Integrated Photothermal Nanoreactors for Effi cient Hydrogenation of CO_(2)

To alleviate the energy crisis and global warming,photothermal catalysis is an attractive way to effi ciently convert CO_(2)and renewable H_(2) into value-added fuels and chemicals.However,the catalytic performance is usually restricted by the trade-off between the dispersity and light absorption property of metal catalysts.Here we demonstrate a simple SiO 2-protected metal-organic framework pyrolysis strategy to fabricate a new type of integrated photothermal nanoreactor with a comparatively high metal loading,dispersity,and stability.The core-satellite structured Co@SiO_(2)exhibits strong sunlight-absorptive abil-ity and excellent catalytic activity in CO_(2)hydrogenation,which is ascribed to the functional separation of diff erent sizes of Co nanoparticles.Large-sized plasmonic Co nanoparticles are mainly responsible for the light absorption and conversion to heat(nanoheaters),whereas small-sized Co nanoparticles with high intrinsic activities are responsible for the catalysis(nanoreactors).This study provides a new concept for designing effi cient photothermal catalytic materials.

Preparation of Pd/c-Al_(2)O_(3)/nickel foam monolithic catalyst and its performance for selective hydrogenation in a rotating packed bed reactor

Selective hydrogenation plays an important role in chemical industries,yet its selectivity is usually limited by the mass transfer.In this work,the enhanced hydrogenation selectivity was achieved in a rotating packed bed(RPB)reactor with excellent mass transfer efficiency.Aiming to be used under the centrifugal filed,a monolithic catalyst Pd/c-Al_(2)O_(3)/nickel foam suiting for the shape and size of the rotor of RPB reactor was prepared by the electrophoretic deposition method.The mechanical strength of the catalyst can meet the requirement of high centrifugal force in the RPB.The hydrogenation selectivity in the RPB reactor using the 3-methyl-1-pentyn-3-ol hydrogenation system was 3–8 times higher than that in a stirred tank reactor under similar conditions.This work proves the feasibility of intensifying the selectivity of hydrogenation process in the RPB reactor.

Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

Development of CONTHAC-3D and hydrogen distribution analysis of HPR1000

An in-house code,CONTHAC-3D,was developed to calculate and analyze thermal-hydraulic phenomena in containments during severe accidents.CONTHAC-3D is a three-dimensional computational fluid dynamics code that can be applied to predict gas flow,diffusion,and steam condensation in a containment during a severe hypothetical accident,as well as to obtain an estimate of the local hydrogen concentration in various zones of the containment.CONTHAC-3D was developed using multiple models to simulate the features of the proprietary systems and equipment of HPR1000 and ACP100,such as the passive cooling system,passive autocatalytic recombiners and the passive air cooling system.To validate CONTHAC-3D,a GX6 test was performed at the Battelle Model Containment facility.The hydrogen concentration and temperature monitored by the GX6 test are accurately predicted by CONTHAC-3D.Subsequently,the hydrogen distribution in the HPR1000 containment during a severe accident was studied.The results show that the hydrogen removal rates calculated using CONTHAC-3D for different types of PARs agree well with the theoretical values,with an error of less than 1%.As the accident progresses,the hydrogen concentration in the lower compartment becomes higher than that in the large space,which implies that the lower compartment has a higher hydrogen risk than the dome and large space at a later stage of the accident.The amount of hydrogen removed by the PARs placed on the floor of the compartment is small;therefore,raising the installation height of these recombiners appropriately is recommended.However,we do not recommend installing all autocatalytic recombiners at high positions.The study findings in regard to the hydrogen distribution in the HPR1000 containment indicate that CONTHAC-3D can be applied to the study of hydrogen risk containment.

A METHOD FOR DETERMINATION OF CONCENTRATION OF ATOMIC HYDROGEN PERMEATED IN MULTI-LAYER STRUCTURE WALL OF HYDROGENATION REACTORS

It was proposed how the concentration distribution was calculated in the treble lager wall of hgdrogenation reactor according to the principle of hydrogen diffusion at the steady state in this paper. Based on the steady hydrogen permeation current density i∞ measund with the hydrogen probe at a given temperature, the hydmpen concentrationson the key interfaces and hydrogen distribution at any given mdial profile in the single, double or treble layer wall of hydrogenation reactor could be found by applying the presented equations throoph suitable parmeters ioput. The theoretical bases were provided for developing the nondestructive probing technique of the concentration of atomic hydmpen in the wallS of hydrogenation reactors.

