Chlorination reactions of 1,2,3,4-tetrachlorodibenzo-p-dioxin on fly ash with HC1 in air

Chlorine substitution reactions of 1,2,3,4-TCDD to higher chlorinated PCDD occurred on fly ash between 50°C to 250°C with an HC1 in air atmosphere in a laboratory reaction apparatus used to simulate emission conditions in municipal incinerators. Percent conversion of 1,2,3,4-TCDD through such reactions was as high as 66% by mass corrected for losses to irreversable absorption. Production of penta-, hexa-, hepta- and octa-CDD was evident and a maximum in production of P₅CDD and H₆CDD was reached in 10 to 30 min. Results showed that these reactions may involve complex mechanisms which include several states of adsorption with different reactivities of 1,2,3,4-TCDD on fly ash.     

PVC-induced chlorine-bromine exchange in the pyrolysis of polybrominated diphenyl ethers, -biphenyls, -dibenzodioxins and dibenzofurans

Extensive chlorine-for-bromine exchange occurs when 1,2,3,4-tetrabromodibenzodioxin (TBrDD), polybromodibenzodioxin/furan mixtures (PBrDD/F), and technical brominated diphenyl ethers and -biphenyls are pyrolyzed at 800°C in the presence of PVC. Tetra-ClDD, BrCl₃DD, Br₂Cl₂DD, and Br₃ClDD could be detected from the pyrolysis of 1,2,3,4-TBrDD. A number of chloro/bromodibenzodioxins and furans as well as chlorinated dibenzodioxins and furans are formed in the residues of the PBrDD/F mixtures. Only chlorinated and chlorinated/brominated diphenyl ethers and no dioxins and furans occured during the pyrolysis of brominated diphenyl ethers in the presence of PVC. Through the exchange of bromine with chlorine, chlorinated and chlorinated/brominated biphenyls could be detected from the pyrolysates of hexabromobiphenyl.     

Presence of nitro-chlorinated dioxins on fly ash from municipal incinerators and from laboratory production through reactions between NO2 and T4CDD on fly ash

Treatment of tetrachlorodibenzo-p-dioxin (T₄CDD) on municipal incinerator fly ash at 30 to 150°C for 10 minutes using 5% (Vol/Vol) NO₂ in air resulted in production of nitro-T₄CDD. Percent conversion was between 40% at 50°C to 100% at 150°C. Nitro-T₄CDD produced in the laboratory was unstable in hexane/methanol or hexane/acetone solutions and decomposed at ?5°C with half-lives of 8–10 days^?1 to the original T₄CDD.Fly ash from a municipal incinerator in Toronto, Ontario was extracted using toluene/methanol for 12 hrs in a Soxhlet extractor. Condensate of this extract was analyzed using capillary gas chromatography with flame ionization, nitrogen-selective, and mass spectrometric detectors. Retention times for nitro-T₄CDD, multi-ion selected ion monitoring, and nitrogen detector response were used as supporting evidence for the presence of nitro-chlorinated dioxins as naturally occurring in this sample.     

Aircraft Release of Sulfur Hexafluoride as an Atmospheric Tracer

Abstract

The effect of temperature on polyvinylchloride (PVC) combustion using a downstream tubular furnace was investigated for the formation of polycylcic aromatic hydrocarbons (PAHs) and chlorinated compounds. As the temperature increased, higher levels of PAHs were generated. Chlorinated compounds reached a peak at 600°C, with low emissions recorded at 300 and 900°C. There was a close correlation (R² = 0.97) among polychlorinated bi-phenyls (PCBs), hexachlorobenzene, pentachloroben-zene, and polychlorinated dibenzo-p-dioxins and poly-chlorinated dibenzofurans (PCDD/Fs). PAHs at all temperatures were analyzed in the gas phase. PCDD/Fs and PCBs were emitted as a solid phase at 300 and 600°C and as a gas phase at 900°C. For some PAHs, chloroben-zenes, and PCDD/Fs, a mathematical equation between the gas and solid phase and the reciprocal temperature in semilog proportion was derived. The proposed equation, which is log (amount in gas phase/amount in solid phase) = ?A/T + B, where T is the temperature of the furnace and A and B are constants, for these species relating their gas/solid distributions showed a good relationship.     

