Document pm3rDjDRzvx7Nq9b1REDYg2eB

The University o fDayton May 10, 1984 D r v Fred D. Hileman Senior Research Chemist Monsanto Research Corporation 1515 Nicholas Road Dayton, OH 45418 Dear Fred: v I have enclosed a preliminary cost estimate for the work we . discussed on the phone concerning the determination of the thermals degradation properties of 1,2,4-trichlorobenzene (1,2,4-TCBz). I *>'*' have outlined a fairly comprehensive program which may be broken -ft; down into three experimental tasks. yfv? Task 1 is designed to determine tfie thermal properties of 1,2,4-TCBz under conditions that could be encountered in a trans-. former fire. We would determine the degree of destruction of the parent compound and the identity of combustion products at a minimum of six temperatures. This work would be performed at a mean gas phase residence time (fcr) of 1.0 seconds in three pos sible reaction atmospheres (pyrolysis, oxygen starved, and oxidation). We feel this residence time is representative of that encountered in the high-temperature zone of a transformer fire; however, the three reaction atmospheres are necessary to identify all possible formation products. The determination of possible dibenzodioxins and dibenzofurans is clearly of interest. We would propose that Monsanto furnish the standards for these analyses. We would also propose to trap a few samples of the thermal reactor effluent and deliver them to you for confirmatory analysis. We may want to trap additional samples for your analysis if our initial research findings indicate further analysis to be desirable. Tasks 2 and 3 represent a detailed study of the pyrolysis and oxidation reaction kinetics of 1,2,4-TCBz. A minimum of six gasphase residence times (tr ranging from 0.25 to 2.0 seconds) and RESEARCH INSTITUTE 300 College Park D ayton, O h io 45469-0001 NfcV 0 3 6 9 2 4 Dr. Fred D. Hileman -2 - May 10, 1984 six temperatures will be necessary for each task. The kinetic data should be sufficient to predict the rate of destruction of 1,2,4-TCBz under the range of conditions experienced in a trans former fire. As I am not aware of your budget for this program, I have attempted to provide something of a "shopping list" for your inspection. We feel a detailed complete kinetics and mechanistic study, which would be the result of this proposed total program, will be of immense value. The kinetics studies outlined under tasks 2 and 3 in combination with product identification should clarify many questions concerning the mechanism of formation of dibenzodioxins and dibenzofurans from chlorobenzenes (if indeed they are formed). We are most interested in performing this work and are willing to be as flexible as possible in arriving at final arrangements. If you decide to proceed with the program, I would point out that we can also accept grants or possibly an equipment donation as <; . full or partial payment for our research. Such options may be & more practical or economically advantageous to Monsanto. 4 We would be in position to initiate this program by no later* than September of this year. Allowing for other scheduled actlv~ ities, I would estimate the full program would be completed 8 to 10 months following program initiation. I have also included some literature which describes the equipment and facilities which would be used to perform this work. Please do not hesitate to contact me if you have additionsl ques tions or identify some points in need of clarification. Sincerely, mab Enclosures Barry ueiunger, rn.D. Group Leader Environmental Sciences NEV 0 3 6 9 2 5 PRELIMINARY COST ESTIMATE MONSANTO THERMAL DEGRADATION PROPERTIES OF 1,2,4-TRICHLOROBENZENE May 10, 1984 1. Thermal Decomposition Profiles and Product Identification for 1,2,4-TCBz 1-1 Pyrolysis 1.2 Oxygen starved 1.3 Oxidation 2- pyrolysis Kinetics 2.1 Reaction Order determination 2.2 Determination of Pyrolysis rate constants, activation energy, and Arrhenius coefficient 3, Oxidation Kinetics 3.1 Reaction order determination w.r.t. 1,2,4-TCBz 3.2 Reaction order determination w-r-t. oxygen 3-3 Determination of oxidation rate constants, activation energy, and Arrhenius coefficient $39,985 $18,960 .j? J $21,443 ft:*' ** Total $80,3B8 NEV 0 3 6 9 2 6 labilities ft 'itineration and ^Thermal Degradation The success of the KefJone and other related thermal ..degradation studies resulted In