REUSE AND RECYCLING OF AUTOMOTIVE PAINT SLUDGE: A BRIEF OVERVIEW

B. RUFFINO and M.C. ZANETTI DITAG, Land, Environment and Geo-Engineering Department, Politecnico di Torino, Corso Duca degli Abruzzi 24 , 10129 Torino, Italy

SUMMARY: The application of solvent-based paints and water-based paints by spraying is extensively used in the automotive industry both to protect metallic parts and to provide a desirable aesthetic appearance for the vehicle. This operation is a significant source of solid waste (paint sludge), liquid waste (boothwater) and, when solvent-based paints are used, also volatile organic compounds (VOCs). Paint sludge represents an important problem both from a managerial and from an environmental point of view owing to its huge volumes and hazardous characteristics. This paper aims to provide an overview of the processes developed over the last twenty years to treat automotive paint sludge in order to recover useful products from the waste or reuse it in the industry of sealants, paints and building materials.

1. INTRODUCTION The most serious problem in industries that make use of paint processes is the generation of a waste known as paint sludge. Italian automotive plants produce from 2.5 to 5.0 kg paint sludge per painted car. The painting of vehicle bodies at a large assembly plant generally occurs in a series of large enclosures called paint spray booths. The protective coating, the primecoat, the basecoat and the clearcoat are applied in the main color booths. Painting by spraying generates wastes due to the overspray presence or the paint not reaching the target. The overspray washed with the help of circulating water gets collected in a sludge pit. This mixture of water and oversprayed paint is called paint sludge. Paint sludge is a very complex material; the paint component contains uncured polymer resins, pigments, curing agents, surfactants and other minor formulation ingredients. In addition, paint sludge contains water and a variety of organic solvents. The presence of uncured paint resins, which cure and form a film upon heating, make the sludge very sticky and difficult to handle. Therefore, detackification agents are often added to the sludge (Gerace et al., 1993). Over the last twenty years several attempts have been made to employ paint sludge for producing various useful byproducts rather than to dispose of it in a landfill or to incinerate: these attempts have particularly involved the extraction of valuable materials (fuels and titanium

compounds) taking advantage of pyrolytic processes and the reuse of the treated waste in the sealant and paint industry and in the production of building materials.

2. PYROLYTIC PROCESSES FOR THE PRODUCTION OF USEFUL MATERIALS Towards the middle of Nineties, Ford researches investigated the technical feasibility of converting paint sludge to activated char and reusing it in paint spray-booth to capture paint solvents from spray booth air. Kim and Coauthors (1996) describe a process for pyrolyzing paint sludge (mixed with potassium hydroxide) at 600C to prepare activated carbon. This activated carbon is a high surface-area char containing inorganic oxides which is suggested to be useful to adsorb volatile compounds in manufacturing plants. In particular, Kim and Coauthors suggest adding the char into the paint booth scrubber water to remove volatile organic compounds from the spray booth air. This pyrolysis process for converting the paint sludge to char recovers less than 30-40% of the total mass of the dried paint waste. Another approach foreseeing a pyrolytic process for the paint sludge reclamation is described by Agarwal in US Patent 5,129,995 and 5,198,018 (Agarwal, 1992; Agarwal, 1993). In the two afore-mentioned patents the author describes a process for the continuous pyrolitic decomposition of the waste materials containing organic and inorganic components. The inorganic components are recovered, carbon free, and recycled into essentially the same source materials from which they originated. The organic components are collected in liquid or gaseous form, as pyro-oil and pyro-gas, respectively. Hence, the organics are expected to be merely burnt. Agarwals focus is on the recycling of inorganic oxides. In the latter patent, for example, dried paint sludge, which comprises about 40% non-aqueous content, is pyrolized and about 25% of the non-aqueous content is recovered as inorganic oxide material which is reused as a paint filler. United States Patent N 5,543,367 by Ford researches (Narula et al., 1996) presents a process for the decomposition of a dried paint sludge which aims to recover the organic and inorganic components of the paint sludge as gaseous, liquid and composite materials. The afore-mentioned patent suggests that the paint sludge is first subjected to drying. Drying processes is carried out by undergoing the paint sludge at a temperature value below 200C, preferably under vacuum, for a time sufficient to remove water and organic solvents present in the sludge. The dried paint sludge is then pyrolized in an inert atmosphere selected from nitrogen or argon at a temperature up to about 600C. This relatively low-temperature pyrolysis is carried out for a time sufficient to convert the dried paint sludge into three types of materials: gaseous decomposition materials; liquid decomposition materials; solid residue materials. In the course of the pyrolysis tests, researchers have been found that the paint sludge is converted into these materials in a ratio by weight (b.w.) of about 1:1:1. The gaseous materials were eliminated in a temperature range of between about 50-550C. These off-gases may be trapped and cooled, for example, in a dry ice-isopropanol trap. This is desirable because they can be converted to a liquid form for easier handling. Chemical analyses of these liquefied gaseous materials indicated that they were hydrocarbons or organic compounds like 2-butene and 1-methoxy-1-propene or their isomers. These gaseous decomposition materials are useful as precursors for preparation of carbon and fuel gas. The liquid fraction was generally collected when the pyrolysis is carried out in a temperature range of about 50-600C. The collected liquid was found to contain a variety of organic

