Simple removal of dioxins by injecting combustion gas into water

A simple, low-cost method for suppression of dioxins/furans (hereinafter referred to as dioxins) is required because many middle- and, especially, small-scale incinerators have fallen into disuse or have been dismantled because of the high running and system costs of measures for the suppression of dioxins. Therefore, the purpose of the present study was to develop a simple removal method for dioxins from combustion gas and to evaluate the basic removal rate of dioxins. The removal method for suspended matter in a gas mixture (cold model) and dioxins in exhaust gases (hot model) has been investigated by means of gas injection into water, the mechanism of which is that the suspended matter in the gas gathers at the gas–liquid interface. In the cold model, the removal ratio of fine particles (R_P) by gas injection into water was reproduced well by the following equation: R_P (%) = 100 × {1−exp(−0.8 · S_S · t_C)}, where S_S (cm²/cm³) is the specific surface area of bubbles and t_C (s) is the residence time of bubbles in water. The removal ratio of fine particles increased as the product S_s · t_C increased. In a hot model using the exhaust gas from combustion experiments of polyvinyl chloride, the removal ratio of dioxins (R_D) by injecting the exhaust gas into water was estimated by the following equation: R_D (%) = 100 × {1−exp(−0.8 · S_S · t_C · C_D0 ^0.07)}, where C_D0 [ng/cm³ (at standard temperature and pressure)] is the dioxins concentration in the exhaust gas before injection into water. R_D depends greatly on the specific surface area of bubbles and the residence time of the bubbles in water, and only weakly on the dioxins concentration in the exhaust gas. Injection of the exhaust gas into water has been shown to be effective and was evaluated as a simple method for the removal of dioxins from exhaust gas.     

Experimental research on emission and removal of dioxins in flue gas from a co-combustion of MSW and coal incinerator

This paper describes the experimental study of dioxins removal from flue gas from a co-combustion municipal solid waste and coal incinerator by means of a fluidized absorption tower and a fabric filter. A test rig has been set up. The flow rate of flue gas of the test rig is 150-2000 m3/h. The system was composed of a humidification and cooling system, an absorption tower, a demister, a slurry make-up tank, a desilter, a fabric filter and a measurement system. The total height of the absorption tower was 6.5m, and the diameter of the reactor pool was 1.2 m. When the absorbent was 1% limestone slurry, the recirculation ratio was 3, the jet rate was 5-15 m/s and the submerged depth of the bubbling pipe under the slurry was 0.14 m, the removal efficiency for dioxins was 99.35%. The concentration of dioxins in the treated flue gas was 0.1573 x 10(-13)kg/Nm3 and the concentration of oxygen was 11%. This concentration is comparable to the emission standards of other developed countries.     

Treating landfill gas hydrogen sulphide with mineral wool waste (MWW) and rod mill waste (RMW)

Hydrogen sulphide (H₂S) gas is a major odorant at municipal landfills. The gas can be generated from different waste fractions, for example demolition waste containing gypsum based plaster board. The removal of H₂S from landfill gas was investigated by filtering it through mineral wool waste products. The flow of gas varied from 0.3 l/min to 3.0 l/min. The gas was typical for landfill gas with a mean H₂S concentration of ca. 4500 ppm. The results show that the sulphide gas can effectively be removed by mineral wool waste products. The ratios of the estimated potential for sulphide precipitation were 19:1 for rod mill waste (RMW) and mineral wool waste (MWW). A filter consisting of a mixture of MWW and RMW, with a vertical perforated gas tube through the center of filter material and with a downward gas flow, removed 98% of the sulfide gas over a period of 80 days. A downward gas flow was more efficient in contacting the filter materials. Mineral wool waste products are effective in removing hydrogen sulphide from landfill gas given an adequate contact time and water content in the filter material. Based on the estimated sulphide removal potential of mineral wool and rod mill waste of 14 g/kg and 261 g/kg, and assuming an average sulphide gas concentration of 4500 ppm, the removal capacity in the filter materials has been estimated to last between 11 and 308 days. At the studied location the experimental gas flow was 100 times less than the actual gas flow. We believe that the system described here can be upscaled in order to treat this gas flow.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

生物滴滤塔处理甲苯废气

分别以生物陶粒和聚氨酯泡沫为生物滴滤塔填料，对甲苯废气进行处理，考察不同生物滴滤塔挂膜启动时间以及气体流量和甲苯质量浓度条件下生物滴滤塔对甲苯废气的去除效果。实验结果表明：生物陶粒为填料的生物滴滤塔所需要的挂膜启动时间更短；在气体流量为450L/h时，以生物陶粒为填料的生物滴滤塔甲苯去除率稳定在72%左右，聚氨酯泡沫为填料时甲苯去除率稳定在65%左右。以聚氨酯泡沫为填料时，随甲苯质量浓度提高，甲苯去除率下降幅度较小，甲苯质量浓度为1.80g/m3时，甲苯去除率仍在72%以上。     

