Paper No.

09334 2009

FAILURE OF AMINE REGENERATING COLUMN OF AMINE TREATMENT

UNIT

Nitin Raut
Bharat Petroleum Corporation Limited, Refinery Division,
Mahul, Mumbai – 400074, Maharastra, India.

R M Chaudhari
Bharat Petroleum Corporation Limited, Refinery Division,
Mahul, Mumbai – 400074, Maharastra, India.

V S Naik
Bharat Petroleum Corporation Limited, Refinery Division,
Mahul, Mumbai – 400074, Maharastra, India.

ABSTRACT

This paper intends to provide a detailed description of a corrosion problem1 observed in the amine regenerating
column in Amine Treatment Unit at a refinery. A leak was observed in a section of the column that had previously
been repaired. Localized groove marks were observed on the internal surfaces of the column. Grooving was
determined to be the result of acid gas out break inside the column which resulted in highly accelerated metal loss.
This paper also discusses the probable causes of such corrosion attack, and likely remedies to control corrosion of the
column. Insight and a description of the refinery’s adopted corrosion mitigation strategy have also been discussed.

Key Words: Amine Regenerator Column, DEA, Acid gas

INTRODUCTION

The amine treatment unit at the BPCL Mumbai refinery is designed to treat the fuel gas and LPG generated in various
refinery units like the Crude Distillation Unit (CDU) and the Fluidized Catalytic Cracking Unit (FCCU). The acid gas
treatment involves removal of hydrogen sulphide and carbon dioxide gases from refinery fuel gas and LPG in an
amine absorber column. Acid gases are removed by extraction using diethanol amine (DEA) solvent, which has the
tendency to absorb both the gases at low temperature and high pressure. The amine unit was designed for acid gas
loadings associated with Mumbai High (MH) and Iranian Mix (IM) crude oils. (Refer Table 1)

In the Amine Regenerator Column, H2S and CO2 (acid gases) absorbed in the DEA solvent (rich amine) are stripped at
high temperature and low pressure, using steam as the heating medium. Stripped acid gases exit the regenerator

Copyright
©2009 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Copyright Division, 1440 South creek Drive, Houston, Texas 777084. The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

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column overhead and are processed in the sulfur recovery unit. Regenerated “lean amine” is cooled, and then pumped
back to the absorber for reuse.
The Amine Regenerator Column is a vertical column 18.3 m high, and has an outside diameter of 2.5 m at the bottom
and 2.0 m at the top. (Refer Table 2) After exchanging heat with lean amine leaving the regenerator in the lean-rich
heat exchanger, the rich amine feed enters near the top of the column, at the 20th tray, at 95ºC. The Amine Reboiler
uses LP steam as a heating media, heating the solvent to 121ºC. The reboiler outlet stream enters the column near the
bottom, below the 1st tray. The Reboiler steam strips out the absorbed H2S and CO2 present in the DEA solution
(Refer Figure 1).

The chemical reactions involved are:

R2NH3S---------> R2NH + H2S (1)

(R2NH3) CO3 ---------> R2NH + CO2 + H2O (2)

where R is a CH2CH2OH group.

Liberated acid gases and steam exit from the top of the regenerator column, and are cooled in the overhead
condensers. Un-condensed gas is sent to the Sulfur Recovery Unit, and the condensed liquid is pumped back to the
column as a total reflux. Stripped lean amine at 121ºC and 147 KPa exits the regenerator at the bottom, and then
exchanges heat with the feed rich amine before re-entering in the absorber columns.

CORROSION IN AMINE PLANTS 2, 3, 4

Most corrosion problems in amine plants can usually be traced back to deficiencies in either the design or operation of
the amine unit. However, experience has shown that even a well designed and well operated amine unit will likely
experience some degree of corrosion related problems during its operational life. This unit was commissioned in
1985, and since then, at a frequency of 3 to 4 years, the column bottom outlet has plugged due to corrosion products
and charcoal from the filters. Internal corrosion of the column increased considerably over the past 6 to 8 years,
which has resulted in leak. While it is not uncommon to have corrosion problems in older units, more severe
corrosion has been observed in the regenerator, re-boiler and lean/rich amine exchanger in this amine unit.