1985 Directory of Governmental Air Pollution Control Agencies

Abstract

Clay that contains kaolinite has been used extensively as a raw material for manufacturing of bricks and china at 900–1100 °C. This study used clay to stabilize the contaminant chromium(VI) [Cr(VI)] through a heating process at 500–1100 °C. X-ray absorption spectroscopic results indicated that the 500–900 °C heating process transformed hazardous Cr(VI) to nontoxic Cr(III); Cr₂O₃ was the species detected as most abundant. The 1100 °C heating process caused the formation of Cr₂SiO₅, which was not detected in the samples heated at 500–900 °C. Fourier transformed extended X-ray absorption fine structure spectra were fitted by use of WinXAS software. Phase shifts and backscatter(ing) amplitudes for specific atom pairs, based on the crystallographic data for CrO₃ and Cr₂O₃, were theoretically calculated with the FEFF software. The processed XAS data show that the first shell coordination numbers were similar to each other as the temperature was increased from 500 to 900 °C and 1100 °C, implying that their Cr(III) crystallite size was relatively similar. The interatomic distance between the target center element and the first shell for the 500– 1100 °C samples was 1.98Å. The Debye-Waller factor for the 1100 °C sample was increased compared with the 500 and 900 °C samples and probably indicates the formation of Cr₂SiO₅.     

Effect of Fractionation and Pyrolysis on Fuel Properties of Poultry Litter

Abstract

Raw poultry litter has certain drawbacks for energy production such as high ash and moisture content, a corrosive nature, and low heating values. A combined solution to utilization of raw poultry litter may involve fractionation and pyrolysis. Fractionation divides poultry litter into a fine, nutrient-rich fraction and a coarse, carbon-dense fraction. Pyrolysis of the coarse fraction would remove the corrosive volatiles as bio-oil, leaving clean char. This paper presents the effect of fractionation and pyrolysis process parameters on the calorific value of char and on the characterization of bio-oil. Poultry litter samples collected from three commercial poultry farms were divided into 10 treatments that included 2 controls (raw poultry litter and its coarse fraction having particle size greater than 0.85 mm) and 8 other treatments that were combinations of three factors: type (raw poultry litter or its coarse fraction), heating rate (30 or 10 °C/min), and pyrolysis temperature (300 or 500 °C). After the screening process, the poultry litter samples were dried and pyrolyzed in a batch reactor under nitrogen atmosphere and char and condensate yields were recorded. The condensate was separated into three fractions on the basis of their density: heavy, medium, and light phase. Calorific value and proximate and nutrient analysis were performed for char, condensate, and feedstock. Results show that the char with the highest calorific value (17.39 ± 1.37 MJ/kg) was made from the coarse fraction at 300 °C, which captured 68.71 ± 9.37% of the feedstock energy. The char produced at 300 °C had 42 ± 11 mg/kg arsenic content but no mercury. Almost all of the Al, Ca, Fe, K, Mg, Na, and P remained in the char. The pyrolysis process reduced ammoniacal-nitrogen (NH₄-N) in char by 99.14 ± 0.47% and nitrate-nitrogen (NO₃-N) by 95.79 ± 5.45% at 500 °C.     

Kinetics and the mass transfer mechanism of hydrogen sulfide removal by biochar derived from rice hull

The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The biochar derived from rice hull was evaluated for its abilities to remove hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperature has great influence on the adsorption of H₂S. At the different pyrolysis temperature, the H₂S removal efficiency of rice hull-derived biochar was different. The adsorption capacities of biochar were 2.09 mg·g^–1, 2.65 mg·g^–1, 16.30 mg·g^–1, 20.80 mg·g^–1, and 382.70 mg·g^–1, which their pyrolysis temperatures were 100 °C, 200 °C, 300 °C, 400 °C and 500 °C respectively. Based on the Yoon-Nelson model, it analyzed the mass transfer mechanism of hydrogen sulfide adsorption by biochar.

Implications: The paper focuses on the biochar derived from rice hull–removed hydrogen sulfide (H₂S) from gas phase. The surface area and pH of the biochar were compared. The different pyrolysis temperatures have great influence on the adsorption of H₂S. At the different pyrolysis temperatures, the H₂S removal efficiency of rice hull–derived biohar was different. The adsorption capacities of biochar were 2.09, 2.65, 16.30, 20.80, and 382.70 mg·g^?1, and their pyrolysis temperatures were 100, 200, 300, 400, and 500 °C, respectively. Based on the Yoon-Nelson model, the mass transfer mechanism of hydrogen sulfide adsorption by biochar was analyzed.     

