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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

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

The collected gaseous and liquid decomposition materials may be subjected to further pyrolysis at temperatures above about 800°C (preferably between about 800 and 1200°C.polymers. Carbon products may be used in numerous applications: carbon black fillers. 1990).2-0. 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. The particular composition of the titanium compounds depends on the particular pyrolysis atmosphere used.030 (Johnson and Slater. both the afore-mentioned patents completely cure any uncured polymers in the paint sludge during their heating and/or calcining steps. 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.3 micrometers. in the form of liquid hydrocarbons. Various shape and form (amorphous or turbostratic) of carbon materials may be prepared and depend on the pyrolysis condition.980. • it produces a powder which is somewhat easier to handle than the wet sludge. However. Chemical analyses of the liquid fractions revealed that it comprised amides. 3. in an inert atmosphere such as nitrogen or argon). A similar process is shown in US Patent 5. carbon-carbon composites. 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. are evaporated so that the solid discharged after heating is in a substantially dried particulate solid form. This is done by subjecting the solid residue to a temperature ranging between about 900 and 1300°C in an atmosphere selected from a group consisting of nitrogen.263 (Gerace et al. These fraction did not contain any aromatic materials. typically in the form of sludge. uncured resin and liquid hydrocarbons.367 foresees a possible subsequent pyrolysis at elevated temperature in order to convert the solid residue by sintering to useful composite materials.087. 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. Accordingly. The invention shown in the afore-mentioned patent is directed to a method for treating waste paint sludge including water. An improved process is shown in US Patent 5. The waste material. A distillation process may be able to separate the liquid product into various fractions. brittle. solvent and uncured polymer resin which . formed from a paint sludge. the resulting product is an inert. containing water. 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. The heating step is also designed to cure the uncured polymeric paint resins. 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.254. abrasive particulate material. are bound into the cured resin product. particularly heavy metals. melamine and aliphatic esters. • it reduces the hazardous characteristics of the waste because the potentially toxic materials in the sludge. inorganic.. 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. carbon ceramic composites. argon and ammonia. These composite materials produced according to the presented invention are useful for incorporation into other materials to act as reinforcing fillers. Patent N° 5.375 (Weinwurm. 1993) and presents a product.543. is processed in a heating and resin curing procedure whereby water and VOCs.

.489. and polymers. thus producing an overall expansion of the system. 1996).333 (Soroushian and Okwuegbu. acrylic and melamine resins). 1999 b) and 5. of the total raw sludge composition.w. as a first step. which are admixed in Portland cement as reactive expansion additives in shrinkage compensating concrete. 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. decatalyzing and adding processing fillers.880. usually account for a significant portion of the cost of sealant formulations. The potential expansion produced by ettringite formation is controlled by the use of ordinary steel . triisopropanol amine. Ettringite is able to attract a large number of water molecules which cause interparticle repulsion. potassium hydroxide and sodium hydroxide) having a pH range from 8 to 13. 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. USE OF PAINT SLUDGE IN PRODUCING BUILDING MATERIALS US Patent N° 5. particularly paint sludge powders. 1999 a) show a method of treating paint sludge that. diisopropanol amine. US Patents 5.w. Shrinkage cracking is unsightly and destroys the integrity of the concrete (Soroushian and Okwuegbu. The development of expansion additives for the production of shrinkage compensating concrete dates back about fifty years.834 (Gerace et al.may be used as a filler in sealant compositions. The amount of base preferably ranges from about 0. the above described treatment process yields a putty. 1996) relates to the employment of a polymer containing one or more calcium compounds in its matrix. After the steps of drying. For this reason. in particular. 2-amino-2methyl-2-propanol. These components typically comprise up to 75% or more of the total sealant composition. This process requires that the heating temperature must not exceed 38°C so that the polymer remains uncured and the resulting product is soft and easily dispersible. clay and a mixture thereof. Shrinkage compensating concrete has found particular application in parking structures and other buildings. pressure sensitive sealants. fillers are only one of the several components of sealants.. pavements. 4. 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. bridge deck overlays and water storage tanks in order to control cracking caused by shrinkage movements in concrete structure. Further. These putties can be converted in a powder by the addition of 5 to 75% b. This is preferably achieved by agitating the raw sludge under vacuum at a temperature of about 110°C. In the presence of a traditional solvent based paint sludge (containing polyester. 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. caulking sealants and automotive paintable seam sealers. 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. which are generally comprised of other components such as polymers and plasticizers. The preferred processing fillers are carbon black. In fact.922. 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. removes a substantial portion of water and solvent by drying the sludge without curing the polymer.218 (Gerace et al.1 to 10% b. processing fillers during the treatment process.

