Improvements in Gas Analysis using a Flexible Valve Oven Housing and Selective, High Sensitivity Multiple GC Detectors

F. Pigozzo, F. Ponciroli, D. Cavagnino Thermo Finnigan Italia, Strada Rivoltana , Rodano, Milan, Italy
INTRODUCTION Analysis of gas mixtures has always represented a challenging tasks for a GC platform due to the need to set up the proper multicolumn configuration and therefore accommodate in the same GC platform the suitable detectors, columns and injection/switching systems. Additionally the requirements of gas industry, which very often is looking for a single analyzer able to characterize a wide variety of gas mixtures obtained from production processes, is setting a further complication in the development of this type of instrumentation. Several new solutions available on the TRACE GC platform is making the construction, operation and serviceability of dedicated gas analyzers simple and user-friendly. A dedicated oven for housing sampling and/or switching valves is added to the left side of a standard TRACE GC mainframe, providing easy access to both the valve oven and the programmable GC oven. This valve oven offers an additional isothermal heated zone for valves and columns and it is designed to accommodate up to four heated valves, two unheated valves and several meters of metal packed columns. The modularity of the standard GC platform has been further extended adding the capability to operate simultaneously with three detectors, selected between TCD, FID, FPD, PID and the new Pulse Discharge Detector for part per billion determination of gases. The availability of a high efficient methanizer is completing the range of accessories for gas analyzers. Several type of applications serving gas industries have been developed all featuring three analytical channels with multiple columns/switching valves. Trace GC with Valve Oven
Stream D

CONTINUOUS MONITORING OF IMPURITIES FROM A CO-PLANT

The first analyzer described in this report is used for the continuous determination of impurities in a CO-plant. In order to measure and quantify the wide range of components in the different sample streams which are daily collected by the operators, the analyzer is equipped with four different analytical channels: Hydrocarbon channel Incorporates a capillary column, Alumina type placed into the GC oven and a FID detector. The sample is injected by a gas sampling valve, with 0.25 ml sample loop. Permanent gas channel Incorporates two packed columns: HayeSep Q, and MolSieve 5A and a TCD detector. Both columns are housed into the isothermal heated valve oven. A gas sampling valve with 1 ml sample loop is used to inject the sample. The channel also features of a Backflush and a column selection valve. CO and CO2 channel This channel includes an HayeSep Q column, a methanizer and the FID detector. The channel is able to quantify up to 10 ppb of CO and CO2. Hydrogen channel Incorporates two packed columns in series connected: HayeSep QS, and MolSieve 13X and a TCD detector. The sample is introduced by dedicated gas sampling valve with 1 ml sample loop. The extremely high flexibility and versatility of the system permit, by a proper selection of the analytical path and carrier gas, to characterize completely the sample streams reported in table 1.

DETERMINATION OF IMPURITIES FROM AIR-SEPARATION PLANT

Typical output products from an air separation unit include liquid nitrogen, oxygen and argon, and nitrogen and oxygen gases. Usually these streams are contaminated by a number of different undesired components which must be precisely measured and quantified in order to assess the market value of the different sample streams. Table 2 illustrates the large variety of impurities which have to be analyzed and their relative concentrations. A dedicated TRACE GC analyzer equipped with FID (Flame Ionization Detector) and PDD (Pulse Discharge Detector) has been able to perform the complete analysis of the different sample streams included in table 2.

Sample streams / GC Analytical channel

Sample gas main composition Title Sample 1 & 2 Sample 3 Sample 4 Sample 5 Liquid air (N2, O2, Ar) Total hydrocarbon Liquid oxygen Total hydrocarbon Ambient air Total hydrocarbon Oxygen gases Total hydrocarbon Estimated maximum concentration 100% (liquid oxygen = 40%) 200 ppm 100% 500 ppm 50 ppm 100% 200 ppm Max concentration 200 ppm 100 ppm 100 ppm 75 ppm 75 ppm 50 ppm 75 ppm 5 ppm 50 ppm 50 ppm 30 ppm 10 ppm 30 ppm 0.5 ppm 0.1 ppm 30 ppm 30 ppm 10 ppm -

Table 2
Sample temperature 180C, liquid phase 180C, liquid phase Ambient temp., gas phase 5C-30C, gas phase

Sample streams / GC Analytical channel

Matrix No Sample 1 Stream A Sample 2 Compounds CH4, C2H6, C3H8, C4H10, C5H12, C6+, CO2, N2 CH4, C2H6, C3H8, C4H10, C5H12, C6+, CO2, N2, H2 CO2 (95-100%), N2 (0-1%), H2 (0-2%) CO2 (0-20%), N2 (80-100%), O2 (0-5%) CO (10-45%), CO2 (0-30%), CH4 (0-5%), N2 (0-2%), H2 (10-80%) CO (0-15%), CH4 (0-1%), N2 (0-1%), H2 (80-100%) CO (10-60%), CO2 (0-200ppm), CH4 (0-5%), N2 (0-2%), H2 (30-90%) CO (0-0.5%), CO2 (99-100%), CH4 (0-0.1%), N2 (0-0.1%), H2 (0-1%) CO (10-30%), CO2 (20-60%), CH4 (0-5%), N2 (0-2%), H2 (10-40%) CO (0-15%), CH4 (0-5%), N2 (0-5%), H2 (70-100%) CO (10-60%), CO2 (0-200ppm), CH4 (0-5%), N2 (0-2%), H2 (30-90%) CO (98-100%), CH4 (0-100ppm), H2 (0-1000ppm) CO (95-100%), CO2 (0-5ppm), CH4 (0-100ppm), H2 (0-100ppm) Carrier Gas He He He He N2 He N2 He He He He He N2 He He He He N2 He N2 Channel