Production of hydrogen and syngas via pyrolysis of bagasse in a dual bed reactor

Pyrolysis of bagasse followed by thermal cracking of tar was carded out at atmospheric pressure using a dual bed reactor. The first bed was used for the pyrolysis and the second bed was used for thermal cracking of tar. Iron fillings were used as the packed bed material in the second bed. The effects of reaction time （20 to 40 rain）, reactor temperature （600 to 900 ℃） and packed bed height （40-100 mm） on the product （char, tar and gas） yield and gas （H2, CO, CO2, CH4, CnHm） composition were studied. Over the ranges of the experimental conditions used, the operating conditions were optimized for pyrolysis temperature around 850 ℃, a reaction time of 30 min and packed bed height of 100 mm, thus we could obtain a gas richer in hydrogen and carbon monoxide and poorer in carbon dioxide and hydrocarbons. It was observed that compared with single bed process, dual bed process increased the gas yield from 0.397 to 0.750 m3/kg and decreased the tar yield from 0.445 to 0.268 g/g while the heating value of the product gas remained almost constant （10-11 M J/m3）.

Hydrogen production by catalytic decomposition of methane using a Fe-based catalyst in a fluidized bed reactor

Catalytic decomposition of methane using a Fe-based catalyst for hydrogen production has been studied in this work. A Fe/Al2O3 catalyst previously developed by our research group has been tested in a fluidized bed reactor （FBR）. A parametric study ot the effects of some process variables, including reaction temperature and space velocity, is undertaken. The operating conditions strongly affect the catalyst performance. Methane conversion was increased by increasing the temperature and lowering the space velocity. Using temperatures between 700 and 900℃ and space velocities between 3 and 6 LN/（gcat·h）, a methane conversion in the range of 25%-40% for the gas exiting the reactor could be obtained during a 6 h run. In addition, carbon was deposited in the form of nanofilaments （chain like nanofibers and multiwall nanotubes） with similar properties to those obtained in a fixed bed reactor.

Hydrogen energy recovery from high strength organic wastewater with ethanol type fermentation using acidogenic EGSB reactor

A lab-scale expanded granular sludge bed （EGSB） reactor was employed to evaluate the feasibility of the hydrogen energy recovery potential from high strength organic wastewater. The results showed that a maximum hydrogen production rate of 7.43 m^3 H2/m^3 reactor · d and an average hydrogen production rate of 6.44- ms H^2/ms reactor · d were achieved with the hydrogen content of 50% -56% in the biogas during the 90-day operation. At the acidogenic phase, COD removal rate was stable at about 15%. In the steady operation period, the main liquid end products were ethanol and acetic acid, which represented ethanol type fermentation. Among the liquid end products, the concentration percentage of ethanol and acetic acid amounted to 69.5% - 89. 8% and the concentration percentage of ethanol took prominent about 51.7% - 59. 1%, which is better than the utilization of substrate for the methanogenic bacteria. An ethanol type fermentation pathway was suggested in the operation of enlarged industrial continuous hydrogen bio-producing reactors.

Bio-reduction of nitrate from groundwater using a hydrogen-based membrane biofilm reactor

A hydrogen-based membrane biofilm reactor （MBfR） using H2 as electron donor was investigated to remove nitrate from groundwater. When nitrate was first introduced to the MBfR, denitrification took place on the shell side of the membranes immediately, and the effluent concentration of nitrate continuously decreased with 100% removal rate on day 45 under the influent nitrate concentration of 5 mg NO3^--N/L, which described the acclimating and enriching process of autohydrogenotrophic denitrification bacteria. A series of short-term experiments were applied to investigate the effects of hydrogen pressures and nitrate loadings on deniWification. The results showed that nitrate reduction rate improved as H2 pressure increasing, and over 97% of total nitrogen removal rate was achieved when the nitrate loading increased from 0.17 to 0.34 g NO3^--N/（m^2.day） without nitrite accumulation. The maximum deniwification rate was 384 g N/（m^3.day）. Partial sulfate reduction, which occurred in parallel to nitrate reduction, was inhibited by denitrififcation due to the competition for H2. This research showed that MBfR is effective for removing nitrate from the contaminated groundwater.

Enantioselective Hydrogenation of Ethyl 2-Oxo-4-phenylbutyrate on Cinchona-Platinum Catalysts

Enantioselective hydrogenation of ethyl 2-oxo-4-phenylbutyrate to ethyl （R）-2-hydroxy-4-phenyl- bu- tyrate on Pt/γ-Al2O3 modified by 10,11-dihydrocinchonidine was studied by investigating the influences of the amount of modifier, initial concentration of reactant, pressure and temperature on conversion and enantiometric excess in a stirred autoclave and the effects of the liquid velocity, gas velocity, modifier concentration and various catalytic beds in a trickle-bed reactor. The maximum optical yields were about 50% and 60% in the two types of reactors, respectively. It was assumed that the total hydrogenation rate included the reaction rates over the unmodified and modified active sites on platinum surface and a kinetic model, which fitted the experimental data well in autoclave, was obtained. A simplified plug-flow model was proposed to describe the bed average efficiency of trickle-bed reactor.

