Polyethylene conversion by partial oxidation in supercritical water

This paper gives the results of partial oxidation experiments of polyethylene (PE) in supercritical water (SCW). The experiments were carried out at a reaction temperature of 693K and a reaction time of 30 min using 6 cm³ of a batch-type reactor. The loaded sample weight was 0.3 g and there was 2.52 g water (0.42 g/cm³). The ratio of oxygen atoms to carbon atoms was 0.3. The results show a significant CO formation in O₂–SCW, and the 1-alkene/n-alkane ratio in partial oxidation was higher than that in SCW pyrolysis. These results suggest the possibility of the hydrogenation of hydrocarbon through partial oxidation followed by a water–gas shift reaction. Received: July 19, 2000 / Accepted: September 28, 2000     

USING ISOTOPIC AND MOLECULAR DATA TO MODEL LANDFILL GAS PROCESSES

Using a large data set, a preliminary investigation has been made to evaluate the usefulness of stable isotope ratios for improving our understanding of methane and carbon dioxide generation in landfills. Included are approximately 130 landfill gas samples from across the U.S.A., and 18 recent samples from: (1) an Argonne Laboratory study area in the Brea-Olinda Landfill, Orange County, California (U.S.A); and (2) several Los Angeles County landfills, California (U.S.A). The following isotope ratios were examined: δ¹³C for methane, δ¹³C for carbon dioxide and δD for methane. Using simple ratio plots supplemented by mass-balance calculations, these data show promise for indicating the relative contributions of the four major carbon cycle processes in landfills, namely: (1) direct oxidation of organic material to carbon dioxide; (2) methane generation from fermentation (acetate cleavage); (3) methane generation from carbon dioxide reduction; and (4) methane oxidation to carbon dioxide by methanotrophic bacteria. Both the methane generation and oxidation reactions are central to an explanation of the trends discussed herein. The data also suggest that direct oxidation of organic matter in the refuse may be contributing to the observed isotopic ratios in some cases. The trends observed at the Brea-Olinda site were similar to trends using the large U.S. database, suggesting that isotopic techniques may be useful to better constrain carbon cycle processes common to all landfill settings.     

Treatment of MTBE‐Contaminated Waters with Fenton's Reagent

Methyl tertiary‐butyl ether (MTBE) is commonly used as a fuel additive because of its many favorable properties that allow it to improve fuel combustion and reduce resulting concentrations of carbon monoxide and unburnt hydrocarbons. Unfortunately, increased production and use have led to its introduction into the environment. Of particular concern is its introduction into drinking water supplies. Accordingly, research studies have been initiated to investigate the treatment of MTBE‐contaminated soil and groundwater. The summer 2000 issue of Remediation reported the results of an initial study conducted by the authors to evaluate the treatment of MTBE using Fenton's reagent. In this follow‐up study, experiments were conducted to further demonstrate the effectiveness of using Fenton's reagent (H₂O₂:Fe⁺²) to treat MTBE‐contaminated groundwater. The concentration of MTBE was reduced from an initial concentration of 1,300 μg/l (14.77 μ moles) to the regulatory level of 20 μg/l (0.23 μ moles) at a H₂O₂:Fe⁺² molar ratio of 1:1, with ten minutes of contact time and an optimum pH of 5. The by‐products, acetone and tertiary butyl alcohol, which are always present in MTBE in trace amounts, were not removed even after 60 minutes of reaction time. © 2002 Wiley Periodicals, Inc. *     

