Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Carbon dioxide utilization with carbonation using industrial waste-desulfurization gypsum and waste concrete

In this study, we propose a process making calcium carbonate and calcium sulfate and recovering absorbent using ammonia absorbent, carbon dioxide, and industrial waste. The main objective of this study is to confirm the possibility of carbon capture and utilization based on waste materials. We assumed desulfurization gypsum and construction waste (ready mixed concrete washing water, waste concrete, etc.) are CaSO₄, Ca(OH)₂, respectively. And concentration of simulated carbon dioxide gas was 15 vol% similar to flue gas. Calcium carbonate was produced by combination reaction between ionic CO₂ in absorbent and metal ion in the solid waste. Experiments were conducted at normal temperature and pressure. Furthermore, the generated products were characterized by X-ray diffraction, and scanning electron microscope.     

Effect of Metal Compounds and Experimental Conditions on Distribution of Products from PVC Pyrolysis

Effects of heating rate, gas flow rate, and type of metal compounds on the amount of hydrogen chloride, liquid, gas, and solid pyrolyzate obtained from the pyrolysis of poly(vinyl chloride) (PVC) were investigated. The pyrolysis experiments were carried out in both a thermogravimetric analysis (TGA) instrument and a fixed-bed reactor. Products from the fixed-bed reactor were collected and analyzed by using Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectroscopy (GC-MS), titration technique, and gravimetry. It was found that heating rate in the TGA experiments did not affect the amount of released hydrogen chloride. However, the TGA profiles significantly changed with the rate. The onset of dehydrochlorination increased with the rate. In addition, as the heating rate was increased from 10 to 20°C/min, there was no solid residue left. The amount of liquid pyrolyzate obtained from the fixed-bed reactor can be either increased or decreased with the heating rate, depending on the gas flow rate and the actual residence time in the reactor. FTIR and GC-MS analysis indicated that the liquid pyrolyzates were mainly benzene, toluene, and styrene. By comparing the efficiency of various metal compounds in trapping the HCl, it was found that Ca(OH)₂ was more efficient than Mg(OH)₂, and that CaO was more efficient than MgO. These results are discussed in light of the reaction mechanism between HCl and the metal compounds.     

Alkyd-amino resins based on waste PET for coating applications

Waste polyethylene terephthalate (PET) flakes were depolymerized by using propylene glycol (PG) in the presence of zinc acetate as catalyst. Glycolysis reaction products of waste PET obtained by using PET/glycol molar ratio 1/2. Two short oil alkyd resins of high acid values (30-40mgKOH/g) were prepared from phthalic anhydride (PA), glycerin (G), coconut oil fatty acids (COFA) and glycolyzed products of waste PET (PET-based alkyd resins) or glycols (PG) (reference alkyd resins). These alkyd resins were blended with 30%, 40%, and 50% of a commercial urea-formaldehyde, melamine-formaldehyde and urea-formaldehyde/melamine-formaldehyde mixture (1/1 weight ratio) and heated at 140 degrees C. The physical and chemical properties such as drying time, hardness, abrasion resistance, adhesion strength, water resistance, alkaline resistance, acid resistance, gelation time, and thermal oxidative degradation resistance (with thermogravimetric analysis, TGA) of these alkyd-amino resins were investigated. The properties of the waste PET-based resins were found to be compatible with the properties of the reference resins.     

Supercritical water gasification of sewage sludge using bench-scale batch reactor: advantages and drawbacks

Sewage sludge, a byproduct of municipal wastewater treatment, was gasified by supercritical water using a bench-scale batch reactor. Configuration of bench-scale batch reactor and operation procedures are discussed in detail. Experience and challenges that arose during the experiment are also shared. Using the bench-scale reactor under the condition of 600 °C, 23 MPa, and a reaction time of 60 min without catalyst presence, a total gas yield of 9.8 mol/(kg-sewage sludge) was obtained. Furthermore, investigations on operational parameters were conducted. Extension of reaction time up to 60 min increased the gasification, reaching a plateau thereafter. Investigation on pressure indicated the superiority of supercritical pressure. The addition of Ni as a catalyst also promoted gasification, although inorganic salts and char seemed to cover the catalyst surface. With regard to the prospect of future operation at a municipal waste water treatment plant, the effect of operational parameters on heavy metal concentration in the liquid phase is also discussed.     

