Dry Reforming of Methane by The Reformation Hussain Alsukairi Alexander Fox Sean Kasprisin Timothy Poppert Nykyta Olegovich Vovk

AGENDA Problem Statement Business Opportunities Alternatives Assumptions Process Flowsheets Economic Evaluation Future Work Conclusions

Project Statement The goal of this project is to design a plant for the dry reforming of methane to syngas and subsequent products. Feed to Syngas: CH4 + CO2 → 2CO + 2H2 Syngas to Acetic Acid: 2CO + 2H2 → CH3COOH Refined Objective: Determine R&D needed to further develop the Process

Business Opportunities Many Opportunities Pertaining to Syngas Location: Green River Basin, Wyoming Broader Impact: Industrial use of CO2 as a feed instead of byproduct – Further R&D needed Safety issues with temperatures and pressures Contemporary Issues: Catalyst conversion rates and longevity Current Emission Issues/possible benefits with more R&D

Business Opportunities: Products Applications: Acetic Acid 25 c/lb Vinyl Acetate Monomer Acetate Esters Food Industry Propionic Acid 72 c/lb Preservative for animal feed and grains Herbicides Flavoring agent

Alternatives Steam Reforming of Methane Formation of syngas: CH4 + H2O → CO + 3H2 Water-gas shift for ratio adjustments: CO + H2O → CO2 + H2 Main Differences: Economic and Environmental Acetic Acid through Methanol Syngas to Methanol: CO + 2 H2 ↔ CH3OH Methanol to Acetic Acid: CH3OH+CO→CH3COOH

Assumptions 35% conversion for Syngas Reactor Isentropic Compressors (72% efficiency) Linear  Price Scaling for Compressors  2 year catalyst lifespan Pure Methane burn stream Acetic Acid Reactor at 90% of equilibrium  Linear scaling of Products for economic sensitivity

Dry Methane Reforming Flow Sheet

DMR Catalyst Rh.1Ni10/BN or Rh.1Ni/-Al2O3 : Around $500,000 per year Potential issues: CH4 Deposition:     CH4     C(s) + 2H2 Boudouard reaction:   2CO   C(s) + CO2 BN experiences less carbon deposition

Direct Acetic Acid Flow Sheet

Acetic acid catalyst Ru(acac)3-CoI2 catalyst precursor on quaternary salt Bu4PBr: $467,000 per year Potential issues:  482 bar 18 hour residence time

Economic Evaluation: Feed Cost Capital Cost, and revenue CO2 costs $0 CH4 costs $375,000/yr Equipment Cost Compressors $29,915,000 Heat Exchangers $321,250 Reactors $22,634,790 Towers & Trays $802,850 The Catalysts Costs $4,705,592 Utilities Cost $11,824,196 Total Capital Cost $470,559,152 Revenue Acetic Acid sold $6.3 million/yr or roughly 25 million lbs/yr Propionic Acid sold $40 million/yr or roughly 55 million lbs/yr

Economic Evaluation: NPV & IRR Our Current IRR and NPV are negative. NPV12: -$675.34 million IRR: -11% Largely due to Electricity $11.26 million/yr Cooling Water $56 thousand/yr Capital cost of $470 million To achieve a positive IRR, Research should be put towards reducing the pressure needed for the catalyst to work in the Acetic Acid reactor, and into increasing the yield from the DMR. If the price of Acetic acid, or Propionic Acid increased by 50% the process becomes more economically viable.

Economic Sensitivity Analysis: Tornado Plots

Future Work Refining and selling byproducts Recycle streams from Burn Stream Further products from Ethyl acetate Develop an Acetic Acid Catalyst to operate at lower pressures Develop a DMR Catalyst with higher yield Carbon Capture from the Burn Stream Possible water cooling integration

Conclusions Physically possible process Not economically viable unless: 80% Syngas Gas Conversion 150% current Propionic and Acetic Acids prices With all current assumptions holding true Catalyst development for lower pressures is needed for this to proceed Increased syngas conversion