PhD. Victor Alva, Conferencia-Hydrocarbon Fundamentals San Marcos
PhD. Victor Alva, Conferencia-Hydrocarbon Fundamentals San Marcos
PhD. Victor Alva, Conferencia-Hydrocarbon Fundamentals San Marcos
OBJECTIVES
Provide awareness of the following:
1) The two fundamental principles of hydrocarbon chemistry that we take
advantage of to add value and make money
2) How our refinery processes use those principles to put hydrocarbon
molecules in the right place, and
3) How our refinery strategy ties in
.
BASIC PREMISES FOR A REFINERY
Alkylate
HGO
HCU Syn-Jet/Diesel
OP
Cutterstock
CCU Cat Gasoline
FL.D/VGO (FCC)
Cracked Pitch
Gas Oil
Pitch Coke
Coker LGO
Pitch
COKER
4
REFINERY FLOW SCHEME : HYDROSKIMMING REFINERY
N aphtha Hydro
Crude Reformer Mogas
Crude Treater
Distilling Hydro
Unit Kero / Gasoil Desulf. Kero
Unit Gasoil/Diesel
Long Residue (LR)
Fuel Oil
LPG
LPG
Naphtha
N aphtha Hydro
Crude Reformer Mogas
Crude Treater
Distilling Hydro
Unit Kero / Gasoil Desulf. Kero
Unit Gasoil/Diesel
Cracked
N aphtha
Fuel Oil
LPG
LPG
Naphth
a
N aphtha Hydro
Crude Reformer Moga
Crude Treater s
Distilling Hydro
Unit Kero / Gasoil Desulf. Kero
Gasoil/Diese
Unit l
Fuel Oil
Long Residue (LR) Hydro
Treater
Alkylation
FCC
Vacuum Gasoline
Distilling Waxy Distillate Cat-Cracking
LC O
Unit (VGO) Unit
H C O / Slurry
LPG
LPG
Naphtha Reforming Naphtha
Isomerization
Kero Mogas
H2
Gasoil
Hydro- Desulfurization
Kero
Fuel
(Long Waxy Cat Cracking / Gasoil/
High Diesel
Residue) Distillates Hydrocracking
Vacuum
Distillatio Fuel
Short
n Visbreaking /
Residue
Coking / Hycon
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feed flexibility
volume expansion
energy efficiency
utilisation
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Distillation / Separation
Physical separation of molecules by boiling point
Conversion
Breaking large molecules into smaller ones
Treating
Removing contaminants or modifying molecules to meet product specifications
5.0
2.0 Mars
Arab Lt
WTS
Chemical composition 1.5
SJV Heavy
1.0 Loreto
ANS
Paraffinic 0.5 Brent WTI
LLS
Naphthenic - Bakken
10 15 20 25 30 35 40 45
Aromatic Crude Gravity, deg API
1
2
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100
Volume 90
Fractions 80
70
Naphtha - 60
Kero 50
Diesel 40
Conv Feed 30
20
Pitch
10
Paraffins
Stable to decomposition.
Straight chain low octane, isomers higher octane.
Olefins
Relatively unstable; double bond can be saturated .
Not in conventional crude oil. Produced by chemical reaction/cracking.
Naphthenes
Stable
Good catalytic reformer feed stock.
Neither really good nor really bad for gasoline and diesel product.
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Aromatics
Stable. Does not crack (ring open) easily. Need catalyst and H 2 .
Often has paraffinic side chains that crack off.
High octane. Benzene, toluene, xylene are gasoline boiling range aromatics
that are also petro-chemical feed stocks.
Crude oil will also have hetero compounds which are those containing
chemically bound non hydrocarbon (sulfur, nitrogen, nickel, vanadium, oxygen).
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C3 C4 C6 C 10 C 15 ~C 2 0 ~C 3 0 # Carbon atoms
Naphtha
LPG
Distillation is the refinery process that separates streams according to boiling range.
Ranges overlap, allowing for optimization based on current product values.
