The catalytic hydrogenation of 2-nitro-4-acetylamino anisole (NMA) is a less-polluting and efficient method to produce 2-amino-4-acetamino anisole (AMA). However, the kinetics of catalytic hydrogenation of NMA to AMA remains obscure. In this work, the kinetic models including power-law model and Langmuir-Hinshelwood-Hougen-Watson (LHHW) model of NMA hydrogenation to AMA catalyzed by Raney nickel catalyst were investigated. All experiments were carried out under the elimination of mass transfer resistance within the temperature range of 70–100 ℃ and the hydrogen pressure of 0.8–1.5 MPa. The reaction was found to follow 0.52-order kinetics with respect to the NMA concentration and 1.10-order kinetics in terms of hydrogen pressure. Based on the LHHW model, the dual-site dissociation adsorption of hydrogen was analyzed to be the rate determining step. The research of intrinsic kinetics of NMA to AMA provides the guidance for the reactor design and inspires the catalyst modification.

Ensuring the consistency of electrode structure in proton-exchange-membrane fuel cells is highly desired yet challenging because of wide-existing and unguided cracks in the microporous layer (MPL). The first thing is to evaluate the homogeneity of MPL with cracks quantitatively. This paper proposes the homogeneity index of a full-scale MPL with an area of 50 cm², which is yet to be reported in the literature to our knowledge. Besides, the effects of the carbon material and surfactant on the ink and resulting MPL structure have been studied. The ink with a high network development degree produces an MPL with low crack density, but the ink with high PDI produces an MPL with low crack homogeneity. The polarity of the surfactant and the non-polarity of polytetrafluoroethylene (PTFE) are not mutually soluble, resulting in the heterogeneous PTFE distribution. The findings of this study provide guidelines for MPL fabrication.

Biochar is a reactive carrier as it may be partially gasified with steam in steam reforming, which could influence the formation of reaction intermediates and modify catalytic behaviors. Herein, the Ni/biochar as well as two comparative catalysts, Ni/Al₂O₃ and Ni/SiO₂, with low nickel loading (2% (mass)) was conducted to probe involvement of the varied carriers in the steam reforming. The results indicated that the Ni/biochar performed excellent catalytic activity than Ni/SiO₂ and Ni/Al₂O₃, as the biochar carrier facilitated quick conversion of the -OH from dissociation of steam to gasify the oxygen-rich carbonaceous intermediates like C=O and C-O-C, resulting in low coverage while high exposure of nickel species for maintaining the superior catalytic performance. In converse, strong adsorption of aliphatic intermediates over Ni/Al₂O₃ and Ni/SiO₂ induced serious coking with polymeric coke as the main type (21.5% and 32.1%, respectively), which was significantly higher than that over Ni/biochar (3.9%). The coke over Ni/biochar was mainly aromatic or catalytic type with nanotube morphology and high crystallinity. The high resistivity of Ni/biochar towards coking was due to the balance between formation of coke and gasification of coke and partially biochar with steam, which created developed mesopores in spent Ni/biochar while the coke blocked pores in Ni/Al₂O₃ and Ni/SiO₂ catalysts.

In response to the lack of reliable physical parameters in the process simulation of the butadiene extraction, a large amount of phase equilibrium data were collected in the context of the actual process of butadiene production by acetonitrile. The accuracy of five prediction methods, UNIFAC (UNIQUAC Functional-group Activity Coefficients), UNIFAC-LL, UNIFAC-LBY, UNIFAC-DMD and COSMO-RS, applied to the butadiene extraction process was verified using partial phase equilibrium data. The results showed that the UNIFAC-DMD method had the highest accuracy in predicting phase equilibrium data for the missing system. COSMO-RS-predicted multiple systems showed good accuracy, and a large number of missing phase equilibrium data were estimated using the UNIFAC-DMD method and COSMO-RS method. The predicted phase equilibrium data were checked for consistency. The NRTL-RK (non-Random Two Liquid-Redlich-Kwong Equation of State) and UNIQUAC thermodynamic models were used to correlate the phase equilibrium data. Industrial device simulations were used to verify the accuracy of the thermodynamic model applied to the butadiene extraction process. The simulation results showed that the average deviations of the simulated results using the correlated thermodynamic model from the actual values were less than 2% compared to that using the commercial simulation software, Aspen Plus and its database. The average deviation was much smaller than that of the simulations using the Aspen Plus database (>10%), indicating that the obtained phase equilibrium data are highly accurate and reliable. The best phase equilibrium data and thermodynamic model parameters for butadiene extraction are provided. This improves the accuracy and reliability of the design, optimization and control of the process, and provides a basis and guarantee for developing a more environmentally friendly and economical butadiene extraction process.

