Upgrading of bio-oil from palm kernel shell by catalytic cracking in the presence of HZSM-5

Upgrading of bio-oil extracted from palm kernel shell (PKS) was performed using a lab-scale fixed-bed reactor with HZSM-5 as a catalyst. The catalytic cracking was carried out at optimized conditions: 0.3-MPa pressure, temperature of 500°C, and oil to catalyst ratio of 1:5. One of the challenges in upgrading bio-oil by catalytic cracking is deactivation of catalyst due to coke formation on catalyst surface. To overcome coke deposition, the upgrading process was carried out at 0.3-MPa pressure. Characterization of raw and upgraded bio-oil obtained through catalytic cracking was discussed in detail, indicating improvement in its physical properties. The distribution of products after cracking of bio-oil includes 58.89 wt% of organic liquid product, 15.63 wt% of aqueous fraction, 7.84 wt% of coke, and 17.64 wt% of gases. The degree of deoxygenation and calorific value of organic liquid product is 43.74% and 31.65 MJ/kg respectively. Organic liquid product obtained comprises 17.55% of hydrocarbons within the gasoline range. Hence, HZSM-5 proved its effectiveness for upgrading the bio-oil in a continuous mode.     

Preparation of jet engine range fuel from biomass pyrolysis oil through hydrogenation and its comparison with aviation kerosene

The Bio-oil was produced from the pyrolysis of agricultural wastes (Eucalyptus sawdust) and discarded soybean frying oil. The temperature of the pyrolysis system was initiated at 28°C and increased to 850°C. Atmospheric distillation of crude bio-oil was performed and a fraction at a temperature range 160–240°C (pyrolysis oil) was separated and subjected to GC-MS, ¹H-NMR, TGA and FTIR analysis to identify the different properties and compounds present in pyrolysis oil. It was noticed that there was an abundance of oxygen and nitrogen containing compounds as well as other reactive species in pyrolysis oil. To reduce the amount of these species, the pyrolysis oil was subjected to hydrogenation in the presence of NiMo as a catalyst. After hydrogenation, the atmospheric distillation of hydrogenated bio-oil was performed and another fraction at temperature range 160–240°C (hydrogenated bio-oil) was separated and analyzed by the same techniques. It was noticed that during hydrogenation, more than 60% oxygenated and other reactive species were converted into hydrocarbons. Hydrogenated bio-oil showed very similar physico-chemical properties such as distillation curve, density, viscosity, freezing point, flash point, the presence of hydrocarbons and enthalpy of combustion as aviation kerosene also known as QAV-1.     

TGA analysis of tobacco rob pyrolysis and release characteristics of noncondensable gas in a fixed-bed reactor

In this study, the size of tobacco rob (TR) particle was considered as a major factor in determining the mass loss in thermogravimetric analysis (TGA) and product yield and composition at different reactor temperatures in the fixed-bed reactor. The TGA results showed that the conversion rate increased and the activation energy (ranged from 53.29 to 58.25 kJ/mol) decreased with a decrease in particle size. The experiments demonstrated that fuel gas yield (from 0.76 to 0.82 Nm³/kg at 900 °C) increased with a decrease in particle size while char and tar yield decreased. Smaller particle sizes resulted in higher H₂ (25.68%) and CO (27.36%) contents. Minimizing the size of raw materials is an alternative method to improve the gas quality of TR pyrolysis. The increase of gas yield was attributed to the decomposition of char and tar vapor as temperature increased.     

The effect of pyrolysis atmosphere on bio-oil yields and structure

A food industry waste, almond shell, was pyrolyzed under three different environment static, nitrogen, and steam to produce bio-oil and its derivatives. The oil yield obtained at pyrolysis temperature of 600°C was 24.23% in a static atmosphere, whereas it increased to 27.25% and 33.05% in nitrogen and steam atmospheres, respectively. The bio-oil obtained under steam atmosphere is very efficient due to the production of high liquid and gas yields. Moreover, co-feeding steam during the pyrolysis altered the bio-oil structure by increasing the aliphatics and reducing the asphaltenes. Moreover, steam treatment also increases H/C and heating value of bio-oils. According to the obtained results, steam pyrolysis is an alternative option for future applications in refineries.     