Treatment of tar pond sludge in a circulating fluidized bed combustor

A series of tests to burn mixtures of tar pond sludge and coal was carried out using a mini‐circulating fluidized bed combustor (mini‐CFBC). During the tests, carbon dioxide, oxygen, carbon monoxide, sulfur dioxide, and nitrogen oxides in the flue gas were monitored continuously. Stack gas sampling was carried out for hydrochloric acid, metals, particulate matter, volatile organic compounds (VOCs), total hydrocarbons, semivolatile organic compounds (SVOCs), dioxins and furans (PCDD/Fs), and polychlorinated biphenyls (PCBs). Results showed that hydrochloric acid, mercury, particulate matter, PCDD/F, and metal concentrations were all below both the current limits and the gas‐release limits to be implemented in 2008 in Canada. The new 2008 emissions limits will reduce the maximum allowable concentrations of most pollutants by half. Thus, the maximum concentration for particulate matter will be 5 mg/m³ (from the current maximum concentration of 10 mg/m³);the maximum concentration for hydrochloric acid will be 5 mg/m³ (from 10 mg/m³); and the‐maximum concentration for dioxins and furans will be 0.032 ng/m toxic equivalent (from 0.08 ng/mcurrently). Sulfur capture efficiency was 89–91 percent. The percentage of fuel nitrogen converted to nitrogen oxides was of the order of 4.7 to 6.1, which is significantly lower than that of conventional pulverized coal‐fired boilers and well within the normal range for fluidized bed combustors (FBCs). PCB and polycyclic aromatic hydrocarbon (PAH) emissions levels were comparable or lower than levels reported in the literature for industrial‐scale FBCs. VOC concentrations were low except for benzene, for which the concentration was higher than that reported for pulverized coal‐fired utility boilers. In addition, carbon monoxide concentration was high at 1,200 to 2,200 parts per million. However, these carbon monoxide concentrations are typical of the mini‐CFBC firing coal. The trials showed that for 10 percent by weight tar pond sludge mixed with 90 percent by weight coal, the combustion was both stable and efficient. The tests demonstrated that CFBC technology is an environmentally sound option for eliminating tar pond waste sludge. © 2005 Wiley Periodicals, Inc.     

Co-combustion of agricultural residues with coal in a fluidized bed combustor

Power generation from biomass is an attractive technology that utilizes agricultural residual waste. In order to explain the behavior of biomass-fired fluidized bed incinerator, biomass sources from agricultural residues (rice husk and palm kernel) were co-fired with coal in a 0.15m diameter and 2.3m high fluidized bed combustor. The combustion efficiency and carbon monoxide emissions were studied and compared with those for pure coal combustion. Co-combustion of a mixture of biomass with coal in a fluidized bed combustor designed for coal combustion increased combustion efficiency up to 20% depending upon excess air levels. Observed carbon monoxide levels fluctuated between 200 and 900 ppm with the addition of coal. It is evident from this research that efficient co-firing of biomass with coal can be achieved with minimal modifications to existing coal-fired boilers.     

Combustion characteristics of coal and refuse from passenger trains

Refuse from passenger trains is becoming a significant issue with the development of the Chinese railway. Co-firing is regarded as a promising thermal technology, both environmentally and economically, in reducing the quantity of refuse. The co-firing property of passenger train refuse with coal, however, may differ due to the differences in the composition of the refuse. In the present study, combustion properties of refuse from passenger train samples and the mixture of refuse with coal were studied in a tube furnace. Thermo analysis methods, such as thermogravimetry (TG), differential scanning calorimetry (DSC), differential thermal analysis (DTA) and derivative thermogravimetry (DTG) analyses were employed to evaluate combustion performance. We found that the mixture of passenger train refuse and coal at a ratio of 1:1 has a lower ignition and burnout temperature than the coal-only sample. Moreover, refuse from railway passenger trains has more reactive combustion properties than the coal-only sample, and the addition of railway passenger train refuse to coal can promote the reactivity of coal.     

