Separation of Heat Stable Amine Salts in

Tec hnic al N o te 1 2 2
Methyldiethanolamine (MDEA) Solutions
Using High-Pressure IC
Terri Christison and Linda Lopez
Thermo Fisher Scientific, Sunnyvale, CA, USA

Key Words The latest advancement in ion chromatography (IC)

Petrochemical, Dionex IonPac AS11-HC-4µm, HPIC, heat stable salts, instrumentation, the high-pressure Thermo Scientific™
amine wastewater, methyldiethanolamine, MDEA, Dionex ICS-5000+, HPIC Dionex™ ICS-5000+ HPIC™ system, can operate
continuously at 5000 psi for both analytical and capillary
Goal scale formats. The Dionex ICS-5000+ HPIC system can
Demonstrate high efficiency separations of heat stable salts in amine therefore exploit the high-efficiency separations offered by
solutions using 4 µm anion-exchange separation columns on a high smaller particle size separation columns. When combined
pressure ion chromatography system. with the advantages and ease-of-use of a Reagent-Free™ IC
(RFIC™) system, this system permits excellent enhanced
resolution of closely eluting peaks with excellent
Introduction reproducibility, thereby yielding greater quantification
Crude natural gas (methane) must be chemically processed accuracy and consistently reliable results.
to remove impurities before the gas can be sold as a pure In this study, we determined the anions in mixtures of both
product. Some natural gas wells may contain high common inorganic anions and heat stable amine salts
concentrations of carbon dioxide (CO2) and hydrogen (fluoride, chloride, nitrate, nitrite, bromide, sulfate,
sulfide (H2S), the later known as “sour gas” because of phosphate, acetate, formate, propionate, sulfite, thiosulfate,
the mercaptan odor.1,2 The high sulfide content and acidity thiocyanate) added to methyldiethanolamine solutions. The
from dissolved carbon dioxide causes corrosion of metal anions were separated by anion-exchange chromatography
pipes and acid rain, making sour gas undesirable as a using a Thermo Scientific™ Dionex™ IonPac™ AS11-HC-4µm
commercial product. Therefore, sour gas is typically (2 × 250 mm) high-efficiency guard column and detected
treated with amine (amine rich) solutions (e.g., using suppressed conductivity. This column is optimized for
ethanolamine, methanolamine, and methyldiethanolamine) high-efficiency separations of organic acids and is well
to absorb hydrogen sulfide and carbon dioxide.1,2 suited for this application.
The resulting pure natural gas, defined as containing
< 5.7 mg/m3 hydrogen sulfide, is called “sweet” gas Table 1. Consumables list.
by the industry.1 The amine processing solutions Dionex Part
(amine lean) are stripped and regenerated to remove Product name Type
Number
the sulfur compounds as elemental sulfur. However, Anion Eluent Generator
the amine solutions also extract other contaminants Dionex EGC 500 KOH 075778
cartridge*
which form salts of organic acids and sulfur species, Dionex CR-ATC 500 Anion electrolytic trap column* 075550
such as oxalic acid, propanoic acid, formic acid,
acetic acid, thiosulfate, and thiocyanate.2 These Dionex IonPac AG11-HC-4µm Anion guard column* 078036
respective anions are collectively termed “heat stable Dionex IonPac AS11-HC-4µm Anion separation column* 078035
amine salts” because the salts are not removed by
the amine stripping process. Furthermore, the high Dionex ASRS 300 Anion suppressor 064555
salt content in the amine solution increases the Dionex HP Degas Module Degas module* 075522
solution viscosity, reduces acid-absorbing capacity
074449 /
and increases corrosion-induced maintenance costs. Dionex HP fittings (blue) Bolts / Ferrules*
074373
These amine waste solutions must also be
* high pressure
characterized to comply with discharge permits.
2 Dionex AS-AP Autosampler Dionex ICS-5000+ Reagent-Free HPIC System
Regen
Fresh 18 M Ω-cm
Deionized Water
SRS 300*
Eluent In suppressor CD

Syringe

Needle Columns*

Tray carousel

Fresh 18 M Ω-cm
Heat Exchange Regen Deionized Water
Tubing

Degas CR-TC
Module* 500 * EGC 500* Pump*
Sample Loop
Waste
Vent Waste
* High-pressure device
Figure 1. Flow diagram for the high-pressure, Reagent-Free Dionex ICS-5000+ HPIC system.