polymers. A distillation process may be able to separate the liquid product into various fractions. Chemical analyses of the liquid fractions revealed that it comprised amides, melamine and aliphatic esters. These fraction did not contain any aromatic materials. These materials may be reused as precursors for the preparation of carbon which may be made by passing the liquid materials through a preheated tube. The collected gaseous and liquid decomposition materials may be subjected to further pyrolysis at temperatures above about 800C (preferably between about 800 and 1200C, in an inert atmosphere such as nitrogen or argon). Gaseous and liquid decomposition materials can be collected (separately or together) and maintained at this elevated temperature for a time sufficient to convert the materials to carbon products. Various shape and form (amorphous or turbostratic) of carbon materials may be prepared and depend on the pyrolysis condition. Carbon products may be used in numerous applications: carbon black fillers, carbon-carbon composites, carbon ceramic composites. The solid residue produced by the low temperature pyrolysis was analyzed and found to contain materials like barium titanate (BaTiO3) and rutile titanate dioxide (TiO2); the particle size distribution of the solid residue is approximately 0.2-0.3 micrometers. Patent N 5,543,367 foresees a possible subsequent pyrolysis at elevated temperature in order to convert the solid residue by sintering to useful composite materials. This is done by subjecting the solid residue to a temperature ranging between about 900 and 1300C in an atmosphere selected from a group consisting of nitrogen, argon and ammonia. This further pyrolysis is carried out for a time sufficient to sinter the solid residue to an inorganic composite material comprising barium titanate and titanium compounds. The particular composition of the titanium compounds depends on the particular pyrolysis atmosphere used. These composite materials produced according to the presented invention are useful for incorporation into other materials to act as reinforcing fillers.

3. EMPLOYMENT OF THE PAINT SLUDGE IN THE SEALANT INDUSTRY The first attempt for using paint sludge in the sealant industry is presented in US Patent N 4,980,030 (Johnson and Slater, 1990). The invention shown in the afore-mentioned patent is directed to a method for treating waste paint sludge including water, uncured resin and liquid hydrocarbons. The waste material, typically in the form of sludge, is processed in a heating and resin curing procedure whereby water and VOCs, in the form of liquid hydrocarbons, are evaporated so that the solid discharged after heating is in a substantially dried particulate solid form. The heating step is also designed to cure the uncured polymeric paint resins. The process is advantageous because of the following three main reasons: it reduces the final volume of the waste and makes its disposal easier and more economical; it produces a powder which is somewhat easier to handle than the wet sludge; it reduces the hazardous characteristics of the waste because the potentially toxic materials in the sludge, particularly heavy metals, are bound into the cured resin product. A similar process is shown in US Patent 5,087,375 (Weinwurm, 1992) which discloses a method of heating and calcing the paint sludge to form a product which may be used as a filler for sealants. However, both the afore-mentioned patents completely cure any uncured polymers in the paint sludge during their heating and/or calcining steps. Accordingly, the resulting product is an inert, inorganic, brittle, abrasive particulate material. An improved process is shown in US Patent 5,254,263 (Gerace et al., 1993) and presents a product, formed from a paint sludge, containing water, solvent and uncured polymer resin which

