Effect of moisture content on oil extraction from spent coffee grounds

Spent coffee grounds (SCG) were used in this study for oil extraction. It was observed that oil extraction increased with water content up to 20 wt% for non-polar solvents and up to 40 wt% for polar solvents. At 80 wt% moisture, no oil was observed instead a black gel was formed. Oil extraction was observed to increase with time but it was concluded that increasing extraction time beyond 60 min had no significant benefit for both solvents (ethanol and toluene). The highest amount of oil extracted was observed when using ethanol at 40 wt% moisture and it was around 20%. The saponification values for oil extracted from SCG were observed to be between 175 and 180 but were lower than those obtained for soybean (193). The SCG oil was observed to contain the following fatty acids in this quantity order: palmitic> linoleic acid > stearic acid.     

Physicochemical and structural characterization of biochar derived from the pyrolysis of biosolids,cattle manure and spent coffee grounds

In the framework of circular economy, the need of new feedstock materials for the production of alternative new products is of high priority. Biowastes such as manure, sewage sludge (biosolids, BS) and food-waste are used as raw materials for the production of biochar. The present study aims at characterizing biochars produced from three distinct biowastes (i) manure from cattle waste (manure-derived biochar; MDB), (ii) biosolids (BS) from a conventional Urban Wastewater Treatment Plant (UWTP) (biosolids-derived biochar; BDB), and (iii) spent coffee grounds (SCG)-derived biochar (SCGDB). Samples were slowly pyrolyzed in a small-scale kiln with a capacity of 20–24 kg. The samples were heated under nitrogen atmosphere at approximately 6–7 °C min⁻¹ up to the desired temperature (550 °C) and held for 1.5h. The physicochemical characterization of biochars showed the production of alkaline materials with similarities and variations in their characteristics, which depend to the type of feedstock used. The surface area of the raw materials was considerably low (<0.1 m²/g) and increased after pyrolysis to 14.03 m²/g, 3.98 m²/g and 1.53 m²/g for MDB, BDB and SCGDB, respectively. The high %C content, the low H/C ratio and the FTIR adsorption peaks revealed high aromaticity, polymerization and carbonization of the biochars and the presence of several functional groups. These, are some of the biochar properties which could lead to different sorption mechanisms of organic and inorganic contaminants. Also, they presented good stability in soil, which enables to be used as soil amendment and C sequestration mechanism. Finally, the produced biochars showed promising properties for environmental applications.     

Hydrothermal catalytic liquefaction mechanisms of agal biomass to bio-oil

The liquefaction mechanisms of the algal biomass to bio-oil were investigated by using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy, respectively. It was found that NaOH was a satisfactory catalyst and contributed to helping the liquefaction of algal biomass. The bio-oil from algal biomass was composed of many compounds, including carbohydrates, alcohol, hydroxybenzene, carboxylic acid, alkene, ester, and others. The mechanism of hydrothermal catalytic liquefaction was discussed. It was found that, comparing with the husk bio-fuel, the algal bio-oil as a promising alternative fuel was more close to the traditional diesel fuel in physicochemical properties. The novel research outcomes contribute to improving the yield of bio-oil from microalgae, reducing the cost of the bio-oil and accelerating the commercial application of the algal bio-oil in the near future.     

污泥直接液化制取生物质油试验研究

采用热化学直接液化技术处理污泥,考察了试验过程中温度、催化剂和反应停留时间3个因素对反应的影响,成功获取生物质油,并对反应产物进行分析。结果表明,温度控制在250℃、采用催化剂N且停留70 min时,可获取较高生物质油产量,产油率达25.4%。同时,处理后固体残渣体积仅为原料污泥的10%,不含寄生虫、病毒等有害微生物。该处理方法为污泥资源化、减量化、无害化处理提供了一个新途径。     

Biofuel production from spent coffee grounds via lipase catalysis

Lipases namely Mucor miehei, Pseudomonas cepacia, Rhizopus delemar, Geotrichum candidum, Candida rugosa, Porcine pancreas-II, Pseudomonas fluorescence, and Candida antarctica lipase-B (Novozyme-435) were employed for biodiesel synthesis from spent coffee oil. Around 96% oil-to-biodiesel conversion was obtained using Novozyme-435 as a catalyst at 1:5 oil-to-methanol molar ratio and 40ºC. Total spent coffee grounds generated at the North-West University, Potchefstroom Campus (NWU PC) was estimated which could be used to produce 162 L of biodiesel. A waste valorization strategy was devised for converting organic wastes produced at the NWU PC to bioenergy.     

