OIL

 REFINING  PROCESSES
Advanced  course
Assoc.Prof.  Pham  Huyen
huyen.phamthanh@hust.edu.vn
References
• Chang  Samuel  Hsu  and  Paul  R.  Robinson,  Practical  Advances  in  
Petroleum  Processing,  Vol 1,  Springer,  2006
• Mohamed  A.  Fahim,  Taher A.  Alsahhaf and  Amal Elkilani,  
Fundamentals  of  Petroleum  Refining,  Elsevier,  2010
Outline

Unit  1.  Introduction

Unit  2.  Refinery  Feedstocks and  Products

Unit  3.  Modern  Petroleum  Processing  

Unit  4.  Auxiliary  Processes  &  Utilities  

 Unit  1.  Introduction
Largest  Worldwide   Refineries

Approximately
650  Refineries   in
the  world

Source:   Oil  &  Gas  Journal

Unit  1.  Introduction
• High   sulfur,  heavy  crude  is  lowest   cost.  
àRequires   extremely  complex  
refinery  to  convert  into  high  value  
products.
• Low  sulfur,  light  crude  is  highest  cost.    
à Simple  refining  yields  high  value  
products.
• a  function  of  location   of  crude  supply  
versus  refining  centers.
à Refiners  close  to  crude  production  
enjoy  advantage   over  refineries  
distant  from   supply
Unit  1.  Introduction
 Unit  1.  Introduction

Note:  product  blending  and  sulfur  

recovery  units  are  not  shown,  but  
these  are  almost  always  present
Unit  1.  Introduction
• DQR  Introduction
• NSRP  Introduction
Unit  2.  Refinery   Feedstocks and  Products