tlie establish ment of the Environmental Chemis try Laboratory at the University of Dayton Research Institute. Using state-of-the-art equipment devel oped by Research Institute person nel, thermal degradation data has been generated on a range of sam ples from pesticides to complex Industrial mixtures and chloromethanes to dlbenzo-p-dloxlns. The Environmental Chemistry Laboratory contains two proven Instrumentation systems that deter mine the hlgh-tempersture thermal degradation properties of virtually any organic substance. The Ther mal Decomposition Analytical System (TDAS) consists of a con trolled hlgh-tempereture decompo sition unit with a dedicated in-line LKB 2091 gas chromatographymass spectrometer to measure des truction efficiency and analyze pro ducts of Incomplete combustion. The Thermal Decomposition UnitGas Chrom atographic system (TDU-GC) Is a similar thermal decomposition unit, which uses a high-resolutlon capillary gas chro matography system with cryogenic capabilities to perform the neces sary analyses. Both systems allow a prediction of the temperature at which, fo r example, 99.99 per cent of the parent compound has been destroyed for a given set of inciner ator conditions. These systems can also be used to IdentlfyJhermally stable products of Incomplete com bustion which also may be hazardous. There are many advantages to generating fundamental ' thermal degradation data In the laboratory. First, such thermal degradation ex periments are conducted safely, using microgram quantities of the sample In a properly equipped lab oratory with an experienced staff. Second, data generated In the lab oratory are much more precise and comprehensive than thermal degra dation data generated In field-scale studies. Third, In the laboratory, thermal degradation data can be ob tained quickly and economically. The lab orato ry approach is par ticularly economical in that the guesswork and complexity involved in a trial burn are significantly re duced, thus greatly decreasing the probability of having to conduct a second burn. Furthermore, Environ mental Protection Agency regula tions require the identification of the principle organic hazardous consti tuents. those components of the waste streams that are most highly concentrated, toxic, and thermally stable. Such identification usually requires a cosily chemical analysis of the waste sample. However, by first subjecting the sample to high temperatures, the most stable com ponents can be identified, thus reducing the required chemical analysis from hundreds of com pounds to less than a dozen. Their identity can be determined on the Thermal Decomposition Analysis System (TDAS) without additional analysis. Instrumentation Development The proficiency of the Environ mental Sciences Group In ascer taining thermal degradation pro perties of organic compdunds is the result of innovative application of state-of-the-art technology from a variety of technical disciplines. Since 1969, researchers in the Group have designed and assem bled thermal instrumentation sys tems that are used to study the ther mal degradation properties or haz ardous wastes and other organic materials. Initially, thermal analysis systems were designed to obtain simultaneous analytical data on the thermal decomposition characteri zation of polymeric organic sub stances. As the Environmental Sci ences Groups* ability to design thermal Instrumentation became known, requests grew for the devel opment of additional thermal sys tems that would determine thermal decomposition properties of pesti cides, Industrial organic wastes, and various environmentally sensitive organic materials. In these thermal systems, highresolutlon gas chromatography is the major technique used to analyze products or effluents. For example, the TDAS is a versatile system that incorporates a gas chromatographmass spectrom eter-com puter downstream of a thermal decompo sition unit, while the TDU-GC sys tem uses an in-line h ig h -p erfor mance multifunctional gas chroma tograph. With both laboratory sys tems, toxic organic substances can be studied and products of decom position Identified and quantified. These systems are designed so that the major thermal decomposition variables -- exposure temperature, composition of atmosphere, mean residence time, residence time distribution, and reactor internal pressure -- can be varied and ex perimentally evaluated. Although these relatively sophis ticated systems are the workhorses for the Environmental Chemistry. Laboratory, other thermal systems are currently being developed to address more routine thermal degradation problems. Research grade systems being developed.can. be used to address very specific and -1 complex questloni^isociatedwith / Incineration andk.