Mg-Al-hydrotalcite with alkaline sites protects Ni/KIT-6 from formation of amorphous coke in glycerol steam reforming via tailoring reaction intermediates

Abstract

During steam reforming, the performance of a catalyst and amount/property of coke are closely related to reaction intermediates reaching surface of a catalyst. Herein, modification of reaction intermediates by placing Mg-Al-hydrotalcite above Ni/KIT-6 catalyst in steam reforming of glycerol was conducted at 300 to 600 °C. The results revealed that the catalytic activity of Ni/KIT-6 in the lower bed was enhanced with either Mg₁-Al₅-hydrotalcite (containing more acidic sites) or Mg₅-Al₁-hydrotalcite (containing more alkaline sites) as upper-layer catalyst. The in situ infrared characterization of steam reforming demonstrated that Mg-Al-hydrotalcite catalyzed the deoxygenation of glycerol, facilitating the reforming of the partially deoxygenated intermediates over Ni/KIT-6. Mg-Al-hydrotalcite as protective catalyst, however, did not protect the Ni/KIT-6 from formation of more coke. Nonetheless, this did not lead to further deactivation of Ni/KIT-6 while Mg₅-Al₁-hydrotalcite even substantially enhanced the catalytic stability, even though the coke was much more significant than that in the use of single Ni/KIT-6 (52.7% vs. 28.6%). The reason beneath this was change of the property of coke from more aliphatic to more aromatic. Mg₅-Al₁-hydrotalcite catalyzed dehydration of glycerol, producing dominantly reaction intermediates bearing C=C, which formed the catalytic coke of with carbon nanotube as the main form with smooth outer walls as well as higher aromaticity, C/H ratio, crystallinity, crystal carbon size, thermal stability, and resistivity toward oxidation on Ni/KIT-6 in the lower bed. In comparison, the abundance of acidic sites on Mg₁-Al₅-hydrotalcite catalyzed the formation of more oxygen-containing species, leading to the formation of carbon nanotubes of rough surface on Ni/KIT-6.

Graphical abstract

Keywords

steam reforming of glycerol / Mg-Al-hydrotalcite / sacrificial catalyst / reaction intermediates / property of coke

References

[1] Ismaila A , Chen X , Gao X , Fan X . Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure. Frontiers of Chemical Science and Engineering, 2021, 15(1): 60–71

[2] Zhang J , Wang Y , Muldoon V L , Deng S . Crude glycerol and glycerol as fuels and fuel additives in combustion applications. Renewable & Sustainable Energy Reviews, 2022, 159: 112206

[3] Thyssen V , Maia T A , Assaf E M . Ni supported on La₂O₃–SiO₂ used to catalyze glycerol steam reforming. Fuel, 2013, 105: 358–363

[4] Chen M , Zhou Z , Wang Y , Liang T , Li X , Yang Z , Chen M , Wang J . Effects of attapulgite-supported transition metals catalysts on glycerol steam reforming for hydrogen production. International Journal of Hydrogen Energy, 2018, 43(45): 20451–20464

[5] Cheng W , Wang Y , Chen M , Liang D , Li C , Yang Z , Wang J . Hydrogen production from aqueous phase reforming of glycerol over attapulgite-supported nickel catalysts: effect of acid/base treatment and Fe additive. International Journal of Hydrogen Energy, 2022, 47(11): 7082–7099

[6] Bac S , Keskin S , Avci A . Recent advances in materials for high purity H₂ production by ethanol and glycerol steam reforming. Industrial & Engineering Chemistry Research, 2020, 45(60): 34888–34917

[7] Wu G , Zhang C , Li S , Han Z , Wang T , Ma X , Gong J . Hydrogen production via glycerol steam reforming over Ni/Al₂O₃: influence of nickel precursors. ACS Sustainable Chemistry & Engineering, 2013, 1(8): 1052–1062

[8] Iriondo A , Barrio V L , Cambra J F , Arias P L , Guemez M B , Sanchez-Sanchez M C , Navarro R M , Fierro J L G . Glycerol steam reforming over Ni catalysts supported on ceria and ceria-promoted alumina. International Journal of Hydrogen Energy, 2010, 35(20): 11622–11633

[9] Rahmat N , Abdullah A Z , Mohamed A R . Recent progress on innovative and potential technologies for glycerol transformation into fuel additives: a critical review. Renewable & Sustainable Energy Reviews, 2010, 14(3): 987–1000

[10] Crabtree R H . Transfer hydrogenation with glycerol as H-donor: catalyst activation, deactivation and homogeneity. ACS Sustainable Chemistry & Engineering, 2019, 7(19): 15845–15853

[11] Gupta M , Kumar N . Scope and opportunities of using glycerol as an energy source. Renewable & Sustainable Energy Reviews, 2012, 16(7): 4551–4556

[12] Díaz-Álvarez A E , Francos J , Lastra-Barreira B , Crochet P , Cadierno V . Glycerol and derived solvents: new sustainable reaction media for organic synthesis. Chemical Communications, 2011, 47(22): 6208–6227

