Waste stream

Raw materials efficiency. In choosing the reactor, the overriding consideration is usually raw materials efficiency (bearing in mind materials of construction, safety, etc.). Raw material costs are usually the most important costs in the whole process. Also, any inefficiency in raw materials use is likely to create waste streams that become an environmental problem. The reactor creates inefficiency in the use of raw materials in the following ways ... 

Separation and recycle systems. Waste is produced from separation and recycle systems through the inadequate recovery and recycling of valuable materials from waste streams. 

Employ additional separation of waste streams to allow increased recovery. 

Recycle waste streams directly. Sometimes waste can be reduced by recycling waste streams directly. If this can be done, it is clearly the simplest way to reduce waste and should be considered first. Most often, the waste streams that can be recycled directly are aqueous streams which, although contaminated, can substitute part of the freshwater feed to the process. 

Sometimes waste streams can be recycled directly, but between different processes. Waste streams from one process can become the feedstock for another. The scope for such waste exchanges is often not fully realized, since it often means waste being transferred between different companies. 

If waste streams can be recycled directly, this is clearly the simplest method for reducing waste. Most often, though, additional separation is required or a different separation method is needed to reduce waste. 

In early designs, the reaction heat typically was removed by cooling water. Crude dichloroethane was withdrawn from the reactor as a liquid, acid-washed to remove ferric chloride, then neutralized with dilute caustic, and purified by distillation. The material used for separation of the ferric chloride can be recycled up to a point, but a purge must be done. This creates waste streams contaminated with chlorinated hydrocarbons which must be treated prior to disposal. 

Additional separation and recycling. Once the possibilities for recycling streams directly, feed purification, and eliminating the use of extraneous materials for separation that cannot be recycled efiiciently have been exhausted, attention is turned to the fourth option, the degree of material recovery from the waste streams that are left. One very important point which should not be forgotten is that once the waste stream is rejected, any valuable material turns into a liability as an effluent material. The level of recovery in such situations needs careful consideration. It may be economical to carry out additional separation of the valuable material with a view to recycling that additional recovered material, particularly when the cost of downstream effluent treatment is taken into consideration. 

Figure 10.7 shows the basic tradeoff to be considered as additional feed and product materials are recovered from waste streams and recycled. As the fractional recovery increases, the cost of the separation and recycle increases. On the dther hand, the cost of the lost materials decreases. It should be noted that the raw materials cost is a net cost, which means that the cost of lost materials should be adjusted to either... 

Additional reaction and separation of waste streams. Sometimes it is possible to cany out further reaction as well as separation on waste streams. Some examples have already been discussed in Chap. 4. 

When working at unsteady conditions, separators which normally split useful material from waste streams might lose material unnecessarily to the waste streams. 

Combustion in an incinerator is the only practical way to deal with many waste streams.This is particularly true of solid and concentrated wastes and toxic wastes such as those containing halogenated hydrocarbons, pesticides, herbicides, etc. Many of the toxic substances encountered resist biological degradation and persist in the natural environment for a long period of time. Unless they are in dilute aqueous solution, the most effective treatment is usually incineration. 

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. 

If the composition of the waste stream is known, then the theoretical oxygen demand can be calculated from the appropriate stoichiometric equations. As a first level of approximation, we can assume that this theoretical oxygen demand would be equal to the COD. Then, experience with domestic sewage indicates that the average ratio of COD to BOD will be on the order 1.5 to 2. The following example will help to clarify these relationships. 

Example 11.1 A process produces an aqueous waste stream containing 0.1 mol% acetone. Estimate the COD and BOD of the stream. 

Approximating the molar density of the waste stream to be that of pure water (i.e., 56kmolm ), then... 

The pretreatment processes may be most effective when applied to individual waste streams from particular processes or process steps before effluent streams are combined for biological treatment. 

The concentration of lead in an industrial waste stream is 0.28 ppm. What is its molar concentration ... 

The determination of Fe in an industrial waste stream was carried out by the o-phenanthroline described in Method 10.1. Using the data shown in the following table, determine the concentration of Fe in the waste stream. 

When processing municipal solid wastes, an eddy current separation unit is often used to separate aluminum and other nonferrous metals from the waste stream. This is done after removal of the ferrous metals (see Fig. 1). The eddy current separator produces an electromagnetic field through which the waste passes. The nonferrous metals produce currents having a magnetic moment that is phased to repel the moment of the appHed magnetic field. This repulsion causes the nonferrous metals to be thrown out of the process stream away from nonmetallic objects (13). 

The thermal degradation of mixtures of the common automotive plastics polypropylene, ABS, PVC, and polyurethane can produce low molecular weight chemicals (57). Composition of the blend affected reaction rates. Sequential thermolysis and gasification of commingled plastics found in other waste streams to produce a syngas containing primarily carbon monoxide and hydrogen has been reported (58). 

This process yields satisfactory monomer, either as crystals or in solution, but it also produces unwanted sulfates and waste streams. The reaction was usually mn in glass-lined equipment at 90—100°C with a residence time of 1 h. Long residence time and high reaction temperatures increase the selectivity to impurities, especially polymers and acrylic acid, which controls the properties of subsequent polymer products. 

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... 

The heat of hydration is approximately —70 kj /mol (—17 kcal/mol). This process usually produces no waste streams, but if the acrylonitrile feed contains other nitrile impurities, they will be converted to the corresponding amides. Another reaction that is prone to take place is the hydrolysis of acrylamide to acryhc acid and ammonia. However, this impurity can usually be kept at very low concentrations. American Cyanamid uses a similar process ia both the United States and Europe, which provides for their own needs and for sales to the merchant market. 

Regardless of the techniques used to purify the KA oil, several waste streams are generated during the overall oxidation—separation processes and must be disposed of. The spent oxidation gas stream must be scmbbed to remove residual cyclohexane, but afterwards will stiU contain CO, CO2, and volatile hydrocarbons (especially propane, butane, and pentane). This gas stream is either burned and the energy recovered, or it is catalyticaHy abated. 

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