Synthesizing active and durable cubic ceria catalysts(<6 nm)for fast dehydrogenation of bio-polyols to carboxylic acids coproducing green H_(2)

Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large particle size(>20 nm)and less surface defects,however,hinder further application of ceria materials.Herein,an alternative strategy involving lactic acid(LA)assisted hydrothermal method was developed to synthesize active,selective and durable cubic ceria of<6 nm for dehydrogenation reactions.Detailed studies of growth mechanism revealed that,the carboxyl and hydroxyl groups in LA molecule synergistically manipulate the morphological evolution of ceria precursors.Carboxyl groups determine the cubic shape and particle size,while hydroxyl groups promote compositional transformation of ceria precursors into CeO_(2) phases.Moreover,enhanced oxygen vacancies(Vo)on the surface of CeO_(2) were obtained owing to continuous removal of O species under reductive atmosphere.Cubic CeO_(2) catalysts synthesized by the LA-assisted method,immobilized with bimetallic PtCo clusters,exhibit a record high activity(TOF:29,241 h^(-1))and Vo-dependent synergism for dehydrogenation of bio-derived polyols at 200℃.We also found that quenching Vo defects at air atmosphere causes activity loss of PtCo/CeO_(2) catalysts.To regenerate Vo defects,a simple strategy was developed by irradiating deactivated catalysts using hernia lamp.The outcome of this work will provide new insights into manufacturing durable catalyst materials for aqueous phase dehydrogenation applications.

A Real-time Prediction System for Molecular-level Information of Heavy Oil Based on Machine Learning

Acquiring accurate molecular-level information about petroleum is crucial for refining and chemical enterprises to implement the“selection of the optimal processing route”strategy.With the development of data prediction systems represented by machine learning,it has become possible for real-time prediction systems of petroleum fraction molecular information to replace analyses such as gas chromatography and mass spectrometry.However,the biggest difficulty lies in acquiring the data required for training the neural network.To address these issues,this work proposes an innovative method that utilizes the Aspen HYSYS and full two-dimensional gas chromatography-time-of-flight mass spectrometry to establish a comprehensive training database.Subsequently,a deep neural network prediction model is developed for heavy distillate oil to predict its composition in terms of molecular structure.After training,the model accurately predicts the molecular composition of catalytically cracked raw oil in a refinery.The validation and test sets exhibit R2 values of 0.99769 and 0.99807,respectively,and the average relative error of molecular composition prediction for raw materials of the catalytic cracking unit is less than 7%.Finally,the SHAP(SHapley Additive ExPlanation)interpretation method is used to disclose the relationship among different variables by performing global and local weight comparisons and correlation analyses.

Investigation on the threshold control of safety blasting vibration velocity for the extraction of complicated orebody under railway

The threshold control of safety blasting vibration velocity is a significant process for the underground mining of complicated ore deposit under construction,road,and water.According to the equivalent principle of displacement and velocity of mass point,differential evolution is put forward based on 3DEC dynamic analysis,making the calculation more efficient and accurate.The 3DEC model of the complicated orebody under railway is established according to the topographic maps and geological data of the eastern Pyrite Mine.The stimulus-response distribution of internal stress and displacement fields are demonstrated by analyzing the on-site monitoring vibration displacement and velocity data of the mass point.The reliability of parameter selection,such as blasting simulation waveforms,rock damping,is identified.The safety vibration velocity of railway is set to 4.5 cm/s in line with the requirement of safety blasting rules.Thus,the maximum amount of single-stage explosive in this region is 44.978 kg.The simulation result is in good agreement with the on-site monitoring datum.No displacement and settlement of the 701 railway special line was achieved by choosing the critical amount of the single-stage explosive.

Experimental study of polyurea-coated fiber-reinforced cement boards under gas explosions

Five types of polyurea elastomers were synthesized by changing the isocyanate component and the mechanical properties of polyurea materials were measured. Fiber-reinforced cement boards(FRCB)strengthened by polyurea with different formulations were processed, and a series of experiments were carried out on the specimens with gas explosion devices. The results showed that the conventional mechanical properties of different types of polyureas had their own advantages. Based on the gas explosion overpressure criterion, the blast resistances of reinforced plates were quantitatively evaluated,and the best polyurea was selected to guide the formulation design. The three typical failure modes of polyurea-reinforced FRCBs were flexural, shear, and flexural-shear failure. Dynamic thermodynamics and shock wave spectral analysis revealed that the polyurea did not undergo a glass transition in the gas explosion tests but retained its elastic properties, allowing it to effectively wrap the fragments formed by the brittle substrates.

