Investigating the potential for energy,fuel, materials and chemicals production from corn residues (cobs and stalks) by non-catalytic and catalytic pyrolysis in two reactor configurations

The results of thermogravimetric analysis (TGA), non-catalytic and catalytic pyrolysis of corn cobs and corn stalks are reported in this paper. Pyrolysis took place in two different reactor configurations for both feedstocks: (1) fast pyrolysis in a captive sample reactor; and (2) non-catalytic slow pyrolysis and catalytic pyrolysis in a fixed-bed reactor. Experiments were carried out in atmospheric pressure at three temperatures: low temperature (360–380 °C), medium temperature (500–600 °C) and at high temperature (600–700 °C). The results of the experimental study were compared with data reported in the literature. Investigating the potential of corn residues for energy, fuel, materials and chemicals production according to their thermochemical treatment products yields and quality, it can be stated that: (a) corn stalks could be suitable raw material for energy production via gasification at high temperature, due to their medium low heating value (LHV) of pyrolysis gas (13–15 MJ/m³); (b) corn cob could be a good solid biofuel, due to the high LHV (24–26 MJ/kg) of the produced char; (c) additionally, corn cobs could be a good material for activated carbon production after being activated or gasified with steam, due to its high fixed carbon content(～74 wt%); (d) liquid was the major pyrolysis product from catalytic pyrolysis (about 40–44 wt% on biomass) for both feedstocks; further analysis of the organic phase of the liquid products were hydrocarbons and phenols, which make them interesting for chemicals production.     

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.     

Electrodeposited PtRu on cryogel carbon–Nafion supports for DMFC anodes

For a high catalytic activity of the anodes in DMFC at low noble metal content a fine dispersion of PtRu on carbon supports is required and to this purpose we prepared and investigated high specific surface area cryogel carbons of controlled mesoporosity. Two carbons CC1 and CC2 with pore-size distribution centered at 6 and 20 nm were obtained by sol–gel polycondensation of resorcinol and formaldehyde, followed by a freeze-drying procedure, a versatile and low-cost method to provide after pyrolysis carbons of controlled porosity. Electrodeposited PtRu on CC2-Nafion support with ca. 100 μg cm⁻² of Pt displayed a good catalytic activity for methanol oxidation of 85 mA mg⁻¹ of Pt after 600 s at 492 mV versus NHE and 60 °C in H₂SO₄ 0.1 M–CH₃OH 0.5 M when the Pt-to-C mass ratio was ca. 10%. The catalytic activity tests and XRD and SEM analyses demonstrated the stability of the prepared electrodes upon catalysis in the time scale of our measurements. Strategies to further increase the catalytic activity of the PtRu/cryogel carbon–Nafion electrodes for methanol oxidation are discussed.     

Catalytic pyrolysis of LDPE leads to valuable resource recovery and reduction of waste problems

Recycling of waste polymers has become a necessity because huge piles of those polymers represent a threat to the environment. Used polymers are also a source of energy and valuable chemicals.Used low density polyethylenes (LDPE) were catalytically pyrolysed in a home assembled batch reactor under atmospheric pressure. For maximum conversion into chemicals which could be used for feedstock recovery optimum conditions like temperature, catalyst weight and reaction time were optimized. A wide range of acidic and basic catalysts like silica, calcium carbide, alumina, magnesium oxide, zinc oxide and homogeneous mixture of silica and alumina were tried for this purpose.Though CaC₂ was better on the basis of reaction time, however the efficiency of conversion into liquid for SiO₂ was found to be maximum at optimum conditions. These two catalysts could be picked up as suitable catalysts for catalytic pyrolysis of polyethylene. The results of the column separation using different solvents indicate that the oxide containing catalyst could be best suited for selective conversion into polar and aromatic products while CaC₂ catalyst could be adopted for selective conversion into aliphatic products.The liquid product obtained from catalytic pyrolysis was also characterized by physical and chemical tests. Among the physical tests density, specific gravity, API gravity, viscosity, kinematic viscosity, aniline point, flash point, Watson characterization constant, freezing point, diesel index, refractive index, gross calorific value, Net calorific value and ASTM Distillation were determined according to IP and ASTM standard methods for fuel values. From the physical tests it was observed that the results for the liquid fractions are comparable with the standard results of physical tests for gasoline, kerosene and diesel fuel oil. From the Bromine water and KMnO₄ tests it was observed that liquid obtained is a mixture of olefin and aromatic hydrocarbons. This was further confirmed by Bromine number tests. The values of which lie in the range of 0.1–12.8 g/ml, which fall in the range for olefin mixture. Phenol and carbonyl contents were quantified using UV/Visible spectroscopy and the values lie in the range of 1–8920 μg/ml and 5–169 μg/ml for both phenols and carbonyls respectively. The components of different hydrocarbons in the oil mixture were separated by using column chromatography and fractional distillation followed by characterization with FT-IR spectroscopy.The interpretation of FT-IR spectra shows that catalytic pyrolysis of LDPE leads to the formation of a complex mixture of alkanes, alkenes, carbonyl group containing compounds like aldehydes, ketones, aromatic compounds and substituted aromatic compounds like phenols. It could be concluded, that catalytic pyrolysis of LDPE leads to valuable resource recovery and reduction of waste problem.     