^intirm aldegra dation. - I'* - Chemical A n a ly s la o )v > The Environmental C h $ *ls iry * Laboratory contalrii s e v e r |J f y i-` terns which aid characterization of complex b lg t* . nic samples. The LKB 2091 'gas chromatograph-mass spectrometer and the Vista 44 gas chromatogra phic systems are used for surveying chemical analysis and identification of principal organic hazardous constituents and products of In complete combustion in hazardous waste samples. Other gas chroma tographic, analytical, and research grade systems are used to study specific problems in the analysis of very complex systems. The Environm ental Science Groups' proficiency in routine and survey chemical analysis is comple mented by research activities in the analysis of highly complex mixtures of volatile organic compounds. Work being done in the Environ mental Chemistry Laboratory in cludes research experiments and methods development work with high-resolutlon gas chromato graphic columns and associated system components. In addition to using gas chromatographic tech niques to analyze hazardous or ganic compounds of various types, sophisticated techniques for the chemical analysis of jet fuels and shale oil samples for the Air Force are being developed. --7-- NEV 0 3 6 9 2 7 Unities / ' Environmental Sciences Laboratories The activities of the Environ mental Sciences Qroup are per formed In seven different labora tories which are located within the Eugene W. Kettering Engineering and Research Laboratories. This building was constructed in 1969 on the University of Dayton campus, and an annex built in 1978 added laboratory and office space to the Research Institute's main facilities, bringing the total floor space In this facility to approximately 56,000 square feet. In addition, the Re search Institute occupies slightly more than 58,000 square feet In other buildings of the University. The seven laboratories of the Environmental Sciences Group are located in one Interconnected com plex and constitute approximately 2,100 square feet of floor space. Three of these laboratories are dedicated to conducting thermal decomposition studies with special analytical Instrum entation that has been designed and developed at the University of Dayton. Also, there is an Environmental Chem istry Laboratory and an Environ mental Engineering Laboratory that are used for a variety of different tasks associated with experimental activities. In addition, there Is a laboratory that Is devoted to ana lytical instrumental research In the fields of high resolution gas chro matography and thermal Instru mentation system development. The hub of this laboratory com plex consists of a hazardous ma terials handling facility, which Is fully equipped for dealing with toxic organic substances as It has a mini mum of five levels of containment. This hazardous materials handling facility enhances our capability to prepare and analyze highly toxic organic substances. EQUIPMENT LIST Thermal Decomposition Equipment Thermal Decomposition Analytical System' Thermal Decomposition Unit-Gas Chromatograph Packaged Thermal Reactor System Analytical Equipment LBK Model 2091 GC-Mass Spectrometer Varlan Modal 1800 Gas Chromatograph Vartan Model 2400 Gas Chromatograph Varlan Model 3700 (Modified) Varlan Model Vista 44 (Modltlad) Tracor Model 550 (M o d iH ed )^7'* : . f t fti 8peclal Purpose Oectsclofi" _ ^ Tracor Model 310 and SfHVftK tf C t) Computar 8upport . Digital Vax 11/780 (Adctsslbt^ Unlvac 90/80-3 (Accessible) Digital PDP 11/04 *. VT^.S- . Versatac Prlnter rV- Tektronix 4012 Graphlci Terminal T I Sllent 700 ASR Terminal ANALYTICAL INSTRUMENTATION RESEARCH LABORATORY \ THERMAL DECOMPOSITION STUDIES {TDM LABORATORY! THERMAL DECOMPOSITION STUDIES (TDV-CC LABORATORY) T-- HAZARDOUS MATERIALS r \ ZHANDLING FACILITY II ENVIRONMENTAL CHEMISTRY LABORATORY PPM 7 \ ENVIRONMENTAL ENGINEERING LABORATORY THERMAL DECOMPOSITION STUDIES (PTftS LABORATORY) NORTH NEV 0 3 6 9 2 8 SCALE) r* 10 FEET