There following are contributing factors affecting amine unit corrosion:

x Design deficiencies
x Change in process conditions like different types of crude processing
x Process upsets
x Fouling of trays

Corrosion in amine plants is complex in nature, and many times cannot be attributed to a single factor. Many times it
results from the combined effect of H2S, CO2, and heat stable salts which are formed from a reaction of amines and
acidic components other than H2S & CO2. These salts do not dissociate with application of heat, and hence are called
heat stable salts. These salts increase the corrosivity of the amine solution.2

The forms of corrosion observed in amine plants are in one of three forms: uniform metal loss, localized metal loss, or
alkaline stress corrosion cracking.

Uniform Corrosion

Uniform corrosion results in a uniform metal loss from the metal surface. If this is the predominant mechanism, then
the corrosion rate can be determined, and remaining life of the equipment can be calculated. Uniform corrosion can

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be due to wet H2S or CO2 or due to the combine effect of both. Variations in pH due to Acid Gas Break out (which is
explained at the end of the discussion), process upsets or design deficiencies can increase the corrosion rate.

Localized Corrosion

Localized metal loss is an area of a serious problem. Premature failure due to localized metal loss can occur even if
the remaining life of the equipment based on the uniform corrosion has been predicted. Under-deposit corrosion due
to heat stable salts, high fluid velocities at the down comers, and condensation of highly acidic vapors on the internal
surfaces are the causes of localized corrosion. Figure 1 shows the location of corrosion. Figures 2 and 3 show groove
marks on the internal surface of the regenerator. Some of the corroded surface resembles the skin of a rhinoceros.
The top surface of a tray support ring, adjacent to the column shell, tray decks, surface areas around bolting bars,
entry and exit nozzles are some of the locations where localized corrosion occurs.

Alkaline Stress Corrosion Cracking

Alkanolamine solutions containing CO2 and/or H2S can promote Alkaline Stress Corrosion Cracking. This mechanism
can result in branched and inter-granular cracks in carbon steel. Stress Corrosion Cracking is a very dangerous form
of corrosion, sometimes resulting in failure, even if the measured wall thickness is sufficient as per the mechanical
design. Increasing in process temperature increases the possibility of Alkaline Stress Corrosion Cracking. Surface
discontinuities (e.g. erosion marks) provide locations which can become anodic creating conditions ripe for the
initiation of stress corrosion cracks.

INVESTIGATION / DISCUSSION

Following methodology was adopted to study the corrosion problem.

¾ Historical data on H2S loading of rich DEA and lean DEA in the unit was analyzed.
¾ Historical data on the process operating parameters was compiled and analyzed. Refer Table 3.
¾ Chemical analysis of lean DEA from the plant was carried out in the laboratory. Refer Table 4.
¾ Data on percentage of high sulfur (Middle East) crude processed year wise was collected and plotted as
shown in the figure 4.

After analyzing data the salient observations are as described below.

Operating parameters

DEA Strength:

DEA concentration has varied through out the run. The average DEA concentration was 13 wt % compared to the
design value of 25 wt%. Operating at lower amine concentration increased the acid gas loading.

