Oxidizer effluent

Fig. 8.7 Comparisons of screening result by (a) gas sensor system with (b) conventional FID-GC for the propane oxidation effluents over Fe/Si02 and alkali-modified Fe/Si02 (reproduced by permission of Elsevier from [19]).

Throughput rate is the gallons of sludge fed to the unit per unit time (gpm or gpd). If the sludge is treated by chlorine (a disinfectant/oxidizing agent), the oxidized sludge is the chemical oxidation effluent. Chlorination is an oxidation process. 

Adipic acid is an important intermediate extensively used for the manufacture of nylon 66. It is currently produced from cyclohexane oxidation by a two steps process [1]. During the first step, oxidation of cyclohexane by air in the liquid phase forms cyclohexanol and cyclohexanone. Further oxidation of this mixture by nitric acid gives adipic acid. In addition to its cost, the use of nitric acid generates corrosion risks and requires recovery of the nitrogen oxides effluents. 

Thermodynamic predictions for the equilibrium syngas ratio in the oxidizer effluent as a function of HzOiCOz feed ratio and operating temperature in chemical-looping mixed reforming process with an Fe-based oxygen carrier [3]. 

The oxidant effluent composition is calculated in a similar manner. Note that in the MCFC, both oxygen and carbon dioxide are consumed on the cathode (air) side. This can be seen from the cathode reaction listed below and the following table listing the fuel cell reaction quantities. 

The minimum amount required to achieve complete conversion of the hydrocarbon feedstock is 0.5 mol 02 per mol carbon. Steam is added to control the reaction temperature, which leads to additional H2 generation via CO shift [Eq. (3)]. The final partial oxidation effluent gas composition is governed by the following chemical equilibrium expressions ... 

The process is designed from a knowledge of physical concentrations, whereas aqueous effluent treatment systems are designed from a knowledge of BOD and COD. Thus we need to somehow establish the relationship between BOD, COD, and the concentration of waste streams leaving the process. Without measurements, relationships can only be established approximately. The relationship between BOD and COD is not easy to establish, since different materials will oxidize at different rates. To compound the problem, many wastes contain complex mixtures of oxidizable materials, perhaps together with chemicals that inhibit the oxidation reactions. 

Electrochemical Detectors Another common group of HPLC detectors are those based on electrochemical measurements such as amperometry, voltammetry, coulometry, and conductivity. Figure 12.29b, for example, shows an amperometric flow cell. Effluent from the column passes over the working electrode, which is held at a potential favorable for oxidizing or reducing the analytes. The potential is held constant relative to a downstream reference electrode, and the current flowing between the working and auxiliary electrodes is measured. Detection limits for amperometric electrochemical detection are 10 pg-1 ng of injected analyte. 

Although the selectivity of isopropyl alcohol to acetone via vapor-phase dehydrogenation is high, there are a number of by-products that must be removed from the acetone. The hot reactor effluent contains acetone, unconverted isopropyl alcohol, and hydrogen, and may also contain propylene, polypropylene, mesityl oxide, diisopropyl ether, acetaldehyde, propionaldehyde, and many other hydrocarbons and carbon oxides (25,28). 

Single-reaction-step processes have been studied. However, higher selectivity is possible by optimizing catalyst composition and reaction conditions for each of these two steps (40,41). This more efficient utilization of raw material has led to two separate oxidation stages in all commercial faciUties. A two-step continuous process without isolation of the intermediate acrolein was first described by the Toyo Soda Company (42). A mixture of propylene, air, and steam is converted to acrolein in the first reactor. The effluent from the first reactor is then passed directiy to the second reactor where the acrolein is oxidized to acryUc acid. The products are absorbed in water to give about 30—60% aqueous acryUc acid in about 80—85% yield based on propylene. 

If necessary, first-stage reactor effluent maybe further cooled to 200—250°C by an iaterstage cooler to prevent homogeneous and unselective oxidation of acroleia taking place in the pipes leading to the second-stage reactor (56,59). 

It is possible to dispense with the extraction step if the oxidation section is operated at high propylene concentrations and low steam levels to give a concentrated absorber effluent. In this case, the solvent recovery column operates at total organic reflux to effect a2eotropic dehydration of the concentrated aqueous acryflc acid. This results in a reduction of aqueous waste at the cost of somewhat higher energy usage. 

