过氧化氢法制备环境友好氧化剂二氧化氯工艺及反应动力学研究
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摘要
二氧化氯是一种日益受到重视的绿色化学品,可应用于纸浆漂白、饮用水净化、脂肪漂白和工业废水处理等领域。二氧化氯能克服传统氯气在纸浆漂白、饮用水净化等应用过程中产生的种种弊端,以其高效广谱的杀菌和漂白能力日益受到人们的关注和亲睐。在中国,有关二氧化氯的应用研究较多,而针对二氧化氯的开发研究的较少。因此,研究具有特色的先进二氧化氯生产工艺是目前非常急迫也非常有意义的一项工作。
本文首先对过氧化氢法制备二氧化氯的发生技术进行了实验研究。研究了反应温度、反应压力、硫酸浓度、氯酸钠浓度、过氧化氢和氯酸钠摩尔比、反应时间等反应条件对二氧化氯收率和纯度的影响。得出了实验室制备二氧化氯的最佳反应条件和参数。该方法制取的二氧化氯纯度可达100%,收率一般超过95%,成本低(≤1.1万元人民币/吨),完全能够满足实际给水处理的需要。同时在实验室对废酸进行了循环利用实验,采用集反应-蒸发-结晶为一体的工艺过程,能大大减少废酸量。
在实验室成功实现生产高纯高收率二氧化氯的基础上,进一步提出了生产稳定性二氧化氯-高纯亚氯酸钠的工艺。采用低温碱液和过氧化氢的混合吸收液吸收过氧化氢法制备的二氧化氯,能生产收率和纯度均超过95%的亚氯酸钠,大大降低了亚氯酸钠的生产成本。最后给出了亚氯酸钠的清洁生产方案。
本文对过氧化氢法制备二氧化氯的反应机理进行了研究。分析了与过氧化氢相关的反应和含氯分子之间的一些反应,提出了反应中间产物—活性络合物H_2ClO_3-ClO_3的存在,结合现有的实验结果,统一了前人在低高温情况下生成机理的不同,提出了过氧化氢法生成二氧化氯的更为合理的反应历程。
本文还分别进行了有硫酸钠情况下和无硫酸钠情况下二氧化氯的反应动力学实验,并结合由机理推导得到的反应速率方程,最终确定过氧化氢法制备二氧化氯的普遍化反应动力学模型为:
R_(ClO_2)=2.87×10~6·e~(63288/RT)·(C_(ClO_3~-))·(h_)~(1.69)·(C_(H_2O_2))~(0.5)。
Chlorine dioxide, as a green chemical, is increasingly be used in water purification, pulp bleaching, fat whitening and industrial wastes treating. In this paper, hydrogen peroxide based chlorine dioxide production is first investigated in a bench-scale experiment. Effects of reaction temperature, reaction pressure, sulfuric acid concentration, and sodium chlorate concentration, molar ratio of hydrogen peroxide to sodium chlorate on yield and purity of chlorine dioxide are studied. The optimum reaction conditions and parameters in producing chlorine dioxide are achieved. The present method can serve the demand of water treatment due to the sample chlorine dioxide had some advantages such as high purity attached 100% and reclaim rate(≥95%), low cost(≤11,000 RMB/ton). Meanwhile, recycle reclaiming of waste acid is researched. Waste acid can be greatly reduced by integrating reaction-evaporation-crystallization into a reactor.Based on the succeeding experiment for achieving chlorine dioxide with high purity and yield, the technique of producing stabilized chlorine dioxide solution- high purity sodium chlorite is put forward. The mixing cold solution of sodium hydroxide and hydrogen peroxide absorbs the chlorine dioxide production based on hydrogen peroxide. And purity and yield of generated sodium chlorite are both more than 95%. Product cost is reduced greatly. A clean production process of sodium chlorite is presented.Reaction mechanism is studied in this paper. Relevant reactions of hydrogen peroxide with species present in chlorine dioxide formation and other reactions relating to chlorine are analyzed. And an intermediate species, H2ClO3-ClO3 (activated complex) is proposed in existence. A best reasonable reaction course is achieved based on present experimental result, and also consolidates previous different mechanisms in different temperatures.The kinetic experiments for the formation of chlorine dioxide with or without sodium sulfate are also carried on in the paper. Combined with theoretical rate law derived from proposed hydrogen peroxide-chlorate mechanism, the general kinetic rate model is built. The following equation is found to be best correlate with experimental data:
本文首先对过氧化氢法制备二氧化氯的发生技术进行了实验研究。研究了反应温度、反应压力、硫酸浓度、氯酸钠浓度、过氧化氢和氯酸钠摩尔比、反应时间等反应条件对二氧化氯收率和纯度的影响。得出了实验室制备二氧化氯的最佳反应条件和参数。该方法制取的二氧化氯纯度可达100%,收率一般超过95%,成本低(≤1.1万元人民币/吨),完全能够满足实际给水处理的需要。同时在实验室对废酸进行了循环利用实验,采用集反应-蒸发-结晶为一体的工艺过程,能大大减少废酸量。
在实验室成功实现生产高纯高收率二氧化氯的基础上,进一步提出了生产稳定性二氧化氯-高纯亚氯酸钠的工艺。采用低温碱液和过氧化氢的混合吸收液吸收过氧化氢法制备的二氧化氯,能生产收率和纯度均超过95%的亚氯酸钠,大大降低了亚氯酸钠的生产成本。最后给出了亚氯酸钠的清洁生产方案。
本文对过氧化氢法制备二氧化氯的反应机理进行了研究。分析了与过氧化氢相关的反应和含氯分子之间的一些反应,提出了反应中间产物—活性络合物H_2ClO_3-ClO_3的存在,结合现有的实验结果,统一了前人在低高温情况下生成机理的不同,提出了过氧化氢法生成二氧化氯的更为合理的反应历程。
本文还分别进行了有硫酸钠情况下和无硫酸钠情况下二氧化氯的反应动力学实验,并结合由机理推导得到的反应速率方程,最终确定过氧化氢法制备二氧化氯的普遍化反应动力学模型为:
R_(ClO_2)=2.87×10~6·e~(63288/RT)·(C_(ClO_3~-))·(h_)~(1.69)·(C_(H_2O_2))~(0.5)。
Chlorine dioxide, as a green chemical, is increasingly be used in water purification, pulp bleaching, fat whitening and industrial wastes treating. In this paper, hydrogen peroxide based chlorine dioxide production is first investigated in a bench-scale experiment. Effects of reaction temperature, reaction pressure, sulfuric acid concentration, and sodium chlorate concentration, molar ratio of hydrogen peroxide to sodium chlorate on yield and purity of chlorine dioxide are studied. The optimum reaction conditions and parameters in producing chlorine dioxide are achieved. The present method can serve the demand of water treatment due to the sample chlorine dioxide had some advantages such as high purity attached 100% and reclaim rate(≥95%), low cost(≤11,000 RMB/ton). Meanwhile, recycle reclaiming of waste acid is researched. Waste acid can be greatly reduced by integrating reaction-evaporation-crystallization into a reactor.Based on the succeeding experiment for achieving chlorine dioxide with high purity and yield, the technique of producing stabilized chlorine dioxide solution- high purity sodium chlorite is put forward. The mixing cold solution of sodium hydroxide and hydrogen peroxide absorbs the chlorine dioxide production based on hydrogen peroxide. And purity and yield of generated sodium chlorite are both more than 95%. Product cost is reduced greatly. A clean production process of sodium chlorite is presented.Reaction mechanism is studied in this paper. Relevant reactions of hydrogen peroxide with species present in chlorine dioxide formation and other reactions relating to chlorine are analyzed. And an intermediate species, H2ClO3-ClO3 (activated complex) is proposed in existence. A best reasonable reaction course is achieved based on present experimental result, and also consolidates previous different mechanisms in different temperatures.The kinetic experiments for the formation of chlorine dioxide with or without sodium sulfate are also carried on in the paper. Combined with theoretical rate law derived from proposed hydrogen peroxide-chlorate mechanism, the general kinetic rate model is built. The following equation is found to be best correlate with experimental data:
引文
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