hydrocracking of deasphalted oilconclusions • dao hydrocracking – an emre technology based on...
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Hydrocracking of Deasphalted Oil
IMP/IMP/PemexPemex RefinacionRefinacionRefining Technology SeminarRefining Technology SeminarSeptember 6, 2006September 6, 2006
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Agenda
Hydroprocessing Role in Upgrading DAO Hydrocracking
Why DAO Hydrocracking?Lab Data and Catalyst evaluation (Fuels and Lubes)Advanced Reactor Design
Spider Vortex InternalsAutomatic Bed By-pass
Conclusions
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EMRE Technologies for Quality FuelsEMRE Technologies for Quality Fuels
EMRE HYDROFINING
Distillate
LCO Upgrading
Waxy Feeds Heavy Feeds
ULSD MPHC(+PTU)
MPHC +
MIDW
MIDWMDDWGOfining
ULSD +HDHDC
ULSD +MAXSAT RESIDfining
Naphtha
FCC Naphtha
OCTGAIN
Hydrofining
SCANfining
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0
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14
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18
20
1 10 100 1000 1000Metals Content (Ni+V, ppm)
Con
rads
on C
arbo
n (%
)
Hydroprocessing
Resid Quality Drives Conversion Options• Very Low CCR/Metals
• Once through Hydrocracking
• Low CCR/Low Metals:• Resid FCC possible
• Mid CCR/Mid Metals:• Utilize hydroprocessing to
upgrade slate+ ARDS+ LC-Fining/H-Oil+ Microcat-RC
• High CCR/High Metals:• Reject carbon to coke
product- FXK, DLK
Hydroprocessing
Thermal Processing
Resid FCC
Maya
Hydrocracking
• Segregate hydrogen to liquids/gas
• ROSE allows a % of high CCR/High metals to HP or Resid FCC applications and reduce the size of the coker
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Removing Asphaltenes from Resid
• Removes CCR• Removes Metals• Removes Polars (i.e. sulfur, nitrogen)• Reduces viscosity• DAO becomes viable HDC feedstock• FXK or DLK unit is smaller capacity
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Typical Contaminant Distribution in ROSE DAO
% COMPONENT IN DAO
100
80
0 10 20 30 40 50 60 70 80 90 100
METALS
SULFUR
NITROGEN
CCR
ASPHALTENES
60
40
20
0
DAO YIELD, VOL %
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Flow Diagram For DAO Hydrocracking
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
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HDC Reaction Zones
Reactor Catalyst HDCConfiguration Type Reactions
Metal
Bifunctional(Metal + Acid)
TreatingZone
CrackingZone
HDM
HDN
selectivecracking
with low arosat
Sulfur polishingIf needed
Post TreatZone Metal
HDS
HDA
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Bitumen Derived DAOBitumen Derived DAO
Example HP Pilot Plant Studies at EMRE
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ROSE and Hydrotreating StudyFeed
• DAO Source – Solvent extraction of 650+ Alberta bitumen
• DAO Quality– API Gravity 14.4– Sulfur, wt% 3.5– Nitrogen, wt% 0.20– Vanadium, ppmw 12– Nickel, ppmw 6– ConCarbon, wt% 3.3– C5 Insolubles, ppmw 100
• Laboratory Tests on Bitumen Derived DAO• Parallel sets of tests with two catalysts • Product yield and quality
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Bitumen DAO HydrotreatingTest Results – Bitumen Feed
26.2 145 63
25.1 481 359
Treated Product QualityAPI GravitySulfur, wt%Nitrogen, ppmw
1500700 0.62
1500700 0.62
Operating ConditionsPressure, psigTemperature, FLHSV, 1/hr
Light DAOCatalyst B
Light DAOCatalyst A
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DAO HydrocrackingDAO Hydrocracking
Example HP Pilot Plant Studies at EMRE
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Pilot Plant StudyDAO Partial Conversion Hydrocracking
