钾基复合催化剂对高硫石油焦气化性能的影响  

Effect of Potassium-Based Composite Catalyst on Steam Gasification Performance of High Sulfur Petroleum Coke

作　　者：欧阳平 崔佃淼 张然[1] 崔龙鹏[1] 刘艳芳[1] 侯吉礼 李红伟[1] OUYANG Ping;CUI Dianmiao;ZHANG Ran;CUI Longpeng;LIU Yanfang;HOU Jili;LI Hongwei(Research Institute of Petroleum Processing,SINOPEC,Beijing 100083,China)

机构地区：[1]中国石化石油化工科学研究院,北京100083

出　　处：《石油学报（石油加工）》2020年第2期262-272,共11页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(418020-5,R17054)资助。

摘　　要：以高硫石油焦为研究对象,探讨了水蒸气气氛下不同钾基催化剂、铁基催化剂以及K-Fe、K-Ca复合催化剂对高硫石油焦气化性能的影响。在1023 K、0.1 MPa下,钾基催化剂中KOH催化活性最高,而铁基催化剂中FeSO4催化活性最高;在KOH基础上添加铁基催化剂后其催化性能有所降低;在K-Ca复合催化剂中,5%KOH和3%CaO(质量分数)复配时,催化剂的催化性能最好,石油焦碳转化率达到最高值61.33%,继续增加CaO添加量,K-Ca复合催化剂的催化性能降低。采用BET和XRD对K-Ca复合催化剂的催化作用机理进行研究,发现CaO的造孔作用以及石油焦气化反应过程中生成的双金属碳酸盐K2Ca(CO3)2共同促进了气化反应的进行。而在压力增大的条件下,由于K-Ca复合催化剂中双金属碳酸盐K2Ca(CO3)2的晶型发生转变,导致其催化活性相比添加KOH催化剂时降低。Effect of K,Fe,K-Fe and K-Ca based composite catalyst on the steam gasification of high sulfur petroleum coke(PC)was investigated with using a pressurized fixed-bed reactor at conditions of 1023 K and 0.1 MPa.Experimental results show that,among potassium-based and iron-based catalysts,KOH and FeSO4 have the best catalytic activity and highest carbon conversion rate for PC samples,respectively.After adding iron-based catalysts in KOH catalyst,carbon conversion rate of PC sample decreases.K-Ca catalyst,composed mass fraction of 5% KOH and 3% CaO,exhibits the best catalytic activity and can improve carbon conversion to 61.33%.Catalytic mechanism of K-Ca catalyst was also studied with BET and XRD analyses.It is found that CaO in the K-Ca composite catalyst plays an important role on pore formation.These formed pores can promote potassium compounds diffusion and contact with petroleum coke,and subsequently enhance the steam gasification reaction due to the formation of K-Ca bimetallic carbonate(K2Ca(CO3)2)during the gasification process.Furthermore,at the experimental conditions,the crystalline formed of K2Ca(CO3)2 can be changed from buetschliite to fairchildite,and thus reduce K-Ca composite catalyst activity compared with just adding KOH alone.

关 键 词：复合催化剂 高硫石油焦 催化气化 KOH CAO 

分 类 号：TQ544[化学工程—煤化学工程]