Composting of food refuse from a student restaurant in Hokkaido University

Over a period of 21 months, we composted food refuse from a student restaurant in Hokkaido University using a commercially available composting machine. The machine had two reactors, each with a working volume of 250 l. The refuse was mixed with sawdust in a ratio of 5 l sawdust to 10 kg refuse, and this mixture was fed into the machine daily. We studied the characteristics of the refuse, the composting mixture, and the finished compost in an effort to optimize the operating parameters. We also evaluated the effectiveness of the composting process by determining the decomposition rates of the composting materials. The optimum moisture content of the composting mixture was between 30% wet basis (wb) and 40% wb in this machine. The composting machine worked well when the first reactor was filled with composting mixture and 0.5 kg lime was added once per week. The mass of the materials supplied was reduced by 84% over the study period. The decomposition rate of the volatile matter in all composting materials was 66%. The mass of the food refuse supplied was 14.8 kg/day on average, and the moisture content of the refuse was 77% wb on average. Received: October 4, 1999 / Accepted: April 4, 2000     

Removal potential of toxic 2378-substituted PCDD/F from incinerator flue gases by waste-derived activated carbons

The application of activated carbons has become a commonly used emission control protocol for the removal or adsorption of persistent organic pollutants from the flue gas streams of waste incinerators. In this study, the 2378-substituted PCDD/F removal efficiency of three types of activated carbons derived from the pyrolysis of refuse derived fuel, textile waste and scrap tyre was investigated and compared with that of a commercial carbon. Experiments were carried out in a laboratory scale fixed-bed reactor under a simulated flue gas at 275 °C with a reaction period of four days. The PCDD/F in the solid matrices and exhaust gas, were analyzed using gas chromatography coupled with a triple quadrupole mass spectrometer. In the absence of activated carbon adsorbent, there was a significant increase in the concentration of toxic PCDD/F produced in the reacted flyash, reaching up to 6.6 times higher than in the raw flyash. In addition, there was a substantial release of PCDD/F into the gas phase, which was found in the flue gas trapping system. By application of the different commercial, refuse derived fuel, textile and tyre activated carbons the total PCDD/F toxic equivalent removal efficiencies in the exhaust gas stream were 58%, 57%, 64% and 52%, respectively. In general, the removal of the PCDDs was much higher with an average of 85% compared to PCDFs at 41%. Analysis of the reacted activated carbons showed that there was some formation of PCDD/F, for instance, a total of 60.6 μg I-TEQ kg⁻¹ toxic PCDD/F was formed in the refuse derived fuel activated carbon compared to 34 μg I-TEQ kg⁻¹ in the commercial activated carbon. The activated carbons derived from the pyrolysis of waste, therefore, showed good potential as a control material for PCDD/F emissions in waste incinerator flue gases.     

Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine

This paper presents the study of the combustion of char residues produced during co-gasification of coal with pine with the aim of characterizing them for their potential use for energy. These residues are generally rich in carbon with the presence of other elements, with particular concern for heavy metals and pollutant precursors, depending on the original fuel used.The evaluation of environmental toxicity of the char residues was performed through application of different leaching tests (EN12457-2, US EPA-1311 TCLP and EA NEN 7371:2004). The results showed that the residues present quite low toxicity for some of pollutants. However, depending on the fuel used, possible presence of other pollutants may bring environmental risks.The utilization of these char residues for energy was in this study evaluated, by burning them as a first step pre-treatment prior to landfilling. The thermo-gravimetric analysis and ash fusibility studies revealed an adequate thermochemical behavior, without presenting any major operational risks.Fluidized bed combustion was applied to char residues. Above 700 °C, very high carbon conversion ratios were obtained and it seemed that the thermal oxidation of char residues was easier than that of the coals. It was found that the char tendency for releasing SO₂ during its oxidation was lower than for the parent coal, while for NO_X emissions, the trend was observed to increase NO_X formation. However, for both pollutants the same control techniques might be applied during char combustion, as for coal. Furthermore, the leachability of ashes resulting from the combustion of char residues appeared to be lower than those produced from direct coal combustion.     

