Processes in the oil refinery

LPG and Gas

LPG

Alkylation

Refinery fuel
gas

Alkylate

Straight run gasoline

Naphtha

Hydrotreating

Catalytic
reforming

Reformate
Gasoline

Middle distillates
Heavy atm. gas
oil

Vacuum
Distillation

Vacuum gas
oil

Hydrotreating

Slurry oil
Cycle oil
Solvent
extraction

Hydrocracking

Gasoline, Naphtha, Middle distillates

Lube base stocks

Propane
deasphalter

Solvent
dewaxing

Delayed coker /
Flexicoker

Lube oils
Waxes

LPG and Gas

Gasoline, Naphtha, Middle distillates
Visbreaker

TUDelft

Gasoline

Catalytic
cracking

Hydrotreating

Solvents
Kerosene
Treating and Blending

Atmospheric
Distillation

Crude oil

LPG

Diesel
Heating oil
Lube oil
Greases
Asphalt

Fuel oil
Asphalt
Gasoline, Naphtha, Middle distillates

Industrial
fuels
Coke

Crude Oil Refining

Distillate fraction
Gases
Gasoline
Naphtha
Kerosine (jet fuel)
Diesel, Fuel oil
Atmospheric
Gasoil
Heavy Fuel Oil
Atmospheric
Residue
Vacuum Residue

TUDelft

Boiling point
(oC)
<30
30-210
100-200
150-250
160-400
220-345

C-atoms/
molecule
1-4
5-12
8-12
11-13 Middle
13-17 Distillates

315-540
>540

20-45
>30

>615

>60

Processes in an Oil Refinery

Physical processes

Chemical processes
Thermal
Catalytic

Distillation
Solvent extraction
Propane
deasphalting
Solvent dewaxing
Blending

Visbreaking
Delayed coking
Flexicoking

TUDelft

Hydrotreating
Catalytic reforming
Catalytic cracking
Hydrocracking
Catalytic dewaxing
Alkylation
Polymerization
Isomerization

Simple Crude Distillation

Gases

C1 - C4
water

reflux

Gasoline

620 K
steam

steam

Kerosene

steam

Gas oil
Crude oil

TUDelft

Residue
Furnace

Fractionator

Stripper

Stripper

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
water

reflux

Gasoline

620 K
steam

steam

Kerosene

steam

Gas oil
Crude oil

TUDelft

Residue
Furnace

Fractionator

Stripper

Stripper

Modern Crude Distillation Unit

Gases

Crude Oil

reflux

water

Gasoline

circulating reflux

Slops
vacuum

circulating reflux
steam

Intermediate
gas oil

vacuum

vacuum
residue

Heavy
gas oil
Kerosene
Light
gas oil

steam

Furnace

TUDelft

Main
fractionator

Strippers

Furnace

Mild vacuum
column

Driers

Propane Deasphalting
Extraction
Reason
Coke-forming tendencies of asphaltenic materials
How?
Reduction by removal of suitable solvent
propane
butane, pentane

Why propane?
Easy separation
Available
...

TUDelft

Conditions?
Modest temperature
High pressure

Flow scheme?

Propane Deasphalting
Condensers
Propane recycle

Steam condenser
Steam

Vacuum
residue

Make-up
propane

Cond.

Propane evaporator

Water

310 - 330 K
35 - 40 bar

Steam

Deasphalted oil

Steam

Liquid propane

Asphalt
Propane storage

TUDelft

Deasphalting tower

Flash drum

Strippers

Thermal Processes
gas
Feed

Furnace

oil

T, tres

coke

Visbreaking
mild conditions

Delayed Coking
long residence time (24 h)

Flexicoking
combination thermal cracking and coke gasification/combustion
Steam Cracking
production lower olefins
TUDelft

