Analysis and Characterization of ARC’s Injet Methanizer for Permanent Gases, Carbon Dioxide, and Light Hydrocarbons

No. SSI-GC-2103

 
■ Background 
Utilizing a methanizer in a gas chromatograph, 
carbon monoxide and carbon dioxide can be 
converted to methane which allows them to be 
detected by a flame ionization detector (FID) providing 
higher sensitivity over detection with a thermal 
conductivity detector (TCD). Traditional methanizers 
use an activated nickel catalyst that is toxic to the 
environment and is susceptible to poisoning from 
analytes such as oxygen and sulfurs, which reduces its 
effectiveness. Additionally, the response generated 
from traditional methanizers with FID have a limited 
range of linearity.  
 
Activated Research Company® (ARC) produces an in-
jet methanizer, the Jetanizer™, which uses a 
proprietary catalyst material that purports to be a 
more environmentally friendly and more robust 
methanizer that offers linearity over low ppm to high 
percentage concentrations of carbon monoxide and 
carbon dioxide. This analysis will assess the limits of 
detection and quantification of carbon monoxide, 
carbon dioxide, methane and C2 hydrocarbons 
(ethane, ethylene, and acetylene) using the 
Jetanizer™ on the GC-2030. 
 
■ Instrumentation 
The GC-2030 gas chromatograph equipped with an 
LVO-2030, and 6-port gas loop sampling valve was 
used for this analysis. The Jetanizer™ is a drop-in 
replacement for the traditional GC-2030 FID jet which 
requires no additional hardware or special plumbing. 
Both capillary and packed columns were used in this 
analysis to test the capabilities of the Jetanizer™.   
 
 
 
 

 
To determine the effects of the capillary column phase 
on the analysis, two different PLOT column phases 
were used for this analysis, molecular sieve and 
carbonized molecular sieve. Two different columns of 
each PLOT phase were used to address if a specific 
column had any effect on the Jetanizer™ linearity. To 
confirm the viability of packed column analysis, a 
custom 1 m carbonized molecular sieve column was 
used.  
 
For both capillary and packed columns, a ~20 cm 
piece of 0.53 mm ID MXT tubing was joined with a 
union to the end of the analytical column and installed 
in the FID. This capillary tubing acted as a guard 
column protecting the end of the column from the 
high operating temperatures of the Jetanizer™ and to 
serve as a particle trap for any residual particles 
evolved from the columns used in the analysis. The 
guard column insertion depth into the FID was 45 mm 
to ensure the eluting analytes would encounter the 
catalyst bed in the Jetanizer™ 
 
■ Experimentation and Observation 
Gas standards containing carbon monoxide, 
methane, and carbon dioxide at various 
concentrations were utilized for this analysis. The 
concentrations tested ranged from 1 ppm up to 
99.99%. 
  
Capillary Column Analysis 
A total of four capillary columns were used to test the 
effects of specific columns on the overall response of 
the Jetanizer™. Two molecular sieve columns were 
used, and two carbonized molecular sieve columns 
were used. Linearity and limits of detection and 
quantitation were determined for each column. 

System GC 

Analysis and Characterization of ARC’s In-
jet Methanizer for Permanent Gases, 
Carbon Dioxide, and Light Hydrocarbons  

No. GC-2103 

No. SSI-GC-2103

Molecular sieve column 
A calibration curve to test the linearity of the 
Jetanizer™ with molecular sieve columns was 
produced from a 0.96 ppm to approximately 20% for 
carbon monoxide and 0.87 ppm to approximately 
15% for methane. 