Hydrothermal liquefaction of biomass: A review of subcritical water technologies

This article reviews the hydrothermal liquefaction of biomass with the aim of describing the current status of the technology. Hydrothermal liquefaction is a medium-temperature, high-pressure thermochemical process, which produces a liquid product, often called bio-oil or bi-crude. During the hydrothermal liquefaction process, the macromolecules of the biomass are first hydrolyzed and/or degraded into smaller molecules. Many of the produced molecules are unstable and reactive and can recombine into larger ones. During this process, a substantial part of the oxygen in the biomass is removed by dehydration or decarboxylation. The chemical properties of bio-oil are highly dependent of the biomass substrate composition. Biomass constitutes of various components such as protein; carbohydrates, lignin and fat, and each of them produce distinct spectra of compounds during hydrothermal liquefaction. In spite of the potential for hydrothermal production of renewable fuels, only a few hydrothermal technologies have so far gone beyond lab- or bench-scale.     

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.     

Liquefaction of palm kernel shell in sub- and supercritical water for bio-oil production

The heavy palm oil industry in Malaysia has generated various oil palm biomass residues. These residues can be converted into liquids (bio-oil) for replacing fossil-based fuels and chemicals. Studies on the conversion of these residues to bio-oil via pyrolysis technology are widely available in the literature. However, thermochemical liquefaction of oil palm biomass for bio-oil production is rarely studied and reported. In this study, palm kernel shell (PKS) was hydrothermally liquefied under subcritical and supercritical conditions to produce bio-oil. Effects of reaction temperature, pressure and biomass-to-water ratio on the characteristics of bio-oil were investigated. The bio-oils were analyzed for their chemical compositions (by GC–MS and FT-IR) and higher heating values (HHV). It was found that phenolic compounds were the main constituents of bio-oils derived from PKS for all reaction conditions investigated. Based on the chemical composition of the bio-oil, a general reaction pathway of hydrothermal liquefaction of PKS was postulated. The HHV of the bio-oils ranged from 10.5 to 16.1 MJ/kg, which were comparable to the findings reported in the literature.     

Co-liquefaction of swine manure with waste vegetable oil for enhanced bio-oil production

Waste vegetable oil was co-liquefied with swine manure to determine the bio-oil potential in this study. The result shows that co-liquefaction of waste vegetable oil with swine manure can improve the bio-oil production and decarboxylation of waste vegetable oil. The weight ratio of swine manure to waste vegetable oil exerted a great effect on both the yield and quality of the bio-oil. The optimum weight ratio of swine manure to waste cooking oil was 1:3, where a maximum oil yield of 80% was obtained with higher calorific value up to 38 MJ/kg.     

Optimization study of sub/supercritical water liquefication of lignite: Fast liquefaction for high bio-oil yield

Sub/supercritical water liquefication (SCWL) is a water-based thermochemical technology as well as an environmentally friendly treatment by converting wet feedstock into bioenergy. In the present study, a systematic investigation of SCWL of lignite was carried out covering a temperature range between 320 and 440 °C when residence time increased from 5 min to 40 min. The highest bio-oil oil yield of 34.3% with solid residue of 52.7% was obtained at 440 °C for 5 min. Phenol derivatives, carboxylic acids, long chain hydrocarbons, ketones, and naphthalene were the main bio-oil composition through FTIR and GC-MS analysis. Gas yields and their exact compositions were also determined and CO₂ was the dominate gas product but the percentage of CH₄ became significant at severe SCWL conditions. A conclusion was drawn that fast liquefaction (e.g. 5 min) at relative higher temperature (e.g. 400 °C) which avoid excessive gasification and repolymerization reactions was an optimization strategy for high yield bio-oil production from SCWL of lignite.     

