HAZARDOUS WASTE MINIMIZATION: PART 111 Waste Minimization in the Paint and Allied Products Industry Gregory A. Lorton Jacobs Engineering Group Pasadena, California plied dry onto the object. The object is then baked, causing the resins to melt and/or polymerize. Upon cooling, a tough, durable coating results. Radiation-cured coatings are applied to the object, which is then irradiated with ultraviolet light or electron beams, causing the coatings to polymerize and harden. Two-part catalyzed paints are mixed together immediately before being applied to the object. These paints then polymerize, forming a hard, dry surface. None of these coating systems relies on the evaporation of solvent or water. This paper looks at waste minimization practices available to the paint and coatings industry. The paper begins with an introduction to the industry and a description of the products. The steps involved in the manufacture of paints and coatings are then described. The paper then identifies the wastes generated. Source reduction and recycling techniques are the predominant means o f minimizing waste in this industry. Equipment cleaning wastes are the largest category o f wastes, and the paper concentrates on equipment and techniques available \ to reduce or eliminate these wastes. Techniques are described to reduce the other wastes from manufacturing operations. The paper concludes with a discussion o f changing industry product trends and the effect that these trends will have on the generation o f waste. Paint Production Processes The paints and allied products industry consists of firms that manufacture paints, varnishes, lacquers, enamels and shellacs, putties, wood fillers and sealers, paint and varnish removers, paint brush cleaners, and allied paint products. The manufacture of pigments, resins, printing inks, adhesives and sealants, or artists’ materials is not included in this category. In 1986,sales in the paints and allied products industry were just over $11billion.’ The paint manufacturing industry terids to concentrate in poplilatioii ceiiters because of high transportation costs. Nearly half of all paint manufacturing plants are located in California, New York, New Jersey, Illinois, and Ohio. Two-thirds of all plants are located ih ten states. Table I presents the size of paint manufacturing companies as a function of the number of employees. product coatings, and special purpose coatings. Table I1 presents the quantities and sales volume, as well as the major uses of coatings within these categories. Paint products are also categorized by the vehicle, or carrier (solvent-based or water-based). The vehicle, solvent or water, evaporates after the paint has been applied to the surface of the object being painted. The paint cures as the evaporation takes place. Nonvolatile coatings are categorized according io the method of curing. These include powder coatings, radiation-cured coatings, and two-part catalyzed paints. Powder coatings consist of a finely divided powder of thermoplastic or thermosetting resins mixed with pigments. Powder coatings are ap- A typical plant produces both solvent-based and water-based paints. The processes for both types of paints are generally similar, although the ingredients vary. Water-based paints are typically composed of water, pigments, resins, extenders (to extend drying time), ammonia, dispersant, antifoam additives, polyvinyl alcohol emulsion, and a preservative. Solvent-based paints are typically composed of a solvent, pigments, extenders, resins, plasticizers, and drying oils. Figure 1 is a simpiified flow diagram of the paint manufacturing steps. The manufacture of water-based paints begins by mixing water, ammonia, and dispersant together in a mixing tank. Ground pigment and extenders are then added to this mixture. Table I. Company size distribution.a Products 1-19 Number of employees per facility 100+ 2049 50-99 ~ Paint industry products are broadly categorized according to their use, The categories are architectural coatings, ~ Number of companies Number of emdovees 819 6.400 331 10.500 171 11.800 120 25.400 Total ~ 1,441 54.100 ~~ Source: U.S. Department of Commerce, Bureau of Census, 1982 Census of Manufacturers, Washington, D.C., 1985. a Copyright 1988-APCA A 3 3 .