Sulfur dioxide oxidation removal

The reverse-flow chemical reactor (RFR) has been shown to be a potentially effective technique for many industrial chemical processes, including oxidation of volatile organic compounds such as propane, propylene, and carbon monoxide removal of nitrogen oxides sulfur dioxide oxidation or reduction production of synthesis gas methanol formation and ethylbenzene dehydration into styrene. An excellent introductory article in the topic is given by Eigenberger and Nieken on the effect of the kinetic reaction parameters, reactor size, and operating parameters on RFR performance. A detailed review that summarizes the applications and theory of RFR operation is given by Matros and Bunimovich. 

Iron modified zeolites and ordered mesoporous oxides have been studied as catalysts for the sulfur dioxide oxidation in sulfur rich gases. Both zeolitic materials and mesoporous oxides show very good activity in this reaction. Other than solid state or incipient wetness loaded MCM-41 materials, the zeolites do not show an initial loss of activity. However, they loose activity upon prolonged exposure to reaction conditions around 700°C. The zeolitic samples were analyzed via X-ray absorption spectroscopy, and the deactivation could be related to removal of iron from framework sites to result in the formation of hematite-like species. If the iron can be stabilized in the framework, these materials could be an interesting alternative to other iron based catalysts for the commercial application in sulfur rich gases. 

Which chemical would be most likely to react with sulfur dioxide to remove it from combustion gases—sodium chloride (NaCl), lime (CaO), or nitric oxide (NO) ... 

One of the products of the roasting of a sulfide ore is sulfur dioxide gas. Until recently, this gas was simply vented to the atmosphere. Sulfur dioxide oxidizes further in polluted air to yield sulfur trioxide, which dissolves in moisture in the air to yield acid rain. Considerable damage to the environment has occurred as a result. Modem ore-roasting facilities use sulfur dioxide to produce sulfuric acid or otherwise remove it from the gases vented to the atmosphere. ... 

In the SCR process, NOX impurities are reduced with added ammonia in the presence of some residual oxygen from the furnace. The main NOX reduction reactions are shown in Table 11.5 together with some of the undesirable oxidation reactions, which can both produce sulfur trioxide and waste some of the added ammonia. Between 0.6-0.9 moles of ammonia per mole of NOX are added to limit the aimnonia shp to downstream equipment where it would deposit as sulfates. NOX conversion is therefore hmited to between 60-90%. At low NOX levels, there is little conversion to itrous oxide. Nitrous oxide formation is also inhibited by water. Gas leaving the boiler is usually at a temperature in the range 300-430°C and contains dust Dust is removed in an elee-trostatic precipitator with little heat loss before sulfur dioxide is removed as gypsum by reaction with lime. Alternatively, sulfur dioxide can also be eonvert-ed to sulfuric acid. The effluent is then vented to atmosphere. In the first power plants to be retrofitted with SCR units there were three possible loeations for the catalyst bed ... 

Catalysts may therefore be designed for nse in specific duties. For power plant, the design must balance the reaction rates of NOX reduction and sulfur dioxide oxidation in the restricted range of temperature of flue gas leaving the boiler, or at the dust and sulfur dioxide removal stages. A low activity catalyst that reaches maximum NOX reduction between, say 380°-400°C, can be more efficient than a catalyst that is more active between 300°-350°C because, overall, it produces less sulfur trioxide at the fixed operating temperature. ... 

Product removal during reaction. Sometimes the equilibrium conversion can be increased by removing the product (or one of the products) continuously from the reactor as the reaction progresses, e.g., by allowing it to vaporize from a liquid-phase reactor. Another way is to carry out the reaction in stages with intermediate separation of the products. As an example of intermediate separation, consider the production of sulfuric acid as illustrated in Fig. 2.4. Sulfur dioxide is oxidized to sulfur trioxide ... 

Impurities can be removed by formation of a gaseous compound, as in the fire-refining of copper (qv). Sulfur is removed from the molten metal by oxidation with air and evolution of sulfur dioxide. Oxygen is then removed by reduction with C, CO, in the form of natural gas, reformed... 

Nickel sulfate also is made by the reaction of black nickel oxide and hot dilute sulfuric acid, or of dilute sulfuric acid and nickel carbonate. The reaction of nickel oxide and sulfuric acid has been studied and a reaction induction temperature of 49°C deterrnined (39). High purity nickel sulfate is made from the reaction of nickel carbonyl, sulfur dioxide, and oxygen in the gas phase at 100°C (40). Another method for the continuous manufacture of nickel sulfate is the gas-phase reaction of nickel carbonyl and nitric acid, recovering the soHd product in sulfuric acid, and continuously removing the soHd nickel sulfate from the acid mixture (41). In this last method, nickel carbonyl and sulfuric acid are fed into a closed-loop reactor. Nickel sulfate and carbon monoxide are produced the CO is thus recycled to form nickel carbonyl. 

The absorption of sulfur dioxide in alkaline (even weakly alkaline) aqueous solutions affords sulfites, bisulfites, and metabisulfites. The chemistry of the interaction of sulfur dioxide with alkaline substances, either in solution, slurry, or soHd form, is also of great technological importance in connection with air pollution control and sulfur recovery (25,227,235—241). Even weak bases such as 2inc oxide absorb sulfur dioxide. A slurry of 2inc oxide in a smelter can be used to remove sulfur dioxide and the resultant product can be recycled to the roaster (242). 

Manufacture. Aqueous sodium hydroxide, sodium bicarbonate, sodium carbonate, or sodium sulfite solution are treated with sulfur dioxide to produce sodium metabisulfite solution. In one operation, the mother Hquor from the previous batch is reinforced with additional sodium carbonate, which need not be totally in solution, and then is treated with sulfur dioxide (341,342). In some plants, the reaction is conducted in a series of two or more stainless steel vessels or columns in which the sulfur dioxide is passed countercurrent to the alkaH. The solution is cooled and the sodium metabisulfite is removed by centrifuging or filtration. Rapid drying, eg, in a stream-heated shelf dryer or a flash dryer, avoids excessive decomposition or oxidation to which moist sodium metabisulfite is susceptible. 

An additional benefit of adsorption-based sulfur dioxide removal processes is that nitrogen oxides, NO, are also removed by the sorbent. Nitrogen oxides desorb when the sorbent is heated using hot air. 

Minor and potential new uses for ammonium thiosulfate include flue-gas desulfurization (76,77), removal of nitrogen oxides and sulfur dioxide from flue gases (78,79), converting sulfur ia hydrocarbons to a water-soluble form (80), and converting cellulose to hydrocarbons (81,82) (see Sulfur REMOVAL AND RECOVERY). 

Sulfur Dioxide Reductant. The Mathieson process uses sulfur dioxide, sodium chlorate, and sulfuric acid to produce chlorine dioxide gas with a much lower chlorine content. The sulfur dioxide gas reductant is oxidized to make sulfuric acid, reducing the overall acid requirement of the process. Air is used to dilute the chlorine dioxide produced by this process. The exit gases flow through a scmbber to which chlorate is added in order to remove any unreacted sulfur dioxide. Spent Hquor, containing some unreacted chlorate, sulfuric acid, and sodium sulfate, continuously overflows from this process. 

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