1. 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

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

3. Project Background
LeAnne
Two-Step Conversion of Ethanol to Butadiene

4. 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

5. One-Step Mechanism 2 Ethanol 1,3 Butadiene + 2 Water + Hydrogen
2 C2H5OH C4H H2O H2
1,3 Butadiene
LeAnne
Two-Step Conversion of Ethanol to Butadiene

6. 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

7. 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

8. 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

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

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

11. 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

12. 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

13. Section 1: Reactions Ethanol  Acetaldehyde + Hydrogen
C2H5OH  CH3CHO H2
2 Ethanol + Water  Ethyl Acetate + 2 Hydrogen
2 C2H5OH + H2O  C4H8O H2
Murtada
Two-Step Conversion of Ethanol to Butadiene

14. 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

15. 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

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

17. 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

18. Section 3: Reactions Ethanol + Acetaldehyde  1,3 Butadiene +2 Water
C2H5OH + CH3CHO  C4H H2O
2 Acetaldehyde  Ethyl Acetate
2 CH3CHO  C4H8O2
Ethanol  Ethylene + Water
C2H5OH  C2H H2O
LeAnne
Two-Step Conversion of Ethanol to Butadiene

19. 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

20. 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

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

22. 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

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

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

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

26. Economics Discount Rate = 10% Aug 2013 March 2014 Butadiene, c/lb
42.50
65.77
73.40
Revenue, MM$/yr
60.71
93.95
104.85
NPV10, MM$
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

27. Closing Remarks
LeAnne
Two-Step Conversion of Ethanol to Butadiene

28. 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

29. 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

30. References Mentioned specifically in the PowerPoint:
Acquaviva, Jim. "High-Performance, Durable, Palladium Alloy Membrane for Hydrogen Separation and Purification." 19 May Web. 7 Dec <
Kvisle, S., A. Aguero, and R.P.A. Sneeden. "Transformation of Ethanol into 1,3- butadiene over Magnesium Oxide/silica Catalysts." ScienceDirect. 1 Jan Web. 24 Oct <
”Butadiene price rises by third." Supply Management. 19 Mar Web. 01 Dec < 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 Jan Web. 22 Oct <
LeAnne
Two-Step Conversion of Ethanol to Butadiene

31. Questions?
LeAnne
Two-Step Conversion of Ethanol to Butadiene