In-depth into the mechanism of aromatic production from catalytic pyrolysis of wet-torrefied microalgae with HZSM-5 coated biochar

Jinye Hu , Yunpu Wang , Haiwei Jiang , Jiabo Wu , Ting Luo , Qi Wang , Yuhang Hu , Kaisong Hu , Wenguang Zhou , Liangliang Fan

Biochar ›› 2026, Vol. 8 ›› Issue (1) : 91

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Biochar ›› 2026, Vol. 8 ›› Issue (1) :91 DOI: 10.1007/s42773-026-00612-0
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In-depth into the mechanism of aromatic production from catalytic pyrolysis of wet-torrefied microalgae with HZSM-5 coated biochar
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Abstract

Bio-oil from pyrolysis of microalgal biomass tends to exhibit high oxygen and nitrogen content, which is challenging for the commercial application of algae-based fuels. This study started with wet torrefaction of Chlorella to improve its fuel properties, and then Zeolite Socony Mobile-5 (HZSM-5) was used to synthesize HZSM-5 coated biochar (HZSM-5@biochar) catalyst for catalytic pyrolysis. During the process, up to 96.06% of aromatics with benzene, toluene and xylene (BTX) selectivity of 83.24% and a yield of 94.64 mg g−1 was obtained under specific conditions (wet torrefaction at 200 °C, pyrolysis at 500 °C, catalyst-to-feedstock ratio of 20:1). Meanwhile, the content of oxygenates and nitrogenates was reduced from 82.14% under non-catalytic condition to 3.26%. The catalytic conversion pathway was hypothesized by catalytic experiments with model compounds. The transformation process of oxygen- and nitrogen-containing functional groups was probed by XPS and in situ DRIFTS to help elucidate the deoxygenation and denitrogenation mechanism during the catalytic pyrolysis of Chlorella. Besides, the excellent stability of HZSM-5@biochar was demonstrated by six-cycle experiments. The composite catalyst also showed lower yield of coke (0.33%) with less aromaticity after a single use compared to HZSM-5, whose coke yield was 1.87%. Scanning electron microscopy analysis revealed that compared to HZSM-5@biochar, the used HZSM-5 formed more amorphous components suspected to be coke.

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Keywords

HZSM-5@biochar / Aromatic hydrocarbons / Deoxygenation and denitrogenation / Biomass catalytic pyrolysis / Catalyst stability

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Jinye Hu, Yunpu Wang, Haiwei Jiang, Jiabo Wu, Ting Luo, Qi Wang, Yuhang Hu, Kaisong Hu, Wenguang Zhou, Liangliang Fan. In-depth into the mechanism of aromatic production from catalytic pyrolysis of wet-torrefied microalgae with HZSM-5 coated biochar. Biochar, 2026, 8(1): 91 DOI:10.1007/s42773-026-00612-0

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References

[1]

Abbas-Abadi MS, Ureel Y, Eschenbacher A, et al. . Challenges and opportunities of light olefin production via thermal and catalytic pyrolysis of end-of-life polyolefins: towards full recyclability. Prog Energy Combust Sci, 2023, 96 101046

[2]

Anand V, Gautam R, Vinu R. Non-catalytic and catalytic fast pyrolysis of microalga. Fuel, 2017, 205: 1-10

[3]

Ayiania M, Smith M, Hensley AJR, et al. . Deconvoluting the XPS spectra for nitrogen-doped chars: an analysis from first principles. Carbon, 2020, 162: 528-544

[4]

Ayiania M, Weiss-Hortala E, Smith M, et al. . Microstructural analysis of nitrogen-doped char by Raman spectroscopy: Raman shift analysis from first principles. Carbon, 2020, 167: 559-574

[5]

Bach QV, Chen WH. A comprehensive study on pyrolysis kinetics of microalgal biomass. Energy Convers Manag, 2017, 131: 109-116

[6]

Bach QV, Skreiberg O. Upgrading biomass fuels via wet torrefaction: a review and comparison with dry torrefaction. Renew Sust Energ Rev, 2016, 54: 665-677

[7]

Bondue CJ, Koper MTM. A mechanistic investigation on the electrocatalytic reduction of aliphatic ketones at platinum. J Catal, 2019, 369: 302-311

[8]

Chen YJ, Syed-Hassan SSA, Xiong Z, et al. . Temporal and spatial evolution of biochar chemical structure during biomass pellet pyrolysis from the insights of micro-Raman spectroscopy. Fuel Process Technol, 2021, 218 106839

[9]

Cheng K, Zhou W, Kang J, et al. . Bifunctional catalysts for one-step conversion of syngas into aromatics with excellent selectivity and stability. Chem-Us, 2017, 3(2): 334-347

