油脂加氢处理催化剂活性影响因素研究进展  

Research Progress on Factors Affecting the Activity of Oil Hydrotreating Catalysts

作　　者：韩坤 习远兵 丁石 葛泮珠 HAN Kun;XI Yuanbing;DING Shi;GE Panzhu(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083

出　　处：《石油学报（石油加工）》2024年第5期1287-1299,共13页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点研发计划项目(2021YFC2103705)基金资助。

摘　　要：随着中国“碳达峰”和“碳中和”战略的提出,可再生能源的占比要求逐渐提升。以废弃油脂为原料生产开发的生物质燃料不仅具有大幅降低碳排放的效果,而且具备大规模连续化生产的特点,因而受到广泛关注。而废弃油脂中氧含量较高,难以满足作为燃料的热值高、稳定性好的要求,因此要进行加氢处理过程脱氧。在工业上常用硫化态加氢脱氧催化剂,催化剂的活性和稳定性等问题受到重点关注。综述了对废弃油脂组成、硫化态加氢脱氧催化剂结构、活性位点的认识,总结了加氢脱氧过程中影响催化剂活性的不同因素、失活原因及提高催化剂活性和稳定性的方法。对于氧硫交换反应,宜采用添加硫化剂(H_(2)S)的方法,以保持催化剂上硫化态催化剂活性中心的数量;对于积炭反应,宜采用提高氢分压助力积炭前驱物加氢以及降低脱氧温度以避免含氧化合物生成积炭的方法;对于载体水合作用,宜采用水热处理改善载体表面性质以及添加金属阳离子助剂增强其抑制水合能力的方法;对于产物分子H2O和CO的影响,宜采用负载Ni等金属助剂的方法来减少CO对活性中心竞争吸附和H2O对活性中心的影响。提出了硫化态加氢脱氧催化剂未来的发展方向,旨在为提高硫化态加氢脱氧催化剂活性稳定性并为推动生物质燃料的开发利用提供理论依据。With the proposal of the"carbon dioxide emission peak"and"carbon neutrality"strategy,the proportion of renewable energy is gradually increasing.The production and development of biomass fuel using waste oil as raw material can not only significantly reduce carbon emissions,but also boast of large-scale continuous production,thus receiving widespread attention.However,the oxygen content in waste oil is relatively high,making it difficult to meet the requirements of high calorific value and good stability for a fuel.Therefore,it is necessary to undergo deoxidation during the hydrogenation process.Sulfurized hydrodeoxygenation catalysts are commonly used in industry,and the activity and stability of the catalysts have received special attention.The paper reviews the composition of waste oils,the structure of sulfurized hydrodeoxygenation catalysts,and the understanding of active sites.and also summarizes the different factors that affect catalyst activity,reasons for deactivation,and methods of improving catalyst activity and stability during the hydrodeoxygenation process.For oxygen sulfur exchange reactions,it is advisable to use the method of adding sulfurizing agent(H_(2)S)to maintain the content of sulfurized catalyst active centers on the catalyst;for the coking reaction,it is advisable to use methods such as increasing hydrogen partial pressure to assist in the hydrogenation of coking precursors,and reducing the deoxygenation temperature to avoid the formation of carbon deposits from oxygen-containing compounds;for the hydration of the carrier,it is advisable to use hydrothermal treatment to improve the surface properties of the carrier,and add metal cation additives to enhance its ability to inhibit hydration;for the influence of product molecules H 2O and CO,it is advisable to use the method of loading metal additives such as Ni to reduce the competitive adsorption of CO on the active center and the influence of H 2O on the active center.The future development direction of sulfurized hydrodeoxygenation cata

关 键 词：含氧化合物 加氢脱氧催化剂 活性 活性位点 失活 

分 类 号：TE624.9[石油与天然气工程—油气加工工程]