脱硝催化剂的失活机理及其再生技术

采用SEM、XRD和XRF对电厂失活脱硝催化剂进行表征,探讨其失活原因和机理。结果表明:电厂脱硝催化剂失活的主要原因是活性组分V的流失及碱金属K、碱土金属Ca和As元素造成的催化剂中毒,烟气中飞灰的沉积也有一定的影响。经吹扫、水洗、酸洗和V负载再生,催化剂的各项物化性质基本恢复,NOx转化率基本达到新鲜催化剂的水平。水洗主要去除催化剂中的碱金属,酸洗主要去除As2O3,负载V补充催化剂活性组分。V再生催化剂在较高温度下的抗硫性能更好。     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

石灰石-石膏湿法烟气脱硫喷淋塔除尘机理分析

介绍了石灰石-石膏湿法烟气脱硫装置的典型工艺流程以及逆流喷淋塔内气液流动状况，分析了脱硫喷淋塔在惯性碰撞、截留和布朗扩散三方面的除尘机理，给出了计算脱硫喷淋塔除尘效率的思路。     

Decomposition of mixed plastics consisting of polypropylene and polyethylene terephthalate into oils over titania/silica catalysts

The catalytic decomposition of mixed plastics consisting of polypropylene (PP) and polyethylene terephthalate (PET) has been investigated over titania/silica catalysts at 698 K. The yield of oil produced was about 70%, and the large amounts of C₁₈₊ hydrocarbons this contained was from the aromatics in PET. Gas was also produced, including C₃–C₅ hydrocarbons. The carbon-number fractions in the oil was influenced by the PET/(PP + PET) ratios and the catalyst weight. The titania/silica catalysts could be used repeatedly, and after they had been fouled, could be regenerated. From the Fourier Transform Infrared (FT–IR) spectroscopic data of adsorbed pyridine on the catalyst surface, most of the acid sites of the titania/silica catalysts were found to be Lewis sites where the hydride abstracted from PP pyrolysates react with PET pyrolysates to form oil and gas. Received: July 19, 2000 / Accepted: October 20, 2000     

MnOx/TiO2催化剂催化燃烧去除废气中的正己烷

采用溶胶-凝胶法制备了MnOx/TiO2催化剂,考察了n(Mn):n(Ti)、催化剂载体、气体流量对催化燃烧去除废气中正己烷效果的影响.实验结果表明:随着n(Mn):n(Ti)的增加,正己烷去除率先增加后减小,气体流量减小正己烷去除率增大;当n (Mn):n(Ti)为7.85％、气体流量为100 mL/min时,在240℃时正己烷的去除率为90％,MnOx/TiO2催化活性最大;MnOx/TiO2的催化活性优于MnOx/SiO2;SEM和XRD表征结果表明,所制备的MnOx/TiO2是一种活性物种MnOx高度分散的纳米结构催化剂.     

Treatment of Stormwater using Fibre Filter Media

In this study, a high-rate fibre filter was used as a pre-treatment to stormwater in conjunction with in-line flocculation. The effect of operating the fibre filter with different packing densities (105, 115 and 125 kg/m³) and filtration velocities (20, 40, 60 m/h) with and without in-line flocculation was investigated. In-line flocculation was provided using 5, 10 and 15 mg/L of ferric chloride (FeCl₃·6H₂O). The filter performance was studied in terms of pressure drop (ΔP), solids removal efficiency, heavy metals (total) removal efficiency and total organic carbon (TOC) removal efficiency. It is found that the use of in-line flocculation at a dose of 15 mg/L improved the performance of fibre filter as measured by turbidity removal (95%), total suspended solids reduction (98%), colour removal efficiency (99%), TOC removal (reduced by 30–40 %) and total coliform removal (93%). The modified fouling index reduced from 750–950 to 12 s/L² proving that fibre filter can be an excellent pre-treatment to membrane filtration that may be consider as post-treatment. The removal efficiency of heavy metal was variable as their concentration in raw water was small. Even though the concentration of some of these metals such as iron, aluminium, copper and zinc were reduced, others like nickel, chromium and cadmium showed lower removal rates.     

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     

Catalytic destruction of PCDD/F in a fabric filter: experience at a municipal waste incinerator in Belgium

In order to comply with dioxin and furan (PCDD/F) emission regulations in Belgium, the IVRO municipal waste incinerator adopted catalytic filters for use in the plant's two existing fabric filters. This system replaced the injection of powdered activated carbon (PAC) because of concerns that PAC, used at temperatures above 200 degrees C, would ignite and lead to fires and plant down-time. The performance of the catalytic filter system, since its installation in 1997, is described. PCDD/F emissions are controlled to well below the regulatory limit of 0.1 ng I-TEQ/Nm3. The amount of PCDD/F entering and exiting the fabric filter is quantified. The resulting mass balance shows that greater than 99.5% of the gaseous PCDD/F entering the fabric filter is destroyed by the catalyst within the filter media.     

