Coconut Fiber Pyrolysis: Bio-Oil Characterization for Potential Application as an Alternative Energy Source and Production of Bio-Degradable Plastics

The current energy crisis could be alleviated by enhancing energy generation using the abundant biomass waste resources. Agricultural and forest wastes are the leading organic waste streams that can be transformed into useful alternative energy resources. Pyrolysis is one of the technologies for converting biomass into more valuable products, such as bio-oil, bio-char, and syngas. This work investigated the production of bio-oil through batch pyrolysis technology. A fixed bed pyrolyzer was designed and fabricated for bio-oil production. The major components of the system include a fixed bed reactor, a condenser, and a bio-oil collector. The reactor was heated using a cylindrical biomass external heater. The pyrolysis process was carried out in a reactor at a pressure of 1atm and a varying operating temperature of 150˚C, 250˚C, 350˚C to 450˚C for 120 minutes. The mass of 1kg of coconut fiber was used with particle sizes between 2.36 mm - 4.75 mm. The results show that the higher the temperature, the more volume of bio-oil produced, with the highest yield being 39.2%, at 450˚C with a heating rate of 10˚C/min. The Fourier transformation Infrared (FTIR) Spectroscopy analysis was used to analyze the bio-oil components. The obtained bio-oil has a pH of 2.4, a density of 1019.385 kg/m3, and a calorific value of 17.5 MJ/kg. The analysis also showed the presence of high-oxygenated compounds;carboxylic acids, phenols, alcohols, and branched oxygenated hydrocarbons as the main compounds present in the bio-oil. The results inferred that the liquid product could be bestowed as an alternative resource for polycarbonate material production.

Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

Biochar and bio-oil are produced simultaneously in one pyrolysis process,and they inevitably contact and may interact,influencing the composition of bio-oil and modifying the structure of biochar.In this sense,biochar is an inherent catalyst for pyrolysis.In this study,in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil,three char catalysts(600C,800C,and 800AC)produced via pyrolysis of poplar wood at 600 or 800℃or activated at 800℃,were used for catalyzing pyrolysis of homologous poplar wood at 600℃,respectively.The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas(yield increase by 40.2%)and aromatization of volatiles to form more light or heavy phenolics,due to its abundant oxygen-containing functionalities acting as active sites.The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization.Nevertheless,the interaction with the volatiles consumed oxygen on 600C(decrease by 50%),enhancing the aromatic degree and increasing thermal stability.The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores.The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of -OH,while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.

Sustainable Biofuel Production from Brown and Green Macroalgae through the Pyrolysis

The escalating demand for energy coupled with environmental concerns necessitates exploring sustainable alternatives to fossil fuels.The study explores the viability of using large ocean-based seaweeds as a source of thirdgeneration biomass,specifically focusing on their conversion to biofuel via the process of pyrolysis.Sargassum plagiophyllum and Ulva lactuca represent prevalent forms of macroalgae,posing significant discharge challenges for coastal regions globally.However,the exploration of their potential for bio-oil generation via pyrolysis remains limited.This study investigates the pyrolysis process of S.plagiophyllum and U.lactuca for biofuel production,aiming to provide valuable insights into their utilization and optimization.Pyrolysis experiments were conducted within temperature ranges of 400°C to 600°C and durations of 10 to 50 min using a batch reactor.The chemical analysis of the synthesized bio-oil indicated it contains critical compounds such as organic acid derivatives,furans,nitrogenous aromatics,and aliphatic hydrocarbons.The effectiveness of converting the initial biomass into bio-oil is significantly influenced by the pace at which the biomass undergoes decomposition,underscoring the importance of comprehending the kinetic aspects of this conversion.By applying the Arrhenius formula,we calculated the activation energies and frequency factors,with the findings for S.plagiophyllum being 15.27 kJ/mol and 0.477 s^(-1),and for U.lactuca,the values were 43.17 kJ/mol and 0.351 s^(-1),correspondingly.These findings underscore the potential of brown and green macroalgae as sustainable sources for biofuel production via pyrolysis,offering insights for further optimization and valorization efforts in the quest for renewable energy solutions.

