污泥焚烧中铅的形态转化及脱除的热力学平衡研究

利用热力学平衡模型预测了污泥焚烧过程中铅的形态转化和迁移规律, 并采用系统吉布斯自由能最小的原理对Al₂O₃, SiO₂, TiO₂和CaO 4种吸附剂吸附污泥燃烧中铅的效果进行了模拟计算. 探讨了痕量元素Pb与S, Cl的相互作用及S和Cl的存在对吸附剂与Pb反应的影响. 研究结果表明, 污泥焚烧中Pb的形态转化受到S, Cl及矿物质的影响较大. 有S存在情况下, Pb在低温条件下主要以固态PbSO₄存在, 温度较高时以气态PbO存在; Cl较易和Pb结合形成低沸点的金属氯化物而导致Pb的挥发, 并且Cl含量的增加会加速Pb的挥发. 4种吸附剂对污泥焚烧中Pb都有一定的脱除能力, 其中Al₂O₃可以在较宽温度范围对Pb进行捕集, 而CaO对Pb的化学吸附能力较差. 由于S, Cl与Pb有更强的反应性, 因此S, Cl的存在对吸附剂与铅的反应有抑制作用, 使有效吸附的温度范围变窄, 吸附效率降低, 甚至失去脱除Pb的能力, 并且Cl的影响大于S.     

Novel method of deoxidation of alcohols and its use in synthesis of covalent perchlorates

Alcohols can be effectively deoxidated by treatment with chlorine and sulfur in the presence of pyridine with incorporation of an external nucleophile from added salts.     

The Determination of Sulfur and Chlorine in Coals and Oil Shales Using Ion Chromatography

Abstract

The determination of sulfur and chlorine in coal and oil shale standards is reported. The procedure utilizes a sample decomposition using Eschka's mixture, followed by an ion chromatographic determination. The method was tested on samples with concentrations ranging from 0.004 to 0.35 percent chlorine and 0.05 to 4.4 percent sulfur. Results compare favorably with values reported in the literature. The detection limits for chlorine and sulfur were 10 and 13 ppm and the precision of the method expressed as a percent relative standard deviation was 6 percent and 5 percent for chlorine and sulfur respectively. Using this method a single operator can prepare and analyze as many as 30 samples per day.     

氧瓶-离子色谱法测定树脂中的卤素和硫元素

含有卤素和硫元素的树脂样品经氧瓶法燃烧分解，用含H2O2的去离子水溶液吸收，离子色谱法分离测定．本法简便、快速，特别适于测定树脂中不活泼的卤族元素，且可同时测定。CI、S的相对标准偏差分别为0．22%,0．36％，最大绝对误差分别为0．43％和0．80％。树脂中CI、S的含量在0．28mmol/g～14mmol／g内可用此法准确测定，其最低检测限为0．05mmol／g。     

用离子色谱法测定水中的二氧化氯、氯、亚氯酸根及氯酸根

建立了一种测定水中的ClO2、Cl2、ClO2^-、ClO3^-离子色谱法,在含有碳酸氢钠缓冲溶液的中性条件下,用NaNO2将ClO2、Cl2还原为ClO2^-、Cl^-,通过测定ClO^-和NO3^-的变化值,间接测定ClO2和Cl2。加入硫代乙酰胺(TAA)作掩蔽剂测定ClO2^-。     

Radiation-induced gas evolution in chlorine- containing polymer. Poly(vinyl chloride), chloroprene rubber,and chlorosulfonated- polyethylene

Gas evolution and oxygen consumption induced by the γ-irradiation of poly(vinyl chloride), chloroprene rubber, and chlorosulfonated-polyethylene were studied. The evolved gases and oxygen consumption were measured by means of gas chromatography. When a chlorine containing polymer is irradiated in vacuum or in oxygen, a large amount of hydrogen chloride (HCl) is evolved. The presence of oxygen is found to increase the HCl evolution in pure poly(vinyl chloride) twofold. The gas evolution and oxygen consumption from chlorine containing polymers are retarded by the presence of plasticezer, vulcanizer and stabilizer. For chlorosulfonated-polyethylene, sulfur dioxide (SO₂ is one of the major products in pure state, but its gas evolution decreases markedly by the addition of vulcanizers and stabilizers.     

