Catalytic Pyrolysis of Sewage Sludge for Upgrading Bio-Oil Quality Using Sludge-Based Activated Char as an Alternative to HZSM5

Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Kinetic Parameter Estimation from Thermogravimetry and Microscale Combustion Calorimetry

Flammability analysis of extruded polystyrene (XPS) has become crucial due to its utilization as insulation material for energy efficient buildings. Using the Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods, the degradation kinetics of two pure XPS from the local market, red and grey ones, were obtained from the results of thermogravity analysis (TG) and microscale combustion calorimetry (MCC) experiments performed under the same heating rates. From the experiments, it was discovered that red XPS released more heat than grey XPS and both materials showed two mass loss stages. Consequently, the kinetic parameters for red XPS were higher than grey XPS. A comparative evaluation of activation energies from MCC and TG showed an insignificant degree of deviation signifying an equivalent apparent activation energy from both methods. However, different activation energy profiles as a result of the different chemical pathways were presented when the dependencies of the activation energies on extent of conversion for TG and MCC were compared.

Homogenization of Cocoa Beans Fermentation to Upgrade Quality Using an Original Improved Fermenter

Cocoa beans (Theobroma cocoa L.) are the main components for chocolate manufacturing. The beans must be correctly fermented at first. Traditional process to perform the first fermentation (lactic fermentation) often consists in confining cacao beans using banana leaves or a fermentation basket, both of them leading to a poor product thermal insulation and to an inability to mix the product. Box fermenter reduces this loss by using a wood with large thickness (e>3cm), but mixing to homogenize the product is still hard to perform. Automatic fermenters are not rentable for most of producers. Heat (T>45°C) and acidity produced during the fermentation by microbiology activity of yeasts and bacteria are enabling the emergence of potential flavor and taste of future chocolate. In this study, a cylindro-rotative fermenter (FCR-V1) has been built and coconut fibers were used in its structure to confine heat. An axis of rotation (360°) has been integrated to facilitate the turning and homogenization of beans in the fermenter. This axis permits to put fermenter in a vertical position during the anaerobic alcoholic phase of fermentation, and horizontally during acetic phase to take advantage of the mid height filling. For circulation of air flow during turning in acetic phase, two woven rattan with grid have been made, one for the top and second for the bottom of the fermenter. In order to reduce air flow during acetic phase, two airtight covers are put on each grid cover. The efficiency of the turning by this kind of rotation, coupled with homogenization of the temperature, caused by the horizontal position in the acetic phase of the fermenter, contribute to having a good proportion of well-fermented beans (83.23%). In addition, beans’pH values ranged between 4.5 and 5.5. These values are ideal for enzymatic activity in the production of the aromatic compounds inside beans. The regularity of mass loss during all fermentation makes it possible to predict the drying surface corresponding to the amount being fermented.

Effect of Fire Retardant Painting Product on Smoke Optical Density of Burning Natural Wood Samples

Natural wood is used in many applications in Jordan such as furniture, partitions constructions, and cupboards. Experimental work for smoke produced by the combustion of certain wood samples was studied. Smoke generated from burning of natural wood, is considered as a major cause of death in furniture fires. The critical parameter for life safety in fires is the available time for escape, so the visual obscuration due to smoke release during fire is taken into consideration. The effect of smoke, produced by burning of wood, depends on the amount of smoke released in case of fire. The amount of smoke production, apparently, affects the time available for the occupants to escape. To achieve the protection of life of building occupants during fire growth, fire retardant painting products are tested. The tested samples of natural wood include Beech, Ash, Beech Pine, and white Beech Pine. A smoke density chamber manufactured by fire testing technology has been used to perform measurement of smoke properties. The procedure of test was carried out according to the ISO-5659. A nonflammable vertical radiant heat flux of 25 kW/m2 is exposed to the wood samples in a horizontal orientation. The main objective of the current study is to carry out the experimental tests for samples of natural woods to evaluate the capability to escape in case of fire and the fire safety requirements. Specific optical density, transmittance, thermal conductivity, and mass loss are main measured parameters. Also, comparisons between samples with paint and with no paint are carried out between the selected samples of woods.

