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BTU Anlisis Utilizando un

Cromatgrafo de Gases

GC Division

Objetivos

Qu es unalizador de BTU?
Por qu utilizamos analizadores
de BTU?
Cmo trabaja un analizador de
BTU?

Qu es un Cromtogrado de Gases en Lnea ?

Un Cromatgrafo de Gases en Lnea es

Es un instrumento que mide, ya sea, un componente o varios


componentes en una corriente de gas. (Proporciona la composicin
de todas las partes del gas).
Algunas propiedades fsicas de interes comn en el rea de
aplicacin de gas natural (BTU) son:
1. Poder Calorfico (BTU, Joules, calories, etc.)
2. Densidad Relativa
3. Compresibilidad

Componentes Tpicos Medidos


Analizador de BTU en Gas Natural

Componentes
Hexanos+
Propano
Isobutano
Normal Butano
Neo Pentano
Isopentano
Normal Pentano
Nitrogeno
Methano
Dioxid de Carbono
Ethano

Rangos Tpicos
C6+
C3
IC4
NC4
Neo C5
IC5
NC5
N2
C1
CO2
C2

0 0.7 %
05%
0 1%
0 1%
0 1%
0 1%
0 1%
0 15%
0 100%
0 10%
0 15%

Por qu utilizamos un Cromatgrafo


de Gases (GC)?

Un Mercado Creciente

Actualmente mas del 80% de las necesidades de energa


mundial es proporcionada por combustibles fsiless. Estas
necesidades pueden ser divididas entre 40% aceite, 30% gas
natural, y 10% carbn.
La demanda global de gas est creciendo alrededor de dos veces
mas rpido que la demanda de aceite.

Taken from Pipeline & Gas Indusry (Sept. 2000) WGC Panel

Reservas Probadas
United States
Canada
Western Europe
Former Soviet Union
Latin America
Middle East
Africa
Asia Pacific

164,041 bcf
63,874 bcf
156,578 bcf
2,002,107 bcf
252,719 bcf
1,749,241 bcf
394,177 bcf
363,470 bcf

Taken from Oil & GasJounal (June 25 . 2001) Worldwide Gas-Processing Roundup

Transferencia de Custodia (Volumen)

Las compaas han acostumbrado comprar y vender gas


por volumen (SCF)
Debera existir un acuerdo contractual de rango aceptable de BTU.
El gas debera ser analizado peridicamente (al menos una ves por
mes o mas frecuentemente dependiendo del contrato) para verificar
que los BTUs estuviesen en rango.

Transferencia de Custodia Energa

Desde el comienzo de los aos 80s ha llegado as er muy comn que


las comapas compren y vendar energa (Dekatherm, MMBTU).
AGA 5 / ISO 6976
Energa= Volumen Corregido (del FC) X Poder Calorfico (del GC)
AGA 8
Usado para calcular
Volumen Corregido

Mtodos de Supercompressibilidad
Gross 1: SG, BTU, CO2 (From GC)
Gross 2: SG, N2, CO2 (From GC)
Detail Method: Utiliza toda la composicin del
Gas Natural (del GC)

Importancia de la medicin exacta de la


energa

Pequeos errores en la medicin se suman a las prdidas $$$


Ej. Usando 1020 BTUs / SCF y un Volumen of 20,000,000 SCFD
con 0.1% error en BTU. @ $4.00 / Dekatherm
1020 BTU/SCF X 20,000,000 SCFD = 20,400 Dkthm/Da (asumido)
1,000,000 BTU/Dkthm
1018.98 BTU/SCF X 20,000,000 SCFD = 20,379.6 Dkthm/Da(actual)
1,000,000 BTU/Dkthm
20,400 20,379.6 = 20.4 Dkthm/Da (error)
@ $4.00/Dkthm = $81.60/Da
$2,448/Mes
$29,376/Ao
Resultado: +/-1 BTU error puede costar cerca de $30,000 al ao

