Synthesis, characterization and catalytic methanation performance of modified kaolin-supported Ni-based catalysts

Kaolin as a raw material for mesoporous support was firstly modified by calcination,acid treatment,and then was used to prepare nickel catalysts.The amount of alumina which was activated in kaolin during thermal treatment and then leached out in the acid was different.XRD pattern of the kaolin calcined at 600°C or 900°C exhibited only the diffraction peaks for amorphous silica and quartz while that calcined at 1100°C showed obvious peaks forγ-Al2 O3.Therefore,the nickel-based catalysts exhibited different physic-chemical properties.Atmospheric syngas methanation over the catalysts clarified an activity order of CA-1100 N CA-900 N CA-1400 N CA-600 N KA≈0 at temperatures of 350–650°C and a space velocity of 120 L·g-1·h-1.Metallic nickel with small diameter which has medium interaction with the modified kaolin and is well dispersed on the support would have reasonably good activity and carbon-resistance for syngas methanation.

Rapid Microwave-Assisted Ionothermal Dissolution of Cellulose and Its Regeneration Properties

Introduction of the strategy of anhydrous calcium carbonate protection incorporated with the drop by drop reaction,high-purity 1-butyl-3-methylimidazolium chloride([Bmim]Cl)was prepared at reaction temperature of 80°C for only 10 h.Cellulose samples from different biomass sources(with different degree of polymerization characteristic)could be rapidly(no more than 10 minutes)and completely dissolved in the[Bmim]Cl using a microwave-assisted ionothermal route.Homogeneous cellulosic regenerates with high degree of polymerization and thermal stability characteristics were obtained through a coagulation process in water.Furthermore,the dissolved celluloses were readily regenerated into solid products such as casting films and spinning fibers,which exhibited high transparency and flexibility,as well as superior mechanical properties of over 300 MPa(tensile strength)more than those of cellulose samples reported.This study therefore provides a new process for the synthesis of high-purity[Bmim]Cl for the highly efficient dissolution of cellulose to produce high performance cellulosic materials for various applications such as flexible electronic,optoelectronic,soft robots.

High-performance Si-Containing anode materials in lithium-ion batteries: A superstructure of Si@Co-NC composite works effectively

To mitigate the massive volume expansion of Si-based anode during the charge/discharge cycles,we synthesized a superstructure of Si@Co±NC composite via the carbonization of zeolite imidazolate frameworks incorporated with Si nanoparticles.The Si@Co±NC is comprised of Sinanoparticle core and N-doped/Co-incorporated carbon shell,and there is void space between the core and the shell.When using as anode material for LIBs,Si@Co±NC displayed a super performance with a charge/discharge capacity of 191.6/191.4 mA h g^(-1)and a coulombic efficiency of 100.1%at 1000 mA g^(-1)after 3000 cycles,and the capacity loss rate is 0.022%per cycle only.The excellent electrochemical property of Si@Co±NC is because its electronic conductivity is enhanced by doping the carbon shell with N atoms and by incorporating with Co particles,and the pathway of lithium ions transmission is shortened by the hollow structure and abundant mesopores in the carbon shell.Also,the volume expansion of Si nanoparticles is well accommodated in the void space and suppressed by the carbon host matrix.This work shows that,through designing a superstructure for the anode materials,we can synergistically reduce the work function and introduce the confinement effect,thus significantly enhancing the anode materials’electrochemical performance in LIBs.

Enhanced electrocatalytic CO_(2)reduction to formic acid using nanocomposites of In_(2)O_(3)@C with graphene