may be used as a filler in sealant compositions. This process requires that the heating temperature must not exceed 38C so that the polymer remains uncured and the resulting product is soft and easily dispersible. Further, fillers are only one of the several components of sealants, which are generally comprised of other components such as polymers and plasticizers. These components typically comprise up to 75% or more of the total sealant composition, and polymers, in particular, usually account for a significant portion of the cost of sealant formulations. For this reason, it would be desirable to be able to use paint sludge as a replacement for one of the polymeric components in sealants in order to reduce the production costs. US Patents 5,880,218 (Gerace et al., 1999 b) and 5,922,834 (Gerace et al., 1999 a) show a method of treating paint sludge that, as a first step, removes a substantial portion of water and solvent by drying the sludge without curing the polymer. This is preferably achieved by agitating the raw sludge under vacuum at a temperature of about 110C. In a subsequent step the sludge is decalalyzed by means of a treatment with a decatalyzing agent comprising a base (which is selected from the group consisting of diethanolamine, 2-amino-2methyl-2-propanol, diisopropanol amine, triisopropanol amine, potassium hydroxide and sodium hydroxide) having a pH range from 8 to 13. The amount of base preferably ranges from about 0.1 to 10% b.w. of the total raw sludge composition. By the term decatalyzed it is meant that the catalyst normally present in the paint sludge is neutralized so that the curing component in the paint sludge is not activated upon heating. In the presence of a traditional solvent based paint sludge (containing polyester, acrylic and melamine resins), the above described treatment process yields a putty. These putties can be converted in a powder by the addition of 5 to 75% b.w. processing fillers during the treatment process. The preferred processing fillers are carbon black, clay and a mixture thereof. After the steps of drying, decatalyzing and adding processing fillers, the treated paint sludge containing uncured polymers may be used as a replacement for at least a portion of the polymeric components in the formulation of products like heat-curable sealants, pressure sensitive sealants, caulking sealants and automotive paintable seam sealers.

4. USE OF PAINT SLUDGE IN PRODUCING BUILDING MATERIALS US Patent N 5,489,333 (Soroushian and Okwuegbu, 1996) relates to the employment of a polymer containing one or more calcium compounds in its matrix, particularly paint sludge powders, which are admixed in Portland cement as reactive expansion additives in shrinkage compensating concrete. Shrinkage compensating concrete has found particular application in parking structures and other buildings, pavements, bridge deck overlays and water storage tanks in order to control cracking caused by shrinkage movements in concrete structure. In fact, one of the main disadvantages of Portland cement concrete is its susceptibility to tensile cracking when volume contractions associated with drying shrinkage are completely or partially restrained. Shrinkage cracking is unsightly and destroys the integrity of the concrete (Soroushian and Okwuegbu, 1996). The development of expansion additives for the production of shrinkage compensating concrete dates back about fifty years. All the variants of these expansion additives are based on the formation of ettringite (calcium sulfoaluminate hydrate) in considerable amounts during the first days of curing. Ettringite is able to attract a large number of water molecules which cause interparticle repulsion, thus producing an overall expansion of the system. The potential expansion produced by ettringite formation is controlled by the use of ordinary steel

reinforcement. If less expensive expansion additives could be found, their employment would be more widespread. In the afore-mentioned patent the expansion additives are produced from a dried paint sludge powder containing particles from overspray. In fact, according to the inventors of US Patent N 5,489,333, the paint sludge powder is able to act as an expansion additive in conventional Portland cement concrete mixtures. Sludge from overspray is composed of polymers and incorporates various calcium compounds as fillers or bulking agents. The overspray is collected in water and dried. The drying is performed at a temperature value ranging from 100C to 400C with the aim of removing volatile compounds, preferably using a screw retort apparatus. The expansion additive can contain water, even other liquids, so long as they do not interfere with the curing of the concrete. The expansion properties of Portland cement mortars incorporating the paint sludge powder are comparable to those obtained with some on purpose-made expansion additives. The results of the tests indicate that desirable expansion properties can be obtained at an amount of paint sludge powder-to-cement of about 5% b.w., although for most applications amounts of 1 to 2% b.w. are preferred. Larger amounts cause the cracking of the concrete at the surface. Tests performed by the authors confirmed that the paint sludge powder did not adversely influence the concrete resistance to chemical and physical causes of deterioration, particularly to sulfate attack. The environmental impacts of using the paint sludge powder in concrete were found not to be a problem. Patent 5,573,587 (St. Louis, 1996) provides a process for producing building materials (concrete, mortar or asphalt) from some water-based paint sludge from paint booth operations. The process comprises the following three steps: mixing the paint sludge with caustic soda (NaOH) so as to chemically stabilize free aluminum contained in the sludge; mixing the paint sludge and caustic soda admixture with quick-lime (CaO) so as to chemically react and adsorb water within paint sludge; agitating paint sludge-caustic soda and quick-lime admixture so as to minimize any localized concentrations of paint solids. The raw paint sludge from the paint booth operations considered in Patent 5,573,587 contains about 50% b.w. paint solids and 50% b.w. water. According to the inventor, the process should be able to treat paint sludge having a solid content ranging from approximately 30% to almost 100% b.w. Any paint sludge mixtures having less than 30% b.w. paint solids could be further concentrated by placing the mixture in a settling pond where the separated, concentrated paint sludge could be treated. Any paint sludge mixture with a too high concentration of paint solids could be pretreated with a sufficient amount of water so as to be capable of completely reacting with the quick-lime. As afore mentioned, the first step of the treatment includes the mixing of the raw paint sludge with NaOH. Sodium hydroxide is used to stabilize any aluminum that is often found in automotive paint sludge. Free aluminum, typically aluminum flakes, are commonly used in automotive paint for producing greater reflectivity or shininess. Aluminum adversely impacts the performance of cement produced through the admixture of the presented process. Powdered NaOH is the preferred agent for pre-treating paint sludge that is intended for final use in cement products because: it does not alter the mechanical properties of the lime/paint solid product; it is strong, inexpensive and ready available; it generates sufficient heat upon dissolution into the paint sludge to facilitate the reaction with the free aluminum.

