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Bromine Transformation during Catalytic Pyrolysis of Waste Electronic Circuit Boards (WECBs) in an Auger Reactor over the Dual Catalyst HZSM-5/CaO
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process. (Energy and Furnace Technology)ORCID iD: 0000-0002-5967-0338
Division of Bioeconomy and Health, Department of Biorefinery and Energy, RISE Research Institutes of Sweden AB, SE-941 28 Piteå, Sweden.ORCID iD: 0000-0002-8284-4172
Paper and Forest Product Manufacturing, SCA Munksund AB, SE-941 87 Piteå, Sweden.
KTH, School of Industrial Engineering and Management (ITM), Energy Technology, Heat and Power Technology.ORCID iD: 0000-0001-9884-1278
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2025 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 10, no 45, p. 54720-54732Article in journal (Refereed) Published
Abstract [en]

Effective bromine mitigation is a critical challenge in the sustainable recycling of electronic waste, where uncontrolled release of brominated species compromises both environmental safety and product quality. This study unveils a novel synergistic transformation pathway of bromine (Br) during ex-situ dual-catalyst pyrolysis of waste electronic circuit boards (WECBs). Experiments were conducted in a continuous auger reactor integrated with a fixed-bed catalytic unit employing a dual HZSM-5/CaO catalyst system. By tuning the weight hour space velocity WHSV from 0.6 to 1.0 h⁻¹, the catalytic process not only doubled the gas yield from 2.7 to 6.5 wt.% but also selectively suppressed liquid formation from 18.0 to12.5 wt.%, while driving deeper deoxygenation and aromatic hydrocarbon enrichment. At lower WHSV, intensified secondary reactions promoted light aromatic generation but also accelerated coke deposition, highlighting the need for WHSV optimization. Mechanistic insights reveal that brominated phenols and aromatic hydrocarbons dominate the primary volatile fraction, where Br+ radicals undergo dual pathways: recombination with H+ and small fragments forming HBr/CH3Br, or neutralization by CaO to yield stable CaBr2. Importantly, 44 wt.% of total bromine was retained in the solid residue as CaBr2, drastically lowering bromine content in pyrolysis oils. The dual-catalyst strategy thus enables simultaneous Br-fixation, hydrocarbon upgrading, and catalyst regeneration, drastically reducing bromine in pyrolysis oils. These findings advance a scalable,3 mechanistically guided route for cleaner electronic waste valorization, coupling environmental protection with high-value fuel production.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2025. Vol. 10, no 45, p. 54720-54732
Keywords [en]
WECBs, Catalytic pyrolysis, HZSM-5/CaO, Auger reactor, Bromine transformation, WHSV
National Category
Chemical Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-372268DOI: 10.1021/acsomega.5c08152ISI: 001609311000001PubMedID: 41280862Scopus ID: 2-s2.0-105022214985OAI: oai:DiVA.org:kth-372268DiVA, id: diva2:2010758
Note

QC 20251126

Available from: 2025-11-03 Created: 2025-11-03 Last updated: 2025-11-26Bibliographically approved
In thesis
1. Catalytic Pyrolysis of Waste Electrical and Electronic Equipment (WEEE): Cleaner Pathways to Resource Recovery
Open this publication in new window or tab >>Catalytic Pyrolysis of Waste Electrical and Electronic Equipment (WEEE): Cleaner Pathways to Resource Recovery
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

As one of the fastest-growing waste streams worldwide, waste electrical and electronic equipment (WEEE) poses major challenges for environmental sustainability and resource management. Existing practices, such as landfilling and incineration, release toxic emissions, while recycling and other recovery methods are often constrained by technical and economic limitations. In this context, pyrolysis combined with catalytic upgrading offers a promising thermochemical pathway to convert complex WEEE into valuable hydrocarbons, energy carriers, and recyclable residues, thereby supporting circular economy objectives.

This thesis aims to develop feasible thermochemical processes to enhance material circularity through catalytic pyrolysis of WEEE. To achieve this, fundamental studies were carried out involving both experimental investigations and process developments at the lab scale. This thesis is written based on the results from five interconnected studies, which together examine the decomposition kinetics of WEEE polymers, catalytic upgrading strategies, and process optimization in both batch and continuous systems. Particular emphasis is placed on understanding how feedstock properties, catalyst design, and operating conditions influence the performance of pyrolysis and in line catalytic upgrading, as well as on advancing process configurations that improve product quality and environmental outcomes.