Bio‐oil production from rapid pyrolysis of cottonseed cake: product yields and compositions

Fixed‐bed fast pyrolysis experiments have been conducted on a sample of cottonseed cake to determine the effects of pyrolysis temperature, heating rate and sweep gas flow rate on pyrolysis yields and chemical compositions of the product oil. The liquid products and the subfractions of pentane soluble part were characterized by elemental analysis, FT‐IR spectroscopy, ¹H‐NMR spectroscopy and pentane subfraction was analysed by gas chromatography. The maximum oil yield of 34.8% was obtained at final temperature of 550°C with a heating rate of 700°C min^?1 and nitrogen flow rate of 100 cm³ min^?1. Chromatographic and spectroscopic studies on bio‐oil have shown that the oils obtained from cottonseed cake can be used as a renewable fuel and chemical feedstock. Copyright © 2005 John Wiley & Sons, Ltd.     

Hydrogen production with integrated microchannel fuel processor for portable fuel cell systems

An integrated microchannel methanol processor was developed by assembling unit reactors, which were fabricated by stacking and bonding microchannel patterned stainless steel plates, including fuel vaporizer, heat exchanger, catalytic combustor and steam reformer. Commercially available Cu/ZnO/Al₂O₃ catalyst was coated inside the microchannel of the unit reactor for steam reforming. Pt/Al₂O₃ pellets prepared by ‘incipient wetness’ were filled in the cavity reactor for catalytic combustion. Those unit reactors were integrated to develop the fuel processor and operated at different reaction conditions to optimize the reactor performance, including methanol steam reformer and methanol catalytic combustor. The optimized fuel processor has the dimensions of 60 mm × 40 mm × 30 mm, and produced 450sccm reformed gas containing 73.3% H₂, 24.5% CO₂ and 2.2% CO at 230–260 °C which can produce power output of 59 Wt.     

Measurement of the heat of smoldering combustion in straws and stalks by means of simultaneous thermal analysis

In order to investigate reaction heat of agro-stalks smoldering, wheat straw, corn stalk, cotton stalk, millet straw, sorghum stalk and sweet potato rattan powder were smoldered and pyrolyzed in a simultaneous thermal analyzer (STA). The samples were placed in a platinum crucible (?5 mm×5 mm) with a lid (with a ?1 mm hole) on a high-accuracy differential scanning calorimetry–heat capacity (DSC-cp) holder in the furnace of an STA and heated from 303 to 1073 K at a heating rate of 10 K min^?1. Sweeping gas with a flow rate of 25 ml min^?1 was air and nitrogen during smoldering and pyrolysis, respectively. Results showed that the heat emission characteristic of the smoldering process differed remarkably from the pyrolysis process. Based on the analysis of the DSC curves, oxidative polymer degradation heat and char oxidation heat were obtained from experimental data. It showed that the oxidative polymer degradation heat of the agro-stalks is more than 6.92 MJ kg^?1 consumed matter, higher than that of cellulose paper. And char oxidation heat is around 23 MJ kg^?1 consumed matter, similar to that of cellulose paper, but higher than that of cigarette. Total net heat emission of smoldering in STA was also obtained. These data can be used as reference data in analyzing smoldering of agro-stalks under similar conditions.     

