双氧水工作液新型再生剂的研制及工作液成分的分析研究

发布时间：2018-05-02 17:57

本文选题：蒽醌法 + 降解物　；参考：《湘潭大学》2017年硕士论文

【摘要】：蒽醌法是生产双氧水的主要方法。在生产双氧水过程中,工作液中容易产生降解物,如不进行再生处理,将引起2-乙基蒽醌和四氢-2-乙基蒽醌(EAQ和H4EAQ有效蒽醌)含量的降低,降解物含量的增多,这不仅会导致工作液物理性质的改变,使双氧水产品质量下降,还会减少双氧水的产量。针对以上问题,本文对用于双氧水工作液再生的新型再生剂制备方法和双氧水工作液中四氢-2-乙基蒽醌和2-乙基蒽醌及降解物的定量分析方法进行了研究。首先,本文利用拟薄水铝石和MgO为原料制备了用于双氧水工作液蒽醌降解物再生的新型再生剂。通过研究新型再生剂捏合酸碱介质种类及浓度、水热处理时间和MgO含量等制备条件对再生剂再生效果的影响,采用面积归一法分析了工作液中有效蒽醌百分含量变化情况,并与原始工作液和工厂目前使用氧化铝料球再生剂再生后的工作液进行了对比。结果表明,用5%硝酸溶液捏合、12h的水热处理时间和加入10%MgO含量制备的再生剂再生效果较好,有效蒽醌百分含量达97.55%,与原始工作液和经工厂再生剂氧化铝料球再生后的工作液相比分别提高了0.53%、0.28%。其次,建立了一种双氧水工作液中EAQ、H4EAQ和降解物总量的液相色谱定量分析方法。在ShimadzuLC-20A液相色谱仪上,采用Agilent ZORBAX SIL柱,选取正己烷-二氯甲烷-乙酸乙酯体系作流动相,利用硝基苯为内标物,苯为内标物溶剂,EAQ和H4EAQ标准物与内标物的面积比与标准物浓度在30~140mg/L范围内呈线性相关系,线性相关系数大于0.9999。该法在保留时间漂移和峰面积发生变化的情况下,测定双氧水工作液中EAQ和H4EAQ的含量,定量结果相对标准偏差在1%以内,回收率在99~102%之间。而降解物的计算方法是由面积归一法与有效蒽醌总量关联得到,即降解物各峰面积之和/(2-乙基蒽醌+四氢-2-乙基蒽醌)面积之和×(2-乙基蒽醌+四氢-2-乙基蒽醌)测定总量,计算得降解物含量。论文最后研究了正相液相色谱法中保留时间漂移的影响因素和解决办法。采用单因素实验法,考察了流动相组成和温度变化对保留时间的影响。在分析过程中,选取了正己烷-二氯甲烷-乙酸乙酯和正己烷-二氧六环流动相体系对双氧水工作液进行了研究,结果表明,流动相组分中含有挥发性组分时保留时间漂移影响明显;当流动相组分中含有易挥发性溶剂时环境温度和柱温的改变对保留时间的漂移影响明显。并针对影响保留时间漂移的因素,提出了对应的解决办法。
[Abstract]:Anthraquinone method is the main method to produce hydrogen peroxide. In the process of producing hydrogen peroxide, degradation products are easy to be produced in the working liquid. If not treated by regeneration, the contents of 2-ethylanthraquinone and tetrahydro-2-ethylanthraquinone (EAQ and H4EAQ effective anthraquinone) will decrease, and the content of degradable substances will increase. This will not only lead to the change of the physical properties of the working fluid, but also reduce the production of hydrogen peroxide. In order to solve the above problems, the preparation method of new regenerating agent and the quantitative analysis method of tetrahydro-2-ethylanthraquinone and 2-ethylanthraquinone in hydrogen peroxide working liquid were studied in this paper. Firstly, a new regeneration agent was prepared by using pseudo-boehmite and MgO as raw materials for the regeneration of anthraquinone degradation in hydrogen peroxide working fluid. By studying the effects of preparation conditions such as the type and concentration of kneading acid-base medium, hydrothermal treatment time and MgO content on the regeneration effect of regenerator, the change of effective anthraquinone content in working liquid was analyzed by area normalization method. The results were compared with the original working liquid and the regenerated liquid of alumina ball regenerator. The results showed that the regeneration effect of regenerator prepared by kneading 5% nitric acid solution for 12 h and adding 10%MgO content was better. The effective anthraquinone content reached 97.55%, which increased 0.53% and 0.28% compared with the original working liquid and the working liquid regenerated by alumina ball, respectively. Secondly, a liquid chromatographic method for quantitative analysis of EAQ- H4EAQ and total amount of degradation in hydrogen peroxide working solution was established. In ShimadzuLC-20A liquid chromatograph, Agilent ZORBAX SIL column was used, n-hexane-dichloromethane ethyl acetate system was selected as mobile phase, and nitrobenzene was used as internal standard. There was a linear phase relationship between the area ratio of the standard substance and the concentration of the reference material in the range of 30~140mg/L, and the linear correlation coefficient was greater than 0.9999. With the change of retention time and peak area, the content of EAQ and H4EAQ in hydrogen peroxide solution was determined. The relative standard deviation of the quantitative results was less than 1% and the recovery rate was between 99 and 102%. However, the method of calculating the degradable substance is obtained by the correlation between the total amount of effective anthraquinone and the area normalization method, that is, the sum of the total area of the degradation product, that is, the sum of the total area of each peak area of the degradable product, namely, the sum of the area of the degradation product is the sum of the area of the degradation product 脳 2-ethylanthraquinone tetrahydro-2-ethyl anthraquinone). The content of degradation matter was calculated. Finally, the influence factors and solutions of retention time drift in normal phase liquid chromatography were studied. The influence of mobile phase composition and temperature on retention time was investigated by single factor experiment. In the process of analysis, the mobile phase system of n-hexane-dichloromethane acetate and n-hexane-dioxane ring mobile phase was selected to study the hydrogen peroxide working liquid. When the mobile phase contains volatile components, the retention time drift is obviously affected, and when the mobile phase component contains volatile solvents, the change of ambient temperature and column temperature has a significant effect on the retention time drift. According to the factors that affect the retention time drift, the corresponding solutions are put forward.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ123.6

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