Equipment Standard and Sample Preparation

Dionex ICS-5000+ HPIC system Prepare individual stock solutions and a combined
• SP/DP Pump module spiking solution of propionate, acetate, bromide, formate,
chloride, nitrate, nitrite, sulfate, oxalate, carbonate,
• EG Eluent Generator module with high pressure
thiocyanate, thiosulfate, and sulfite by mixing the
degas module
appropriate amounts with DI water to achieve the
• DC Detector/Chromatography module concentrations in Figure 2. Prepare 10, 20, 30, 40, and
• Dionex AS-AP Autosampler 50 wt% MDEA solutions spiked with the above anions
• Thermo Scientific™ Dionex™ Chromeleon™ Chromatogra- in deionized water. The standards containing sulfite must
phy Data System (CDS) software ver. 6.8 or 7.1. be prepared daily. Calibration standards were prepared
by diluting the stock standards appropriately.
Reagents and Standards
18 MΩ-cm degassed deionized water Tip: It is important to use 18 MΩ-cm resistivity, deionized
ACS Grade reagents, Fisher Scientific water for standards, eluent, and autosampler flush
solution. It is recommended to degas the deionized
Samples water intended for eluent in anion determinations. (An
Synthetic mixtures of heat stable salts added to deionized appropriate degassing method is vacuum filtration.) Using
water, and 10, 20, 30, 50 wt% MDEA deionized water with resistivity less than 18 MΩ-cm can
reduce sensitivity, introduce contamination, and affect
Conditions calibration, thereby resulting in inaccurate quantification.
Columns: Dionex IonPac AG11-HC-4µm (2 × 50 mm) Results can vary and contamination introduced from
AS11-HC-4µm (2 × 250 mm) samples can affect the chromatography
Eluent Source: Thermo Scientific Dionex EGC 500 KOH Eluent
Instrument Setup and Installation
Generator Cartridge
Tip: To achieve the best chromatography with high
Thermo Scientific Dionex CR-ATC 500 pressure IC, it is important to use high pressure
Continuously Regenerated Cation Trap Column
connectors and ferrules (see Table 1) for all connections
Gradient: 1 mM from -10 to 8 min, 1–30 mM from prior to the suppressor. The high pressure Dionex
8 to 28 min, 30–72 mM from 28 to 38 min, ICS-5000+ HPIC Reagent-Free system is designed to
(72–100 mM from 38 to 60 min for elution operate up to 5000 psi. To setup this application, plumb
of thiocyanate)
the consumables and modules of the Dionex ICS-5000+
Flow Rate: 0.38 mL/min HPIC system, according to Figure 1.
Column Temp.: 30 °C
Install and hydrate the Dionex EGC 500 KOH cartridge,
Inj. Volume: 25 µL Dionex CR-ATC 500, and 2 mm Dionex ASRS 300
Detection: Suppressed conductivity, Thermo Scientific™ suppressor according to the product manual instructions.
Dionex™ ASRS™ 300 Anion Self-Regenerating Complete the installation according to flow diagram. Use
Suppressor™, recycle mode, 68 mA high-pressure connectors and ferrules (blue) for all of the
Background fittings from the pump to prior to the suppressor. Standard
Conductance: 0.2–0.5 µS pressure fittings can be used for the suppressor and
Noise: 2–3 nS detector connections. Detailed instructions are described
System in Technical Note (TN) 129, the product manuals, and the
backpressure: 3200–3600 psi instrument installation and operator’s manuals.3–6
Results and Discussion Figure 3 shows the separation of thiocyanate and 14 3
Determinations of heat stable amine salts is needed to anions spiked into 30% MDEA solution. The gradient
monitor the efficiency of the amine processing of the sour was increased at 38 min to elute thiocyanate from the
natural gas. To resolve these peaks, a high-capacity, column within 50 min. A step change could also be used
high-efficiency Dionex AS11-HC-4µm anion-exchange to reduce the run time. The peaks in both chromatograms
column is used. show very high efficiency which is characteristic of this
4 µm particle size column. The system pressure is 3620 psi
Figure 2 compares the separations of the 14 heat stable
which is only possible with RFIC technology when using
amine salts in deionized water, 10% and 30% MDEA
a high-pressure IC system, such as the Dionex ICS-5000+
with excellent recoveries from 95 to 100% as compared
HPIC system.
to the deionized water. Recoveries are reduced to ~80%
when spiked into the 50% MDEA (not shown here). All
peaks elute within 35 min from the column with large
separations between peaks 4 and 5 and between peaks
12 and 13.

Column: Dionex IonPac AG11-HC-4µm, AS11-HC-4µm, 2 × 250 mm Column: Dionex IonPac AG11-HC-4µm, AS11-HC-4µm, 2 × 250 mm
Eluent Source: Dionex, EGC 500 KOH Eluent Source: Dionex, EGC 500 KOH
Gradient: Potassium hydroxide 1 mM from -10 to 8 min, Gradient: Potassium hydroxide 1 mM from -10 to 8 min,
1–30 mM from 8 to 28 min 1–30 mM from 8 to 28 min
3–72 mM from 28 to 38 min 3–72 mM from 28 to 38 min
Flow Rate: 0.38 mL/min Flow Rate: 0.38 mL/min
Inj. Volume: 25 µL Inj. Volume: 25 µL
Column Temp.: 30 °C Column Temp.: 30 °C
Detection: Suppressed conductivity Dionex ASRS 300, 2 mm, Detection: Suppressed conductivity Dionex ASRS 300, 2 mm,
recycle mode recycle mode
Samples: Heat stable salts in A: Water; B: 10% MDEA*; C: 30% MDEA* Samples: Heat stable salts in 30% MDEA*
IC System: High-pressure Dionex ICS-5000+ HPIC IC System: High-pressure Dionex ICS-5000+ HPIC

