Properties Of Bio-oil Research Articles

Effects of pyrolysis parameters on physicochemical properties of biochar and bio-oil and application in asphalt.

Adoption of renewable energy sources such as biomass has been increasing worldwide. In this study, fast pyrolysis as an acceptable and viable method to get renewable bio-oil and biochar is used. Different temperatures and N2 flow velocities were used in the fast pyrolysis process to evaluate the pyrolysis yield of biochar and bio-oil. The waste wood and pig manure were utilized to prepare biochar and bio-oil. X-ray fluorescence, X-ray diffraction, high-pressure liquid chromatograph, Micro confocal laser Raman spectrometer, Fourier transform infrared spectrometer, and dynamic shear rheometer were used to measure the chemical compositions, structure, and pyrolysis yield of biochar and bio-oil. The obtained results indicate that pyrolysis temperature increases the purity of inorganic oxide in biochar and N2 flow velocity promotes the yield of carbon in biochar. The increase of N2 flow velocity would increase the acid property of bio-oil and damage the products yield of bio-oil. It was also observed that biochar could remarkably alter the fundamental performances of petroleum asphalt including penetration, softening point, ductility, viscosity, and complex modulus. The most important is that the upgraded bio-oil can be used to replace partly or fully the petroleum asphalt which is a promising biomass application.

Upgradation of Nostoc punctriforme under subcritical conditions into liquid hydrocarbons (bio-oil) via hydro-deoxygenation: Optimization and engine tests

In this present study, hydro-deoxygenation (HDO) process was performed to upgrade the liquefied bio-oil of Nostoc punctriforme biomass. The engine performance and emission properties of the enriched bio-oil and blends (with diesel) were evaluated. The HTL resulted in highest bio-oil yield of 47.5 wt% at a temperature of 300 °C at 60 min with calorific value of 32.5 MJ/kg. At 60 min and temperature of 300 °C with 1 wt% of heterogeneous catalyst the upgraded HDO-bio-oil yield reached 38.4 wt% with deoxygenation percentage of 70%. The properties of upgraded bio-oil are HHV of 44.74 MJ/kg, Kinematic viscosity of 6.23 mm2/s and density 923 kg/m3 respectively. The response surface methodology (RSM) was used for modeling and optimizing the upgraded bio-oil yield. The optimized RSM conditions for upgraded bio-oil yield (44.5 wt%) are temperature of 280 °C, catalyst load of 0.6 wt%, and time of 120 min. The physiochemical properties of upgraded bio-oil are in agreement with ASTM standards. Equal proportion of bio-oil to diesel (D50: B50) reduced the brake thermal efficiency to 6.66% with reduced NOx emission and slight increase in CO emission. This study highlights that microalga fuels are better renewable energy resource with reduced greenhouse gas emission.

Converting Biomass into Bio-Asphalt – A Review

The partial substitution of bio-binder for petroleum asphalt binder is possible in the pavement application. Biomass commonly employed renewable energy origin is normally a raw substance used for the production of bio-binder, which includes palm oil, microalgae, soybean oil, vegetable oil, engine oil residue, grape remains, swine waste and many others. This review addresses the diverse bio-oils produced from different biomasses, followed by the properties of bio-oils and performance of bio-asphalt. This review also emphasises on the hydrothermal processing of biomass and the parameters affecting the quality and quantity of the yield for the use in asphalt. Notably, hydrothermal processing is a crucial thermochemical converting procedure employed on biomass into materials or biofuel. Following the aimed products, such as bio-gas, bio-oil, or bio-carbon, the variables selected during the operation (pressure, temperature, and time) is very critical. A notable impact has been placed in assessing a wide range of biomass supplies for hydrothermal processing due to the suitability of the operation for any biomass category. Provided that the majority of the biomass supplies are highly moisturised, the hydrothermal operation is the most efficacious method of processing the supplies. On the other hand, the physical, and rheological properties of the biobinders or bio-asphalt were highlighted and discussed. Majority of the bio-oils were found to improve the low-temperature performance, but reduce the resistance against deformation at high temperature of the bio-asphalt. It was also suggested that further studies should emphasise on the interaction between the asphalt matrix and bio-oils added at the microscale.

