Agglomeration-influenced transformation of heavy metals in gas-solid phases during simulated sewage sludge co-incineration: Effects of phosphorus and operating temperature.

Phosphorus and operating temperature not only affect the agglomeration behavior but also the transformation and migration of heavy metals. Accordingly, this study examined the effect of temperature and phosphorus in a fluidized bed combustion process to understand the emission and distribution of heavy metals by both experimental and thermodynamic calculations. The experimental results indicated that the sodium-phosphate reactions occur before the sodium-silicate reaction in the solid phase when the ratio of P/Na was 1/2. A low-melting-point sodium phosphate component, such as NaPO3, leads to easier particle agglomeration than Na2O-SiO2. In terms of the emissions of heavy metals, Pb and Cd show a similar trend: both the amount of emission smaller than that without adding phosphorus and the amount of emission share an upward trend with the operating time increased during MSS fluidized bed combustion. However, with the presence of phosphorus, the emission of Cr shows slightly decreased, and then sharply dropped, after that, increasing with operating time increased. Generally speaking, the maximum amount of Pb and Cd emitted was at 900 °C, followed by 800 °C and 700 °C. The higher temperature would promote the volatilization of Pb and Cd to emit. On the other hand, Cr emitted at the beginning tended to increase but later decreases when the temperatures were 700 and 900 °C, which may be due to the emission of Cr being influenced by the different affinities of both Al and Cr, reacting with Na in a fluidized bed incinerator. As for the distribution of heavy metals in the solid phase, a higher concentration of heavy metals was found in both the coarsest and finest particles during the process of agglomeration/defluidization.

Influence of different fluidization and gasification parameters on syngas composition and heavy metal retention in a two-stage fluidized bed gasification process.

Herein, we investigated the influence of gasification and fluidization parameters on the H2 content of syngas and the retention of heavy metals (Cu and Pb) in a bed material during a two-stage fluidized bed gasification process. The results indicated that a temperature of 900 °C in both stages resulted in the highest H2 content (32.4 mol%) in syngas. When different equivalence ratios (ERs) were investigated, it was found that the highest H2 content in syngas (25.4 mol%) was achieved at an ER of 0.3. A particle size of 0.46 mm in the fluidized bed led to an increase in the H2 content of syngas. Moreover, increasing the operating gas velocity led to an increase in the H2 content of syngas. The heavy metal concentration in the bed material was the highest at 500 °C. When the influences of different particle sizes and operating gas velocities were compared, it was observed that a particle size of 0.46 mm and gas velocity of 1.5 U/Umf resulted in increased heavy metal concentrations in the bed material, which indicates that the reduction in the particle size and the increase in the operating gas velocity enhanced gasification and improved the retention of heavy metals.

Sequential extraction for heavy metal distribution of bottom ash from fluidized bed co-combusted phosphorus-rich sludge under the agglomeration/defluidization process.

Agglomeration that occurs during municipal sewage sludge (MSS) fluidized bed co-combustion might affect heavy metal distribution and the transformation of bottom ash. A study on the mobility and speciation of heavy metals that accompanies agglomeration behavior and phosphorus addition should be examined during MSS co-combustion. Meanwhile, the aim of this study was to evaluate the total content and speciation of heavy metals during the MSS fluidized bed co-combustion by the chemical sequential extraction procedure (SEP). The risk assessment code (RAC) and individual contamination factor (ICF) are calculated to evaluate the mobility of heavy metals and their environmental risks in agglomerates. Moreover, identification of agglomerates is established by both characterization (scanning electron microscopy/energy-dispersive spectroscopy, X-ray photoelectron spectroscopy) and thermodynamic simulation (HSC chemistry software). The experimental results indicated that P and Na would form the lower melting-point compounds such as NaPO3 and Na2O in the bottom ash, which promoted agglomeration during MSS fluidized bed co-combustion. According to the simulation, Na and P have a stronger affinity than Si and Cr, and this reaction is not only influenced by particle agglomeration, but also by heavy metal distribution during modified MSS co-combustion. Nevertheless, the results of ICFs and RACs obtained from the SEP indicated that for heavy metals trapped in agglomerates, a weaker binding such as physical covering by eutectics might be considered as the dominant reaction compared with chemical binding to form a metal complex.

