高变质福建无烟煤连续流化床混合气催化气化

连续流化床（内径123mm、高1．2m）中，采用工业纯碱（碳酸钠）为催化剂进行了高变质程度无烟煤一福建永安煤（低挥发分k=5．47％、高灰Aad=29．45％）混合气（空气／水蒸气）催化气化的研究，考察了催化剂质量分数、气化温度、水汽比等操作参数的影响。实验结果表明，工业纯碱作为催化剂添加5％可使碳转化率增加3倍，实现了煤的高效转化；气化温度有明显催化气化促进作用，超过900℃时，流化床内易结渣。从同时满足高产气率及高煤气热值两个指标出发，在适宜操作条件（碳酸钠质量分数5％、850℃～880℃、适宜水汽比）下，产气率提高2倍，从无催化剂时的2．13m^3／kg～2．15m^3／kg提高到4．2m^3／kg～5．1m^3／kg；煤气热值提高5倍，从1．0MJ／m^3左右提高到5．0MJ／m^3；表明工业纯碱进行高变质福建无烟煤流化床混合气催化气化具有重要的工业应用价值和现实的开发意义。     

在线电生锰(Ⅲ)流动注射化学发光法测定地塞米松磷酸钠

采用在线恒电流电解产生Mn(Ⅲ)与流动注射化学发光法相结合,基于地塞米松磷酸钠可使Mn*#-Na2SO3新体系化学发光大大加强的现象,建立了测定地塞米松磷酸钠的新分析方法.其线性范围为1×10-4～1×10-2 g/L;检出限为7×10-5 g/L;RSD为1.2%.该法成功地应用于针剂中地塞米松磷酸钠的测定.     

Viscosity of aqueous calcium chloride solutions at high temperatures and high pressures

Viscosity of six (0.10, 0.33, 0.65, 0.97, 1.40, and 2.00) mol kg⁻¹ binary aqueous CaCl₂ solutions has been measured with a capillary-flow technique. Measurements were made at pressures up to 60 MPa. The range of temperature was from 293 to 575 K. The total uncertainty of viscosity, pressure, temperature, and composition measurements was estimated to be less than 1.6%, 0.05%, 15 mK, and 0.014%, respectively. The effect of temperature, pressure, and concentration on viscosity of binary aqueous CaCl₂ solutions was studied. The measured values of viscosity of CaCl₂(aq) were compared with data, predictions, and correlations reported in the literature. The temperature and pressure coefficients of viscosity of CaCl₂(aq) were studied as a function of concentration and temperature. The viscosity data have been interpreted in terms of the extended Jones–Dole equation for the relative viscosity (η/η₀) to accurate calculate the values of viscosity A- and B-coefficients as a function of temperature. The derived values of the viscosity B-coefficients were compared with the values calculated from the ionic B-coefficient data. The physical meaning parameters V and E in the absolute rate theory of viscosity and hydrodynamic molar volume (effective rigid molar volume of salt) V_k were calculated using present experimental viscosity data. TTG model has been used to compare predicted values of the viscosity of CaCl₂(aq) solutions with experimental values at high pressures.     

Über die quasi-binären Systeme NaNO2/Na2O und NaCN/Na2O. Phasendiagramme und Natrium-Ionenleitung in Na3O(NO2) und Na3O(CN)

On the Quasi-Binary Systems NaNO₂/Na₂O and NaCN/Na₂O. Phase Diagrams and Sodium Ion Conductivity of Na₃O(NO₂) and Na₃O(CN) Measurements of the electrical conductivities of Na₃O(NO₂) and Na₃O(CN) show sharp increases in conductivity at temperatures between 200° and 250°C, According to the phase diagrams of the quasi-binary systems NaNO₂/Na₂O and NaCN/Na₂O this is not an effect established by fusion. It seems to be a consequence of a “melting” of the sodium sublattice or the rotational disorder of complex anions.     

Modulation of Tartrates with Various Counterions on the Phases of Calcium Oxalate in Gelatinous Systems

Effect of various counterions of tartrate on the crystallization of calcium oxalate in gel system was investigated using scanning electron microscopy and X-ray diffraction. Various tartrates with hydrogen (H2tart), sodium (Na2tart), potassium (K2tart), ammonium ((NH4)2tart), and a mixture of sodium and potassium cations (NaKtart) were considered. For H2tart, Na2tart, and (NH4)2tart, calcium oxalate dihydrate (COD) was induced. However, for K2tart and NaKtart,calcium oxalate trihydrate (COT) was obtained.     

Conductivity of Sodium Chloride in Water + 1,4-Dioxane Mixtures from 5 to 35°C II. Concentrated Solution

Conductivity data of sodium chloride in binary mixtures of water and 1,4-dioxanefrom 5 to 35°C were measured, covering an electrolyte concentration range upto the limit of solubility in the solvent mixtures and up to 5 mol-dm^–3 inpure water. Data analysis is based on the mean spherical approximation (MSA).Comparison is made with the data representation by the empirical Casteel-Amisequation. The association constants of the MSA are compared with those fromchemical model calculations at low concentrations (lcCM).     

Diffusion of ionic species labeled with35S in various aqueous electrolyte solutions at 25°C

Composite diffusion coeffcients have been measured for the various species labeled with³⁵S which are present in a number of aqueous solutions due to the introduction of the labeled material as³⁵SO ₄ ^2– . The solutions were of two components consisting of water and either sodium sulfate. The diffusion coeffcient measured for sodium chloride solutions is similar to literature data for the corresponding diffusion in sodium sulfate solutions. The results for sulfuric acid and ammonium hydrogen sulfate have been interpreted using literature data for the relative concentrations of the hydrogen sulfate and sulfate ions to obtain estimates for the diffusion coefficents of those ions. The results for perchloric acid, regarded as representing the diffusion coefficient of the hydrogen sulfate ion, have a much different concentration dependence to that observed for the estimates for that ion in sulfuric acid and ammonuim hydrogen sulfate. The difference is attributed to the effect of the perchlorate ion on the water structure.     

1．4──二氢吡啶类钙拮抗剂的合成法研究Ⅲ非洛地平的合成

在无水氯化锌的存在下，２，３－二氯苯甲醛与乙酰乙酸甲酯经Ｋｎｏｅｖｅｎａｇｅｌ－Ｄｏｅｂｎｅｒ缩合反应，制成２，３－二氯亚苄基乙酰乙酸甲酯（２），继而与３－氨基丁烯酸甲酯在阳离子交换树脂Ｄ６１的催化下进行环合Ｍｉｃｈａｅｌ加成反应，得非洛地平（１），以２，３－二氯苯甲醛计算，总收率７６．５％。探计了无水氯化锌的用量，反应温度对２收率的影响，还考察了不同阳离子交换成树脂对１的收率和质量的影响。     

Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

A comparative quantitative analysis of the effect of solventmodifiers on the ion-pair extraction of an inorganic salt by a crown ether was conducted with the aim of advancing the understanding of transport of highly hydrophilic metal ions from aqueous salt solutions. Two classes of solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (compound 1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenylacetamide—the enhancement of the NaNO₃ extraction by compound 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier as quantified by the β solvatochromic parameter. A HBD modifier 3,5-di-t-butylphenol (compound 8), which forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO₃ extraction by compound 1. The determined extraction constants were correlated with the β- or α-solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between compound 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phaseswas studied by vibrational spectroscopy.