| Hydrogen sulfide is an odorous gas, with a strong corroding effect for the equipment and piping in the process of production and transportation even under low concentration. And it’s difficult to remove at high temperature conditions until now. Raw manganese oxides are thought as ideal desulphurization materials for their relatively large specific surface area and high chemical activity after some modification treatment. In this work, heat treatment products annealed by four kinds of manganese oxides as Ocean Manganese Nodule Leached Residue(OMNLR), Pyrolusite, Yeshan limonite and Qingyang manganese ore were used for H2S removal experiments at high temperatures.In the experiment, a combined surface characterizations like XRD, XRF, SEM and TG-DTG etc were performed on these four kinds of manganese oxide sorbents firstly. By comparing the desulfurization results of different grains material to determine the particle size effects on the reaction, the same grain materials were used to explore influence on the reaction by different reaction temperatures and gas speeds. At the same time, the desulfurization mechanism of manganese oxide sorbents was roughly suggested by detecting the influent and effluent gas as well as the study of desulfurization products. The results of in-situ regeneration performance tests of these four kinds of manganese oxide sorbents under air atmosphere were also shown n this thesis.The characterization results show that the main ingredients of the heating treatment products of OMNLR is MnO while the heating treatment products of Pyrolusite and Qingyang manganese ore are MnO2 and Mn3O4 respectively, the main heating treatment products of Yeshan limonite is Fe2O3. Among them, the manganese oxide and iron oxide both were the main desulfurization ingredients It was found that particle size had no significantly effects for this reaction, the desulfurization capacity would enhance with the rising of reaction temperature, and decline with the increasing of gas speed. The optimized conditions of reaction is a temperature of 700 ℃ and a gas speed of 40mL/min. On this condition, OMNLR, Pyrolusite, Qingyang manganese ore and Yeshan limonite as the desulfurization material can reached the desulfurization capacity of 12、122.1、149.2、161.8 (mgS/g sorbent) respectively. These four kinds of sorbents has a good in-situ regeneration performance under the condition of high temperature air, the total desulfurization capacity of the first time reaction and nine times regeneration can reached 1233.2、1240.4、1634.9 and 1608.7 (mgS/g sorbent) respectively. |
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