Composition Of Bio-oil Research Articles

Production of MAH-Rich bio-oil from co-pyrolysis of biomass and plastics using carbonized MOF catalysts under microwave irradiation

This study investigates the effects of various carbonized MOF catalysts on the properties of products derived from microwave-assisted co-pyrolysis of biomass and plastics. The Cr@C catalysts were prepared from MIL-101(Cr) precursors at different microwave carbonization temperatures, while Fe/Cr@C catalysts were synthesized under varying Fe loadings. Characterization of the catalysts was performed using XRD, BET, and FT-IR. The distribution of solid, liquid, and gaseous products, as well as the composition of bio-oil and syngas, were analyzed. The results show that the 5Fe/Cr@C catalyst achieved the highest pyrolysis gas yield (33.05 wt%), while the 15Fe/Cr@C catalyst produced the highest hydrogen yield (24.97 vol%). The Cr@C catalyst promoted hydrocarbon production, with Cr@C-700 achieving a total hydrocarbon content of 51.04%. The incorporation of Fe enhanced the selectivity of Cr@C catalysts for monocyclic aromatic hydrocarbons(MAHs) in the bio-oil. The aromatic content reached a maximum of 19.88% with the 15Fe/Cr@C catalyst. Notably, the MAHs content in the 5Fe/Cr@C catalyst accounted for 97.1% of the total aromatic hydrocarbons. This research provides valuable insights into the potential of carbonized MOF catalysts for producing bio-oil rich in single-ring aromatic hydrocarbons from microwave-assisted co-pyrolysis of biomass and plastics.

Pyrolysis of açai stems (Euterpe oleracea Mart.) and cocoa husks (Theobroma cacao L.) residues for the generation of added-value products in rural areas

AbstractGenerally, agriculture activities represent the main economic income of rural areas, and during these, huge amounts of biomass are generated. This biomass is considered as garbage due to its high storage cost. However, energy and added-value products can be recovered from biomass. Within this context, açai stems and cocoa husks were collected from different rural areas of Bolivia due to their high importance in the local and international markets as two of the most available products of the country. The preliminary study will contribute in the field of green energy recovery and resource management. Thus, in this study, both residues were tested as renewable feedstocks for the generation of added-value products from pyrolysis at 500 °C for 30 min. Açai stems were found to be more suitable to biochar based with yields up to 49.1% ± 2.4%, but also for biogas production (33.9% ± 2.0%). Cocoa husk was also found to be more suitable for biochar production (38.1% ± 1.7%) but also for bio-oils (33.6% ± 17.6%). Both resulting biochars had basic pH (between 10 and 12) and low density (287.2 kg/m3 and 401.7 kg/m3). Additionally, the lack of heavy metals on the surface makes both biochar products good candidates for soil amendment applications. Furthermore, the bio-oil composition is complex and varied, and products such as Maltol, 2-methyl furane, and D-allose have direct applications in the food industry. Moreover, the presence of phenolic compounds and hydrocarbons with more than five carbons in the structure makes the obtained bio-oils suitable for upgrading processes for biofuel production. Finally, the obtained biogases can be applied for local electricity generation, or to reduce the energy requirements for the pyrolysis reactor. Graphical Abstract

Catalytic vapor phase upgrading of sawdust pyrolysis using metal oxide catalysts: The support effect