Copper-based metal-organic frameworks (Cu-MOFs) are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions. However, the unpleasant odor and instability of the organosulfur, as well as the mass-transfer resistance that exists in multiphase catalysis, have often limited the catalytic application of Cu-MOFs in C-S coupling reactions. In this paper, a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide (CTAB) was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB. Concurrently, elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.

With the increasing demand for high-purity products, the industrial application of melt crystallization technology has been highly concerned. In this study, the purification process of nitrochlorobenzene binary eutectic system (NBES) and naphthalene–benzothiophene solid solution system (NBSSS) in tower melting crystallizer is analyzed, and a mathematical model of crystallization process is established. The key parameters in terms of feed concentration, crystal bed height, reflux ratio and stirring speed efficiency on purification effects were discussed by the established model. The results show that the concentration of p-nitrochlorobenzene was purified from 90.85% to 99.99%, when the crystal bed height is 600 mm, the reflux ratio is 2.5, and the stirring speed is 12 r·min^-1. The naphthalene concentration is purified from 95.89% to 99.99%, when the crystal bed height is 400 mm, the reflux ratio is 1.43, and the stirring speed is 16 r·min^-1. The quality of the model is evaluated by the ARD (average relative deviation). The minimum ARD values of the NBES and NBSSS are 2.39% and 5.22%, respectively, indicating the model satisfactorily explains the purification process.

The Co₃O₄ nanoparticles, dominated by a catalytically active (110) lattice plane, were synthesized as a low-temperature NO_x adsorbent to control the cold start emissions from vehicles. These nanoparticles boast a substantial quantity of active chemisorbed oxygen and lattice oxygen, which exhibited a NO_x uptake capacity commensurate with Pd/SSZ-13 at 100°C. The primary NO_x release temperature falls within a temperature range of 200–350°C, making it perfectly suitable for diesel engines. The characterization results demonstrate that chemisorbed oxygen facilitate nitro/nitrites intermediates formation, contributing to the NO_x storage at 100°C, while the nitrites begin to decompose within the 150–200°C range. Fortunately, lattice oxygen likely becomes involved in the activation of nitrites into more stable nitrate within this particular temperature range. The concurrent processes of nitrites decomposition and its conversion to nitrates results in a minimal NO_x release between the temperatures of 150–200°C. The nitrate formed via lattice oxygen mainly induces the NO_x to be released as NO₂ within a temperature range of 200–350°C, which is advantageous in enhancing the NO_x activity of downstream NH₃-SCR catalysts, by boosting the fast SCR reaction pathway. Thanks to its low cost, considerable NO_x absorption capacity, and optimal release temperature, Co₃O₄ demonstrates potential as an effective material for passive NO_x adsorber applications.

The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry. Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux, and selectivity. In this study, the hyperbranched polymer (HBP) was deposited on the outer surface of a polyvinylidene fluoride (PVDF) hollow-fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure. The obtained HBP/PVDF hollow-fiber-composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50% (mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g·m^-2·h^-1, with a separation factor of 4.1 at 60 ℃. Therefore, the HBP/PVDF hollow-fiber-composite membrane has great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures.

Silicone rubber (SR) is widely used in the field of electronic packaging because of its low dielectric properties. In this work, the porosity of the SR was improved, and the dielectric constant of the SR foam was reduced by adding expanded microspheres (EM). Then, the thermal conductivity of the system was improved by combining the modified boron nitride (f-BN). The results showed that after the f-BN was added, the dielectric constant and dielectric loss were much lower than those of pure SR. Micron-sized modified boron nitride (f-mBN) improved the dielectric and thermal conductivity of the SR foam better than that of nano-sized modified boron nitride (f-nBN), but f-nBN improved the volume resistivity, tensile strength, and thermal stability of the SR better than f-mBN. When the mass ratio of f-mBN and f-nBN is 2:1, the thermal conductivity of the SR foam reaches the maximum value of 0.808 W·m^-1·K^-1, which is 6.5 times that before the addition. The heat release rate and fire growth index are the lowest, and the improvement in flame retardancy is mainly attributed to the high thermal stability and physical barrier of f-BN.

