Heterogeneous dynamic modeling and simulation of an industrial ethylene oxide reactor experiencing catalyst deactivation

This paper investigates steady-state and dynamic simulation of an industrial fixed-bed ethylene oxide reactor. A mathematical heterogeneous one-dimensional model is developed for simulation of reactor performance in the presence of long term deactivation of silver/a-alumina catalyst. In this paper, steady-state model of the reactor is solved and results of steady state simulation are fed to dynamic simulator as initial condition. When results of dynamic simulation are compared with industrial reactor data, it is found that there were good agreements between simulation results and industrial data. The proposed model is also validated by industrial process data for a period of 1100 operating days.

Simulation and assessment of manufacturing ethylene carbonate from ethylene oxide in multiple process routes

Ethylene oxide(EO)is an important raw material for producing ethylene carbonate(EC).However,the traditional method for the separation of EO from mixture gas by water in the refining process is high energy consumption.In this paper,two processes of manufacturing EC from EO mixture gas were studied by process simulation.Two processes for producing EC from EO mixture as raw materials without EO purification,called the OSAC process and the Modified OSAC process,were developed and assessed systematically.Both processes use EC as the absorbent to capture EO,avoiding the separation process of EO from solution.For comparisons,the EC producing process containing EO absorption by water,EO refinement and carbonylation process were also modeled,which was called the ERC process.Three schemes were designed for the EO absorber using EC as absorbent.Compared with the initial absorber scheme,the optimal liquid–vapor ratio is reduced from 1.66 to 1.45(mass).Moreover,the mass distribution analysis for the three processes were carried out in the form of the material chain.It was found that,compared with the ERC process,the energy consumption of the OSAC and the Modified OSAC process is reduced by 56.89%and 30.03%,respectively.This work will provide helpful information for the industrialization of the OSAC process.

Exfoliation of poly(ethylene glycol)-intercalated graphite oxide composite in water without sonication

A novel method for exfoliating graphite oxide(GrO)was implemented through the mass water absorption of a GrO–poly(ethylene glycol)(GrO–PEG)composite.The GrO–PEG composite was prepared by intercalating PEG into the lamellae of GrO,and the variation of the basal spacing was measured by X-ray diffraction analysis.The yield of graphene was measured with an ultraviolet–visible spectrophotometer,and the properties of graphene oxide(GO)were characterized by atomic force microscopy,transmission electron microscopy(TEM),Raman spectrometry,and Fourier transform infrared spectroscopy.Increasing intercalation time was found to improve the yield of GO,whereas increasing the PEG molecular weight had the opposite effect.The GO sheets produced from the intercalation–absorption–exfoliation process were found to be a four-layer structure.TEM and Raman analyses indicate that the graphitized structure and oxygen groups of GO were preserved during the exfoliation process.Most importantly,the results show that good-quality GO could be prepared via a mild method involving water absorption of a GrO–PEG composite.

Ethylene glycol solution-induced DNA conformational transitions

We study the properties of the ethylene glycol solutions and the conformational transitions of DNA segment in the ethylene glycol solutions by molecular dynamics simulations based on GROMACS. The hydrogen network structures of water–water and ethylene glycol–water are reinforced by ethylene glycol molecules when the concentrations of the solutions increase from 0% to 80%. As illustrated by the results, conformation of the double-stranded DNA in ethylene glycol solutions, although more compact, is similar to the structure of DNA in the aqueous solutions. In contrast, the DNA structure is an A–B hybrid state in the ethanol/water mixed solution. A fraying of terminal base-pairs is observed for the terminal cytosine. The ethylene glycol molecules preferentially form a ring structure around the phosphate groups to influence DNA conformation by hydrogen interactions, while water molecules tend to reside in the grooves. The repulsion between the negatively charged phosphate groups is screened by ethylene glycol molecules, preventing the repulsion from unwinding and extending the helix and thus making the conformation of DNA more compact.

Effect of poly(ethylene glycol) molecular weight on CO_2/N_2 separation performance of poly(amide-12-b-ethylene oxide)/poly(ethylene glycol) blend membranes

Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.

