Sulfate emissions

Begeman, C. R., M. L. Jackson, and G. J. Nebel. Sulfate Emissions frmn Catalyst-Equipped Automobiles. Society of Automotive Engineers Paper 741060 Presented at Automotive Engineers Meeting, Toronto, Canada, Oct. 21-25, 1974. 

Point source plume trapping assumptions used in the Eugene airshed modeling were verified by comparing alternative modeling assumptions of sulfate emission impacts to measured sulfate levels. 

Dietz. R. N., Wieser, R. E. (1983) Sulfate formation in oil-fired power plant plumes Vol. 1. Parameters affecting primary sulfate emissions and a model for predicting emissions and plume capacity. Electric Power Research Institute, EPRI EA-3231, Pinal Report. 

A second concern was that under some conditions sulfur dioxide in exhaust could be emitted as sulfuric acid as a result of catalytic oxidation over the noble metal catalyst. To answer this concern General Motors conducted a 350-car test designed to simulate sulfate emissions on a busy expressway. The U.S. Environmental Protection Agency, other vehicle manufacturers, and several independent environmental monitoring organizations participated in the experiment. This experiment showed conclusively that ambient levels of sulfuric acid under this worse-case simulated exposure situation were far below threshold levels known to produce adverse health effects. 

Ammonia slip t)T)ically occurs when overstoichiometric amoimts of urea/ammonia are injected. Due to the ammonia storage capacity of the catalyst this is not emitted directly so if an appropriate control action is taken, ammonia slip can be avoided. However, up to today an inexpensive and fast NOx and/or ammonia sensor is not available to accommodate such a control action. Solutions have been proposed in the use of engine maps for predicting the NOx output [9] and/or an additional oxidation catalyst for avoiding ammonia slip [3]. The latter is detrimental to the sulfate emissions and as most of the oxidized ammonia will leave the system as NO, the overall NOx removal efficiency will be lowered. Therefore, it would be convenient if a possible overdose of ammonia will leave the system in the form of nitrogen (N2)- This would solve the SCR control problem. 

Steel and coke complexes were once far more widespread than today, when more steel was made domestically. Sulfate emissions from such facilities were high because large amounts of coal were coked, then consumed in steelmaking. 

Sulfate emissions would have been eorrelated with PAH and other carbonaceous emissions from coking facihties and with metal emissions from steelmaking. Sulfate emissions from steehnaking are now down considerably for two reasons (1) far fewer steehnaking facihties use coke, as these inefficient facihties have been retired or replaced by electric arc steelmaking, which is now used to make 60% of US steel and (2) stricter environmental controls for emissions from srih-existing integrated steelmakers. 

Fig. 15.11 Fluoride emissirai during OCV hold test (6% of fluorine in the membrane is released over a 48 h hold) and sulfate emissions during recovery operation [37]...

There are, however, technological means available to burn incompletely desulfurized fuels at the same time minimizing SO2 emissions. In the auto-desulfurizing AUDE boiler developed by IFF, the effluent is treated in place by an absorbent based on lime and limestone calcium sulfate is obtained. This system enables a gas desulfurization of 80% it requires nevertheless a relatively large amount of solid material, on the order of 200 kg per ton of fuel. 

Surface heterogeneity may be inferred from emission studies such as those studies by de Schrijver and co-workers on P and on R adsorbed on clay minerals [197,198]. In the case of adsorbed pyrene and its derivatives, there is considerable evidence for surface mobility (on clays, metal oxides, sulfides), as from the work of Thomas [199], de Mayo and co-workers [200], Singer [201] and Stahlberg et al. [202]. There has also been evidence for ground-state bimolecular association of adsorbed pyrene [66,203]. The sensitivity of pyrene to the polarity of its environment allows its use as a probe of surface polarity [204,205]. Pyrene or ofter emitters may be used as probes to study the structure of an adsorbate film, as in the case of Triton X-100 on silica [206], sodium dodecyl sulfate at the alumina surface [207] and hexadecyltrimethylammonium chloride adsorbed onto silver electrodes from water and dimethylformamide [208]. In all cases progressive structural changes were concluded to occur with increasing surfactant adsorption. 

The abatement of fluorine emissions and disposal of by-product calcium sulfate from phosphoric acid plants are environmental concerns. 

Formation of emissions from fluidised-bed combustion is considerably different from that associated with grate-fired systems. Flyash generation is a design parameter, and typically >90% of all soHds are removed from the system as flyash. SO2 and HCl are controlled by reactions with calcium in the bed, where the lime-stone fed to the bed first calcines to CaO and CO2, and then the lime reacts with sulfur dioxide and oxygen, or with hydrogen chloride, to form calcium sulfate and calcium chloride, respectively. SO2 and HCl capture rates of 70—90% are readily achieved with fluidi2ed beds. The limestone in the bed plus the very low combustion temperatures inhibit conversion of fuel N to NO. ... 

The lignitic coals of the northern United States tend to have low sulfur contents, making them attractive for boilet fuels to meet sulfur-emission standards. However, low sulfur content coals have impaired the performance of electrostatic precipitators. The ash of these coals tends to be high in alkaline earths (Ca, Mg) and alkaUes (Na, K). As a result, the ash can trap sulfur as sulfites and sulfates (see Airpollution control methods). 

The alkah metals are commonly separated from all other elements except chlorine before gravimetric determination. In the absence of other alkaUes, sodium maybe weighed as the chloride or converted to the sulfate and weighed. WeU-known gravimetric procedures employ precipitation as the uranyl acetate of sodium—2inc or sodium—magnesium. Quantitative determination of sodium without separation is frequently possible by emission or atomic-absorption spectrometric techniques. 

Commercially produced barium is analyzed for metallic impurities by means of emission spectroscopy. Carbon content can be deterrnined by combustion, and nitrogen by the Kjeldahl method. Total barium can best be deterrnined gravimetricaHy by precipitation as the sulfate. 

Black and colored plates can also be obtained from chromic acid baths. The plates are mostly oxides (177). Black chromium plating bath compositions are proprietary, but most do not contain sulfate. The deposit has been considered for use in solar panels because of its high absorptivity and low emissivity (175). 

Pretreatment of the collected particulate matter may be required for chemical analysis. Pretreatment generally involves extraction of the particulate matter into a liquid. The solution may be further treated to transform the material into a form suitable for analysis. Trace metals may be determined by atomic absorption spectroscopy (AA), emission spectroscopy, polarogra-phy, and anodic stripping voltammetry. Analysis of anions is possible by colorimetric techniques and ion chromatography. Sulfate (S04 ), sulfite (SO-, ), nitrate (NO3 ), chloride Cl ), and fluoride (F ) may be determined by ion chromatography (15). 

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