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
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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 Hydro cracking Commercial Results Recycle Pump Capital & Operating Cost Comparisons Commercial Offerings Conclusion
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DuPont Sustainable Solutions
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Clean Technologies
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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
Comprehensive products and services for sulfuric acid alkylation units, sulfuric acid plants, as well as sulfuric acid storage, handling and transfer systems
BELCO
Technology and proprietary equipment for scrubbing refinery emissions of SOx, NOx and particulates
MECS
Market leader in sulphuric acid production & technology with 1000 client references. Became part of DuPont on 1st January 2011
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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
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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
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IsoTherming Commercial Operation
Country China Midwest, USA Holly Corp, Artesia, NM, USA Holly Corp, Wood X Utah, USA Western-Yorktown, VA, USA Western-Ciniza, NM, USA Western-Ciniza, NM, USA Capacity (BPSD) 8000 55000 30000 15000 12000 5000 3800
Description
LCO Mild Hydrocracker - Grassroots VGO Hydrotreater - Revamp VGO Mild Hydrocracker - Grassroots VGO Mild Hydrocracker - Grassroots ULSD Hydrotreater - Grassroots ULSD Hydrotreater - Revamp ULSD Hydrotreater Revamp
Date Jun-2011 Dec-2010 Jan-2009 Dec-2008 Apr-2006 Mar-2006 Apr-2003
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IsoTherming Current Project Status
Country India China China China Russia China USA China China China USA Capacity (BPSD) 50,000 12,500 6,000 6,000 2,250 20,000 10,000 78,000 6,000 6,000 46,000
Description
ULSD Hydrotreater Revamp (S < 10 PPM) Diesel Hydrotreater Grassroots (S < 50 PPM) LCO Mild Hydrocracker Grassroots ( d = 80) LCO Mild Hydrocracker Grassroots ( d = 80) ULSD Hydrotreater Grassroots (S < 10 PPM) Hy. Dist. Hydrotreater Grassroots (S < 150 PPM) ULSD Hydrotreater Grassroots (S < 10 PPM) ULSD Hydrotreater Grassroots (S < 40 PPM) LCO Hydrotreater Grassroots (S < 350 PPM) LCO Hydrotreater Grassroots (S < 350 PPM) ULSD Hydrotreater Revamp (S < 10 PPM)
Status Detailed Design Detailed Design Detailed Design Detailed Design Detailed Design Pre-commissioning Proj. On Hold Detailed Design Pre-commissioning Pre-commissioning 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
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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 FEED RECYCLE GAS COMPRESSOR 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
FEED
H2 Consumption 60 Nm3/m3 FF (356 SCF/bbl)
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
FEED
H2 Consumption 51 Nm3/m3 FF (300 SCF/bbl)
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 Hot High Pressure Separator Cold High Pressure Separator Recycle Gas Compressor High Pressure Off Gas Cooler Hot Low Pressure Separator High Pressure Amine Contactor High Pressure Amine Pump Stripper Preheat Exchangers Reactor Circulation Pump Feed/Effluent Heat Exchange Surface Area Charge Heater Duty No No No No Yes No No No Yes Low Low Conventional Yes Yes Yes Yes No Yes Yes Yes No High 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 fabricators 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
LC
REACTOR EFFLUENT COOLER
LC
OFF GAS TO FUEL GAS TREATING
LC
REACTOR CHARGE HEATER
COLD LOW PRESSURE SEPARATOR
SOUR WATER TO B.L.
STRIPPER CONDENSER
ISOTHERMING REACTOR
STRIPPER ACCUMULATOR
R
ISOTHERMING REACTOR RECYCLE PUMP FEED-EFFLUENT EXCHANGER
SOAK GAS
SOUR WATER TO B.L. 1
STRIPPER REFLUX PUMP
SOUR WILD NAPTHA TO B.L.
HOT LOW PRESSURE SEPARATOR
STEAM
30
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
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VGO HYDROTREATING ISOTHERMING
MAKEUP HYDROGEN FROM COMPRESSOR WASH WATER OFF GAS TO FUEL GAS TREATING/HYDROGEN RECOVERY OFF GAS TO FUEL GAS TREATING
REACTOR EFFLUENT COOLER
LC
STRIPPER CONDENSER STRIPPER ACCUMULATOR
SOUR WATER TO B.L.
