United States Environmental Protection Agency Air and Energy Engineering Research Laboratory Research Triangle Park NC 27711 K^ 1 Research and Development EPA/600/S2-85/064 Aug. 1985 Project Summary Destruction of VOCs by a Catalytic Paint Drying (IR) Device C. David Cooper Volatile Organic Compounds (VOCs) are emitted from a number of different types of sources, one of which is paint drying and curing ovens. A device that catalytically oxidizes fuel to generate infrared (IR) radiation recently has been introduced by SUNKISS Thermoreac- tors. Inc., as a new technology for paint drying and curing. During its operation, the device also oxidizes some of the paint solvents that are evaporated in the oven, thus reducing overall emis- sions of VOCs into the atmosphere. A system was constructed at the Uni- versity of Central Florida (UCF) to ex- perimentally test the SUNKISS device, to quantify its VOC destruction capabil- ities. The system consists of flow con- trol and measuring devices, analytical equipment, and aim3 chamber in which the SUNKISS device was mounted. Three paint solvents— hexane, methyl ethyl ketone (MEK), and toluene—were dispersed in air streams that flowed through the cham- ber at various rates. The solvent de- struction efficiency of the device was shown to be a strong function of the air residence time in the chamber, but was independent of VOC concentration. Hexane and MEK behaved similarly, while toluene was more reactive. Ob- served VOC destruction efficiencies ranged from less than 20 to over 50%. Some slight degree of fuel non- combustion was observed, as was a very small amount of CO generation. This Project Summary was devel- oped by EPA's Air and Energy Engineer- ing Research Laboratory, Research Tri- angle Park, NC, to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report or- dering information at back). Introduction " Volatile Organic Compounds (VOCs) are emitted from a number of different types of sources, one of which is paint drying and curing ovens. In conven- tional ovens, items are dried by hot air or by electric infrared (IR) lamps. The solvents that evaporate are discharged to the atmosphere with the dryer efflu- ent air unless that air is routed through a Final Control Device (FCD), such as an incinerator. Solvent concentrations in the oven exhaust air are typically 100- 1000 ppm. The amounts and types of VOC emit- ted from any process depend greatly on the type of paint, the type of process, and the configuration and rate of air flow through the paint booth, flash dryer, and oven. Many VOCs are photo- chemically reactive and can contribute to high oxidant levels in the ambient air. As a result, many large paint drying and curing operations have been required to reduce emissions of VOC to the atmos- phere. Recently, a novel type of paint drying device was introduced commercially. It oxidizes fuel gas on a catalyst and emits IR radiation in wavelengths adsorbed by paint pigments. A number of such devices are placed in the oven and ori- ented toward the painted parts to dry and cure the pairit. According to tests by the manufacturer, the SUNKISS units achieve significant energy savings com- ------- pared to conventional hot air or IR (elec- tric) lamp ovens. Recent installations of the SUNKISS system include several automotive, bus, and truck painting fa- cilities in the U.S. and Canada. Another benefit of the device is that some of the solvent vapors in the oven are oxidized on the catalytic surface dur- ing the drying process. Because of this concurrent VOC destruction, total mass emission rates of VOC from the oven can be reduced substantially. The de- gree of VOC destruction was of interest to the U.S. EPA and the American Elec- troplaters' Society because of the po- tential benefits of the device to the envi- ronment and to industry. The main objective of the study con- ducted at UCF was to quantify the VOC destruction efficiency of the SUNKISS device under controlled laboratory con- ditions. Secondary objectives were (1) to test the effect on the VOC destruction efficiency of a painted object placed in the oven, and (2) to test the effective- ness of recent engineering modifica- tions (i.e., a higher pressure fuel jet and thicker catalyst pad) on the VOC de- struction efficiency. Experimental Equipment and Procedures System Description The experimental apparatus, con- structed specially for this project, is shown schematically in Figure 1. Basi- cally, the equipment consists of air flow measurement and control devices, a solvent saturator system, a reaction chamber, and sampling and analytical apparatus. House