Fu Wei , Jing-Pei Cao , Jing-Ping Zhao , Xiao-Yan Zhao
{"title":"Unlocking biofuel potential: Synergistic production of biofuel precursors from acid-loaded corncobs via staged pyrolysis","authors":"Fu Wei , Jing-Pei Cao , Jing-Ping Zhao , Xiao-Yan Zhao","doi":"10.1016/j.jaap.2025.107059","DOIUrl":"10.1016/j.jaap.2025.107059","url":null,"abstract":"<div><div>Biomass, a renewable resource, presents inherent challenges for selective conversion into high-value chemicals based on the compositional structure of biomass via conventional pyrolysis. This study introduced an innovative two-stage pyrolysis, combining acid-catalyzed low-temperature pyrolysis with catalytic upgrading over ZSM-5, for the targeted valorization of H<sub>3</sub>PO<sub>4</sub>-loaded corncobs. This approach notably outperformed conventional non-catalytic/catalytic and two-stage non-catalytic pyrolysis, achieving higher yields of levoglucosenone, furfural, and cumulative target products. Mechanistic analyses revealed that H<sub>3</sub>PO<sub>4</sub> loading enhanced selective conversion of cellulose and hemicellulose to levoglucosenone and furfural at reduced temperatures by passivating metals and enhancing dehydration reactions. Notably, the maximum furfural yield remained stable across a broad range of acid loadings, ensuring that fluctuations in the actual H<sub>3</sub>PO<sub>4</sub> loading did not significantly impact maximum levoglucosenone yield within practical limits. Furthermore, lignin-rich char residue was effectively converted to light aromatics in the catalytic upgrading stage with high selectivity, albeit at a lower overall yield. Optimal conditions were achieved with 5.5 wt% H<sub>3</sub>PO<sub>4</sub> at 325 °C for the first stage, followed by catalytic upgrading at 550 °C, producing a maximum total yield of 62.6 mg/g of target products. Peak yields of levoglucosenone and furfural reached 23.5 and 34.5 mg/g, respectively, while light aromatics reached 4.6 mg/g with over 98 % selectivity. This study underscores the potential of coupling acid-catalyzed pyrolysis with catalytic upgrading to achieve targeted co-production of valuable chemicals, providing new insights into biomass valorization.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107059"},"PeriodicalIF":5.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487637","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Oybek Mirzayev, Firdavs Aliev , Sergei Sitnov, Temurali Kholmurodov, Rezeda Mukhamatdinova, Mustafa Ismael, Sofya Trubitsina, Abdulvahhab Mohammed Al-Qaz, Alexey Vakhin
{"title":"Carbon dioxide-assisted aqueous pyrolysis of heavy oil in the presence of oil-soluble catalysts and sodium nanoparticles","authors":"Oybek Mirzayev, Firdavs Aliev , Sergei Sitnov, Temurali Kholmurodov, Rezeda Mukhamatdinova, Mustafa Ismael, Sofya Trubitsina, Abdulvahhab Mohammed Al-Qaz, Alexey Vakhin","doi":"10.1016/j.jaap.2025.107061","DOIUrl":"10.1016/j.jaap.2025.107061","url":null,"abstract":"<div><div>The CO<sub>2</sub>-assisted aqueous pyrolysis of heavy oil in the reservoir formations is one of the most promising methods to enhance heavy oil recovery and utilize carbon dioxide into value-added products. The study examines the performance of the oil-soluble catalysts and dispersed sodium nanoparticles on the upgrading degree of heavy oil and carbon dioxide hydrogenation degree. Various analytical tools such as SARA analysis, viscosity measurements, elemental analysis, gas chromatography, spectroscopy-based analysis methods (EPR, GC-MS and FT-IR analysis) were employed to evaluate the upgrading efficiency of the synthesized catalysts. The relative content of the evolved CO<sub>2</sub> in the presence of Fe-Na nanoparticles was reduced from 78 % (blank) to 31 %, while the sum of C1-C5 n-alkanes was increased from 9.2 % to 41.6 %. The Ni-Na nanoparticles exhibited high activity on destructive hydrogenation of resins and asphaltenes such that reduced the mass ratio of heavy fragments by 35 % and increased the mass content of light fractions by 21 %. The CO<sub>2</sub>-assisted aqueous pyrolysis of heavy oil in the presence of sodium-promoted transition metal oxides and sulfides contributed to the viscosity reduction by 89 %. Taken together, we have found a cutting-edge solution for carbon dioxide utilization and obtained comprehensive experimental results for upgrading of heavy oil in-situ.