Experimental investigation of synthetic gas composition in a two-stage fluidized bed gasification process: effect of activated carbon as bed material.

In this study, a two-stage fluidized bed gasifier was used to investigate the effect of the equivalence ratio (ER) and steam/biomass ratio (S/B) on the synthetic gas distribution while activated carbon (AC) was added as the bed material in secondary gasifier (Stage II). The experimental results showed that when the empty bed (without the bed material) was used for the Stage II reaction, the hydrogen (H2) content in the synthetic gas emitted from the Stage II reactor was 2-3 mol% higher than that from the first-stage gasifier (Stage I). It was supposed that using the Stage II reactor prolongs the reaction time and thereby increases the H2 production. Besides, when the AC was added in the Stage II gasifier, the H2 concentration, the total gas yield, and gas heating value reached their maximum (30 mol%) when ER and S/B were 0.3 and 1.5, respectively.

Waste-gasification efficiency of a two-stage fluidized-bed gasification system.

This study employed a two-stage fluidized-bed gasifier as a gasification reactor and two additives (CaO and activated carbon) as the Stage-II bed material to investigate the effects of the operating temperature (700°C, 800°C, and 900°C) on the syngas composition, total gas yield, and gas-heating value during simulated waste gasification. The results showed that when the operating temperature increased from 700 to 900°C, the molar percentage of H2 in the syngas produced by the two-stage gasification process increased from 19.4 to 29.7mol% and that the total gas yield and gas-heating value also increased. When CaO was used as the additive, the molar percentage of CO2 in the syngas decreased, and the molar percentage of H2 increased. When activated carbon was used, the molar percentage of CH4 in the syngas increased, and the total gas yield and gas-heating value increased. Overall, CaO had better effects on the production of H2, whereas activated carbon clearly enhanced the total gas yield and gas-heating value.

Effect of biomass containing zinc metal at different operating parameters on gasification efficiency.

This paper describes the effect of Zn on the gas production of a fluidized-bed gasifier to determine the relationship between Zn and the gasification process. Different concentrations of Zn were used in the preparation of artificial waste to elucidate the effect on gas product composition, gas product heat value, gas production rate, and H2 yield in the gasification process. Zn served to increase H2 generation during the gasification process. The molar percentage of H2 with more than 0.1 wt% additional Zn increased by 33.02% and the H2 yield was increased by 11.34% compared to that without Zn. However, the gas heat value decreased, and no significant change in the gas production rate was noted.

Determination of the Pb, Cr, and Cd distribution patterns with various chlorine additives in the bottom ashes of a low-temperature two-stage fluidized bed incinerator by chemical sequential extraction.

A novel low-temperature two-stage fluidized bed (LTTSFB) incinerator has been successfully developed to control heavy-metal emissions during municipal solid waste (MSW) treatment. However, the characteristics of the residual metal patterns during this process are still unclear. The aim of this study was to investigate the metal patterns in the different partitions of the LTTSFB bottom ash by chemical sequential extraction. Artificial waste was used to simulate the MSW. Different parameters including the first-stage temperature, chloride additives, and operating gas velocity were also considered. Results indicated that during the low-temperature treatment process, a high metal mobility phase exists in the first-stage sand bed. The main patterns of Cd, Pb, and Cr observed were the water-soluble, exchangeable, and residual forms, respectively. With the different Cl additives, the results showed that polyvinyl chloride addition increased metal mobility in the LTTSFB bottom ash, while, sodium chloride addition may have reduced metal mobility due to the formation of eutectic material. The second-stage sand bed was found to have a lower risk of metal leaching. The results also suggested that, the residual ashes produced by the LTTSFB system must be taken into consideration given their high metal mobility.

Influence of various chlorine additives on the partitioning of heavy metals during low-temperature two-stage fluidized bed incineration.

