制备方法对Co-Pd/TiO2催化剂催化CH4-CO2梯阶转化的影响

doi:10.16085/j.issn.1000-6613.2015.03.024

化工进展 ›› 2015, Vol. 34 ›› Issue (3): 738-744,757.DOI: 10.16085/j.issn.1000-6613.2015.03.024

制备方法对Co-Pd/TiO₂催化剂催化CH₄-CO₂梯阶转化的影响

李静, 王乐, 孙维周, 左志军, 黄伟

太原理工大学煤科学与技术教育部与山西省共建重点实验室, 山西太原 030024

收稿日期:2014-09-05 修回日期:2014-10-31 出版日期:2015-03-05 发布日期:2015-03-05
通讯作者: 黄伟,教授,博士生导师。E-mail:huangwei@tyut.edu.cn。
作者简介:李静(1990-),女,硕士研究生。
基金资助:
国家自然科学基金(21306125)及国家自然科学基金重点项目(20336006)

Effect of preparation method on the catalytic performance of Co-Pd/TiO₂ catalysts for the step-wise conversion of CH₄ and CO₂

LI Jing, WANG Le, SUN Weizhou, ZUO Zhijun, HUANG Wei

Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2014-09-05 Revised:2014-10-31 Online:2015-03-05 Published:2015-03-05

摘要/Abstract

摘要： 以钴、钯为活性金属, 分别采用浸渍法和溶胶-凝胶法制备了Co-Pd/TiO₂催化剂, 考察了不同制备方法制备的Co-Pd/TiO₂催化剂对CH₄-CO₂梯阶转化直接合成C₂含氧化合物的影响。利用XRD、XPS和N₂-吸附-脱附对催化剂进行了表征。结果表明:两种方法制备的催化剂反应前与反应后表面织构都存在较大变化, 且催化剂中均存在CoTiO₃物种, 这是活性金属Co与载体TiO₂之间发生强相互作用, CO²⁺替代TiO₂晶格中的Ti⁴⁺的结果;CoO和金属Pd可能是该反应的活性中心;反应前与反应后溶胶-凝胶法制备的催化剂的表面Co含量均低于浸渍法制备的催化剂, 而表面Pd含量则均高于浸渍法制备的催化剂, 且溶胶-凝胶法制备的催化剂各种产物的生成速率均高于浸渍法制备的催化剂, 因此, 与浸渍法制备的催化剂相比, 溶胶-凝胶法制备的催化剂具有更好的催化活性。

关键词: 甲烷, 二氧化碳, Co-Pd/TiO₂催化剂, 浸渍法, 溶胶-凝胶法, 制备

Abstract: Co-Pd/TiO₂ catalysts are prepared by impregnation and sol-gel methods, separately. The effect of preparation methods on Co-Pd/TiO₂ catalyst performance is investigated for the direct synthesis of C₂ oxygenates from CH₄ and CO₂ by a step-wise reaction technology. The as-prepared catalysts are characterized by XRD, XPS and nitrogen adsorption-desorption. The results show that the surface property and texture of both impregnation catalyst and sol-gel catalyst have obvious changes after reaction. The existence of CoTiO₃ species in all catalyst samples shows that there is a strong interaction between active metal Co and the carrier TiO₂, and that CO²⁺ can substitute Ti⁴⁺ in the titania lattice. CoO and Pd may act as the active center for this reaction. For both fresh and used catalyst samples, surface Co contents of sol-gel catalyst samples are lower than those of impregnation catalyst samples, while surface Pd contents of sol-gel catalyst samples are higher than those of impregnation catalyst samples. For sol-gel catalyst samples, the formation rates of all products are higher than those of impregnation catalyst samples. Consequently, sol-gel catalyst performs a better catalytic activity compared with impregnation catalyst.

Key words: methane, carbon dioxide, Co-Pd/TiO₂ catalysts, impregnation, sol-gel, preparation

中图分类号:

O643

李静, 王乐, 孙维周, 左志军, 黄伟. 制备方法对Co-Pd/TiO₂催化剂催化CH₄-CO₂梯阶转化的影响[J]. 化工进展, 2015, 34(3): 738-744,757.

LI Jing, WANG Le, SUN Weizhou, ZUO Zhijun, HUANG Wei. Effect of preparation method on the catalytic performance of Co-Pd/TiO₂ catalysts for the step-wise conversion of CH₄ and CO₂[J]. Chemical Industry and Engineering Progree, 2015, 34(3): 738-744,757.

参考文献

[1] 张志智, 孙潇磊, 张喜文, 等.CO₂与乙炔反应合成丙烯酸的可行性研究[J].天然气化工, 2014, 39(1):42-46.

[2] Kale G R, Kulkarni B D.Hydrogen generation with CO₂ utilization:A solvay cluster study[J].Int.J.Hydrogen Energ., 2013, 38(6):2624-2633.

