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Towards a Sustainable Biomass and Waste Refinery Based on Pyrolysis Combined with a Pretreatment Process
KTH, School of Industrial Engineering and Management (ITM), Materials Science and Engineering, Process. (Energy and Furnace Technology group)ORCID iD: 0000-0003-4946-6525
2022 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Some of the naturally accumulated biomass and the massive production of waste by human activities have caused serious environmental problems. The degradation of biomass and waste is one of the main greenhouse gasses (GHG) emission sources. Pyrolysis is a technique that can convert the organic feedstock into char, bio-oil, and gas at 350 - 800 °C and in the absence of oxygen. The diversity of the pyro-products makes pyrolysis one of the most promising techniques for biomass and waste refineries. One of the main challenges of the technique is that the unfavorable physical and/or chemical properties of the feedstock would increase the energy and cost required for the whole refinery process. Combining feedstock pretreatment with a pyro-refinery has the potential to make the entire process more efficient from a cost, energy, and climate perspective.

 

In this thesis, the performance of the peat moss pyrolysis is firstly investigated. It was found that it has a potential to convert peat moss into fuels through pyrolysis. Thereafter, beach-cast seaweed is further considered as a feedstock for the process, which is a high-ash content biomass. Three refinery processes were designed and simulated based on the pyrolysis results. Results showed that it was necessary to have a washing pretreatment for the beach-cast seaweed pyro-refinery. The implementation of washing pretreatment could decrease the direct energy for the whole process from 1485.8 to 1121.0 MJ for treating one ton of dry beach-cast seaweed. The further life cycle assessment (LCA) analysis showed that using the pyro-refinery process with washing pretreatment to treat one ton of dry beach-cast seaweed for the electricity production had the lowest cumulated energy demand (CED). Specifically, it has a value of -3.0 GJ and the lowest global warming potential within a 100-year time frame (GWP100) with a value of -790.9 kg CO2eq compared to the other scenarios of producing liquid biofuel and syngas.

 

Digestate from anaerobic digestion (AD) requires proper treatment. The third work of this thesis compares the pyrolysis behavior of the organic fraction of municipal solid waste (OFMSW) and its digestate. It was found that the AD process could decrease the pyrolytic activation energy of OFMSW. Due to digestate’s higher ash content, the char yield rate of digestate was higher than that of OFMSW. On the other hand, the yield rates of bio-oil and gas of OFMSW pyrolysis were higher than that of its digestate.

 

The moisture content of the digestate is hard to be removed by traditional mechanical dewatering techniques due to digestate’s hydrophilic properties. Thus, the use of a pretreatment combined with hydrothermal carbonization (HTC) and mechanical dewatering has the potential to contribute to the digestate pyro-refinery. In the last work, the effect of HTC on the kinetics and thermodynamics of the agricultural waste digestate (AWD) pyrolysis was investigated. It was revealed that the HTC pretreatment could decrease the pyrolytic activation energy of AWD from 182.9 - 274.4 kJ/mol to 144.6 - 205.2 kJ/mol. Bench-scale pyrolysis experiments, process simulations, and LCA were then conducted based on the kinetic prediction results. In the process simulations and LCA, four scenarios of AWD refinery with different pretreatment combinations with HTC and mechanical dewatering were designed. It was found that the different pretreatment processes could benefit the designed AWD refinery for different targets. The implementation of both HTC and mechanical dewatering pretreatment for refinery based on a 650 °C-pyrolysis presented the lowest CED value of 10.3 GJ for treating one ton of AWD. The least emission of carbon dioxide equivalents (-843.3 kg) was achieved in the case of using a 650 °C-pyrolysis temperature with the pretreatment with only a dewatering process when treating 1-ton dry AWD.