2.1.  Composition  of  Crude  Oils

2.2.  Products  Composition

2.3.  Physical  Property  Characterization  Data

2.4.  Chemical  Analysis  Data

2.1.  Composition   of  Crude  Oils

Impurities  (sulphur,   nitrogen,  oxygen  

and  metals):
-­‐ low  concentrations
-­‐ undesirable
-­‐ affect  the  quality  of  the  produced  
products
-­‐ Catalyst  poisoning   and  corrosion  
2.1.  Composition   of  Crude  Oils
Hydrogen  to  carbon  ratios  affect  the  physical  properties  of  crude  oil.  
-­‐ As the hydrogen to carbon ratio decreases, the gravity and boiling
point of the hydrocarbon compounds increases.
-­‐ the  higher  the  hydrogen  to  carbon  ratio  of  the  feedstock,  the  higher  its  
value  is  to  a  refinery  because  less  hydrogen  is  required.
2.1.  Composition   of  Crude  Oils
 2.1.  Composition   of  Crude  Oils
Hydrocarbons:
-­‐ Paraffins
-­‐ Olefins are  not  naturally   present  in  crude  oils  
but  they  are  formed  during   the  conversion  
processes
-­‐ Naphthenes (cycloalkanes):  
Mutli-­‐ring   naphthenes are  present  in  the  heavier  
parts  of  the  crude  oil
-­‐ Aromatics
Polynuclear aromatic  compounds  are  found  in  
the  heavy  petroleum   cuts
à cause  catalyst  deactivation   and  coke  
deposition   during   processing
à environmental   problems  
2.1.  Composition   of  Crude  Oils
 2.1.  Composition   of  Crude  Oils
-­‐ Sulphur Compounds
• varies  from  less  than  0.05  to  more  than  10  
wt%  (but  generally   falls  in  the  range  1–4  
wt%).  
• Crude  oil  with  less  than  1  wt%  sulphur is  
referred  to  as  low  sulphur or  sweet,  and  
that  with  more  than  1  wt%  sulphur is  
referred  to  as  high  sulphur or  sour.
• Sulphur heteroatoms
• inorganic   forms:  elemental  sulphur S,  
dissolved   hydrogen  sulphide   H2S,  
carbonyl  sulphide   COS
• organic  forms:  mercaptans and  
sulphides,   Sulphides and   disulphides,  
Thiophenes
 2.1.  Composition   of  Crude  Oils
-­‐ Oxygen  Compounds
• less  than  2  wt%.  
• include   alcohols,   ethers,  carboxylic   acids,  
phenolic   compounds,   ketones,  esters  and  
anhydrides.  
• causes  the  crude  to  be  acidic  with  
consequent  processing   problems  such  as  
corrosion.
 2.1.  Composition   of  Crude  Oils
-­‐ Nitrogen  Compounds
• Crude  oils  contain  very  low  amounts  of  
nitrogen  compounds.  
• the  more  asphaltic   the  oil,  the  higher  its  
nitrogen  content.  
• more  stable  than  sulphur compounds   à harder  
to  remove.  
• be  responsible   for  the  poisoning   of  a  cracking  
catalyst,  and  contribute  to  gum  formation   in  
finished   products.
• The  nitrogen   compounds   in  crude  oils  may  be  
classified  as  basic  or  non-­‐basic.  
• Basic  nitrogen  compounds:  pyridines.
• Non-­‐basic  nitrogen  compounds:  pyrrole types.
 2.1.  Composition   of  Crude  Oils
-­‐ Metallic  Compounds
• exist  in  all   crude  oil  types   in  very  small  amounts
• cause  operational  problems  and  contaminate  the  products,  affect  upgrading  processes
• cause  poisoning  to  the  catalysts used  for  hydroprocessing and  cracking.  
• small  amounts  of  metals  (iron,  nickel  and  vanadium)  in  the  feedstock   to  the  catalytic  cracker  affect  
the  activity   of  the  catalyst  à increased  gas  and  coke   formation  and  reduced  gasoline  yields.
• For  high-­‐temperature  power  generators,  the  presence  of  vanadium  in  the  fuel  may  lead  to  ash  
deposits on  turbine  blades  and  cause  severe  corrosion,  and  the  deterioration of  refractory  furnace  
linings.
• inorganic  water-­‐soluble  salts,  mainly  as  chlorides  and  sulphates of  sodium,  potassium,  magnesium  
and  calcium  à removed  in  desalting  operations.  
• oil-­‐soluble  organometallic  compounds:  Zinc,  titanium,  calcium  and  magnesium  appear  in  the  form  
of  organometallic  soaps.
• oil-­‐soluble  compounds:  vanadium,  nickel,  copper  and  iron  àcomplexing with  pyrrole compounds.
 2.1.  Composition   of  Crude  Oils
-­‐ Asphaltenes:
-­‐ condensed   polynuclear aromatic  layers  linked   by  saturated  links,  
-­‐ lead  to  coke  formation  and   metal  deposition   on  the  catalyst  surface  causing  catalyst  
deactivation.
-­‐ Resins  
-­‐ polar   molecules  in  the  molecular   weight  range  of  500–1000,
-­‐ insoluble   in  liquid   propane   but  soluble   in  n-­‐heptane.  
-­‐ responsible   for  dissolving   and  stabilizing   the  solid  asphaltene molecules   in  petroleum.  
The  resin  molecules   surround   the  asphaltene clusters  (micelles)  and   suspend  them  in  
liquid   oil.  Because  each  asphaltene is  surrounded   by  a  number  of  resin  molecules,  the  
content  of  resins  in  crude  oils  is  higher  than  that  of  the  asphaltenes.
2.2.  Products  Composition
-­‐ Liquefied   Petroleum  Gas  (LPG)
-­‐ Gasoline
-­‐ Kerosene
-­‐ Jet  Fuel
-­‐ Diesel  Fuel
