1. 1 Mariano Savelski 1, C. Stewart Slater 1, Dave Aycock 2, Bogdan Comanita 2, Steve Prescott 2, Jeff Shifflette 2 1 Rowan University, Glassboro, NJ 2 PennAKem, Memphis, TN sprescott@pennakem.com Life Cycle Analysis of Biobased Pennakem’s ecoMeTHF™ : Green Solvents for the Pharmaceutical and Fine Chemical Industry Session: Green Chemistry Metrics for Innovation and Driving Sustainability 16 th Annual Green Chemistry & Engineering Conference Washington, DC June 18-20, 2012

2. 2 Pennakem: Renewable Resources Acid Pentoses Furfural Rubber AgChem FineChem Food & Cosmetics - 3H 2 O 2

3. 3 Solvents & Pharma Mass Balance Lessons Learned From The Pharmaceutical Industry, a) Richard K Henderson,GlaxoSmithKline, Park Road, Ware, Herts, SG12 ODP, UK; b) John Kindervater, Eli Lilly and Company, Indianapolis, IN,46285 USA; c) Julie B Manley, ACS Green Chemistry Institute, 1155 Sixteenth St., NW, Washington, DC 20036, USA 3

4. 4 Solvent Choice  GHG Fossil Solvent? Solvent Reagents Product Aqueous waste Solvent waste Solvent recycling Reaction Recycled solvent Incineration Solvent residue CO 2 Mandatory Declaration Anthropogenic CO 2 YesNo Informative Declaration Biogenic CO 2 4

5. 5 Strategic Switch to Biobased Solvents Up to 35% GHG reduction 5

6. 6 Pennakem’s ecoMeTHF™ value proposition Reduced costs Improved process Green product & process Comparable/better safety PurchasingR&D/Manufacturing Safety Environmental 6

7. 7 Pennakem’s ecoMeTHF™ savings sources Improved chemical properties –Higher yields in a wide range of reactions –Improved impurity profile Improved physical properties –Easy work-up (5% water solubility) –Powerful extraction solvent (less steps) –Easy drying (azeotrope)  telescopic reactions –Easy recycling (simple distillation ambient pressure) visit: pennakem.com 7

8. 8 Pennakem’s ecoMeTHF™ use in Pharma Adapted from “Moving Towards Greener Solvents In Pharmaceutical Manufacturing” ; Peter Dunn (Pfizer), Richard Henderson (GSK), Ingrid Merlgesberg (Schering-Plough) & Andrew Wells (Astra-Zeneca) Website: www.acs.org/gcipharmaroundtable 8

9. 9 Pennakem’s ecoMeTHF™ Synthesis Derived from agriculturally-produced furfural Pennakem’s ecoMeTHF™ 9

10. 10 Life Cycle Analysis Route to synthesize Pennakem’s ecoMeTHF™ divided into individual processes LCIs were calculated for the key intermediates in the process steps: o Corn cob collection, furfural, MeF product stream, Pennakem’s ecoMeTHF™, and all required materials and utilities o SimaPro ® and EcoSolvent ® were used for most chemicals, energy, wastes o Furfural, MeFuran were several of the chemicals modeled Corn cob collection Furfural MeFuran ecoMeTHF™ 10

11. 11 Biogenic Carbon Approach (BCA) CO 2 Biomass Waste (e.g.: corn cobs) Incineration Fossil Fuel CO 2 Byproduct Waste Incineration Emissions = 0 Fossil Fuel Emissions < 0 (credit) “ Biogenic CO 2 is no CO 2 ” “Incineration of Solvents obtained from renewable resources results in biogenic CO 2 ”, which “under international legislation and guidelines does not contribute to the national inventory of GHG emissions” * * B. Comanita, Live Webinar: “Carbon-Neutral Solvents: A Natural Choice In A Carbon-Neutral Future”, April 15, 2010 11 Byproducts

12. 12 Furfural Production Based on “Westpro” process 8.33 kg corn cob waste yields 1 kg furfural Waste lignin and solvent byproducts burned to generate stream for process –Modeled as “heat from biomass” and solvent incineration – credit taken Excess lignin residue treated with limestone, sold as fertilizer and credit taken Furfural Production Corn cob waste Steam H 2 SO 4 H2OH2O Furfural MeOH Acetone Lignin Excess Lignin Acetic Acid to WWTP to sell as fertilizer 12

13. 13 Furfural Raw Material and Energy LCIs Corn cob collection and waste treatment contribute the most emissions Credits come from sale of excess lignin and burning waste solvents 13

14. 14 Furfural LCI The negative CED is due to the credits LCI of Furfural (per 1 kg furfural) Byproduct credits are subtracted from Raw Material, Utilities and Waste to obtain Total Emissions CED, MJ-Eq-1.24E+01 Air Emissions, kg6.43E-01 CO 2, kg6.31E-01 CO, kg4.90E-03 CH 4, kg6.57E-04 NO X, kg9.69E-03 NMVOC, kg1.65E-03 Particulates, kg1.20E-03 SO 2, kg-9.75E-04 Water Emissions, kg1.26E-02 VOCs, kg3.72E-06 Soil Emissions, kg1.30E-03 Total Emissions, kg6.56E-01 14

