Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

Recent progress of green sorbents-based technologies for low concentration CO_(2) capture

The increased concentration of CO_(2) due to continuous breathing and no discharge of human beings in the manned closed space,like spacecraft and submarines,can be a threat to health and safety.Effective removal of low concentration CO_(2) from the manned closed space is essential to meet the requirements of long-term space or deep-sea exploration,which is an international frontier and trend.Ionic liquids(ILs),as a widespread and green solvent,already showed its excellent performance on CO_(2) capture and absorption,indicating its potential application in low concentration CO_(2) capture.In this review,we first summarized the current methods and strategies for direct capture from low concentration CO_(2) in both the atmosphere and manned closed spaces.Then,the multi-scale simulation methods of CO_(2) capture by ionic liquids are described in detail,including screening ionic liquids by COSMO-RS methods,capture mechanism by density functional theory and molecular dynamics simulation,and absorption process by computational fluid dynamics simulation.Lastly,some typical IL-based green technologies for low concentration CO_(2) capture,such as functionalized ILs,co-solvent systems with ILs,and supported materials based on ILs,are introduced,and analyzed the subtle possibility in manned closed spaces.Finally,we look forward to the technology and development of low concentration CO_(2) capture,which can meet the needs of human survival in closed space and proposed that supported materials with ionic liquids have great advantages and infinite possibilities in the vital area.

Mechanism of CO_(2)reduction in carbonylation reaction promoted by ionic liquid additives:A computational and experimental study

The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).

Occurrence,leaching behavior,and detoxification of heavy metal Cr in coal gasification slag

Coal gasification slag(CGS)is a type of solid waste produced during coal gasification,in which heavy metals severely restrict its resource utilization.In this work,the mineral occurrence and distribution of typical heavy metal Cr in CGS is investigated.The leaching behavior of Cr under different conditions is studied in detail.Acid leaching-selective oxidation-coprecipitation method is proposed based on the characteristics of Cr in CGS.The detoxification of Cr in CGS is realized,and the detoxification mechanism is clarified.Results show that Cr is highly enriched in CGS.The speciation of Cr is mainly residual fraction(74.47%-86.12%),which is combined with amorphous aluminosilicate.Cr^(3+)and Cr^(6+)account for 90.93%-94.82%and 5.18%-9.07%of total Cr,respectively.High acid concentration and high liquid-solid ratio are beneficial to destroy the lattice structure of amorphous aluminosilicate,thus improving the leaching efficiency of Cr,which can reach 97.93%under the optimal conditions.Acid leaching-selective oxidation-coprecipitation method can realize the detoxification of Cr in CGS.Under the optimal conditions,the removal rates of Fe^(3+)and Cr^(3+)in the leaching solution are 80.99%-84.79%and 70.58%-71.69%,respectively,while the loss rate of Al^(3+)is only 1.10%-3.35%.Detoxification slag exists in the form of Fe-Cr coprecipitation(Fe_(1-x)Cr_xOOH),which can be used for smelting.The detoxification acid leaching solution can be used to prepare inorganic polymer composite coagulant poly-aluminum chloride(PAC).This study can provide theoretical and data guidance for detoxification of heavy metal Cr in CGS and achieve resource utilization of coal gasification solid waste.

Increasing the greenness of an organic acid through deep eutectic solvation and further polymerisation

Acrylic acid(AA)is an important and widely used industrial chemical,but its high toxicity renders its use incompatible with the concept of green development.By leveraging its terminal carboxyl group and unsaturated bond,we designed and explored a new strategy to increase the greenness of AA via its eutectic melting using a quaternary ammonium salt(choline chloride)to form a deep eutectic solvent(DES),followed by polymerisation of the DES to form a polymer(poly(DES)).The greenness of AA,DES,and poly(DES)was evaluated via an in vitro test using MGC80-3 cells and an in vivo test using Kunming mice.The toxicity improved from Grade 2(moderately toxic)for AA to Grade 1(slightly toxic)for DESs and Grade 0(non-toxic)for poly(DES)in the in vitro test.Moreover,the poly(DES)s showed a lower toxicity in mice than the DESs in the in vivo test.Thus,greenness enhancement was successfully achieved,with the greenness following the order AA<DES<poly(DES).Furthermore,the mechanisms underlying the change in toxicity were explored through microscopy and flow cytometry,which revealed that the DES can permeate the MGC80-3 cell membrane during the G_(0)/G_(1) phase to adversely affect DNA synthesis in the S phase,but the poly(DES)cannot.Finally,the green poly(DES),which showed good adsorption properties and flexible functionality,was successfully applied as a carrier or excipient of drugs.Through the novel strategy reported herein,greenness enhancement and the broadening of the application scope of a toxic organic acid were achieved,making such acids applicable for green development.

