On Purpose Propylene Production UOP

“On-Purpose” Propylene Technology DevelopmentsTim Foley UOP LLC © 2005 UOP LLC. All rights reserved. UOP 4288K-1 “On-Purpose” Propylene: Propylene supply/demand overview Alternatives to steam cracking for propylene production – Refinery FCC – Propane Dehydrogenation – Methanol to Olefins – Olefin Conversion Selection of a propylene process C3H6 UOP 4288K-2 35 2004 2006 2008 2010 2012 Year Data Source: CMAI 2005 UOP 4399A-4 Demand 0.62 Demand ~ 18 M MTA Sup ply from stea m cr acke rs 0.C3=/C2= Ratios Worldwide 0.59 .40 0.64 MT Propylene / MT Ethylene Steam Cracker Production 0.54 2014 0.36 0.45 0. Propylene Supply & Demand Polymer Grade & Chemical Grade 100 Million MTA se po r Pu 2004 Supply Steam Cracker ~ 67% 90 80 70 ta To d On n er ma th e O lD Refinery Steam Crackers Dehydro Others Current Capacity 60 2004 2006 2008 2010 2012 2014 Year Substantially more propylene will have Substantially more propylene will have to come from on-purpose technologies to come from on-purpose technologies UOP 4399A-2 Source: CMAI 38% Refinery . Methanol Mixed C4= to C8= UOP 4399A-5 . Coal.On-Purpose Propylene Technologies VGO. ATM Resid Propane High-Severity FCC High-Severity TM PetroFCCTM Process TM OleflexTM Process MTO Olefin Cracking Natural Gas. ATM Resid Propane High-Severity FCC High-Severity TM PetroFCCTM Process TM OleflexTM Process MTO Olefin Cracking Natural Gas. Coal.On-Purpose Propylene Technologies VGO. Methanol Mixed C4= to C8= UOP 4399A-6 . Propylene from Refineries Crude Column C4 and Lighter Straight Run Gasoline Kerosene AGO Crude Oil Downstream Processing Gasoline Diesel PRU Propylene Fuel Gas LPG FCC VGO Vacuum Column Vacuum Residue Heavy Fuel Oil UOP 4288K-4 . Gasoline 3 .Propylene from FCC tion duc Pro lene opy High-Severity g Pr n Enhanced Propylene 5 – 7 wt% C3= Gasoline FCC 10 -16 wt% C2= C3= Gasoline Propylene Yield PetroFCC 20 + wt% C2= C3= Aromatics easi Incr Max.5 wt% Gasoline Unit Design and Operation UOP 4399A-7 . High Severity FCC A Flexible Process Steps to increase propylene Increase riser temperature Use low H-transfer catalyst Use shape selective additive Use new reactor technology – RxCatTM Designed with the flexibility to operate Designed with the flexibility to operate in aapropylene or gasoline mode in propylene or gasoline mode UOP 4399A-8 . What is the PetroFCC Process? RxCat and PetroFCC Benefits: Enhanced catalytic cracking – Increased propylene yield Reduced thermal cracking – Decreased dry gas yield Catalyst selection flexibility – Choice of catalyst supply – Optimized for feedstock and product objectives RxCat Technology UOP 4399A-11 . 5 19 14 Naphtha 28 14 7 5 Aromatics BTX 18 Distillate Fuel Oil Coke 9.5 5 5.Typical PetroFCC Process Yield.5 UOP 4399A-12 .5 11 C2C3’s C4’s C3= 24 C4= 53. wt-% (VGO Feed) Traditional FCC PetroFCC Process C2= 9 Light Olefins 6 22 3 6. Is Integration an Objective? Other Feeds Olefin OCP Cracking Olefins Recovery Gas Con Light gases Ethylene Propylene Mixed C4’s Gas Oil Aromatic Naphtha SulfolaneTM Process SulfolaneTM Process Fractionation Fractionation Process Process TatorayTM TatorayTM Process Process IsomarTM IsomarTM Process Process ParexTM ParexTM Process Process Benzene p-Xylene UOP 4399A-27 . On-Purpose Propylene Technologies VGO. Methanol Mixed C4= to C8= UOP 4399A-13 . Coal. ATM Resid Propane High-Severity FCC PetroFCCTM Process OleflexTM Process MTO Olefin Cracking Natural Gas. What is Propane Dehydrogenation (PDH)? On-purpose production of propylene from propane Produces propylene and hydrogen Catalyst Propane −Δ T C3H8 Propylene & Hydrogen C3H6 & H2 UOP 4354J-12 . C3 Oleflex Process Net Gas Propane H2 C2 Deethanizer Propylene Oleflex SHP Propane Feed C4+ Six operating units with capacities ranging from 100.000 MTA propylene 1.P Splitter .25 M MTA operating capacity 40 plus plant years of operating experience Larger unit capacities in design UOP 4399A-15 Depropanizer P .000 to 350. ATM Resid Propane High-Severity FCC PetroFCCTM Process OleflexTM Process MTO Olefin Cracking Natural Gas. Methanol Mixed C4= to C8= UOP 4399A-16 .On-Purpose Propylene Technologies VGO. Coal. What is MTO? Gas to Olefins (GTO) Natural Gas Synthesis Gas Production Methanol Methanol Synthesis MTO Ethylene & Propylene Coal Coal to Olefins (CTO) UOP 4399A-17 . UOP/HYDRO MTO Process Reactor Regenerator Quench Tower Regen Gas High selectivity to light olefins Ethylene & Propylene Oxygenate Recovery Light Olefin Recovery – Minimizes feedstock costs – High value product mix with little C5+ co-product – Little hydrogen & methane Air Water Flexibility of C2=/C3= product ratios Water Methanol UOP 4399a-18 . Why MTO? 100% 80% 60% 40% 20% Naphtha Cracker MTO ge nta a Adv O MT Product values generally increase with crude oil prices Naphtha cracker feedstock prices are closely linked to crude oil prices – High feedstock costs offset most of the economic benefits as product values increase ROI MTO feedstock is from dedicated sources using cost advantaged feedstock – Fixed price not tied to crude oil – Can support increased methanol prices when olefin values are higher (high crude oil prices) MTO is competitive with steam crackers when crude oil is above $16 per barrel – Huge advantage when crude oil prices are high UOP 4399A-19 0% 10 20 30 40 50 Crude Oil Benchmark. $/BBL . ATM Resid Propane High-Severity FCC PetroFCCTM Process OleflexTM Process MTO Olefin Cracking Natural Gas.On-Purpose Propylene Technologies VGO. Coal. Methanol Mixed C4= to C8= UOP 4399A-20 . What is Olefin Cracking? Production of propylene and ethylene from C4 to C8 olefins C4 to C8 Olefins C4H8 to C8H16 Catalyst Olefin Cracking −Δ T Ethylene & Propylene C2H4 & C3H6 UOP 4399A-21 . ATOFINA/UOP Olefin Cracking Process Naphtha Product Recovery & Product Purification Recovery & Applications C2= C3= Fuel Gas Pygas Gas Oils MeOH MTO C2= C3= Light Olefins Furnace Furnace Refineries FCC Gasoline Cycle Oils C2= C3= C4-C5 Olefins C4/C5 C5/C6 Paraffin-Rich Light Olefins FCC Olefin Cracking C4-C8 Olefin Cracking C4+ Naphtha Crackers Olefin Olefin Recovery LPG Light Olefins MTO Plants Olefin Cracking UOP 4399A-22 Olefin Cracking can be integrated Olefin Cracking can be integrated with aavariety of processes with variety of processes . Selection of Propylene Options Key Issues Feedstock – Cost – Flexibility Yields – Co-products – Integration Capacity – Incremental – New complex Capital UOP 4399A-23 . Cracking + OC Nap.What Products are Desired? MTO + OC MTO + OC MTO MTO Propane Dehydro Propane Dehydro PetroFCC + ARU +OC PetroFCC + ARU +OC FCC FCC Nap. Cracking + OC Naphtha Cracking Naphtha Cracking 0% 0% 20% 20% 40% 40% 60% 60% 80% 100% 80% 100% Issues to Consider Propylene yield Co-products Integration Product Mix Product Mix Propylene Propylene Gasoline Gasoline Ethylene Ethylene Cycle Oil Cycle Oil BTX BTX Slurry Oil Slurry Oil Butadiene Butadiene Light Ends Light Ends Mixed C4s Mixed C4s UOP 4399A-24 . How Much Propylene Is Desired? Propylene Capacity. kMTA 600 500 400 300 200 100 0 Cracker Furnaces FCC revamp PRU Oleflex Olefin Cracking MTO High Severity FCC Naphtha Cracker Oleflex MTO PetroFCC Olefin Cracking Incremental (<200 kMTA) – Revamp existing assets Intermediate (100 – 300 kMTA) – Integrate new units with existing assets World scale (>250 kMTA) New Unit Grass Roots Integrations – New complexes – Integration Revamps UOP 4399A-25 . FCC/PetroFCC Naphtha Cracker 0 200 400 600 800 1000 BTX MeOH Low capital (<$200 M) – – – FCC PRU FCC Revamp OC Intermediate capital (<$500 M) – Oleflex – PetroFCC – MTO Large capital (>$500 M) – GTO – PetroFCC/ARU/OC Millions US$ Excludes Olefin Derivative Units UOP 4399A-26 . FCC PRU Add.How Much Capital is Available? MTO / GTO Olefin Cracking Propane Dehydro. Methanol Mixed C4= to C8= UOP 4399A-28 . Coal. ATM Resid High-Severity FCC & PetroFCC Process Proximity to C3= users C3= & gasoline flexibility Refinery / PC integration Propane OleflexTM Process Propylene/Propane price differential Simple back-integration – one feed – one product MTO Monetize natural gas or coal High yields of C3= & C2= Competitive with steam cracking Olefin Cracking Feedstock flexibility Integration flexibility Economic over a broad range of C3= / C2= prices Natural Gas.On-Purpose Propylene Technologies Summary VGO. Conclusions New options must be considered to meet future propylene demand Several options available for increasing propylene Each producer must consider key selection factors UOP can help! UOP 4399A-29 . Jim Andersen – UOP Henning R Nilsen.Acknowledgments: Bipin Vora. Bob James. Joe Gregor. Mark Houdek. Steinar Kvisle – Norsk Hydro Walter Vermieren – Total Petrochemicals UOP 4288K-27 . Chuck Hemler.