| 1. |
- Jin, Yanghao, et al.
(författare)
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A novel three-stage ex-situ catalytic pyrolysis process for improved bio-oil yield and quality from lignocellulosic biomass
- 2024
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Ingår i: Energy. - : Elsevier Ltd. - 0360-5442 .- 1873-6785. ; 295
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Tidskriftsartikel (refereegranskat)abstract
- This study aims to improve the quality and yield of bio-oil produced from ex-situ catalytic pyrolysis of lignocellulosic biomass (sawdust) using a combination of stage catalysts with Al-MCM-41, HZSM-5, and ZrO2. The research employed various methods, including thermogravimetric analysis (TGA), differential scanning calorimetry, bench-scale experiments, and process simulations to analyze the kinetics, thermodynamics, products, and energy flows of the catalytic upgrading process. The introduction of ZrO2 enhances the yield of monoaromatic hydrocarbons (MAHs) in heavy organics. Compared with the dual-catalyst case, the MAHs yield escalates by approximately 344% at a catalyst ratio of 1:3:0.25. Additionally, GC-MS data indicate that the incorporation of ZrO2 promotes the deoxygenation reaction of the guaiacol compound and the oligomerization reactions of PAHs. The integration of ZrO2 as the third catalyst enhances the yield of heavy organics significantly, achieving 16.85% at a catalyst ratio of 1:3:1, which increases by nearly 35.6% compared to the dual-catalyst case. Also, the addition of ZrO2 as the third catalyst enhanced the energy distribution in heavy organics. These findings suggest that the combination of these catalysts improves the fuel properties and yields of the bio-oil.
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| 2. |
- Aragon-Briceno, Christian, et al.
(författare)
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Integration of hydrothermal carbonization treatment for water and energy recovery from organic fraction of municipal solid waste digestate
- 2022
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Ingår i: Renewable energy. - : Elsevier BV. - 0960-1481 .- 1879-0682. ; 184, s. 577-591
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Tidskriftsartikel (refereegranskat)abstract
- Anaerobic digestion is an efficient way of using a wet fraction of municipal solid waste (MSW) for energy purposes as it can produce biogas. The moisture content of the digestate after application of mechanical dewatering is still high, and the amount of heat needed for drying is significant. Hydrothermal carbonization (HTC) is a process that can potentially offer great benefits by improved mechanical dewatering and valorization of the digestate into a better quality solid fuel. This study focuses on the determination of the optimum HTC process conditions to recover water from the MSW digestate. Different process conditions as temperature (180, 200, and 230 °C) and residence time (30, 60, and 120 min) were tested. Furthermore, a mass and energy balance was carried out and a process model in Aspen Plus was built. Results showed that HTC treatment increased the water recovery (40–48%) during the dewatering process compared with the original feedstock (18%). The process model showed a positive energy balance of 110 kWh per ton of MSW digestate treated with an electrical efficiency of 23.9%.
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| 3. |
- Persson, Henry, et al.
(författare)
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Catalytic pyrolysis over transition metal-modified zeolites: a comparative study between catalyst activity and deactivation
- 2019
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Ingår i: Journal of Analytical and Applied Pyrolysis. - : Elsevier. - 0165-2370 .- 1873-250X. ; 138, s. 54-61
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Tidskriftsartikel (refereegranskat)abstract
- The utilization of metal-doped zeolites in catalytic pyrolysis of biomass is a well-known approach to promote the formation of certain compounds. One major technical issue of using zeolites in biomass pyrolysis processes is their rapid deactivation due to coke formation. However, little is known about how metal-doping influences the characteristics of coking, such as coking rate and its composition.In this study, four different materials were experimentally evaluated based on their catalytic activity and coking characteristics: HZSM-5, Fe/ZSM-5, Ni/ZSM-5 and FeNi/ZSM-5. The materials were prepared and characterized followed by screening in a bench-scale setup for in-situ catalytic pyrolysis. The mass balance and composition of pyrolysis products including catalyst coke were analyzed.It was found that metal-doping increases the concentration of aromatic hydrocarbons in the liquid product from 59.0 to 82.8 % of GC/MS peak area, especially monoaromatic hydrocarbons (MAHs) and naphthalenes. Fe mainly promotes MAHs whereas Ni additionally promotes naphthalenes. FeNi/ZSM-5 enhances the production of both compound groups as well as further reducing the total acid number (TAN). Regarding the catalyst coke, metal-doped catalysts present an increased concentration of aromatic hydrocarbons in terms of MAHs, naphthalenes and polyaromatic hydrocarbons. For each catalyst, the chemical composition of catalyst coke reflects the catalyst’s activity seen in vapor upgrading. A reaction pathway based on the observed catalyst activities of metal-doped ZSM-5 and HZSM-5 is proposed.The results also show that metal-doping of catalysts increases the formation of catalyst coke, mainly due to a higher concentration of strong acid sites. Also, the rate of coking is dependent on the strength of acid sites, where the strength correlates with the severity of coking. The coke yield was seen to increase from 3.5 wt% in the case of HZSM-5 to maximum 7.2 wt% over Fe/ZSM-5. However, the metal-doping of catalysts reduces the temperature of catalyst regeneration and catalyzes the oxidation of coke. Overall, this work presents a comparative study between catalyst activity and deactivation during thermochemical conversion of biomass.
