Chemical Characterization of Biogas from Varied Organic ...30/1415-youn… · Dan Cuthbertson and Stephan Baumann . Title: PowerPoint Presentation Author: christoph Created Date:

Chemical Characterization of Biogas from Varied Organic Feedstocks:

Air Quality Implications

Y. Li1, C.P. Alaimo1, P.L. Wylie2, M.J. Kleeman, T.M. Young1

1 University of California, Davis, CA, USA 2Agilent Technologies, Wilmington, DE, USA

ICCE Oslo

June 2017

California’s Renewable Energy Future

By 2050 California has pledged to cut greenhouse gas emissions by 80% below 1990 levels

• Renewable methane sources are essential to achieving the goal

• Need to confirm that biomethane use does not create other air quality or health issues

Objectives: Characterize trace organic constituent composition of raw biogas, upgraded biomethane, and combustion byproducts from different biogas sources using GC- and LC-high resolution mass spectrometry techniques

Raw Biogas Sampling

Van Warmerdam Dairy

New Hope Dairy

Kiefer Landfill

Sampling System

Sources tested: • Food waste digesters (2) • Dairy waste (2; one

lagoon, one digester) • Landfill (newer and

older zones) Each tested 3 times

Biogas Upgrading System

SATS Food Waste Digester

HELEE membrane unit tested for removal of CO2

and trace constituents

Stove Appliance Testing

Atmospheric Aging Experiments

Field Deployment of Aging System

Organics Collection and Analysis

Collection Instrumental Analysis

Analyte Classes Representative Compounds

Tedlar bag

GC-TCD Fixed gases C3-C5 hydrocarbons

CH4, CO2

Butane, pentane

TD-GC-MS Volatile sulfur TO-15 / halocarbons

Methyl mercaptan, carbon disulfide Chloropropanes, chlorobenzenes

GC-FPD Volatile sulfur H2S

Charcoal sorbent tube

GC-QTOF-MS Extended hydrocarbons Siloxanes

Cyclohexane, C3 benzenes Tetramethyl disiloxane

XAD sorbent tube

GC-QTOF-MS SVOCs / PAHs Pesticides / PCBs

Nitroanilines, pyrene Methoxychlor, PCB-53

DNPH sorbent LC-QTOF-MS Aldehydes / ketones 2-butanone, acetone

Nontarget Analysis Approaches

Collection Extract w/ DCM

LC-QTOF-MS GC-QTOF-MS

Instrument pictures: www.agilent.com

Zorbax Eclipse Plus C 18 ESI+: H2O+FA / ACN+FA

ESI-: H2O+NH4F / ACN Data Acquisition:

All-Ion CE 0, 10, 20, 40 (target + suspect)

Full scan MS (non-target)

HP-5MS (30m x 0.25mm, 025µm) Temp gradient: linear increase 35-325°C in 80 min Data Acquisition: EI (target + suspect + non-target)

Agilent 6530

Agilent 7200B

Collection Concentrate or Solvent Extract

100’s-1000’s of constituents detected on each platform

Small fraction of mass spectra in database

XAD-2 and charcoal sorbent tubes

DNPH coated sorbent tubes

Impingers pH 10

Representative VOC Target Results

Temperature Effect on Landfill BTEX

0

500

1000

1500

2000

2500

3000

3500

14 19 24 29 34 39

Co

nce

ntr

atio

n (

pp

bv)

Temp (C)

Benzene Toluene Ethylbenzene m-xylene

Linear (Benzene ) Linear (Toluene ) Linear (Ethylbenzene ) Linear (m-xylene)

Example Unknown: Limonene

Ingredient in: Paints and coatings Personal care products Cleaning products

Found in: READ D50, D500, L500 Kiefer D50

Multi-halogen Benzene Derivatives

Found in: Kiefer D500. L500

Unique Features: Food Waste

1,3-Dioxolane, 2,4,5-trimethyl- 2,2-Dimethyl-propyl 2,2-dimethyl-propanesulfinyl sulfone 2,4-Di-tert-butylphenol 2,5-cyclohexadien-1-one, 2,6-bis(1,1-dimethylethyl)-4-hydroxy-4-methyl- 2-Pentanone 2-Pentanone, 3-methyl- Benzoic acid, 4-ethoxy-, ethyl ester Butanoic acid, 2-methyl-, ethyl ester Dodecyl acrylate Tris(2,4-di-tert-butylphenyl) phosphate

