Effect of pyrolysis temperature on the composition of the oils obtained from sewage sludge

Sewage sludge was pyrolysed in a quartz reactor at 350, 450, 550 and 950 °C. The pyrolysis oils from the sewage sludge were characterized in detail by means of gas chromatography–mass spectrometry (GC–MS). Changes in the composition of the oils related to the process conditions were assessed by normalizing the areas of the peaks. It was demonstrated that, as the temperature of pyrolysis increased from 350 to 950 °C, the concentration of mono-aromatic hydrocarbons in the oils also increased. Conversely, phenol and its alkyl derivatives showed a strong decrease in their concentration as temperature rose. Polycyclic aromatic hydrocarbons (PAHs) with two to three rings passed through a maximum at a pyrolysis temperature of 450 °C. PAHs with 4–5 rings also presented a major increase as temperature increased up to 450 °C, the concentration at 950 °C being slightly higher than that at 450 °C. Quantification of the main compounds showed that sewage sludge pyrolysis oils contain significant quantities of potentially high-value hydrocarbons such as mono-aromatic hydrocarbons and phenolic compounds. The oils also contain substantial concentrations of PAHs, even at the lowest temperature of 350 °C. The pathway to PAH formation is believed to be via the Diels–Alder reaction and also via secondary reactions of oxygenated compounds such as phenols.     

Production of bio-fuels from cottonseed cake by catalytic pyrolysis under steam atmosphere

The purpose of this study is to evaluate the amounts of catalytic pyrolysis products of cottonseed cake in steam atmosphere and investigate the effects of both zeolite and steam on pyrolysis yields. The effect of steam was investigated by co-feeding steam at various velocities (0.6:1.3:2.7 cm s⁻¹) in the presence of zeolite (20 wt% of feed). Liquid pyrolysis products obtained at the most appropriate conditions were fractionated by column chromatography. Elemental analysis and FT-IR were applied on both of these liquid products and their sub-fractions. The H/C ratios obtained from elemental analysis were compared with the petroleum products. The aliphatic sub-fractions of the oils were then analysed by capillary column gas chromatography. Further structural analysis of pyrolysis oil was conducted using ¹H-NMR spectroscopy. The characterization has shown that the bio-oil obtained from catalytic and steam pyrolysis of cottonseed cake was more beneficial than those obtained from non-catalytic and catalytic works under static and nitrogen atmospheres.     

Comparison of biodiesel production from crude Jatropha oil and Krating oil by supercritical methanol transesterification

This work compared the production of biodiesel from two different non-edible oils with relatively high acid values (Jatropha oil and Krating oil). Using non-catalytic supercritical methanol transesterification, high methyl ester yield (85–90%) can be obtained in a very short time (5–10 min). However, the dependence of fatty acid methyl ester yield on reaction conditions (i.e., temperature and pressure) and the optimum conditions were different by the source of oils and were correlated to the amount of free fatty acids (FFAs) and unsaturated fatty acid content in oils. Krating oil, which has higher FFAs and unsaturated fatty acid content, gave higher fatty acid methyl ester yield of 90.4% at 260 °C, 16 MPa, and 10 min whereas biodiesel from Jatropha oil gave fatty acid methyl ester yield of 84.6% at 320 °C, 15 MPa and 5 min using the same molar ratio of methanol to oil 40:1. The product quality from crude Krating oil met the biodiesel standard. Pre-processing steps such as degumming or oil purification are not necessary.     

Hydrogen production by low-temperature reforming of organic compounds in bio-oil over a CNT-promoting Ni catalyst

Present study reports on high catalytic activity of CNTs-supported Ni catalyst (x% Ni-CNTs) synthesized by the homogeneous deposition–precipitation method, which was successfully applied for low-temperature reforming of organic compounds in bio-oil. The optimal Ni-loading content was about 15 wt%. The H₂ yield over the 15 wt% Ni-CNTs catalyst reached about 92.5% at 550 °C. The influences of the reforming temperature (T), the molar ratio of steam to carbon fed (S/C) and the current (I) passing through the catalyst, on the reforming process of the bio-oil over the Ni-CNTs' catalysts were investigated using the stream as the carrier gas in the reforming reactor. The features of the Ni-CNTs' catalysts with different loading contents of Ni were investigated via XRD, XPS, TEM, ICP/AES, H₂-TPD and the N₂ adsorption–desorption isotherms. From these analyses, it was found that the uniform and narrow distribution with smaller Ni particle size as well as higher Ni dispersion was realized for the CNTs-supported Ni catalyst, leading to excellent low-temperature reforming of oxygenated organic compounds in bio-oil.     