The first part of the work investigates the pyrolysis behavior of low-grade (LGE) and medium-grade (MGE) WEEE fractions using kinetic modeling, thermogravimetric analysis and micro-scale pyrolyzer coupled with GC-MS/FID, revealing complex multi-stage decomposition associated with PVC, PE, PET, PP, PS, and ABS in feedstock fractions. Catalytic studies showed that acidic zeolites, especially HBeta and HZSM-5, promoted a selective production of benzene, toluene, and xylene (BTX). TiO2 and HZSM-5 reduced activation energies for pseudo 3 and 4 reactions, while higher pyrolysis temperatures in the range of 500-600 oC promoted styrene intermediates that enhanced BTX formation. Importantly, pyrolysis configuration influenced outcomes, with ex-situ catalysis favoring BTX production in LGE and in-situ catalysis proving more effective for MGE.

The second part focuses on the ex-situ catalytic pyrolysis of engineered WEEE fractions (LGEW and MGEW) using HZSM-5 and modified catalysts in both single and dual configurations to optimize system performance. HZSM-5 at 450 oC achieved the highest organic fraction (28.5 wt.%), improved monoaromatic selectivity, and enhanced syngas composition while lowering CO2 emissions and total acid number. Higher catalyst-to-feedstock ratios improved gas yield and aromatic selectivity. The use of Fe-modified HZSM-5 catalyst further enhanced the BTXE production via hydrogen transfer and β-scission pathways but suffered from higher coke deposition, whereas CaO was effective for deoxygenation and CO2 adsorption. A dual CaO/HZSM-5 configuration balancing cracking and deoxygenation activities, yielding higher oil production, improved aromatic selectivity, and reduced CO2 emissions.

The third part demonstrates continuous catalytic pyrolysis of waste electronic circuit boards (WECB) in an auger reactor using a dual HZSM-5/CaO system. This setup improved aromatic yields, reduced oxygenates, generated hydrogen-rich syngas, and stabilized bromine as inorganic bromides in solid residues. Operating at lower weight hourly space velocity (WHSV) further enhanced deoxygenation efficiency, increased H2 production, and minimized CO2 emissions, highlighting the industrial promise of dual-catalyst strategies.

Overall, this thesis demonstrates that catalytic pyrolysis, particularly with dual HZSM-5/CaO systems, provides a feasible and scalable pathway for WEEE valorization. By fulfilling the defined objectives from kinetic assessment to pilot-scale validation, the work enhanced aromatic hydrocarbon recovery, improved syngas quality, and achieved bromine stabilization in solid residues. These outcomes confirm that the central aim of developing thermochemical processes to enhance material circularity through catalytic pyrolysis has been substantially achieved, offering both scientific insight and practical solutions for sustainable e-waste recycling.

Abstract [sv]

Avfall från elektrisk och elektronisk utrustning (WEEE), representerar en av de snabbast växande avfallsströmmarna globalt vilket orsakar stora utmaningar med avseende på en miljömässig hållbarhet och resursförvaltning. Befintliga metoder såsom deponering och förbränning ger upphov till giftiga utsläpp, medan återvinning och andra återvinningsmetoder ofta begränsas av tekniska och ekonomiska hinder. I detta sammanhang erbjuder pyrolys i kombination med en katalytisk uppgradering en lovande termokemisk väg för att omvandla komplexa WEEE-fraktioner till värdefulla kolväten, energibärare och återvinningsbara restprodukter, och därmed bidra till cirkulära ekonomiska mål.

Syftet med denna avhandling är att utveckla termokemiska processer för att stärka materialcirkulariteten genom en katalytisk pyrolys av WEEE. För att uppnå detta genomfördes grundläggande studier som omfattade både experimentella undersökningar och processutveckling i laboratorieskala. Avhandlingen bygger på resultaten från fem sammanlänkade studier, vilka tillsammans undersöker nedbrytningskinetiken hos WEEE-polymerer, strategier för katalytisk uppgradering samt processoptimering i både satsvisa och kontinuerliga system. Särskild tonvikt läggs på att förstå hur bränslets egenskaper, katalysatordesign och driftförhållanden påverkar pyrolysens och den linjära katalytiska uppgraderingens prestanda, samt på att utveckla processkonfigurationer som förbättrar produktkvalitet och miljöprestanda.