Pyrolysis Investigation For Bio-Oil Production From Various Biomass Feedstocks In Thailand

This study investigated the bio-oil production from vacuum pyrolysis of potential biomass feedstocks in Thailand. Experiments were carried out on palm empty fruit bunch, rice straw, rice husk, eucalyptus wood, rubber wood (Hevea Brasiliensis), and Teng wood (Shorea Obtuse) in a lab-scale-fixed bed reactor. The results showed that the product distribution was strongly dependent on temperature and biomass properties. Maximum oil yields, i.e., 50–60 wt %, were reached at 450–550°C. Due to mild temperature, most of alkalis originally present in biomass concentrated in product char, and only traces were detected in oil. Two-third of energy in biomass was in the product oil.     

Experimental evaluation of the catalytic efficiency of calcium based natural and modified catalyst for biodiesel synthesis

Transesterification of a mixture of vegetable oils with methanol using metal oxide catalysts derived from snail shell (SS) for biodiesel production was investigated. The metal oxides obtained from calcined snail shells in the temperature range of 650°–950 °C and modified by loading different potassium salts were used as a catalyst in the process. The catalysts were characterized by FT-IR, XRD, SEM-EDS, XPS and TGA. Catalytic activities of developed catalysts were also tested by Hammet indicator method and ion exchange method. The best calcination conditions were observed at 850°C for 4 hours based on biodiesel yield. The KF loaded snail shell gave highest biodiesel yield of 98 ± 1% in a batch reactor with highest basicity (15.9 mmoles/g) and basic strength measured by Hammet method. The optimized reaction conditions were: reaction temperature 65°C, reaction time 3 hours, methanol to oil molar ratio 9:1 and catalyst concentration 3wt%. Leaching and reusability tests confirm the stability of the catalyst as it encounters only 3% of leaching and small changes in catalytic activity up to five runs in terms of biodiesel yield.     

Production of bio-oil from algal biomass and its upgradation to biodiesel using CaO-based heterogeneous catalysts

The present article deals with the production of bio-oil from algal biomass as well as the preparation and characterization of noble CaO-based heterogeneous catalyst for upgradation of bio-oil to biodiesel. The bio-oil has been extracted from algal biomass using hexane as solvent in soxhlet apparatus and upgraded to biodiesel by transesterification using noble CaO-based heterogeneous catalysts. Catalyst with TiO₂:CaO molar ratio of 0.25 and calcination temperature of 700°C has been found to be most suitable among all the catalysts developed. Characterization of the catalysts has been done by using X-ray diffraction (XRD), scanning electron microscope (SEM), and thermo-gravimetric analysis (TGA). The input--output model has been developed to correlate experimental and predicted value of biodiesel yield. Optimization of process parameters has been done using response surface methodology. Various properties and elemental composition of algal bio-oil and biodiesel have been determined and compared with biodiesel.     

Yield and quality of charcoals from olive mill residues and its stone and pulp fractions: An enhanced comparative study

Pyrolysis is a promising way to upgrade large amounts of residues from olive oil processing into charcoal. Pyrolysis of the stone and pulp fractions needed to be investigated before conclusions could be drawn. We subjected the olive stone fraction, the pulp fraction, and a mixture of the two to dynamic pyrolysis and isothermal pyrolysis at 360°C. We characterized the charcoals resulting from isothermal pyrolysis at 360°C for different durations in terms of the fixed-carbon content (FCC), carbon content (CC), and high heating value (HHV). We found that charcoal yield from the pulp was higher than that from the stones, which were 38.1% and 32.9%, respectively, after pyrolysis for 360 min. This seemingly unexpected result was due to the high contents of ash (6.22%) and extractives (13%) in the pulp, which remained completely and partially undecomposed, respectively, in the charcoals and are accounted for when calculating yields. However, charcoals obtained from the stones were of higher quality than charcoals from the pulp, with lower ash content and higher FCC, CC, and HHV. In particular, the FCC, CC, and HHV after pyrolysis for 360 min were 73.2%, 74.4%, and 30.2 MJ/kg for the stones and only 61.8%, 63.2%, and 25.9 MJ/kg for the pulp, respectively. Depending on the required quality of the final charcoal, our results help decide whether to pyrolyse the entire olive residues or only one of the two fractions, more likely the stones.     