Physicochemical Characterization of Waste from Vegetal Extracts Industry for Use as Briquettes

Wastes from a vegetal extracts industry (cocoa, oak, Guarana and mate) were characterized by particle size, proximate and ultimate analysis, lignocellulosic fractions, high heating value, thermal analysis (Thermogravimetric analysis – TGA, and Differential thermal analysis - DTA) and energy density to evaluate their potential as biomass in the form of briquettes for power generation. All wastes presented adequate particle sizes to briquettes production. The wastes showed high moisture content, requiring previous drying for use as briquettes. Cocoa and oak wastes had the highest volatile matter contents with maximum mass loss at 310 ºC and 450 ºC, respectively. The solvents used in the aroma extraction process influenced in the moisture content of the wastes, which was higher for mate due to water has been used as solvent. All wastes showed an insignificant loss mass after 565 °C, hence resulting in low ash content. High carbon and hydrogen contents and low sulfur and nitrogen contents were observed ensuring a low generation of sulfur and nitrous oxides. Mate and cocoa exhibited the highest carbon and lignin content, and high heating value. The dried wastes had high heating value, from 17.1 MJ/kg to 20.8 MJ/kg. The results indicate the energy potential of wastes for use as fuel in power generation.

Prediction of Time to Crack Reinforced Concrete by Chloride Induced Corrosion

In this paper, a review of different mathematical models which can be used as prediction tools to assess the time to crack reinforced concrete (RC) due to corrosion is investigated. This investigation leads to an experimental study to validate a selected prediction model. Most of these mathematical models depend upon the mechanical behaviors, chemical behaviors, electrochemical behaviors or geometric aspects of the RC members during a corrosion process. The experimental program is designed to verify the accuracy of a well-selected mathematical model from a rigorous literature study. Fundamentally, the experimental program exemplifies both one-dimensional chloride diffusion using RC squared slab elements of 500 mm by 500 mm and two-dimensional chloride diffusion using RC squared column elements of 225 mm by 225 mm by 500 mm. Each set consists of three water-to-cement ratios (w/c); 0.4, 0.5, 0.6 and two cover depths; 25 mm and 50 mm. 12 mm bars are used for column elements and 16 mm bars are used for slab elements. All the samples are subjected to accelerated chloride corrosion in a chloride bath of 5% (w/w) sodium chloride (NaCl) solution. Based on a pre-screening of different models, it is clear that the well-selected mathematical model had included mechanical properties, chemical and electrochemical properties, nature of corrosion whether it is accelerated or natural, and the amount of porous area that rust products can accommodate before exerting expansive pressure on the surrounding concrete. The experimental results have shown that the selected model for both one-dimensional and two-dimensional chloride diffusion had ±20% and ±10% respective accuracies compared to the experimental output. The half-cell potential readings are also used to see the corrosion probability, and experimental results have shown that the mass loss is proportional to the negative half-cell potential readings that are obtained. Additionally, a statistical analysis is carried out in order to determine the most influential factor that affects the time to corrode the reinforcement in the concrete due to chloride diffusion. The factors considered for this analysis are w/c, bar diameter, and cover depth. The analysis is accomplished by using Minitab statistical software, and it showed that cover depth is the significant effect on the time to crack the concrete from chloride induced corrosion than other factors considered. Thus, the time predictions can be illustrated through the selected mathematical model as it covers a wide range of factors affecting the corrosion process, and it can be used to predetermine the durability concern of RC structures that are vulnerable to chloride exposure. And eventually, it is further concluded that cover thickness plays a vital role in durability in terms of chloride diffusion.

