Sulfate decomposition, H2SO4 production

Other acetyl chloride preparations include the reaction of acetic acid and chlorinated ethylenes in the presence of ferric chloride [7705-08-0] (29) a combination of ben2yl chloride [100-44-7] and acetic acid at 85% yield (30) conversion of ethyUdene dichloride, in 91% yield (31) and decomposition of ethyl acetate [141-78-6] by the action of phosgene [75-44-5] producing also ethyl chloride [75-00-3] (32). The expense of raw material and capital cost of plant probably make this last route prohibitive. Chlorination of acetic acid to monochloroacetic acid [79-11-8] also generates acetyl chloride as a by-product (33). Because acetyl chloride is cosdy to recover, it is usually recycled to be converted into monochloroacetic acid. A salvage method in which the mixture of HCl and acetyl chloride is scmbbed with H2SO4 to form acetyl sulfate has been patented (33). 

The reaction is mn for several hours at temperatures typically below 100°C under a pressure of carbon monoxide to minimise formamide decomposition (73). Conversions of a-hydroxyisobutyramide are near 65% with selectivities to methyl a-hydroxyisobutyrate and formamide in excess of 99%. It is this step that is responsible for the elimination of the acid sludge stream characteristic of the conventional H2SO4—ACH processes. Because methyl formate, and not methanol, is used as the methylating agent, formamide is the co-product instead of ammonium sulfate. Formamide can be dehydrated to recover HCN for recycle to ACH generation. 

As discussed above, FSEC s S-NH3 cycle also utilizes decomposition of sulfuric acid as the endothermic step for the absorption of solar thermal heat and production of oxygen. However, high temperature concentration and decomposition of sulfur acid presents daunting materials of construction issues. Like the metal sulfate based TCWSCs, it is possible to modify the S-NH3 cycle and do without the decomposition of H2SO4. There are two ways to accomplish this. The first approach is to decompose ammonium sulfate produced in the hydrogen production step of the S-NH3 cycle (Reaction (111)) to a metal sulfate in the presence of a metal oxide catalyst. The second approach is to convert ammonium sulfate to metal pyrosulfate e.g. Zto 20i)-... 

To produce viscose silk (rayon), the next stage is spinning under 3-5 bar pressure into what is known as a Muller bath, which consists of 7-12% H2SO4, 16-23% Na2S04, and 1-6% Zn-Mg-NH4-sulfate. Here, two events occur simultaneously coagulation of the cellulose xanthate and hydrolytic decomposition to cellulose with the reformation of CS2. As by-products, H2S and COS are found in the exhaust air and elementary sulfur (as sodium polysulfides) in the bath and on the fibers. Sodium sulfate should decrease dissociation and thus lessen the osmotic pressure drop of the bath with its high electrolyte content relative to the fiber gel, which is low in electrolytes. 

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