Troubleshooting

Tips & Tricks for

your GC Analyzer &
CFT Application

7890 Detectors

October 29, 2014

1
Detector Types

Flame Ionization Detector (FID)

Thermal Conductivity Detector (TCD)
Electron Capture Detector (µECD)
Nitrogen-Phosphorous Detector (NPD)
Flame Photometric Detector (FPD)
Photo Ionization Detector (PID)
Electrolytic Conductivity Detector (ELCD)
Infrared Detector (IRD)
Mass Selective Detector (MSD) Items in red covered in this course
Agilent 7890 FID Theory of Operation

H2 – Air Flame
Sample is burned in
flame.
Charged Ions
produced.
Ions attracted to
collector.
Collector current
converted to output
via Electrometer.
FID Problem #1

#6

#9
#7
#8
#3
#2
#1

#5
#4
Before After
Normal

Peak Peak Peak Before After

No. Width Width Area Area Type

#1 0.014 0.102 288 6213 TBB

#2 0.020 0.111 559 2922 TBB
#3 0.022 738 BB
#4 0.026 0.024 585 227 BV
#5 0.025 267 VB
#1

#6 0.029 0.030 1231 543 BB

#2

#7 0.035 0.036 1010 396 BB

#8 0.030 1041 BV
Problem

#6
#7

#9
#4

#9 0.031 0.031 1195 478 BB

FID Problem #2

#1

#9
#2

#5

#7
#4
#3

#8
#6
Before After
Normal

Peak Peak Peak Before After

No. Width Width Area Area Type

#1 0.014 0.031 288 259 BB

#2 0.020 0.020 559 503 BB
#3 0.022 0.022 738 664 BB
#4 0.026 0.026 585 526 BV
#5 0.025 0.024 267 240 VB
#6 0.029 0.028 1231 1170 BB
#9
#6
#7
#1

#8
#2

#5
#4
#3

#7 0.035 0.034 1010 909 BB

Problem

#8 0.030 0.030 1041 936 BV

#9 0.031 0.030 1195 1075 BB
Agilent 7890 FID Jets
Adaptable FID Jets
Jet Type Part# Jet Tip ID

0.29 mm
Capillary 19244-80560
0.011 in.

0.47 mm
Packed 18710-20119
0.018 in.
0.79 mm
Paced Wide Bore 18789-80070
0.030 in.
0.47 mm
High Temp G1531-80620
0.018 in.

Capillary-Optimized FID Jets

Jet Type Part# Jet Tip ID
0.29 mm
Capillary G1531-80560
0.011 in.

0.47 mm
High Temp G1531-80620
0.018 in.
Agilent 7890 FID Setup – Column Installation
General Rule:
Push to tip of Jet
then withdraw 1 mm.

Capillary Optimized FID Adaptable FID

0 10 20 30 40 50

mm
0 10 20
mm

48mm
68mm 1mm
30 40 50 60 70
Exploded Parts View of the FID
Agilent 7890 FID EPC Flow Module
FID EPC Module
Agilent 7890 Flame Ionization Detector

Typical Problems
• Flame blowing out or not lighting

• Spiking

• Low Sensitivity

• Noise

• Drift
Solving FID Lighting Problems

Check detector parameter settings (keyboard).

• Flows
• Flame on
• Detector on
• Lit offset
Check jet.
Check igniter.
Check column connections.
Check gas supply pressures.
Check solvent and injection size.
Solving FID Noise Problems
Turn off
H2 and Air.

Yes Still No
Noisy?

Check/Clean/Replace: Check/Clean/Replace:
•Interconnect/collector connection. •Filters, traps, gases.
•Collector and insulators. •FID jet.
•Detector interconnect. •Column and connections.
•Detector board. •Inlet and consumables.

Electrical Problem. Contamination Problem.

Routine FID Maintenance
Monitor the background signal.
Check pressures/flows.
Clean or replace the jet.
Inspect the igniter assembly.
Clean the collector assembly.
Remove, trim and reinstall column.
Agilent 7890 Flame Lighting Problems

Check the following:

Measure flows.