air, filtered through glass wool, silica gel, and activated car- bon, flowed through at least two ro- tameters in parallel. A measured rate of air, bubbled through liquid solvent in a double saturator system, produced a saturated stream of solvent vapor in air at 0°C. That stream, diluted by another measured flow of pure air to create a stream of air at a desired concentration and desired total flow rate, was fed into the reaction chamber. The reaction chamber is a welded steel box enclosing about 1 m3 of space. The SUNKISS device was mounted on the side opposite the air inlet, and an exhaust stack was mounted on the top on the inlet end of the chamber. The SUNKISS unit has an internal 60 cfm (1,700 l/min) fan that provided some mixing of the air in the chamber, and was augmented by a 200 cfm (5,700 l/min) fan mounted coaxially with the air flow inlet. The SUNKISS fan blew cham- ber air across the front face of the cata- lyst pad; some of the VOC was ab- sorbed and oxidized on the surface of the catalyst. Several sample lines and thermocou- ples were at strategic locations in the chamber. Samples were withdrawn by a vacuum pump through a gas sam- pling valve mounted on an ANTEK 2400 chromatograph equipped with a flame ionization detector. Samples were also routed to a Thermoelectron Model 48 CO analyzer. Flow Measurement and Con- trol Air flow was measured and con- trolled, using manually controlled ro- tameters, each calibrated carefully with either an accurate wet test meter or an accurate dry gas meter. UCF house air first was passed through a filter package consisting of a layer of glass wool, fol- lowed by granular activated carbon, sil- ica gel, and glass wool. The air was then split into four possible streams, the flow rate of each of which could be individu- ally measured and adjusted. Piping per- mitted the main air flow rate to bypass the solvent saturator system, while one, two, or three of the other streams were routed through the saturator. Thus, al- most any combination of total air flow rate (2-8 cfm; 57-227 l/min) and solvent- in-air concentration from 200 to 2000 ppm could be created and maintained during the operation. Solvent Saturator System The solvent saturator system pro- duced a reproducible and reasonably Exhaust , Thermoreactor CO Analyzer Vacuum Pump Figure 1. Schematic flow diagram of system. 2 ------- accurately known concentration of VOC in air. A wide range of concentrations could be produced by blending a stream of solvent-free air with an indepen- dently controlled stream of completely saturated air. Primary air was passed through a dual saturator system consisting of two 1000 ml Erlenmeyer flasks, Teflon tube bubblers, and a copper cooling coil. Sat- uration of 40-50% was obtained in the first stage which operated at 25°C. The air then was passed through copper coils submerged in a 10°C water bath and then into a second saturator, sur- rounded by a 0°C water/ice bath. In the second stage, 100% saturation was achieved due to additional vapor/liquid contact, and probable condensation of VOC picked up in the first saturator. Di- lution air was metered through a sec- ond calibrated rotameter, bypassing the saturator system, and was blended with the saturated stream to achieve des'--pd concentrations. A mixing tank ensured complete mixing prior to the combined stream's flowing to the reaction cham- ber. Reaction Chamber The chamber was designed to en- close about 1m3 of space. The chamber was built from 11-gauge steel welded at all seams. Thus, it was structurally sound, leakproof, able to withstand all possible operating temperatures, and did not have any potential for self- emission of fumes (as plywood or com- posites might). The SUNKISS unit was mounted at the end of the chamber, op- posite the air entrance. The inlet gas (the premixed stream of air with a low concentration of VOC) en- tered through a diffuser-type entrance near the bottom of the chamber and di- rectly across from the SUNKISS unit. Both the total inlet gas flow rate (2-8 cfm; 57-227 l/min) and the inlet VOC concentration (from about 200 to 2000 ppm) could be independently con- trolled. Inlet and outlet gases were mon- itored for concentration and tempera- ture (sample ports built into the chamber enabled samples to be taken from within the chamber). Test Procedure A typical experimental run is de- scribed below. All instruments (i.e., gas chromatograph, Co analyzer, chart recorder) were allowed sufficient time for warmup and stabilization. The ap- ropriate solvent was poured into the aturators, and all fittings were checked for leaks. The GC column temperature