Renewable hydrogen generation by steam reforming of glycerol over zirconia promoted ceria supported catalyst

The study focuses on hydrogen production from steam reforming of glycerol over nickel based catalyst promoted by zirconia and supported over ceria. Catalyst was prepared by the wet-impregnation method and characterized by BET surface area analysis, X-ray diffraction technique and scanning electron microscopy (SEM) analysis. The performance of the catalyst was evaluated in terms of hydrogen yield, selectivity and glycerol conversion at 700 °C in a tubular fixed bed reactor. The effect of glycerol concentration in feed, space time (W/F_AO), temperature and time on stream (TOS) was analyzed for the catalyst Ni–ZrO₂/CeO₂ which showed the complete conversion of glycerol and high H₂ yield that corresponds to 3.95 mol of H₂ out of 7 mol. Thermodynamic analysis was also carried out using Aspen HYSYS for system having glycerol concentration 10 wt% and 20 wt% and experimental results were compared with thermodynamics. Kinetic study was carried out for the steam reforming of glycerol over Ni–ZrO₂/CeO₂ catalyst using the power law model. The values of activation energy and order of reaction were found to be 43.4 kJ/mol and 0.3 respectively.     

Hydrogen production for fuel cells by autothermal reforming of methane over sulfide nickel catalyst on a gamma alumina support

Experimental and modelling studies have been conducted on catalytic autothermal reforming (ATR) of methane for hydrogen production over a sulfide nickel catalyst on a gamma alumina support. The experiments are performed with different feedstock under thermally neutral conditions. The results show that the performance of the reformer is dependent on the molar air-to-fuel ratio (A/F), the molar water-to-fuel ratio (W/F) and the flowrate of the feedstock mixture. The optimum conditions for high methane conversion and high hydrogen yield are A/F = 3–3.5, W/F = 2–2.5 and a fuel flowrate below 120–250 l h⁻¹. Under these conditions, a methane conversion of 95–99% and a hydrogen yield of 39–41% on a dry basis can be achieved and 1 mole of methane can produce 1.8 moles of hydrogen at an equilibrium reactor temperature of not exceeding 850 °C.A two-dimensional reactor model is developed to simulate the conversion behaviour of the reactor for further study of the reforming process. The model includes all aspects of the major chemical kinetics and the heat and mass transfer phenomena in the reactor. The predicted results are successfully validated with experimental data.     

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.     

Year round test of a solar adsorption ice maker in Kunming,China

A solar adsorption ice maker with activated carbon–methanol adsorption pair was developed for a practical application. Its main features include utilization of a water cooled condenser and removing all valves in the refrigerant circuit except the one that is necessary for refrigerant charging. Year round performance tests of the solar ice maker were performed in Kunming, Yunnan Province, China. Test results show that the COP (coefficient of performance) of the solar ice maker is about 0.083–0.127, and its daily ice production varies within the range of 3.2–6.5 kg/m² under the climatic conditions of daily solar radiation on the surface of the adsorbent bed being about 15–23 MJ/m² and the daily average ambient temperature being within 7.7–21.1 °C. The suitable daily solar radiation under which the solar ice maker can run effectively in Kunming is above 16 MJ/m².     

Low temperature anaerobic digestion of mixtures of llama,cow and sheep manure for improved methane production

Biogas production in anaerobic digestion in farm-scale units is typically performed under mesophilic conditions when used for producing domestic fuel and stabilizing animal waste for the use of digested manure as a fertilizer. Previous studies on the digestion of llama and cow manure have shown the feasibility of producing biogas under altiplano conditions (low pressure and low temperature) and of llama manure as a promising feedstock. The present study concerns the utilization of various mixtures of feedstocks from the Bolivian altiplano under low temperature conditions (18–25 °C). Laboratory scale experiments were performed on the digestion of mixtures of llama, sheep and cow manure in a semi-continuous process using ten 2-L stainless steel digesters to determine the effects of organic loading rate (OLR) and the feed composition. The semi-continuous operation of mixture of llama–cow–sheep manure proved to be a reliable system, which could be operated with good stability. The results suggest that in a system digesting a mixture of llama-cow-sheep manure at low temperature (18–25 °C) the maximum OLR value is between 4 and 6 kg VS m³ d^?1. The methane yields obtained in the mixture experiments were in the range 0.07–0.14 m³ kg^?1 VS added, with a methane concentration in the gas of between 47 and 55%.     