The coal-to-ethanol process, as the clean coal utilization, faces challenges from the energy-intensive distillation that separates multi-component effluents for pure ethanol. Referring to at least eight columns, the synthesis of the ethanol distillation system is impracticable for exhaustive comparison and difficult for conventional superstructure-based optimization as rigorous models are used. This work adopts a superstructure-based framework, which combines the strategy that adaptively selects branches of the state-equipment network and the parallel stochastic algorithm for process synthesis. High-performance computing significantly reduces time consumption, and the adaptive strategy substantially lowers the complexity of the superstructure model. Moreover, parallel computing, elite search, population redistribution, and retention strategies for irrelevant parameters are used to improve the optimization efficiency further. The optimization terminates after 3000 generations, providing a flowsheet solution that applies two non-sharp splitting options in its distillation sequence. As a result, the 59-dimension superstructure-based optimization was solved efficiently via a differential evolution algorithm, and a high-quality solution with a 28.34% lower total annual cost than the benchmark was obtained. Meanwhile, the solution of the superstructure-based optimization is comparable to that obtained by optimizing a single specific configuration one by one. It indicates that the superstructure-based optimization that combines the adaptive strategy can be a promising approach to handling the process synthesis of large-scale and complex chemical processes.

In order to comprehend the applicability of microwave irradiation for recovering coalbed methane, it is necessary to evaluate the microwave irradiation-induced alterations in coals with varying levels of metamorphism. In this work, the carbon molecular sieve combined with KMnO₄ oxidation was selected to fabricate carbon molecular sieve with diverse oxidation degrees, which can serve as model substances toward coals. Afterwards, the microwave irradiation dependences of pores, functional groups, and high-pressure methane adsorption characteristics of model substances were studied. The results indicated that microwave irradiation causes rearrangement of oxygen-containing functional groups, which could block the micropores with a size of 0.40-0.60 nm in carbon molecular sieve; meanwhile, naphthalene and phenanthrene generated by macro-molecular structure pyrolysis due to microwave irradiation could block the micropores with a size of 0.70-0.90 nm. These alterations in micropore structure weaken the saturated methane adsorption capacity of oxidized carbon molecular sieve by 2.91%-23.28%, suggesting that microwave irradiation could promote methane desorption. Moreover, the increased mesopores found for oxidized carbon molecular sieve after microwave irradiation could benefit CH₄ diffusion. In summary, the oxidized carbon molecular sieve can act as model substances toward coals with different ranks. Additionally, microwave irradiation is a promising technology to enhance coalbed methane recovery.

In this work, a new ZnO/CoNiO₂/CoO/C metal oxides composite is prepared by cost-effective hydrothermal method coupled with annealing process under N₂ atmosphere. Notably, the oxidation-defect annealing environment is conducive to both morphology and component of the composite, which flower-like ZnO/CoNiO₂/CoO/C is obtained. Benefited from good chemical stability of ZnO, high energy capacity of CoNiO₂ and CoO and good conductivity of C, the as-prepared sample shows promising electrochemical behavior, including the specific capacity of 1435 C·g^-1 at 1 A·g^-1, capacity retention of 87.3% at 20 A·g^-1, and cycling stability of 90.5% for 3000 cycles at 5 A·g^-1, respectively. Furthermore, the prepared ZnO/CoNiO₂/CoO/C/NF//AC aqueous hybrid supercapacitors device delivers the best specific energy of 55.9 W·h·kg^-1 at 850 W·kg^-1. The results reflect that the as-prepared ZnO/CoNiO₂/CoO/C microflowers are considered as high performance electrode materials for supercapacitor, and the strategy mentioned in this paper is benefit to prepare mixed metal oxides composite for energy conversion and storage.

