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LPG and Gas

Modern oil refinery
Refinery fuel
LPG Alkylate
Alkylation gas
Straight run gasoline
LPG
Atmospheric
Distillation

Naphtha Hydro- Catalytic Reformate
treating reforming
Gasoline
Crude oil
Middle distillates Hydro-
treating Solvents
Heavy atm. gas
oil Gasoline
Hydro- Catalytic
Kerosene
treating cracking
Vacuum gas

Treating and Blending
Slurry oil
oil Diesel
Cycle oil
Distillation
Vacuum

Solvent
Gasoline, Naphtha, Middle distillates Heating oil
extraction Hydro-
cracking
Lube base stocks Lube oils Lube oil
Solvent
dewaxing Waxes
Greases
Propane LPG and Gas
deasphalter
Gasoline, Naphtha, Middle distillates
Asphalt
Visbreaker Fuel oil
Asphalt Industrial
Delayed coker / fuels
Gasoline, Naphtha, Middle distillates
Flexicoker
TUDelft Coke
Crude Oil Refining
Distillate fraction Boiling point C-atoms/
(oC) molecule
Gases <30 1-4
Gasoline 30-210 5-12
Naphta 100-200 8-12
Kerosine (jet fuel) 150-250 11-13 Middle
Diesel, Fuel oil 160-400 13-17 Distillates
Atmospheric 220-345
Gasoil
Heavy Fuel Oil 315-540 20-45
Atmospheric >540 >30
Residue
Vacuum Residue >615 >60

TUDelft
Processes
Processes in
in an
an Oil
Oil Refinery
Refinery

Physical processes Chemical processes
Thermal Catalytic

Distillation Visbreaking Hydrotreating
Solvent extraction Delayed coking Catalytic reforming
Propane deasphalting Flexicoking Catalytic cracking
Solvent dewaxing Hydrocracking
Blending Catalytic dewaxing
Alkylation
Polymerization
Isomerization

TUDelft
Simple
Simple Crude
Crude Distillation
Distillation
Gases
C1 - C4

reflux water
Gasoline

620 K
steam

steam Kerosene
steam

Gas oil
Crude oil
Residue

Furnace Fractionator Stripper Stripper
TUDelft
Market
Market Demands
Demands

• Clean products (no S, N, O, metals, etc.)
• More gasoline (high octane number)
• More diesel (high cetane number)
• Specific products (Aromatics, alkenes, etc.)
• Less residue

How to meet these demands?

• More sophisticated distillation
• Physical separation steps
• Chemical conversion steps

TUDelft
More sophisticated ???
Higher T distillation ??
Gases
C1 - C4

reflux water
Gasoline

620 K
steam

steam Kerosene
steam

Gas oil
Crude oil
Residue

Furnace Fractionator Stripper Stripper
TUDelft
Modern Crude Distillation Unit
Crude Oil
Gases

reflux water
Gasoline

circulating reflux
Slops
vacuum

circulating reflux

steam Intermediate
vacuum
gas oil

vacuum Heavy
residue
gas oil

Kerosene

steam Light
gas oil

Furnace Main Strippers Furnace Mild vacuum Driers
fractionator column
TUDelft
Propane Deasphalting
Extraction
Reason
Coke-forming tendencies of asphaltenic materials

How?
Reduction by removal of suitable solvent
propane
butane, pentane

Why propane? Conditions? Flow scheme?
Easy separation Modest temperature
Available High pressure
...

TUDelft
Propane Deasphalting
Condensers
Propane recycle
Steam condenser
Steam

Vacuum
residue Cond. Water
Propane evaporator

310 - 330 K
35 - 40 bar Steam
Make-up Deasphalted oil
propane

Liquid propane Steam

Asphalt

Propane storage Deasphalting tower Flash drum Strippers

TUDelft
Thermal Processes

gas
Feed Furnace oil
T, tres coke

Visbreaking Delayed Coking
•mild conditions •long residence time (24 h)

Flexicoking
•combination thermal cracking and coke gasification/combustion

Steam Cracking
•production lower olefins
TUDelft
Thermal Processes

• VISBREAKING
– Mild thermal cracking
– Reduction of viscosity

• DELAYED COKING
– Long residence times (24 h)
– Heavy feed → coke + oil + gas

• FLEXICOKING
– Combination of thermal cracking and
– coke gasification / combustion

TUDelft
Visbreaking

Gasoline ~ 10 wt%

Heavy gas oil

Vacuum
residue
730 K
20 bar

~ 80 wt%
Cracked residue
Light gas oil

Furnace Reactor Flash Fractionator Vacuum
fractionator

TUDelft
Delayed Coking

Gas

710 K
Unstabilized
Naphtha
2 bar

770 K

Gas oil

Coke
Feed

Coke drums Furnace Fractionator Gas oil stripper

TUDelft
Market
Market Demands
Demands

• Clean products (no S, N, O, metals, etc.)
• More gasoline (high octane number)
• More diesel (high cetane number)
• Specific products (Aromatics, alkenes, etc.)
• Less residue

How to meet these demands?

• More sophisticated distillation
• Physical separation steps
• Chemical conversion steps

TUDelft
Crude Oil Refining
Distillate fraction Boiling point C-atoms/
(oC) molecule
Gases <30 1-4
Gasoline 30-210 5-12
Naphta 100-200 8-12
Kerosine (jet fuel) 150-250 11-13 Middle
Diesel, Fuel oil 160-400 13-17 Distillates
Atmospheric 220-345
Gasoil
Heavy Fuel Oil 315-540 20-45
Atmospheric >540 >30
Residue
Vacuum Residue >615 >60

TUDelft
Octane Numbers, Boiling Points
• n-pentane 62 309 K
• 2-methyl butane 90 301
• cyclopentane 85 322
• n-hexane 26 342
• 2,2-dimethylbutane 93 323
• benzene >100 353
• cyclohexane 77 354
• n-octane 0 399
• 2,2,3-trimethylpentane 100 372
• methyl-tertiary-butyl-ether 118 328

• straight run gasoline 68 67 (MON)
• FCC light gasoline 93 82
• alkylate 95 92
• reformate (CCR) 99 88
TUDelft
Cetane Numbers
• n-alkanes 100-110
• n-hexadecane (cetane) 100
• iso-alkanes 30-70
• alkenes 40-60
• cycloalkanes 40-70
• alkylbenzenes 20-60
• naphtalenes 0-20
• α-methyl naphthalene 0

• straight run gas oil 40-50
• FCC cycle oil 0-25
• thermal gas oil 30-50
• hydrocracking gas oil 55-60

TUDelft
Product Distribution
Thermal versus Catalytic Cracking
140

mol per 100 mol cracked n-C16
Thermal
120

100

80

Catalytic
60

40

20

0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Carbon Number

TUDelft
Catalytic Cracking
• World capacity: > 500 million metric ton/year

CH3 CH3
H3C C+ CH2 C CH3 H3C C CH2 + + C CH3 “β scission”
CH3 CH3 CH3 CH3

• Reactions:
– C-C bond cleavage:
– Isomerization
– Protonation/deprotonation
– Alkylation
– Polymerization
– Cyclization, condensation coke formation

TUDelft
Cracking Mechanism
Alkenes: H
R CH C H2 + H+ R C H2 C + or R C+ C H3
via carbenium ions H H

Stability: tertiary > secondary > primary > ethyl > methyl

H
Alkanes:
R C H2 C H3 + H+ R C+ C H3 R C+ C H3 + H2
via carbonium ions H H H

H
+
Or, if carbenium ions H 3C C C H2 C H2 C H2 C H3 H 3C C C H2 C H2 C H2 C H3
H H
are present: + +
H 3C C+ C H2 C H2 C H3 H 3C CH C H2 C H2 C H3
C H3 C H3

TUDelft
Cracking Mechanism
H3C CH2 CH2 CH2 CH2 CH2 CH3 n-Alkane
Initation

+
H3C CH CH2 CH2 CH2 CH2 CH3 Classical carbenium ion

H3C CH CH CH2 CH2 CH3 Protonated cyclopropane
H+ CH2
hydride shifts + Isomerization
C-C bond breaking

+ +
H3C CH CH3 + H2C CH CH3 H3C CH CH CH2 CH2 CH3
CH3 n-Alkene CH3
etc.
hydride transfer

H3C CH CH3
CH3
iso-Alkane
TUDelft
Catalysts for FCC
Mechanism: H+ donor or H- acceptor
acid sites

Originally
• AlCl3 solution:
– corrosion
– waste streams
Subsequently
• Clays (acid-treated)
• Amorphous silica-alumina
– more stable and more selective
– better pore structure
– better attrition stability
• Zeolites
– even more active and stable (less
TUDelft coke, higher thermal stability
Catalytic Cracking Capacity in the US
7

Feed throughput (million barrels/day) 6.5 Capacity required with
amorphous catalysts
(extrapolated)
6

5.5

Capacity with
zeolitic catalysts
5
(actual situation)

4.5
1960 1965 1970 1975 1980 1985 1990 1995
Year
TUDelft
Cracking Catalysts

silica: Si Si
O O
Si O Si OH Si O Si O - + H+
O O
Si Si

silica-alumina: Weak acid
Si Si
O O
-
Si O Al HO Si Si O Al O Si + H+
O O
Si Si Strong acid