In_(2)O_(3)is an effective electrocatalyst to convert CO_(2)to formic acid(HCOOH),but its inherent poor electrical conductivity limits the efficient charge transfer during the reaction.Additionally,the tendency of In_(2)O_(3)particles to agglomerate during synthesis further limits the exposure of active sites.Here we address these issues by leveraging the template effect of graphene oxide and employing InBDC as a self-sacrificing template for the pyrolysis synthesis of In_(2)O_(3)@C.The resulting In_(2)O_(3)@C/rGO-600 material features In_(2)O_(3)@C nanocubes uniformly anchored on a support of reduced graphene oxide(rGO),significantly enhancing the active sites exposure.The conductive rGO network facilitates charge transfer during electrocatalysis,and the presence of oxygen vacancies generated during pyrolysis,combined with the strong electron-donating ability of rGO,enhances the adsorption and activation of CO_(2).In performance evaluation,In_(2)O_(3)@C/rGO-600 exhibits a remarkable HCOOH Faradaic efficiency exceeding 94.0%over a broad potential window of−0.7 to−1.0 V(vs.reversible hydrogen electrode(RHE)),with the highest value of 97.9%at−0.9 V(vs.RHE)in a H-cell.Moreover,the material demonstrates an excellent cathodic energy efficiency of 71.6%at−0.7 V(vs.RHE).The study underscores the efficacy of uniformly anchoring metal oxide nanoparticles onto rGO for enhancing the electrocatalytic CO_(2)reduction performance of materials.

以环状硝胺为基的几种塑料黏结炸药的初步研究(英文)

用聚异丁烯(PIB),丙烯腈-聚丁橡胶(ABR),维通A黏结剂和RDX,HMX,BCHMX和ε-HNIW四种硝胺炸药制备了一系列塑性炸药。PETN和以PETN为基的三种塑性炸药用于比较。测试了这些炸药的爆速,撞击和摩擦感度。摩擦感度与撞击感度的关系以及两种感度与D2的关系表明摩擦力向硝胺炸药分子反应中心的转移机理不同于撞击能的转移机理。从摩擦和撞击反应的相互比较以及降低ε-HNIW感度等级中发现撞击感度依赖于硝铵炸药的晶体品质,而摩擦感度的依赖却不明显。测试爆速D与含PIB和ABR黏结剂的PBX装药密度之间的关系表明,ε-HNIW的密度为2.04 g·cm-3时,爆速D为9.800 mm·μs-1。

含钝感炸药的塑性炸药配方感度研究(英文)

采用低感、钝感炸药NTO、NGU作为添加剂,获得了以RDX、HMX为基的低感高能炸药配方,研究了 NTO、NUG对其撞击和摩擦感度的影响。实验表明NTO可降低撞击和摩擦感度,并对其他性能产生不大影响。这 说明低感或钝感炸药的加入是降低塑性炸药感度的有效方法。

Synergetic NO reduction by biomass pyrolysis products simulating their reburning in circulating fluidized bed decoupling combustion

The present work investigated the synergetic effect of pyrolysis-derived char,tar and gas(py-gas)on NO reduction,which may occur in circulating fluidized-bed decoupling combustion(CFBDC)system treating N-rich fuel.Experiments were carried out in a lab-scale drop-tube reactor for NO reduction by some binary mixtures of reagents including char/py-gas,tar/py-gas and tar/char.At a specified total mass rate of0.15 g·min^-1 for NO-reduction reagent,the char/py-gas(binary reagent)enabled the best synergetic NO reduction in comparison with the others.There existed effective interactions between char and some species in py-gas(i.e.,H2,CxHy)during NO reduction by pyrolysis products,meanwhile the tar/py-gas or tar/char mixture only caused a positive effect when tar proportion was necessarily lowered to about 26%.On the other hand,the synergetic effects were not improved for all tested binary reagents by increasing the reaction temperature and residence time.

Characterization and pilot scale test of a fluidized bed two-stage gasification process for the production of clean industrial fuel gas from low-rank coal

To utilize low rank coal efficiently,a fluidized bed two-stage(FBTS)gasification process,mainly consisting of a FB pyrolyzer and a transport FB(TFB)gasifier,has been proposed for the production of clean fuel gas.To verify the feasibility and technical features of this novel gasification technology,a pilot autothermal platform,with a treating capacity of 100 kg/h for coal,was designed and built up.By adopting a kind of lignite from Inner Mongolia,the running state and fuel gas quality were compared systematically under typical operational conditions.The results show that by keeping the reaction temperatures of pyrolyzer and gasifier at around 840
C and 1000
C,respectively,the corresponding tar content in fuel gas at the outlets of pyrolyzer and gasifier were 1127 mg/Nm3 and 365 mg/Nm3,reaching a high tar removal efficiency.Under the stable operation state,the volume fractions of CO,H2,CH4 and CO2 in fuel gas were 14.4%,8.3%,3.4%and 11.3%,respectively,and the corresponding higher heating value of fuel gas was about 1100 kcal/Nm3.Compared with the tar from pyrolyzer,the heavy oil fraction in tar from gasifier reduced significantly,while the light oil components increased sharply simultaneously,showing significant effect of catalytic reforming by hot char bed on tar removal.

