Catalytic gasification of tars from a dumping site

The work deals with catalytic gasification, pyrolysis and non-catalytic gasification of tar from an industrial dumping site. All experiments were carried out in a vertical stainless steel gasification reactor at 800 °C. Crushed calcined dolomite was used as the gasification catalyst. Parameters such as addition of water and air, and the influence of the catalyst in regard to the composition of the process gas were investigated. The catalytic gasification experiment in the steady state produced process gas with the composition: 56 % of H₂, 9 % of CO, 11 % of CH₄ and 12 % of CO₂ (mol.%). Concentration of the C₂ fraction was lower than 1 mol.%. Volume flow of air was later changed from 120 to 230 ml min^?1 reducing the amount of hydrogen to 51 mol.% and that of methane to 10 mol.%. Process gas created in a non-catalytic gasification process contained 26–30 mol.% of methane, 13–15 mol.% of carbon monoxide and 15–17 mol.% of the C₂ fraction and lower amounts of hydrogen (20 mol.%) and carbon dioxide (2–3 mol.%). The highest apparent conversion of tar was reached in the catalytic gasification processes. A higher rate of catalyst deactivation can be observed when water or air is not added.     

Utilization of Cellulosic Wastes in Textile and Garment Industries: 2. Synthesis and Characterization of Cellulose Acetate from Knitted Rag

Cellulose acetate (CA) was synthesized from knitted rag, a cellulosic waste of Textile and Garment industries, in the glacial acetic acid, and subsequently acetic anhydride (Ac₂O) in presence of concentrated H₂SO₄ reaction medium. A low to high substitution products were obtained from single step up to seven steps acetylation of cellulose. In this way, it was possible to produce low cost and different grades or substituted acetylation derivatives of cellulose. The synthesized CA was characterized and investigation of its physical characteristics was done. Solubility, acetyl content, acetic acid content, degree of substitution, and molecular weight of CA increased gradually with the increase of the number of reaction steps attaining optimum value at the fourth step. The acetyl and acetic acid content of CA were increased from 39.95 % to 44.25 %, and from 55.73 % to 61.73 % respectively. Similarly, degree of substitution and molecular weight of CA were increased from 2.47 to 2.94, and from 74,249 to 121,437 respectively.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

Thermogravimetric and XRD study of the effects of chloride salts on the thermal decomposition of mercury compounds

In this paper, the effects of chloride salt (MgCl₂, CaCl₂ or NaCl) addition on the thermal decomposition of five inorganic mercury compounds (HgCl₂, HgS, Hg(NO₃)₂·H₂O, HgO, and HgSO₄) were investigated by thermogravimetric analysis. Mercury-contaminated soil samples collected from Inner Mongolia were used to verify the results. The desorption temperatures of the mercury compounds increased in the following order: HgCl = HgCl₂ < HgS < Hg(NO₃)₂·H₂O < HgO < HgSO₄. Among the chloride salts, MgCl₂ had the greatest effect on thermal desorption of the mercury compounds, with the greatest reduction in the initial temperature of thermal desorption. After MgCl₂ treatment, the mercury removal rates for the soil were 65.67–81.35 % (sample A), 70.74–84.91 % (sample B), and 69.08 % (sample C). The increase in the mercury removal rate for sample C with addition of MgCl₂ was particularly large (34.96–69.08 %). X-Ray diffraction analysis of white crystals from the thermal desorption with MgCl₂ indicated that MgCl₂ promoted conversion of the mercury compounds in the soil to mercury(II) chloride and dimercury dichloride. This transformation is beneficial for applying thermal desorption to remedy mercury-contaminated soils and treat of mercury containing waste.     

Experimental and numerical calculations of waste R-134a thermal decomposition for energy and fluorine material recovery

Considering the global warming potential of R-134a (C₂H₂F₄) with the substantial generation of this refrigerant as waste material in various industrial sectors, the development of proper thermal destruction method of R-134a is of great practical significance. For this, experiment and numerical calculations have initially made for a tubular-type furnace in order to figure out the basic combustion characteristics of R-134a. A series of experimental investigations for the thermal decomposition of R-134a have been made as a function of wall temperature of tubular furnace and important reacting species such as O₂ and H₂O necessary for the decomposition of C₂H₂F₄ into HF, CO₂ and H₂O. In general, the thermal decomposition of R-134a is successfully made for the condition of temperature above 800 °C with the supply of stoichiometric amount of O₂ and these results are well agreed with numerical prediction. And this information is employed for the simulation of a full-scale, practical incinerator used for the CDM project. For this, numerical investigation has been made for a commercial-scale incinerator using CH₄–air flames for the proper destruction C₂H₂F₄ together with the control of pollutants such as CO and NO. In general, the destruction rate of C₂H₂F₄ appears more than 99.99 % and the generation of CO and NO species appears rather sensitive to the operational condition such as amount of water vapor. The numerical method of HFCs (hydrofluorocarbons) thermal treatment shows high possibility as a viable tool for the proper design and optimal determination of the operational condition for a HFCs incinerator.     