Abstract [sv]

En del av den naturligt ackumulerade biomassan samt den stora avfallsproduktionen som orsakats av mänskliga aktiviteter har orsakat allvarliga miljöproblem. Nedbrytningen av biomassa och avfall utgör några av de största källorna till utsläpp av växthusgaser. Pyrolys är en teknik som kan omvandla organiska råmaterial till biokol, bioolja och gas vid 350 till 800 °C i en syrefri atmosfär. Mångfalden av produkter från pyrolys gör att tekniken är en av de mest lovande för raffinering av biomassa och avfall. En av de största utmaningarna med tekniken är att ofördelaktiga fysikaliska och kemiska egenskaper hos råmaterial kan leda till ökad kostnad och energiåtgång för hela raffineringsprocessen. Det finns dock en potential att göra hela processen mer hållbar genom att kombinera förbehandling av råvaran med ett pyrolysbaserat raffinaderi.

I avhandlingen så behandlas inledningsvis pyrolys av torv. Resultaten visar att det finns en potential att kunna omvandla torv till bränslen genom att använda pyrolysprocessen. Därefter behandlar avhandlingen tång, vilken är en biomassa med ett högt askinnehåll. Tre raffineringsprocesser designades och simulerades baserat på pyrolysprocessen. Resultaten visar att det är nödvändigt att använda tvättning av tången som en förbehandling innan pyrolyssteget. Införandet av denna förbehandling kan minska den direkta energiförbrukningen för hela processen från 1485.8 till 1121.0 MJ vid behandling av ett ton torr tång från stränder. Dessutom visar resultaten från en efterföljande livscykelanalys (LCA) att denna kombination av en tvättning som förbehandling följt av pyrolys av ett ton torr tång från stränder med en efterföljande elproduktion leder till den minsta ackumulerade energiåtgången (CED) med ett värde av -2.98 GJ. Dessutom så är värdet på den globala uppvärmningspotentialen inom en hundraårsperiod (GWP100) -790.89 kg CO2eq, vilket är lägre i jämförelse med de andra scenarierna fokuserade på en produktion av flytande biobränslen och syntetiska gaser.

Produkten från en anaerobisk nedbrytning (AD) kräver en lämplig behandling. Den tredje delen av avhandlingen är fokuserad på att jämföra resultat från pyrolys av den organiska andelen kommunalt fast avfall (OFMSW) och den resulterade nedbrutna produkten. Resultaten visar att

en anaerobisk nedbrytning kan minska den aktiveringsenergin för pyrolys hos OFMSW. På grund av det högre askinnehållet hos den nedbrutna produkten så blev även utbytet av biokol högre i jämförelse med OFMSW. Däremot blev utbytet av bioolja och gas högre för OFMSW än för den nedbrutna produkten vid en pyrolytisk behandling.

Det är svårt att minska fuktinnehållet i den nedbrutna produkten genom användning av traditionella mekaniska avvattningstekniker, på grund av materialets hydrofila egenskaper. Resultaten visar att användandet av en förbehandling kombinerat med en hydrotermisk förkolning (HTC) och en mekanisk avvattning har en potential att kunna förbättra den pyrolytiska raffineringen av den nedbrutna produkten. I avhandlings sista del studerades påverkan av HTC på kinetiken och termodynamiken vid pyrolys av nedbrutet avfall från jordbruk (AWD). Resultaten visar att förbehandling genom HTC kan minska den pyrolytiska aktiveringsenergin hos AWD från 182.91 - 274.43 kJ/mol till 144.59 - 205.20 kJ/mol. Utöver detta arbete så utfördes laboratorieförsök, processimuleringar och livscykelanalyser fokuserat på kinetiska beräkningar. Vid processimuleringarna och livscykelanalys designades fyra olika scenarion fokuserade på raffinering av AWD, genom användande av olika kombinationer av HTC och avvattningstekniker. Resultaten visar att de olika valen av förbehandlingsprocesser kan ha olika positiva påverkningar vid raffinering av AWD beroende på vad den önskade produkten är. En användning av både HTC och en mekanisk avvattning som förbehandling baserat på en pyrolys vid 650℃ resulterade i det lägsta CED värdet, vilket motsvarade 10.26 GJ vid en behandling av ett ton av AWD. Den lägsta emissionen av koldioxidekvivalenter motsvarande ett värde på -843.28 kg erhölls vid användande av en 650℃ pyrolystemperatur och endast en avvattningsprocess som förbehandling vid pyrolys av 1 ton torrt AWD material.

