SPE-178074-MS

Novel Use of Spent Amine Solution of Gas Sweetening Plant as H2S

Scavenger, Corrosion Inhibitor & Biocide
Dr. A. K. Shukla, P. S. Chauhan, and S. K. Sahu, ONGC, Uran Plant

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Oil and Gas India Conference and Exhibition held in Mumbai, India, 24 –26 November 2015.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Gas Sweetening is the most important operation of any Natural Gas Processing Plant. At ONGC, Uran
Plant, gas received from offshore is combined with the crude stabilization off gas (CSU off gas) and
condensate fractionating off gas and then passed through Gas Sweetening Units (GSU) to remove CO2
and H2S from the gas before further processing in LPG and EPRU for extraction of value added products.
GSU plant was originally designed for and operated with gas sweetening solvent system consisting of
DIPA (Di-Isopropanol Amine) & Sulfolane. Contamination of solvent by amine degradation products and
comingled composition of solvent system became a bottleneck for increasing gas processing capacity and
to enhance plant capacity, comingled solvent system was replaced with a third generation solvent system
consisting of MDEA, Sulfolane & Piperazine.
After change-over, approximately 500 MT of comingled amine solution having a mixture of DIPA,
MDEA, Sulfolane, Piperazine and Oxazolidone (an amine degradation product), was available as a
hazardous waste. Owing to the complexity of the mixture having five different chemicals, reclaiming of
useful solvent from the comingled solution was ruled out and the only option left was its disposal by
incineration.
Keeping in view the large quantity of spent solution & huge cost of disposal, study was undertaken to
explore possibility of use of spent solution for some other in house applications.
Extensive lab studies carried out to evaluate anti-corrosive, anti-microbial and H2S scavenging
properties of spent solution & found that amine solution has adequate H2S Scavenging & corrosion
inhibition efficiency at 400 –500 ppm and bactericidal efficiency at 30 ppm of dosage.
The subsequent field trial at 400 –500 ppm of doses in one of the Oil trunk line having three phase flow
(oil, associated gas and water) for quite a period has shown substantial reduction of H2S content in the
off gas.

Introduction
Uran Plant in Maharashtra, India is a prestigious Oil and Natural gas processing complex of Oil and
Natural Gas Corporation (ONGC). The crude oil and natural gas produced from ONGC’s western offshore
fields are transported to onshore facilities at the Uran Plant through separate subsea pipelines. The crude
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oil received at Uran Plant is further processed and the stabilized crude is sent to refineries via pipeline &
oil tankers.
The gas received at Uran Plant is having H2S (Hydrogen Sulfide) in the range of 60 –120 ppm and CO2
(Carbon Di-Oxide) in the range of 2–3%. This gas is combined with the off gas of Crude Stabilization Unit
(CSU Off gas) and Condensate Fractionating Unit (CFU Off gas) and passed through the Gas Sweetening
Units GSU-12, GSU-13 & GSU-14 for removal of H2S and CO2. After sweetening, sweet gas is taken
through LPG recovery units LPG-I, LPG-II & LPG-III for recovery of LPG (Liquefied Petroleum Gas)
and natural gas liquid (NGL) and then to ethane/propane recovery units to recover C2 / C3 (Ethane-
Propane) product. The lean gas is then routed to consumers via pipeline.
The two gas sweetening units, GSU-12 & GSU-13 were originally designed for and operated with gas
sweetening solvent system consisting of Di-iso Propanol Amine (DIPA) and Sulfolane. Due to severe
foaming & capacity loss, solvent was partially swapped to second generation solvent system by adding
MDEA (Methyl Di ethanolamine) & Piperazine. However, contamination of solvent by amine degradation
products & heat stable salts such as Oxazolidone and comingled composition of solvent system became
a bottleneck for increasing gas processing capacity and to enhance plant capacity, comingled solvent
system is replaced with a third generation solvent system consisting of MDEA, Sulfolane & Piperazine.
Severe foaming problem was encountered in the year 2005 in both the units which was, probably due
to low solvent inventory and contamination of solvent by amine degradation products, heat stable salt
(Oxazolidone). To overcome this problem, as an immediate remedial measure, as per recommendations
of process licensor, solvent was partially swapped to second generation solvent system by adding MDEA
(Methyl Di ethanolamine) & Piperazine. Though, further addition of DIPA, the source of formation of
Oxazolidone in the solvent system, was discontinued and only MDEA and Piperazine were only added,
the solvent system was still having DIPA, Sulfolane and degradation products Oxazolidone.
Presence of the amine degradation product and comingled composition of the solvent system became
a bottleneck for increasing the gas processing capacity of GSU-12 & 13. In order to enhance the gas
processing capacity, it was decided to change-over the existing solvent system with MDEA, Piperazine
& Sulfolane solvent system which is a third generation gas sweetening solvent system. The change-over
was to be done in the phases and GSU-12 was changed first. The existing solution of GSU-12 was
transferred to GSU-13 and a fresh solution consisting of MDEA, Piperazine & Sulfolane was prepared.
The plant was put under operation and is being operated successfully at a higher capacity. The solvent
system of GSU-13 was also replaced subsequently with MDEA, Piperazine & Sulfolane solvent system.
After changing the gas sweetening solvent system of GSU-12 & 13, approximately 500 MT of
comingled amine solution having a mixture of DIPA, MDEA, Sulfolane, Piperazine and Oxazolidone
(Table -1) was available as a hazardous waste. Owing to the complexity of the mixture having five
different chemicals, reclaiming of useful solvent from the comingled solution was economically not
feasible.
SPE-178074-MS 3