Characterization and Properties of Hydrophilic Cellulose Acetate Propionate Derivative

The chemical modification of Acrylamidomethyl Cellulose Acetate Propionate (AMCAP) was carried out by radical addition of acrylic acid. The structural modification was confirmed with the aid of FTIR, MS and NMR techniques. Thermal properties of hydrophilic cellulose derivative (AMCAP–H₂O₂) such as glass transition (T_g 153 °C) and thermal stability (372.7 °C) were determined by DSC and TGA techniques, respectively. These thermal properties confirmed the introduction of carboxylic groups into AMCAP structure, which causes an impact in their properties. The AMCAP–H₂O₂ shows minor contact angle compared to AMCAP, giving a more hydrophilic characteristic, due to acrylic acid addition into the side chains of AMCAP polymer.     

Recovery of Nd and Dy from rare earth magnetic waste sludge by hydrometallurgical process

This paper describes a hydrometallurgical process for recovering neodymium (Nd) and dysprosium (Dy) from a magnetic waste sludge generated from the Nd–Fe–B(–Dy) manufacturing process. Phase analysis by XRD study revealed Nd(OH)₃ and Fe₂O₃ as main mineral phases, and chemical analysis by ICP showed the contents of 35.1 wt% Nd, 29.5 wt% Fe, 1.1 wt% Dy and 0.5 wt% B. A solution of 1 M HNO₃ + 0.3 M H₂O₂ was used to dissolve up to 98 % Nd and 81 % Dy, while keeping Fe dissolution below 15 % within 10 min. Fe dissolved in solution was completely removed as Fe(OH)₃ at pH 3 followed by precipitation of Nd and Dy with oxalic acid (H₂C₂O₄) and recovered 91.5 % of Nd and 81.8 % of Dy from solution. The precipitate containing Nd and Dy was calcined at 800 °C to obtain Nd₂O₃ as final product with 68 % purity, and final recovery of 69.7 % Nd and 51 % of Dy was reported in this process.     

The behaviors of H2, CH4, C2H4 and C3H6 from the decomposition of polypropylene by NiO/Si–Al catalyst

The purpose of this study was to investigate the possibility of light gases produced from polypropylene, specifically hydrogen. In particular, we examined the effect of operating conditions on gaseous product and compositions in the catalytic cracking of polypropylene. We also characterized the gaseous product generated from polypropylene cracking. The feedstock (2.0 g) mixed with NiO/SiO₂–Al₂O₃ (Si–Al) was used, under non-isothermal conditions at low temperature range between 380 and 500 °C. Argon gas was used to carry the pyrolyzed gas, and the gas collected in a tedlar bag was analyzed for its behavior. We observed the behavior of major gases (H₂, CH₄, C₂H₄ and C₃H₆, etc.) according to reaction time and temperature. Finally, the effect of reaction conditions on evolved gases from catalytic cracking of polypropylene was analyzed.     

Matrix stability and leaching behaviour in ettringite-based stabilization systems doped with heavy metals

A stabilizing matrix able to generate ettringite from calcium sulphoaluminate in the presence of CaSO₄·2H₂O and Ca(OH)₂ has been studied. Ten series of stabilized samples have been produced, each containing 10% of one of the following heavy metal salts: Cd(NO₃)₂, Cr(NO₃)₃ Cu(NO₃)₂, Fe(NO₃)₃, Mn(NO₃)₃, Ni(NO₃)₂, Pb(NO₃)₂, Zn(NO₃)₂, K₂CrO₄ and K₂MoO₄. The study has been directed towards the matrix stability and metal release behaviour in three different dynamic leaching tests carried out with the following media: distilled water, pH 4 HNO₃ solution and pH 4.74 acetic acid/sodium acetate buffer solution. It has been found that the matrix stability and leaching behaviour strongly depend on the nature of the dopant salt, as well as on the nature of the leaching medium. In many cases the leaching medium attack causes disaggregation of the matrix but this does not imply complete dissolution of the dopant metal. When the leaching medium is the acetate buffer the chemical resistance to dissolution increases as the physico-mechanical resistance to disgregation decreases. This apparently contradictory result has been explained in terms of microstructure of the stabilized samples.     