Biodegradable kinetics of plastics under controlled composting conditions

This study models and evaluates the kinetics of C-CO₂ evolution during biodegradation of plastic materials including Polyethylene (PE), PE/starch blend (PE/starch), microcrystalline cellulose (MCE), and Polylactic acid (PLA). The aerobic biodegradation under controlled composting conditions was monitorated according to ISO 14855-1, 2004. The kinetics model was based on first order reaction in series with a flat lag phase. A non-linear regression technique was used to analyze the experimental data. SEM studies of the morphology of the samples before and after biodegradation testing were used to confirm the biodegradability of plastics and the accuracy of the model. The work showed that MCE and PLA produced the high amounts of C-CO₂ evolution, which gave readily hydrolysable carbon values of 55.49% and 40.17%, respectively with readily hydrolysis rates of 0.338 day⁻¹ and 0.025 day⁻¹, respectively. Whereas, a lower amount of C-CO₂ evolution was found in PE/starch, which had a high concentration of moderately hydrolysable carbon of 97.74% and a moderate hydrolysis rate of 0.00098 day⁻¹. The mineralization rate of PLA was 0.500 day⁻¹ as a lag phase was observed at the beginning of the biodegradability test. No lag phase was observed in the biodegradability testing of the PE/starch and MCE. The mineralization rates of the PE/starch and MCE were found to be 1.000 day⁻¹, and 1.234 day⁻¹, respectively. No C-CO₂ evolution was observed during biodegradability testing of PE, which was used for reference as a non-biodegradable plastics sample.     

Self-heating of dried wastewater sludge

We experimentally studied the occurrence of spontaneous self-heating of sludge after drying, to understand its nature, course and remediation. The sludge originates from primary and biological treatment of both municipal and industrial wastewater, the latter largely dominant (approx. 90% total organic carbon, mainly from local tanneries). Dried sludge is collected into big–bags (approx. 1.5 m³) and landfilled in a dedicated site. After several years of regular operation of the landfill, without any management or environmental issue, indications of local warming emerged, together with smoke and smelling emissions, and local subsidence. During a two year monitoring activity, temperatures locally as high as 80 °C have been detected, 6–10 m deep. Experiments were carried out on large quantities of dried sludge (～1 t), monitoring the temperature of the samples over long periods of time (months), aiming to reproduce the spontaneous self-heating, under different conditions, to spot enhancing and damping factors. Results demonstrate that air is a key factor to trigger and modulate the self-heating. Water, in addition to air, supports and emphasizes the heating. Unusual drying operation was found to affect dramatically the self-heating activity, up to spontaneous combustion, while ordinary drying conditions yield a sludge with a moderate self-heating inclination. Temperature values as well as heating time scales suggest that the exothermic process nature is mainly chemical and physical, while microbiological activity might be a co-factor.     

Two-stage thermal gasification of polyolefins

Plastic pellets of polyethylene (PE), polypropylene (PP), and polystyrene (PS) were gasified in a two-stage thermal degradation process. The first stage is the conversion of polyolefins to distilled oils using a melting vessel. In the second stage, the oils from the first stage are gasified using a tubular reactor. The distilled oil yields of PE, PP, and PS in the first stage were 84, 89, 92 wt%, respectively, each at 470°C. The total gas yields of PE, PP, and PS in the second stage were 80, 74, and 6.2 wt%, respectively, each at 800°C. The main components of the product gas for PE and PP were methane and olefins such as ethene and propene. Some aromatic oils, including benzene, toluene, and xylene, were also produced as by-products. The amount of carbonaceous residue, or coke, was very low (less than 1 wt%). By dividing the process into two stages, the coking rate was considerably reduced compared with direct gasification of the polyolefins. Received: July 19, 2000 / Accepted: September 17, 2000     

