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纳米羟基磷灰石负载镍甲烷干重整催化剂的载体形貌效应

王彦博 贺雷 李文翠

王彦博, 贺雷, 李文翠. 纳米羟基磷灰石负载镍甲烷干重整催化剂的载体形貌效应[J]. 燃料化学学报. doi: 10.1016/S1872-5813(23)60332-9
引用本文: 王彦博, 贺雷, 李文翠. 纳米羟基磷灰石负载镍甲烷干重整催化剂的载体形貌效应[J]. 燃料化学学报. doi: 10.1016/S1872-5813(23)60332-9
WANG Yan-Bo, HE Lei, LI Wen-Cui. Morphology Effect of Nano-hydroxyapatite as Support for Loading Ni in Methane Dry Reforming[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(23)60332-9
Citation: WANG Yan-Bo, HE Lei, LI Wen-Cui. Morphology Effect of Nano-hydroxyapatite as Support for Loading Ni in Methane Dry Reforming[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(23)60332-9

纳米羟基磷灰石负载镍甲烷干重整催化剂的载体形貌效应

doi: 10.1016/S1872-5813(23)60332-9
详细信息
    通讯作者:

    E-mail: helei@dlut.edu.cn

    wencuili@dlut.edu.cn

  • 中图分类号: O643.3

Morphology Effect of Nano-hydroxyapatite as Support for Loading Ni in Methane Dry Reforming

  • 摘要: 甲烷干重整能同时将甲烷与二氧化碳两种主要温室气体转化为合成气(CO和H2),衔接费托过程生产燃料及化学品,实现高值转化利用,减少碳足迹,是“双碳”背景下含碳资源利用的重要反应。高效、稳定的催化剂是甲烷干重整实现工业应用的关键之一。载体的结构性质会影响活性组分的稳定固载和积碳–消碳反应的平衡,从而影响催化剂在甲烷干重整中的活性和稳定性。本文通过对羟基磷灰石(HAP)的形貌调控,得到表面Ca、O、P分布不同的纳米棒状、片状和线状的HAP载体,负载1.25wt%的活性组分镍后,得到Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂进行甲烷干重整性能研究。其中,Ni/HAP-R催化剂表现出最优的活性和抗积碳性能。利用XRD、氮吸附、FT–IR、XPS及CO2–TPD,对催化剂晶相结构、电子性质及表面酸碱性进行表征,证实棒状HAP具有最高的比表面积,有利于Ni的分散锚定,因此活性最佳。且棒状HAP表面富Ca–O–P碱性位点,能够有效活化CO2,促进积碳消除。TPSR实验进一步证实Ni/HAP-R催化剂上甲烷的深度裂解生成积碳的过程受到抑制,且在CO2存在时能够迅速转化为CO和H2,因此具有良好的抗积碳性能。该研究为高稳定负载型催化剂的设计合成提供了新的思路。
  • 图  1  (a, d) HAP-R,(b, e) HAP-S,(c, f) HAP-W的SEM照片

    Figure  1  SEM images for (a, d) HAP-R,(b, e) HAP-S,(c, f) HAP-W

    图  2  三种不同形貌羟基磷灰石的(a) XRD结果和(b) FT–IR谱图

    Figure  2  (a) XRD patterns and (b) FT–IR results for the as-prepared HAP samples

    图  3  (a) Ni/HAP-R,(b) Ni/HAP-S,(c) Ni/HAP-W还原后催化剂的TEM照片,以及(d)对应的XRD结果

    Figure  3  TEM images for reduced (a) Ni/HAP-R, (b) Ni/HAP-S and (c) Ni/HAP-W catalysts; (d) the corresponding XRD results

    图  4  Ni/HAP-R,Ni/HAP-S,Ni/HAP-W还原后催化剂的氮气吸脱附曲线以及对应的比表面积和孔容

    Figure  4  Nitrogen sorption isotherms of reduced Ni/HAP-R,Ni/HAP-S,Ni/HAP-W catalysts and the corresponding specific surface area and pore volume

    图  5  (a) HAP-R、HAP-S和HAP-W的CO2–TPD质谱(m/z=44)结果;(b) Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂的H2–TPR结果

    Figure  5  (a) Mass spectra (m/z=44) of CO2–TPD for HAP-R, HAP-S and HAP-W; (b) H2–TPR results for Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

