合成二甲氧基甲烷技术研究进展

二甲氧基甲烷作为用途广泛的化工原料,其合成技术在不断创新与发展。根据反应原料和工艺流程的不同对二甲氧基甲烷合成技术进行了概述与简评,该技术包含甲醇与甲醛催化缩合制备二甲氧基甲烷、甲醇与多聚甲醛反应制备二甲氧基甲烷、甲醇一步法制取二甲氧基甲烷、离子液体电催化氧化甲醇制取二甲氧基甲烷、二甲醚氧化生成二甲氧基甲烷、二溴甲烷合成二甲氧基甲烷、合成气制备二甲氧基甲烷、甲醇与二氧化碳反应制取二甲氧基甲烷等。醇醛缩合制备二甲氧基甲烷仍是当前主流的生产工艺,甲醇一步法制取二甲氧基甲烷工艺因在环境和投资上有优势而被广泛研究,是最具工业化前景的新技术,该技术尚需突破的是兼具氧化还原性与酸性的双功能催化剂。     

煤与不同原料重整气化制甲醇对CO2排放的影响

通过介绍煤制甲醇对整个煤化工行业CO2排放的影响,选择以煤制甲醇工艺CO2排放为研究对象,分别叙述了煤气化制合成气,煤与天然气、煤与焦炉气以及煤与重质油重整气化制合成气联合生产甲醇过程中,吨甲醇产品工艺CO2排放情况,探讨不同煤气化形式对工艺CO2排放的影响因素,为如何通过气化工艺选型,降低煤制甲醇生产过程中工艺CO2排放量提供理论判断依据。     

Effect of particle shape on methanol partial oxidation in a fixed bed using CFD reactor modeling

Particle shape is one of the most important parameters in the design and optimization of fixed-bed processes. To address the impact of particle shape on methanol partial oxidation to formaldehyde over molybdate catalyst, packings of spheres, cylinders, rings, and trilobes are numerically generated. The generated packings are used to carry out resolved particle Computational Fluid Dynamics (CFD) simulations under industrial conditions. Pressure drop, voidage and velocity profiles, radial heat transfer, and local and overall conversion and selectivity results are presented. Despite their lower particle surface area, lower particle effectiveness and more uneven flow distribution than trilobes, and lower overall heat transfer coefficient than cylinders, rings had the best conversion and selectivity due to their balance between the factors. Three longer tubes of rings, rings and cylinders, and rings and trilobes are simulated and show a small gain in selectivity for the rings and trilobes.     

低温甲醇洗系统贫富甲醇换热器泄漏原因分析及处理

介绍了晋煤天溪煤制油分公司低温甲醇洗系统贫富甲醇换热器的泄漏情况。分析了贫富甲醇换热器泄漏初期生产运行指标的异常现象和造成泄漏的原因,认为泄漏是不同物质对设备的腐蚀、冲刷造成的,并针对泄漏的具体情况,提出了不同的检修处理措施:管束泄漏量低于10%时,可采用焊接锲形堵头将泄漏列管两端进行封堵;管束泄漏量高于10%时,如换热器设计余量足,可将封头内部隔板取出,短接进出口;将换热管材质由10#钢换为06Cr19Ni10不锈钢。     

Molecular sieve as an effective barrier for methanol crossover in direct methanol fuel cells

Methanol crossover is still a significant barrier to the commercialization of direct methanol fuel cells with wide-used Nafion® membrane. Herein, molecular sieve is introduced into the design of polymer electrolyte membrane to alleviate methanol crossover. The UZM-9 zeolite with an intermediate window size of 0.42 nm can effectively separate hydrated methanol (ca. 1.10 nm) and hydrated proton (ca. 0.23 nm). The methanol diffusion rate through the membrane is effectively suppressed after modified with UZM-9, which is about four times lower than the origin Nafion® membrane. The resulted peak power density reached 80 mW cm⁻² with 2 mol L⁻¹ methanol solution feed, which is 2.5-fold higher than that of direct methanol fuel cell with commercial Nafion® membrane. These results open a promising route to alleviate methanol crossover in direct methanol fuel cells.     

Preparation and characterization of polyvinylchloride membrane embedded with Cu nanoparticles for electrochemical oxidation in direct methanol fuel cell

Copper nanoparticles were prepared by the chemical reduction method. These copper particles were embedded into the polyvinylchloride (PVC) matrix as support and used as an electrode (PVC/Cu) for the oxidation of methanol fuel for improving the current response. The PVC/Cu electrodes were characterized by thermal gravimetric analysis (TGA) for thermal stability of the electrode, X-ray diffraction (XRD) for identification of copper nanoparticles in the electrode, Fourier transform infrared spectroscopy (FTIR) to identify the interaction between PVC and Cu and scan electron microscopy (SEM) with EDAX for the morphology of the electrode. The electrocatalytic activity of the electrode was characterized by the cyclic voltammetry, linear sweep voltammetry, and chronoamperometry techniques. An increase in the electrode activity was observed with the increase of copper quantity from 0.18 g (PVC/Cu-0.18 g) to 0.24 g (PVC/Cu-0.24 g) and the maximum was found at 0.24 g of copper in the electrode. Also, it was observed that the electrode achieved the maximum catalytic current in 0.5 mol/L CH₃OH + 1 mol/L NaOH solution. FTIR identified that water molecules, C—H group, copper nanoparticle and its oxide were available in the electrode. SEM images with EDAX showed that copper particles were properly embedded in the polyvinylchloride matrix.     

