浸渍法制备高选择性1-丁烯齐聚催化剂

肖林久， 陈家欢， 盛永刚， 李文泽， 王金豹

(沈阳化工大学 应用化学学院 辽宁省稀土化学及重点应用实验室， 辽宁 沈阳 110142)



肖林久， 陈家欢， 盛永刚， 李文泽， 王金豹

(沈阳化工大学 应用化学学院 辽宁省稀土化学及重点应用实验室， 辽宁 沈阳 110142)

摘要：通过分步浸渍法制备/γ-Al2O3催化剂，并用于催化1-丁烯齐聚反应，考察了催化剂制备条件和反应条件对催化性能的影响，并与Fe2(SO4)3/γ-Al2O3催化剂进行性能比较。结果表明，在0.96 MPa、60℃、液时空速为5 h-1的反应条件下，采用Fe负载量为负载量为1.2 mmol/g(γ-Al2O3)的/γ-Al2O3 催化剂，1-丁烯齐聚反应的转化率达到68.0%，二聚物选择性为95.0%。α-Fe2O3是催化1-丁烯齐聚反应的活性组分，并能提高二聚体选择性；此外，α-Fe2O3晶相与的相互作用对其催化1-丁烯齐聚反应的活性有重要影响，γ-Al2O3与的相互作用也对催化活性有一定的影响。Fe负载量为6%的/γ-Al2O3催化活性最高，此时NH3-TPD结果显示，催化剂只存在较弱的酸中心和适中的酸量。

关键词：1-丁烯齐聚； 催化剂；； 硫酸铁

1　实验部分

1.1原料和试剂

γ-Al2O3(Al2O3质量分数98%，比表面积227.41 m2/g，平均孔径5.08 nm)，济南鲁淮商贸有限公司产品；Fe(NO3)3·9H2O、(NH4)2SO4，分析纯，天津市大茂化工试剂厂产品；Fe2(SO4)3，分析纯，天津市耀华化工厂产品。

1.2催化剂的制备

将载体γ-Al2O3研磨、筛分，选用粒径20～40目部分。将称量的Fe(NO3)3溶于一定量的去离子水中，待溶解后快速加入定量的γ-Al2O3，使其浸渍均匀，超声波下充分震荡1 h，放置120℃下烘干，然后移至马福炉中500℃焙烧1 h，取出冷却至室温，制得Fe负载量(质量分数，以下同)分别为2%、4%、6%、8%、10%的Fe2O3/γ-Al2O3催化剂。

1.2.2Fe2(SO4)3/γ-Al2O3的制备

将载体γ-Al2O3研磨、筛分，选用粒径20～40目部分。将称量的Fe2(SO4)3溶于一定量的去离子水中，待溶解后快速加入定量的γ-Al2O3，使其浸渍均匀，超声波下充分震荡1 h，放置120℃下烘干，然后移至马福炉中500℃焙烧3 h，取出冷却至室温，制得Fe担载量为6%的Fe2(SO4)3/γ-Al2O3催化剂。

1.3反应装置和流程

采用高压微型固定床连续流动的不锈钢反应器(内径8 mm，长70 mm)进行1-丁烯齐聚反应。采用北京东方仪器厂产SB-2型双柱塞微量泵将反应原料从反应器底部送入反应床层。反应温度控制在40～200℃范围，由背压调压器控制反应压力在0.8～1.8 MPa范围。反应产物从背压阀流出后，经六通阀进入气相色谱完成在线分析，随时监测反应状况。

1.4聚合产物分析

采用北京北分瑞利分析仪器公司3420A型气相色谱仪和面积归一化法分析液体产物和尾气组成。色谱仪配有30 m HJ.624毛细管柱和FID检测器；气化温度240℃，柱温220℃，检测器温度250℃；由色谱分析工作站处理数据。根据分析结果计算1-丁烯转化率和液体产物各组分的选择性。

1.5负载量计算方法

(1)

(2)

2　结果与讨论

2.1.1表面分散状态

图1　不同焙烧温度下负载Fe2O3得到的的XRD谱Fig.1　XRD patterns of Fe2O3·different calcination temperatures ●Fe2(SO4)3；■α-Fe2O3；▲γ-Al2O3；★Fe2O3

