Download pdf - IsoTherming Hydroprocessing · PDF fileIsoTherming ® Hydroprocessing Technology Technology and proprietary equipment for refiners to hydrotreatmiddle distillates to reduce sulfur

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® Hydroprocessing Technology

International Conference on Refining Challenges & Way Forward – Technologies for Improved

Product Quality

Ravi Srinivas J

April,17, 2012 at New Delhi, India


reserved.

ContentDuPont 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


reserved.

DuPont Sustainable Solutions

Safety ResourcesSafety Resources

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

Sustainable OperationsSustainable OperationsTraining Solutions Training Solutions

powered by powered by Clean TechnologiesClean Technologies

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

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

Blended learning solutions that integrate eLearning technologies, instructor-led courses, and traditional media tools to help develop

employee skills, reinforce desired

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Strategic Businesses and Offerings Strategic Businesses and Offerings


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DuPont Sustainable Solutions: Clean TechnologiesClean Technologies

AlkylationAlkylation

STRATCO®

Technology and

proprietary

equipment for

refiners to produce

alkylate for blending

into clean gasoline

HydroprocessingHydroprocessingGlobal Engineered Global Engineered

SolutionsSolutionsAir Pollution Air Pollution

ControlControl

IsoTherming®

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

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

Sulfuric AcidSulfuric Acid

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





VGO Processing & Mild Hydrocracking

Commercial Results

Recycle Pump



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

Apr-2003ULSD Hydrotreater – Revamp3800Western-Ciniza, NM,

USA

Mar-2006ULSD Hydrotreater - Revamp5000Western-Ciniza, NM,

USA

Apr-2006ULSD Hydrotreater - Grassroots12000Western-Yorktown,

VA, USA

Dec-2008VGO Mild Hydrocracker - Grassroots15000Holly Corp, Wood X

Utah, USA

Jan-2009VGO Mild Hydrocracker - Grassroots30000Holly Corp, Artesia,

NM, USA

Dec-2010VGO Hydrotreater - Revamp 55000Midwest, USA

Jun-2011LCO Mild Hydrocracker - Grassroots8000China

DateDescriptionCapacity (BPSD)

Country


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IsoTherming® Current Project Status

Proj. On HoldULSD Hydrotreater – Revamp (S < 10 PPM)46,000USA

Pre-commissioningLCO Hydrotreater – Grassroots (S < 350 PPM)6,000China

Pre-commissioningLCO Hydrotreater – Grassroots (S < 350 PPM)6,000China

Detailed DesignULSD Hydrotreater – Grassroots (S < 40 PPM)78,000China

Proj. On HoldULSD Hydrotreater – Grassroots (S < 10 PPM)10,000USA

Pre-commissioningHy. Dist. Hydrotreater – Grassroots (S < 150 PPM)20,000China

Detailed DesignULSD Hydrotreater – Grassroots (S < 10 PPM)2,250Russia

Detailed DesignLCO Mild Hydrocracker – Grassroots (∆ d = 80)6,000China

Detailed DesignLCO Mild Hydrocracker – Grassroots (∆ d = 80)6,000China

Detailed DesignDiesel Hydrotreater – Grassroots (S < 50 PPM)12,500China

Detailed DesignULSD Hydrotreater – Revamp (S < 10 PPM)50,000India

StatusDescriptionCapacity

(BPSD)Country


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Commercial Results

Recycle Pump



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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MAKE UPHYDROGEN

HOT HPSEPARATOR

AMINE

SCRUBBER

RECYCLE GASCOMPRESSOR

Conventional Trickle Bed Process Flow scheme

FEED

MAKE UPCOMPRESSOR

COLD HPSEPARATOR

REACTOR

TO FRACTIONATION

CONDENSER

� Two Phase Reactor

� Once Through Liquid

� Gas Recycle

� Hydrogen diffuses into liquid as it is consumed in the catalyst bed

� Distribution critical


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MAKE UPHYDROGEN

FEED

MAKE UPCOMPRESSOR

REACTOR

RECYCLEPUMP

IsoTherming® Process Flow scheme

� Single Phase Reactor

� Once Through Hydrogen

� Liquid Recycle

� All Hydrogen in liquid phase

Within the catalyst bed� Distribution less critical

TO FRACTIONATION

HOT LPSEPARATOR

COLD LPSEPARATOR

CONDENSER

OFF GAS FOR RECOVERY


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Recycle 3:1

NOTE: TYPICAL NUMBERS ONLY – ACTUAL DESIGNS WILL DIFFER

IsoTherming® Example Hydrogen Balance

RECYCLEPUMP

Reactor Pressure 60 barg (870 psig)

H2 Solubility 15 Nm3/m3 FF (89 SCF/bbl)

H2 Consumption 60 Nm3/m3 FF (356 SCF/bbl)

Hydrogen 60 Nm3/m3 FF (356 SCF/bbl) at top of each bed

FEED

H2 Consumption: 30 Nm3/m3 FF ( 178 SCF/bbl) in each bed

Hydrogen at bed outlet: 30 Nm3/m3 FF (178 SCF/bbl) or 7.5

Nm3/m3 (45 SCF/bbl) Oil for each bed

H2

H2


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Recycle 2:1

NOTE: TYPICAL NUMBERS ONLY – ACTUAL DESIGNS WILL DIFFER

IsoTherming® Example Hydrogen Balance

RECYCLEPUMP

Reactor Pressure 69 barg (1000 psig)

H2 Solubility 17 Nm3/m3 FF (100 SCF/bbl)

H2 Consumption 51 Nm3/m3 FF (300 SCF/bbl)

Hydrogen 51 Nm3/m3 FF (300 SCF/bbl) at top of each bed

FEED

H2 Consumption: 25.5 Nm3/m3

FF ( 150 SCF/bbl) in each bed

Hydrogen at bed outlet: 8.5 Nm3/m3 (50 SCF/bbl)

H2

H2


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Major Equipment Differences

HighLowCharge Heater Duty

HighLowFeed/Effluent Heat Exchange Surface Area

Reactor Circulation Pump

Stripper Preheat Exchangers

High Pressure Amine Pump

High Pressure Amine Contactor

Hot Low Pressure Separator

High Pressure Off Gas Cooler

Recycle Gas Compressor

Cold High Pressure Separator

Hot High Pressure Separator

NoYes

YesNo

YesNo

YesNo

NoYes

YesNo

YesNo

YesNo

YesNo

ConventionalIsoTherming®


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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 shapeL/D and bed depth not dependent on two phase flow regime

� Reactor FabricationOften, 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


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Content







Commercial Results

Recycle Pump



Conclusion


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DIESEL HYDROTREATING ISOTHERMING®

F

FEED FROM

STORAGE

DIESEL PRODUCTCOOLER

FEED SURGEDRUM

STRIPPER BOTTOMPUMP

STEAM

REACTOR CHARGE

HEATER

REACTOR

EFFLUENTCOOLER

COLD LOW

PRESSURESEPARATOR

FEED-EFFLUENT

EXCHANGER

TREATED DIESELPRODUCT TO B.L.

CHARGEPUMP

SOUR WATER

TO OWS

SOUR WATER

TO B.L.

MAKEUP HYDROGEN FROM COMPRESSOR

FEEDFILTER

ISOTHERMINGREACTOR

R

STRIPPER

STRIPPERCONDENSER

STRIPPERACCUMULATOR

STRIPPER REFLUX

PUMP

SOUR WATER

TO B.L.

1

30

OFF GAS TO FUEL

GAS TREATING

SOUR WILD

NAPTHA TO B.L.

FEED-DIESELEXCHANGER

ISOTHERMING REACTORRECYCLE PUMP

R

HOT LOW PRESSURE

SEPARATOR

LC

LC

LC

OFF GAS TO FUEL GASTREATING/HYDROGEN

RECOVERY

SOAK GAS

WASHWATER


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VGO HYDROTREATING ISOTHERMING®

F

1

30

1

30

FEED

FILTER

FEED-PREHEAT

EXCHANGER

PRODUCT

COOLER

FEED SURGE

DRUM

CHARGEPUMP

FRACTIONATOR

FEED-EFFLUENT

EXCHANGER

REACTOR

CHARGE

HEATER

HOT LOW

PRESSURESEPARATOR

FRACTIONATOR

OVERHEAD CONDENSER

FRACTIONATORACCUMULATOR

FRACTIONATOR

REFLUX PUMP

STRIPPER

COLD LOW

PRESSURE

SEPARATOR

REACTOR EFFLUENT

COOLER

STRIPPER REFLUX

PUMP

STRIPPER

ACCUMULATOR

STRIPPERCONDENSER

ISOTHERMINGREACTOR

R

ISOTHERMING REACTOR

RECYCLE PUMP

R

SOUR WATERTO B.L.