Char Production from Cassava Rhizome Mixed Soil Improvement by Fast Pyrolysis in a Free-Fall Reactor

This research is to study the pyrolysis process of cassava rhizome (CR) in a free-fall reactor. The objective was to study the effect of mixed soil improvement on the properties of bio-oil and char products. The rhizome cassava mixed soil improvement was 200 g / hr. Mixing ratio of cassava rhizome and soil improvement is 50 to 50 by weight. The mixed soil improvement were granular pH11 plus soil conditioner (L11), volcanic rock (VR), TPI pelletized organic fertilizer (OF) and super dolomite (SD). Temperature pyrolysis was at 500 degrees Celsius. The results showed that bio-oil yield and gas yield decreased while char yields increased. For mixed soil improvement, made higher heating value in bio-oil increased, while the char properties of higher heating value decreases.

Bio-oil production from agricultural crop residues - a review

India generates approximately 500 million tons of agricultural crop residues per year. This crop residue (waste) can be converted into fuel by using thermo-chemical and bio-chemical conversion routes. Thermo-chemical conversion routes mainly include gasification, pyrolysis, and liquefaction. In recent years, the pyrolysis technology for the production of bio-oil is gaining attention globally, due to its simple and efficient conversion techniques. This paper provides the updated review of bio-oil production mainly from agricultural crop residues and focuses on the different bio-oil production techniques such as fast pyrolysis and hydrothermal liquefaction; the reactor used for bio-oil production, properties, and application of bio-oil. The bio-oil produced from agricultural residues has a heating value of between 17-21 MJ/kg, exactly half of the diesel fuel. The properties of bio-oil showed the potential ability to be used as fuel in many applications such as boiler, furnaces, and diesel engines.

Bio-oil production from agricultural crop residues - a review

India generates approximately 500 million tons of agricultural crop residues per year. This crop residue (waste) can be converted into fuel by using thermo-chemical and bio-chemical conversion routes. Thermo-chemical conversion routes mainly include gasification, pyrolysis, and liquefaction. In recent years, the pyrolysis technology for the production of bio-oil is gaining attention globally, due to its simple and efficient conversion techniques. This paper provides the updated review of bio-oil production mainly from agricultural crop residues and focuses on the different bio-oil production techniques such as fast pyrolysis and hydrothermal liquefaction; the reactor used for bio-oil production, properties, and application of bio-oil. The bio-oil produced from agricultural residues has a heating value of between 17-21 MJ/kg, exactly half of the diesel fuel. The properties of bio-oil showed the potential ability to be used as fuel in many applications such as boiler, furnaces, and diesel engines.

Experimental investigation on the production of bio-oil from maize straw at a pilot scale

The production of biofuel from agricultural crop residue via fast pyrolysis is becoming a popular option. It can help to build a robust renewable fuel market and ensure environmental sustainability. In this study, the widely available maize straw was used for the production of bio-oil in a fluidized bed reactor at a pilot scale. The effect of pyrolysis parameters such as temperature, biomass particle size, and carrier gas flow rate on the production of bio-oil, char, and syngas was investigated. The maximum bio-oil yield of 44.6 wt.% was achieved at a pyrolysis temperature of 500℃. The physicochemical properties of bio-oil were determined, and the heating value was found to be 18.5 MJ/kg. Furthermore, the chemical composition of maize straw bio-oil was analyzed by GC-MS and FTIR. The compounds such as phenol (22.83%), carboxylic acids (27.36%), ketone (19.14%) alcohols (2.09%), esters, furfural, hydrocarbon and aromatic compounds, etc. were identified in the bio-oil. The cost analysis of the developed system showed that the cost of production of bio-oil from maize straw was 0.47 US$/L and the calculated payback period was 1.47 year.