2.1.2催化剂的酸性

图2　不同Fe负载量的的 NH3-TPD曲线Fig.with different Fe loadings

w(Fe)/%: (1) 2; (2) 4; (3) 6; (4) 10; (4) 12

2.2.1负载Fe2O3焙烧温度的影响

图3　负载Fe2O3的焙烧温度对所得催化剂催化1-丁烯齐聚反应转化率的影响Fig.3　Effect of calcination temperature for loading Fe2O3 of/γ-Al2O3 catalyst on oligomerization conversion of 1-butene over the catalyst

2.2.2Fe负载量的影响

图4　Fe负载量对催化剂催化 1-丁烯齐聚反应的影响Fig.catalyst on oligomerization of 1-butene at different temperatures

(a)x; (b)s(Dimers); (c)s(Trimers)

图负载量对催化剂催化1-丁烯齐聚反应的影响Fig.catalyst on oligomerization of 1-buteneT=60℃; p=0.96 MPa; LHSV=5 h-1; w(Fe)=6% (1) x; (2) s(Dimers); (3) s(Trimers)

图6　不同反应温度下Fe负载量为6%的Fe2(SO4)3/γ-Al2O3催化剂催化1-丁烯齐聚反应的转化率Fig.6　Conversion of 1-butene oligomerization vs reaction temperatures over Fe2(SO4)3/γ-Al2O3catalyst with 6% Fe loadingp=1.2 MPa; LHSV=1 h-1

2.4.1反应温度的影响

图7　反应温度对催化剂催化 1-丁烯齐聚反应的影响Fig.7　Effects of reaction temperature on oligomerization of

(1)x; (2)s(Dimers); (3)s(Trimers)

2.4.2反应压力的影响

图8　反应压力对催化剂催化 1-丁烯齐聚反应的影响Fig.8　Effects of reaction pressure on oligomerization of

(1)x; (2)s(Dimers); (3)s(Trimers)

2.4.3液时空速的影响

图9　反应液时空速对催化剂催化 1-丁烯齐聚反应的影响Fig.9　Effects of liquid hourly space velocity on oligomerization of 1-butene over

(1)x; (2)s(Dimers); (3)s(Trimers)

3　结　论

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收稿日期：2015-05-18

基金项目：辽宁省科技技术攻关项目(2011223006)资助

文章编号：1001-8719(2016)04-0695-08

中图分类号：O643.32

文献标识码：A

doi:10.3969/j.issn.1001-8719.2016.04.006

XIAO Linjiu, CHEN Jiahuan, SHENG Yonggang, LI Wenze, WANG Jinbao

(LiaoningProvince,KeyLaboratoryforRare-EarthChemistryandApplication,CollegeofAppliedChemistry,ShenyangUniversityofChemicalTechnology,Shenyang110142,China)

Abstract：/γ-Al2O3 catalyst was prepared by step-impregnation method, and its catalytic performance for 1-butene oligomerization was studied and compared with Fe2(SO4)3/γ-Al2O3 catalyst. The influences of the preparation and reaction conditions on the catalytic activity of /γ-Al2O3 for 1-butene oligomerization were investigated. The results showed that, on the reaction condition of pressure of 0.96 MPa, reaction temperature of 60℃ and liquid hourly space velocity of 5 h-1, with the /γ-Al2O3 of 6% Fe loading and 1.2 mmol/g(γ-Al2O3) loading as catalyst, the conversion rate of 1-butene oligomerization reached 68.0% and the dimerization selectivity was 95.0%. α-Fe2O3 is an active component in catalytic 1-butene oligomerization and high dimerization selectivity can be obtained. In addition, the interaction between α-Fe2O3 crystal phase and had an important influence on the catalytic activity of /γ-Al2O3 in 1-butene oligomerization and the interaction between γ-Al2O3and also had some influence. Catalyst activity of /γ-Al2O3 was maximum with 6% Fe loading, and its NH3-TPD results showed there existed weak acid sites and only a moderate amount of acid.

Key words：1-butene oligomerization； catalyst； /γ-Al2O3； ferric sulfate

通讯联系人： 肖林久，男，教授，博士，从事精细化工、稀土材料、催化等方面的研究；Tel：024-89381616；E-mail：x109@163.com