LC
COLD LOW PRESSURE SEPARATOR
SOUR WATER TO B.L.
LC
REACTOR CHARGE HEATER
HOT LOW PRESSURE SEPARATOR
STRIPPER REFLUX PUMP
SOUR WILD NAPTHA TO B.L.
ISOTHERMING REACTOR
R 30 STEAM
ISOTHERMING REACTOR RECYCLE PUMP FEED-EFFLUENT EXCHANGER
SOAK GAS
STRIPPER FRACTIONATOR OVERHEAD CONDENSER
STRIPPER BOTTOM PUMP
SOUR WATER TO B.L.
1
FRACTIONATOR ACCUMULATOR
FEED FROM STORAGE
FEED-PREHEAT EXCHANGER
F
FEED FILTER
FRACTIONATOR REFLUX PUMP
DIESEL TO B.L.
TREATED PRODUCT TO B.L.
FEED SURGE DRUM PRODUCT COOLER
SOUR WATER TO B.L.
FRACTIONATOR FEED BOTTOM EXCHANGER
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
SOUR WATER TO B.L. 1
LC
STRIPPER ACCUMULATOR
SOUR WATER TO B.L.
LC
REACTOR CAHRGE HEATER
STIPPER FEED REACTOR EFFLUENT EXCHANGER
STRIPPER REFLUX PUMP
SOUR WILD NAPTHA TO B.L.
ISOTHERMING REACTOR
30
FEED/EFFLUENT EXCHANGER
SOAK GAS
STRIPPER REBOILER HEATER
STRIPPER
FEED FROM STORAGE
F FEED FILTER
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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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
F
FEED FILTER
TREATED DIESEL PRODUCT TO B.L.
RECYCLE GAS COMPRESSOR
MAKEUP GAS FROM MAKEUP COMMPRESSOR
DIESEL PRODUCT COOLER
STRIPPER BOTTOMS/ FEED EXCHANGER
1
LEAN AMINE FROM B.L.
LEAN AMINE PUMPS
FEED SURGE DRUM
SOAK GAS
CHARGE HEATER
ISOTHERMING REACTOR
RECYCLE GAS SCRUBBER CWR
RICH AMINE TO B.L.
OFF GAS TO FUEL GAS TREATING
SOUR WATER TO OWS
FEED PUMPS STRIPPER CONDENSER
FEED/EFFLUENT EXCHANGER
ISOTHERMING REACTOR RECYCLE PUMP
TRICKLE BED REACTOR
CWS
RECYCLE GAS COOLER
STRIPPER RECEIVER
SOUR WATER TO B.L. 1
STRIPPER FEED/ REACTOR EFFLUENT EXCHANGER
RECYCLE GAS/REACTOR EFFLUENT EXCHANGER
SEPARATOR CONDENSER
STRIPPER OVERHEAD PUMPS
SOUR WILD NAPTHA TO B.L. SOUR WATER TO B.L. 30 STEAM
SEPARATOR REVAMP MODIFICATIONS
STRIPPER FEED/ BOTTOMS EXCHANGER STRIPPER
STRIPPER BOTTOMS PUMP
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Revamp of Diesel Unit Comparison
Conventional Additional Reactor Existing Reactor Operating Pressure Hot High Pressure Separator Cold High Pressure Separator Recycle Gas Compressor High Pressure Off Gas Cooler High Pressure Amine Contactor Feed/Effluent Exchangers High Pressure Piping Work Reactor Circulation Pump Heater Make Up Compressors Shut Down Period Large Lower Replace Replace Replace/Add Replace/Add Revamp Replace/Add Significant No Revamp If Required LONGER IsoTherming Smaller Same No No No No No No Minimum Yes No / Revamp If Required MINIMUM
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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) (<40%) Under Development : Partial Conversion Hydrocracking (40% 85%) Full Conversion Hydrocracking ( > 85%)
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Mild Hydrocracker Case Studies
Design Feed Properties
Feed Components Feed Rate, m3/hr Specific Gravity S, ppm N, ppm Con Carbon, wt% D-2887 deg C IBP 50% 90% Total metals, ppm 218 478 574 12.8 231 444 548 4.5 213 363 441 3.5 Case A VGO, DAO 100 0.944 28,000 1,750 1.81 Case B VGO, HCGO 367 0.935 26,700 1,580 0.71 Case C VGO, HCGO, CGO 215 0.906 25,600 1,300 0.25
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Mild Hydrocracker Case Studies
Design Products
Case A Feed Light naphtha, S Naphtha, S Kerosene, S Diesel, S FCC Feed, S Conversion, % < 10 ppm < 8 ppm No sulphur spec. < 700 ppm 40 No sulphur spec. No sulphur spec. No sulphur spec. < 800 ppm 22 VGO, DAO Case B VGO, HCGO Case C VGO, HCGO, CGO < 20 ppm < 5 ppm < 8 ppm < 8 ppm < 100 ppm 46
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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
