Integrated Shale Gas Industrial Complex: Fischer- Tropsch Liquids Refining Plant

1. Integrated Shale Gas Industrial Complex: Fischer-Tropsch Liquids Refining Plant Senior Design II Spring 2013 Mentor: Dan Rusinak Group Presentation #1 Team Foxtrot Ali, Mudassir Drake, Stephen Meaux, Kevin (Team Leader) Sieve, Brandon

2. Design Project Outline-Executive Summary-Discussion-RecommendationsAppendices:Design Basis Block Flow DiagramProcess Flow Diagram Material and Energy Balance, including Integration ReviewCalculationsAnnotated Equipment ListEconomic Evaluation factored from Equipment CostsUtilitiesConceptual Control SchemeGeneral ArrangementDistribution and End-use Issues ReviewConstraints ReviewApplicable StandardsProject Communications FileInformation Sources and References

3. Background • FT was designed in 1920 by Franz Fischer and HanzTropsch in Germany. • The Fischer-Tropsch (FT) synthesis is a commercially proven method for converting synthesis gas (a mixture of hydrogen and carbon monoxide) to a broad range of hydrocarbon

4. Feed stock • The feed stock is Syngas (CO +H2) • The sources of syngas are Coal Biomass Natural Gas CO + H2 Fisher Tropsch

5. Why Fischer-Tropsch liquids? • FTL are neat fuels with no sulfur content and no aromatics. • Can be used in various fuel blends with conventional diesel. • FTL can power today's engines at dramatically reduced emission levels without sacrificing performance. • Actually FTL improvises the engines efficiency and a cetane rating of 72 can be attained. • They can also be transported with todays infrastructure

6. Design Basis • Temp: 220-250 C • Feed Stock: CO+H2 • Targeted intermediates and products: Wax; Diesel and Jet oil • Reactor: Slurry Bubble Column Reactor • Catalyst: Precipitated Fe promoted with K

7. Most important FTL plants Geboren te Stellenbosch, Zuid-Afrika

8. Specifications • ASTM D 975 will be the target product of the FTL plant. • It has a cetane rating of 40 and no specific gravity specification since we are in the US.

9. Our mission Producing transportation liquids such as Diesel and Jet fuel. Increasing trend http://online.wsj.com/article/SB122660972377725619.html http://www.eia.gov/dnav/pet/hist/LeafHandler.ashx?n=pet&s=emd_epd2d_pte_nus_dpg&f=a

11. Commercial FTL Production Increasing trend http://www.airlines.org/Pages/Aviation-Fuels---Needs,-Challenges-and-Alternatives.aspx http://www.eia.gov/dnav/pet/hist/LeafHandler.ashx?n=PET&s=EER_EPJK_PF4_RGC_DPG&f=D

13. Environmental Review

14. Competing Processes Fe catalyst Increasing trend http://crtc.caer.uky.edu/ft6/ft_6.htm http://ir.sxicc.ac.cn/bitstream/0/2142/1/1358-1364.pdf

15. Competing Processes Cobalt catalyst

16. Competing Process • Longer deactivation time and longer life time due to greater resistance to re-oxidation by water • Provides a good and limited distribution of desirable hydrocarbons. • Promotes water formation and also methane formation which is what we don’t want. • Used at low operation temperatures. • Cost is expensive. • Works best on a 2:1 ratio. • Longer life time when compared to Co and better selectivity when promoted with K. • Provides a wide distribution of desirable; 58.3% diesel yield and is better for wax production. • Promotes the formation of CO2 and reduces methane formation by 30% therefore the water gas shift reaction. • Promotes up to 80% CO conversion. • Used at high and low operation temperatures. • Costs is much cheaper than Co. • Typical ratio of 3:1 but a ratio of 2:1 can be used. Co Catalyst Fe Catalyst

17. Why Fe catalyst? To reduce the CH4 production Cheaper than Cobalt Better life Catalysis Research Unit, Department of Chemical Engineering, University of Cape Town, Private Bag, Rondebosch 7701, South Africa

18. Fischer–Tropsch Refining, First Edition. Arno de Klerk

19. Competing Process • The distillate and residue fractions from HTFT syncrude can be hydroprocessed to produce an on-specification diesel fuel that meets both the minimum density and cetanenumber requirements[3], but since we are in the US we don’t need to meet the minimum density requirements. • There is a high carbon cost associated with the HTFT light hydrocarbons and the HTFT aqueous product[3]. • Gives a relatively lower cetane number of 47 • All of the scenarios highlighted the constrained nature of diesel fuel production, as well as the negative impact that it has on the blending flexibility of other fuel types. • No minimum density specification to be met which serves our criteria fully as we are in the US. • An acceptable cetane rating of 72 can be met. • Clearly LTFT is the way to go HTFT LTFT

