Determinations of Heat Stable Amine Salts and

Amines in Amine Scrubbing Solutions Using

Suppressed Conductivity and Charge Detection
Terri Christison, Monika Verma, Pranathi Perati, Linda Lopez
Thermo Fisher Scientific, Sunnyvale, CA, USA
 Overview Results
 Heat stable amine (HSA) salts, such as organic acids, inorganic anions, and sulfur
based salts, in amine scrubber solutions were separated by anion-exchange on a 4 µm Charge Detection
particle high-efficiency capillary column.
The Dionex QD Ch
 This method utilizes two different but complementary detectors, suppressed dissociated compo
conductivity and charge detection. Charge detection provides higher relative the charge respon
responses for multi-charged anions, such as found in heat stable amine salt solutions, proportionally high
than chloride and sulfate.
FIGURE 3. Mecha
 Using these two detectors with different responses were used to confirm peak purity
and the presence of co-eluting peaks, thereby improving reporting accuracy.
.
Introduction An

Sour crude natural gas (methane) is typically treated with amine rich scrubber solutions
to neutralize carbon dioxide and remove hydrogen sulfide gas impurities before it can be
sold as a pure natural gas product.1,2 When the neutralizing capacity is deemed
inefficient, the amine solutions are regenerated and stripped of elemental sulfur.
Dissolved salts (heat stable amine salts) remain, building up over time resulting in higher
maintenance costs, and higher incidents of corrosion.2,3 Analysis of both the amine
concentrations and the heat stable amine salts are needed to ensure a pure product and
an efficient scrubbing process.

The Thermo Scientific™ Dionex™ QD Charge Detector promotes complete dissociation of

many weakly dissociated compounds as a result, the charge responses of singly- Figures 4–5 demon
charged, doubly-charged, and triply-charged ions are proportionally higher than used for improved
conductivity. CD and QD detector provided different responses were used to confirm
peak identity and the presence of unknown co-eluting peaks. Figure 4 shows an
detection (R1) whic
Methods and R4) clearly def
Samples / Sample Preparation Figure 5 illustrates
Sour gas amine samples were diluted 100-fold with deionized water. Some amine C2 concentrations
samples were treated with Thermo Scientific™ Dionex™ OnGuard™ II RP and Dionex concentration.
OnGuard II Na cartridges to remove interfering cations and organic compounds.

Instrumentation FIGURE 4. Using

Thermo Scientific™ Dionex™ ICS-5000+ HPIC™ Ion Chromatography dual capillary Example 1: QD co
system.
 DP Dual Pump, EG Eluent Generator, DC Detector Chromatography, and Thermo
Scientific™ Dionex™ IC Cube™ modules
 Thermo Scientific Dionex Detectors: CD Conductivity Detector, QD Charge Detector
with Thermo Scientific Dionex QDC 300 Cell
 Autosampler: Thermo Scientific Dionex AS-AP Autosampler
Data Analysis:
Thermo Scientific™ Dionex™ Chromeleon™ Chromatography Data System
Conditions:
Columns: Thermo Scientific™ Dionex™ IonPac™ AG11HC-4µm,
Dionex IonPac AS11HC-4µm, 0.4  250 mm
Eluent Source: Thermo Scientific Dionex EGC KOH cartridge, capillary
Gradient: 1 mM KOH (-7–8 min), 1–30 mM (8–28 min), 30–85 mM
(28–38 min), 85 mM (38–45 min)
Flow Rate: 0.015 mL/min FIGURE 5. Using
Column Temp.: 30 C
Example 2: CD co
Inj. Volume: 0.4 µL
Detection: A: Suppressed conductivity, Thermo Scientific™ Dionex™
ACES™ 300 Anion Capillary Eleyctolytic Suppressor, recycle
mode; 13 mA
B: Charge detection, Dionex QDC 300 cell, 6 V
FIGURE
2 Determinations of Heat 1. Flow
Stable Amine Salts diagram
and Aminesfor the IC
in Amine system
Scrubbing using
Solutions CDSuppressed
Using and QD detectors.
Conductivity and Charge Detection
  Thermo Scientific Dionex Detectors: CD Conductivity Detector, QD Charge Detector
with Thermo Scientific Dionex QDC 300 Cell
 Autosampler: Thermo Scientific Dionex AS-AP Autosampler
Data Analysis:
Thermo Scientific™ Dionex™ Chromeleon™ Chromatography Data System
Conditions:
Columns: Thermo Scientific™ Dionex™ IonPac™ AG11HC-4µm,
Dionex IonPac AS11HC-4µm, 0.4  250 mm
Eluent Source: Thermo Scientific Dionex EGC KOH cartridge, capillary
Gradient: 1 mM KOH (-7–8 min), 1–30 mM (8–28 min), 30–85 mM
(28–38 min), 85 mM (38–45 min)
Flow Rate: 0.015 mL/min FIGURE 5. Using C
Column Temp.: 30 C
Example 2: CD co
Inj. Volume: 0.4 µL
Detection: A: Suppressed conductivity, Thermo Scientific™ Dionex™
ACES™ 300 Anion Capillary Eleyctolytic Suppressor, recycle
mode; 13 mA
B: Charge detection, Dionex QDC 300 cell, 6 V
FIGURE 1. Flow diagram for the IC system using CD and QD detectors.