Optimization of Carbon Dioxide and Valeric Acid Utilization for Polyhydroxyalkanoates Synthesis by Cupriavidus necator

The utilization of captured CO₂ as a part of the CO₂ capture and storage system to produce biopolymers could address current environmental issues such as global warming and depletion of resources. In this study, the effect of feeding strategies of CO₂ and valeric acid on cell growth and synthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] in Cupriavidus necator was investigated to determine the optimal conditions for microbial growth and biopolymer accumulation. Among the studied CO₂ concentrations (1–20 %), microbial growth and poly(3-hydroxybutyrate) accumulation were optimal at 1 % CO₂ using a gas mixture at H₂:O₂:N₂ = 7:1:91 % (v/v). When valeric acid was fed together with 1 % CO₂, (R)-3-hydroxyvalerate synthesis increased with increasing valeric acid concentration up to 0.1 %, but (R)-3-hydroxybutyrate synthesis was inhibited at >0.05 % valeric acid. Sequential addition of valeric acid (0.05 % at Day 0 followed by 0.025 % at Day 2) showed an increase in 3HV fraction without inhibitory effects on 3HB synthesis during 4 d accumulation period. The resulting P(3HB-co-3HV) with 17–32 mol  % of 3HV is likely to be biocompatible. The optimal concentrations and feeding strategies of CO₂ and valeric acid determined in this study for microbial P(3HB-co-3HV) synthesis can be used to produce biocompatible P(3HB-co-3HV).     

Extracellular Biopolymer Production by Aureobasidium pullulans MTCC 2195 Using Jackfruit Seed Powder

In this present paper, statistical screening and optimization of jackfruit seed powder based medium components were investigated for pullulan production from Aureobasidium pullulans. Seven medium variables jackfruit seed powder, K₂HPO₄, yeast extract, (NH₄)₂SO₄, NaCl, MgSO₄·7H₂O and ZnSO₄·7H₂O were screened by employing Plackett–Burman (PB) method. PB method showed jackfruit seed powder, ZnSO₄·7H₂O, K₂HPO₄ and yeast extract were significant. Central composite design of response surface method applied to optimize the significant variables identified from the PB experiment. Statistical analysis of the experimental results showed optimal values were found to be jackfruit seed powder 2 % (w/v), K₂HPO₄ 0.55 % (w/v), yeast extract 0.30 % (w/v) and ZnSO₄·7H₂O 0.006 % (w/v) with maximum pullulan concentration of 18.76 (g/L). Maximum pullulan concentration of 17.95 (g/L) was observed in the validation experiment. This experimental result explained the model was fitted 96 % as compare with the result predicted by response surface method.     

Study of nitrogen oxide absorption in the calcium sulfite slurry

Experiments were conducted using a bubbling reactor to investigate nitrogen oxide absorption in the calcium sulfite slurry. The effects of CaSO₃ concentration, NO₂/NO mole ratio and O₂ concentrations on NO₂ and SO₂ absorption efficiencies were investigated. Five types of additives, including MgSO₄, Na₂SO₄, FeSO₄, MgSO₄/Na₂SO₄ and FeSO₄/Na₂SO₄, had been evaluated for enhancing NO₂ absorption in CaSO₃ slurry. Results showed that CaSO₃ concentration had significant impact on NO₂ and SO₂ absorption efficiencies, and the highest absorption efficiencies of SO₂ and NO₂ could reach about 99.5 and 75.0 %, respectively. Furthermore, the NO₂ absorption was closely related to the NO₂/NO mole ratio, and the existence of NO₂ in flue gas may promote NO absorption. The presence of O₂ in simulated flue gas was disadvantage for NO _x removal because it can oxidize sulfite to sulfate. It was worth pointing out that FeSO₄/Na₂SO₄ was the best additive among those investigated additives, as the NO₂ removal efficiency was significantly increased from 74.8 to 95.0 %. IC and in situ FTIR results suggest that the main products were NO₃ ^? and NO₂ ^? in liquid phase and N₂O, N₂O₅ and HNO₃ in gas phase during the CaSO₃ absorption process.     