Table 1—Composition of Spent Amine Solution:Composition of Spent Amine Solution

The left over amine solution, being hazardous in nature, was to be safely disposed of. As per the
operations manual of GSU (Gas Sweetening Unit), recommended method for disposal of spent amine
solution is through incineration. Such facility of disposal was not available in the Uran Plant and an
outside agency duly approved by statutory bodies was to be hired for transportation and safe disposal of
the huge quantity of spent solution through incineration.
Keeping in view the large quantity of spent solution & huge cost of disposal, study was undertaken to
explore possibility of use of spent solution for some other in house applications.
The use of DIPA, MDEA, Pipearzine and Sulfolane as a gas sweetening solvent is well-established
[1–4]. Scientific & Technical literatures are full of the fact that amines and sulphur compunds having
structural and functional groups similarity with DIPA, MDEA, Pipearzine and Sulfolane acts as an
effective Corrosion Inhibitor [5–11], H2S Scavengers [11–13] & Biocides [14,15]. Piperazine derivatives
are also used as anti-helminthic medicines [16,17].
On the above premise, extensive lab studies carried out to evaluate anti-corrosive, anti-microbial and
H2S scavenging properties of spent solution & found that amine solution has adequate H2S Scavenging
& corrosion inhibition efficiency at 400 –500 ppm and bactericidal efficiency at 30 ppm of dosage. (Table
2–5).
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Table 2—Scavenging efficiency of Spent Amine Solution:Performance evaluation of spent amine solution as a H2S scavenger

Table 3—Efficiency of solution as GCI- H2S corrosion inhibitor (As per ONGC Standard):Performance evaluation of spent amine
solution as corrosion inhibitor
SPE-178074-MS 5

Table 4 —Efficiency of solution as corrosion inhibitor (As per NACE Standard):

Table 5—Efficiency of spent amine solution as a Biocide:Performance evaluation of spent amine solution as Biocide

Note- The spent amine solution also possess the property of controlling algae and fungi-specifically Aspergillus Niger.
6 SPE-178074-MS

Table 6 —Field Trial (H2S ppm in Associated Gas of HUT Oil Line and CSU-Off gas):

The details of the study carried out are as under:

H2S Scavenger for Hydrocarbon Streams

Amines, such as Triazines made from Mono Ethanol Amine (MEA) or Methylamine (MA) are used as
water soluble H2S scavenger for hydrocarbon streams [12,13,18]. The spent amine solution contains
SPE-178074-MS 7

DIPA, MDEA, Piperazine which are also amines & used in various combinations with or without
Sulfolane for removal of H2S and CO2 from sour gas. Based on the functional group similarity in the
industry proven water soluble H2S scavengers and various constituents of the spent amine solution, a
study was carried out to evaluate the performance of spent amine solution as H2S scavenger for
hydrocarbon streams (Table-2).
The scavenging efficiency of spent amine solution was carried out at different doses and exposure time
in sea water media giving adequate contact time between the scavenger and H2S and it was found that the
solution is having a good H2S scavenging property with maximum scavenging efficiency of 82.0 % and
193.1 % at doses of 400 and 500 ppm respectively (Table-2).
Corrosion Inhibiter & Biocide
On the premise that most of the N-heterocyclic & acyclic amines and derivatives are having corrosion
inhibitive properties [5–11], antimicrobial properties [14,15] and since, the spent solution is a mixture of
these amines (Table-1), studies were carried out to investigate corrosion inhibitive properties & antimi-
crobial properties of the solution.
Corrosion Inhibition Efficiency
1. The corrosion inhibition efficiency of the solution was carried out at ONGC laboratory as per
ONGC test procedure of Corrosion Inhibitors for Oil & Gas line in presence of H2S and the
performance efficiency was found to be 86% at 500 ppm dose (Table-3) as against the required
efficiency of 80% as per existing ONGC specification for Gas line Corrosion Inhibitor (GCI)-H2S.
2. Corrosion Inhibition Efficiency test was also carried out as per NACE test methods (NACE
1D182) and performance efficiency of the spent amine solution was found to be more than 80.6%
& 83.1% at 400 and 500 ppm doses respectively (Table-4).
It is evident from the above studies that performance of the spent amine solution as Oil line Corrosion
Inhibitor (CI) at 400/500ppm conforms to ONGC and NACE standard of Oil & Gas line CI. Though, the
doses of 400 & 500 ppm are a bit high for such applications, solution can be used as an effective Corrosion
Inhibitor for Oil & Gas line.
Antimicrobial Properties
1. The sample of spent amine solution was also evaluated for its antimicrobial properties. As per
analysis report (Table-4):
i. No growth of IRB (Iron Reducing Bacteria) and SRB (Sulphate Reducing Bacteria) were
observed even after 18 days at a dosing of 30 ppm. At a dose of 20 ppm, growth of microbes
were noticed on 15th day (Table-5).
ii. Spent amine solution also possess the property of controlling algae and fungi- specifically
Aspergillus Niger.
iii. Significant antimicrobial activities on GAB (General Aerobic Bacteria) growth was not
observed.
8 SPE-178074-MS

It may be concluded from the above microbiological studies that the amine solution is an effective
bactericide against IRB (Iron Reducing Bacteria) and SRB (Sulphate Reducing Bacteria) with optimum
efficiency at 30 ppm. However, during the lab study, solution did not showed any significant antimicrobial
activity against GAB (General Aerobic Bacteria)

Conclusion
1. The spent amine solution is found to be having H2S Scavenger efficiency of 82% & 193% at 400
and 500 ppm respectively.
2. The Optimum concentration of spent amine solution as H2S scavenger is 400 ppm at which 82 %
inhibition efficiency is achieved.
3. The spent amine solution is found to be having corrosion inhibition efficiency of 76% & 86% at
400 and 500 ppm respectively which is a bit high for such applications.
4. The Optimum concentration of spent amine solution as GCI-H2S corrosion inhibition is 500 ppm
at which 86 % inhibition efficiency is achieved.
5. The Optimum concentration of spent amine solution as bactericide against IRB (Iron Reducing
Bacteria) and SRB (Sulphate Reducing Bacteria) is 30 ppm at which no growth observed even
after 18 days.

