金属载体强相互作用对二苯并呋喃加氢脱氧反应影响  

Effect of the strong metal-support interaction on the hydrodeoxygenation of dibenzofuran

作　　者：王栋 杜朕屹 WANG Dong;DU Zhenyi(State Key Laboratory of Clean and Efficient Coal Utilization,College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan030002,China)

机构地区：[1]太原理工大学化学工程与技术学院省部共建煤基能源清洁高效利用国家重点实验室,山西太原030002

出　　处：《洁净煤技术》2024年第7期109-119,共11页Clean Coal Technology

基　　金：国家重点研发计划资助项目(2022YFB4101100);国家自然科学基金面上资助项目(22078220)。

摘　　要：煤焦油作为煤炭热解的主要产品之一,产量大、用途广,合理有效地利用中低温煤焦油可促进煤炭资源的清洁高效转化。通过催化加氢脱氧实现对中低温煤焦油中氧原子脱除,可提高油品的氢碳比和稳定性,获得高品质燃料。二苯并呋喃含量高,反应活性低,选择其作为模型化合物,用于加氢脱氧反应研究。金属载体强作用(SMSI)的调控被广泛用于多相催化领域,但其对加氢脱氧反应影响尚不清楚。为探究SMSI对加氢脱氧反应的作用机理,用镍钛锆水滑石作为催化剂前驱体,通过改变Zr的比例,制备不同金属载体强相互作用的Ni基催化剂(Ni/mZrO_(2)@TiO_(2-x),m=0~0.5),用于模型化合物二苯并呋喃的加氢脱氧反应。通过HRTEM、H_(2)-TPD和CO-pulse等表征发现催化剂在还原中部分载体被还原为TiO_(2-x)并在Ni颗粒表面形成包覆层,产生氧空位。随着Zr比例增大,SMSI强度降低,导致包覆层和氧空位含量减少。280℃、6 MPa下对不同SMSI强度的催化剂进行活性评价,发现随着SMSI强度降低(Zr比例增大),脱氧产物收率由60.7%增至94.8%后降至66.9%,在Ni/0.4ZrO_(2)@TiO_(2-x)催化剂上呈现最佳脱氧性能;且该催化剂经5次循环活性未出现明显下降,稳定性好。研究结果表明,催化剂加氢脱氧性能由SMSI产生的包覆层和氧空位共同决定,Ni的包覆程度与加氢性能呈负相关,而氧空位含量与脱氧性能呈正相关。As an important product of coal pyrolysis,coal tar has the characteristics of large output and wide application.The rational and efficient use of medium and low temperature coal tar can promote the clean and efficient conversion of coal resources.The removal of oxy-gen atoms from medium and low temperature coal tar is achieved by catalytic hydrodeoxygenation,which improves the hydrogen/carbon ra-tio and stability of the oil to obtain a high-quality fuel.Dibenzofuran was characterized by its high content and low reactivity,which was chosen as a model compound for the hydrodeoxygenation reaction study in this study.Modulation of Strong Metal-Support Interactions(SMSI)is widely used in heterogeneous catalysis field,but its effect on the hydrodeoxygenation is unclear.To investigate the effect of SM-SI on the hydrodeoxygenation,nickel-titanium-zirconium layered double hydroxides were used as catalyst precursors,and Ni-based cata-lysts(denoted as Ni/mZrO_(2)@TiO_(2-x),m=0-0.5)with different SMSI were prepared for the hydrodeoxygenation reaction of the coal tar model compound dibenzofuran by varying the Zr ratio.Characterization by HRTEM,H2-TPD and CO-pulse show that after high tem-perature calcination of the precursors,during the reduction process,part of the support is reduced to TiO_(2-x) to form an encapsulation layer on the surface of the Ni particles,and oxygen vacancies are simultaneously generated.As the Zr ratio increases,the SMSI strength decrea-ses,resulting in a decrease in the encapsulation and oxygen vacancy content.The activity of the catalysts with different SMSI strengths was evaluated and it was found that the yield of the deoxygenated product increased from 60.7%to 94.8%and then decreased to 66.9%with decreasing SMSI strength(increasing Zr ratio)at 280℃and 6 MPa.The Ni/0.4ZrO_(2)@TiO_(2-x) catalyst exhibites the highest deoxygenation performance,which show no decrease in activity after 5 cycles,indicating good stability.The results show that the hydrodeoxygenation per-formance of the catalyst is det

关 键 词：二苯并呋喃 加氢脱氧反应 金属载体强相互作用 镍包覆 氧空位 

分 类 号：TQ032[化学工程]