Resid Upgrade and Sulfur Offerings

16 April Hotel Le Meridien New DelhiGTC Technology Day

GTC Technology Day

Unlock the Value of Heavy Oil

• 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

Heavy Oil Processing is Increasingly Important in the Refining Industry

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Global Heavy Oil Daily Production

2010

2035

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MARPOL Annex VI Rules for Heavy Oil

• 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

• Incentive to upgrade high sulfur residual is rising to $350 per ton or more

Heavy Fuel Sulfur Reduction Has Been Set

2005 2010 2015 2020 2025 2030

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Option 1: Avoid Benzene Production

Slurry Bed Hydrocracking Maximizes Light Product Yields

GT-SACT℠92-95%

Light

Product

Yields

50-55%

65-70%

80-95%

Delayed

Coking

Resid Catalytic

Cracking

Slurry Bed

Hydrocracking

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Heavy Oil Hydrocracking

Fixed Bed

Reactor

Ebullated Bed

Reactor

Slurry Bed

Reactor

Operating Temp, oC 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

The Slurry Bed Reactor Outperforms Other Technologies

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GT-SACT℠ Process Overview

H

Slu

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Hyd

roc

rac

ke

r

Slu

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Hyd

rofi

nis

he

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Str

ipp

ing

To

wer

Offgas

Purification

Heavy Oil

Feed

Catalyst

Mixer

H2

Qu

en

ch

ing H

2

Hot High

Separator

Recycled H2

Cold High

Separator

Fired

Heater

Design eliminates

errosion potential

Hot Low

Separator

Vacuum

Distillation

Tower

Cold Low

Separator

Residue +

Catalyst

Cold High

Separator

FractionatorVGO

Diesel

Naphtha

Dry Gas/

LPG

Dry Gas

Offgas to

Sulfur Recovery

Fixed Bed

Cracker

Slurry Bed Hydrocracking Conventional Hydrocracking

APRS

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GT-SACT℠ Flow Dynamics

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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

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GT-SACT℠ Technology Features

Slurry Bed Reactor

• Three-phase complete back-mixing

• Consistent temperature control

• Consistent catalyst distribution

• Adjustable catalyst concentration (5% to 30%)

Slu

rry B

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Hydro

cra

cker

Slu

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ed H

ydro

finis

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Hydrogenation

saturation &

hydrofinishing

Hydrocracking

with high temp

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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

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GT-SACT℠ Technology Features

Anti-pluggingHeat Exchanger

Anti-plugging

Valve

Anti-plugging

High-pressure PumpAnti-plugging/coking

Furnace

Robust anti-plugging designs for long, stable operations

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GT-SACT℠ Commercial Unit

158 KTA Commercial Unit operational since Q1 2016

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GT-SACT℠ Commercial Unit Proven Performance

Light Product Yields: 92-95 wt%

Conversion Rate: 96-98 wt%

Feed Unit Products

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GT-SACT℠ Commercial Unit Performance Parameters

Feedstock Residual Feed

IBP 445 oC

5% 495 oC

20% 535 oC

50% 570 oC

95% 615 oC

Con. Carbon 17%

Density (at 20 oC) 1.0 kg/m3

Viscosity (at 100 oC) 850 mm2/s

Sulfur 1 – 2%

Resid Hydrocracker Yields Wt.%

C1-C4 3 – 4

Naphtha 14 – 18

Distillate 28 – 34

Gas Oil 40 – 46

Residue + Catalyst 2 – 4

Resid + Gas Oil

Hydrocracker YieldsWt.%

C1-C4 8 – 9

Naphtha (<5 ppm S) 24 – 26

Diesel (<2 ppm S) 67 – 68

Residue + Catalyst 2 – 4

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GT-SACT℠ Residue Feed from a Urals Type CrudePreliminary Yields and Utilities

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 Nm3/t

Nitrogen 0.56 Nm3/t

Hydrogen 358 Nm3/t

Catalyst 0.01 t/t

GT-SACT℠ Residue Feedstock

Residue VR FCC Slurry

Percentage 80-100% 0-20%

D-1160: IBP 376 oC 239 oC

D-1160: 5% 491 oC 335 oC

D-1160: 10% 515 oC 363 oC

D-1160: 30% 559 oC 411 oC

D-1160: FBP 562 oC 549 oC

Con. Carbon 34.48% 14.33%

Density (@ 15 oC) 1.06 g/cm3 1.12 g/cm3

Viscosity (@ 100 oC) 6504 cSt 16.6 cSt

Sulfur 3.42% 1.96%

LHSV 0.5 h-1

Hydrogen Addition 3.2%

Catalyst Addition 1.0%

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GT-SACT℠ Commercial Unit Operation

Maintenance Report from Planned Inspection

No Coking, No PluggingMinimal Erosion

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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

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GT-SACT℠ Licenses

GT-SACT℠ is helping refiners to upgrade a wide-range of heavy feeds

LicenseesSlurry Feed

CapacityFeedstock Status

Henan ShitongGreen Energy

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 KTANaphthenicResidue Oil

Feasibility Study

Ningbo Bohui 500 KTAIntermediate

VR + FCC SlurryEngineering

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A better way to deal with SWSG and incremental H2S

H2S ThioSolv SWAATS Process

(Sour Water Ammonia to Ammonium ThioSulfate)

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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

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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.

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Factors that result in relatively greater increases in NH3 than of H2S

• 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.

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Sour Water Stripper Gas Composition

• NH3 dissolves in the HDS effluent wash water and dissolves about an equal volume of H2S, so SWSG contains about 1:1 NH3:H2S.

• To prevent condensation of solid NH4HS, SWS outlet temperature has to be > 175⁰F, resulting in concentration of H2O vapor in SWSG > about 1/3 H2O molar. Higher outlet temperatures dilute the acid gas with more H2O vapor.

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Claus Reaction Processing H2S

Gas Flow

H2S + O

2 + N

2 ==> H

2O + N

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.

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Claus Reaction Processing SWSG

Gas H2S-eq

Flow Factor

H2S + O

2 + N

2 ==> H

2O + N

2 + S

1 0.5 1.9 1 1.9 1 2.9 1

NH3 + O

2 + N

2 ==> H

2O + N

2

1 0.75 2.8 1.5 3.3 4.8 1.7

H2O ==> H

2O

1 1 1.0 0.3

Total 8.7 3.0

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SWAATS Process Chemistry

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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

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SWAATS Process

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SWAATS for SWSG + TGT

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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

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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

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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.

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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

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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.

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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.

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