Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.

Compositional modeling and simulation of dimethyl ether (DME)-enhanced waterflood to investigate oil mobility improvement

Dimethyl ether （DME） is a widely used industrial compound, and Shell developed a chemical EOR technique called DME- enhanced waterflood （DEW）. DME is applied as a miscible solvent for EOR application to enhance the performance of conventional waterflood. When DME is injected into the reservoir and contacts the oil, the first-contact miscibility process occurs, which leads to oil swelling and viscosity reduction. The reduction in oil density and viscosity improves oil mobility and reduces residual oil saturation, enhancing oil production. A numerical study based on compositional simulation has been developed to describe the phase behavior in the DEW model. An accurate compositional model is imperative because DME has a unique advantage of solubility in both oil and water. For DEW, oil recovery increased by 34% and 12% compared to conventional waterflood and CO2 flood, respectively. Compositional modeling and simulation of the DEW process indicated the unique solubility effect of DME on EOR performance.

Harnessing dimethyl ether and methyl formate fuels for direct electrochemical energy conversion

In this work,the oxidation of a mixture of dimethyl ether(DME) and methyl formate(MF) was studied in both an aqueous electrochemical cell and a vapor-fed polymer electrolyte membrane fuel cell(PEMFC)utilizing a multi-metallic alloy catalyst,Pt_(3)Pd_(3)Sn_(2)/C,discovered earlier by us.The current obtained during the bulk oxidation of a DME-saturated 1 M MF was higher than the summation of the currents provided by the two fuels separately,suggesting the cooperative effect of mixing these fuels.A significant increase in the anodic charge was realized during oxidative stripping of a pre-adsorbed DME+MF mixture as compared to DME or MF individually.This is ascribed to greater utilization of specific catalytic sites on account of the relatively lower adsorption energy of the dual-molecules than of the sum of the individual molecules as confirmed by the density fu nctional theory(DFT) calculations.Fuel cell polarization was also conducted using a Pt_(3)Pd_(3)Sn_(2)/C(anode) and Pt/C(cathode) catalysts-coated membrane(CCM).The enhanced surface coverage and active site utilization resulted in providing a higher peak power density by the DME+MF mixture-fed fuel cell(123 mW cm^(-2)at 0.45 V) than with DME(84mW cm^(-2)at 0.35 V) or MF(28 mW cm^(-2)at 0.2 V) at the same total anode hydrocarbon flow rate,temperature,and ambient pressure.

Multidimensional modeling of Dimethyl Ether(DME) spray combustion in DI diesel engine

In the present study a modified CFD code KIVA3V was used to simulate the spray combustion in a small DI diesel engine fueled with DME. The improved spray models consider more spray phenomena such as cavitation flow in nozzle hole, jet atomization, droplet second breakup and spray wall interaction. Otherwise, a reduced DME reaction mechanism is implemented in the combustion model, and a new turbulent combustion model?Partial Stirred Reactor (PaSR) model is selected to simulate the spray combustion process, the effects of turbulent mixing on the reaction rate are considered. The results of engine modeling based on those models agreed well with the experimental measurements. Study of temperature fields variation and particle traces in the combustion chamber revealed that the engine combustion system originally used for diesel fuel must be optimized for DME.

基于OH^(*)的NH_(3)-H_(2)-DME高温自着火特性

氨(NH_(3))作为一种十分有前景的零碳替代燃料,其低反应性限制了它的发展和应用,而掺混与其特性互补的其他低碳或零碳燃料,可明显改善其燃烧特性.基于此,在激波管试验平台上利用反射激波和燃料激发态羟基(OH^(*))的自发光特性,测量了温度T为1 300~2 000 K、压力p为0.14 MPa与1.00 MPa且当量比φ为0.5、1.0和2.0条件下,NH_(3)-氢(H_(2))-二甲醚(DME)三元燃料与空气混合燃料的着火延迟期(IDT),并研究了H_(2)+DME作为二元活性剂,其比例在各工况下对纯NH_(3)混合燃料着火延迟期缩短率的影响.结果表明:活性组分比例会影响活性剂的着火促进效果,活性剂H_(2)+DME(摩尔分数比为1∶1)相比同比例下的单一活性剂可以降低混合燃料更多的活化能.三元混合燃料的着火特性随活性剂比例、反应条件不同,有截然不同的特点,其中,在稀燃条件下,H_(2)+DME(摩尔分数比为2∶1)着火促进效果更好,而在富燃条件下,H_(2)+DME(摩尔分数比为1∶2)活性更高.

