Objectives

What is a BTU analyzer?

Why do we use BTU analyzers?

How does a BTU analyzer work?

What is an on-line Gas Chromatograph ?
 An on-line Gas Chromatograph is

•An instrument that measures either a single component or

multiple components in a flowing pipeline stream consisting of
gases or liquids. (Gives you the composition of all or part of the
gas or liquid).

Some physical properties of common interest for natural gas

(BTU) applications are:
1. Heating value (BTU, Joules, calories, etc.)
2. Relative Density
3. Compressibility
 Danalyzer BTU/CV Chromatographs

Controller and analyzer

3 valves 2 valves
.
(+/- .50 BTU, 4 min. analysis time) (+/- 1 BTU, 12 min. analysis time)
Gas Chromatographs- Principle of Operation
GC Analyzers Consist of Subsystems

•Injection

•Separation

•Detection

•Integration / Calculations

•Reports
 Brains of the GC “Controller”

The controller can be integral to the analyzer or

remote mounted. Sends control signals (valve firing
stream switching etc.) and interprets signals from
the analyzer.

•Integration / Calculations

•Reporting
 Heart of the GC “Oven”

Typically a heat sink oven. Kept at a constant

temperature, and has constant flow of
carrier gas (Usually High Grade Helium).

•Injection

•Separation

•Detection
 GC Oven
The GC oven contains 3 main components mounted together in an
electrically heated heat-sink-oven:

 GC Valves (Inject sample, direct carrier flow)

 Micro-packed Columns (separation of the components)

 TCD Detectors (Detection of the separated components)

 Core Technology
Chromatograph Valves

Sample inject and

Column Switching Valves
• 6 port, Piston-operated diaphragm
Valve
• Unique air-to-air diaphragm actuation
based on original NASA design
• No springs, washers, or lubricants
• Sample does not come in contact with
internal moving parts
• >5 Million operations per valve
• Lifetime warranty
 Core Technology
Micro-Packed Columns
• Faster analysis times. with extremely
low carrier consumption (10-15
cc/min. typical)
• Superior component separation
enhances baseline separation and
sharpens peak resolution
.043” ID
• Combines durability of packed
columns with advantages of capillary
columns
• Designed together with valve and
detector to minimize internal dead
volume
• 2 year warranty under normal
operation
 Core Technology
Micro-Thermal Conductivity Detector

• Uses (TCD) thermistors to

measure the concentration of
each component.
• Improved sensitivity for low
level measurements (eliminates
FID requirement for some
applications)
• Rugged -- Immune to carrier
gas failure and vibration.
• Detector block and column
blocks are heated. A thermal
cutout prevents heating beyond
85° C.
Core Technology
Heat Sink Oven

• Integral Heat Sink Oven contains

all columns, valves and TCD
detectors
• Approved for Class I Div I
Groups B, C, & D
• Minimal Utilities -- No Air or
Hydrogen Required
• +/- 0.1 C over ambient
temperature (-18 to 55C)
• Ensures maximum stability and
repeatability in outdoor
environments.
 HEATSINK
OVEN COLUMNS

SAMPLE
LOOP
6 PORT
VALVE
MEASUREMENT
DETECTORS

REFERENCE
DETECTOR
Flow Path in GC Oven
 Analyzer Oven

Step 1: Start of an analysis. Sample valve (V-1) OFF, backflush

valve (V-2) ON, and dual column valve (V-3) ON. The sample
purging system maintains a sample in the gaseous phase and passes
the sample through transport tubing to the sample valve, and
through the sample loop.
 Analyzer Oven

STEP 2: The sample valve is turned ON to capture a precise

volume of sample and to allow carrier gas (Helium) to sweep the
sample loop into the first column. Column 1 separates C6, and
heavier components (C6+) from the other constituents in the gas.
 Analyzer Oven

Step 3: The sample valve turns back OFF to purge the next stream.
The backflush valve turns OFF reversing the carrier flow through
column 1 so that C6+ components elute first (all combined as a single
peak) to the measure detector. Note: by switching the direction of flow
through the first column, C6+ components bypass columns 2 and 3.
This helps to expedite the analysis.
 Analyzer Oven

Step 4: C6+ (heavies combined) is on its way to the detector.

Column 2 separates the mediums C3, C4’s, and C5’s while the lightest
components N2, C1, CO2, and C2 continue traveling through column 2
into column 3.
 Analyzer Oven

Step 5: Dual column turns OFF after trapping the lightest

components N2, C1, CO2, and C2. The medium components
bypass column 3 by going through the restrictor column (R-1) and
Follow C6+ to the detector. Once again this helps speed up the
analysis.
 Analyzer Oven

Step 6: After the heavy and medium components elute to the

detector the dual column valve is turned back ON freeing the
light components and allowing them to cross the detector next.
This is the end of the analysis and the next one is ready to begin.
Typical
 Qualitative Information

•Carrier Gas Flow Is Constant

•Temperature Of Oven Is Constant

•Sample Size Is Constant

The time each peak elutes across the detector

will also be constant. This time is known as
Retention Time of each peak. This time is
programmed into the controller.
Quantitative information

Thermal Conductivity Detectors

TCD
 Thermal Conductivity
Examples

NAME SYMBOL THERMAL

CONDUCTIVITY AT
ZERO DEGREES C
Air 5.8
Hydrogen H2 39.6
Helium He 33.6
Nitrogen N2 5.7
Argon A 3.9
Carbon Dioxide CO2 3.4
Methane CH4 7.2
Propane C3H8 3.6
Acetylene C2H2 4.5
Benzene C6H6 2.2
Butane C4H10 3.2
Chloroform CHCL3 1.6
Freon 12 CL2CF2 2.0
(Dichlorodifluoromethane)
Methanol CH3OH 3.4
Acetone C3H6O 2.4
Detector Bridge Circuit
 Idealized Chromatogram

The signal from the detector is read by the controller.