Biocrude derived from biomass is unstable and has limited applications and vapor-phase upgrading of biomass pyrolysis over a catalyst can enhance bio-oil quality and yield, yet catalyst deactivation due to coke formation remains a major challenge. This study explores the effects of different magnesium oxide (MgO) catalysts supported on ZSM-5, Al2O3, ZrO2, TiO2 on the pyrolysis product yield, composition, and the extent of coke formation. Studies were conducted in a fixed-bed reactor at 550 °C at two different catalyst to biomass loadings (C/B) of 1:6, and 1:1. Non catalytic pyrolysis of sawdust resulted in the biocrude, gas, and char yields of ∼32 wt%, ∼29 wt%, and ∼39 wt% respectively. At a low C/B ratio, pyrolysis product yields were approximately comparable to those under non-catalytic conditions. However, at a high C/B ratio, biocrude yield decreased significantly with increase in gas yield, while char yield showed only minor changes. Using ZSM-5 and Al2O3 supported catalysts, low C/B ratios significantly increased phenolic content in the biocrude (∼58%). In contrast, higher C/B ratios enhanced the hydrocarbons (∼10%) and aromatics (∼32%) content, reducing phenolics and thereby lowering the biocrude's overall oxygen content, enhancing its stability. TiO2 and ZrO2 supports produced higher proportions of lower carbon chain length compounds, though with reduced hydrocarbon content compared to ZSM-5. ZSM-5 supported catalysts yield a high proportion of aromatic compounds, attributed to the synergy between the acidic sites of ZSM-5 and the basic sites of MgO that favored conversion of phenolics to aromatics through dehydroxylation and demethoxylation. Overall, this study highlights the influence of different catalyst supports in catalytic vapor phase upgrading of sawdust derived biocrude to selectively optimize bio-oil composition, increasing fuel or chemical potential while addressing coke formation.

Upgrading co-pyrolysis products from ternary biomass: An investigative study of commercial and locally-made catalysts

Catalysts play a pivotal role in influencing product yields and compositions in pyrolysis processes, offering significant advantages for biomass conversion. This study investigates the impact of natural and commercial catalysts on the co-pyrolysis of ternary biomass at two different temperatures (550 °C and 750 °C). At higher temperatures, secondary decompositions become prominent, leading to increased gas yields and decreased char and liquid oil yields. The introduction of catalysts generally enhances char yields across both temperature regimes. Notably, CaCO3 exhibits the highest bio-oil yield, while Ca(OH)2 shows the lowest, with reversed trends observed for gas yields. The influence of catalysts extends to gas composition, with Ca(OH)2 and zeolite notably increasing CH4 and CO2 concentrations at 750 °C. Each catalyst type exerts specific effects on gas production and composition, underscoring the intricate interplay between catalysts and reaction pathways. Additionally, catalysts significantly alter the composition of bio-oil, with calcium-based catalysts reducing acid content and increasing aromatics, while zeolites exhibit contrasting trends at different temperatures. Noteworthy compounds identified in the resulting bio-oil include bisphenol A, levoglucosan, phenols, and p-cresol, offering potential applications in plastics, biofuels, resins, and more. Overall, catalysts offer the potential to enhance specific compound yields, reduce corrosiveness, and optimize bio-oil and char composition for diverse industrial applications, highlighting the need for further research into synergistic effects when combining different catalysts.

Hydrothermal Liquefaction of Sugarcane Bagasse and Straw: Effect of Operational Conditions on Product Fractionation and Bio-Oil Composition

In the energy transition process, aiming for zero disposal and clean production in the elimination of waste is crucial; consequently, agricultural residues have significant potential for reduction in the use of fossil fuels. This study investigates the hydrothermal liquefaction (HTL) of sugarcane bagasse (BSC) and straw (SSC), examining the products’ distribution and bio-oil composition relative to the reaction conditions. The experiments used a 23 factorial design, evaluating the temperature (300–350 °C), constant heating time (0–30 min), and the use of the K2CO3 concentration as the catalyst (0–0.5 mol/L−1). The main factor affecting the biocrude yield from BSC and SSC was the use of K2CO3. Statistically significant interaction effects were also observed. Milder conditions resulted in the highest bio-oil yields, 36% for BSC and 31% for SSC. The catalyst had no impact on the biocrude production. The bio-oils were analyzed by GC/MS and FTIR; a principal component analysis (PCA) was performed to evaluate the samples’ variability. The FTIR highlighted bands associated with common oxygenated compounds in lignocellulosic biomass-derived bio-oils. The GC-MS results indicated a predominance of oxygenated compounds, and these were highest in the presence of the catalyst for both the BSC (90.6%) and SSC (91.7%) bio-oils. The SSC bio-oils presented higher oxygenated compound contents than the BSC bio-oils. Statistical analysis provided valuable insights for optimizing biomass conversion processes, such as determining the optimal conditions for maximizing product yields.