Mechanical Strengths of Self-Compacting Mortars Prepared with the Pozzolanic Cement in Aggressive Environments

The objective of this research is to study the physical and mechanical properties and durability of self-compacting mortars prepared by substituting a part of cement up to a percentage of 30% pozzolan according to different Blaine specific surface area (SSB1=7000 cm2/g and SSB=9000 cm2/g)). Order to evaluate durability, mortars were subjected to chemical attacks in various aggressive environments, a solution of a mixture of nitric acid and ammonium nitrate (HNO3 + NH4NO3) and a magnesium sulfate salt solution (MgSO4)) with a concentration of 10%, for a period of one month. This study is complemented by a comparative study of the durability of mortars elaborated with sulphate resistant cement (SRC). The results show that these mortars develop long-term, mechanical and chemical resistance better than mortars based Portland cement with 5% gypsum (CEM 1) and SRC. We found that the mass losses are lowest in mortars elaborated with pozzolanic cement (30% substitution with SSB2) in both of chemical attack solutions (3.28% in the solution acid and 1.16% in the salt solution) and the compressive strength gains of 14.68% and 8.5% respectively in the two media. This is due to the action of pozzolan which fixes portlandite to form hydrated calcium silicate (CSH) from the hydration of tricalcic silicate (C3S).

Physicochemical Stability of Pulse Spreads during Storage after Sous Vide Treatment and High Pressure Processing

Pulses are high in plant protein and dietary fiber, and contain slowly digestible starches. Innovative products from pulses could increase their consumption and benefit consumer health. This study was conducted to evaluate physicochemical stability of processed cowpea (Vigna unguiculata (L.) Walp. cv. Fradel) and maple pea (Pisum sativum var. arvense L. cv. Bruno) spreads at 5 °C temperature during 62-day storage. Physicochemical stability of pulse spreads was compared after sous vide treatment (80 °C/15 min) and high pressure processing (700 MPa/10 min/20 °C). Pulse spreads were made by homogenizing cooked pulses in a food processor together with salt, citric acid, oil, and bruschetta seasoning. A total of four different pulse spreads were studied: Cowpea spread without and with seasoning, maple pea spread without and with seasoning. Transparent PA/PE and light proof PET/ALU/PA/PP film pouches were used for packaging of pulse spreads under vacuum. The parameters investigated were pH, water activity and mass losses. Pulse spreads were tested on days 0, 15, 29, 42, 50, 57 and 62. The results showed that sous-vide treatment and high pressure processing had an insignificant influence on pH, water activity and mass losses after processing, irrespective of packaging material did not change (p>0.1). pH and water activity of sous-vide treated and high pressure processed pulse spreads in different packaging materials proved to be stable throughout the storage. Mass losses during storage accounted to 0.1% losses. Chosen sous-vide treatment and high pressure processing regimes and packaging materials are suitable to maintain consistent physicochemical quality of the new products during 62-day storage.

Study of the Tribological Behavior of a Pin on Disc Type of Contact

The present work aims at contributing to the study of the complex phenomenon of wear of pin on disc contact in dry sliding friction between two material couples (bronze/steel and unsaturated polyester virgin and charged with graphite powder/steel). The work consists of the determination of the coefficient of friction, the study of the influence of the tribological parameters on this coefficient and the determination of the mass loss and the wear rate of the pin. This study is also widened to the highlighting of the influence of the addition of graphite powder on the tribological properties of the polymer constituting the pin. The experiments are carried out on a pin-disc type tribometer that we have designed and manufactured. Tests are conducted according to the standards DIN 50321 and DIN EN 50324. The discs are made of annealed XC48 steel and quenched and tempered XC48 steel. The main results are described here after. The increase of the normal load and the sliding speed causes the increase of the friction coefficient, whereas the increase of the percentage of graphite and the hardness of the disc surface contributes to its reduction. The mass loss also increases with the normal load. The influence of the normal load on the friction coefficient is more significant than that of the sliding speed. The effect of the sliding speed decreases for large speed values. The increase of the amount of graphite powder leads to a decrease of the coefficient of friction, the mass loss and the wear rate. The addition of graphite to the UP resin is beneficial; it plays the role of solid lubricant.