Enhancing the production of biofuels from cottonseed oil by fixed-fluidized bed catalytic cracking

The production of biofuels from cottonseed oil by fixed-fluidized bed catalytic cracking at ambient pressure was studied. The effect of reaction temperature (400–500 °C), catalyst-to-oil ratio (6–10)and residence time (50–90 s) were studied over the yields of bio-gasoline and light fuel oil (≤360 °C). Design of experiments was used to study the effect of operating conditions over yield of hydrocarbon fuel. The response surface methodology was used to determine the optimum values of the operating variables for maximum yield of biofuels in the liquid product obtained.     

Field-testing of SPRERI's open core gasifier for thermal application

One unit of Sardar Patel Renewable Energy Research Institute (SPRERI's) 1.25 GJ h⁻¹ capacity open core down draft gasifier burner system, suitable for thermal application was installed at M/s Dinesh Pharmaceutical Pvt. Ltd., Nandesari, for steam generation. Producer gas burner was used in dual fuel mode (60% LDO (light diesel oil)+40% producer gas). Gasifier consumed 78–80 kg h⁻¹ of wood, and replaced 40% (20 l h⁻¹) LDO. The system was tested for a cumulative period of 600 h using sawmill woody waste as feedstock in test runs of 15–18 h. Financial analysis of the gasifier system showed that user could save about Rs. 221.8 per hour by using dual fuel (60% LDO+40% producer gas) for steam generation. Economic analysis of the system tested in the field indicated the viability of the gasifier-based operation.     

Inverse analyses of diffusion processes in type 13X zeolite particles

To determine effective surface self-diffusion coefficients of CO₂ within type 13X zeolite particles, at various temperatures (25–70 °C), inverse analyses of observed CO₂-uptake curves were successfully performed. The obtained effective surface self-diffusion coefficients increase with both the amount adsorbed and the temperature and ranged from 7.8 × 10⁻¹⁰ to 1.95 × 10⁻⁹ m²/s under the present experimental conditions.     

Biomass estimates,characteristics, biochemical methane potential,kinetics and energy flow from Jatropha curcus on dry lands

In this study, we examined the production of Jatropha curcus plants on 1 ha of rain fed dry lands. All of the plant components that would result from plantation tending, fruit harvesting and processing were sampled for their yield and chemical composition, and then subjected to the biochemical methane potential (BMP) assay. The component parts exhibited significant variation in BMP which was reflected in their ultimate methane yield which ranged from 0.08 to 0.97 L g^?1 VS added, and their first order kinetics which ranged from 0.07 to 0.14 d^?1. We examined two integrated utilization schemes: the first which converted plant prunings, fruit hulls and de-oiled seed cake to methane, and the oil to fatty acid methyl-ester (FAME); the second was to convert the seeds, plant prunings and fruit hulls entirely to methane. The basis for the plantation was, a density of 4444 plant ha^?1 (1.5 m × 1.5 m spacing), with a seed yield of 0.911 kg TS plant^?1 (1 kg total weight) with an oil content of 35% providing an annual oil yield of 1.42 t y^?1. The corresponding yields of pruned leaves, fruit hulls and de-oiled cake are 0.97, 1.0, and 2.35 t VS ha y^?1, respectively. An integrated scheme of producing biogas by means of anaerobic digestion of the latter components and oil for biodiesel would produce 90 GJ ha^?1 y^?1 in total with the oil being 54 GJ. The alternative biogas only option which would convert the seed oil into methane instead of biodiesel would produce 97 GJ ha^?1 y^?1.     

Hydrogen production by steam reforming of liquefied natural gas (LNG) over Ni/Al2O3–ZrO2 xerogel catalysts: Effect of calcination temperature of Al2O3–ZrO2 xerogel supports

