Phase Behaviors and Fuel Properties of Bio-Oil-Diesel-Alcohol Blends

Attempt was made to improve certain characteristics of bio-oil derived from palm kernel pyrolysis by blending it with diesel fuel and alcohols. Two types of alcohol, ethanol or butanol, was used as cosolvent to stabilize the phase of ternary systems. Phase behaviors and basic fuel properties of palm kernel bio-oildiesel- alcohol systems were investigated in this study. Alcohol types showed a significant influence on the phase characteristics with palm kernel bio-oil-diesel-butanol system giving larger soluble area than that of palm kernel bio-oil-diesel-ethanol system. For fuel properties, blended fuels showed superior properties including lower values of density (~860 kg/m3 at 25°C), viscosity (~4.12 mm2/s at 40°C), carbon residue (1.02-2.53 wt%), ash (0.018-0.034 wt%) and pour point (

Thermogravimetry Study on Pyrolysis of Various Lignocellulosic Biomass for Potential Hydrogen Production

This paper aims to study decomposition behavior in pyrolytic environment of four lignocellulosic biomass (oil palm shell, oil palm frond, rice husk and paddy straw), and two commercial components of biomass (pure cellulose and lignin), performed in a thermogravimetry analyzer (TGA). The unit which consists of a microbalance and a furnace flowed with 100 cc (STP) min-1 Nitrogen, N2 as inert. Heating rate was set at 20⁰C min-1 and temperature started from 50 to 900⁰C. Hydrogen gas production during the pyrolysis was observed using Agilent Gas Chromatography Analyzer 7890A. Oil palm shell, oil palm frond, paddy straw and rice husk were found to be reactive enough in a pyrolytic environment of up to 900°C since pyrolysis of these biomass starts at temperature as low as 200°C and maximum value of weight loss is achieved at about 500°C. Since there was not much different in the cellulose, hemicelluloses and lignin fractions between oil palm shell, oil palm frond, paddy straw and rice husk, the T-50 and R-50 values obtained are almost similar. H2 productions started rapidly at this temperature as well due to the decompositions of biomass inside the TGA. Biomass with more lignin content such as oil palm shell was found to have longer duration of H2 production compared to materials of high cellulose and hemicelluloses contents.

Investigation of Nickel as a Metal Substitute of Palladium Supported on HBeta Zeolite for Waste Tire Pyrolysis

Pyrolysis of waste tire is one of alternative technique to produce petrochemicals, such as light olefins, mixed C4, and monoaromatics. Noble metals supported on acid zeolite catalysts were reported as potential catalysts to produce the high valuable products from waste tire pyrolysis. Especially, Pd supported on HBeta gave a high yield of olefins, mixed C4, and mono-aromatics. Due to the high prices of noble metals, the objective of this work was to investigate whether or not a non-noble Ni metal can be used as a substitute of a noble metal, Pd, supported on HBeta as a catalyst for waste tire pyrolysis. Ni metal was selected in this work because Ni has high activity in cracking, isomerization, hydrogenation and the ring opening of hydrocarbons Moreover, Ni is an element in the same group as Pd noble metal, which is VIIIB group, aiming to produce high valuable products similarly obtained from Pd. The amount of Ni was varied as 5, 10, and 20% by weight, for comparison with a fixed 1 wt% Pd, using incipient wetness impregnation. The results showed that as a petrochemical-producing catalyst, 10%Ni/HBeta performed better than 1%Pd/HBeta because it did not only produce the highest yield of olefins and cooking gases, but the yields were also higher than 1%Pd/HBeta. 5%Ni/HBeta can be used as a substitute of 1%Pd/HBeta for similar crude production because its crude contains the similar amounts of naphtha and saturated HCs, although it gave no concentration of light mono-aromatics (C6-C11) in the oil. Additionally, 10%Ni/HBeta that gave high olefins and cooking gases was found to give a fairly high concentration of the light mono-aromatics in the oil.

Effect of Oxygen on Biochar Yield and Properties

Air infiltration in mass scale industrial applications of bio char production is inevitable. The presence of oxygen during the carbonization process is detrimental to the production of biochar yield and properties. The experiment was carried out on several wood species in a fixed-bed pyrolyser under various fractions of oxygen ranging from 0% to 11% by varying nitrogen and oxygen composition in the pyrolysing gas mixtures at desired compositions. The bed temperature and holding time were also varied. Process optimization was carried out by Response Surface Methodology (RSM) by employing Central Composite Design (CCD) using Design Expert 6.0 Software. The effect of oxygen ratio and holding time on biochar yield within the range studied were statistically significant. From the analysis result, optimum condition of 15.2% biochar yield of mangrove wood was predicted at pyrolysis temperature of 403 oC, oxygen percentage of 2.3% and holding time of two hours. This prediction agreed well with the experiment finding of 15.1% biochar yield.