Development of graphitic and non-graphitic carbons using different grade biopitch sources

The growing demand for bio-renewable alternatives to fossil fuels in the production of sustainable carbon materials, aimed at reducing environmental impact, is crucial for advancing a greener future. This research explores an innovative approach for producing biopitches from bio-oils, which are subsequently utilized as a sustainable precursor for developing advanced graphitic carbons (GC) and non-graphitic carbons (NGC) through carbonization and graphitization processes. The study emphasizes the impact of the chemical composition of bio-oils and biopitches, including heteroatom structures, aromatic/aliphatic ratio, and oxygen content with oxygen-bearing functional groups, on the production of GC and NGC. The research also examines their structural parameters at various heating temperatures using characterization techniques such as X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. XRD analysis revealed that GC samples have lower interplanar spacing (d002) and larger crystallite size than NGC, while Raman shows more short-range order and defects in NGC. Furthermore, HRTEM images and fringe analysis demonstrated differences in lamellae structures, tortuosity, and fringe length. These observations, unveiling differences in crystallite size and degree of graphitization between GC and NGC, underscore the influence of temperature on structural order and defect annealing, which is crucial for optimizing material properties.

Bio-oil production from hydrothermal liquefaction of algal biomass: Effects of feedstock properties and reaction parameters

In this study, two different algal biomass types, including fresh algal biomass (HS) and dewatered algal biomass (TH and CH), were selected to explore the effects of their properties and hydrothermal liquefaction (HTL) reaction parameters on bio-oil yields and quality. The obtained results showed higher bio-oil yields through the HTL process of the HS algal biomass than those obtained from the TH and CH algal biomass. The observed bio-oil yields increasing-decreasing trends with increasing reaction temperatures and times. The optimal reaction temperature and time were 325 °C and 30 min, respectively. These conditions resulted in HS, TH, and CH algal biomass bio-oil yields of 31.6, 24.2, and 14.4 wt%, respectively. The HS algal biomass-derived bio-oil exhibited higher H/C ratios and HHV values, as well as lower N/C ratios, than those of the dewatered algal biomass-derived bio-oils. The bio-oil composition results demonstrated the enhancement effects of flocculant additions to the dewatered algal biomass on the bio-oil fractions. The TH and CH algal biomass-derived bio-oils exhibited substantially higher hydrocarbon contents than those in bio-oils of the HS algal biomass. In addition, the nitrogenous compound and hydrocarbon contents exhibited decreasing and increasing trends, respectively, with increasing reaction temperatures from 275 to 325 °C, improving the bio-oil quality.

Degradative solvent-catalyzed extraction of sewage sludge

It is necessary for the further development of sludge degradative solvent extraction (DSE) to significantly increase the bio-oil yield and adjust its composition. In this study, the effects of MCM-41, HZSM-5, and SSZ-13 on the physical properties, yield, and composition of bio-oil were compared. Results show that all three catalysts effectively promote the conversion of volatiles in the residue to the heavy component (heavy-s). The addition of MCM-41 improved the yieldof both the light component (light-s) and heavy-s. Their yields increased from 8.11% and 20.47% to 14.39% and 29.18%, respectively. Its all-silicon structure and weak acidity have no significant effect on the composition of the bio-oil. HZSM-5 addition increases the light-s yield to 25.58%. Its MFI structure and proper acidity are beneficial to the formation of aromatic hydrocarbons and olefins, while effectively reducing oxygenates. SSZ-13 increases the heavy-s yield to 27.89%, and promoted the formation of nitrogen-containing compounds significantly.

Bio-oil production from the catalytic pyrolysis of raw and torrefied corn waste by using MgO and CaO catalysts

Abstract This research investigates the influence of torrefaction and catalytic pyrolysis of raw corn waste (RCW) to upgrade the quality of bio-oil. RCW was torrefied at 280°C for 16 mins to produce torrefied corn waste (TCW). Natural basic oxides (CaO and MgO) catalysts were selected because of inexpensive and high catalytic performance. Pyrolysis experiments were conducted in a bench-scaled bubbling fluidized bed reactor at 500°C. The effects of torrefaction and the presence of a catalyst on the pyrolysis product both yield and composition were investigated. The results from non-catalytic pyrolysis revealed that TCW pyrolysis gave 15 wt.% lower in oil yield, and about 6.8 wt.% lower in gas yield but the char yield was approximately 22 wt.% higher compared to the pyrolysis of RCW. Considering the effect of catalyst, the yield of bio-oil reduced slightly, while the yield of char and gas increased compared to non-catalytic pyrolysis for both RCW and TCW. The bio-oil composition derived from TCW pyrolysis contained more phenolic and aromatic compounds and significantly lower oxygenated compounds when compared to that of RCW pyrolysis. Moreover, with the presence of the catalysts, the bio-oil composition and HHVs of bio-oil was also improved.