    图  6  Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂的(a) Ni 2p XPS谱图和(b) UV–vis–DRS

    Figure  6  (a) Ni 2p XPS and (b) UV–vis–DRS results for Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

    图  7  Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂在800 ℃甲烷干重整反应中的(a) CH4和(b) CO2的转化率

    Figure  7  (a) CH4 and (b) CO2 conversion for Ni/HAP-R、Ni/HAP-S和Ni/HAP-W catalysts in MDR tests

    图  8  反应后Ni/HAP-R、Ni/HAP-S和Ni/HAP-W催化剂的(a)TG曲线和(b)对应的质谱(m/z=44)结果

    Figure  8  (a) TG curves and (b) corresponding mass spectra (m/z=44) for the spent Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

    图  9  (a) Ni/HAP-R催化剂的800 ℃稳定性测试; (b) 稳定性测试后的XRD结果; (c) 稳定性测试后的TG及质谱结果

    Figure  9  (a) stability test of Ni/HAP-R catalyst at 800 ℃; (b) XRD for the catalyst after stability test; (c) TG and the corresponding mass spectra (m/z=44)

    图  10  Ni/HAP-R, Ni/HAP-S和Ni/HAP-W催化剂的程序升温反应质谱结果: (a–c) CH4–TPSR, (d–f) CH4/CO2–TPSR

    Figure  10  Mass spectra of (a–c) CH4–TPSR and (d–f) CH4/CO2–TPSR for Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts

  • [1] 付彧, 孙予罕. CH4–CO2重整技术的挑战与展望[J]. 中国科学(化学), 2020, 50(7): 816–831.

    FU Yu, SUN Yu-han. CH4-CO2 reforming: challenges and outlook. Sci Sin Chim, 2020, 50: 816–831
    [2] 张涛, 刘志成, 杨为民. 低碳烷烃与二氧化碳催化转化研究进展[J]. 中国科学(化学),2021,51(2):154−164. doi: 10.1360/SSC-2020-0171

    ZHANG T, LIU ZC, YANG WM. Progress in the catalytic conversion of light alkanes with carbon dioxide[J]. Sci Sin Chim,2021,51(2):154−164. doi: 10.1360/SSC-2020-0171
    [3] 阮勇哲, 卢遥, 王胜平. 甲烷干重整Ni基催化剂失活及抑制失活研究进展[J]. 化工进展,2018,37(10):3850−3857. doi: 10.16085/j.issn.1000-6613.2017-2241

    RUAN Y, LU Y, WANG S. Progress in deactivation and anti-deactivation of nickel-based catalysts for methane dry reforming[J]. Chem. Ind. Eng. Progr.,2018,37(10):3850−3857. doi: 10.16085/j.issn.1000-6613.2017-2241
    [4] 张荣俊, 夏国富, 李明丰, 吴玉, 聂红, 李大东. 载体类型对Ni基催化剂甲烷干重整反应性能的影响[J]. 燃料化学学报,2015,43(11):1359−1365. doi: 10.3969/j.issn.0253-2409.2015.11.011

