Keggin结构杂多酸盐的合成、表征及催化燃油超深度脱硫  

Synthesis, Characterization and Catalytic Fuel Ultra-Deep Desulfurization of Keggin-Type Polyoxometalates

作　　者：刘日嘉[1] 王睿[1] Korchak Vladimir 

机构地区：[1]山东大学环境科学与工程学院,济南250100 [2]俄罗斯科学院西蒙诺夫化学物理研究所多相催化实验室,莫斯科119991

出　　处：《无机化学学报》2014年第3期563-572,共10页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20976097;21076116;21211120165;21311120297);中国石油天然气集团公司石油科技创新基金(2010D-5006-0405);山东省自然科学基金(ZR2011BM023)资助项目

摘　　要：以六种金属盐和磷钨酸为原料制备了Keggin结构杂多酸盐Mx/nH0.6PW(Zr0.6H0.6PW、Al0.8H0.6PW、Zn1.2H0.6PW、Fe0.8H0.6PW、Ti0.6H0.6PW和Sn0.6H0.6PW)和Alx/3H3-xPW(AlPW、Al0.8H0.6PW、Al0.5H1.5PW、Al0.3H2.1PW和Al0.1H2.7PW)催化剂,并对催化剂进行了FTIR、XRD、DSC/TGA、ICP等表征。对催化剂进行催化活性筛选后,确定Al0.5H1.5PW为最佳催化剂。研究了以Al0.5H1.5PW为催化剂,过氧化氢为氧化剂,乙腈为萃取剂的催化氧化萃取燃油超深度脱硫技术。考察了催化剂用量、氧硫比、催化剂与氧化剂预接触时间、反应温度和初始硫含量对脱硫效果的影响。结果表明,在催化剂用量为模拟油品质量的0.25%,氧硫比为10,催化剂与过氧化氢预接触8 min,反应温度60℃,初始硫含量为350 mg·L-1的条件下,反应到60 min时硫含量已降至2.5 mg·L-1,脱硫率达99.3%。催化氧化萃取时的脱硫率比单纯萃取时的脱硫率高45.3%,效果十分显著。此外,催化剂用于真实汽、柴油的催化氧化脱硫实验也得到了很好的脱硫效果,且催化剂重复使用5次后,脱硫效率未见明显降低。Keggin-type polyoxometalate catalysts Mx/nH0.6PW（Zr0.6H0.6PW, Al0.8H0.6PW, Zn1.2H0.6PW, Fe0.8 H0.6PW, Ti0.6H0.6PW and Sn0.6H0.6PW） and Alx/3H3-xPW（AlPW, Al0.8H0.6PW, Al0.5H1.5PW, Al0.3H2.1PW and Al0.1H2.7PW） were prepared using 6 metal salts and phosphotungstate. The prepared catalysts were characterized by FTIR, XRD, DSC/TGA and ICP. Al0.5H1.5PW is the best catalyst based on the catalytic activity screening results. The catalytic oxidation extraction for fuel ultra-deep desulfurization was studied using hydrogen peroxide as the oxidant and MeCN as the extractant. The effect of catalyst dosage, O/S molar ratio, pre-immersion time of the catalyst in H2O2 solution, reaction temperature and initial sulfur content on the desulfurization efficiency was studied. The results show that the sulfur content of simulated diesel is reduced from 350 mg·L-1 to 2.45 mg·L-1 with a desulfurization efficiency of 99.3% at 60 min under the following operating conditions： Al0.5H1.5PW catalyst/simulated diesel, 0.25%（m/m）; molar ratio of O/S=10; pre-immersion time of the catalyst in H2O2 solution, 8 min; reaction temperature, 60 ℃; initial sulfur content, 350 mg·L-1. The efficiency of the oxidation extraction desulfurization is much higher than that of extraction only （45.3% higher）. Moreover, very good desulfurization efficiency is obtained for real gasoline and diesel catalytic oxidative desulfurization over Al0.5H1.5PW catalyst, and the desulfurization efficiency is not reduced obviously after 5 cycles.

关 键 词：杂多化合物 氧化脱硫 硫化物 过氧化氢 

分 类 号：O614.612[理学—无机化学] X701.3[理学—化学]