Clean/replace jet.

Are column and fittings tight?

Do we have supply gases?

Is detector on?
Agilent 7890 Thermal Conductivity Detector

Thermal Conductivity Values of Common Gases/Solvents

Compound Relative Thermal Conductivity

Carbon Tetrachloride 0.05

Benzene 0.11

Hexane 0.12
Argon 0.12
Methanol 0.13
Nitrogen 0.17
Helium 1.00
Hydrogen 1.28

Thermal Conductivity Relative to Helium

Thermal Conductivity Basics
The TCD is a nondestructive, When the carrier gas is contaminated
concentration sensing detector. by sample , the cooling effect of
A heated filament is cooled by the gas changes. The difference in
the flow of carrier gas . cooling is used to generate the detector
signal.
Flow

Flow
The TCD will respond to any substance different
from the carrier gas as long as its concentration is
sufficiently high enough.
Agilent 7890 TCD 5 Hertz Pneumatic Switching

COLUMN flow enters the center of

three ports.

REFERENCE flow is directed to either

one of the outside ports into the
detector cell. The port entered is
determined by the SWITCHING
SOLENOID.

AUXILIARY, or makeup, flow passes

along the outside of the column and
merges with the column flow prior to
entering the detector’s center port.
TCD Normal Flow Ratio

20 mL/min
Col + MUG 30 mL/min
Reference Sample
Filament

Filament
+ Reference
10 mL/min Ref
Reading Reading

20 mL/min
Reference 20 mL/min
Col + MUG

30 mL/min 30 mL/min
Reference 20 mL/min 20 mL/min Reference
Column + MUG Column + MUG

Signal (+ polarity) = Sample - Reference

TCD Problem #1

#6
#3

#8
#2

#9
#7
#4
#5
#1
Before After
Normal

Peak Peak Peak Before After

No. Width Width Area Area Type

#1 0.030 0.028 1920 1643 BB

#2 0.033 0.031 4279 3215 BB
#3 0.028 0.027 4503 3803 BB
#4 0.033 0.031 3380 3043 BV
#8 #5 0.026 0.023 2109 1810 VB
#3

#6

#6 BB
#2

#9 0.038 0.036 7233 6528

#7

#7 0.044 0.040 4386 3551 BV

#4
#5
#1

#8 0.046 0.043 6898 6124 VB

Problem

#9 0.050 0.049 6817 6252 BB

Choosing Reference Flow Rate
Ratio of Ref flow to Column + MUG

3.5

2.5

1.5

0.5
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70

Column + Makeup flow (mL/min)

Column + MUG Flow = 10 mL/min

Ref flow = 2.3 X 10 = 23 mL/min
Agilent 7890 TCD EPC Flow Diagram
Agilent 7890 TCD EPC Module
Reference Gas Line

Switching Valve

Make Up Gas Line

Agilent 7890 TCD Filament Drive – ΔT Sensor
500 DT 50C
400

Response Filament 300

Temp C
200
DT135C
100

100 200 300 400 100 200 300 400

Detector Temp (body temp) C
Detector response versus detector temperature. Filament Temperature versus Block Temperature.
TCD Typical Problems
Drifting or wandering baseline
• Normal in temperature programmed analysis
• Check heaters/sensors.
• Remove contamination by thermal cleaning the detector.

Low sensitivity
• Check gas flows.
• Check column installation.
• Contamination – thermal clean the detector.

Elevated background signal or increased noise level

• Contamination – thermal clean

Conditions that prevent the detector from operating

• Temperature set below 100°C
• Broken or shorted filament
• Reference gas flow set to 0
Valves
What are Valves?

Valves are mechanical devices used to switch gas streams.

They are the pneumatic equivalent to the electrical switch.
4 Port LSV with Internal Sample Volume
Gas Tight Syringe versus Gas Valve Injection

Typical values for valve injection reproducibility is <0.5% RSD.

Typical values for manual gas tight syringe injection reproducibility is <5.0%
RSD.

Multiple valves can be filled in series with a gas sample.

Manual syringe can only fill 1 injector port.