Den första delen av arbetet undersöker pyrolysbeteendet hos låg (LGE) och medelstora-kvalitet (MGE) WEEE-fraktioner med hjälp av kinetisk modellering, termogravimetrisk analys och mikroskalig pyrolys kopplad till GC-FID. Resultaten visade att en komplex fler-stegs nedbrytning associerad med PVC, PE, PET, PP, PS och ABS i bränslefraktionerna. Katalytiska studier visade att sura zeoliter, särskilt HBeta och HZSM-5, främjade en selektiv produktion av bensen, toluen och xylener (BTX). TiO2 och HZSM-5 minskade aktiveringsenergierna för pseudo 3 och 4 reaktioner, medan högre pyrolys temperaturer i intervallet 500–600 oC gynnade bildandet av styren intermediärer som ökade BTX-utbytet. Viktigt var att pyrolys konfigurationen påverkade resultaten, där ex-situ katalys gynnade en BTX-produktion i LGE och medan en in-situ katalys var mer effektiv för MGE.

Den andra delen av avhandlingen fokuserar på ex-situ katalytisk pyrolys av konstruerade WEEE-fraktioner (LGEW och MGEW) med HZSM-5 och modifierade katalysatorer i enkel och dubbelkonfiguration. HZSM-5 vid 450 oC

gav den högsta organiska fraktionen (28,5 wt.%), en förbättrad selektivitet för monoaromater samt en förbättrad sammansättning av syntesgas samtidigt som CO₂-utsläpp och det totala syratalet minskade. Högre katalysator-till-bränsleförhållanden ökade gasutbytet och den aromatiska selektiviteten. Fe-modifierad HZSM-5 förbättrade ytterligare BTXE-produktionen genom väteöverföring och β-klyvningsmekanismer men drabbades av högre kokbildning, medan CaO var effektivt för deoxygenering och CO2-adsorption. En dubbelkonfiguration av CaO/HZSM-5 balanserade sprickbildning och deoxygenering, vilket resulterade i ett högre oljeutbyte, en förbättrad aromatselektivitet och minskade CO₂-utsläpp.

Den tredje delen demonstrerar resultaten från en kontinuerlig katalytisk pyrolys av elektroniska kretskort (WECB) i en skruvreaktor med ett dubbelt HZSM-5/CaO-system. Denna konfiguration förbättrade aromatutbytet, minskade mängden oxygenater, genererade väterik syntesgas och stabiliserade brom som oorganiska bromider i fasta rester. Drift vid lägre vikt-timrymdhastighet (WHSV) förbättrade ytterligare deoxygeneringseffektiviteten, ökade H2-produktionen och minskade CO2-utsläppen, vilket visar den industriella potentialen hos dubbelkatalytiska strategier.

Sammanfattningsvis visar denna avhandling att katalytisk pyrolys, särskilt med dubbla HZSM-5/CaO-system, erbjuder en genomförbar och skalbar väg för värdeskapande av WEEE. Genom att uppfylla de definierade målen från kinetiska analyser till validering i pilotskala har arbetet förbättrat återvinningen av aromatiska kolväten, höjt kvaliteten på syntesgasen och uppnått bromstabilisering i fasta rester. Dessa resultat bekräftar att det centrala målet, att utveckla termokemiska processer för att stärka materialcirkulariteten genom katalytisk pyrolys, i hög grad har uppnåtts och erbjuder både vetenskapliga insikter och praktiska lösningar för en hållbar återvinning av elektronikavfall.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. p. 105
Series
TRITA-ITM-AVL ; 2025:42
Keywords
WEEE, pyrolysis, catalytic upgrading, WECB, BTX, circular economy, WEEE, pyrolys, katalytisk uppgradering, WECB, BTX, cirkulär ekonomi
National Category
Chemical Engineering Materials Engineering
Research subject
Materials Science and Engineering
Identifiers
urn:nbn:se:kth:diva-372263 (URN)978-91-8106-435-3 (ISBN)
Public defence
2025-11-28, D 37, Lindstedtsvägen 5, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Energy Agency, 51219–1
Note

QC 20241107

Available from: 2025-11-06 Created: 2025-11-03 Last updated: 2025-11-12Bibliographically approved

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