Properties of Bio-oil from Fast Pyrolysis of Rice Husk

Physicochemical properties of bio-oil obtained from fast pyrolysis of rice husk were studied in the present work.Molecular distillation was used to separate the crude bio-oil into three fractions viz.light fraction,middle fraction and heavy fraction.Their chemical composition was analyzed by gas chromatograph and mass spectrometer（GC-MS）.The thermal behavior,including evaporation and decomposition,was investigated using thermogravimetric analyzer coupled with Fourier transform infrared spectrometer（TG-FTIR）.The product distribution was significantly affected by contents of cellulose,hemicellulose and lignin.The bio-oil yield was 46.36%（by mass） and the yield of gaseous products was 27%（by mass）.The chemicals in the bio-oil included acids,aldehydes,ketones,alcohols,phenols,sugars,etc.The light fraction was mainly composed of acids and compounds with lower boiling point temperature,the middle and heavy fractions were consisted of phenols and levoglucosan.The thermal stability of the bio-oil was determined by the interactions and intersolubility of compounds.It was found that the thermal stability of bio-oil was better than the light fraction,but worse than the middle and heavy fractions.

Correlation between solubility parameters and recovery of phenolic compounds from fast pyrolysis bio-oil by diesel extraction

Fast pyrolysis bio-oils(fpBO)were extracted with two alternative commercial transportation fuels,hydrocarbon diesel and bio-diesel.The extraction of fpBO with commercial diesel fuel provided a yield of 4.3 wt%,but the yield increased significantly to 26.6 wt%when bio-diesel was the extractant.The molecular weight of fpBO before and after extraction were consistent with the loss of a more soluble,low molecular weight fraction from the crude fpBO.The relative energy difference(RED),based on the Hansen solubility parameter(HSP),is used to examine the extraction efficiency of specific compounds in the two different‘solvents’.Differences in the RED values could be used to rationalize differences in the partitioning of common fpBO phenolics.

Fractional pyrolysis of Cyanobacteria from water blooms over HZSM-5 for high quality bio-oil production

Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.

In situ catalytic conversion of biomass fast pyrolysis vapors on HZSM–5

In situ catalytic conversion of biomass fast pyrolysis vapors was carried out on HZSM-5 with varying Si/Al ratios(ranging from 20 to 300) at 450 °C. The effects of Si/Al ratios of HZSM-5 zeolites on the distribution of biomass fast pyrolysis products and carbon deposits on catalysts were investigated. It was quite remarkable that after in situ catalytic conversion the amount of light phenols and hydrocarbons increased significantly while that of heavy phenols decreased a lot. Besides, the yield of cyclopentenones with relatively low oxygen content generally increased. It also indicated that as the Si/Al ratios of HZSM-5 increased, the amount of hydrocarbons and light phenols was found to drop greatly. The amount of carbon deposits was found to be around 8.5% with the exception of HZSM-5 with the Si/Al ratio of 300,which is much lower. Moreover, the carbon deposits yield dropped gradually with increasing Si/Al ratios of HZSM-5.Calcination of spent catalysts at 600 °C helped to restore the catalytic activity to a large extent despite a relatively lower efficiency of deoxygenation. Results indicated that HZSM-5 with relatively high acidity displayed great catalytic performance.

Pyrolysis of Rice Husk in a Fluidized Bed Reactor:Evaluate the Characteristics of Fractional Bio-Oil and Particulate Emission of Carbonaceous Aerosol(CA)

Bio-oil production via pyrolysis is one of promising technologies for renewable energy production from bio-wastes.However,the complicated biooil is still a challenge for high-valued application and during biomass pyrolysis,the emission of non-cleaned aerosol,the potential emission,namely carbonaceous aerosol(CA)increased the difficulty of the commercial promotion.In this study,Rice husk pyrolysis was performed in a semi-continuous fluidized bed reactor coupled with fractional condensers.The effects of pyrolysis and condensation temperature on the properties of bio-oil and emission of CAwere investigated systemically.Results indicated that the in-situ separation of vapors was accomplished via condensers of different temperatures(85℃and−10℃).The bio-oil with different physiochemical properties were obtained in the high content of phenols and lower acids of BO1 and high content of acids and better liquidity.The size distribution of CA was found primarily classified as sub-micrometer grade particles,which have a diameter of less than 1.1μm.In particular,CA existed in three representative forms:bead,granular aggregate,and liquidoid.The results of light absorption of total organic carbon(TOC)and non-volatile organic carbon(NVOC)indicated that the absorption per mass increased in the single temperature with the decrement of wavelength and it improved as the pyrolysis temperature increased at the specified wavelength.The absorption per mass was to maximum value(3.7 m^(2)/g)at 360 nm wavelength and 600℃.TOC demonstrated a strong light absorption and a wide spectral range dependence(AAE:5.08-10.05)which enhanced the light absorption in the ultra-violet and low-visible regions.

