Technology for Producing Clean Diesel Utilizing Moderate Technology for Producing Clean Diesel Utilizing Moderate Pressure Pressure HydrocrackingHydrocracking With With HydroisomerizationHydroisomerization

XIII Refining Technology ForumXIII Refining Technology ForumIMPIMP--PemexPemex RefinacionRefinacionMexico City, MexicoMexico City, MexicoNovember 14, 2007November 14, 2007

J. F. StanleyJ. F. StanleyW. J. TracyW. J. TracyExxonMobil Research andExxonMobil Research and

Engineering Company (EMRE)Engineering Company (EMRE)VasantVasant PatelPatelAnandAnand Subramanian Subramanian -- KBRKBR

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KBREnergy and Chemicals

Outline

• Overview of selected ExxonMobil technologies• MPHC for plus production of diesel• Use of post treat units to adjust diesel properties through

HDT,HDC and Hydroisomerization (MIDW™)• Combining MIDW with MPHC for incremental high quality

diesel• Case study

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KBREnergy and Chemicals

EMRE Technologies for Quality Fuels

MPHC +MIDW

EMRE HYDROFINING

Waxy FeedsDistillate Heavy Feeds

ULSD MPHC

LCO Upgrading

MIDW™MDDW™

GO-fining™

ULSD +HDHDC

ULSD +MAXSAT™

Residfining

Naphtha

FCC Naphtha

OCTGAINSM

Hydrofining

SCANfining™

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KBREnergy and Chemicals

Processing Options for Clean Distillate Fuels

Optimum Depends Upon Desired Diesel Quantity and Quality

Ultra Low Sulfur HDS

Dearomatization

Dewaxing

MPHC for Plus Production

Processing LCO and other Tough Feeds

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KBREnergy and Chemicals

MPHC - Typical Operations

Range of Conditions Conversion Pressure LHSV Recycle Gas WABT Operating Cycle

%wt. barg v/v-hr Nm3/m3 oC months

20 – 70

70 – 140 0.3 – 1.0

335 – 840 370 - 440 12 - 36

Utilities per 1000 BPSD * Electric Power Fuel (abs duty) MP Steam BFW Cooling Water Lean Amine Wash Water

kW kW kg/hr m3/hr m3/hr m3/hr m3/hr

240 835

(350) 0.5 22 5.

0.3

*Note: Middle East VGO Feed

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KBREnergy and Chemicals

Typical MPHC PerformanceConversionH2 Pressure

%wt.bar

3055

5055

5084

70100

H2 Consumption Nm3/m3 90 115 160 219

Kerosene PropertiesSulfurSmoke Pt.

wppmmm

3013

1014

517

<522

Diesel PropertiesSulfurCetane No.AromaticsPoly-Aromatics

wppm

%wt.%wt.

50435018

30455520

1050357

555255

Note: Middle East VGO Feedstock

ConversionH2 Pressure

%wt.bar

3055

5055

5084

70100

H2 Consumption Nm3/m3 90 115 160 219

Kerosene PropertiesSulfurSmoke Pt.

wppmmm

3013

1014

517

<522

Diesel PropertiesSulfurCetane No.AromaticsPoly-Aromatics

wppm

%wt.%wt.

50435018

30455520

1050357

555255

Note: Middle East VGO Feedstock

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KBREnergy and Chemicals

MPHC Process Flow Diagram• Typical hydroprocessing flow sheet• Reactor design and internals important• Post treating unit or MIDW reactor to improve quality / conversion

VGO/DAO

Hydrogen Feed

Low Temp.Separator

Steam

HighTemp.Separator

Reactor

LeanAmine

RichAmine

Off-Gas

Stripper

RecycleCompressor

Fractionator

Gasoline

Naphtha

Kerosene

Diesel

Steam

WaxyBasestocks or FCC Feed

PTU or MIDW if desired

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KBREnergy and Chemicals

High vs. Moderate Pressure

Unit MPHC HPHCConversion, % 50 50

Pressure, barg 100 165

Installed Cost, US$ Base Base + 20

Diesel PropertiesSulfurCetane Indexp- Aromatics

<5045 - 555 - 10

<1055 - 65

<1

Hydrogen Demand Base Base x 1.4

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KBREnergy and Chemicals

MPHC with Integrated Diesel Treating Design (1)

