Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br₂) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400 °C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT_HT) was set at 0.25, 0.5, or 0.75 s.Combustion efficiency depends on temperature, EAF and RT_HT; temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br₂ depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br₂, whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25 s. High temperature is required to improve the combustion performance: at 1200 °C or higher, an EAF of 1.3 or more, and a RT_HT exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%).According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br₂/HBr in flue gas greatly.     

Oxidation catalyst of iron oxide suppressing dioxin formation in polyethylene combustion

A new iron oxide catalyst, which has a superior oxidation activity in carbon monoxide and polyethylene (PE) combustion, was synthesized by an aqueous solution reaction. Catalytic oxidation of carbon monoxide over six kinds of hematite obtained from the goethite was done using a microcatalytic pulse reactor, and the composition of the hematite with the highest oxidation activity was determined. With the aim of suppressing dioxin formation on combustion, incineration tests of solid wastes in PE refuse bags with and without the goethite were carried out using a commercial semibatch-type incinerator with a combustion chamber of 6.2 m³. The result confirmed that the concentration of dioxins in the flue gas decreased considerably when the refuse was incinerated in PE bags manufactured with goethite. Received: July 24, 2000 / Accepted: October 18, 2000     

Pyrrolidinium Imides: Promising Ionic Liquids for Direct Capture of Elemental Mercury from Flue Gas

A new approach to vapor phase elemental mercury capture has been explored; this approach exploits an ionic liquid coating layer to oxidize elemental mercury for subsequent immobilization by chelating ligands. The room temperature ionic liquid 1-butyl-1-methyl pyrrolidinium bis(trifluoromethane sulfonyl)imide (P₁₄) was selected for study based on its oxidation potential window, thermal stability, and low vapor pressure. Tests were also completed in which KMnO₄ was added to P₁₄ to form a new ionic liquid, P₁₄–KMnO₄, with a higher oxidation potential. In room-temperature bulk liquid phase capture experiments, 59% of the elemental mercury in the inlet gas was captured using P₁₄ alone; mercury capture using P₁₄–KMnO₄ was quantitative. P₁₄ and P₁₄–KMnO₄ coatings were successfully applied to mesoporous silica substrates and to silica substrates functionalized with mercury chelating ligands. The coating layers were found to be thermally stable up to 300°C. Fixed-bed tests of nonfunctionalized silica coated with P₁₄ showed an elemental mercury uptake of 2.7 mg/g adsorbent at 160°C; at the same temperature, functionalized silica coated with P₁₄–KMnO₄ showed an elemental mercury capacity of at least 7.2 mg/g adsorbent, several times higher than that of activated carbon. The empty bed gas residence time in these tests was 0.04 s. A chelating adsorbent incorporating P₁₄ in the coating layer, may be capable of simultaneous removal of elemental and oxidized mercury from coal combustion flue gases.     

Energy from Waste – Clean,efficient, renewable: Transitions in combustion efficiency and NOx control

Traditionally EfW (Energy from Waste) plants apply a reciprocating grate to combust waste fuel. An integrated steam generator recovers the heat of combustion and converts it to steam for use in a steam turbine/generator set. This is followed by an array of flue gas cleaning technologies to meet regulatory limitations.Modern combustion applies a two-step method using primary air to fuel the combustion process on the grate. This generates a complex mixture of pyrolysis gases, combustion gases and unused combustion air. The post-combustion step in the first pass of the boiler above the grate is intended to “clean up” this mixture by oxidizing unburned gases with secondary air.This paper describes modifications to the combustion process to minimize exhaust gas volumes and the generation of noxious gases and thus improving the overall thermal efficiency of the EfW plant. The resulting process can be coupled with an innovative SNCR (Selective Non-Catalytic Reduction) technology to form a clean and efficient solid waste combustion system.Measurements immediately above the grate show that gas compositions along the grate vary from 10% CO, 5% H₂ and 0% O₂ to essentially unused “pure” air, in good agreement with results from a mathematical model. Introducing these diverse gas compositions to the post combustion process will overwhelm its ability to process all these gas fractions in an optimal manner. Inserting an intermediate step aimed at homogenizing the mixture above the grate has shown to significantly improve the quality of combustion, allowing for optimized process parameters. These measures also resulted in reduced formation of NO_x (nitrogenous oxides) due to a lower oxygen level at which the combustion process was run (2.6 vol% O_2, wet instead of 6.0 vol% O_2, wet).This reduction establishes optimal conditions for the DyNOR? (Dynamic NO_x Reduction) NO_x reduction process. This innovative SNCR technology is adapted to situations typically encountered in solid fuel combustion. DyNOR? measures temperature in small furnace segments and delivers the reducing reagent to the exact location where it is most effective. The DyNOR? distributor reacts precisely and dynamically to rapid changes in combustion conditions, resulting in very low NO_x emissions from the stack.     