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Hydrogen Hydrogen
Basic Structure Formula Density pct wt Formula Density pct wt
CRACKINGBIGMOLECULESINTOSMALLERMOLECULES
RESULTS IN A VOLUME EXPANSION
Next, we will do some math to calculate the mass and volume balances,
based on the above molecule balance
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CRACKING VOLUMEEXPANSION
By cracking a big molecule into seven smaller molecules, we end up with 2% additional
volumeFREE BARRELS available to sell:
C3 C4 C6 C 10 C 15 ~C 2 0 ~C 3 0 # Carbon atoms
Distillation is the refinery process that separates streams according to boiling range
Conversion processes change molecule size to move across these thresholds
Cat Cracking, Hydrocracking, Thermal Cracking, Coking
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Molecules that boil at less than 650 0 F are already the right size for
inclusion in high value products, such as gasoline or diesel;
So, dont need to crack them further in an CCU or HCU
Cracked stocks may need some additional processing, such as hydrotreating to
saturate olefins or to remove sulfur.
Molecules that boil in the 650 0 F to 1000 0 F range are of medium value;
Much higher than pitch, less than gasoline or diesel;
So, should be routed to a conversion unit like CCU or HCU; to break them into
smaller molecules that will boil in the gasoline or diesel range
If a DCU or VBU is not available, theses streams are routed to fuel oil
blending
Cutterstock is used to blend residual fuel to density and viscosity
specifications
Cutterstock selection:
should be of low boiling range (i.e. low density, to minimize volume required)
have low hydrogen content (i.e. lower alternate value).
Exception:
some straight run1000+ molecules from a low metals crude may also have low carbon
content and be suitable as CCU feed.
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Distillation / Separation
Right Molecule, Right Place
DISTILLATION IS USED IN ALMOST EVERY PROCESS UNIT
Primary Work-up
Distillation Sections
Naphtha Stabilizing
crude oil CDU Reforming
Straight run
Middle
Distillates products
Treating Stripping
Long Residue
RESTRIC TED
CRUDE DESALTER
June 2013 26
Crude Oil Atmospheric Column
Distillation
Vacuum Column
June 2013 27
CONVERSION PROCESSES
Carbon Concentration or Hydrogen Addition
Right Molecule, Right Place
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Thermal Conversion
Coking (Residue) 25
Visbreaking (Residue) Dry Gas
20 Bubble size
Hydrogenation
represents
C3 / C4 mass yield
5 Slurry Oil
C racking
Major Considerations Coke
0
Yield controlled by starting hydrogen 0 20 40 60
content
Average Carbon Number (Atoms per Molecule)
Liquid product properties function of
depth of conversion Carbon concentrates in Coke,
Metals, nitrogen critical to catalytic activity allowing for hydrogen in light products
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Hydrocracking
Low hydrogen content distillates
25
Vacuum Gas Oils
20 Dry Gas Hydrowax
Hydrogenation
Hydrogen Content, %wt
Hydroconversion (Residue) C3/C 4
15
Diesel
H-Oil at Convent Vacuum
10 Lt Naphtha Gas Oil
LC-Fining at Scotford Upgrader Hvy
Naphtha
5 Bubble size
represents
Cracking mass yield
Major Considerations 0
0 10 20 30 40
Yields for a given conversion are fairly
constant, only H 2 uptake changes Average Carbon Number (Atoms per Molecule)
Liquid product properties are also fairly All products have higher hydrogen
constant.
content than the feed
Ideal for taking low hydrogen content material
from carbon concentrating processes
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Regenerator
Cyclones x2
Cyclones
Stripping
Section
Feed nozzles
Solids Flow
RESTRICTED
FCC WORK-UP SECTION
RESTRICTED
THERMAL GASOIL UNIT (TGU)
Combitower
Naphtha minus
TC Gasoil
Vacuum
Cyclone Flasher
Long
residue
Distillate
Furnace
Residue
Furnace
Thermally
cracked
residue
THERMAL GASOIL UNIT
Combitower Vacuum
Flasher
Soaker
Cyclone
21
Coking
Delayed Coking
Most common of coking technologies
Drums are taken off line and coke removed via HP water cutting
Coke bed fluid and is partially burned to provide heat for process
25
TYPICAL COKER YIELDS & PRODUCT QUALITIES
34
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ENABLING PROCESSES
Molecular Rearrangement
Refinery Engines & Enablers
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MOLECULAR REARRANGEMENT
These process units are necessary and important parts of the refinery, but
dont drive molecules across the boiling point value thresholds.
Catalytic Reformers
convert low octane paraffins to higher octane aromatics
By-product of making a cyclic molecule is hydrogen that can be used
in hydrotreating or hydrocracking
Isomerization
Convert straight chain paraffin molecule to a branched molecule
Increases octane rating of the stream, but also increases vapor
pressure
Hydrotreating
Remove sulfur and nitrogen from streams to protect catalyst of next
process unit or to meet product specifications.