In this study, a pilot-scale low-temperature two-stage fluidized bed incinerator was evaluated for the control of heavy metal emissions using various chlorine (Cl) additives. Artificial waste containing heavy metals was selected to simulate municipal solid waste (MSW). Operating parameters considered included the first-stage combustion temperature, gas velocity, and different kinds of Cl additives. Results showed that the low-temperature two-stage fluidized bed reactor can be an effective system for the treatment of MSW because of its low NO(x), CO, HCl, and heavy metal emissions. The NO(x) and HCl emissions could be decreased by 42% and 70%, respectively. Further, the results showed that heavy metal emissions were reduced by bed material adsorption and filtration in the second stage. Regarding the Cl addition, although the Cl addition would reduce the metal capture in the first-stage sand bed, but those emitted metals could be effectively captured by the filtration of second stage. No matter choose what kind of additive, metal emissions in the low-temperature two-stage system are still lower than in a traditional high-temperature one-stage system. The results also showed that metal emissions depend not only on the combustion temperature but also on the physicochemical properties of the different metal species.

Effect of incinerator bottom-ash composition on the mechanical behavior of backfill material.

This study explores the influence of the chemical composition (SiO(2), CaO, Fe(2)O(3), and Al(2)O(3)) of incinerator bottom ash on its friction angle. Direct shear tests were performed to measure the strength of bottom ash with two distinctly different compositions. Then, an empirical equation was regressed to determine the correlation between each composition and the friction angle. The experimental results showed that the main constituent material of the incinerator bottom ash from general municipal wastes is SiO(2), and the friction angle is 48.04°-52.66°. The bottom ash from incineration plants treating both municipal wastes and general industrial wastes has a high content of iron-aluminum oxides, and its friction angle is 44.60°-52.52°. According to the multivariate regression analysis result, the friction angle of bottom ash of any composition is influenced mainly by the Fe(2)O(3) and Al(2)O(3) contents. This study used the friction angle of the bottom ash from four different incineration plants to validate the empirical equation, and found that the error between actual friction angles and the predicted values was -1.36% to 5.34%. Therefore, the regressed empirical equation in this study can be employed in engineering applications to preliminarily identify the backfill quality of incinerator bottom ash.

Copper emission during thermal treatment of simulated copper sludge.

This study evaluates Cu emissions in air-particulate and gas phases during thermal treatment of simulated copper sludge by a rotary kiln. Influences of operating parameters, including treatment temperature (400-700 degrees C), rotary speed (0.89-2.00 rpm) and copper content in sludge (1% to 5% by weight) on copper emissions were investigated. The toxicity characteristic leaching procedure (TCLP) and scanning electron microscopy (SEM) were also conducted to evaluate copper leaching and the surface structure of thermally treated sludge, respectively. The results indicated that (1) low Cu emissions in air-particulate and gas phases were associated with the two operating conditions of 400-500 degrees C at 0.89-1.39 rpm and 600-700 degrees C at 2.00 rpm; (2) temperatures and rotary speeds did not affect gaseous copper emission, except for the operating condition of 400 degrees C at 2.00 rpm; (3) rising copper content of sludge at 600 degrees C and 2.00 rpm increased the particulate copper emission, but not the gaseous copper emission; (5) the TCLP copper leaching concentrations of sludge treated at 400 degrees C were obviously higher than those treated at 500-700 degrees C; however, all of the thermally treated products agreed with the Taiwan EPA TCLP regulations.

Effects of bed material size distribution, operating conditions and agglomeration phenomenon on heavy metal emission in fluidized bed combustion process.

This study investigates the effects of the bed material size distribution, the operating conditions and the agglomeration/defluidization phenomenon on the heavy metal pollutant emissions in the combustion process. After defluidization, the emission concentration of heavy metals increased, because Na may form a low melting eutectic material that enhances bed material adherence. The emission of Cd increased when the feed simulated urban residues contained sodium; however, the presence of Na had no significant effect on the emission of Cr. Furthermore, the Cd emission concentration was low when the material had a Gaussian distribution; however, the decreases in the Cd emission when the bed material had narrow, binary or flat distributions were not significant. The heavy metal Cr showed the same trend. In addition to the operating parameters, the bed material size distribution may influence the heavy metal emissions during combustion processes.

Metal catalysts supported on activated carbon fibers for removal of polycyclic aromatic hydrocarbons from incineration flue gas.