Note for small sample volumes (<2mL) can only use gas tight syringe.
Injection with Gas Sampling Valves

Loop of known volume switched into carrier gas stream.

Factors that affect the amount of sample transferred onto the column:

• PV=nRT
- Temp = temperature of valve box
- R = ideal gas constant
- V= volume of sample loop

Pressure is proportional to the amount of mole of gas within sample

loop.
How Are Gas Samples Injected?

Gas sampling valves are the most common way of sampling a

gas and are used in almost all cases on bench top GC’s.

Almost all gas sampling valves installed on GC’s are produced

by VICI™. Spare valve parts can be ordered directly from VICI
if required.
www.vici.com

Gas tight syringes can also be used for injection but they are
not as reproducible and are more cumbersome.
In This Section, We Will Discuss:
Valve rotor replacement
Problems associated with valve GCs
Dealing with water vapor
Backflushing
Reconditioning mol sieve columns
Nafion driers
Genie membrane filter
Trace sulfur gases
SCD potential problems
Other problem compounds
Gas Sample Valves
Liquid Sample Valves
Valve Timing
Valve Rotor Replacement

Number of ports ID letter toward

3 Port 2
4 Port 3
6 Port 4
8 Port 5
10 Port 6
Problems Associated with Valve GC’s
-Moisture is far more important when you are using columns who performance will drop
dramatically with moisture absorption.

-Many valved GC’s will have at least 1 x Molecular Sieve column installed so water
handling is very important.

-The system should be designed to restrict moisture from reaching these columns from
the sample (there are rare exceptions to this).

-Carrier gas is typically at volume of at least 1000 times that of the sample throughout the
period of day so it’s dryness is absolutely critical (indicating moisture filters must be used).

- In many cases the sample is not visible before it is connected to the GC so

contamination of GSV lines with liquid or metal particles (especially the later) can cause
immediate damage.

-Use an inline filter wherever possible to minimize sample impact to system.

Dealing with Water Vapor
Benchtop GC
Water can be chromatographed and analyzed but this is not
recommended.

• Problems with preparation of accurate standards

• Poor peak shape

• Memory effects

• On non polar columns it appears as very broad peak which can interfere
with other components (RT can shift dramatically too)

It is possible to analyze on polar columns.

Dealing with Water Vapor (cont.)

PROBLEMS

If sample gas stream is saturated with moisture then

condensation can occur on cold internal tubing surfaces and
cause loss of analytes and other more serious problems.

Absorbed onto Molecular Sieve columns deactivating them,

thus less retention and separation of components.

Absorbed onto Alumina columns with resulting shifting in RT’s.

Backflushing

In many cases it is possible to backflush water from the sample

to Vent.

This option is available on either the Micro GC or Bench top GC

unit.

Backflushing of water is only possible if analytical compound

elutes before C3, as water will typically elute between C2 and
C3 on most columns.
Backflush Micro GC
Sample in

injector

CP-Sil 5 CB
µ-TCD µ-TCD µ-TCD µ-TCD
Backflushing - Bench Top Unit

0.5m Hayesep N columns used for backflush of water.

Loss of Resolution Due to H2O Absorption
Reconditioning Molecular Sieve Columns
Molecular Sieve columns can be reconditioned.

• Bench top GC
- heat Molecular Sieve column to 300°C for a minimum of 4 hours.

• Micro GC
- heat 180°C, pressure 45psi O/N minimum

NOTE:

• Remove any other columns from GC oven not suited to temperature, replace
with empty ss column.

• Must turn off TCD filaments and ensure carrier gas is dry during
reconditioning.
Removing Water Vapor

There are many ways to remove moisture from your samples

prior to analysis.

Condensing - run sample through cooler with collecting coil.

