IsoTherming® Hydroprocessing Technology International Conference on Refining Challenges & Way Forward – Technologies for Improved Product Quality April,17, 2012 at New Delhi, India
Ravi Srinivas J
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydro cracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
DuPont Sustainable Solutions Strategic Businesses and Offerings
Safety Resources
Sustainable Operations
Training Solutions powered by
Clean Technologies
Proven consulting methodologies, expertise and best practices in employee, contractor and process safety management to help transform workplace culture, develop employee skills, reduce incidents and injuries, and improve operational performance
Real-world experience and approaches proven in DuPont facilities to help improve energy efficiency, asset productivity and reliability, and capital effectiveness, and reduce environmental footprint, leading to a sustainable return on operations and assets
Blended learning solutions that integrate eLearning technologies, instructor-led courses, and traditional media tools to help develop employee skills, reinforce desired behaviors and, sustain the transfer of learning
Best-in-class technologies, equipment and services combined with strong technical and engineering capabilities, and solution design to help improve productivity, reduce air emissions and produce cleaner fuels
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DuPont Sustainable Solutions: Clean Technologies A global leader in integrated Clean Air and Clean Fuel sustainability solutions through best-in-class technologies, equipment and service offerings to improve productivity, reduce air emissions and produce cleaner fuels Alkylation
Hydroprocessing
Global Engineered Solutions
Air Pollution Control
Sulfuric Acid
IsoTherming® STRATCO® Technology and proprietary equipment for refiners to produce alkylate for blending into clean gasoline
Hydroprocessing Technology Technology and proprietary equipment for refiners to hydrotreat middle distillates to reduce sulfur content
GES
BELCO®
Comprehensive products and services for sulfuric acid alkylation units, sulfuric acid plants, as well as sulfuric acid storage, handling and transfer systems
Technology and proprietary equipment for scrubbing refinery emissions of SOx, NOx and particulates
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MECS® Market leader in sulphuric acid production & technology with 1000 client references. Became part of DuPont on 1st January 2011
Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydrocracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
IsoTherming® History IsoTherming® developed by Process Dynamics – technology development company based in Fayetteville, AR, U.S.A. First commercial unit: Diesel Hydrotreater Unit revamp in April 2003 for USA ULSD Sulfur (< 10 ppmwt) DuPont acquired IsoTherming® Clean Fuel Technology in 2007. Licensed by DuPont Sustainable Solutions Eighteen (18) Licenses 8 Grassroots DHT & LCO HT Units (Includes < 100 ppm S Diesel) 4 Revamp DHT Units (Includes < 10 ppm S Diesel) 2 Grassroots Gas Oil Mild Hydrocracker Units 1 Revamp Gas Oil Hydrotreater Unit 3 Grassroots LCO Mild Hydrocracker Unit
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
IsoTherming® Commercial Operation Country
Capacity (BPSD)
Description
Date
China
8000
LCO Mild Hydrocracker - Grassroots
Jun-2011
Midwest, USA
55000
VGO Hydrotreater - Revamp
Dec-2010
Holly Corp, Artesia, NM, USA
30000
VGO Mild Hydrocracker - Grassroots
Jan-2009
Holly Corp, Wood X Utah, USA
15000
VGO Mild Hydrocracker - Grassroots
Dec-2008
Western-Yorktown, VA, USA
12000
ULSD Hydrotreater - Grassroots
Apr-2006
Western-Ciniza, NM, USA
5000
ULSD Hydrotreater - Revamp
Mar-2006
Western-Ciniza, NM, USA
3800
ULSD Hydrotreater – Revamp
Apr-2003
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IsoTherming® Current Project Status Country
Capacity (BPSD)
Description
Status
India
50,000
ULSD Hydrotreater – Revamp (S < 10 PPM)
Detailed Design
China
12,500
Diesel Hydrotreater – Grassroots (S < 50 PPM)
Detailed Design
China
6,000
LCO Mild Hydrocracker – Grassroots (∆ d = 80)
Detailed Design
China
6,000
LCO Mild Hydrocracker – Grassroots (∆ d = 80)
Detailed Design
Russia
2,250
ULSD Hydrotreater – Grassroots (S < 10 PPM)
Detailed Design
China
20,000
Hy. Dist. Hydrotreater – Grassroots (S < 150 PPM)
Pre-commissioning
USA
10,000
ULSD Hydrotreater – Grassroots (S < 10 PPM)
Proj. On Hold
China
78,000
ULSD Hydrotreater – Grassroots (S < 40 PPM)
Detailed Design
China
6,000
LCO Hydrotreater – Grassroots (S < 350 PPM)
Pre-commissioning
China
6,000
LCO Hydrotreater – Grassroots (S < 350 PPM)
Pre-commissioning
USA
46,000