Pyrolysis and GC/MS-analysis of brominated flame retardants in on-line operation

Flame retardants such as brominated diphenyl ethers (Bromkal 70-5-DE, FR 300 BA), 2,4,6-tribromophenol, pentabromophenol and hexabromobiphenyl were pyrolyzed at 600°C, 700°C, 800°C and 900°C in absence of oxygen in a SGE pyrojector, and the residues were analyzed by means of GC/MS in on-line operation. The pyrolysis of Bromkal 70-5-DE hereby yielded bromobenzenes (PBBz), bromophenols (PBP) and brominated dibenzofurans (PBDF). PBBz, bromonaphthalenes (PBN) and PBDF could be detected in the FR 300 BA pyrolysate, whereas brominated benzenes and dibenzodioxins formed during the pyrolysis of 2,4,6-tribromophenol. Unlike the pyrolysis of 2,4,6-tribromophenol, pentabromophenol pyrolysis produced mainly bromobenzenes along with traces of bromonaphthalenes, bromodioxins and bromodiphenyl ethers. The pyrogram of hexabromobiphenyl showed bromobenzenes and brominated biphenyls as key pyrolysate components.     

Production of Activated Carbons from Pyrolysis of Waste Tires Impregnated with Potassium Hydroxide

ABSTRACT

Activated carbons were produced from waste tires using a chemical activation method. The carbon production process consisted of potassium hydroxide (KOH) impregnation followed by pyrolysis in N₂ at 600-900 °C for 0-2 hr. The activation method can produce carbons with a surface area (SA) and total pore volume as high as 470 m²/g and 0.57 cm³/g, respectively. The influence of different parameters during chemical activation, such as pyrolysis temperature, holding time, and KOH/tire ratio, on the carbon yield and the surface characteristics was explored, and the optimum preparation conditions were recommended. The pore volume of the resulting carbons generally increases with the extent of carbon gasified by KOH and its derivatives, whereas the SA increases with degree of gasification to reach a maximum value, and then decreases upon further gasification.     

Preparation of Sulfurized Powdered Activated Carbon from Waste Tires Using an Innovative Compositive Impregnation Process

Abstract

The objective of this study is to develop an innovative compositive impregnation process for preparing sulfurized powdered activated carbon (PAC) from waste tires. An experimental apparatus, including a pyrolysis and activation system and a sulfur (S) impregnation system, was designed and applied to produce sulfurized PAC with a high specific surface area. Experimental tests involved the pyrolysis, activation, and sulfurization of waste tires. Waste-tire-derived PAC (WPAC) was initially produced in the pyrolysis and activation system. Experimental results indicated that the Brunauer-Emmett-Teller (BET) surface area of WPAC increased, and the average pore radius of WPAC decreased, as water feed rate and activation time increased. In this study, a conventional direct impregnation process was used to prepare the sulfurized PAC by impregnating WPAC with sodium sulfide (Na₂S) solution. Furthermore, an innovative compositive impregnation process was developed and then compared with the conventional direct impregnation process. Experimental results showed that the compositive impregnation process produced the sulfurized WPAC with high BET surface area and a high S content. A maximum BET surface area of 886 m²/g and the S content of 2.61% by mass were obtained at 900°C and at the S feed ratio of 2160 mg Na₂S/g C. However, the direct impregnation process led to a BET surface area of sulfurized WPAC that decreased significantly as the S content increased.     

Polybrominated dibenzodioxins and -furans from the pyrolysis of some flame retardants

Purified 2,4,6-Tribromophenol, Pentabromophenol, Tetrabromobisphenol A and Tetrabromophthalic anhydride were pyrolyzed at 700°C, 800°C and 900°C. DBrDD, T3BrDD, T4BrDD (up to 89.6%), PBrDD, DBrDF, T3BrDF, and PBrDF were formed from 2,4,6-tribromophenol. From pentabromophenol PBrDD, H6BrDD, H7BrDD, OBrDD, PBrDF, H6BrDF, H7BrDF and OBrDF were formed. The burning of tetrabromobisphenol A gave MBrDD, DBrDD, T3BrDD, T4BrDD, MBrDF, DBrDF, T3BrDF and T4BrDF. In the residues of thermal reactions from tetrabromophthalic anhydride no PBrDD/PBrDF could be found. In all these studies the maximum of PBrDD/PBrDF-formation was at 800°C. The absence of PBrDD(PBrDF from the pyrolysate of tetrabromophthalic anhydride may guide the development of new brominated flame retardants, since certain structural features may suppress the formation of PBrDD/PBrDF.     