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IsoTherming Reactor Skid Ciniza Ist Project
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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% SR, vol% Sulphur, ppm Nitrogen, ppm API Gravity (SG) Cetane Index H2 Consumption, SCF/BBL (Nm3/m3) LHSV per Catalyst Bed, Hr-1 H2 Pressure, psig (barg) 40 60 2146 230 32.0 (0.865) 46.3 280 (47) 10/10 600 (41.4) 275 16 6 <1 35.7 (0.846) 51.2 210 (35) 3 600 (41.4) IsoTherming Final Product
Unit originally achieved 500 ppm Sulphur with similar feed IsoTherming Reactors sizing based on Trickle Bed Capability
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IsoTherming Mild Hydrocracker Operating Data
Nitrogen and Sulfur Removal of Vacuum Gas Oil (VGO) Average: 5,100 ppm S / 1,000 ppm N
100 Sulfur Nitrogen 90
% Removal
80
70
60
50 7/6/2009 8/25/2009 10/14/2009 12/3/2009 1/22/2010 3/13/2010 5/2/2010
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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 Recycle Pump
Available through DuPont Low head, high flow application Due to auto-ignition risk, assured containment is critical
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Horizontal Configuration of Recycle Pump
Casing
Ordinary sealed Pump
Mechanical Seal Shaft
Eliminate Shaft Seal
Casing Impeller Leakage Coupling
Canned Motor Pump
Casing Impeller Frame Stator Assy Bearing
still two separate shafts Eliminate coupling
Rotor with one piece shaft
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42
Liquid flow path in IsoTherming Recycle Pump
Process fluid out
CW out CW in
Process fluid in Positive Diesel flush
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Vertical Configuration of Recycle Pump - Flowserve
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Vertical Configuration of Recycle Pump - Flowserve
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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.
Capital Cost Comparison (30,000 bbl/day basis)
IsoTherming
Conventional
US$/bbl (US$/m3/hr)
US$/bbl (US$/m3/hr)
Gas Oil Hydrotreating (FCCFeed) Mild Hydrocracking Diesel Revamp Grassroots Diesel
1530 (1) (229,500) 2110 (1) (316,500) 470 (2) (70,500) 1537 (2) (230,550)
2910 (1) (436,500) 4500 (1) (675,000) 700-1500 (105,000225,000) 2000 (300,000)
(1) Estimated by U.S. Engineering Contractor (2) Actual Project Cost
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Capital and Operating Cost Estimate
Basis: 30,000 bpd (200 m3/hr) Mild Hydrocracker 2000 psig (138 barg) Operating Pressure
IsoTherming Capital Utilities Fuel Gas Power Steam Prodn. MW MW kg/hr 6.6 4.36 27,000 MMUS$ 67.3* est.
Conventional 135.0 est.
7 6.52 21,000
* Actual capital cost later confirmed to be US$ 59.3 MM
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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.
Commercial Offerings
License Agreement Technology Transfer One-time fee based on capacity and technology application Process Design Services Agreement Process Design Package Scope and timing of engineering Performance Guarantee Agreement Performance Guarantee values and test run protocol Operator Training Startup Assistance Proprietary Equipment Agreement Reactor Internals (trickle bed reactor, where applicable) Catalyst Reactor Recycle 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.
Thank you
Ravi Srinivas J
Technology & Business Manager Clean Technologies DuPont Sustainable Solutions [email protected] +91 91 777 222 90
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.
