Pyrolysis Bio-oil Research Articles

Mesoporous Silica Nanocatalyst-Based Pyrolysis of a By-Product of Paper Manufacturing, Black Liquor

The valorization of black liquor, a by-product produced in considerable quantities from the paper manufacturing processes, has demonstrated the effectiveness of thermal reconversion into pyrolysis gas, bio-oil, and bio-char, a sustainable approach placing the feedstock into a circular economy concept. The present study focused on developing disposal solutions through energy recovery via pyrolysis at 300 °C and 450 °C when lignite and nanomaterials (such as Cu-Zn-MCM-41, Ni-SBA-3, or Ni-SBA16) were used as catalysts. The results were compared to those of non-catalytic pyrolysis. The use of the Cu-Zn-MCM-41 catalyst proved to be efficient for pyrolysis gas production, reaching 55.22 vol% CH4. The increase in the calorific value of the pyrolysis gas was associated with the use of the Cu-Zn-MCM-41, showing a value of 42.23 MJ/m3 compared to that of the non-catalytic process, which yielded 39.56 MJ/m3. The bio-oil resulting from the pyrolysis with Cu-Zn-MCM-41 showed the highest energy value at 6457 kcal/kg compared to that obtained with the other two nanocatalysts, Ni-SBA-3 and Ni-SBA-16, as well as that of the raw material, which had a value of 3769 kcal/kg. The analysis of bio-char revealed no statistically significant differences when comparing the outcomes from using the various nanocatalysts, suggesting their minimal impact on the energy content.

Anti-IL-17 bioactivity-guided fractionation of a pine bio-oil: Chemical characterization and impact on HaCaT human keratinocytes gene expression

Psoriasis is a dermatological inflammatory disease treated for centuries with pyrolytic pine bio-oils (pine tars), although their chemical composition and mechanism of action are poorly investigated. This study focuses on the fractionation of a standardized pine pyrolysis bio-oil, its chemical characterization (GC–MS, UV fluorescence, ESI-MS, and NMR), and the analysis of the anti-IL17 activity of fractions on HaCaT keratinocytes. Furthermore, the impact of the fraction showing the highest anti-IL-17 activity on keratinocyte gene expression was determined. Pine bio-oil comprises molecules derived from cellulose, hemicellulose, and lignin thermochemical degradation reactions, such as hydroxyacetaldehyde, levoglucosan, acetic acid, and phenols. The aqueous fraction exhibited the most consistent anti-IL-17 activity. The functional analysis suggested that this fraction affected the expression of 29 genes associated with the negative regulation of the mitogen-activated protein kinase (MAPK) activity, a pathway known for its crucial role in the inflammatory immune response.

Catalytic hydrodeoxygenation of pyrolysis bio-oil to jet fuel: A review

Catalytic hydrodeoxygenation of pyrolysis bio-oil to jet fuel: A review

Insecticidal effects of the fast pyrolysis bio-oil against Spodoptera littoralis and Aphis gossypii insect pests

The detrimental effects of agricultural pesticides on human and environmental health necessitate the development of alternatives to conventional pesticides. In the laboratory, the cotton leafworm (Spodoptera littoralis) and aphid (Aphis gossypii) insects were used to evaluate the insecticidal activity of bio-oil derived from olive cake. The application of bio-oil by leaf dipping against S. littoralis demonstrated no mortality at a concentration of 1 % bio-oil. In contrast, the bio-oil showed better results against A. gossypii by slide dip method with LC50 = 1310.40 mg/l and LC90 = 3117.40 mg/l. The combined activity of bio-oil and the biopesticide Beauveria bassiana (bio-oil/B.b) was comparable, with LC50 = 1386.94 mg/L and LC90 = 3142.05 mg/L. The field application (two sprays) of bio-oil, bio-oil/B.b, and a commercial insecticide (alpha super) on aphids revealed a reduction of 52 %, 74.33 %, and 74.67 % in the first spray and 59.67 %, 63.33 %, and73.67 % in the second spray for, bio-oil, bio-oil/B.b, and super alpha respectively. The bio-oil and bio-oil/B.b had significantly less effect on the population densities of two predators (predator mite Amblyseius swirskii and aphid lion Chrysoperla carnea) than the insecticide used. Analyses of bio-oil by gaschromatography–mass spectrometry (GC–MS) identified 30 compounds possibly have pesticidal activity. The most abundant compounds are 9 octadecenoicacid methyl ester, hexadecanoic acid, methyl ester, 6 octadecenoic acid, methyl ester and Phenol, 2methoxy. The pyrolysis byproduct (bio-oil) of olive cake biomass contains bioactive compounds that can be used as biopesticide.

