Two - Step Conversion of Ethanol to Butadiene Murtada Al Aradi A.J Beemer LeAnne Hazard Ben McFarland Alex Thompson University of Wyoming, CHE4080 Senior Design II LeAnne

Overview of Presentation Project Background Process Breakdown Materials and Economics Closing Remarks LeAnne Two-Step Conversion of Ethanol to Butadiene

Project Background LeAnne Two-Step Conversion of Ethanol to Butadiene

Butadiene Background Technology used since 1940’s Steam cracking from unsaturated hydrocarbon mixture One-Step vs. Two-Step Reactions LeAnne Two-Step Conversion of Ethanol to Butadiene

One-Step Mechanism 2 Ethanol 1,3 Butadiene + 2 Water + Hydrogen 2 C2H5OH C4H6 + 2 H2O + H2 1,3 Butadiene LeAnne Two-Step Conversion of Ethanol to Butadiene

Two-Step Mechanism 1.) Ethanol  Acetaldehyde + Hydrogen C2H5OH  CH3CHO + H2 Acetaldehyde 2.) Ethanol +Acetaldehyde  1,3 Butadiene +2 Water C2H5OH + CH3CHO  C4H6 + 2 H2O 1,3 Butadiene LeAnne Two-Step Conversion of Ethanol to Butadiene

Proposal The need: Oil prices can fluctuate drastically Many uses Butadiene can be created economically from ethanol as an alternative to crude oil Agricultural areas Geologically unfavorable locations LeAnne Two-Step Conversion of Ethanol to Butadiene

Business Opportunity Growing demand Correlation with crude C4’s Price Variance Price Reduction as addition to existing plant Golden, Colorado 64.7 million gallons per year (gal/yr) 8410 operating hours per year (hr/yr) AJ Two-Step Conversion of Ethanol to Butadiene

Butadiene Uses Break-Down Major Uses: Rubber (Automobile tires) Butadiene and SBR Murtada Two-Step Conversion of Ethanol to Butadiene

Project Breakdown By Section Murtada Two-Step Conversion of Ethanol to Butadiene

Process Flow Diagram Dehydrogenation of Ethanol Hydrogen Separation System Section 2 Catalysis of Acetaldehyde-Ethanol Section 3 Energy FEED (Ethanol) PRODUCT (1,3 Butadiene) RECYCLE Butadiene Separation System Section 4 BY-PRODUCTS HYDROGEN Dehydrogenation of Ethanol Section 1 Process Flow Diagram Alex

Dehydrogenation of Ethanol Energy HYDROGEN Dehydrogenation of Ethanol Section 1 Hydrogen Separation System Section 2 FEED (Ethanol) RECYCLE Butadiene Separation System Section 4 Catalysis of Acetaldehyde-Ethanol Section 3 Murtada PRODUCT (1,3 Butadiene) Energy BY-PRODUCTS

Section 1: Reactions Ethanol  Acetaldehyde + Hydrogen C2H5OH  CH3CHO + H2   2 Ethanol + Water  Ethyl Acetate + 2 Hydrogen 2 C2H5OH + H2O  C4H8O2 + 2 H2 Murtada Two-Step Conversion of Ethanol to Butadiene

Section 1: Reactor 1 Catalyst Specifications Catalyst: BASF K-310 CuO/ZnO/Al2O3 Conversion of Ethanol: 52.7% Selectivity: Acetaldehyde: 87.5% Ethyl Acetate: 12.5% Reference: E. Santacesaria, et. al. ScienceDirect article. Type: Packed Bed Temperature: 392oF Pressure: 14.7 psia Murtada Two-Step Conversion of Ethanol to Butadiene

Process Flow Diagram Dehydrogenation of Ethanol Hydrogen Separation System Section 2 Catalysis of Acetaldehyde-Ethanol Section 3 Energy FEED (Ethanol) PRODUCT (1,3 Butadiene) RECYCLE Butadiene Separation System Section 4 BY-PRODUCTS HYDROGEN Dehydrogenation of Ethanol Section 1 Process Flow Diagram AJ

Section 2: Hydrogen Separation Flash all H2 Purge vs. Purification Purification units Membrane vs. PSA AJ Two-Step Conversion of Ethanol to Butadiene

Process Flow Diagram Dehydrogenation of Ethanol Hydrogen Separation System Section 2 Catalysis of Acetaldehyde-Ethanol Section 3 Energy FEED (Ethanol) PRODUCT (1,3 Butadiene) RECYCLE Butadiene Separation System Section 4 BY-PRODUCTS HYDROGEN Dehydrogenation of Ethanol Section 1 Process Flow Diagram LeAnne

