16 April Hotel Le Meridien New Delhi Resid Upgrade and Sulfur Offerings
10 3 bbl oil equivalent Unlock the Value of Heavy Oil Heavy Oil Processing is Increasingly Important in the Refining Industry 20000 18000 16000 14000 12000 10000 8000 6000 4000 2000 0 2010 2035 Global Heavy Oil Daily Production Cost of feedstock makes up majority of total operation cost of a refinery $10+ per barrel price difference between light and heavy crude Soaring growth projected for heavy oil, oil sand, and asphalt production Diminished demand for heavy fuel oil 2
Sulfur, Wt% Max MARPOL Annex VI Rules for Heavy Oil Heavy Fuel Sulfur Reduction Has Been Set 5.0 4.0 3.0 2.0 Global ECA Heavy Fuel Sulfur limit is being reduced: 3.5% to 0.5% by January 1, 2020 Attempts to defer to 2025 have failed To meet the new specification, high sulfur resid is being displaced by ultra-low sulfur distillate material 1.0 0 2005 2010 2015 2020 2025 2030 Incentive to upgrade high sulfur residual is rising to $350 per ton or more 3
Option 1: Avoid Benzene Production Slurry Bed Hydrocracking Maximizes Light Product Yields 80-95% Light Product Yields 50-55% 65-70% GT-SACT 92-95% Delayed Coking Resid Catalytic Cracking Slurry Bed Hydrocracking 4
Heavy Oil Hydrocracking The Slurry Bed Reactor Outperforms Other Technologies Fixed Bed Reactor Ebullated Bed Reactor Slurry Bed Reactor Operating Temp, o C 370-420 400-450 430-460 Operating Pressure, MPag 10-20 15-21 10-30 LHSV, h -1 0.2-0.5 0.2-0.8 0.3-1.0 Feed Conversion, % 20-50 50-90 >90 Conradson Carbon Limitation, % <15% <25% None Carbon Residue Removal, % 50-70 60-80 70-90 Metals Limitation, wppm <150 <800 None Metals Removal, % 70-90 70-95 80-95 5
Slurry Bed Hydrocracker Slurry Bed Hydrofinisher Stripping Tower GT-SACT Process Overview Slurry Bed Hydrocracking Conventional Hydrocracking Dry Gas Recycled H 2 Offgas to Sulfur Recovery Quenching H 2 Hot High Separator H Cold High Separator Cold Low Separator Cold High Separator Offgas Purification Dry Gas/ LPG Heavy Oil Feed Mixer Catalyst H 2 Fired Heater Design eliminates errosion potential APRS Hot Low Separator Vacuum Distillation Tower Residue + Catalyst Fixed Bed Cracker Fractionator Naphtha Diesel VGO 6
GT-SACT Flow Dynamics 7
GT-SACT Technology Features Proprietary Multifunctional Catalyst In-house engineered with full flexibility Customized formula to meet different feed and product requirements Superior anti-coking, sulfur removal, cracking and hydrogenation 8
Slurry Bed Hydrocracker Slurry Bed Hydrofinisher GT-SACT Technology Features Slurry Bed Reactor Three-phase complete back-mixing Consistent temperature control Consistent catalyst distribution Adjustable catalyst concentration (5% to 30%) Hydrogenation saturation & hydrofinishing Hydrocracking with high temp 9
GT-SACT Technology Features Advanced Pressure Reduction System (APRS) Safely lets down high pressure reactor effluent conditions Velocity just downstream of pressure letdown >300 m/s APRS tolerates high-solid content (10-20%) with proprietary designs in: Metallurgy Coating Temperature control Catalyst size (5-200 µm) Catalyst formula 10
GT-SACT Technology Features Robust anti-plugging designs for long, stable operations Anti-plugging Valve Anti-plugging Heat Exchanger Anti-plugging High-pressure Pump Anti-plugging/coking Furnace 11
GT-SACT Commercial Unit 158 KTA Commercial Unit operational since Q1 2016 112
GT-SACT Commercial Unit Proven Performance Light Product Yields: 92-95 wt% Conversion Rate: 96-98 wt% Feed Unit Products 13
