磷对Re基催化剂上丁烯自歧化反应性能的影响  

Effect of Phosphorus on Butene Self-Metathesis Reaction on Rhenium-Based Catalyst

作　　者：李鹏[1] 田志坚[1] 曲炜[1] 王炳春[1] 徐云鹏[1] 徐竹生[1] 

机构地区：[1]中国科学院大连化学物理研究所,辽宁大连116023

出　　处：《石油化工》2013年第4期374-378,共5页Petrochemical Technology

基　　金：国家自然科学基金项目(20903092)

摘　　要：采用等体积浸渍法制备了不同磷含量的Re2O7/γ-Al2O3催化剂,同时以混合丁烯为原料,在固定床反应器上考察了该催化剂在混合丁烯自歧化反应中的催化性能,并采用XRD、NH3-TPD、H2-TPR、N2吸附和TG等方法对催化剂进行了表征。实验结果表明,磷的引入增加了催化剂的酸量和不易还原Re物种的含量,有利于提高催化剂在丁烯自歧化反应中的稳定性。当磷含量为8%(相对于载体质量)时,催化剂的比表面积下降明显,反应稳定性降低。以5%P-1%Re2O7/γ-Al2O33(磷含量5%(w),Re2O7负载量1%(w))为催化剂,在80℃、1.0 MPa、n(1-丁烯)∶n(2-丁烯)=3、混合丁烯WHSV=1.2 h-1、催化剂用量4.9 g的条件下,混合丁烯自歧化反应连续进行55 h,丁烯转化率达到50%以上,丙烯收率达到12%以上。Re207/γ-A1203 catalysts with different phosphorus contents were prepared via conventional incipient-wetness impregnation method. Mixed butene self-metathesis reactions over the catalysts were investigated in a fixed-bed reactor. The catalysts were characterized by means of XRD, NH3-TPD, H2-TPR, N2-adsorption and TG. The results indicated that the amounts of acid and Re species which are difficult to be reduced on the catalysts increased when phosphorus was added. The addition of phosphorus enhanced the stability of the catalysts. But when the phosphorus content reached 8%（based on the mass of support）, the BET specific surface areas of the catalysts and the stability of the mixed butene self-metathesis reactions reduced significantly. Under the reaction conditions of 5%P- l%Re2OT/y-A1203 as the catalyst（phosphorus content 5%（w）, Re207 loading l%（w））, catalyst dosage 4.9 g, 80℃, 1.0 MPa, n（1-butene） ： n（2-butene） 3, WHSV of the mixed butene 1.2 hq and 55 h on stream, the mixed butene conversion and the propene yield reached more than 50% and more than 12%, respectively.

关 键 词：丁烯自歧化 丙烯 铼基催化剂 磷 

分 类 号：TE624.4[石油与天然气工程—油气加工工程]