    ZHANG R, XIA G, LI M, WU Y, NIE H, LI D. Effect of support on catalytic performance of Ni-based catayst in methane dry reforming[J]. J. Fuel Chem. Technol.,2015,43(11):1359−1365. doi: 10.3969/j.issn.0253-2409.2015.11.011
    [5] WANG Y-B, HE L, ZHOU B-C, SHENG J, FAN J, LI W-C. Anti-coking NiCe /HAP catalyst with well-balanced carbon formation and gasification in methane dry reforming[J]. Fuel,2022,329:125477. doi: 10.1016/j.fuel.2022.125477
    [6] YANG B, DENG J, LI H, YAN T, ZHANG J, ZHANG D. Coking-resistant dry reforming of methane over Ni/γ-Al2O3 catalysts by rationally steering metal-support interaction[J]. iScience,2021,24:102747. doi: 10.1016/j.isci.2021.102747
    [7] BIAN Z, ZHONG W, YU Y, WANG Z, JIANG B, KAWI S. Dry reforming of methane on Ni/mesoporous-Al2O3 catalysts: effect of calcination temperature[J]. Int. J. Hydrogen Energy,2021,46:31041−31053. doi: 10.1016/j.ijhydene.2020.12.064
    [8] JOO S, SEONG A, KWON O, KIM K, LEE J H, GORTE R J, VOHS J M, HAN J W, KIM G. Highly active dry methane reforming catalysts with boosted in situ grown Ni-Fe nanoparticles on perovskite via atomic layer deposition[J]. Sci. Adv.,2020,6:eabb1573. doi: 10.1126/sciadv.abb1573
    [9] HE L, LI M, LI W-C, XU W, WANG Y, WANG Y-B, SHEN W, LU A-H. Robust and coke-free Ni catalyst stabilized by 1–2 nm–thick multielement oxide for methane dry reforming. ACS Catal. , 2021, 11: 12409–12416.
    [10] ALIPOUR Z, REZAEI M, MESHKANI F. Effect of alkaline earth promoters (MgO, CaO, and BaO) on the activity and coke formation of Ni catalysts supported on nanocrystalline Al2O3 in dry reforming of methane[J]. J. Ind. Eng. Chem.,2014,20(5):2858−2863. doi: 10.1016/j.jiec.2013.11.018
    [11] HU Y H. Solid-solution catalysts for CO2 reforming of methane[J]. Catal. Today, 2009, 148 (3–4): 206–211.
    [12] SONG Y, OZDEMIR E, RAMESH S, ADISHEV A, SUBRAMANIAN S, HARALE A, ALBUALI M, FADHEL B A, JAMAL A, MOON D, CHOI S H, YAVUZ C T. Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO[J]. Science,2020,367:777−781. doi: 10.1126/science.aav2412
    [13] AKRI M, ZHAO S, LI X, ZANG K, LEE A F, ISAACS M A, XI W, GANGARAJULA Y, LUO J, REN Y, CUI Y-T, LI L, SU Y, PAN X, WEN W, PAN Y, WILSON K, LI L, QIAO B, ISHII H, LIAO Y-F, WANG A, WANG X, ZHANG T. Atomically dispersed nickel as coke-resistant active sites for methane dry reforming[J]. Nat. Commun.,2019,10(1):5181. doi: 10.1038/s41467-019-12843-w
    [14] 张三兵, 李作鹏, 鲁润华, 王晓来. 羟基磷灰石负载Ni催化剂中Ni含量对催化甲烷二氧化碳重整制合成气性能的影响[J]. 燃料化学学报,2014,42(4):461−466.

    ZHANG S, LI Z, LU R, WANG X. Effects of Ni content of Ni/hydroxyapatite catalysts on catalytic properties for carbon dioxide reforming of methane[J]. J. Fuel Chem. Technol.,2014,42(4):461−466.
    [15] 王庆楠. 乙醇催化转化制高值含氧化学品[D]. 辽宁: 大连理工大学, 2019.

