磷钨酸、氧化锆催化剂催化氧化柴油脱硫.pdf

石油化工
1024
PETROCHEMICAL TECHNOLOGY
2014年第43卷第9期
磷钨酸/氧化锆催化剂催化氧化柴油脱硫
李瑞丽,李波,张平
(中国石油大学(北京)重质油国家重点实验室,北京102249
[摘要」采用过饱和浸渍法制备了负载型催化剂HPW/ZrO2(HPW为磷钨酸),利用XRD、FTIR和N2吸附-脱附方法对催化剂进
行了表征。以HO2为氧化剂、十六烷基三甲基溴化铵(CTAB)为相转移催化剂,对比研究了HPW和 HPW/Zro2催化剂的氧化脱
硫性能,同时考察了氧化反应条件、催化剂的循环使用性能和氧化反应动力学。实验结果表明, HPW/Zro2催化剂的脱硫效果
优于HPW催化剂;在n(H2O2):(S)=4.0、 HPW/Zrc21催化剂用量为2.5%(基于柴油质量)、CTAB用量为0.25%(基于柴油质
量)、氧化温度60℃、氧化时间90min的条件下脱碗效果最住,柴油中硫的含量由3647mg/L降至72mgL,脱硫率达98.0%。
催化剂循环使用3次后脱碗率仍达95.3%,且该氧化脱硫反应符合一级动力学。GC-SCD分析结果显示, HIPW/Zro2催化氧化法
易脱除柴油中加氢法难以脱除的二苯并噻吩及其衍生物。
关键词]磷钨酸氧化催化剂;氧化脱硫;柴油;动力学模型
文章编号」1000-8144(2014)09-1024-07
「中图分类号]TQ221.21
文献标志码]A
Desulfurization of Diesel Oil by Catalytic Oidation over Phosphotungstic Acid/Zirconia
Liruili, Li Bo, Zhang Ping
State Key Laboratory of Heavy Oil Processing, China University of Petroleum-beijing, Beijing 102249, China
Abstract ] Phosphotungstic acid(HPW)/Zro catalysts were prepared by supersaturated
impregnation and characterized by means of FTIR, XRD and BET. The oxidative desulfurization of
diesel oil over HPW and HPW/Zro, was studied with H, O, as oxidant and cetyltrimethylammonium
bromide(CTAB as phase transfer catalyst. The reaction conditions, catalyst recycling and reaction
kinetics were investigated. The results showed that the performance of HPW/Zro, was better than that
of HPW. The sulfur content in the diesel oil was lowered from 3 647 mg/L to 72 mg/L and the sulfur
removal reached 98.0% under the optimal oxidation conditions of n(H,O): n(S)4.0, mass fraction
of HPW/Zro, 2.5%(based on the diesel oil), mass fraction of CTAB 0.25%(based on the diesel oil
temperature 60 C and oxidation time 90 min. The sulfur removal still reached 95.3% after the catalyst
was recycled three times. The oxidation reaction of the diesel oil accords well with first-order kinetics
According to GC-SCD anal ysis, dibenzothiophene and its derivatives can be removed easily by the
catalytic oxidation over HPW/Zro, which is hard for hydrodesulfurization
E Keywords phosphotungstic acid/ zirconia catalyst; oxidative desulfurization; diesel oil; kinetic
mode
随着环保意识的增强,世界各国对柴油中硫
加氢脱硫是常用的柴油脱硫方法,但操作成
的含量做出了严格的限制】。欧洲的欧V标准和本高,故非加氢脱硫方法迅速发展。9。其中,氧
日本的JISK2204-2007标准要求柴油中硫的含量化脱硫工艺反应条件温和、脱硫率高且绿色环保
不得高于10ug/g,已进入无硫化阶段。自2006近年来得到广泛关注01?。李瑞丽等研究了在
年起,美国环境保护署要求全美车用柴油中硫的含相转移催化剂十六烷基三甲基溴化铵(CTAB)作用
量不高于15Hg/g?。我国在车用柴油(Ⅳ)标准中
[收稿日期」2014-03-21;[修改稿日期]2014-06-16
规定柴油中硫的含量不高于50Hgg”2。柴油的超『作者介」李間(96-),女、山东菜西市人,上,副
深度脱硫是大势所趋。
教授,电话010~-89734806,电邮1rl4806C163.co0m