Biocrude production by catalytic hydrothermal liquefaction of wood chips using NiMo series catalysts

In this work, hydrothermal liquefaction of wood chips was studied for biocrude production using a mix of Ni–Mo nitrides and carbides. The catalytic materials were synthesized by a temperature-programmed reaction method at 800 °C under a hydrogen atmosphere with nickel loads from 0 to 20 wt%. Lignin contained in the lignocellulosic biomass was successfully release via Kraft process. Hydrothermal liquefaction was carried out in a batch reactor at 320 °C with an initial pressure of 1000 psi of H₂. According to characterization results, nanostructured catalysts with a mix of Ni₂Mo₃N/Mo₂C compo4unds were obtained. NiMo series catalysts composition varies with nickel loads. The catalytic activity shows a reduction in the amount of solid products and an increase in the production of gaseous products as a function of the increase Ni loadings on the catalyst. The most optimal production of biocrude was obtained with the NiMo-10 catalyst, since 81.43% of the total product corresponded to water soluble products (WPS) fraction and the oil fraction, while the solids fraction represented the 6.43% of the total product. Hydrothermal liquefaction catalytic processes were selective towards WSP fraction, improving biocrude quality and favoring biocrude conversion into advanced biofuels.     

稻草水热法液化的实验研究

以农业废物稻草为研究对象,利用非等温技术,考察了农业废物在亚临界水（温度350℃,压力约20MPa）及超临界水（温度380℃,压力约30MPa）中的液化行为,并对反应获得的固体残渣和生物油进行了分析。实验结果表明。固体残渣的结构遭到较严重的破坏,质地变得松散,有利于进行生物发酵。实验获得的生物油成分主要为酮类和酚类的衍生物,其能量密度比原料提高将近一倍,但是黏度较大,酸性较强。在超临界状态下,固体残渣得率较低,液化效率高,获得的生物油的组分相对简单,酸性较弱,故稻草在超临界水中的液化优于其在亚临界水中的液化。     

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.     

Hydrothermal liquefaction of macroalgae: Influence of zeolites based catalyst on products

Hydrothermal liquefaction (HTL) of Ulva prolifera macroalgae (UP) was carried out in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different weight percentage (10–20 wt%) at 260–300 °C for 15–45 min. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite, and Mordenite in the conversion of Ulva prolifera showed that is affected by properties of zeolites. Maximum bio-oil yield for non-catalytic liquefaction was 16.6 wt% at 280 °C for 15 min. The bio-oil yield increased to 29.3 wt% with ZSM-5 catalyst (15.0 wt%) at 280 °C. The chemical components and functional groups present in the bio-oils are identified by GC-MS, FT-IR, ¹H-NMR, and elemental analysis techniques. Higher heating value (HHV) of bio-oil (32.2–34.8 MJ/kg) obtained when catalyst was used compared to the non-catalytic reaction (21.2 MJ/kg). The higher de-oxygenation occurred in the case of ZSM-5 catalytic liquefaction reaction compared to the other catalyst such as Y-zeolite and mordenite. The maximum percentage of the aromatic proton was observed in bio-oil of ZSM-5 (29.7%) catalyzed reaction and minimum (1.4%) was observed in the non-catalyst reaction bio-oil. The use of zeolites catalyst during the liquefaction, the oxygen content in the bio-oil reduced to 17.7%. Aqueous phase analysis exposed that presence of valuables nutrients.     