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

The effect of calcination temperature on the catalytic activity for the dimethyl ether （DME） carbonylation into methyl acetate （MA） was investigated over mordenite supported copper （Cu/HMOR） prepared by ion-exchange process. The results showed that the catalytic activity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃, 1.5 MPa, and GSHV of 4883 h^-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.

Attrition resistant catalyst for dimethyl ether synthesis in fluidized-bed reactor

Fluidized-bed reactor is a candidate for dimethyl ether （DME） synthesis from syngas because of its excellent heat removal capability. In order to improve the attrition resistance of catalyst, an amount of silica sol as binder was added to the catalyst composed of methanol synthesis component CuO/ZnO/Al2O3 and methanol dehydration component HZSM-5, which was prepared by coprecipitation and shaped by spray drying to get spherical particles. The effect of silica sol on the catalytic activity was investigated in a fixed-bed flow microreactor. Based on the experiment results, silica sol in the range of 0-20wt% had small effect on the catalytic activity. Generally, the CO conversion and DME yield decreased with the increase in concentration of silica sol, while the attrition resistance of catalysts increased with increasing silica sol, indicating that it was feasible to improve the attrition resistance without greatly sacrificing the activity of catalyst. In addition, the characterizations of catalysts were carried out using Brunauer-Emmett-Teller （BET）, X-ray powder diffraction （XRD） and temperature programmed reduction （TPR）.

Production of Light Olefins from Biosyngas by Two-stage Catalytic Conversion Process via Dimethyl Ether

NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas （H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%） with low H/C ratio of 1.0 was used as feed gas.

Polymethoxy Dimethyl Ether/汽油混合燃料喷雾特性实验研究

为了明确聚甲氧基二甲醚(PODE)掺混对汽油喷雾特性的影响,利用定容弹试验台和高速纹影摄像装置对不同喷射压力和环境温度下的汽油(G100)、PODE(P100)及其混合燃料(G80P20、G50P50)的宏观喷雾特性进行了实验研究,获得了燃料的喷雾过程图像,并提取了喷雾贯穿距离、喷雾锥角和喷雾投影面积等特征参数。实验结果表明,随PODE掺混比增大,混合燃料喷雾贯穿距离和喷雾锥角增大,且环境温度较高时,不同燃料之间的差异较大;喷射压力较大时,燃料喷雾投影面积较大,4种燃料的喷雾投影面积的差异也较大;随环境温度升高,混合燃料喷雾投影面积减小,且其减小幅度随PODE掺混比增大而减弱。G100的喷雾投影面积随环境温度升高大幅度减小,而P100的喷雾投影面积几乎不随实验范围内环境温度的升高而改变;掺混20%PODE的混合燃料具有比汽油略大的喷雾贯穿距离、喷雾锥角和喷雾投影面积,油气混合质量与汽油类似,更高比例PODE掺混会使燃料与空气混合程度和蒸发性能变差。

Direct Dimethyl Ether Synthesis

Dimethyl ether (DME) is a clean and economical alternative fuel which can beproduced from natural gas through synthesis gas. The properties of DME are very similar to those ofLP gas. DME can be used for various fields as a fuel such as power generation, transportation, homeheating and cooking, etc. It contains no sulfur or nitrogen. It is not corrosive to any metal andnot harmful to human body. An innovative process of direct synthesis of DME from synthesis gas hasbeen developed. Newly developed catalyst in a slurry phase reactor gave a high conversion and highselectivity of DME production. One and half year pilot scale plant (5 tons per day) testing, whichwas supported by METI, had successfully finished with about 400 tons DME production.

Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flory distribution law.The chain propagation proceeds through the insertion of an individual segment of CH2O one by one,while the simultaneous insertion of a few CH2O segments or their assembly is unlikely.Due to the restriction of this law,it is difficult to increase the selectivity to the desired products(e.g.,PODE3 4).

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.

Effects of ZrO_2 on the Performance of CuO-ZnO-Al_2O_3/HZSM-5 Catalyst for Dimethyl Ether Synthesis from CO_2 Hydrogenation

A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.

Preparation of nanocrystalline γ-Al_2O_3 catalyst using different procedures for methanol dehydration to dimethyl ether

A series of nanocrystalline γ-alumina are synthesized by different procedures, namely, thermal decomposition method （sample A）, precipita-tion method （sample B） and sol-gel method using sucrose and hexadecyltrimethyl ammonium bromide （CTAB） as templates （samples C and D, respectively）. Textural and acidic properties of γ-alumina samples are characterized by XRD, N2 adsorption-desorption and NH3-TPD techniques. Vapor-phase dehydration of methanol into dimethyl ether is carried out over these samples. Among them, sample C shows the highest catalytic activity. NH3-TPD analysis reveals that the sample with smaller crystallite size possesses higher concentration of medium acidic sites and consequently higher catalytic activity. Thermal decomposition method leads to decrease in both surface area and moderate acidity, therefore it is the cause of lower catalytic activity.