Selective Leaching of Valuable Metals from Waste Printed Circuit Boards

Abstract

This study was carried out to recover valuable metals from the printed circuit boards (PCBs) of waste computers. PCB samples were crushed to smaller than 1 mm by a shredder and initially separated into 30% conducting and 70% nonconducting materials by an electrostatic separator. The conducting materials, which contained the valuable metals, were then used as the feed material for magnetic separation, where it was found that 42% of the conducting materials were magnetic and 58% were nonmagnetic. Leaching of the nonmagnetic component using 2 M H₂SO₄ and 0.2 M H₂O₂ at 85 °C for 12 hr resulted in greater than 95% extraction of Cu, Fe, Zn, Ni, and Al. Au and Ag were extracted at 40 °C with a leaching solution of 0.2 M (NH₄)₂S₂O₃, 0.02 M CuSO₄, and 0.4 M NH₄OH, which resulted in recovery of more than 95% of the Au within 48 hr and 100% of the Ag within 24 hr. The residues were next reacted with a 2 M NaCl solution to leach out Pb, which took place within 2 hr at room temperature.     

Ni-Co bimetallic catalysts on coconut shell activated carbon prepared using solid-phase method for highly efficient dry reforming of methane

Ni-Co bimetallic catalysts supported on coconut shell activated carbon are synthesized using solid-phase method and investigated for dry reforming of methane, to explore the impact of Ni:Co ratio on the catalyst activity and stability. The catalyst performances are evaluated under the temperature varying from 600 to 900 °C and gas hourly space velocity (GHSV) of 7200 mL/h·g-cat. The characterization results show that metal nanoparticles are produced on the support, and the bimetallic catalyst with an explicit Ni:Co ratio (2:1) is the most beneficial for metal particle dispersion and acquires the minimum particle size of 4.41 nm. The bimetallic catalysts with an explicit Ni:Co ratio of 1:2 and 1:1 exhibit a synergistic effect towards the conversions of CH₄ and CO₂, respectively. The experimental results reveal that the highest CH₄ and CO₂ conversions rise to 94.0% and 97.5% within 12 h at 900 °C on average, respectively, assisted with the two bimetallic catalysts. The intensity of disordered carbon and thermal stability are enhanced with the extension of reforming process, contributing to a long-term catalytic stability. Besides, no obvious carbon deposition is detected, leading to a highly catalytic stability for the bimetallic catalysts.

     

Application of 1D and 2D MFR reactor technology for the isolation of insecticidal and anti-microbial properties from pyrolysis bio-oils

Valuable chemicals can be separated from agricultural residues by chemical or thermochemical processes. The application of pyrolysis has already been demonstrated as an efficient means to produce a liquid with a high concentration of desired product. The objective of this study was to apply an insect and microorganism bioassay-guided approach to separate and isolate pesticidal compounds from bio-oil produced through biomass pyrolysis. Tobacco leaf (Nicotianata bacum), tomato plant (Solanum lycopersicum), and spent coffee (Coffea arabica) grounds were pyrolyzed at 10°C/min from ambient to 565°C using the mechanically fluidized reactor (MFR). With one-dimensional (1D) MFR pyrolysis, the composition of the product vapors varied as the reactor temperature was raised allowing for the selection of the temperature range that corresponds to vapors with a high concentration of pesticidal properties. Further product separation was performed in a fractional condensation train, or 2D MFR pyrolysis, thus allowing for the separation of vapor components according to their condensation temperature. The 300–400°C tobacco and tomato bio-oil cuts from the 1D MFR showed the highest insecticidal and anti-microbial activity compared to the other bio-oil cuts. The 300–350 and 350–400°C bio-oil cuts produced by 2D MFR had the highest insecticidal activity when the bio-oil was collected from the 210°C condenser. The tobacco and tomato bio-oil had similar insecticidal activity (LC₅₀ of 2.1 and 2.2 mg/mL) when the bio-oil was collected in the 210°C condenser from the 300–350°C reactor temperature gases. The 2D MFR does concentrate the pesticidal products compared to the 1D MFR and thus can reduce the need for further separation steps such as solvent extraction.     