- ^^ . * . In some manufacturing planta, a single high-speed mixer is used in place of the separate grinding and mixing steps. Paint batch sizes typically range from 10to 500 gallons in smallplants and for specialty paints, to lo00 to 3000 gallons in large facilities. Table 11. Distribution of paint products by use, quantity, and sales.a Percent Architectural coatings Interior, solvent-based Interior, water-based Exterior,solvent-based Exterior, water-based Lacquers Other and not specified Product coatings Metal Containers Automotive Machinery Sheet, Strip, and Coil Metal Furniture Other Special purpose coatings High performance maintenance Automotive and machinery refinishing Traffic paint Other Production (1986) (million gallondyear) Sales (1986) ($ billion) 525 4.5 11 43 16 23 2 5 Wastes from Paint Manufacturing 371 3.9 250 2.7 The predominant wastes from paint manufacturing facilities include: 0 Equipment cleaning wastes, including: -waste rinsewater -waste solvent -paint sludge from cleaning operations 0 Off-spec paint 0 Obsolete paints and returned paints 0 Empty raw material packages, bags, and containers Pigment dusts from air pollution control equipment 0 Air emissions 0 Paint filter bags and cartridges 0 Accidental spills and discharges Of these wastes, equipment cleaning wastes are by far the largest, accounting for over 80 percent of the industry’s wastes.2 Since paint manufacturing is essentially a blending operation and not a chemical conversion operation, the compounds present in the waste are the same compounds that are present in the input materials. Paint manufacturing facilities typically segregate their wastes to the extent required by the waste disposal contractor. With increasing treatment and disposal costs, and impending land disposal bans, 19 16 6 6 5 48 31 29 14 26 a Sources:D. Webber, “Coatingindustry headed for a record year,” Chemical and Engineering News, Val. 62, No. 40, p. 51; and J. M. Winton, “Coatings ’87,” Chemical Week,Vol. 141, No. 15, p. 30. When mixing is complete, the material is then ground in a mill and transferred to an agitated mix tank. In the agitated mix tank, resin and plasticizers are added to the mixture, followed by the preservative and antifoaming agent, and then the polyvinyl acetate emulsion. Finally, water is added as a thinner to reach the desired consistency. At this point, the paint is filtered to remove any undispersed pigment and then loaded into cans. The cans are labeled, packed into shipping cartons, and moved into storage. The steps in the manufacture of solvent-based paints are similar to waterbased paints. Solvent-based paints are made by first mixing ground pigments, resins, and extenders in a high speed mixer. Solvents and plasticizers are also added during this operation. The batch is then transferred to a mixing tank, and tints and solvent thinner are added. Once the desired consistency is reached, the paint is filtered, packaged, and loaded into shipping containers. Solvent or Water Resins Additives Solvent 01Water Additives BATCHING I 1 !3 I f L Products into Packages Figure 1. Steps in the paint manufacturing process. April 1988 Volume 38,NO.4 423 WASTE MANAGEMENT Fresh solvcni make-up Solvent still botlom o blending (dF rework) Flgure 2. Recycling and reusing cleaning solvent. paint companies are turning to waste minimization, which includes source reduction and recycling. Waste Minimization Waste minimization provides companies with the following incentives: Reduced operating costs for: -waste treatment and disposal -raw materials and cleaning solutions/solvents Improved regulatory compliance Reduced environmental liability and workplace safety liability Also, successful waste minimization will often result in an improved image within the eyes of the community and the employees. Minimizing Equipment Cleaning Wastes Equipment for making solventbased paints is often cleaned with solvents. The resulting waste consists of a mixture of solvent and paint. Water or caustic solutions are used to clean equipment for making water-based paints. Caustic cleaning solutions are generally preferable, since they can more easily remove dried paint from the equipment surfaces. Two methods of caustic cleaning are generally employed. In one method, the solution is prepared in a holding tank, pumped through the equipment to be cleaned, and then returned to the holding tank. In the second method, the caustic solution is made up in the mixing tank to be cleaned and allowed to soak the tank until the tank is clean. Source Reduction of Cleaning Wastes. Equipment cleaning wastes can be reduced by reducing the frequency of required cleaning and/or reducing the amount of cleaning solvent or solution used for cleaning. The toxicity of equipment cleaning wastes can be reduced by using less toxic or nontoxic cleaning materials. Wastes from equipment cleaning can be reduced by reducing the frequency of equipment cleaning. Scheduling for long production runs, or scheduling batches from light colors to dark can reduce the need for need for caustic increases the yield of paint and also reduces the amount of solvent or solution required to subsequently clean the pipes. Inert gas is used to push the pigs through the pipes, since air might increase the rate a t which the paint dries in the pipes. The pig launcher and catcher must be carefully designed t o prevent accidental spills, sprays, and injuries.2 High pressure water spray systems have been designed to limit the amount of water used in cleaning water-based paint manufacturing equipment. These systems can reduce cleaning water use by 80 to 90 percent. Also, high pressure water sprays can remove partially dried paint, thereby reducing the need for caustic cleaning.5 Mix tanks used for making