Comparison of criteria for prediction of runaway reactions in the sulphuric acid catalyzed esterification of acetic anhydride and methanol

Loss of temperature control is one of the major reasons that can lead to runaway reaction. This occurrence is commonly named thermal runway. The aim of this paper is the application of thermal runaway criteria in order to predict the onset of runaway phenomena and define the range of stability related to operating conditions in the reactor, with specific reference to the esterification of acetic anhydride and methanol catalysed by sulphuric acid tested in isoperibolic conditions. The isoperibolic calorimeter has also been used to obtain thermodynamic, kinetic and physical chemistry data necessary to develop a model for the reaction. Some runaway criteria applied in this work require a model for the process, so a model for the analyzed system been developed.Because of the modest reaction enthalpy and low activation energy this reacting system provide a severe test to the runaway criteria.In this work, various runaway criteria have been applied to the experimental and simulated data and the results obtained have been compared.     

骨炭对水中不同形态Sb吸附和解吸的影响

采用骨炭作为吸附剂，研究其在不同骨炭用量、pH值和温度条件下对水中Sb（Ⅲ）和Sb（Ⅴ）吸附和解吸的影响。结果表明，骨炭对Sb（Ⅲ）的吸附效果远好于Sb（Ⅴ），在0.2~8.0 mmol/L的Sb（Ⅲ）和Sb（Ⅴ）浓度下，骨炭对这2种形态Sb的去除率分别为46.1%~78.6%和9.6%~31.7%。采用Langmuir方程和Freundlich方程均可以很好地拟合骨炭对Sb（Ⅲ）和Sb（Ⅴ）的吸附，Sb（Ⅲ）和Sb（Ⅴ）的最大吸附容量分别为110.1034 mg/g和17.4167 mg/g。骨炭对Sb（Ⅲ）的解吸也大于对Sb（Ⅴ）的解吸。骨炭对Sb（Ⅲ）和Sb（Ⅴ）的吸附受不同骨炭用量、pH值和温度影响。     

环丁砜-哌嗪溶液吸收烟道气中二氧化碳

采用搅拌实验装置,研究环丁砜溶液及不同配比的环丁砜-PZ复合溶液对烟道气中二氧化碳的吸收和解吸性能,揭示了吸收容量与酸碱度、时间之间的内在联系,并对CO2初始逸出温度、试液再生温度、试液再生率、再生pH下降率进行了细致记录分析。实验结果表明,环丁砜-PZ复合溶液配比为0.4∶0.6时:吸收效果最佳,吸收量约为0.126 mol;再生温度最高,为105℃;再生率最高,为90.34%。同时与相同配比的MEA、DEA相比具有较大再生优势。实验结果还表明,环丁砜-PZ复合体系之间存在负交互作用。     

改性多壁碳纳米管对水中Cd~（2＋）的去除

为了增加多壁碳纳米管（multiwall carbon nanotubers,MWNTs）对水中Cd2＋的吸附量,使用混酸对多壁碳纳米管进行氧化处理,采用红外光谱进行结果表征,并探讨了吸附时间、pH值和MWNTs的使用量、Cd2＋的浓度及干扰离子对镉离子吸附的影响。结果表明,吸附时间为1.5 h、pH为5.3、吸附效果最佳,随MWNTs量的增加Cd2＋去除量增加,共存的阳离子会降低对Cd2＋的吸附效果,对Cd2＋的吸附符合Longmuir吸附定律。研究同时表明,pH小于2时Cd2＋能容易从碳纳米管上解吸。初步探讨了Cd2＋吸附机制。     

水中乙醛、丙烯醛和丙烯腈3种测定方法的对比

对比研究了大体积直接进样填充柱气相色谱法、顶空-气相色谱法和吹扫捕集-气相色谱法等3种测定水中乙醛、丙烯醛和丙烯腈的方法.结果表明,大体积直接进样法设备简单,但手动进样耗力费时,且灵敏度低,精密度差,直接水样分析易影响色谱柱和检测器的使用寿命;顶空法稳定性好,线性范围宽,相关性和精密度好,适合较高浓度水样的分析;吹扫捕集法操作简便,峰形好,检出限低,回收率高,适合低浓度水样的分析.顶空法和吹扫捕集法自动化程度高,均适用于大批量样品分析.     

Sorption and desorption kinetics of diuron,fluometuron, prometryn and pyrithiobac sodium in soils

Abstract

The sorption and desorption characteristics of four herbicides (diuron, fluometuron, prometryn and pyrithiobac‐sodium) in three different cotton growing soils of Australia was investigated. Kinetics and equilibrium sorption and desorption isotherms were determined using the batch equilibrium technique. Sorption was rapid (> 80% in 2 h) and sorption equilibrium was achieved within a short period of time (ca 4 h) for all herbicides. Sorption isotherms of the four herbicides were described by Freundlich equation with an r² value > 0.98. The herbicide sorption as measured by the distribution coefficient (K_d) values ranged from 3.24 to 5.71 L/kg for diuron, 0.44 to 1.13 L/kg for fluometuron, 1.78 to 6.04 L/kg for prometryn and 0.22 to 0.59 L/kg for pyrithiobac‐sodium. Sorption of herbicides was higher in the Moree soil than in Narrabri and Wee Waa soils. When the K_d values were normalised to organic carbon content of the soils (K_oC), it suggested that the affinity of the herbicides to the organic carbon increased in the order: pyrithiobac‐sodium < fluometuron < prometryn < diuron. The desorption isotherms were also adequately described by the Freundlich equation. For desorption, all herbicides exhibited hysteresis and the hysteresis was stronger for highly sorbed herbicides (diuron and prometryn) than the weakly sorbed herbicides (fluometuron and pyrithiobac‐sodium). Hysteresis was also quantified as the percentage of sorbed herbicides which is not released during the desorption step ω = [n_ad / n_de ‐1] x 100). Soil type and initial concentration had significant effect on ω. The effect of sorption and desorption properties of these four herbicides on the off‐site transport to contaminate surface and groundwater are also discussed in this paper.     

低温等离子体技术降解含氮硫废气的研究进展

论述了采用低温等离子体技术处理含氮硫废气以及恶臭气体的反应机理和研究现状，重点介绍了低温等离子体技术与催化、吸附、光催化等技术的联合技术，分析了低温等离子体联合技术存在的问题及发展方向。     

水体中高锰酸盐指数的流动注射分析方法

研究了用流动注射分析技术测定水体中高锰酸盐指数。使用新发明的耐腐蚀恒流泵、低记忆高效混合器、不存留气泡流通池等部件，通过高温高压，缩短消解时间，从而建立了一种可用于无人值守的自动在线快速监测水体中高锰酸盐指数的分析方法。     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

FS—IV^＋流动注射仪测定地表水中氨氮

铵与碱性酚和次氯酸钠反应生成靛蓝化合物，其色度与铵的浓度成正比，亚硝基氰化物使蓝色增强，在660nm处测量吸光度值；采用Flow Solution-IV^＋（FS-IV^＋）流动注射仪测定地表水中氨氮，检测范围0～10．00mg／L，检出限0．008mg／L，分析速率51个样S／h；对方法精密度、准确度、加标回收进行了实验，结果令人满意。该方法具有自动进样、分析速率快、试剂耗量低等优点，可应用于大批量常规地表水分析。