GT-SACT Commercial Unit Performance Parameters Feedstock Residual Feed Resid Hydrocracker Yields Wt.% IBP 445 o C C1-C4 3 4 5% 495 o C 20% 535 o C 50% 570 o C 95% 615 o C Con. Carbon 17% Density (at 20 o C) 1.0 kg/m 3 Viscosity (at 100 o C) 850 mm 2 /s Sulfur 1 2% Naphtha 14 18 Distillate 28 34 Gas Oil 40 46 Residue + Catalyst 2 4 Resid + Gas Oil Hydrocracker Yields Wt.% C1-C4 8 9 Naphtha (<5 ppm S) 24 26 Diesel (<2 ppm S) 67 68 Residue + Catalyst 2 4 14
GT-SACT Residue Feed from a Urals Type Crude Preliminary Yields and Utilities GT-SACT Residue Feedstock Residue VR FCC Slurry Percentage 80-100% 0-20% D-1160: IBP 376 o C 239 o C D-1160: 5% 491 o C 335 o C D-1160: 10% 515 o C 363 o C D-1160: 30% 559 o C 411 o C D-1160: FBP 562 o C 549 o C Con. Carbon 34.48% 14.33% Density (@ 15 o C) 1.06 g/cm 3 1.12 g/cm 3 Viscosity (@ 100 o C) 6504 cst 16.6 cst Sulfur 3.42% 1.96% LHSV 0.5 h -1 Hydrogen Addition 3.2% Catalyst Addition 1.0% Resid Cracker Yields Wt.% Off-Gas 6.5% LPG 1.5% Naphtha 11.0% Distillate 32.6% Gas Oil 46.6% Residue + Catalyst 6.0% Utilities Usage per ton Circulating Water 12 t/t Electricity 125 kwh/t 1.0 MPa Steam 0.11 t/t Fuel Gas 10.4 kg/t Instrument Air 1.6 Nm 3 /t Nitrogen 0.56 Nm 3 /t Hydrogen 358 Nm 3 /t Catalyst 0.01 t/t 15
GT-SACT Commercial Unit Operation Maintenance Report from Planned Inspection Minimal Erosion No Coking, No Plugging 16
Slurry Bed Hydrocracking Operability Slurry Bed Hydrocracking outperforms other technologies. It is critical to have long, stable operation. Technical Issues Coking in reactor None noted with GT-SACT Plugging in major equipment Clean and clear Erosions of valves and pipelines Proven operation with no failures GT-SACT offers excellent performance in every aspect of operation 17
GT-SACT Licenses GT-SACT is helping refiners to upgrade a wide-range of heavy feeds Licensees Henan Shitong Green Energy Slurry Feed Capacity Feedstock Status 1,000 KTA Coal Tar Q4 2018 Startup Daqing Lianyi 1,000 KTA Paraffinic VR Q4 2018 Startup Shanxi Xiaoyi 1,000 KTA High-temp Coal Tar Q4 2018 Startup CNPC 1,000 KTA Naphthenic Residue Oil Feasibility Study Ningbo Bohui 500 KTA Intermediate VR + FCC Slurry Engineering 18
A better way to deal with SWSG and incremental H2S H 2 S ThioSolv SWAATS Process (Sour Water Ammonia to Ammonium ThioSulfate) 19
GT-SWAATS Process Patented process owned by ThioSolv converts SWSG into ATS Diverts SWSG to unload the SRU by 3x reduces SRU revamp costs Uses the valuable ammonia instead of destroying it away Can also be used to treat tail gas (idling the TGTU) to further reduce sulfur processing costs -- Could also idle the Incinerator GT-SWAATS lowers the cost of sulfur processing: Process only has 16 pieces of equipment Low CAPEX plus OPEX is negative Positive economics Could avoid the TGTU and Incinerator for grassroots unit designs Designated as BACT by US EPA also reduces the H2S footprint Commercial deal includes guarantee off-take of the ATS 200
Factors that increase SRU Load Increasing in crude capacity Processing a larger percentage of higher-sulfur, lower priced crudes in the crude blend Hydrotreatingheavier and more refractory streams Increasing hydrotreatingseverity to meet tighter sulfur specs of some products. 211
Factors that result in relatively greater increases in NH 3 than of H 2 S Refinery crude blend has more higher-nitrogen crude. Process conditions that increase S removal toward 100% also increase HDN toward 95%. Heavier and cracked streams previously allowed as off-road or marine diesel products with higher S specs now have to be treated to lower S spec. These contain more refractory S species and more N than the lighter, straight run fractions. 222
