Optimisation of bio-oil production by hydrothermal liquefaction of agro-industrial residues: Blackcurrant pomace (Ribes nigrum L.) as an example

This work reports bio-oil production by hydrothermal liquefaction of blackcurrant pomace (Ribes nigrum L.), a fruit residue obtained after berry pressing. The bio-oil has a higher heating value of 35.9 MJ kg⁻¹ and low ash content, which makes it suitable for energy applications. We report the influence of process parameters on yields and carbon distribution between products: temperature (563–608 K), holding time (0–240 min), mass fraction of dry biomass in the slurry (0.05–0.29), and initial pH (3.1–12.8) by adding sodium hydroxide (NaOH). Depending on the experiments, the bio-oil accounts for at least 24% mass fraction of the initial dry biomass, while char yields ranges from 24 to 40%. A temperature of 583 K enhances the bio-oil yield, up to 30%, while holding time does not have a significant influence on the results. Increasing biomass concentrations decreases bio-oil yields from 29% to 24%. Adding sodium hydroxide decreases the char yield from 35% at pH = 3.1 (without NaOH) to 24% at pH = 12.8. It also increases the bio-oil yield and carbon transfer to the aqueous phase. Thermogravimetric analysis shows that a 43% mass fraction of the bio-oil boils in the medium naphtha petroleum fraction range. The bio-oil is highly acidic and unsaturated, and its dynamic viscosity is high (1.7 Pa s at 298 K), underlining the need for further upgrading before any use for fuel applications.     

Comparison of pyrolysis and hydrothermal liquefaction of Chlamydomonas reinhardtii. Growth studies on the recovered hydrothermal aqueous phase

The production of bio-oil by pyrolysis with a high heating rate (500 K s⁻¹) and hydrothermal liquefaction (HTL) of Chlamydomonas reinhardtii was compared. HTL led to bio-oil yield decreasing from 67% mass fraction at 220 °C to 59% mass fraction at 310 °C whereas the bio-oil yield increased from 53% mass fraction at 400 °C to 60% mass fraction at 550 °C for pyrolysis. Energy ratios (energy produced in the form of bio-oil divided by the energy content of the initial microalgae) between 66% at 220 °C and 90% at 310 °C in HTL were obtained whereas it was in the range 73–83% at 400–550 °C for pyrolysis. The Higher Heating Value of the HTL bio-oil was increasing with the temperature while it was constant for pyrolysis. Microalgae cultivation in aqueous phase produced by HTL was also investigated and showed promising results.     

Production and detailed characterization of bio-oil from fast pyrolysis of palm kernel shell

Bio-oil has been produced from palm kernel shell in a fluidized bed reactor. The process conditions were optimized and the detailed characteristics of bio-oil were carried out. The higher feeding rate and higher gas flow rate attributed to higher bio-oil yield. The maximum mass fraction of biomass (57%) converted to bio-oil at 550 °C when 2 L min⁻¹ of gas and 10 g min⁻¹ of biomass were fed. The bio-oil produced up to 500 °C existed in two distinct phases, while it formed one homogeneous phase when it was produced above 500 °C. The higher heating value of bio-oil produced at 550 °C was found to be 23.48 MJ kg⁻¹. As GC–MS data shows, the area ratio of phenol is the maximum among the area ratio of identified compounds in 550 °C bio-oil. The UV–Fluorescence absorption, which is the indication of aromatic content, is also the highest in 550 °C bio-oil.     

Production of crude bio-oil via direct liquefaction of spent K-Cups

Spent K-Cups were liquefied into crude bio-oil in a water-ethanol co-solvent mixture and reaction conditions were optimized using response surface methodology (RSM) with a central composite design (CCD). The effects of three independent variables on the yield of crude bio-oil were examined, including the reaction temperature (varied from 255 °C to 350 °C), reaction time (varied from 0 min to 25 min) and solvent/feedstock mass ratio (varied from 2:1 to 12:1). The optimum reaction conditions identified were 276 °C, 3 min, and solvent/feedstock mass ratio of 11:1, giving a mass fraction yield of crude bio-oil of 60.0%. The overall carbon recovery at the optimum conditions was 93% in mass fraction. The effects of catalyst addition (NaOH and H₂SO₄) on the yield of crude bio-oil were also investigated under the optimized reaction conditions. The results revealed that the presence of NaOH promoted the decomposition of feedstock and significantly enhanced the bio-oil production and liquefaction efficiency, whereas the addition of H₂SO₄ resulted in a negative impact on the liquefaction process, decreasing the yield of crude bio-oil.     

