Synthesis of Propionic acid from Syngas

1. Synthesis of Propionic acid from Syngas Date:22 January 2011 Team Echo: Sabah Basrawi Alex Guerrero Mrunal Patel Kevin Thompson Client Mentor: Shannon Brown

2. Project Outline 1. Design Basis2. Block Flow Diagram3. Process Flow Diagram4. Material and Energy Balance5. Calculations6. Annotated Equipment List7. Economic Evaluation8. Utilities

3. Project Outline Pt.2 9. Conceptual Control Scheme10. General Arrangement11. Distribution and End-use Issues Review12. Constraints Review13. Applicable Standards14. Project Communications File15. Information Sources and References

4. Focal Points • Flowsheet • Materials and Energy Balances • Hand Calculations • Rough Economics

5. Project Goal • The goal of this project is to take the syngas from group Foxtrot ,and utilize it for the production of Propionic Acid to be used in industrial processes. • The goal is to synthesize 33,000 ton/year • The syngas feed will be reacted with Ethylene under a Nickel Carbonyl Catalyst to produce Propionaldehyde. • This aldehyde will then be oxidized to become Propionic Acid.

6. Design Basis • Propionic acid is a commonly used chemical in industry that will be synthesized from syngas (with a 1:1 ratio of CO and H2), ethylene and  water catalyzed by metal ion in solution •  Propionic acid: • Naturally occurring • Made from ethylene and carbon monoxide • Uses and advantages:    • Analgesic • Intermediate product for thermoplastics • Plastics are used in many daily processes and by creating an abundance of this resource it will increase affordability and stimulate the economy.

7. Environmental Review • Industrially, the majority of propionic acid is used as a bactericide and fungicide to protect hay and grains that are being stored as well as an ingredient for pesticides. • EPA determined it has “low toxicity to fish, invertebrates, birds and mammals.” • Nickel Carbonyl catalyst: • EPA classified as group 2B – Probable Human Carcinogen • OSHA Permissible Exposure Limit (PEL): 0.001 ppm

8. Competing Processes • Coal based syngas is the major feed stock of our process and is available in great abundance. • Industry standard – Hydrocarboxylation of ethylene using nickel carbonyl or ruthenium as catalyst: • H2C=CH2 + H2O + CO → CH3CH2COOH • Hydroformylation involves addition of a formyl group (CHO) and a hydrogen atom to a carbon-carbon double bond. • Most Hydroformylation relies on expensive rhodium based catalysts.

9. Competing Processes Pt. 2 • Syngas is chosen as the feed for the process because it is the most thermodynamically efficient • The Wacker process is similar to Hydroformylation, but Hydroformylation promotes chain extension and the Wacker process uses a Tetrachloropalladate catalyst. • Our process involves the Carbonylation of ethylene to produce Propionaldehyde, which is then oxidized in the presence of cobalt ions to produce Propionic Acid.

10. Block Flow Diagram

11. Flowsheet

12. Equipment List • Compressors • Expander • CSTR Reactors • Storage Tanks • Mixer • Water Reservoir • Heat Exchangers • Flash Separator

13. Propionic Acid Consumption

14. Demand for Propionic Acid

15. Plant Location • We have decided to base our plant operations in Morris, IL • Close to Lyondellbasell Plant which produces ethylene. • Also near rail line so team Foxtrot can obtain Illinois Basin #6 coal from southern Illinois.

16. Chemical Economics • Estimated Chemical Cost • Ethylene – $ 7.84 million • Syngas – $23 million • Estimated Cost of Cooling Water - $ 22,000 • Catalyst Price – $15 million • Total Cost - $ 45.86 million • Estimated Propionic Acid Sales – 62.4 million

17. Plant Economics • Project Capital Cost: $15.4 million • Estimated Operating Cost: $3.74 million • Estimated Break Even Point: ~3 years • Total Year One Cost: $ 65 million • Gross Revenue: 62.4 million

18. Preliminary Rough Economic Analysis • Because of the Break-even point the process is estimated to be within a reasonable range to be economical • The estimated revenue will be increasing with time as the demand for propionic acid increases • The economy should not have a great effect on this business due to us selling to food companies

19. Control Scheme • Conceptual control scheme: Dual man/mechanically run • Plans for plant to be operated 337 days per year • Plans to sell propionic acid to food companies

20. Chemical Information Analysis • Reaction Mechanism(1) CO + H2 +C2H4  CH3CH2CHO (2) CH3CH2CHO + ½ O2  CH3CH2COOH • Material & Energy Balance: basic material and energy balances were done over all streams in the system

21. Catalyst Information:Nickel Carbonyl • Used in the formation of the Propionate • Poisons: • Sulfur • Needs to be less than 5 ppm/6 hours • Price: • $14.06-17.23/lb

22. Catalyst InformationCobalt Halides • Used in the oxidation of Propionate to Propionic acid • Reaction calls for Cobalt ion • Dissolve cobalt halide in water to obtain ion • Poisons: • Potassium Carbonate

23. Material Balance

24. Material Balance

25. Material Balance (Aspen)

26. Material Balance (Aspen 2)

27. Energy Balance

28. Contact Information • Wiki link: http://seniorecho.wikispaces.com/ • Email: designecho@listserv.uic.edu

29. References • "Acetic Acid Production." Acetic Acid Production. 2009. Web. 22 Jan. 2011. <http://www.starcontrols.com/Application/Application_min_e.asp?MinID=34>. • Boyaval, P., and C. Corre. Production of Propionic Acid. 1995. Print. • Perlack, Robert D., Lynn L. Wright, Robin L. Graham, Bryce J. Stokes, and Donald C. Erbach. Biomass as a Feedstock for a Bioenergy and Bioproducts Industry: The Technical Feasibility of a Billion-Ton Annual Supply. Print. • "Propanoic Acid." Wikipedia, the Free Encyclopedia. Web. 22 Jan. 2011. <http://en.wikipedia.org/wiki/Propanoic_acid>. • Registration Review Document for Propionic Acid and Salts. Mar. 2008. Print. • Spivey, James J., Makarand R. Gogate, Ben W. Jang, Eric D. Middlemas, Joseph R. Zoeller, Gerald N. Choi, and Samuel S. Tam. Synthesis of Acrylates and Methacrylates from Coal-Derived Syngas. 1997. Print.

30. References Pt. 2 • http://www.engineeringtoolbox.com/air-compressor-types-d_441.html

31. QUESTIONS