Metal oxides removal

The reaction involves cyclic operation alternating between sulfidation, in which the absorbent (a metal oxide) removes the sulfur from the feed stream and oxidation, in which the sulfided adsorbent is oxidized to regenerate the original oxide of the adsorbent. 

In the dry desulfurization process, metal oxides are reduced by coal gasification gas, and the rednced metal oxides remove snlfnr componnds from the gas and are then converted to sulfides. This method can be used more than once by letting the sulfides react with oxygen to release the sulfur contents as SO2 to retnrn them to metal oxides. 

Perhaps the simplest case of reaction of a solid surface is that where the reaction product is continuously removed, as in the dissolving of a soluble salt in water or that of a metal or metal oxide in an acidic solution. This situation is discussed in Section XVII-2 in connection with surface area determination. 

Surface heterogeneity is difficult to remove from crystalline inorganic substances, such as metal oxides, without causing large loss of surface areas by sintering. Thus in Fig. 2.14 in which the adsorbent was rutile (TiO ) all three adsorbates show a continuous diminution in the heat of adsorption as the surface coverage increases, but with an accelerated rate of fall as monolayer completion is approached. 

The hydrophobic character exhibited by dehydroxylated silica is not shared by the metal oxides on which detailed adsorption studies have been made, in particular the oxides of Al, Cr, Fe, Mg, Ti and Zn. With these oxides, the progressive removal of chemisorbed water leads to an increase, rather than a decrease, in the affinity for water. In recent years much attention has been devoted, notably by use of spectroscopic and adsorption techniques, to the elucidation of the mechanism of the physisorption and chemisorption of water by those oxides the following brief account brings out some of the salient features. 

Reduction of metal oxides with hydrogen is of interest in the metals refining industry (94,95) (see Metallurgy). Hydrogen is also used to reduce sulfites to sulfides in one step in the removal of SO2 pollutants (see Airpollution) (96). Hydrogen reacts directiy with SO2 under catalytic conditions to produce elemental sulfur and H2S (97—98). Under certain conditions, hydrogen reacts with nitric oxide, an atmospheric poUutant and contributor to photochemical smog, to produce N2 ... 

HCl gas reacts with metal oxides to form chlorides, oxychlorides, and water. Therefore, all the steel equipment should be pickled to remove the oxide scales before it is put in service. Because oxidi2ing agents in the HCl gas such as oxygen or chlorine significantly affect the corrosion rate, it is essential that the operating temperature of the steel equipment be kept below the temperature (316°C) at which ferric chloride is vapori2ed from the metal surface. 

Two methods are used to measure pH electrometric and chemical indicator (1 7). The most common is electrometric and uses the commercial pH meter with a glass electrode. This procedure is based on the measurement of the difference between the pH of an unknown or test solution and that of a standard solution. The instmment measures the emf developed between the glass electrode and a reference electrode of constant potential. The difference in emf when the electrodes are removed from the standard solution and placed in the test solution is converted to a difference in pH. Electrodes based on metal—metal oxides, eg, antimony—antimony oxide (see Antimony AND ANTIMONY ALLOYS Antimony COMPOUNDS), have also found use as pH sensors (8), especially for industrial appHcations where superior mechanical stabiUty is needed (see Sensors). However, because of the presence of the metallic element, these electrodes suffer from interferences by oxidation—reduction systems in the test solution. 

Alkali metal haHdes can be volatile at incineration temperatures. Rapid quenching of volatile salts results in the formation of a submicrometer aerosol which must be removed or else exhaust stack opacity is likely to exceed allowed limits. Sulfates have low volatiHty and should end up in the ash. Alkaline earths also form basic oxides. Calcium is the most common and sulfates are formed ahead of haHdes. Calcium carbonate is not stable at incineration temperatures (see Calcium compounds). Transition metals are more likely to form an oxide ash. Iron (qv), for example, forms ferric oxide in preference to haHdes, sulfates, or carbonates. SiHca and alumina form complexes with the basic oxides, eg, alkaH metals, alkaline earths, and some transition-metal oxidation states, in the ash. 