Hydrodeoxygenation of lignin bio-oil model compounds and surrogate mixtures over zeolite supported nickel catalysts

Bifunctional catalysts based on nickel supported on ZSM-5 and BETA zeolites were studied in the hydrodeoxygenation of lignin derived model compounds as well as in surrogate mixtures simulating the light fraction of lignin fast pyrolysis bio-oil. A screening of the hydrodeoxygenation reaction conditions (temperature, time, H2 pressure, catalyst amount) was carried out using the simplest phenolic compound, phenol. As in real lignin bio-oils more complex phenolic compounds are present, a series of relevant alkyl- and methoxy-substituted phenol and benzene (o- and m-cresol, catechol, anisole, guaiacol, syringol, creosol and 1,2,3-trimethoxybenzene) were also investigated as feedstocks. Furthermore, the effect of the different porous and acidic properties of the zeolitic supports was investigated in the hydrodeoxygenation of guaiacol. The conversion of the model phenolics and the yield of the respective (alkyl)cyclohexanes at relatively mild conditions (220 °C, 50 bar H2, 1 h) were in the range of 80–100% and 47–83%, respectively, being dependent mainly on the complexity/side-chain group of the phenolic/benzylic ring and on the balanced content of Brønsted acid sites of increased strength. Regarding the hydrodeoxygenation of the surrogate mixture (C7-C10 phenolics), 100% hydrodeoxygenation efficiency was achieved towards >60% yield of (alkyl)cyclohexanes (C6-C9 hydrocarbons). All hydrodeoxygenation tests were conducted in hexadecane as solvent/substrate in order to simulate model co-processing (i.e. bio-based phenolics with petroleum derived feedstocks) conditions. Reusability tests revealed the stability of the catalysts which showed partial (30%) deactivation after the third catalytic cycle.

Viscosity Reduction of Fast Pyrolysis Bio-Oil by Using CO2 as an Additive

Viscosity Reduction of Fast Pyrolysis Bio-Oil by Using CO₂ as an Additive

Catalytic upgrading of the heavy fraction of waste coffee grounds pyrolysis bio-oil using supercritical ethanol as a hydrogen source to produce marine biofuel

Biomass pyrolysis oil has the potential to serve as a sustainable fuel in the maritime sector, either through the production of marine biofuel or as fuel blends. However, the production of biofuels with high energy value and low oxygen content during the upgrading process calls for a more in-depth understanding. Herein, the heavy fraction of bio-oil was upgraded in supercritical ethanol in order to produce a biofuel which can be used as an alternative for heavy fuel oil (HFO). The impact of distinct operational factors such as temperature, holding time, and amount of catalyst was experimentally evaluated on the upgrading process. Using an MgNiMo/SAPO-11 catalyst, the supercritical ethanol upgrading of CG-BO heavy fraction at 325 °C and 4 h reaction time yielded a biofuel product with a 63.2 % yield, 0.07O/C ratio and high heating values over 39 MJ/kg. The prevailing fractions observed in the upgraded bio-oil primarily encompassed esters and hydrocarbons.

Catalytic bio-oil upgrading using Fe-Co/Al2O3 and co-processing with vacuum gas oil

The current study explores the hydrodeoxygenation (HDO) of pine sawdust derived pyrolysis bio-oil and co-processing of raw bio-oil with Vacuum Gas Oil (VGO) in a micro-activity testing (MAT) unit. The catalytic performance of mono- and bi-metallic catalysts were tested for bio-oil upgrading. Notably, FeCo (2:1)/Al2O3 catalysts exhibited superior HDO activity compared to their mono-metallic counterparts. Co-processing of raw bio-oil (2–10 wt%) with VGO led to a notable increase in gasoline yield of ∼48% with a 6 wt% blend. Maximum conversion was achieved with 8 wt% blend, further increasing the proportion, conversion decreased significantly affecting the product distribution.