TUDelft
Zeolites
• Large number found and/or synthesized
• Total porosity up to 0.5 ml/g
• Examples:

Supercage Sodalite cage
0.8 nm

SOD
Sodalite

FAU
Y (Faujasite)
LTA
Zeolite A

TUDelft
Production of FCC catalyst

RECl3, NH4Cl
Micro pores < 3 nm
Wash liquor Meso pores 3 - 50 nm
Sodium silicate Macro pores > 50 nm
Sodium aluminate
zeolite
Water
matrix (dp = 2-10 µm)
NaOH Ion exchange
Na zeolite Filter Dryer
crystallization Zeolite 50-70 µm

Al2O3 source
SiO2 source
Water FCC catalyst
Matrix material particles
NaOH

Silica-alumina Mixer Spray dryer
synthesis

TUDelft
Product Distribution of Gas Oil Cracking
100 Gas
LPG
80
% wt on feed

Coke: carbon deposited
Gasoline
60
“Mixed Blessing”

40 • Catalyst poisoned

LCO • Regeneration provides heat
20
HCO/slurry

0 Coke
1950s 1960s 1970s 1980s
Amorphous Zeolite
Low Al High Al REY USY

TUDelft
FCC: Fluidized-bed Reactor and Regenerator
C + O2 → CO / CO2 To fractionation

Flue gas
2-stage
Cyclones Cracking
2-stage 775 K
Cyclones
Fluidized bed
970 K
Fluidized bed
Later
Grid Steam much more
Spent active catalyst
Riser
catalyst

Regenerated
Consequences
Air
catalyst for process?
Feed
Regenerator Reactor
TUDelft
Modern FCC Unit: Riser Reactor

gas (C2 and lighter)
G/L sep.
flue gas propane
cyclones
propene

waste
L/L sep.
heat catalyst
boiler fines water
spent
cat. steam

light cycle oil
regenerated riser
expansion cat.
compression heavy cycle oil
Air butane
Feed butene
slurry oil Gasoline
steam

Regenerator Reactor Fractionator Absorber Debu- Depro-
tanizer panizer

TUDelft
Riser Reactor: Plug flow Reactor??
Residence Time Distribution ?

Catalyst fraction (a.u)

Total area = 1

0 20
Time (s)

TUDelft
Typical Conditions in Riser FCC

Reactor Regenerator
Temperature (K) 775 973
Pressure (bar) 1 2
Residence time 1-5 s minutes/half hour

TUDelft
Sulfur Distribution in FCC Products
• Capacity: 50000 barrels /day
• catalyst / oil ratio: 6 kg/kg
• Catalyst inventory: 500 ton
• Catalyst recirculation rate: 50000 ton/day
• feedstock sulfur content: 2 wt%

“product” % of sulfur in feed ton/day* S (SO2)
H2S 50 ± 10 83.6
liquid products 43 ± 5 71.9
coke → SOx 7±3 11.7 (23.3)

TUDelft
Removal of SO2 in FCC unit

Oxidation of SO2 in regenerator 2 SO2 + O2 → 2 SO3
and adsorption of SO3 on MO:
SO3 + MO → MSO4 Stable in oxidizing
conditions
Reduction of metal sulfate in MSO4 + H2 → MSO3 + H2O
riser and release of H2S:

M: Ce, Mg,..
MO + H2S
or
MS + H2O
Regeneration of metal oxide in
stripper with release of H2S: MS + H2O → MO + H2S

TUDelft
Novel Developments in FCC
0.51 - 0.55 nm

Production of light alkenes (C3=, C4=)
– addition of ZSM-5
– Application
» petrochemical feedstock
» isobutene for MTBE, ETBE

Processing of heavier feedstocks
– improved reactors, strippers, feed injection, gas/solid separation
– application of catalyst cooling and high T
» much higher coke production, metal deposits, more sulfur

TUDelft
Hydrotreating and Hydrocracking
HYDROTREATING
• Conversion with hydrogen
• Reactions: hydrogenation & hydrogenolysis
• Removal of hetero-atoms (S, N, O)
• Some hydrogenation of double bonds &
aromatic rings
• Molecular size not drastically altered
• Also termed hydropurification

HYDROCRACKING
• Similar to hydrotreating
• But, drastic reduction in molecular size

TUDelft
Objectives Hydrotreating

• Protection of the environment
– reduction acid rain
• Protection of downstream catalysts
– in further processing
– S-compounds in Diesel fuel give difficulties in catalytic
cleaning of exhaust gases
• Improvement of gasoline properties
– odour, colour, stability, corrosion