[13] Stošić D , Bennici S , Couturier J L , Dubois J L , Auroux A . Influence of surface acid-base properties of zirconia and titania based catalysts on the product selectivity in gas phase dehydration of glycerol. Chemical Communications, 2012, 17: 23–28

[14] Feng R , Qi Y , Liu S , Cui L , Dai Q , Bai C . Production of renewable 1,3-pentadiene over LaPO₄ via dehydration of 2,3-pentanediol derived from 2,3-pentanedione. Applied Catalysis A: General, 2022, 633: 118514

[15] Ren J , Liu Y L . Promoting syngas production from steam reforming of toluene using a highly stable Ni/(Mg, Al)O_x catalyst. Applied Catalysis B: Environmental, 2022, 300: 120743

[16] Choong C K , Huang L , Zhong Z , Lin J , Hong L , Chen L . Effect of calcium addition on catalytic ethanol steam reforming of Ni/Al₂O₃: II. Acidity/basicity, water adsorption and catalytic activity. Applied Catalysis A: General, 2011, 407(1–2): 155–162

[17] Da Costa-Serra J F , Navarro M T , Rey F , Chica A . Bioethanol steam reforming on Ni-based modified mordenite. Effect of mesoporosity, acid sites and alkaline metals. International Journal of Hydrogen Energy, 2012, 37(8): 7101–7108

[18] Zhang Z , Wang Y , Sun K , Shao Y , Zhang L , Zhang S , Zhang X , Liu Q , Chen Z , Hu X . Steam reforming of acetic acid over Ni–Ba/Al₂O₃ catalysts: impacts of barium addition on coking behaviors and formation of reaction intermediates. Journal of Energy Chemistry, 2020, 43: 208–219

[19] Zhang Z , Zhang L , Gao Z , Sun K , Shao Y , Zhang S , Liu Q , Gao G , Wei T , Hu X . Catalyst experiencing distinct reaction histories in one reactor bed results in coke of different properties in steam reforming. Fuel, 2020, 269: 117427

[20] Gao Z , Li C , Shao Y , Gao G , Xu Q , Tian H , Zhang S , Hu X . Sequence of Ni/SiO₂ and Cu/SiO₂ in dual catalyst bed significantly impacts coke properties in glycerol steam reforming. International Journal of Hydrogen Energy, 2021, 46(52): 26367–26380

[21] He F , Luo J , Liu S . Novel metal loaded KIT-6 catalysts and their applications in the catalytic combustion of chlorobenzene. Chemical Engineering Journal, 2016, 294: 362–370

[22] Shao Y , Wang J , Sun K , Gao G , Li C , Zhang L , Zhang S , Xu L , Hu G , Hu X . Selective hydrogenation of furfural and its derivative over bimetallic NiFe-based catalysts: understanding the synergy between Ni sites and Ni–Fe alloy. Renewable Energy, 2021, 170: 1114–1128

[23] Li X , Zhang L , Zhang S , Xu L , Hu X . Steam reforming of sugar and its derivatives: functionality dictates thermal properties and morphologies of coke. Fuel, 2022, 307: 121798

[24] Bkangmo Kontchouo F M , Shao Y , Zhang S , Gholizadeh M , Hu X . Steam reforming of ethanol, acetaldehyde, acetone and acetic acid: understanding the reaction intermediates and nature of coke. Chemical Engineering Science, 2023, 265: 118257

[25] Goula M A , Charisiou N D , Papageridis K N , Delimitis A , Pachatouridou E , Iliopoulou E F . Nickel on alumina catalysts for the production of hydrogen rich mixtures via the biogas dry reforming reaction: influence of the synthesis method. International Journal of Hydrogen Energy, 2015, 40(30): 9183–9200

[26] Gai C , Zhang F , Guo Y , Liu Z . A novel strategy for the fabrication of highly active and stable hydrochar-based catalysts for efficient dry reforming of methane. Chemical Engineering Journal, 2023, 475: 146437

[27] Zhang H , Li M , Xiao P , Liu D , Zou C J . Structure and catalytic performance of Mg-SBA-15-supported nickel catalysts for CO₂ reforming of methane to syngas. Chemical Engineering & Technology, 2013, 36(10): 1701–1707

[28] Nie R , Lei H , Pan S , Wang L , Fei J , Hou Z . Core–shell structured CuO–ZnO@H-ZSM-5 catalysts for CO hydrogenation to dimethyl ether. Fuel, 2012, 96: 419–425

[29] Ramírez-Hernández G Y , Viveros-García T , Fuentes-Ramírez R , Galindo-Esquivel I R . Promoting behavior of yttrium over nickel supported on alumina-yttria catalysts in the ethanol steam reforming reaction. International Journal of Hydrogen Energy, 2016, 41(22): 9332–9343

[30] Wang Y , Lu Z , Chen M , Liang D , Wang J . Hydrogen production from catalytic steam reforming of toluene over trace Fe and Mn doping Ni/attapulgite. Journal of Analytical and Applied Pyrolysis, 2022, 165: 105584