Slow, Wet and Catalytic Pyrolysis of Fowl Manure

This work presents the experimental results obtained at a pilot plant which works with a slow, wet and catalytic pyrolysis process of dry fowl manure. This kind of process mainly consists in the cracking of the organic matrix and in the following reaction of carbon with water, which is either already contained in the organic feed or added, to produce carbon monoxide and hydrogen. Reactions are conducted in a rotating reactor maintained at a temperature of 500°C; the required amount of water is about 30% of the dry organic feed. This operation yields a gas containing about 59% (on a volume basis) of hydrogen, 17% of carbon monoxide and other products such as light hydrocarbons (methane, ethane, propane) and carbon monoxide in lesser amounts. The gas coming from the reactor can be used to produce not only electricity, through internal combustion engines, but also heat, through direct combustion in industrial boilers. Furthermore, as the produced gas is devoid of both solid particles and pollutant species (such as dioxins and furans), the process (in this case applied to fowl manure) can be considered as an optimal way for the disposal and the contemporary energetic valorization of organic materials, in such a way that is not damaging to the environment.

An Investigation on Thermo Chemical Conversions of Solid Waste for Energy Recovery

Solid waste can be considered as an urban burden or as a valuable resource depending on how it is managed. To meet the rising demand for energy and to address environmental concerns, a conversion from conventional energy systems to renewable resources is essential. For the sustainability of human civilization, an environmentally sound and techno-economically feasible waste treatment method is very important to treat recyclable waste. Several technologies are available for realizing the potential of solid waste as an energy source, ranging from very simple systems for disposing of dry waste to more complex technologies capable of dealing with large amounts of industrial waste. There are three main pathways for conversion of waste material to energy: thermo chemical, biochemical and physicochemical. This paper investigates the thermo chemical conversion of solid waste for energy recovery. The processes, advantages and dis-advantages of various thermo chemical conversion processes are discussed and compared. Special attention is given to Gasification process as it provides better solutions regarding public acceptance, feedstock flexibility, near-zero emissions, efficiency and security. Finally this paper presents comparative statements of thermo chemical processes and introduces an integrated waste management system.

Injection Molding of Inconel718 Parts for Aerospace Application Using Novel Binder System Based On Palm Oil Derivatives

Inconel718 has been widely used as a super alloy in aerospace application due to the high strength at elevated temperatures, satisfactory oxidation resistance and heat corrosion resistance. In this study, the Inconel718 has been fabricated using high technology of Metal Injection Molding (MIM) process due to the cost effective technique for producing small, complex and precision parts in high volume compared with conventional method through machining. Through MIM, the binder system is one of the most important criteria in order to successfully fabricate the Inconel718. Even though, the binder system is a temporary, but failure in the selection and removal of the binder system will affect on the final properties of the sintered parts. Therefore, the binder system based on palm oil derivative which is palm stearin has been formulated and developed to replace the conventional binder system. The rheological studies of the mixture between the powder and binders system have been determined properly in order to be successful during injection into injection molding machine. After molding, the binder holds the particles in place. The binder system has to be removed completely through debinding step. During debinding step, solvent debinding and thermal pyrolysis has been used to remove completely of the binder system. The debound part is then sintered to give the required physical and mechanical properties. The results show that the properties of the final sintered parts fulfill the Standard Metal Powder Industries Federation (MPIF) 35 for MIM parts.

Development of Fen4/C And Fen2/C Catalysts for Hydrodesulfurization and Hydrodearomitization of Model Compounds of Heavy Oil

Two novel hydrodesulfurization (HDS) catalysts: FeN4/C and FeN2/C, were prepared using an impregnation-pyrolysis method. The two materials were investigated as catalysts for hydrodesulfurization (HDS) and hydrodearomitization (HDA) of model compounds. The turnover frequency of the two FeN catalysts is comparable to (FeN4/C) or even higher (FeN2/C) than that of MoNi/Al2O3. The FeN4/C catalyst also exhibited catalytic activity toward HDA.

