Hydroprocessing Units

November 2004

Pedro da Silva

Why Hydroprocessing?
BEFORE

CO, NOx, HC,

Particulates

NOW

Why Hydroprocessing?

Desulphurisation units become more and more

important in refineries

Why Hydroprocessing?
Market of solid catalysts in refining, (IFP data,1994)
Catalytic cracking
Hydroprocessing
Claus
Hydrocracking
Reforming
isomerization
other
TOTAL

tons /year
440 000
80 000
20 000
8 000
5 000
1 000
12 000
566 000

More than 80% of refined molecules see at least

one catalyst in their liver !

Hydroprocessing Units Layout

in a Refinery Scheme
Amine wash

propane
butane

HDT

Reforming

gasoline

H2
kerosene
Hydrodesulphurisation
diesel

Vacuum Distillation

Crude

Atmospheric Distillation

naphtha

Catalytic
Cracker
FCC

Visbreaking
Heavy fuel

Hydroprocessing Units Layout

in a Refinery Scheme
Amine wash

propane
butane

HDT

Reforming

gasoline

H2
kerosene
Hydrodesulphurisation
diesel

Vacuum Distillation

Crude

Atmospheric Distillation

naphtha

HDS

Catalytic
Cracker
FCC

Visbreaking
Heavy fuel

Hydroprocessing Units Layout

in a Refinery Scheme
Amine wash

propane
butane
naphtha

Atmospheric Distillation

Reforming

gasoline

H2
kerosene
Hydrodesulphurisation
diesel

HDS

Vacuum Distillation

Crude

HDT

Catalytic
Cracker
FCC

Visbreaking
Heavy fuel

Typical operating conditions of

Hydrodesulphurisation Units
PROCESS

Pressure
(bar)

Temperature
(C)

Flowrate/
catalyst volume
(h-1)

Naptha
Kerosene
Diesel oil
VGO
ARDS
VGO, residue
hydrocracker

7-30
15-50
15-90
30-100
80-200

280-320
300-330
320-390
340-410
370-410

3-10
2-6
1-4
1-2
0.2-0.5

100-200

370-410

0.5-1.5

- The most important parameters followed in these units (apart from product
qualities!) are the temperature and unit pressure drop
- The difference on activity and stability of different catalysts is measured by C

Chemical Reactions in
Hydroprocessing
Hydrogen consumption

Refractory compound

Not limited by thermodynamics

Chemical Reactions in
Hydroprocessing
A21 41838-01_1.DATA

C1

C3

BT:Benzothiophne

C2

DBT:Dibenzothiophne
S
C2

C4
S

C3

S
S

C4+

STH 10.00 TI OFF

48 000 V
46 000
44 000
42 000
40 000
38 000
36 000
34 000
32 000
30 000
28 000
26 000
24 000
22 000
20 000
18 000
16 000
14 000
12 000
10 000
8 000
6 000
4 000
2 000
0
-2 000
-4 000
-6 000
0
1

C1

SPW 0.20

C5

Soufre peu rfractaire

2

10

11

Soufre
rfractaire
12

13

14

Soufre trs rfractaire

15

16

17

18

19

20

RT [min]
21

22

Chemical Reactions in
Hydroprocessing

4,6-DiMeDBT

Soufre total=6 ppm

2,4,6-TriMeDBT
S

1,4,6-TriMeDBT

4,6-EtMeDBT

4,6-DiEtDBT

3,4,6-TriMeDBT

4,6-PrMeDBT

Chemical Reactions in
Hydroprocessing

Chemical Reactions in
Hydroprocessing

Chemical Reactions in
Hydroprocessing
Rgime thermodynamique
(HDA)

Equilibre thermodynamique

% HDA

HDA

Soufre effluent (ppm)

Rgime cintique
(HDA)

HDS

T1

T2
Temprature (C)