Hydrogen production from bio-oil aqueous fraction with in situ carbon dioxide capture

This paper presents the results of the investigation on steam reforming bio-oil aqueous fraction coupled with in situ carbon dioxide capture for hydrogen production. Experiments were carried out in a bench-scale fixed-bed reactor with calcined dolomite as the sorbent. The effects of temperature and water to bio-oil ratio on hydrogen production are reported. In the presence of calcined dolomite, maximum hydrogen yield of 75% was obtained among without sorbent, with CaO and with calcined dolomite at 600 °C, whereas hydrogen content was 83%, a little lower than that of 85% when CaO was used. Hydrogen content varies little at different water to bio-oil ratios and hydrogen yield was the greatest at the water to bio-oil ratio of 1:1. After regeneration of the sorbent, hydrogen content was back to the initial level but the hydrogen yield dropped.     

Study of bio-oil and bio-char production from algae by slow pyrolysis

This study examined bio-oil and bio-char fuel produced from Spirulina Sp. by slow pyrolysis. A thermogravimetric analyser (TGA) was used to investigate the pyrolytic characteristics and essential components of algae. It was found that the temperature for the maximum degradation, 322 °C, is lower than that of other biomass. With our fixed-bed reactor, 125 g of dried Spirulina Sp. algae was fed under a nitrogen atmosphere until the temperature reached a set temperature between 450 and 600 °C. It was found that the suitable temperature to obtain bio-char and bio-oil were at approximately 500 and 550 °C respectively. The bio-oil components were identified by a gas chromatography/mass spectrometry (GC–MS). The saturated functional carbon of the bio-oil was in a range of heavy naphtha, kerosene and diesel oil. The energy consumption ratio (ECR) of bio-oil and bio-char was calculated, and the net energy output was positive. The ECR had an average value of 0.49.     

Sustainable hydrogen production from steam reforming of bio-oil model compound based on carbon deposition/elimination

Steam reforming of crude bio-oil or some heavy component present in bio-oil is a great challenge for sustainable hydrogen production due to the extensive coke formation and catalyst deactivation. Catalyst regeneration will be an unavoidable operation in this process. In this paper, m-cresol (a model compound derived from bio-oil) was steam reformed on commercial Ni-based catalyst. Two conventional carbon elimination methods for coked catalyst were applied and the results showed that sustainable hydrogen production can be obtained based on carbon deposition/elimination. The carbon deposition can be gasified easily under certain temperature. The activity of regenerated catalyst samples can be nearly recovered as the fresh ones. Under the reaction conditions of 850 °C and steam to carbon ratio 5:1, >66% hydrogen mole fraction, >81% hydrogen yield, and >97% carbon conversion can be achieved based on regenerated catalyst. Catalyst characterization indicated that the loss of active metal can be considered as the main reason for tiny activity drop. Ni redispersion and Fe contamination may be another two factors that influence catalyst activity.     

Potentiality of combined catalyst for high quality bio-oil production from catalytic pyrolysis of pinewood using an analytical Py-GC/MS and fixed bed reactor

The aim of this study was to investigate the potential of combined catalyst (ZSM-5 and CaO) for high quality bio-oil production from the catalytic pyrolysis of pinewood sawdust that was performed in Py-GC/MS and fixed bed reactor at 500 °C. In Py-GC/MS, the maximum yield of aromatic hydrocarbon was 36 wt% at biomass to combined catalyst ratio of 1:4 where the mass ratio of ZSM-5 to CaO in the combined catalyst was 4:1. An increasing trend of phenolic compounds was observed with an increasing amount of CaO, whereas the highest yield of phenolic compounds (31 wt%) was recorded at biomass to combined catalyst ratio of 1:4 (ZSM-5: CaO - 4:1). Large molecule compounds could be found to crack into small molecules over CaO and then undergo further reactions over zeolites. The water content, higher heating value, and acidity of bio-oil from the fixed bed reactor were 21%, 24.27 MJkg⁻¹, and 4.1, respectively, which indicates that the quality of obtained bio-oil meets the liquid biofuel standard ASTM D7544-12 for grade G biofuel. This research will provide a significant reference to produce a high-quality bio-oil from the catalytic pyrolysis of woody biomass over the combined catalyst at different mass ratios of biomass to catalyst.     