Desiccants - may alter conc. of other analytes)

Nafion Dryer - a good solution but can result in the loss of

some amount of some polar analytes such as methanol.
Nafion Dryers

• Wet feed gas in

• Dry purge gas, typically at
min of 10x sample flow in
opposite direction
• Dry feed gas to analyzer
http://www.permapure.com/
Nafion Dryers

• Nafion is a special extremely

hydroscopic membrane type
material.
• Allows easy removal of moisture
with little if any alternation to
sample.
• Highly recommended for Micro GC
applications.
• Also useful for bench top.
Genie Membrane Filter
Removes droplets – only • Protects the analyzer from damage and contamination
required for µGC
• Fully inert membrane technology

• Proven and widely accepted filtering technique

• Removes liquids from gas samples

• Removes particles from gas samples

• No interference with sample composition

• Compliant for BTU calorific value applications

• Suitable for PPB, PPM and percentage level analysis

• Standard Swagelok™ connections

• High and low flow membranes

Genie Model 170
• Stainless Steel, Polypropylene and Kynar housing

• Standard Viton housing seal

Moisture from Sample or Carrier Gas
Remember moisture from carrier gas is far more susceptible to cause problems with
columns and BF will not remove.

On a Micro GC, typical column flow 2mL/min.

Typical sample Introduction volume is 200nL.

If you inject one sample every 5 min(s) total sample volume introduced, 2400nL.

In 1 hour you have 120 mL of carrier gas through your column, so the moisture
content of your carrier gas is 50,000 times more important than your sample gas.

Always use a carrier gas filter with certain types of packed columns.
Trace Sulfur Gases
Low level sulfur analysis requires the following:

•Inert surfaces at every point.

•Accurate standard(s)
• Shelf lifetime is limited due to reactivity of sulfur components (consider Dynacalibrators).

•Agilent uses Hastelloy C Valves with all sample path material including the
detector in Ultimetal.

•Use the most inert stationary phase where possible, CP-Sil5CB.

Trace Sulfur Gases

•H2S, SO2, COS are the most reactive components, with

CH3SH, EtSH and on being increasingly less reactive.

•RSD’s for reproducibility typically 3-5% for H2S, SO2 and

COS, 5-10% for SO2 maybe 1-3% for other sulfur
components.
Percent Level Sulfur Determination

High levels of sulfur species >0.1% should not be analyzed on

a FPD due to linear range issues but instead on a TCD.

Use a small loop size to limit impact on corrosive sulfur species

generated by reaction of sulfur components with moisture on
filaments in TCD.

Dry sample stream if it contains appreciable amounts of

moisture and sulfur species such as SO2, H2S, etc.
SCD Potential Problems

•High maintenance detector, vacuum pump, ozone generator

etc.

•Ceramic tubes can easily become contaminated and need

replacement.

• indication through loss of sensitivity,

• thick film methyl silicone columns can cause this if heated to

higher temperatures
Other Problem Compounds

•Chlorine

•Ammonia, if not to be analyzed can be removed using an acid

solution with a pH indicator present.

•Special columns designed for ammonia analysis.

• Volamine or Chromosorb 103

•No ammonia analysis by µGC.

Sample Introduction Systems (Problems)

Bench Top

• Gas Sampling Valve

• Liquid Sampling Valve
• Injector Port

Micro GC

• Specific injection technique

Gas Sampling valves

Valve cores are rated for different temperature ranges.

• Ambient - 175°C
• 100-300°C
• ambient to 225°C (valcon E)

Do not overheat or they will no longer function correctly!

Gas Sampling Valves-6 Port
Valves - WCGW

•Valve core damaged due to overheating.

•Valve core scratched- gives leaks.
• Use Inline filters to stop this occurring
•Valve core or channels blocked.
•Loop blocked
•Leaks at fittings although this is unlikely.
•Always use correct Valco ferrules and nuts.

Replace valve core and body as one unit, carry a spare if

at all possible.
Valves- WCGW

Actuators may not turn

• Insufficient gas pressure or not on, require 60psi

Actuators may not be aligned correctly

• incorrect removal from valve

Wrong angle actuator

• check degree turn
• Agilent actuators versus other actuators

Micro Electric Actuators

Liquid Sampling Valves

Fixed volume - internal groove -1µl

Liquid must be under pressure to remain in liquid phase.

Easily blocked - use filters to remove particles before the

sample inlet.

