Sulfur Chemiluminescence Detectors for Gas Chromatography

Wenmin Liu, Mario Morales, Thomas F Daniels. Agilent Technologies

Introduction
Chromatogram of standard real sample
Method 2 (ASTM 5504) Experimental conditions of sulfur compounds in natural gas Chromatogram of standards 14
8/9

15 µV 15 µV
11.8 ppm (W/W)
GC conditions 34
2500
8/9 15 Calculated by
2500
Petroleum feeds and products contain varying amounts and Front Inlet SS Sulfinert® treated capillary inlet Sample loop 1 ml 11 2
11
2000 13 2000 CStot= ΣCn
system 1500 1500 7 12 14
types of sulfur compounds. Many sulfur compounds can be 12 7 12 3
13
RSD=2.7%, n=5
Pressure On 14.5 psi Oven 30°C (1.5min) 15°C/min 200°C (3min) 1000 56
10
1000
4 56
corrosive to equipment, inhibit or destroy catalysts employed 500 500
Septum Purge On 3 mL/min Column HP-1 60m×0.53mm × 5um 0 0
in downstream processing, and impart undesirable odors to Flow 0 2 4 6 8 10 12 14 16 18 min 0 2 4 6 8 10 12 14 16 18 min

products. Mode Splitless Injection mode Static flow & dynamic flow mode
SCD conditions
Analysis of sulfur compounds is difficult because they are
Burner temperature 800°C H2 40 ml/min Method 2 (ASTM5504) Results of sulfurs analysis in natural gas
polar, reactive and present at trace level. They pose Vacuum of burner 372 torr Air 53 ml/min Peak Identification
problems both in sampling and analysis. Vacuum of reaction cell 5 torr 1. Hydrogen Sulfide; 2.Carbonyl Sulfide; 3. Methyl Mercaptan; 4. Ethyl Mercaptan; 5. Dimethyl Sulfide; 6. Carbon Disulfide; 7. 2-
Propanethiol; 8. tert-Buthyl Mercaptan; 9. 1-Propanethiol; 10. Thiophene; 11. n-Butanethiol; 12. Diethyl sulfide; 13.Methyl ethyl
Gas chromatography with sulfur chemiluminescent detection Sulfide14 2-Methyl-1-Propanethiol; 15. 1-Methyl-1-Propanethiol.
Diagram of on-line gas
(SCD) provides a rapid and highly specific means to identify 15 µ V
blending-GC-SCD 600
Chromatogram of sulfur compounds at 1.35 ppb
and quantify various sulfur compounds that may be present
6
in miscellaneous petroleum feeds and products, such as zOn-line gas blending system 500
1

gasoline, natural gas. Agilent technologies has further zSample injection valve 400 11
2 13
300 5 10
enhanced 355 SCD performance and ease of use by zTwo injection mode realized by On/Off 4 7 12
3 8 9 14
developing the dual plasma (DP) technology with its valve (dynamic and static injection 200 15

modes) 100
patented detection method. The key features of DP SCD are
0
as follows: 0 1 2 3 4 5 6 7 8 9 m in

z Highest selectivity over carbon S/N of sulfurs at 1.35 ppb

z Little or no quenching
z Linear and equimolar response
z Simultaneous serial FID response is available
Results Peak No.
S/N
1
12.0
2
5.0
3
2.1
4
2.6
5
4.9
6
11.5
7
4.0
8
2.7
9
3.7
10
9.1
11
7.6
12
2.3
13
5.7
14
1.0
15
1.1
z Fast amplifier available for comprehensive GC X GC Method stability of long term and short term
Method 1 (ASTM 5623) Results of sulfur analysis in gasoline
This poster shows the results of two ASTM sulfurs analysis Peak identification 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
methods (ASTM5504, ASTM5623) developed on Agilent 7890 1.Ethyl Mercaptan; 2.Dimethyl Sulfide; 3. Carbon Disulfide; 4. Iso-Propylpropyl Mercaptan; 5. t-Butyl Mercaptan; 6. n- 20.79 ppb 2.7 2.6 2.9 3.0 0.9 1.4 2.8 4.0 2.6 1.7 1.7 3.3 3.2 8.6 7.9
GC DP SCD. Propyl Mercaptan ; 7. Methylethl Sulfide ; 8. Thipphene ; 9. Sec-butyl Mercaptan; 10. n-Butyl Mercaptan ; 11.Dimethyl S.T. RSD (%)
Disulfide; 12. 2-Methyl Thiophene; 13.3-Methyl Thiophene; 14.Diethyl Disulfide; 15. Benzo(B)thiophene.
L.T. RSD (%) 3.0 2.7 2.4 2.5 1.4 1.5 2.6 4.3 3.8 2.7 2.0 4.9 3.2 7.9 6.9

Experimental Method repeatability of sulfurs at different concentrations.

1 2 3 4 5 6 7 8 10 11 12 13 14 15
1.38 ppb
S.T. RSD (%)
6.6 10.1 11.7 22.8 30.4 4.1 6.9 18.7 10.7 25.1 5.1 11.1 5.8 29.6 24.1

L.T. RSD (%) 14.4 7.5 16.3 20.8 21.7 4.6 6.1 27.7 23.7 25.3 12.2 24.6 6.1 35.7 38.4
Con.
Method 1 (ASTM 5623) Experimental conditions of sulfur compounds in gasoline 1.16 1.79 1.78 3.42 1.13 0.59 1.19 3.80 0.59 1.47 1.43 2.14 2.80 4.0
ppm S.T.: Short term (8h); L.T.: Long term (72h)
GC conditions RSD (%)
Summary
2.8 3.6 3.1 1.9 3.0 2.7 3.9 3.9 2.9 2.1 2.2 2.9 0.4 3.7
Front Inlet SS Sulfinert® treated capillary Mode Split
inlet system Con.
0.12 0.18 0.18 0.34 0.11 0.06 0.12 0.38 0.06 0.15 0.14 0.21 0.28 0.4
Pressure 10.951 psi Split Ratio 10 :1 ppm
Column HP-1 30m×0.32mm × 4um RSD (%) zThe compact DP advances the established technology by improving performance;
Oven 30°C (1min) 10°C/min 250°C 5.7 7.4 3.4 3.7 6.6 4.8 5.7 4.8 8.0 4.0 3.3 4.7 7.3 3.1
(1min) z GC-SCD provides a highly sensitive, selective, and linear response to sulfur compounds in different matrix.
SCD Conditions S/N of sulfurs at 20 ppb zThe detection limits for the trace sulfurs detection are down to ppb level;
Burner temperature 800°C H2 40 ml/min Peak No. 1 2 3 4 5 6 7 8/9 10 11 12 13 14 15 zOn-line dilutor combining with GC DP SCD is suitable for the gaseous sulfurs analysis especially for the low
Vacuum of burner 372 torr Air 53ml/min
Vacuum of reaction cell 5 torr S/N 2.0 2.5 5.0 4.6 1.8 1.6 2.4 5.0 1.5 3.6 2.0 4.6 3.2 5.2 level components