H20

High-Pressure
Non-Metallic Data
Pump Management

Eluent
Generator
(OH–) Separation Column Charge Detector
Figure 6 shows the
CR-TC acids, and sulfur-b
Electrolytic Conductivity were normalized to
Waste Eluent Detector 14 which are triply
Suppressor charged nitrite. Th
response when no
Figure 2 shows the Dionex IC Cube module and Dionex QDC 300 Charge Detector cell.
The Dionex IC Cube is designed to minimize the flow path needed for a capillary flow FIGURE 6. Separ
rate system by containing the columns and consumables in close proximity.
.
FIGURE 2. Dionex IC Cube with capillary modules

Guard and Separation Column tray

Thermo Scientific
Dionex CRD 180 Dionex IC Cube
Carbonate Removal 20

Device cartridge Thermo Scientific

Dionex Degas
Dionex ACES 300
4-Port Injection Valve cartridge
Suppressor µS

Dionex QDC 300 2

1 34
Charge Detector Cell B
Dionex Conductivity A
-0.5
Detector (CD) 0 10

Thermo Scientific Poster Note • PN71118_HPLC_2014_E_05/14S 3

 Results Figures 7–9 show
neutralizing sam
ons, and sulfur was pretreated w
xchange on a 4 µm Charge Detection
compounds and
Dionex sample p
The Dionex QD Charge Detector promotes complete dissociation of many weakly
pressed without introduci
dissociated compounds by drawing a current at a fixed potential (Figure 3). As a result,
relative QD chromatgram
the charge responses of singly-charged, doubly-charged, and triply-charged ions are
mine salt solutions, comparison. In F
proportionally higher than conductivity.
boxes) not notice
FIGURE 3. Mechanism of QD Charged Detector
nfirm peak purity FIGURE 7–8: An
ccuracy.
6V
. Cathode
FIGURE 7: CD v
Anode
H20
Y2-
crubber solutions A+
es before it can be
A+ Y2-
s deemed 25 3
tal sulfur. A+
resulting in higher
th the amine 1
pure product and H20 µS

5 6
Cation-Exchange Anion-Exchange
Membrane 2 4 7
ete dissociation of Membrane B
es of singly- Figures 4–5 demonstrate how the different peak responses by the CD and QD can be
A
-5.0
gher than used for improved data analysis. 0 10 20
M
sed to confirm
Figure 4 shows an example where the peaks have with the same response by CD
detection (R1) which could be either C1 or C2 concentrations; but with QD detection (R3
and R4) clearly defines the concentrations. Figure 9 show th
Figure 5 illustrates another example were QD detection (R4) correspond to both C1 and contamination, s
ome amine C2 concentrations but is clarified by CD detection where R1 and R2 confirm C2
RP and Dionex concentration. FIGURE 9. 100
mpounds.

26
FIGURE 4. Using CD and QD detection for peak analysis.
ual capillary Example 1: QD confirmation.

phy, and Thermo

µS
CD A QD A or B
QD Charge Detector
B
1
R3 R4
R1

A
B
-0.5
0 10

tem
C1 C2 C1 C2
C-4µm, Concentration Concentration

capillary Conclusio
0–85 mM • Heat stable am
organic acids
FIGURE 5. Using CD and QD detection for peak analysis.
• Here we demo
Example 2: CD confirmation.
stable amine s
™Dionex™
essor, recycle • This method h
CD A QD capillary-size
A or B
R2

B (HPIC) capilla
ors.
R4

4 Determinations of Heat Stable Amine Salts and Amines in Amine Scrubbing Solutions Using Suppressed Conductivity and Charge Detection
R1

• Using differen
 pillary Conclusion
85 mM • Heat stable amin
organic acids an
FIGURE 5. Using CD and QD detection for peak analysis.
• Here we demon
Example 2: CD confirmation.
stable amine sal
Dionex™
sor, recycle • This method has
CD A QD capillary-size Dio
A or B

R2
B (HPIC) capillary
s.

