Sulfur acidic impurities

Lab investigation of multiphase nitration of cellulose) 243)P-Lhoste, MP 40, 77-81(1958) CA 55, 3055(196l)(Sulfuric acid impurity in cellulose trinitrate prepd by mixed acids) -244) P.Lhoste O.Naud, MP 40, 83 92(1958) CA 55, 3053(196l)(Stability of cellulose trinitrate... 

About 80% of the world s production of zinc is based on electrolytic methods. The roasted concentrate is dissolved in sulfuric acid. Impurities such as Cu, Co and Cd are removed from the solution by adding zinc dust. The precipitation reactions are exemphfied by... 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Normally, a slight excess of sulfuric acid is used to bring the reaction to completion. There are, of course, many side reactions involving siHca and other impurity minerals in the rock. Fluorine—silica reactions are especially important as these affect the nature of the calcium sulfate by-product and of fluorine recovery methods. Thermodynamic and kinetic details of the chemistry have been described (34). 

There are numerous variations of the wet process, but all involve an initial step in which the ore is solubilized in sulfuric acid, or, in a few special instances, in some other acid. Because of this requirement for sulfuric acid, it is obvious that sulfur is a raw material of considerable importance to the fertilizer industry. The acid—rock reaction results in formation of phosphoric acid and the precipitation of calcium sulfate. The second principal step in the wet processes is filtration to separate the phosphoric acid from the precipitated calcium sulfate. Wet-process phosphoric acid (WPA) is much less pure than electric furnace acid, but for most fertilizer production the impurities, such as iron, aluminum, and magnesium, are not objectionable and actually contribute to improved physical condition of the finished fertilizer (35). Impurities also furnish some micronutrient fertilizer elements. 

Chemistry ndProperties. The chemistry of phosphoric acid manufacture and purification is highly complex, largely because of the presence of impurities in the rock. The main chemical reaction in the acidulation of phosphate rock using sulfuric acid to produce phosphoric acid is... 

In all HF processes, the HF leaves the furnace as a gas, contaminated with small amounts of impurities such as water, sulfuric acid, SO2, or SiF. Various manufacturers utilize different gas handling operations, which generally include scmbbing and cooling. Cmde HF is condensed with refrigerant, and is further purified by distillation (qv). Plant vent gases are scmbbed with the incoming sulfuric acid stream to remove the bulk of the HF. The sulfuric acid is then fed to the furnace. Water or alkah scmbbers remove the remainder of the HF from the plant vent stream. 

The free sulfur trioxide can be titrated with water the end point is deterrnined conductimetricaHy. The sulfuric acid content is deterrnined from the specific conductivity of the Hquid at the point in the titration where no free SO or excess water is present. If the presence of HF is suspected, a known amount of SO is added to the acid and the excess SO is deterrnined as above. The content of another common impurity, SO2, may be determined iodometricaHy in a dilute, aqueous solution. 

The typical SEA process uses a manganese catalyst with a potassium promoter (for solubilization) in a batch reactor. A manganese catalyst increases the relative rate of attack on carbonyl intermediates. Low conversions are followed by recovery and recycle of complex intermediate streams. Acid recovery and purification involve extraction with caustic and heat treatment to further decrease small amounts of impurities (particularly carbonyls). The fatty acids are recovered by freeing with sulfuric acid and, hence, sodium sulfate is a by-product. 

The brine clean-up consists of skimming and settling steps to free the solution from oil, clays, and other impurities. Sulfuric acid is then added until a pH of <2.5 is reached ensuring iodine Hberation by oxidation, precipitation of the soluble barium contained in the brine, and recovery of the remaining iodine. 

The crystallized iodine is decanted and transferred into a fusion kettie. The melted product is contacted with strong sulfuric acid to remove organic impurities and humidity. Finally the iodine is flaked or prilled and packed. 

Specifications and Standards, Shipping. Commercial iodine has a minimum purity of 99.8%. The Committee of Analytical reagents of the American Chemical Society (67) and the U.S. Pharmacopoeia XXII (68) specify an iodine content not less than 99.8%, a maximum nonvolatile residue of 0.01%, and chlorine—bromine (expressed as chlorine) of 0.005% (ACS) and 0.028% (USP), respectively. In the past these requirements were attained basicaHy only by sublimation, but with processing changes these specifications can be met by direct production of iodine. Previously the impurities of the Chilean product were chiefly water, sulfuric acid, and insoluble materials. Improvements in the production process, and especiaHy in the refining step, aHow the direct obtainment of ACS-type iodine. Also, because of its origin and production process, the Chilean iodine has a chlorine—bromine impurity level of no more than 0.002%. 