 
A linear regression analysis was performed for each 
calibration curve. The following method conditions 
were used: 

Table 1: Method Parameters for Molecular sieve PLOT Column 

Parameter 

Value 

Column 

HP-Plot MS-5A 30 m X 0.53 mm X 50 μm (19095P-MS0), 

CP-Molsieve 5A 25 m X 0.53 mm X 50 μm (CP7538) 

Valve Box Temperature 

80° C 

Injection Volume 

1 mL gas sampling loop 

Injector Temperature 

200° C 

Linear Velocity 

36.6 cm/sec He 

Split Ratio 

7:1 

Oven Ramp 

Isothermal 100° C 

FID Temperature 

400° C 

FID Gas Flows 

Makeup (He): 24 mL/min, H2: 32 mL/min, Air: 250 mL/min 

FID Column Insertion Depth 

45 mm 

Table 2: Concentrations used for calibration curve for Molecular Sieve Columns 

Concentration of Standards (ppm) 

Analytes 

Low TOGAS 

Standard 1 

Low ppm Std 

Standard 2 

12% CO2 

Standard 3 

14% CO2 

Standard 4 

8% CO2 

Standard 5 

High TOGAS 

Standard 6 

Carbon 
Monoxide 

100 0.96 

59800 

9900 

199900 

4200 

Methane 

100 0.87 

149900 

60100 

11900 

4200 

Carbon Dioxide 

400 2.55 

120100 

140100 

78900 

20000 

 
Figure 1A: Representative Stacked Calibration Curve 
Chromatograms for HP-PLOT MS5A

 
Figure 1B: Calibration curve for methane using the HP-PLOT 
MS5A 

 
Figure 1C: Calibration curve for carbon monoxide using the 
HP-PLOT MS5A 
 
It was noted that there was a high degree of linearity 
within the tested range for methane though some 
nonlinearity was observed between the 6% and 20% 
standard for carbon monoxide.  

2.50

2.75

3.00

3.25

3.50

3.75

4.00

4.25

4.50

4.75

min

0

25000000

50000000

75000000

100000000

uV

No. SSI-GC-2103

 
Figure 2A: Representative Stacked Calibration Curve 
Chromatograms for CP-Molesieve 5A  
 

 
Figure 2B: Calibration curve for methane using the CP-
Molesieve 5A

 
Figure 2C: Calibration curve for carbon monoxide using the 
CP-Molesieve 5A 
 
Within the tested range of both methane and carbon 
monoxide, both are observed to be nonlinear 
between 1 percent and 6 percent. This may indicate a 
column dependency on linear range given the 
differences observed between the two molecular 
sieve columns used in this analysis.  

 
 
Carbonized Molecular Sieve Column Linearity  
A calibration curve to test the linearity of the 
Jetanizer™ with carbonized molecular sieve columns 
was produced from a 0.96 ppm to approximately 
20% for carbon monoxide, 0.87 ppm to 
approximately 15% for methane and between 2.55 
ppm and 99.99% carbon dioxide. 

 
 
A linear regression analysis was performed for each 
calibration curve. The following method conditions 
were used: 

Table 3: Method Parameters for Carbonized Molecular sieve PLOT Column 

Parameter 

Value 

Column 

GS-Carbon Plot 30 m X 0.53 mm X 3 μm (115-3133), 

CarboBond 25 m X 0.53 mm X 10 μm (CP7374) 

Valve Box Temperature 

80° C 

Injection Volume 

1 mL gas sampling loop 

Injector Temperature 

200° C 

Linear Velocity 

36.6 cm/sec He 

Split Ratio 

7:1 

Oven Ramp 

Isothermal 60° C 

FID Temperature 

400° C 

FID Gas Flows 

Makeup (He): 24 mL/min, H2: 32 mL/min, Air: 250 mL/min 

FID Column Insertion Depth 

45 mm 

Table 4: Concentrations used for calibration curve for Carbonized Molecular Sieve Columns 

Concentration of Standards (ppm) 

Analytes 

Low TOGAS 

Standard 1 

Low ppm Std 

Standard 2 

12% CO2 

Standard 3 

14% CO2 

Standard 4 

8% CO2 

Standard 5 

CO2 Balance 

Standard 7 

Carbon Monoxide 

100 

0.96 

59800 

9900 

199900 

0 

Methane 100 

0.87 

149900 

60100 

11900 

53.5 

Carbon Dioxide 

400 

2.55 

120100 

140100 

78900 

999935 

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

min

0

10000000

20000000

30000000

40000000

50000000

uV

No. SSI-GC-2103

Figure 3A: Representative Stacked Calibration Curve 
Chromatograms for GS-CarbonPLOT 
 