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.     

Assessing Aerobic Biodegradability of Plastics in Aqueous Environment by GC-Analyzing Composition of Equilibrium Gaseous Phase

Testing biodegradability of plastics under varied conditions of the environment as well as under laboratory conditions in accordance with valid international standards is very laborious, lengthy and often also economically demanding. For this reason, applicability was verified of gas chromatography to analyze gaseous phase when investigating the biodegradation course of plastics in an aqueous environment as an alternative to customary employed methods. A mathematical model of acid–basic CO₂ equilibrium in a gas–liquid system was worked out, enabling to determine quantity of produced CO₂ through chromatographic analysis of gaseous phase, in dependence on ratio of liquid and gas phase volumes (V _l/V _g) and on actual pH of liquid phase. Experimental conditions for organizing the tests were optimized. A ratio that proved suitable was V _l/V _g ≅ 0.1 at pH ≈ 7.1 of liquid phase. Under these test conditions, biodegradability of model samples, PHB, Gellan gum and Xanthan gum, was explored; course of biodegradation was studied through produced CO₂ (values ) determined by analyzing gaseous phase through gas chromatography on the one hand, and through customary “titration” procedure on the other. With water-soluble polymers, the decrement in dissolved organic carbon (values D _DOC) was also studied. Difference between values does not exceed 5%. The procedures in question are alternative “substituting” procedures for observing course of aerobic biodegradation of substances in an aqueous environment.     

Effect of Crystalline and Amorphous Structures on Biodegradability of Poly(Tetramethylene Succinate)

The effect of orientation in the amorphous and crystalline regions on the biodegradability of PTMS [poly(tetramethylene succinate)] was studied using the amorphous orientation function, birefringence, and crystallinity. The crystalline and amorphous intrinsic lateral sonic moduli, E _t,c ⁰ and E _t,am ⁰ , were 2.61 × 10³ and 0.41 × 10³ MPa, respectively. Using the data on birefringence, crystalline and amorphous orientation function (f and f _am), crystallinity, and sonic modulus of the oriented PTMS fibers, the intrinsic birefringence of the crystalline ( _c ⁰ ) and amorphous ( _am ⁰ ) regions were evaluated to be 0.0561 and 0.0634, respectively. The biodegradabilities of oriented PTMS films were reduced as the elongation increased, i.e., the amorphous orientation increased. At low elongation (100 and 150%), however, biodegradabilities remained unchanged when the degradation test was performed in activated sludge, which was attributed to the amorphous orientation occurring even at 100% elongation, though the amorphous orientation direction was perpendicular to the fiber axis.     

Formation and decomposition of tetrafluoroborate ions in the presence of aluminum

The formation and decomposition of tetrafluoroborate ions (BF₄⁻) in H₃BO₃-Al³⁺-F⁻ solutions were investigated via experiments and thermodynamic calculations. The concentration of the formed BF₄⁻ increased with decreasing pH, raising the total fluoride concentration and lowering the total aluminum ion concentration. Once formed, BF₄⁻ was stable under neutral and alkaline conditions. Fluoride in the form of BF₄⁻ was converted to fluoroaluminate ions by adding an aluminum compound under acidic conditions. A method for removing fluoride in the form of BF₄⁻ is proposed whereby fluoroaluminate ions formed by the reaction of BF₄⁻ with aluminum are decomposed with calcium ions. This process was applied to the treatment of wastewater from flue gas desulfurization plants, and resulted in a satisfying level of reduction in the range of the fluoride emission limit of 8 mg/l.     