Comparative study on pyrolysis and catalytic pyrolysis upgrading of biomass model compounds: Thermochemical behaviors,kinetics, and aromatic hydrocarbon formation

In order to understand the pyrolysis mechanism, reaction kinetic and product properties of biomass and select suitable agricultural and forestry residues for the generation desired products, the pyrolysis and catalytic pyrolysis characteristics of three main components (hemicellulose, cellulose, and lignin) of biomass were investigated using a thermogravimetric analyzer (TGA) with a fixed-bed reactor. Fourier transform infrared spectroscopy (FTIR) and elemental analysis were used for further characterization. The results showed that: the thermal stability of hemicellulose was the worst, while that of cellulose was higher with a narrow range of pyrolysis temperatures. Lignin decomposed over a wider range of temperatures and generated a higher char yield. After catalytic pyrolysis over HZSM-5 catalyst, the conversion ratio increased. The ratio for the three components was in the following order: lignincellulose < biomass < xylan. The Starink method was introduced to analyze the thermal reaction kinetics, activation energy (Ea), and the pre-exponential factor (A). The addition of HZSM-5 improved the reactivity and decreased the activation energy in the following order: xylan (30.54%) > biomass(15.41%) > lignin (14.75%) > cellulose (6.73%). The pyrolysis of cellulose gave the highest yield of bio-oil rich in levoglucosan and other anhydrosugars with minimal coke formation. Xylan gave a high gas yield and moderate yield of bio-oil rich in furfural, while lignin gave the highest solid residue and produced the lowest yield of bio-oil that was rich in phenolic compounds. After catalytic pyrolysis, xylan gave the highest yield of monocyclic aromatic hydrocarbons, 76.40%, and showed selectivity for benzene and toluene. Cellulose showed higher selectivity for xylene and naphthalene; however, lignin showed enhanced for selectivity of C10 + polycyclic aromatic hydrocarbons. Thus, catalytic pyrolysis method can effectively improve the properties of bio-oil and bio-char.     

Understanding the pyrolysis behavior of agriculture,forest and aquatic biomass: Products distribution and characterization

Pyrolysis studies on agricultural (rice straw), forest (pine) and aquatic (Ulva lactuca) biomass were carried out in a fixed bed reactor at different temperature range of 300–550 °C. The product distributions and their characterization of products were compared among these biomasses. The maximum liquid product yield 29.4, 57.5 and 25.6 wt% obtained at 400, 500 and 400 °C respectively from rice straw (RS), pine (PN) and Ulva lactuca (UL) biomass. However, the higher conversion was observed in the case of pine wood biomass 77.0% at 550 °C. From the GC-MS analysis, it is observed that RS and PN bio-oil mostly composed of derivatives of phenolic compounds, while UL bio-oil composed of cyclopentenone derivatives compounds. The highest higher heating value (HHV) was found in pine bio-oil 34.8 MJ/kg. Also PN pyrolytic bio-oil had higher boiling point differences compounds. The bio-char analysis showed that the PN bio-char is a carbon rich and porous in nature as compared to the RS and UL bio-char.     