Acid Gas loading:

• It was also observed that the average rich amine loading was 0.65 mole H2S /mole DEA (m/m), which is
much higher than the design loading of 0.19 m/m. This might be the reason for acid gas break out.
• Average H2S loading in Lean amine was 0.073 m/m, more than 8 times the design value of 0.009 m/m. One
possible reason for higher lean amine loading is poor stripping in the regenerator or processing high sulfur
crudes.
• Presently the CO2 concentration in rich and lean DEA is not analyzed. However acid gas exiting the top of
the regenerator column was analyzed to determine the CO2 absorbed in the amine treater. The average
concentration of CO2 in the untreated fuel gas was 2.9 %, much lower than the design value of 4.19 wt %.
The volumetric ratio of H2S to CO2 in the acid gas was 2.13 compared to a design value of 4.13. The average
value of 2.13 is well below the design ratio

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Quality of DEA

• DEA samples were analyzed for the suspended particles. The dust loading was 462 mg/l. In the 2006
turnaround cartridge filters were also found chocked and damaged. The entire system needed to be cleaned to
control the dust loading.
• Heat stable salts in the amine were found to be within the range 0.32 wt % of amine in relation to 10 wt% as
mentioned in the literature2.
• Chlorides are found on higher side (389 ppmw).

From a review of the equipment inspection log1 it was found that the column was having operational problems since
the time of commissioning. The column has faced problems like distortion of tray decks and plugging at the column
bottom.

Distortion of tray decks was due to flashing of two-phase feed. Vibration, due to Mechanical forces, resulted in
loosening of tray clamps and subsequently deformation of the tray decks. During inspection some tray clamps were
found broken and fallen.

Prior to February 1998, only moderate uniform corrosion was observed in the un-cladded section of the column, as
shown in the Figure 5. No localized corrosion was observed. The corrosion products and poor efficiency of filters
were the main reasons of plugging of column bottom. Use of a finer filter mesh has eliminated the problem of column
bottom plugging.

After February 1998, the percentage of high sulfur crude processing was increased due to non-availability of low
sulfur crude. The percentage of high sulfur crude led to an increase in H2S loading in amine treatment unit without
changing the design conditions, which is a favorable condition for acid gas break out, an important mechanism
responsible for localized corrosion. In the regenerator most of the acid gas stripped out in the top 1/3 section of the
regenerator column5, but due to high amount of acid gas in the amine solution, acid gases are liberated from the
solution below the stripping zone, which is not clad. Thus liberated acid gas form highly concentrated acidic streams.
These streams flow over the walls of the vessel, bolting bars, nozzles, and also accumulate at the weld joints at tray
support rings to column shell, which causes severe localized corrosion.

MITIGATION STRATEGY

The corrosion mitigation strategy adopted for the amine regenerating column comprised of:

1. Cleaning suspended particles from the DEA system by providing three stage filtration of lean amine through
cartridge pre filter, charcoal filter and cartridge post filter.
2. Monitoring of CO2 loading in DEA on a regular basis by analyzing untreated fuel gas and regenerator
overhead acid gas for CO2 content and CO2 in lean amine solvent stream.
3. Maintaining DEA strength on the high side (18 – 20 %wt) in order to reduce the acid gas loading in DEA.
4. Reflux flow indicator was found to be out of calibration. This resulted in a higher degree of stripping in the
regenerator. Since the flow indicator was faulty, the exact flow was not known. After the flow indicator was
repaired, it was adjusted to 18 - 20 MT/ Day i.e. about ~ 10 % of steam to re-boiler.

CONCLUSION

The failure of the amine regenerating column was due to the accelerated corrosion. While it is reported in the
literature6 that carbon steel is a suitable material for amine service equipment, this is based on proper operation. In
present case, the regenerator column corrosion difficulties were the result of abnormal conditions, mainly related to
design, process upsets, and changed operating conditions.

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 ACKNOWLEDGEMENTS

The authors gratefully acknowledge Mr. M. K. Kaul, Mr. C Majumdar for guidance and Mr. R. Wadhawan and others
for their supports to publish this paper.

REFERENCES

1. History Records of BPCL Inspection Department.

2. Amine Experts Inc. “Amine Treating India-2003, Reference Material” (Amine Experts Inc. Canada).

3. NACE Standard RP0472-2000, “Methods and Control to Prevent In-Service Environmental Cracking of Carbon
Steel Weldments in Corrosive Petroleum Refining Environments” (Houston, TX: NACE International).