Two-dimensional Simulation for Hydrogen/Air Combustion in a Monolith Reactor

Recent studies on hydrogen combustion were reviewed briefly. The laminar flow and combustion of premixed hydrogen/air mixture in a cylindrical channel of a monolith reactor with and without catalytic wall was numerically modeled by solving two-dimensional (2-D) Navier-Stokes (N-S) equations, energy equation, and species equations. Eight gas species and twenty reversible gas reactions were considered. The control volume technique and the SIMPLE algorithm were used to solve the partial differential equations. The streamlines of the flow field, temperature contours, the entrance length, and the concentration fields were computed. It is found that the entrance zone plays an important role on flow and temperature as well as species distribution. Therefore, the flow cannot be assumed either as fully developed or as plug flow. There is a small but strong thermal expansion zone between the wall and the entrance. Both diffusion and convection affect the heat and mass transfer processes in the expansion zone. Thus the equations of momentum, energy and species conservations should be used to describe hydrogen/air combustion in the monolith reactor. The hot-spot location and concentration field of the homogeneous combustion is strongly influenced by the inlet velocity and temperature, and the equivalence ratio. The catalytic combustion of premixed hydrogen/air mixture over platinum catalyst-coated wall in a cylindrical channel was also simulated.

Effect of vacuum gas oil hydrotreating reactor on multiple reactors and hydrogen network

The inlet temperature of the Vacuum Gas Oil(VGO)hydrotreating reactor of a refinery is analyzed with the integration of multiple series reactors and hydrogen network considered.The effect of the inlet temperature(T1)on hydrogen sinks/sources and the product output is analyzed systematically based on the simulation of the series reactors,including VGO hydrotreating reactor,hydrocracking reactor,fluid catalytic cracking reactor and visbreaking reactor.The general relation between the Hydrogen Utility Adjustment(HUA)and multiple pairs of varying sinks and sources is deduced,and correlations between varying streams and T1 are linearly fitted.Based on this,the quantitative equation between HUA and T1 is derived,and corresponding diagram is constructed.The T1 corresponding the minimum hydrogen consumption is identified to be 345°C.

Technology of automatic cladding on internal surface of hydrogenated reactor elbow

A newly developed automatic spiral cladding machine for internal surface of hydrogenated reactor elbow is introduced.Workpiece being welded is rotated at various speeds and fed in along axial direction.TIG welding process with filler metal is applied with this machine.Welding is performed in flat position. The machine is intellectually controlled by a microprocessor. Torch waving width and welding speed is varied according to a formula,that the product of waving width and welding speed is constant. So the thickness of cladding layers at different points is uniform. The requirements of hydrogenation to cladding are conformed with this machine.

A solvent-free,selective liquid phase hydrogenation of nitroarenes to aniline in slurry bubble mode on porous NiMo bimetallic catalyst

NiMo bimetallic catalysts were prepared by a solid reaction method.On the NiMo catalyst,the selective liquid phase hydrogenation of nitrobenzene to aniline was achieved in slurry bubble mode.And the high yields(98.9%)were obtained under the conditions of 80℃,solvent-free and atmospheric pressure.The effect of Mo on the catalytic behavior of Ni based catalyst was investigated.The characterization displayed that the inclusion of Mo could improve the specific surface area and pore volume,and the solid reaction method made metal Mo enrichment on the surface of catalyst.These two aspects should be responsible for excellent catalytic performance of NiMo catalyst.In sum,we described a simple and efficient NiMo catalyst and provided a facile and green procedure for liquid phase hydrogenation of nitrobenzene to aniline.

Role of Periodic Input Composition and Sweeping Gas for Improvement of Hydrogen Production in a Palladium Membrane Reactor by Partial Oxidation of Methane

The partial oxidation of methane under periodic operation over Ni/y/-Al2O3 catalyst was investigated in a Pd-membrane reactor. The effects of key parameters such as the inlet composition and the sweeping, gas on methane conversion and the hydrogen recovery are numerically estalallshed with two penodtc input ttmctlons. In order to analyze the effect of the inputs modulation, the reaction was performed under low steam to methane ratio at a mod-erate temperature and pressure. It was obtained that to achieve process intensification is to operate the process in a periodic way. The main results show that the periodic input functions can improve the performance of the process compared to the optimal steady state operation. Moreover, there is an optimum amplitude of manipulated inputs leads to a maximum of hydrogen recovery. It is noteworthy that the comparison between the predicted performancevia the sinusoidal and the＇square ways show that the better＇average performance was obtainedwith the square way.

