碳酸二甲酯生产中液体二氧化碳冷量利用的研究

研究了碳酸二甲酯装置生产过程中液体二氧化碳冷量利用的问题。通过合理利用液体二氧化碳的冷量,起到了既能替代冷水机组制冷,又能降低装置蒸汽消耗量的作用。装置经过二氧化碳冷量利用改造后,经济效益大大提高。     

Degradation of phthalate esters (PAEs) in soil and the effects of PAEs on soil microcosm activity

BACKGROUND: Phthalate esters (PAEs), a class of refractory and toxic organic compounds, are becoming one of the most widespread contaminants in the environment. Degradation of PAEs in soil has been investigated, but limited to one or a few kinds of PAEs. Microorganisms could be regarded as a sensitive bio‐indicator for soil contaminants. Therefore, four commonly used PAEs were chosen to investigate their degradation patterns and potential impacts on soil microbial activity with a series of bioassays. RESULT: PAEs in sterile soils changed slightly, while degradation of PAEs in non‐sterile soil followed a single first‐order kinetic. Higher concentrations of PAEs led to lower β‐glucosidase activity and higher protease activity, with smooth changes of phosphatase and urease activities. PAEs decreased average well color development (AWCD), while Shannon index (H) showed a tendency to increase after a decrease. Carbon utilization profile was affected significantly by PAEs, especially at 10 mg kg^?1 soil. CONCLUSION: Degradation of PAEs was driven mainly by microbial mediated processes. PAEs affected carbon, nitrogen and phosphorus cycles variously, and had temporal effects on metabolic diversity, owing to the adaptation of microbes. Carbon substrates utilization changed from easily degradable sugars and carboxylic acids to recalcitrant compounds during the simulation. Copyright © 2010 Society of Chemical Industry     

Measurement and chemical kinetic prediction of detonation sensitivity and cellular structure characteristics in dimethyl ether-oxygen mixtures

In this work, experiments have been performed to measure the detonation velocities and characteristic cell sizes in the dimethyl ether (DME) fuel-oxygen mixtures. Equilibrium calculation and detailed chemical kinetics modeling of the ZND structure of detonations are also carried out to investigate the detonation characteristics of DME. Detonation cell sizes estimated using a correlation model by Ng et al. [Ng HD, Ju Y, Lee JHS. Assessment of detonation hazards in high-pressure hydrogen storage from chemical sensitivity analysis. Int J Hydrogen Energy 2007;32:93-99] are in good agreement with experimental data. It is found that the cell size values for DME-oxygen mixtures are comparable to those of propane or ethane fuels. At low initial pressure, double cell like detonation structures have been observed in all equivalence ratios considered in this study. Chemical kinetic results reveal that DME oxidation under detonation environment exhibits similarly a two-stage heat release process inside the reaction zone. This effect may play a significant role in the existence and scaling of the multi-cell detonation pattern in stoichiometric and fuel-rich DME mixtures. On the lean side, multiple cells appear to be caused primarily by the strong intrinsic instability of the unsteady detonation front. The present experimental results and chemical kinetic sensitivity analyses provide some basic information to assess detonation hazards in DME-based mixtures.     

Recovery of 1,4‐Dimethyl Piperazine from Aqueous Solutions Using Polymeric Adsorbent and Ion‐Exchange Resins

Abstract

Strong and weakly acidic ion exchange resins and polymeric adsorbents are used for recovery of 1,4‐dimethyl piperazine (DMP) from aqueous solutions. Sorption of the amine in undissociated form is the primary mechanism of uptake of DMP on the ion‐exchange resins. Equilibrium adsorption data for DMP on the resins, at various temperatures, are fitted in Langmuir adsorption isotherm. Kinetic studies show that intraparticle diffusional resistance controls the sorption of DMP into the resin matrix. A mathematical model based on intraparticle diffusion and external mass transfer is used for simulating breakthrough profiles and compared with the experimental results for a fixed bed of weakly acidic Indion‐652 resin. The DMP loaded bed of the resin was effectively regenerated with methanol.     

Characteristics of integrated micro packed bed reactor-heat exchanger configurations in the direct synthesis of dimethyl ether

The performance of three integrated micro packed bed reactor-heat exchangers (IMPBRHEs) for direct DME synthesis over physical mixtures of CuO–ZnO–Al₂O₃ and γ-Al₂O₃ catalysts was experimentally investigated. Systematic variations in reactor and slit dimensions and configuration were analyzed in terms of thermal behaviour, mass transfer, pressure drop and residence time distribution (RTD). The pressure drop was always small (<0.12 bar) relative to the total pressure (50 bar), and linear dependence with GHSV confirms the predicted laminar flow for Re = 0.1–2. A narrow RTD was estimated by the dispersion analysis. Careful temperature measurements confirmed that the reaction temperature is mainly controlled by the oil heat exchange to give a practically uniform temperature profile for set inlet oil temperatures of 220–320 °C. The micro packed beds were found free of the internal as well as external mass transfer limitations, as showed by no significant change in the CO conversion and DME yield for different catalyst particle sizes, no effect of varying the linear gas velocity, and no effect of manipulating reactant diffusion coefficient. Packed bed microstructured reactors hence provide an isobaric and isothermal environment free from transport limitations for the direct DME synthesis, in the kinetic regime as well as at equilibrium conversion.     

SYNTHESIS OF DIMETHYL SULPHIDE DURING FERMENTATION BY A ROUTE NOT INVOLVING THE HEAT-LABILE DMS PRECURSOR OF MALT

Pilot scale brewing studies showed that dimethyl sulphide (DMS) can be produced during fermentation substantially in excess of that predicted by measurement of the DMS potential of the wort. This occurred in low temperature fermentations conducted in conical vessels but not if open vessels were used. Neither the type of malt used nor the length of the wort boil substantially influenced the extent of this excess DMS production although they may have affected liberation from the yeast of unidentified material which released DMS on treatment with hot alkali. It is suggested that yeast can synthesise S-methyl-L-methionine (SMM) and that metabolic breakdown of this compound was responsible for some of the DMS produced.     

Formation and nanoscale-characteristics of soot from pyrolysis of ethylene blended with ethanol/dimethyl ether

Ethanol and dimethyl ether (DME) have been considered to be two of the most potential additives for conventional hydrocarbon fuels. This paper focused on the nanoscale characteristics of soot from ethylene pyrolysis with ethanol and DME additions. The pyrolysis experiments were conducted in a α-alumina tube flow reactor at 1273 K, 1373 K and 1473 K, with the replacement of 0%, 50% and 100% (mole fraction) ethylene by the two oxygenated fuels. The gas-phase kinetic modeling was also performed to explore and understand the soot formation process. The main pathways and some key soot precursors in the pyrolysis have been obtained. Soot samples were characterized by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) to acquire their internal structure and oxidation reactivity. Results showed that the mass of collected soot diminished with the increase of the replacement of ethylene by ethanol/DME. The effects of DME to inhibit the formation of soot were more obvious. The least amount of soot was collected in the pyrolysis of pure DME. Peak mole fraction of C₂H₂, C₄H₂, C₄H₄ and C₅H₅ also decreased with the increase of replacement of ethylene by ethanol/DME, displaying the same tendency with the variation trend of soot mass in the different pyrolysis conditions. According to TEM and HRTEM results, the additions of ethanol and DME could decrease the growth rate of soot contrasted with the pyrolysis of pure ethylene. Soot collected from the pyrolysis of pure DME at 1273 K and 1373 K showed a typical amorphous structure with short, highly-curved and turbulent fringe. With the reduction of the replacement of ethylene by DME, mature soot with longer and more ordered fringe formed at 1373 K and 1473 K. The sequence of the mean fringe tortuosity of soot samples was 100% ethylene<50% DME<100% ethanol<50% ethanol< 100% DME. The order was the same as the sequence of oxidation reactivity. Furthermore, with the increase of temperature, the mass of soot increased. More mature soot with higher degree of graphization, longer fringe length, smaller fringe tortuosity and lower oxidation reactivity was obtained. High correlation between soot nanostructure and soot oxidation reactivity was found.     

Adsorption and catalytic decomposition of dimethyl sulfide on H-BEA zeolite

Catalytic direct decomposition of dimethyl sulfide (DMS) was performed using solid acid catalysts to develop an on-site hydrogen-free desulfurization system for utilization in small systems, such as fuel cells. DMS was decomposed to CH₃SH and H₂S at 500 °C on SiO₂–Al₂O₃ and various zeolite catalysts. Among the catalysts, H-BEA zeolite with Si/Al = 18.5 (H-BEA-18.5) showed the highest performance for DMS decomposition at 500 °C. While the catalytic activity at 500 °C maintained a DMS conversion of greater than 30% for up to 114 h, a large amount of carbon deposition caused gradual deterioration. At a low temperature of 400 °C, DMS decomposition to CH₃SH on H-BEA-18.5 continued for 100 h with a stable conversion of approximately 30%, although the adsorption of DMS on the catalyst surface was also confirmed. To achieve a high performance for the DMS decomposition, high temperatures were required to avoid the adsorption of sulfur species.