NiO@Ni nanoparticles embedded in N-doped carbon for efficient photothermal CO_(2) methanation coupled with H_(2)O splitting

Photothermal carbon dioxide(CO_(2))methanation has attracted increasing interest in solar fuel synthesis,which employs the advantages of photocatalytic H_(2)O splitting as a hydrogen source and photothermal catalytic CO_(2) reduction.This work prepared three-dimensional(3D)honeycomb N-doped carbon(NC)loaded with core–shell NiO@Ni nanoparticles generated in situ at 500℃(NiO@Ni/NC-500).Under the photothermal catalysis(200℃,1.5 W/cm^(2)),the CH_(4) evolution rate of NiO@Ni/NC-500 reached 5.5 mmol/(g·h),which is much higher than that of the photocatalysis(0.8 mmol/(g·h))and the thermal catalysis(3.7 mmol/(g·h)).It is found that the generated localized surface plasmon resonance enhances the injection of hot electrons from Ni to NiO,while thermal heating accelerates the thermal motion of radicals,thus generating a strong photo-thermal synergistic effect on the reaction.The CO_(2) reduction to CH_(4) follows the*OCH pathway.This work demonstrates the synergistic effect of NiO@Ni and NC can enhance the catalytic performance of photothermal CO_(2) reduction reaction coupled with water splitting reaction.

Size control of monodisperse nonporous silica particles by seed particle growth

Monodisperse nonporous silica particles were prepared by sol-precipitation via seed particle growth method, and the particle size, which varied from 1.0 to 4.7 μm, was strictly controlled in our experiment, The formation of secondary particles, which resulted in a multimodaI distribution of particle size, was suppressed by changing tetraethoxysilane （TEOS） concentration and reaction temperature. Furthermore, the effect of adding small amounts of electrolyte to the hydrolysis mixture was examined.

Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange--Influence of material properties,sorption mechanism and modeling

Perfluorooctane sulfonate（PFOS） has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force（LDF） approach for surface diffusion after introducing a load dependency of the mass transfer coefficient βs.The big difference in the initial mass transfer coefficient βs,0, when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate.But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range.

A review on transesterification of propylene carbonate and methanol for dimethyl carbonate synthesis

Dimethyl carbonate(DMC)is widely applied in various fields according to its outstanding physico-chemical properties,especially as a solvent in electrolyte of lithium-ion batteries.More than 90%DMC in China is industrially produced from the propylene carbonate(PC)and methanol(MeOH)route because it is an environmentally friendly and highly efficient process.This review summarizes different DMC production technologies,homogeneous and heterogeneous catalysts,catalytic mechanisms,reaction kinetics and engineering,with particular focus on the relationship between catalyst preparation and catalytic performances.The advantages and disadvantages of various catalysts are categorically compared.Homogeneous catalysts are highly efficient but prone to deactivate and are difficult to separate.Heterogeneous catalysts are easy to separate and have the promising future in industrial application,but their low catalytic efficiency is still the critical bottleneck.From process aspect,the catalytic distillation technology would be promising to overcome the efficiency problem of solid catalysts.

From fundamentals to chemical engineering on oxidative coupling of methane for ethylene production:A review

A comprehensive overview is presented to summarize the research works since 1982 on oxidative coupling of methane(OCM),a complex reaction network combining heterogeneous and homogeneous reaction steps.Fundamentals on reaction mechanisms and thermodynamics have revealed that the OCM process is highly exothermic and its C2+selectivity and yield is critical in evaluating its commercial viability.Catalytic strategies have been put to enhance C2+selectivity,improve C2+yield and lower reaction temperature.The catalyst MnNa2WO4/SiO2 enables methane activation at a temperature of 800◦C and simultaneously a high C2+selectivity of 70–80%,while the nanowire and La2O3-based catalysts enable to lower the reaction temperature to 200–300◦C and 500◦C,respectively.Reaction engineering aspects have also been dealt in many investigations in order to make the process technically feasible.Particularly,research works on reaction kinetics,reactor selection and reactor operating mode choice have been addressed.Intermediate cooling and distributed oxygen feed have been integrated into a multi-stage adiabatic fixed-bed reactor system to suppress the side oxidation reactions and improve the performance of the catalysts towards CH4 conversion and C2+yield.This review paper proposes employing a circulating reactor system coupled with catalyst fine particles but having little internal diffusion resistance to maximize one-pass C2+selectivity and yield of the OCM reaction and evaluate its industrial application potential.