The aim of this research was to use metal catalysts supported on activated carbon fibers (ACFs) to remove 16 species of polycyclic aromatic hydrocarbons (PAHs) from incineration flue gas. We tested three different metal loadings (0.11 wt%, 0.29 wt%, and 0.34 wt%) and metals (Pt, Pd, and Cu), and two different pretreatment solutions (HNO(3) and NaOH). The results demonstrated that the ACF-supported metal catalysts removed the PAHs through adsorption and catalysis. Among the three metals, Pt was most easily adsorbed on the ACFs and was the most active in oxidation of PAHs. The mesopore volumes and density of new functional groups increased significantly after the ACFs were pretreated with either solutions, and this increased the measured metal loading in HNO(3)-0.48% Pd/ACFs and NaOH-0.52% Pd/ACFs. These data confirm that improved PAH removal can be achieved with HNO(3)-0.48% Pd/ACFs and NaOH-0.52% Pd/ACFs.

Effects of dissolved oxygen on dye removal by zero-valent iron.

Effects of dissolved oxygen concentrations on dye removal by zero-valent iron (Fe(0)) were investigated. The Vibrio fischeri light inhibition test was employed to evaluate toxicity of decolorized solution. Three dyes, Acid Orange 7 (AO7, monoazo), Reactive Red 120 (RR120, diazo), and Acid Blue 9 (AB9, triphenylmethane), were selected as model dyes. The dye concentration and Fe(0) dose used were 100 mg L(-1) and 30 g L(-1), respectively. Under anoxic condition, the order for dye decolorization was AO7>RR120>AB9. An increase in the dissolved oxygen concentrations enhanced decolorization and chemical oxygen demand (COD) removal of the three dyes. An increase in gas flow rates also improved dye and COD removals by Fe(0). At dissolved oxygen of 6 mg L(-1), more than 99% of each dye was decolorized within 12 min and high COD removals were obtained (97% for AO7, 87% for RR120, and 93% for AB9). The toxicity of decolorized dye solutions was low (I(5)<40%). An increase in DO concentrations obviously reduced the toxicity. When DO above 2 mg L(-1) was applied, low iron ion concentration (13.6 mg L(-1)) was obtained in the decolorized AO7 solution.

Effect of Cu species on leaching behavior of simulated copper sludge after thermal treatment: ESCA analysis.

The aim of this study is to evaluate the efficiency of thermal treatment on residual copper sludge after separation treatment. The toxicity characteristic leaching procedure (TCLP) concentration, pattern distribution and possible Cu species of simulated copper sludge were analyzed. Parameters such as different reaction time and temperature are also discussed in this study. The TCLP leaching results showed that the TCLP concentration of Cu in thermally treated simulated copper sludge decreased (T=900 degrees C) as the reaction time increased to 4 h. The sequential extraction results showed that the main fraction of raw simulated copper sludge was carbonate. When temperatures were 500 and 700 degrees C, the main fraction of thermally treated simulated copper sludge was also carbonate. The percentage of Fe-Mn oxides and residue increased when T=900 degrees C. Electron Spectroscopy for Chemical Analysis (ESCA) showed that the possible Cu species of raw simulated copper sludge was Cu(OH)(2). The main possible Cu species of thermally treated simulated copper sludge were CuO and Cu(2)O when T was 500 and 700 degrees C, respectively. CuO, Cu(2)O, and Cu(3)O(2) were the possible Cu species in thermally treated simulated copper sludge when T=900 degrees C.

Mechanical properties of incineration bottom ash: the influence of composite species.

The mechanical properties, including strength, deformational behavior, and wetting softening phenomena of municipal solid waste incinerator (MSWI) bottom ash are one of the major concerns for reuse applications. However, owing to the complex constituents of municipal solid waste, the properties of MSWI bottom ash are often highly variable. A series of artificial specimens with controlled chemical components were tested in this study. The test results show that the artificial bottom ash possesses the following mechanical characteristics: (1) for the strength, the frictional angles of the bottom ash under dry and saturated conditions vary from 34.8 degrees to 51.1 degrees and 26.0 degrees to 37.2 degrees, respectively; (2) for the deformation, the shear stiffness increases with the normal stress arises and degrades upon increased shearing; (3) significant wetting degradation of the strength and stiffness were observed. The multi-variable regression analysis was conducted to evaluate the associated influence of the chemical components on the strength. Among the evaluated components, Fe(2)O(3) and Al(2)O(3) are key factors; an increase in either results in higher strength at both dry and saturated conditions. The results were used to propose empirical relationships for phi(dry) and phi(sat), expressed in terms of Fe(2)O(3) and Al(2)O(3). Accordingly, a strength classification chart is proposed for engineering purposes.