TUDelft
Hydrotreating Reactions

1) Mercaptans RSH + H2 RH + H2S HDS

HDS
2) Thiophenes + 3 H2 + H2S
S

3) Benzothiophenes + 5 H2 + H2S HDS
S

4) Pyridines + 5 H2 + NH3 HDN
N
OH
5) Phenols + H2 + H2O HDO

TUDelft
Equilibrium data
100

90
S
80

70
Industrial conditions
60 S 600-650 K
lnKeq

50

40

30
CH3SH
20

10

0
0 1 2 3 4 5
1000/Temperature (1/K)

TUDelft
Typical process conditions
Naphtha Gas Oil
■ Temperature (K): 590 - 650 600 - 670
■ Pressure (bar): 15 - 40 40 - 100
■ H2/oil (Nm3/kg): 0.1 - 0.3 0.15 - 0.3
■ WHSV (kg feed/(m3 catalyst)/h) 2000 - 5000 500 - 3000
■ Catalyst: mixed metal sulfides (CoS and MoS2 or NiS and WS2
on Al2O3)
‘CoMoS’
S
Co
Mo

γ-Al2O3

Process design ???
TUDelft
Trickle-bed Reactor

Gas + liquid

Deflector
Gas
Liquid Distributor
Inert beads
Gas Complete wetting
Catalyst bed

Incomplete wetting

Support grid
Catalyst particle
with liquid film

Product

TUDelft
Hydrotreating Process (trickle bed)
H2S

hydrogen recycle to H2S removal
Recycle gas
scrubbing Gas
Hydrogen
(C3-)

Cold HP
water separator Naphtha

Sour steam
water

Product
Feed
Furnace Reactor Hot HP Hot LP Stripper Separator
separator separator

TUDelft
Development of maximum Sulfur
Content in automotive Diesel in Europe
3500

3000
3000

2500

2000
Max S in Diesel
1500 ppm
1000

500
500
350
50
0
1 2 3 4
< 1996 1996 2000 2005
Year
TUDelft
Activity of Various Catalysts for HDS of
Pretreated Gas Oil
S
CH3

S
CH3 CH3

S S
C2H5 CH3

Feed 760 ppm

260 ppm
CoMo/γ-Al2O3

230 ppm
NiMo/γ-Al2O3

200 ppm
NiW/γ-Al2O3

140 ppm
Pt/ASA

60 ppm
PtPd/ASA (I)

TUDelft
Retention time
Effect of HDS of FCC feedstock
on gasoline sulfur content

10000
FCC gasoline sulfur, ppmw

FCC gasoline S 1000
untreated feed
ppmw untreated feed
100

10

1
0 0.5 1 1.5 2

FCC
FCCfeedstock sulfur,wt.%
feedstock sulfur, wt.%

TUDelft
Hydrocracking
Similar to FCC
– but H2 inhibits some secondary reactions
– (e.g. coke formation)

Catalyst ??? ‘NiMoS’
S
Ni
Mo
• Acid sites
– SiO2, Al2O3, silica-alumina, zeolites Silica-alumina

• Hydrogenation sites
– NiS/MoS, NiS/WS2, Pt
» NH3 inhibits reaction
» H2S inhibits reaction

TUDelft
Reactions during Hydrocracking

∆ H0208 (kJ/mol)
Hetero-atom removal + 6 H2 + NH3
N - 374
H
+ 2 H2 + 3 H2
Aromatics hydrogenation - 326

Hydrodecyclization + 3 H2 +
- 119

Alkanes hydrocracking + H2 + - 44

Hydro-isomerization -4

TUDelft
Process Configurations for
Hydrocracking
Gas
Gas
Naphtha
MD Naphtha
Feed HT/HC MD
Feed HT HC

Hydrowax

Single stage / once through Two stage
low investment high investment
inhibition high rates
Gas
Naphtha
HT = hydrotreating
MD
Feed HT HC HC = hydrocracking
MD = middle distillates

Series flow
TUDelft
Two-stage Hydrocracker
Fresh
hydrogen
Hydrogen recycle
Purge

to acid gas and C1 − C4
NH3 removal

Naphtha
Quench H2 Quench H2

Middle
distillates

Feed

Furnace Reactor Furnace Reactor High/Low pressure Fractionator
separators

TUDelft
Summary of Processing Conditions

Mild single stage / second stage
first stage
Temperature (K) 670 – 700 610 – 710 530 – 650
Hydrogen pressure (bar) 50 – 80 80 – 130 80 – 130
Total pressure (bar) 70 – 100 100 – 150 100 – 150
Catalyst Ni/Mo/S/γ-Al2O3 +P* Ni/Mo/S/γ-Al2O3 Ni/W/S/USY zeolite
+P*

TUDelft