Effects of chronic exposure to radiofrequency electromagnetic fields on energy balance in developing rats

The effects of radiofrequency electromagnetic fields (RF-EMF) on the control of body energy balance in developing organisms have not been studied, despite the involvement of energy status in vital physiological functions. We examined the effects of chronic RF-EMF exposure (900 MHz, 1 V?m^?1) on the main functions involved in body energy homeostasis (feeding behaviour, sleep and thermoregulatory processes). Thirteen juvenile male Wistar rats were exposed to continuous RF-EMF for 5 weeks at 24 °C of air temperature (T _a) and compared with 11 non-exposed animals. Hence, at the beginning of the 6th week of exposure, the functions were recorded at T _a of 24 °C and then at 31 °C. We showed that the frequency of rapid eye movement sleep episodes was greater in the RF-EMF-exposed group, independently of T _a (+42.1 % at 24 °C and +31.6 % at 31 °C). The other effects of RF-EMF exposure on several sleep parameters were dependent on T _a. At 31 °C, RF-EMF-exposed animals had a significantly lower subcutaneous tail temperature (?1.21 °C) than controls at all sleep stages; this suggested peripheral vasoconstriction, which was confirmed in an experiment with the vasodilatator prazosin. Exposure to RF-EMF also increased daytime food intake (+0.22 g?h^?1). Most of the observed effects of RF-EMF exposure were dependent on T _a. Exposure to RF-EMF appears to modify the functioning of vasomotor tone by acting peripherally through α-adrenoceptors. The elicited vasoconstriction may restrict body cooling, whereas energy intake increases. Our results show that RF-EMF exposure can induce energy-saving processes without strongly disturbing the overall sleep pattern.     

Temperature Dependence of Nickel Stabilization in Inorganic Oxide Matrices

Abstract

Scanning electron microscopy, X‐ray diffractometry, X‐ray absorption spectroscopy, and other means are used to investigate the effect of thermal treatment temperature, 105–1100 °C, on the immobilization of nickel (Ni) by the inorganic oxides of latosol. Ni is more firmly immobilized by the latosol with increasing temperature. Spectral analyses indicate that a shoulder toward the edge‐jump appears in the spectra of X‐ray absorption near‐edge structure for the samples heated at 900 and 1100 °C. Moreover, the intensity of the main peak at the edge increases with higher temperature; this information indicates the distortion of the divalent nickel [Ni(II)] environment in the samples heated at 900 and 1100 °C. Nevertheless, the distortion is absent from the samples heated at 105 and 500 °C. The fact of the distortion of the Ni(II) environment suggests the occurrence of a chemical reaction between the Ni compound and the inorganic matrices of the latosol soil during the heating process at 900 and 1100 °C. In addition, the extended X‐ray absorption fine structure results correspond well to the X‐ray absorption near‐edge structure results; the former are supportive of the occurrence of a distorted Ni(II) environment in the samples heated at 900 and 1100 °C. The wet‐chemistry results show that the samples heated at 900–1100 °C leach less Ni than the 105–500 °C samples do. The change of the Ni environment is related to the observation that less Ni is leached from the samples heated at 900–1100 °C. Furthermore, the pore closing phenomenon is observed only in the 1100 °C sample; this phenomenon corresponds with the fact that the 1100 °C sample leaches less Ni than the 900 °C sample does.     

Characteristics of penicillin bacterial residue

A hybrid selective noncatalytic reduction/selective catalytic reduction (SNCR/SCR) system that uses two types of technology, low-temperature SCR process and SNCR process, was designed to develop nitrogen oxide (NO_x) reduction technology. SCR was conducted with space velocity (SV) = 2400 hr^?1 and hybrid SNCR/SCR with SV = 6000 hr^?1, since the study focused on reducing the amount of catalyst and both achieved 98% NO_x reduction efficiency. Characteristics of NO_x reduction by NH₃ were studied for low-temperature SCR system at 150 °C using Mn-V₂O₅/TiO₂ catalyst. Mn-added V₂O₅/TiO₂ catalyst was produced, and selective catalyst reduction of NO_x by NH₃ was experimented. NO_x reduction rate according to added Mn content in Mn-V₂O₅/TiO₂ catalyst was studied with varying conditions of reaction temperature, normalized stoichiometric ratio (NSR), SV, and O₂ concentration. In the catalyst experiment according to V₂O₅ concentration, 1 wt.% V₂O₅ catalyst showed the highest NO_x reduction rate: 98% reduction at temperature window of 200~250 °C. As a promoter of the V₂O₅ catalyst, 5 wt.% Mn was added, and the catalyst showed 47~90% higher efficiency even with low temperatures, 100~200 °C. Mn-V₂O₅/TiO₂ catalyst, prepared by adding 5 wt.% Mn in V₂O₅/TiO₂ catalyst, showed increments of catalyst activation at 150 °C as well as NO_x reduction. Mn-V₂O₅/TiO₂ catalyst showed 8% higher rate for NO_x reduction compared with V₂O₅/TiO₂ catalyst in 150 °C SCR. Thus, (5 wt.%)Mn-(1 wt.%)V₂O₅/TiO₂ catalyst was applied in SCR of hybrid SNCR/SCR system of low temperature at 150 °C. Low-temperature SCR hybrid SNCR/SCR (150 °C) system and hybrid SNCR/SCR (350 °C) showed 91~95% total reduction rate with conditions of SV = 2400~6000 hr^?1 SCR and 850~1050 °C SNCR, NSR = 1.5~2.0, and 5% O₂. Hybrid SNCR/SCR (150 °C) system proved to be more effective than the hybrid SNCR/SCR (350 °C) system at low temperature.