Nyckelord: pyrolys, anaerobisk nedbrytning, hydrotermisk förkolning, raffinering, biomassa, avfall, kinetik, LCA

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2022.
Series
TRITA-ITM-AVL ; 2022:29
Keywords [en]
pyrolysis, anaerobic digestion, hydrothermal carbonization, refinery, biomass, waste, kinetics, LCA
National Category
Environmental Management Energy Engineering
Research subject
Energy Technology; Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-319156ISBN: 978-91-8040-350-4 (print)OAI: oai:DiVA.org:kth-319156DiVA, id: diva2:1699192
Public defence
2022-10-21, Sal D3 / https://kth-se.zoom.us/j/67119090983, Lindstedtsvägen 5, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2022-09-27 Created: 2022-09-27 Last updated: 2025-02-10Bibliographically approved
List of papers
1. Pyrolysis performance of peat moss: A simultaneous in-situ thermal analysis and bench-scale experimental study
Open this publication in new window or tab >>Pyrolysis performance of peat moss: A simultaneous in-situ thermal analysis and bench-scale experimental study
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2020 (English)In: Fuel, ISSN 0016-2361, E-ISSN 1873-7153, Vol. 277, article id 118173Article in journal (Refereed) Published
Abstract [en]

Peat moss in drained peatlands has become a non-negligible source of greenhouse gases (GHG) emission. Pyrolysis is a potential technique to convert carbon-emitting peat moss to carbon-storage materials. This work investigates the behavior of peat moss pyrolysis by a combined in-situ thermal analysis and bench-scale pyrolysis experiment methodology. The simultaneous thermal analyzer, which provides the simultaneous TG/DTA analysis, was employed to reveal the thermal decomposition behavior of peat moss. The samples were heated up to 900 degrees C with different heating rates of 10, 15, and 20 degrees C/min. Thereafter, pyrolysis experiments with peak temperatures of 450, 500, 550 and 600 degrees C were performed in a bench-scale pyrolyzer. It was found that there are four main stages and two micro stages of mass loss during peat moss pyrolysis from room temperature to 900 degrees C. Also, kinetic parameters were calculated based on the results of TG and DTG by the Kissinger-Akahira-Sunose (KAS) method and the Coats-Redfern (CR) method. In the bench-scale pyrolysis experiments, four phases, i.e., char, tar, aqueous phase, and gas, were obtained and characterized. The carbon distribution and the GHG emission from peat moss pyrolysis were determined.

Place, publisher, year, edition, pages
Elsevier BV, 2020
Keywords
Peat moss, Pyrolysis, Carbon storage, Thermal analysis, Kinetic analysis
National Category
Environmental Sciences
Identifiers
urn:nbn:se:kth:diva-278432 (URN)10.1016/j.fuel.2020.118173 (DOI)000541255200060 ()2-s2.0-85085752282 (Scopus ID)
Note

QC 20200715

Available from: 2020-07-15 Created: 2020-07-15 Last updated: 2022-09-27Bibliographically approved
2. Pyrolysis of engineered beach-cast seaweed: Performances and life cycle assessment
Open this publication in new window or tab >>Pyrolysis of engineered beach-cast seaweed: Performances and life cycle assessment
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2022 (English)In: Water Research, ISSN 0043-1354, E-ISSN 1879-2448, Vol. 222, article id 118875Article in journal (Refereed) Published
Abstract [en]

The blooming of beach-cast seaweed has caused environmental degradation in some coastal regions. Therefore, a proper treating and utilizing method of beach-cast seaweed is demanded. This study investigated the potential of producing power or biofuel from pyrolysis of beach-cast seaweed and the effect of the ash-washing process. First, the raw and washed beach-cast seaweeds (RS and WS) were prepared. Thereafter, thermogravimetric analysis (TG), bench-scale pyrolysis experiment, process simulation, and life cycle assessment (LCA) were conducted. The TG results showed that the activation energies of thermal decomposition of the main organic contents of RS and WS were 44.23 and 58.45 kJ/mol, respectively. Three peak temperatures of 400, 500, and 600 degrees C were used in the bench-scale pyrolysis experiments of WS. The 600 degrees C case yielded the most desirable gas and liquid products. The bench-scale pyrolysis experiment of RS was conducted at 600 degrees C as well. Also, an LCA was conducted based on the simulation result of 600 degrees C pyrolysis of WS. The further process simulation and LCA results show that compare to producing liquid biofuel and syngas, a process designed for electricity production is most favored. It was estimated that treating 1 ton of dry WS can result in a negative cumulative energy demand of -2.98 GJ and carbon emissions of -790.89 kg CO2 equivalence.