Interfacial engineering of transition-metal sulfides heterostructures with built-in electric-field effects for enhanced oxygen evolution reaction

Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.

Simulation and design of a heat-integrated double-effect reactive distillation process for propylene glycol methyl ether production

A double-effect reactive distillation(DERD)process was proposed for the production of propylene glycol methyl ether from propylene oxide and methanol to overcome the shortcoming of low selectivity and high-energy consumption in the tubular plug-flow reactor.A single-column reactive distillation(RD)process was conducted under optimized operating conditions based on sensitivity analysis as a reference.The results demonstrated that the proposed DERD process is able to achieve more than 95%selectivity of the desired product.After that,a design approach of the DERD process with an objective of the minimum operating cost was proposed to achieve further energy savings in the RD process.The proposed DERD configuration can provide a large energy-savings by totally utilization of the overhead vapor steam in the high-pressure RD column.A comparison of the single-column RD process revealed that the proposed DERD process can reduce the operating cost and the total annual cost of 25.3%and 30.7%,respectively,even though the total capital cost of DERD process is larger than that of the RD process.

Reconstruction and recovery of anatase TiO_(2) from spent selective catalytic reduction catalyst by Na OH hydrothermal method

The improper disposal of spent selective catalytic reduction (SCR) catalysts causes environmental pollution and metal resource waste.A novel process to recover anatase titanium dioxide (TiO_(2)) from spent SCR catalysts was proposed.The process included alkali (NaOH) hydrothermal treatment,sulfuric acid washing,and calcination.Anatase TiO_(2) in spent SCR catalyst was reconstructed by forming Na_(2)Ti_(2)O_(4)(OH)_(2) nanosheet during NaOH hydrothermal treatment and H_(2)Ti_(2)O_(4)(OH)_(2) during sulfuric acid washing.Anatase TiO_(2) was recovered by decomposing H_(2)Ti_(2)O_(4)(OH)_(2) during calcination.The surface pore properties of the recovered anatase TiO_(2) were adequately improved,and its specific surface area (SSA) and pore volume (PV) were 85 m^(2)·g^(-1)and 0.40 cm^(3)·g^(-1),respectively.The elements affecting catalytic abilities(arsenic and sodium) were also removed.The SCR catalyst was resynthesized using the recovered TiO_(2) as raw material,and its catalytic performance in NO selective reduction was comparable with that of commercial SCR catalyst.This study realized the sustainable recycling of anatase TiO_(2) from spent SCR catalyst.

Ultra-deep Removal of Metal Ions from Coal Tar by Complexation:Experimental Studies and Density Functional Theory Simulations

As one of the important aspects of upgrading coal tar,the ultra-deep removal of metal ions via the complexation method was investigated by screening four complexing agents and performing density functional theory(DFT)simulations.Analysis of the compositions and contents of the metallic compounds in the coal tar revealed that the main components were iron and calcium naphthenates.Direct filtration reduced the mechanical impurity content from 0.24%to 0.0752%,indicating that most of the large particles could be easily removed.Among the four complexing agents,namely,acetic acid,oxalic acid,citric acid,and ethylenediaminetetraacetic acid,oxalic acid exhibited the best demetallization performance.The DFT simulations suggested that the high performance of oxalic acid originated from its 1:1 coordination mode,rigid dicarboxyl structure,and greater binding energy.

Prediction of atomization characteristics of pressure swirl nozzle with different structures

The structure of the pressure swirl nozzle is an important factor affecting its spray performance.This work aims to study pressure swirl nozzles with different structures by experiment and simulation.In the experiment,10 nozzles with different structures are designed to comprehensively cover various geometric factors.In terms of simulation,steady-state simulation with less computational complexity is used to study the flow inside the nozzle.The results show that the diameter of the inlet and outlet,the direction of the inlet,the diameter of the swirl chamber,and the height of the swirl chamber all affect the atomization performance,and the diameter of the inlet and outlet has a greater impact.It is found that under the same flow rate and pressure,the geometric differences do have a significant impact on the atomization characteristics,such as spray angle and SMD(Sauter mean diameter).Specific nozzle structures can be customized according to the actual needs.Data analysis shows that the spray angle is related to the swirl number,and the SMD is related to turbulent kinetic energy.Through data fitting,the equations for predicting the spray angle and the SMD are obtained.The error range of the fitting equation for the prediction of spray angle and SMD is within 15% and 10% respectively.The prediction is expected to be used in engineering to estimate the spray performance at the beginning of a real project.