Non-catalytic and catalytic pyrolysis of Ulva prolifera macroalgae for production of quality bio-oil

Pyrolysis of Ulva prolifera macroalgae (UM), an aquatic biomass, was carried out in a fixed-bed reactor in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different catalyst to biomass ratio. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite and Mordenite catalyst in the conversion of UM showed that is affected by properties of zeolites. Bio-oil yield was increased in the presence of Y-Zeolite while decreased with ZSM-5 and Mordenite catalyst. Maximum bio-oil yield for non-catalytic pyrolysis was (38.5 wt%) and with Y-Zeolite catalyst (41.3 wt%) was obtained at 400 °C respectively. All catalyst showed a higher gas yield. The higher gas yield might be attributed to that catalytic pyrolysis did the secondary cracking of pyrolytic volatiles and promoted the larger small molecules. The chemical components and functional groups present in the pyrolytic bio-oils are identified by GC–MS, FT-IR, ¹H-NMR and elemental analysis techniques. Phenol observed very less percentage in the case of non-catalytic pyrolysis bio-oil (9.9%), whereas catalytic pyrolysis bio-oil showed a higher percentage (16.1%). The higher amount of oxygen present in raw biomass reduced significantly when used catalyst due to the oxygen reacts with carbon and produce (CO and CO₂) and water.     

Hybrid sulfur flowsheets using PEM electrolysis and a bayonet decomposition reactor

A conceptual design is presented for a hybrid sulfur process for the production of hydrogen using a high-temperature nuclear heat source to split water. The process combines proton exchange membrane-based SO₂-depolarized electrolyzer technology being developed at Savannah River National Laboratory with silicon carbide bayonet decomposition reactor technology being developed at Sandia National Laboratories. Both are part of the US DOE Nuclear Hydrogen Initiative. The flowsheet otherwise uses only proven chemical process components. Electrolyzer product is concentrated from 50 wt% sulfuric acid to 75 wt% via recuperative vacuum distillation. Pinch analysis is used to predict the high-temperature heat requirement for sulfuric acid decomposition. An Aspen Plus? model of the flowsheet indicates 340.3 kJ high-temperature heat, 75.5 kJ low-temperature heat, 1.31 kJ low-pressure steam, and 120.9 kJ electric power are consumed per mole of H₂ product, giving an LHV efficiency of 35.3% (41.7% HHV efficiency) if electric power is available at a conversion efficiency of 45%.     

Production of FAME by palm oil transesterification via supercritical methanol technology

The present study employed non-catalytic supercritical methanol technology to produce biodiesel from palm oil. The research was carried out in a batch-type tube reactor and heated beyond supercritical temperature and pressure of methanol, which are at 239 °C and 8.1 MPa respectively. The effects of temperature, reaction time and molar ratio of methanol to palm oil on the yield of fatty acid methyl esters (FAME) or biodiesel were investigated. The results obtained showed that non-catalytic supercritical methanol technology only required a mere 20 min reaction time to produce more than 70% yield of FAME. Compared to conventional catalytic methods, which required at least 1 h reaction time to obtain similar yield, supercritical methanol technology has been shown to be superior in terms of time and energy consumption. Apart from the shorter reaction time, it was found that separation and purification of the products were simpler since no catalyst is involved in the process. Hence, formation of side products such as soap in catalytic reactions does not occur in the supercritical methanol method.     