Synthesis and cost estimation of ethylene oxide process using PRO/Ⅱ

Ethylene oxide （EO） is a sold-out intermediate material for producing various chemicals.Major chemical companies are interested in whether new EO plant can create profit.This research is undertaken to investigate the economic feasibility of EO production.Direct oxidation of ethylene using silver on alpha-A12O3 catalyst type is adapted to produce EO of 60 000 t/year.We conduct the conceptual design.Firstly,we synthesize the optimal structure and then determine optimal conditions and the size of the equipments.Feasibility study shows that profit and loss turning point turns out to be 3.2 years based on the present market price.In addition,we conducts the economic analysis to prepare the risk of raw material market price variation ranging from 70％ to 130％.

One-Stage Technology for Production of Concentrated Ethylene Glycol-Water Solutions （Automotive Antifreeze）

The reactor unit for one-stage technology for production of concentrated ethylene glycol-water solutions is described.Such solutions could be useful for production of automotive antifreezes. The technology is based on the highly selective hydration ofethylene oxide in the presence of heterogeneous catalyst-anion-exchange resin in HCO3-/CO/3/2-_form. The mathematical model of reactor allowed evaluating of economical benefit in comparison with conventional method.

Nanostructure and Formation Mechanism of Pt-WO_3/C Nanocatalyst by Ethylene Glycol Method

Pt-WO3 nanoparticles uniformly dispersed on Vulcan XC-72R carbon black were prepared by an ethylene glycol method.The morphology,composition,nanostructure,electrochemical characteristics and electrocatalytic activity were characterized,and the formation mechanism was investigated.The average particle size was 2.3 nm,the same as that of Pt/C catalyst.The W/Pt atomic ratio was 1/20,much lower than the design of 1/3.The deposition of WO3·xH2O nanoparticles on Vulcan XC-72R carbon black was found to be very difficult by TEM.From XPS and XRD,the Pt nanoparticles were formed in the colloidal solution of Na2WO4,the EG insoluble Na2WO4 resulted in the decreased relative crystallinity and increased crystalline lattice constant compared with those of Pt/C catalyst and,subsequently,the higher specific electrocatalytic activity as determined by CV.The Pt-mass and Pt-electrochemically-active-specific-surface-area based anodic peak current densities for ethanol oxidation were 422.2 mA·mg-1Pt and 0.43 mA·cm-2Pt,1.2 and 1.1 times higher than those of Pt/C catalyst,respectively.

Poly Ethylene Glycols (PEG) and Micelles as Efficient Catalysts for the Oxidation of Xanthine Derivatives under Conventional and Non-Conventional Conditions

Oxidation of Xanthine alkaloid have been studied with various one and two electron oxidizing agents using PEGs and micelle forming surfactants. The reaction is too sluggish in solution phase, but moderately fast in presence of PEGs and micelles. However, the reactions are dramatically enhanced under microwave irradiations. Present protocol has several advantages, such as solvent-free conditions, during work-up, fast reaction times, high yields, eco-friendly operational and experimental simplicity, readily available additives as catalysts.

Co-electrolysis of ethylene glycol and carbon dioxide for formate synthesis

Co-electrolysis of waste plastics and carbon dioxide(CO_(2)) into value-added chemicals or fuels is a promising pathway for a sustainable society, but efficient and selective conversion remains a challenge. Herein, a gold-mediated nickel hydroxide(Au/Ni(OH)_(2)) is developed to oxidize waste plastic-derived ethylene glycol(EG) into formate. In-situ electrochemical experiments and theoretical results reveal that the introduction of Au favors the redox properties and EG adsorption behavior of Ni(OH)_(2). The Au/Ni(OH)_(2) catalyst shows an excellent formate selectivity of >90% at high current densities of above 100 m A cm^(-2). When coupled with sputtered bismuth(Bi) cathode for CO_(2) reduction, a high formate Faradic efficiency(FE) of 188.2% at 200 m A cm^(-2)and a good formate productivity of 7.33 mmol m^(-2)s^(-1)at 10 A are obtained in a flow cell and a zero-gap membrane electrode assembly(MEA) cell, respectively. This work demonstrates a promising strategy to convert waste plastics and CO_(2) into valuable products.

