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PROCESS WASTE MINIMIZATION AND TREATMENT
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CHEMICAL TREATMENT SYSTEMS
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Definition Chemical treatment of wastes involves the addition of chemicals to precipitate metals out of solution. This results in a sludge which must be disposed of. The sludge is then typically sent to a reclaimer for recovery of the metals or licensed disposal site. The latter option is becoming increasingly difficult and expensive. It should be avoided due to the unknown risks associated with the landfill of hazardous wastes. Chemical treatment of wastes should be utilized only when pollution prevention or recycling is not technically or economically feasible.
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Treatment Process Nonchelated metal rinses and dumps are typically treated in a two-stage process. In the first stage, rough pH control is accomplished with the addition of caustic soda and sulfuric acid. In the second stage, the pH is elevated with caustic to precipitate the metals in the hydoxide form. Lime has been used in this step in the past, but its use has been discouraged since it increases the sludge volume significantly. Alternatively, the metals can be precipitated as in the sulfide form with the addition of FeS at pH 9. This process is more difficult to control and presents a potential hazard due to the possible evolution of H2S. However, the lower solubility of the metal sulfides provides an advantage where discharge limits are more stringent. Chelated metal rinses and dumps such as those from the electroless copper process provide more challenge in chemical treatment since the chelating agents bind the metals and keep them in solution. This problem is often addressed by the addition of ferrous sulfate to break down the chelated metal complexes, allowing the metal to precipitate as the hydroxide. It is often necessary to add large quantities of this reagent such that the ratio of iron to copper is 8:1. The disadvantage of this method is that iron will precipitate out as well, thus significantly increasing the volume of sludge produced. Regardless of the specific treatment chemistry used, there are common components to all chemical treatment systems.
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Collection System The collection system is the tank or group of tanks where wastes are collected prior to treatment. The collection tanks should be sized to provide a minimum residence time of 20 min. Segregation of wastes can improve the efficiency of the waste treatment system. For example, process bath dumps can be collected in separate tanks and metered into the rinse waste stream at a low flow rate. Also, chelated wastes can be collected and treated separately from nonchelated streams, thus minimizing the use of ferrous sulfate.
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pH Adjust This is typically a dual-tank system where the pH is elevated and metals are precipitated as either the hydroxide or the sulfide, as previously described. Each stage must be adequately sized to provide adequate retention time (usually a minimum of 30 min) to ensure the completion of the reaction. Each tank is equipped with a mixer, pH probe, and controller. In addition, pH recorders should be provided to effectively monitor system performance.
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FIGURE 60.6 Treatment of metal-bearing wastes. MX = mixer; PHT = pH transmitter; FRL = filter, regulator, lubricator; SV = solenoid valve; SS = surge suppressor; DP = diaphragm pump; LC = level control. (Courtesy of Baker Brothers/Systems.)
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FIGURE 60.7 Cross-flow filtration. MX = mixer; PHT = pH transmitter; PG = pressure gauge; LC = level control; PS = pressure switch; MBV = motorized ball valve; CP = centrifugal pump; SV = solenoid valve; FRL = filter, regulator, lubricator; DP = diaphragm pump; SS = surge suppressor. (Courtesy of Baker Brothers/Systems.)
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60.24 TABLE 60.2 Advantages and Disadvantages of Various PCB Wastewater Treatment Alternatives
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Categories of major wastes 1. Copper-containing acidic rinses. Category of waste minimization or treatment Selective rinse water recycling with copper recovery. Advantages Recovered copper metal can be sold. Recycling will reduce the quantity of waste being discharged. Reduced sewer use charges. Recovered copper metal can be sold. Minimizes the quantity of copper discharged. Least capital cost. Requires clarification with filtration and proper pretreatment chemistry. Reduce or eliminate the need to dump a bath. Recovered copper can be sold. Recovered copper can be sold. Minimizes quantity of copper discharged. Less frequent need to dump a process bath. Most copper recovery using least floor space and cost. Used to concentrate copper into sludge. Reduces fresh chemical and hauling purchases. Recovered copper can be sold. Reduces waste quantity. Disadvantages Most expensive. Requires flow control. Requires thorough and periodic bath analysis. Must address spent process baths. More expensive equipment than used for chemical treatment. Requires expensive selective cation resins. Must address spent baths. Produces sludge. Increasing liability. Requires intensive effort for labor. Must address spent process baths. Requires through and periodic bath analysis. Optimum application is copper removal from rinse waters. More expensive equipment than used for chemical treatment. Requires through and periodic bath analysis. Requires that these wastes be collected and processed separately. Produces sludge. Increasing liability. Requires intensive effort for labor. May be justified only when both inner and outer layers are etched with this chemistry. Ammonium sulfate etchant requires a different method for recycling. More expensive equipment than used for chemical treatment. Must continue to haul spent etchant. Copper removal from preselected rinses using selective ion exchange with copper recovery by electroplating. Chemical treatment to precipitate copper. 2. Copper-containing acidic spent process baths. Bath purification with partial or total reuse using crystallization, ion exchange, filtration,and/or diffusion dialysis. Bleed spent bath into rinses for copper removal with copper recovery. Allow a higher contaminant concentration before dumping. Copper recovery from microetchants. Chemical treatment to precipitate copper. 3. Ammonium chloride etchants and rinses. Recycle 95 percent etchant and rinse water. Pipe rinse into copper removal with copper recovery system. Recovered copper can be sold.
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