-­‐ Fuel  Oil  (Residual  Fuel  Oil)
-­‐ Lube  Oil
-­‐ Asphalt
-­‐ Petroleum  Coke
2.2.  Products  Composition
2.2.  Products  Composition
2.2.  Products  Composition
2.2.  Products  Composition
Major  quality  aspects  of  main  petroleum  products  
2.2.  Products  Composition
2.3.  Physical  Property  Characterization  Data
2.3.1.  Fractionation 2.3.10.  Aniline   Point
2.3.2.  True  Boiling   Point  Distillation 2.3.11.  Flash  Point
2.3.3.  ASTM  Distillation 2.3.12.  Octane  Number
2.3.4.  Simulated   Distillation   by  Gas   2.3.13.  Cetane Number
Chromatography 2.3.14.  Smoke  Point
2.3.5.  API  Gravity 2.3.15.  Reid  Vapour Pressure
2.3.6.  Pour  Point 2.3.16.  Water,  Salt  and  Sediment
2.3.7.  Viscosity 2.3.17.  Molecular   Weight
2.3.8.  Refractive  Index
2.3.9.  Freezing  Point
2.4.  Chemical  Analysis  Data
2.4.1.  Elemental  Analysis
2.4.2.  Carbon   Residue
2.4.3.  Detailed   Hydrocarbon   Analysis
2.4.4.  Hydrocarbon   Family   Analysis
2.4.5.  Aromatic  Carbon  Content
2.4.6.  SARA  Analysis
ASTM  testing  grid  for  crude  oil  and  petroleum  fractions
Unit  3.  Modern  Petroleum  Processing  
Unit  3.  Modern  Petroleum  Processing  
3.1.  SEPARATION  
3.1.1.  Distillation
3.1.2.  Solvent  Refining
3.2.  CONVERSION  
3.2.1.  Thermal  cracking
3.2.2.  FCC
3.2.3.  Hydrotreating and  hydrocracking
3.3.  UPGRADING  NAPHTHA  
3.3.1.  Catalytic  Reforming  
3.3.2.  Isomerization  
3.3.3.  Catalytic  Oligomerization
3.3.4.  Alkylation  
 3.1.1.   Distillation
• the  biggest  unit  in  most  plants
• Many  downstream  conversion  
units  also  use  distillation  for  
production  separation
• To  reduce  corrosion,  plugging,  
and  fouling  in  crude  heaters  
and  towers,  and  to  prevent  
the  poisoning  of  catalysts  in  
downstream  units,  these  
contaminants  are  removed  by  
a  process  called  desalting
3.1.1.   Distillation
 Atmospheric  distillation
• At  the  bottom  of  the  stripping  
section,  steam  is  injected  into  the  
column  
• to  strip  the  atmospheric  residue  of  
any  light  hydrocarbon  and  
• To  lower  the  partial  pressure  of  the  
hydrocarbon  vapours in  the  flash  
zone.  
àlowering  the  boiling  point  of  the  
hydrocarbons  
àcausing  more  hydrocarbons  to  boil  
and  go  up  the  column  to  be  
eventually  condensed  and  withdrawn  
as  side  streams.  
 Vacuum  Distillation  
-­‐ residue  from  an  atmospheric  
distillation  tower
-­‐ The  vacuum,  which  is  created  by  a  
vacuum  pump  or  steam  ejector,  is  
pulled  from  the  top  of  the  tower.
-­‐ vacuum  columns  have  larger  
diameters  and  their  internals  are  
simpler  (random  packing  and  
demister  pads  are  used)
-­‐ The  overhead  stream  à lube  
base  stock,  heavy  fuel  oil,  or  as  
feed  to  a  conversion  unit
-­‐ The  vacuum  residue  à asphalt,  or  
feedstock  for  coker or  visbreaker
unit
3.1.2.   Solvent  Refining
a. Solvent  Deasphalting
b. Solvent  Extraction  
c. Solvent  Dewaxing,  Wax  Deoiling
a. Solvent  Deasphalting (SDA)  
• Solvent  deasphalting takes  advantage  of  the  fact  
that  aromatic  compounds  are  insoluble  in  
paraffins.  
• Propane  deasphalting is  commonly  used  to  
precipitate  asphaltenes from  residual  oils.  
• Deasphalted oil  (DAO)  is  sent  to  hydrotreaters,  
FCC  units,  hydrocrackers,  or  fuel-­‐oil  blending.  In  
hydrocrackers  and  FCC  units,  DAO  is  easier  to  
process  than  straight-­‐run  residual  oils.  This  is  
because  asphaltenes easily  form  coke  and  often  
contain  catalyst  poisons  such  as  nickel  and  
vanadium,  and  the  asphaltene content  of  DAO  is  
(by  definition)  almost  zero.  
 a. Solvent  Deasphalting (SDA)  
• An  advanced  version  of  solvent  deasphalting is  “residuum  oil  supercritical  
extraction,”  or  ROSE.  
• In  this  process,  the  oil  and  solvent  are  mixed  and  heated  to  above  the  
critical  temperature  of  the  solvent,  where  the  oil  is  almost  totally  insoluble
• Advantages  include  higher  recovery  of  deasphalted liquids,  lower  operating  
costs  due  to  improved  solvent  recovery,  and  improved  energy  efficiency.
• The  ROSE  process  can  employ  three  different  solvents,
-­‐ Propane:    Preparation  of  lube  base  stocks
-­‐ Butane  :    Asphalt  production
-­‐ Pentane:    Maximum  recovery  of  liquid
Schematic  of   the  ROSE   process
Refinery  with  solvent  deasphalting,  Rose-­‐residue  oil  supercritical  extraction  unit
b.  Solvent   Extraction  
• to  remove  aromatics  and  other  
impurities  from  lube  and  grease  
stocks.
• The  solvent  is  separated  from  the  
product  stream  by  heating,  
evaporation,  or  fractionation.
• Remaining  traces  of  solvent  are  
removed  from  the  raffinate by  
steam  stripping  or  flashing.
• NMP,  phenol,  furfural,  and  cresylic  
acid  are  widely  used  as  solvents.
 c.  Solvent  Dewaxing,  Wax  Deoiling

