Purification of

Hydrocarbon Feedstocks

Research I Technology I Catalysts

MRPL Phase-III Refinery Project, Hydrogen Generation Unit

Agenda – Gas Purification

Hydrogenation (organic sulphur → H2S)

Sulphur Absorption

Trace Sulphur Removal

Chlorine Removal

Start-up

Feed purification section

Feed

H2
Chlorine Chlorine
Absorption Absorption
HTG-1 HTG-1

Hydro-
genation Sulphur Sulphur
TK-250 Absorption Absorption
HTZ-3 HTZ-3

RSH + H2 → H2S + RH H2S + ZnO ↔ H2O + ZnS

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Why desulphurise?
Sulphur poisoned reformer Well working
catalyst – hotbands reformer

Agenda - Hydrogenation

Operation ranges

Types of catalyst

Reactions

Important operating parameters

Operating ranges (hydrogenator)

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

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 Topsøe hydrogenation catalyst
Catalyst TK-250 TK-261
Shape Extruded Ring Quadralobe
Carrier material Al2O3 Al2O3
Dimensions OD x ID, mm 5.0x2.5 mm 2.5 x -
NiO, wt% - 2.3
CoO, wt% 3.4 -
MoO3, wt% 14 10

TK-250 TK-261

(CoMo) (NiMo)

Hydrogenation Reactions

Organic Sulphur

RSH + H2 ⇒ H2S + RH
R1SR2+ 2H2 ⇒ H2S + R1H + R2H
R1SSR2 + 3H2 ⇒ 2H2S + R1H + R2H
(CH)4S + 4H2 ⇒ H2S + C4H10
COS + H2 ⇒ H2S + CO
Olefins + H2 ⇒ Saturated hydrocarbons

Important Parameters - Hydrogenation

Sulphur content

Temperature

Hydrogen

Poisons

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The active phase
CH3SH + H2 CoMoSx
Sulphur
Molybdenum
Cobalt

TK-250

H2S + CH4

Activity as a Function of Sulphur Content

Catalyst Activity

Sulphur in Feed, ppm

Sulphur - Fluctuating Levels

Sulphur Concentration, ppm

Time
H2S Inlet Organic sulphur Inlet
H2S outlet Organic sulphur Outlet

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 Activity as a Function of Temperature
HDS Activity

280 300 320 340 360 380 400

Temperature, oC

Temperature in HDS Section

High Temperature: Potential risk of carbon lay-down

from cracking of hydrocarbons resulting in
reduced catalyst activity

CH4 ⇒ C + 2H2

Low Temperature: Risk of organic sulphur

breakthrough due to insufficient catalyst activity

Hydrogen to hydrogenator

To low hydrogen content

– Risk of organic sulphur breakthrough as no hydrogenation takes place
– The affinity for carbon lay-down on the catalyst is increased
– The heavier the feed the more hydrogen is needed

Feedstock Hydrogen content, mole%

Natural gas 2-5 mole%
LPG >0,05 Nm3 H2/kg Hydrocarbon
Naphtha >0,1 Nm3 H2/kg Hydrocarbon

To high hydrogen content

– Reduction of un-sulphuided catalyst (operation with low sulphur feedstock
and high hydrogen during initial start-up)
H2 + MoO3 ⇒ MoO2 + H2O

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 Poisons – Heavy Metals (As,V,Si etc)

Pore Mouth Plugging

New catalyst Plugged catalyst
CH3SH

Catalyst pore

Questions ?

Chlorine absorber – HTG-1

HTG

Purpose
– Absorb HX (X=F-, Cl-, Br-, I-)

Physical description
– K2CO3/Al2O3 base catalyst
– Size: Extrudates, 5 mm
– Safety precautions: Dust irritation, pyrophoric
– Poison: Oxygen, condensate

Catalytic reactions:
K2CO3 + 2HCl
KCl+KHCO3+HCl
2KCl + H2O + CO 2

Operation condition
– Maximum operating temperature: 400°C
– Chlorine slip: Catalyst replacement if ≥ 0.1 ppm
– Chlorine uptake: 0.7 kg/l

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Chlorine absorption
Feed

H2
Chlorine
absorption HTG
Hydro- Sulphur Sulphur
genation absorption absorption

Unwanted reaction

2HCl + ZnO ↔ ZnCl2 + H2O

Chlorine absorption

K2CO3 + 2HCl → 2KCl + CO2 + H2O

Questions ?

Agenda - Sulphur Absorption

Types of absorbents

Reactions

Mechanism for sulphur pick-up

Sulphur profile

Selection of absorbent

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 Topsøe sulphur absorbents
Catalyst HTZ-3 HTZ-5 HTZ-51
Shape Cylindrical extrudates
Size, mm 4
ZnO, wt% >99 >99 >97
Al2O3, wt% <1 <1 1
Filling density, kg/l 1.3 1.1 1.1
Porosity, ml/kg 300 350 350
Max Abs. cap., kg S/m3 505 420 420
HTZ-3/5 HTZ-51

The sulphur absorption reaction

H2S + ZnO → ZnS + H2O
Molecular weight: 2+32 81.4 97.4 18

100 kg pure ZnO can absorb maximum:

– (32/81.4) x 100 = 39.3 kg sulphur

Sulphur content in spent ZnO can max. be:

– (32/97.4) x 100 = 32.8 wt%

Sulphur Pick-up Mechanism for ZnO

Pore Diffusion

Solid Diffusion

Chemisorption

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Sulphur Pick-up Mechanism for ZnO

Sulphur Pick-up Mechanism for ZnO

Sulphur pick-up mechanism

H 2S
H 2O
ZnS

ZnO

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Sulphur profile

Bulk saturation

Main absorption front

Chemisorption front

Sulphur-free HTZ

Sulphur uptake for HTZ

40
Sulphur uptake, wt %

Long time of operation

Short time of operation
0
100 200 300 400
Operating temperature, °C

Equilibrium Constant for the Reaction:

ZnO + H2S ⇔ ZnS + H2O

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10

8
Log Kp

6
PH2O
4 Kp =
PH2S
2

0
0 100 200 300 400 °C
(32) (212) (392) (572) (752) (°F)
Temperature

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 Selection of Absorbent

Sulphur content in hydrocarbon feed(s)

Lifetime

Operating temperature

Density and porosity of ZnO

Equilibrium level of sulphur

Chemisorption capacity

Topsøe Sulphur Absorption Catalyst

Application and Features of HTZ:

Catalyst Application Features

HTZ-3 High sulphur feedstocks
High temperature operation
HTZ-5 Low sulphur feedstocks
Low temperature operation
HTZ-51 Low sulphur feedstocks
Low temperature operation
High purity (<99%)
High density (1.3 kg/l)
High sulphur pick-up (>500 kg S/m3)
High purity (<99%)
High surface area
High surface area
Hydrogenation activity

Start-Up

Avoid operation on pure H2

Presulphiding of HDS when olefines or high H2

Heat up in N2 to higher than dew point

H2 when temperature is higher than 300oC

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Questions ?

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