Co-gasification of wood and polyethylene with the aim of CO and H2 production

This article describes the gasification of polyethylene–wood mixtures to form syngas (H₂ and CO) with the aim of feedstock recycling via direct fermentation of syngas to ethanol. The aim was to determine the effects of four process parameters on process properties that give insight into the efficiency of gasification in general, and particularly into the optimum gasification conditions for the production of ethanol by fermentation of producer gas. Gasification experiments (fluidized bed, 800°–950°C) were done under different conditions to optimize the composition of syngas suitable for fermentation purposes. The data obtained were used for statistical analysis and modeling. In this way, the effect of each parameter on the process properties was determined and the model was used to predict the optimum gasification conditions. The parameters varied during the experiment were gasification temperature, equivalence ratio, the ratio of plastic to wood in the feed, and the amount of steam added to the process. The response models obtained proved to be statistically significant in the experimental domain. The optimum gasification conditions for maximization of carbon monoxide and hydrogen production were identified. The conditions are: temperature 900°C, equivalence ratio 0.15, amount of plastic in the feed 0.11 g/g feed, and amount of steam added 0.42 g/g feed. These optimum conditions are at the edge of the present experimental domain. The maximum combined CO and H₂ efficiency was 42%, and for the maximum yield of CO and H₂ it is necessary to minimize the polyethylene content, minimize the added steam and the equivalence ratio, and maximize temperature.     

Effect of mixing on NO removal in the selective noncatalytic reduction reaction process

The effect of mixing of NH₃ and NO on the selective noncatalytic reduction (SNCR) reaction was investigated using a bench-scale reactor. Three different experimental conditions were compared for the removal of NO in the bulk gas with NH₃, a reducing agent, by means of mixing and contacting. The temperature that gave the highest NO removal efficiency was about 800°C when NH₃ was injected with air or NH₃ was premixed and air was injected. It is suggested that control of mixing of the reducing agent and the injection conditions could be a good way to increase NO removal efficiency as well as to lower the reaction temperature. When NH₃ was injected with air, the NO removal efficiency increased with increasing injected air flow if the initial NO concentration was low, whereas for high NO concentrations, the NO removal efficiency slightly increased up to an injected air flow rate of 100 ml/min. A proposed mixed-flow model can be used as a prediction tool for the NO removal efficiency covering various conditions of the real SNCR process.     

Chemical, dimensional and morphological ultrafine particle characterization from a waste-to-energy plant

Waste combustion processes are responsible of particles and gaseous emissions. Referring to the particle emission, in the last years specific attention was paid to ultrafine particles (UFPs, diameter less than 0.1 μm), mainly emitted by combustion processes. In fact, recent findings of toxicological and epidemiological studies indicate that fine and ultrafine particles could represent a risk for health and environment. Therefore, it is necessary to quantify particle emissions from incinerators also to perform an exposure assessment for the human populations living in their surrounding areas.To these purposes, in the present work an experimental campaign aimed to monitor UFPs was carried out at the incineration plant in San Vittore del Lazio (Italy). Particle size distributions and total concentrations were measured both at the stack and before the fabric filter inlet in order to evaluate the removal efficiency of the filter in terms of UFPs. A chemical characterization of UFPs in terms of heavy metal concentration was performed through a nuclear method, i.e. Instrumental Neutron Activation Analysis (INAA), as well as a mineralogical investigation was carried out through a Transmission Electron Microscope (TEM) equipped with an Energy Dispersive Spectrometer (EDS) in order to evaluate shape, crystalline state and mineral compound of sampled particles.Maximum values of 2.7 × 10⁷ part. cm⁻³ and 2.0 × 10³ part. cm⁻³ were found, respectively, for number concentration before and after the fabric filter showing a very high efficiency in particle removing by the fabric filter. With regard to heavy metal concentrations, the elements with higher boiling temperature present higher concentrations at lower diameters showing a not complete evaporation in the combustion section and the consequent condensation of semi-volatile compounds on solid nuclei. In terms of mineralogical and morphological analysis, the most abundant compounds found in samples collected before the fabric filter are Na–K–Pb oxides followed by phyllosilicates, otherwise, different oxides of comparable abundance were detected in the samples collected at the stack.     