4. API Recommended Practice 945, 3rd Edition, June 2003: “Avoiding Environmental Cracking in Amine Units”,
American Petroleum Institute, Washington D. C.

5. Sidney F. Bosen, “Causes of Amine Plant Corrosion-Design Considerations” (Houston, TX: The DOW Chemical
Company)

6. R. A. White, “Material Selection for Petroleum Refineries & Gathering Facilities” (NACE International, 1998,
Houston, Texas).

EXCHANGE
ACID
GAS ACID GAS

RICH AMINE+
H2S+CO2
SOLUTION
REFLUX
RICH DRUM
DEA

EXCHANGE
LEAN
AMINE PUMP

CORRODED AREA
LEAN GENERATED
AMINE STEAM+GAS

LP
STEAM
RICH AMINE+ REGENERATOR
H2S+CO2 REBOILER
DEA
PUMP REGENERATOR
RICH DEA FLASH
COLUMN

FIGURE 1 – Amine Regenerating Unit

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FIGURE 2 - Groove Marks on the Inside of the column

FIGURE 3 - Groove Marks on the Inside of the column

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 FIGURE 4 – Middle East (High Sulfur) Crude
Processed (Years wise)

CORROSION RATE

0.6
CORROSION RATE

0.5
(MM/YEAR)

0.4
0.3
0.2
0.1
0
Mar-88 to Mar-92 to Feb-98 to
Mar-92 Feb-98 Jul-02
DURATION

FIGURE 5: Corrosion Rate

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 TABLE 1
ACID GAS LOADING DESIGN VALUES
Mumbai high Iranian mix
Description
Lean Ammine
(moles H2S / 0.0056 0.0094
mole of amine)
Rich Amine
(moles H2S / 0.11 0.19
mole of amine)
Strength of DEA 25 %

TABLE 2
DETAILS OF AMMINE REGENERATING COLUMN
Main Shell ( Unclad)
Material SA 515 Gr. 60
UTS 60000 psi (413.7MPa)
Size 2.0m x 2.5 m
Corrosion Allowance 4.5 mm
Design Temperature 140 ºC
Design Pressure 343.23 KPa
Clad Shell & Top Dish
SA 515 Gr. 60 +
Material
SA 240 TP 304L
UTS 60000 psi (413.7MPa)
Thickness 8.0mm + 3.0 mm clad
General
Heat Treatment Complete Equipment
Stress Relieved

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 TABLE 3
Regenerator Operating Parameters
Parameter Unit Design From 2000 to From 2002 to Average
values 2002 2006 value
Max value Max value
Inlet Feed
flow Tpd 2148 1453 1200 1037
(rich DEA)
Feed temp Deg C 96.4 100.10 100.20 93.9
Pressure KPa 93 88.3 93 74.5
Top temp Deg C 111 116.6 115 110.0
Re-boiler inlet Not
Deg C 121.1 119.6 117.3
temp specified
Re-boiler
Deg C 121 120.9 120.6 116.8
vapor temp
Re-boiler
liquid outlet Deg C 121 121.1 121.3 118
temp

TABLE 4
Lean Amine Analysis

Sample Type Lean Ammine from FCCU

(ATU)
Appearance Light brown liquid with black
particulate matter
Ammine Concentration
Total base by titration (% DEA) 16.5 %
Total suspended solids 462 mg/l
Acid Gas Loading
H2S (wt %) 0.015
H2S (mole/mole) 0.0028
CO2 (wt %) 0.20
CO2 (mole/mole) 0.028
Heat Stable Salts
Heat Stable Ammine salts, wt.%
0.314
amine
Inorganic Heat Stable salts, wt.%
0.006
amine
Total Heat Stable salts, wt.% amine 0.32
pH of amine solution 9.35