[10]

Chhabra V, Bambery K, Bhattacharya S, et al. . Thermal and in situ infrared analysis to characterise the slow pyrolysis of mixed municipal solid waste (MSW) and its components. Renew Energy, 2020, 148: 388-401

[11]

Cnudde P, De Wispelaere K, Vanduyfhuys L, et al. . How chain length and branching influence the alkene cracking reactivity on H-ZSM-5. ACS Catal, 2018, 8(10): 9579-9595

[12]

Costil R, Lefebvre Q, Clayden J. Medium-sized-ring analogues of dibenzodiazepines by a conformationally induced smiles ring expansion. Angew Chem Int Ed, 2017, 56(46): 14602-14606

[13]

Dai LL, Wang YP, Liu YH, et al. . Integrated process of lignocellulosic biomass torrefaction and pyrolysis for upgrading bio-oil production: a state-of-the-art review. Renew Sustain Energy Rev, 2019, 107: 20-36

[14]

Dong S, Shen X, Guo Q, et al. . Valorization of soybean plant wastes in preparation of N-doped biochar for catalytic ozonation of organic contaminants: Atrazine degradation performance and mechanistic considerations. Chem Eng J, 2023, 472 145153

[15]

Dong W, Xing J, Chen Q, et al. . Hydrogen bonds between the oxygen-containing functional groups of biochar and organic contaminants significantly enhance sorption affinity. Chem Eng J, 2024, 499 156654

[16]

Du JL, Hu JH, Yang SL, et al. . A comprehensive investigation of thermal coke formation during rapid non-catalytic pyrolysis of rubber seed oil. Renew Energy, 2024, 232 121034

[17]

Eibner S, Margeriat A, Broust F, et al. . Catalytic deoxygenation of model compounds from flash pyrolysis of lignocellulosic biomass over activated charcoal-based catalysts. Appl Catal B-Environ, 2017, 219: 517-525

[18]

Fan LL, Ruan R, Li J, et al. . Aromatics production from fast co-pyrolysis of lignin and waste cooking oil catalyzed by HZSM-5 zeolite. Appl Energy, 2020, 263 114629

[19]

Figueiredo MC, Ledezma-Yanez I, Koper MTM. In situ spectroscopic study of CO electroreduction at copper electrodes in acetonitrile. Acs Catal, 2016, 6(4): 2382-2392

[20]

Gan YY, Ong HC, Show PL, et al. . Torrefaction of microalgal biochar as potential coal fuel and application as bio-adsorbent. Energy Convers Manage, 2018, 165: 152-162

[21]

Gu B, Cao JP, Wei F, et al. . Nitrogen migration mechanism and formation of aromatics during catalytic fast pyrolysis of sewage sludge over metal-loaded HZSM-5. Fuel, 2019, 244: 151-158

[22]

Guo S, Wang Y, Yang L, et al. . ReaxFF-based molecular dynamics simulation of the impact of potassium on the formation of NH3 during protein pyrolysis. Energy, 2024, 313 134059

[23]

Guo JL, Foo JLC, Ge LY, et al. . Steam-assisted one-step fabrication of Ni-Ce biochar catalysts for enhanced biomass pyrolysis-steam reforming. Chem Eng J, 2025, 509 161302

[24]

He PP, Chen B, Huang L, et al. . Heterogeneous manganese-oxide-catalyzed successive cleavage and functionalization of alcohols to access amides and nitriles. Chem-Us, 2022, 8(7): 1906-1927

[25]

He M, Ali MF, Song YQ, et al. . Study on the deactivation mechanism of HZSM-5 in the process of catalytic cracking of n-hexane. Chem Eng J, 2023, 451 138793

[26]

He Y, Chen J, Mo Z, et al. . Controlling Diels-Alder reactions in catalytic pyrolysis of sawdust and polypropylene by coupling CO2 atmosphere and Fe-modified zeolite for enhanced light aromatics production. J Hazard Mater, 2023, 455 131547

[27]

Hou C, Zhou CX, Li N, et al. . Interaction effects between the main components of protein-rich biomass during microwave-assisted pyrolysis. Environ Sci Technol, 2024, 58(18): 7826-7837

[28]

Hu CS, Zhang HY, Wu SL, et al. . Molecular shape selectivity of HZSM-5 in catalytic conversion of biomass pyrolysis vapors: the effective pore size. Energy Convers Manag, 2020, 210 112678

[29]

Hu JY, Zhou WG, Wang YP, et al. . Synthesis of HZSM-5@activated carbon for improving aromatic production from catalytic pyrolysis of biomass. Chem Eng J, 2024, 494 153031

[30]

