Reducing acids

A first operation on the crude, desalting (washing by water and caustic), extracts salts (NaCl, KCl and the MgCb that is cdn eft4rdJt6 NaCl by the caustic), reduces acid corrosion as well as it minimizes fouling and deposits. /... 

It will also reduce acid chlorides, acid anhydrides and aldehydes to primary alcohols, ketones to secondary alcohols, and amides to the corresponding amines R-CONHi -> R CHiNH. Nitro-hydrocarbons if aromatic are... 

Large sources of SO2 and NO may also require additional emission reductions because of the 1990 Clean Air Act Amendments. To reduce acid... 

A variation of this process is Mobil s methanol-to-olefins (MTO) process, in which up to 80% C2—olefins are produced over ZSM-5 of reduced acidity and at much higher temperatures. 

The amine ends also react with atmospheric contaminants, such as SO2 and oxides of nitrogen and ozone, under ambient storage conditions (50). This phenomenon is referred to as aging and results in reduced acid dye affinity. 

Acid modifiers have been used to a limited extent to reduce acid consumption in the H2SO4 alkylation process (27). Increased catalyst costs will encourage the further development and appHcation of such acid modification techniques in the future. In addition, the development of new technology, such as two-step alkylation, may be accelerated based on the incentive to reduce catalyst consumption and increase product octane (28). 

Improved feedstock pretreatment is important to minimize catalyst consumption and reduce subsequent spent-catalyst handling requirements. Selective hydrogenation of dienes can be used to reduce acid consumption, both in HF and H2SO4 alkylation (29). More effective adsorptive treating systems have been appHed to remove oxygen-containing contaminants that are frequently introduced in upstream processing steps. 

Calcareous minerals such as gypsum [13397-24-5] when added in stoichiometric amounts relative to the barite impurities, reduce acid-soluble barium losses (16). 

Improvements to the methanol reductant processes may be found in the patent Hterature. These include methods of operation to reduce acidity in the crystallisation 2one of the generator to promote crystallisation of sodium sulfate and to reduce sulfuric acid consumption (48). Other improvements sought are the elimination of formic acid and chlorine impurities from the chlorine dioxide, as weU as methods of recovering acid and sodium hydroxide, or acid and neutral sodium sulfate from the soHd sodium sesquisulfate salt waste stream (48—52). 

Alloy C Better for reducing acid strengths (<60% concentration)... 

Lithium aluminum hydride (LiAlH4) is the most powerful of the hydride reagents. It reduces acid chlorides, esters, lactones, acids, anhydrides, aldehydes, ketones and epoxides to alcohols amides, nitriles, imines and oximes to amines primary and secondary alkyl halides and toluenesulfonates to... 

Copper chromite 14) and barium-promoted copper chromite (75,/7) have been used for acid reductions but very high temperatures (300 C) are required. The necessary temperature is sufficiently higher than that required foresters to permit selective reduction of half-acid esters to the hydroxy acid 23). The reverse selectivity can be achieved by reduction over H Ru4 CO)a PBu3)4 at I00-200 C and 1500-3000 psig. This homogeneous catalyst will reduce acids and anhydrides, but not esters (2). 

Acid deposition is a regional problem wherever large amounts of fossil fuels are consumed. There have been significant efforts in both Europe and North America to reduce acid deposition because of its many deleterious effects. This effort has focused mainly on the reduction of SO, emissions. In the future acid deposition tvill have to be addressed in eastern Asia, where rapid industrialization and increased use of fossil fuels is likely. 

Duplex stainless steels are mostly composed of alternate austenite and ferrite grains. Their structure improves resistance to chloride-induced stress corrosion cracking. In certain reducing acids, such as acetic and formic, preferential attack of the ferrite is a serious problem. 

Gold is stable in most strong reducing acids, whereas iron corrodes rapidly, yet finely divided gold can be quickly dissolved in oxygenated cyanide solutions which may be contained in steel tanks. A mixture of caustic soda and sodium nitrate can be fused in an iron or nickel crucible, whereas this melt would have a disastrous effect on a platinum crucible. 

Reaction of iron with oxygenated water or with reducing acids— inseparable A/C type. 

The standard electrode potentials , or the standard chemical potentials /X , may be used to calculate the free energy decrease —AG and the equilibrium constant /T of a corrosion reaction (see Appendix 20.2). Any corrosion reaction in aqueous solution must involve oxidation of the metal and reduction of a species in solution (an electron acceptor) with consequent electron transfer between the two reactants. Thus the corrosion of zinc ( In +zzn = —0-76 V) in a reducing acid of pH = 4 (a = 10 ) may be represented by the reaction ... 

In this example of the corrosion of zinc in a reducing acid of pH = 4, the corrosion product is Zn (aq.), but at higher pHs the thermodynamically stable phase will be Zn(OH)j and the equilibrium activity of Zn will be governed by the solubility product of Zn(OH)j and the pH of the solution at still higher pHs ZnOj-anions will become the stable phase and both Zn and Zn(OH)2 will become unstable. However, a similar thermodynamic approach may be adopted to that shown in this example. 

For these reasons a somewhat different approach will be adopted here, and an attempt will be made to show how a corrosion reaction may be represented by a well-defined reversible electrochemical cell, although again there are a number of difficulties. Consider the corrosion of metallic zinc in a reducing acid... 

Fig, 1,26 E Vi, log (curves for the corrosion of a metal in a reducing acid in which there are two exchange processes (c,f. Fig, L24) involving oxidation of M—are reduction of —vH2. Note that (o) the reverse reactions for exchange process are negligible at potentials removed from E, (b) the potential actually measured is the corrosion potential E , which is mixed potential, and (c) the E vs. (,pp curves (where ijppi is the applied current density) when extrapolated intersect at corr. 

Oxidising conditions severely reduce molybdenum s corrosion resistance, and aeration of the above acids causes a pronounced increase in the corrosion rate. It is rapidly attacked by oxidising acids such as nitric acid, and by reducing acids containing oxidisers such as HNO3, FeCh, etc. It is less resistant at 100°C, particularly in 10% acetic acid (the corrosion rate being 0-33 mm/y), 10% formic acid (0-2 mm/y) and 0-25% benzoic acid (0-25 mm/y). 

Other alloys of molybdenum which have been investigated for their corrosion resistance contain 10-50% Ta and were found to have excellent resistance to hydrochloric acid. Ti-Mo alloys were found to resist chemicals that attack titanium and Ti-Pd alloys, notably strong reducing acids such as hot concentrated hydrochloric, sulphuric, phosphoric, oxalic, formic and trichloroacetic. For example, a Ti-30Mo alloy has the following corrosion rates in boiling 20% hydrochloric acid, 0-127-0-254 mm/y in 10% oxalic acid at 100°C, 0-038 mm/y, which compares favourably with the respective rates of 19-5 and 122 mm/y for the Ti-0-2Pd alloy. 

On the other hand, the presence of CN ions greatly increases the zone of corrosion, owing to the formation of complex ions. Silver, therefore, is thermodynamically stable in reducing acids, e.g. hydrochloric acid, acetic acid, phosphoric acid, provided oxidising substances are absent. 

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