Effect of Storage Time on the Physicochemical Properties of Waste Fish Oils and Used Cooking Vegetable Oils

Waste fish oils (FOs) and used cooking vegetable oils (UCOs) are increasingly becoming alternative renewable fuels. However, different physicochemical aspects of these renewable fuels, including the effect of storage, are not well-known. In this work, the effect of the storage period on physicochemical properties of selected samples of FOs and UCOs was investigated. The bio-oils were stored at 4 °C for up to five years before each experimentation. The chemical properties were characterized using capillary gas chromatography with flame ionization detection (GC-FID) and high-performance size exclusion chromatography including an evaporative light scattering detector (HPSEC-ELSD). Water contents and acid numbers of the bio-oils were determined using the Karl Fischer (KF) titration and the ASTM D 664 methods. Furthermore, the average heating values and surface tension of the bio-oils were determined. According to the results obtained, for all bio-oil types, the concentrations of polymerized triglycerides, diglycerides, and fatty acids and monoglycerides had increased during the storage periods. The physical properties of the bio-oils also showed a small variation as a function of the storage period. The overall results observed indicate that the deterioration of the physicochemical properties of bio-oils can be controlled through storage in dark, dry, and cold conditions.

Development of bio oil and bio asphalt by hydrothermal liquefaction using lignocellulose

Abstract Bio asphalt is an organic polymer derived from biomass resources, which has the potential to partially or completely replace petroleum asphalt. This study used lignocellulose to prepare bio oil by hydrothermal liquefaction method. A mixed solvent of ethanol and ethylene glycol was introduced to increase the oil yield and decrease the reaction temperature. The oil yield reached the highest when solvent mixing ratio of 1:1, liquid-solid ratio of 6:1, catalyst dosage of 3%, and reaction temperature of 250 °C respectively. The bio oil and 50# asphalt were mixed in proportion sheared for 30 min (1000 rpm) under the condition of 135 °C to produce bio asphalt. The chemical structures and rheological properties of bio oil and bio asphalt were investigated and compared with petroleum asphalt. Fourier transform infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance analysis indicate that the bio oil expressed a lower H/C ratio, higher O content and more light components including liquid compounds comparing to the petroleum asphalt. The content of the polar group including O–H and C=O of bio oil was higher than that of petroleum asphalt. Gas Chromatography-Mass Spectrometry (GC-MS) was used to prove the presence of olefins and alcohols in bio oil. Thermogravimetric analysis showed that the bio oil expressed better thermal stability than that of petroleum asphalt, which expressed a potential of using as a pavement material. The dynamic shear rheometer (DSR) results showed that the complex shear modulus, G∗ decreased as the content of bio oil. The Glass transition temperature Tg indicated that the bio asphalt with 10% bio oil content showed similar performance with that of 70# asphalt.

Bio-based refinery intermediate production via hydrodeoxygenation of fast pyrolysis bio-oil

Pyrolysis bio-oil is unsuitable as transportation fuel due to its chemical composition and high oxygen (>30 wt%) and water (>20 wt%) content rendering the upgrading essential prior any downstream use. The current work investigates the upgrading of a flash pyrolysis bio-oil via mild hydrotreatment (HDT), targeting to a potential intermediate refinery feed. Various operating parameters of HDT were tested, including three temperatures (573, 603 and 633 K), two pressures (4 and 7 MPa) and two H2/bio-oil ratios (506 and 843 NL/L). According to the results, during HDT of bio-oil, massive plugging by coke formed in the reactor. The unsaturated oxygenates in bio-oil are regarded as the predominant coke precursors since they can interact with the catalytic surface. From all the examined conditions, it was found that the longest catalyst life, (5 days on stream), was achieved at 7 MPa pressure, 843 NL/L H2/bio-oil ratio and 603 K temperature. Furthermore, several properties of the initial bio-oil were improved, such as viscosity (156 → 4.9 cSt), carboxylic acids (78 → 0.2 mgKOH/g), density (1.024 → 0.9162 g/ml), and oxygen content (37 → 4 wt%). Conclusively, mild HDT constitutes a promising technological pathway for bio-oil upgrading towards a reliable intermediate refinery feed.

