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Catalytic graphitization of engineered pyrolysis bio-oil for sustainable graphite and hydrogen Co-production
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process.ORCID iD: 0009-0006-6246-8399
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process.ORCID iD: 0000-0002-1709-5283
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process.
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process.ORCID iD: 0000-0001-9884-1278
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2026 (English)In: Renewable energy, ISSN 0960-1481, E-ISSN 1879-0682, Vol. 256, article id 124149Article in journal (Refereed) Published
Abstract [en]

The decarbonization of energy systems requires both clean fuel alternatives and sustainable materials for energy storage. This study explores catalytic graphitization of engineered pyrolysis bio-oil, a renewable, carbon-rich by-product of biomass conversion, to produce graphite for lithium-ion battery anodes and renewable hydrogen. Four engineered bio-oils derived from sawdust pyrolysis at 550 °C were evaluated at 1300 °C using reduced iron powder as a catalyst. Among these, heavy-phase filtered bio-oil (HFB) demonstrated superior graphitization efficiency, achieving a graphitization degree of 94.51% and generating a significant hydrogen yield of 5.25 g H<inf>2</inf>/100 g bio-oil. Compared to conventional synthetic graphite production, which relies on fossil coke and extreme temperatures (>2500 °C), this method significantly reduces energy demand and CO<inf>2</inf> emissions. A liquid–solid catalytic mechanism is proposed for the first time, enabling efficient carbon transformation and hydrogen release without the need for steam input. This work contributes to advancing circular bioeconomy strategies and highlights the role of biomass valorization in future sustainable energy systems.

Place, publisher, year, edition, pages
Elsevier BV , 2026. Vol. 256, article id 124149
Keywords [en]
Anode materials, Graphite, Hydrogen, Lithium-ion battery, Pyrolysis bio-oil
National Category
Energy Engineering Energy Systems
Identifiers
URN: urn:nbn:se:kth:diva-369936DOI: 10.1016/j.renene.2025.124149ISI: 001583131300009Scopus ID: 2-s2.0-105013134516OAI: oai:DiVA.org:kth-369936DiVA, id: diva2:1998895
Note

QC 20250918

Available from: 2025-09-18 Created: 2025-09-18 Last updated: 2026-03-12Bibliographically approved
In thesis
1. Catalytic Graphitization of Bio-based Carbon Precursors: A Sustainable Process to Produce Bio-graphite
Open this publication in new window or tab >>Catalytic Graphitization of Bio-based Carbon Precursors: A Sustainable Process to Produce Bio-graphite
2026 (English)Doctoral thesis, comprehensive summary (Other academic) [Artistic work]
Abstract [en]

The rapid growth of lithium-ion batteries and electric arc furnace steelmaking has led to a sharp increase in global demand for graphite, while conventional natural and synthetic graphite production routes face critical challenges related to resource security, fossil feedstock dependence, high energy consumption, and environmental impact. This thesis investigates sustainable pathways for producing high-quality graphite from renewable bio-based carbon precursors through catalytic graphitization.

Biochar and pyrolysis bio-oil derived from woody biomass were systematically evaluated as carbon precursors. Laboratory scale catalytic graphitization processes were developed to elucidate the influence of precursor type on graphite yield, crystallinity, microstructure, and reaction pathways. Bio-oil was shown to enable superior graphitic ordering through a gas-solid mediated reconstruction mechanism, while biochar provided substantially higher solid carbon yield, making it more suitable for scalable production.

Key operational parameters influencing catalytic graphitization were then systematically investigated, including catalyst compound, catalyst precursor mixing strategy, graphitization temperature, residence time, catalyst loading amount, and catalyst composition. Nitrate based metal salts exhibited better catalytic efficiency compared with metal powders due to improved dispersion, and wet impregnation significantly enhanced graphitic ordering relative to dry mixing. Elevated temperatures and optimized residence times promoted structural reorganization. Hybrid catalyst systems, particularly trimetallic Fe-Ni-Mn catalysts, demonstrated synergistic effects that significantly improved graphitic crystallinity and microstructural development.

To address scalability limitations and environmental concerns associated with metal salt catalysts, a novel molten metal pool based catalytic graphitization process was developed. Inspired by laboratory observations of a density driven phase separation between molten iron and graphitized carbon, this previously unreported process enables direct high temperature separation of graphite from catalyst without purification. Pilot scale experiments demonstrated semi-continuous production of highly ordered graphite with a minimal residual metal content.

The applicability of the produced bio-graphite was validated in two strategically important applications. In electric arc furnace electrodes, bio-graphite exhibited low electrical resistivity and effective metal melting performance. In lithium-ion batteries, bio-graphite anodes exhibited stable cycling behavior in both half-cell and full-cell configurations. Finally, process simulation and life cycle assessment showed that the proposed biomass-based graphite production pathway achieves substantially lower cumulative energy demand and greenhouse gas emissions compared with conventional natural and fossil derived synthetic graphite routes.

Overall, this thesis establishes a comprehensive framework for sustainable graphite production from bio-based carbon precursors, integrating process development, parameter optimization, scale-up strategy, application validation, and environmental assessment. This work demonstrates that catalytic graphitization is a commercially viable and environmentally superior alternative to conventional graphite supply chains.

Abstract [sv]

Den snabba tillväxten av litiumjonbatterier och elektriska ljusbågsugnar inom stålindustrin har lett till en kraftigt ökad global efterfrågan på grafit. Samtidigt står konventionella produktionsvägar för naturlig och syntetisk grafit inför betydande utmaningar kopplade till resursbegränsningar, beroende av fossila råvaror, hög energiförbrukning och negativ miljöpåverkan. Denna avhandling undersöker hållbara processvägar för framställning av högkvalitativ grafit från förnybara biobaserade kolprekursorer genom katalytisk grafitisering.

Biokol och pyrolysolja som härrör från träbaserad biomassa utvärderades systematiskt som kolprekursorer. Laboratoriebaserade försök med katalytisk grafitisering genomfördes för att klarlägga hur prekursorernas egenskaper påverkar grafitutbyte, kristallinitet, mikrostruktur och reaktionsmekanismer. Resultaten visar att pyrolysolja möjliggör högre grad av grafitisk ordning genom en gas fastmedierad omstrukturering, medan biokol ger ett avsevärt högre fast kolutbyte och därmed är mer lämpligt för uppskalad produktion.

Centrala driftparametrar som styr den katalytiska grafitiseringen undersöktes därefter systematiskt, inklusive katalysatorns form, blandningsstrategi mellan katalysator och prekursor, grafitiseringstemperatur, uppehållstid, katalysatorhalt samt katalysatorsammansättning. Nitratbaserade metallsalter uppvisade högre katalytisk effektivitet än metallpulver på grund av bättre dispersion, och våtimpregnering visade sig ge avsevärt förbättrad grafitisk ordning jämfört med torrblandning. Förhöjda temperaturer och optimerade uppehållstider främjade strukturell omvandling, medan hybrida katalysatorsystem, särskilt trimetalliska Fe Ni Mn katalysatorer, uppvisade synergistiska effekter som markant förbättrade grafitens kristallinitet och mikrostrukturella utveckling.

För att hantera skalbarhetsbegränsningar och miljöutmaningar förknippade med metallsaltkatalysatorer utvecklades en ny katalytisk grafitiseringsprocess baserad på ett smält metallbad. Processen, som inspirerades av laboratorieobservationer av densitetsdriven fasuppdelning mellan smält järn och grafitiserat kol, har inte tidigare rapporterats i litteraturen. Den möjliggör direkt separation av grafit från katalysator vid hög temperatur utan behov av syrarensning. Försök i pilotskala visade att processen möjliggör kontinuerlig produktion av högordnad grafit med mycket låg kvarvarande metallhalt.

Den framställda biografitens användbarhet verifierades i två industriellt viktiga tillämpningar. Som elektroder i elektriska ljusbågsugnar uppvisade biografiten låg elektrisk resistivitet och effektiv metallsmältning. Som anodmaterial i litiumjonbatterier visade biografiten god cyklingsstabilitet i både halvcell- och fullcellskonfigurationer. Slutligen visade processimulering i Aspen Plus i kombination med livscykelanalys att den föreslagna biobaserade grafitproduktionsvägen har avsevärt lägre kumulativ energianvändning och växthusgasutsläpp jämfört med konventionella produktionsvägar för naturlig och fossilbaserad syntetisk grafit.

Sammanfattningsvis etablerar denna avhandling ett heltäckande ramverk för hållbar grafitproduktion från biobaserat kol, där processutveckling, parameteroptimering, uppskalningsstrategi och miljöutvärdering integreras. Resultaten visar att katalytisk grafitisering utgör ett industriellt relevant och hållbart alternativ till dagens grafitförsörjningskedjor.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2026. p. xiv, 92
Series
TRITA-ITM-AVL ; 2026:8
Keywords
Bio-graphite, catalytic graphitization, biochar, bio-oil, molten metal pool, lithium-ion batteries, electric arc furnace, life cycle assessment
National Category
Materials Engineering
Research subject
Materials Science and Engineering
Identifiers
urn:nbn:se:kth:diva-378022 (URN)978-91-8106-556-5 (ISBN)
Public defence
2026-04-10, https://kth-se.zoom.us/j/65790986425, Kollegiesalen, Brinellvägen 8, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Energy Agency
Available from: 2026-03-16 Created: 2026-03-12 Last updated: 2026-05-11Bibliographically approved

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Shi, ZiyiWang, YazheLu, MingkangYang, HanminHan, TongJin, YanghaoJönsson, PärYang, Weihong

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