Acrolein and Other Volatile Organic Emissions from the Combustion of Crude

Scott A. Steinmetz1, Jason S. Herrington2, Chris Winterrowd3, Daniel Janek3, William L. Roberts1, Jost O.L. Wendt4 and William P. Linak2

1Department of Mechanical and Aerospace Engineering North Carolina State University Raleigh, NC 27695 USA

2Air Pollution Prevention and Control Division National Risk Management Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 USA

3ARCADIS Geraghty & Miller, Inc. Durham, NC 27709 USA

4Department of Chemical Engineering University of Utah Salt Lake City, UT 84112, USA

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Introduction

• Crude glycerol • Acrolein • Experimental Setup • Results • Future Work • Conclusions

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Crude Glycerol

• By-product of bio-diesel production • Composition varies – Triglyceride feedstock, alcohol, catalyst, acid – Methylated - 22.4 MJ/kg • 20% glycerol, 69% , 11% MONG – Demethylated - 26.8 MJ/kg • 66% glycerol, 34% MONG – Pure - 16 MJ/kg • Challenging to burn • Previous work (Bohon et. al.) has shown crude glycerol can be effectively combusted in high swirl refractory-lined furnace

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Acrolein

• Stigma associated with glycerol combustion • Toxic, acrid (grease fire) • Eye and throat irritation at 100 ppb • Lethal at ppm level – during WWI • Glycerol decomposes into acrolein at 280 C

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Acrolein Measurement

• Routinely measured ambiently by derivatization and HPLC analysis (DNPH, DNSH, CNET) – Impinger trains or solid sorbents – Acrolein reacts with DNPH – Acrolein – hydrazone detectable by HPLC • Unsaturated derivatization techniques can be inaccurate in sources

– Presence of NOx – Further derivatization – PM and • Reliable methods of measuring acrolein in sources are under development

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Method Evaluation

• Modified CARB 430 w/ toluene – Ashland Chemical Company – Based on method CARB 430 • 2 x 10 mL DNPH impingers • Silica gel impinger • HPLC – UV analysis – 2 mL toluene added to DNPH solution for in-situ derivative extraction – 95% recoveries by Ashland – Tested with acrolein spiked – ~30% recoveries observed

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Method Evaluation

• Stack gas collected in tedlar bags – Dried stack gas collected in tedlar (pvf) bags – GC – FID analysis – N.D. at 0.5 ppm limit • GC – MS analysis of stack gas collected in SUMMA cans – Diluted stack gas pulled into SUMMA cans – GC – MS analysis (TO-15) – Low ppt detection limit for acrolein and other VOCs (varies with compound) – Has been used for ambient detection

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Experimental Setup

• IFRF movable block swirler • Preheat furnace with natural gas • Furnace conditions monitored with CEMs

– O2

– CO2 – CO – THC

– NOx • Burner and stack temperature • Stack gas collected far downstream from burner

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Experimental Setup

Experimental Conditions Natural Methylated Demethylated Pure Units Gas Glycerol Glycerol Glycerol Fuel Flowrate LPM 108 0.104 0.142 0.272 Air Flowrate SLPM 1560 863 1144 1312 Equivalence Ratio 0.79 0.65 0.81 0.73 Power Output kW 67.0 38.8 62.0 100.6 • 4 fuels – Natural gas, methylated, demethylated, pure glycerol • Constant equivalence ratio and power level desired – Fuel feel issues led to variation • Viscosity, ash content – Equivalence ratio determined from fuel flow rate and

excess O2 in exhaust • Swirl = 1.8

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Experimental Setup

• Dynamically diluted with nitrogen at sampling probe tip to prevent condensation – Dilution ratio calculated from

average NOx measurements before and after dilution • Spiking performed before sampling using acrolein permeation device – 0.5 L standard air with 100 ppb acrolein – Also humidified to aid recovery • 3 pairs of samples for each fuel • 1 field spike per fuel

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Experimental Setup

• Ran parallel sampling trains – One spiked can (4.5 standard L) – One non-spiked can (5 STDL) – Spike recoveries determined by the difference in concentration • Heated filters in line to limit PM into cans – Heated to prevent condensation • Flow rate controlled with needle valves • Monitored SUMMA can pressure to determine fill level • 20 min. runs

