固体超强酸催化合成对羟基苯甲酸乙酯的研究

以固体超强酸ＳＯ４２－／ＴｉＯ２为催化剂，４Ａ分子筛作脱水剂，合成了对羟基苯甲酸乙酯。应用该方法，酯化反应产率高达８４％，同时对影响产率的诸因素进行了考察，其最佳反应条件为：醇酸摩尔比４∶１，催化剂用量９％，反应时间３ｈ，反应温度１１５～１３５℃。     

An apparent kinetic model for the carbonation of calcium oxide by carbon dioxide

For the apparent kinetics of the carbonation reaction of calcium oxide by carbon dioxide, as a kind of noncatalytic gas–solid reaction, a model equation has been proposed as follows: X=kbt/(b+t), where X is the conversion of CaO; k, a kinetic rate constant (time⁻¹); b, a constant (time) equivalent to the time taken to attain half the ultimate conversion of CaO, and t, the time. As a result of analyses for some literature-reported data of CaO-carbonation conversion, it has been found that the rate of the carbonation can be well represented by dX/dt=k(1−X/X_u)², where X_u is the ultimate conversion of CaO, which is given by the product of two parametric constants, k and b. The constants k and b in the two rate control regimes of CaO-carbonation, chemical reaction control and diffusion control, have been determined as functions of temperature, respectively. The activation energy in the carbonation of surface CaO with CO₂ is estimated to about 72 kJ/mol regardless of the sources of CaO, however, that in the diffusion control regime appears differently as 102.5 (mesoporous CaO) or 189.3 kJ/mol (commercial-available CaO), possibly due to the morphological differences of the two CaO samples. From a practical point of view, the simple model equation proposed in this study deserves attention in that the CaO-carbonation behavior at working temperatures higher than 700 °C could be closely predicted.     

高固体分丙烯酸树脂相对分子质量的研究

采用溶液聚合法合成高固体分丙烯酸树脂,用凝胶渗透色谱(GPC)法分析引发剂的种类和用量、反应温度及聚合工艺对丙烯酸树脂的相对分子质量及其分布的影响。结果表明,选用偶氮二异丁腈和过氧化苯甲酰两种引发剂进行复配可提高聚合物的相对分子质量;采用“饥饿态”聚合工艺进行聚合反应可有效控制聚合物的相对分子质量,且相对分子质量分布均匀,分散度小于2;当引发剂用量为2%,在110℃的反应条件下制得的丙烯酸树脂的综合性能优异,固含量超过70%,相对分子质量可达4万。     

有机颜料开发的新动向

有机颜料是一类重要的着色剂。本文综述了近年的开发动向，除了开发新结构颜料外，重点放在现有颜料的改良，新的有机颜料诱导体与固溶体颜料的合成上。它们对促进有机颜料的发展具有重要的价值。     

固体超强酸S_2O_8~(2-)/Fe_2O_3—CoO催化合成乙酸异戊酯

制备固体超强酸催化剂S2O82-/Fe2O3—CoO,并用于乙酸异戊酯合成反应。用该催化剂通过正交试验合成乙酸异戊酯的最佳条件为:醇酸物质的量比为1.5,催化剂用量为0.8 g(以0.2 mol乙酸为准),带水剂用量为10 mL,反应时间为2.5 h,其酯化率可达98%以上。     

对羟基苯甲酸酯的催化剂研究

综述了固体超强酸TiO2/SO42-,磷钨、硅钨杂多酸及固载杂多酸盐TiSiW12O40/TiO2,浓硫酸(微波常压法),Lewis酸(FeCl3·6H2O,Fe2(SO4)3·xH2O)等几种不同催化剂催化合成对羟基苯甲酸酯的实验结果.分析各种固体催化剂对该酯化反应的催化活性、选择性、重复使用性能及使用范围.     

Ignition and Combustion of Dust-Gas Suspensions

The ignition and combustion of dust-gas suspensions are considered. It is shown that the ability of these systems to accumulate heat is determined not only by their kinetic and thermal properties but also by the relation between their reaction surface and the heat-removal surface (f). Experimental information on flame temperatures, ignition delays, and flame propagation over gas suspensions is processed using the parameter f, and the postulate on the stimulating role of the developed reaction surface in activating these processes is validated. It is shown that during overall burning, diffusion combustion of particles occurs only for rather small values of f. The ambiguous effect of the parameter f on the ignition and combustion processes leads to the necessity of optimizing the fuel size distribution and concentration for the effective operation of the power devices. The role of the macroparameters of two-phase flames of refractory metals in the synthesis of combustion nanoproducts is analyzed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 6, pp. 3–14, November–December, 2005.     

半参数广义线性模型惩罚似然估计的几个性质

本文在给出了半参数广义线性模型惩罚似然估计及惩罚准似然估计的基础上,得到了下面几个性质:(Ⅰ)极小惩罚似然估计及惩罚准似然估计等价于惩罚加权最小二乘估计;(Ⅱ)估计的收敛性及加速收敛法;(Ⅲ)估计的一种 Bayes 解释。     

气固相氢氟化催化剂的研究

对于气固相氢氟化反应制备七氟丙烷的催化剂,进行了系统的研究。采用浸渍法制备催化剂,当催化活性组分Ａ为载体的８．５％～１０％,组分Ｃ２为１．０％～２．５％、二者之和为１１％时,达到了较佳的催化性能,将其应用于由六氟丙烯制备七氟丙烷时,在反应温度≥２１０℃时,粗品气中的Ｆ－２２７含量≥９８．５％。     

锐钛型TiO2对尿素热解过程的影响

通过实验的方法收集了不同温度下纯尿素和尿素/TiO₂混合物热解后的固体残留物，使用红外光谱（IR）及气相色谱质谱联机（GC-MS）方法对这些热解残留物进行成分分析；使用热重-红外联机（TG-FTIR）技术研究尿素及三聚氰酸在有无催化剂TiO₂的情况下的热解特性及气体产物的生成规律；根据Coats-Renfern方法对尿素热解第一阶段的非等温热失重率曲线的数据进行动力学研究，建立动力学方程。结果表明，100~250℃的尿素热解残留物中主要为尿素和缩二脲，300~400℃的尿素热解残留物中主要为三聚氰酸等含氮杂环有机化合物；锐钛型TiO₂能促进尿素和三聚氰酸的热解反应，缩短其反应进程，HNCO与水蒸气在TiO₂表面易发生反应；尿素第一阶段热解的反应级数为2，单独热解时活化能为113.25kJ/mol，指前因子A为2.01×10¹¹min^-1，在催化剂TiO₂的作用下，活化能E为77.42kJ/mol，指前因子A为4.82×10⁷min^-1。