Effects of torrefaction on the physiochemical properties of oil palm empty fruit bunches,mesocarp fiber and kernel shell

In this work, the effects of torrefaction on the physiochemical properties of empty fruit bunches (EFB), palm mesocarp fiber (PMF) and palm kernel shell (PKS) are investigated. The change of properties of these biomass residues such as CHNS mass fraction, gross calorific value (GCV), mass and energy yields and surface structure when subjected to torrefaction process are studied. In this work, these materials with particle size in the range of 355–500 μm are torrefied under light torrefaction conditions (200, 220 and 240 °C) and severe torrefaction conditions (260, 280 and 300 °C). TGA is used to monitor the mass loss during torrefaction while tube furnace is used to produce significant amount of products for chemical analyses. In general, the study reveals torrefaction process of palm oil biomass can be divided into two main stages through the observation on the mass loss distribution. The first stage is the dehydration process at the temperature below than 105 °C where the mass loss is in the range of 3–5%. In the second stage, the decomposition reaction takes place at temperature of 200–300 °C. Furthermore, the study reveals that carbon mass fraction and gross calorific value (GCV) increase with the increase of torrefaction temperature but the O/C ratio, hydrogen and oxygen mass fractions decrease for all biomass. Among the biomass, torrefied PKS has the highest carbon mass fraction of 55.6% when torrefied at 300 °C while PMF has the highest GCV of 23.73 MJ kg⁻¹ when torrefied at the same temperature. Both EFB and PMF produce lower mass fraction than PKS when subjected to same torrefaction temperature. In terms of energy yield, PKS produces 86–92% yield when torrefied at light to severe torrefaction conditions, until 280 °C. However, both EFB and PMF only produce 70–78% yield at light torrefaction conditions, until 240 °C. Overall, the mass loss of 45–55% of these biomasses is observed when subjected to torrefaction process. Moreover, SEM images reveal that torrefaction has more severe impact on surface structure of EFB and PMF than that of PKS especially under severe torrefaction conditions. The study concludes that the torrefaction process of these biomass has to be optimized based on the type of the biomass in order to offset the mass loss of these materials through the process and increase the energy value of the solid product.     

Hydrogen production via catalytic steam reforming of the aqueous fraction of bio-oil using nickel-based coprecipitated catalysts

Hydrogen production was studied in the catalytic steam reforming of a synthetic and a real aqueous fraction of bio-oil. Ni/Al coprecipitated catalysts with varying nickel content (23, 28 and 33 relative atomic %) were prepared by an increasing pH technique and tested during 2 h under different experimental conditions in a small bench scale fixed bed setup. The 28% Ni catalyst yielded a more stable performance over time (steam-to-carbon molar ratio, S/C = 5.58) at 650 °C and a catalyst weight/organic flow rate (W/m_org) ratio of 1.7 g catalyst min/g organic. Using the synthetic aqueous fraction as feed, almost complete overall carbon conversion to gas and hydrogen yields close to equilibrium could be obtained with the 28% Ni catalyst throughout. Up to 63% of overall carbon conversion to gas and an overall hydrogen yield of 0.09 g/g organic could be achieved when using the real aqueous fraction of bio-oil, but the catalyst performance showed a decay with time after 20 min of reaction due to severe coke deposition. Increasing the W/m_org ratio up to 5 g catalyst min/g organic yielded a more stable catalyst performance throughout, but overall carbon conversion to gas did not surpass 83% and the overall hydrogen yield was only ca. 77% of the thermodynamic equilibrium. Increasing reaction temperatures (600–800 °C) up to 750 °C enhanced the overall carbon conversion to gas and the overall yield to hydrogen. However, at 800 °C the catalyst performance was slightly worse, as a result of an increase in thermal cracking reactions leading to an increased formation of carbon deposits.     

Analysis of coke precursor on catalyst and study on regeneration of catalyst in upgrading of bio-oil

Catalyst HZSM-5 was used in bio-oil catalytic cracking upgrading. The precursor of coke on the catalyst was analyzed by means of TGA, FTIR and C13 NMR. Precursors of coke deposited in the pore of the molecular sieve were mainly aromatic hydrocarbon with the boiling point range from 350 °C to 650 °C. Those on the outer surface of the pellet precursor were identified as saturated aliphatic hydrocarbons with the boiling point below 200 °C. The activity of HZSM-5 was studied after regeneration. In terms of yield of organic distillate and formation rate of coke, results showed that catalytic activity change moderately during the first three times of regeneration.     

