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 kinetics of dimethyl ether one-step synthesis over CeO_2–CaO–Pd/HZSM-5 catalyst in sulfur-containing syngas process

CeO_2–CaO–Pd/HZSM-5 catalyst was prepared for the dimethyl ether(DME) one-step synthesis in a continuous fixed-bed micro-reactor from the sulfur-containing syngas. The catalytic stability over hybrid catalyst of CeO_2–CaO–Pd/HZSM-5 was investigated to ensure that the kinetics experimental results were not significantly influenced by induction period and catalytic deactivation. A large number of kinetic data points(40 sets) were obtained over a range of temperature(240–300 °C), pressure(3–4 MPa), gas hourly space velocity(GHSV)(2000–3000 L·kg^(-1)·h^(-1)) and H_2/CO mole ratio(2–3). Kinetic model for the methanol synthesis reaction and the dehydration of methanol were obtained separately according to reaction mechanism and Langmuir–Hinshelwood mechanism. Regression parameters were investigated by the method combining the simplex method and Runge–Kutta method. The model calculations were in appropriate accordance with the experimental data.

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME)by CO2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO2 catalysts that were physically mixed with a commercial ferrierite(FER)zeolite.The catalysts were characterized by N2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO2(CO2-TPD),temperature programmed desorption of NH3(NH3-TPD),and temperature programmed H2 reduction(H2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO)species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.