[31] Bkangmo Kontchouo F M , Sun K , Li C , Fu Z , Zhang S , Xu L , Hu X . Steam reforming of acetone and isopropanol: investigation of correlation of ketone and alcohol functional groups with properties of coke. Journal of the Energy Institute, 2022, 101: 32–44

[32] Tang W , Cao J P , Wang Z Y , Jiang W , Zhao X Y , He Z M , Wang Z H , Bai H C . Preparation of highly dispersed lignite-char-supported cobalt catalyst for stably steam reforming of biomass tar at low temperature. Fuel, 2023, 334: 126814

[33] Du Z Y , Zhang Z H , Xu C , Wang X B , Li W Y . Low-temperature steam reforming of toluene and biomass tar over biochar-supported Ni nanoparticles. ACS Sustainable Chemistry & Engineering, 2019, 7(3): 3111–3119

[34] Wang Y , Chen M , Yang Z , Liang T , Liu S , Zhou Z , Li X . Bimetallic Ni-M (M = Co, Cu and Zn) supported on attapulgite as catalysts for hydrogen production from glycerol steam reforming. Applied Catalysis A: General, 2018, 550: 214–227

[35] Wang Y , Li N , Chen M , Liang D , Li C , Liu Q , Yang Z L , Wang J . Glycerol steam reforming over hydrothermal synthetic Ni–Ca/attapulgite for green hydrogen generation. Chinese Journal of Chemical Engineering, 2022, 48: 176–190

[36] Wang Z H , Cao J P , Tang W , He Z M , Yang F L , Wang Z Y , Zhao X Y . Facile synthesis of low-cost Co–Cu/C alloy catalysts for hydrogen-rich syngas production from low-temperature steam reforming of biomass tar. Chemical Engineering Science, 2023, 267: 118370

[37] Wang F , Han K , Yu W , Zhao L , Wang Y , Wang X , Yu H , Shi W . Low temperature CO₂ reforming with methane reaction over CeO₂-modified Ni@SiO₂ catalysts. ACS Applied Materials & Interfaces, 2020, 12(31): 35022–35034

[38] Manoj B . Investigation of nanocrystalline structure in selected carbonaceous materials. International Journal of Minerals Metallurgy and Materials, 2014, 21(9): 940–946

[39] Maximiano R V , Beams R , Novotny L , Jorio A , Cançado L . Mechanism of near-field Raman enhancement in two-dimensional systems. Physical Review B: Condensed Matter and Materials Physics, 2012, 85(23): 235434

[40] Li X , Shao Y , Zhang S , Wang Y , Xiang J , Hu S , Xu L , Hu X . Pore diameters of Ni/ZrO₂ catalysts affect properties of the coke in steam reforming of acetic acid. International Journal of Hydrogen Energy, 2021, 46(46): 23642–23657

[41] Wang Z , Bao B . Investigation on coking performance with sulfur/phosphorous-containing additive and anti-coking SiO₂/S coating during thermal cracking of light naphtha. Energy Procedia, 2017, 105: 5122–5127

[42] Charisiou N D , Siakavelas G I , Dou B , Shao Y , Sebastian V , Hinder S J , Baker M A , Polychronopoulou K , Goula M A . Nickel supported on AlCeO₃ as a highly selective and stable catalyst for hydrogen production via the glycerol steam reforming reaction. Catalysts, 2019, 9(5): 411

[43] Wang C , Wang Y , Chen M , Liang D , Cheng W , Li C , Yang Z L , Wang J . Understanding relationship of sepiolite structure tailoring and the catalytic behaviors in glycerol steam reforming over Co/sepiolite derived Co-phyllosilicate catalyst. Renewable Energy, 2022, 183: 304–320

[44] Purushothaman R , Palanichamy M , Mohammed Bilal I . Functionalized KIT‐6/terpolyimide composites with ultra‐low dielectric constant. Journal of Applied Polymer Science, 2014, 131(15): 40508

[45] Wang Y , Hu X , Mourant D , Song Y , Zhang L , Lievens C , Xiang J , Li C Z . Evolution of aromatic structures during the reforming of bio-oil: importance of the interactions among bio-oil components. Fuel, 2013, 111: 805–812

[46] Bkangmo Kontchouo F M , Fan M , Inkoua S , Sun Y , Zhang S , Hu X . Steam reforming of toluene: impacts of externally added oxygen-containing intermediates on property of coke. International Journal of Hydrogen Energy, 2023, 48(43): 16206–16222

[47] Bkangmo Kontchouo F M , Zhang L , Zhang S , Hu G , Hu X . Distinct coking depth in steam reforming of oxygen-containing organics and hydrocarbons. Journal of Colloid and Interface Science, 2023, 639: 385–400

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 52276195), the Program for Supporting Innovative Research of Jinan (Grant No. 202228072), and the Program for Agricultural Development of Shandong (Grant No. SD2019NJ015).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2399-z and is accessible for authorized users.

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