【作者】 冀刚；

【导师】 仇汝臣；

【作者基本信息】 青岛科技大学 ， 化学工艺， 2009， 硕士

【摘要】 随着全球含硫原油和天然气资源的大量开发,采用克劳斯(Claus)法回收元素硫的工艺已成为天然气或炼厂气加工的一个重要组成部分。2004年全球以克劳斯法工艺生产的硫磺量已达到4.6×107t以上,比2002年增加了约3.5×106t。我国自20世纪90年代初开始引进国外原油,目前年进口量已超过1×108 t ,且其中大部分是含硫或高硫原油。近年来我国新建了数十套克劳斯法装置,目前总数100余套装置中,约有70%建于炼油厂。本文主要研究了克劳斯硫磺回收过程中各设备的工艺计算方法,其中包括反应炉、各级转化器、再热炉的复杂气相反应平衡及物料平衡、热量平衡计算,废热锅炉、冷凝器的热负荷及参数计算,过程气中硫元素各种分子态的平衡计算及硫露点计算等等。对直流法克劳斯硫磺回收工艺采用非线性单纯形算法相关的热力学图表关系曲线进行了拟合,便于使各种图表能直接应用于计算机。并对拟合公式进行了误差分析,与文献中的公式进行了比较。误差分析结果表明:拟合的公式明显优于文献公式。参考近期文献报道并运用最小自由能法,关联物料平衡、化学平衡和热量平衡计算,建立了克劳斯硫磺回收工艺的数学计算模型。并以此为基础编写了程序软件,开发出克劳斯硫磺回收工艺模拟软件。该软件可计算克劳斯工艺的平衡组成、硫的转化率、设备热负荷以及火焰温度等。既能够对整个克劳斯硫磺回收系统进行模拟计算,也可对系统中的各操作单元设备分别进行计算。为验证软件的可靠性,对该工艺中两个重要的设备反应炉和转化器进行了实例分析。结果表明:该软件的可靠性较好,可以达到满意的效果。更多还原

【Abstract】 With the global mass mining of the oil and natural gas, Claus Sulfur Recovery has been the most important part of those processes. In 2004, the amount of the sulfur recovered by Claus has reached 4.6×107 tons ,which is about 3.5×106 more than it was in 2002.Sulfur-contained oil been importing from abroad since 1990’s, of which the amount has reached 108 tons. We have built dozens of equipments these years out of 100 overall, of which about 70 percents are in oil refinery factories.It was mainly studied in this paper that the calculation method of each equipment in Claus sulfur recovery process,including the complex gas phase reactions, the mass balance, and the heat balance calculation of the reaction furnace, catalytic reactor and reheater, the equipment heat load of the waste heat boiler and condenser and parameter calculation, balance calculation of sulfur element molecule in process gas and sulfur dew point calculation and so on. Using the non-linear simplex method, the relevant thermodynamics graph relation curves were fitted, making them comfortably applicable to direct computer use. And an error analysis of fitted formula has been carried out with a comparison with the literature. The result indicates that the fitting formula is obviously better than literature formulas.With the Minimum Free Energy method and associating the chemical equilibrium, the mass and heat balance was calculated, and the calculation model of straight Claus sulfur recovery process was set up. On the foundation of that, a corresponding program was developed, which simulates the process of Claus sulfur recovery. This software can be used in calculating the equilibrium composition of Claus process, sulfur conversion ratio, the equipment heat load and the flame temperature. It can be applied not only in the entire simulation calculation of Claus sulfur recovery system; but also in the unit equipment separately. In order to show the reliability of this software, the reaction furnace and catalytic reactor were analyzed as an example. Result indicates: This software is confidentially reliable and satisfaction satisfiable results were obtained.更多还原