Alkaline solution neutralization capacity of soil

Alkaline eluate from municipal solid waste (MSW) incineration residue deposited in landfill alkalizes waste and soil layers. From the viewpoint of accelerating stability and preventing heavy metal elution, pH of the landfill layer (waste and daily cover soil) should be controlled. On the other hand, pH of leachate from existing MSW landfill sites is usually approximately neutral. One of the reasons is that daily cover soil can neutralize alkaline solution containing Ca²⁺ as cation. However, in landfill layer where various types of wastes and reactions should be taken into consideration, the ability to neutralize alkaline solutions other than Ca(OH)₂ by soil should be evaluated. In this study, the neutralization capacities of various types of soils were measured using Ca(OH)₂ and NaOH solutions. Each soil used in this study showed approximately the same capacity to neutralize both alkaline solutions of Ca(OH)₂ and NaOH. The cation exchange capacity was less than 30% of the maximum alkali neutralization capacity obtained by the titration test. The mechanism of neutralization by the pH-dependent charge can explain the same neutralization capacities of the soils. Although further investigation on the neutralization capacity of the soils for alkaline substances other than NaOH is required, daily cover soil could serve as a buffer zone for alkaline leachates containing Ca(OH)₂ or other alkaline substances.     

Effect of aerobic pretreatment of waste on the rate of anaerobic treatment processes

The efficiency of waste degradation can be expressed by the rate of waste decomposition in individual phases. This article presents the durations of degradation phases of pretreated and untreated waste stabilized in anaerobic laboratory reactors. In this investigation, the quantities of organic and nitrogen contaminants emitted from the waste during the study are presented. The study confirmed the beneficial effects of aerobic pretreatment of waste before landfilling on reducing the duration of hydrolysis and acid phases, and speeding up the start of the stable methane phase. In the pretreated waste reactor, the stable methane phase began about 19 weeks earlier than in the untreated waste. The total amounts of contaminants removed from the aerobic pretreatment waste were lower than from untreated waste, with values of COD, TOC, BOD₅, and VFA corresponding to 21, 18, 6, and 23 %, respectively, and values of TKN and NH₄ of 7 and 50 %, respectively.     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

Anaerobic co-digestion of tannery waste water and tannery solid waste using two-stage anaerobic sequencing batch reactor: focus on performances of methanogenic step

In this study, anaerobic co-digestion of the tannery waste water (TWW) and tannery solid waste (TSW) with four TWW to TSW mixing ratios (100:0, 75:25, 50:50 and 25:75) was carried out using semi-continuous two-phase anaerobic sequencing batch reactor system under mesophilic temperature (38?±?2 °C). During the experimental study, effluents resulted from previously optimized acidogenic reactors were used to feed subsequent methanogenic reactors and then operated at hydraulic retention time (HRT) of 20, 15 and 10 days and equivalent organic loading rate. The findings revealed that methanogenic reactor of 50:50 (TWW:TSW) treating the effluent from previously optimized acidogenic step exhibits best process performances in terms of daily biogas (415 ml/day), methane production (251 ml/day), methane content (60.5%) and COD removal efficiency (75%) when operated at HRT of 20 days. Process stability of methanogenic step also evaluated and the obtained results showed suitable pH (6.8), no VFA accumulation, i.e., VFA/Alkalinity (0.305), alkalinity (3210 mgCaCO₃/l) and ammonia (246 mg/l with in optimum operating range). In general, improved process stability as well as performance was achieved during anaerobic co-digestion of TWW with TSW compared to mono-digestion of TWW.     