was adjusted (based on experience in this study) to provide the most consis- tent and accurate results for each sol- vent used. The individual stream flow rates to achieve desired solvent concentrations and total inlet air flow rates were ad- justed via inline rotameters. To ensure representative results, steady state con- ditions had to be maintained in the test chamber. The chamber average resi- dence time, tp (chamber volume/air flow rate), varied for the different flow rates. At each different flow rate, sample test- ing was delayed a period of 4 x tR. Each time a sample was analyzed for VOC, three or four samples at 1 minute intervals were analyzed, and the aver- age of the peak heights on the chart recorder was allowed to represent the true VOC concentration. Chamber inlet and outlet samples were taken. The mean of the outlet solvent peaks was compared to the mean of the inlet tank peaks, and both were recorded. CO was also measured. Propane peaks were also observed and recorded. VOC de- struction efficiencies were calculated based on inlet air molar flow rate x VOC inlet concentration vs. estimated outlet gas molar flow rate (including propane combustion products plus any en- trained air) x outlet VOC concentration. The above procedure was repeated at least three times for each specific test (each air flow rate and concentration), and a final destruction efficiency was calculated as the average of all the repli- cations. Results and Discussion Initial Operating Tests The SUNKISS unit was initially tested with the SUNKISS unit on with only fresh air (no VOC) entering the cham- ber. A VOC response was observed on the GC, which implied that some un- combusted propane fuel might be es- caping into the chamber. Introduction of some hexane into the inlet air and observation of two separate peaks on the GC confirmed that propane gas was indeed entering the chamber. Dis- appearance of one peak when the propane fuel valve was shut further proved that one peak was propane. Recognition of the problem of propane non-combustion led to more detailed testing during the solvent destruction efficiency tests. In later tests, the per- cent propane combustion was calcu- lated to be 98-99.8%, depending on the total air flow rate. Also, modifications of the SUNKISS device during the latter part of this research partially alleviated this problem of propane non- combustion. Quantitative propane re- sults will be presented later. Effect of Solvent Concentration Several tests were conducted at 170 1/min (6 cfm) air flow, but at different inlet concentrations of hexane in air. Ba- sically, chamber inlet and outlet (and some interior point) concentrations were measured to determine the per- centage destruction efficiency of the SUNKISS unit. Because the total molar flow rate out of the chamber was not equal to the inflow rate of solvent laden air (the fuel gas plus entrained ambient air also entered the chamber), the VOC destruction efficiency was calculated as: n0C0 - neCe n0C0 neCe nnC0 (1) where n0 = inlet molar flow rate of stream of air with VOC C0 = inlet concentration ne = total molar flow rate of exhaust gases Ce = exit concentration Equation (1) properly accounts for the dilution effect; i.e., that VOC concentra- tions in the outlet stream will be some- what lower than in the inlet due solely to dilution by the addition of other gases. It was determined from data supplied by the manufacturer that the propane injection rate was about 0.087 gmole/ min. Furthermore, based on data from the manufacturer, the ambient air en- trained by the inlet jet of the fuel (the primary air) was calculated to be about 0.133 gmole/min. Complete propane combustion produces 7 moles of gases for 6 consumed. Thus, the total molar flow of gases exiting the chamber wa.s equal to the sum of the moles of solvent laden air flowing in, plus 7/6 times the propane flow, plus the entrained ambi- ent air flow. In other words, the molar flow rate out was equal to moles of sol- vent laden air in, plus 0.23 gmoles/min. Molar expansion due to oxidation of the VOC was ignored. Several individual solvent destruction tests were carried out using hexane in air. All replications of individual tests were quite reproducible. Certain con- ------- 40 p 30 I ,2 i Q 20 10 ® © © - © © Figure 2. 500 1000 1500 2000 Intel Hexane Concentration, ppm Hexane destruction efficiency vs. inlet hexane concentration. 