Desulphurisation of Hydrocarbon

Feedstocks
Using
Hydrogenation & Zinc Oxide Catalysts
Desulphurisation System Lay-outs
Feed

H2 HDS ZnO ZnO

TK HTZ HTZ
 Hydrogenation Reactions
Organic Sulphur
RSH + H2  H2S + RH
COS + H2  H2S + CO
R1SR2+ 2H2  H2S + R1H + R2H
R1SSR2 + 3H2  2H2S + R1H + R2H
Thiophenes + 4H2  H2S + Hydrocarbons
Other Reactions
CO2 + H2  CO+H2O
RCl +H2  HCL + RH
 Topsøe Hydrogenation Catalyst
Physical and Chemical Characteristics

Catalyst TK-550
TK-250

Shape Rings
Dimensions OD x ID, mm 4.8 x 2.4
Active Component CoMoSx
Carrier Al2O3
 CoMoSx Phase
Sulphur

Molybdenum

Catalyst pore Cobalt

H2 + CH3SH H2S+ CH4

CoMo Catalyst Activity as a Function
of Sulphur Content in Natural Gas
Catalyst Activity

0 5 10 15 20 25
Sulphur in Feed, ppm
CoMo Catalyst Activity as a Function
of Operating Temperature
HDS Activity

250 300 350 400

Operating Temperature, C
 Catalyst Deactivation
Reduction of Unsulphided Catalyst

H2 + MoO3  MoO2 + H2O

• Operation with low sulphur feedstock and

high hydrogen during initial start-up
Catalyst Deactivation - Carbon
CH4  C + 2H2

H2 + CH3SH H2 + CH3SH
 Catalyst Deactivation
Pore Mouth Plugging
New catalyst Plugged catalyst
CH3SH

Catalyst pore
The Sulphur Absorption Reaction

ZnO + H2S  ZnS + H2O

Other Reactions

CO2 + H2  CO + H2O

2 HCl + ZnO  ZnCl2 + H2O

 Equilibrium H2S Outlet ZnO
Vessel
5% CO2 in Natural Gas
100 5 % H2

80 3 % H2

2 % H2
H2S eq. ppb

60

40

20

0
300 320 340 360 380 400 420 440
Temperature C
 Sulphur Profile in a Zinc Oxide Bed
Zone 1: Bulk Saturation

Zone 2: Main Absorption Front

Sulphur Uptake

Zone 3: Chemisorption Front

Zone 1 Zone 2 Zone 3

Top Bed Bottom Bed

Direction of Gas Flow

Typical Sulphur Uptake for HTZ-3
40
Sulphur Uptake, wt%

35
30
25
20
15
10
5
0
100 200 300 400
Operating Temperature, C
Absorption Front - Zone 2
Pore Diffusion

H2S

H2O
Absorption Front - Zone 2
Solid Diffusion

H2S
Chemisorption Front - Zone 3

H2S
ZnO
 Topsøe Zinc Oxide Catalyst
Physical & Chemical Characteristics

Catalyst HTZ-3 HTZ-5

Shape Cylinders Cylinders
Dimensions OD, mm 4 4
Active Component ZnO ZnO
Other Compounds Traces Traces
Bulk Density, kg/l 1.3 1.0
Common Problems Experienced
in the HDS Section
• Too low operating temperature
• Too high operating temperature
• No hydrogen recycle to HDS
• Operation with fluctuating sulphur
content in feedstock
• CO2 in feedstock
 Low Operating Temperature
in HDS Section

• Risk of organic sulphur breakthrough due

to insufficient catalyst activity
• Decreased lifetime of zinc oxide due to
less sulphur pick-up capacity
 High Operating Temperature
in HDS Section
CH4  C + 2H2

• Potential risk of carbon lay-down from

cracking of hydrocarbons resulting in
reduced catalyst activity
 No Hydrogen Recycle to HDS

• Risk of organic sulphur breakthrough as

no hydrogenation takes place
• The affinity for carbon lay-down on the
catalyst is increased
 Fluctuating Sulphur Levels

3
H2S-in
ppm Sulphur

org-S-in
2 org-S-exit

0
Time
 Monitoring the Performance of
the HDS Section
• Measure
- Organic sulphur & H2S in the feedstock
- Organic sulphur slip from hydrogenator
- H2S concentration exit both desulphurisers

• Check the pressure drop across the

hydrogenator & desulphurisers and evaluate
the trend
Normal Operation of HDS Section
• Maintain an operating temperature of
360-380°C
• Ensure an hydrogen recycle which is
close to the recommended (design)
value
• Replace ZnO in lead vessel when H2S
slip increases from this reactor
 Safety Precautions for
TK-550/250 & HTZ-3

• Catalyst which has been in operation may

be pyrophoric and could heat up when
getting in contact with air
• Catalyst should be cooled down before
opening the reactor manholes