Desulphurisation

Research I Technology I Catalysts

Bo Hartvigsen
Agenda

Hydrogenation

Sulphur absorption

Operational challenges

Product quality
Why desulphurise?
Sulphur poisoned reformer Well working
catalyst – hotbands reformer
Desulphurisation section

Feed

H2

CLA CLA
HDS ZnO ZnO

TSR
Operating ranges

Operating range Typical range

Temperature, °C 320 - 400 350 - 380

Pressure, kg/cm2 15 - 50 20 - 40

Sulphur, ppm 0- ∞ 1 - 50

Chlorine, ppm 0- ∞ 0-2

Feedstock Natural gas – heavy naphtha

Hydrogenation reactions

Organic sulphur
RSH + H2 ⇒ H2S + RH
COS + H2 ⇒ H2S + CO

Other reactions
CO2 + H2 ⇔ CO + H2O
RCl + H2 ⇒ HCl + RH
The active phase
CH3SH + H2 CoMoSx
Sulphur
Molybdenum
Cobalt

TK-250

H2S + CH4
Catalyst activity
Activity Sulphur dependency

0 5 10 15 20 25
Sulphur in feed, ppm

Temperature dependency
Activity

320 340 360 380

Operating temperature, °C
Sulphur absorption reactions

Sulphur absorption
ZnO + H2S ⇔ ZnS + H2O

Unwanted reaction
2 HCl + ZnO ⇔ ZnCl2 + H2O

HTG HTZ
Sulphur trap catalyst ST- 101
Application
ST- 101

CO2 in the feed

Fluctuating sulphur levels

Properties

Final sulphur clean-up

Pick-up of H2S and organic sulphur

Very high chemisorption capacity

High and low temperature operation

Cu-based
Sulphur profile

Bulk saturation

Main absorption front

Chemisorption front

Sulphur-free HTZ
Sulphur uptake for HTZ

40
Sulphur uptake, wt%

20

0
100 200 300 400
Operating temperature, °C
Operational challenges
Too low temperature

Risk of organic sulphur breakthrough

Decreased lifetime of zinc oxide

Too high temperature

Risk of carbon lay-down
CH4 ⇒ C + 2H2
Operational challenges

Fluctuating sulphur concentration

Sulphur

Organic S-inlet
Organic S-outlet
H2S-outlet

Time
Operational challenges
No hydrogen recycle

Organic sulphur breakthrough

Affinity for carbon lay-down
CO2 in feedstock

Equilibrium sulphur breakthrough
CO2 + H2 ⇔ CO + H2O
ZnS + H2O ⇔ ZnO + H2S
Deactivation - reduction

Start-up • high H2 • low S
H2 + MoO3 ⇒ MoO2 + H2O
Monitoring performance
Measure
• Organic S and H2S in the feedstock
• Organic S slip from hydrogenator
• Organic S and H2S exit both desulphurisers
• Pressure drop
 Trouble shooting
Feed

H
2

HDS HDS

ZnO ZnO

Plant routine measurements

• No H2S detected outlet desulphurisation section
Topsøe analyses gas samples
Sample DMS(ppb) COS(ppb) H2S(ppb) Total S (ppb)

Lead inlet 4200 12 1100 5300

Lead outlet 3750 50 <3 3800

Lag outlet 160 20 <3 180

 Trouble shooting
Feed

H (As)
2

HDS HDS

ZnO ZnO

Topsøe analyses HDS catalyst samples

• Carbon ~ 10% wt (No H2 during start-ups)
• As ~ 1.5% wt (As in feed)
Reforming catalyst skimmed
HDS and ZnO catalyst replaced
Monitoring performance
Measure

Organic S and H2S in the feedstock

Organic S slip from hydrogenator

Organic S and H2S exit both desulphurisers

Pressure drop
 Calculation tool
60
Exit
Feed

H2S (ppm)
50 40
CATABS
ppm
H2S 20

0
0 100 200 300 400 500
Time (hours)

Development of calculation tools

Long time testing

Test at various conditions

P, T, S content and feed composition

Many combinations – many tests
CT scanning - density distribution
CT scan of ZnO product Density along the shown path
Dynamic CT scan
Catalyst quality
Production in Frederikssund

Quality control

10-20 values for each product

Raw materials

Intermediate products

Final product
40 years of experience
More than 1000 charges
Thank you for your attention