    WANG Q-N. Upgrading of ethanol to value-added oxygen-containing chemicals[D]. Dalian University of Technology, 2019.
    [16] TSUCHIDA T, KUBO J, YOSHIOKA T, SAKUMA S, TAKEGUCHI T, UEDA W. Reaction of ethanol over hydroxyapatite affected by Ca/P ratio of catalyst[J]. J. Catal.,2008,259(2):183−189. doi: 10.1016/j.jcat.2008.08.005
    [17] LIN K, CHANG J, ZHU Y, WU W, CHENG G, ZENG Y, RUAN M A. facile one-step surfactant-free and low-temperature hydrothermal method to prepare uniform 3D structured carbonated apatite flowers[J]. Cryst. Growth Des.,2009,9(1):177−181. doi: 10.1021/cg800129u
    [18] WANG X, ZHUANG J, PENG Q, LI Y D. Liquid–solid–solution synthesis of biomedical hydroxyapatite nanorods[J]. Adv. Mater.,2006,18(15):2031−2034. doi: 10.1002/adma.200600033
    [19] MOBASHERPOUR I, HESHAJIN M S, KAZEMZADEH A, ZAKERI M. Synthesis of nanocrystalline hydroxyapatite by using precipitation method[J]. J. Alloys Compd.,2007,430:330−333. doi: 10.1016/j.jallcom.2006.05.018
    [20] WANG Q-N, ZHOU B-C, WENG X-F, LV S-P, SCHÜTH F, LU A-H. Hydroxyapatite nanowires rich in [Ca–O–P] sites for ethanol direct coupling showing high C612 alcohol yield[J]. Chem. Commun.,2019,55(70):10420−10423. doi: 10.1039/C9CC05454E
    [21] LONDOñO-RESTREPO S M, ZUBIETA-OTERO L F, JERONIMO-CRUZ R, MONDRAGON M A, RODRIGUEZ-GARCÍA M E. Effect of the crystal size on the infrared and Raman spectra of bio hydroxyapatite of human, bovine, and porcine bones[J]. J. Raman Spectrosc.,2019,50:1120−1129. doi: 10.1002/jrs.5614
    [22] WANG Q-N, WENG X-F, ZHOU B-C, LV S-P, MIAO S, ZHANG D, HAN Y, SCOTT S L, SCHÜTH F, LU A-H. Direct, selective production of aromatic alcohols from ethanol using a tailored bifunctional cobalt-hydroxyapatite catalyst[J]. ACS Catal.,2019,9(8):7204−7216. doi: 10.1021/acscatal.9b02566
    [23] JUN J H, LEE T-J, LIM T H, NAM S-W, HONG S-A, YOON K J. Nickel–calcium phosphate/hydroxyapatite catalysts for partial oxidation of methane to syngas: characterization and activation[J]. J. Catal.,2004,221(1):178−190. doi: 10.1016/j.jcat.2003.07.004
    [24] MENG J, PAN W, GU T, BU C, ZHANG J, WANG X, LIU C, XIE H, PIAO G. One-pot synthesis of a highly active and stable Ni-embedded hydroxyapatite catalyst for syngas production via dry reforming of methane[J]. Energy Fuels,2021,35:19568−19580. doi: 10.1021/acs.energyfuels.1c02851
    [25] MENG J, GU T, PAN W, BU C, ZHANG J, WANG X, LIU C, XIE H, PIAO G. Promotional effects of defects on Ni/HAP catalyst for carbon resistance and durability during dry reforming of methane[J], Fuel, 2022, 310: 122363.
    [26] WANG Y-B, HE L, ZHOU B-C, TANG F, FAN J, WANG D-Q, LU A-H, LI W-C. Hydroxyapatite Nanorods Rich in [Ca–O–P] Sites Stabilized Ni Species for Methane Dry Reforming. Ind. Eng. Chem. Res. 2021, 60: 15064–15073.
    [27] DAMYANOVA S, PAWELEC B, PALCHEVA R, KARAKIROVA Y, SANCHEZ M C C, TYULIEV G, GAIGNEAUX E, FIERRO J L G. Structure and surface properties of ceria-modified Ni-based catalysts for hydrogen production[J]. Appl. Catal. B-Environ.,2018,225:340−353. doi: 10.1016/j.apcatb.2017.12.002
    [28] ZHU Y, ZHANG S, CHEN B, ZHANG Z, SHI C. Effect of Mg/Al ratio of NiMgAl mixed oxide catalyst derived from hydrotalcite for carbon dioxide reforming of methane[J]. Catal. Today,2016,264:163−170. doi: 10.1016/j.cattod.2015.07.037
    [29] 李睿杰, 章菊萍, 史健, 李孔斋, 刘慧利, 祝星. Ni/CeO2催化剂的金属-载体界面调控及其低温化学链甲烷干重整性能研究[J]. 燃料化学学报,2022,50(11):1458−1470. doi: 10.1016/S1872-5813(22)60032-X

    LI R, ZHANG J, SHI J, LI K, LIU H, ZHU X. Regulation of metal-support interface of Ni/CeO2 catalyst and the performance of low temperature chemical looping dry reforming of methane[J]. J. Fuel Chem. Technol.,2022,50(11):1458−1470. doi: 10.1016/S1872-5813(22)60032-X
    [30] BHATTAR S, KRISHNAKUMAR A, KANITKAR S, ABEDIN A, SHEKHAWAT D, HAYNES D J, SPIVEY J J. 110th anniversary: dry reforming of methane over Ni- and Sr-substituted lanthanum zirconate pyrochlore catalysts: effect of Ni loading. Ind. Eng. Chem. Res. [J]. 2019, 58(42): 19386–19396.
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  • 收稿日期:  2022-11-07
  • 录用日期:  2022-12-25
  • 修回日期:  2022-12-24
  • 网络出版日期:  2023-01-10

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