Adsorption and Adsorption-Photocatalytic Degradation of VOCs Based on Carbon Materials

Adsorption and the combination of adsorption and photocatalysis are prospective strategies for treating lowconcentrationvolatile organic compounds (VOCs). Behind the adsorption technology of VOC treatments are carbon-basedmaterials with large surface areas and high VOC uptake. This review summarizes the research progress in carbon-basedadsorbents and adsorbent-photocatalysts for VOC removal. Firstly, the VOC adsorption performances of various carbonmaterials, including activated carbon, activated carbon fiber, biochar, graphene and its derivatives, and carbon nanotubes,are summarized, and the adsorption mechanism of VOCs on carbon materials is analyzed. Then, the VOC adsorptionphotocatalyticproperties of composites comprised of different carbon materials and photocatalysts are presented. Finally,perspectives on the adsorption and adsorption-photocatalysis of VOCs via carbon materials are proposed. This reviewprovides an optimal reference for the research and development of adsorbents and adsorption-photocatalysts of VOCs.

A covering liquid method to intensify self-preservation effect for safety of methane hydrate storage and transportation

In this work,experiments and comprehensive insights into the proposed covering liquid method to intensify self-preservation effect for methane(CH_(4))storage are presented.The CH_(4)hydrate decomposition percentage was 17.6%with the pressure of 0.61 MPa after 12 h at 266.0 K without a covering liquid,which can be reduced to 12.4%,13.8%,13.0%,and 8.3%with the pressure of 0.26 MPa,0.33 MPa,0.51 MPa,and 0.37 MPa by covering with tetrahydrofuran(THF),cyclopentane(CP),cyclohexane,and n-tetradecane,respectively.When the temperature for CH_(4)hydrate decompositionwas 274.2 K,covering with THF,CP,cyclohexane,and n-tetradecane failed to inhibit CH_(4)hydrate decomposition.The results suggested that the covering liquid may form a new solid layer(a hydrate layer or other solidified layer)around the CH_(4)hydrate,which inhibit CH_(4)transfer below the freezing point of water.However,the new solid layer cannot resist the fast transfer of CH_(4)from decomposed CH_(4)hydrate above the freezing point of water.The same phenomenon was also observed in a sodium dodecyl sulfonate(SDS)-dry solution CH_(4)hydrate formation system.Therefore,the covering method can only intensify the self-preservation effect below the freezing point of water,but cannot generate a self-preservation effect.

Hydrothermal conversion of fructose to lactic acid and derivatives:Synergies of metal and acid/base catalysts

With increasing strict regulation on single-use plastics,lactic acid(LA)and alkyl lactates,as essential monomers for bio-degradable polylactic acid(PLA)plastic products,have gained worldwide attention in both academia and industry.While LA is still dominantly produced through fermentation processes from start,chemical synthesis from cellulosic biomass remains a grand challenge,owing to poor selectivity in activating CAH and CAC bonds in sugar molecules.To our best knowledge,recent publications have been focused on hydrothermal conversion of glucose to LA,while this review summarizes the highlights on direct thermal conversion of fructose as starting material to LA and derivatives.In particular,the synergies of metal/metal cations and acid/base catalysts will be critically revised on retro-aldol and dehydration reactions.This work will provide insights into rational design of active and selective catalysts for the production of carboxylic acids from biomass feedstocks.

QSPR modeling of azeotropic temperatures and compositions for binary azeotropes containing lower alcohols using a genetic function approximation

Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing lower alcohols. Experimental techniques and ab initio approaches can produce accurate results;however, these two processes are time consuming and labor intensive. Although thermodynamic equations such as UNIFAC are widely used, experimental values are required, and it is difficult to choose the best groups to represent a complex system. Because of their high efficiency and fast calculation speed, quantitative structure–property relationship(QSPR) tools were used in this work to predict the azeotropic temperatures and compositions of binary azeotropes containing lower alcohols. The QSPR models for 64 binary azeotropes based on centroid approximation and weighted-contribution-factor approximation were established using the genetic function approximation(GFA) procedure in Materials Studio software, and a leave-one-out cross-validation procedure was conducted.External tests of an additional 16 azeotropes were also investigated, and high determination coefficient values were obtained. The best QSPR models were explained in terms of the molecular structure of the azeotropes,and good predictive ability was obtained within acceptable prediction error levels.