Ejemplo de 1% Error en medicin de BTU


Ej. Usando 1020 BTUs / SCF y un Volumen de 20,000,000 SCFD
con 1% error en BTU. @ $4.00 / Dekatherm

20,400 Dkthm/Da (asumido)


1009.8 BTU/SCF X 20,000,000 SCFD
= 20,196 Dkthm/Da (actual)
1,000,000 BTU/Dkthm
20,400 20,196 = 204 Dkthm/Da (error)
@ $4.00/Dkthm = $816/Da
$24,480/Mes
$293,760/Ao
Nota: El error composicional que causara el erro de BTU, tambin
causara errores en los clculos de AGA3/ ISO 5167.

Cromatgrafos Danalyzer BTU/CV

Controlador y analyzador
3 vlvulas
.
(+/- .50 BTU, 4 min. anlisis)

2 vlvulas
(+/- 1 BTU, 12 min. anlisis)

Cromatgrafo de Gases Principio de


Operacin

Los Analizadores GC Consisten de Subsistemas

Inyeccin
Separacin
Deteccin
Integracin / Clculos
Reportes

Cerebro del del GC Controlador

El controlador puede estar integrado al analizador o


montado remotamente. Enva seales de control
(activacin de vlvulas, cambio de corriente, etc.) e
interpreta seales provenientes del analyzador.
Integracin / Clculos
Reportes

Corazn del GC Horno

Tpicamente un horno elctrico. Se mantiene a una


Temperatura constante, y tiene flujo constante de
gas de arrastre (Usualmente Helio de Alta Pureza).
Inyeccn
Separacin
Deteccin

GC Horno
El horno del GC contiene 3 componentes principales montados juntos
en un horno calentado elctricamente:
GC Vlvulas (Inyeccin de muestra, direccionamiento flujo
de gas de arrastre)
Columnas Micro-empacadas (separacin de los componentes)
Detectores TCD (Deteccin de los componentes separados)

Tecnologa
Vlvulas Cromatogrficas
Vlvulas de inyeccin de
muestra y activacin de
columnas
6 purtos, Vlvula de diafragma operada
por pistn
Actuacin nica de diafragma basada
en un diseo orignal de la NASA
Sin resortes, lavadores o lubricantes.
La muestra nunca estpa en contacto
con las las partes internas.
>5 Millones de operaciones por vlvula
Garanta de por vida.

Tecnologa
Columnas Micro-empacadas
.

Tiempos de anlisis menores con


consumo de gas de arrastre
extremadamente bajo (10-15 cc/min.
tpicamente)
Alto grado de separacin de
componentes dfine la linea base y una
mejor resolucin de forma de los
picos.
Combina la durabilidad e las
columnas empacadas con la ventaja
de las columnas capilares.
Diseadas en forma conjunta con
vlvulas y detectores para minimizar
el volumen muerto interno.
2 aos de garanta bajo condiciones
normales de operacin.

.043 ID

Tecnologa
Detector de Conductividad Trmica

Utiliza (TCD) termistores para


medir la concentracin de cada
componente.
Mejora la sensibilidad para
mediciones de bajo nivel
(elimina el requerimiento de
FID para algunas aplicaciones)
Rudo -- Immune a fallas de gas
de arrastre y vibracin.
El bloque de detector y el
bloque de columnasson
calentados. Cuenta con arreglo
para prevenir calentamiento por
encima de 85 C.

Tecnologa
Horno elctrico
El horno elctrico contiene
las columnas, vlvulas y
detectores TCD
Aprobado para Clase I Div I
Grupos B, C, & D
Utilidades Mnims -- No
requiere Aire o Hidrgeno
+/- 0.1 C sobre la
temperatura ambiente (-18
to 55C)
Asegura mxima estabilidad
y repetibilidad a temperatura
y condiciones ambientales.