Liquid phase equilibrium of phenol extraction from bio-oil produced by biomass pyrolysis using thermodynamic models

Utilization of biomass as a new and renewable energy source is being actively conducted by various parties. One of the technologies for utilizing or converting biomass as an energy source is pyrolysis, to convert biomass into a more valuable product which is bio-oil. Bio-oil is a condensed liquid from the vapor phase of biomass pyrolysis such as coconut shells and coffee shells. Biomass composition consisting of hemicellulose, cellulose, and lignin will oxidize to phenol which is the main content in bio-oil. The total phenolic compounds contained in bio-oil are 47.03%(coconut shell) and 45%(coffee shell). The content of phenol compounds in corrosive bio-oils still quite high, the use of this bio-oil directly will cause various difficulties in the combustion system due to high viscosity, low calorific value, corrosivity, and instability. Phenol compounds have some benefits as one of the compounds for floor cleaners and disinfectants which are contained in bio-oil.The correlation between experimental data and calculations shows that the UNIQUAC Functional-group Activity Coefficients(UNIFAC) equilibrium model can be used to predict the liquid–liquid equilibrium in the phenol extraction process of the coconut shell pyrolysis bio-oil. While the Non-Random Two Liquid(NRTL) equilibrium model can be used to predict liquid–liquid equilibrium in the extraction process of phenol from bio-oil pyrolysis of coffee shells.

Scalable Synthesis of LiF-rich 3D Architected Li Metal Anode via Direct Lithium-Fluoropolymer Pyrolysis to Enable Fast Li Cycling

Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.

Online upgrading of organic vapors from the fast pyrolysis of biomass

The online upgrading process that combined the fast pyrolysis of biomass and catalytic cracking of bio-oil was developed to produce a high quality liquid product from the biomass.The installation consisted of a fluidized bed reactor for pyrolysis and a packed bed reactor for upgrading.The proper pyrolysis processing conditions with a temperature of 500℃ and a flow rate of 4m3·h-1 were determined in advance.Under such conditions,the effects of temperature and weight hourly space velocity(WHSV) on both the liquid yields and the oil qualities of the online catalytic cracking process were investigated.The results showed that such a combined process had the superiority of increasing the liquid yield and improving the product quality over the separate processes.Furthermore,when the temperature was 500℃,with a WHSV of 3h-1,the liquid yield reached the maximum and the oxygenic compounds also decreased obviously.

Ceria on alumina support for catalytic pyrolysis of Pavlova sp. microalgae to high-quality bio-oils

In this work,we report for the first time the in-situ catalytic pyrolysis of Pavlova sp.microalgae,which has been performed in a fixed-bed reactor in presence of Ce/Al2O3-based catalysts.The effects of pyrolysis parameters,such as temperature and catalyst were studied on the products yield distribution and biooil composition,among others.Results showed that all catalysts increased the bio-oil yield with respect to the non-catalytic runs and reduced the O/C ratio from 0.69（Pavlova sp.）to 0.1–0.15,which is close to that of crude oil.In terms of bio-oil oxygen content,Mg Ce/Al2O3presented the best performance with a reduction of more than 30%,from 14.1 to 9.8 wt%,of the oxygen concentration in comparison with thermal pyrolysis.However,Ni Ce/Al2O3gave rise to the highest aliphatics/aromatics fractions.The elemental and gas analysis indicates that N was partially removed from the catalytic bio-oils in the gas phase in forms of NH3and HCN.