R4
R1
• Using different d
detector provide
result in improve

C1 C2 C1 C2 References
Concentration Concentration 1. Natural Gas.or
2. Rooney, P.C.;
Corrosivity, Pa
rge Detector 65–71.
Figure 6 shows the separation of a standard containing 15 inorganic anions, organic 3. Thermo Fisher
acids, and sulfur-based anions typically found as heat stable amine salts. QD responses in Methyldietha
ty were normalized to the nitrite peak. Peak 10 which is doubly charged and Peaks 13 and Sunnyvale, CA
14 which are triply charged have higher QD response than strongly ionized singlely http://www.the
charged nitrite. Thiocyanate is a singly charged ion which had a comparable relative lication%20&%
response when normalized to nitrite. 20and%20RFI
Detector cell. Methyldiethano
pillary flow FIGURE 6. Separation of mixed standard using CD and QD detection
y. Columns: Dionex IonPac AS11-HC-4µm with guard
Capillary (0.4  50 mm, 0.4  250 mm)
Eluent Source: Dionex, EGC-KOH (Capillary) cartridge
5 11 7.5 Gradient: Potassium hydroxide
1 mM (-7–8 min), 1–30 mM (8–28 min),
30–85 mM (28–38 min),
85 mM (38–45 min)
Flow Rate: 0.015 mL/min
Inj. Volume: 0.4 µL
Cube Column Temp.: 30 ˚C
20 Detection: A: Suppressed conductivity,
Dionex ACES 300 suppressor, recycle
8
Scientific 10
mode
B: Dionex QD Charge Detection, 6 V All trademarks are the
µA
egas Sample Prep.:
This information is no
Peaks: the intellectual proper
µS 1. Fluoride 0.4 mg/L 9. Carbonate 10 mg/L
2. Acetate 2.0 10. Sulfite 20
13 3. Propionate 2.0 11. Sulfate* 20
C 300 2
6
12 4. Formate 2.0 12. Oxalate 4
1 34 7 9 15
tector Cell B
14 5. Chloride* 20
6. Nitrite 2.0
13. Phosphate
14. Thiosulfate
4
2
A 7. Bromide 2.0 15. Thiocyanate 2
-0.5 0.5 8. Nitrate 20
0 10 20 30 40 45
Minutes * CD response for chloride and sulfate was truncated
at 20 µS. QD chromatogram was normalized at the nitrite
peak.

Thermo Scientific Poster Note • PN71118_HPLC_2014_E_05/14S 5

 Figures 7–9 show the determination of heat stable amine salts (HSA) in amine
neutralizing samples. Prior to injection, the diluted scrubber sample in Figures 7 and 8
was pretreated with Dionex OnGuard RP and Dionex OnGuard Na to remove organic
compounds and cation contaminants that were affecting the chromatography. These
Dionex sample preparation cartridges are designed to remove select contaminants
y weakly
without introducing IC-detectable ionic contaminants. In Figure 7, the chloride peak in the
3). As a result,
QD chromatgram was normalized to the same peak in the CD chromatogram for easier
ged ions are
comparison. In Figure 8, an expanded QD chromatogram reveals additional peaks (in
boxes) not noticeable by CD, thereby providing additional information and peak purity.

FIGURE 7–8: Anion determinations in 100-fold diluted amine scrubber solution.

FIGURE 7: CD versus QD FIGURE 8: Expanded scale of QD

11 10 detection. Additional peaks are revealed.

Conditions:: see Figure 6.

3 11 4. Detection: A: Suppressed conductivity,
1 5 Dionex ACES 300 suppressor,
25 3 recycle mode
B: QD Charge Detection, 6 V
Sample Prep.: 100-fold dilution with deionized
µA water, Dionex OnGuard RP and
OnGuard Na treatment
1 6 12 µA
5 Peaks (mg/L):
µS 1. Acetate 19 9. Oxalate 0.2
8 2. Propionate 0.8 10. Unknown --
5 6 12 13
9 3. Formate 33 11. Phosphate 98
8 13 10
2 7 4. Unknown -- 12. Thiosulfate 6.0
2 4 7 9 10 5. Chloride 1.9 13. Thiocyanate 3.8
B 4
B 6. Unknown --
A 7. Carbonate --
d QD can be -5.0 1 1.0 8. Sulfate 1.9
0 10 20 30 40 45 0 10 20 30 40 45
Minutes * QD was normalized to the chloride peak
*Boxes denote detection of
se by CD additional peaks
D detection (R3
Figure 9 show the CD and QD chromatograms of an amine solution with less HSA
o both C1 and contamination, sampled at an overhead actuator.
rm C2
FIGURE 9. 100-fold Dilution of an amine solution from an overhead actuator.