A Facile Synthesis of Stable Phosphorus Ylides Containing Chlorine and Sulfur Derived from 6-Chloro-2-benzoxazolethiol and 2-Chloro-phenothiazine

Stable crystalline phosphorus ylides containing chlorine and sulfur were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylene-dicarboxylates in the presence of 6-chloro-2-benzoxazolethiol and 2-chloro-phenothiazine. These stable ylides exist in solution as a mixture of two geometrical isomers. This is caused by the conjugation of the ylide moiety with the adjacent carbonyl group, which results in a restricted rotation around the respective carbon-carbon bond.     

Comparative study of the determination of peroxomonosulfate, in the presence of other oxidants, by capillary zone electrophoresis, ion chromatography, and photometry

Several methods for quantitative determination of peroxomonosulfate in detergents, in the presence of other oxidants, have been investigated. The photometric technique applied was based on the well-known starch-iodine reaction. The oxidizing agent was quantified by determining the amount of iodine produced. The influence of other oxidants present was examined. Ion analysis was performed by capillary zone electrophoresis (CZE) and ion chromatography (IC). Because peroxomonosulfate in detergents is always accompanied by sulfate, the main goal was to separate the sulfur species without causing the decomposition of the unstable peroxomonosulfate ion. The sulfur species could be separated within less than 4 min by CZE with a pyromellitic acid electrolyte at pH 3.5 to 5.0. Sulfate and peroxomonosulfate were separated by IC within 11 min by use of a phthalic acid mobile phase at pH 3.0. The peroxomonosulfate content was determined by calibration. The calibration plot was linear from 5 to 50 microg mL(-1) SO5(2-) for IC and from 7.3 to 182.3 microg mL(-1) SO5(2-) (corresponding to 20 to 500 microg mL(-1) triple salt) for CZE.     

城市生活垃圾氯含量测定方法的研究

为了明确垃圾焚烧中氯的确切来源和种类，为垃圾焚烧炉的设计、运行提供参考和促进垃圾焚烧过程中二恶英类物质等二次污染物的生成机理和控制措施的研究，采用硝酸银容量法、硫氰酸汞分光光度法和离子色谱法等研究了城市生活垃圾各主要成分中氯元素的含量。实验结果表明，PVC类塑料和厨余中的灰尘部分含氯量相对较高，均在100mg/g以上；当含氯量大于100mg/g时，可以采用硝酸银容量法测定；含氯量为0.1mg/g-10mg/g时可以采用硫氰酸汞分光光度法和离子色谱法；当含氯量小于0.1mg/g时则只能采用离子色谱法；组分中含硫时只能用离子色谱法测定。     

固态废弃物和煤混合燃烧过程中有机氯化物形成机理的研究

对几种煤和城市固体废弃物（MSW）如PVC和纤维素中的主要可燃成分进行了实验研究,热重－质谱－红外（TGA／MS／FTIR）分析以原料和其混合物为对象,收集得到的燃烧特征图显示出不同的热力学行为。结果表明共燃中快速加热比慢速加热形成有机化合物的可能性要大,管式炉中的实验表明在MSW燃烧过程中Cl2是生成有机氯化物的重要媒介,提出的形成机理包括Deacon反应,用纯有机化合物进行的实验证实此反应为一可能的途径。燃烧过程中SO2对Cl2生成的作用也被检查,结果表明SO2的加入可以降低Cl2的生成量,从而大大减少有机氯化物的生成。     

中国典型超高硫煤有机相中分子氯存在的实验证据

运用,主性能静态二次离子质谱从中国贵州六枝超高硫无烟煤有机相中观测到分子氯（Cl2）的团簇负离子,从而首次获得分子氯在原煤中存在的实验证据。结合不久前从相同原煤有机相观测到元素硫（S8）的研究结果,表明易挥发性元素能够以其化学单质状态在原煤有机相中稳定存在;其来源可能与地球排气作用与原煤的富含纳米孔隙性质和化学还原微环境密切相关。     