Evaluating organic waste sources (spent coffee ground) as metal-free catalyst for hydrogen generation by the methanolysis of sodium borohydride

In this study, organic waste sources (spent coffee ground (SCG)) is used as metal-free catalyst in comparison with conventional noble-metal catalyst materials for hydrogen generation based on the methanolysis of sodium borohydride solution. Spent coffee ground (SCG) is used as a metal-free catalyst for the first time as treated with different chemicals. The aim is to synthesize the metal-free catalyst that can be used for the production of hydrogen, a renewable energy source. SCG, which was collected from coffee shops, was used for preparing the catalyst. To produce hydrogen by sodium borohydride (NaBH₄) methanolysis, SCG is pretreated with different chemical agents (H₃PO₄, KOH, ZnCl₂). According to the acid performances, the choice of phosphoric acid was evaluated at different mixing ratios (10%, 20%, 30%, 40%, 50%, 100%) (w/w), different temperatures (200, 300 and 400 °C) and burning times (30, 45, 60 and 90 min) for the optimization of SCG-catalyst. A detailed characterization of the samples were carried out with the aid of FTIR, SEM, XRD and BET analysis. In this study, the experiments were generally carried out effectively under ambient temperature conditions in10 ml methanol solution containing 0.025 g NaBH₄ and 0.1 g of the catalyst. The hydrogen obtained in the experimental studies was determined volumetrically by the gas measurement system. When evaluating the hydrogen volume, different NaBH₄ concentrations, catalyst amount and different temperature effects were investigated. The effect of the amount of NaBH₄ was investigated with 1%, 2.5%, 5%, and 7.5% ratio of NaBH₄ while the influence of the concentration of catalyst was carried-out at 0.05, 0.1, 0.15, and 0.25 g catalysts. Four different temperatures were tested (20, 30, 40, 50 and 60 °C) to explore the performance of the catalyst under different temperatures. The experiments by using SCG-catalyst treated with H₃PO₄ reveal that the best acid ratio was 100% H₃PO₄. The maximum hydrogen production rate with the use of SCG-catalyst for the methanolysis of NaBH₄ was found to be 8335.5 mL min⁻¹gcat⁻¹. Also, the activation energy was determined to be 9.81 kJ mol⁻¹. Moreover, it was discovered that there was no decline in the percentage of converted catalyst material.     

Catalytic supercritical water gasification of aqueous phase directly derived from microalgae hydrothermal liquefaction

Microalgae (N. chlorella) hydrothermal liquefaction (HTL) was conducted at 320 °C for 30 min to directly obtain original aqueous phase with a solvent-free separation method, and then the supercritical water gasification (SCWG) experiments of the aqueous phase were performed at 450 and 500 °C for 10 min with different catalysts (i.e., Pt-Pd/C, Ru/C, Pd/C, Na₂CO₃ and NaOH). The results show that increasing temperature from 450 to 500 °C could improve H₂ yield and TGE (total gasification efficiency), CGE (carbon gasification efficiency), HGE (hydrogen gasification efficiency), TOC (total organic carbon) removal efficiency and tar removal efficiency. The catalytic activity order in improving the H₂ yield was NaOH > Na₂CO₃ > None > Pd/C > Pt-Pd/C > Ru/C. Ru/C produced the highest CH₄ mole fraction, TGE, CGE, TOC removal efficiency and tar removal efficiency, while NaOH led to the highest H₂ mole fraction, H₂ yield and HGE at 500 °C. Increasing temperature and adding proper catalyst could remarkably improve the SCWG process above, but some N-containing compounds were difficult to be gasified. This information is valuable for guiding the treatment of the aqueous phase derived from microalgae HTL.     

High efficient production of hydrogen from crude bio-oil via an integrative process between gasification and current-enhanced catalytic steam reforming

High efficient production of hydrogen from the crude bio-oil was performed in the gasification-reforming dual beds. A recently developed electrochemical catalytic reforming method was applied in the downstream reforming bed using NiCuZnAl catalyst. Production of hydrogen from the crude bio-oil through both the single gasification and integrative gasification-reforming processes was investigated. The maximum hydrogen yield of 81.4% with carbon conversion of 87.6% was obtained through the integrative process. Hydrogen is a major product (∼73 vol%) together with by-products of CO₂ (∼26 vol%) as well as very low content of CO (<1%) and a trace amount of CH₄ through the integrative route. In particular, the deactivation of the catalyst was significantly depressed by using the integrative gasification-reforming method, comparing to the direct reforming of the crude bio-oil. The mechanism and evaluation for the downstream electrochemical catalytic reforming were also discussed. The integrative process with higher hydrogen yield and carbon conversion, potentially, would be a useful route to produce hydrogen from the crude bio-oil.     