Ke L, Wang X, Peng Y, et al. . Continuous microwave co-pyrolysis of LDPE and PET coupled ex-situ catalysis to monocyclic aromatic hydrocarbons using different structural forms of HZSM-5 as catalysts. Chem Eng J, 2025, 514 163356

[31]

Kostyniuk A, Likozar B. Wet torrefaction of biomass waste into value-added liquid product (5-HMF) and high quality solid fuel (hydrochar) in a nitrogen atmosphere. Renew Energy, 2024, 226 120450

[32]

Kumar A, Yan BB, Tao JY, et al. . Co-pyrolysis of de-oiled microalgal biomass residue and waste tires: deeper insights from thermal kinetics, behaviors, drivers, bio-oils, bio-chars, and in-situ evolved gases analyses. Chem Eng J, 2022, 446 137160

[33]

Kumbhar D, Palliyarayil A, Reghu D, et al. . Rapid discrimination of porous bio-carbon derived from nitrogen rich biomass using Raman spectroscopy and artificial intelligence methods. Carbon, 2021, 178: 792-802

[34]

Leng LJ, Yang LH, Chen JF, et al. . A review on pyrolysis of protein-rich biomass: Nitrogen transformation. Bioresource Technol, 2020, 315 123801

[35]

Li Y, Zhang CS, Liu YG, et al. . Coke formation on the surface of Ni/HZSM-5 and Ni-Cu/HZSM-5 catalysts during bio-oil hydrodeoxygenation. Fuel, 2017, 189: 23-31

[36]

Li B, Huang HM, Xie X, et al. . Volatile-char interactions during biomass pyrolysis: effects of AAEMs removal and KOH addition in char. Renew Energy, 2023, 219 119459

[37]

Li J, Yang B, Li N, et al. . Investigation on deactivation periods of ZSM-5/SAPO-34 catalyst in MTA reaction: carbon deposition behavior. Fuel, 2025,

[38]

Liu X, Fan Y, Zhai Y, et al. . Co-hydrothermal carbonization of rape straw and microalgae: pH-enhanced carbonization process to obtain clean hydrochar. Energy, 2022, 257 124733

[39]

Liu L, Fan L, Jin K, et al. . One-pot synthesis of lignin biochar supported Ni for catalytic pyrolysis of Chlorella vulgaris and its model compounds: the formation mechanism of aromatic hydrocarbons. Fuel, 2023, 341 127558

[40]

Liu HY, Zhang J, Shan R, et al. . Mechanistic insights into Ga-modified hollow ZSM-5 catalyzed fast pyrolysis of cassava residue. Energy, 2024, 295 131068

[41]

Liu Y, Gao LL, Chang GZ, et al. . Enhancing reductive conversion of levulinic acid and levulinates to γ-valerolactone: role of oxygen vacancy in MnOx catalysts. Bioresource Technol, 2024,

[42]

Milanese M, Colangelo G, Mellone A, et al. . Low-energy thermo-chemical conversion processes of municipal wet waste. Therm Sci Eng Prog, 2024, 54 102852

[43]

Nikkhah H, Tavasoli A, Jafarian S. Investigating the influence of acid washing pretreatment and Zn/activated biochar catalyst on thermal conversion of to value-added bio-products. Energy Convers Manag, 2020, 225 113392

[44]

Niu Q, Ghysels S, Wu NN, et al. . Effects of demineralization on the composition of microalgae pyrolysis volatiles in py-GC-MS. Energy Convers Manag, 2022, 251 114979

[45]

Orrego-Restrepo E, Ordonez-Loza J, Chejne F. Novel methodology for evaluation of cellulose pyrolysis kinetics implementing infrared spectroscopy. J Anal Appl Pyrol, 2022, 166 105589

[46]

Oseke GG, Atta AY, Mukhtar B, et al. . Increasing the catalytic stability of microporous Zn/ZSM-5 with copper for enhanced propane aromatization. J King Saud Univ Eng Sci, 2021, 33(8): 531-538

[47]

Pham TN, Sooknoi T, Crossley SP, et al. . Ketonization of carboxylic acids: mechanisms, catalysts, and implications for biomass conversion. ACS Catal, 2013, 3(11): 2456-2473

[48]

Shi JJ, Guan JY, Guo DW, et al. . Nitrogen chemistry and coke transformation of FCC coked catalyst during the regeneration process. Sci Rep, 2016, 6 27309

[49]

Song Q, Wang Q, Lu F, et al. . Influence of Brönsted acid sites on activated carbon-based catalyst for acetylene dimerization. ACS Appl Mater Interfaces, 2024, 16(6): 7345-7352

[50]