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Results

Experimental Conditions and Results Natural Methylated Demethylated Pure Units Gas Glycerol Glycerol Glycerol Fuel Flowrate LPM 108 0.104 0.142 0.272 Air Flowrate SLPM 1560 863 1144 1312 Equivalence Ratio 0.79 0.65 0.81 0.73 Power Output kW 67 39 62 101

Stack O2 % 4.8 7.6 4.2 5.4

Stack CO2 % 9.6 9.2 13.7 14.8 Stack CO ppm 20.6 30.5 321.5 16.7

Stack CO at 0% O2 ppm 26.7 47.8 401.8 22.5 Stack NOx ppm 111.9 44.5 118.9 83.5

Stack NOx at 0% O2 ppm 145.0 69.7 148.6 112.4 Stack HC ppm 9.7 9.7 9.1 17.3

Stack HC at 0% O2 ppm 12.6 15.2 11.4 23.3 Stack Temperature C 518 440 605 751 Burner Temperature C 1072 994 1066 1045 Spike Recovery % 172 96 142 140 Stack Acrolein ppb 13.9 13.2 12.1 29.3

Stack Acrolein at 0% O2 ppb 18.0 20.7 15.1 39.4 Standard Error ppb 1.8 6.7 1.8 1.4

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Results

• Spike recoveries between 96 and 172% – Spikes were ~1 order of magnitude higher than sample concentrations – Permeation rate can vary by 10% – Field spikes indicate spiking method is source of variation • Indicates it is worth pursuing method further – Several improvements can be made • Acrolein emission slightly higher in pure glycerol, but similar in all four fuels

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Results

Average Stack Concentrations (ppb) • TO-15 also allows the Natural Methylated Demethylated Pure Gas Glycerol Glycerol Glycerol detection of 81 other Alcohols 21.5 191.7 173.0 260.7 compounds 64.2 95.1 82.5 118.6 Tert-Butanol 4.5 6.9 2.1 6.6 Ketones • With the exception of 184.0 187.1 184.4 266.0 2-Hexanone 4.2 35.3 49.4 80.4 ethanol, acetone, 2-Butanone 15.2 25.1 22.8 38.4 4-Methy-2-Pentanone 1.9 1.9 9.8 34.9 and IPA, none of Cyclic Compounds Cyclohexane 2.6 36.3 54.9 91.4 these compounds Styrene 1.7 20.8 30.5 49.2 Toluene 2.7 15.9 20.6 38.5 detected in 1,4-Dioxane 2.3 16.3 21.8 36.7 m-Xylene 1.4 7.5 14.3 29.7 concentrations higher Tetrahydrofuran 3.1 10.4 13.3 21.4 p-Xylene 1.2 3.6 8.7 21.2 than 100 ppb in any 1.7 5.2 11.9 13.1 Ethylbenzene 0.6 3.6 6.6 12.8 fuel o-Xylene 0.5 1.1 2.8 8.3 Chlorobenzene 0.3 1.1 2.4 4.7 0.2 0.3 Below Below

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Future Experiments

• Improved Spiking – More similar to expected concentrations – Acrolein standard • Improved Sampling – SilTek coated SUMMA cans – Constant sampling rate – Better controlled combustion – Determine effect of PM filters

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Conclusion

• Acrolein detection in sources utilizing TO-15 is possible • Acrolein emission from glycerol combustion comparable to that of natural gas • Presence of large amounts of other VOCs was not found in any fuel • Pure glycerol emissions consistently higher, most likely due to power level

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Acknowledgements

• This project is being funded by the NCSU/EPA Cooperative Training Program in Environmental Sciences Research, Training Agreement CT833235-01-0 with North Carolina State University

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Thank you

Questions?

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011 Natural Methylated Demethylated Pure Gas Glycerin Glycerin Glycerin