• Solvent  dewaxing removes  wax  (normal  paraffins)  from  deasphalted lube  

base  stocks.
• The  main  process  steps  include  mixing  the  feedstock  with  the  solvent,  
chilling  the  mixture  to  crystallize  wax,  and  recovering  the  solvent.
• Commonly  used  solvents  include  toluene  and  methyl  ethyl  ketone  (MEK).
• Methyl  isobutyl  ketone  (MIBK)  is  used  in  a  wax  deoiling process  to  prepare  
food-­‐grade  wax.  
Unit  3.  Modern  Petroleum  Processing  
3.1.  SEPARATION  
3.1.1.  Distillation
3.1.2.  Solvent  Refining
3.2.  CONVERSION  
3.2.1.  Thermal  cracking
3.2.2.  FCC
3.2.3.  Hydrotreating and  hydrocracking
3.3.  UPGRADING  NAPHTHA  
3.3.1.  Catalytic  Reforming  
3.3.2.  Isomerization  
3.3.3.  Catalytic  Oligomerization
3.3.4.  Alkylation  
3.2.1.   Thermal  cracking  

• Visbreaking
• Delayed  Coking  
• Fluid  Coking  
 3.2.1.   Thermal  cracking  
Visbreaking Delayed  coking Fluid  coking  and  flexicoking
• Feed:  AR  or  VR • Feed:  VR,  FCC  slurry,   • Feed:  VR
• Mild  heating  471–493  C   visbreaking tar • Severe  heating  482–566oC  
(880–920   F)  at  50–200  psig • Moderate  heating  482–516oC   (900–1050F)   at  10  psig
• Reduce  viscosity  of  fuel  oil (900–960F)   at  90  psig • Fluidized  bed  with  steam
• Low  conversion  (10%)  at   • Soak  drums  452–482oC  (845– • Higher  yields  of  light  ends
221oC  (430F) 900F)
• Less  coke  yield  (20%  for  
• Heated  coil  or  soaking   • Residence  time:  until  they  are   fluid  coking  and  2%  for  
drum full  of  coke flexicoking)
• Products:  gases,  naphtha,   • Coke  is  removed  hydraulically • Products:  gas,  naphtha,  
gas  oil,  reridue or  tar • Coke  yield    30  wt%,   LCO,  HCO,  coke
unsaturated  gases,  LN,  HN,  
LCO,  HCO
 Visbreaking