Field trial of Spent Amine Solution as H2S Scavenger

Based on the lab studies, spent amine solution was tried as H2S scavenger in actual field conditions at Uran
Plant. The solution was continuously dosed @ 300 –350 ppm in one of the crude oil trunk line having three
phase flow (Oil, associated gas & water) in the CSU (Crude Stabilization Unit) upstream. The H2S content in
the associated gas and treated gas were monitored before solution dosing point in the CSU upstream and in the
CSU Off gas respectively giving adequate contact time for solution to react with H2S. Field trial was carried
out for a period of 15 days. Field trial study indicates that there is 75– 89% reduction in H2S ppm in the
CSU-Off gas after dosing of spent amine solution @ 300 –350 ppm (Table-6). However, based on the statutory
requirements, effect of spent amine solution on effluent water quality needs to be further investigated.

Takeaway
It was observed that Mumbai offshore installations are facing problem of H2S, Corrosion and microbial
growth. Based on the laboratories studies, it is recommended that the spent amine solution available after
change-over of solution mix of GSU-12 & 13 at Uran Plant may be used as an effective H2S Scavenger,
GCI-H2S Corrosion Inhibitor and as a Bactericide at offshore installations as well as at Uran Plant. This
will help to minimize various safety and operational issues associated with the high H2S content,
Corrosion and bacterial activities.

Advantages at a Glance
1. Spent Amine Solution can be used as H2S scavenger to remove H2S from the crude oil and gas
at onshore & offshore installations. This is an innovative method to contain H2S in Crude Oil &
Gas lines at onshore & offshore installations and will reduce many safety and operational problems
associated with the handling of Crude Oil, Gas containing H2S.
2. It will simultaneously worked as corrosion inhibitor & biocide for oil and gas line to protect the
lines from corrosion and bio-growth & save substantial amount otherwise spent on purchase of
GCI-H2S corrosion inhibitors & biocides.
3. The use of spent amine solution which is a waste product having nil value, will not only convert
an hazardous industrial waste into a useful product but also save lakhs of rupees required for
transportation and disposal through incineration.
SPE-178074-MS 9

Acknowledgement
Sincere thanks are due to Shri K S Pangety, ED-Chief Lab for his stimulating suggestions and concern
for H2S containment in Mumbai offshore oil fields which has been the driving force for this study.
Authors are also grateful to Shri S K Pandey, GGM (P)-Head Operations, Uran Plant for his constant
motivation and support.
The laboratory support for this study is provided by ONGC, RGL, Panvel, Corporate R&D Centre,
BPCL, Greater Noida and M/S Spic Enzymes, a division of Spic Pharmaceutical Limited, Chennai. The
analytical support provided by these laboratories is thankfully acknowledged.
Special thanks are due to Shri S P Singh, GGM (Chemistry),, Shri Harbir Singh, DGM(Chem)-Head
Chemistry Lab, RGL, Panvel, Shri G C Sundriyal, DGM(Chem), RGL, Panvel, Mr. S K Goel, GM(Ops),
BPCL and Dr. S N Natarajan, Head (R&D), Spic Enzymes for providing laboratory support for these
studies.
The guidance and support provided by Shri G P Bahuguna, GM (Chemistry), NH-Asset and Dr. S A
Fazal, GM (Chemistry), PPCL acted as a catalyst to complete the task with ease and we are thankful to
them profusely.
Last but not the least, Shri R N Tiwari, DGM (P), Shri A T Jadav, DGM (P), Shri P G Patil,
DGM(Chem), Dr. A K Saxena, Chief Chemist, Shri D K Ralli, Chief Chemist and all the personnel of
GPG & PPCL, ONGC Uran Plant are also acknowledged for their help and support.

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