• mixing the paint sludge and caustic soda admixture with quick-lime (CaO) so as to chemically react and adsorb water within paint sludge. even other liquids.w. Patent 5.587 contains about 50% b. 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. 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. typically aluminum flakes. The overspray is collected in water and dried.w. are commonly used in automotive paint for producing greater reflectivity or shininess.w.reinforcement. • agitating paint sludge-caustic soda and quick-lime admixture so as to minimize any localized concentrations of paint solids.587 (St. Aluminum adversely impacts the performance of cement produced through the admixture of the presented process. are preferred.333.573. The expansion properties of Portland cement mortars incorporating the paint sludge powder are comparable to those obtained with some on purpose-made expansion additives. According to the inventor. In the afore-mentioned patent the expansion additives are produced from a dried paint sludge powder containing particles from overspray. . • it generates sufficient heat upon dissolution into the paint sludge to facilitate the reaction with the free aluminum. The drying is performed at a temperature value ranging from 100°C to 400°C with the aim of removing volatile compounds. The raw paint sludge from the paint booth operations considered in Patent 5. the first step of the treatment includes the mixing of the raw paint sludge with NaOH. preferably using a screw retort apparatus.w.489. according to the inventors of US Patent N° 5. Free aluminum. particularly to sulfate attack. although for most applications amounts of 1 to 2% b. their employment would be more widespread. 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. Louis. the paint sludge powder is able to act as an expansion additive in conventional Portland cement concrete mixtures.w. Sodium hydroxide is used to stabilize any aluminum that is often found in automotive paint sludge. paint solids could be further concentrated by placing the mixture in a settling pond where the separated. 1996) provides a process for producing building materials (concrete. The environmental impacts of using the paint sludge powder in concrete were found not to be a problem. If less expensive expansion additives could be found. The expansion additive can contain water. Any paint sludge mixtures having less than 30% b.. water. paint solids and 50% b. mortar or asphalt) from some water-based paint sludge from paint booth operations.w. 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. 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. the process should be able to treat paint sludge having a solid content ranging from approximately 30% to almost 100% b. Sludge from overspray is composed of polymers and incorporates various calcium compounds as fillers or bulking agents. Larger amounts cause the cracking of the concrete at the surface. inexpensive and ready available.573. • it is strong. In fact. concentrated paint sludge could be treated. As afore mentioned. so long as they do not interfere with the curing of the concrete.