Section 3: Reactions Ethanol + Acetaldehyde  1,3 Butadiene +2 Water C2H5OH + CH3CHO  C4H6 + 2 H2O 2 Acetaldehyde  Ethyl Acetate 2 CH3CHO  C4H8O2 Ethanol  Ethylene + Water C2H5OH  C2H4 + H2O LeAnne Two-Step Conversion of Ethanol to Butadiene

Section 3: Reactor 2 Catalyst Specifications Catalyst: MgO/SiO2 Conversion of Ethanol and Acetaldehyde: 48% Selectivity: Butadiene: 68% Ethylene: 26% Ethyl Acetate: 9% Type: Packed Bed Temperature: 662oF Pressure: 14.7 psia Reference: Kvisle, et. al. ScienceDirect LeAnne Two-Step Conversion of Ethanol to Butadiene

Process Flow Diagram Dehydrogenation of Ethanol Hydrogen Separation System Section 2 Catalysis of Acetaldehyde-Ethanol Section 3 Energy FEED (Ethanol) PRODUCT (1,3 Butadiene) RECYCLE Butadiene Separation System Section 4 BY-PRODUCTS HYDROGEN Dehydrogenation of Ethanol Section 1 Process Flow Diagram Ben

Section 4: Ternary Azeotrope Butadiene Acetaldehyde Water Wide variety of azeotropes proves to make modeling our separation process difficult Section 4: Ternary Azeotrope Ben

Section 4: Separation System Ethylene 1,3-Butadiene Acetaldehyde Ethanol Ethyl Acetate Water Ethylene 1,3- Butadiene Ethyl Acetate (Mix) Acetaldehyde Recycle (Ethanol) Ben Water

Materials and Economics Alex Two-Step Conversion of Ethanol to Butadiene

Markets For (By)Products Alex Two-Step Conversion of Ethanol to Butadiene

Economics Fixed Capital Investment (FCI): $ 141 MM Operating Costs (OC): $ 65.78 MM/yr Minimum Acceptable Rate of Return (MARR): 10% Price of Butadiene: 65.77 c/lb Sensitivities +10% FCI 67.77 c/lb +10% OC 70.20 c/lb Alex Two-Step Conversion of Ethanol to Butadiene

Economics Discount Rate = 10% Aug 2013 March 2014 Butadiene, c/lb 42.50 65.77 73.40 Revenue, MM$/yr 60.71 93.95 104.85 NPV10, MM$ -147.92 0.02 48.53 IRR, % N/A 10.00 14.20 Pay Back Period, yrs 15 9.10 LeAnne Discount Rate = 10% Two-Step Conversion of Ethanol to Butadiene

Closing Remarks LeAnne Two-Step Conversion of Ethanol to Butadiene

Final Conclusions We used a two-step mechanism Multiple azeotropes make separation difficult Our process is not favorable in the current market LeAnne Two-Step Conversion of Ethanol to Butadiene

A special “thank-you” to: Dr. John Myers and Dr. Joseph Holles Acknowledgements A special “thank-you” to: Dr. John Myers and Dr. Joseph Holles LeAnne Two-Step Conversion of Ethanol to Butadiene

References Mentioned specifically in the PowerPoint: Acquaviva, Jim. "High-Performance, Durable, Palladium Alloy Membrane for Hydrogen Separation and Purification." 19 May 2009. Web. 7 Dec. 2014. <http://www.hydrogen.energy.gov/pdfs/review09/pd_07_acquaviva.pdf>. Kvisle, S., A. Aguero, and R.P.A. Sneeden. "Transformation of Ethanol into 1,3- butadiene over Magnesium Oxide/silica Catalysts." ScienceDirect. 1 Jan. 1988. Web. 24 Oct. 2014. <http://www.sciencedirect.com/science/article/pii/S0166983400809057#>. ”Butadiene price rises by third." Supply Management. 19 Mar. 2014. Web. 01 Dec. 2014. <http://www.icis.com/Articles/2012/01/16/9523382/US-Chemical- profile-Butadiene.html.> Santacesaria, E., Carotenuto, G., Tesser, R. Di Serio, M., "Ethanol Dehydrogenation to Ethyl Acetate by Using Copper and Copper Chromite Catalysts." ScienceDirect. 1 Jan. 2012. Web. 22 Oct. 2014. <http://www.sciencedirect.com/science/article/pii/S1385894711012824>. LeAnne Two-Step Conversion of Ethanol to Butadiene

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