Sour Water Stripper Gas Composition NH 3 dissolves in the HDS effluent wash water and dissolves about an equal volume of H 2 S, so SWSG contains about 1:1 N H 3:H 2 S. To prevent condensation of solid NH4HS, SWS outlet temperature has to be > 175⁰F, resulting in concentration of H 2 O vapor in SWSG > about 1/3 H 2 O molar. Higher outlet temperatures dilute the acid gas with more H 2 O vapor. 233
Claus Reaction Processing H 2 S Gas Flow H 2 S + O2 + N 2 ==> H O + N 2 2 + S 1 0.5 1.9 1 1.9 1 2.9 Claus pressure drop, and hence capacity, are determined by the gas flow rate through the unit. 244
Claus Reaction Processing SWSG Gas Flow H 2 S-eq Factor H 2 S + O 2 + N 2 ==> H 2 O + N 2 + S 1 0.5 1.9 1 1.9 1 2.9 1 NH 3 + O 2 + N 2 ==> H 2 O + N 2 1 0.75 2.8 1.5 3.3 4.8 1.7 H O ==> H O 2 2 1 1 1.0 0.3 Total 8.7 3.0 255
SWAATS Process Chemistry 266
ATS Product 60 wt% salts in aqueous solution Density = 11.2 lb/gal, S.G. = 1.34 Low toxicity No emission of H2S or precipitation of sulfur Nearly odorless NFPA placard 0, 0, 0 Principal use as an advantaged fertilizer blend 277
SWAATS Process 288
SWAATS for SWSG + TGT 299
SWAATS Improves SRU Operation Improves control of H2S/ SO2ratio improved sulfur recovery --reduce emissions less upsets to the TGTU --reduce emissions Reduces deactivation of Claus catalyst no NH3salt deposits less formation of soot in thermal reactor Reduces SRU OPEX (beyond no SWSG) no NH3salts and no soot longer Claus catalyst life less wear on thermal reactor refractory less tail gas lowertgtu + Incinerator Costs 30
SWAATS: Low Operator Attention Controlled closed-loop by in-line analyzers replaceable without shutdown. ph controls N/S ratio --import NH3 or S or export H2S O2 analyzer on combustion gas --feed-forward air control Density meter on liquid circulation --water addition System is buffered by large recirculation flow compared to net feed and product flows. System recovers from upset without intervention. 2 NH3 + SO2 + S + H2O (NH4) 2S2O3 31
SWAATS: Other Benefits Lowers SOXemissions. EPA set SWAATS as Best Available Control Technology (BACT) in a California Highly-toxic H2S is converted to innocuous ATS early in the process, reducing the chance of H2S release from leaks. Recovers a waste to replace on-purpose ammonia ATS improves plant utilization of N fertilizers, reduces loss of N as nitrate to ground water. Produces ATS fertilizer for national use and export. 332
SWAATS CAPEX for SWSG SWAATS can eliminate the need for additional Claus, TGTU, and Incinerator capacity CAPEX has been shown to be considerably less than the cost of the same H2S-equivalent capacityin a conventional SRU: SWAATS CAPEX is: 0.5 to 1.5 MM$ per TPD of S 30-40+% savings vs. SRU/TGTU on TPD of S basis H2S-eq basis: SWSG load takes about 3x AAG load H2S-eq basis: CAPEX savings can be large 33
Summary / Conclusions More Hydrotreating, Capacity and Severity will continue to grow globally yielding more NH3 Destructing NH3 is tough and costly, but necessary Making ATS with the SWAATS Process is a safer, more environmentally friendly, and robust option, with advantaged economics SWAATS can idle the TGTU (even Incin. too) SWAATS can be an advantaged grass-roots sulfur processing option as well. 34
GTC Offerings in Resid Processing Summary GT-SACT is an advantaged solution for MARPOL Slurry hydrocracking yields high resid conversion to light products GT-SACT is the lowest cost slurry hydrocracking option with robust designs and proven sustainable performance Customized catalyst formulations tailored to feedstocks and products Strong expertise on high-solids flow handling GT-SWAATS is the best way to process SWSG and unload the SRU Needed for slurry hydrocracking, residual fuel desulfurization, etc. 35