HORNO
ELECTRICO

COLUMNAS

LAZO DE
MUESTRA
VALVULA
6 PUERTOS

DETECTOR DE
MEDICION

DETECTOR DE
REFERENCIA

Ruta de Flujo en el horno GC

Horno del Analizador

Paso 1: Inicio de anlisis. Vlvula de muetreo (V-1) OFF,


backflush vlvula (V-2) ON, y vlvula de doble columna (V-3) ON.
El sistema de purga de muestra mantiene una muestra en fase
gaseosa y pasa la muestra a travpes del tuving de transporte hacia la
vlvula de muestreo, y a travs del lazo de muestreo.

Horno del Analizador

Paso 2: La vlvula de muestreo es puesta ON para capturar un


volumen preciso demuestra y para permitir al gas de arrastre
(Helio) barrer el lazo de muestreo hacia la primer columna. La
Columna 1 separa C6, y componentes mas pesados (C6+) del resto
de los componentes que constituyen la muestra de gas

Analyzer Oven

Paso 3: La vlvula de muestreo es puesta OFF para purgar la prxima


corriente. La vlvula backflush es puesta OFF reversing the carrier flow
through column 1 so that C6+ components elute first (all combined as a
singlepeak) to the measure detector. Note: by switching the direction of
flowthrough 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, C4s, and C5s 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

Air
Hydrogen
H2
Helium
He
Nitrogen
N2
Argon
A
Carbon Dioxide
CO2
Methane
CH4
Propane
C3H8
Acetylene
C2H2
Benzene
C6H6
Butane
C4H10
Chloroform
CHCL3
Freon 12
CL2CF2
(Dichlorodifluoromethane)
Methanol
CH3OH
Acetone
C3H6O

THERMAL
CONDUCTIVITY AT
ZERO DEGREES C
5.8
39.6
33.6
5.7
3.9
3.4
7.2
3.6
4.5
2.2
3.2
1.6
2.0
3.4
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)


Mole %

= Area(comp x ) / Cal Conc.(Comp x)


= 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 vaporphase 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
Hexanes +
C6+
Propane
C3
Iso-Butane
IC4
N-Butane
NC4
Neo Pentane Neo C5
Iso-Pentane IC5
N Pentane
NC5
Nitrogen
N2
Methane
C1
Carbon dioxide CO2
Ethane
C2
Totals

Standard Heating
Standard Heating
Standard Heating
#1
Value 1
#2
Value 2
#3
Value 3
0.01
0.53
0.03
1.59
0.20
10.58
1.00
25.16
3.00
75.48
7.00
176.13
0.50
16.26
0.10
3.25
0.40
13.01
0.50
16.31
0.10
3.26
0.40
13.05
0.08
3.19
0.00
0.00
0.00
0.00
0.08
3.20
0.30
12.00
0.80
32.01
0.10
4.01
0.30
12.03
0.80
32.07
3.32
0.00
2.00
0.00
1.00
0.00
89.50
904.15
87.67
885.47
77.40
781.74
2.91
0.00
1.50
0.00
1.00
0.00
2.00
35.39
5.00
88.48
11.00
194.66
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
Natural
Gas
Nitrogen
Methane
C02
Ethane
Propane
Iso-Butane
N-Butane
IsoPentane
N-Pentane
C6+
Relative
Density
Gross Dry
BTU

Composition

Pressure
Base @
14.73

Pressure
Base @
14.696

Pressure
Base @
15.023

.6222

.6222

.6223

1053.70

1051.26

1074.73

2.46
89.709
1.001
5.001
.999
.300
.300
.100
.100
.03

Physical Property Calculations-GPA Standards


Constants that are not so constant

Typical
Natural Gas

GPA 2145-96

Rich Gas
Typical US
Gulf Coast

1300 BTU
1078 BTU
Table 4

GPA 21452000 (Jan 1


release)
+0.0138 BTU
+0.0032 BTU

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

Questions and
Answers