Al₂O₃–ZrO₂ (AZ) xerogel supports prepared by a sol-gel method were calcined at various temperatures. Ni/Al₂O₃–ZrO₂ (Ni/AZ) catalysts were then prepared by an impregnation method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of calcination temperature of AZ supports on the catalytic performance of Ni/AZ catalysts in the steam reforming of LNG was investigated. Crystalline phase of AZ supports was transformed in the sequence of amorphous γ-Al₂O₃ and amorphous ZrO₂ → θ-Al₂O₃ and tetragonal ZrO₂ → (θ + α)-Al₂O₃ and (tetragonal + monoclinic) ZrO₂ → α-Al₂O₃ and (tetragonal + monoclinic) ZrO₂ with increasing calcination temperature from 700 to 1300 °C. Nickel oxide species were strongly bound to γ-Al₂O₃ and θ-Al₂O₃ in the Ni/AZ catalysts through the formation of solid solution. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to calcination temperature of AZ supports. Nickel surface area of Ni/AZ catalysts was well correlated with catalytic performance of the catalysts. Among the catalysts tested, Ni/AZ1000 (nickel catalyst supported on AZ support that had been calcined at 1000 °C) with the highest nickel surface area showed the best catalytic performance. Well-developed and pure tetragonal phase of ZrO₂ in the AZ1000 support played an important role in the adsorption of steam and the subsequent spillover of steam from the support to the active nickel.     

Two-phase pressure drops in a helically coiled steam generator

An experimental investigation regarding two-phase diabatic pressure drops inside a helically coiled heat exchanger have been carried out at SIET thermo-hydraulics labs in Piacenza (Italy). The experimental campaign is part of a wide program of study of the IRIS innovative reactor steam generator. The test section consists of an AISI 316 stainless steel tube, 32 m length, 12.53 mm inner diameter, curved in helical shape with a bend radius of 0.5 m and a helix pitch of 0.8 m, resulting in a total height of the steam generator tube of 8 m. The explored operating conditions for two-phase flow experiences range from 192 to 824 kg/m² s for the mass flux, from 0 to 1 for the quality, from 1.1 to 6.3 MPa for the pressure, from 50 to 200 kW/m² for the heat fluxes. A frictional two-phase pressure drops correlation, based on an energy balance of the two-phase mixture and including the 940 experimental points, is proposed. Comparison with existing correlations shows the difficulty in predicting two-phase pressure drops in helical coil steam generators.     

LiFePO4/carbon cathode materials prepared by ultrasonic spray pyrolysis

Small crystallites LiFePO₄ powder with conducting carbon coating can be synthesized by ultrasonic spray pyrolysis. Cheaper trivalent iron ion is used as the precursor. The pure olivine phase can be prepared with the duplex process of spray pyrolysis (synthesized at 450, 550 or 650 °C) and subsequent heat-treatment (at 650 °C for 4 h). The results indicate that the pyrolysis temperature of 450 °C is appropriate for best results. The carbon coating on the LiFePO₄ surface is critical to the electrochemical performance of LiFePO₄ cathode materials of the lithium secondary battery, since the carbon coating does not only increase the electronic conductivity via carbon on the surface of particles, but also enhance the ion mobility of lithium ion due to prohibiting the grain growth during post-heat-treatment. The carbon of 15 wt.% evenly distributed on the final LiFePO₄ powders can get the highest initial discharge capacity of 150 mA h g⁻¹ at C/10 and 50 °C.     

Polyaniline/zeolite as the cathode in a novel gel electrolyte primary dry cell

The ability of zeolite to accommodate and neutralize a great number of cations with all three mechanisms, adsorption, intercalation, and cation exchange reaction, combined with the high conductivity and stability of HCl—protonated polyaniline, which interposes into its laminar structure and the good contact between zeolite surface and polyaniline, make polyaniline/zeolite very suitable for a cathode electrode in dry electrical primary coin cells. Polyvinylalcohol (PVA) gel was used as the electrolyte and a Mg foil as the anode. The e.m.f. values of the cells ranged from 1.62 to 1.94 V, their specific energies from 4.34 to 8.88 Wh/kg and their energy densities from 3.10 to 6.34 mWh/cm³ for cathodes containing 10–50% in zeolite. The parameter τ, which characterizes the aging rate of the polyaniline/zeolite cathode ranges between 70 and 320 h. The higher τ is, the slower is the aging of the sample. The best combination of high conductivity, slow aging of the cathode and high specific energy of the cells was obtained between 25 and 35% of zeolite content. Moreover, surface examination of the polyaniline/zeolite samples, was performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques.     