Influence of pyrolysis temperature on production and nutrient properties of wastewater sludge biochar

The important challenge for effective management of wastewater sludge materials in an environmentally and economically acceptable way can be addressed through pyrolytic conversion of the sludge to biochar and agricultural applications of the biochar. The aim of this work is to investigate the influence of pyrolysis temperature on production of wastewater sludge biochar and evaluate the properties required for agronomic applications. Wastewater sludge collected from an urban wastewater treatment plant was pyrolysed in a laboratory scale reactor. It was found that by increasing the pyrolysis temperature (over the range from 300 °C to 700 °C) the yield of biochar decreased. Biochar produced at low temperature was acidic whereas at high temperature it was alkaline in nature. The concentration of nitrogen was found to decrease while micronutrients increased with increasing temperature. Concentrations of trace metals present in wastewater sludge varied with temperature and were found to primarily enriched in the biochar.     

Pyrolysis of cellulose under catalysis of SAPO-34, ZSM-5, and Y zeolite via the Py-GC/MS method

Bio-oil from pyrolysis of biomass is an important renewable source for liquid fuel and/or for chemicals. However, the application of bio-oil was severely restricted due to its high viscosity, acidity, and low heating value. Hence, it is necessary to upgrade the bio-oil for deoxygenation or for chemicals by catalytic reactions. In this paper, the catalytic behaviors of SAPO-34, ZSM-5, and Y zeolite on pyrolysis of cellulose were investigated via pyrolyzer combined with gas chromatography and mass spectrometer (Py-GC/MS) method in Py-mode. The results showed that ZSM-5 and Y zeolite could promote the conversions of oxygen-containing components to gases, water, aromatics, and phenols. Comparatively, more gas and water were generated under the catalysis of Y zeolite at lower temperatures, while at temperatures above 700°C, the effect of ZSM-5 became more distinct; aromatics were more generated under the catalysis of ZSM-5, while Y zeolite exerted a more distinct role in promoting the formation of phenols. The effect of SAPO-34 caused more water and furfural derivatives, less aromatics and phenols, and exerted a weak influence on gases.     

Co-pyrolysis of paper waste and mustard press cake in a semi-batch pyrolyzer—optimization and bio-oil characterization

Under the present research study, the co-pyrolysis of paper waste and mustard press cake was conducted in a 50 mm diameter and 640 mm long semi-batch pyrolyzer in the temperature range of 673 to 1173 K in nitrogen atmosphere and synergistic relationship between the pyrolysis of two feed stocks has been observed. The paper wastes were composed of local packing paper, newspaper-based food packets of grocery, and printing paper in the ratio of 6:3:1. During co-pyrolysis, response surface methodology (RSM) technique has been employed using Design Expert Version 7.0.0 to determine the collective effects of factors, namely, A: ratio of paper waste to mustard press cake and B: pyrolysis temperature, on the yield of bio-oil, energy yield, and oxygen content of bio-oil. Optimization has been done by using RSM to identify the individual sets of values of independent parameters corresponding to maximum bio-oil yield (A: 9.0:1, B: 874.75 K), energy yield (A: 8.80:1, B: 812 K), and minimum oxygen content of bio-oil (A: 2.75:1, B: 883.06 K). Bio-oil obtained at maximum energy yield condition has been characterized using the Gas chromatography–mass spectrometry (GC-MS) and Fourier transform infrared spectroscopy (FTIR) spectroscopic analyses. The array of compounds present in the bio-oil compounds has been compared with literature data available on pyro-oil obtained from similar feed stocks.     

Sorption-enhanced hydrogen production for pre-combustion CO2 capture: Thermodynamic analysis and experimental results

Hydrotalcite-based materials have been identified as suitable materials for high temperature (400 °C) adsorption of CO₂. In pre-combustion decarbonisation processes for natural gas based power cycles, it should be possible to use this material to improve conversions in the water-gas shift (WGS) and steam-reforming (SMR) reaction. The efficiencies for electricity production from natural gas have been calculated for some different system configurations, in which hydrotalcite-based material could be used. The calculated efficiency penalties ranged from 5.5 to 8.6 percentage points. The assumptions made in the system study have been tested on the laboratory scale. Hydrotalcite-based materials are found to be an excellent choice for use in the sorption-enhanced WGS reactor. The requirements for very low residual concentrations of CO₂ at 400 °C and large amounts of catalyst in the sorption-enhanced SMR reactor make its application less likely. Suggestions are made to how the SE-SMR could be improved.     