Recycling nickel from spent catalyst of Phu My fertilizer plant as a precursor for exhaust gas treatment catalysts preparation

In this study, a very promising way of treating and recycling spent nickel catalysts of fertilizer plants in Vietnam was proposed. Firstly, nickel was recovered from spent catalyst using HNO₃—leaching process. Results show that nickel recovery of over 90% with a purity of over 90% can be achieved with HNO₃ 2.1–2.5 M at 100?°C in 75 min. The residue after leaching is not considered as a hazardous waste according to the Vietnamese regulations. Then, the leachate solution was used as a precursor to prepare a model catalyst for exhaust gas (CO, HC, NO_x) treatment. In comparison with the catalyst prepared from the commercial nickel nitrate solution, the catalyst synthesized from recovered nickel exhibits similar properties and activities. The influence of Ni loading of Ni/alumina catalyst as well as the modification of active phase by some metals addition (Mn, Ba, Ce) was also investigated. It is feasible to modify active phase by transition metals such as Mn, Ba, and Ce for complete oxidation of CO and HC at 270?°C and a reduction of NO_x below 350?°C at high volumetric flow condition (GHSV?=?110.000 h^?1).     

Indoor Air Quality Assessment of Elementary Schools in Curitiba, Brazil

The promotion of good indoor air quality in schools is of particular public concern for two main reasons: (1) school-age children spend at least 30% of their time inside classrooms and (2) indoor air quality in urban areas is substantially influenced by the outdoor pollutants, exposing tenants to potentially toxic substances. Two schools in Curitiba, Brazil, were selected to characterize the gaseous compounds indoor and outdoor of the classrooms. The concentrations of benzene, toluene, ethylbenzene, and the isomers xylenes (BTEX); NO₂; SO₂; O₃; acetic acid (HAc); and formic acid (HFor) were assessed using passive diffusion tubes. BTEX were analyzed by gas chromatography–ion trap mass spectrometry and other collected gasses by ion chromatography. The concentration of NO₂ varied between 9.5 and 23?µg m^?3, whereas SO₂ showed an interval from 0.1 to 4.8?µg m^?3. Within the schools, BTEX concentrations were predominant. Formic and acetic acids inside the classrooms revealed intermediate concentrations of 1.5?µg m^?3 and 1.2?µg m^?3, respectively.     

Characteristics of NO2 Pollution in the City of Gothenburg, South-West Sweden—Relation to NO x and O3 Levels, Photochemistry and Monitoring Location

Concentrations of NO₂, NO, and O₃ from a rooftop monitoring station in Gothenburg, Sweden (2002–2006) were analysed to characterise NO₂ pollution. [NO₂] was shown to correlate strongly and non-linearly with [NO _x ] (NO _x ?=?NO?+?NO₂), in line with observations in other cities. The [NO₂] to [NO _x ] fraction fell initially with increasing [NO _x ]. At [NO _x ] levels >200 ppb, the decline in [NO₂]/[NO _x ] with increasing [NO _x ] levelled out and [NO₂]/[NO _x ] converged towards approximately 0.15–0.16, independent of [NO _x ]. Data from a traffic route site showed the same pattern. This value of [NO₂]/[NO _x ] at high [NO _x ] can be interpreted as the NO₂ fraction of the NO _x emissions from vehicle exhaust. Situations with high NO _x pollution and minimum [NO₂]/[NO _x ] were always associated with [O₃] close to zero. Plotting [Ox] (Ox?=?NO₂?+?O₃) vs. [NO _x ] provided a strong linear correlation for situations dominated by local pollution ([NO]/[NO₂]>1). The slope of the regression, a measure of the primary NO₂ fraction in NO _x emissions, was 0.13 during the day and 0.14 during the night. With stronger winds, the rooftop monitoring station became more similar, in terms of NO₂ pollution, to a city street site and a traffic route site, although [NO₂] was almost always higher at the street/traffic route locations. The EU standard for the annual average of [NO₂] (40 μg m^?3) was exceeded, while the hourly standard (200 μg m^?3, not to be exceeded more than 18 times per year by 2010) was not exceeded at any of the sites.     

Thermal processing of paper sludge and characterisation of its pyrolysis products

Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 °C/min were found to be CO and CO₂, contributing to almost 25% of the paper sludge dry weight loss at 500 °C. The hydrocarbons (CH₄, C₂H₄, C₂H₆) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 °C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 °C had a calorific value of 13.3 MJ/kg.     

Preparation and characterization of high surface area activated carbon from pine wood sawdust by fast activation with H<Subscript>3</Subscript>PO<Subscript>4</Subscript> in a spouted bed

Activated carbons were produced from waste pine wood sawdust using fast activation with H₃PO₄ in a spouted bed. In this study, activation temperature was set as 800 °C, and activation time ranged from 1 to 15 min. Experimental results show that sawdust impregnated with higher mass ratio of H₃PO₄ would be agglomerated in spouted bed, and difficult to fluidize. Therefore, an amount of quartz sand was added to assist for good fluidization. Fluidization of particle can improve the BET surface area or micropore volume of activated carbons. High BET surface area activated carbons can be obtained with activation time of only 1–5 min by combining the fluidization and H₃PO₄ fast activation. The obtained activated carbons contained developed pore structure and abundant surface functional groups (carboxyl, carbonyl and P-containing groups) by SEM–EDS, FTIR and XPS techniques. The particles of impregnation ratio of 1:1 can achieve fluidization without adding the quartz sand, which was convenient for experimental operation and even industrial production, and the BET surface area can reach more than 1000 m²/g in activation time of only 5 min.     