The technological revolution has spawned a new generation of industrial systems, but it has also put forward higher requirements for safety management accuracy, timeliness, and systematicness. Risk assessment needs to evolve to address the existing and future challenges by considering the new demands and advancements in safety management. The study aims to propose a systematic and comprehensive risk assessment method to meet the needs of process system safety management. The methodology first incorporates possibility, severity, and dynamicity (PSD) to structure the “51X” evaluation indicator system, including the inherent, management, and disturbance risk factors. Subsequently, the four-tier (risk point-unit-enterprise-region) risk assessment (RA) mathematical model has been established to consider supervision needs. And in conclusion, the application of the PSD-RA method in ammonia refrigeration workshop cases and safety risk monitoring systems is presented to illustrate the feasibility and effectiveness of the proposed PSD-RA method in safety management. The findings show that the PSD-RA method can be well integrated with the needs of safety work informatization, which is also helpful for implementing the enterprise's safety work responsibility and the government's safety supervision responsibility.

In the industrial treatment of waste volatile organic compound (VOC) streams by membrane technology, a third impurity, generally, water vapor, coexists in the mixture of VOC and nitrogen or air, and can affect membrane performance and the design of the industrial process. This study focused on the investigation of the effect of water vapor on the separation performance of the separation of VOC/water/nitrogen mixtures by a polydimethylsiloxane (PDMS) membrane. Three types of VOCs: water-miscible ethanol, water-semi-miscible butanol, and water-immiscible cyclohexane, were selected for the study. Different operating parameters including, concentration of the feed VOC, feed temperature, and concentration of the feed water were compared for the separation of binary and ternary VOC/nitrogen mixtures. The interaction between the VOC and water was analyzed to explain the transportation mechanism after analyzing the difference in the membrane performance for the separation of binary and ternary mixtures. The results indicated that the interaction between the VOC (or nitrogen) and water is the key factor affecting membrane performance. Water can promote the permeation of hydrophilic VOC but prevent hydrophobic VOC through the membrane for the separation of ternary VOC/water/nitrogen mixtures. These results will provide fundamental insights for the design of the recovery application process for industrial membrane-based VOCs, and also guidance for the investigation of the separation mechanism in vapor permeation.

It is quite important to ensure the safety and sustainable development of nuclear energy for the treatment of radioactive wastewater. To treat radioactive wastewater efficiently and rapidly, two multi-amine β-cyclodextrin polymers (diethylenetriamine β-cyclodextrin polymer (DETA-TFCDP) and triethylenetetramine β-cyclodextrin polymer (TETA-TFCDP)) were prepared and applied to capture uranium. Results exhibited that DETA-TFCDP and TETA-TFCDP displayed the advantages of high adsorption amounts (612.2 and 628.2 mg·g^-1, respectively) and rapid adsorption rates, which can reach (88 ±1)% of their equilibrium adsorption amounts in 10 min. Moreover, the adsorbent processes of DETA-TFCDP and TETA-TFCDP on uranium(VI) followed the Langmuir model and pseudo-second-order model, stating they were mainly chemisorption and self-endothermic. Besides, TETA-TFCDP also showed excellent selectivity in the presence of seven competing cations and could be effectively reused five times via Na₂CO₃ as the desorption reagent. Meanwhile, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy illustrated that the enriched multi-amine groups and oxygen-containing functional groups on the surface of TETA-TFCDP were the main active sites for capturing uranium(VI). Hence, multi-amine β-cyclodextrin polymers are a highly efficient, rapid, and promising adsorbent for capturing uranium(VI) from radioactive wastewater.

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route, for it can get rid of the dependence on fossil resource. In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali, we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance. The results showed that the ionic liquid [Bmim]BF₄ can affect the crystal growth of hydroxyapatite, provide fluoride ion for fluorination of hydroxyapatite, and adjust the surface acidity and basicity, morphology, textural properties, crystallinity, and composition of hydroxyapatite. The [Bmim]BF₄ dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system, thus changing the degree of fluoridation of hydroxyapatite. High fluoride-ion concentration can lead to the formation of CaF₂ and thus significantly decrease the catalytic performance of hydroxyapatite. The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis, leading to different catalytic performance. The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows: a mass ratio of [Bmim]BF₄ to calcium salt =≥0.2:1, a hydrothermal time of 12 h, and a hydrothermal temperature of 130℃. A maximal methacrylic acid yield of 54.7% was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions (250℃ and 2 MPa of N₂) in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