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| 4. |
- Wang, Shule, 1994-, et al.
(författare)
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A machine learning model to predict the pyrolytic kinetics of different types of feedstocks
- 2022
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Ingår i: Energy Conversion and Management. - : Elsevier BV. - 0196-8904 .- 1879-2227. ; 260, s. 115613-
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Tidskriftsartikel (refereegranskat)abstract
- An in-depth knowledge of pyrolytic kinetics is vital for understanding the thermal decomposition process. Numerous experimental studies have investigated the kinetic performance of the pyrolysis of different raw materials. An accurate prediction of pyrolysis kinetics could substantially reduce the efforts of researchers and decrease the cost of experiments. In this work, a model to predict the mean values of model-free activation energies of pyrolysis for five types of feedstocks was successfully constructed using the random forest machine learning method. The coefficient of determination of the fitting result reached a value as high as 0.9964, which indicates significant potential for making a quick initial pyrolytic kinetic estimation using machine learning methods. Specifically, from the results of a partial dependence analysis of the lignocellulose-type feedstock, the atomic ratios of H/C and O/C were found to have negative correlations with the pyrolytic activation energies. However, the effect of the ash content on the activation energy strongly depended on the organic component species present in the lignocellulose feedstocks. This work confirms the possibility of predicting model-free pyrolytic activation energies by utilizing machine learning methods, which can improve the efficiency and understanding of the kinetic analysis of pyrolysis for biomass and fossil investigations.
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| 5. |
- Wang, Shule, 1994-, et al.
(författare)
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Effect of H2 as Pyrolytic Agent on the Product Distribution during Catalytic Fast Pyrolysis of Biomass Using Zeolites
- 2018
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Ingår i: Energy & Fuels. - : American Chemical Society (ACS). - 0887-0624 .- 1520-5029. ; 32:8, s. 8530-8536
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Tidskriftsartikel (refereegranskat)abstract
- Bio-oil generated from catalytic fast pyrolysis or hydrotreating processes represents one of the most promising alternatives to liquid fossil fuels. The use of H2 as carrier gas in the pyrolysis of biomass requires further research to study the catalytic fast pyrolysis reactions in the case of using reactive atmosphere. In this work, pyrolysis experiments with lignocellulosic biomass have been performed in a fixed bed reactor in H2 and N2 atmospheres with/without HZSM-5 additions to investigate the influence of the pyrolytic agents during fast pyrolysis of biomass and upgrading of pyrolytic vapors over a zeolitic catalyst. It was found that in a H2 atmosphere, H2 was consumed in both noncatalytic and catalytic pyrolysis processes, respectively. Higher yields of nonaqueous liquids and permanent gases are obtained in a H2 atmosphere compared to a N2 atmosphere. A catalytic pyrolysis process using HZSM-5 in a H2 atmosphere increased the production of polymer aromatic hydrocarbons and suppressed the production of monomer aromatic hydrocarbons compared to similar tests performed in a N2 atmosphere. The results show an overall increased activity of HZSM-5 in the reactive H2 atmosphere compared to a N2 atmosphere.
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| 6. |
- Wang, Shule, 1994-, et al.
(författare)
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Effect of hydrothermal carbonization pretreatment on the pyrolysis behavior of the digestate of agricultural waste : A view on kinetics and thermodynamics
- 2022
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Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947 .- 1873-3212. ; 431, s. 133881-
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 7. |
- Wang, Shule, 1994-, et al.