Optimization of Bio Asphalt Derived from Pyrolysis Bio Oil for Bitumen Modification

Due to inadequate crude oil supply and a rising demand for petroleum asphalt in roadconstruction, the asphalt sector faces a continuing shortage. Continous research was conducted on renewable materials such as bio-oils derived via pyrolysis from local palm oil industries. Bio-oil is currently a viable option due to its renewability, environmental friendliness, and variety of sources. Despite numerous studies indicating that biooils enhance the properties of bitumen, the research on the effects of PKS biooil on bitumen properties is minimal and needed further investigations. The application of 2,4-diphenylmethane diisocyanate (MDI) in this study is established to enhance the properties of bio-oil modified bitumen. The objectives of this study are to analyse the relationship between the percentage andratio of PKS bio-oil and 2,4-diphenylmethane diisocyanate (MDI) of the modified bitumen, its physical and chemical effects and the optimization of bio-asphalt mixture after the 2,4diphenylmethane diisocyanate (MDI) has been blended with PKS bio-oil and bitumen. PKS bio-oil and MDI were applied into the bitumen as additive and replacement of bitumen at 3%, 5% and 7% with two different ratios; 1.0:0.6 and 1.0:1.0. The functional groups of the bitumen are identified using Fourier Transform Infrared (FTIR) analysis. The result generated from FTIR analysis showed that the modified bitumen samples were slightly different when compared to the conventional bitumen regarding the functional group. Response surface methodology (RSM)was implemented to determine the statistical analysis and optimum amount of PKS bio-oil and MDI content in the bitumen, through central composite design.

Effects of pyrolysis bio-oil derived from palm kernel shell on modified bitumen properties

Economical and environmental friendly materials that able to replace petroleum based binder has become an urgent demand in road industry. Bio oil from palm oil waste is relatively more economical and has the potential to used as bitumen replacement as bio asphalt. The performance of bio asphalt derived from different source and process to produce bio oils are varies. Hence, this study aims to investigate the effects of palm kernel shell bio-oil in terms of physical properties, the chemical functional group, and the morphology. The bitumen properties were evaluated by the conventional physical tests, Fourier Transform Infrared Spectroscopy, and Scanning Electron Microscopy. The palm kernel shell bio-oil was added into the bitumen by weight of bitumen at 0%, 2%, 3%, 5%, 10%, 15%, and 20% and blended using mechanical stirrer. From the conventional physical test, it was found that bio-oil modified bitumen increased in penetration and ductility with decreased softening point. This indicate that direct addition of bio oil soften the modified bitumen. The change of the functional group in FTIR is significantly influenced by the increasing content of bio-oil. The morphology of the modified bitumen showed inhomogenous surface with noticeable wrinkles as the bio oil content increase. Based on the physicochemical evaluation, 3% bio oil replacement passed all the physical tests requirement with less changes in FTIR result. Therefore, 3% bio oil content is proposed for further tests for direct inclusion of bio oil into bitumen for local road construction utilization.

Improving the analysis of phase-separated bio-fuel samples with slice-selective total correlation NMR spectroscopy.

Separated samples are a particular challenge for NMR experiments. The boundary is severely detrimental to high-resolution spectra and normal NMR experiments simply add the two spectra of the two layers together. Pyrolysis bio-oils represent an increasingly important alternative fuel resource yet readily separate, whether due to naturally high water content or due to blending, a common practice for producing a more viable fuel. Slice-selective NMR, where the NMR spectrum of only a thin slice of the total sample is acquired, is extended here and improved, with slice-selective two-dimensional correlation experiments used to resolve the distinct chemical spectra of the various components of the phase-separated blended fuel mixtures. Analysis of how the components of any blended biofuel samples partition between the two layers is an important step towards understanding the separation process and may provide insight into mitigating the problem.