solvent-based paints equipment to manufacturing a single solution necessary to clean the tank. type of paint. In this way, the equip- 1 ment is cleaned only occasionally, rathRecycling and Reuse of Cleaning er than after each batch. In a California Wastes. Cleaning wastes can usuallv be plant, tanks that are dedicated to a sinreused in any of the following ways: gle product are washed with solvent collected and used in the next comthat remains in the tank and becomes patible batch of paint as part of the formulation. part of the formulation of the next batch.3 collected and distilled for reuse eiAny technique t h a t reduces t h e ther onsite or offsite. amount of paint adhering to the surcollected and reused over and over faces of the process equipment and for equipment cleaning until it is connecting pipes will reduce t h e too contaminated for further reuse. Allowing the solids to settle out of the amount of solvent, caustic solution, or solvent can extend the solvent’s life for water needed to clean the equipment. cleaning. Cleaning solvent wastes can Manual scraping with spatulas can inbe distilled to recover solvent for reuse. crease the yield of product and reduce Caustic solution wastes are typically the quantity of waste paint. This, in neutralized and then disposed of. The turn, reduces the amount of cleaning reuse of cleaning solution or solvent solvent or solution required to clean the tank. In larger mix tanks, rubber can be increased by removing the accuwipers can be installed to scrape off the mulated paint sludge. This can be acpaint that clings to the tank walls. New complished by decantation, filtration, or centrifugation. Simply allowing mix tanks are available with automatic enough time for the paint sludge to setwall scraper^.^ It has been recommendtle will allow the solvent to be decanted ed that tanks lined with non-stick suroff and reused. faces, such as TeflonTM (Du Pont tradeSegregating, collecting, and reusing mark), be used to reduce the amount of solvents can significantly reduce the paint clinging to the tank walls.2 By generation of waste solvents. In one designing mix tanks with length-to-diNorth Carolina company, waste solameter ratios of 1:1, the surface area to vent was reduced from 25,000 gallons volume of the tank can be minimized. in 1981to 400 gallons in 1982 by schedThis reduces the amount of paint adhering to the sides of the tank for a uling compatible paint batches and -given batch size. segregating, collecting, and reusing The piping connecting the various Icleaning solvents from different color mixing tanks and the loading hoppers batches. However, a second North Carretains paint after batches are comolina company tried this practice and pleted. Plastic or foam “pigs” have then abandoned it, because it proved been used to remove paint from these too complicated. This second company pipes. The pig is forced through the produced a wide variety of high-quality specialty products. The high cost of pipe, pushing paint ahead of it that had been clinging to the pipe walls. This raw materials and the risk of contami- - 3 nating an entire product batch outweighed the savings in virgin solvent costs and waste solvent disposal.6 The attractiveness of solvent reuse and waste segregation varies from company to company. However, as treatment and disposal costs continue to rise, these practices will become more and more attractive. Figures 2 and 3 are simplified flow diagrams of cleaning systems for solvent-based paints and water-based paints, respectively. These systems reduce waste by reusing cleaning solvent or solution as much as possible. In the solvent system, a periodic bleed of the reused solvent is taken and sent to the solvent still. The volatile solvent is reclaimed from the still and returned for reuse. The still bottoms are blended into paint product. In the rinse water and alkaline solution system, a periodic bleed is taken and sent to a settling tank. When the bleed i s alkaline sludge, pH adjustment is necessary. The clarified solution is discharged to the plant's wastewater treatment unit. The sludge from the settling tank is reworked into product. A paint manufacturer in California operates systems similar to these. The sludge from the rinse water and alkaline cleaning solution system is reworked with fresh materials to produce a beige-colored water-based paint. The still bottoms from the solvent cleaning system is reworked with fresh materials to produce a primer p r ~ d u c t . ~ Cleaning Material Substitution. Noncaustic alkaline cleaning solutions are available that can be used in place of caustic cleaning solutions. These solutions tend to be more stable than caustic solutions, less toxic, and do not present the disposal problems that caustic solutions do. At one facility, the frequency of cleaning solution replacement has been reduced by a factor of two by replacing caustic solutions with alkaline cleaner^.