稀土改性对SO42-/ZrO2固体酸催化剂结构与催化性能的影响

陈颖; 孙雪; 李慧; 白云波

稀土改性对SO₄^2-/ZrO₂固体酸催化剂结构与催化性能的影响

陈颖¹,
孙雪²,
李慧³,
白云波⁴

1.
东北石油大学石油与天然气加工重点实验室, 黑龙江大庆 163318;
2.
大庆油田化工集团轻烃分馏分公司, 黑龙江大庆 163000;
3.
大庆石化工程有限公司, 黑龙江大庆 163714;
4.
大庆炼化公司质量安全环保处, 黑龙江大庆 163411

基金项目: 黑龙江省科技攻关资助项目(G209A302)。

详细信息

中图分类号: TE667; TQ426
计量
- 文章访问数: 1508
- HTML全文浏览量: 22
- PDF下载量: 876
- 被引次数: 0
出版历程
- 收稿日期: 2011-03-11
- 修回日期: 2011-07-04
- 刊出日期: 2012-04-30

Effect of rare earth modification on structure and catalytic properties of SO₄^2-/ZrO₂ solid acid catalyst

1.
Critical Laboratory of Oil and Natural Gasprocessing|Northeast Petroleum University|Daqing 163318, China;
2.
Petro China Daqing Oilfield, Daqing 163000, China;
3.
Daqing Petrochemical Engineering Co.,LTD, Daqing 163714, China;
4.
Quality Safety Environmental Place|Daqing Refining &|Chemical Company, Daqing 163411, China

摘要

摘要: 采用共沉淀法和浸渍法在不同条件下制备了稀土-SO₄^2-/ZrO₂系列固体酸催化剂。使用废油脂与甲醇的酯交换反应评价了催化剂活性,并通过X射线衍射、红外光谱、比表面积测定表征方法考察了催化剂结构和性能的关系。结果表明,La摩尔掺杂量4%、焙烧温度600℃时制得的SO₄^2-/ZrO₂-La₂O₃催化剂活性最高,此时脂肪酸甲酯的产率为64.68%,且具有较好的重复使用性。稀土的引入使活性四方相ZrO₂更加稳定,600℃焙烧使催化剂既具有较多活性四方相ZrO₂,又具有较大比表面积,从而提高了催化剂活性。催化剂中形成了固体超强酸结构,且改性后酸强度增大,催化剂活性中心数目增加。
- 固体酸 /
- 稀土 /
- 生物柴油 /
- 酯交换 /
- 焙烧温度
Abstract: The rare earth-promoted SO₄^2-/ZrO₂solid super acid catalyst was prepared by the co-precipitation and impregnation method under different conditions. The catalytic properties of the samples were evaluated through transesterification of waste oil and methanol and characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and BET surface area measurement. The results showed that among all the prepared samples the one that was calcined at 600℃ with La doping 4% had the highest production rate of 64.68%. An analysis of XRD patterns revealed that the incorporation of rare earth into tetragonal zirconia stabilizes the compound, and the calcination at 600℃ increases the reactivity of the catalyst by producing a greater fraction of active tetragonal zirconia with a larger surface area. It could be seen from the FT-IR spectra that super acid structures were formed in the catalysts and the acidity was strengthened remarkably and the activated centre of the catalyst were increased.
- solid super acid /
- rare earth elements /
- biodiesel /
- transesterification /
- calcination temperature

HTML全文

参考文献(7)

冯喜兰, 田孟超, 赵旭娜. 固体超强酸SO₄/ZnO-TiO₂催化合成柠檬酸三丁酯[J]. 化学研究与应用, 2011, (2): 213-216. (FENG Xi-lan, TIAN Meng-chao, ZHAO Xu-na. Catalytic synthesis of TBC by solid superacid SO₄/ZnO-TiO₂[J]. Chemical Research and Application, 2011, (2): 213-216.)

MARTINS R L, SHMAL M. Methane activation on superacidic catalysts based on oxoanion modified zirconium oxide[J]. Appl Catal A, 2006, 308(10): 143-152.

宋华, 董鹏飞, 张旭. 制备条件对Pt-S₂O_82-/ZrO₂-Al₂O₃异构化催化性能的影响[J]. 石油学报(石油加工), 2010, (6):877-882. (SONG Hua, DONG Peng-fei, ZHANG Xu. Effect of preparation conditions on the catalytic isomerization performance of Pt-S₂O_82-/ZrO₂-Al₂O₃[J]. Acta Petrolei Sinica(Petroleum Processing Section, 2010, (6): 877-882.)

战瑞瑞,张荣昌. 稀土改性纳米固体超强酸SO₄^2-/ZrO₂-CeO₂-SiO₂催化剂的研究[J]. 北师大学报(自然科学版), 2008, (3): 80-83. (ZHAN Rui-rui, ZHANG Rong-chang. Research of nanosolid superacid catalyst of rare earth modified SO₄^2-/ZrO₂-CeO₂-SiO₂[J]. Journal of Northeast Normal University(Natural Science Edition), 2008, (3): 80-83.)

SHU Q, ANG B, YUAN H, QING S, ZHU G. Synthesis of biodiesel from soybean oil and methanol catalyzed by zeolite beta modified with La³⁺[J]. Catal Commun, 2007, 8(12): 2159-2165.

陈秀宇, 吴萍萍. 稀土固体超强酸催化剂SO₄^2-/TiO₂/La³⁺催化合成柠檬酸三辛酯[J]. 应用化工, 2009, (7): 1022-1024. (CHEN Xiu-yu, WU Ping-ping. The catalytic synthesis of trioctylcitrate by rare earth solid superacid SO₄^2-/TiO₂/La³⁺[J]. Applied Chemical Industry, 2009, (7): 1022-1024.)

LÓPEZ D E, SUWANNAKAM K, BRUCE D A, GOODWIN J G Jr. Esterification and transesterification on tungstated zirconia: Effect of calcination temperature[J]. J Catal, 2007, 247(1): 43-50.

施引文献

资源附件(0)

访问统计