ULSD Hydrotreater – Revamp (S < 10 PPM)
Proj. On Hold
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Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydrocracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
IsoTherming® Overview This is a step-change versus standard (trickle bed) technology for Hydrotreating :
Commercially Available Catalysts Lower Capital Investment Lower Cost Revamp Lower Operating Expense Operating Flexibility Ultra low sulphur and nitrogen Increased Liquid Yield (Less Cracking)
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IsoTherming® Applications Kerosene Hydrotreating Euro-V Diesel or USA - ULSD (Both < 10 ppm Sulphur) Vacuum Gas Oil (FCC Feed) Hydrotreating VGO & LCO Mild Hydrocracking Low Cost Revamps of Existing Trickle bed Units
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Conventional Trickle Bed Process Flow scheme MAKE UP HYDROGEN
MAKE UP COMPRESSOR RECYCLE GAS COMPRESSOR
FEED
AMINE SCRUBBER
REACTOR CONDENSER
Two Phase Reactor Once Through Liquid Gas Recycle Hydrogen diffuses into liquid as it is consumed in the catalyst bed Distribution critical
COLD HP SEPARATOR HOT HP SEPARATOR
TO FRACTIONATION
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IsoTherming® Process Flow scheme MAKE UP COMPRESSOR MAKE UP HYDROGEN
FEED OFF GAS FOR RECOVERY
Single Phase Reactor Once Through Hydrogen Liquid Recycle All Hydrogen in liquid phase Within the catalyst bed Distribution less critical
REACTOR
CONDENSER COLD LP SEPARATOR HOT LP SEPARATOR
RECYCLE PUMP TO FRACTIONATION
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IsoTherming® Example Hydrogen Balance Reactor Pressure 60 barg (870 psig) H2 Solubility 15 Nm3/m3 FF (89 SCF/bbl) H2 Consumption 60 Nm3/m3 FF (356 SCF/bbl)
H2 FEED
H2 Consumption: 30 Nm3/m3 FF ( 178 SCF/bbl) in each bed
Hydrogen 60 Nm3/m3 FF (356 SCF/bbl) at top of each bed
H2 Hydrogen at bed outlet: 30 Nm3/m3 FF (178 SCF/bbl) or 7.5 Nm3/m3 (45 SCF/bbl) Oil for each bed RECYCLE PUMP
Recycle 3:1 NOTE: TYPICAL NUMBERS ONLY – ACTUAL DESIGNS WILL DIFFER
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IsoTherming® Example Hydrogen Balance Reactor Pressure 69 barg (1000 psig) H2 Solubility 17 Nm3/m3 FF (100 SCF/bbl) H2 Consumption 51 Nm3/m3 FF (300 SCF/bbl)
H2 FEED
H2 Consumption: 25.5 Nm3/m3 FF ( 150 SCF/bbl) in each bed
Hydrogen 51 Nm3/m3 FF (300 SCF/bbl) at top of each bed
H2 Hydrogen at bed outlet: 8.5 Nm3/m3 (50 SCF/bbl)
RECYCLE PUMP
Recycle 2:1 NOTE: TYPICAL NUMBERS ONLY – ACTUAL DESIGNS WILL DIFFER
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Major Equipment Differences IsoTherming®
Conventional
Hot High Pressure Separator
No
Yes
Cold High Pressure Separator
No
Yes
Recycle Gas Compressor
No
Yes
High Pressure Off Gas Cooler
No
Yes
Hot Low Pressure Separator
Yes
No
High Pressure Amine Contactor
No
Yes
High Pressure Amine Pump
No
Yes
Stripper Preheat Exchangers
No
Yes
Reactor Circulation Pump
Yes
No
Feed/Effluent Heat Exchange Surface Area
Low
High
Charge Heater Duty
Low
High
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IsoTherming® Advantages
Recycle of hydrogen accomplished by liquid recycle
Elimination of Recycle Gas equipment in Grassroots Units
Catalyst bed completely wetted 1) All catalyst sites utilized • More effective use of catalyst 2) Minimizes hot spot formation • Decreased catalyst deactivation / coking / thermal cracking • Decreased light end formation • Increased liquid yield 3) Heat of Reaction Absorbed by High Liquid Recycle Rate • Adiabatic temperature rise less than conventional technology • Reactor temperature rise tends toward isothermal operation • Lower heater firing rates in normal operation
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IsoTherming® Advantages Flexibility in reactor shape L/D and bed depth not dependent on two phase flow regime Reactor Fabrication Often, reactor diameter and wall thickness can be minimized to allow use of cold-rolled plate instead of forged plate Reactor design can be optimized for local fabricator capabilities and transportation logistics Projects not dependent on just a few fabricators worldwide Shorter reactor delivery time possible Can be optimized based on fabricator’s capabilities Plot plan will be smaller than conventional Heat integration may lead to smaller carbon/GHG footprint
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydrocracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
DIESEL HYDROTREATING ISOTHERMING® WASH WATER MAKEUP HYDROGEN FROM COMPRESSOR OFF GAS TO FUEL GAS TREATING/HYDROGEN RECOVERY
REACTOR EFFLUENT COOLER
LC
OFF GAS TO FUEL GAS TREATING
LC
LC
REACTOR CHARGE HEATER
COLD LOW PRESSURE SEPARATOR
STRIPPER CONDENSER
SOUR WATER TO B.L.