A Simple Chemical Precipitation Method of Titanium Dioxide Nanoparticles Using Polyvinyl Pyrrolidone as a Capping Agent and Their Characterization

In this paper, a simple chemical precipitation route for the preparation of titanium dioxide nanoparticles, synthesized by using titanium tetra isopropoxide as a precursor and polyvinyl pyrrolidone (PVP) as a capping agent, is reported. The Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA) of the samples were recorded and the phase transformation temperature of titanium hydroxide, Ti(OH)4 to titanium oxide, TiO2 was investigated. The as-prepared Ti(OH)4 precipitate was annealed at 800°C to obtain TiO2 nanoparticles. The thermal, structural, morphological and textural characterizations of the TiO2 nanoparticle samples were carried out by different techniques such as DSC-TGA, X-Ray Diffraction (XRD), Fourier Transform Infra-Red spectroscopy (FTIR), Micro Raman spectroscopy, UV-Visible absorption spectroscopy (UV-Vis), Photoluminescence spectroscopy (PL) and Field Effect Scanning Electron Microscopy (FESEM) techniques. The as-prepared precipitate was characterized using DSC-TGA and confirmed the mass loss of around 30%. XRD results exhibited no diffraction peaks attributable to anatase phase, for the reaction products, after the solvent removal. The results indicate that the product is purely rutile. The vibrational frequencies of two main absorption bands of prepared samples are discussed from the results of the FTIR analysis. The formation of nanosphere of diameter of the order of 10 nm, has been confirmed by FESEM. The optical band gap was found by using UV-Visible spectrum. From photoluminescence spectra, a strong emission was observed. The obtained results suggest that this method provides a simple, efficient and versatile technique for preparing TiO2 nanoparticles and it has the potential to be applied to other systems for photocatalytic activity.

Parametric Studies of Wood Pyrolysis Particles

In the present study, a numerical approach to describe the pyrolysis of a single solid particle of wood is used to study the influence of various conditions such as particle size, heat transfer coefficient, reactor temperature and heating rate. The influence of these parameters in the change of the duration of the pyrolysis cycle was studied. Mathematical modeling was employed to simulate the heat, mass transfer, and kinetic processes inside the reactor. The evolutions of the mass loss as well as the evolution of temperature inside the thick piece are investigated numerically. The elaborated model was also employed to study the effect of the reactor temperature and the rate of heating on the change of the temperature and the local loss of the mass inside the piece of wood. The obtained results are in good agreement with the experimental data available in the literature.

The Effect of Randomly Distributed Polypropylene Fibers Borogypsum Fly Ash and Cement on Freezing-Thawing Durability of a Fine-Grained Soil

A number of studies have been conducted recently to investigate the influence of randomly oriented fibers on some engineering properties of cohesive and cohesionless soils. However, few studies have been carried out on freezing-thawing behavior of fine-grained soils modified with discrete fiber inclusions and additive materials. This experimental study was performed to investigate the effect of randomly distributed polypropylene fibers (PP) and some additive materials [e.g.., borogypsum (BG), fly ash (FA) and cement (C)] on freezing-thawing durability (mass losses) of a fine-grained soil for 6, 12, and 18 cycles. The Taguchi method was applied to the experiments and a standard L9 orthogonal array (OA) with four factors and three levels were chosen. A series of freezing-thawing tests were conducted on each specimen. 0-20% BG, 0-20% FA, 0- 0.25% PP and 0-3% of C by total dry weight of mixture were used in the preparation of specimens. Experimental results showed that the most effective materials for the freezing-thawing durability (mass losses) of the samples were borogypsum and fly ash. The values of mass losses for 6, 12 and 18 cycles in optimum conditions were 16.1%, 5.1% and 3.6%, respectively.