The internal circulations on internal mass transfer rate of a single drop in nonlinear uniaxial extensional flow

The internal flow of a droplet in the nonlinear extensional flow field will exhibit more than two internal circulations with the variation of nonlinear intensity(E).In this paper,the effect of positions and sizes of internal circulations on internal mass transfer rate of a single spherical droplet in a nonlinear extensional flow field is studied and compared with that in a linear extensional flow field.The simulation results show that when E≥0,there are two symmetrical internal circulations in the droplet,which is the same with that in a linear extensional flow.The limit value of mass transfer rate Sh is 15,which is equal to that in a linear extensional flow,no matter how large E is.When E≤-3/7,the number of internal flow circulation of a droplet increase to four and the transfer rate Sh increases.When E=-1,the maximum internal transfer rate Sh equals 30 which is twice of that in a linear extensional flow.The generation of new flow circulations in droplets and the circulation positions will enhance mass transfer when E≤-3/7,which provides a new idea for enhancing the internal mass transfer rate of droplets.

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.

Long‐life lithium batteries enabled by a pseudo‐oversaturated electrolyte

The specific energy of Li metal batteries(LMBs)can be improved by using high‐voltage cathode materials;however,achieving long‐term stable cycling performance in the corresponding system is particularly challenging for the liquid electrolyte.Herein,a novel pseudo‐oversaturated electrolyte(POSE)is prepared by introducing 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether(TTE)to adjust the coordination structure between diglyme(G2)and lithium bis(trifluoromethanesulfonyl)imide(LiTFSI).Surprisingly,although TTE shows little solubility to LiTFSI,the molar ratio between LiTFSI and G2 in the POSE can be increased to 1:1,which is much higher than that of the saturation state,1:2.8.Simulation and experimental results prove that TTE promotes closer contact of the G2 molecular with Li^(+)in the POSE.Moreover,it also participates in the formation of electrolyte/electrode interphases.The electrolyte shows outstanding compatibility with both the Li metal anode and typical high‐voltage cathodes.Li||Li symmetric cells show a long life of more than 2000 h at 1 mA cm^(−2),1 mAh cm^(−2).In the meantime,Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cell with the POSE shows a high reversible capacity of 134.8 mAh g^(−1 )after 900 cycles at 4.5 V,1 C rate.The concept of POSE can provide new insight into the Li^(+)solvation structure and in the design of advanced electrolytes for LMBs.

CFD-PBE simulation of a bubble column in OpenFOAM

A general CFD-PBE(computational fluid dynamics-population balance equation) solver for gas–liquid poly-dispersed flows of both low and high gas volume fractions is developed in OpenFOAM(open-source field operation and manipulation) in this work. Implementation of this solver in OpenFOAM is illustrated in detail. The PBE is solved with the cell average technique. The coupling between pressure and velocity is dealt with the transient PIMPLE algorithm, which is a merged PISO-SIMPLE(pressure implicit split operator-semi-implicit method for pressure-linked equations) algorithm. Results show generally good agreement with the published experimental data, whereas the modeling precision could be improved further with more sophisticated closure models for interfacial forces, the models for the bubble-induced turbulence and those for bubble coalescence and breakage.The results also indicate that the PBE could be solved out the PIMPLE loop to save much computation time while still preserving the time information on variables. This is important for CFD-PBE modeling of many actual gas–liquid problems, which are commonly high-turbulent flows with intrinsic transient and 3 D characteristics.

Three-liquid-phase extraction and separation of V(V) and Cr(VI) from acidic leach solutions of high-chromium vanadium–titanium magnetite

A new method by liquid–liquid–liquid three phase system, consisting of acidified primary amine N1923(abbreviated as A-N1923), poly(ethylene glycol)(PEG) and (NH_4)_2SO_4 aqueous solution, was suggested for the separation and simultaneous extraction of V(V) and Cr(VI) from the acidic leach solutions of highchromium vanadium–titanium magnetite. Experimental results indicated that V(V) and Cr(VI) could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while Al(III)and other co-existing impurity ions, such as Si(IV), Fe(III), Ti(IV), Mg(II) and Ca(II) in acidic leach solutions,could be enriched in the(NH_4)_2SO_4 bottom aqueous phase. During the process for extraction and separation of V(V) and Cr(VI), almost all of impurity ions could be removed. The separation factors between V(V) and Cr(VI) could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered V(V) and Cr(VI) in the top phase and middle phase respectively were all above 90%.Various effects including aqueous p H, A-N1923 concentration, PEG added amount and(NH_4)_2SO_4 concentration on three-phase partitioning of V(V) and Cr(VI) were discussed. It was found that the partition of Cr(VI) into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of V(V) by A-N1923 resulted of anion exchange between NO_3^- and H_2V_(10)O_(28)^(-4). Stripping of V(V) and Cr(VI) from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NaNO_3 aqueous solutions and Na OH-((NH_4)_2SO_4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium–titanium magnetite.