Bio-Oil Production from Biomass by Flash Pyrolysis in a Three-Stage Fluidized Bed Reactors System

A novel system of fast pyrolysis and vapour quenching was developed at pilot scale to obtain bio-oil from biomass. The system uses three-stage of interconnected fluidized bed reactors that continuously circulate silica sand from an internal pyrolysis reactor to a second external annular reactor for char burning, which generates most of the heat required by the pyrolysis reactor, and a third sand-preheating reactor that burns non-condensable pyrolysis gas. The hot vapours, after high temperature cleaning, are quenched in a flash cooling system. The process generates up to 62% of bio-oil, 25% of char and 13% of non-condensable gas. The heat requirements for the total system are provided by burning part of the char and non-condensable gases generated in the pyrolysis step and by preheating the fluidizing gas for the pyrolysis reactor.

The effect of hydrothermal pretreatment on the structure and fast pyrolysis behaviors of Sheng Li lignite

The structure and composition of coal determine its fast pyrolysis characteristics,and the study of the relationship between them can play an important role in the efficient and clean utilization of coal.So,in this work,hydrothermal pretreatment was used to artificially change the structure and composition of Sheng Li(SL)lignite,which was used to investigate the influence of structural changes on pyrolysis.The physicochemical structure and composition of samples were characterized by X-ray diffraction,specific surface area and porosity analyzer,solid-state 13C nuclear magnetic resonance,Fourier transform infrared spectroscopy,and elemental analyzer.Pyrolysis experiments were carried out in a powderparticle fluidized bed reactor,and the distribution and composition of the pyrolysis products were analyzed.The gasification activity of char was investigated by thermogravimetric analysis with a CO_(2) atmosphere.The results show that hydrothermal pretreatment(HTP)can destroy the cross-linking structure of SL lignite,and affect its aromaticity,pore structure,functional group,and carbon structure to change the distribution and composition of pyrolysis products of SL lignite,especially the composition of tar.Finally,the structure–activity relationship between the structure,composition,and pyrolysis characteristics of coal was comprehensively studied.

Conversion of Biomass to Hydrocarbon-rich Bio-oil via Microwave-assisted Catalytic Pyrolysis： A Review

The method for pyrolysis of biomass to manufacture hydrocarbon-rich fuel remains challenging in terms of conversion of multifunctional biomass with high oxygen content and low thermal stability into a high-quality compound, featuring high content of hydrocarbons, low oxygen content, few functional groups, and high thermal stability. This study offers a promising prospect to derive hydrocarbon-rich oil through microwave-assisted fast catalytic pyrolysis by improving the effective hydrogen to carbon ratio(H/Ceff) of the raw materials. The proposed technique can promote the production of high-quality bio-oil through the molecular sieve catalyzed reduction of oxygenated compounds and mutagenic polyaromatic hydrocarbons. This work aims to review and summarize the research progress on microwave copyrolysis and microwave catalytic copyrolysis to demonstrate their benefits on enhancement of bio-oils derived from the biomass. This review focuses on the potential of optimizing the H/Ceff ratio, the microwave absorbent, and the HZSM-5 catalyst during the microwave copyrolysis to produce the valuable liquid fuel. This paper also proposes future directions for the use of this technique to obtain high yields of bio-oils.

Physicochemical Properties of Pyrolysis Bio-Oil from Sugarcane Straw and Sugarcane in Natura

Under the renewable energy context, sugarcane biomass pyrolysis has been growing as a convenient route to produce bio-oil, which can be set into the chemical industry and refineries as building blocks or combustion fuel. In this work sugarcane straw was submitted to direct pyrolysis in a fluidized bed pilot plant at 500°C, in presence of air. Sugarcane in natura was also pyrolysed as a model for comparison, in order to determine the viability of processing different sources of raw biomass. The physicochemical characterization of the biomass precursors as well as of the bio-oils was also carried out, which points both biomass feedstocks as suitable for bio-oil production in terms of viscosity, surface tension, density and acidity. The bio-oil obtained from sugarcane in natura presented higher carbon and hydrogen content as well as lower oxygen content. On the other hand, the metal content is higher in the bio-oil obtained from sugarcane straw, in special the iron and potassium contents were 807 ppm and 123 ppm against 27 ppm and 1 ppm in the bio-oil from sugarcane in natura. Aliphatic and aromatic compounds as well as carbohydrates scaffolds were identified as the main components of the bio-oil. GC-MS analyses showed aromatic products from lignine fragmentation and free sugars and sugar derivatives.

