NiCe(x)/FLRC-TiO_(2)催化剂的制备及其加氢脱氧性能研究  

Preparation of NiCe(x)/FLRC-TiO_(2) Catalyst and Its Performance in Hydrodeoxygenation

作　　者：张强 王欢[1] 王帅 王园园[1] 张梅[1] 宋华[1] Qiang Zhang;Huan Wang;Shuai Wang;Yuanyuan Wang;Mei Zhang;Hua Song(College of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing 163318,Heilongjiang Province,China)

机构地区：[1]东北石油大学化学化工学院,黑龙江省大庆市163318

出　　处：《化学学报》2024年第3期287-294,共8页Acta Chimica Sinica

基　　金：国家自然科学基金(No.22278068)资助。

摘　　要：生物质作为自然界唯一可再生的有机碳源,其转化利用具有重要意义.本工作制备了具有特殊形貌和孔道结构的放射状二氧化钛(FLRC-TiO_(2))载体,并在高加氢活性Ni基础上,引入Ce赋予催化剂酸活性位,制备了负载型金属-酸双功能NiCe(x)/FLRC-TiO_(2)催化剂(x为Ni和Ce的原子比),并以对甲酚为模型化合物,研究了Ni/Ce比对催化剂加氢脱氧(HDO)性能的影响.结果表明,Ce的引入能够增强催化剂的酸性,增强催化剂C—OH键氢解能力,从而提高甲基环己烷(MCH)选择性.与单金属Ni/FLRC-TiO_(2)相比,双金属NiCe(1)/FLRC-TiO_(2)的目标产物MCH的选择性显著提高.在275℃、3 MPa、2.5 h的反应条件下, NiCe(1)/FLRC-TiO_(2)催化剂对对甲酚转化率为100%,脱氧产物选择性为97.9%,且MCH的选择性高达95.4%. NiCe(1)/FLRC-TiO_(2)催化剂上的HDO以hydrogenation (HYD)反应路径为主.As the only renewable organic carbon source in nature, the conversion and utilization of biomass is of great significance. The bio-oil obtained from biomass pyrolysis has low calorific value, poor stability, high viscosity and high acidity due to the high content of oxygenated compounds. The hydrodeoxygenation (HDO) is considered as the most efficient technology to remove oxygen and the development of the efficient HDO catalysts remains a great challenge. In this paper, aimed to improve mass transfer rate and HDO intrinsic activity, a novel strategy of preparing a titanium dioxide (FLRC-TiO_(2)) support with special morphology and radial pore structure was proposed. In addition, the supported metal-acid bifunctional NiCe(x)/FLRC-TiO_(2) catalyst (x is the atomic ratio of Ni and Ce) was prepared by introducing metal Ce to induce the acid active site on the basis of high hydrogenation activity metal Ni sites. The as-prepared catalysts were characterized by various methods. Using p-cresol as a model compound, the effects of different Ni/Ce ratios and reaction condition on the HDO performance of the catalysts were studied. The results show that the total acid amount of NiCe(1)/FLRC-TiO_(2) doped with the metal Ce was 148.7 μmol•g−1, which is significantly increased as compared to that of Ni/FLRC-TiO_(2) (45.3 μmol•g−1). The introduction of Ce can enhance the acidity of the catalyst and promote the hydrogen hydrolysis ability of the C—OH bond, thus improving the selectivity of cycloalkanes. Under the reaction conditions of 250 ℃, 3 MPa, 2 h, the selectivity to the target product methylcyclohexane (MCH) was significantly improved over the bimetallic NiCe(1)/FLRC-TiO_(2) (55.5%) compared to the monometallic Ni/FLRC-TiO_(2) (27.2%), demonstrating that introduction of Ce can greatly improve the efficiency of HDO. Increasing temperature and pressure, and extending reaction time are beneficial to HDO of p-cresol in the test range. The intersecting radial channels structure with flower-like morphology of FLRC-T

关 键 词：加氢脱氧 NiCe催化剂 放射状孔道结构 二氧化钛 对甲酚 

分 类 号：O643.36[理学—物理化学] TK6[理学—化学]