ARCO has developed a coproduct process which produces KA along with propylene oxide [75-56-9] (95—97). Cyclohexane is oxidized as in the high peroxide process to maximize the quantity of CHHP. The reactor effluent then is concentrated to about 20% CHHP by distilling off unreacted cyclohexane and cosolvent tert-huty alcohol [75-65-0]. This concentrate then is contacted with propylene [115-07-1] in another reactor in which the propylene is epoxidized with CHHP to form propylene oxide and KA. A molybdenum catalyst is employed. The product ratio is about 2.5 kg of KA pet kilogram of propylene oxide. 

This reaction is first conducted on a chromium-promoted iron oxide catalyst in the high temperature shift (HTS) reactor at about 370°C at the inlet. This catalyst is usually in the form of 6 x 6-mm or 9.5 x 9.5-mm tablets, SV about 4000 h . Converted gases are cooled outside of the HTS by producing steam or heating boiler feed water and are sent to the low temperature shift (LTS) converter at about 200—215°C to complete the water gas shift reaction. The LTS catalyst is a copper—zinc oxide catalyst supported on alumina. CO content of the effluent gas is usually 0.1—0.25% on a dry gas basis and has a 14°C approach to equihbrium, ie, an equihbrium temperature 14°C higher than actual, and SV about 4000 h . Operating at as low a temperature as possible is advantageous because of the more favorable equihbrium constants. The product gas from this section contains about 77% H2, 18% CO2, 0.30% CO, and 4.7% CH. ... 

Fig. 4. Schematic of a leather tanning faciUty fitted with a wastewater treatment plant. Treatment of the combined wastes using sulfide oxidation and waste effluent pH adjustment greatiy decreases the suspended soHds and BOD loading (3). Courtesy of Krieger Publishing Co.

Industrial Wastewater Treatment. Industrial wastewaters require different treatments depending on their sources. Plating waste contains toxic metals that are precipitated and insolubiHzed with lime (see Electroplating). Iron and other heavy metals are also precipitated from waste-pidde Hquor, which requires acid neutralization. Akin to pickle Hquor is the concentrated sulfuric acid waste, high in iron, that accumulates in smokeless powder ordinance and chemical plants. Lime is also useful in clarifying wastes from textile dyeworks and paper pulp mills and a wide variety of other wastes. Effluents from active and abandoned coal mines also have a high sulfuric acid and iron oxide content because of the presence of pyrite in coal. 

In typical processes, the gaseous effluent from the second-stage oxidation is cooled and fed to an absorber to isolate the MAA as a 20—40% aqueous solution. The MAA may then be concentrated by extraction into a suitable organic solvent such as butyl acetate, toluene, or dibutyl ketone. Azeotropic dehydration and solvent recovery, followed by fractional distillation, is used to obtain the pure product. Water, solvent, and low boiling by-products are removed in a first-stage column. The column bottoms are then fed to a second column where MAA is taken overhead. Esterification to MMA or other esters is readily achieved using acid catalysis. 

Several variations of the above process are practiced. In the Sumitomo-Nippon Shokubai process, the effluent from the first-stage reactor containing methacrolein and methacrylic acid is fed directiy to the second-stage oxidation without isolation or purification (125,126). In this process, overall yields are maximized by optimizing selectivity to methacrolein plus methacrylic acid in the first stage. Conversion of isobutjiene or tert-huty alcohol must be high because no recycling of material is possible. In another variation, Asahi Chemical has reported the oxidative esterification of methacrolein directiy to MMA in 80% yield without isolation of the intermediate MAA (127,128). 

Phenols. The first stable ozone oxidation product of phenol in water is ds ds-raucomc acid, which requires - 2 mol O /mol phenol. In practice, larger dosage levels of ozone are required because other ozone-reactive substances are present in most wastes. Ozone oxidation of phenoHc effluents is employed in paper mills, coke mills, oil refineries, and thermoplastic resin manufacture, producing effluents that are safe to freshwater biota (122,123) (see Lignin Pulp). 

Caro s acid has been used ia AustraUa as an oxidant ia the acid-leaching of uranium ores. It acts by oxidising the iron present ia the solution from Fe " to Fe ". This Fe " then oxidizes the uranium. Alternative oxidants that have been used iaclude pyrolusite and chlorate ion. These are both undesirable because their effluents, containing Mn " or CF, contaminate watercourses. 

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