(A) Coil type visbreaker. (B) Soaker type visbreaker

• more stable visbreaker products • less  capital  investment,  

• more  flexible  and  allows  the  production  of   • consumes  less  fuel
heavy  cuts,  boiling  in  the  vacuum  gas  oil  range • longer  on-­‐stream  times
Delayed  coking
3.2.2.   Fluid  Catalytic  Cracking  
• A  typical  FCC  unit  comprises  three  major  sections  
• riser/reactor,
• Regenerator
• fractionation.
• Purpose
• Convert  heavy  oils  into  gasoline  and/or  light  olefins
• Licensors
• Axens (IFP)   ExxonMobil  
• KBR   Stone  &  Webster
• UOP
3.2.2.   Fluid  Catalytic  Cracking  
• Catalysts  and  Additives
• Zeolite  (highly  acidic,  catalyzes  cracking)  
• Rare-­‐earth  oxide  (increases  catalyst  stability)
• ZSM-­‐5  (increases  octane  and  production  of  light  olefins)
• Pt (promotes  combustion  of  CO  to  CO  in  regenerator)
• Desox (transfers  SOx from  regenerator  to  riser/reactor)  .
• Feeds
• Atmospheric  gas  oil   Vacuum  gas  oil
• Coker  gas  oil   Deasphalted oil
• Lube  extracts   Vacuum  resid (up  to  20  vol%)  
3.2.2.   Fluid  Catalytic  Cracking  
• Typical  Feed  Properties
• Nitrogen   <3000  wppm
• Carbon  residue   <5.0  wt%
• Nickel  +  Vanadium   <50  wppm
• 90%  boiling  point   <1300°F  (704°C)
• Typical  Process  Conditions
• Feed  temperature   300  – 700°F  (150  – 370°C)
• Reactor  temperature   920  – 1020°F  (493  – 550°C)
• Regenerator  temperature 1200  – 1350°F  (650  – 732°C)
• Catalyst/Oil  ratio   4.0  – 10.0
• Reactor  pressure   10  – 35  psig  (170  – 343  kPa)
3.2.2.   Fluid  Catalytic  Cracking  
• Typical  Product  Yields
• Conversion   70  – 84  vol%
• H2,  H2S,  methane,  ethane   3.0  – 3.5  wt%
• Propane  and  propylene   4.5  – 6.5  wt%
• Butanes  and  butenes 9.0  – 12.0  wt%
• Gasoline   44  – 56  wt%  
• LCO   13  – 20  wt%  
• Slurry  oil   4  – 12  wt%
• Coke   5  – 6  wt%
• Total  C3-­‐ plus   106  – 112  vol%
 3.2.3.   Hydrotreating and  hydrocacking