Landfill: Diverse Benzene Derivatives

Benzene, (1-methylethyl)- * Benzene, (propoxymethyl)- * Benzene, 1,2,3,5-tetramethyl- Benzene, 1,2,4-trimethyl- Benzene, 1,2-dichloro- * Benzene, 1-chloro-2-methyl- * Benzene, 1-chloro-4-(trifluoromethyl)- Benzene, 1-ethenyl-3-ethyl- Benzene, 1-ethyl-2-methyl- Benzene, 1-ethyl-4-methyl- Benzene, 1-methyl-3-(1-methylethyl)- * Benzene, 1-methyl-3-propyl- * Benzene, 1-methyl-4-propyl- * Benzene, n-butyl- Benzene, propyl-

* Found only in Kiefer samples

DNPH Method for Target Carbonyls

2,4-Dinitrophenyl hydrazine (DNPH)

2,4-dinitrophenylhydrazone product

Formaldehyde

+

Representative target carbonyl compounds

17 compounds on target list All molecular formulas CaHbOc

propionaldehyde

2-butanone

hexanaldehyde

crotonaldehyde

P-tolualdehyde

benzaldehyde

methacrolein

Target Carbonyl Results

Total Aldehydes (mg/m3) Total Ketones (mg/m3)

Finding Nontarget Carbonyls

• Carbonyl species important because of atmospheric reactivity

• Peaks aligned across all samples using Agilent Profinder B08

• 517 features met criteria: Not in blank Not on target list Target score>95

• Export features to Mass Profiler Professional 14 for formula generation and statistical analysis

2x10

0

2

Counts vs. Acquisition Time (min)

18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20

Cpd 218: -ESI EIC(331.1402) Scan Frag=110.0V 170606_01_Blank.d

2x10

0

2


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20

Cpd 218: -ESI EIC(331.1402) Scan Frag=110.0V 170606_02_STD_750pp…

4x10

0

5


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20

Cpd 218: -ESI EIC(331.1402) Scan Frag=110.0V 170606_03_READ_061…

19.098

5x10

0

1


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20


19.120

4x10

0

5


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20


19.109

5x10

0

1


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20

Cpd 218: -ESI EIC(331.1402) Scan Frag=110.0V 170606_06_SATS_0919…

19.120

5x10

0

1


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20


19.126

5x10

0

1


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20


19.106

4x10

0

5


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20


19.101

4x10

0

2


18.2 18.4 18.6 18.8 19 19.2 19.4 19.6 19.8 20

Cpd 218: -ESI EIC(331.1402) Scan Frag=110.0V 170606_10_VAN_05271…

5x10

0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

0.4

0.45

0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1

1.05

1.1

1.15

1.2

1.25

1.3

Cpd 183: C16 H20 N4 O4; 19.112: -ESI FBF Spectrum (rt: 19.112 min)

331.1403(M-H)-

332.1438(M-H)-

Counts vs. Mass-to-Charge (m/z)

331.1 331.15 331.2 331.25 331.3 331.35 331.4 331.45 331.5 331.55 331.6 331.65 331.7 331.75 331.8 331.85 331.9 331.95 332 332.05 332.1 332.15 332.2

Formula Generation Examples

2-(3-methyl-2-cyclopenten-1-yl)-2- methylpropionaldehyde

Cluster Analysis of Nontarget Carbonyls

PCA of Nontarget Carbonyls

Unique Carbonyl Source Markers

• Biogas samples have far more diverse carbonyl signatures than the target compounds

• Roughly 40% of ion abundance is associated with compounds present in the standard

Conclusions and Future Directions

• Nontarget fraction of carbonyl compounds appears significant

• Characterizing the complex carbonyl compounds in biogas is a priority

• Tracking atmospheric reaction products of carbonyls provides a focus for nontarget analysis of chamber experiments

• Understanding sources and signatures of trace VOCs in different biogas sources and their combustion products is another future direction

• Combining nontarget results with bioassays (ongoing) will further focus identification efforts

Acknowledgements

Funding:

• California Air Resources Board and California Energy Commission

• UC Davis Superfund Research Center, National Institutes of Health, NIEHS award (P42ES004699)

Thanks:

• Agilent Technologies Inc. for technical assistance, especially Dan Cuthbertson and Stephan Baumann

Documents

Chemical Characterization of Biogas from Varied Organic ...30/1415-youn… · Dan Cuthbertson and Stephan Baumann . Title: PowerPoint Presentation Author: christoph Created Date: