Corrosion Control for Gas Treating Amines: New Technology Leads to Increased
Amine Unit Efficiency
Since the early 2000s, the US Onshore Shale Boom has significantly increased oil and gas production and associated
Natural Gas Liquids (NGLs). Using advances in horizonal drilling (unconventional), drillers have been able to drill wells in
less than one week and realize full initial production in less than one month from spud. This fast “spud-to-production”
cycle has increased the new commissioning activities of new gathering lines and field production units. Accelerated
basin activities combined with increased fugitive gas emission capture technologies in the drilling basins have increased
trace oxygen levels in midstream natural gas more than ever encountered over the last several decades.
Positioned at the end of the drilling basins, midstream gas plants typically use MDEA-blended amines for complete
removal of H2S and CO2. However, the trace oxygen levels now existing in the new gathering systems will degrade these
amines to corrosive amino acids and heat stable amine salts. We can never eliminate oxygen entirely. If we ignore it,
oxygen will cause significant capacity and equipment reliability problems leading to higher operating costs with amine
losses, higher frequency of mechanical filter changeouts, and lost NGL recovery revenue from downtime
or residue gas flaring.
The midstream industry has been using more and more formulated methyl dietholamineamine solutions for acid gas
removal over the past several decades. These tertiary amines are more efficient than the primary and secondary amines,
and do not form particularly corrosive compounds, such as tris-hydroxyethylethylenediamine (THEED) with the acid
gases extracted. However, the industry observed unexpected corrosion in amine units even when the typical heat-stable
amine salts were within their recommended operating ranges. Subsequently, it was determined that MDEA was being
degraded by oxygen to amino acids such as bicine and glycine. While significant effort has focused on research and the
sharing of bicine formation and corrosivity, little information and technology was available on how to minimize its
impact on amine destruction, until now.
There are now new technologies that can increase amine efficiency and reduce costs associated with corrosion. These
innovations inhibit the degradation of amines from oxygen and control corrosion in process gas, stabilizing the amine
from degradation into bicine and other heat-stable amine salts.
BASF’s PuraTreat Stabilizer Technology used in conjunction with Nalco Water’s INTERCEPT corrosion-inhibitor system to
successfully inhibits the degradation of amines from oxygen attack and controls corrosion in plants that process gas
containing greater than 1.0 mole percent oxygen.
BASF created a chemistry to shield the methyl-diethanolamine (MDEA) molecule from the oxygen-free radical and to
stabilize the amine from degradation into bicine and other heat stable amine salts. The combination of PuraTreat
Stabilizer additive with Nalco Water’s INTERCEPT Corrosion Control and Monitoring program has been proven to both
mitigate oxygen degradation of amine, measure and control the overall corrosivity of amine units.
Two case studies are presented where oxygen attack in the amine unit led to costly mechanical reliability challenges for
the midstream operators, and how our new technology mitigates future plant challenges.
PuraTreat® is a registered trademark of BASF SE.
INTERCEPT is a trademark of Nalco Water
CASE HISTORY 1
Background
This plant operated with a 45-50 weight percent amine strength. The amine solution removed the CO 2 to acceptable
levels at conditions within the suggested operating parameters of their current amine supplier. However, oxygen
present in the raw gas stream began quickly degrading the amine into the heat stable amine salts and amine acids
(bicine and glycine). To maintain the amine capacity and to reduce the CO2 from 8.5 percent to ppm levels under
degraded amine conditions, fresh amine was added to maintain the active. This also worked to reduce the growing
corrosivity of the degraded amine blend by neutralizing the heat-stable salts created with a stronger base. The
neutralization program required frequent amine samples to verify the level of neutralization prior to any subsequent
chemical additions. While the additions of new amine allowed the plant to continue to meet the outlet CO 2 specification,
neutralization was a challenge to maintain due to the remoteness of the facility. Within a short time the bicine levels
rose “unchecked,” and free iron (Fe) in the amine skyrocketed. This increased amine corrosivity led to carbon steel pipe
failures which became a common occurrence at the facility.
To prevent future pipe failures, Nalco Water’s Midstream group was asked in April 2015 to begin adding a
passivator/inhibitor to the existing amine to help mitigate the bicine corrosivity. This corrosion protection was too late.
Six months after the metal passivator application began and after the fifth year of operating with bicine levels as high as
1,000 ppm (total anions were 60% neutralized), the plant realized structural failure in the absorber tower.
Solution
A new replacement tower was installed. Nalco Water was asked to begin monitoring amine unit corrosion (lean and rich
amine) and begin the INTERCEPT passivator corrosion inhibitor program.
In March 2017, the plant switched to a BASF Amine and OASE® Stabilizer was applied to the system. Nalco Water’s
passivator/inhibitor corrosion control and monitoring program continued in place.
Plant results after amine changeover were successful in controlling formation of bicine and corrosion.
For the first seven years of operation, the plant realized active corrosion and free iron levels in the amine as high as 308
ppm. For the last three years, the OASE Stabilizer mitigated oxygen-induced amine degradation.
Each anion species, including bicine, was maintained to a level below 1000 ppm. The free iron levels were measured as
high as 100 ppm, but when properly monitored, the Nalco Water INTERCEPT program maintained the levels to <50 ppm.
No additional equipment has been changed-out since 2017.
CASE HISTORY 2
Background
This facility gathers natural gas from several oil wells and processes the gas to extract NGLs via propane refrigeration or
turbo expander. With much of the gathering system operating under vacuum, the gas contains as much as 850 ppm
oxygen from air leaks in the system.
OASE® is a registered trademark of BASF SE.
The gas plant receives unprocessed gas flows with a composition of 80% methane, 5.5% ethane, 1.8 % propane, 10%
CO2, 1.7% nitrogen and 0.5 % oxygen at a flowrate of 5-7 MMSCFD. The high inlet O2 in the sour gas stream had been
degrading the amine at such a high rate that neutralization was not an option to reduce the corrosivity of the resulting
amine. Within three months of operation, the heat stable salts and amino acids would climb to levels as high as 4 w eight
percent (10% of the amine strength). Bicine, at levels of 27,800 ppm, represented 70% of those degradation compounds.
Every three months, the 80 gpm gas plant was shut down for 7-8 hours and the amine system flushed. A fresh 1300-
1500 gallons of amine was then charged to the plant and restarted.
While this was probably the best way to handle high degradation rates in a smaller amine unit, the high bicine level was
never less than 9,400 ppm, per monthly system sampling. Corrosion-induced leaks in flanges and pipe spools were
commonplace. Baseline free iron levels in the amine were 330 ppm, with peaks prior to 3-month purges as high as 1,800
ppm. Over a short period of time, much of the equipment (other than the towers) was replaced with stainless steel.
The plant operating team had grown accustomed to the corrosion challenges, but product availability was now
becoming a problem with the relatively small volumes (less than one truckload) and high replenishment frequency.
Solution
Nalco Water provided PuraTreat AGX1600 amine blend immediately to cover the normal plant losses. PuraTreat
Stabilizer and Nalco Water’s Amine Corrosion Control Program, including the Amine Corrosion Analyzer began when a
plant shutdown was scheduled.
After nearly three months of operations, the PuraTreat Stabilizer maintained the bicine levels to increases of no greater
than 400 ppm (5 ppm/day). Previous analytical data from un-stabilized amine operations measured bicine increases of
~17,000 ppm (190 ppm/day). Even with total anion levels reaching > 5,000 ppm (acetates, formates and bicine),
INTERCEPT maintained free iron levels in the amine to less than 70 ppm.
Bicine and free Fe levels controlled with PuraTreat Stabilizer and Nalco Water Intercept.
The Nalco Water Amine Corrosion Analyzer continues to provide visibility into corrosion and oxygen excursions enabling
the plant to have a proactive response to protect their amine unit assets. Key system parameters – inlet oxygen,
corrosion rate and pH are actively monitored in real time and compared to plant performance targets. The plant has
seen verification of the effectiveness of the BASF and Nalco Water solution, and as a result they have been able to
identify and anticipate potential problems and thus accelerate decisions to mitigate oxygen-related asset issues.
Even the more efficient formulated gas treating amines that are available today remain susceptible to oxygen
contamination. These gas-treating chemicals must be protected from degradation or they will contribute to unexpected
amine unit shutdowns and shortened asset life.
In the two gas plant cases presented, BASF’s PuraTreat Stabilizer and Nalco Water’s Amine Corrosion Control Program
both offered by Nalco Water’s Midstream Team was shown to mitigate the oxygen degradation of formulated amines
and maintain gas plant asset life.
