FCC过程中MgO基硫转移剂的研究
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摘要
近年来,在环境保护加强的形势下,SOx污染的延续性引起了世界各国的普遍重视。SOx污染的来源极其广泛,其中工业生产中产生的SOx气体是环境污染的主要源头。从炼油厂产生的SOx占总SOx排放量的6～7%,其中催化裂化过程所排放的SOx约占5%,因此研究FCC脱硫技术具有重要的意义。
本论文采用共沉淀法制备出MgO基助剂掺杂型硫转移剂,围绕硫转移剂结构与性能的关系这一关键问题,来探索硫转移剂的脱硫性和再生性,探讨影响硫转移剂性能的物理化学及结构因素。
选择稀土元素Ce、La和过渡金属Fe、Cu、Zn、Mn分别作为助剂掺杂到MgO基硫转移剂中,以SO2为目标污染物质进行SOx吸附性能研究。结果表明,稀土元素Ce的掺杂其脱硫活性是纯MgO和其它元素掺杂的10倍左右,Fe、Cu、Zn的效果次之；设计一阶响应面试验,在MgO中同时掺入Ce和Fe、Cu、Zn两种金属氧化物,得到MgO-Ce-Fe类硫转移剂的SO2吸附效果最好,最大硫容为1.60 gSO2/g absorbent。
研究了MgO-Ce-Fe、MgO-Ce-Cu和MgO-Ce-Zn三种硫转移剂的再生性能,发现MgO-Ce-Cu、MgO-Ce-Zn的再生温度较高、再生速率低,不适于循环脱硫使用。而MgO-Ce-Fe可在480℃～580℃最低的温度下再生速率最快、再生彻底；利用H2进行10次脱硫后再生,仍然保持着62.2%的SO2吸附性水平；MgO-Ce-Fe的再生循环性能优越。
利用XRD、比表面积和孔结构以及FT-IR等表征手段对上述硫转移剂反应前后结构进行了分析。与纯MgO相比,掺杂助剂的MgO基硫转移剂粒径减小,比表面积和孔容增大,特别地掺杂Fe的硫转移剂粒径减小、表面积和孔容增加程度为最大；并且有明显的CeO2出现,这些都有利于SO2气体的吸附和硫转移剂的还原再生。吸附SOx的硫转移剂由于出现闭孔现象,所以其比表面积和孔容减小,团聚现象严重；再生的MgO-Ce-Fe硫转移剂晶粒尺寸、比表积和孔容与新鲜的硫转移剂相比均变化不大。
结果表明,MgO是吸附SO2的唯一活性组元,最后形成了稳定的MgSO4; CeO2是一种很好的氧化SO2的促进剂,但对MgSO4的还原没有贡献；Fe2O3既是氧化SO2的促进剂又是还原MgSO4的促进剂；CuO与ZnO对氧化吸硫与还原脱硫贡献较小。MgO-Ce-Fe类硫转移剂是兼具SO2吸附性和再生性优良的硫转移剂。
本论文的工作为FCC硫转移剂的应用研究提供了有意义的数据和理论参考。
In recent years,with the enhancement in environmental protection, the SOx incremental pollutions brought about the widely attention in every country. Sources of SOx pollution are very popullar, among which main roots are from industrial production process. SOx from refinery factories is about 6-7%of total SOx releases in atmosphere, but SOx from the feed stock of fluld catalytic cracking(FCC) process is about 5%. So the reasearch of desulfurization techniques in FCC is significant.
In the paper, coprecipitations were adopted in the preparation of MgO based sulfur transfer absorbents(STC) added with minor promoters, based on the key issue of construction and performance of sulfur-transfer absorbents, the performance of desulfurization and regeneration of sulfur transfer absorbents were studied, and physical and chemical, as well as structural factors that affect desulfurization performance(DP) were discussed.