Su Z, Jin K, Wu J, et al. . Phosphorus doped biochar as a deoxygenation and denitrogenation catalyst for ex-situ upgrading of vapors from microwave-assisted co-pyrolysis of microalgae and waste cooking oil. J Anal Appl Pyrol, 2022,

[51]

Suarez Ruiz CA, Cabau-Peinado O, van den Berg C, et al. . Efficient fractionation of lipids in a multiproduct microalgal biorefinery by polymers and ionic liquid-based aqueous two-phase systems. ACS Sustain Chem Eng, 2022, 10(2): 789-799

[52]

Tang ZY, Chen W, Chen YQ, et al. . Preparation of low-nitrogen and high-quality bio-oil from microalgae catalytic pyrolysis with zeolites and activated carbon. J Anal Appl Pyrol, 2021, 159 105182

[53]

Tian H, Chen L, Huang ZJ, et al. . Increasing the bio-aromatics yield in the biomass pyrolysis oils by the integration of torrefaction deoxygenation pretreatment and catalytic fast pyrolysis with a dual catalyst system. Renew Energy, 2022, 187: 561-571

[54]

Vogt ETC, Fu DL, Weckhuysen BM. Carbon deposit analysis in catalyst deactivation, regeneration, and rejuvenation. Angew Chem Int Ed, 2023, 62(29): e202300319

[55]

Wang AG, Austin D, Karmakar A, et al. . Methane upgrading of acetic acid as a model compound for a biomass-derived liquid over a modified zeolite catalyst. Acs Catal, 2017, 7(5): 3681-3692

[56]

Wang X, Tang X, Yang X. Pyrolysis mechanism of microalgae Nannochloropsis sp. based on model compounds and their interaction. Energy Conv Manag, 2017, 140: 203-210

[57]

Wang YN, Ma WH, Wang DY, et al. . Study on the reaction mechanism of the propylene oxide rearrangement via in situ DRIFTS. Chem Eng J, 2017, 307: 1047-1054

[58]

Wang YP, Wu QH, Dai LL, et al. . Co-pyrolysis of wet torrefied bamboo sawdust and soapstock. J Anal Appl Pyrol, 2018, 132: 211-216

[59]

Wang S, Shang H, Abomohra AEF, et al. . One-step conversion of microalgae to alcohols and esters through co-pyrolysis with biodiesel-derived glycerol. Energy Convers Manage, 2019, 198 111792

[60]

Wang YP, Ke LY, Peng YJ, et al. . Ex-situ catalytic fast pyrolysis of soapstock for aromatic oil over microwave-driven HZSM-5@SiC ceramic foam. Chem Eng J, 2020, 402 126239

[61]

Wu JB, Zhou WG, Wang YP, et al. . Preparation of hierarchical HZSM-5 loaded Ni for high-grade bio-oil and low coke formation from catalytic co-pyrolysis of microalgae and LDPE. Chem Eng J, 2025, 526 171240

[62]

Yu ZY, Guo W, Yang PX, et al. . In-situ infrared and kinetic characteristics analysis on pyrolysis of tar-rich coal and macerals. Fuel, 2023, 348 128601

[63]

Zhang LQ, Liu JJ, Li DW, et al. . Research on the thermochemical conversion utilization of nitrogen-rich microalgae: two-step catalytic pyrolysis of Nannochloropsis sp over ZSM-5. Energy Convers Manag, 2022, 258 115475

[64]

Zhang J, Wang Z, Cai Y, et al. . Ultralow-loading subnano [Ptn–Gam]δ+ clusters with Lewis and Brønsted acid functionalities for active Diels-Alder cycloaddition between biomass-derived furans and normal-pressure alkenes. ACS Sustain Chem Eng, 2025, 13(21): 8173-8183

[65]

Zheng YW, Wang Z, Liu C, et al. . Integrated production of aromatic amines, aromatic hydrocarbon and N-heterocyclic bio-char from catalytic pyrolysis of biomass impregnated with ammonia sources over Zn/HZSM-5 catalyst. J Energy Inst, 2020, 93(1): 210-223

[66]

Ziyue T, Chen W, Chen X, et al. . Thermal behavior and kinetic mechanism of microalgae and model compounds. Fuel, 2023, 344 128037

[67]

Zuo Y, Ye L, Yang W, et al. . Optimizing ethylene production through enhanced monomolecular β-scission in confined catalytic cracking of olefin. ACS Catal, 2025, 15(3): 1576-1585

Funding

National Natural Science Foundation of China(No. 52566015)

Young Talents (academic) of the Ganpo Juncai Support Program of Jiangxi Province(20243BCE51078)

Natural Science Foundation of Jiangxi Province(No. 20242BAB20105)

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