A green environmental protection and enhanced leaching process was proposed to recover all elements from spent lithium iron phosphate (LiFePO₄) lithium batteries. In order to reduce the influence of Al impurity in the recovery process, NaOH was used to remove impurity. After impurity removal, the spent LiFePO₄ cathode material was used as raw material under the H₂SO₄ system, and the pressure oxidation leaching process was adopted to achieve the preferential leaching of lithium. The E-pH diagram of the Fe-P-Al-H₂O system can determine the stable region of each element in the recovery process of spent LiFePO₄ Li-batteries. Under the optimal conditions (500 r·min^-1, 15 h, 363.15 K, 0.4 MPa, the liquid-solid ratio was 4:1 ml·g^-1 and the acid-material ratio was 0.29), the leaching rate of Li was 99.24%, Fe, Al, and Ti were 0.10%, 2.07%, and 0.03%, respectively. The Fe and P were precipitated and recovered as FePO₄·2H₂O. The kinetic analysis shows that the process of high-pressure acid leaching of spent LiFePO₄ materials depends on the surface chemical reaction. Through the life cycle assessment (LCA) of the spent LiFePO₄ whole recovery process, eight midpoint impact categories were selected to assess the impact of recovery process. The results can provide basic environmental information on production process for recycling industry.

In this study, the open-source software MFIX-DEM simulations of a bubbling fluidized bed (BFB) are applied to assess nine drag models according to experimental and direct numerical simulation (DNS) results. The influence of superficial gas velocity on gas–solid flow is also examined. The results show that according to the distribution of time-averaged particle axial velocity in y direction, except for Wen–Yu and Tenneti–Garg–Subramaniam (TGS), other drag models are consistent with the experimental and DNS results. For the TGS drag model, the layer-by-layer movement of particles is observed, which indicates the particle velocity is not correctly predicted. The time domain and frequency domain analysis results of pressure drop of each drag model are similar. It is recommended to use the drag model derived from DNS or fine grid computational fluid dynamics–discrete element method (CFD-DEM) data first for CFD-DEM simulations. For the investigated BFB, the superficial gas velocity less than 0.9 m·s^-1 should be adopted to obtain normal hydrodynamics.

The objective in this study is to investigate the adsorption-degradation of the methylene blue (MB) dye using a fabricated heterojunction Ag@TiO₂ nanocomposite. The batch factors used in photo catalytic reactions were pH, UV-irradiation time, temperature, catalytic dosage, and concentration of MB. The results showed that 0.2×10³ g·ml^-1) of the catalytic dose caused the Ag@TiO₂ adsorption to degrade by 96.67% with darks and UV exposure. Using the Langmuir-Hinshelwood model to determine the kinetic, the Ag@TiO₂ displays a greater kinetic rate than TiO₂ and silver nanoparticle (AgNPs). The photocatalytic degradation of MB, which is an endothermic reaction involving all catalysts, is shown by the thermodynamic parameter to have the positive value of enthalpy (ΔH°). The enthalpies observed were Ag@TiO₂ (126.80 kJ·mol^-1) < AgNPs (354.47 kJ·mol^-1) < TiO₂ (430.04 kJ·mol^-1). Ascorbic acid (^·OH scavenger), 2-propanol (^·O₂ scavenger), and ammonium oxalate (AO) (hole h⁺ scavenger) were employed to conduct the scavenger effects. The Ag@TiO₂ demonstrated a reduction in MB degradation when combined with 2-propanol, and this clearly demonstrated that, in contrast to hydroxyl radicals (^·OH) and hole (h⁺) scavengers, superoxide radical anion (^·O₂ scavenger) plays a significant role in MB degradation. Utilizing density functional theory (DFT) to elucidate the mechanism and B3LYP/6-311+G(d,p) level optimization, the degradation-adsorption process was explained. When the N-N, C-N or C-C bonds were severed, the Fukui faction was demonstrated for nucleophilic, electrophilic, and radical attack.