Metal chlorides-promoted ammonia absorption of deep eutectic solvent

Ammonia is considered as a promising hydrogen or energy carrier. Ammonia absorption or adsorption is an important aspect for both ammonia removal, storage and separation applications. To these ends, a wide range of solid and liquid sorbents have been investigated. Among these, the deep eutectic solvent (DES) is emerging as a promising class of ammonia absorbers. Herein, we report a novel type of DES, i.e., metal-containing DESs for ammonia absorption. Specifically, the NH₃ absorption capacity is enhanced by ca. 18.1–36.9% when a small amount of metal chlorides, such as MgCl₂, MnCl₂ etc., are added into a DES composed of resorcinol (Res) and ethylene glycol (EG). To our knowledge, the MgCl₂/Res/EG (0.1:1:2) DES outperforms most of the reported DESs. The excellent NH₃ absorption performances of metal–containing DESs have been attributed to the synergy of Lewis acid–base and hydrogen bonding interactions. Additionally, good reversibility and high NH₃/CO₂ selectivity are achieved over the MgCl₂/Res/EG (0.1:1:2) DES, which enables it to be a potential NH₃ absorber for further investigations.     

二(二甲苯基)丙烷合成工艺的研究

二氯丙烷(DCP)与二甲苯在混合金属氯化物催化剂(HD90)作用下合成二(二甲苯基)丙烷,生产过程简单,产品收率高。在60—80℃的温度下,二甲苯与二氯丙烷摩尔比为6∶1,HD用量50克/摩尔DCP的条件下反应5—6小时,二(二甲苯基)丙烷的收率可达88％以上。     

Increasing the corrosion resistance of equipment due to the use of film-forming amines

Results of a study of tube specimens cut from hot-water boilers show that film-forming octadecyl amine (ODA) used in the process of preservation removes deposition from the surface of the metal. An ODA film is preserved on the surface after repeated washing of the latter with hot water. The concentration of chlorides at the surface of the metal after treatment with ODA is lower than before the treatment. __________ Translated from élektricheskie Stantsii, No. 11, November 2005, pp. 15–18.     

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Benzylation of thiophene using zinc and iron chloride modified montmorillinite clay

Montmorillinite clays, modified with either Zn(II) or Fe(III) chlorides have been used to catalyze the Friedel-Crafts alkylation of thiophene. High yields (ca. 80%) of 2- and 3-benzylthiophene mixtures were obtained using either catalyst in chlorobenzene or nitrobenzene solvent at 80°C. The ratio of 2–3-products was found to be controlled by their relative stability. Reactions were most rapid in nitrobenzene solution (<5 min) and resulted in formation of the 2-isomer as the only mono-substituted product. This is believed to be the first example in which an alkylation of thiophene has been limited to one regio-isomer.     

Electrochemical behaviour of indium ions in molten equimolar CaCl2–NaCl mixture at 550 ∘C

The stability of indium chloride and oxide as well as the electrochemical behaviour of indium ions have been studied in the equimolar CaCl2–NaCl melt at 550 C by X-ray diffraction (XRD) and different electrochemical techniques, using molybdenum and tungsten wires as working electrodes. Voltammetric and chronopotentiometric studies showed signals attributed to the presence of three oxidation states of indium, i.e. 0, i and iii. The standard potential of the redox couples, as well as the solubility products of indium oxides have been determined, showing that In(iii) ions are completely reduced to monovalent indium by the indium metal according to the reaction: In () + 2 In 3 In () and that In₂O is a strong oxide donor according to the reaction: In₂O(s) 2 In() + O^2- These results have allowed the construction of E-pO2– equilibrium diagrams summarising the properties of In–O compounds. The electrodeposition of indium was uncomplicated at Mo and W electrodes. Very good adherence of liquid indium to the electrode materials was observed, with the formation of Na–In alloys at highly reducing potentials, and there was no evidence of indium dissolution into the melt. Moreover, the voltammograms corresponding to the electrochemical In(iii)/In(i) exchange were well defined. The two electrochemical steps were found to be quasi-reversible, and the values of the kinetic parameters, ko and , for both reactions, as well as the diffusion coefficients, DIn(III) and DIn(I) were calculated.     