Development of index system for inherently safer process design using an integrated approach

With a growing population, an increasing number of petrochemical facilities are built with larger capacity and more complexity, which pose a great risk to assets, community and environment. The value of inherently safer design is recognized with time by all stakeholders, and an effective tool is needed to evaluate and compare inherent safety of alternative technologies. This study developed a safety index to evaluate existing technologies for their safety levels and guide inherently safer design. The Integrated Risk-based Safety Index(IRSI) was developed based on a comprehensive review of petrochemical processes, incident cases from Sinopec and US Chemical Safety Board, and existing safety index systems. The IRSI included all major hazards, including fire, explosion,toxic release, dust explosion, physical explosion, and runaway. Also, the integrated life cycle approach considered chemical hazards, equipment failure rates and safety measures in this risk-based index. Advanced modeling techniques, PHAST simulation and Neural Network, were used in the development of three novel sub-indices in the projects, fire, explosion and toxic release. The index system could be easily incorporated into a user friendly tool for the ease of application. A case study of hydrogen dioxide was conducted using the IRSI, which showed its capability for evaluating the safety level of process facilities.

Identification of abnormal conditions in high-dimensional chemical process based on feature selection and deep learning

Identification of abnormal conditions is essential in the chemical process.With the rapid development of artificial intelligence technology,deep learning has attracted a lot of attention as a promising fault identification method in chemical process recently.In the high-dimensional data identification using deep neural networks,problems such as insufficient data and missing data,measurement noise,redundant variables,and high coupling of data are often encountered.To tackle these problems,a feature based deep belief networks(DBN)method is proposed in this paper.First,a generative adversarial network(GAN)is used to reconstruct the random and non-random missing data of chemical process.Second,the feature variables are selected by Spearman’s rank correlation coefficient(SRCC)from high-dimensional data to eliminate the noise and redundant variables and,as a consequence,compress data dimension of chemical process.Finally,the feature filtered data is deeply abstracted,learned and tuned by DBN for multi-case fault identification.The application in the Tennessee Eastman(TE)process demonstrates the fast convergence and high accuracy of this proposal in identifying abnormal conditions for chemical process,compared with the traditional fault identification algorithms.

Effect of thermodynamic parameters on prediction of phase behavior and process design of extractive distillation

Extractive distillation was investigated for separation of the minimum azeotrope of n-propanol/water, via the Aspen Plus simulation platform. Experimental data of n-propanol/water, which could pass the thermodynamic consistency test, were regressed to get suitable binary interaction parameters(BIPs) by the UNIQUAC thermodynamic model. The azeotrope system was heterogeneous in the simulation with built-in BIPs, which was contrary to the experimental data. The study focused on the effect of thermodynamic parameters on the prediction of phase behavior, and process design of extractive distillation. N-methyl-2-pyrrolidone(NMP) and ethylene glycol were used as solvents to implement the separation. Processes with built-in and regressed BIPs were explored,based on the minimum total annual cost(TAC). There were significant differences in the phase behavior simulation using different thermodynamic parameters, which showed the importance of BIPs in the design and optimization of extractive distillation.

Engineering three-layer core–shell S-1/TS-1@dendritic-SiO_(2) supported Au catalysts towards improved performance for propene epoxidation with H_(2) and O_(2)

The advocacy of green chemical industry has led to the development of highly efficient catalysts for direct gas-phase propene epoxidation with green,sustainable and simple essence.The S-1/TS-1@dendritic-SiO_(2) material with three-layer core–shell structure was developed and used as the support for Au catalysts,which showed simultaneously fantastic PO formation rate,PO selectivity and stability(over 100 h)for propene epoxidation with H_(2) and O_(2).It is found that silicalite-1(S-1)core and the middle thin layer of TS-1 offer great mass transfer ability,which could be responsible for the excellent stability.The designed dendritic SiO_(2) shell covers part of the acid sites on the external surface of TS-1,inhibiting the side reactions and improving the PO selectivity.Furthermore,three kinds of SiO_(2) shell morphologies(i.e.,dendritic,net,mesoporous shell)were designed,and relationship between shell morphology and catalytic performance was elucidated.The results in this paper harbour tremendous guiding significance for the design of highly efficient epoxidation catalysts.

Erosion characteristic of slope sandstone soaking in acid mine drainage

Acid mine drainage（AMD） is one of the main reasons of slope instability in chemical mines with high sulfide. The pH values of the solution inside the mining pit decrease with the increasing of distance from ore body and vary from 1.2 to 4.6, according to the results of the water environmental investigation and the composition test of the slope sandstone in Xinqiao Pyrite Mine. Comparative experiments between original sandstone and AMD eroded sandstone samples show that after AMD erosion the uniaxial compressive strength and elastic modulus decrease by 30%-50% and 25%-45%, respectively, the cohesion and internal friction angle decrease obviously, and the Poisson ratio fluctuates between 0.20-0.29. The greater joints development, the higher residual stress after peak value, and the longer time to damage. Besides above, the reaction mechanism analysis of AMD eroded sandstone shows that the fillings in joints and fissures of sandstone are frequently decomposed and polyreacted, resulting in changes of interior molecule structure and fi＇amework composition, and decreases of cohesion and angle of internal friction between rock structure interfaces.