Effect of long chain fatty acids removal as a pretreatment on the anaerobic digestion of food waste

This study investigated the effect of long chain fatty acids (LCFAs) removal as a pretreatment prior to anaerobic digestion on the production of methane from food waste. The results showed that the anaerobic digestion of food waste containing 1.6 g COD/L of LCFAs was not inhibited (4 days lag-time, 78.3 % methane recovery in 35 days) compared to that of lipid free food waste (3 days lag time, 72.5 % methane recovery in 35 days); however, some unsaturated LCFAs, which are toxic to microorganism, were accumulated in the batch anaerobic digestion reactor. Meanwhile, in a methanogenic activity study, the activity of methanogens was observed to be linearly inhibited by the presence of more than 1 g COD/L of LCFAs. The possibility of the accumulation of unsaturated LCFAs in the reactor should be considered when operating a large-scale continuous system.     

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.     

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.     

Preparation and characterization of mesoporous γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> recovered from aluminum cans waste and its use in the dehydration of methanol to dimethyl ether

The present study includes synthesis of two γ-Al₂O₃ samples from waste aluminum cans using a simple precipitation method. Precipitation was carried out using two different precipitating agents (i.e. NaOH and NH₄OH). The two prepared alumina samples were characterized by means of X-ray diffraction (XRD) and N₂ adsorption–desorption techniques. Surface acidity of γ-Al₂O₃ samples was measured by adsorption of two different probe molecules (i.e. pyridine and dimethyl pyridine) followed by desorption measurements using thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Catalytic activity of the two prepared alumina samples towards the dehydration of methanol (to dimethyl ether) was studied in a fixed bed reactor at 300 °C. For comparison reasons, commercial γ-Al₂O₃ sample was, also, tested for the same catalytic reaction under the same conditions. Results showed that the alumina sample prepared using NaOH as a precipitating agent exhibited a better catalytic activity and stability compared with that prepared using NH₄OH and showed a similar activity as the commercial γ-Al₂O₃ sample.     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

Dechlorination and decomposition of Aroclor 1242 in real waste transformer oil using a nucleophilic material with a modified domestic microwave oven

This research was done to assess the dechlorination and decomposition of polychlorinated biphenyls (PCBs) in real waste transformer oil through a modified domestic microwave oven (MDMW). The influence of microwave power (200–1000 W), reaction time (30–600 s), polyethylene glycol (PEG) (1.5–7.5 g), iron powder (0.3–1.5 g), NaOH (0.3–1.5 g), and H₂O (0.4–2 ml) were investigated on the decomposition efficiency of PCBs existing in real waste transformer oil with MDMW. Obtained data indicate that PEG and NaOH have the greatest influence on decomposition of PCBs; while, iron did not influence, and H₂O decreased, the decomposition efficiency of PCBs. Experimental data also indicated that with the optimum amount of variables through a central composites design method (PEG = 5.34 g, NaOH = 1.17 g, Fe = 0.6 g, H₂O = 0.8 ml and microwave power 800 W), 78 % of PCBs was degraded at a reaction time of about 6 min. In addition, the PCBs decomposition without using water increased up to 100 % in the reactor with the MDMW at 6 min. Accordingly, results showed that MDMW was a very efficient factor for PCBs decomposition from waste transformer oil. Also, using microwave irradiation, availability and inexpensive materials (PEG, NaOH), and iron suggest this method as a fast, effective, and cheap method for PCB decomposition of waste oils.     

Comparison of different liquid anaerobic digestion effluents as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover

Effluents from three liquid anaerobic digesters, fed with municipal sewage sludge, food waste, or dairy waste, were evaluated as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover in mesophilic reactors. Three feedstock-to-effluent (F/E) ratios (i.e., 2, 4, and 6) were tested for each effluent. At an F/E ratio of 2, the reactor inoculated by dairy waste effluent achieved the highest methane yield of 238.5 L/kgVS_feed, while at an F/E ratio of 4, the reactor inoculated by food waste effluent achieved the highest methane yield of 199.6 L/kgVS_feed. The microbial population and chemical composition of the three effluents were substantially different. Food waste effluent had the largest population of acetoclastic methanogens, while dairy waste effluent had the largest populations of cellulolytic and xylanolytic bacteria. Dairy waste also had the highest C/N ratio of 8.5 and the highest alkalinity of 19.3 g CaCO₃/kg. The performance of solid-state batch anaerobic digestion reactors was closely related to the microbial status in the liquid anaerobic digestion effluents.     