钙钛矿型催化剂对VOCs催化燃烧的抗毒性和稳定性研究

采用共沉淀法制备了钙钛矿型La0.8Cu0.2MnO3和La0.8Sr0.2MnO3催化剂,考察了两种催化剂对含硫、含氯VOCs气体催化燃烧的抗毒性和稳定性.结果发现,两种催化剂具有良好的抗氯性,但在SO2存在下会出现中毒失活现象,相比较而言,La0.8Sr0.2MnO3比La0.8Cu0.2MnO3具有更好的抗硫性和结构稳定性;采用XRD和XPS分析方法研究催化剂硫中毒机理,发现其失活原因在于催化剂表面生成CuSO4和SrSO4,形成屏蔽效应导致催化剂失活.     

Pesticide residue analysis in foodstuffs applying capillary gas chromatography with atomic emission detection State-of-the-art use of modified multimethod S19 of the Deutsche Forschungsgemeinschaft and automated large-volume injection with programmed-temperature vaporization and solvent venting

Atomic emission detection (AED) provides high element-specific detection of all compounds amenable to gas chromatography (GC). The heteroatoms nitrogen, chlorine, phosphorus, sulfur, bromine and fluorine, which are important elements in pesticide residue analysis, are of major interest. A main drawback of AED is its lower sensitivity with respect to other selective detection methods used in pesticide residue analysis such as electron-capture and nitrogen-phosphorus detection. This holds true especially for the important nitrogen trace. For this reason, more sensitive detection can be achieved by injection of larger volumes or higher concentrations of sample extracts, because matrix compounds were usually registered only in the carbon, hydrogen and oxygen traces. This paper focuses on recent developments from the authors' laboratory in order to demonstrate the feasibility of screening analyses with the identification of pesticide residues down to the 0.01 ppm concentration level in plant foodstuffs. This has been achieved by means of automated large volume injection with programmed-temperature vaporization and solvent venting as well as careful optimization of make-up and reactant gases with AED. Clean up follows the principle of multimethod S19 of the Deutsche Forschungsgemeinschaft in a reduced procedure. After elimination of lipids and waxes by gel permeation chromatography, extracts from 10 g of the food samples were concentrated to 200 μl, of which 12.5 μl were introduced into the GC-AED system. Two analyses were usually performed with the element traces of sulfur, phosphorus, nitrogen and carbon in the first run and chlorine and bromine in the second run. Fluorine and oxygen were not detected in any screening analyses. The method has proved to be of great value especially with “problem foodstuffs”. The limits of detection were determined for 385 pesticides and are presented together with their retention data.     

Exploiting soft and hard X-ray absorption spectroscopy to characterize metallodrug/protein interactions: the binding of [trans-RuCl4(Im)(dimethylsulfoxide)][ImH] (Im = imidazole) to bovine serum albumin

The reaction of bovine serum albumin (BSA) with [ trans-RuCl 4(Im)(dimethylsulfoxide)][ImH] (Im = imidazole) (NAMI-A), an experimental ruthenium(III) anticancer drug, and the formation of the respective NAMI-A/BSA adduct were investigated by X-ray absorption spectroscopy (XAS) at the sulfur and chlorine K-edges and at the ruthenium K- and L 3-edges. Ruthenium K and L 3-edge spectra proved unambiguously that the ruthenium center remains in the oxidation state +3 after protein binding. Comparative analysis of the chlorine K-edge XAS spectra of NAMI-A and NAMI-A/BSA, revealed that the chlorine environment is greatly perturbed upon protein binding. Only modest changes were observed in the sulfur K-edge spectra that are dominated by several protein sulfur groups. Overall, valuable information on the nature of this metallodrug/protein adduct and on the mechanism of its formation was gained; XAS spectroscopy turns out to be a very suitable method for the characterization of this kind of systems.     