^ Water washing can be used to clean equipment producing water-based paints. When water is used to wash the equipment, considerable quantities of wastewater is generated. However, this wastewater can be collected and reused in subsequent compatible paint batches as part of the formulation, or can be reused for equipment cleaning until it loses its cleaning ability. Although water washing may be less effective than caustic solution washing, it eliminates the toxicity problems associated with caustic. Good Operating Practicesto Minimize Other Wastes Good operating practices offer the primary means for dealing with many of the other wastes from paint manufacturing operations. Good operating practices are defined as organizational or administrative methods of influencing the work patterns of employees so as to promote their participation in waste minimization activities. Careful attention to production and maintenance operations will reduce waste generation resulting from spills or the production of off-spec paints. Making employees aware of the impact of hazardous wastes on a company's costs, as well as the impact on the environment, can help to reinforce this. Employee training is another important good operating practice. Most off-spec paint is generated by small shops t h a t produce specialty paints. Since the production costs for specialty paints are typically high, most off-spec paints are reworked into marketable products. There is a clear economic incentive for this. However, the costs of reworking off-spec paints are avoided if better trained and supervised operators and quality control are p i n , water reuse Imp, Rinse solution reuse loop * I I Make-up solution Auraline Cleaning Equipment * I Equipment 10 tK clcancd i Waler Rinsing Equipment f- Mike-up water < Acid (for pH adjustment) Sepdrdtor overflow 10 WdSleWdlr trC.ItrIIWl Settled solids Io blending (ds rework) Figure 3. Recycling and reuslng rinse water and alkaline cleaning solution. April 1988 Volume 38,No. 4 reinforced so that the generation of offspec products is avoided in the first place. Obsolete paint products and customer returns can be blended into new batches of paint. Obsolete products result from changes in customer demand, new superior products, and expired shelf life. Careful production planning and inventory control can reduce obsolescence resulting from expired shelf life. Marketing policies, such as discounting older paints, can also reduce the amount of obsolete products. A variety of good operating practices are available for minimizing waste. Soliciting employees' suggestions for ways to minimize waste often works since the employees understand the process operation. This can also make it easier to implement waste minimization plans, since the employees are taking part in the planning. Incentives, rewards, and bonuses can be used to support a waste minimization program. In large facilities where cost center accounting is used, consider apportioning waste management costs to the departments or cost centers that generate the waste. Plant Automation The intent of plant automation is to avoid operational accidents and improve production efficiency. The effect is to reduce waste in much the same way as good operating practices. The use of automation also reduces operating and maintenance labor costs. Examples of this include programmable controllers and automatic batching. As the costs of plant automation equipment decrease, the use of automation in paint manufacturing facilities will increase. Minlmizing Empty Bag, Package, and Container Wastes Pigments may contain hazardous compounds. The bag used for packaging dry pigments will typically contain several ounces of pigment after they have been emptied. As such, these bags become hazardous waste themselves unless they are cleaned. Cleaning and drying the bag allows it to be disposed of as nonhazardous waste. Ordering pigments in slurry or paste form eliminates the problem of waste bags or packages. Empty containers of liquid raw materials that contain hazardous compounds (such as solvents, resins, or 'fungicides) are typically cleaned or recycled back to the original raw material manufacturer or to a local drum recycler. This avoids the cost of disposing of the containers. Used cans that con425 . ’. . ‘WASTE MANAGEMENT tained non-hazardous containers can be sold to metal recyclers. Water-soluble bags and packages have been developed for water-based paint pigments and for toxic additives, such as bactericides. These bags will dissolve in the paint, thus eliminating the disposal problems with the bags. However, the use of water-soluble bags does not lend itself to high-quality paints designed to give smooth finishes. input Material Substitution Some additives, solvents, and pigments are hazardous materials, and thus render waste paint as hazardous when the paint is discarded. Lead and chrome pigments are well-known for their toxicity. Similarly, solvents render solvent-based paints as hazardous because of their flammability and/or toxicity. In addition to pigments and solvents, other additives are occasionally used