[3] 李美芳, 莫文龙, 马凤云, 等.胶体磨循环浸渍法在CO₂-CH₄重整催化剂NiO/γ-Al₂O₃制备中的应用[J].天然气化工, 2014, 39(3):1-4.

[4] Sarkar B, Tiwari R, Singha R K, et al.Reforming of methane with CO₂ over Ni nanoparticle supported on mesoporous ZSM-5[J].Catal.Today, 2012, 198(1):209-214.

[5] 黄伟, 刘桂英, 阴丽华, 等."短接触"CH₄-CO₂两步反应和CO₂加氢研究[J].催化学报, 2004, 25(6):490-494.

[6] Silva F A, Hori C E, da Silva A M, et al.Hydrogen production through CO₂ reforming of CH₄ over Pt/CeZrO₂/Al₂O₃ catalysts using a Pd-Ag membrane reactor[J].Catal.Today, 2012, 193(1):64-73.

[7] 谢克昌, 黄伟, 王晓红, 等.CH₄-CO₂两步反应直接合成含氧有机物的研究——添加氢的影响[J].催化学报, 2003, 24(3):213-218.

[8] 黄伟, 王晓红, 王建平, 等.CH₄-CO₂两步反应直接转化合成含氧化合物的研究[J].催化学报, 2001, 22(4):321-325.

[9] Huang W, Xie K C, Wang J P, et al.Possibility of direct conversion of CH₄ and CO₂ to high-value products[J].J.Catal., 2001, 201(1):100-104.

[10] 丁一慧, 黄伟, 晋萍, 等.甲烷低温催化直接合成乙酸的新途径[J].煤炭转化, 2001, 24(2):32-36.

[11] 章日光, 黄伟, 王宝俊.Co/Pd催化剂上CH₄/CO₂等温两步反应直接合成乙酸的热力学[J].催化学报, 2008, 29(9):913-920.

[12] Zuo Z, Huang W, Han P, et al.A density functional theory study of CH₄ dehydrogenation on Co(111)[J].Appl.Surf.Sci., 2010, 256(20):5929-5934.

[13] 高仲良, 黄伟, 阴丽华, 等.混合钴源对Co-Pd/TiO₂催化剂催化CH₄-CO₂两步梯阶转化法合成乙酸的性能影响[J].高等学校化学学报, 2012, 33(1):158-165.

[14] Koerts T, Deelen M J A G, Van Santen R A.Hydrocarbon formation from methane by a low-temperature two-step reaction sequence[J].J.Catal., 1992, 138(1):101-114.

[15] Guczi L, van Santen R A, Sarma K V.Low-temperature coupling of methane[J].Catal.Rev., 1996, 38(2):249-296.

[16] RaskóJ, Solymosi F.Adsorption of CH₃ and its reactions with CO₂ over TiO₂[J].Catal.Lett., 1998, 54(1-2):49-54.

[17] Guczi L, Sarma K V, BorkóL.Low-temperature methane activation under nonoxidative conditions over supported ruthenium-cobalt bimetallic catalysts[J].J.Catal., 1997, 167(2):495-502.

[18] 方奕文, 余林, 余坚, 等.Pd改性TiO₂的光谱特性及气相甲苯光催化降解性能[J].湖南师范大学自然科学学报, 2012, 35(3):40-44.

[19] 翟淑波, 孙景辉, 高爽, 等.二氧化硅负载氧化锌催化剂的溶胶-凝胶和浸渍法制备及对仲丁醇分解反应的催化性能[J].高等学校化学学报, 2012, 33(10):2282-2288.

[20] Huang W, Zuo Z, Han P, et al.XPS and XRD investigation of Co/Pd/TiO₂ catalysts by different preparation methods[J].J.Electron Spectrosc.Relat.Phenom., 2009, 173(2):88-95.

[21] Zsoldos Z, Guczi L.Structure and catalytic activity of alumina supported platinum-cobalt bimetallic catalysts.3.Effect of treatment on the interface layer[J].J.Phys.Chem., 1992, 96(23):9393-9400.

[22] Mathew T, Shiju N R, Sreekumar K, et al.Cu-Co synergism in Cu1-xCoxFe₂O₄-catalysis and XPS aspects[J].J.Catal., 2002, 210(2):405-417.

[23] Chai J W, Pan J S, Wang S J, et al.Thermal behaviour of ultra-thin Co overlayers on rutile TiO₂(100) surface[J].Surf.Sci., 2005, 589(1):32-41.

[24] Cao C, Hu C, Shen W, et al.Fabrication of a novel heterostructure of Co₃O₄-modified TiO₂ nanorod arrays and its enhanced photoelectrochemical property[J].J.Alloy.Compd., 2013, 550:137-143.

