石油炼制与化工 ›› 2023, Vol. 54 ›› Issue (10): 65-72.

• 加工工艺 • 上一篇    下一篇

S Zorb脱硫过程中硅酸锌的生成规律研究

姜宝丰1,朱凯2,王磊2   

  1. 1. 中石化催化剂有限公司南京分公司
    2. 中石化石油化工科学研究院有限公司
  • 收稿日期:2023-03-28 修回日期:2023-07-04 出版日期:2023-10-12 发布日期:2023-09-24
  • 通讯作者: 王磊 E-mail:wl.ripp@sinopec.com

STUDY ON FORMATION OF ZINC SILICATE IN S Zorb CATALYST DURING DESULFURIZATION

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  • Received:2023-03-28 Revised:2023-07-04 Online:2023-10-12 Published:2023-09-24

摘要: 针对S Zorb装置运行过程中出现不同程度的催化剂失活、破碎等问题,进行了S Zorb催化剂中硅酸锌生成规律的研究。制备锌源固定、硅源不同的系列催化剂以及硅源固定、锌源不同的系列催化剂,并在井式老化炉中采用不同温度、气氛条件对催化剂进行老化试验,结合X射线衍射物相全谱拟合(Rietveld)方法定量分析,模拟考察硅源形态及其SiO2含量和ZnO粒径大小对S Zorb催化剂中硅酸锌生成的影响。结果表明:无定形SiO2比有晶体结构的SiO2更容易与ZnO反应生成硅酸锌,并且当硅源中的SiO2为无定形状态时,硅酸锌的生成量与硅源中的SiO2含量呈正相关关系;在温度800 ℃下,以无定形SiO2作为硅源时硅酸锌收率(w)高达68.7%,而有晶体结构的纯SiO2与ZnO反应时的硅酸锌收率(w)为10.3%;小粒径的ZnO更容易与硅源发生反应生成硅酸锌,ZnO的粒径越大,越不容易生成硅酸锌。通过对比不同气氛环境中硅酸锌的生成情况,发现水蒸气和SO2的存在均会促进硅酸锌的生成,且当SO2和水蒸气共同存在时,会进一步加快硅酸锌生成。

关键词: S Zorb, 脱硫, 硅酸锌, 失活

Abstract: The formation mechanism of zinc silicate in S Zorb catalyst was studied in view of deactivation and breakage of the catalyst in different degrees during the operation of the S Zorb unit. A series of catalysts with fixed zinc source, different silicon sources and different zinc source were prepared, and the aging tests were carried out in a well type aging furnace under different temperature and atmosphere conditions. The formation of zinc silicate in the catalyst was investigated by the Rietveld method, and the impact of silicon source morphology, SiO2 content, and ZnO particle size on the formation of zinc silicate in S Zorb catalyst was simulated. The results showed that amorphous SiO2 reacted with ZnO more easily than the crystalline SiO2 to form zinc silicate. At 800 ℃, the yield (w) of zinc silicate reached 68.7% when amorphous SiO2 was used as the silicon source, while the yield (w) of zinc silicate was 10.3% when pure SiOwith crystal structure reacted with ZnO. The larger particle size of ZnO, the less zinc silicate was formed. By comparing the formation of zinc silicate in different atmospheres, it was found that the formation of zinc silicate was promoted by the presence of water vapor and SO2, and the formation of zinc silicate was further accelerated by the co-existence of SO2 and water vapor.

Key words: S Zorb, desulfurization, zinc silicate, deactivation