Hydrothermal liquefaction phase behavior of microalgae & model compounds in fused silica capillary reactor

A fused silica capillary reactor combined with a heating/cooling stage, a microscope and a digital camera were used to investigate phase behavior during the hydrothermal liquefaction of microalgae (Dunaliella tertiolecta) and model compounds, including soya protein and glycine, starch, glucose and xylose, stearic acid and palmitic acid. Bubbles were generated at 246°C and disappeared at 360°C upon heating when Dunaliella tertiolecta used as feedstocks. Moreover, liquid products were generated at 300°C upon heating and oily liquid products began to separate out at 250°C upon cooling. The phase behavior of soya protein was similar to that of the Dunaliella tertiolecta. Meanwhile, there only observed the bubbles generation during hydrothermal liquefaction of glycine. Heating the starch, glucose and xylose above 350°C generated black solids from carbonization. Stearic acid and palmitic acid only had the process of melting, dissolution, dispersion and precipitation.     

Renewable biofuel production from hydrocracking of soybean biodiesel with a commercial petroleum Ni-W catalyst

As a potential hydrocarbon production method, the hydrocracking of soybean biodiesel, using a commercial petroleum hydrocracking catalyst, was studied. Experiments were carried out in a 1,000 mL, high-pressure autoclave for 2–4 hr over the temperature range of 200–280°C under an initial hydrogen pressure of 10 MPa. Hydrocracking of soybean biodiesel produced n-paraffins in the C₈–C₁₇ boiling range, which includes both green gasoline and diesel. Both pressure and temperature play important roles in the transformation of soybean biodiesel. Hydrocarbons can be formed above 220°C with a liquid yield of 81.76%. The n-alkanes content of the liquid product reached 32.29% at 280°C, with 88.32% C₁₁–C₁₄ selectivity. In addition, hydrocracking results in many changes of catalyst such as physical properties, morphology, etc. For the used catalyst, the concentrations of Ni and C increased, and the pore channels were significantly reduced.     

Application of response surface methodology for the optimization of biodiesel production from yellow mustard (Sinapis alba L.) seed oil

In the present study, response surface methodology (RSM) involving central composite design (CCD) was applied to optimize the reaction parameters of biodiesel production from yellow mustard (Sinapis alba L.) seed oil during the single-step transesterification process. A total of 30 experiments were designed and performed to determine under the effects of variables on the biodiesel yield such as methanol to oil molar ratio (2:1–10:1), catalyst concentration (0.2–1.0 wt.% NaOH), reaction temperature (50–70°C), and reaction time (30–90 min). The second order polynomial model was used to predict the biodiesel yield and coefficient of determination (R²) was found to be at 0.9818. The optimum biodiesel yield was calculated as 96.695% from the model with the following reaction conditions: 7.41:1 of methanol to oil molar ratio, 0.63 wt. % NaOH of catalyst concentration, 61.84°C of reaction temperature, and 62.12 min of reaction time. It is seen that the regression model results were in agreement with the experimental data. The results showed that RSM is a suitable statistical technique for optimizing the reaction parameters in the transesterification process in order to maximize the biodiesel yield.     

Characterization of aromatic hydrocarbon formation from pyrolysis of polyethylene-polystyrene mixtures

Design and operating parameters, and cause and effect relationships among feedstocks and products in the pyrolysis of waste polymers are needed if this method of processing is to be used for energy recovery from waste plastics. The purpose of this study was to quantify the effect of various operating factors for the pyrolysis of common polymeric wastes. Experiments were performed using a conventional retort tube as a batch reactor. The operating factors considered were temperature and reaction time at constant heating rate. High density polyethylene (PE) and polystyrene (PS), the most common plastic waste in Korea, were used singly and in mixture.The pyrolysis time for maximum oil production from a PE-PS mixture was shorter than in the case of PE alone, showing an enhancement effect from the PS. The maximum gas production time from PE-PS mixtures was shorter than for PE alone at 500° C; above 600° C, this does not occur. Small aromatic compounds (which can be valuable) are produced at maximum with an 1:1 mixture of PE and PS at 600° C, showing the possibility of process control for the maximum recovery of desirable pyrolysis products. The maximum yield of toluene, xylene, styrene, and 1-propenyl benzene were 8.6, 8.9, 51.0 and 7.4 wt.% of feed for pyrolysis PS at 700° C, respectively. For naphthalene, it was at 700° C with 1:1 PE:PS (by wt.). The maximum recovery was 1.3 wt.%. Diels-Alder theory can explain the formation of aromatic compounds in the pyrolysis products. The yield of these secondary pyrolysis products can be controlled by reaction time, pyrolysis temperature and mixing ratio of plastic wastes in the pyrolysis feed.     

