2018 03 25 Commons Problem at Primary Reformer-Workshop PSP 27-28 Mar 2018 PDF

Carbon Formation
Problem at Fired Steam-

Hydrocarbon Reformer
Muhammad Ikhlasillah
BU Catalysts
PT. Clariant Kujang Catalysts
26.03.2018
2 Carbon formation problem at fired steam-hydrocarbon reformer
Muhammad Ikhlasillah, BU Catalysts, PT. Clariant Kujang Catalysts, 26.03.2018
PROBLEMS
Common Problems at Fired Steam-HC Reformer
Burner/combustion
Radiant tubes Catalyst
related
• High tube metal • Flame • Poisoning

temperature impingement • Carbon deposit
• Tube coking • Long flame length • Catalyst breakage
• High pressure drop • Burner tip plugging
• Poor flow • High temperature
distribution in convection
• Tube section
sagging/bowing • Positive pressure
in the radiant
section
Possible Causes of Carbon Formation
CO Content
Operating
in Reformer
Temperature
Gas Feed
Hot Spots &

Liquid HC
Increase in
Carried
Gas
Over
Temperature
Low S/C Carbon Poisoned

ratio Formation Catalyst
Carbon Formation Mechanism
1. No or loss of steam: Carbon formation from CO is

3-10 times faster than from
 Thermal cracking:
CH4.
CH4 === C + 2H2 …………….. (1)
Path 2 >>> Path 1
2. Low S/C ratio or too high CO content feed

streams:
 Boudourd:
2CO === C + CO2 ……….…… (2)
 CO reduction:
CO + H2 === C + H2O ………. (3)
Carbon Formation - Kinetics
The formation and accumulation of When the rate of carbon formation

carbon on the catalyst is controlled by exceeds the rate of removal,
reaction kinetics. accumulation of carbon on the catalyst
reduces its activity and void fraction.
During upset condition:
During normal operation:
Rate of carbon removal < rate of carbon
Rate of carbon removal > rate of carbon
formation
formation
Carbon Deposit
No carbon formation
Increase CH4
Increase dP High TWT
leak
Carbon Formation Tendency – Thermal Craking and

CO Disproportion Cases
Favor by high temperature and low Favor by higher CO partial pressure, low
steam to carbon ratio. temperature, and high CO2 content feed
stream.
Heavy HC in the feed will crack first.
Carbon formation area Carbon formation area

Carbon Formation Cycle Effect
Catalyst
Deactivation
Carbon Possible
Deposit Causes
Suppression of Carbon Formation
The carbon can be formed by following The carbon formation can be

reactions: suppressed by:
1). CH4 === C + 2H2 (thermal cracking) • Decreasing the acidity of the
catalyst.
2). 2CO === C + CO2 (CO disproportion)
• Acceleration the carbon
3). CO + H2 === C + H2O (CO reduction)
gasification reactions once
4). CO2 + 2H2 === C + 2H2O (CO2 reduction) carbon has been formed:
5). C + 2H2O === CO2 + 2H2
6). C + CO2 === 2CO
The overall carbon accumulation is
determined by the difference in the
rate of carbon formation and carbon
gasification.
SOLUTIONS
Select the Appropriate Catalyst
Feed gas Catalyst type Remarks

Light Hydrocarbon 100% RM 330 LDP Pre-reformed feeds
30-40% RM 210 LDP Natural gas, refinery off-gas
60-70% RM 330 LDP
Medium 50% RM 210 LDP Hydrocarbon feed with
hydrocarbon 50% RM 330 LDP significant C2+ content up to
LPG
Heavy Hydrocarbon RM 250 Naphtha
Steam to Carbon Ratio Adjustment
Depends on feed gas characteritics:
Steam to • Natural Gas - 2.6 or higher

Carbon ratio
• Refinery Off Gas - 2.0 or higher
• LPG - 3.2 or higher
• Naphtha - 3.0 or higher
Higher steam is usually better

Carbon Deposition
Carbon deposition occurs when:
Carbon formation rate > carbon removal rate

Efforts to Mitigate Carbon Formation
 To maintain poisonous content  Never let gas flowing into the

(such as: sulfur, chloride etc.) no catalyst without steam flow.
exceed permitted limit.
 Prevent flame impingement that

 Preventing any liquid heavy could causes local hot tube.
hydrocarbon carried over.
 Limit CO content in reformer feed

 Maintain H2 content in the feed stream
stream as target to keep top layer
catalyst remains in reduce state as
low reforming reaction at top 30%.
Carbon Removal Rate Improvement
Carbon removal rate can be improved by:

• Installed low acidity catalyst type (such as: potash)
Increase Steam Flow to Remove Carbon Deposit
Increasing S/C ratio during normal operation after catalyst deactivated by

carbon deposit is not effective
Because…..
Steam consumption is competing with the main

reaction
Questions
Muhammad Ikhlasillah
BU Catalysts
PT. Clariant Kujang Catalysts
26.03.2018
APPENDIX

2018 03 25 Commons Problem at Primary Reformer-Workshop PSP 27-28 Mar 2018 PDF

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Carbon Formation

Problem at Fired Steam-

Common Problems at Fired Steam-HC Reformer

• High tube metal • Flame • Poisoning

Possible Causes of Carbon Formation

Hot Spots &

Low S/C Carbon Poisoned

Carbon Formation Mechanism

1. No or loss of steam: Carbon formation from CO is

2. Low S/C ratio or too high CO content feed

Carbon Formation - Kinetics

The formation and accumulation of When the rate of carbon formation

Carbon Formation Tendency – Thermal Craking and

Carbon formation area Carbon formation area

Carbon Formation Cycle Effect

Suppression of Carbon Formation

The carbon can be formed by following The carbon formation can be

Select the Appropriate Catalyst

Feed gas Catalyst type Remarks

Steam to Carbon Ratio Adjustment

Depends on feed gas characteritics:

Steam to • Natural Gas - 2.6 or higher

• LPG - 3.2 or higher

• Naphtha - 3.0 or higher

Higher steam is usually better

Carbon deposition occurs when:

Carbon formation rate > carbon removal rate

Efforts to Mitigate Carbon Formation

 To maintain poisonous content  Never let gas flowing into the

 Prevent flame impingement that

 Limit CO content in reformer feed

Carbon Removal Rate Improvement

Carbon removal rate can be improved by:

Increase Steam Flow to Remove Carbon Deposit

Increasing S/C ratio during normal operation after catalyst deactivated by

Steam consumption is competing with the main

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