STRIPPER ACCUMULATOR
R
ISOTHERMING REACTOR
R
SOUR WATER TO B.L.
ISOTHERMING REACTOR RECYCLE PUMP
1
FEED-EFFLUENT EXCHANGER
STRIPPER REFLUX PUMP
SOAK GAS
HOT LOW PRESSURE SEPARATOR
30 STEAM
FEED FROM STORAGE
STRIPPER F FEED FILTER
FEED-DIESEL EXCHANGER STRIPPER BOTTOM PUMP FEED SURGE DRUM
TREATED DIESEL PRODUCT TO B.L.
SOUR WATER TO OWS
DIESEL PRODUCT COOLER
CHARGE PUMP
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
SOUR WILD NAPTHA TO B.L.
VGO HYDROTREATING ISOTHERMING® MAKEUP HYDROGEN FROM COMPRESSOR
WASH WATER
OFF GAS TO FUEL GAS TREATING/HYDROGEN RECOVERY
REACTOR EFFLUENT COOLER
OFF GAS TO FUEL GAS TREATING
STRIPPER CONDENSER
LC
LC
REACTOR CHARGE HEATER
LC
ISOTHERMING REACTOR
STRIPPER ACCUMULATOR
COLD LOW PRESSURE SEPARATOR
HOT LOW PRESSURE SEPARATOR
SOUR WATER TO B.L.
1
SOUR WATER TO B.L.
STRIPPER REFLUX PUMP SOUR WILD NAPTHA TO B.L.
R 30 STEAM
R
ISOTHERMING REACTOR RECYCLE PUMP
STRIPPER FRACTIONATOR OVERHEAD CONDENSER
FEED-EFFLUENT EXCHANGER SOAK GAS
FRACTIONATOR ACCUMULATOR
STRIPPER BOTTOM PUMP SOUR WATER TO B.L.
FEED FROM STORAGE
1
FEED-PREHEAT EXCHANGER
FRACTIONATOR REFLUX PUMP
F FEED FILTER
DIESEL TO B.L.
FEED SURGE DRUM
TREATED PRODUCT TO B.L.
PRODUCT COOLER
FRACTIONATOR FEED BOTTOM EXCHANGER
SOUR WATER TO B.L.
FRACTIONATOR FEED HEATER
30 STEAM
FRACTIONATOR FRACTIONATOR BOTTOM PUMP
CHARGE PUMP
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Unique Advantage of Kerosene IsoTherming® Refiners are often in a dilemma over selection of Kerosene Sweetening over Hydrotreating. Due to lower capital /operating cost advantages, highly inflexible sweetening units are often selected. With Sweetening option, Refinery lose the flexibility of producing superior Aviation Fuel and blend component to ULSD (for cetane, cold flow properties etc.). With Kerosene IsoTherming® advantages can be further enhanced: Typical KHT can be designed without Reactor Recycle Pump. Depending on refinery configuration/hydrogen recovery requirements unit can be designed with one separator or without separator. Due to the above reasons there will be substantial capital cost and operating cost benefit (>50%) when compared to conventional trickle bed configuration. This makes IsoTherming® KHT an attractive alternative to refineries when compared to cheap but inflexible Sweetening units.
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KERO HYDROTREATING ISOTHERMING® WASH WATER MAKEUP HYDROGEN FROM COMPRESSOR
OFF GAS TO FUEL GAS TREATING/HYDROGEN RECOVERY
OFF GAS TO FUEL GAS TREATING
REACTOR EFFLUENT COOLER LC
STRIPPER CONDENSER COLD LOW PRESSURE SEPARATOR
LC
SOUR WATER TO B.L. LC
REACTOR CAHRGE HEATER
ISOTHERMING REACTOR
STRIPPER ACCUMULATOR SOUR WATER TO B.L. 1
STRIPPER REFLUX PUMP
STIPPER FEED REACTOR EFFLUENT EXCHANGER
R
30
FEED/EFFLUENT EXCHANGER SOAK GAS
FEED FROM STORAGE
F FEED FILTER
STRIPPER REBOILER HEATER
STRIPPER
STRIPPER BOTTOM PUMP FEED KERO EXCHANGER
FEED SURGE DRUM TREATED KEROSENE PRODUCT TO B.L.