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107061"},"PeriodicalIF":5.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Comprehensive evaluation and analysis of coal used for direct reduction in rotary kiln","authors":"Weiyang Zhang , Hanjie Guo , Shusen Cheng , Xiaodong Ren , Jing Guo","doi":"10.1016/j.jaap.2025.107060","DOIUrl":"10.1016/j.jaap.2025.107060","url":null,"abstract":"<div><div>To explore the coal types appropriate for direct reduction in rotary kiln, this paper focuses on three distinct coal types—lignite, bituminous coal, and anthracite—as the subjects of our experiments. The aim is to comprehend their pyrolysis properties and evaluate their suitability for direct reduction in rotary kiln. First, the requirement of coal quality in direct reduction process of rotary kiln was analyzed. Pyrolysis experiments and thermogravimetry–mass spectrometry (TG–MS) analyses of different coal types were carried out. Brunauer–Emmett–Teller (BET) method and thermogravimetry–differential scanning calorimetry (TG–DSC) were employed to analyze pore structure characteristics reactivity of the coals at different ranks. Furthermore, In order to further characterize properties of coals at different ranks,X-ray diffraction (XRD) was employed to analyze the molecular configuration of the raw coal and resulting coke samples after pyrolysis. Finally, a comprehensive evaluation system for coal was established by comparing the pyrolysis products, pore structural parameters, and gasification reactivity of coals at different ranks. The results indicate that the proportions of pyrolysis gas from lignite and bituminous coal are relatively high. The char of lignite has the largest BET surface area and total pore volume. In the gasification stage, the maximum weight loss rate of lignite reaches 5.89(%·min<sup>−1</sup>) for the first time at 894℃.The crystallite structure parameters confirm the accuracy of pore parameters and gasification reaction results from the microscopic perspective. Comprehensive analysis shows thatlignite have the highest pyrolysis gas content was, the largest BET specific surface area and total pore volume, and the lowest peak temperature of gasification rate, which is undoubtedly more suitable for the direct iron reduction process in rotary kiln.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107060"},"PeriodicalIF":5.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Irek I. Mukhamatdinov , Saleem M.A. Saif , Mohammed O.N. Ali , Rezeda E. Mukhamatdinova , Boudkhil Affane , Alexey V. Vakhin , Sergey V. Tsvetkov , Alexander N. Protsenko , Dmitry A. Volkov
{"title":"Development of a catalyst based on metal tallates for intensification of heavy oil production","authors":"Irek I. Mukhamatdinov , Saleem M.A. Saif , Mohammed O.N. Ali , Rezeda E. Mukhamatdinova , Boudkhil Affane , Alexey V. Vakhin , Sergey V. Tsvetkov , Alexander N. Protsenko , Dmitry A. Volkov","doi":"10.1016/j.jaap.2025.107058","DOIUrl":"10.1016/j.jaap.2025.107058","url":null,"abstract":"<div><div>This study explored the catalytic upgrading of high-viscosity oil from the Aksenovsk field in the Samara region during catalytic aquathermolysis on the composition and properties of the resulting products. Catalysts containing iron, nickel, cobalt, chromium, and copper were successfully synthesized. The results revealed significant oil transformation with copper tallate, leading to a 2.6-fold reduction in viscosity compared to the control. SARA analysis showed an 8 % mass decrease in high-molecular-weight compounds, especially resins, when using an iron-nickel (1:1) catalyst mixture. Iron tallate in the conversion products resulted in a 17 % increase in light saturates. X-ray structural analysis revealed that nickel, cobalt, and copper tallates primarily decompose into metal sulfides, while iron and chromium tallates break down into oxides and hydroxides. Based on these findings, a catalyst precursor with an 85/15 iron-nickel ratio was selected, and field tests at well 407 G in the Aksenovsk field demonstrated increased production rates and reduced water content.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107058"},"PeriodicalIF":5.8,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bing Wang , Ying-Bo Song , Feng Wang , Yun-Chang Fan , Nuo Cheng , Pei-Gao Duan