Effects of Sampling Conditions on Composition and Emission Characteristics of Volatile Organic Compounds in Process Units from Different Refineries

This study investigates the effects of sampling conditions on volatile organic compound(VOC)compositions including different flow restrictors,SUMMA volumes,sampling heights,and wind speeds.Results show that at the six sampling heights the concentrations of main VOC species were slightly different,while the wind speed had a greater impact on the VOC composition of source profiles.With the increase of wind speed,the weighted percentage of high-carbon aromatic hydrocarbons was higher.Besides,there was an extremely different profile between the normal production and shutdown conditions of the delayed coking unit.To compare the emission characteristics of VOCs in various process units of the S and the C refineries,the samples were collected from the catalytic cracking unit,the continuous catalytic reforming unit,and the delayed coking unit.In the continuous catalytic reforming unit,C3-C5 alkanes and low-carbon aromatic hydrocarbons were the main components collected from the S and the C refineries,accounting for 67.1%and 34.9%,respectively.For the delayed coking unit,the total weighted percentage of high carbon C6-C12 alkanes was significantly higher than other units in the S and the C refineries,accounting for 30.5%and 24.4%,respectively.In the catalytic cracking unit,the low-carbon C2-C5 alkanes were abundant,and the weighted percentage of propylene was higher.The emission characteristics obtained were consistent with the processing technology of production units.The results indicate that the VOC emission characteristics from the same production unit in different refineries have similarities and significant differences which are related to the technological process.The emission characteristics of VOCs could provide the data support for source apportionment work in the production units.

Analysis and Prediction of Corrosion Risk in Atmospheric Distillation Tower Overhead System

In order to optimize the atmospheric tower overhead low-temperature system,the physical parameters,multiphase composition,aqueous dew point temperature,and ammonium salt crystallization temperature are simulated with process simulation software.The temperature distribution in overhead heat exchanger is calculated by heat transfer calculation.The special parts with elbows near the inlet and outlet of heat exchanger are studied by fluid field analysis.Results indicate that under current operating conditions,the aqueous dew point temperature and initial crystallization temperature of NH4Cl are 91°C and 128°C,respectively.Ammonium salt appears in the distillation tower and liquid water occurs in heat exchanger tubes,in which the dew point induced corrosion is the most direct factor for heat exchanger corrosion.In the heat exchanger,condensate water appearing in the area 2.7 meters away from the bundle inlet can give rise to corrosion risk under the moist NH4Cl and high concentration of acidic solution circumstance.For the pipes and elbows located near the inlet and the outlet of heat exchanger,the flow field presents an unsymmetrical distribution.High risk areas are mainly concentrated on the external bend of elbows where the liquid water concentration is higher.The coupling of simulation methods established thereby is approved as an effective way to evaluate the corrosion risk in the atmospheric column overhead system and can provide a scientific basis for corrosion control.

Hydrogenation Behavior of Hydrogen Peroxide in a Microreactor

The hydrogenation of hydrogen peroxide is an unwanted side reaction in the direct synthesis of hydrogen peroxide and remains a problem to solve.The mechanism of this reaction has been studied with batch reactors but the slow heat and mass transfer in batch reactors hindered the understanding of its intrinsic kinetics.In this study,a microreactor is employed to investigate the parameters that influence the hydrogenation reaction,including flow rate,channel length,hydrogen pressure,solvent composition,and initial hydrogen peroxide concentration.The activity of different catalysts was compared and the hydrogenation law was confirmed,providing guiding information to better control the hydrogenation process.

Experimental investigation on ablation characteristics of coated and uncoated steel under 30/80 μs impulse current

The ablation tests on coated and uncoated Q235 B steel sheets were conducted under 30/80 μs impulse current simulating the lightning first return stroke current, aimed at further understanding the ablation characteristics of steel and investigating the impact of anti-corrosion coating on these characteristics. Ablation characteristics were investigated through the macroscopic morphology and x-ray diffraction patterns on the surface of damaged zones, the microstructure and micro Vickers hardness on the cross-section of damaged zones, and the maximum rear-face temperature of sample sheets. It can be concluded that the ablation areas of uncoated sheet consist of the melted layer and the heat-affect layer. These ablation areas include not only the area ablated directly by the arc root, of which the depth is deeper, but also the area forming due to the splashing of molten steel, of which the depth is shallower and decreases when the area’s distance from the arc attachment point increases. For coated sheet, coating materials have decomposed and evaporated forming an ablation pit on the sheet surface, in which the steel surface is exposed, and zinc filler of coating primer has infused into the exposed surface. The ablation diameter of uncoated sheet relates to the amplitude of the 30/80 μs impulse current in quadratic function, while for coated sheet, the relation is linear. In general, under the 30/80 μs impulse current, the coating can decrease the energy injected from the arc to the steel sheet and reduce the melting and splashing of steel. As a result, the ablation severity of uncoated sheet is severer than that of coated sheet.

Effect of power parameters on microdischarge induced by corona discharge

This research mainly describes the generation and diagnosis of plasma using a wire-plate discharge device driven by different power supplies, aimed at investigating the effect of driving source parameters on micro-discharge induced by a corona. The influence of parameters such as waveform, duty ratio and bias voltage on discharge characteristics was explored preliminarily.Experiment results show that the determination of volt-ampere characteristics under different driving source waveforms indicates that the application of square and pulse waveforms shows great advantages over that of sawtooth and sinusoidal waveforms. Similarly, the photo-thermal effects of the system were investigated by comparing the high-voltage electrode temperature and relative emission intensity of N2(C3Пu → B3Пg, 0–0, 337 nm), where square and pulse waveforms also achieved better performance. But the pulse waveform had a slight advantage over the square waveform in terms of energy conversion. Further, investigations of the duty ratio and bias voltage applied on the pulse waveform were conducted, and the results indicate that the duty ratio could effectively improve the discharge power and thermal effect to a certain extent;however, the application of bias voltage on the pulse signal had little influence on the discharge power and thermal effect.

Dynamic Adsorption of Toluene on Hierarchical Porous Carbons with Varying Pore Structure

Hierarchical porous carbon material(MMC)was successfully fabricated via hard template synthesis method by carbonization of furfury alcohol within the template(MCM-41).The prepared MMC was studied with characterization methods including scanning electron microscopy(SEM),transmission electron microscopy(TEM),nitrogen adsorption-desorption analyses,and infrared spectral analysis(FTIR).To investigate kinetics of toluene adsorption of hierarchical porous carbon materials,the adsorption performances of these carbon samples with varying pore structure(MC-1,MMC,MMHPC)were analyzed via dynamic adsorption.And the Langmuir model and Freundlich equation were employed to correspond with adsorption isotherms to study the adsorption mechanism.The experimental results demonstrate that the Langmuir model is more appropriate to describe the adsorption process.The capacities of toluene adsorption follow the order of MMC<MMHPC(micro-meso hierarchical porous carbon)<MC-1(microporous carbon).MC-1 has satisfactory absorption performance due to its large pore volume and high ratio of micropores.MMHPC has excellent toluene adsorption performance for proper amounts of surface oxygen containing groups.Long saturation time,interconnected hierarchical pore channels,and large specific surface area make MMC also a promising material for VOCs treatment.These data reveal that the pore channel structure,rational pore distribution,high surface area and reasonable amounts of surface oxygen groups are the main factors contributed to excellent toluene adsorption performance,which proposes theoretical basis for hierarchical porous carbon materials to further engineering application.

Influences of spark plasma sintering temperature on the microstructures and thermoelectric properties of(Sr_(0.95)Gd_(0.05))TiO_3 ceramics

（Sr0.95Gd0.05）WiO3 （SGTO） ceramics are successfully prepared via spark plasma sintering （SPS） respectively at 1548, 1648, and 1748 K by using submicron-sized SGTO powders synthesized from a sol-gel method. The densities, microstruc- tures, and thermoelectric properties of the SGTO ceramics are studied. Though the Seebeck coefficient shows no obvious difference in the case that SPS temperatures range from 1548 K to 1648 K, the electrical conductivity and the thermal conductivity increase remarkably due to the increase in grain size and density. The sample has a density higher than 98% theoretical density as the sintering temperature increases up to 1648 K and shows average grain sizes increasing from 0.7 tma to 7 Ixm until 1748 K. As a result, the maximum of the dimensionless figure of merit of ,~ 0.24 is achieved at ~ 1000 K for the samples sintered at 1648 K and 1748 K, which was ~ 71% larger than that （0.14 at ~ 1000 K） for the sample sintered at 1548 K due to the enhancement of the power factor.