R. A. Culp, J. E. Noakes, D. R. Smith, L. N. Greenway, F. S. Smith and B. K. Markowicz

Transcription

1 Bio-base Product Determination by ASTM Method Using Liquid Scintillation Counting and Benzene Synthesis: Progress and Performance in an Expanding Market. R. A. Culp, J. E. Noakes, D. R. Smith, L. N. Greenway, F. S. Smith and B. K. Markowicz Center for Applied Isotope Studies University of Georgia Athens, Georgia 30602, USA

2 Outline: Mandate for Bio-based products and testing Bio-based product Research Challenges since 2005 Liquid Scintillation Counting: Bio-based product methodology and performance Comparison: LSC and AMS for heterogeneous sample types Summary Market trends and future research

3 Mandate for Bio-based products and testing 2002 U.S. Farm Security Act authorizes Federal Biobased Preferred Products Procurement Program (FB4P) rather than petroleum based products U.S. Dept. of Agriculture published guidelines for identifying and evaluating bio-based based products. ~2008 European Committee for Standardization (CEN) develops standards for bio-plastics, bio-polymers and bio- lubricants.

4 Bio-based Products Research 2000,, Currie, Klinedinst,, Burch, Feltham and Dorsch, Authentication and dating of biomass components of industrial materials; links to sustainable technology. Nucl.. Instr. and Meth. in Phys. Res. B 172, ,, Noakes, Norton, Culp, Nigam and Dvoracek, A comparison of analytical methods for the certification of biobased products.. In: LSC 2005, Advances in Liquid Scintillation Spectrometry ,, Norton and Devlin, Determining the modern carbon content of biobased products using radiocarbon analysis. Bioresources Tech. 2006, Dijs,, van der Windt, Kaihola and van der Borg, Quantitative Determination by 14C analysis of the biological component in fuels. Radiocarbon, Vol 48, Nr 3, ,, American Society for Testing and Materials (ASTM), Standard test methods for determining the biobased content of natural range materials using radiocarbon and isotope ratio mass spectrometry analysis. (Method D ). 2008, Edler, The use of liquid scintillation counting technology for the determination of biogenic materials.. In: LSC 2008, Advances in Liquid Scintillation Spectrometry ,, Culp and Noakes, Evaluation of biobased content ASTM method A: Improvements revealed by liquid scintillation counting, accelerator mass spectrometry, and d stable isotopes for products containing inorganic carbon. In: LSC 2008, Advances in Liquid Scintillation Spectrometry ,, American Society for Testing and Materials (ASTM), Standard practice for collection of integrated samples for the speciation of biomass (biogenic) and fossil-derived carbon dioxide emitted from stationary emissions sources.. (Method D ).

5 Challenges since 2005 Low carbon content: Spray cleaners, sealants & carpet - addressed with AMS technique Dilution with water or alcoholic solution: Various cleaning solutions, lubricants - requires two-step combustion. Inorganic carbon (Calcium carbonate) exclusion: Paints, dyes, ceiling tile - requires expensive two-step AMS analysis Decreasing atmospheric 14 C activity level: Uptake by photosynthesizing Bio-base plants Sample heterogeneity: Advantageous to use gram size quantities and LSC

6 Challenges since 2005 Low carbon content: Spray cleaners, sealants & carpet - addressed with AMS technique Dilution with water or alcoholic solution: Various cleaning solutions, lubricants - requires two-step combustion.

7 Challenges since 2005 Low carbon content: Spray cleaners, sealants & carpet - addressed with AMS technique Dilution with water or alcoholic solution: Various cleaning solutions, lubricants - requires two-step combustion. Inorganic carbon (Calcium Carbonate) exclusion: Paints, dyes, ceiling tile - requires expensive two-step AMS analysis Biobased Material % Carbon Determination Carbonate Determination 14 C AMS Determination Sample Size Determination on acid extracted CO 2 14 C by LSC $ C by AMS $ C by AMS $ C by AMS $450 Differential 14 C by AMS $900

8 BioPreferred Designated Items January 2010 Min. Biobased Content Min. Biobased Content Construction and Industrial Food Service Carpets 7% Disposable Containers 72% Chain and Cable Lubricants 77% Disposable Cutlery 48% Composite Panels: Food Cleaners 53% Acoustical 37% Facility Operations and Maintenance Interior Panels 55% 2-Cycle Engine Oils 34% Plastic Lumber 23% Corrosion Preventatives 53% Structural Interior Panels 89% Diesel Fuel Additives 90% Structural Wall Panels 94% Dust Suppressants 85% Concrete and Asphalt Release Fluids 87% Fertilizers 71% Forming Lubricants 68% Gear Lubricants 58% Fluid-Filled Filled Transformers: General Purpose De-Icers 93% Synthetic Ester-Based 66% Greases: Vegetable Oil-Based 95% Food Grade 42% Hydraulic Fluids: Multipurpose 72% Mobile Equipment 44% Other 75% Stationary Equipment 44% Rail Track 30% Industrial Cleaners 41% Truck 71% Metalworking Fluids: Penetrating Lubricants 68% General Purpose Soluble, Semi-Synthetic, Synthetic, and Synthetic Oils 57% Sorbents 89% High Performance Soluble, Semi-Synthetic, Synthetic, and Synthetic Oils 40% Janitorial Straight Oils 66% Adhesive and Mastic Removers 58% Parts Wash Solutions 65% Bathroom and Spa Cleaners 74% Plastic Insulating Foam for Residential and Commercial Construction 7% Carpet and Upholstery Cleaners: Roof Coatings 20% General Purpose 54% Water Tank Coatings 59% Spot Removers 7% Wood and Concrete Sealers: Floor strippers 78% Membrane Concrete Sealers 11% General Purpose Household Cleaners 39% Penetrating Liquids 79% Glass Cleaners 49% Miscellaneous Graffiti and Grease Removers 34% Bedding, Bed Linens, and Towels 12% Laundry Products: Firearm Lubricants 49% General Purpose 34% Hand Cleaners 64% Pretreatment/Spot Removers 46% Hand Sanitizers 73% Multipurpose Cleaners 56% Lip Care Products 82% Films: Non-Durable 85% Semi-Durable 45%

