Technology for Producing Clean Diesel Utilizing Moderate...
Transcript of Technology for Producing Clean Diesel Utilizing Moderate...
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
– 2 –
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
– 3 –
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™
– 4 –
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
– 5 –
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
– 6 –
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
– 7 –
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
– 8 –
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
– 9 –
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
– 10 –
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
– 11 –
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
– 12 –
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
– 13 –
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
– 14 –
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
– 15 –
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”
– 16 –
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
– 17 –
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
– 18 –
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
– 19 –
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
– 20 –
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
– 21 –
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
– 22 –
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%
– 23 –
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
– 24 –
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
– 25 –
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