Novel P-doping-tuned Pd nanoflowers/S,N-GQDs photo-electrocatalyst for high-efficient ethylene glycol oxidation

Traditional photo-electcatalyst structures of small noble metal nanoparticles assembling into large-scale photoactive semiconductors still suffer from agglomeration of noble metal nanoparticles,insufficient charge transfer,undesirable photoresponse ability that restricted the photo-electrocatalytic performance.To this end,a novel design strategy is proposed in this work,namely integrating small-scale photoactive materials(doped graphene quantum dots,S,N-GQDs)with large-sized noble metal(Pd P)nanoflowers to form novel photo-electrocatalysts for high-efficient alcohol oxidation reaction.As expected,superior electrocatalytic performance of Pd P/S,N-GQDs for ethylene glycol oxidation is acquired,thanks to the nanoflower structure with larger specific surface area and abundant active sites.Furthermore,nonmetal P are demonstrated,especially optimizing the adsorption strength,enhancing the interfacial contact,reducing metal agglomeration,ensuring uniform and efficient doping of S,N-GQDs,and ultimately significantly boost the catalytic activity of photo-electrocatalysts.

Oxidative coupling of methane in a fixed bed reactor over perovskite catalyst:A simulation study using experimental kinetic model

The oxidative coupling of methane （OCM） to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx （CO2, CO）, and C2 （C2H4 and C2H6） was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity （GHSV） and the methane conversion also decreases by increasing the methane to oxygen ratio.

The Synthesis of Poly(ethylene oxide)-Block-Polybutylacrylate

Poly(ethylene oxide) containing azogroups(pre PEO) was prepared by reacting azoisobutyronitrile (AIBN) with poly( ethylene glycol ) (PEG). The molecular weight of pre PEO was depended on the reaction time, the ratio of PEG to AIBN and the molecular weight of PEG. Pre PEO decomposed in the presence of butylacrylate (BA) monomer to form poly ethylene oxide block butylacrylate copolymers(PEO b PBA). The molecular weights of PEO b PBA and the homopolymer of PBA were proportional to the ratio of BA to pre PEO. The purified block copolymers were charactherized using IR, 1H NMR and GPC.

Fabrication of 3D hollow acorn-shell-like PtBi intermetallics via a surfactant-free pathway for efficient ethylene glycol electrooxidation

The synthesis of atomically ordered Pt-based intermetallic electrocatalysts for the direct alcohol fuel cells generally requires the addition of surfactants or the high-temperature annealing.However,some residual surfactants on the surface of the assynthesized catalysts would prevent the exposure of catalytic active sites,the high-temperature annealing process is easy to accelerate the sintering of the metal,which both lead to the decline of electrocatalytic performance.Herein,we construct the atomically ordered bimetallic PtBi intermetallics with clean surfaces and unique three-dimensional hollow acorn-shell-like structure(3D PtBi HASL)by a simple,low-temperature,surfactant-free one-pot synthetic approach.Benefiting from the special hollow structures,the obtained 3D PtBi HASL intermetallics expose abundant accessible active sites.Moreover,the introduction of oxophilic metal Bi can enhance adsorption of OHads,thereby significantly facilitating removal of poisoned intermediates.Density functional theory(DFT)simulations further indicate that formation of the PtBi intermetallic phase with the downshift of the Pt d-band center endows 3D Pt49.4Bi50.6 HASL intermetallics with significantly attenuated COads and enhanced OHads adsorption,bringing about the boosting electrocatalytic property.The mass activity of the 3D Pt49.4Bi50.6 HASL intermetallics for ethylene glycol oxidation reaction is as high as 24.67 A·mgPt^(−1),which is 12.98 times higher than that of commercial Pt/C(1.90 A·mgPt^(−1)).This work may inspire the design of Pt-based intermetallics as high-efficiency anode electrocatalysts for fuel cell applications.