BMP estimation of landfilled municipal solid waste by multivariate statistical methods using specific waste parameters: case study of a sanitary landfill in Turkey

The main objective of this study was to determine whether methane potential of waste could be estimated more easily by a limited number of waste characterization variables. 36 samples were collected from 12 locations and 3 waste depths in order to represent almost all waste ages at the landfill. Actual remaining methane potential of all samples was determined by the biochemical methane potential (BMP) tests. The cumulative methane production of closed landfill (cLF) samples reached 75–125 mL at the end of experiment duration, while the samples from active landfill (aLF) produced in average 216–266 mL methane. The average experimental k and L ₀ values of cLF and aLF were determined by non-linear regression using BMP data with first-order kinetic equation as 0.0269 day^?1–30.38 mL/g dry MSW and 0.0125 day^?1–102.1 mL/g dry MSW, respectively. The principal component analysis (PCA) was applied to analyze the results for cLF and aLF along with BMP results. Three PCs for the data set were extracted explaining 72.34 % variability. The best MLR model for BMP prediction was determined for seven variables (pH–Cl–TKN–NH4–TOC–LOI–Ca). R ² and Adj. R ² values of this best model were determined as 80.4 and 75.3 %, respectively.     

The chemical characteristics of ashes from cattle, swine and poultry manure

Animal manure is waste that contains large amounts of fertilizer resources. Incineration technology is effective in decreasing the volume of animal manure and concentrating the nutrients. In this study, the nutrient concentration and chemical compounds of several types of animal manure ash were examined to promote their recycling for agriculture. The nutrient concentration of manure ash was dependent on the reduction rate of solid materials by incineration. The phosphorus (P) and potassium (K) of cattle and layer manure were not concentrated greatly because of high silicon (Si) and calcium (Ca) concentrations, respectively. On the other hand, the P concentration of swine manure and broiler litter was increased to 10.1–12.0 % (3.6–4.6 times compared with original materials), equivalent to that of phosphate rock used as fertilizer material. The K concentration of broiler litter ash (16.1 %) was highest of all. The phosphate compounds of cattle and swine manure ashes were determined as Ca₉Fe(PO₄)₇ or Ca₉MgK(PO₄)₇. Hydroxyapatite (Ca₅(PO₄)₃(OH)) was detected in layer manure and broiler litter ashes. By acid treatment of ash, P and K availability of the fertilizer made from layer manure ash (33 % of materials) was equivalent to that of conventional chemical fertilizer.     

Effect of polyethylene terephthalate (PET) on the pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br)

Pyrolysis of brominated flame retardant-containing high-impact polystyrene (HIPS-Br) was performed at 430°C in the presence of 0.1 wt% of polyethylene terephthalate (PET) in a Pyrex glass reactor. Two different types of brominated flame retardants (decabromodiphenyl ether and decabromodiphenyl ethane) with or without antimony trioxide (as synergist) 5 wt% were used. The presence of PET had a significant effect on the material balance, decreasing the gaseous product and increasing the residue. The type of flame retardant had no effect on the yield of liquid product; however, the presence of Sb resulted in a marked difference in the distribution of decomposition products. Analysis by a gas chromatograph equipped with a flame ionization detector showed that the hydrocarbons were distributed in the range n-C₇ to n-C₂₅ with major peaks at n-C₉ and n-C₁₇. The presence of PET increased the formation of brominated compounds by several times and affected both the type and quantity of polybrominated compounds. The liquid products obtained from the pyrolysis of HIPS-Br/PET have to be treated before they can be used     

Bio-oil production by fast pyrolysis of cellulose/polyethylene mixtures in the presence of metal chloride

Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak wastes with and without metal chloride (ZnCl₂, AlCl₃, CuCl₂, FeCl₃) addition were subjected to a fast pyrolysis process at 350–500 °C and heating rate 100 °C/s to evaluate the possibility of liquid product formation with a high yield. The addition of zinc, aluminum, iron and copper chlorides has influenced the range of samples decomposition as well as the chemical composition of resulting pyrolytic oils. It was found that formation of levoglucosan, the main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presence of metal chlorides. Non-catalytic fast pyrolysis of polyethylene leads to the formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of more liquid hydrocarbons.