水滑石衍生镍基纳米催化剂对邻苯二甲酸二辛酯加氢反应的调控

doi:10.3969/j.issn.1000-1565.2021.05.007

摘要/Abstract

摘要： 邻苯二甲酸二辛酯加氢是合成环保型增塑剂环己烷-1, 2-二甲酸二辛酯最重要的方法.本文以镍铝水滑石作为前驱体,制备了一种Ni-AlO纳米催化剂.在此催化剂作用下,邻苯二甲酸二辛酯的转化率和环己烷-1, 2-二甲酸二辛酯的选择性均可达99%,而在对比催化剂Ni-Al₂O₃作用下,邻苯二甲酸二辛酯的转化率仅为20%.此外,Ni-AlO催化剂的稳定性也明显优于后者.透射电子显微镜、程序升温还原和X光电子能谱等表征表明水滑石前驱体的生成对活性组分镍起到了分散作用,并提高了其与载体的相互作用,使Ni-AlO催化剂具有优异的催化性能.

关键词: 邻苯二甲酸二辛酯, 环己烷-1, 2-二甲酸二辛酯, 加氢, 催化剂, 水滑石

Abstract: Hydrogenation of dioctyl phthalate is the most important method for the synthesis of cyclohexane-1, 2-dioctyl diphthalate, which is an environmentally friendly plasticizer. A nickel-based nano-catalyst Ni-AlO was prepared from a nickel-aluminum hydrotalcite precursor. The conversion of dioctyl phthalate- DOI:10.3969/j.issn.1000-1565.2021.05.007水滑石衍生镍基纳米催化剂对邻苯二甲酸二辛酯加氢反应的调控白国义,聂世琳,李文炅(河北大学化学与环境科学学院,河北保定 071002)白国义河北大学教授,博士生导师.国家百千万人才工程人选、河北省杰出专业技术人才、河北省政府特殊津贴专家、河北省"三三三人才工程"第一层次人选.现任河北大学学术委员会副主任、化学与环境科学学院副院长、中国化工学会精细化工专业委员会常务委员、河北省化学会常务理事、《精细化工》等杂志编委.主持了国家自然科学基金、河北省自然科学基金杰出青年基金、河北省自然科学基金重点项目等20余项纵向和横向课题;近5年作为通信作者在ACS Catalysis等国内外学术期刊上发表论文37篇,包括中科院一区论文13篇;积极致力于科技成果转化和服务社会,作为第一完成人获得2018年度河北省科学技术进步一等奖.摘要:邻苯二甲酸二辛酯加氢是合成环保型增塑剂环己烷-1, 2-二甲酸二辛酯最重要的方法.本文以镍铝水滑石作为前驱体,制备了一种Ni-AlO纳米催化剂.在此催化剂作用下,邻苯二甲酸二辛酯的转化率和环己烷-1, 2-二甲酸二辛酯的选择性均可达99%,而在对比催化剂Ni-Al₂O₃作用下,邻苯二甲酸二辛酯的转化率仅为20%.此外,Ni-AlO催化剂的稳定性也明显优于后者.透射电子显微镜、程序升温还原和X光电子能谱等表征表明水滑石前驱体的生成对活性组分镍起到了分散作用,并提高了其与载体的相互作用,使Ni-AlO催化剂具有优异的催化性能.关键词:邻苯二甲酸二辛酯;环己烷-1, 2-二甲酸二辛酯;加氢;催化剂;水滑石中图分类号:O643.38 文献标志码:A 文章编号:1000-1565(2021)05-0503-08Regulation of hydrogenation performance of dioctyl phthalate over nickel-based nano-catalysts derived from hydrotalciteBAI Guoyi, NIE Shilin, LI Wenjiong(College of Chemistry and Enviromental Science, Hebei University, Baoding 071002,China)Abstract: Hydrogenation of dioctyl phthalate is the most important method for the synthesis of cyclohexane-1, 2-dioctyl diphthalate, which is an environmentally friendly plasticizer. A nickel-based nano-catalyst Ni-AlO was prepared from a nickel-aluminum hydrotalcite precursor. The conversion of dioctyl phthalate- 收稿日期:2021-05-01 基金项目:国家自然科学基金面上项目(22078080;21676068);河北省自然科学基金重点项目(B2019201341) 第一作者:白国义(1975—),男,回族,河北沧州人,河北大学教授,博士生导师,博士,主要从事精细化工和催化领域研究.E-mail:baiguoyi@hotmail.com.第5期白国义等:水滑石衍生镍基纳米催化剂对邻苯二甲酸二辛酯加氢反应的调控and the selectiviy for dioctyl cyclohexane-1, 2-dioctyl diphthalate were both 99% catalyzed by this catalyst, however, the conversion of dioctyl phthalate was only 20% over a Ni-Al₂O₃ catalyst. Furthermore, Ni-AlO was more stable than Ni-Al₂O₃. TEM, TPR and XPS characterizations revealed that the hydrotalcite precursor benefited for not only the dispersion of Ni, but also its interaction with the support, and in turn improved the catalytic performance of Ni-AlO.

Key words: dioctyl phthalate, dioctyl cyclohexane-1, 2-diphthalate, hydrogenation, catalyst, hydrotalcite

中图分类号:

O643.38

白国义,聂世琳,李文炅. 水滑石衍生镍基纳米催化剂对邻苯二甲酸二辛酯加氢反应的调控[J]. 河北大学学报(自然科学版), 2021, 41(5): 503-510.

BAI Guoyi, NIE Shilin, LI Wenjiong. Regulation of hydrogenation performance of dioctyl phthalate over nickel-based nano-catalysts derived from hydrotalcite[J]. Journal of Hebei University(Natural Science Edition), 2021, 41(5): 503-510.

参考文献

[1] 刘仲毅.增塑剂绿色催化技术[M].北京:科学出版社, 2018.
[2] LEE Y S, LEE S, LIM J E, et al. Occurrence and emission of phthalates and non-phthalate plasticizers in sludge from wastewater treatment plants in Korea[J]. Science of the Total Environment, 2019, 692(20): 354-360. DOI:10.1016/j.scitotenv.2019.07.301.
[3] URBANCOVA K, LANKOVA D, SRAM R J, et al. Urinary metabolites of phthalates and di-iso-nonyl cyclohexane-1,2-dicarboxylate(DINCH)-Czech mothers and newborns exposure biomarkers[J]. Environmental Research, 2019, 173: 342-348. DOI:10.1016/j.envres.2019.03.067.
[4] CORREIA-SA L, SCHUTZE A, NORBERTO S, et al. Exposure of portuguese children to the novel non-phthalate plasticizer di-(iso-nonyl)-cyclohexane-1,2-dicarboxylate(DINCH)[J]. Environment International, 2017, 102: 79-86. DOI:10.1016/j.envint.2017.02.001.
[5] LENDE A B, BHATTACHARJEE S, LU W Y, et al. Hydrogenation of dioctyl phthalate over a Rh-supported Al modified mesocellular foam catalyst[J]. New Journal of Chemistry, 2019, 43(14): 5623-5631. DOI:10.1039/c9nj00404a.
[6] ZHAO J, XUE M W, HUANG Y, et al. Hydrogenation of dioctyl phthalate over supported Ni Catalysts[J].Catalysis Communicats, 2011,16(1): 30-34.DOI:10.1016/j.catcom.2011.08.035.
[7] MIYAMURA H, SUZUKI A, YASUKAWA T, et al. Polysilane-immobilized Rh-Pt bimetallic nanoparticles as powerful arene hydrogenation catalysts: synthesis, reactions under batch and flow conditions and reaction mechanism[J]. Journal of the American Chemical Society, 2018, 140(36): 11325-11334. DOI:10.1021/jacs.8b06015.
[8] BONITA Y, O’ CONNELL T P, MILLER H E, et al. Revealing the hydrogenation performance of RuMo phosphide for chemoselective reduction of functionalized aromatic hydrocarbons[J]. Industrial & Engineering Chemistry Research, 2019, 58(9): 3650-3658. DOI:10.1021/acs.iecr.8b06295.
[9] XU Y, WANG Y, WU C G, et al. Structure effect of activated carbon in Ru/AC catalysts for hydrogenation of phthalates[J]. Catalysis Communications, 2019, 132: 105825. DOI:10.1016/j.catcom.2019.105825.
[10] NIE S L, LI H F, QIN J R, et al. An active and stable Ni/MMT-AE catalyst for dioctyl phthalate hydrogenation[J]. Molecular Catalysis, 2020, 495: 111156. DOI:10.1016/j.mcat.2020.111156.
