M-oxy Coupling By: Muhammad Ali, Don Dennert, Jesse Hinshaw, Spencer Moul

Project Definition Utilize excess natural gas into useful higher hydrocarbon Design a Gulf-Coast based plant of world wide scale Create a 99% chemical grade purity ethylene product Create a process with feed streams of air and natural gas

Ethylene One of the largest commodity chemicals in the world. Worldwide production exceeds all other organic compounds. Uses Polymerization: Polyethylene Oxidation: Ethylene oxide Alkylation: Polystyrene Halogenation and Hydrohalogenation: Polyvinyl chloride

What is Methane Oxidative Coupling(MOC) ? Reaction of 2 methane molecules to create a higher hydrocarbon /

Why use MOC? One step reaction for direct conversion of C1’s to C2’s Uses natural gas Petroleum independent Ethylene demand is high and rising by 3.5% annually

Business Opportunity Primary component of natural gas: methane Natural gas is a very attractive feedstock Estimated reserves: 6,000 trillion ft 3 Low price in the US

Plant Location-Houston, TX Reasons for plant location No state corporate tax Concentration of major incoming and outgoing pipelines International export ability due to ocean proximity Proximity to Texas fracking operations

Modeling Focus on ethylene purity of 99% 6% of US market Carbon dioxide, carbon monoxide, water, and hydrogen Recycle stream contains non-reacted methane 2:1 oxygen to methane ratio to increase selectivity of our reaction Oxygen is completely consumed

Overall Flowsheet Reactor Air Separation Unit (ASU) Scrubbers Cryogenic Tower AirO2O2 Methane Ethylene CO 2, CO, H 2 De-Methanizer Recycle Ethane Mixture Flash Column H2OH2O

Reactor section Reactor Information Operates at 750˚C and 4.1 bar Stoichiometric reactions Catalyst La 2 O 3 /CaO Need 79% conversion for solely ethylene plant Reactor 2 2H 2 + O 2 = 2H 2 O Reactor 1 2CH 4 = C 2 H 4 + 2H 2 CH 4 + O 2 = CO 2 + 2H 2 2CH 4 = C 2 H 6 + H 2 CH 4 + 1/2 O 2 = CO + 2H 2 Reactants Products

Scrubbers 12 M kg/hr of CO removed pressure swing adsorption using an activated carbon based catalyst 150 M kg/hr of carbon dioxide is taken out MEA absorption. 6 M kg/hr of hydrogen removed using a Prism Unit by Lunde COCO 2 H2H2

De-Methanizer and Ethylene Separation Towers De-Methanizer Recycle is 99.8% methane Recycle rate is 130 Mkg/hr Bottoms rate is 40 Mkg/hr Ethylene Separation Tower Ethylene is 99% pure 36 Mkg/hr ethylene produced By product mixture is a mixture of ethylene and ethane

Process Alternatives Methanol Unit Use of syngas to create methanol Raw By-products Will market by-products if methanol unit is not feasible or not as profitable.

Economic Analysis Feedstock Estimate: Natural Gas (Methane) 108 Mkg/hr $4.88 per thousand cubic feet Methane is 28 M$/hr Oxygen 99% from air separation unit 237 Mkg/hr Utilities are 0.8 M$/hr Total Feed Cost: 29 M$/hr

Product Economics Product Estimate: 1.4 M$/metric ton ethylene 50 M$/hr from ethylene Product – Feedstock: 21 M$/hr

By-Products Varies based on CO/H vs CH 3 OH Must take into consideration which products will be more easily marketed Without Methanol ($MM/yr)Methanol ($MM/yr) CO CO200 H2H CH 3 OH045 Total

Equipment Breakdown and Cash Flow Analysis EquipmentCost Without Methanol (MM$) Cost Using Methanol Plant (MM$) Reactor 0.5 Catalyst 0.3 Compressors 5061 Heat Exchangers Towers and Trays 4.0 Separators 179 ASU 175 ISBL Total ISBL Installed OSBL Installed

Economics Without Methanol PlantWith Methanol Plant NPV MMM$9.8 MMM$ NPV MMM$1.7 MMM$ IRR 21%19% PBP (Approx) (yrs) 5.6 MARR 0.12 Therefore, we have chosen to not make the methanol plant

Conclusion/Future Work At the current state of research MOC plant is not feasible. Find a better catalyst New technology allowing oxygen evolution reaction of CO 2 to methanol and ethylene Membrane reactors and separators

Acknowledgments Dr. Joseph Holles – Our project advisor Dr. David Bell – Instructor/Assisted with certain difficulties Professor John Myers – 1 st Semester instructor/assigned project/helped with initial project difficulties

References 1. Weinberger, Sam, Erik Scher, and Rahul Iyer. Natural Gas to Ethylene in One Step. Tech. Houston: AIChE, Print. 2. Hutchings, G. J., Scurrell, M. S., Woodhouse, J. R.. Oxidative Coupling of Methane using Oxide Catalysts. South Africa: Chem. Soc. Rev., 18, , Salerno-Paredes,. Optimal Synthesis of Downstream Processes using the Oxidative Coupling of Methane Reaction. Berlin: Universität Berlin Masters Thesis, Print. 4. Jack Peckham. Siluria Q&A on Methane Oxidative-Coupling Scheme. Houston: ProQuest, Print. 5. Martin, G. A., Mirodatos, C.. Surface Chemistry in the oxidative coupling of methane. Cédex, France: Fuel Processing Technology, 42, , Lunsford, J. H. The Catalytic Oxidative Coupling of Methane. Weinheim: Angew. Chem Int. Ed. Engl, 34, , Lomonosov, V. I, Usmanov, T. R., Sinev, M. Y., Bychkov, V. Y. Ethylene Oxidation under Conditions of the Oxidative Coupling of Methane. Kinetics and Catalysis Vol. 55, No. 4, ; Ras, E. J., Gomex-Quero, S. Oxidative Coupling of Methane in Small Scale Parallel Reactors. Top Catal, 57, , "FAQs - Consumer Purchases." Dry Ice FAQs. Web. 24 Nov Tye, C. T., Mohamed, A. R., Bhatia, S. Modeling of catalytic reactor for oxidative coupling of methane using La 2 O 3 /CaO catalyst. Chemical Engineering Journal 87, 49-59, Yaghobi, N. The role of gas hourly space velocity and feed composition for catalytic oxidative coupling of methane: Experimental study. Journal of King Sand University-Engineering Sciences 25, 1-10, Schweer, D., Mleczko, L., Baerns, M. OCM in a fixed-bed reactor: limits and perspectives. Catalysis Today 21, , Ma, Jinghong, Li Li, Jin Ren, and Ruifeng Li. "CO Adsorption on Activated Carbon-supported Cu-based Adsorbent Prepared by a Facile Route." Separation and Purification Technology (2010): Print.

Questions

Hydrogen Membrane Separation Unit

CO2 Separation Unit Developed by Hitachi

CO Adsorption Activated Carbon impregnated with Copper (II) Chloride and Copper (II) Carboxylate