• Feed: 30/70 blend of DAO/VGO• MPHC Feed quality
– API 22.2– Sulfur 1.42 w%– Nitrogen 1300 ppmw– RI@70C 1.491– Ni+V, ppmw 5.8– SimDis 10/90% 692/11171F– CCR ~2 wt%
• Conversion 13-60%• With DAO/VGO feeds yields similar to VGO only
except increased hydrogen use
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DAO HDC Pilot Study
Operating Conditions and Yields on 30/70 DAO/VGO
Pressure, psig 1,960H2 Circulation, SCF/BBL 6,000
Temperature Base Base + 25650 F+ Conversion 13 53
H2 Consumption 825 1530
Yields, Vol%C5-180 F 0.2 7.2180-330 F 1.8 17.0330-440 F 2.1 17.8440-650 F 12.5 22.1650 F+ 87.2 47.5
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DAO HDC Pilot Study
Product Qualities for 53% Conversion
Lt. Hvy. Kero. Diesel FCCUNaphtha Naphtha Feed
Gravity 80 53 44.1 40.2 35.1Sulfur, ppmw <10 <100 <200 <200 <200Nitrogen, ppmw <0.5 <0.5 <0.5 <1.0 <5RON Clear 77 60Smoke 26Cetane Index 40 58Ni+V, ppmw <0.3
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HDC DAO for Lubes
• High Viscosity of HDC DAO bottoms can be a potential lubes feedstock• VI must be increased to meet lube
specifications (related to conversion)• Sulfur and nitrogen must be reduced
sufficiently to allow hydroisomerization• ExxonMobil Licenses such a
hydroisomerization process (MSDW) with 16 Licensees. Some process HDC and HDT DAO.
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HDC DAO for Lubes using MSDW
Results of 6 month pilot study with 2 different DAO feeds
DAO A DAO B
Feed# 1 2 1 2HDC severity high low high low
MSDW FeedNitrogen, ppmw 2 24 22 157Sulfur, ppmw 8 283 146 704CCR, wt% 0.01 0.06 0.14 0.57
MSDW Product (bottoms fraction)
kV@100 C,cst 20.7 28.9 24.1 40.1VI 120 100 107 93Pour point,C -14 -11 -2 -8
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Reactor Internals DesignReactor Internals Design
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Importance of Reactor Design
• Internal design is more and more critical for higher conversion/ more stringent product specifications
• low sulfur specs unforgiving for any maldistribution
• lower radial delta T minimizes peak temperature and gives longer life
Solution:ExxonMobil Spider-Vortex
BED OUTLET
COLLECT
QUENCH
REDISTRIBUTE
BED INLET
Quench ZoneFundamentals
X
X
XXX
X
X
X
RADIAL ∆T
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Automatic Bed Bypass Technology: Simple and Effective
Bed Segmentwith Bypass
Main Catalyst Bed(s)
Liquid and Gasspecial
internals• Proprietary design enables automatic bypassing of flows around fouled catalyst layer
• Simple, low-cost construction
• Automatic operation with no moving parts
• Protects against unavoidable bed fouling events by “buying time”
Liquid and Gas
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Conclusions
• DAO Hydrocracking – an EMRE technology based on understanding of fundamentals and backed by extensive development and operating experience
• DAO is an effective HDC Feedstock for single pass hydrocracking units
• Bottoms products make excellent FCC feed • Making 10 ppm diesel from DAO is possible but a
post treat unit is preferred to maintain performance
• HDC DAO bottoms can make excellent lubes with <10 ppm sulfur product diesel possible when processing over MSDW.
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Back up
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Materials with Complex Structures
• AsphaltenesPrecipitated from Crude Oils by Aliphatic Solvents (e.g. n-C5). Soluble in Benzene. Mol. Wt. 1000-3000. High in S, N, O, and Metals (V + Ni).
S
S
O
H
OO
N
N
C84H98N2S2O31248 Mol. Wt.40.4% Aromatic Carbons
80.85 wt%C7.92 wt%H2.24 wt%N5.14 wt%S3.85 wt%O