High Quality Bio-Oil Obtained from Catalyzed Pyrolysis of Olive Mill Solid Wastes in a Bi-Functional Reactor

Olive Mill Solid Wastes (OMSW) released in nature without any treatment is a major environmental problem in the Mediterranean region. In this work, the catalyzed pyrolysis of OMSW has been investigated. A catalyst based on SBA-15 mesoporous silica doped with chromium ferrite nanoparticles was prepared by the double solvent technique (DS). The prepared catalyst was characterized by scanning electron microscopy (SEM), Wide and Small Angle X-ray Scattering (WAXS, SAXS), Energy Dispersive X-ray (EDX) and FT-IR spectroscopies. Reverse spinel chromium ferrite nanoparticles were located inside the SBA-15 pores as confirmed by SEM images. The obtained catalyst was tested for pyrolysis reactions of OMSW. Several parameters were studied to optimize the conditions of the pyrolysis reaction in order to increase the bio-oil conversion yield. The GC-MS results demonstrated that the quality of the obtained bio-oil was improved by decreasing the quantity of phenolic and oxygenated components as well as the size of the obtained molecules. The produced bio-oil from pyrolysis of OMSW is identical to that obtained from the pyrolysis of commercial cellulose under the same conditions. A 37% conversion yield of bio-oil was obtained for the best conditions.

Production of Bio-Oil from Pyrolysis of Olive Biomass with/without Catalyst

In this study olive biomass was pyrolysis in a 400 cm3 stainless steel reactor. It was externally heated by an electrical furnace in which the temperature is measured by a thermocouple inserted into the bed. The effect of the catalyst ratio to the biomass (5%, 10%, 15%, 20%, 30% and 40%) on the pyrolysis yield was investigated and compared with the uncatalyzed pyrolysis yield product. The bio-oil products yield from the pyrolysis process was found to increase as the catalyst ratio increased. The bio-oil yield from the olive oil-cake, which was 36.1% without the catalyst, reached the maximum value of 39.3% on using activated catalyst at 10% by weight. The gas products yield was found to increase upon using catalyst compared to the non-catalytic pyrolysis. The reduction in the bio-oil yield product was accompanied with a significant reduction in the oxygen content. The pyrolysis oil was examined using chromatographic analysis techniques. The chemical characterization showed that the bio-oil obtained from olive oil cake might be potentially valuable as a fuel and chemical feedstock.

Study on fluidized-bed pyrolysis of waste paper

A lab-scale fluidized bed is setup and pyrolysis experiments are carried out. When temperature ranges from 400 to 700 ℃, the yields of solid residue, bio-oil and syngas range from 36% to 18%, 19% to 30% and 9% to 42%, respectively, and the mass balance of pyrolysis ranges from 80% to 95%. At 400 to 700 ℃, the characteristics of bio-oil are similar and the heat value is about 10 MJ/kg. When the temperature is over 600℃, the yield of syngas increases approximately twice as much as that at 500 ℃. The yields of CO2 and CO increase from 70 to 230 L/kg and 50 to 106 L/kg, respectively, while the yield of syngas only increases about 5% when the temperature increases from 600 to 700 ℃. The results indicate that the pyrolysis mechanism of waste paper is similar from 400 to 700 ℃, while the yield of syngas can be affected by secondary pyrolysis of bio-oil.

Renewable p-Xylene Production by Co-catalytic Pyrolysis of Cellulose and Methanol

This work developed a one-step process for renewable p-xylene production by co-catalytic fast pyrolysis (co-CFP) of cellulose and methanol over the different metal oxides modified ZSM5 catalysts. It has been proven that La2O3-modified ZSM5(80) catalyst was an effective one for the production of biobased p-xylene. The selectivity and yield of p-xylene strongly depended on the acidity of the catalysts, reaction temperature, and methanol content. The highest p-xylene yield of 14.5 C-mol% with a p-xylene/xylenes ratio of 86.8% was obtained by the co-CFP of cellulose with 33wt% methanol over 20%La2O3-ZSM5(80) catalyst. The deactivation of the catalysts during the catalytic pyrolysis process was investigated in detail.The reaction pathway for the formation of p-xylene from cellulose was proposed based on the analysis of products and the characterization of catalysts.