Synergistic Effects of Catalyst Mixtures on Biomass Catalytic Pyrolysis.

This paper studied the synergistic effects of catalyst mixtures on biomass catalytic pyrolysis in comparison with the single catalyst in a microwave reactor and a TGA. In general, positive synergistic effects were identified based on increased mass loss rate, reduced activation energy, and improved bio-oil quality compared to the case with a single catalyst at higher catalyst loads. 10KP/10Bento (a mixture of 10% K3PO4 and 10% bentonite) increased the mass loss rate by 85 and 45% at heating rates of 100 and 25°C/min, respectively, compared to switchgrass without catalyst. The activation energy for 10KP/10Bento and 10KP/10Clino (a mixture of 10% K3PO4 and 10% clinoptilolite) was slightly lower or similar to other catalysts at 30 wt.% load. The reduction in the activation energy by the catalyst mixture was higher at 100°C/min than 25°C/min due to the improved catalytic activity at higher heating rates. Synergistic effects are also reflected in the improved properties of bio-oil, as acids, aldehydes, and anhydrosugars were significantly decreased, whereas phenol and aromatic compounds were substantially increased. 30KP (30% K3PO4) and 10KP/10Bento increased the content of alkylated phenols by 341 and 207%, respectively, in comparison with switchgrass without catalyst. Finally, the use of catalyst mixtures improved the catalytic performance markedly, which shows the potential to reduce the production cost of bio-oil and biochar from microwave catalytic pyrolysis.

Tracking Elemental Composition through Hydrotreatment of an Upgraded Pyrolysis Oil Blended with a Light Gas Oil

The physical properties of crude bio-oils preclude their direct use as fuel. Specifically, their high oxygen content results in undesirable acidity and poor thermal stability. Therefore, the remova...

Effect of different pre-treatments and addition of plastic on the properties of bio-oil obtained by pyrolysis of greenhouse crop residue

The bio-oil properties and yields during pyrolysis at 400, 500 and 600 °C of the residues from the cultivation of the pepper in greenhouse (Capsicum annuum L.) were studied. Different solid samples were investigated: the biomass fraction of the residue, the water-washed biomass sample, the cobalt-loaded biomass sample and three mixtures made with the biomass and plastic fractions of the residue. Results showed that temperature of pyrolysis has a moderate impact on the products’ yields and bio-oil properties for all solid samples. In general, the highest bio-oil yield was achieved operating at 600 °C while the higher char yield was reached at 400 °C. The pH of all the bio-oil samples was low, specially bio-oil from the cobalt-loaded biomass sample. Density, viscosity, cetane number, average boiling temperature, flashpoint, elemental analysis and ash content of the samples were analyzed and compared.The highest higher heating value was achieved for bio-oil (4218.6 kcal/kg) obtained from pyrolysis of the cobalt-loaded biomass sample. Infrared spectra and chromatography analysis revealed the presence of numerous compounds. Acetic acid is the main acid component of the bio-oil samples obtained from the biomass, the water-washed biomass and the cobalt-loaded biomass, although there are some differences in relative area. Other compounds such as ketones, phenolic or furans were also found. In bio-oils obtained from biomass and plastic mixtures, in general there was a decrease in the content of oxygenated compounds and acidic compounds, favoring the presence of non-oxygenated compounds. This work shows the feasibility of the obtaining of bio-oil from the greenhouse crop residue at the temperature range between 400 and 600 °C.