Cooled dust-laden gas is dedusted in an electrostatic precipitator and sent to the cleaning unit to remove impurities such as arsenic, fluorine, and chlorine before being sent on to the sulfuric acid production plant. 

The newly formed y-Mn02 actually coats the surfaces of the particles of the soHd phase the MnSO dissolves in the Hquid phase, along with the majority of the ore impurities. The effective surface area is expanded by the etching action of the sulfuric acid. Following the acid treatment step, the slurry is filtered and the cake is carefiiUy washed and dried at a controlled temperature. 

The concentrated mother Hquor contains a large amount of sulfuric acid in a free form, as titanium oxy-sulfate, and as some metal impurity sulfates. To yield the purest form of hydrated TiOg, the hydrolysis is carried out by a dding crystallizing seeds to the filtrate and heating the mixture close to its boiling temperature, - 109° C. The crystal stmcture of the seeds (anatase or mtile) and their physical properties affect the pigmentary characteristics of the final product. 

Analytical and Laboratory Operations. Sulfamic acid has been recommended as a reference standard in acidimetry (55). It can be purified by recrystaUization to give a stable product that is 99.95 wt % pure. The reaction with nitrite as used in the sulfamic acid analytical method has also been adapted for determination of nitrites with the acid as the reagent. This reaction is used commercially in other systems for removal of nitrous acid impurities, eg, in sulfuric and hydrochloric acid purification operations. 

Relatively high (typically 980—1200°C) temperatures are required to decompose spent acids at reasonable burner retention times. Temperatures depend on the type of spent acid. A wide variety of spent acids can be processed in this way, but costs escalate rapidly when the sulfuric acid concentration in spent acid (impurity-free basis) falls below about 75%. A few relatively uncontaminated spent acids can be reused without decomposition by evaporating the excess water in concentrators, or by mixing in fresh sulfuric acid of high concentration. Weak spent acids are frequently concentrated by evaporation prior to decomposition. 

Materials of Construction. Resistance of alloys to concentrated sulfuric acid corrosion iacreases with increasing chromium, molybdenum, copper, and siUcon content. The corrosiveness of sulfuric acid solutions is highly dependent on concentration, temperature, acid velocity, and acid impurities. An excellent summary is available (114). Good general discussions of materials of constmction used ia modem sulfuric acid plants may be found ia References 115 and 116. More detailed discussions are also available (117—121). For nickel-containing alloys Reference 122 is appropriate. An excellent compilation of the relatively scarce Hterature data on corrosion of alloys ia Hquid sulfur trioxide and oleum may be found ia Reference 122. 

Black Liquor Soap Acidulation. Only two-thirds of a typical black Hquor soap consists of the sodium salts of fatty acids and resin acids (rosin). These acids are layered in a Hquid crystal fashion. In between these layers is black Hquor at the concentration of the soap skimmer, with various impurities, such as sodium carbonate, sodium sulfide, sodium sulfate, sodium hydroxide, sodium Hgnate, and calcium salts. This makes up the remaining one-third of the soap. Cmde tall oil is generated by acidifying the black Hquor soap with 30% sulfuric acid to a pH of 3. This is usually done in a vessel at 95°C with 20—30 minutes of vigorous agitation. Caution should be taken to scmb the hydrogen sulfide from the exhaust gas. 

Alternatively, if teUurium dioxide is the product desired, the sodium teUurite solution can be neutralized in a controUed fashion with sulfuric acid. As the pH is lowered, precipitates containing impurities such as lead and sUica that form ate filtered off. At pH 5.6 the solubUity of teUurous acid teaches a minimum and essentiaUy aU of the teUurium precipitates (>98%). After filtration and drying, commercial teUurium dioxide is obtained. A diagram for the process of deteUurizing of slimes and recovering teUurium products is shown in Figure 1. 

Isolation. Isolation procedures rely primarily on solubiHty, adsorption, and ionic characteristics of the P-lactam antibiotic to separate it from the large number of other components present in the fermentation mixture. The penicillins ate monobasic catboxyHc acids which lend themselves to solvent extraction techniques (154). Pencillin V, because of its improved acid stabiHty over other penicillins, can be precipitated dkecdy from broth filtrates by addition of dilute sulfuric acid (154,156). The separation process for cephalosporin C is more complex because the amphoteric nature of cephalosporin C precludes dkect extraction into organic solvents. This antibiotic is isolated through the use of a combination of ion-exchange and precipitation procedures (157). The use of neutral, macroporous resins such as XAD-2 or XAD-4, allows for a more rapid elimination of impurities in the initial steps of the isolation (158). The isolation procedure for cephamycin C also involves a series of ion exchange treatments (103). 

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