 
Figure 3B: Calibration curve for carbon monoxide using the 
GS-CarbonPLOT 
 

 
Figure 3C: Calibration curve for methane using the GS-
CarbonPLOT

 
Figure 3D: Calibration curve for carbon dioxide using the GS-
CarbonPLOT 
 
There was a high degree of linearity for all analytes 
within the calibration curve ranges. Some nonlinearity 
was observed on the 99.99% carbon dioxide standard 
and 2.55 ppm carbon dioxide standard. This effect is 
likely due to overloading the column in which the 
method conditions could be adjusted for higher 
concentrations.  

1.25

1.50

1.75

2.00

2.25

2.50

min

0

50000000

100000000

150000000

200000000

250000000

300000000

350000000

uV

No. SSI-GC-2103

 
Figure 4A: Representative Stacked Calibration Curve 
Chromatograms for CP-Carbobond  
 

 
Figure 4B: Calibration curve for carbon monoxide using the 
CarbonBond 
 

 
Figure 4C: Calibration curve for methane using the 
CarbonBond

 
Figure 4D: Calibration curve for carbon dioxide using the 
CarbonBond 
 
There was a high degree of linearity for all analytes 
within the calibration curve ranges. Some nonlinearity 
was observed on the 99.99% carbon dioxide standard 
and 2.55 ppm carbon dioxide standard in a similar 
behavior to the other column tested in this analysis.  

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

2.75

3.00

min

0

50000000

100000000

150000000

200000000

250000000

300000000

uV

No. SSI-GC-2103

Capillary Column Analysis of Limits of Detection and 
Quantitation  
For limit of detection and quantitation 
determinations, the following standard was selected 
due to the presence of light hydrocarbons:  

Table 5: Concentrations of Low TOGAS Standard (Standard 1) 
 

Analyte 

Concentration (ppm) 

Methane 

100 

Carbon monoxide 

100 

Carbon dioxide 

400 

Acetylene 

100 

Ethylene 

100 

Ethane 

100 

Figure 5: Representative Chromatogram for each capillary 
column with Standard 1

Table 6. Determined Limits of Quantitation from Standard 1 
Results 
 

LOQ 

Concentration (ppm) 

Analyte 

HP-MS 

CP-MS 

CarboB 

GS-Carb 

Methane 0.6  1.4  0.7 

0.7 

Carbon 

Monoxide 

0.7 

2.4 

0.7 

0.7 

Carbon 
Dioxide 

N/D N/D  0.9 

0.8 

Acetylene 

N/D 

N/D 

0.9 

0.6 

Ethylene N/D N/D  1.4 

0.7 

Ethane 

N/D 

N/D 

2.5 

1.3 

*N/D = not determined 
 
Table 7. Determined Limits of Detection from Standard 1 
Results 
 

LOD 

Concentration (ppm) 

Analyte 

HP-MS 

CP-MS 

CarboB 

GS-Carb 

Methane 0.2 0.5  0.2 

0.2 

Carbon 

Monoxide 

0.2 

0.8 

0.2 

0.2 

Carbon 
Dioxide 

N/D N/D  0.3 

0.3 

Acetylene 

N/D 

N/D 

0.3 

0.2 

Ethylene N/D N/D  0.4 

0.2 

Ethane 

N/D 

N/D 

0.8 

0.4 

*N/D = not determined 

No. SSI-GC-2103

Packed Column Limit of Detection and Quantitation 
The packed column used for this analysis was a 
custom packed carbonized molecular sieve column 
which was selected to provide sufficient separation 
between a composite permanent gas peak, carbon 
monoxide, methane, carbon dioxide and C2 
hydrocarbons while minimizing run times required. 
The method conditions below were used for this 
analysis:  
 