Novel heterocycles. 7. Reaction of 2-chloronicotinonitrile with thioureas. Synthesis of the pyrido[2,3-d]pyrimido-[2,1-b][1,3]thiazine ring system

N,N'-Dimethylthiourea and 3,4,5,6-tetrahydro-2-pyrimidinethiol were allowed to react with 2-chloro-nicotinonitrile ( 1 ) and their products investigated by standard methods and by carbon-13 nmr. In both instances, displacement of the chlorine occurred by nitrogen not the sulfur of the thioureas. Secondary cyclizations occurred by attack of nitrogen on the nitrile to furnish 3a , and by sulfur on the nitrile to give 4b , a new ring system. Tricyclic 4b was hydrolyzed in dilute acid to give 5 , or alkylated with methyl iodide in the presence of sodium hydride to give the ring opened product 6 .     

大同烟煤增压富氧燃烧过程中硫、氯和氟的析出特性

利用高压热重结合傅里叶红外研究了大同烟煤在增压富氧燃烧过程中硫、氯和氟的释放行为,主要考察压力对其析出特性的影响。实验结果表明,压力的改变对煤中硫、氯和氟的迁移转化均有显著影响。随着压力的升高,黄铁矿硫向COS等中间产物的转化率逐渐增加,导致SO2的收率逐步上升,但在3 MPa时,燃煤SO2收率却有所降低。此外,压力升高后反应气氛中CO分压的增加促进了COS的生成,导致其收率逐渐上升。因为煤中有机氯析出和转化与挥发分的释放密切相关,所以高压下挥发分释放量的增加使得煤中有更多的有机氯析出并转化为HCl,而且压力升高后,挥发分燃烧速率和温度的升高促进了无机氟化物分解,HF生成量相应增加。此外,高压下水解反应的强化也提高了HF的收率。     

Sulfur-containing polymer and carbon materials based on poly(vinyl chloride)

New sulfur-containing copolymers based on poly(vinyl chloride) have been prepared by the nucleophilic substitution of chlorine atoms by sulfur atoms using sodium tetra- and pentasulfides. It has been shown that these copolymers can be carbonized to produce sulfur-containing carbon materials with residual chlorine content about 2 wt %.     

Radicals formed in cytosine–hydrochloride(thiocytosine) single crystals: Insights from a DFT study

Specific properties of chlorine interaction with thiocytosine in comparison to chlorine interaction with cytosine in the system formed by the incorporation of small amount of thiocytosine in a cytosine–hydrochloride crystal lattice have been investigated by DFT calculations of the g-tensor of sulfur centered radical. Taking account of the crystal environment of the radical site it has been shown that the main reason for difficulties in interpretation of spectroscopic as well as theoretical results in this model system is the considerable spin density spread on both chlorine and sulfur atoms. From comparison of the results for the proposed model structure with accessible spectroscopic data, the specific direction in which charge transfer in the investigated system may take place has been pointed out.     

多次高温裂解、富集-离子色谱法检测己内酰胺中的痕量氯

建立了多次高温裂解、富集-离子色谱检测己内酰胺(CPL)中痕量氯的分析方法。CPL样品在富氧环境下经3次高温(800℃)裂解后,痕量有机氯转化为氯气或氯化氢气体,经5 mL 10 mmol/L的NaOH溶液吸收、富集,然后转化为氯离子,在阴离子抑制电导检测模式下进行离子色谱分析,检测其中氯离子(Cl-)的含量。在优化的条件下,Cl-在0.05~1.0 mg/L范围内呈良好线性,相关系数为0.999 7,方法检出限为0.37μg/g。对0.8 mg/L的Cl-标准溶液连续进样7次,其保留时间、峰面积、峰高的RSD分别为0.04%、0.24%和0.20%;分别对CPL样品进行处理和检测,得到痕量氯含量的RSD为1.52%(n=4);Cl-标准溶液的转化率为93.3%~104.0%,CPL样品的加标回收率为95.3%~113.1%。该方法操作简单、前处理条件可控、重复性好、检出限低,可满足实际样品中痕量氯的检测。     

Remarks on the article by brandsma and arens: “di-(alkyne-1-yl)sulfides”

Summary When sulfur dichloride is added to 1-hexyne the sulfur atom attaches itself to the second carbon atom, and the chlorine atom to the first carbon atom.