Table 1

The analyzer is equipped with three different analytical channels: Hydrocarbon channel Incorporates a capillary column, Alumina type placed into the GC oven and a FID detector. The sample is injected by a gas sampling valve, with 0.25 ml sample loop. CO and CO2 channel This channel includes an HayeSep Q column, a methanizer and the FID detector. The channel is able to quantify up to 10 ppb of CO and CO2. Permanent gas channel The channel includes an highly sensitive PDD detector for ppb determination of all permanent gases. Two packed columns, HayeSep Q, and MolSieve 5A, can be consecutively selected according to the composition of the sample stream. Both columns are housed into the isothermal heated valve oven. The channel also includes a gas sampling valve with 1 ml sample loop and a column selection valve.

Components Methane Ethane Ethylene Propane Propylene Iso-butane N-butane Acetylene 1-butene Iso-butylene Iso-pentane N-pentane 1,3-butadiene Hexane Benzene Carbon monoxide Carbon dioxide Nitrous oxide Oxygen Nitrogen

Level of concentration Accuracy 0-300 ppm 0-200 ppm 0-200 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm 0-100 ppm ppm ppm 1 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm 0.5 ppm

Channel Hydrocarbons Permanent gases/ PDD Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Hydrocarbons Permanent gases/PDD Methanizer/FID Permanent gases/ PDD Methanizer/FID Permanent gases/ PDD Permanent gases/PDD Permanent gases/PDD

Sample 3 Stream B Sample 6 Sample 8 Sample 9 Sample 1 Sample 3 Sample 6 Sample 1 Sample 2 Sample 3 Stream E Sample 4

Stream C

Hydrocarbons Permanent gases/ TCD Hydrocarbons Permanent gases/ TCD Hydrogen channel Permanent gases/ TCD Hydrogen channel Permanent gases/TCD Permanent gases/TCD Permanent gases/TCD Permanent gases/TCD /methanizer /FID Permanent gases/TCD Hydrogen channel Permanent gases/TCD Permanent gases/TCD Permanent gases/TCD /methanizer /FID Permanent gases/TCD /methanizer /FID Hydrogen channel Permanent gases/TCD /methanizer /FID Hydrogen channel

Pneumatic configuration
Loop 1 ml Loop 1 ml Sample out

C 2H 6 C3H6 C2H4 C 3H 8 isoC4 nC4

Hydrocarbon analysis
Operating conditions Carrier gas Right DPFC mode Right carrier gas flow rate Split flow FID temperature Initial oven temperature Initial time Rate Final temperature Final time Valve oven temperature Helium Constant Flow 6.5 ml/min 150 ml/min 250C 40C 5 min 20C/min 120C 10 min 60C

Pneumatic configuration
Loop 1 ml Sample in He purge Sample out

Molecular sieve PDD

Analysis of Liquid oxygen stream with HayeSep column

Operating conditions PDD temperature: Pulse generator: CO2 Initial oven temperature: Initial time: N 2O Valve oven temperature: C2H6 120C ON 50C 8 min 60C

HayeSep CG4 He waste Loop 1 ml Sample in Sample out Sample in Loop 250 ml

He

CG1

NV CG4 Vent CG5 Loop 250 ml

NV Vent

CG1

CG2

HayeSep Q HayeSep/Molecular sieve NV TCD

Sample out

Sample in

CH4

CG2 Vent CG5 Purge

CG3 FID Top Split injector Bottom Air H2

Molecular sieve

isoC5 nC5
CG3 FID HayeSep FID H2 Make-up Air Methanizer Make-up Alumina

Split

C2H4

H2

TCD CG6

nC6

Air H2

Alumina

Methanizer

min

10

15

min

N2 + CO O2 CH4

O2

Permanent gas analysis

Operating conditions Carrier gas: Left DPFC mode: Left DPFC pressure: TCD temperature: Initial oven temperature: Valve oven temperature: Backflush time: Bypass MS column: Helium Constant pressure 170 kPa 200C 60C 60C after 3.5 min from 2.4 to 3.5 min CO

CH4 CO2

Trace of CO and CO2

Operating conditions Carrier gas: Left DPFC mode: Left DPFC pressure: Aux FID temperature: Valve oven temperature: Methanizer temperature: Backflush time: Helium Constant pressure 170 kPa 250C 60C 350C after 4 min

Analysis of air stream with HayeSep column

Operating conditions PDD temperature: Pulse generator: Initial oven temperature: Initial time: Valve oven temperature: 120C ON 50C 8 min 60C

N2

Analysis with Molecular sieve column

Operating conditions PDD temperature: Pulse generator: Initial oven temperature: Initial time: Valve oven temperature: 120C ON 50C 8 min 60C

Conclusion The examples described in this report are showing the advantages of using a flexible GC platform equipped with valve oven, sampling and switching valves and a combination of different sensitive detectors for complex gas analysis. Rapidity of response and capability to quantify a wide variety of impurities contained in production processes are the key benefits. Selecting a combination of sensitive detectors, such as the PDD, FPD and others, permits to selectively quantify impurities at ppb levels.
0

O2

CO2 N2 CH4

CO2 N O 2 CH4

H2
5

CO

H2

CO

10

15 min

min

min

10

15 min