(författare)
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Novel carbon-negative methane production via integrating anaerobic digestion and pyrolysis of organic fraction of municipal solid waste
- 2021
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The use of bioenergy with carbon capture and storage (BECCS) is vital to reaching the desired climate goals. This study proposed a novel process combining anaerobic digestion, pyrolysis, catalytic reforming and methanation (APRM) to produce biomethane and to capture carbon emission from the organic fraction of municipal solid waste (OFMSW). The evaluation of the process was conducted by using modelling software and techno-economic analysis. The process modelling and evaluation result showed that 151.4 kg CH4 and 355.64 kg stored carbon emission can be produced from 1 ton dry matter of OFMSW with an energy efficiency of 0.40. 6.74 MJ electricity was required to capture 1 kg of CO2 via the proposed process. The energy balance of the pyrolysis reaction was investigated. The sensitivities of the pyrolysis temperatures, dewatering technologies and conversion of catalytic reforming on the process performance were analyzed. The result also indicated a positive net profit when using the APRM process to treat the OFMSW based on the calculation of operating expenses and revenue, when the CO2 negativity can be sold as commodity.
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| 8. |
- Wang, Shule, 1994-, et al.
(författare)
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Novel carbon-negative methane production via integrating anaerobic digestion and pyrolysis of organic fraction of municipal solid waste
- 2022
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Ingår i: Energy Conversion and Management. - : Elsevier BV. - 0196-8904 .- 1879-2227. ; 252, s. 115042-
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Tidskriftsartikel (refereegranskat)abstract
- The use of bioenergy with carbon capture and storage (BECCS) is vital to reaching the desired climate goals. This study proposed a novel process combining anaerobic digestion, pyrolysis, catalytic reforming and methanation (APRM) to produce biomethane and to capture carbon emission from the organic fraction of municipal solid waste (OFMSW). The evaluation of the process was conducted by using modelling software and techno-economic analysis. The process modelling and evaluation result showed that 151.4 kg CH4 and 355.64 kg stored carbon emission can be produced from 1 ton dry matter of OFMSW with an energy efficiency of 0.40. 6.74 MJ electricity was required to capture 1 kg of CO2 via the proposed process. The energy balance of the pyrolysis reaction was investigated. The sensitivities of the pyrolysis temperatures, dewatering technologies and conversion of catalytic reforming on the process performance were analyzed. The result also indicated a positive net profit when using the APRM process to treat the OFMSW based on the calculation of operating expenses and revenue, when the CO2 negativity can be sold as commodity.
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| 9. |
- Wang, Shule, 1994-, et al.
(författare)
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Pyrolysis behaviour, kinetics and thermodynamic data of hydrothermal carbonization-Treated pulp and paper mill sludge
- 2021
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Ingår i: Renewable energy. - : Elsevier BV. - 0960-1481 .- 1879-0682. ; 177, s. 1282-1292
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Tidskriftsartikel (refereegranskat)abstract
- Organic-rich pulp and paper mill sludge (PPMS) has the potential to become a renewable carbon source for producing alternatives to fossil-based product. In this work, PPMS treated by hydrothermal carbonization (HTC) was investigated based on its pyrolysis properties. The pyrolytic mechanism, kinetics data and product of the sample were studied using TG as well as pyrolysis tests in Py-GC/MS and a bench-scale reactor at 450, 550, and 650 degrees C. The results show that the thermal decomposition of feedstock is a two-stage reaction. The mean activation energy of the pyrolysis of HTC treated PPMS was estimated as 233.08 kl/mol, which is higher than that of the pyrolysis of paper sludge reported before. The changes in enthalpies, entropies and Gibbs free energies from the reactants to the activated complex were estimated. The concentration of monocyclic aromatic hydrocarbons in the derived organic liquid fraction shows a positive correlation with the pyrolysis temperature. At 550 degrees C, the organic liquid fraction reached its highest yield at 13.7% with an oxygen level of 10.7 wt% and a higher heating value of 35.9 MJ/ kg. The pyrolytic chars show that a molar ratio of O:C is less than 0.2, which shows potential for use as a carbon sink.