Controlled synthesis of MOF-derived hollow and yolk–shell nanocages for improved water oxidation and selective ethylene glycol reformation

Delicately designed metal–organic framework(MOF)-derived nanostructured electrocatalysts are essential for improving the reaction kinetics of the oxygen evolution reaction and tuning the selectivity of small organic molecule oxidation reactions.Herein,novel oxalate-modified hollow CoFe-based layered double hydroxide nanocages(h-CoFe-LDH NCs)and yolk–shell ZIF@CoFe-LDH nanocages(ys-ZIF@CoFe-LDH NCs)are developed through an etching–doping reconstruction strategy from a Co-based MOF precursor(ZIF-67).The distinctive nanostructures,along with the incorporation of the secondary metal element and intercalated oxalate groups,enable h-CoFe-LDH NCs and ys-ZIF@CoFe-LDH NCs to expose more active sites with high intrinsic activity.The resultant h-CoFe-LDH NCs exhibit outstanding OER activity with an overpotential of only 278 mV to deliver a current density of 50 mA cm^(-2).Additionally,controlling the reconstruction degree enables the formation of ys-ZIF@CoFe-LDH NCs with a yolk–shell nanocage nanostructure,which show outstanding electrocatalytic performance for the selective ethylene glycol oxidation reaction(EGOR)toward formate,with a Faradaic efficiency of up to 91%.Consequently,a hybrid water electrolysis system integrating the EGOR and the hydrogen evolution reaction using Pt/C||ys-ZIF@CoFe-LDH NCs is explored for energy-saving hydrogen production,requiring a cell voltage 127 mV lower than water electrolysis to achieve a current density of 50 mA cm^(-2).This work demonstrates a feasible way to design advanced MOF-derived electrocatalysts toward enhanced electrocatalytic reactions.

PdPbBi nanoalloys anchored reduced graphene-wrapped metal-organic framework-derived catalyst for enhancing ethylene glycol electrooxidation

For future clean energy demand,it is essential to develop highly efficient and durable materials for use in renewable energy conversion devices.Herein,we report an electrocatalyst loaded with Pd-Pb-Bi nanoalloys on reduced graphene(rGO)-wrapped In_(2)O_(3)(PdPbBi@rGO/In_(2)O_(3))prepared by a hydrothermal method.PdPbBi@rGO/In_(2)O_(3)exhibits higher forward current density(229.12 mA·cm^(-2)),larger electrochemical active surface area(ECSA)(85.87 m^(2)·g^(-1)Pd),smaller impedance(12.68Ω)and lower E_(onset)(-0.56 V)than commercial Pd/C.Specifically,the current density and ECS A are 8.46 and3.38 times higher than those of commercial Pd/C(27.07 mA·cm^(-2),25.41 m^(2)·g^(-1)Pd),respectively.Furthermore,the oxidation mechanism of ethylene glycol and the removal of carbon monoxide[CO]_(ads)from the surface of Pd are also discussed in detail.The columnar support structure wrapped by rGO provides a huge active surface area for catalysis.Moreover,the electronic effect of Pd-PbBi nanoalloys can accelerate the removal of CO intermediate species,obtain more Pd active sites and improve the electrocatalytic performance.Our first synthesis of this highly electrocatalyst offers promising value for commercial application in direct fuel cells.

Bimetallic Au/Pd catalyzed aerobic oxidation of alcohols in the poly(ethylene glycol)/CO_(2) system

Bimetallic Au/Pd nanoparticles were prepared and used to catalyze oxidation of alcohols in the poly(ethylene glycol) (PEG)/CO_(2) biphasic system using O2 as the oxidant without adding any base.The catalytic activity of Au/Pd bimetal with different mole ratios was studied using benzyl alcohol as the substrate.It was found that bimetallic Au/Pd nanoparticles with Au:Pd=1:3.5 had higher catalytic activity than monometallic Au,Pd and the bimetallic Au/Pd nanoparticles with other molar ratios.The effect of CO_(2) pressure on the oxidation of benzyl alcohol and 1-phenylethanol in PEG/CO_(2) was investigated.It was demonstrated that CO_(2) pressure could be used to tune the conversion and selectivity of the reactions effectively.α,β-Unsaturated alcohols were also studied and found to be more reactive than benzyl alcohol and 1-phenylethanol.Recycling experiments showed that the Au/Pd/PEG/CO_(2) catalytic system could be recycled at least four times without reducing the activity.In addition,the catalytic system is clean and the products can be separated easily.