[11] CAO Y Y, NIU L B, WEN X, et al. Novel layered double hydroxide/oxide-coated nickel-based core-shell nanocomposites for benzonitrile selective hydrogenation: An interesting water switch[J]. Journal of Catalysis, 2016, 339: 9-13. DOI:10.1016/j.jcat.2016.03.015.
[12] ZHANG H L, DONG J, QIAO X L, et al. In-situ generated highly dispersed nickel nanoclusters confined in MgAl mixed metal oxide platelets for benzoic acid hydrogenation[J]. Journal of Catalysis, 2019, 372: 258-265. DOI:10.1016/j.jcat.2019.03.012.
[13] QIAO X L, SHE T T, ZHANG H L, et al. One-pot synthesis of porous silica-supported ultrafine Ni nanoparticles as efficient and stable catalyst for selective hydrogenation of benzophenone[J]. Applied Catalysis B: Environmental, 2019, 259: 118111. DOI:10.1016/j.apcatb.2019.118111.
[14] QIAO X L, NIU L B, ZHANG H L, et al. Controllable fabrication of a novel porous Ni-alginate hybrid material for hydrogenation[J]. Applied Catalysis B: Environmental, 2017, 218: 721-730. DOI:10.1016/j.apcatb.2017.06.088.
[15] 聂世琳.镍基纳米催化剂的制备及其对邻苯二甲酸二辛酯加氢反应的性能[D].保定:河北大学, 2020.
[16] SING K S W, EVERETT D H, HAUL R A W, et al. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity(Recommendations 1984)[J]. Pure and Applied Chemistry, 1985, 57: 603-619. DOI:10.1351/pac198557040603.
[17] GRAD O, MIHET M, BLANITA G, et al. MIL-101-Al₂O₃ as catalytic support in the methanation of CO₂- Comparative study between Ni/MIL-101 and Ni/MIL-101-Al₂O₃ catalysts[J]. Catalysis Today, 2021, 366: 114-122. DOI:10.1016/J.CATTOD.2020.05.003.
[18] FAN Q N, LI X F, YANG Z X, et al. Double-confined nickel nanocatalystderived from layered double hydroxide precursor: atomic scale insight into microstructure evolution[J]. Chemistry of Materials, 2016, 28(17): 6296-6304. DOI:10.1021/acs.chemmater.6b02553.
[19] PARK J, KANG E, SON S, et al. Monodisperse nanoparticles of Ni and NiO: Synthesis, characterization, self-assembled superlattices, and catalytic applications in the Suzuki coupling reaction[J]. Advanced Materials, 2005, 17(4): 429-434. DOI:10.1002/adma.200400611.
[20] LI C J, ZHANG J, LIN Y Y, et al. In situ growth of layered double hydroxide on disordered platelets of montmorillonite[J]. Applied Clay Science, 2016, 119: 103-108. DOI:10.1016/j.clay.2015.06.032.
[21] GARCIA-DIEGUEZ M, PIETA I S, HERRERA M C, et al. Nanostructured Pt- and Ni-based catalysts for CO₂-reforming of methane[J]. Journal of Catalysis, 2010, 270(1): 136-145. DOI:10.1016/j.jcat.2009.12.010. (