Towards Electrobiofuels: Economics and Environmental Impacts

Our changing climate necessitates a transition to biomass-based hydrocarbon fuels to power aviation, shipping, and long-haul trucks that service essential supply chains to deliver food, textiles, and other consumer goods including electronic devices. To accomplish this transition, renewable energy systems are needed that efficiently deconstruct biomass and superimpose non-carbon emitting electrical energy with bioenergy to increase output energy in liquid fuels. Fast pyrolysis and electrocatalytic hydrogenation (py-ECH) is a technology sequence that first converts biomass into a liquid, known as bio-oil, which is then electrocatalytically hydrogenated to stabilize its properties. Products formed after py-ECH include linear and branched polyols, tetrahydrofurans, and alkyl cyclohexanols. Evidence of lignin oligomer cleavage has also been observed, as has the subsequent appearance of monomeric cyclohexanols. Building on these encouraging results, the commercialization potential of py-ECH was determined by economic analysis and life cycle assessment. These analyses co-locate ECH after pyrolysis at decentralized biomass upgrading depots, with the aim of stabilizing pyrolysis bio-oil for subsequent transport to centralized hydroprocessing refineries. The results of these analyses suggest that electrocatalytic hydrogenation is the keystone technology for coupling non-carbon emitting electrical energy with biomass carbon to generate a greater amount of liquid fuel than otherwise possible. A pathway to liquid fuel less than $3 per gallon of hydrocarbon equivalent fuel can be established, especially if renewable electricity is provided at low cost. Finally, “electrobiofuels” can be made with negative net carbon emissions with well-managed agriculture, biochar soil amendment, and when renewable electricity powers ECH.

Removal of Inorganic Impurities in the Fast Pyrolysis Bio-oil Using Sorbents at Ambient Temperature

Removal of Inorganic Impurities in the Fast Pyrolysis Bio-oil Using Sorbents at Ambient Temperature

Identifying the coking of bio-oil in pyrolysis: An in-situ EPR investigation

Serious coking from the bio-oil polymerisation is a bottle-neck challenge for bio-oil thermal upgrading. Probing the mechanism of bio-oil coking is the first step to achieve high carbon conversion efficiency. In this study, in-situ electron paramagnetic resonance (EPR) spectroscopy was used to characterise the stable free radical generation during bio-oil pyrolysis at 250–350 °C with reaction time of 2–10 min, which identify the coking process of bio-oil. The liquid and solid products were characterised using gas chromatography-mass spectrometer (GC–MS), ultraviolet fluorescence (UV-F) and Raman spectroscopy. The results indicate that the coking of bio-oil in pyrolysis can be divided into three stages of varied characteristics. The coke formation precedes with an initial induction period that lasts for 2–8 min and shortens with increasing pyrolysis temperature. In the period, light components polymerise into heavy ones, including polycyclic aromatics as the essential coke precursors. After the induction period, significant amounts of stable free radicals are generated with coke formation, and the content increases from 0.2 to 1.6–7.8 μmol/g bio-oil in the early stage of coking. Meanwhile, the coke precursors, polycyclic aromatics, are rapidly depleted. Afterwards, in the late stage, the nascent coke gradually condenses and the stable free radical content increases slowly.

Upgrading of fast pyrolysis bio-oils to renewable hydrocarbons using slurry- and fixed bed hydroprocessing

Liquefaction of lignocellulosic biomass through fast pyrolysis, to yield fast pyrolysis bio-oil (FPBO), is a technique that has been extensively researched in the quest for finding alternatives to fossil feedstocks to produce fuels, chemicals, etc. Properties such as high oxygen content, acidity, and poor storage stability greatly limit the direct use of this bio-oil. Furthermore, high coking tendencies make upgrading of the FPBO by hydrodeoxygenation in fixed-bed bed hydrotreaters challenging due to plugging and catalyst deactivation. This study investigates a novel two-step hydroprocessing concept; a continuous slurry-based process using a dispersed NiMo-catalyst, followed by a fixed bed process using a supported NiMo-catalyst. The oil product from the slurry-process, having a reduced oxygen content (15 wt%) compared to the FPBO and a comparatively low coking tendency (TGA residue of 1.4 wt%), was successfully processed in the downstream fixed bed process for 58 h without any noticeable decrease in catalyst activity, or increase in pressure drop. The overall process resulted in a 29 wt% yield of deoxygenated oil product (0.5 wt% oxygen) from FPBO with an overall carbon recovery of 68%.