MPHC

Integrated Product

Recovery Section

IntegratedULSD Distillate

TreaterFEED

JET FUEL

PREMIUM DIESEL

VLS FCC FEED

HAGOVGO

HVGOLCO

HCGOLCGODAO

HYDROGEN

DISTILLATES

(1) Danzinger at al. ERTC 2006

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KBREnergy and Chemicals

LEANAMINE

VGOFEED

WATERWASH

SOURWATER

RECYCLECOMPRESSOR

MAKE-UPCOMPRESSOR

HYDROGEN

HEATER

HIGH TEMPSEPARATOR

LOW TEMPSEPARATOR

RICHAMINE

SPIDER VORTEXSPIDER VORTEXREACTORREACTOR

CHARGEPUMP

ABSORBER

WILDNAPHTHA

FUELGAS

STEAMPRODUCTSTRIPPER

HIGH AROMATICSDIESEL FROM

FRACTIONATOR

PTUPTUREACTORREACTOR

High QualityDIESEL

PTUPREHEAT

STEAM

PRODUCTFRACTIONATOR

LEANAMINE

VGOFEED

WATERWASH

SOURWATER

RECYCLECOMPRESSOR

MAKE-UPCOMPRESSOR

HYDROGEN

HEATER

HIGH TEMPSEPARATOR

LOW TEMPSEPARATOR

RICHAMINE

SPIDER VORTEXSPIDER VORTEXREACTORREACTOR

CHARGEPUMP

ABSORBER

WILDNAPHTHA

FUELGAS

STEAMPRODUCTSTRIPPER

HIGH AROMATICSDIESEL FROM

FRACTIONATOR

PTUPTUREACTORREACTOR

High QualityDIESEL

PTUPREHEAT

STEAM

PRODUCTFRACTIONATOR

MPHC With PTU Integrated

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KBREnergy and Chemicals

Effect of Composition on cetane Number

-20

0

20

40

60

80

100

100 150 200 250 300Molecular Weight

Cet

ane

Num

ber

LCO

SRGO

Naphthalenes

Teralins

Decalins

BenzenesCyclohexanes

n-paraffins

Diesel Composition Strongly Effects Cetane• Long branched single rings best for cetane• N- Parrafins have good cetane but poor cold flow properties• LCO composition limits cetane improvement

+ Aromatics saturation provides some improvement low 40’s+ Hydrocracking and ring opening required

MPHC and MIDW Excellent Technology Choices

Arosat MPHC

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KBREnergy and Chemicals

Cetane and Gravity Improvement

vs. Aromatic Saturation

0

2

4

6

8

10

0 10 20 30

Aromatics Removed, wt%

Cet

ane

No.

Incr

ease

0

0.5

1

1.5

2

2.5

3

0 10 20 30

Aromatics Removed, wt%

API

Gra

vity

Incr

ease

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KBREnergy and Chemicals

Diesel Cetane Improvement - Hydrocracking

Pressure = 600 psig

56575859606162

600 700 800Temperature, F

Cet

ane

Inde

x

HDT only HDHDC

Pressure = 1000 psig

56575859606162

600 650 700 750 800

Temperature, FC

etan

e In

dex

HDT only HDHDC

Feed Cetane Index = 52

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KBREnergy and Chemicals

MIDW - A Novel Dewaxing Process

• Mobil Isomerization Dewaxing

• Isomerizes waxy n-paraffins in gas oils

• Proprietary ExxonMobil family of catalysts

• Low pressure fixed-bed process

• Commercially proven

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KBREnergy and Chemicals

ExxonMobil Diesel Dewaxing Technology• Diesel selectivity controlled by zeolite type, formulation and

conditions

50

60

70

80

90

100

0 20 40 60 80 100

Cloud Point Reduction, Deg F

300F

+ (1

50C

+) Y

ield

, wt%

MIDW Operating “Range”

MDDW (ZSM-5) Operating “Line”

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KBREnergy and Chemicals

Technology for Producing Winter Diesel• Reduce sulfur and convert paraffins to improve cold flow properties• Maintain or improve cetane with high yields of quality diesel fuel

MULTI-BEDSPIDER-VORTEX

REACTORSRECYCLE

COMPRESSOR

LTS

MAKEUPCOMPRESSOR

DEWAXED

DIESEL

NAPHTHA

OFF GAS

STRIPPER

Rxr-1

Rxr-2(optional )