that cause waste paint to be hazardous. For example, mercurybased fungicides and bactericides are used to prevent paints from deteriorating. The presence of these compounds in an otherwise nonhazardous paint will render the waste paint hazardous. The substitution of nonhazardous additives for hazardous ones is taking place to some extent in the industry. However, this substitution is hampered, since many of the substitute additives are less effective than the original materials. Other hazardous compounds t h a t are now undergoing scrutiny are tributyltin, used in marine paints, and methylenedianiline, used -in making urethane coatings. As the costs of waste disposal and the regulation of hazardous materials increases, the incentives to find acceptable substitutes will increase. Some paint pigments are available in slurry or paste form. By using pigments in these forms, rather than powders, the need for air pollution equipment to control pigment dusts can be reduced or eliminated. This, in turn, reduces or eliminates the generation of pigment dust wastes. Waste Paint Filters Cartridge filters are commonly used to remove large particles of pigment from paints before packaging. Bag filters or fine mesh metal screen filters are preferable to cartridge filters from a waste point of view, since used cartridge filters retain substantially more paint. Bag or screen filters are more easily cleaned, leading to reuse of the filter or disposal as a nonhazardous waste. Wastes from Spill Cleanup Wastes resulting from accidental spills can be reduced by recovering as much of the spilled materials as practical. A California paint manufacturer sends scooped up water-based paint spills to its water treatment unit and sends solvent-based spills to its solvent recovery unit.3 If possible, the recovered material should be blended into another batch to reduce the amount of 1M 64 Roduction Volume (Millions of Dry Gallons) 4c 2c a 19ai Flgure 4. Production trends In coating systems. 1983 1993 waste. After scooping up as much of the spilled material as possible, the remaining spill should be cleaned up with dry absorbent. On the other hand, cleaning up a spill with large quantities of solvents, alkaline solutions, or water should be avoided. Of course, wastes from the cleanup of spills can be minimized by preventing spills in the first place. Trends in Product Substitution The Clean Air Act and the Occupational Safety and Health Act were both passed in 1970. These acts have been largely responsible for the major shift in paint products from solvent-based products and toxic materials to waterbased products and nontoxic materials. The switch from toxic heavy metal pigments, such as lead and chrome pigments, to less toxic or nontoxic materials has resulted from toxic materials regulations, as well as a general public desire to use less toxic paints. Air pollution regulations are responsible for the switch from volatile solvent-based products to water-based products and solvent-based products with lower volativity. The markets for powder coatings and radiation-cured coatings are also benefitting from the need to use paints with low volatility. Figure 4 illustrates the shift in paint industry products between 1983 and 1993. Pigment Substitution The paint industry has eliminated the use of lead pigments to a large extent. The toxicity of lead-based paints is well known, and these paints are no longer available for general consumer use. However, there still is a market for red lead primers. Red lead pigments are excellent as industrial primers, and there are few substitutes in some applications. However, red lead primers represent only a small fraction of the output of most plants. With the increasing regulation of lead compounds as toxic materials, the market for lead-based paint is expected to continue to decrease.’ Chrome-based paints are no longer available for general consumer use. Chrome yellow produces a bright color and is now used mainly in traffic paint (for example, lines on streets and parking lots). The current alternatives are yellow organic.+igments, which are generally more expensive, and yellow iron oxide, which is not as bright. The replacement of chrome yellow pigment is impeded by governmental regulations requiring the use of these pigments in traffic paint. Lead-based and chrome-based pig- ments generally produce a more durable paint. Also, these pigments produce desirable colors. The extent to which these pigments are replaced by less hazardous substitutes is a function of both environmental regulations and consumer demand for these products. Reducing Air Emissions The federal Clean Air Act and state air emission laws have had a profound effect on paint and coating products. For example, in California, the EPA has implemented requirements for solvent content in paints. Since September 1987, all nonflat architectural paints must contain less than 250 grams of volatile organic compounds (VOCs) per liter of paint. In some cases, technical difficulties in formulating compliant products have resulted in delay in making these changes. For example, alkyd gloss architectural paints containing less than 380 g/L of VOCs have been plagued by yellowing problems and poor application and drying characteristics.’ The ultimate result of these regulations is increased consumer demand for products with high-solids (low solvent) paints, powder coatings, and water-based substitutes. The use of solvents is generally decreasing in light of the air quality environmental regulations. The production of conventional solvent-based coatings has dropped from about 100 million dry gallons in 1983 to 65 million dry gallons in 1987. It is expected to drop to 40 million dry gallons by 1993. On the other hand, production of the newer high-solids solvent-based coatings has jumped from 18 million dry gallons in 1983 to 35 million in 1987, and is expected to grow to 35 million dry gallons in 1993. Powder coatings contain little or no solvents in their formulation. These coatings are sprayed on dry, usually with electrostatic spray equipment. The coated part is then baked, forming a polymeric coating on the surface of the part. Powder coatings are now finding increasing applications, including use in the automotive industry.’ Radiation-cured coatings have little or no volatile solvents in their formulation. These coatings are cured in the presence of either ultraviolet light (W-cured paints) or high-energy electron beams (EB-cured paints). These coating techniques do not require high temperatures to cure the coatings and, therefore, are especially useful on heatsensitive materials, such as paper, wood, or plastics. Two-part catalyzed paints also avoid the use of solvents and, therefore, are finding increasing April 1988 Volume 38,No. 4 applications in place of solvent-based paints. The industry is feeling pressure from alternative products, such as prefinished interior wallboard, vinyl siding and laminates, wallpaper, plastic panels, and glass. For example, plastic panels are now used increasingly on new us. cars.1 Conclusion Environmental and health issues have had a major impact on the paint manufacturing industry since the early 1970s. The industry is seeing substantial pressure from environmental regulators and consumers to change the formulation of paint products. In particular, the paint industry has significantly reduced its use of toxic heavy metal pigments and is gradually shifting from solvent-based coatings to water-based coatings, powder coatings, and radiation-cured coatings. Although environmental and safety issues have a major impact on the formulation of paints and coatings, customer preferences and requirements are also very important. The customer’s preference for a durable finish may warrant the continued use of hazardous components. Similarly, military requirements dictate the use of certain coatings that give high performance in harsh environments. I n many instances, paint companies are facing strong counteracting pressures to provide paints and coatings that are compliant with governmental regulations, on one hand, and meet the customers’ needs on the other hand. Waste minimization is making significant inroads into paint manufacturing plants. Since equipment cleaning operations are the largest source of waste in the industry, source reduction and recycling techniques will be important in the industry’s efforts to further reduce wastes. Because of the increasing costs of waste treatment and disposal, most companies see attractive economics in waste minimization. The future will see continuing efforts and developments to minimize waste from paint manufacturing operations. fornia Department of Health Services, Sacramento, CA, 1987. 4. G. Weismantel, S. Guggilam, “Mixing and size reduction,” Chemical Engineering 9 2 13 (1985). 5. “Development Document for Proposed Effluent Limitation Guidelines, New Source Performance Standards, and Pretreatment Standards for the Paint Formulating Point Source Category,” EPA440-1-79-049b, US. Environmental Protection Agency, Office of Water and Waste Management, Washington, DC, 1979. 6. J. Kohl, P. Moses, B.Triplett, “Managing and Recycling Solvents: North Carolina Practices, Facilities, and Regulations,” North Carolina State University, Raleigh, NC, 1984. References 1. J. M. Winton, “Coatings ’87,”Chemical Week 141: 30 (!987). 2. Waste Minamlzataon Issues and Options, Volume 2, Appendix B, “Process Studies,” US.Environmental Protection Agency, Office of Solid Waste and Emergency Response, Washington, DC, Oct6ber 1986,pages B8-1to B8-24. 3. Waste Audit Study: Paint Manufacturing Industry, Jacobs Engineerin Group Inc., Alternative Technology .lection, Toxic Substances Control Divlsion, Cali- Gregory A. Lorton is a senior chemical engineer and project manager for the Hazardous and Toxic Materials Division of Jacobs Engineering Group Inc., 251 S. Lake Avenue, Pasadena, CA 91101.This paper was submitted for peer review February 1, 1988; the revised manuscript was received February 23,1988. 427