In situ time-resolved FTIRS study of adsorption and oxidation of ethylene glycol on Pt(100) electrode

Adsorption and oxidation of ethylene glyco(EG) on Pt(100) electrode were studied by in situ timeresolved FTIRS (TRFTIRS). The TRFTIR spectra recordedat 0.10 V illustrate that an IR band appears near 2050 cm?at t > 5 s, corresponding to linearly bonded CO formed indissociative adsorption of EG. The TRFTIR results haveconfirmed also that CO species are distributed uniformly onPt(100) surface. Another band appears near 2342 cm?1 at > 70 s, associating with IR absorption of CO2 produced inthe direct oxidation of EG. With the increase of electrodepotential, the direct oxidation of EG becomes gradually themain reaction. When the potential is above 0.40 V, the oxidation of EG occurs mainly via the reactive intermediates, i.especies containing –COOH determined by in situ TRFTIRS.

Cascade degradation and electrocatalytic upcycling of waste poly(ethylene terephthalate)to valued products

The global annual production of poly(ethylene terephthalate)(PET)has reached 82 million tons,yet only a small fraction(less than 20%)is recycled.The ultra-slow degradation rate of PET results in the accumulation of PET waste in the environment,causing serious plastic pollution and posing severe challenges to ecosystems.In response,great efforts have been directed toward developing a cascade degradation and electrocatalytic upcycling strategy,which serves as a“waste-towealth”pathway.This strategy involves electro-reforming PEThydrolyzed intermediates or using PET pyrolyzed products as electrocatalysts to generate high-value products.This review provides an overview of the state-of-the-art strategies for the“degradation-electrocatalytic upcycling(De-eUp)”of PET waste.Initially,an introduction to the strategy is provided,categorizing it into two main frameworks:“pyrolysis-electrocatalytic upcycling”and“hydrolysis-electrocatalytic upcycling”.The section on“pyrolysis-electrocatalytic upcycling”delves into the degradation methods for designing derived carbon nanomaterials and their utilization as high-performance electrocatalysts.The“hydrolysis-electrocatalytic upcycling”section discusses recent advancements in electro-reforming of PET hydrolyzed intermediates for the production of C_(1) and C_(2) products.The review concludes by examining the challenges and future prospects in developing an efficient and economical PET upcycling strategy.It is anticipated that this review will stimulate further progress in plastic waste valorization.

Upgrading ethylene via renewable energy-driven electrocatalysis

Ethylene oxide(EO)and ethylene glycol(EG)are two important commodity chemicals and are industrially produced from petroleum-derived ethylene via thermocatalytic processes.The overoxidation of ethylene and the implementation of high temperature and pressure lead to substantial CO_(2)emission.Renewable energy-driven electrocatalysis provides a low-carbon route for upgrading ethylene under mild conditions,especially when it couples with ethylene electrosynthesis from CO_(2).In this minireview,we summarize recent achievements in the selective electrocatalytic oxidation of ethylene to EO and EG.Three main reaction routes including direct electrocatalytic oxidation with water,indirect electrocatalytic oxidation with halide mediators,and tandem electrocatalytic and thermocatalytic oxidation with hydrogen peroxide intermediate,are discussed.Some representative catalyst systems and reactor designs are exemplified.We discuss the existing scientific and technical challenges of electrocatalytic ethylene upgrading in terms of reaction rate,selectivity,and long-term stability,and propose future research directions and opportunities for pushing the process towards practical application.