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| 10. |
- Wang, Shule, 1994-
(författare)
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Pyrolysis of Biodegradable Waste for Negative Carbon Emissions
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Bioenergy with Carbon Capture and Storage represents a crucial technology that enables an energy production with negative carbon emissions, which is needed to achieve global climate goals. Appropriated management of biodegradable waste, including biodegradable lignocellulosic waste, sewage sludge, organic fraction of municipal solid waste, can make this contribution. The implementation of pyrolysis process is able to produce biochar, liquid and gas product from biodegradable waste. Based on the pyrolysis technology, a sustainable management of biodegradable waste for negative carbon emission is proposed in this work. The proposed novel process combines an anaerobic digestion, pyrolysis of the digestate following by catalytic reforming the pyrolytic vapor, then methanation of the reforming gas, separating the stream of CH4 and CO2. The storage of separated CO2 streams and biochar can be considered as negative emissions. Furthermore, the pyrolysis behaviors of the solid residue, which was produced from hydrothermal carbonization pretreatment of biodegradable wastes, are investigated. The pyrolytic liquid was further upgraded to a higher quality product with a less oxygen content, a higher calorific value by using ex-situ and in-situ hydrogen donors. Carbon stability of the pyrolytic biochar, which is one of key parameters to assess the biochar as carbon sink, was evaluated by using the accelerated oxidation method. Finally, energy and mass balance on the proposed process was obtained. The pyrolysis behavior of hydrothermal carbonization-treated sewage sludge digestate, and paper sludges were investigated. Thermogravimetric analysis, Py- Gas chromatography–Mass spectrometry and bench-scale experiments were employed to fulfil this objective. The thermal degradation behavior of these two feedstocks was investigated. Initially, the compounds in the pyrolytic vapor were identified. Thereafter, the pyrolytic product from the bench-scale experiment was characterized. It was found that the pyrolysis reaction of both feedstocks was a two-stage reaction. The organic fraction with a higher heating value around 28.47 to 38.46 MJ/kg was produced from the pyrolysis of hydrothermal carbonization-treated biodegradable waste. More organic fraction can be produced from the pyrolysis of the paper sludge than that from sewage sludge digestate. It was also found that the fixed carbon content in raw materials is difficult to be determined by using the standard method due to the ash oxidation behavior in such materials. Therefore, a method to determine the sample's fixed carbon content without affected by the ash oxidation behavior was developed. Introducing hydrogen donors to upgrade the pyrolytic liquid products for a higher quality product with a lower oxygen content and a higher calorific value is investigated. The H2 was used as an ex-situ hydrogen donor in the lignocellulosic waste pyrolysis in both non-catalytic and catalytic cases. The catalyst used in this study was a commercial HZSM-5, catalyst with a strong selectivity of aromatics. The hydrogen consumption during pyrolysis in the H2 atmosphere was indicated by experiments. The gas and liquid production were promoted while the biochar yield was suppressed in the presence of the H2 atmosphere. However, the presence of an H2 atmosphere was found to increase the acidity of the HZSM-5 and enhance the production of polyaromatics during the pyrolysis process. Further, the study using the sewage sludge digestate as an in-situ hydrogen donor to pyrolysis of lignocellulosic biomass obtained from the salix family was investigated. The sewage sludge digestate was premixed with salix in five blended ratios and pyrolyzed in a bench-scale reactor. The composite of 75% sludge digestate and 25% salix presented the highest mass and energy yields of the organic fraction in the liquid product. The yield of biochar was suppressed in this copyrolysis. The synergistic effect between the sludge digestate and salix was studied with respect to reaction mechanisms, carbon number distribution of the compounds in organic fraction, and biochar stability. The competition reaction between the short-chain carboxylic acid from salix pyrolysis and a long-chain carboxylic acid from digestate pyrolysis was one of the main reasons for the synergistic reaction regarding the composition of the organic fraction. This competition reaction results in a higher amount of long-chain carboxylic acid esters and N-heterocyclic compounds, a lower amount of the long-chain nitriles in the organic fraction produced from copyrolysis compared to it from individual pyrolysis. The stabilities of the biochar products from the copyrolysis of sewage sludge digestate and salix, were determined by using the accelerated oxidation method. It was found that the biochar stabilities are promoted by this copyrolysis. The nitrogen yield in the biochar product was also enhanced by the copyrolysis process. The proposed CO2 negative process was modelled using the process simulation software, and the modelling results were validated by using an experimental data. The pyrolysis temperature and dewatering technology were used for sensitivity analysis. In this process, methane was chosen as the final product. Pyrolytic biochar and compressed CO2 was captured and stored as the negative carbon emission. It was found that for 1000 kg of dry matter digestate, one can obtain 151.4 kg CH4 in a purity of 96 vol%, 304.5kg compressed CO2, and 80.8 kg biochar. The latter two are equal to 355.64 kg negative CO2 emission.
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