Pyrolysis of commingled waste textile fibers in a batch reactor: Analysis of the pyrolysis gases and solid product

The main object of this study was the investigation of the thermal recycling of commingled waste textile fibers, with the aim of the production of useful end products. Differential scanning calorimetry/Thermo gravimetric analysis (DSC/TGA) was applied to determine the thermal degradation characteristics of the commingled waste textile fibers and there are two peaks located at the temperature ranges of 299–360°C and 399–500°C. Commingled waste fiber was pyrolyzed in a nitrogen atmosphere in relation to three different temperatures (500, 600, and 700°C), heating rates (25 and 50°C min^?1), and retention times (15 and 30 min). The effect of the experimental conditions such as pyrolysis temperature, heating rates, and retention time on the formation of char and gas--liquid products was investigated and the product yields were determined from the rate of the weight loss. The highest conversion rate 82.9 wt.% liquid--gas product and 17.1 wt.% char product was achieved at 700°C. Pyrolysis gases were taken for every 7, 15, and 25 min and were analyzed for major components such as CO, CO₂, CH₄, and H₂ by gas chromatography. The pyrolysis char called as carbon black derived from the pyrolysis of commingled waste textile fibers was analyzed for a range of properties, including the elemental analysis, moisture content, ash content, calorific value, and trace metal analysis.     

Adsorption of Cu(II) ions from aqueous solutions on biochars prepared from agricultural by-products

In this study, the adsorption of Cu(II) from aqueous solutions by agricultural by-products, such as rice husks, olive pomace and orange waste, as well as compost, was evaluated. The aim was to obtain sorbent materials (biochars) through hydrothermal treatment (300?°C) and pyrolysis (300?°C and 600?°C). The effect of adsorbent dose, pH, contact time and initial Cu(II) concentration in batch-mode experiments was investigated. The optimum Cu(II) adsorption conditions was found to occur at 5-12?g/L adsorbent dose, initial pH 5-6, and reaction time 2-4?h. Furthermore, the adsorption kinetics were best described by the pseudo-second order model for all the tested materials, while the adsorption equilibrium best fitted by the linear and Freundlich isotherms. Comparing rice husks and olive pomace, the higher adsorption capacity resulted after pyrolysis at 300?°C. With respect to the orange waste and compost, the highest adsorption capacity was observed using biochars obtained after hydrothermal treatment and pyrolysis at 300?°C.     

Some Physical Properties of CdO Thin Films Used as Window Material in Photovoltaic Solar Cells

Abstract

CdO thin films which can be used in photovoltaic solar cells as window material were obtained on glass substrates at 250°C and 300°C substrate temperatures using Ultrasonic Spray Pyrolysis (USP) technique. The electrical, optical, structural, and surface properties of the films were investigated for two different substrate temperatures. After all investigations, it is concluded that, the CdO thin films can be used in photovoltaic solar cells as window materials and cell efficiencies can be increased using different growth parameters.     

ZrxMg1-xO supported cobalt catalysts for methane decomposition into COx-free hydrogen and carbon nanotubes

Zirconia-magnesia supported cobalt catalysts with various Zr/Mg atomic ratios were prepared and evaluated for non-oxidative catalytic decomposition of methane to produce CO_x-free hydrogen and carbon nanotube. The catalytic performance of the catalysts was performed in a continuous fixed bed flow reactor at 700°C under atmospheric pressure. The fresh and spent catalysts were characterized by XRD, TPR, BET, TEM, and Raman spectroscopy. The results showed that the change in Zr/Mg ratio of the mixed oxide support has a significant effect on the catalytic performance of the active Co metal. The catalyst 30%Co/Zr_0.8Mg_0.2 showed the highest activity and stability within the used series of catalysts with hydrogen yield reached up to 79%. Both Co/Mg_1.0 and Co/Zr_1.0 showed poor stability due to strong Co-Mg interaction and aggregation of Co species on Zr support, respectively. All catalysts produced mainly MWCNTs with different diameters depending on the Zr/Mg ratio. The outer diameter increased with increasing Zr content in the catalyst due to the enlargement of the particle size of cobalt as a result of aggregation.