Fiberboard plant emissions control using a silent discharge plasma

A silent discharge plasma reactor was constructed to test a potential industrial application for controlling volatile organic carbon emission from fiberboard manufacturing plants. The reactor consisted of a cylindrical single barrier dielectric barrier discharge cell connected to a high‐voltage ac power supply. Various concentrations of turpene in air were introduced into the reactor under dry and wet conditions. The destruction removal efficiencies (DRE) were monitored using a gas chromatograph mass spectrometer (GCMS) and the concentrations of carbon dioxide generated from the oxidation ofturpene were monitored using a Fourier Transform Infrared Spectrometer (FTIR). It was found that 90 percent of the turpenes could be removed at modest energy densities and that adding water to the gas mix greatly enhanced the destruction of the turpenes. However, even at high energy densities, the oxidation of turpenes did not completely form carbon dioxide. The results suggest that the Silent Discharge Plasma (SDP) system can be used to control the emission of volatile organic compounds (VOCs) from fiberboard plants, but that further testing is needed to limit the emission of carbon monoxide.     

Carbon materials-catalyzed hydroliquefaction of flame-retardant plastics in organic solvents

Flame-retardant plastics, such as desktop and laptop personal computer bodies, could be completely liquefied by carbon materials-catalyzed hydroliquefaction in tetralin without using H₂ as a hydrogen source. Active carbons with larger surface areas (1450–3450 m²/g) acted as superior catalysts in transferring tetralin hydrogens to plastics. On the other hand, carbon blacks and fullerene-rich soot were less active catalysts. Graphite and mesocarbon microbeads did not show any catalytic effects. Benzene, toluene, and ethylbenzene were obtained as recyclable hydrocarbons; their total amounts varied from 4 wt% to 12 wt% depending on the types of plastics and the carbon materials used. Organic bromides such as polybromodioxins were not contained in the gases and oils of the product. Received: July 19, 2000 / Accepted: September 17, 2000     

Pyrolysis of polyethylene mixed with paper and wood: Interaction effects on tar, char and gas yields

In the present study the interactions between the main constituents of the refuse derived fuel (plastics, paper, and wood) during pyrolysis were studied. Binary mixtures of polyethylene-paper and polyethylene/sawdust have been transformed into pellets and pyrolyzed. Various mixtures with different composition were analyzed and pyrolysis products (tar, gas, and char) were collected. The mixtures of wood/PE and paper/PE have a different behavior. The wood/PE mixtures showed a much reduced interaction of the various compounds because the yields of pyrolysis products of the mixture can be predicted as linear combination of those of the pure components. On the contrary, a strong char yield increase was found at a low heating rate for paper/PE mixtures. In order to explain the results, the ability of wood and paper char to adsorb and convert the products of PE pyrolysis into was studied. Adsorption and desorption tests were performed on the char obtained by paper and wood by using n-hexadecane as a model compound for the heavy products of PE pyrolysis.     

SLP250二段式垃圾焚烧炉的燃烧调整

由于垃圾的热值和干、湿度等变化较大,所以,垃圾焚烧炉的燃烧调整具有一定的难度。简要论述了如何调整和控制垃圾焚烧炉的稳定燃烧,以供相关人员参考。     

Air Quality Management in Izmir Region of Turkey as Required by Clean Air Plans

As a first step to work out an abatement plan against air pollution, a local emission inventory with 1 hr temporal and 1 km spatial resolution in the city of Izmir and its surroundings was prepared. The study area consisted of a 200 × 170 km² rectangle having the city of Izmir at the centre. The studied pollutants were total particulate matter (PM), sulfur oxides (SO_x), nitrogen oxides (NO_x), volatile organic compounds (VOC) and carbon monoxide (CO). Emissions of these pollutants were determined by estimation methods making use of suitable emission factors. Emission sources were evaluated in three categories; point, area and line sources. For year 2000 total emissions in the study area on an average day were estimated as 173 tons PM, 299 tons SOx, 136 tons NOx, 68 tons VOC and 320 tons CO. At the second part of the study, calculated emissions were transformed into air quality predictions in the area by using the Industrial Source Complex – Short Term (ISCST3) dispersion model. Model results were tested with monitoring data from urban air quality stations obtained during the year 2000. Results of the past, present and future air quality estimates in the region were discussed. In order to do so, future scenarios including various control technology applications were formulated and tested to see their effect on the future air quality.     