Layer formation on quartz bed particles during fast pyrolysis of grass

Commercial fast pyrolysis technologies use bed materials, normally natural sand mainly consisting of quartz, acting as circulating heat carrier materials. Nowadays, the commercial conversion of biomass into fast pyrolysis bio-oil (FPBO) is still using ash-lean woody residues as a feedstock since the application of more abundant and possibly cheaper ash-rich agricultural biomass is currently at a significantly lower technology readiness level (TRL). To promote FPBO production from ash-rich biomass, the ash-related issues during the operation process need to be further studied. In the present investigation, the characteristics and formation process of layers formed on quartz bed particles, collected from a bench-scale fast pyrolysis unit based on the rotating cone technology, were studied. Two grass residues, representative of typical Si-K-rich agricultural biomass fuels, were used as feedstocks. Quartz bed particles at different sampling times from startup with fresh bed particles were collected. Scanning Electron Microscopy/Energy-Dispersive Spectroscopy (SEM/EDS) was employed to characterize the layer properties. Bed particle layers exhibited an uneven and discontinuous distribution on the quartz surface. This distribution over bed particles, as well as layer thickness, increased with the operational time. The dominating elements contained in layers were Si, K, Ca, and Cl (excluding O), which resembled that of individual bed ash particles found in the bed samples. In addition, the interpretation of the results was supported by thermodynamic equilibrium calculations. The findings suggest that the process of layer formation was governed by the direct adhesion of non-melted bed ash particles during the fast pyrolysis of grass.

A study on the production of low-viscosity bio-oil from rapeseed by magnetic field pyrolysis

In order to investigate the biomass pyrolysis mechanism of rapeseed under magnetic field for their conversion to bio-oil, a technical study was carried out for reducing the bio-oil viscosity to enhance its quality. Rapeseed were used as the raw material, and pyrolysis experiments were conducted at the final temperature of 500 ℃ under four different conditions: no magnetic field, three normal magnetic fields with different magnetic induction intensities (3000 GS, 6000 GS, and 9000 Gs), and a Halbach array magnetic field with 6000 GS. An analysis was conducted on the yield of pyrolysis products, as well as the physicochemical properties and composition of bio-oil. The results indicated that, compared to pyrolysis in the absence of magnetic field, the pyrolysis under magnetic field accelerated the heating process of rapeseeds and affected the pyrolysis reaction. Compared to the pyrolysis without magnetic field, the yield of pyrolysis gas increased from 19.09% to 20.23%, 20.83%, and 21.41% for the magnetic induction intensities of 3000, 6000 and 9000 Gs, respectively. Additionally, with the change in the magnetic induction intensities through values of 3000, 6000 and 9000 Gs, the viscosity of bio-oil decreased from 17.21 mPa·s to 13.99 mPa·s, 11.45 mPa·s, and 10.09 mPa·s, respectively. This suggests that the magnetic field significantly reduced the viscosity of bio-oil derived from rapeseeds, and slightly promoted the conversion of pyrolysis products into pyrolysis gas. When the volume of the magnet decreased by 53.69%, the proportion of pyrolysis bio-oil increased by 8.99%, while the viscosity of the oil decreased by 23.47%, indicating a significant optimization effect. Physicochemical analysis reveals that the moisture content of the pyrolysis oil as well as the hydrophilic groups in the oil obtained under magnetic field conditions increased, which is the main reason for the reduction in the viscosity of the oil. Combined with the in-depth mechanism analysis of magnetic field pyrolysis using simulations in the software package COMSOL, it is concluded that magnetic field pyrolysis enhances heat transfer through magnetoconvection and alters the pyrolysis reaction pathway by affecting the combinations of free radicals.

Evaluation of Bio-Oils in Terms of Fuel Properties

In response to the global climate challenge and the increasing demand for energy, exploring renewable energy alternatives has become crucial. Bio-oils derived from biomass pyrolysis are emerging as potential replacements for fossil fuel-based liquid fuels. This paper shares findings from the Institute of Energy and Fuel Processing Technology on the quality of crude biomass pyrolysis bio-oil samples. These findings highlight their potential as motor liquid fuels. The article details the results of tests on the physicochemical properties of four distinct bio-oil samples. Additionally, it presents preliminary test results on the hydrodeoxygenation of bio-oils in a batch reactor. The production of homogeneous, stable mixtures using other fuel additives, such as diesel oil, rapeseed methyl ester (RME), and butanol, is also discussed.