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.     

Balance of NH3 and behavior of polychlorinated dioxins and furans in the course of the selective non-catalytic reduction of nitric oxide at the TAMARA waste incineration plant

Investigations were performed on the selective non-catalytic reduction (SNCR) of nitric oxide (NO) at TAMARA, the pilot-scale waste incineration plant of the Karlsruhe Research Center. Aqueous ammonia (NH₃) was injected into the combustion chamber as reductant. The influence of NH₃ on various inorganic and organic compounds in the flue gas was investigated. The concentrations of NO were reduced by up to about 90% by NH₃ injection. The concentrations of most of the other inorganic and organic compounds, including in particular PCDD and PCDF, did not change significantly.     

Identification,Abundance and Origin of Aliphatic Hydrocarbons in the Fine Atmospheric Particulate Matter of Athens,Greece

The organic chemical composition of the fine fraction of atmospheric particulate matter in Athens has been studied, in order to establish emission sources. The results of the analyses of the aliphatic fraction indicate that all samples contain n-alkanes ranging from C₁₄ to C₃₂, with C₂₅, C₂₆, C₂₇ and C₂₉ being the more abundant congeners. Fossil fuels biomarkers such as extended tricyclic terpanes (hopanes, steranes) and isoprenoid hydrocarbons (pristane, phytane) were observed in our samples on a daily basis. Source reconciliation was conducted using molecular diagnostic ratios (such as the carbon preference index – CPI). The mean CPI value (1.84) indicates the mixed origin of the Athenian fine particles. The notable presence of an unresolved complex mixture or “hump” of hydrocarbons in our gas chromatograms is indicative of petrogenic hydrocarbon inputs. An approximate measure of this kind of contamination is the ratio of the concentrations of unresolved components to the resolved n-alkanes and other major compounds (U:R). The high U:R value of 25.25 further confirmed the major contribution of fossil fuels. Yet, the percent contribution of leaf wax n-alkanes (25.15%) indicated the parallel contribution of biogenic sources. This work supports the conclusion that vehicular emissions were the major source of aliphatic organic compounds with a smaller contribution of biogenic n-alkanes during the study period in Athens.     

Fate and behavior of selected heavy metals with mercury mass distribution in a fluidized bed sewage sludge incinerator

In this paper, emission and distribution behavior of six heavy metals (As, Cd, Cr, Ni, Pb, and Hg), particulate matter and mass distribution of mercury within the different streams of a fluidized bed sewage sludge incinerator are presented. At the inlet of air pollution control devices (APCDs); Cd, Cr, Ni and Pb were mainly enriched in coarse particles; comparatively As content was higher in fine particles (<PM_2.5). The concentration of heavy metals in total particulate matter and PM_2.5, at the inlet of APCDs, were in the order of Cr > Ni > Pb > As > Cd. Mercury was almost always distributed in flue gas. Metals, other than mercury, were efficiently removed in APCDs and their concentrations in bottom ash, with fly ash being higher, whereas for that in wastewater, then waste sand was lesser. Overall mercury removal efficiency of APCDs was 98.6 %. More than 83.3 % of mercury was speciated into oxidized form at the inlet of APCDs, attributed by higher chlorine content in sludge. Mercury was mainly distributed in wastewater (78.4 %), wastewater from a spray dry reactor (16.8 %), fly ash in a hopper (3.4 %) and flue gas (1.4 %). This result is one of the first for data to be obtained; more experiments are required to control emission from such sources.     