Synergistic effects of Fe@C catalysts prepared at different carbonization temperatures on microwave co-pyrolysis of biomass and plastic for high-value oil and gas production

This study explores the impact of Fe@C catalysts, prepared at different carbonization temperatures, on the microwave co-pyrolysis of bamboo and polyethylene (BP) for the production of high-value oil and gas. In the synthesis of MIL-101(Fe), bamboo-derived pyrolytic carbon was added, and this was used as a precursor to synthesize Fe@C catalysts through microwave carbonization. Various properties and characteristics of Fe@C catalysts were analyzed using XRD, BET, SEM, FT-IR, and Raman spectroscopy to understand its structure and performance comprehensively. The composition of bio-oil, pyrolysis gas, and product distribution were analyzed. The results show that Fe@C catalysts enhances the yield of pyrolysis gas, as well as the selectivity of H2 in the pyrolysis gas and aromatic hydrocarbons in the bio-oil. Among them, Fe@C-700 catalysts achieved the highest synthesis gas yield (89.35 vol%) and aromatic hydrocarbon yield (27.13 %). Additionally, the proportion of light aromatic hydrocarbons (BTX) in the aromatic hydrocarbon compounds can reach up to 31.33 %. This study provides valuable insights into the synergistic effects of Fe@C catalysts during BP microwave co-pyrolysis, highlighting their potential for the production of high-value oil and gas from biomass and plastic.

Investigation of products characteristics from microwave catalytic pyrolysis of furfural residue based on the effects of Fe/Mn modified biochar

In this paper, the effect of MnCl2 and FeCl3 modified biochar catalysts on the catalytic pyrolysis products of furfural residue (FR) under microwave field was investigated. The results showed that the highest content in the pyrolysis gas obtained from microwave catalytic pyrolysis (MCP) with modified biochar catalysts was CO, while phenols were found in bio-oil. After metal loading, the specific surface area of the catalyst decreased significantly. The CO production was promoted by microwave pyrolysis of FR over modified biochar catalyst, and MFRC gain was more obvious. The content of H2 all continued to increase with increasing mass of loaded metals, and the opposite was true for CO. The highest relative content of phenols in the bio-oils of FFRC and MFRC were 66.76 % for 2FFRC and 63.66 % for 4MFRC, where the relative content of phenols was 15.50 % and 19.27 %, respectively. The production of sugars and ketones was also promoted by Fe and Mn. The lower loading of active metals significantly promoted the conversion of pyrolysis vapors to phenols while releasing more CO. A possible mechanism of MCP of FR was proposed. The results showed that Fe/Mn-modified char-based catalysts could effectively modulate the composition of bio-oil.

Comprehensive pyrolysis investigation of Lemongrass and Tagetes minuta residual biomass: bio-oil composition and biochar physicochemical properties

Comprehensive pyrolysis investigation of Lemongrass and Tagetes minuta residual biomass: bio-oil composition and biochar physicochemical properties

Pyrolysis of coffee residues, tobacco, and algae biomasses as a source of nitrogen-containing compounds

Agro-industrial residues hold immense potential as sustainable energy and bioproduct sources. Thermoconversion through pyrolysis, which generates bio-oil, is a promising approach that simultaneously reduces environmental impact and adds value to biomass. Notably, biomasses with high nitrogen content yield bio-oils rich in diverse, industrially valuable nitrogen-containing compounds (N-compounds). This study investigates the rapid pyrolysis of five such biomasses: spent coffee grounds (SCG), silverskin (SVK), microalgae (MIA), macroalgae (MAA), and tobacco (TBC). A pretreatment step was employed to reduce fat content and enhance bio-oil quality. Gas chromatography analysis subsequently identified the generated N-compounds. The bio-oils revealed a significant presence of oxygenated compounds and hydrocarbons beside N-compounds. The use of Principal Component Analysis (PCA) effectively allowed to group the samples based on their bio-oil compositions, highlighting microalgae as the richest source of N-compounds, particularly after fat pre-extraction.