Evaluation of Guaiacol and Syringol Emission upon Wood Pyrolysis for some Fast Growing Species

Wood pyrolysis for Casuarina glauca, Casuarina cunninghamiana, Eucalyptus camaldulensis, Eucalyptus microtheca was made at 450°C with 2.5°C/min. in a flowing N2-atmosphere. The Eucalyptus genus wood gave higher values of specific gravity, ash , total extractives, lignin, N2-liquid trap distillate (NLTD) and water trap distillate (WSP) than those for Casuarina genus. The GHC of NLTD was higher for Casuarina genus than that for Eucalyptus genus with the highest value for Casuarina cunninghamiana. Guiacol, 4-ethyl-2-methoxyphenol and syringol were observed in the NLTD of all the four wood species reflecting their parent hardwood lignin origin. Eucalyptus camaldulensis wood had the highest lignin content (28.89%) and was pyrolyzed to the highest values of phenolics (73.01%), guaiacol (11.2%) and syringol (32.28%) contents in methylene chloride fraction (MCF) of NLTD. Accordingly, recoveries of syringol and guaiacol may become economically attractive from Eucalyptus camaldulensis.

The Catalytic Effects of Potassium Dichromate on the Pyrolysis of Polymeric Mixtures Part II: Hazelnut Shell and Ultra-high Molecular Weight Polyethylene and their Blend Cases

Renewable energy sources have gained ultimate urgency due to the need of the preservation of the environment for a sustainable development. Pyrolysis is an ultimate promising process in the recycling and acquisition of precious chemicals from wastes. Here, the co-pyrolysis of hazelnut shell with ultra-high molecular weight polyethylene was carried out catalytically and noncatalytically at 500 and 650 ºC. Potassium dichromate was added in certain amounts to act as a catalyst. The liquid, solid and gas products quantities were determined by gravimetry. As a main result, remarkable increases in gasification were observed by using this catalyst for pure components and their blends especially at 650 ºC. The increase in gas product quantity was compensated mainly with the decreases in the solid products and additionally in some cases liquid products quantities. These observations may stem from mainly the activation of carbon-carbon bonds rather than carbon-hydrogen bonds via potassium dichromate. Also, the catalytic effect of potassium dichromate on HS: PEO and HS: UHMWPE co-pyrolysis was compared.

Effect of Tube Materials and Special Coating on Coke Deposition in the Steam Cracking of Hydrocarbons

The steam cracking reactions are always accompanied with the formation of coke which deposits on the walls of the tubular reactors. The investigation has attempted to control catalytic coking by the applying aluminum, zinc and ceramic coating like aluminum-magnesium by thermal spray and pack cementation method. Rate of coke formation during steam cracking of naphtha has been investigated both for uncoated stainless steel (with different alloys) and metal coating constructed with thermal Spray and pack cementation method with metal powders of Aluminum, Aluminum-Magnesium, zinc, silicon, nickel and chromium. The results of the study show that passivating the surface of SS321 with a coating of Aluminum and Aluminum-Magnesium can significantly reduce the rate of coke deposition during naphtha pyrolysis. SEM and EDAX techniques (Philips XL Series) were used to examine the coke deposits formed by the metal-hydrocarbon reactions. Our objective was to separate the different stages by identifying the characteristic morphologies.

Replacement of Commercial Anti-Corrosion Material with a More Effective and Cost Efficient Compound Based on Electrolytic System Simulation

There was a high rate of corrosion in Pyrolysis Gasoline Hydrogenation (PGH) unit of Arak Petrochemical Company (ARPC), and it caused some operational problem in this plant. A commercial chemical had been used as anti-corrosion in the depentanizer column overhead in order to control the corrosion rate. Injection of commercial corrosion inhibitor caused some operational problems such as fouling in some heat exchangers. It was proposed to replace this commercial material with another more effective trouble free, and well-known additive by R&D and operation specialists. At first, the system was simulated by commercial simulation software in electrolytic system to specify low pH points inside the plant. After a very comprehensive study of the situation and technical investigations ,ammonia / monoethanol amine solution was proposed as neutralizer or corrosion inhibitor to be injected in a suitable point of the plant. For this purpose, the depentanizer column and its accessories system was simulated again in case of this solution injection. According to the simulation results, injection of new anticorrosion substance has no any side effect on C5 cut product and operating conditions of the column. The corrosion rate will be cotrolled, if the pH remains at the range of 6.5 to 8 . Aactual plant test run was also carried out by injection of ammonia / monoethanol amine solution at the rate of 0.6 Kg/hr and the results of iron content of water samples and corrosion test coupons confirmed the simulation results. Now, ammonia / monoethanol amine solution is injected to a suitable pint inside the plant and corrosion rate has decreased significantly.

Performance and Emission Characteristics of a DI Diesel Engine Fuelled with Cashew Nut Shell Liquid (CNSL)-Diesel Blends

The increased number of automobiles in recent years has resulted in great demand for fossil fuel. This has led to the development of automobile by using alternative fuels which include gaseous fuels, biofuels and vegetables oils as fuel. Energy from biomass and more specific bio-diesel is one of the opportunities that could cover the future demand of fossil fuel shortage. Biomass in the form of cashew nut shell represents a new energy source and abundant source of energy in India. The bio-fuel is derived from cashew nut shell oil and its blend with diesel are promising alternative fuel for diesel engine. In this work the pyrolysis Cashew Nut Shell Liquid (CNSL)-Diesel Blends (CDB) was used to run the Direct Injection (DI) diesel engine. The experiments were conducted with various blends of CNSL and Diesel namely B20, B40, B60, B80 and B100. The results are compared with neat diesel operation. The brake thermal efficiency was decreased for blends of CNSL and Diesel except the lower blends of B20. The brake thermal efficiency of B20 is nearly closer to that of diesel fuel. Also the emission level of the all CNSL and Diesel blends was increased compared to neat diesel. The higher viscosity and lower volatility of CNSL leads to poor mixture formation and hence lower brake thermal efficiency and higher emission levels. The higher emission level can be reduced by adding suitable additives and oxygenates with CNSL and Diesel blends.

Kinetics of Polyethylene Terephthalate (PET)and Polystyrene (PS) Dynamic Pyrolysis

Thermo-chemical treatment (TCT) such as pyrolysis is getting recognized as a valid route for (i) materials and valuable products and petrochemicals recovery; (ii) waste recycling; and (iii) elemental characterization. Pyrolysis is also receiving renewed attention for its operational, economical and environmental advantages. In this study, samples of polyethylene terephthalate (PET) and polystyrene (PS) were pyrolysed in a microthermobalance reactor (using a thermogravimetric-TGA setup). Both polymers were prepared and conditioned prior to experimentation. The main objective was to determine the kinetic parameters of the depolymerization reactions that occur within the thermal degradation process. Overall kinetic rate constants (ko) and activation energies (Eo) were determined using the general kinetics theory (GKT) method previously used by a number of authors. Fitted correlations were found and validated using the GKT, errors were within ± 5%. This study represents a fundamental step to pave the way towards the development of scaling relationship for the investigation of larger scale reactors relevant to industry.

Development of Better Quality Low-Cost Activated Carbon from South African Pine Tree (Pinus patula) Sawdust: Characterization and Comparative Phenol Adsorption

The remediation of water resources pollution in developing countries requires the application of alternative sustainable cheaper and efficient end-of-pipe wastewater treatment technologies. The feasibility of use of South African cheap and abundant pine tree (Pinus patula) sawdust for development of lowcost AC of comparable quality to expensive commercial ACs in the abatement of water pollution was investigated. AC was developed at optimized two-stage N2-superheated steam activation conditions in a fixed bed reactor, and characterized for proximate and ultimate properties, N2-BET surface area, pore size distribution, SEM, pHPZC and FTIR. The sawdust pyrolysis activation energy was evaluated by TGA. Results indicated that the chars prepared at 800oC and 2hrs were suitable for development of better quality AC at 800oC and 47% burn-off having BET surface area (1086m2/g), micropore volume (0.26cm3/g), and mesopore volume (0.43cm3/g) comparable to expensive commercial ACs, and suitable for water contaminants removal. The developed AC showed basic surface functionality at pHPZC at 10.3, and a phenol adsorption capacity that was higher than that of commercial Norit (RO 0.8) AC. Thus, it is feasible to develop better quality low-cost AC from (Pinus patula) sawdust using twostage N2-steam activation in fixed-bed reactor.

Size Controlled Synthesis and Photocatalytic Activity of Anatase TiO2 Hollow Microspheres

Titanium oxide hollow microspheres were synthesized from organic precursor titanium tetraisopropoxide (TTIP) using continuous spray pyrolysis reactor. Effects of precursor concentration, applied voltage and annealing have been investigated. It was observed that the annealing of the as-synthesized TiO2 hollow microspheres at 2500C, which had an average external diameter of 200 nm, leads to an increase in the size and also more spherical shape. The precursor concentration was found to have a direct impact on the size of the microspheres, which is also evident in the absorption spectrum. The as-prepared TiO2 hollow microspheres exhibited good photocatalytic activity for the degradation of MO.

Hydrogen from Waste Tyres

Hydrogen is regarded to play an important role in future energy systems because it can be produced from abundant resources and its combustion only generates water. The disposal of waste tyres is a major problem in environmental management throughout the world. The use of waste materials as a source of hydrogen is particularly of interest in that it would also solve a waste treatment problem. There is much interest in the use of alternative feedstocks for the production of hydrogen since more than 95% of current production is from fossil fuels. The pyrolysis of waste tyres for the production of liquid fuels, activated carbons and gases has been extensively researched. However, combining pyrolysis with gasification is a novel process that can gasify the gaseous products from pyrolysis. In this paper, an experimental investigation into the production of hydrogen and other gases from the bench scale pyrolysis-gasification of tyres has been investigated. Experiments were carried using a two stage system consisting of pyrolysis of the waste tyres followed by catalytic steam gasification of the evolved gases and vapours in a second reactor. Experiments were conducted at a pyrolysis temperature of 500 °C using Ni/Al2O3 as a catalyst. The results showed that there was a dramatic increase in gas yield and the potential H2 production when the gasification temperature was increased from 600 to 900 oC. Overall, the process showed that high yields of hydrogen can be produced from waste tyres.

Pyrolysis Characteristics and Kinetics of Macroalgae Biomass Using Thermogravimetric Analyzer

The pyrolysis characteristics and kinetics of seven marine biomass, which are fixed Enteromorpha clathrata, floating Enteromorpha clathrata, Ulva lactuca L., Zosterae Marinae L., Thallus Laminariae, Asparagus schoberioides kunth and Undaria pinnatifida (Harv.), were studied with thermogravimetric analysis method. Simultaneously, cornstalk, which is a grass biomass, and sawdust, which is a lignocellulosic biomass, were references. The basic pyrolysis characteristics were studied by using TG- DTG-DTA curves. The results showed that there were three stages (dehydration, dramatic weight loss and slow weight loss) during the whole pyrolysis process of samples. The Tmax of marine biomass was significantly lower than two kinds of terrestrial biomass. Zosterae Marinae L. had a relatively high stability of pyrolysis, but floating Enteromorpha clathrata had lowest stability of pyrolysis and a good combustion characteristics. The corresponding activation energy E and frequency factor A were obtained by Coats-Redfern method. It was found that the pyrolysis reaction mechanism functions of three kinds of biomass are different.

Simulation of Enhanced Biomass Gasification for Hydrogen Production using iCON

Due to the environmental and price issues of current energy crisis, scientists and technologists around the globe are intensively searching for new environmentally less-impact form of clean energy that will reduce the high dependency on fossil fuel. Particularly hydrogen can be produced from biomass via thermochemical processes including pyrolysis and gasification due to the economic advantage and can be further enhanced through in-situ carbon dioxide removal using calcium oxide. This work focuses on the synthesis and development of the flowsheet for the enhanced biomass gasification process in PETRONAS-s iCON process simulation software. This hydrogen prediction model is conducted at operating temperature between 600 to 1000oC at atmospheric pressure. Effects of temperature, steam-to-biomass ratio and adsorbent-to-biomass ratio were studied and 0.85 mol fraction of hydrogen is predicted in the product gas. Comparisons of the results are also made with experimental data from literature. The preliminary economic potential of developed system is RM 12.57 x 106 which equivalent to USD 3.77 x 106 annually shows economic viability of this process.

Pyrolysis of Rice Husk in a Fixed Bed Reactor

Fixed-bed slow pyrolysis experiments of rice husk have been conducted to determine the effect of pyrolysis temperature, heating rate, particle size and reactor length on the pyrolysis product yields. Pyrolysis experiments were performed at pyrolysis temperature between 400 and 600°C with a constant heating rate of 60°C/min and particle sizes of 0.60-1.18 mm. The optimum process conditions for maximum liquid yield from the rice husk pyrolysis in a fixed bed reactor were also identified. The highest liquid yield was obtained at a pyrolysis temperature of 500°C, particle size of 1.18-1.80 mm, with a heating rate of 60°C/min in a 300 mm length reactor. The obtained yield of, liquid, gas and solid were found be in the range of 22.57-31.78 %, 27.75-42.26 % and 34.17-42.52 % (all weight basics) respectively at different pyrolysis conditions. The results indicate that the effects of pyrolysis temperature and particle size on the pyrolysis yield are more significant than that of heating rate and reactor length. The functional groups and chemical compositions present in the liquid obtained at optimum conditions were identified by Fourier Transform-Infrared (FT-IR) spectroscopy and Gas Chromatography/ Mass Spectroscopy (GC/MS) analysis respectively.