Characterisation of polycyclic aromatic hydrocarbons in flue gas and residues of a full scale fluidized bed combustor combusting non-hazardous industrial waste

This paper studies the fate of PAHs in full scale incinerators by analysing the concentration of the 16 EPA-PAHs in both the input waste and all the outputs of a full scale Fluidized Bed Combustor (FBC). Of the analysed waste inputs i.e. Waste Water Treatment (WWT) sludge, Refuse Derived Fuel (RDF) and Automotive Shredder Residue (ASR), RDF and ASR were the main PAH sources, with phenanthrene, fluoranthene and pyrene being the most important PAHs. In the flue gas sampled at the stack, naphthalene was the only predominant PAH, indicating that the PAHs in FBC’s combustion gas were newly formed and did not remain from the input waste. Of the other outputs, the boiler and fly ash contained no detectable levels of PAHs, whereas the flue gas cleaning residue contained only low concentrations of naphthalene, probably adsorbed from the flue gas. The PAH fingerprint of the bottom ash corresponded rather well to the PAH fingerprint of the RDF and ASR, indicating that the PAHs in this output, in contrast to the other outputs, were mainly remainders from the PAHs in the waste inputs. A PAH mass balance showed that the total PAH input/output ratio of the FBC ranged from about 100 to about 2600 depending on the waste input composition and the obtained combustion conditions. In all cases, the FBC was clearly a net PAH sink.     

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

Effect of Lignosulfonate on the Thermal and Morphological Behavior of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The effect of lignosulfonate on poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV, was studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The PHBV/lignosulfonate samples were prepared by melt mixing in an internal mixer. SEM showed that PHBV/lignosulfonate samples present a cracked surface that is more intense in mixtures with high lignosulfonate proportions. According to DSC, melting and glass transition temperatures of the PHBV matrix decrease with lignosulfonate addition. The same effect was observed for melting enthalpies (ΔH_m), which indicates a decrease of crystallinity. TGA showed that thermal stability of PHBV/lignosulfonate samples was shifted to lower temperatures, which indicates the existence of an interaction between the thermal decomposition processes of PHBV and lignosulfonate.     

Connectivity of Hybrid Polymer by Tight Binding Approximation: Example of (Si(CH3)2) n (OSiO) p (OH) q

We computed by a tight binding calculation taking into account hybridization, the total electronic energy of different connectivities (amorphous, fractal and linear) of (Si−(CH₃)₂) _n −(OSiO) _p (OH) _q . We found that the total electronic energy of the amorphous connectivity was the smallest as a function of the number of atoms contained by the hybrid polymer. As the total electronic energy is linked to the stability, we may say that the connectivity of such hybrid polymer has the highest stability for the amorphous connectivity.     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

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     

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     

An LCA model for waste incineration enhanced with new technologies for metal recovery and application to the case of Switzerland

A process model of municipal solid waste incinerators (MSWIs) and new technologies for metal recovery from combustion residues was developed. The environmental impact is modeled as a function of waste composition as well as waste treatment and material recovery technologies. The model includes combustion with a grate incinerator, several flue gas treatment technologies, electricity and steam production from waste heat recovery, metal recovery from slag and fly ash, and landfilling of residues and can be tailored to specific plants and sites (software tools can be downloaded free of charge). Application of the model to Switzerland shows that the treatment of one tonne of municipal solid waste results on average in 425 kg CO₂-eq. generated in the incineration process, and 54 kg CO₂-eq. accrue in upstream processes such as waste transport and the production of operating materials. Downstream processes, i.e. residue disposal, generates 5 kg CO₂-eq. Savings from energy recovery are in the range of 67 to 752 kg CO₂-eq. depending on the assumptions regarding the substituted energy production, while the recovery of metals from slag and fly ash currently results in a net saving of approximately 35 kg CO₂-eq. A similar impact pattern is observed when assessing the MSWI model for aggregated environmental impacts (ReCiPe) and for non-renewable resource consumption (cumulative exergy demand), except that direct emissions have less and no relevance, respectively, on the total score. The study illustrates that MSWI plants can be an important element of industrial ecology as they provide waste disposal services and can help to close material and energetic cycles.