Catalytic Hydrogenation of Aromatic Compounds in the Liquid Phase

Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic compounds, whereas the following processes are evaluated： （l） partial hydrogenation of benzene to cyclohexene; （2） hydrogenation of aniline; （3） hydrogenation of diphenylamine; （4） preparation of aniline from nitrobenzene; （5） hydrogenation of chloronitrobenzenes; （6） hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture. Processes （1） and （6） are typically carried out in the water-oil system. Generally, this type of system allows reaching a higher selectivity to desired products. In the case of hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture, the water phase extracts a water soluble catalyst; which is recycled and used for condensation of aniline and nitrobenzene. Problems of reaction kinetics, as well as catalysts deactivation are here discussed.

Resolving a Challenge in the Modeling of Hydrogen Production Using Steam Reforming of Methane in Monolith Reactors Using CFD Methods

Reaction modeling of SMR (Steam Methane Reforming) process inside monolith reactors using two approaches were investigated and compared with each other. In the first approach, the reactions were assumed to take place exactly on the wall surfaces, while in the second approach they considered inside a thin thickness near the walls. Experiments of SMR were carried out in a lab-scale monolith reactor. A single-channel was considered and CFD model were developed for each of aforementioned approaches. Comparisons between modeling results and experimental data showed that the first approach (surface model) gives better results. Performing reactions are difficult and expensive, CFD simulations are considered as numerical experiments in many cases. It was concluded that obtained results from CFD analysis gives precise guidelines for further studies on optimization of SMR monolithic reactor performance.

3D fluid model analysis on the generation of negative hydrogen ions for negative ion source of NBI

A radio-frequency(RF) inductively coupled negative hydrogen ion source(NHIS) has been adopted in the China Fusion Engineering Test Reactor(CFETR) to generate negative hydrogen ions.By incorporating the level-lumping method into a three-dimensional fluid model,the volume production and transportation of H^(-) in the NHIS,which consists of a cylindrical driver region and a rectangular expansion chamber,are investigated self-consistently at a large input power(40 k W) and different pressures(0.3–2.0 Pa).The results indicate that with the increase of pressure,the H^(-) density at the bottom of the expansion region first increases and then decreases.In addition,the effect of the magnetic filter is examined.It is noteworthy that a significant increase in the H^(-) density is observed when the magnetic filter is introduced.As the permanent magnets move towards the driver region,the H^(-) density decreases monotonically and the asymmetry is enhanced.This study contributes to the understanding of H-distribution under various conditions and facilitates the optimization of volume production of negative hydrogen ions in the NHIS.

船用金属氢化物储氢技术研究综述

金属氢化物储氢是一种基于化学吸收原理的氢气储存方法,具有高体积储氢密度和高安全性的特点,在船舶储氢领域的应用潜力备受关注。在此背景下,对于金属氢化物储氢技术在船舶上的应用,有着材料性能、反应器性能、热管理系统、成本等一系列有待研究的问题。首先,对金属氢化物储氢技术进行归纳,总结梳理金属氢化物的工作原理及材料性能方面的研究进展,并介绍金属氢化物在船舶上的应用情况;然后,结合氢能船舶的应用环境及需求,分析金属氢化物储氢技术在船舶上应用的技术、经济可行性,并以满足氢能船舶对氢气储量和放氢速率要求为目标,介绍船用金属氢化物储氢系统的研究,包括储氢系统性能研究、储氢反应器结构、反应器结构优化、耦合船舶燃料电池的热管理系统和储氢系统设计思路;最后,结合上述研究内容,对船用金属氢化物储氢系统的研究方向进行总结与展望。

表面完整性对制氢反应器材料耐腐蚀性影响

为研究某制氢反应器用钢表面完整性对其耐腐蚀性的影响,基于制氢反应器所产生的酸性介质腐蚀工况,对某制氢反应器用钢开展静态腐蚀试验。分别分析了不同表面粗糙度、不同表面残余应力对某制氢反应器用钢腐蚀速率、腐蚀后表面粗糙度与拉伸性能衰退的影响规律,并从晶间应力等方面分析表面完整性对耐腐蚀性的影响。通过试验发现:粗糙度较大的试样随腐蚀时间增加腐蚀速率降低,当表面粗糙度Ra为0.05μm时试样腐蚀速率随腐蚀时间增加而增大;腐蚀后粗糙度较大的试样表面粗糙度增大,而较小的试样表面粗糙度减小;腐蚀后材料的力学性能出现随表面粗糙度先增大后减小的趋势;随试件表面残余应力增大,腐蚀速率出现先减小后增大的趋势;腐蚀后表面粗糙度随初始残余应力的增大而增大;当初始表面残余应力为-293 MPa时,试样腐蚀后力学性能相对较好。