Chemical Reactions in
Hydroprocessing
- Hydroprocessing reactions are exothermic
- Temperature and pressure are needed for hydroprocessing reactions
- Reactor delta temperature:
8-9C rise per 1 wt% sulphur removal
1-2C rise per 1vol% of polyaromatics removal
1C rise per bromine number removal
Opration normale

four

0
R1

lit 1
quench

lit 2
R1

temprature

Simplified Scheme of an
Hydrodesulphurisation Unit
Make-up
hydrogen
Make-up
compressor

to fuel
gas

Heat
Exchangers

Partial by-pass

Raw feed
Furnace
2
Quench

Reactor

Recycle
compressor
H.P.
Flash drum

Air
coolers

Stripper

Hydroprocessing reactor and

internals
Inlet diffuser

Reactor diameter varies

between 1,5 to 4,5 m

Catalyst bed
Varies between 3 to 15 m
Catalyst support
grid

Mixing chamber

Quench
distributor

Vapor/liquid
distribution tray

Unloading nozzle
Outlet collector

Hydroprocessing Reactor and

Internals

Catalyst bed

reactor outlet
collector

Hydroprocessing Reactor and

Internals

Additional
gasketing

Hydroprocessing Reactor and

Internals
What techniques can be used to check the gas-liquid distribution inside the
reactor?
20
R1 B2 outlet
R2 B1 outlet
R2 B2 outlet

Radial T dispersion (C)

15

10

0
0

100

200

300

400

Days on stream

Radial temperature dispersion

Radioactive tracers
Unit start-up
Unit response to flow variations

500

600

Hydroprocessing Catalysts
- Generally HDS catalysts are constituted by metal oxides from columns
VIA (Mo,W) and VIIIA ((Co),Ni) periodic table

- The active phase of HDS catalysts consists in the sulphided form of these
oxides MoS2 slabs

..
.
.
.. .

Co

..
.
.

30
Mo
S
Mo

Al2O3
- Co or Ni are activity promoters and decorate the edge of MoS2 slabs
- CoMo catalysts are generally used for low pressure units and were the main
objective are HDS reactions
- NiMo catalysts are generally used for higher pressure units and were the
main objective is density and cetane gain (hydrogenation reactions)

Hydroprocessing Catalysts

Fresh CoMo cataltyst 1.2-2.5 mm

Oxide state

Used catalyst
Sulphide + coke

Regeneration of used catalyst is possible by carefully burning sulphur and

coke. The resulting catalyst will in its oxide form.

Hydroprocessing Catalysts Life

catalyst
loading
Nice staying here, its always hot!
however, its also always raining
and it smells !!

Were should I go on holidays?

Why not a reactor of a
diesel hydrotreater?

Unloading under inert

atmosphere as Im
quite keen to react
with air

Lets do it again

Rotary Kiln
Oven
Spent Catalyst
Hot Air

Catalyst Loading

Catalyst loading

Local porosity,

Catalyst loading

Catalyst bed grading must be adapted in order

to avoid pressure drop build-up

Catalyst loading

good hold inert balls or

Different particles are available to be loaded above the

main catalyst and minimize pressure drop build-up

Catalyst Activation
in situ
Sulphidation

Oxide catalyst
MoO3

reactor

H2S
DMDS

H2 Activation

Active catalyst
MoS2

reactor

preSulphided preSulphiding
Sulficat, Acticat,
MoOxSy
EasyActive

ex situ

Final step

Oxide catalyst
MoO3

ex situ
Under H2
T > 230-250C

Reduction
to MoO2
Unactive phase

Active catalyst ex situ sulphiding

Totsucat, XpresS
MoS2

ex situ

Catalyst Activation
Reactor inlet temperature (C)

350
300

Catalyst sulphiding
(320-350C)

Pre sulphiding step

(reactor T < 15C)

250

Catalyst wetting
200 (liquid flow)
DMDS injection

150
100
50
0

Drying
(120-150C)
Unit under pressure

8
10
12
Time (hours)

14

16

18

20

1. Catalyst wetting at lower temperature allows better gas-liquid distribution

2. The drying step should always be below 150C to avoid molybdenum oxide reduction
3. DMDS injection 1 hour before reaching presulphiding step
4. Maximum reactor exotherm should be below 15C to avoid high catalyst temperatures
in without H2S
5. Catalyst sulphiding step temperature depends on catalyst type and unit operation

Kinetic Models
d [S ]
= k [S ]
dt

Feed + H2

Sout

Sin

tc
Sin d [S ]
tc
d [S ]
= k dt
= k dt
0
0
Sout [S ]
[S ]