Exploring molecular composition of upgraded pyrolysis bio-oil using GC×GC-(EI/PI)-TOF MS with different column set-ups

Bio-oils produced from the pyrolysis of lignocellulosic biomass are rich in oxygen, which causes instability and corrosion problems. Therefore, dedicated post-pyrolysis treatments such as hydrotreatment are required to increase the H/C ratio of the products to be used as fuel or chemicals. Here, a characterization method based on two-dimensional gas chromatography (GC×GC) was developed to highlight the evolution of the volatile fraction during hydrotreatment. Six samples obtained at different times of the hydrotreatment were analyzed. In this way, information on catalyst deactivation was obtained. The combination of information from normal and reversed phase GC×GC analysis provides a detailed characterization of the hydrotreated bio-oils. Furthermore, the use of soft photoionization (PI), in addition to conventional electron impact ionization (EI), yields a better understanding of the compound structures present in the sample. Identification and semi-quantification of the sample components indicate that the concentration of paraffins, cycloalkanes, and monoaromatics have largely decreased during hydrotreatment, while the concentration of oxygenated species and polycyclic aromatic hydrocarbons have increased. Using complementary GC methods highlights changes in the molecular composition of volatile species that correlate with catalyst performance. This approach can be used to follow the decrease in hydrodeoxygenation activity as a function of time on stream to estimate the catalyst aging during the hydrotreating process.

Co-hydrothermal conversion of kitchen waste and agricultural solid waste biomass components by simple mixture: study based on bio-oil yield and composition

The co-hydrothermal conversion of kitchen waste and lignocellulosic biomass solid waste into bio-oil holds the potential to revolutionize the production of multi-source biomass hydrothermal bio-oil. In this study, the interaction between kitchen waste and agricultural solid waste during the hydrothermal conversion process was investigated, focusing on the yield and properties of the resulting bio-oil, the obtained bio-oil was characterized. Results reveal that the Maillard reaction plays a pivotal role in influencing the production of hydrothermal bio-oil during the co-hydrothermal conversion process. Proteins and amino acids, in particular, exhibit a strong promotional effect on the generation of hydrothermal bio-oil. The introduction of kitchen waste did not significantly change the chemical and elemental composition of the bio-oil derived from agricultural solid waste. However, the specific content of compounds within the hydrothermal bio-oil varied widely. When compared to single-component hydrothermal bio-oils derived from lignin, cellulose, and hemicellulose respectively, the addition of kitchen waste resulted in a notable enhancement of the bio-oil's overall calorific value and a reduction in its oxygen content. The findings of this study have the potential to pave the way for sustainable and economically viable processes for multi-source biomass hydrothermal bio-oil preparation.

Hydrothermal Pyrolysis of Sargassum Marine Macroalgae: "Synthesis and Characterization of Products"

Abstract In recent years, there has been an explosive growth and overabundance of pelagic Sargassum macroalgae in the North Atlantic Ocean, which wash up on the beaches in the United States, Mexico and the Caribbeans, causing both environmental and health issues in those coastal regions. Hydrothermal carbonization (HTC) process was investigated as a potential solution by converting this wet algae biomass into solid and liquid products, namely hydrochar and organic process water, respectively. In this study, the effects of HTC reaction temperatures on the yields and physicochemical properties of hydrochar and organic process water derived from Sargassum algae sample obtained from a coastal region in South Florida were evaluated by using various analytical techniques, including SEM, TGA, BET, FTIR and GC-MS. As a result of the increase in temperature, hydrochar yield decreased, while the yield of bio-oil increased. During the heating process, the volatile matter in hydrochar decreases, whereas the fixed carbon increases. Ash content in hydrochar increases as temperature increases. There were some interconnected pores on the surfaces of all three temperatures. It has been shown that a change in temperature has a significant effect on the chemical composition of bio-oils. In some cases, certain compounds increased as the temperature increased, but in others, it was temperature dependent. This study demonstrated that HTC technology could be a potential solution for mitigating Sargassum pollution issue by converting it into value-added bio-based products.

