Shift Section

Research I Technology I Catalysts

MRPL Phase-III Refinery Project, Hydrogen Generation Unit

Shift catalyst - Agenda

Shift section in H2 plant

MTS catalyst

LTS catalyst

Evaluation and optimization

MTS and LTS

Feed

200-210°C 200°C
Primary reforming
Hydrogenation

Prereformer

temperature

temperature
absorption

Medium
Sulphur

Low
shift

shift

PSA

330°C 220°C

CO + H2O ↔ CO2 + H2

1
 Shift section in H2 plant

HTS + LTS setup

MTS setup (+ LTS) setup
CO + H2O ⇔ CO2 + H2 + Q
20
MTS
PR Exit
CO concentration, mole % dry

16

S/C = 2.5
12 HTS
PR Exit

8
S/C = 4.0
4 LTS

0
0 200 400 600 800 1000
Temperature, °C

The shift reaction

CO + H2O ⇔ CO2 + H2 + Q

Equilibrium curve
6 S/DG=0.4
S/DG=0.5
5
S/DG=0.6
CO, mole % dry

0
100 200 300 400 500 600
Temperature, °C

Increasing ∆P in LTS / MTS

Condensation
– Tinlet 15-20 °C above dew point
4
– T dew = PH O x 100 (± 2°C accuracy)
2

Boiler leaks

Carry over of boiler solids

Catalyst milling

2
 Topsøe MTS catalysts
LK-813

Catalyst LK-811 LK-813

OD x H, mm 4.5 x 4.5 4.5 x 3.4
Components, % wt.
Cu >12 >34
Zn >23 >19
Al - >4
Cr >26 -

Medium Temperature Shift

Features of LK-811

High and stable activity

Water resistant

High resistance against chlorine and silica poisoning

Features of LK-813

High resistance against sulphur poisoning

High activity (at temperatures below 270oC)

MTS Standard loading

Triple-decker ’sandwich’ loading
– 5% LK-811 / 45% LK-813 / 50% LK-811

Features for this loading

Top Layer
– is water resistant and has a high Chlorine capacity

Middle Layer
– High Sulphur capacity and higher activity in the cold zone

Bottom Layer
– Thermo-stable – giving a longer lifetime

3
MTS catalyst poisons
Poison Source Effect

HC feedstock

Sulphur
Covers the active Cu-surface

Steam/quench

HC feedstock
Covers the active Cu-surface

Chlorine

Steam/quench
Growth of Cu-crystals

Steam/quench

Silica
Refractory material
Physical blocking surface and
pores

Inert material/support

Steam/quench
Physical blocking surface and

Phosphor and alkali pores

Boiler leakage

Monitoring the MTS performance

Simulate catalyst activity
CO leakage, %

Evaluate ∆P

Estimate CO slip

Normally No DC zone
Time

Follow the trend

Temperature

∆P

0 Bed depth, % 100

Time

Topsøe LTS catalysts

LK-821-2
LK-821-2

Catalyst LK-821-2
OD x H, mm 4.5 x 4.5
Components, % wt.
Cu >38
Zn 22 ± 2
Al 6 ±2

4
 LTS catalyst poisons
Poison Source Effect

HC feedstock

Sulphur
Covers the active Cu-surface

Steam/quench

HC feedstock
Covers the active Cu-surface

Chlorine
Growth of Cu-crystals

Steam/quench

Reduced catalyst strength

Steam/quench

Silica
Refractory material
Physical blocking surface and
pores

Inert material/support

Steam/quench
Physical blocking surface and

Phosphor and alkali pores

Boiler leakage

LTS performance
LK-821-2 and LK-823
Predict performance
LK-821-2
• Estimate remaining lifetime
LK-823
• Estimate future CO slip
Topsøe
LTS
model
Relative Catalyst Activity

Recommend optimal inlet

temperature

Report on catalyst condition

0 10 20 30 40 50 60 70 80 90 100
Age, months

Monitoring the LTS performance

Monitor ∆P

Measure CO leakage
CO leakage, %

Record bed temperatures

Development in DC

Follow the trend
Temperature

DC, %

0 Bed depth, % 100 Time

5
Optimising shift operation
Too cold Optimal Too hot
Inlet CO
CO concentration

Operational
curve Equilibrium
curve

Optimal
ATE
5-10°C

Temperature

Reduction of MTS & LTS catalyst

N2 H2

Purge
Heater

Shift
H2O Converter
Separation
Cooler

CuO + H2 → Cu + H2O
1% H2 ~ 30°C ∆T

Reduction of MTS & LTS catalyst

MTS & LTS catalyst reduction

Reduction of CuO to Cu (active sites)

Reduction of Cr6+ to Cr3+ (strong exothermic)

Carrier gas is nitrogen

Addition of H2

CuO + H2 => Cu + H2O + Q

2 CrO3 + 3 H2 => Cr2O3 + 3 H2O + QQQQ

1% H2 ~ 60°C in N2

∆T controlled at ~60°C

Duration ~36-48 hours

6
 Reduction timeline
Before N2 circulation Heating to 170-180°C Bulk reduction

Loop examined
N2 source composition
In-bed thermo couples will drop

Blinds checked
H2 source composition
Online H2 analysis every 30 minutes

Loop composition
Loop gas analysis every 2 hours

H2 breakthrough observed towards the end
Heating to 120°C Introducing H2 Finishing reduction

N2 source composition
H2 gradually increased to ~2%
Inlet temperature gradually

H2 source composition
Inlet temperature decreased to 160- increased to 220°C

Loop composition 170°C
H2 gradually increased to 4-6%

H2 Analyser installed
Hotspot temperature max 220-225°C
Finished when ∆H2 < 0.2% for 2

H2 valve calibrated hours

6-12 Hours 24-48 Hours 6-12 Hours

Online analyser

Online H2 measurements

Inlet

Outlet

Every 30 minutes

MTS Reduction
0%

240 16.00 22.40%

220 14.00 22.40%

200 12.00 27.80%

180 10.00 27.80%

Temperature (°C)

160 8.00 51.90%

140 6.00 51.90%

120 4.00
76.00%

76.00%
100 2.00

100%
80 0.00
-8 -4 0 4 8 12 16 20 24 28 32 36 40 44 48 52 56
Time (hours) H2 inlet %

7
LTS Reduction

Hotspot temperature
Hotspot temperature

220-225°C - Expected

> 230°C - Turn down H2 flow

> 250°C - Cut H2 flow - Depressurise - Circulate cold N2

Compressor trip

Cut H2 flow

Purge reactor for H2

Purge loop for H2

Thank you for your attention