Crystallization behavior-dependent electrocatalytic activity and stability of Ti/IrO2RuO2SiO2 anodes for oxygen evolution reaction

IrO₂RuO₂SiO₂ ternary oxide coatings were fabricated on Ti substrate using a sol-gel route. The impacts of calcination conditions (e.g., temperature and time) on the electrocatalytic activity and stability of the anodes were explored. It was found that the calcination temperature and time significantly impact the electrocatalytic properties of the anode for the oxygen evolution reaction (OER). This can result from the properties of the surface (e.g., defects, crystallinity and crystallite size) as well as the preferred orientation of the active components. The amount of the defects of the coatings decreases with the increase of the calcination temperature and time. Besides, the crystallinity and crystallite size increase with the increase of calcination temperature and time. The amorphous oxide coating can be observed from the sample calcined at 350 °C for 15 min, while this coating can be crystallized when the calcination time is 60 min. The coatings calcined in the temperature range between 350 and 450 °C show preferred (101) planes of IrO₂ and RuO₂ crystallites, whereas the coatings calcined at the temperatures higher than 450 °C show the (211) orientation. The increase of calcination time does not change the preferred orientation of IrO₂ and RuO₂. The calculated voltammetric charges suggest that the active surface area of the prepared coating is dominated by the “outer” active surface area over the entire calcination temperature and time ranges. Given the electrocatalytic activity and stability of all investigated anodes, the anode calcined at 450 °C for 15 min is considered the most suitable for applications.     

Selective catalytic fast pyrolysis of Jatropha curcas residue with metal oxide impregnated activated carbon for upgrading bio-oil

Jatropha curcas waste was subjected to catalytic pyrolysis at 873 K using an analytical pyrolysis–gas chromatography/mass spectrometry in order to investigate the relative effect of various metal oxide/activated carbon (M/AC) catalysts on upgrading bio-oil from fast pyrolysis vapors of Jatropha waste residue. A commercial AC support was impregnated with Ce, Pd, Ru or Ni salts and calcined at 523 K to yield the 5 wt.% M/AC catalysts, which were then evaluated for their catalytic deoxygenation ability and selectivity towards desirable compounds. Without a catalyst, the main vapor products were fatty acids of 60.74% (area of GC/MS chromatogram), while aromatic and aliphatic hydrocarbon compounds were presented at only 11.32%. Catalytic pyrolysis with the AC and the M/AC catalysts reduced the oxygen-containing (including carboxylic acids) products in the pyrolytic vapors from 73.68% (no catalyst) to 1.60–36.25%, with Ce/AC being the most effective catalyst. Increasing the Jatropha waste residue to catalyst (J/C) ratio to 1:10 increased the aromatic and aliphatic hydrocarbon yields in the order of Ce/AC > AC > Pd/AC > Ni/AC, with the highest total hydrocarbon proportion obtained being 86.57%. Thus, these catalysts were effective for deoxygenation of the pyrolysis vapors to form hydrocarbons, with Ce/AC, which promotes aromatics, Pd/AC and Ni/AC as promising catalysts. In addition, only a low yield (0.62–7.80%) of toxic polycyclic aromatic hydrocarbons was obtained in the catalytic fast pyrolysis (highest with AC), which is one advantage of applying these catalysts to the pyrolysis process. The overall performance of these catalysts was acceptable and they can be considered for upgrading bio-oil.     

Upgraded biofuel from residue biomass by Thermo-Catalytic Reforming and hydrodeoxygenation

Research is focused on the utilisation of waste or residue biomass for bioenergy conversion. A promising conversion technology for the production of liquid biofuels from residue biomass is a process called Thermo-Catalytic Reforming (TCR^®​) which is a combination of prior thermal treatment of the biomass at mild temperatures (intermediate pyrolysis) followed by a second catalytic treatment step at elevated temperatures (reforming). This article focuses on the conversion of TCR^® liquids from digestate as a feedstock for subsequent hydrocarbon production. The generated bio-oil showed a lower heating value of 34.0 MJ kg⁻¹ with an oxygen content of 7.0% and a water content of 2.2%. The bio-oil was hydrodeoxygenated using an industrial NiMo–Al₂O₃ catalyst at temperatures of 503 K–643 K and a pressure of 14 MPa. The hydrodeoxygenated bio-oil reached a lower heating value of 42.3 MJ kg⁻¹ with an oxygen content below 0.8 mg kg⁻¹ and water content of 30 ppm. Product yields and catalyst life give confidence that upgrading of the TCR^®​ bio-oil offers a suitable option to meet the high standards of common fuels.     