Rare earth elements cerium(Ce), lanthanum(La), and transient metal elements iron(Fe), copper(Cu), zinc(Zn) and manganese(Mn) were respectively doped into MgO as the additive to study the DP of them, and SO2 was chosen as object contamination. The results indicated that, the DP of MgO indoped with Ce is about 10 times of undoped and indoped with other elements.The DP of MgO indoped with Fe, Cu, Zn is better. Using one step response surface method(RSM) to choose the optimal composition of the STCs of MgO indoped with two promoters of Ce and Fe, Cu, Zn when the STCs DP is best. Finally, the DP of MgO-Ce-Fe is best and its sulfur capacity is 1.60 gSO2/g absorbent.
In the research on the regeneration performance(RP) of MgO-Ce-Fe, MgO-Ce-Cu and MgO-Ce-Zn, it could be found that beacause regeneration temperature of MgO-Ce-Cu and MgO-Ce-Zn are higher, and their regeneration rate are smaller, so they are unsuitable as STCs. But MgO-Ce-Fe can be regenerated in lower temperature quickly and completely. The sulfur capacities were 62.2%of fresh STCs after ten times sulfuration and regeneration. MgO-Ce-Fe has best regeneration performance.
X ray diffraction(XRD), Special surface area, pore structure and FT-IR and other characterization means were adopted in the structure analysis of the upper three STCs before and after reaction. Compared with pure MgO, MgO indoped with promoters decreased in particle size, and increased in special surface area and pore volume. Especially the exchange extent is very obvious adulterating Fe2O3. Morever, there was CeO2. All of characteristics are positive to improve the STCs DP and RP. On the contrary, because of emerging blocks in STCs pores, special surface area and pore capacity decrease much after first desulfurization, and there is much particles reunion in them. There is much difference MgO-Ce-Fe after regeneration desulfurization.After the regeneration of MgO-Ce-Fe, the average pore size, species states, special surface area and pore capacity doesn't change obviously comparing with fresh STCs.
Results showed that MgO was the only active material for SOx adsorption, Fe2O3 was not only the absorbent for oxidatlng SO2 to SO3, but also the absorbent for reducing MgSO4, CeO2 was a very nice absorbent for oxidating SO2 to SO3, but had no contribute to the reduction of MgSO4.
This work will provide the valued data and theoretie bases for the application in reasearch of sulfur transfer additive.
本论文采用共沉淀法制备出MgO基助剂掺杂型硫转移剂,围绕硫转移剂结构与性能的关系这一关键问题,来探索硫转移剂的脱硫性和再生性,探讨影响硫转移剂性能的物理化学及结构因素。
选择稀土元素Ce、La和过渡金属Fe、Cu、Zn、Mn分别作为助剂掺杂到MgO基硫转移剂中,以SO2为目标污染物质进行SOx吸附性能研究。结果表明,稀土元素Ce的掺杂其脱硫活性是纯MgO和其它元素掺杂的10倍左右,Fe、Cu、Zn的效果次之；设计一阶响应面试验,在MgO中同时掺入Ce和Fe、Cu、Zn两种金属氧化物,得到MgO-Ce-Fe类硫转移剂的SO2吸附效果最好,最大硫容为1.60 gSO2/g absorbent。
研究了MgO-Ce-Fe、MgO-Ce-Cu和MgO-Ce-Zn三种硫转移剂的再生性能,发现MgO-Ce-Cu、MgO-Ce-Zn的再生温度较高、再生速率低,不适于循环脱硫使用。而MgO-Ce-Fe可在480℃～580℃最低的温度下再生速率最快、再生彻底；利用H2进行10次脱硫后再生,仍然保持着62.2%的SO2吸附性水平；MgO-Ce-Fe的再生循环性能优越。
利用XRD、比表面积和孔结构以及FT-IR等表征手段对上述硫转移剂反应前后结构进行了分析。与纯MgO相比,掺杂助剂的MgO基硫转移剂粒径减小,比表面积和孔容增大,特别地掺杂Fe的硫转移剂粒径减小、表面积和孔容增加程度为最大；并且有明显的CeO2出现,这些都有利于SO2气体的吸附和硫转移剂的还原再生。吸附SOx的硫转移剂由于出现闭孔现象,所以其比表面积和孔容减小,团聚现象严重；再生的MgO-Ce-Fe硫转移剂晶粒尺寸、比表积和孔容与新鲜的硫转移剂相比均变化不大。
结果表明,MgO是吸附SO2的唯一活性组元,最后形成了稳定的MgSO4; CeO2是一种很好的氧化SO2的促进剂,但对MgSO4的还原没有贡献；Fe2O3既是氧化SO2的促进剂又是还原MgSO4的促进剂；CuO与ZnO对氧化吸硫与还原脱硫贡献较小。MgO-Ce-Fe类硫转移剂是兼具SO2吸附性和再生性优良的硫转移剂。
本论文的工作为FCC硫转移剂的应用研究提供了有意义的数据和理论参考。