Pyrolysis characteristics of waste tire particles in fixed-bed reactor with internals

This study investigated the characteristics of pyrolysis for waste tire particles in the newly developed fixed-bed reactor with internals that are a central gas collection channel mounted inside reactor.And a few metallic plates vertically welded on the internal wall of the reactors and extending to the region closing their central gas collection pipe walls.Experiments were conducted in two laboratory fixed bed reactors with or without the internals.The results shown that employing internals produced more light oil at externally heating temperatures above 700℃due to the inhibited secondary reactions in the reactor.The oil from the reactor with internals contained more aliphatic hydrocarbons and fewer aromatic hydrocarbons,leading to its higher H/C atomic ratios as for crude petroleum oil.The char yield was relatively stable for two beds and showed the higher heating values(HHVs)of about 23 MJ/kg.The gaseous product of pyrolysis mainly consisted of H2 and CH4,but the use of internals led to less pyrolysis gas through its promotion of oil production.

Secondary cracking of volatile and its avoidance in infrared-heating pyrolysis reactor

This study aims to compare the pyrolysis behavior of Huadian oil shale in two infrared heating fixed bed reactors with different directions of infrared beam.Our previous work has shown that fast pyrolysis of oil shale conducted in the shallow fixed bed infrared heating reactor(co-current)presented the massive secondary reactions,which lowered the shale oil production(Siramard et al.,2017).Conversely,the cross-current infrared achieved shale oil yields higher than the Fischer Assay oil yield(13.07 wt%of dry basis),such as 117.7%of the Fischer Assay yield at our realized highest heating rate of 7℃/s under a specified pyrolysis temperature of 550℃.The shale oil from the cross-current infrared heating reactor was obviously heavier than the oil obtained from the cocurrent heating reactor.Thus,the infrared cross heating evidently suppressed the secondary reactions toward volatile.Our realized shale oil yield could reach 13.67 wt%or 122.5%of the Fischer Assay yield under reducing pyrolysis pressure of 0.6 atm,indicating that lower pressure is also beneficial to the release of volatile and reduction of the secondary cracking reactions.This work shows essentially that the infrared cross heating provides an effective merge of the advantages from quick heating and minimization of secondary cracking reactions to enable the shale oil yields being higher than the Fischer Assay oil yield.

A general bottom-up synthesis of CuO-based trimetallic oxide mesocrystal superstructures for efficient catalytic production of trichlorosilane

Mesocrystals, the non-classical crystals with highly ordered nanoparticle superstructures, have shown great potential in many applications because of their newly collective properties. However, there is still a lack of a facile and general synthesis strategy to organize and integrate distinct components into complex mesocrystals, and of reported application for them in industrial catalytic reactions. Herein we report a general bottom-up synthesis of CuO-based trimetallic oxide mesocrystals (denoted as CuO-M1Ox-M2Oy, where M1 and M2 = Zn, In, Fe, Ni, Mn, and Co) using a simple precipitation method followed by a hydrothermal treatment and a topotactic transformation via calcination. When these mesocrystals were used as the catalyst to produce trichlorosilane (TCS) via Si hydrochlorination reaction, they exhibited excellent catalytic performance with much increased Si conversion and TCS selectivity. In particular, the TCS yield was increased 19-fold than that of the catalyst-free process. The latter is the current industrial process. The efficiently catalytic property of these mesocrystals is attributed to the formation of well-defined nanoscale heterointerfaces that can effectively facilitate the charge transfer, and the generation of the compressive and tensile strain on CuO near the interfaces among different metal oxides. The synthetic approach developed here could be applicable to fabricate versatile complicated metal oxide mesocrystals as novel catalysts for various industrial chemical reactions.