UTILIZATION OF BAGASSE WASTE FOR BIO-OIL EXTRACTION FROM SUGARCANE JUICE VENDORS IN BANYUWANGI REGENCY

The disposal of sugarcane bagasse waste, often done through open dumping without further treatment, poses environmental pollution and unpleasant odors. Consequently, the implementation of technology is essential to address this issue, specifically by employing a solid waste recycling technology to produce bio-oil, which holds significant value. Utilizing sugarcane bagasse waste to create bio-oil presents an alternative to minimize aesthetic pollution. This research, sourced from sugarcane bagasse waste obtained from sugarcane beverage vendors in Banyuwangi Regency, explores the conversion of bagasse into bio-oil through the pyrolysis process. Bio-oil is an inorganic compound produced during the pyrolysis process. The aim of this study is to generate bio-oil from underutilized sugarcane bagasse, providing a functional and economically valuable alternative energy source that is both high-quality and environmentally friendly. Additionally, the research aims to determine the concentration and composition of bio-oil resulting from the pyrolysis of sugarcane bagasse. The analysis reveals that the high lignocellulosic content in sugarcane bagasse has the potential to be utilized for bio-oil production.

Harnessing the energy potential of rosehip wastes towards sustainable energy supply

Using renewable energy technologies comes to the forefront for sustainable energy, economy, and environmental management. In regions with high agricultural production, it is becoming increasingly important to contribute to sustainable energy production by using agricultural wastes as biomass. For this purpose, the evaluation of the energy potential and catalytic pyrolysis of rosehip seed (RS) and rosehip pomace (RP), which are considered the main wastes of rosehip, were investigated to obtain improved bio-oil. While C10+ hydrocarbons of alkane and alkene origin were mostly found in the composition of bio-oil, the highest ratio belongs to 50CL50RP650. Especially when only RS and RP were present, both the temperature of 650°C and the presence of catalyst were more effective in obtaining aliphatics. In the use of the blend, one of these parameters was sufficient and the volatile matter increased and fixed carbon decreased, especially as the RP ratio (70%) in the blend increased. The heating value (18.5–19 MJ/kg) and volatile matter (63–66%) of the wastes were high, while ash (0%) and moisture (2%-3%) contents were low, which is important in terms of energy potential. In the combustion profiles, the Tmax was generally higher for the blends.

A Review of Hydrothermal Biomass Liquefaction: Operating Parameters, Reaction Mechanism, and Bio-Oil Yields and Compositions

A Review of Hydrothermal Biomass Liquefaction: Operating Parameters, Reaction Mechanism, and Bio-Oil Yields and Compositions

Interaction Effects between the Main Components of Protein-Rich Biomass during Microwave-Assisted Pyrolysis.

The interaction effects between the main components (proteins (P), carbohydrates (C), and lipids (L)) of protein-rich biomass during microwave-assisted pyrolysis were investigated in depth with an exploration of individual pyrolysis and copyrolysis (PC, PL, and CL) of model compounds. The average heating rate of P was higher than those of C and L, and the interactions in all copyrolysis groups reduced the max instant heating rate. The synergistic extent (S) of PC and PL for bio-oil yield was 16.78 and 18.24%, respectively, indicating that the interactions promoted the production of bio-oil. Besides, all of the copyrolysis groups exhibited a synergistic effect on biochar production (S = 19.43-28.24%), while inhibiting the gas generation, with S ranging from -20.17 to -6.09%. Regarding the gaseous products, apart from H2, P, C, and L primarily generated CO2, CO, and CH4, respectively. Regarding bio-oil composition, the interactions occurring within PC, PL, and CL exhibited a significantly synergistic effect (S = 47.81-412.96%) on the formation of N-heterocyclics/amides, amides/nitriles, and acids/esters, respectively. Finally, the favorable applicability of the proposed interaction effects was verified with microalgae. This study offers valuable insights for understanding the microwave-assisted pyrolysis of protein-rich biomass, laying the groundwork for further research and process optimization.