Implications:?NO_x control is very important, since they are the part of greenhouse gases as well as the cause of acid rain and ozone hole. A technology, so-called hybrid SNCR/SCR process, was tested using Mn-V₂O₅/TiO₂ monolithic catalyst for NO_x reduction, and the method is promising. The results of this study would provide some ideas to parties such as policy makers, environmental engineers, and so on.     

Desulfurization of Flue Gases in A Fluidized Bed of Modified Limestone

This publication concerns the dry removal of SO₂ from gases using limestone absorbents. It reports bench-scale experiments made with commercial samples of powdered limestone (CaCO₃) activated by addition of a cheap substance, namely CaCl₂. The absorption was carried out in a fluidized bed traversed by the flue gases, between 600° and 900° C. The degree and rate of transformation of CaCO₃ to CaSO₄ in the presence of SO₂ and air have been compared for unmodified and modified absorbents. Initial rates of reaction, and the variation of the rate of absorption with time have been measured. The influence of the SO₂ content of the gas has been assessed. At 700° C, the maximum degree of transformation of activated limestone to sulfate exceeds 90%, whereas untreated CaCO₃ transforms only to 16–20%. At the same temperature, more than 90% of SO₂ contained In a gas carrying 0.35% SO₂ is removed. Because of the much smaller quantity of solid absorbent required, dry absorption processes based on the modified absorbents might get renewed interest. The modified absorbents might also be used for in situ absorption in fluidized bed combustion, in which the temperatures are in the range studied in the present paper.     

Laboratory testing of a continuous emissions monitor for hydrochloric acid

Continuous monitoring of exhaust flue gas has become a common practice in power plants in response to Federal Mercury and Air Toxics Standards (MATS) standards. Under the current rules, hydrochloric acid (HCl) is not continuously measured at most plants; however, MATS standards have been proposed for HCl, and tunable diode laser (TDL) absorption spectroscopy is one method that can be used to measure HCl continuously. The focus of this work is on the evaluation and verification of the operation performance of an HCL TDL over a range of real-world operating environments. The testing was conducted at the University of California at Riverside (UCR) spectroscopy evaluation laboratory. Laboratory tests were conducted at three separate temperatures, 25ºC, 100ºC, and 200ºC, and two distinct moisture levels for the enhanced temperatures, 0%, (2 tests) and 4%, over a concentration range from 0 ppmv to 25 ppmv-m at each of the elevated temperatures. The results showed good instrument accuracy as a function of changing temperature and moisture. Data analysis showed that the average percentage difference between the ammonia concentration and the calibration source was 3.33% for varying moisture from 0% to 4% and 2.69% for varying temperature from 25 to 100/200ºC. An HCl absorption line of 1.742 μm was selected for by the manufacturer for this instrument. The Hi Tran database indicated that CO₂ is probably the only major interferent, although the CO₂ absorption is very weak at that wavelength. Interference tests for NO, CO, SO₂, NH₃, and CO₂ for a range of concentrations typical of flue gasses in coal-fired power plants did not show any interference with TDL HCl measurements at 1.742 μm. For these interference tests, CO₂ was tested at a concentration of 11.9% concentration in N₂ for these tests. Average precision over the entire range for all 10 tests is 3.12%.

Implications: The focus of this study was an evaluation of the operation performance of a tunable diode laser (TDL) for the measurement of hydrochloric acid (HCl) over a range of real-world operating environments. The results showed good instrument accuracy as a function of changing temperature from 25ºC to 200ºC and moisture from 0% to 4%. Such as an instrument could be used for continuous monitoring of exhaust flue gas in power plants once the Federal Mercury and Air Toxics Standards (MATS) standards have been fully implemented.     

Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.