Fig. 9. Fabrication sequence for an oxide-isolated -weU CMOS process, where is boron and X is arsenic. See text, (a) Formation of blanket pod oxide and Si N layer resist patterning (mask 1) ion implantation of channel stoppers (chanstop) (steps 1—3). (b) Growth of isolation field oxide removal of resist, Si N, and pod oxide growth of thin (<200 nm) Si02 gate oxide layer (steps 4—6). (c) Deposition and patterning of polysihcon gate formation of -source and drain (steps 7,8). (d) Deposition of thick Si02 blanket layer etch to form contact windows down to source, drain, and gate (step 9). (e) Metallisation of contact windows with W blanket deposition of Al patterning of metal (steps 10,11). The deposition of intermetal dielectric or final...

From Metal Oxides and Hydroxides This reaction is usually an equihbrium ia which the water must be removed by physical or chemical... 

Ion Removal and Metal Oxide Electrodes. The ethylenediamine ( )-functional silane, shown in Table 3 (No. 5), has been studied extensively as a sdylating agent on siUca gel to preconcentrate polyvalent anions and cations from dilute aqueous solutions (26,27). Numerous other chelate-functional silanes have been immobilized on siUca gel, controUed-pore glass, and fiber glass for removal of metal ions from solution (28,29). 

The sulfur removed via these fixed-bed metal oxide processes is generally not recovered. Rather the sulfur and sorbent material both undergo disposal. Because the sorbent bed has a limited capacity and the sulfur is not recovered, the appHcation of these processes is limited to gas streams of limited volumetric rate having low concentrations of hydrogen sulfide. 

Oxygen Control. To meet industrial standards for both oxygen content and the allowable metal oxide levels in feed water, nearly complete oxygen removal is required. This can be accompHshed only by efficient mechanical deaeration supplemented by an effective and properly controlled chemical oxygen scavenger. 

Anhydrous zinc chloride can be made from the reaction of the metal with chlorine or hydrogen chloride. It is usually made commercially by the reaction of aqueous hydrochloric acid with scrap zinc materials or roasted ore, ie, cmde zinc oxide. The solution is purified in various ways depending upon the impurities present. For example, iron and manganese precipitate after partial neutralization with zinc oxide or other alkah and oxidation with chlorine or sodium hypochlorite. Heavy metals are removed with zinc powder. The solution is concentrated by boiling, and hydrochloric acid is added to prevent the formation of basic chlorides. Zinc chloride is usually sold as a 47.4 wt % (sp gr 1.53) solution, but is also produced in soHd form by further evaporation until, upon cooling, an almost anhydrous salt crystallizes. The soHd is sometimes sold in fused form. 

In this method, a metal oxide or hydroxide is slurried in an organic solvent, neodecanoic acid is slowly added, and the mixture is refluxed to remove the water. Salts that are basic can be prepared by using less than stoichiometric amounts of acid. This method has been used in the preparation of metal salts of silver (80) and vanadium (81). The third method of preparation is similar to the fusion process, the difference is the use of finely divided metal as the starting material instead of the metal oxide or hydroxide. This method has been appHed to the preparation of cobalt neodecanoate (82). Salts of tin (83) and antimony (84) have been prepared by the fusion method, starting with lower carboxyHc acids, then replacing these acids with neodecanoic acid. 

Metal Cleaning. Citric acid, partially neutralized to - pH 3.5 with ammonia or triethanolamine, is used to clean metal oxides from the water side of steam boilers and nuclear reactors with a two-step single fill operation (104—122). The resulting surface is clean and passivated. This process has a low corrosion rate and is used for both pre-operational mill scale removal and operational cleaning to restore heat-transfer efficiency. 

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