2) allowing the mixture to cure. different kinds of paint sludge can be involved in the reclamation process. 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. Invention presented in US Patent 7.2 M to 0.780 (Matheson et al.. 2007).573.. epoxy paint sludge. additional water can be added to provide the desired amount of water to the building material. 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.w. 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. This agitation is produced mechanically through standard plow-paddle or pug mill mixers. 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. although concentrations ranging from 0. This second mixing step is performed ideally by adding approximately 1. The second step is to heat the caustic soda / paint sludge mixture to a temperature of approximately 60°C for about 10 minutes. aminopolyester based paint sludge. This ratio is assumed to be optimal as the water content in the paint sludge is approximately 50% b. The heating step facilitates the reaction of the caustic soda and the free aluminum in the paint sludge. 1996) provides a process for directly using liquid paint sludge as an integral component in the production of cement and concrete-type building materials. This pretreatment prevents any subsequent “bulging” problems with the resulting cement product and is believed to avoid weakening the structure where cement is employed. 5.587 results in a hydrated lime Ca(OH)2 / paint solids mixture that is approximately 75%/25% b. however. Quick-lime mixes with water in the paint sludge in a highly exothermic reaction. among them amino alkyd based paint sludge. thus providing an efficient method for the recycling of paint sludge. However. The process presented in Patent 5. polyester melamine based paint sludge.w. besides this.1 kg of quick-lime to react completely with 1 kg water. This process is summarized in patent WO 2007 072502 (Bhatia et al. thereby producing a building material. and includes a final step of agitating the admixture so as to minimize any localized concentrations of paint solids. . heat may be provided from another source. Ideally. the ratio between the molecular weight of quick-lime (56 g/mol) and water (18 g/mol) requires about 3. The agitation further ensures the efficient mixing of the quick lime with the raw paint sludge. The process comprises two subsequent steps: 1) mixing the liquid paint sludge with one or more materials used to produce building materials. This step is inherent in the case of mixing powdered NaOH with the paint sludge.128. acrylic based paint sludge.0 M concentration.5 M are also acceptable. if sodium hydroxide in aqueous solution is used. such as cement mix or concrete mix or portions thereof. thus causing the formation of hydrogen bubbles. thus quickly eliminating any unpleasant odor produced by the raw paint sludge. the paint sludge is the sole source of hydrating material. Optionally. This range of concentrations is directly proportional to the amount of aluminum within the paint sludge.6 kg of quick-lime for each kilogram of paint sludge. Preferably.. As in Patent WO 2007 072502.The first mixing step preferably requires NaOH at approximately 1.

According to the inventors. The sludge is then dried and soaked in one or more solvents depending on the type of paint sludge taken as a raw material.995.thermosetting acrylic sludge. The chemical treatment may be performed taking advantage of either a solution of sodium bicarbonate. the soaking is carried out for a period ranging from 1 and 48 hours and the stirring for a period in the range 0. REFERENCES Agarwal K. urea based sludge. in this last case the pressed sludge is dried at a temperature in the range of 35-75°C or at ambient temperature for a period ranging from 1 and 72 hours. The process foresees an initial water rinse of the wet paint sludge followed by a chemical treatment and a further rinsing with water. . conventional additives and pigments. The pulverized particles undergo further filtration at 150-200 mesh and one or more resins. if the booth additive is alkaline.129. the involved cost for the both afore-mentioned processes ranges from 250 to 350 €/t. The obtained mixture is grinded till a particle size of +6 Hegman’s Gauge fineness. of the sludge. 6. The inventors suggest using sodium bicarbonate solution in the measure of 3-10% b. 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. if necessary.w. In Italy. depending on the sludge condition and quality. During the conversion process several pigments have to be added to achieve the desired color paint.5% b. the soaked sludge is stirred to obtain a homogeneous mixture. if the booth additive is acidic. are added to the filtrate. on the other hand. silicone or modified silicone based sludge and acrylated alkyd paint sludge. The sludge is subsequently rinsed with methyl alcohol and subjected to an extraction in order to remove the liquid content in it. Jul. Anyway. United States Patent N° 5. CONCLUSIONS The main actual fate of an automotive paint sludge is the incineration and / or the landfill disposal. 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. (1992) Pyrolysis Process and Apparatus. the choice of the most suitable additive depends on the type of the paint sludge. The afore mentioned mixture undergoes sequential filtration and pulverization steps: the first filtration step aims to remove particles larger 100 mesh.w of the sludge and PTSA in the measure of 0. or a solution of paratoluene sulphonic acid (PTSA).5 – 4 hours.B. The conversion of the treated paint sludge into a reusable paint needs several additives. 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 filtrate product is subjected to pulverization to reduce the size of the particles to +2 to +3 Hegman’s Gauge fineness.2-0. processes like the extraction of combustible materials out of the pyrolysis or the production of building materials are nearly ready to be applied. individually or in combination. The liquid extraction may be carried out taking advantage of pressing or centrifugation or mild heating conditions. 1992. 14.

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