Table 8: Parameters for Packed Carboxen Column 

Parameter 

Value 

Column 

Custom Carboxen 1006 60/80, 1 m x 1/8” 

Valve Box 
Temperature 

80° C 

Injection 
Volume 

1 mL gas sampling loop 

Injector 
Temperature 

250° C 

Linear Velocity 

124.5 cm/sec He 

Split Ratio 

0.7:1 

Oven Ramp 

40° C hold for 2.0 min, ramp 30° C/min to 

170° C hold for 6 min 

FID Temperature 

400° C 

FID Gas Flows 

Makeup (He): 24 mL/min, H2: 32 mL/min, 

Air: 250 mL/min 

FID Column 
Insertion Depth 

45 mm 

 
Figure 6: Representative Chromatogram for Packed Carboxen 
Analysis

 
Limits of detection were determined based on 
triplicate injections of the Low TOGAS standard.  
 
Table 9: LOD and LOQ values for Packed Column Analysis

Analyte 

LOD 

LOQ 

Carbon monoxide 

0.15 

0.45 

Methane 

0.12 

0.36 

Carbon dioxide 

0.11 

0.33 

Acetylene 

0.07 

0.23 

Ethylene 

0.12 

0.35 

Ethane 

0.17 

0.51 

 
The overall response between the methane and 
carbon dioxide was fairly consistent with the expected 
concentrations. Carbon monoxide displayed a 
marginally higher LOD and LOQ which is suspected to 
related to inadequate separation of carbon monoxide 
from the composite permanent gas peak.  
 
■ Conclusion 
The Jetanizer™ is a simple and effective way to add a 
methanizer to an existing GC-2030 for both packed 
and capillary columns with only a replacement of the 
FID jet and no additional hardware required. The 
increased ruggedness toward oxygen allows for more 
simplified flowpaths compared to traditional systems. 
The difference in column phase materials may play an 
impact on the linearity of the detector. The more 
retentive MS-5A capillary experienced more issues 
with nonlinearity which may be due to adhesion of 
the lower concentration analytes or other column 
specific factors. Adjustments to the method such as 
increasing the split ratio for higher concentrations 
may aid in overcoming issues of overloading the 
column and provide superior peak shape over the 
displayed chromatograms. Despite column 
overloading, the response was mostly linear over the 
concentration ranges analyzed in this study. Further 
testing at a more evenly distributed standard 
concentrations may be required for a more accurate 
assessment of linearity. 
 
The limits of detection for each column and analyte 
were shown to be sub-ppm levels for both the packed 
and capillary columns. The lower limits of detection 
and quantitation observed on the packed columns are 
likely due to more standard being injected on column. 
Further optimization for lower concentration analytes 
could be performed but the method conditions used 
were intended to meet the broad concentration range 
required for linearity testing.  Adverse effects from the 
repeated injections of oxygen onto the Jetanizer™ 
were not observed during this study, indicating a 
higher tolerance of oxygen than traditional 
methanizers.

For Research Use Only. Not for use in diagnostic procedure. 
This publication may contain references to products that are not available in your country. Please contact us to check the availability of 
these products in your country. 
 
The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of 
Shimadzu. Shimadzu disclaims any proprietary interest in trademarks and trade names used in this publication other than its own. 
See http://www.shimadzu.com/about/trademarks/index.html for details. 
 
The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its 
accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to 
the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and 
subject 

First Edition: January 2021 

© Shimadzu Corporation, 2021 

SHIMADZU SCIENTIFIC INSTRUMENTS 
7102 Riverwood Drive, Columbia, MD 21046, USA 
Phone: 800-477-1227/410-381-1227, Fax: 410-381-1222 
URL: www.ssi.shimadzu.com 

SHIMADZU Corporation 
www.shimadzu.com/an/  

Jetanizer is a trademark of Activated Research Company