20. Competing Processes http://alfin2300.blogspot.com/2010/05/award-winning-microchannel-fischer.html http://www.axens.net/document/19/conversion-of-syngas-to-diesel---article-ptq/english.html

21. Micro Channel Reactor (The future)

22. Ebullating Bed reactor/ H-star reactor

23. Competing Processes Slurry Bed Column reactor: PROS • Easy Isothermal operation in the reactor • Flexible when regenerating (oxidizing environment) / rejuvenating catalyst (reducing environment) • Lower modeling cost CONS • Causes to produce more light ends and lighter hydrocarbons because of short circuiting of the reaction Solution: Have 2 SBCR is series or increase the size of the reactor, so the production of light ends is reduced. Ebullating Bed reactor/ hydrotreator: • 2 or more cstrs in series • Larger catalysts are used • Catalyst can therefor withstand more agitation • Primarily used to obtain methanol from syngas • Eliminates the pressure drop problem Fixed Bed Column reactor: • This technology requires heavy work up for raw materials and provides a limited selectivity of transportation fuels and specialty chemicals Fluidized Bed Column reactor: • Simple scale up, provides easy separation of solids and liquids but almost impossible for easy catalyst rejuvenation and regeneration. PROS • Micro channel reactors are compact reactors that have channels with diameters in the millimeter range[2]. • they greatly intensify chemical reactions, enabling them to occur at rates 10 to 1000 times faster than in conventional systems.[2] • Excellent tool for small scale distribution. • Achieved a 70% conversion per single pass as compared to 50 % conversion pass of the conventional units. CONS • The tubes can get easily clogged • Catalyst and reactor costs are high • Loading and unloading the catalyst is a hassle Bed Column reactors Micro-Channel Reactor

24. Conceptual Process Block Flow Aqueous Waste water Catalyst Rejuvenation/Regeneration SBCR with Fe/k Catalyst C3-C10 Oligomerization 5000bpd LPG Jet fuel diesel Motor Gasoline C5-C10 Distillation unit C22+ > C23 Exhaustive Hydrocracker C11-C22 Syngas (2:1)

25. Estimated Mass Balance

26. Relevant Stoichiometry Syngas production : CH4 + H2O  CO + 3H2 -Delta_Hrx @298K = 206 kJ/mol Riedels number : Alpha: Wn/n = (1 − α)2αn−1 ; -Wn is the weight fraction of hydrocarbon molecules containing n carbon atoms. α is the chain growth probability or the probability that a molecule will continue reacting to form a longer chain.  -Alpha numbers above about 0.9 are, in general, representation of wax producing processes Alpha distribution LPG --C2-C4; Naptha-- C5-C8; Jet-- C9-C14; Diesel-- C14-C20; Wax-- C19 and so on

28. Riedels Value • The Riedels or the SN number helps in manipulation of the H2: CO ratio. • Since we need a 2:1 internal ratio, we can still accept a greater ratio and still correct the ratio through the RWGS CO2 produced. • CO2 consumed H2 and produces CO and the ratio comes down to 2.

29. Future Steps • The wastewater will be pretreated with caustic soda to lower the pH before being sent to the water treatment plant. • We can use the CO2 produced by other groups and produce CO • The Naptha produced may be sell/transferred to the gas treatment plant • The Methane build up (Tail gas) produced is going to be syngas plant as a feed stock or the CHP plant to produce energy thus can be used as fuel gas. • Upgrade the crude olefins and transfer to the MTO plant • Left over H2 and CO will be internally recycled to obtain high superficial velocity in the SBCR or can be sent back to the syngas plant • LPG would be transferred to the plant that is processing Natural Gas as NGL is Naptha

30. Bibliography • Department of Chemical Engineering, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, Netherlands • Faculty of Chemical Technology and Materials Science, Delft University of Technology, Julianalaan 136, 2628 BL Delft, Netherlands • Velocys, Inc., 7950 Corporate Blvd, Plain City, Ohio 43064, USA (Registered in the State of Delaware, USA). Velocys, Inc. is a subsidiary of Oxford Catalysts Group PLC • ExxonMobil Research and Engineering Company • Journal of Chemical technology and Biotechnology ,2001 society of chemical industry • Axens,2011 • Chevron Products Company, 2007 • Rentech Inc, 2013 • Stoichiometry, B I Bhatt • Applied Catalysis,Vol 186, oct 1999 • Fischer–Tropsch Refining, First Edition. Arno de Klerk. • FUNDAMENTALS OF INDUSTRIAL CATALYTIC PROCESSES, second edition • Fuel Processing Technology, Vol 64, May 2000

31. Thank you kindly! , Questions please?