High-performance molecular-separation ceramic membranes derived from oxidative cross-linked polytitanocarbosilane

Polytitanocarbosilane (TiPCS)-derived ceramic membranes were fabricated using a pre-ceramic polymer. Special attention was focused on a process of thermal-oxidative curing that was used to induce cross-linking and the effect of this process on the ceramic yield, thermal stability, oxidation resistance, and microstructure of TiPCS. The cross-linked TiPCS powders showed a ceramic yield and thermal stability that were higher than that from the non-cross-linked version. In addition, the cross-linked TiPCS with uniform micropores showed higher levels of N₂ and CO₂ adsorption capacity, BET surface area, and micropore volume than the non-cross-linked versions, and the cross-linking process enhanced the stability of the pore structure at high temperature. The cross-linked TiPCS membranes showed high H₂ permeance (1.49 × 10⁻⁶ mol/(m² s Pa)) with sub-nanopores (H₂/SF₆ selectivity: 12 000, H₂/N₂: 10), and in addition higher oxidation resistance than their non-cross-linked counterparts. Furthermore, the influence of the concentration of the TiPCS precursor coating solution was optimized and the hydrothermal stability of the membranes at high temperatures was also evaluated. The optimized membrane demonstrated great performance for the pervaporation removal of methanol in binary azeotropic systems of either MeOH/butyl acetate or MeOH/toluene, and it also showed high hydrothermal stability with excellent dehumidification performance under high temperatures.     

Methanol and proton transport through chitosan-phosphotungstic acid membranes for direct methanol fuel cell

Composite chitosan-phosphotungstic acid membranes were synthesized by ionotropic gelation. Their liquid uptake is higher for thin membranes (23 ± 2 μm), while it is lower (~70%) for thicker membranes (50-70 μm). Polarization curves recorded using single module fuel cell at 70°C allowed to estimate a peak power density of 60 mW cm⁻² by using 1 M as methanol and low Pt and Pt/Ru loadings (0.5 and 3 mg cm⁻²) at the cathode and at the anode, respectively. Electrochemical impedance spectroscopy was used to estimate the membrane conductivity and to model the electrochemical behavior of methanol electrooxidation inside the fuel cell revealing a two-step mechanism mainly responsible of overall kinetic losses. Transport of methanol inside the membrane was studied by potentiostatic measurements, allowing to estimate a methanol diffusivity of 3.6 × 10⁻⁶ cm² s⁻¹.     

Investigation of the versatility of SPES membranes customized with sulfonated molybdenum disulfide nanosheets for DMFC applications

Sulfonated poly(ether sulfone) (SPES) based proton exchange membranes (PEMs) are fabricated using sulfonated molybdenum disulfide (S-MoS₂) nanosheets via facile solution casting method. SPES (DS = 30%) and S-MoS₂ are synthesized and sulfonation is evidently observed in FTIR and XRD analysis. The anchoring of sulfonic acid group on exfoliated molybdenum disulfide (E-MoS₂) and elemental composition of S-MoS₂ are confirmed by XPS spectrum. Physico-chemical characteristics such as ion-exchange capacity (IEC), water uptake, swelling ratio and oxidation stability are found to be increases after the addition of S-MoS₂ into SPES matrix. Increment in S-MoS₂ content in SPES matrix decreases the surface contact angle due to the increase in hydrophilicity. Further, the dispersing ability of S-MoS₂ in SPES matrix is evidently shown by an increase in surface roughness, tensile strength and thermal stability of the SPES/S-MoS₂ nanocomposite membranes. On the whole, SPES/S-MoS₂-1 membrane showed the highest proton conductivity of 5.98 × 10⁻³ Scm⁻¹, selectivity of 19.6 × 10⁴ Scm⁻³s, peak power density of 28.28 mWcm⁻² and lesser methanol permeability of 3.05 × 10⁻⁸ cm²s⁻¹. The strong interfacial interaction between SPES and S-MoS₂ in nanocomposite membranes create strong hydrogen bond network to facilitate the proton conduction pathway via both vehicle and Grotthuss type mechanisms. Overall results suggested that the SPES/S-MoS₂ nanocomposite membranes are superior and appropriate alternative for commercially high-cost Nafion® membranes for use in renewable direct methanol fuel cell (DMFC) devices.