Use apparatus as described (drawing) for ensuring liquefied

gas remains in liquid state.
Sample Introduction Devices
Gas (Refinery gas, Natural gas)
• Pressure
Sample
• 1015 PSI for Natural gas treatment
• Up to 290 PSI for Refinery gas

Controlled pressure reduction

Why
• Max 45 PSI sample inlet pressure for bench GCs and max 15 PSI
for the 490 Micro-GC Controlled sample flush flow.
• Constant sample pressure prior injection.
• Pressure reduction cools down the sample.
• Cold spots GASIFIER
• Retention outside the GC
• Sample discrimination
Sample Introduction Devices
Liquefied gas (LPG)
• Pressure
• Temperature Sample
treatment

Inject as Gas or as Liquid?

1% gas in sample volume is

Liquid 0.004% of composition

1% liquid in sample volume is

Gas 250% of composition

Preferably as a Liquid !
Sample Introduction Devices
Liquefied gas (LPG)
• Pressure
• Temperature Sample
treatment
SAMPLE
Inject as a Liquid BUMB

How ?

SAMPLE
IN
TESCOM
REGULATOR
PR
Carrier
HIGH GAS Gas
PRESSURE IN

SAMPLE OUT
TO VENT
RESTRICTION

Pressure station
Sample Introduction Devices

Use fully filled bombs

Else sample discrimination

Propane and Butane Mixture in a 1 liter bottle

100 ml gas
500 ml
gas
800 ml
gas
C3=50.0
C4=50.0 C3=49.9
C4=50.1 C3=49.3
C4=50.7 C3=47.0
C4=53.0
What about Valve Timing?
•Valve timing is either set at the factory if it is SP1 solution or
setup in the field typically by an Agilent engineer. SP1’s have
detailed manuals for setting up valve timing.

•Valve timing should not require adjustment and original settings

should be recorded and kept with the instrument at all times.

•If new columns are purchased they either need to be

preconditioned or conditioned on site prior to being set up within
the instrument (typically 20C below max temperature for at least
4 hours).
Natural Gas Analyzer (SP1 7890-0042)

Prior to Injection
Natural Gas Analyzer (SP1 7890-0042)
Injection
Natural Gas Analyzer (SP1 7890-0042)
Elution of Hydrocarbons
Natural Gas Analyzer (SP1 7890-0042)
Elution of Permanent Gasses
Typical NGA Chromatogram (SP1 7890-0042)
Configuration:
• 3-valve/4-column (packed column)/TCD
Sample type:
• Natural gas and similar gaseous mixtures

Page 67
Natural Gas Analyzer (SP1 7890-0192)
Configuration:
• 3-valve/4-column (packed column)/TCD
Sample type:
• Natural gas and similar gaseous mixtures
SP2 Wasson Tiger Program
Operation Conditions and Catalyst Check

Typical operation temperature is 400°C with 20mL/min of H2

being added post column, pre catalyst

You can check Catalyst functionality by having a standard with

known amounts of CH4, CO and CO2

Typically conversion efficiency is >70% so peak areas for the

same concentration of CH4, CO and CO2 should be around the
same size
Linearity of Methanizer
•DL is approx. 200 ppb using a 0.5 mL sample loop and
linear to approx. 10%.

•Large loops (up to 2mL) will result in a lower DL limit but

also a lower max. concentration.

•TCD and Methanizer / FID may be used in combination to

detect sub ppm levels of these gases as well as high %
levels.
Catalyst Poisoning and Practical Tips

•Very small amounts of H2S, SF6 and most other sulfur gases
cause immediate and complete deactivation of the catalyst,
Regeneration is not possible.

•It is uncertain as to whether large concentrations of O2 can

have a negative impact on the catalyst. For this reason it is
best to avoid sending large concentrations of O2 to the catalyst.
Catalyst Poisoning and Practical Tips

•Unsaturated hydrocarbons such as pure ethylene cause

immediate, but partial, degradation of the catalyst as evidenced
by slight tailing of CO and CO2 peaks.

•Any catalyst that is suspected of being poisoned should be

replaced and no attempt made to regenerate the material.
Questions?

October 29, 2014

74