Diesel Product< 10 wppm S

Cetane improv. +5Cloud point: – 50 oC

FeedsVirgin & cracked

0.2 to 2.0 % S30 – 50 CI

Process Conditions+ 1 or 2 stage reactors + Conv. or MIDW catalysts + Long cycle lengths+ Low H2 consumption

ExxonMobil’s MIDW is Leading Technology for Winter Diesel

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KBREnergy and Chemicals

MIDW Reactor Configurations

MIDW

MPHC MIDW

H2S, NH3, Distillates

HDT MIDW

HDT

H2S, NH3

MIDW

Waxy Feed Low Pour, High Cetane Diesel

Moderate S, N

Lower Reactor TemperaturesHigher Distillate YieldsHigh S, N

VGO Feed

Lower Reactor TemperaturesLow Sulfur Distillates

Premium Quality DistillatesLow Pour Point BottomsLong Catalyst Life

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KBREnergy and Chemicals

MPHC(Stage 1)

Integrated Product

Recovery Section

MIDW(Stage 2)FEED

JET FUEL

PREMIUM DIESEL

VLS FCC FEED

HAGOVGO

HVGOLCO

HCGOLCGODAO

HYDROGEN

DISTILLATES

MPHC/MIDW Integration for High Conversion

Stage 1bottoms

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KBREnergy and Chemicals

MIDW Product InspectionsFeedstock Naphtha Kerosene Diesel LSHFO

Boiling Range, oC 350-510 C5-150 150-255 255-388 388+Yield, Vol% 100.0 22.9 21.5 19.2 36.8

Gravity, o API 32.0 73.0 49.5 34.7 29.5Sulfur,ppm wt 260 <1 2 20 40

Smoke,mm - - 32 - -Freeze,o C - - <-54 - -Pour Point,o C >38 - - -43 <-7Cetane Index - - 52 56 -

P/N/A, wt% 44/39/17 - -/-/10 45/31/24 36/42/22

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KBREnergy and Chemicals

Case Study• Goal: achieve high conversion economically

• Feed: Middle East crude HVGO

• Configuration: MPHC for stage 1 and MIDW for stage 2

• Optimize conversion in each stage

• High jet yield preferred

• Estimate yields and qualities

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KBREnergy and Chemicals

MPHC/MIDW Reactor Operating Conditions

45100Feed Rate, % of Fresh Feed

4824MonthsMinimum Cycle Length

100100BargReactor Inlet Pressure

280Nm3/m3Chemical H2 Consumption

80%55%55%Conversion, wt%CombinedMIDWMPHC

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KBREnergy and Chemicals

Yields and Product Qualities (SOR)

-50oCFreeze Point

56Centane Index, D976-80

1012.2wt%Total Aromatics

0.11.6wt%PNA

>14wt%Hydrogen Content

66Centane Index, D4737

25mmSmoke Point

-18oCCloud Point

<2<6<10ppmwSulfur

0.8020.8370.850SG

312020wt%Yield on Fresh Feed

JetDieselBottomswt%

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KBREnergy and Chemicals

Comparison of Options for High Conversion

ForgedForgedRolled PlateReactor Fabrication

36-40 months36-40 months24-26 monthsReactor Delivery

Base +6%Base – 2%BaseDistillate Yield

Base x 1.3Base x 1.2BaseHydrogen Consumption

Base +50%BaseBaseCapital Investment

>95%75-85%85%Conversion

2 Stage MPHC with Recycle

1 Stage HPHC

2 Stage MPHC

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KBREnergy and Chemicals

2 Stage Integrated MPHC/MIDW Advantages• Better overall yield

• No extra cracking to lighter products. • Better product properties

• MIDW catalyst in 2nd stage - better distillate qualities and cold flow properties• Unit will make Euro IV diesel spec - density, CI better than HP operations• Jet - better smoke point and freeze point

• Flexible 2 stage design • Easy transition between max-diesel or max-jet operation• Optimize conversion between two systems• Option to process external feeds

• Lower pressure and no reprocessing hydraulics • Lower TIC• Lower hydrogen consumption/compression • Lower ops cost• Improved operability, reliability, and safety• Easier and shorter turnaround• Favorable project execution • Better reactors/compressor delivery

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KBREnergy and Chemicals

Conclusions

• A number of processing and catalyst options available+ Optimum choice depends upon specific quality / quantity needed

• MPHC combined with MIDW allows high pressure performance at low operating cost

• ExxonMobil has the technology and extensive operating experience+ Well positioned to assist customers in meeting their requirements