SCANFINING TECHNOLOGY: A PROVEN OPTION FOR PRODUCING ULTRA-LOW SULFUR CLEAN GASOLINE Mohan Kalyanaraman Sean Smyth John Greeley Monica Pena LARTC 3rd Annual Meeting 9-10 April 2014 Cancun, Mexico
Agenda Drivers of Ultra-Low Sulfur Clean Gasoline Sulfur Challenge in Mogas pool Using Chemistry of Sulfur Molecules Configuration Alternatives SCANfining I Process SCANfining II Process ZEROMER TM Process SCANfining Catalyst Summary 2
Regulatory Concerns Have Forced Lower S in Gasoline Removal of sulfur improves catalytic converter performance & reduces emissions Sulfur Reduction increasingly mandated in countries around the world US EPA has proposed rule to lower gasoline S to 10 ppm as part of Tier 3 Refiners are looking to future proof their investment 3
Gasoline Pool and Sulfur Removal Challenge Reformate Hi Octane, Low S Straight Run Low Octane, Moderate S Alkylate Hi Octane, Low S FCC naphtha Hi Octane, Hi S FCC Naphtha is a major component of Mogas pool Challenge is to maintain the high Octane Olefins & remove the Sulfur 4
Options to Lower S in Gasoline in Current Refineries Increased severity in FCC pre-treat Increased H 2 consumption, decreased catalyst cycle length Use of Gasoline Sulfur Reduction additives in FCC Additional cost, low sulfur removal Post treatment of FCC Naphtha Required for ULS Gasoline For refiners with existing post treatment, increased severity may be required Investment to augment/ revamp existing post treating units can be profitable in a high Octane value environment 5
Molecular Understanding of FCC Naphtha 300 250 S (wppm) 200 150 100 Mercaptan sulfur Non mercaptan sulfur 50 0 0 20 40 60 80 wt% Olefins are distributed unevenly with Light Cat Naphtha having more olefins Intermediate Cat Naphtha, Heavy Cat Naphtha have lower Olefins but higher amount of Sulfur Mercaptan Sulfur is higher in the front end of FCC Naphtha 6
Processing Schemes for FCC Naphtha UNIT Design option based on Feed & Product Sulfur target, refiners preference, constraints For Ultra Low Sulfur Gasoline from high Sulfur streams, a combination of approaches may be required Revamps using change of catalyst, some post modification may be cost effective 7
SCANfining Process: Selective Cat Naphtha Hydrofining provides the highest value at lowest Capex SCANfining process utilizes proprietary catalyst and conditions targeted to: Maximize desulfurization to meet S specification below 10 ppmw Minimize olefin saturation/octane loss Minimize mercaptan recombination Fixed bed hydroprocessing with variety of configurations allow processing feedstocks with wide or narrow boiling range, high or low sulfur content Relatively small, low pressure reactors Conventional hydrotreating temperatures EMRE proprietary catalyst EMRE proprietary reactor internals extend cycle length Low hydrogen consumption No hydrocracking reactions that lead to RVP increase Retrofit easily into spare equipment such as semi-regen reformer, kerosene hydrotreater or naphtha hydrotreater 8
Large Base of Installed SCANfining Process Applications 43 ExxonMobil or Licensed SCANfining Units worldwide Over 1.3 Million BD Capacity SCANfining I and SCANfining II, many making 10 ppm S SCANfining I with Zeromer Cumulative SCANfining Unit Capacity, KBD 1400 1200 1000 ExxonMobil Licensee 800 600 400 200 0 2H02 & Earlier 1H03 2H03 1H04 2H04 Current 9
Sulfur Removal Chemistry Mercaptans R-SH Caustic Treat Hydrotreat R-S-S-R R-H + H 2 S Thiophenes Olefins R S Hydrotreat R-H + H 2 S Octane Loss R = R ' Hydrotreat R-R ' H-S-H + R = R Reversion R-SH Recombinant Mercaptans 10
Evolution of SCANfining Process: SCANfining I SCANfining I HDS Range:Feed S ~1500 to ~Product S 30 wppm Relatively low capital investment, retrofit capability For lower S feeds, 10 ppm S achievable; For higher S feeds, need additional treatments (e.g., mercaptan removal) 11
Mercaptans Limit SCANfining Process Selectivity SCANfining I Processing Full Range Cat Naphtha: Low S, High Olefins wppm Sulfur 140 120 100 80 60 Total Sulfur Non-Mercaptan Sulfur Mercaptan Sulfur 40 20 0 0 10 20 30 40 50 60 70 % Olefin Saturation Better olefin retention leads to higher mercaptan contribution to total S Reversion mercaptan levels governed by process conditions Alternative process designs control mercaptans content in product based on development of mercaptan reversion kinetics 12
Preferred Regions for SCANfining Process Options Technology Selection Depends on Feed Sulfur and Bromine Number For Ultra-Low Product Sulfur Targets ZEROMER Process SF-II break-even ZEROMER Process SF-I break-even Increasing Feed Sulfur, ppm ZEROMER SF-II (SF-1 with Mercaptan Conversion Preferred) SF-I Preferred Increasing Feed Bromine Number 13
Ultra-low Sulfur by Mercaptan Removal with Incremental Investment FCC Naphtha (Full Range or Fractionated) SCANfining I Process (For Near-Term Sulphur Needs) Small increase in capital vs. 1-Stage unit +10-15% increase for ZEROMER Process +20-25% increase for SCANFining II Process Add-Ons for Ultra-Low Sulfur SCANfining II Process ZEROMER Process Catalytic Destruction of Mercaptans 14
Robustness of Catalyst - 2-Stage Unit with High Feed Sulfur making 10 ppm Product Sulfur European 2-stage unit with high Feed Sulfur and 10 ppm product Sulfur Catalyst on stream for many years 15
EMRE has Developed Newer SCANfining Catalysts Proprietary RT-225 TM : proven Designed specifically for selective HDS of FCC naphtha Minimizes olefin saturation / octane loss Reliable, high selectivity, good activity maintenance Octane loss stays the same or improves as catalyst ages RT-225 Catalyst Proprietary RT-235 TM : proven Designed for selective HDS of FCC naphtha Higher Selectivity Higher activity Proven, Reliable in multiple units Robust, CO tolerant RT-235 Catalyst 16
RT-235 Octane Savings in Commercial Applications Match Pilot Runs Side by side tests of RT- 225 and RT-235 on light cat naphtha Engine tests on products showed expected octane savings Olefin Saturation (%) 20 15 10 5 RT-225 RT-235 Average of 25% Octane savings 0 75 80 85 90 95 100 HDS (%) 17 17
Summary Reducing Sulfur levels in Mogas requires a variety of approaches Understanding the Chemistry of FCC Naphthas is critical to designing post treat systems EMRE has wide experience base with variety of feeds and designing for high to low feed Sulfur 43 ExxonMobil or Licensed SCANfining Units worldwide Over 1.3 Million BD Capacity EMRE has continued research into refinement of process / catalyst configuration New generation of SCANfining catalyst further improves selectivity Proven cost effective approach to provide robust solution 18
Questions