SOUR WATER TO OWS
KERO PRODUCT COOLER
CHARGE PUMP
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SOUR WILD NAPTHA TO B.L.
Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydrocracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
ISOTHERMING® DIESEL HYDROTREATER REVAMP FEED FROM STORAGE
RECYCLE GAS COMPRESSOR
F FEED FILTER
MAKEUP GAS FROM MAKEUP COMMPRESSOR
TREATED DIESEL PRODUCT TO B.L.
STRIPPER BOTTOMS/ FEED EXCHANGER
DIESEL PRODUCT COOLER
LEAN AMINE FROM B.L. 1
LEAN AMINE PUMPS
9
FEED SURGE DRUM
CHARGE HEATER
ISOTHERMING REACTOR
R
RECYCLE GAS SCRUBBER CWR
OFF GAS TO FUEL GAS TREATING
SOAK GAS
SOUR WATER TO OWS
TRICKLE BED REACTOR
R
FEED/EFFLUENT EXCHANGER
FEED PUMPS
ISOTHERMING REACTOR RECYCLE PUMP
CWS
RICH AMINE TO B.L.
RECYCLE GAS COOLER
STRIPPER CONDENSER STRIPPER FEED/ REACTOR EFFLUENT EXCHANGER
STRIPPER RECEIVER SOUR WATER TO B.L.
RECYCLE GAS/REACTOR EFFLUENT EXCHANGER
SEPARATOR CONDENSER 1
STRIPPER OVERHEAD PUMPS
SEPARATOR
SOUR WILD NAPTHA TO B.L. SOUR WATER TO B.L. 30 STEAM
STRIPPER FEED/ BOTTOMS EXCHANGER STRIPPER
STRIPPER BOTTOMS PUMP
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REVAMP MODIFICATIONS
Revamp of Diesel Unit Comparison Conventional
IsoTherming®
Additional Reactor
Large
Smaller
Existing Reactor Operating Pressure
Lower
Same
Hot High Pressure Separator
Replace
No
Cold High Pressure Separator
Replace
No
Recycle Gas Compressor
Replace/Add
No
High Pressure Off Gas Cooler
Replace/Add
No
Revamp
No
Feed/Effluent Exchangers
Replace/Add
No
High Pressure Piping Work
Significant
Minimum
No
Yes
Revamp
No / Revamp
If Required
If Required
LONGER
MINIMUM
High Pressure Amine Contactor
Reactor Circulation Pump Heater Make Up Compressors Shut Down Period
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Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydrocracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Vacuum Gas Oil Hydroprocessing Currently offered : FCC Feed Hydrotreating Mild Hydrocracking (MHC) ( 85%)
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Mild Hydrocracker Case Studies Design Feed Properties Feed
Case A
Case B
Case C
VGO, DAO
VGO, HCGO
VGO, HCGO, CGO
100
367
215
Specific Gravity
0.944
0.935
0.906
S, ppm
28,000
26,700
25,600
N, ppm
1,750
1,580
1,300
Con Carbon, wt%
1.81
0.71
0.25
IBP
218
231
213
50%
478
444
363
90%
574
548
441
Total metals, ppm
12.8
4.5
3.5
Components Feed Rate, m3/hr
D-2887 deg C
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Mild Hydrocracker Case Studies
Design Products Feed
Case A
Case B
Case C
VGO, DAO
VGO, HCGO
VGO, HCGO, CGO
Light naphtha, S
< 20 ppm
Naphtha, S
< 10 ppm
No sulphur spec.
< 5 ppm
Kerosene, S
< 8 ppm
No sulphur spec.
< 8 ppm
No sulphur spec.
No sulphur spec.
< 8 ppm
< 700 ppm
< 800 ppm
< 100 ppm
40
22
46
Diesel, S FCC Feed, S Conversion, %
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Content DuPont Sustainable Solutions – Clean Technologies IsoTherming® History & Experience List IsoTherming® Technology & Principles IsoTherming® Grassroots Designs Revamps using IsoTherming® Technology VGO Processing & Mild Hydrocracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
IsoTherming® Reactor Skid Ciniza Ist Project
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Copyright ® 2012 DuPont. The DuPont Oval Logo, DuPont™, and The miracles of science™ are trademarks or registered trademarks of E.I. du Pont de Nemours and Company or its affiliates. All rights reserved.
Woods Cross, UT, USA
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IsoTherming® 3D Plot Layout
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IsoTherming® 3D Plot Layout
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Revamp Example – Actual Data from First Unit Feed LCO, vol%
40
SR, vol%
60
IsoTherming®
Final Product
Sulphur, ppm
2146
275
6
Nitrogen, ppm
230
16