In recent years,with the enhancement in environmental protection, the SOx incremental pollutions brought about the widely attention in every country. Sources of SOx pollution are very popullar, among which main roots are from industrial production process. SOx from refinery factories is about 6-7%of total SOx releases in atmosphere, but SOx from the feed stock of fluld catalytic cracking(FCC) process is about 5%. So the reasearch of desulfurization techniques in FCC is significant.
In the paper, coprecipitations were adopted in the preparation of MgO based sulfur transfer absorbents(STC) added with minor promoters, based on the key issue of construction and performance of sulfur-transfer absorbents, the performance of desulfurization and regeneration of sulfur transfer absorbents were studied, and physical and chemical, as well as structural factors that affect desulfurization performance(DP) were discussed.
Rare earth elements cerium(Ce), lanthanum(La), and transient metal elements iron(Fe), copper(Cu), zinc(Zn) and manganese(Mn) were respectively doped into MgO as the additive to study the DP of them, and SO2 was chosen as object contamination. The results indicated that, the DP of MgO indoped with Ce is about 10 times of undoped and indoped with other elements.The DP of MgO indoped with Fe, Cu, Zn is better. Using one step response surface method(RSM) to choose the optimal composition of the STCs of MgO indoped with two promoters of Ce and Fe, Cu, Zn when the STCs DP is best. Finally, the DP of MgO-Ce-Fe is best and its sulfur capacity is 1.60 gSO2/g absorbent.
In the research on the regeneration performance(RP) of MgO-Ce-Fe, MgO-Ce-Cu and MgO-Ce-Zn, it could be found that beacause regeneration temperature of MgO-Ce-Cu and MgO-Ce-Zn are higher, and their regeneration rate are smaller, so they are unsuitable as STCs. But MgO-Ce-Fe can be regenerated in lower temperature quickly and completely. The sulfur capacities were 62.2%of fresh STCs after ten times sulfuration and regeneration. MgO-Ce-Fe has best regeneration performance.
X ray diffraction(XRD), Special surface area, pore structure and FT-IR and other characterization means were adopted in the structure analysis of the upper three STCs before and after reaction. Compared with pure MgO, MgO indoped with promoters decreased in particle size, and increased in special surface area and pore volume. Especially the exchange extent is very obvious adulterating Fe2O3. Morever, there was CeO2. All of characteristics are positive to improve the STCs DP and RP. On the contrary, because of emerging blocks in STCs pores, special surface area and pore capacity decrease much after first desulfurization, and there is much particles reunion in them. There is much difference MgO-Ce-Fe after regeneration desulfurization.After the regeneration of MgO-Ce-Fe, the average pore size, species states, special surface area and pore capacity doesn't change obviously comparing with fresh STCs.
Results showed that MgO was the only active material for SOx adsorption, Fe2O3 was not only the absorbent for oxidatlng SO2 to SO3, but also the absorbent for reducing MgSO4, CeO2 was a very nice absorbent for oxidating SO2 to SO3, but had no contribute to the reduction of MgSO4.
This work will provide the valued data and theoretie bases for the application in reasearch of sulfur transfer additive.
引文
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