CaO—SiO2-FeO—Cl体系中Zn、Pb挥发物的热力学研究

应用FaetSage热力学软件对不同温度下的FeO—CaO—SiO2-Cl体系中Zn、Ph挥发行为进行分析,采用气流携带法对FeO—CaO-SiO2-Cl体系中Zn、Pb挥发物的饱和蒸气压进行测定,并通过试验分析了温度对其体系中Zn、Pb挥发率的影响。结果表明,温度为970～1030K条件下FeO-CaO-SiO2-Cl体系中Zn、Pb主要以氯化物形式存在,氯化物的饱和蒸气压均随着温度的升高而增加,且InP～1／T呈较好的线性关系,其体系中Zn、Pb挥发率亦随着温度的升高而增加。     

FeO-CaO-SiO2-Al2O3-ZnO—PbO-Cl体系中Zn、Pb氯化物饱和蒸气压的测定

采用气流携带法对FeO-CaO-SiO2-Al2O3-ZnO-PbO-Cl体系中Zn、Pb氯化物的饱和蒸气压进行测定,并对温度、渣成分、Cl含量等影响因素进行了分析。结果表明,温度为970～1030K条件下FeO-CaO-SiO2-Al2O3-ZnO-PbO-Cl体系中Zn、Pb氯化物饱和蒸气压均随着温度的升高而增加,且P1）氯化物蒸气压值的对数与温度的倒数之间呈较好的线性关系。碱度、FeO含量均对Zn、Pb氯化物的饱和蒸气压影响很大,低碱度可提高Zn、Pb氯化物的饱和蒸气压,高FeO含量虽可增加ZnCl2饱和蒸气压,却降低了Pb氯化物的饱和蒸气压。Cl含量越高,该体系中Zn、Pb氯化物的饱和蒸气压越大。     

Corrosion of Three Commercial Steels Under ZnCl2 –KCl Deposits in a Reducing Atmosphere Containing HCl and H2S at 400–500°C

The corrosion of three commercial steels in a reducing atmosphere containing HCl plus H₂S in the presence of ZnCl₂–KCl deposits has been investigated at 400–500°C and compared with the corrosion of the same materials in a similar gas mixture free from H₂S. The presence of H₂S in the gas accelerated the corrosion of the three commercial steels beneath ZnCl₂–KCl deposits. All materials suffered from severe corrosion with partial detachment and spalling of the external scales. Degradation of the steels resulted from the penetration of chlorine-containing species through the scale formed initially down to the metal matrix, because chorine-rich species were detected close to the alloy/scale interface. Although the corrosion resistance generally increased with increasing Cr content, even the high-Cr stainless steel SS304 is still unable to provide good corrosion resistance against the ZnCl₂–KCl deposits in the presence of H₂S due to the bad adherence of the scales to the alloy. The mechanisms of attack are discussed on the basis of thermodynamic considerations and of the active-oxidation model.     

氯化物排放与燃烧脱氯技术工业性试验研究

对某电厂煤粉炉除尘器前后HC1排放量进行了实测，并在垃圾流化床锅炉和链条炉上进行了燃烧脱氯试验。研究结果表明：(1)含氯废弃物是垃圾焚烧炉HC1排放最主要来源；(2)在流化床中，煤中氯化物排放浓度和排放率较低，单一钙基吸收剂的固氯效果比在链条炉中明显，脱氯剂种类与脱氯剂添加量对脱氯效果有一定影响；(3)链条炉燃烧温度高、燃料停留时间长，燃烧脱氯应采用耐高温脱氯剂，以解决脱氯产物CaCl2的再分解问题；(4)对于链条炉，采用脱氯剂半预混半喷射两段燃烧脱氯方式可使脱氯产物在炉内停留时间大大缩短，有效降低脱氯产物的分解率，因此可获得较好的脱氯效果。