Effects of pore structure and electrolyte on the capacitive characteristics of steam- and KOH-activated carbons for supercapacitors

Four kinds of activated carbons (denoted as ACs) with specific surface area of ca. 1050 m² g⁻¹ were fabricated from fir wood and pistachio shell by means of steam activation or chemical activation with KOH. Pore structures of ACs were characterized by a t-plot method based on N₂ adsorption isotherms. The amount of mesopores within KOH-activated carbons ranged from 9.2 to 15.3% while 33.3–49.5% of mesopores were obtained for the steam-activated carbons. The pore structure, surface functional groups, and raw materials of ACs, as well as pH and the supporting electrolyte were also found to be significant factors determining the capacitive characteristics of ACs. The excellent capacitive characteristics in both acidic and neutral media and the weak dependence of the specific capacitance on the scan rate of cyclic voltammetry (CV) for the ACs derived from the pistachio shell with steam activation (denoted as P-H₂O-AC) revealed their promising potential in the application of supercapacitors. The ACs derived from fir wood with KOH activation (denoted as F-KOH-AC), on the other hand, showed the best capacitive performance in H₂SO₄ due to excellent reversibility and high specific capacitance (180 F g⁻¹ measured at 10 mV s⁻¹), which is obviously larger than 100 F g⁻¹ (a typical value of activated carbons with specific surface areas equal to/above 1000 m² g⁻¹).     

Heat transfer during condensation of moving steam in a narrow channel

The paper presents the results of experimental investigation of heat transfer and hydrodynamics during condensation of moving steam in a narrow channel of square cross-section 2 mm × 2 mm. The channel had a serpentine shape, the channel length was 660 mm. An experimental cell simulated conditions of heat transfer in the condenser of loop heat pipes. The steam velocity at the channel inlet ranged from 13 to 52 m/s, the pressure was 1 atm. The temperature of the cooling water varied from 70 to 95 °C. The annular flow pattern was noted in the whole range of the regime parameters. There was a clear boundary between the condensation zone and the zone occupied by the condensed phase downstream. Temperature has measured along the channel, and the heat-transfer coefficients have been determined. The coefficient values varied from 10,000 to 55,000 W/K m² depending on the steam velocity at the channel inlet and the cooling temperature. The efficiency of the condenser – heat exchanger has been investigated.     

Model for predicting evaporation characteristics of vegetable oils droplets based on their fatty acid composition

In this work, a model for predicting evaporation characteristics (constant of evaporation and evaporation time) of cottonseed oil and diesel fuel has been developed and validated experimentally in the temperature range of 684–917 K under atmospheric pressure.The experimental study is based on the fibre-suspended droplet evaporation technique. The theoretical model for predicting evaporation characteristics is based on the determination of transport properties and thermodynamic properties of different phases of cottonseed oil using the properties of its predominant fatty acids (linoleic, oleic and palmitic). Results show that taking into account convection in the quasi-steady model by the correlation of Ranz and Marshall is enough to give a good prediction of the constant of evaporation of diesel fuel in the studied temperature range. For cottonseed oil, the quasi-steady model gives a good prediction for temperatures from 684 K to 773 K while for temperatures from 773 K to 917 K, it is necessary to take into account the convection and the influence of the heating period of the droplet for a good prediction of the constant of evaporation. For the duration of heating and evaporation time, the model gives a rather good prediction for cottonseed oil for the temperature range from 840 K to 917 K.     

Preparation and characterization of activated carbon from rubber-seed shell by physical activation with steam

The use of rubber-seed shell as a raw material for the production of activated carbon with physical activation was investigated. The produced activated carbons were characterized by Nitrogen adsorption isotherms, Scanning electron microscope, Thermo-gravimetric and Differential scanning calorimetric in order to understand the rubber-seed shell activated carbon. The results showed that rubber-seed shell is a good precursor for activated carbon. The optimal activation condition is: temperature 880 °C, steam flow 6 kg h^?1, residence time 60 min. Characteristics of activated carbon with a high yield (30.5%) are: specific surface area (S_BET) 948 m² g^?1, total volume 0.988 m³ kg^?1, iodine number of adsorbent (q_iodine) 1.326 g g^?1, amount of methylene blue adsorption of adsorbent (q_mb) 265 mg g^?1, hardness 94.7%. It is demonstrated that rubber-seed shell is an attractive source of raw material for producing high capacity activated carbon by physical activation with steam.