酯交换法合成碳酸甲乙酯催化剂的研究进展

碳酸甲乙酯（EMC）是一种环境友好型的不对称碳酸酯，因其独特的结构性质被广泛用作溶剂或有机合成中间体，特别是随着锂离子电池的迅猛发展，其作为电池电解液主要成分市场需求量急增。文中简单介绍了光气法、氧化羰化法和酯交换法合成碳酸甲乙酯的研究进展。重点针对最具发展前景的酯交换法合成EMC工艺路线中所用催化剂进行了综述；讨论和分析了该路线所用催化剂的类型、结构、性质及性能，并对当前研究中存在的问题进行了归纳和分析总结。最后本文分析并展望了酯交换法合成EMC催化剂的研究方向及新型合成工艺发展趋势，提出研发经济、高效、稳定且制备工艺简单的非均相催化剂，并与反应精馏技术耦合是今后的主要发展趋势，期望为EMC的高效合成提供参考和借鉴。     

多壁碳纳米管负载FeS2的制备及脱汞性能分析

采用硝酸铁与硫脲在溶剂热反应条件下制备FeS₂，利用物理浸渍法将FeS₂负载至多壁碳纳米管（MWCNTs）上，借助扫描电镜（SEM）、X射线衍射（XRD）、X光电子能谱（XPS）等分析测试手段对制备样品的结构特性进行探究，通过固定床反应器研究模拟烟气氛围下吸附剂对烟气中单质汞的吸附特性。实验考察了不同FeS₂负载量、烟气初始汞浓度、床层温度以及O₂、NO和SO₂对吸附剂脱汞效率的影响。结果表明，制备出的FeS₂分散性较好，呈球状晶体，表面均匀覆盖着MWCNTs，成团簇状。当负载量为10%、反应温度为70℃时，FeS₂/MWCNTs的吸附效果最好，最高脱除效率能达到100%，60min后脱除效率仍有80.3%。TPD脱附曲线和XPS分析结果进一步表明烟气中的Hg⁰被氧化成Hg²⁺以HgS的形式附着在吸附剂表面，证实吸附剂以化学吸附为主。此外，汞脱除效率随初始汞浓度的增加而降低，汞吸附容量却随之增加，60min最高能达到5.1μg/g。酸性气体NO和SO₂的存在，占据了吸附剂表面的活性点位，不利于Hg⁰的吸附，但低浓度NO对吸附剂的整体效果影响不大，抗NO性能较好。     

Water leakage due to the welding defect and improvement to reach 1-MW beam operation in the mercury target of J-PARC

ABSTRACT

Neutron flux per pulse reached world record at neutron source in Japan Proton Accelerator Research Complex (J-PARC). In the J-PARC, mercury target system is used as a spallation neutron source. A target vessel has a multi-walled protection system that comprises a mercury vessel enclosed with a double-walled water shroud. This is to prevent the leakage of the mercury outside the target vessel. The multi-walled structure needed to be complicated with a lot of welding lines. However, during the operation, we faced an unscheduled shutdown due to water leakage to the intermediate layer between the mercury vessel and water shroud. An investigation on the cause of the leakage was carried out. It is deduced that the leakage path was formed due to the crack propagation from welding defects that are caused by the complicated multi-walled structure. The crack propagation is attributed to the repeated stress by pressure waves generated in the mercury target. Based on the investigation results, the design was improved to remove the welding line on the complicated structure and to realize the stable operation with 1 MW proton beam, which is the final design value of the neutron source in J-PARC.     

甲乙酮装置剩余丁烯的循环利用

对甲乙酮装置剩余丁烯的循环利用进行了研究,采用聚结器脱水-净化的方法,脱除了剩余丁烯中的仲丁醇、仲丁醚、甲乙酮和水分等杂质,使得剩余丁烯得到了循环使用,满足了水合工段的进料要求,同时提高了甲乙酮的产品质量。     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

Total mercury levels in crustacean species from Italian fishery

This study investigated mercury contamination levels in eight commercially valuable crustacean species caught off the Central Adriatic and Tyrrhenian coasts of Italy. Total mercury levels were measured by Thermal Decomposition-Amalgamation-Atomic Absorption Spectrophotometry. Results showed a high variability among species with values ranging from 0.070 to 1.24 (mg kg^?1 wet weight). The lowest mercury levels were detected in caramote prawn (Penaeus kerathurus), warty crab (Eriphia verrucosa) and European spider crab (Maja squinado), decapods living in shallow waters. Levels exceeding the limits established by the European Commission were found in species living in close contact with bottom sediments: deepwater rose shrimp (Parapenaeus longirostris), blue and red shrimp (Aristeus antennatus) and Norway lobster (Nephrops norvegicus). For shrimps, the inter-individual variability observed was mostly related to the body size, indicating the accumulation of mercury with age. An estimation of the human intake of mercury associated to the consumption of the crustaceans sampled and its comparison with the Tolerable Weekly Intake are provided.     

Process design and techno‐economic analysis of ethyl levulinate production from carbon dioxide and 1,4‐butanediol as an alternative biofuel and fuel additive

Carbon dioxide capture, utilization, and storage (CCUS) is one of the promising negative emission technologies (NET). Within various CCUS routes available, CO₂ conversion into fuels is one of the attractive options. Currently, most of CO₂ conversion into fuels requires hydrogen, which is expensive and consume large energy to produce. Hence, a different route of producing fuel from CO₂ by utilizing 1,4‐butanediol as the raw material is proposed and evaluated in this study. This alternative route comprises production of levulinic acid from the reaction between CO₂ and 1,4‐butanediol and production of ethyl levulinate, an alternative biofuel and biofuel additive, via an esterification reaction of levulinic acid with ethanol. The process is designed and simulated according to the available data and evaluated in terms of its technical features. Because of the unavailability of reaction data for synthesis of levulinic acid from 1,4‐butanediol and CO₂, several assumptions were taken, which may implicate the accuracy of the studied design. This technical evaluation is followed by cost estimations and sensitivity analysis. Because of the free CO₂, the profitability of the plant depends strongly on the prices of the other chemicals and the price difference between 1,4‐butanediol (raw material) and ethyl levulinate (product). Monte Carlo simulation indicates that the proposed plant will always be profitable if the ethyl levulinate is slightly more expensive than the 1,4‐butanediol, highlighting that the process of producing ethyl levulinate from CO₂ is economically profitable. Future research should be directed towards a catalytic system that can effectively convert CO₂ into levulinic acid, by‐products produced from the two reaction steps, and reduce the excess ethanol used in the second reaction.