Place, publisher, year, edition, pages
Elsevier BV, 2022
Keywords
Pyrolysis, Beach-cast seaweed, Biochar, LCA, Negative emission
National Category
Water Engineering Materials Engineering
Identifiers
urn:nbn:se:kth:diva-347671 (URN)10.1016/j.watres.2022.118875 (DOI)000878990900003 ()35870392 (PubMedID)2-s2.0-85134683870 (Scopus ID)
Note

QC 20240613

Available from: 2024-06-13 Created: 2024-06-13 Last updated: 2024-06-13Bibliographically approved
3. Pyrolysis of raw and anaerobically digested organic fractions of municipal solid waste: Kinetics, thermodynamics, and product characterization
Open this publication in new window or tab >>Pyrolysis of raw and anaerobically digested organic fractions of municipal solid waste: Kinetics, thermodynamics, and product characterization
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2021 (English)In: Chemical Engineering Journal, ISSN 1385-8947, E-ISSN 1873-3212, Vol. 415, article id 129064Article in journal (Refereed) Published
Abstract [en]

Treating the solid residue after anaerobic digestion (AD) of the organic fraction of municipal solid waste (OFMSW) is currently a challenge. Here, pyrolysis is a promising way of recovering energy and materials from these solid residues. Thus, the objective of this study was to investigate the pyrolysis performance of these solid residues. The effect of AD on the pyrolysis of OFMSW was also studied. Thermogravimetry (TG), differential thermal analysis (DTA), and bench-scale pyrolysis experiments were performed by using OFMSW and anaembically digested OFMSW. Mathematical deconvolution analysis (MDA), model-free methods, and model-based methods were applied to study the kinetics. Thereafter, thermodynamic parameters were estimated based on the deduced kinetic results. The char, liquid, and permanent gas products from bench-scale experiments were characterized. The pyrolysis results show that the activation energies of the pseudoreactions of OFMSW are higher than those of the corresponding pseudoreactions of digestate. Moreover, the entropy reduction for digestate is larger than that for OFMSW. The characterization results of the products from the bench-scale experiments show that the interactions among feedstock components (lipids, lignocellulose, and proteins) during pyrolysis are enhanced by the application of AD. However, the pyrolysis yields of both heavy organics and gas are inhibited by the application of AD, while the char yield shows the opposite trend.

Place, publisher, year, edition, pages
Elsevier BV, 2021
Keywords
Pyrolysis, Organic fraction of municipal solid waste (OFMSW), Anaerobic digestion, Kinetics, Thermodynamics
National Category
Energy Engineering
Identifiers
urn:nbn:se:kth:diva-303372 (URN)10.1016/j.cej.2021.129064 (DOI)000697605400029 ()2-s2.0-85101316398 (Scopus ID)
Note

QC 20211015

Available from: 2021-10-15 Created: 2021-10-15 Last updated: 2022-09-27Bibliographically approved
4. Effect of hydrothermal carbonization pretreatment on the pyrolysis behavior of the digestate of agricultural waste: A view on kinetics and thermodynamics
Open this publication in new window or tab >>Effect of hydrothermal carbonization pretreatment on the pyrolysis behavior of the digestate of agricultural waste: A view on kinetics and thermodynamics
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2022 (English)In: Chemical Engineering Journal, ISSN 1385-8947, E-ISSN 1873-3212, Vol. 431, p. 133881-, article id 133881Article in journal (Refereed) Published
Abstract [en]