An overview of recent development in bio-oil upgrading and separation techniques

Bio-oil produced from the fast pyrolysis/hydrothermal liquefaction is gaining popularity worldwide as the forerunner to replace fossil fuel. The bio-oil can be produced from agricultural waste, forest residue, and urban organic waste. It is also called pyrolysis oil, renewable fuel, and has the potential to be used as fuel in many applications. The application of bio-oil as transportation fuel helps to reduce the emission of greenhouse gases and to keep up the ecological balance. The bio-oil has the heating value of nearly half of the diesel fuel i.e. 16-19 MJ/kg; but, the inferior properties such as high water content, high viscosity, low pH, and poor stability hinder bio-oil application as a fuel. Thus, this paper provides a detailed review of bio-oil properties, its limitations and focuses on the recent development of different upgrading and separation techniques, used to date for the improvement of the bio-oil quality. Furthermore, the advantages and disadvantages of each upgrading method along with the application and environmental impact of bio-oil are also discussed in this article.

Effects of MgCl2 Solution Pretreatment at Room Temperature on the Pyrolytic Behavior of Pubescens and the Properties of Bio-oil Obtained

Pyrolytic behavior of pubescens samples pretreated by 0 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.% MgCl2 solution, and HCl solution (with same pH value as 5 wt.% MgCl2 solution, namely pH=5.11) at roo...

The effect of torrefaction pre-treatment on the pyrolysis of corn cobs

Production of green fuels and chemicals from non-edible corn cob residues presents an excellent opportunity to produce sustainable low carbon energy vectors as an alternative to fossil fuels. The objective of this study was to optimize the fuel physical and chemical properties of torrefied corn cobs bio-oil by investigating the relationship between feedstock pre-treatment (torrefaction) temperatures (240, 260, 280 and 300 ​°C), and subsequent pyrolysis temperatures (400, 450, 500 and 550 ​°C). This experimental methodology aimed to improve both yields and properties of bio-oils from corn cobs. Torrefaction was first carried out as a pre-treatment step using a custom-built torrefaction reactor followed by pyrolysis using a continuous fluidized bed reactor. Torrefaction was found to be a promising pre-treatment step because it had the effect of reducing the water content and viscosity within the bio-oil. Corn cobs grinding energy requirements could be reduced by 69% when torrefaction was applied from 240 ​°C to 260 ​°C. A maximum bio-oil yield of 51.7% was achieved when the optimal temperatures (torrefaction 260 ​°C and pyrolysis 450 ​°C) was applied. Overall, using torrefaction as a pre-treatment step before pyrolysis was shown to be a promising approach for improving some physiochemical properties of bio-oil for its application as a fuel.

Effects of mixture of CO2 /CH4 as pyrolysis atmosphere on pine wood pyrolysis products

The aim of the present work is to provide a preliminary support and research foundation for developing integrated technology of methane dry reforming and pine wood pyrolysis to produce high value chemicals and fuels. The chemical properties of bio-oil produced by pine wood pyrolysis under traditional N2, H2, CO2, CH4 atmospheres and mixtures of CH4 and CO2 were investigated. Experimental studies were conducted in a fixed bed reactor at a temperature of 500 °C. The results show that pine wood pyrolysis under mixtures of methane and CO2 can promote bio-oil production (0.98% increase) compared with traditional pyrolysis (under N2). GC-MS results show that the contents of phenols and sugars in bio-oil decreased, while the amount of alcohols, aldehydes, ketones, and furans increased. NMR spectroscopy provides additional support of the results. Results indicate that bio-oil can be used as a source of value-added chemicals. High proportions of CO were obtained in the gas products from pine wood pyrolysis under CH4 and mixtures of CH4 and CO2. Finally, a possible reaction pathway of pine wood pyrolysis under mixtures of methane and CO2 is proposed. Methane bi-reforming with CO2 and steam from pine wood pyrolysis could promote the production of high value oxygen-containing chemicals during pine wood pyrolysis under mixtures of CH4 and CO2.