Improved fuel properties of whole table olive stones via pyrolytic processing

This paper describes the thermochemical transformation of residual whole olive stones from the industrial production of pitted and stuffed table olives by using a rotary reactor. This experimental investigation describes the chemical, physical and fuel properties of the resulting solids and liquids obtained in the temperature range between 200 °C and 900 °C. Optimum torrefaction conditions, intended to maximize mass and energy yields, were obtained at 278 °C and resulted in a solid product with 68 wt% volatile matter, 29 wt% fixed carbon, 58 wt% elemental carbon, 0.55 O/C ratio, 23.4 MJ/kg of HHV, 11.25 GJ/m³ apparent energy density for an energy yield of 89%. The carbonized solids obtained at temperatures between 500 °C and 900 °C exhibited LHV and apparent energy density up to 57–66% higher than the original biomass. The carbonization process generates a condensable liquid that represents 50–53 wt% of the original biomass and contains between 57 and 61 wt% water and 39–43 wt% organic products. The carbon content (up to 25 wt%) and heating value (HHV and LHV up to 5.2 MJ/kg and 2.8 MJ/kg, respectively) of this liquid is limited. A model has been tested and a series of equations have been produced which allow us to predict the chemical and energy properties of the solid fraction derived from the torrefaction and carbonization process. This model has found linear correlations between the solid yield and elemental/proximate composition of the solids, and exponential correlations between solid and energy yields.     

Coal-gasification kinetics derived from pyrolysis in a fluidized-bed reactor

Coal pyrolysis and gasification reactions were carried out in a fluidized-bed reactor (0.1 m i.d. by 1.6 m height) over a temperature range from 1023 to 1173 K at atmospheric pressure. The overall gasification kinetics for the steam–char and oxygen–char reactions were determined in a thermobalance reactor. The compositions of the product gases from the coal-gasification reactions are 30–40% H₂, 23–28% CO, 27–35% CO₂ and 6–9% CH₄ with heating values of 2000–3750 kJ m⁻³. The heating value increases with increasing temperature and steam/coal ratio but decreases with increasing air/coal ratio. Our kinetic data derived from the two-phase theory on coal gasification in a thermobalance reactor and coal pyrolysis in a fluidized bed may be used to predict the product-gas compositions.     

Pyrolysis characteristics of RDF and HPDE blends with biomass

The main objective of this work was to study refuse-derived fuels (RDF) and high-density polyethylene (HDPE) upgrading by pyrolysis of blends of these materials with wood. The study considered three operational conditions: cracking temperature, heating rate, and different wt.% of RDF and HDPE. The results demonstrate that the cracking temperature of 500 °C and the faster heating rates increased the liquid yield for RDF blends. On the other hand, HDPE blends favor gas production at 550 °C and faster heating rates, which enhance the process operativity because polymeric materials generate waxes and are reduced beneath such conditions. Finally, produced gas LHV increases as RDF and HDPE were added. For example, the LHV of the produced gas only with wood at 550 °C and 20 °C/min was 10.34 MJ/m³ and with 25 wt% HDPE was 14.82 MJ/m³.     

Biodiesel production by esterification of palm fatty acid distillate

Production of fatty acid methyl ester (FAME) from palm fatty acid distillate (PFAD) having high free fatty acids (FFA) was investigated in this work. Batch esterifications of PFAD were carried out to study the influence of: including reaction temperatures of 70–100 °C, molar ratios of methanol to PFAD of 0.4:1–12:1, quantity of catalysts of 0–5.502% (wt of sulfuric acid/wt of PFAD) and reaction times of 15–240 min. The optimum condition for the continuous esterification process (CSTR) was molar ratio of methanol to PFAD at 8:1 with 1.834 wt% of H₂SO₄ at 70 °C under its own pressure with a retention time of 60 min. The amount of FFA was reduced from 93 wt% to less than 2 wt% at the end of the esterification process. The FAME was purified by neutralization with 3 M sodium hydroxide in water solution at a reaction temperature of 80 °C for 15 min followed by transesterification process with 0.396 M sodium hydroxide in methanol solution at a reaction temperature of 65 °C for 15 min. The final FAME product met with the Thai biodiesel quality standard, and ASTM D6751-02.     