HYDROPROCESSING DEFINITIONS (W.R.T.
CONVERSION)
N aphtha
Different
VGO
80
HCU
%Conversion
60
40
HDS
0
0 20 40 60 80 100 120 140 160 180 200
Pressure, bar 100 bar ~ 1450 psia
200 bar ~ 2900 psia
HYDROTREATING PROCESS
Recycle gas
HP
bleed
H2 make-up HPS
Wash LP
off-gas
oil
Quench LPS
Feed Product
HYDROTREATING CATALYST
Reactor
Typical Hydrotreater:
Reactors
Kero
1100-2000
Waxy
distillate LP Separator Gasoil
feed 650 - 800
Desulfurization Recycle
Denitrification
Cracking
Hydrogenation
product separation 2 reactors
ISOMERIZATION PROCESS
TC-naphtha Tops
C4 minus + Isom
HC-
H2S
naphtha
S
S P
T L
N aphth HDT I Control of
A
a minu T
B Tops FBP
s
Kero
N aphth Platformer
a
CDU
Light Platformate
SEMI-REGENERATIVE REFORMER(SR)
20 - 28 bara 500 o C
500 o C 500 o C
Hydrogen-rich
Recycle gas
gas
Liquid product
to stabilizer
Feed/effluent heat exchanger
Recycle gas
Naphtha feed compressor
SEMI-REGENERATIVE
SEMI-REGENERATIVE REFORMER(SR)
REFORMER UNIT
HYSOMER UNIT
245-260 o C
475-500 oF 10-25 bar
150-350 psi
Reactor Recycle
gas
Separator
Furnace
Liquid product
RESTRICTED
ADSORBERS AND 1 HYSOMER REACTOR
REFINERY UTILITY SYSTEMS
Utility Systems Refinery Process Units
BOILER A BOILER B BOILER C BLR A BLR B BLR C $/tSRF $m/yr
Efficiency 89% 87% 85% Fuel Oil, tSRF/h 7.7 7.9 0.0 TBD #VALU
Blowdown %
Blowdown 7.00 t/hr
7% 7%
7.00 t/hr
7%
0.00 t/hr
Natural Gas, tSRF/h
0 0 0 280 0.0
E!
Import NG
Outlet H3136 kJ/kg 3136 kJ/kg 3136 kJ/kg Other refinery Fuel Oil, tSRF/h 0.3 Electricity(STG) 3.8 MW $/MW $m/yr
Fired duty 85.5 MW 87.4 MW 0.0 MW Electricity(Import)14.2 50 6.2
TOTAL Electricity Use MW
18.0
100.0 t/hr 100.0 t/hr 0.0 t/hr
Total SOxbubble, t/yr 2785 TOTAL Fuel for Steam
MW
+ Power Import
#VALUE!
Fuels
HPS 80.0 barg
400 C
200.0 t/hr 20.0 t/hr 60.0 t/hr 60.0 t/hr 30.0 t/hr 30.0 t/hr
3136 kJ/kg
PROCESS
Efficiency 32%
Out H 3033 kJ/kg 1 ST
36%
2919 kJ/kg 2 STs
45%
2674 kJ/kg 2 STs
~
128 kJ/kg
94.16 t/hr Import
Output 1.7 MW 3.6 MW 3.8 MW 124.16 t/hr
40.0 t/hr
Condensers P
-0.78 barg
Electricity
MPS 20.0 barg
235 C
120.0 t/hr
2857 kJ/kg 10.0 t/hr 40.0 t/hr 40.0 t/hr 30.0 t/hr
40%
PROCESS 2741 kJ/kg MPS MPS HPS
4 STs
50.0 t/hr 1.3 MW Users Users Users
LPS 3.5barg
165 C
920 kJ/kg OWS 1321 kJ/kg
HP steam
206.4 t/hr
2782 kJ/kg
214.0 t/hr
82.0 barg
27.3 t/hr 35.0 t/hr 130.0 t/hr
40.85 t/hr
MP steam
108 C 458 LPS LPS
kJ/kg VENT Users Users 5.59 t/hr 83.31 t/hr
0.32 barg 34.41 t/hr
70 C OWS
LP steam
452 kJ/kg
108 C
0.000 C 14.10 t/hr Demi water
PROCESS 184.2 t/hr #######
Condensate
5
7
5/15/2013
SUMMARY
Q &A
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But bigger.
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