2500 centrations of hexane-in-air and certain air flow rates into the chamber were replicated as many as five or six times. The destruction efficiency for each test never varied more than 2 percentage points from the mean. The results are shown in Figure 2. Effect of Chamber Residence Time After it was shown that destruction efficiency was essentially independent of inlet hexane concentration, the effect of inlet air flow rate was investigated. For a fixed volume chamber, the volu- metric air flow rate into the chamber is related to the inverse of the average res- idence time. The average residence time in a CSTR is actually best calcu- lated by the volume of the chamber, di- vided by the exhaust (as opposed to the inlet) gas rate. In these experiments, the exhaust gas volumetric flow rate was higher than the measured air inflow rate due to the fuel and primary air inflow, and due to the volume expansion of the gas in the chamber caused by increased temperature. The ideal gas law was used to calculate the outlet exhaust vol- umetric flow. Effect of Solvent Type In addition to hexane, two other com- mon paint solvents were tested: methyl ethyl ketone (MEK) and toluene. In es- ence, the MEK destruction efficiencies nearly duplicated those observed with hexane. The MEK data trended a slight bit lower than hexane and showed a slight bit more scatter, but the same es- sential behavior was evidenced. The re- sults for toluene showed significantly more solvent destruction than with either hexane or MEK. All the destruc- tion efficiencies are plotted vs. resi- dence time in Figure 3. Painted Object Tests As part of a planned attempt to more closely simulate conditions in a real oven, a painted (black) metal plate was placed in the test chamber during the toluene tests. The plate measured ap- proximately 40 by 65 cm, and was placed normal to the IR from the cata- lyst pad about 40 cm from the device. The plate simulated a painted part being cured. Destruction efficiencies were in- creased only about 2 percentage points over what had previously been ob- served for any given solvent at any given air flow rate. Two similar steel plates (one was painted and the other was not) were placed in the oven. To each plate, a ther- mocouple was attached to measure sur- face temperature. At the start of the test, a steady stream of air was flowing through the oven, and the SUNKISS unit was turned on. The temperature of the painted plate's surface increased quickly to a significantly higher temper- ature than that of the unpainted plate. At steady state, the painted plate was about 40°C hotter than the unpainted plate, which essentially achieved the in- side chamber air temperature. Effect of SUNKISS Device Mod- ifications During the course of this research, the manufacturer modified the basic device to increase solvent destruction effi- ciency and to decrease residual (un- burned) propane concentrations. The modifications were basically: (1) smaller fuel jets with an increased fuel supply pressure, and (2) a thicker cata- lyst pad with more catalyst surface area. Each modification was tested in the UCF experimental test system. To install the new system, the old cat- alyst pad and the old fuel injection ori- fice were replaced with the new ones. The propane fuel pressure was in- creased from 11 in. H20 to 2 psig (3 to 14 kPa). Hexane was used as the solvent, and several air flow rates were tested (all at an inlet hexane concentration of 1000 ppm). Three replications were made at each of six flow rates, and hex- ane destruction efficiencies were deter- mined. Also, propane and CO concen- trations were measured at each inlet air flow rate. The results of the above tests showed a slight (but non-negligible) improve- ment in VOC destruction. In addition, propane non-combustion with the new system (new pad-new jets) was reduced considerably at all flow rates, compared with that observed with the old system. CO concentrations were lower at the high air flow rates, but higher at the low air flow rates. In calculating the destruction efficien- cies, the increase in dilution effect due to the new jets was accounted for. The new jets were designed to pass the same molar rate of fuel into the SUNKISS device, but at a higher veloc- ity. The higher velocity entrains more ambient air in through the back of the catalyst pad and permits more com- plete combustion of propane. However, ------- the additional air adds to the total volu- metric flow of gases through the cham- ber, thus diluting the concentrations of VOC, propane, and CO somewhat com- pared with the original system. Estimates of the air entrainment rate of the newly modified system were ob- tained from SUNKISS, Inc. It had been estimated previously that, with a pro- pane supply pressure of 11 in. H20 (3 kPa) and with the old jets, about 0.113 cfm (about 0.13 gmoles/min) of ambient air was drawn into the chamber. With the new jets, at 2 psig (14 kPa), the ambi- ent air entrainment rate was about 0.663 cfm or 0.78 gmoles/min. At the lower air flow rates into the chamber (2, 3, or 4 cfm: 57, 85, or 113 l/min), there is sig- nificant dilution due to the additional primary air brought in with the new sys- tem. (Note that the calculations of de- struction efficiencies that follow depend 60 h on the above estimates of air entrain- ment rates.) The outlet air flow rates from the chamber were not measured in this work. After accounting for the additional air dilution due to the new jets, the VOC destruction efficiencies were calculated for the new jets—new pad system. Also, because chamber residence times at each inlet air flow rate were decreased due to the additional primary air flow, the residence times were also recalcu- lated. The fairest comparison is to plot the efficiencies against gas residence time as shown in Figure 4. This plot shows that VOC destruction efficiencies did improve with the new system. To fairly compare propane combus- tion under the new system vs. the old system, the molar flow rates of propane out of the chamber were calculated under each system. The rate of propane 50 40 .5 .G i o § 30 20 10 © Hexane Q Toluene A. MEK I I I Figure 3. 2468 Residence Time ft R). minutes VOC destruction efficiency vs. gas residence time. 10 12 into the SUNKISS device was assumed constant at 0.10 gmole/min. The percent of propane combusted was calculated for each system and compared for each inlet air flow rate. To fairly compare CO production under each system, the CO generated was expressed as a percentage of all the carbon atoms combusted. That is, first the molar rate of hexane that was de- stroyed in the chamber was calculated. Then, that rate was multiplied by the number of carbon atoms per molecule of hexane (six). Next, the molar propane combustion rate was multiplied by the number of carbons in propane (three). The two numbers were summed to give a total carbon atom combustion rate. The molar flow rate of CO exiting the chamber was calculated and divided by the total carbon atom combustion rate to give the CO generation percentage. The propane and CO results are given in Table 1. Conclusions and Recommenda- tions The solvent destruction capability of the SUNKISS thermoreactor has been tested under laboratory conditions. This catalytic device has been shown to be effective in oxidizing VOC in air in a completely mixed chamber with de- struction efficiencies primarily depen- dent on air flow rates (residence times) in the chamber. Observed destruction efficiencies ranged from less than 20% to above 50%. The destruction efficien- cies were essentially independent of VOC concentration, but were higher for toluene than for either hexane or MEK. These destruction efficiencies were sig- nificantly lower than those typical of a final control device (such as a vapor in- cinerator), but may be high enough to contribute significantly to an overall VOC control program. Some slight degrees of fuel non- combustion and a very small amount of CO generation were observed, particu- larly at the lower total air flow rates. The IR generated by the device is absorbed by a painted surface resulting in higher surface temperatures than for un- painted steel, thus enhancing the drying and curing process. The newer SUNKISS system (thicker pad, smaller fuel jets, and higher fuel pressure) re- sulted in better VOC destruction effi- ciencies and in more complete propane combustion and is recommended over the older system. The SUNKISS system can dry and cure painted objects and ------- I .§ I I % 0.07 0.05 0.06 0.06 0.05 0.05 Based on molar flow rates of propane into and out of the chamber. Based on total moles of carbon atoms combusted. help reduce VOC emissions to the atmosphere. It is worthy of considera- tion as part of any proposed operation that involves solvent evaporation inside enclosures. •&U. S. GOVERNMENT PRINTING OFFICE-.1985/559-111/20646 ------- C. Cooper is with the University of Central Florida, Orlando, FL 32816. Charles H. Darvin is the EPA Project Officer (see below). The complete report, entitled "Destruction of VOCs by a Catalytic Paint Drying(IR) Device," (Order No. PB 85-215 333/AS; Cost: $ 10.00, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield. VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Air and Energy Engineering Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 EPA/600/S2-85/064 OOOC329 PS U S ENVIR PROTECTION AGENCY REGION 5 LIERARK 230 S DEAR8CRN STREET CHICAGO IL ------- |