15. 15 Furfural LCI (BCA) Utilities emissions are lower in the biogenic carbon approach because lignin CO 2 emissions are zero LCI of Furfural (per 1 kg furfural) Byproduct credits are subtracted from Raw Material, Utilities and Waste to obtain Total Emissions CED, MJ-Eq-1.24E+01 Air Emissions, kg3.84E-01 CO 2, kg3.72E-01 CO, kg4.90E-03 CH 4, kg6.57E-04 NO X, kg9.69E-03 NMVOC, kg1.65E-03 Particulates, kg1.20E-03 SO 2, kg-9.75E-04 Water Emissions, kg1.26E-02 VOCs, kg3.72E-06 Soil Emissions, kg1.30E-03 Total Emissions, kg3.98E-01 15

16. 16 Pennakem’s ecoMeTHF™ Process Utilities –Electricity modeled from TVA –Steam generated on-site Waste –Solvent incineration –Water emissions Furfural Steam Electricity H2H2 Waste: MeF MeTHF H 2 O Other MeF MeTHF Furan H 2 O MeFuran Product stream: eco MeTHF™ Steam Electricity H2H2 Waste: MeF MeTHF H 2 O 1-Pentanol Other MeF step eco MeTHF™ step 16

17. 17 MeF Product Stream Raw Material and Energy LCIs Furfural is the highest contributor Byproduct credits are greater than the emissions from waste treatment 17

18. 18 MeF Product Stream LCI LCI of MeF Product Stream (per 1 kg of MeF) The credits negate all emissions from waste treatment and utility use CED, MJ-Eq-1.93E+01 Air Emissions, kg8.95E-01 CO 2, kg8.83E-01 CO, kg6.43E-03 CH 4, kg-5.34E-04 NO X, kg1.31E-02 NMVOC, kg2.34E-03 Particulates, kg1.22E-03 SO 2, kg-3.77E-03 Water Emissions, kg1.45E-02 VOCs, kg5.29E-06 Soil Emissions, kg1.85E-03 Total Emissions, kg9.11E-01 Byproduct credits are subtracted from Raw Material, Utilities and Waste to obtain Total Emissions 18

19. 19 MeF Product Stream LCI (BCA) LCI of MeF Product Stream (per 1 kg of MeF) CO 2 solvent waste incineration emissions are zero in the BCA CED, MJ-Eq-1.93E+01 Air Emissions, kg2.03E-01 CO 2, kg1.91E-01 CO, kg6.43E-03 CH 4, kg-5.34E-04 NO X, kg1.31E-02 NMVOC, kg2.34E-03 Particulates, kg1.22E-03 SO 2, kg-3.77E-03 Water Emissions, kg1.45E-02 VOCs, kg5.29E-06 Soil Emissions, kg1.85E-03 Total Emissions, kg2.19E-01 Byproduct credits are subtracted from Raw Material, Utilities and Waste to obtain Total Emissions 19

20. 20 Pennakem’s ecoMeTHF™ Raw Material and Energy LCIs MeF stream is the highest contributor Byproduct credits negate impacts from waste and utilities 20

21. 21 Pennakem’s ecoMeTHF™ Life Cycle Emissions Life cycle emission of Pennakem’s ecoMeTHF™ (per 1 kg ecoMeTHF) Increased emissions compared to MeF step are due to lower offset credits from solvent waste cement kiln incineration Byproduct credits are subtracted from Raw Material, Utilities and Waste to obtain Total Emissions 21 CED, MJ-Eq-2.00E+01 Air Emissions, kg9.71E-01 CO 2, kg9.59E-01 CO, kg6.63E-03 CH 4, kg-9.38E-04 NO X, kg1.38E-02 NMVOC, kg2.46E-03 Particulates, kg1.26E-03 SO 2, kg-4.55E-03 Water Emissions, kg2.73E-02 VOCs, kg5.56E-06 Soil Emissions, kg1.94E-03 Total Emissions, kg1.00E+00

22. 22 Pennakem’s ecoMeTHF™ Life Cycle Emissions (BCA) Life cycle emission of Pennakem’s ecoMeTHF™ (per 1 kg ecoMeTHF) Total emissions are reduced by 81% in the BCA Raw Material emissions are reduced by 72% in the BCA Byproduct credits are subtracted from Raw Material, Utilities and Waste to obtain Total Emissions 22 CED, MJ-Eq-2.00E+01 Air Emissions, kg1.62E-01 CO 2, kg1.50E-01 CO, kg6.63E-03 CH 4, kg-9.38E-04 NO X, kg1.38E-02 NMVOC, kg2.46E-03 Particulates, kg1.26E-03 SO 2, kg-4.55E-03 Water Emissions, kg2.73E-02 VOCs, kg5.56E-06 Soil Emissions, kg1.94E-03 Total Emissions, kg1.91E-01

23. 23 Life Cycle Emissions Comparison Pennakem’s ecoMeTHF™ has the lowest carbon footprint when compared to other typically used solvents Pennakem’s ecoMeTHF™ (BCA) has 97% lower life cycle emissions than “chemical” THF (derived from 1,4 butanediol, Reppe process) 23 (BCA) = Biogenic Carbon Approach

24. 24 Acknowledgements Rowan Engineering Clinic students –Daniel Cendo –David Hitchcock –Adam Kooker –Mia Korngruen PennAKem For further information on Pennakem’s ecoMeTHF™ contact: Steve Prescott sprescott@pennakem.com Office: 901-320-4091 Cell: 901-832-2929 U.S. EPA Pollution Prevention Program NP97212311-0 24

25. 25 Thank you!