A New Algorithm for Solving Isothermal Carbonization of Wood Particle

A new algorithm based on the lattice Boltzmann method (LBM) is proposed as a potential solver for one-dimensional heat and mass transfer for isothermal carbonization of wood particles. To check the validity of this algorithm, the LBM results have been compared with the published data and a good agreement is obtained. Then, the model is used to study the effect of reactor temperature and particle size on the evolution of the local temperature and mass loss inside the wood particle.

Acid Attack on Cement Mortars Modified with Rubber Aggregates and EVA Polymer Binder

The acid attack on cement mortars modified with rubber aggregates and EVA polymer binder was studied. Mortar specimens were prepared using a type CEM I 42.5 Portland cement and siliceous sand, as well as by substituting 25% of sand with shredded used automobile tires, and by adding EVA polymer in two percentages (5% and 10% of cement mass). Some specimens were only air cured, at laboratory conditions, and their compressive strength and water absorption were determined. The rest specimens were stored in acid solutions (HCl, H2SO4, HNO3) after 28 days of initial curing, and stored at laboratory temperature. Compressive strength tests, mass measurements and visual inspection took place for 28 days. Compressive strength and water absorption of the air-cured specimens were significantly decreased when rubber aggregates are used. The addition of EVA polymer further reduced water absorption, while had no important impact on strength. Compressive strength values were affected in a greater extent by hydrochloric acid solution, followed by sulfate and nitric acid solutions. The addition of EVA polymer decreased compressive strength loss for the specimens with rubber aggregates stored in hydrochloric and nitric acid solutions. The specimens without polymer binder showed similar mass loss, which was higher in sulfate acid solution followed by hydrochloric and nitric acid solutions. The use of EVA polymer delayed mass loss, while its content did not affect it significantly.

Soil Mass Loss Reduction during Rainfalls by Reinforcing the Slopes with the Surficial Confinement

Soil confinement systems serve as effective solutions to any erosion control project. Various confinements systems, namely triangular, circular and rectangular with the size of 50, 100, and 150 mm, and with a depth of 10 mm, were embedded in soil samples at slope angle of 60°. The observed soil mass losses for the confined soil systems were much smaller than those from unconfined system. As a result, the size of confinement and rainfall intensity have a direct effect on the soil mass loss. The triangular and rectangular confinement systems showed the lowest and highest soil loss masses, respectively. The slopes also failed much faster in the unconfined system than in the confined slope.

Evaluating Residual Mechanical and Physical Properties of Concrete at Elevated Temperatures

This paper presents the results of an experimental  study on the effects of elevated temperature on compressive and  flexural strength of Normal Strength Concrete (NSC), High Strength  Concrete (HSC) and High Performance Concrete (HPC). In addition,  the specimen mass and volume were measured before and after  heating in order to determine the loss of mass and volume during the  test. In terms of non-destructive measurement, ultrasonic pulse  velocity test was proposed as a promising initial inspection method  for fire damaged concrete structure. 100 Cube specimens for three  grades of concrete were prepared and heated at a rate of 3°C/min up  to different temperatures (150, 250, 400, 600, and 900°C). The results  show a loss of compressive and flexural strength for all the concretes  heated to temperature exceeding 400°C. The results also revealed that  mass and density of the specimen significantly reduced with an  increase in temperature.  

Prediction Heating Values of Lignocellulosics from Biomass Characteristics

The paper provides biomasses characteristics by proximate analysis (volatile matter, fixed carbon and ash) and ultimate analysis (carbon, hydrogen, nitrogen and oxygen) for the prediction of the heating value equations. The heating value estimation of various biomasses can be used as an energy evaluation. Thirteen types of biomass were studied. Proximate analysis was investigated by mass loss method and infrared moisture analyzer. Ultimate analysis was analyzed by CHNO analyzer. The heating values varied from 15 to 22.4MJ kg-1. Correlations of the calculated heating value with proximate and ultimate analyses were undertaken using multiple regression analysis and summarized into three and two equations, respectively. Correlations based on proximate analysis illustrated that deviation of calculated heating values from experimental heating values was higher than the correlations based on ultimate analysis.