Environmental aspects of ethanol derived from no-tilled corn grain: nonrenewable energy consumption and greenhouse gas emissions

Nonrenewable energy consumption and greenhouse gas (GHG) emissions associated with ethanol (a liquid fuel) derived from corn grain produced in selected counties in Illinois, Indiana, Iowa, Michigan, Minnesota, Ohio, and Wisconsin are presented. Corn is cultivated under no-tillage practice (without plowing). The system boundaries include corn production, ethanol production, and the end use of ethanol as a fuel in a midsize passenger car. The environmental burdens in multi-output biorefinery processes (e.g., corn dry milling and wet milling) are allocated to the ethanol product and its various coproducts by the system expansion allocation approach.The nonrenewable energy requirement for producing 1 kg of ethanol is approximately 13.4–21.5 MJ (based on lower heating value), depending on corn milling technologies employed. Thus, the net energy value of ethanol is positive; the energy consumed in ethanol production is less than the energy content of the ethanol (26.8 MJ kg⁻¹).In the GHG emissions analysis, nitrous oxide (N₂O) emissions from soil and soil organic carbon levels under corn cultivation in each county are estimated by the DAYCENT model. Carbon sequestration rates range from 377 to 681 kg C ha⁻¹ year⁻¹ and N₂O emissions from soil are 0.5–2.8 kg N ha⁻¹ year⁻¹ under no-till conditions. The GHG emissions assigned to 1 kg of ethanol are 260–922 g CO₂ eq. under no-tillage. Using ethanol (E85) fuel in a midsize passenger vehicle can reduce GHG emissions by 41–61% km⁻¹ driven, compared to gasoline-fueled vehicles. Using ethanol as a vehicle fuel, therefore, has the potential to reduce nonrenewable energy consumption and GHG emissions.     

Biodiesel production from palm oil via heterogeneous transesterification

This paper presents the study of the transesterification of palm oil via heterogeneous process using montmorillonite KSF as heterogeneous catalyst. This study was carried out using a design of experiment (DOE), specifically response surface methodology (RSM) based on four-variable central composite design (CCD) with α (alpha) = 2. The transesterification process variables were reaction temperature, x₁ (50–190 °C), reaction period, x₂ (60–300 min), methanol/oil ratio, x₃ (4–12 mol mol^?1) and amount of catalyst, x₄ (1–5 wt%). It was found that the yield of palm oil fatty acid methyl esters (FAME) could reach up to 79.6% using the following reaction conditions: reaction temperature of 190 °C, reaction period at 180 min, ratio of methanol/oil at 8:1 mol mol^?1 and amount of catalyst at 3%.     

Decomposition of hydrogen iodide in the S–I thermochemical cycle over Ni catalyst systems

The sulphur–iodine thermochemical cycle for hydrogen production has been investigated by ENEA (Agency of New Technologies, Energy and Environment, Italy) over the last 5 years, with a particular focus on chemical aspects. Regarding the hydrogen iodide decomposition, four γ-alumina-supported nickel catalysts were produced and characterized, and then tested in terms of catalytic activity and stability by means of a tubular quartz reactor. In particular, the relationship between catalytic activity and preparation procedure was investigated. From the experimental data acquired, it can be concluded that three of the four catalysts tested demonstrated high catalytic activity, since hydrogen iodide conversion was almost coincident with the theoretical equilibrium value. On the other hand, for all the catalysts, a gradual but considerable deactivation phenomenon was observed at 500 °C, while at a temperature higher than 650 °C the catalytic activity was recovered.     

Co-pyrolysis of petrochemical sludge and sawdust for syngas production by TG-MS and fixed bed reactor

The main objective of this work is to investigate the syngas production from petrochemical sludge (PS) and sawdust (SD) co-pyrolysis. In this study, the pyrolysis experiments of PS, SD and their blends were carried out in TG-MS analyzer and fixed bed reactor. The effects of pyrolysis temperature and interactions between PS and SD on gas evolution behavior, products distribution and gas compositions were investigated. The PS pyrolysis result showed high temperature favored the gas production and there was a distinct increase in gas yield when temperature exceeded 700 °C. The Fe₃O₄ in solid was reduced by carbon with the generation of CO and CO₂, leading to the increase of gas yield. During the co-pyrolysis process, significant interactions between PS and SD were observed. SD addition promoted the increase of gas yield, as well as the generation of H₂ and CO. In addition, the activation energy during co-pyrolysis process was reduced due to the interaction. The strongest accelerative effect on gas yield appeared at 60 wt% SD, under which the gas yield was 39.59 wt%, H₂+CO content was 61.34 vol%, LHV was 13.39 MJ/Nm³. It was concluded that SD addition was conductive to syngas production from PS pyrolysis.