Ordered mesoporous Cu-Ca-Zr:A superior catalyst for direct synthesis of methyl formate from syngas

It is still a big challenge to obtain both highly active and stable Cu-based catalysts for direct synthesis of methyl formate(MF)from syngas.To address the issue,we have designed and synthesized a series of ternary Cu-Ca-Zr catalysts,namely,the ordered mesoporous Cu-Ca-Zr catalyst prepared by one-pot evaporation-induced self-assembly(EISA)method,and the supported CuO/CaO-ZrO_(2)catalysts by impregnating with copper precursor or by immobilizing copper nanoparticles.In the latter two catalysts,the ordered mesoporous CaO-ZrO_(2)support was also prepared by the EISA method.The catalysts were characterized by techniques such as ICP,XRD,TEM,N2 isotherm adsorption-desorption,XPS and H2-TPR,and used for direct synthesis of MF.The results indicated that the catalyst prepared by onepot EISA method,in which the CuO species are highly dispersed in frame of CaO-ZrO_(2),exhibits much better activity and stability as compared with the other two catalysts with most of CuO located on the outer surface of the CaO-ZrO_(2)support,because the former has a higher specific surface area,enhanced synergistic effect and stronger interaction between the CaO-ZrO_(2)support and CuO active constituent.

Efficient Synthesis of 2-Arylamino-2-imidazolines and 2-Aminobenzimidazoles with Aminoiminomethanesulfonic Acid Derivatives

从 aminoimino-methanesulfonic 酸衍生物的 2-arylamino-2-imidazolines 和 2-aminobenzimidazoles 的高度有效的合成被描述。方法简单、实际，产生在优秀孤立的收益的 imidazoline 和 benzimidazoline 衍生物。

Dual single-atom Ce-Ti/MnO_(2)catalyst enhances low-temperature NH_(3)-SCR performance with high H_(2)O and SO_(2)resistance

Mn-based catalysts have exhibited promising performance in low-temperature selective catalytic reduction of NOx with NH_(3)(NH_(3)-SCR).However,challenges such as H_(2)O-or SO_(2)-induced poisoning to these catalysts still remain.Herein,we report an efficient strategy to prepare the dual single-atom Ce-Ti/MnO_(2)catalyst via ball-milling and calcination processes to address these issues.Ce-Ti/MnO_(2)showed better catalytic performance with a higher NO conversion and enhanced H_(2)O-and SO_(2)-resistance at a lowtemperature window(100−150°C)than the MnO_(2),single-atom Ce/MnO_(2),and Ti/MnO_(2)catalysts.The in situ infrared Fourier transform spectroscopy analysis confirmed there is no competitive adsorption between NOx and H_(2)O over the Ce-Ti/MnO_(2)catalyst.The calculation results showed that the synergistic interaction of the neighboring Ce-Ti dual atoms as sacrificial sites weakens the ability of the active Mn sites for binding SO_(2)and H_(2)O but enhances their binding to NH_(3).The insight obtained in this work deepens the understanding of catalysis for NH_(3)-SCR.The synthesis strategy developed in this work is easily scaled up to commercialization and applicable to preparing other MnO_(2)-based single-atom catalysts.

Engineering oxygen vacancies and localized amorphous regions in CuO-ZnO separately boost catalytic reactivity and selectivity

Generating different types of defects in heterogeneous catalysts for synergetic promotion of the reactivity and selectivity in catalytic reactions is highly challenging due to the lack of effective theoretical guidance.Herein,we demonstrate a facile strategy to introduce two types of defects into the CuO-ZnO model catalyst,namely oxygen vacancies(OVs)induced by H2 partial reduction and localized amorphous regions(LARs)generated via the ball milling process.Using industrially important Rochow–Müller reaction as a representative,we found OVs predominantly improved the target product selectivity of dimethyldichlorosilane,while LARs significantly increased the conversion of reactant Si.The CuO-ZnO catalyst with optimized OVs and LARs contents achieved the best catalytic property.Theoretical calculation further revealed that LARs promote the generation of the Cu3Si active phase,and OVs impact the electronic structure of the Cu3Si active phase.This work provides a new understanding of the roles of different catalyst defects and a feasible way of engineering the catalyst structure for better catalytic performances.