Columns: Dionex IonPac AS11-HC-4µm with guard

4 Capillary (0.4  50 mm, 0.4  250 mm)
26 Eluent Source: Dionex EGC-KOH (Capillary) cartridge
7.5
Gradient: Potassium hydroxide,
1 mM (-7–8 min), 1–30 mM (8–28 min),
30–85 mM (28–38 min),
85 mM (38–45 min)
Flow Rate: 0.015 mL/min
Inj. Volume: 0.4 µL
µS µA Column Temp.: 30 ˚C
Detection: A: Suppressed conductivity,
Dionex ACES 300 suppressor, recycle
3 mode
B: QD Charge Detection, 6 V
1 2
A Sample Prep.: Diluted 100-fold with deionized water

B Peaks:
-0.5 0.5
1. Acetate -- mg/L
0 10 20 30 40 45 2. Carbonate --
Minutes 3. Sulfite 0.7
4. Sulfate 6.1
5. Thiosulfate 39.7

* QD was normalized to the sulfate peak

Conclusion
• Heat stable amine salts are challenging samples for analysis with many sulfur species,
organic acids and high concentrations of inorganic anions.

• Here we demonstrated an IC method needed by the gas industry to analyze heat

stable amine salts in amines samples.

• This method has high efficiency separations made possible on a 4 µm particle

capillary-size Dionex IonPac AS11-HC-4µm column and facilitated by a high-pressure
(HPIC) capillary IC system.
6 Determinations of Heat Stable Amine Salts and Amines in Amine Scrubbing Solutions Using Suppressed Conductivity and Charge Detection
• Using different detectors, such as the CD conductivity detector and the QD charge
 4. Sulfate 6.1
5. Thiosulfate 39.7

* QD was normalized to the sulfate peak

Conclusion
• Heat stable amine salts are challenging samples for analysis with many sulfur species,
organic acids and high concentrations of inorganic anions.

• Here we demonstrated an IC method needed by the gas industry to analyze heat

stable amine salts in amines samples.

• This method has high efficiency separations made possible on a 4 µm particle

capillary-size Dionex IonPac AS11-HC-4µm column and facilitated by a high-pressure
(HPIC) capillary IC system.

• Using different detectors, such as the CD conductivity detector and the QD charge
detector provide advantages in improved peak identification and peak detection which
result in improved reporting accuracy and information.

References
1. Natural Gas.org Home Page. http://naturalgas.org/ (accessed April 17, 2014).
2. Rooney, P.C.; Bacon, T.R.; DuPart, M.S. Effect of Heat Stable Salts on MDEA
Corrosivity, Parts 1 and 2. Hydrocarbon Processing, 1996, Mar, 95–103; 1997, Apr,
65–71.
ons, organic 3. Thermo Fisher Scientific Technical Note 122: Separation of Heat Stable Amine Salts
s. QD responses in Methyldiethanolamine (MDEA) Solutions. Thermo Scientific P/N TN70192_E,
d Peaks 13 and Sunnyvale, CA, 2013. [Online]
zed singlely http://www.thermoscientific.com/content/dam/tfs/ATG/CMD/CMD%20Documents/App
able relative lication%20&%20Technical%20Notes/Chromatography/Ion%20Chromatography/IC%
20and%20RFIC%20Systems/TN-122-Separation-Heat-Stable-Amine-Salts-
Methyldiethanolamine-Solutions-TN70192-E.pdf (accessed April 17, 2014).
n
AS11-HC-4µm with guard
 50 mm, 0.4  250 mm)
KOH (Capillary) cartridge
droxide
n), 1–30 mM (8–28 min),
–38 min),
min)

d conductivity,
300 suppressor, recycle

Charge Detection, 6 V All trademarks are the property of Thermo Fisher Scientific and its subsidiaries.
This information is not intended to encourage use of these products in any manners that might infringe
the intellectual property rights of others.
arbonate 10 mg/L
lfite 20
lfate* 20
alate 4
osphate 4
iosulfate 2
iocyanate 2

d sulfate was truncated

was normalized at the nitrite

PO7118_E 05/14S

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