Eact
RT

k0 e
Sin
ln
= k tc =
LHSV
Sout
Eact
T =
ln(Sin / Sout ) LHSV
R ln
k0

Desulphurized product
+ H2 + H2

Kinetic Models
Typically, for HDS reactions on diesel and VGO
Eact = 25000 - 29000 cal/mole
Example - Catalyst volume = 200 m3
Catalyst A
Flowrate = 300 m3/h
Bed 1 Tin = 345C, Tout = 365C, Bed 2 Tin = 360C, T = 370C
WABT = 362,5C
Sin = 7000 wtppm
Sout = 40 wtppm
k0 = 1,5E10 h-1
Catalyst B
Flowrate = 280 m3/h
Bed 1 Tin = 342C, Tout = 362C, Bed 2 Tin = 352C, T = 362C
Sin = 7000 wtppm
Sout = 33 wtppm
WABT = 359,9C
k0 = 1,4E10 h-1

Catalyst A is 2C more active than catalyst B

(this value is higher with more precise models!)

Kinetic Models - Cycle Length

Other parameters that must be taken into account in the kinetic models are:
- hydrogen partial pressure
- feed severity (nitrogen, density, aromatics, T95, other)
- hydrogen/oil ratio, hydrogen sulphide and ammoniac partial pressure
Feed rate

Temperature

Regeneration or catalyst changeout

Max temp

Cycle length
SOR

EOR
Time

Kinetic Models - Cycle Length

Poor catalyst performance
Feed rate

High pressure drop

Feed rate

Max temp

Max temp

Temperature

Cycle length
Time

Cycle length
Time

Kinetic Models - Cycle Length

Reactor Average Temperature (C)

400
390

Catalyst A

380
370

10C difference
Catalyst B

360
350
340
330
320
0

40

80

120

160
200
240
Days on stream

280

320

360

- Average Reactor Temperature = 1/3 inlet T + 2/3 outlet T

- Temperature increase with time due to coke formation and poisons adsorption
- 3,5C/month deactivation

Kinetic Models - Cycle Length

Reactor Average Temperature (C)

400
390
380
370
360
350

Normalized temperature
1,5C/month

340

Actual temperature
3,5C/month

330
320
0

40

80

120

160
200
240
Days on stream

280

320

360

- Normalized temperature allows to correct for unit conditions and feed

variations
- Assessment of the real performances of the unit and the catalyst are much
more precise

Hydroprocessing Unit
Cold Scheme

Advantages: higher H2% in recycle gas, simpler, light feeds can be processed
Disadvantages: lower energy efficiency, larger high pressure separator

Hydroprocessing Unit
Hot Scheme

Advantages: better energy efficiency, no need for stripper feed heating (most cases)
Disadvantages: need for recycle gas amine wash, loss of hydrogen

Hydroprocessing Unit
Stripping section

The objective of the stripping section is to removed light ends from the diesel (H2S, CHs)
and/or to remove products lighter than the unit main product

Hydroprocessing Units
Gasoline hydrotreaters
In general, the objective of the gasoline hydrotreaters is to remove sulphur and nitrogen
from reformer or isomerization feeds.Indeed, sulphur and nitrogen will poison and
degrade the performances of reforming and of isomerization catalysts
Gasoline hydrotreaters operate on 100% gaz phase, there is no need for distribution trays

Kerosene and Diesel hydrotreaters

The objective of the diesel hydrotreaters is to remove sulphur, reduce density and improve
cetane index. In the case of kerosene hydrotreaters, the objective is also to respect
aromatics specification (naphthalenes and smoke point)
Diesel hydrotreaters operate in gas/liquid phase reactor needs good distribution trays

Vacuum Gasoil hydrotreaters

The objective of the VGO hydrotreaters is to remove sulphur and nitrogen to prepare the
FCC feed. The objective is to be abble to produce 10 wtppm S gasoline and to improve
FCC yields
VGO hydrotreaters operate in gas/liquid phase reactor needs good distribution trays

Hydroprocessing Units

Kinetic Models
d [S ]
n
= k [S ] , n > 1
dt

Feed + H2

Sout

Sin

tc
Sin d [S ]
tc
d [S ]
= k dt
= k dt
n
n
Sout
0
[S ]
[S ] 0

Eact
RT

1
k0 e
1
1
n 1 n 1 = k tc =
LHSV
n 1 S out S in
T =

Eact
1

1
n 1 n 1 LHSV / k 0
R ln
n 1 S out S in

Desulphurized product
+ H2 + H2