potential of the proposed model.     

Comparative study of gasoline,diesel and biodiesel autothermal reforming over Rh-based FeCrAl-supported composite catalyst

Catalytic autothermal reforming (ATR) of a number of hydrocarbon fuels was studied over composite RhCZ-S catalyst (0.24 wt% Rh supported on structured Ce_0.75Zr_0.25O_2-δ-ƞ-Al₂O₃/FeCrAl carrier). Iso-octane and n-hexadecane as model compounds of gasoline and diesel fuel, respectively, showed similar properties in ATR process, indicating weak influence of molecular weight and branching degree of liquid alkanes on catalyst performance. Biodiesel ATR characteristics were similar to those of n-hexadecane ATR, as the utilized biodiesel predominantly contained alkanes, being products of fatty acid tail fragments hydrogenation. Even in the case of gasoline ATR, sufficient amount of monoaromatics did not influence a lot on the catalyst performance. Diesel ATR showed rather different situation: the catalyst tended to lose activity due to coking, and incomplete fuel conversion was observed. Analysis of unreacted fuel revealed bi- and polyaromatic compounds (mainly naphtalenes and antracenes) were difficult to convert.     

Adaptive robust control of fully-constrained cable driven parallel robots

In this paper, adaptive robust control (ARC) of fully-constrained cable driven parallel robots is studied in detail. Since kinematic and dynamic models of the robot are partly structurally unknown in practice, in this paper an adaptive robust sliding mode controller is proposed based on the adaptation of the upper bound of the uncertainties. This approach does not require pre-knowledge of the uncertainties upper bounds and linear regression form of kinematic and dynamic models. Moreover, to ensure that all cables remain in tension, proposed control algorithm benefit the internal force concept in its structure. The proposed controller not only keeps all cables under tension for the whole workspace of the robot, it is chattering-free, computationally simple and it does not require measurement of the end-effector acceleration. The stability of the closed-loop system with proposed control algorithm is analyzed through Lyapunov second method and it is shown that the tracking error will remain uniformly ultimately bounded (UUB). Finally, the effectiveness of the proposed control algorithm is examined through some experiments on a planar cable driven parallel robot and it is shown that the proposed controller is able to provide suitable tracking performance in practice.     

Multisensor data fusion via Gaussian process models for dimensional and geometric verification

An increasing amount of commercial measurement instruments implementing a wide range of measurement technologies is rapidly becoming available for dimensional and geometric verification. Multiple solutions are often acquired within the shop-floor with the aim of providing alternatives to cover a wider array of measurement needs, thus overcoming the limitations of individual instruments and technologies.In such scenarios, multisensor data fusion aims at going one step further by seeking original and different ways to analyze and combine multiple measurement datasets taken from the same measurand, in order to produce synergistic effects and ultimately obtain overall better measurement results.In this work an original approach to multisensor data fusion is presented, based on the development of Gaussian process models (the technique also known as kriging), starting from point sets acquired from multiple instruments. The approach is illustrated and validated through the application to a simulated test case and two real-life industrial metrology scenarios involving structured light scanners and coordinate measurement machines.The results show that not only the proposed approach allows for obtaining final measurement results whose metrological quality transcends that of the original single-sensor datasets, but also it allows to better characterize metrological performance and potential sources of measurement error originated from within each individual sensor.     

Ultracompact methane steam reforming reactor based on microwaves susceptible structured catalysts for distributed hydrogen production

Hydrogen is a potential green energy vector. Since the heating of the reforming processes commonly used for its production is obtained by burning hydrocarbons, it has a substantial CO₂ footprint. One of the most critical aspects in the methane steam reforming (MSR) reaction is the heat transfer to the catalytic volume, due to the high heat fluxes required to obtain high methane conversions. Consequently, the reactor has complex geometries, along with the heating medium being characterized by temperatures higher than 1000 °C; expensive construction materials and high reaction volumes are therefore needed, resulting in slow thermal transients. These aspects increase the costs (both operative and fixed) as well as cause a decrease in the whole process efficiency. The heat transfer limitations due to the endothermicity of methane steam reforming reaction could be effectively overcome by microwave (MW) heating. This heating technique, that depends only on the dielectric properties of the materials, can result in an efficient and faster method for transferring heat directly to the catalyst, thus generating the heat directly inside the catalytic volume. In this work, Ni-based catalysts, differing from each other by the Ni loading (7 and 15 wt% with respect to the washcoat) were prepared. The catalysts were characterized by means of several techniques and tested in the MW-assisted methane steam reforming reaction. Furthermore, the energy balance of the entire process was performed to calculate the energy efficiency, making a preliminary evaluation of its feasibility in distributed hydrogen production also possible. The results of the preliminary tests showed that the prepared structured catalysts are very susceptible to the MW radiation, and that in the presence of the MSR reaction, it is possible to make the system reach a temperature of 900 °C. In the same tests, the CH₄ conversion showed a good approach to the thermodynamic equilibrium values starting at temperatures of about 800 °C at a value of gas hourly space velocity (GHSV) of about 5000 h^?1. The energy efficiency of the lab-scale system, calculated as the ratio among the energy absorbed by the system and the energy supplied by the microwaves, was about 50%. Future studies will deal with the microwave reactor optimization, aiming at the increase of the energy efficiency of the system, as well as to obtain a higher CH₄ conversion at lower temperatures and increase the H₂ yield and selectivity.