Catalysts of Ni/α-Al2O3 and Ni/La2O3-αAl2O3 for hydrogen production by steam reforming of bio-oil aqueous fraction with pyrolytic lignin retention

This paper reports on the steam reforming, in continuous regime, of the aqueous fraction of bio-oil obtained by flash pyrolysis of lignocellulosic biomass (sawdust). The reaction system is provided with two steps in series: i) thermal step at 200 °C, for the pyrolytic lignin retention, and ii) reforming in-line of the treated bio-oil in a fluidized bed reactor, in the range 600–800 °C, with space-time between 0.10 and 0.45 g_catalyst h (g_bio-oil)⁻¹. The benefits of incorporating La₂O₃ to the Ni/α-Al₂O₃ catalyst on the kinetic behavior (bio-oil conversion, yield and selectivity of hydrogen) and deactivation were determined. The significant role of temperature in gasifying coke precursors was also analyzed. Complete conversion of bio-oil is achieved with the Ni/La₂O₃-αAl₂O₃ catalyst, at 700 °C and space-time of 0.22 g_catalyst h (g_bio-oil)⁻¹. The catalyst deactivation is low and the hydrogen yield and selectivity achieved are 96% and 70%, respectively.     

Catalytic steam reforming of acetic acid in a fluidized bed reactor with oxygen addition

Catalytic steam reforming of bio-oil is a promising process for producing hydrogen in a sustainable environmentally friendly way that can improve the utilization of local resources (natural sources or wastes). However, there remain drawbacks such as coke formation that produce operational problems and deactivation of the catalysts. Coprecipitated Ni/Al catalysts are here used in a fluidized bed for reforming at 650 °C of acetic acid as a model compound of bio-oil–aqueous fraction. Different strategies are applied in order to study their effects on the catalytic steam reforming process: modification of the catalyst by increasing the calcination temperature or adding promoters such as calcium. The addition of small quantities of oxygen is also tested resulting in an optimum percentage to achieve a high carbon conversion process with less coke and without a hydrogen yield penalty production. The results for catalytic steam reforming are compared with other ones from literature.     

Catalytic performance of Ni-Pr supported on delaminated clay in the dry reforming of methane

Mineral clay modified with Al, polyvinyl alcohol (PVA) and microwaves was used as a support to obtain a Ni-Pr catalyst. This catalytic system was evaluated in the reforming of methane with CO₂. The experiments were carried out under drastic conditions for 300 min, with a 50/50 CH₄/CO₂ mixture, total flux of 80 mL min⁻¹, without dilution gas (WHSV = 96 Lg⁻¹h⁻¹) and without previous reduction. The effect of the calcination temperature of the materials was studied at 500 °C and 800 °C as well as the effect of Pr (evaluating nominal quantities of 0, 1, 3 and 5%). The calcination temperature of the solid influenced the formation of the NiO species which had an effect on the activity and formation of coke on the material. The Pr had a promoter effect on the activity of the catalysts increasing the conversions of the CH ₄ as well as the CO₂. The formation of coke for the catalysts calcined at 500 °C presented a correlation with the praseodymium content while for those catalysts calcined at 800 °C there was no formation of coke.     

The study of the performance of Ni supported on gadolinium doped ceria SOFC anode on the steam reforming of ethanol

The catalytic performance of Ni/CeGd SOFC anodes prepared by co-precipitation for steam reforming of ethanol at different reaction temperatures was evaluated. The Ni/CeGd SOFC anode calcined at 1073 K exhibited the highest activity and the lowest by-products formation rates during SR at 773 K. The TG and SEM analyses of the used catalysts showed that the deactivation observed for SR at 773 K was associated with the formation of carbon filaments. It was also observed that the increase of reaction temperature from 773 to 1073 K decreased coke formation, which was no longer detected at 1073 K. This result was attributed to the reverse of the Boudouard reaction and the promoting effect of the support on carbon gasification.