[25] Brik Y, Kacimi M, Ziyad M, et al.Titania-supported cobalt and cobalt-phosphorus catalysts:Characterization and performances in ethane oxidative dehydrogenation[J].J.Catal., 2001, 202(1):118-128.

[26] Kim M H, Choo K H.Low-temperature continuous wet oxidation of trichloroethylene over CoO_x/TiO₂ catalysts[J].Catal.Commun., 2007, 8(3):462-466.

[27] Suriye K, Praserthdam P, Jongsomjit B.Effect of surface sites of TiO₂ support on the formation of cobalt-support compound in Co/TiO₂ catalysts[J].Catal.Commun., 2007, 8(11):1772-1780.

[28] Jalama K, Coville N J, Hildebrandt D, et al.Fischer-Tröpsch synthesis over Co/TiO₂:Effect of ethanol addition[J].Fuel, 2007, 86(1):73-80.

[29] Qin D, Lapszewicz J.Study of mixed steam and CO₂ reforming of CH₄ to syngas on MgO-supported metals[J].Catal.Today, 1994, 21(2):551-560.

[30] Qin D, Lapszewicz J, Jiang X.Comparison of partial oxidation and steam-CO₂ mixed reforming of CH₄ to syngas on MgO-supported metals[J].J.Catal., 1996, 159(1):140-149.

[31] Bi Y, Lu G.Catalytic CO oxidation over palladium supported NaZSM-5 catalysts[J].Appl.Catal.B:Environ., 2003, 41(3):279-286.

[32] Voogt E H, Mens A J M, Gijzeman O L J, et al.Adsorption of oxygen and surface oxide formation on Pd(111) and Pd foil studied with ellipsometry, LEED, AES and XPS[J].Surf.Sci., 1997, 373(2):210-220.

[33] Leisenberger F P, Koller G, Sock M, et al.Surface and subsurface oxygen on Pd(111)[J].Surf.Sci., 2000, 445(2):380-393.

[34] Teschner D, Pestryakov A, Kleimenov E, et al.High-pressure X-ray photoelectron spectroscopy of palladium model hydrogenation catalysts.Part 1:Effect of gas ambient and temperature[J].J.Catal., 2005, 230(1):186-194.

[35] Han J, Zemlyanov D Y, Ribeiro F H.Interaction of O₂ with Pd single crystals in the range 1-150 Torr:Oxygen dissolution and reaction[J].Surf.Sci., 2006, 600(13):2752-2761.

[36] Gopinath C S, Thirunavukkarasu K, Nagarajan S.Kinetic evidence for the influence of subsurface oxygen on palladium surfaces towards CO oxidation at high temperatures[J].Chem-Asian J., 2009, 4(1):74-80.

制备方法对Co-Pd/TiO₂催化剂催化CH₄-CO₂梯阶转化的影响

Effect of preparation method on the catalytic performance of Co-Pd/TiO₂ catalysts for the step-wise conversion of CH₄ and CO₂

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨寒月, 孔令真, 陈家庆, 孙欢, 宋家恺, 王思诚, 孔标. 微气泡型下向流管式气液接触器脱碳性能[J]. 化工进展, 2023, 42(S1): 197-204.
[2]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[3]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[4]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[5]	戴欢涛, 曹苓玉, 游新秀, 徐浩亮, 汪涛, 项玮, 张学杨. 木质素浸渍柚子皮生物炭吸附CO₂特性[J]. 化工进展, 2023, 42(S1): 356-363.
[6]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[7]	赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.
[8]	高彦静. 单原子催化技术国际研究态势分析[J]. 化工进展, 2023, 42(9): 4667-4676.
[9]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[10]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[11]	刘毅, 房强, 钟达忠, 赵强, 李晋平. Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原[J]. 化工进展, 2023, 42(8): 4136-4142.
[12]	黄玉飞, 李子怡, 黄杨强, 金波, 罗潇, 梁志武. 光催化CO₂和CH₄重整催化剂研究进展[J]. 化工进展, 2023, 42(8): 4247-4263.
[13]	李润蕾, 王子彦, 王志苗, 李芳, 薛伟, 赵新强, 王延吉. CuO-CeO₂/TiO ₂ 高效催化CO低温氧化反应性能[J]. 化工进展, 2023, 42(8): 4264-4274.
[14]	奚永兰, 王成成, 叶小梅, 刘洋, 贾昭炎, 曹春晖, 韩挺, 张应鹏, 田雨. 微纳米气泡在厌氧消化中的应用研究进展[J]. 化工进展, 2023, 42(8): 4414-4423.
[15]	储甜甜, 刘润竹, 杜高华, 马嘉浩, 张孝阿, 王成忠, 张军营. 有机胍催化脱氢型RTV硅橡胶的制备和可降解性能[J]. 化工进展, 2023, 42(7): 3664-3673.