DIESEL TO B.L.

SOUR WATER

TO B.L.

FEED FROMSTORAGE

TREATED PRODUCT TO B.L.

MAKEUP HYDROGEN

FROM COMPRESSOR

SOUR WATERTO B.L.

OFF GAS TO FUEL

GAS TREATINGWASH

WATER

LC

LC

LC

STEAM

STEAM

FRACTIONATOR

FEED HEATER

FRACTIONATOR

FEED BOTTOMEXCHANGER

STRIPPER BOTTOM PUMP

SOUR WILD NAPTHA TO B.L.

FRACTIONATOR

BOTTOM PUMP

SOUR WATER

TO B.L.

OFF GAS TO FUEL GAS

TREATING/HYDROGEN RECOVERY

SOAK GAS


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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®

F

ISOTHERMING

REACTOR

FEED FROM

STORAGE

KERO PRODUCTCOOLER

FEED SURGEDRUM

STRIPPER BOTTOM

PUMP

STRIPPERSTRIPPER REBOILER

HEATER

REACTOR CAHRGE

HEATER

REACTOR

EFFLUENTCOOLER

COLD LOW

PRESSURESEPARATOR

STRIPPERCONDENSER

STRIPPER

ACCUMULATOR

STRIPPER REFLUX

PUMP

FEED/EFFLUENT

EXCHANGER

TREATED KEROSENE

PRODUCT TO B.L.

CHARGEPUMP

SOUR WATER

TO OWS

SOUR WATER

TO B.L.

SOUR WATER

TO B.L.

MAKEUP HYDROGEN FROM COMPRESSOR

FEEDFILTER

1

30

R

OFF GAS TO FUEL

GAS TREATING

SOUR WILD

NAPTHA TO B.L.

FEED KEROEXCHANGER

OFF GAS TO FUEL GASTREATING/HYDROGEN

RECOVERY

LC

LC

LC

SOAK GAS

WASH

WATER

STIPPER FEED REACTOREFFLUENT EXCHANGER


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Content







Commercial Results

Recycle Pump



Conclusion


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1

30

CWR

CWS

F

1

9

FEEDFILTER

DIESEL PRODUCT

COOLER

STRIPPER BOTTOMS/FEED EXCHANGER

FEED SURGEDRUM

STRIPPER

CONDENSER

STRIPPER

OVERHEADPUMPS

STRIPPER

RECEIVER

FEEDPUMPS

FEED/EFFLUENTEXCHANGER

CHARGEHEATER

STRIPPER

STRIPPER BOTTOMSPUMP

STRIPPER FEED/REACTOR

EFFLUENT

EXCHANGER

RECYCLE GAS/REACTOR

EFFLUENT EXCHANGER

RECYCLE GASCOMPRESSOR

RECYCLE GASSCRUBBER

RECYCLE GASCOOLER

SEPARATORCONDENSER

STRIPPER FEED/BOTTOMS EXCHANGER

SEPARATOR

SOUR WATER

TO B.L.

SOUR WATER

TO OWS

SOUR WATER

TO B.L.

ISOTHERMING REACTOR

RECYCLE PUMP

R

ISOTHERMING

REACTOR

R

FEED FROM

STORAGE

TREATED DIESELPRODUCT TO B.L.

OFF GAS TOFUEL GAS TREATING

SOUR WILDNAPTHA TO B.L.

LEAN AMINEFROM B.L.