Anaerobic digestion is the most promising disposal methods to treat organic waste. Also, a feasible management is necessary for the resulted digestate. Hydrothermal carbonization (HTC) combination with pyrolysis could be a proper solution to use for the treatment of digestate. In this study, the effect of an HTC on the pyrolysis of the digestate of agricultural waste (AWD) was investigated, focusing on the kinetic and thermodynamic aspects. Three model-free methods, including Friedman, KAS, and OFW methods, were used to evaluate the kinetic performance of the total and pseudo pyrolytic reactions of AWD and its hydrochar. Furthermore, kinetic predictions were made to provide more information for further studies. It was found that the HTC treatment decreased the activation energy ranges of the pyrolysis of AWD from 182.9-274.43 kJ/mol to 144.59-205.20 kJ/mol by using the Friedman method. For a more thorough understanding of the effect of HTC treatment on the pyrolysis of AWD, the pyrolysis reactions of AWD and its hydrochar were divided into two pseudoreactions using the Fraser-Suzuki deconvolution method. The mean activation energy of the deduced pseudo 2 pyrolytic reaction of hydrochar was 175.64 kJ/mol, which was 28.11 kJ/mol less than that of AWD. In addition, the Delta H(double dagger )values of the pseudo 2 reactions of AWD and its hydrochar were 197.97 and 169.68 kJ/mol, respectively. The results of kinetic isothermal predictions suggested that the peak temperature for the further research and application of the pyrolysis of AWD and its hydmchar should not be lower than 450 degrees C.

Place, publisher, year, edition, pages
Elsevier BV, 2022
Keywords
Agricultural waste, Anaerobic digestion, Hydrothermal carbonization, Pyrolysis, Kinetics and thermodynamics, Kinetic prediction
National Category
Bioenergy Other Chemistry Topics Energy Engineering
Identifiers
urn:nbn:se:kth:diva-306765 (URN)10.1016/j.cej.2021.133881 (DOI)000729447000005 ()2-s2.0-85120493301 (Scopus ID)
Note

QC 20211230

Available from: 2021-12-30 Created: 2021-12-30 Last updated: 2022-09-27Bibliographically approved
5. H2-rich syngas production from pyrolysis of agricultural waste digestate coupled with the hydrothermal carbonization process
Open this publication in new window or tab >>H2-rich syngas production from pyrolysis of agricultural waste digestate coupled with the hydrothermal carbonization process
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2022 (English)In: Energy Conversion and Management, ISSN 0196-8904, E-ISSN 1879-2227, Vol. 269, p. 116101-116101, article id 116101Article in journal (Refereed) Published
Abstract [en]

A novel process to produce a H2-rich syngas from a high moisture-containing agricultural waste digestate is proposed. This process combines the use of hydrothermal carbonization (HTC), dewatering, pyrolysis, and catalytic reforming. Due to the feature of the high moisture content in the digestate, the effect of the HTC and dewatering on the process performance is of interest, and four scenarios were considered. Furthermore, three pyrolytic temperatures were chosen to understand the effect of pyrolysis conditions on the produced H2-rich syngas. A life cycle assessment was conducted to investigate the environmental impact of the proposed process. Results show that the application of HTC technology, increases the process efficiency, produces less syngas from one ton of digestate, lowers the cumulative energy demand and the negative carbon emissions. When the dewatering technology is used, the syngas yield is promoted but the H2 concentration in the syngas is reduced. The H2 to CO molar ratio reaches the maximum value of 9.2 when using a 450 ˚C pyrolysis temperature, by only using HTC. When the combining process of HTC and dewatering is used, it results in the highest process efficiency, but the smallest relative negative CO2 equivalent emissions by treating one ton of dry digestate.

Place, publisher, year, edition, pages
Elsevier BV, 2022
Keywords
Advanced biofuel, Agricultural waste digestate, Green hydrogen, Life cycle assessment, Pyrolysis
National Category
Materials Chemistry
Identifiers
urn:nbn:se:kth:diva-319112 (URN)10.1016/j.enconman.2022.116101 (DOI)000861078700001 ()2-s2.0-85136146236 (Scopus ID)
Funder
Swedish Research Council FormasSwedish Research CouncilEuropean CommissionSwedish Research Council FormasSwedish Research CouncilEuropean Commission
Note

QC 20221003

Available from: 2022-09-26 Created: 2022-09-26 Last updated: 2023-09-21Bibliographically approved

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