Calcium sulfate whisker prepared by flue gas desulfurization gypsum:A physical–chemical coupling production process

In this paper,the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects.Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution.A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed.Through the comparison of product morphology,the best grinding time was determined to be 3.5 h.The mechanism of desulfurization gypsum through physical–chemical coupling to reduce energy consumption was clarified.The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate.By calculating the conversion and crystallization rate of calcium sulfate whiskers,it was found that there were obvious"autocatalytic"kinetic characteristics during the crystallization process.

Investigation on the fabrication of lightweight aggregate with acid-leaching tailings of vanadium-bearing stone coal minerals and red mud

Proper treatment of acidleaching tailings(ALTs)of vanadiumbearing stone coal minerals is of great urgency.One approach is adding it into the raw materials during the preparation of lightweight aggregate(LWA).But clay is always needed.In this paper,another solid waste,red mud,was mixed with ALTs as a source of flux components instead of clay.Evaluation of the physical characteristics,morphological structures,as well as crystal phases during the sintering process were investigated.When their mixtures with a proper ratio were sintered at 1080℃,a glassy phase with certain viscosity was formed,and the gases generated simultaneously were encapsulated by the melt.Finally,LWA with a onehour water absorption as low as 1.46%,a bulk density as low as 728.76 kgm 3 and a compressive strength as high as 10.77 MPa was fabricated.

Particle-resolved simulation of packed beds by non-body conforming locally refined orthogonal hexahedral mesh

The traditional fixed-bed reactor design is usually not suitable for the low tube-to-particle diameter ratios(N = D/d b 8) where the local phenomena of channeling near the wall and backflow in the bed are dominant. The recent"solid particle" meshing method is too complicated for mesh generation, especially for non-spherical particles in large random packed beds, which seriously hinders its development. In this work, a novel high-fidelity mesh model is proposed for simulation of fixed bed reactors by combining the immersed boundary and adaptive meshing methods. This method is suitable for different shapes of particles, which ingeniously avoids handling the complex "contact point" problem. Several packed beds with two different shapes of particles are investigated with this model, and the local flow in the bed is simulated without geometrical simplification. The predicted pressure drop across the fixed bed and heat transfer of the single particle are in good agreement with the corresponding empirical relations. Compared with spherical particles, the packed bed packing with pentaphyllous particles has lower pressure drop and better heat/mass transfer performance, and it shows that this method can be used for the screening of particle shapes in a fixed bed.

Measurement methods of particle size distribution in emulsion polymerization

The particle size distribution of polymer always develops in emulsion polymerization systems,and certain key phenomena/mechanisms as well as properties of the final product are significantly affected by this distribution.This review mainly focuses on the measurement methods of particle size distribution rather than average particle size during the emulsion polymerization process,including the existing off-line,on-line,and in-line measurement methods.Moreover,the principle,resolution,performance,advantages,and drawbacks of various methods for evaluating particle size distribution are contrasted and illustrated.Besides,several possible development directions or solutions of the in-line measurement technology are explored.

Recent advances on the reduction of CO2 to important C2+ oxygenated chemicals and fuels

The chemical utilization of CO_2 is a crucial step for the recycling of carbon resource. In recent years, the study on the conversion of CO_2 into a wide variety of C_(2+) important chemicals and fuels has received considerable attention as an emerging technology. Since CO_2 is thermodynamically stable and kinetically inert, the effective activation of CO_2 molecule for the selective transformation to target products still remains a challenge. The welldesigned CO_2 reduction route and efficient catalyst system has imposed the feasibility of CO_2 conversion into C_(2+) chemicals and fuels. In this paper, we have reviewed the recent advances on chemical conversion of CO_2 into C_(2+) chemicals and fuels with wide practical applications, including important alcohols, acetic acid, dimethyl ether, olefins and gasoline. In particular, the synthetic routes for C\\C coupling and carbon chain growth, multifunctional catalyst design and reaction mechanisms are exclusively emphasized.