Peaks: 1. Fluoride 2 mg/L 8. Nitrate 100 Peaks: 1. Fluoride 2 mg/L 8. Nitrate 100
2. Acetate 10 9. Carbonate 50 2. Acetate 10 9. Carbonate 50
3. Propionate 10 10. Sulfite 100 3. Propionate 10 10. Sulfite 100
4. Formate 10 11. Sulfate 100 4. Formate 10 11. Sulfate 100
5. Chloride 100 12. Oxalate 20 5. Chloride 100 12. Oxalate 20
6. Nitrite 10 13. Phosphate 20 6. Nitrite 10 13. Phosphate 20
7. Bromide 10 14. Thiosulfate 10 7. Bromide 10 14. Thiosulfate 10
15. Thiocyanate 10
* Methyldiethanolamine * Methyldiethanolamine

5 11 5 11
25 25
10
3620 psi
3620 psi
14 10

12 µS
µS 14
6
8 13
2 4 7 12
1 3 9
C
6 15
13
B 2 4 78
1 3 9
A
-2 -2
0 10 20 30 38 0 10 20 30 40 51
Minutes Minutes

Figure 2. Separations of heat stable salts in MDEA using a shallow gradient Figure 3. Separation of heat stable salts in 30% MDEA using a shallow
and high-pressure IC. gradient and high-pressure IC.
Conclusion References
This technical note demonstrates the high-resolution, 1. Natural Gas.org, http://www.naturalgas.org/naturalgas/
high-efficiency separations possible using a Dionex IonPac processing_ng.asp#sulphur, accessed Dec. 10, 2012.

Tec hnic al N o te 1 2 2
AS11-HC-4µm and a high-pressure Reagent-Free IC 2. Rooney, P.C.; Bacon, T.R.; DuPart, M.S. Effect of Heat
system, such as the Dionex ICS-5000+ HPIC system. The Stable Salts on MDEA Corrosivity, Parts 1 and 2.
Dionex ICS-5000+ HPIC system permits continuous Hydrocarbon Processing, 1996, Mar, 95–103; 1997,
operations up to 5000 psi to deliver high-resolution Apr, 65–71.
separations across all column formats including standard
3. Christison, T.; Bahten, K.; Briggs, J.; Lopez, L. Technical
bore, microbore, and capillary scale.
Note 129: Configuring High-Pressure IC Systems for
Additional information on inorganic anion determinations Analytical Flow Rates, TN70317_E, Sunnyvale, CA,
in environmental and industrial wastewater samples 2012.
using standard bore and microbore IC are reviewed in 4. Thermo Fisher Scientific. Dionex Anion Self-
application update AU 138, and application notes AN 135 Regenerating Suppressor 300 and Cation
and AN 138.7–9 Self-Regenerating Suppressor 300 Product Manual.
Dionex Doc No. 031956-06, Sunnyvale, CA, 2009.
5. Thermo Fisher Scientific. Dionex ICS-5000+ Ion
Chromatography System Installation instructions.
Dionex Doc No. 065447-01, Sunnyvale, CA, 2012.
6. Thermo Fisher Scientific. Dionex AS-AP Autosampler
Operator’s Manual. Dionex Doc No. 065361-07,
Sunnyvale, CA, 2012.
7. Thermo Fisher Scientific. Application Update 138,
Determination of Ethanolamines in Industrial Waters
by Cation-Exchange Chromaotgraphy, Dionex LPN
0995, Sunnyvale, CA, 1998.
8. Thermo Fisher Scientific. Application Note 135:
Determination of Inorganic Anions in Wastewater by
Ion Chromatography, Dionex LPN 1226, Sunnyvale,
CA, 2000.
9. Thermo Fisher Scientific. Application Note 138:
Determination of Thiosulfate in Refinery and Other
Wastewaters, Dionex LPN 1237, Sunnyvale, CA, 2001.

www.thermofisher.com/dionex
©2016 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific Inc. and
its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scientific Inc. products. It is
not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
Specifications, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local
sales representative for details.

Australia +61 3 9757 4486 Denmark +45 70 23 62 60 Japan +81 6 6885 1213 Switzerland +41 62 205 9966
Austria +43 1 333 50 34 0 France +33 1 60 92 48 00 Korea +82 2 3420 8600 Taiwan +886 2 8751 6655
Belgium +32 53 73 42 41 Germany +49 6126 991 0 Netherlands +31 76 579 55 55 UK/Ireland +44 1442 233555
Brazil +55 11 3731 5140 India +91 22 2764 2735 Singapore +65 6289 1190 USA and Canada +847 295 7500
China +852 2428 3282 Italy +39 02 51 62 1267 Sweden +46 8 473 3380

TN70192_E 09/16S