LGO = Light Gas Oil HGO = heavy Gas Oil LCO = FCC Light Cycle Oil
HCO = FCC Heavy Cycle Oil VGO = Vacuum Gas Oil VBGO = Visbreaker Gas Oil CGO = Coker Gas Oil
3.2.3.   Hydrotreating and  hydrocacking
3.2.3.   Hydrotreating and  hydrocacking
Role  of  hydrotreating (HT)  in  the  refinery
1.  Meeting  finished  product  specification.
• Kerosene,  gas  oil  and  lube  oil  
desulphurization.
• Olefin  saturation  for  stability  
improvement.
• Nitrogen  removal.
• De-­‐aromatization  for  kerosene  to  
improve  cetane number,  
2.  Feed  preparation  for  downstream  
units:
• Naphtha  is  hydrotreated for  removal  of  
metal  and  sulphur.
• Sulphur,  metal,  polyaromatics and  
Conradson carbon  removal  from  
vacuum  gas  oil  (VGO)  to  be  used  as  FCC  
feed.
• Pretreatment  of  hydrocracking  feed  to  
reduce  sulphur,  nitrogen  and  
aromatics.
Naphtha hydrotreating unit Diesel fuel hydrotreating unit
Atmosphere residue desulphurization process
3.2.3.   Hydrotreating and  hydrocacking
3.2.3.   Hydrotreating and  hydrocacking
Unit  3.  Modern  Petroleum  Processing  
3.1.  SEPARATION  
3.1.1.  Distillation
3.1.2.  Solvent  Refining
3.2.  CONVERSION  
3.2.1.  Thermal  cracking
3.2.2.  FCC
3.2.3.  Hydrotreating and  hydrocracking
3.3.  UPGRADING  NAPHTHA  
3.3.1.  Catalytic  Reforming  
3.3.2.  Isomerization  
3.3.3.  Catalytic  Oligomerization
3.3.4.  Alkylation  
3.3.1.   Catalytic  Reforming
3.3.1.   Catalytic  Reforming  
3.3.2.   Isomerization  
3.3.2.   Isomerization  
Sơ đồ công nghệ Penex Sơ đồ quá trình Penex kết hợp
với Deisohexane
3.3.3.   Catalytic  Oligomerization

ΔH  <  0

• Catalysts:  
• Sulfuric  acid,  phosphoric  acid,  and  solid   phosphoric  acid  on  kieselguhr pellets  (SPA)  
are  used  as  catalysts.  
• The  SPA  catalyst  is   non-­‐corrosive,  so  it   can  be   used  in  less-­‐expensive   carbon-­‐steel  
reactors.
• Temperatures:  300  to  450°F  (150  to  230°F)  
• Pressures:  200  to  1,200  psig  (1480  to  8375  kPa).
3.3.3.   Catalytic  Oligomerization
 UOP’s  indirect  Alkylation  (LnAlk)  process  

SPA:  solid  
phosphoric  
acid
3.3.4.   Alkylation    

(H2SO4,   HF)
 3.3.4.   Alkylation    

• Zeolite  catalyst
• Liquid  phase
• 50  – 90oC
• uncommercialized
Unit  4.  Auxiliary  Processes  &  Utilities    
• Steam  Methane  Reformer  (hydrogen   • Waste  Water  Processing  
production)   • Relief  Systems  and  Flares  
• Light  Ends  Recovery  Units   • Plant  and  Instrument  Air  
• Lube  Oil  Units   • Flare  Gas  Recovery  Units  
• Amine  Treater • MSAT  Benzene  Reduction  Units  
• Caustic  and  Merox Treaters (similar  to  ISOM  unit)  
• Sulfur  Recovery,  Tail  Gas  Treating,   • Nitrogen  Systems  
NaHS Units   • Electrical  Systems
• Sour  Water  Strippers  
• Water  Treating  (de-­‐ionization)  
• Steam  Production  
 Energetic   issues  in   an  oil  refinery

• Refinery  gas  +  petroleum  coke  +  other  oil-­‐based  

Energy by source in an oil refinery
by-­‐products  accounts  for  65%  of  the  energy  
Other
7% sources  in  an  oil  refinery.
Electricity
5%
• 38%  of  the  energy  sources  in  an  oil  refinery  are  
Refinery
Natural gas gas
used  to  produce  non-­‐fuel  products  like  lubricant  
25% 46% oils,  wax,  asphalt,  and  petrochemical  feedstocks.
Petroleum • Oil  refineries  generate  large  amounts  of  electricity  
coke
17%
on-­‐site.  
• The  cost  of  energy  for  heat  and  power  accounts  
for  c.a.  40%  of  the  operating  costs  in  a  refinery!!!
Energetic   issues  in   an  oil  refinery   [Worrell   2005]
Sulfur  Recovery
• Purpose
Converts  H2S  gas  into  elemental  sulfur,  “Claus”  Unit
• 1/3  of  H2S  burned  in  Reaction  Furnace  to  produce  SO2 (sulfur  dioxide)    
1.5  O2 +  H2S  àSO2 +  H2O
• Zinc  Oxide  catalyst  beds  convert  SO2 and  H2S  into  elemental  sulfur  and  
water    
SO2 +  2H2S  à3S  +  2H2O
• Sulfur  is  collected  in  pit  or  tank  and  trucked  /  railed.    Used  in  chemical  
manufacture.
• Process  is  about  96%  efficient,  so  Tail  Gas  Treating  (SCOT  Unit  or  other)  
required  to  purify  off  gas
 Steam  Production