Visbreaking
Gasoline ~ 10 wt%
Heavy gas oil

Vacuum
residue

730 K
20 bar
1-8 min

~ 80 wt%
Cracked residue
Light gas oil

Furnace

TUDelft

Reactor

Flash

Fractionator

Vacuum
fractionator

Delayed Coking
Gas
710 K

Unstabilized
Naphtha
2 bar
24 h

770 K

Gas oil

Feed

Coke
Coke drums

TUDelft

Furnace Fractionator

Gas oil stripper

Modern oil refinery

LPG and Gas

LPG

Alkylation

Refinery fuel
gas

Alkylate

Straight run gasoline

Naphtha

Hydrotreating

Catalytic
reforming

Reformate
Gasoline

Middle distillates
Heavy atm. gas
oil

Vacuum
Distillation

Vacuum gas
oil

Hydrotreating

Slurry oil
Cycle oil
Solvent
extraction

Hydrocracking

Gasoline, Naphtha, Middle distillates

Lube base stocks

Propane
deasphalter

Solvent
dewaxing

Delayed coker /
Flexicoker

Lube oils
Waxes

LPG and Gas

Gasoline, Naphtha, Middle distillates
Visbreaker

TUDelft

Gasoline

Catalytic
cracking

Hydrotreating

Solvents
Kerosene
Treating and Blending

Atmospheric
Distillation

Crude oil

LPG

Diesel
Heating oil
Lube oil
Greases
Asphalt

Fuel oil
Asphalt
Gasoline, Naphtha, Middle distillates

Industrial
fuels
Coke

Octane Numbers, Boiling Points

TUDelft

n-pentane
2-methyl butane
cyclopentane
n-hexane
2,2-dimethylbutane
93
benzene
cyclohexane
77
n-octane
2,2,3-trimethylpentane
methyl-tertiary-butyl-ether 118

62
90
85
26

straight run gasoline

FCC light gasoline
alkylate
reformate (CCR)

68
82
95
99

93

309 K
301
322
342
323

>100

353
354

0
100

399
372
328
67 (MON)
92
88

Cetane Numbers

TUDelft

n-alkanes
n-hexadecane (cetane)
iso-alkanes
alkenes
cycloalkanes
alkylbenzenes
naphtalenes
-methyl naphthalene

100-110
100
30-70
40-60
40-70
20-60
0-20
0

straight run gas oil

FCC cycle oil
thermal gas oil
hydrocracking gas oil

40-50
0-25
30-50
55-60

Product Distribution
Thermal versus Catalytic Cracking
mol per 100 mol cracked n-C16

140

Thermal
120
100
80

Catalytic

60
40
20
0
0

9 10 11 12 13 14 15 16

Carbon Number

TUDelft

Catalytic Cracking
World capacity: > 500 million metric ton/year
CH3
H3C C+

CH2 C CH3

CH3

CH3

CH3
+
H3C C CH2 + C CH3
CH3
CH3

Reactions:

TUDelft

C-C bond cleavage:

Isomerization
Protonation/deprotonation
Alkylation
Polymerization
Cyclization, condensation

coke formation

scission

Cracking Mechanism
Alkenes:

H
R

via carbenium ions

CH

C H2

+ H+

C H2 C +

or

C+

C H3

Stability: tertiary > secondary > primary > ethyl > methyl
Alkanes:
via carbonium ions

H
R

+ H+

C H2 C H3

C+
H H

C H3

C+

C H3

+ H2

Or, if carbenium ions

are present:

H 3C

C H2 C H2 C H2 C H3

H 3C

C+
C H3

TUDelft

H 3C

C H2 C H2 C H2 C H3

C H2 C H2 C H3

H 3C

CH
C H3

+
C H2 C H2 C H3

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

H+ CH2

Protonated cyclopropane

hydride shifts +
C-C bond breaking

H3C CH CH3 + H2C CH CH3

CH3
hydride transfer

H3C CH CH3
CH3

TUDelft

iso-Alkane

n-Alkene

Isomerization
+

H3C CH CH CH2 CH2 CH3

CH3

etc.

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 coke, higher thermal stability)

TUDelft

Feed throughput (million barrels/day)

Catalytic Cracking Capacity in the US

7

Capacity required with

amorphous catalysts
(extrapolated)

6.5

5.5

Capacity with
zeolitic catalysts
(actual situation)

4.5
1960

1965

1970

1975

1980

Year

TUDelft

1985

1990

1995

Cracking Catalysts
silica:

Si

Si

Si O Si OH
O

Si

Si

silica-alumina:

TUDelft

H+

Weak acid

Si

Si

Si O Al HO Si

Si O Si O

Si O Al O Si

Si

Si

H+

Strong acid

Zeolites
Large number found and/or synthesized
Total porosity up to 0.5 ml/g
Examples:
Supercage
0.8 nm

Sodalite cage

SOD

Sodalite

FAU

Y (Faujasite)
Zeolite A

TUDelft

LTA

Production of FCC catalyst

Micro pores
Meso pores
Macro pores

RECl3, NH4Cl
Wash liquor
Sodium silicate

< 3 nm
3 - 50 nm
> 50 nm

Sodium aluminate
zeolite
matrix (dp = 2-10 m)