Catalytic performance of hierarchical H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether

Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 were prepared by the hydrothermal technique with alkali-treated H-ZSM-5zeolite as the source and characterized by scanning electron microscopy,transmission electron microscopy,energy dispersive spectroscopy,X-ray diffraction,N2 adsorption-desorption measurement and NH3 temperature-programmed desorption.The catalytic performances for the methanol dehydration to dimethyl ether over H-ZSM-5/MCM-41 were evaluated.Among these catalysts,H-ZSM-5/MCM-41 prepared with NaOH dosage (nNa/nSi) varying from 0.4 to 0.47 presented excellent catalytic activity with more than 80%methanol conversion and 100%dimethyl ether selectivity in a wide temperature range of 170—300℃,and H-ZSM-5/MCM-41 prepared with nNa/nSi=0.47 showed constant methanol conversion of about 88.7%,100% dimethyl ether selectivity and excellent lifetime at 220℃.The excellent catalytic performances were due to the highly active and uniform acidic sites and the hierarchical porosity in the micro-mesoporous composite molecular sieves.The catalytic mechanism of H-ZSM-5/MCM-41 for the methanol dehydration to dimethyl ether process was also discussed.

Mathematical Simulation and Design of Three-Phase Bubble Column Reactor for Direct Synthesis of Dimethyl Ether from Syngas

A three-phase reactor mathematical model was set up to simulate and design a three-phase bubble column reactor for direct synthesis of dimethyl ether （DME） from syngas, considering both the influence of part inert carrier backmixing on transfer and the influence of catalyst grain sedimentation on reaction. On the basis of this model, the influences of the size and reaction conditions of a 100000 t/a DME reactor on capacity were investigated. The optimized size of the 10000 t/a DME synthesis reactor was proposed as follows： diameter 3.2 m, height 20 m, built-in 400 tube heat exchanger （Ф 38×2 mm）, and inert heat carrier paraffin oil 68 t and catalyst 34.46 t. Reaction temperature and pressure were important factors influencing the reaction conversion for different size reactors. Under the condition of uniform catalyst concentration distribution, higher pressure and temperature were proposed to achieve a higher production capacity of DME. The best ratio of fresh syngas for DME synthesis was 2.04.

Catalytic Oxidation of Dimethyl Ether to Hydrocarbons over SnO_2/MgO and SnO_2/CaO Catalysts

A novel reverse microemulsion method was used to prepare SnO2/MgO and SnO2/CaO catalysts. It was found that both the catalysts were active for the reaction of catalytic oxidation of dimethyl ether （DME） in the temperature range of 275 to 300 ℃. SnO2/CaO catalyst exhibits much higher activity than SnO2/MgO. On SnO2/CaO catalyst, DME conversion of 21.8% was obtained at 300℃, while selectivities to methyl formate （MF） and dimethoxyethane （DMET） of 19.1% and 59.0% respectively were obtained at 275 ℃.

Catalytic Oxidation of Dimethyl Ether to Dimethoxymethane over Cs Modified H_3PW_(12)O_(40)/SiO_2 Catalysts

The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40（40%）/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40（40%）/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40（40%）/SiO2.

A1_2O_3 Effect on the Catalytic Activity of Cu-ZnO-Al_2O_3-SiO_2 Catalysts for Dimethyl Ether Synthesis from CO_2 Hydrogenation

The effect of Al2O3 on the Cu-ZnO-Al2O3-SiO2 catalysts prepared by a pseudo sol-gel method has been investigated and these catalysts were characterized by XRD, H2-TPR, XPS, NH3-TPD and CO2- TPD techniques. As revealed by XRD and H2-TPR, the added alumina produces high dispersion of CuO and makes the reduction of CuO difficult. XPS analysis detects a remarkably high Al^3＋ enrichment at the surface of calcined samples, along with a decrease of Eb of Cu 2p3/2, which confirms the Cu-Al interaction. Another important role of Al203 would be to incorporate into the SiO2 structure to form the acid-base sites for ether formation. The reaction results shows that the addition of Al2O3 exhibits a promoting effect on the CO2 conversion only when its content is below 1.4%, and an optimal DME selectivity is obtained when 4.0%Al2O3 is added, indicating a better ＇synergistic effect＇ is present between the methanol forming component and the acidic component in bifunctional catalysts. Possible relationship between the catalytic activity and the Cu-Al interaction as well as the surface acidity is discussed.