Kinetic study of permanganate oxidation of tetrachloroethylene at a high pH under acidic conditions

Since carbon compounds are the main component of dense nonaqueous phase liquids (DNAPLs), the end products of all in situ chemical oxidation (ISCO) will include carbon dioxide. If the production rate of carbon dioxide exceeds the capacity of water to remove the carbon dioxide, degassing will occur. The uncontrolled carbon dioxide gas may change the flow patterns, remobilize the pooled DNAPL, transport DNAPL vapor, and reduce the relative permeability to the aqueous phase. Under high pH buffered conditions, most of the carbon dioxide will be dissolved in water. In this study, potassium permanganate oxidation of tetrachloroethylene (PCE) was conducted using a sodium carbonate buffered solution (1 g/L, pH = 10.6 ± 0.1) at three different temperatures (5, 10, and 20°C) and three potassium permanganate concentrations (0.2, 1, and 5 g/L). Extensive kinetic studies suggest that the overall oxidation is a second‐order reaction and pseudo‐first‐order with respect to PCE and potassium permanganate, respectively. The second‐order rate constant and the activation energy were 0.028 ± 0.001 M^?1s^?1 at 20°C and 43.9 ± 2.85 kJ/M, respectively. This study provides a base for further experimental and field studies on potassium permanganate oxidation of PCE under natural or artificial high pH buffered conditions. © 2004 Wiley Periodicals, Inc.     

Gasification applicability study of polyurethane solid refuse fuel fabricated from electric waste by measuring syngas and nitrogenous pollutant gases

To recycle polyurethane foam waste generated from electric appliance recycling centers for use as fuel in a gasification process, polyurethane solid refuse fuel fabricated as pellets was analyzed for the characteristics of elemental composition, proximate analysis, heating value, and thermo-gravimetric testing. It has a high heating value of 29.06 MJ/kg with a high content of combustibles, which could be feasibly used in any thermal process. However, the nitrogen content, of up to 7 %, was comparably higher than for other fuels such as coal, biomass, and refuse-derived fuel, and may result in the emission of nitrogenous pollutant gases of HCN and NH₃. By conducting gasification experiments on polyurethane solid refuse fuel in a fixed-bed reactor, a syngas with a heating value of 9.76 kJ/m³ and high content of both H₂ and CO were produced with good gasification efficiency; carbon conversion 54 %, and cold gas efficiency 60 %. The nitrogenous pollutant gases in syngas were measured at the concentrations of 160 ppm hydrogen cyanide and 40 ppm ammonia, which may have to be reduced using proper cleaning technologies prior to the commercialization of gasification technology for polyurethane waste.     

Effects of combustion parameters on polychlorinated dibenzodioxin and dibenzofuran homologue profiles from municipal waste and coal co-combustion

Variation in polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD and PCDF) homologue profiles from a pilot scale (0.6 MW_t, 2×10⁶ Btu/h), co-fired-fuel [densified refuse derived fuel (dRDF) and high-sulfur Illinois coal] combustion system was used to provide insights into effects of combustion parameters on PCDD and PCDF pollutant formation. A 24-run, statistically designed test matrix varied dRDF and/or coal firing rates (at a constant targeted energy release rate) along with a range of process variables including calcium hydroxide injection, hydrogen chloride (HCl) concentration, flue gas temperature, quench, and residence time such that the results would be relatable to a wide variety of combustion conditions. Statistical analysis of the molar homologue profiles enabled interpretation based on non-confounding variables. A multivariate, generalized additive model, based on transformations of the design variables, described 83% of the variation of the profiles characterized by log ratios of the homologue molar concentrations. This method identifies the operating parameters that are most significant in determining the PCDD/F homologue profiles. The model can be exercised to predict homologue profiles through input of these system-specific operating parameters. For example, both higher HCl and sulfur dioxide concentrations favor higher relative formation of the lower chlorinated PCDF homologues.