【作者】 刘成军；

【导师】 蒋文举；

【作者基本信息】 四川大学 ， 环境工程， 2004， 硕士

【摘要】 软锰矿的主要成分是MnO₂，它是一种良好的氧化剂，而SO₂是一种很好的还原剂。因此利用软锰矿浆进行烟气脱硫的资源化研究已有很多相关报道。在以往报道中，都是以在较低的软锰矿浆液固比下生成MnSO₄这一过程作为研究对象，而对于较高的液固比下以H₂SO₄作为主要产物的催化氧化过程的研究却鲜有报道，本文在过渡金属离子催化氧化SO₂反应机理的基础上，对这一过程的最优反应条件、各操作条件对产酸的影响以及产酸过程的反应动力学进行了深入研究。 利用L₁₈（3⁷）安排SO₂浓度、氧浓度、矿浆液固比、气速、温度和初始pH值这六个因素的三水平正交试验，试验表明：矿浆液固比、反应温度和氧浓度对反应影响最大，初始pH值的影响可以忽略，同时，试验发现当矿浆液固比为500：1时生成的硫酸浓度最大。进一步的单因子试验对各操作条件对产酸的影响进行了细致研究，结果表明，在这一过程中，锰的浸出速率比铁要快得多，这说明在产酸过程中，Mn²⁺是起催化氧化作用的主要因素。 在软锰矿浆催化氧化SO₂产酸过程中，很容易满足Ha＜1的条件，此时属反应动力学控制。借助于过渡金属离子催化氧化SO₂产酸的反应动力学，可以建立软锰矿浆催化氧化SO₂生成硫酸过程的反应动力学方程：在催化氧化反应过程中，前一阶段的动力学方程可以用来表达；而后一阶段可以用来表达。通过实验得到了相关的参数a’和b的实验值分别为l.6oxlo5L·s/m 01和4.56xlo一3L2·s/molZ。 最后，还使用神经网络建立了催化氧化产酸过程的响应模型，该响应模型平均误差可以控制在21.2%以内，这对软锰矿浆催化氧化50:反应的研究具有一定的创新和探索价值。关键词:软锰矿，二氧化硫，催化氧化，硫酸，反应动力学，神经网络更多还原

【Abstract】 MnO2, a good oxidizer, is the elemental component of pyrolusite. At the same time, SO2 is a good reducer. So there have been many reports on desulfurization using pyrolusite slurry. Most past reports are focused on the production of MnSO4 in the condition of lower liquid-solid ratio of slurry. On the contrary, there are few reports on the production of H2SO4 in the condition of higher liquid-solid ratio. Based on the reaction mechanics of catalytic oxidation of SO2 by transition metals, the paper discussed the effects of various reaction factors on the production of H2SO4, the optimal reaction condition and the reaction kinetics.There are six reaction factors that effect the production of sulfuric acid including the concentration of SO2, the concentration of O2, the liquid-solid ratio of slurry, space velocity, the reaction temperature and initial pH. The factors are test by orthogonal table . It is indicated in the orthogonal experiment that the most important three factors that effects the production of sulfuric acid are the liquid-solid of slurry, the reaction temperature and the concentration of O2, and the least important factor is the initial pH that can be ignored to the production of acid. In addition, it is showed that the highest concentration of sulfuric acid can be obtained when the liquid-solid ratio is 500:1. Furthermore, the result of single factor experiment revealed that the leaching velocity of Mn is much faster than that of Fe. That is to say, Mn2+ is the elemental factor that effects the production of acid.In the production of sulfuric acid, it can be easily satisfied that Ha<\. In thecondition, the reaction is controlled by kinetics. Based on the reaction mechanics of catalytic oxidation of SO2 by transition metals, the reaction kinetic equation of the production of sulfuric acid was established:The course of catalytic oxidation can be divided two phases, and the kinetic equations arerespectively Moreover, by study of the datum of experiment, a’ and b are respectively given thatIn the end, the response model of the catalytic oxidation is established based on neural network. And the average error of the response model less than 21.2%. The model has some value of innovation and exploration to the research of catalytic oxidation of SO2 in pyrolusite slurry.更多还原