LEAN AMINE

PUMPS

RICH AMINE TO B.L.SOAK

GAS

MAKEUP GASFROM MAKEUP COMMPRESSOR

TRICKLE BEDREACTOR

REVAMP MODIFICATIONS

STEAM

ISOTHERMING® DIESEL HYDROTREATER REVAMP


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Revamp of Diesel Unit Comparison

MINIMUMLONGERShut Down Period

If Required If RequiredMake Up Compressors

No / RevampRevampHeater

Yes NoReactor Circulation Pump

MinimumSignificantHigh Pressure Piping Work

No Replace/Add Feed/Effluent Exchangers

No RevampHigh Pressure Amine Contactor

No Replace/AddHigh Pressure Off Gas Cooler

No Replace/AddRecycle Gas Compressor

No ReplaceCold High Pressure Separator

No Replace Hot High Pressure Separator

SameLowerExisting Reactor Operating Pressure

Smaller LargeAdditional Reactor

IsoTherming®Conventional


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Content







Commercial Results

Recycle Pump



Conclusion


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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

Feed Case A Case B Case C

Components VGO, DAO VGO, HCGO VGO, HCGO, CGO

Feed Rate, m3/hr 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

D-2887 deg C

IBP 218 231 213

50% 478 444 363

90% 574 548 441

Total metals, ppm 12.8 4.5 3.5

Design Feed Properties


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Mild Hydrocracker Case Studies

Case A Case B Case C

Feed 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

Diesel, S No sulphur spec. No sulphur spec. < 8 ppm

FCC Feed, S < 700 ppm < 800 ppm < 100 ppm

Conversion, % 40 22 46

Design Products


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Content







Commercial Results

Recycle Pump



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 IsoTherming® Final Product

LCO, vol% 40

SR, vol% 60

Sulphur, ppm 2146 275 6

Nitrogen, ppm 230 16 <1

API Gravity (SG) 32.0 (0.865) 35.7 (0.846)

Cetane Index 46.3 51.2

H2

Consumption, SCF/BBL (Nm3/m3) 280 (47) 210 (35)

LHSV per Catalyst Bed, Hr-1 10/10 3

H2

Pressure, psig (barg) 600 (41.4) 600 (41.4)

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

50

60

70

80

90

100

7/6/2009 8/25/2009 10/14/2009 12/3/2009 1/22/2010 3/13/2010 5/2/2010

% R

emo

val

Sulfur

Nitrogen


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Commercial Results

Recycle Pump



Conclusion


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IsoTherming® Recycle Pump

• Available through DuPont

• Low head, high flow application

• Due to auto-ignition risk, assured containment is critical


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Casing

MechanicalSeal

Shaft

Impeller

LeakageCoupling

Ordinary sealed Pump

Canned Motor Pump

Casing

Impeller

Casing

Frame Stator Ass’y

Rotor with one piece shaft

Bearing

Eliminate Shaft Seal

Eliminate coupling

still two separate shafts

Horizontal Configuration of Recycle Pump


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Liquid flow path in IsoTherming® Recycle Pump

CW in

CW out

Positive Diesel flush

Process fluid out

Process

fluid in


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Vertical Configuration of Recycle Pump - Flowserve


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Vertical Configuration of Recycle Pump - Flowserve


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Commercial Results

Recycle Pump



Conclusion


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Capital Cost Comparison (30,000 bbl/day basis)

2000 (300,000)1537 (2) (230,550)Grassroots Diesel

700-1500 (105,000-225,000)

470 (2) (70,500)Diesel Revamp

4500 (1) (675,000)2110 (1) (316,500)Mild Hydrocracking

2910 (1) (436,500)1530 (1) (229,500)Gas Oil Hydrotreating (FCCFeed)

US$/bbl

(US$/m3/hr)

US$/bbl

(US$/m3/hr)

Conventional IsoTherming®

(1) Estimated by U.S. Engineering Contractor

(2) Actual Project Cost


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Basis: 30,000 bpd (200 m3/hr) Mild Hydrocracker

2000 psig (138 barg) Operating Pressure

Capital and Operating Cost Estimate

21,000 27,000kg/hrSteam Prodn.

6.52 4.36MWPower

7 6.6MWFuel Gas

UtilitiesUtilities

135.0 est.67.3* est.MMUS$ CapitalCapital

Conventional IsoTherming®

* Actual capital cost later confirmed to be US$ 59.3 MM


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Content







Commercial Results

Recycle Pump



Conclusion


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� 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



reserved.

Thank you

Ravi Srinivas JTechnology & Business Manager

Clean Technologies – DuPont Sustainable [email protected]

+91 – 91 777 222 90