Water

Ion exchange

NaOH

Na zeolite Filter
crystallization

Dryer
Zeolite

50-70 m

Al2O3 source
SiO2 source
Water
NaOH

Matrix material

Silica-alumina
synthesis

TUDelft

FCC catalyst
particles

Mixer

Spray dryer

Product Distribution of Gas Oil Cracking

100

Gas
LPG

% wt on feed

80
Gasoline

60

Coke: carbon deposited

Mixed Blessing
Catalyst poisoned

40
LCO
20
HCO/slurry
Coke

0
1950s

1960s

Amorphous
Low Al
High Al

TUDelft

1970s

1980s
Zeolite

REY

USY

Regeneration provides heat

FCC: Fluidized-bed Reactor and Regenerator

C + O2 CO / CO2

To fractionation
Flue gas

2-stage
Cyclones

2-stage
Cyclones

Cracking

775 K
Fluidized bed

970 K
Fluidized bed
Grid

Steam
Spent
catalyst

Air

Feed

TUDelft

Riser

Consequences
for process?

Regenerated
catalyst

Regenerator

Later
much more
active catalyst

Reactor

Modern FCC Unit: Riser Reactor

G/L sep.

flue gas

gas (C2 and lighter)

propane

cyclones

propene

waste
heat
boiler

expansion
Air

L/L sep.

catalyst
fines

spent
cat.
regenerated
cat.

water
steam
riser

light cycle oil

heavy cycle oil

compression

Feed

butane

slurry oil

Gasoline

steam

Regenerator

TUDelft

Reactor

Fractionator

Absorber

Debutanizer

butene

Depropanizer

Catalyst fraction (a.u)

Riser Reactor: Plug flow Reactor??

Residence Time Distribution ?

Total area = 1

20
Time (s)

TUDelft

Typical Conditions in Riser FCC

Reactor

Regenerator

Temperature (K)

775

973

Pressure (bar)

Residence time

1-5 s

minutes/half hour

TUDelft

Sulfur Distribution in FCC Products

Capacity:
catalyst / oil ratio:

50000 barrels /day

6 kg/kg

Catalyst inventory:

500 ton

Catalyst recirculation rate:

50000 ton/day

feedstock sulfur content:

2 wt%

product
H 2S
liquid products
coke SOx

TUDelft

% of sulfur in feed
50 10
43 5
73

ton/day* S (SO2)
83.6
71.9
11.7 (23.3)

Removal of SO2 in FCC unit

Is it possible to reduce emission of SO2 at low
investment???
Change selectivity catalyst?
Add novel catalyst?
..
Clue
Some sulphates stable under oxidation
and unstable under reducing
conditions
TUDelft

Removal of SO2 in FCC unit

Oxidation of SO2 in regenerator
and adsorption of SO3 on MO:

2 SO2 + O2 2 SO3

Reduction of metal sulfate in

riser and release of H2S:

MSO4 + H2 MSO3 + H2O

SO3 + MO MSO4

Stable in oxidizing
conditions

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

TUDelft

MS + H2O MO + H2S

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

+ 3 H2

2) Thiophenes

RH

HDS

H2S

HDS

H2S

S
+ H2S

+ 5 H2

3) Benzothiophenes

HDS

S
+ 5 H2

4) Pyridines

NH3

HDN

N
OH
5) Phenols

TUDelft

H2

H2O

HDO

Equilibrium data
100
90
S

80
70

lnKeq

60

Industrial conditions
600-650 K

50
40
30
CH3SH

20
10
0

1000/Temperature (1/K)

TUDelft

Typical process conditions

I
I
I
I
I

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

Co

S
Mo

-Al2O3

TUDelft

Process design ???

Trickle-bed Reactor
Gas + liquid

Gas
Liquid

Deflector
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

Hydrogen

to H2S removal

Recycle gas
scrubbing

water

Gas
(C3-)
Cold HP
separator

Naphtha

Sour
water

steam

Product
Feed
Furnace

TUDelft

Reactor

Hot HP
separator

Hot LP
separator

Stripper

Separator

Development of maximum Sulfur

Content in automotive Diesel in Europe
3500

3000

3000

2500

Max S in Diesel
ppm

2000

1500

1000

500

500

350
50

< 1996

TUDelft

1996
2000
Year

2005

Activity of Various Catalysts for HDS of

Pretreated Gas Oil
S
CH3

S
CH3

CH3

S
C2H5

CH3

Feed

760 ppm

CoMo/-Al2O3

260 ppm

230 ppm

NiMo/-Al2O3

200 ppm

NiW/-Al2O3

140 ppm

Pt/ASA

60 ppm

PtPd/ASA (I)

TUDelft

Retention time

FCC gasoline sulfur, ppmw

Effect of HDS of FCC feedstock

on gasoline sulfur content

FCC gasoline S
ppmw

10000

1000
untreated feed

untreated feed
100

10

1
0

0.5

1.5

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

TUDelft