9 Decreasing atmospheric 14 C activity level 14 C Pathway Atmospheric Bomb testing effect Recent decreasing 14 C activity level *Modify Modify ASTM 6866 to reflect today s 14 C activity ASTM (2010) now in use

10 14 C Pathway

11 Atmospheric 14 C activity since C activity by year Stuiver et al Hua and Barbetti 2004 Levin and Kromer UGA Bio-base Previous Research pmc

12 Bio-based product 14 C activity: C AVG 14C Corrected AVG Log. (14C AVG) Log. (14C Corrected AVG) 14 C Activity (dpm/gc) y = Ln(x) , 2008=14.31, 2009=14.23 y = Ln(x) , 2008=14.27, 2009=14.19 (del13c corrected) Year

13 LSC Bio-based Product Methodology and Performance Instrumentation for Bio-base testing of heterogeneous samples Mass dependency tests eleven samples Benzene synthesis chemistry Intermediate compound efficiency Overall yield vs Mass

14 BIO-BASE BASE PRODUCT DETERMINATION ASTM Part C: C 1. Parr Bomb Combustion 2. Benzene Synthesis 3. Liquid Scintillation Counting

15 Supporting Analytical Instrumentation For small samples <1 gram, dilute samples <10% in solution, and volatiles Accelerator Mass Spectrometer NEC 0.5 MeV Pelletron Tandem: ASTM Part B Stable Isotope Mass Spectrometer Finnigan MAT 252 IRMS: δ13c stable isotope correction

16 Eleven Samples: LSC 14 C Activity vs Mass (C) Prop Gly 16.0 Cotton 14.0 Bamboo Cardboard Epoxy Hardener Bamboo 2 Soy oil Pet eth C (dpm/gc) Bio eth Bio eth Mass (g)

17 Seven Modern Samples: LSC 14 C Activity (+/- 1σ) vs Mass (C) Prop Gly Cotton Bamboo 1 Cardboard Bamboo C (dpm/gc) Soy oil 13.0 Bio eth Mass (g) 3 2 1

18 Benzene Synthesis 14 C n H 2n O n n CO 2 (,, O 2 ) + H 2 O 10 Li + 2 CO 2 Li 2 C LiO ( ) Li 2 C H 2 O C 2 H LiOH (H2O) 3 C 2 H 2 14 C 6 H 6 (Catalyst)

19 Benzene Synthesis: Intermediate Compound Conversion Efficiency Moles Carbon CO2 C2H2 C6H6 Intermediate Compound Prop Gly 6 Prop Gly 4 Prop Gly 2 Cotton 6 Cotton 4 Cotton 2 Bamboo 1-4 Bamboo 1-2 Cardboard 6 Cardboard 4 Cardboard 2 Epoxy 6 Epoxy 4 Epoxy 2 Hardener 6 Hardener 4 Hardener 2 Bamboo 2-6 Bamboo 2-4 Bamboo 2-2 Soy oil 6 Soy oil 4 Soy oil 2 Pet eth 6 Pet eth 2.6 Bio eth 1-6 Bio eth Bio eth 2-6

20 Benzene Synthesis: Overall Yield vs Mass (C) Prop Gly Cotton Bamboo 1 Cardboard Epoxy Hardener Bamboo 2 Soy oil Pet eth Bio eth % Yield CO2 to C6H6 Bio eth Mass (g)

21 14 C Activity (+/- 1σ) ) LSC vs AMS Mass LSC error AMS error Pro Gly Cotton Bamboo Cardboard Bamboo Soy oil Bio eth Hardener Bio eth Epoxy Pet eth

22 Summary LSC method exhibits uniform 14 C activity for wide range of masses 14 C activity independent of wide range of benzene synthesis yields Precision decreases with lower mass without considerable loss in accuracy Excellent agreement between LSC and AMS methodologies Wide range of capability to access Bio-base materials

23 Market trends and future research Fuel oils and lubricants Bio-fuels octane enhancers Greases, cleaners and sealants Food service consumables Flue gas analysis for bio-base base fuel apportionment (ASTM7459) Bio-degradable - Bio-base products

24 Acknowledgements Dr. Alex Cherkinsky and Dr. Ravi Prasad (CAIS AMS analysis) Dr. Glenn Norton (Iowa State Univ.) Staff and technicians at the University of Georgia s Center for Applied Isotope Studies Various companies supplying challenging bio-base base products for this research Thank you