{"title":"Comparative study on properties of waste tyre pyrolysis oil and its distillates obtained by molecular distillation","authors":"Bing Wang , Ying-Bo Song , Feng Wang , Yun-Chang Fan , Nuo Cheng , Pei-Gao Duan","doi":"10.1016/j.jaap.2025.107046","DOIUrl":"10.1016/j.jaap.2025.107046","url":null,"abstract":"<div><div>Pyrolysis offers significant advantages for the resourceful recycling of waste tyre (WT), while molecular distillation can efficiently separate and non-destructively collect the resulting pyrolysis oil for high-value utilisation of different oil fractions. Herein, WT was pyrolysed at various temperatures (350 °C, 400 °C, 450 °C and 500 °C) to obtain the desired pyrolysis products. The optimal pyrolysis temperature of 400 °C was selected based on the analysis of WT pyrolysis at temperatures ranging from 350 °C to 500 °C. Subsequently, molecular distillation experiments were conducted on the waste tyre pyrolysis oil (WTPO) obtained at 400 °C. The distillation process was carried out at varying temperatures (100 °C, 115 °C, 130 °C, 145 °C and 160 °C) to separate the WTPO into light oil (LO) and heavy oil (HO), including LO<sub>130 °C</sub> (LO obtained at 130 °C) and HO<sub>130 °C</sub> (HO obtained at 130 °C). The characteristics of the pyrolysis products and WTPO fractions were investigated, with a focus on the effect of temperature on the yield and composition distribution of the pyrolysis products as well as the distribution pattern of WTPO fractions. The maximum pyrolysis oil output was obtained at 400 °C (58.23 wt%), with a high proportion of alkane (9.42 %) and aromatics (75.07 %). LO<sub>130 °C</sub> contained more olefins (16.55 %) and ketones (7.37 %) than HO<sub>130 °C</sub>, whereas HO<sub>130 °C</sub> had more alkanes (5.65 %) and aromatic hydrocarbons (61.99 %). The findings of this study suggest the effectiveness of using molecular distillation to separate WTPO fractions.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107046"},"PeriodicalIF":5.8,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Michael Zeller, Daniela Merz, Luca Weigel, Salar Tavakkol, Dieter Stapf
{"title":"TG-FTIR investigations of the pyrolysis of polyurethanes: Quantitative carbon dioxide tracing, decomposition mechanisms, products and mass balances for advanced recycling","authors":"Michael Zeller, Daniela Merz, Luca Weigel, Salar Tavakkol, Dieter Stapf","doi":"10.1016/j.jaap.2025.107048","DOIUrl":"10.1016/j.jaap.2025.107048","url":null,"abstract":"<div><div>Polyurethanes (PUR) are versatile polymers used in a broad range of applications. Conventional mechanical recycling is thus difficult. Chemical recycling such as pyrolytic waste treatment presents new recycling options. Advanced recycling by pyrolysis may help to reduce environmental impacts from PUR wastes. The knowledge of mechanisms, products and yields is essential for the design of efficient pyrolysis processes. Rigid (RPUF) and flexible foams (FPUF), a cast elastomer (CE) and a thermoplastic Polyurethane (TPU) have been investigated by thermogravimetry (TG) and FTIR-spectroscopy. Two decomposition steps have been identified. CO<sub>2</sub> is mainly released in the first decomposition step between 250 °C and 400 °C. The second decomposition step at temperatures above 400 °C releases polyol fragments and marginal amounts of CO<sub>2</sub>. Strong feedstock dependency is evident. Quantitative tracing for the CO<sub>2</sub> release was developed, validated and applied. This allows the resolution of specific decomposition phenomena, mass balancing and distinguishing potentially valuable volatiles from CO<sub>2</sub> and solid residues. CO<sub>2</sub> yields are 12.0 mass-% for RPUF, 4.0 mass-% for FPUF, 3.2 mass-% for CE and 5.3 mass-% for TPU. Considering solids and CO<sub>2</sub> as losses, recycling potentials were determined which are 74 mass-% for RPUF, 90 mass-% for FPUF, 95 mass% for CE and 93 mass-% for TPU. This facilitates further process development based on polymer-specific data.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107048"},"PeriodicalIF":5.8,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Philipp-Henry Rathsack , David Scheithauer , Jörg Kleeberg , Martin Gräbner
{"title":"Chemical recycling of PC/ABS-blends by pyrolysis","authors":"Philipp-Henry Rathsack , David Scheithauer , Jörg Kleeberg , Martin Gräbner","doi":"10.1016/j.jaap.2025.107047","DOIUrl":"10.1016/j.jaap.2025.107047","url":null,"abstract":"<div><div>Not all plastics can be recycled mechanically. Polycarbonate (PC) combined with acrylonitrile butadiene styrene (ABS) is one such material used in applications like electronic casings and automotive components. Since mechanical recycling of PC/ABS results in thermal degradation and the loss of required properties, alternative methods are sought. Pyrolysis, the thermal decomposition without oxygen, preferentially cleaves certain bonds, yielding valuable monomers. This study investigates the pyrolysis of non-flame-retarded and flame-retarded PC/ABS blends at laboratory and pilot plant scales. Analyses utilized thermogravimetry and infrared spectroscopy (TG-IR). The blends exhibited two decomposition stages influenced by flame retardants. The IR spectra provided insights into the structural properties of volatile compounds. CO<sub>2</sub> yield ranged from 6 % to 8 %, with the flame-retarded blend showing 0.5–1 % higher yields. Subsequently, we conducted experiments in a fixed-bed reactor, varying the pyrolysis temperature, heating rate, and blend composition. Masses of gaseous, liquid, and solid products were measured, with a liquid yield optimum at 480–500<sup>∘</sup>C. All product fractions were analyzed. Liquid products contained valuable compounds like phenol, styrene, and bisphenol-A, analyzed using gas chromatography (GC) and comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS). For the non-flame-retardant blend, bisphenol-A was the main product (25–30 %), while phenol dominated (10–15 %) in the flame-retardant blend.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107047"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dezhi Chen , Zhou Fang , Yufan Wei , Jun Xu , Kai Xu , Long Jiang , Yi Wang , Sheng Su , Song Hu , Jun Xiang
{"title":"Micro-Raman spectroscopy and Petrography for unraveling the complex heterogeneous physicochemical structures of biochar from the scale of bulk to micro: A comparison and discussion","authors":"Dezhi Chen , Zhou Fang , Yufan Wei , Jun Xu , Kai Xu , Long Jiang , Yi Wang , Sheng Su , Song Hu , Jun Xiang","doi":"10.1016/j.jaap.2025.107057","DOIUrl":"10.1016/j.jaap.2025.107057","url":null,"abstract":"<div><div>This study produced biochar from coconut shells and corncobs through pyrolysis under a nitrogen atmosphere with temperatures ranging from 350℃ to 1400℃. The surface regions of the biochar were characterized at the micro-scale using a combination of micro-Raman spectroscopy and petrography. Extensive data from both methods were compared and correlated from the scale of bulk to micro- levels. The results indicate that for bulk structures, the average random reflectance (R<sub>f</sub>) increases and Raman parameter α decreases with temperature, indicating a higher thermal maturity and lower C-H, C-O etc. structures. However, A<sub>D</sub>/A<sub>G</sub>, A<sub>(VR+VL+GR)</sub>/A<sub>D</sub> and A<sub>(VR+VL+GR)</sub>/A<sub>G</sub> exhibit significant inflection points at specific temperatures. These inflection points are linked to key structural transformations: aromatization at 600 ℃ and graphitization at 1000 ℃. At microscale, biochar contains pores of varying shapes and sizes (approximately 5–100μm) with ash deposits embedded within them. These features significantly influence the heterogeneity in R<sub>f</sub> measurements, resulting in a broaden distribution of R<sub>f</sub> as the pyrolysis process progressed. Besides, micro-Raman spectroscopy shows that biochar particles with higher substituent and side-chain abundances have a tendency towards preferential reactivity. Furthermore, the chemical structural distribution of biochar became more concentrated and focused below 1000 ℃. However, biochar undergoes heterogeneous graphitization at 1000 ℃, and the distribution of aromatic rings and graphite structure becomes even more dispersed between 1000 ℃-1400 ℃. The correlations between the results of petrographic method and micro-Raman at the bulk and micro-scale have been set up and discussed, and it can provide guidance for the comprehensive characterization of the heterogeneous structure of biochar.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107057"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143465033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Junchen Zhu , Qi Li , Hairong Yang , Yue Xie , Hongru Feng , Huabing Liu , Boka Xiang , Kailong Yuan , Cuirong Sun , Yuanjiang Pan
{"title":"Analysis and pyrolysis study of sucrose esters in flue-cured tobacco","authors":"Junchen Zhu , Qi Li , Hairong Yang , Yue Xie , Hongru Feng , Huabing Liu , Boka Xiang , Kailong Yuan , Cuirong Sun , Yuanjiang Pan","doi":"10.1016/j.jaap.2025.107054","DOIUrl":"10.1016/j.jaap.2025.107054","url":null,"abstract":"<div><div>Pyrolysis behavior of sucrose esters (SEs) significantly impacts the aroma and quality of cigarettes. However, there is limited research on SEs and their pyrolysis in Flue-cured tobacco. In this study, nine SEs and their three pyrolysis products, glucose esters (GEs), were identified using LC-MS<sup>n</sup>, with six esters being reported in Flue-cured tobacco for the first time. The aging and baking processes of tobacco leaves promoted the pyrolysis of most SEs along with the formation of GEs. During long-term storage at 4 ℃, tobacco SE was found to undergo 3-methylvaleryl intramolecular migration from glucose to fructose as well as intermolecular elimination and addition reaction of acetyl groups, greatly enriching the types of tobacco SEs. By comparing different storage temperatures, this acyl migration demonstrated a temperature dependence. Under simulated cigarette smoking conditions via thermal microwave plasma treatment, SE was rapidly degraded into GE intermediates, fatty acids, furfural, and other aroma compounds. These insights advance our understanding of SE pyrolysis and aroma development, and provide potential explanations for the structural diversity of tobacco SEs.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107054"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luis Cutz , Sarvesh Misar , Bernat Font , Majd Al-Naji , Wiebren de Jong
{"title":"Hydrothermal liquefaction of Spanish crude olive pomace for biofuel and biochar production","authors":"Luis Cutz , Sarvesh Misar , Bernat Font , Majd Al-Naji , Wiebren de Jong","doi":"10.1016/j.jaap.2025.107050","DOIUrl":"10.1016/j.jaap.2025.107050","url":null,"abstract":"<div><div>The olive oil industry is an important source of agricultural residues throughout its value chain, ranging from intermediate process slurries to relatively dry content pruning residues. Among them, crude olive pomace (COP) is of particular interest since it is abundant, low cost and can be a promising source for bioenergy. Nevertheless, because COP is phytotoxic and has a high moisture content and low energy density, it represents a challenge to conventional processes that usually require a dry and homogenous material. The main novelty of this study is the use of a transition metal catalyst and a central composite design (CCD) approach to optimize the conversion of COP through hydrothermal liquefaction (HTL) into valuable products. Results show that catalytic HTL is capable of converting up to half of the COP into bio-oil. Higher process temperatures resulted in lower bio-oil yields but larger higher heating value (HHV) and lower N content. The bio-oils produced at higher temperatures also show lower concentration of phenols and regarding biochar, a low inorganic content. Without any further upgrading, COP bio-oils produced by HTL are rich in valuable compounds such as oleic acid, phenolic compounds and ketones that can be used in the polymer industry or as chemical intermediates. The highest bio-oil yield was 51.96 wt% at 330 ºC for 30 min and 7.5 wt% catalyst with a HHV of 22.0 MJ/kg. At those operational conditions, the biochar yield was 16.49 wt% with a HHV of 8.9 MJ/kg. The major minerals found in the biochars (CaO, SiO<sub>2</sub> and P<sub>2</sub>O<sub>5</sub>) suggests that biochar could be well-suited for use in soil applications or as materials for adsorption, especially the non-catalytic ones. Furthermore, the experimental results acquired from HTL of COP were used to develop a global kinetic model. Using an explicit Runge-Kutta method, the kinetic parameters were calculated. After comparing the global kinetic model with a linear system of ordinary differential equations (ODEs) based on the CCD models, results indicate that this approach is more effective in predicting the yields of HTL products.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107050"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143465034","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}