Stabilization of sewage sludge in the presence of nanoscale zero-valent iron (nZVI): abatement of odor and improvement of biogas production

The potential benefits of nanoscale zero-valent iron (nZVI) on sludge stabilization, either the abatement of odor or the improvement of biogas production, were investigated in this study. Two commercial-grade microscale iron powders were also utilized for comparison. Adding 0.10 wt% of nZVI in sludge during anaerobic incubation significantly reduced the concentration of H₂S in biogas by 98.0 % (96.2–98.9 %), probably attributed by reactions between sulfides and the neo-formed hydrous Fe(II)/Fe(III) oxides layer at the surface of ZVI nanoparticles. Meanwhile, the percentage of P in bioavailable fractions decreased from 76.8 to 52.5 %, possibly due to the formation of vivianite [Fe₃(PO₄)₂]. Furthermore, 0.10 wt% of nZVI in anaerobic digestion for 17 days enhanced the concentration of CH₄ in biogas by 5.1–13.2 % and improved the production of biogas and methane by 30.4 and 40.4 %, respectively. The amendment of iron nanoparticles during anaerobic digestion can not only effectively reduce H₂S in biogas, but also potentially boost methane production significantly.     

Organically Modified Nanoclay and Aluminum Hydroxide Incorporated Bionanocomposites towards Enhancement of Physico-mechanical and Thermal Properties of Lignocellulosic Structural Reinforcement

A range of bio-nanocomposites were prepared by incorporation of organo modified montmorillonite nanoclay (OMMT) with or without use of aluminum hydroxide (Al(OH)₃) within polylactic acid (PLA) solution. Furthermore, the solution was employed for modification of ligno-cellulosic (jute) fabric structural reinforcements. The successful incorporation of nanofillers within the host polymer, polylactic acid (PLA) was confirmed by Fourier-transform infrared spectroscopy (FT-IR). Water uptake and swelling behaviour studies revealed that the water uptake and swelling ratio of bio-composites reduced significantly as compared to pristine jute fabric, whereas upon incorporation of OMMT and Al(OH)₃, the water barrier properties reduced even further in the developed bio-nanocomposites. The flexural strength of the bio-nanocomposites also showed improved mechanical and dimensional stability. Synergistic effects of OMMT and Al(OH)₃ were observed in enhancing the aforementioned physico-mechanical properties. Scanning electron microscopy (SEM) studies revealed microstructural details of developed samples. Similarly, the thermo-gravimetric analysis and linear burning rate studies of Al(OH)₃ treated bio-nanocomposite materials revealed enhanced thermal resistance and reduced flammability respectively compared to both pristine woven jute fabric and fabrics treated with PLA alone or those without Al(OH)₃. From the above results it can safely be said that the bio-nanocomposite material can be a prospective candidate for development of flame retardant biopackaging.     

Investigation on thermal dechlorination and catalytic pyrolysis in a continuous process for liquid fuel recovery from mixed plastic wastes

A continuous system (feeding rate >1 kg/h) consisting of thermal dechlorination pre-treatment and catalytic pyrolysis with Fe-restructured clay (Fe-RC) catalyst was developed for feedstock recycling of PVC-containing mixed plastic waste. The vented screw conveyor which was specially designed for continuous dechlorination was able to achieve dechlorination efficiency of over 90 % with a feedstock retention time longer than 35.5 min. The chlorine content of the pyrolytic oil obtained after dechlorination was in the range of 6.08–39.50 ppm, which meet the specification for reclamation pyrolytic oil in Japan. Fe-RC was found to significantly improve the yield of pyrolytic oil (achieved to 83.73 wt%) at the optimized pyrolysis temperature of 450 °C and catalyst dosage of 60 g. With the optimized parameters, Fe-RC showed high selectivity for the C₉–C₁₂ and C₁₃–C₁₉ oil fraction, which are the major constituents of kerosene and diesel fuel, demonstrating that this catalyst can be applied in the pyrolysis of mixed plastic wastes for the production of kerosene and diesel fuel. Overall, the continuous process exhibited high stability and consistently high-oil yield upon reaching steady state, indicating its potential up-scaling application in the industry.