• Purpose  
Provide  steam  for  process  heating,  steam  stripping  in  distillation,  and  steam  turbine  drivers
• Multiple  Boilers  at  various  steam  pressure  levels
• Certain  Process  Units  are  net  producers  of  steam  from  waste  heat
 Waste  Water  Treatment
• Purpose  
Remove  Oil,  Grease  and  other  
contaminants  from  Refinery  Waste  
Water  to  meet  discharge  permit  
requirements
• Many  processes  combined  to  meet  
specific  refinery  waste  characteristics  
and  discharge  requirements
• Oil  removal  and  biological  treatment  are  
1st step
• Can  be  re-­‐used,  injected  underground  
or  sent  to  waterrway
Waste  Water  Treatment

A  refinery  
typically   uses  
more  water  
than  crude  
oil!
Particulate  Emission  Control  
• Wet  gas  scrubbing  (WGS)  is  very  efficient  (>90%)  for  removal  of  
particulates  (4–10  mm)  from  the  FCC  regenerator  exit.  Cyclones  could  
be  the  first  choice  clean-­‐up  device  for  particulates.  
• Electrostatic  precipitators  (ESP)  employ  an  electrostatic  field  to  apply  
a  charge  to  particulate  emissions  and  then  collect  them  on  grounded  
metal  plates.  ESP  units  are  very  efficient  (99.8%)  for  removing  finer  
(4–10  mm)  particulates  from  FCC  regenerator  gas.  
Treatment of FCCflue gases byWGS Treatment of FCC flue gases by ESP
Exercise  1.  Calculating  Properties  Utilizing  UNISIM
Software
Process  simulators  are  used  to  characterize  crude  oil  and  determine  the  
thermophysical properties  of  crude  oil  and  fractions.  
UNISIM  simulator  can  be  utilized  in  defining  pseudo-­‐components  of  a  crude  oil,  
given  its  crude  assay.  It  provides  the  option  of  selecting  the  thermodynamic  model  
for  vapour–liquid  equilibrium  and  thermodynamic  properties  calculations.  
It  is  recommended  to  use  Peng–Robinson  equation  of  state  to  model  hydrocarbon  
and  petroleum  mixtures  in  UNISIM.  Detailed
Consider  the  following  crude  assay  which  
has  API  =  29
à Use  UNISIM  to  divide  the  crude  into  
10  pseudo-­‐components  and  calculate  all  
cut  properties.  

Solution:
• The  crude  assay  (vol%  versus  TBP)  is  
entered  the  oil  environment  and  oil  
manager  data  entry  of  UNISIM,  and  the  
number  of  pseudo-­‐components  (10  
cuts)  is  entered  in  the  Blend  calculation.  
The  properties  calculated  by  UNISIM  are  
listed  in  Table  .1.
Exercise  2:  Design  of  Crude  Distillation  Units  Using
Process  Simulators
The  simulation  or  design  of  the  distillation  columns  involves  dividing  the  crude  oil  
into  pseudo-­‐components  (Exercise  1).  Then  a  thermodynamic  model  is  chosen  for  
vapour liquid  equilibrium  and  thermodynamic  properties  calculations.  A  good  
model  is  the  cubic  equations  of  state,  and  the  Peng–Robinson  equation  is  one  of  
the  most  widely  used  models  for  hydrocarbon  and  petroleum  mixtures.  
Next,  the  unit  operations  stage-­‐wise  or  ‘‘tray  to  tray’’  distillation  calculations  are  
performed.  The  mass,  energy  balance  and  vapour liquid  equilibrium  relations  for  
each  tray  are  written  and  solved  together,  subject  to  certain  specification  for  the  
products.  Computer  simulation  programs  such  as  UNISIM  are  used  for  quick  
simulation  of  CDU  units.
Perform  a  material  balance  for  a  CDU  using  UNISIM  for  
100,000  BPCD  of  29  API  crude  with  the  following  assay.
• The  crude  is   fed  to  a  pre-­‐flash  separator  operating  at  
450  F  and  75  psia.  The  vapour from  this  separator  
bypasses  the   crude  furnace  and  is  remixed  with  the  hot  
(650F)  liquid  leaving  the  furnace.  
• The  combined  stream  is   then  fed  to  the  distillation  
column  (Figure  1).  The  column  operates  with  a  total  
condenser,  three  side   strippers  and  three  pumparounds
(Figure  2).