The first mixing step preferably requires NaOH at approximately 1.0 M concentration, although concentrations ranging from 0.2 M to 0.5 M are also acceptable. This range of concentrations is directly proportional to the amount of aluminum within the paint sludge. Ideally, the process presented in the afore-mentioned patent calls for mixing an amount of NaOH just enough to reduce all the free aluminum in the paint sludge. The second step is to heat the caustic soda / paint sludge mixture to a temperature of approximately 60C for about 10 minutes. This step is inherent in the case of mixing powdered NaOH with the paint sludge. However, if sodium hydroxide in aqueous solution is used, heat may be provided from another source. The heating step facilitates the reaction of the caustic soda and the free aluminum in the paint sludge, thus causing the formation of hydrogen bubbles. This pretreatment prevents any subsequent bulging problems with the resulting cement product and is believed to avoid weakening the structure where cement is employed. The third step is to mix the paint sludge / caustic soda mixture with quick lime (CaO) so as to chemically react and adsorb water in the paint sludge. This second mixing step is performed ideally by adding approximately 1.6 kg of quick-lime for each kilogram of paint sludge. This ratio is assumed to be optimal as the water content in the paint sludge is approximately 50% b.w.; besides this, the ratio between the molecular weight of quick-lime (56 g/mol) and water (18 g/mol) requires about 3.1 kg of quick-lime to react completely with 1 kg water. Quick-lime mixes with water in the paint sludge in a highly exothermic reaction. The process presented in Patent 5,573,587 results in a hydrated lime Ca(OH)2 / paint solids mixture that is approximately 75%/25% b.w. and includes a final step of agitating the admixture so as to minimize any localized concentrations of paint solids. This agitation is produced mechanically through standard plow-paddle or pug mill mixers. The agitation further ensures the efficient mixing of the quick lime with the raw paint sludge, thus quickly eliminating any unpleasant odor produced by the raw paint sludge. Invention presented in US Patent 7,128,780 (Matheson et al., 1996) provides a process for directly using liquid paint sludge as an integral component in the production of cement and concrete-type building materials, thus providing an efficient method for the recycling of paint sludge. The process comprises two subsequent steps: 1) mixing the liquid paint sludge with one or more materials used to produce building materials, such as cement mix or concrete mix or portions thereof; 2) allowing the mixture to cure, thereby producing a building material. Preferably, the paint sludge is the sole source of hydrating material. Optionally, however, additional water can be added to provide the desired amount of water to the building material. Liquid paint sludge is transported from the paint booth and used directly as the liquid hydrating component in preparing cement or concrete or other building materials.

5. CONVERSION OF PAINT SLUDGE INTO A REUSABLE PAINT The most recent process which aims to treat paint sludge relates to a composition for the conversion of the waste into a reusable paint. This process is summarized in patent WO 2007 072502 (Bhatia et al., 2007). As in Patent WO 2007 072502, different kinds of paint sludge can be involved in the reclamation process, among them amino alkyd based paint sludge, epoxy paint sludge, acrylic based paint sludge, polyester melamine based paint sludge, aminopolyester based paint sludge,