Kinetics and mechanisms for catalytic pyrolysis of empty fruit bunch fibre and cellulose with oxides

Current study aimed to evaluate kinetic parameters and mechanisms for the thermal degradation of palm empty fruit bunch fibre (EFBF) in presence of calcium oxide (CaO), magnesium oxide (MgO), and zinc oxide (ZnO). These oxides have been proved to improve the bio-oil properties as a catalyst in pyrolysis. In order to achieve the aim, the amount of oxides (0, 5, and 10 wt%) and heating rates (10, 20, 30, and 40 °C/min) are manipulated in thermogravimetric analyses. In addition, cellulose, the most abundant component in EFBF was taken as another feed to understand the changes in kinetic mechanism due to the presence of other lignocellulosic components. The results showed that the incorporation of these oxides, the average activation energy of EFBF lowered in general, where the most significant decrement was observed for the addition of 10 wt% of MgO (274.5 to 194.8 kJ/mol). This reflected that the oxides pose catalytic activities on biomass pyrolysis. However, the oxides (CaO, MgO, and ZnO) would not affect the mechanisms other than catalysing the reactions. Mainly second order chemical reaction and three-dimensional diffusion are the most suitable mechanisms to describe the degradation of EFBF in presence of oxide catalysts. Whereas the cellulose degradation was controlled by 1.5 order chemical reaction and three-dimensional diffusion mechanisms.

Hydrodeoxygenation of crude bio-oil with various metal catalysts in a continuous-flow reactor and evaluation of emulsion properties of upgraded bio-oil with petroleum fuel

Abstract Crude bio-oil produced from fast pyrolysis of woody biomass was subjected to catalytic hydrodeoxygenation reaction with various metal catalysts (Ni/C, Ni/SBA-15, Ni/Al-SBA-15, NiMn/SBA-15, Pt/C) using for continuous-flow reaction system at 300 °C under H2 pressure. Gas, immiscible liquid phases (light oil and heavy oil), and char was obtained as the primary products. Heavy oil yield was in the range 27.9–42.3 wt%, while char production was 2.3–11.0 wt%, both less than the corresponding figures for batch processing. Hydrodeoxygenation enhanced the fuel properties of bio-oil, yielding higher HHV (32.8–38.0 MJ/kg) than bio-oil (15.7 MJ/kg) and heavy oil produced in a batch type reactor (24.4–34.5 MJ/kg). Additionally, Miscibility of crude bio-oil and upgraded heavy oils with gasoline and diesel were also evaluated with three emulsifiers (Span60, Brij58, or IGEPAL CO-520). Crude bio-oil was hardly emulsified, whereas upgraded heavy oil was well emulsified with Span60. Increasing Span60 concentration also enhance the miscibility of heavy oil and diesel. An emulsion of heavy oil and diesel was stable for 6 months, suggesting that the heavy oil produced might have potential use in blends with diesel.

A new insight into chemical reactions between biomass and alkaline additives during pyrolysis process

Understanding the chemical reactions during biomass and alkaline additives during pyrolysis process is critical to better utilization of biomass resource. In this study, the influence of seven alkaline additives (KOH, K2CO3, KHCO3, CH3COOK, NaOH, Ca(OH)2, and Mg(OH)2) on biomass pyrolysis was investigated in fixed-bed system, as well as the reaction mechanism through combining the evolution properties of biochar, bio-oil, gas products, and alkaline additives. Results showed that alkaline additives promoted the formation of biochar and gas products, while inhibited the generation of bio-oil. The content of phenols (reaching 80% for NaOH, mainly non‑methoxy phenols) and hydrocarbons (reaching 38% for Ca(OH)2, mainly aromatics) increased greatly at the cost of acetic acid and O-species. Carbon content of biochar decreased largely, while oxygen content increased greatly, and the main O-containing species were –OH, -O–CO and -COOH groups. The surface area of biochar also increased greatly (reaching 764 m2/g for KOH). During pyrolysis process, alkaline additives could react with high active O-containing species and carbon fragments to generate lots of vacancies, then some anions of alkaline additive quickly occupied these vacancies to form new O-containing groups in biochar. Alkaline additives also converted into more stable structure (K2CO3, Na2CO3, CaO, and MgO). The possible reaction pathway between biomass and alkaline additives was first proposed.