Figure   1 Figure   2
Solution:
In  the  oil  environment  and   oil  manager  data  entry  of  the  UNISIM  software,  the  crude  assay  is  
entered  as  vol%  and  TBP.  The  yield  distribution   of  the  products  is  shown   in  Figure  3.
The  distillation   column  has  three  inlet  steam  streams,  with  pressures  and  flow  rates  listed  in  
Table  1.  The  main   distillation   column   contains  29  stages  (see  Figure  2).  The  overhead  
condenser  operates  at  19.7  psia and   the  bottoms  at  32.7  psia.  The  side  stripper  connections  
are  also  shown  in  Figure  2.

Figure   3.
 Exercise  3:  Simulation  of  ARDS  Unit
• A heavy residue stream that contains mostly n-­‐C30 (990 lb mol/h) and some amount of
thiophene (10 lb mol/h) is prepared to enter an ARDS process to crack the heavy
component n-­‐C30 to more lighter components such as n-­‐C20, n-­‐C10 and n-­‐C4. In
addition, thiophenes should be completely removed. The feed stream is initially at
100F and 120 psia. This feed needs to be mixed with hydrogen stream (1250 lb mol/h)
available at 150F and 200 psia. The mixed feed should be heated and compressed to
700F and 1500 psia before entering the reactor. The reactions are shown in Table.
• The reactor products are cooled to 200F before entering a gas–liquid separator. 300 lb
mol/h of the hydrogen coming from this separator is recycled back with the feed. The
rest is vented to the atmosphere. The liquid stream coming out from the separator is
then expanded by a valve to reduce the pressure to 250 psia. This makes it ready to
enter a distillation column in order to separate the extra hydrogen left with the
hydrocarbons. A typical flowsheet of the ARDS process is shown in Figure. Perform a
material and energy balance for the ARDS process using UNISIM simulator.
Solution:
1.  Enter  the   simulation  basis   environment  in  UNISIM.
2.  Add  the  components  as  follows:  Thiophene,  n-­‐C30,  n-­‐C20,  n-­‐C10 ,  n-­‐C4,  H2  and  H2S.
3.  Select   Peng–Robinson  as  the   fluid  package.
4.  Insert  Reaction-­‐1  stoichiometry  and  conversion  and  do  the   same   for  Reaction-­‐2.
5.  Enter  simulation   environment.
6.  Insert  the   first  unit  for  the  oil   feed  as  shown  in  the   flow  chart  with  compositions,  temperature  
and  pressure  as  given  in  Table  2.
7.  Continue  inserting   units  as   shown  in  the  flowsheet.
8.  The   reactor  is  a   conversion  reactor.
9.  The   distillation   column  is   15  trays  with  reflux  ratio  equal   to  1.0  and  full  reflux.  The   active  
specification  to  run  the   distillation   column  is  a  hydrogen  recovery  of  100%  and  an  n-­‐decane
recovery  of  90%.
10.  Finally,  add  the   recycle  control  unit  to  optimize  the   connections.
UNISIM  results