thermosetting acrylic sludge, urea based sludge, silicone or modified silicone based sludge and acrylated alkyd paint sludge. The process foresees an initial water rinse of the wet paint sludge followed by a chemical treatment and a further rinsing with water. The chemical treatment may be performed taking advantage of either a solution of sodium bicarbonate, if the booth additive is acidic, or a solution of paratoluene sulphonic acid (PTSA), if the booth additive is alkaline. The inventors suggest using sodium bicarbonate solution in the measure of 3-10% b.w of the sludge and PTSA in the measure of 0.2-0.5% b.w. of the sludge. The sludge is subsequently rinsed with methyl alcohol and subjected to an extraction in order to remove the liquid content in it. The liquid extraction may be carried out taking advantage of pressing or centrifugation or mild heating conditions; in this last case the pressed sludge is dried at a temperature in the range of 35-75C or at ambient temperature for a period ranging from 1 and 72 hours, depending on the sludge condition and quality. The sludge is then dried and soaked in one or more solvents depending on the type of paint sludge taken as a raw material; the soaked sludge is stirred to obtain a homogeneous mixture. According to the inventors, the soaking is carried out for a period ranging from 1 and 48 hours and the stirring for a period in the range 0.5 4 hours. The afore mentioned mixture undergoes sequential filtration and pulverization steps: the first filtration step aims to remove particles larger 100 mesh. The filtrate product is subjected to pulverization to reduce the size of the particles to +2 to +3 Hegmans Gauge fineness. The pulverized particles undergo further filtration at 150-200 mesh and one or more resins, conventional additives and pigments, if necessary, are added to the filtrate. The obtained mixture is grinded till a particle size of +6 Hegmans Gauge fineness; this product is eventually filtered at 300 400 mesh in order to obtain a reusable paint. Particles retained in each filtration step are recycled back for the reduction to smaller size by conventional pulverizing equipments. The conversion of the treated paint sludge into a reusable paint needs several additives, individually or in combination; the choice of the most suitable additive depends on the type of the paint sludge. During the conversion process several pigments have to be added to achieve the desired color paint.

6. CONCLUSIONS The main actual fate of an automotive paint sludge is the incineration and / or the landfill disposal. In Italy, the involved cost for the both afore-mentioned processes ranges from 250 to 350 /t. The solutions proposed in this paper may be interesting both from an economical point of view and from the point of view of the sustainable development because they lead to a raw materials saving. Anyway, processes like the extraction of combustible materials out of the pyrolysis or the production of building materials are nearly ready to be applied; on the other hand, solutions like the recycling of the paint sludge in the industry of paints and sealants still need more research before being applied on an industrial scale.

REFERENCES Agarwal K.B. (1992) Pyrolysis Process and Apparatus. United States Patent N 5,129,995, Jul. 14, 1992.

Agarwal K.B. (1993) Pyrolysis Process and Apparatus. United States Patent N 5,198,018, Mar. 30, 1993. Bhatia R.K., Bhatia V.K., Vishnoi A.S. (2007) Composition and process for conversion of paint sludge into reusable paint. WO/2007/072502, Jul. 13, 2007. Gerace M.J., Gamboa S.C., Landaburu Y.S. (1993) Method of making sludge powder and sealant from paint sludge and sludge powder and sealant composition produced thereby. United States Patent N 5,254,263, Oct. 19, 1993. Gerace M.J., Gamboa S.C., Landaburu Y.S. (1999 a) Method for treating paint sludge. United States Patent N 5,922,834, Jul. 13, 1999. Gerace M.J., Landaburu Y.S., Gamboa S.C. (1999 b) Compounded Polymeric compositions utilizing processed paint sludge as a replacement for polymeric components. United States Patent N 5,880,218, Mar. 9, 1999. Johnson J.C., Slater A. (1990) Method for treating waste paint sludge. United States Patent N 4,980,030, Dec. 25, 1990. Kim B.R., Kalis E.M., Salmeen T., Kruse C.W., Demir I., Carlson S.L., Rostam-Abadi M. (1996) Evaluating paint-sludge chars for adsorption of selected paint solvents. J. Environ. Eng., 122 (6), 532 539. Matheson R.R., Dixon D.M., Moore J.R., Fischer D.A. (2006) Process for producing building materials from raw paint sludge. United States Patent N 7,128,780, Oct. 31, 2006. Narula C.K., Kim B.R., Salmeen I.T. (1996) Pyrolytic conversion of paint sludge to useful materials. United States Patent N 5,543,367, Aug. 6, 1996. Soroushian P., Okwuegbu A.C. (1996) Shrinkage compensating concrete with expansive additive. United Stated Patent N 5,489,333, Feb. 6, 1996. St. Louis D.M. (1996) Process for producing building materials from paint sludge. United States Patent N 5,573,587, Nov. 12, 1996. Weinwurm P. (1992) Method for producing insoluble industrial raw material from waste. United States Patent N 5,087,375, Feb. 11, 1992.