Pyrolysis polygeneration of the marine and terrestrial biomass and the chemical activation of bio-char as adsorbent to remove tetracycline hydrochloride from wastewater

Pyrolysis polygeneration is one of the promising approaches to convert biomass into bio-gas, bio-char, and bio-oil. In this work, the comparison of the properties of pyrolytic products from terrestrial biomass (poplar wood, PW) and marine biomass (microalgae, Chlorella vulgaris, CV) was carried out. Then, three types of activation agents (e.g., KOH, H3PO4, and ZnCl2) were used to improve the SSA and pore structure of bio-char for the removal of tetracycline hydrochloride (HTC) from wastewater. The yield of bio-char decreased with pyrolytic temperature increasing, while the yield of bio-gas increased. The yield of bio-oil reached the maximum value of 500 ºC. The yields of bio-gas and bio-char of CV were higher than that of PW at different temperatures, while the yield of bio-oil presented an opposite trend. Several nitrogenous chemicals were observed in pyrolytic bio-oil of CV due to thermal degradation of proteins. Among the three type of activation agents (H3PO4, KOH, and ZnCl2), KOH was the best activation agent to obtain activation carbon with highest SSA and pore volume. The CV-derived activated carbon by using KOH as activation agent presented highest specific surface area (1638.85 m2/g) and highest adsorption capacity of HTC (42.7 mg/g). Meanwhile, the CV-500-KOH still retained such high adsorption capacity of HTC (35.8 mg/g) after five cycles, suggesting that the N-doped bio-char possessed the excellent recyclability. In conclusion, compared to the PW-derived bio-char, CV-derived bio-char was a better precursor for production of activation carbon due to the higher N content in CV.

Upgrading Pyrolysis Bio-Oil through Esterification Process and Assessing the Performance and Emissions of Diesel-Biodiesel-Esterified Pyrolysis Bio-Oil Blends in Direct Injection Diesel Engines.

This research aimed to evaluate the performance and emissions of direct injection diesel engines using blends of diesel-biodiesel-esterified pyrolysis bio-oil (D-B-EPB). The pyrolysis process was employed to produce pyrolysis bio-oil (PBO) from solid biomass obtained from fresh palm fruits. Furthermore, a simple and effective esterification process was used to upgrade the PBO. The methyl ester (ME) purity of EPB production was studied to optimize three independent variables: methanol (14.8-65.2 wt %), sulfuric acid (1.6-18.4 wt %), and reaction time (16-84 min) using the response surface methodology. The actual experiment yielded a ME purity of 72.73 wt % under the recommended conditions of 40.3 wt % methanol, 13.0 wt % sulfuric acid, 50 min reaction time, 60 °C reaction temperature, and 300 rpm stirrer speed. Additionally, the stability and phase behaviors of D-B-EPB blends were analyzed by using a ternary phase diagram to determine the potential blending proportion. The results revealed that a fuel blend consisting of 30 wt % diesel, 60 wt % biodiesel, and 10 wt % EPB (D30B60EPB10) met the density and viscosity requirements of diesel standards. This D30B60EPB10 blend was subjected to performance and emission tests in diesel engines at various speeds ranging from 1100 to 2300 rpm and different engine loads of 25, 50, and 75%. In terms of performance analysis, the brake thermal efficiencies of biodiesel and D30B60EPB10 were 7.19 and 3.88% higher than that of diesel, respectively. However, the brake-specific fuel consumption of the D30B60EPB10 blend was 6.60% higher than that of diesel due to its higher density and viscosity and lower heating value compared with that of diesel. In the emission analysis, the D30B60EPB10 blend exhibited performance comparable to diesel while being more environmentally friendly, reducing carbon monoxide, carbon dioxide, nitrogen oxide, and smoke opacity by 8.73, 30.13, 37.55, and 59.75%, respectively. The results of this study suggest that the D-B-EPB blend has the potential to serve as a viable biofuel option, reducing the proportion of diesel in blended fuel and benefiting farmers and rural communities..