硫化合物的形态分析与硫氰酸铵合成反应历程研究
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摘要
论文研究是围绕以二硫化碳和氨为原料合成硫氰酸铵的反应过程进行的。针对以氨水和二硫化碳为原料常压合成硫氰酸铵的实际生产过程反应时间长、副反应多、产率低的现状，建立了以OP-4和OP-21为混合乳化剂的相转移催化方案，加快了反应速度，提高了硫氰酸铵产率，优化了反应工艺。同时证实了以液氨为原料，在不同的溶剂条件下气—液反应合成硫氰酸铵的可行性，为塔式设备中连续生产硫氰酸铵提供了借鉴。针对现有反应历程与产物检测结果上存在的差异，建立了(NH_4)_2CS_3，(NH_4)_2S，NH_4SCN和NH_2CS_2NH_4四种可能的产物形式的反相离子对色谱形态分析方法，并用于不同温度、不同溶剂条件下的产物检测。提出并证实了二硫化碳和氨的反应是平行反应，同时还另伴随有两个副反应。不同溶剂条件下产物的定量分析证实了二硫化碳和氨反应中的溶剂效应。双波长倍增示差法和反相离子对色谱法对硫氰酸铵和硫脲的测定揭示了硫氰酸铵异构化反应的热力学规律。芳香族磺酸盐的保留行为研究是反相离子对色谱方法在硫化合物形态分析中应用的进一步拓宽，研究并得出了离子对试剂浓度、有机试剂的种类及含量、流动相的pH值等因素对芳香族磺酸盐的保留行为的影响规律。样品的四丁基溴化铵和二氯甲烷离子对萃取方法与反相离子对色谱分离联用，为水体中芳香族磺酸盐的检测提供了可靠的监测手段。
The research is enclosed the reaction between ammonia and carbon disulfide in the synthesis of ammonium thiocyanate. To accelerate the reaction between the aqueous of ammonia and carbon disulfide under atmospheric pressure, the phase transfer catalysis method is established with OP-4 and OP-21 as mixture catalysts. The number of sub-reaction is decreased under the lower temperature, and the yield of ammonium thiocyanate is improved about 10 %. The gas-liquid reaction between ammonia and carbon disulfide is put into practice in our research, and it is testified that the process is greatly accelerated with solvents such as ether, nitrobenzene, with high ammonium thiocyanate yield of 70-80 %.
The speciation method of (NH4)2CS3, (NH4)2S, NH4SCN and NH2CS2NH4 is established in the need of mechanism research. The excellent analysis condition of (NH4)2CS3, (NH4)2S, NH4SCN and NH2CS2NH4 in reversed-phase ion-pair chromatography is gained through (Uy ) uniformed experiment. The four components are all detected with different amount in reaction products of ammonia with carbon disulfide. The reaction between ammonia and carbon disulfide is a parallel one. Solvent affects the reaction mechanism and reaction rate.
The utilization of the two methods of dual wavelength multiplication subtractive spectrophotometry and the reversed-phase ion-pair chromatography reveal the thermodynamic orderliness in the isomerized reaction of ammonium thiocyanate.
The speciation of aromatic sulfonates is the further utilization of reversed-phase ion-pair chromatography method. We get the reserved rules of the sulfonates under the different condition such as concentration of ion-pair reagent, organic reagents and pH of the mobile phase. The combination of ion-pair extraction technology with reversed-phase ion-pair chromatography method provide a effective inspection measure for the sulfonates in water.
The research is enclosed the reaction between ammonia and carbon disulfide in the synthesis of ammonium thiocyanate. To accelerate the reaction between the aqueous of ammonia and carbon disulfide under atmospheric pressure, the phase transfer catalysis method is established with OP-4 and OP-21 as mixture catalysts. The number of sub-reaction is decreased under the lower temperature, and the yield of ammonium thiocyanate is improved about 10 %. The gas-liquid reaction between ammonia and carbon disulfide is put into practice in our research, and it is testified that the process is greatly accelerated with solvents such as ether, nitrobenzene, with high ammonium thiocyanate yield of 70-80 %.
The speciation method of (NH4)2CS3, (NH4)2S, NH4SCN and NH2CS2NH4 is established in the need of mechanism research. The excellent analysis condition of (NH4)2CS3, (NH4)2S, NH4SCN and NH2CS2NH4 in reversed-phase ion-pair chromatography is gained through (Uy ) uniformed experiment. The four components are all detected with different amount in reaction products of ammonia with carbon disulfide. The reaction between ammonia and carbon disulfide is a parallel one. Solvent affects the reaction mechanism and reaction rate.
The utilization of the two methods of dual wavelength multiplication subtractive spectrophotometry and the reversed-phase ion-pair chromatography reveal the thermodynamic orderliness in the isomerized reaction of ammonium thiocyanate.
The speciation of aromatic sulfonates is the further utilization of reversed-phase ion-pair chromatography method. We get the reserved rules of the sulfonates under the different condition such as concentration of ion-pair reagent, organic reagents and pH of the mobile phase. The combination of ion-pair extraction technology with reversed-phase ion-pair chromatography method provide a effective inspection measure for the sulfonates in water.
引文
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