Relationship between pressure fluctuations and generation of organic pollutants with different particle size distributions in a fluidized bed incinerator.

The hydrodynamic behaviors of fluidization perhaps significantly influence the uniformity of fluidization in fluidized bed incinerator. Good uniformity of fluidization expressed the air across uniformly through the bed and the particles being distributed well in the fluid stream. The aggregates, flocs and channels of particles do not happen during fluidization. The Good uniformity will maintain high heat and mass distribution to improve reaction efficiency. These parameters include the height of static bed, gas velocity, mixing and distribution of bed particle, which have rarely been studied in previous investigations. Consequently, this study examines how the hydrodynamic parameters affect the generation of organic pollutants (BTEXs and PAHs) during incineration. The statistical and power spectral analysis of the measured pressure fluctuation during incineration are used to elucidate the relationship between behaviors of fluidization and generation of pollutants during incineration. Experimental results show the organic concentration does not increase with uniformity of fluidization decreasing. The reason may be the explosion of the gas and the consequent thermal shock destroy the coalescent bubbles to form small bubbles again and enhance the efficiency of transfer of oxygen to increase combustion efficiency. Additionally, the mean amplitude and fluidized index of pressure fluctuation similarly vary with the concentration of organic pollutants. These two indices can be used to assess the efficiency of combustion. The four particle size distributions could be divided into two groups by statistical analysis. The Gaussian and narrow distributions belong to one group and the binary and flat the other. The organic concentration of the Gaussian and narrow distributions are lower than that of the other distributions. Consequently, the bed materials should maintain narrow or Gaussian distributions to maintain a good combustion efficiency during incineration.

Pore structure effects on Ca-based sorbent sulfation capacity at medium temperatures: activated carbon as sorbent/catalyst support.

The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473-773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2 x g Ca(OH)2(-1), and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sulfated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/ activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/catalysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the desulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.

Reaction characteristics of Ca(OH)2, HCl and SO2 at low temperature in a spray dryer integrated with a fabric filter.

The objective of this research was to evaluate the reaction characteristics of CaOH2, HCl and SO2 in the flue gas emitted by a laboratory incinerator. The amount of sulfur retained in the residues (including the spray dryer ash and baghouse ash) was also evaluated in this study. The experimental parameters included HCl concentration (500-2000 ppm), SO2 concentration (500-2000 ppm), relative humidity (40-80% RH), and the addition of CaCl2 (30 wt.%). The results indicated that an HCl concentration of 500-2000 ppm did not affect HCl removal efficiency in the spray dryer at 150 degrees C and 45+/-5% RH. On the other hand, increase in SO2 concentration from 500 to 2000 ppm enhanced SO2 removal at 150 degrees C and 75+/-5% RH. Moreover, increase in removal efficiency of SO2 was more obvious when the relative humidity was greater than 80%. When the flue gas contained both HCl and SO2 simultaneously, the removal efficiency of SO2 could increase from 56.7 to 90.33% at HCl concentration of 236 ppm. However, when the concentration of HCl exceeded 535 ppm, the removal efficiency of SO2 decreased with increasing concentration of HCl. The removal efficiency of SO2 could be increase to 97.7% with the addition of CaCl2.

Simultaneous control of acid gases and PAHs using a spray dryer combined with a fabric filter using different additives.

The purpose of this research was to simultaneously evaluate the removal efficiency of acid gases and PAHs from the flue gas emitted by a laboratory incinerator. This flue gas contained dust, acid gases, organics and heavy metals. A spray dryer combined with a fabric filter was used as the air pollution control device (APCD) in this study. The operating conditions investigated included different feedstock additives (polyvinyl chloride (PVC) and NaCl) and spray dryer additives (SiO2, CaCl2 and NaHCO3). The removal efficiency for SO2 could be enhanced by adding inorganic additives, such as SiO2, CaCl2 and NaHCO3. The presence of PVC in the incinerator feedstock also increased the removal efficiency of SO2in the spray dryer. The improved removal of PAHs could be attributed to the addition of feedstock additives (PVC and NaCl) and spray dryer additives (SiO2, CaCl2 and NaHCO3).