The Role of Catalyst Properties on Methanol Oxidation over V2O5–TiO2 Using Ozone

Oxidation of methanol over V₂O₅ catalysts supported on anatase TiO₂ that were prepared using sol-gel formation and impregnation procedures were investigated. The effects of incorporating Mg in sol-gel to influence the properties of the catalyst were also studied. The process provides an alternative low temperature reaction pathway for reducing emissions of hazardous air pollutant (HAPs) such as methanol and total reduced sulfur compounds (TRS) from pulp and paper mills. The bulk and surface composition of the catalysts were determined by XRD and SEM-EDAX, respectively. The X-ray diffraction patterns of the vanadia–titania catalysts showed mainly the anatase phase of TiO₂. Temperature programmed desorption of methanol from the different catalyst showed that the α and β peaks differ significantly with V content and addition of Mg. The combination of gas phase and surface reactions on the V/TiO₂ catalysts reduced the amount of ozone required for high degradation of methanol to mainly CO _x with small quantities of methyl formate. In the absence of ozone the catalysts showed very low activity. It is hypothesized that the ozone is directly influencing the V⁴⁺ and V⁵⁺ redox cycle of the catalyst. Oxidation of methanol is influenced by the operation variables and catalyst properties. The results of this study revealed that the V content has significant influence on the catalyst activity, and the optimum vanadia loading of about 6 wt%. Higher turnover frequencies were observed over sol-gel catalysts than with catalysts prepared by the impregnation method.     

Determination of nitrous oxide, methane, and ammonia emissions from a swine waste composting process

The amounts of harmful gas emissions from the process of composting swine waste were determined using an experimental composting apparatus. Forced aeration (19.2–96.1 l/m³/min) was carried out continuously, and exhaust gases were collected and analyzed periodically. With weekly turning and the addition of a bulking agent in order to decrease the moisture content and increase air permeability, the temperature of most of the contents rose to 70°C and composting was complete within 3–5 weeks. NH₃, CH₄, and N₂O emissions were high in the early stage of composting. About 10%–25% of the nitrogen in the raw material was lost as NH₃ gas during composting. The emission rate of NH₃ mainly depended on the aeration rate, so that as the aeration rate rose, the level of NH₃ emissions increased. The CH₄ and N₂O emissions could be kept lower with adequate treatment at more than 40 l/m³/min aeration. N₂O may be mainly the result of the denitrification of NO _x -N in the additional matured compost used as a composting accelerator. Received: September 11, 1998 / Accepted: November 8, 1999     

Trends in Chemical Composition of Wet-only Precipitation at Rural French Monitoring Stations Over the 1990–2003 Period

The long-term monitoring of precipitation and its chemical composition are important for identifying trends in rain quality and for assessing the effectiveness of pollution control strategies. A statistical test has been used to the atmospheric concentrations measured in the French rural monitoring network (MERA) in order to bring out spatio-temporal trends in precipitation quality in France over the period 1990–2003. The non-parametric Mann–Kendall test which has been developed for detecting and estimating monotonic trends in the time series was used and applied in our study at annual values of wet-only precipitation concentrations. The emission data suggest that SO₂ and NO _x emissions decreased (−3.3 and −2.0% year⁻¹, respectively) contrary to NH₃ emissions that increased slightly (+0.2% year⁻¹) over the period 1990–2002 in France. On the national scale, the pH values have a significant decreasing trend of −0.025 ± 0.02 unit pH year⁻¹. and concentrations in precipitation have a significant decreasing trend, −3.0 ± 1.6 and −3.3 ± 0.6% year⁻¹, respectively, corresponding with the downward trends in SO₂ emissions in France (−3.3% year⁻¹). A good correlation (R ² = 0.84) between SO₂ emissions and concentrations was obtained. The decreasing trend of was more significant (−5.4 ± 5.2% year⁻¹) than that of (−1.3 ± 2.4% year⁻¹). Globally, the concentration of the major ions showed a clear downward trend including marine and alkaline ions. In addition, the relative contribution of HNO₃ to acidity precipitation increased by 51% over the studied period.     

Development of a catalytic cracking process for converting waste plastics to petrochemicals

The catalytic degradation of polyolefin using H-gallosilicates was examined using a bench-scale reactor (0.8kg/h) with semicontinuous feeding and the following plastics: (1) low-density polyethylene (LDPE) pellets; (2) linear low-density polyethylene (L-LDPE) pellets; (3) high-density polyethylene (HDPE) pellets; (4) polypropylene (PP) pellets; (5) polyolefin obtained from pulverized industrial waste plastics. The yields of liquid compounds from these materials, which were aromatics in most cases, ranged from 55wt% to 68wt%. With an increase in the ratio of total reactant to catalyst, the liquid yield remained the same. Yields of benzene, toluene, and xylenes (BTXs) decreased rapidly to below 50wt% at a ratio of more than 30. Differences in this ratio for BTXs were always small and were independent of the material. Only about half of the gas product was propane with a fresh catalyst. When the experiments were repeated, propylene, isobutane, and isobutene were found to increase.