The controller integrates the area under each peak. This
is known as the raw area, and is used for quantifying the
component concentration.
 Response Factors (RF)

•Response factor is used to tell how much

of a component is present in the gas
RF = Raw Area / Cal Concentration
NOTE: RF are only updated during a calibration

We use the RF to calculate the Mole % of each component

in a sample stream

Mole % of Sample = Raw Area / RF

 A simplified example of how RF is calculated and
used in stream analysis

Given: A calibration was run and a Raw Area for ethane

calculated by the controller is 100.
The known calibration gas has 5% ethane (programmed
into the controller).

RF = Raw Area / Cal. Conc.

RF = 100 / 5 = 20

Given: Sample Stream gas is run, and the raw area of ethane
calculated by the controller is 200.

Mole % = Raw Area / RF

Ethane = 200 / 20 = 10%
Typical Chromatograms
And Reports
 Gas Chromatogram
Shows retention times and raw area under each peak
A Chromatogram is a picture showing the detector output
Gas Chromatogram Comparison
 Typical Raw Data Report

Response Factor (RF) = Area(comp x ) / Cal Conc.(Comp x)

Mole % = Area(comp x) / RF (Comp x)
Typical Analysis Report
Typical Calibration Report
Sample System
Sample Conditioning and Sample Transport

• The sample conditioning system is a very important

component in any analytical system. This is a frequently
overlooked component that must deliver a representative
sample from the pipeline to the GC without changing the
composition.

• This is not a difficult task when low BTU gas is measured

in warm climates. When high BTU gas is measured the
potential exists to lose the heavier components as they
drop into the liquid phase due to sample cooling.
Sample Conditioning and Sample Transport

The Joules-Thompson (JT)

•Cooling effect causes heavier

components to drop into liquid
phase.

•Will bias energy readings low

because the high BTU
contributors drop out of the vapor-
phase sample before the GC even
has a chance to measure it.
Sample Conditioning and Sample Transport

Pressure Balancing stream

to stream.

• Minimizes normalization.
•Minimizes cross-stream
contamination if solenoids do not
seal completely.
Sample Conditioning and Sample Transport

Calibration Standards

• may require heated insulation

blankets when installed in High
BTU applications in cooler
climates.

• Sample transport lines require

heat tracing to a heated area or all
the way to the sample valve.
Sample Conditioning and Sample Transport
Sample Conditioning and Sample Transport
Instrument Performance

•Repeatability

•Accuracy

•Linearity
Repeatability and Accuracy can be checked by your calibration

Response Factor (RF) = Area(comp x)

Cal Conc.(Comp x)

Mole % = Area(comp x)
RF(Comp x)
Instrument Performance-Linearity Check
Using three standards

Component Standard Heating Standard Heating Standard Heating

#1 Value 1 #2 Value 2 #3 Value 3
Hexanes + C6+ 0.01 0.53 0.03 1.59 0.20 10.58
Propane C3 1.00 25.16 3.00 75.48 7.00 176.13
Iso-Butane IC4 0.50 16.26 0.10 3.25 0.40 13.01
N-Butane NC4 0.50 16.31 0.10 3.26 0.40 13.05
Neo Pentane Neo C5 0.08 3.19 0.00 0.00 0.00 0.00
Iso-Pentane IC5 0.08 3.20 0.30 12.00 0.80 32.01
N Pentane NC5 0.10 4.01 0.30 12.03 0.80 32.07
Nitrogen N2 3.32 0.00 2.00 0.00 1.00 0.00
Methane C1 89.50 904.15 87.67 885.47 77.40 781.74
Carbon dioxide CO2 2.91 0.00 1.50 0.00 1.00 0.00
Ethane C2 2.00 35.39 5.00 88.48 11.00 194.66
Totals 100.00 1008.20 100.00 1081.56 100.00 1253.25

Note: Heating values are based on GPA 98 Engineering Data Book Volume II Section 23.
Using 60 F and 14.696 base conditions
Physical Property Calculations-Pressure Base

Typical Composition Pressure Pressure Pressure

Natural Base @ Base @ Base @
Gas 14.73 14.696 15.023
Nitrogen 2.46
Methane 89.709
C02 1.001
Ethane 5.001
Propane .999
Iso-Butane .300
N-Butane .300
Iso- .100
Pentane
N-Pentane .100
C6+ .03
Relative .6222 .6222 .6223
Density
Gross Dry 1053.70 1051.26 1074.73
BTU
Physical Property Calculations-GPA Standards
Constants that are not so constant

Typical GPA 2145-96 GPA 2145-

Natural Gas 2000 (Jan 1
release)
Rich Gas 1300 BTU +0.0138 BTU
Typical US 1078 BTU +0.0032 BTU
Gulf Coast
Table 4
 Conclusion

•BTU Analyzers Play an important part in gas energy measurement

•During the analysis the GC uses columns to separate the gas into its
constituents
•The GC uses thermal conductivity detectors to quantify the mole %
of each component present
•A BTU is calculated for each constituent based on mole %
•By summing up each of these individual values we find the total
BTU value of the gas
 Demon on Gas chromotograph

• Daniel C6+.exe