Bio-oil production from hydrothermal liquefaction of waste Cyanophyta biomass: Influence of process variables and their interactions on the product distributions

Hydrothermal liquefaction (HTL) of waste Cyanophyta biomass at different temperatures (factor A, 260–420 °C), times (factor B, 5–75 min) and algae/water (a/w) ratios (factor C, 0.02–0.3) by single reaction condition and Response Surface Method (RSM) experiments was investigated. By single reaction condition runs, maximum total bio-oil yield (29.24%) was obtained at 350 °C, 60 min and 0.25 a/w ratio. Maximum bio-oil HHV of 40.04 MJ/kg and energy recovery of 51.09% was achieved at 350 °C, 30 min, 0.1 a/w ratio and 350 °C, 60 min, 0.25 a/w ratio, respectively. RSM results indicate that effect of AB interaction was significant on light bio-oil yield. Both AC and AB had more remarkable influence than BC on heavy bio-oil yield and aqueous total organic carbon (TOC) recovery whereas BC was noticeable on ammonia nitrogen (NH₃N) recovery in aqueous products. By model-based optimization of highest bio-oil yield, the highest bio-oil yield reached 31.79%, increasing by 8.72% after RSM optimization, and light and heavy bio-oil yield was 17.44% and 14.35%, respectively. Long-chain alkanes, alkenes, ketones, fatty acids, phenols, benzenes, amides, naphthalenes were the main components in light bio-oil. Some alcohols, phenols and aromatics were primarily found in heavy bio-oil. Solid residue after HTL consisted of numerous microparticles (～5 μm) observed by Scanning Electron Microscopy (SEM). Energy Dispersive Spectrometer (EDS) analysis shows these particles primarily contained C, O, Mg, P and microelements, derived from Cyanophyta cells.     

Kinetic modeling and optimization of biomass pyrolysis for bio-oil production

Thermo-kinetic models for biomass pyrolysis were simulated under both isothermal and non-isothermal conditions to predict the optimum parameters for bio-oil production. A comparative study for wood, sewage sludge, and newspaper print pyrolysis was conducted. The models were numerically solved by using the fourth order Runge–Kutta method in Matlab-7. It was also observed that newspaper print acquired least pyrolysis time to attain optimum bio-oil yield followed by wood and sewage sludge under the identical conditions of temperature and heating rate. Thus, at 10 K/min, the optimum pyrolysis time was 21.0, 23.8, and 42.6 min for newspaper print, wood, and sewage sludge, respectively, whereas the maximum bio-oil yield predicted was 68, 52, and 36%, respectively.     

In-situ hydrodeoxygenation of lignin via hydrothermal liquefaction with water splitting metals: Comparison between autocatalytic and non-autocatalytic processes

In this study, various water splitting metals (Mg, Al, Zn, and Fe) were investigated for lignin HDO-HTL. Their behaviors during autocatalyzed hydrogenation and interactions with Al–Ni alloy catalyst during non-autocatalyzed hydrogenation were studied. The relationships between Mg, Zn, and Fe with Al–Ni catalyst were synergistic in HTL for bio-oils generation, leading to higher bio-oil yields in non-autocatalytic process than in autocatalytic process and Al–Ni catalytic HDO process. In contrast, because the effect of γ-AlO(OH) was strengthened when Al was used, the coking phenomenon was induced, leading to an antagonistic effect towards bio-oil production. Additionally, although the production of hydrogen was the lowest when Fe was applied, the bio-oil yields reached the highest (44.53 wt% in non-autocatalytic process and 49.83 wt% in autocatalytic process, respectively) with the deoxygenation degrees of 8.41% in non-autocatalytic process and 9.75% in autocatalytic process. Accordingly, Fe exhibited significant potential in lignin in-situ HDO-HTL.