1,1,1,2-Tetrachloroethane Below Below Below Below 1,1,1-Trichloroethane 0.6 0.4 8.4 4.1 1,1,2,2-Tetrachloroethane 0.5 4.2 5.8 9.4 1,1,2-Trichloro-1,2,2-... 1.3 2.2 3.1 7.7 1,1,2-Trichloroethane 0.9 11.3 16.6 26.6 1,1-Dichloroethane 0.4 2.2 3.2 5.0 1,1-Dichloroethene 5.5 2.9 14.0 11.8 1,2,4-Trichlorobenzene Below Below Below Below 1,2,4-Trimethylbenzene Below Below Below Below 1,2-Dibromoethane 1.5 Below 15.4 45.2 1,2-Dichlorobenzene Below Below Below Below 1,2-Dichloroethane 0.4 4.4 3.5 N.D. 1,2-Dichloropropane 1.3 8.6 10.6 16.8 1,3,5-Trimethylbenzene Below Below Below Below 1,3-Butadiene 0.3 Below Below Below 1,3-Dichlorobenzene Below Below Below Below 1,4-Dichlorobenzene Below Below Below Below 1,4-Dioxane 2.3 16.3 21.8 36.7 1-Ethyl-4-Methyl Below Below Below Below 2-Butanone 15.2 25.1 22.8 38.4 2-Chloroprene 0.5 6.0 8.8 19.7 2-Hexanone 4.2 35.3 49.4 80.4 3-Chloro-1- 0.6 5.8 5.6 9.9 4-Methy-2-Pentanone 1.9 1.9 9.8 34.9 Acetone 184.0 187.1 184.4 266.0 7.1 56.9 11.1 17.2 Acrolein 13.9 13.2 12.1 29.3 33.7 33.1 35.1 60.0 Benzene 1.7 5.2 11.9 13.1 Bromodichloromethane 1.0 12.2 17.8 28.7 Bromofluorobenzene 9.5 Below Below Below Bromoform 1.8 Below 33.8 N.D. Bromomethane Below Below Below Below Carbon Disulfide 0.6 1.8 1.7 4.8 Carbon Tetrachloride 2.4 13.3 23.2 31.4 Chlorobenzene 0.3 1.1 2.4 4.7 Chloroethane Below Below Below Below Chloroform 0.7 1.1 3.2 2.4 Chloromethane 5.1 30.7 Below Below Chlorotoluenes Below Below Below Below cis-1,2-Dichloroethene 0.4 4.6 6.6 10.7 cis-1,3-Dichloropropene 1.2 14.9 21.8 35.1 Cumene Below Below Below Below Cyclohexane 2.6 36.3 54.9 91.4 Dibromochloromethane 1.8 Below 34.5 55.6 Dichlorodifluoromethane 4.3 3.7 8.9 Below Dichlorotetrafluoroethane 3.7 22.7 51.5 42.5 Ethanol 21.5 191.7 173.0 260.7 Ethyl Acetate 0.6 0.4 9.0 14.6 Ethyl Tert-Butyl Ether 0.5 4.4 6.5 10.5 Ethylbenzene 0.6 3.6 6.6 12.8 Heptane 1.4 10.1 13.7 22.2 Hexachlorobutadiene Below Below Below Below Isooctane 0.6 5.4 7.9 12.5 Isopropyl Alcohol 64.2 95.1 82.5 118.6 Methyl Methacrylate 0.5 3.2 4.2 6.7 Chloride 2.2 9.0 Below Below Methyl-t-Butyl-Ether 1.8 5.7 7.6 12.1 m-Xylene 1.4 7.5 14.3 29.7 Naphthalene 0.2 0.3 Below Below n-Butyl Below Below Below Below n-Hexane 2.3 4.6 5.0 8.5 n-Propylbenzene Below Below Below Below o-Cymene Below Below Below Below o-Xylene 0.5 1.1 2.8 8.3 Propylene 6.1 11.1 6.4 11.6 p-Xylene 1.2 3.6 8.7 21.2 Sec-Butyl Below Below Below Below Styrene 1.7 20.8 30.5 49.2 Tert Amyl Methyl Ether 0.9 22.1 32.9 53.9 Tert-Butanol 4.5 6.9 2.1 6.6 Tert-Butyl Below Below Below Below Tetrachloroethene 0.9 9.9 14.5 23.2 Tetrahydrofuran 3.1 10.4 13.3 21.4 Toluene 2.7 15.9 20.6 38.5 trans-1,2-Dichloroethene 8.2 6.6 9.7 13.7 trans-1,3-Dichloropropene N.D. Below 30.7 15.3 Trichloroethene 0.6 8.0 6.4 18.8 Trichlorofluoromethane 2.6 3.6 1.8 4.6 Vinyl Acetate 14.4 17.7 7.1 29.7 Vinyl Bromide 0.0 0.1 0.1 0.3 Vinyl Chloride Below Below Below Below

Fall Technical Meeting of the Eastern States Section of the Combustion Institute, Oct 9-12, 2011