Comparison of methods for direct and indirect measurement of hydrocarbon dewpoint

Andrew Brown, Martin Milton & Gergely Vargha National Physical Laboratory, Teddington, UK Richard Mounce & Chris Cowper, EffecTech Ltd, Uttoxeter, UK Andrew Stokes, Mike Bannister & Andy Benton, Michell Instruments, Cambridge, UK Dave Lander & Nick Bates, National Grid, Warwick, UK Andy Ridge, Orbital, Swynnerton, UK

Hydrocarbon dewpoint

Pressure (bar)

ISO 14532:2005 (Natural gas Vocabulary) definition: The temperature above which no condensation of hydrocarbons occurs at a specified pressure.

Hydrocarbon dewpoint curve

100 80 60 40 20 0 -30 -20 -10 0 10 20 30 Temperature (C)
Mixture wholly in gas phase Mixture exists in gas and liquid phases

cricondentherm maximum temperature at which condensation can occur (at any pressure)

Hydrocarbon dewpoint curves may be: Calculated from gas composition using an equation of state Measured directly using a chilled mirror method

Hydrocarbon Joint Industry Project Aims and outline

Aims
To compare the performance of
GC methods: Dewpoint instruments: Process methods: process v laboratory manual v automatic process GC v automatic chilled mirror

To produce a definitive dataset for use in future studies and to support ISO standardisation activities

Outline
Five synthetic natural gas mixtures Seven real natural gases

Collaborative project, but all analyses carried out with no prior knowledge of other results

Measurement techniques: Gas chromatography

GC analysis

Component % mol/mol Helium 0.032 Hydrogen 0.008 Oxygen 0.027 Nitrogen 6.112 Carbon dioxide 0.057 Methane 83.507 Ethane 5.760 Propane 2.399 i-Butane 0.486 n-Butane 0.891 neo-Pentane 0.009 i-Pentane 0.282 n-Pentane 0.231 2,2-di-me-C4 0.0085

Component 2,3-di-me-C4 2-me-C5 3-me-C5 n-C6 Benzene cyc-C6 C7 fraction Toluene Me-cyC6 C8 fraction C9 fraction C10 fraction C11 fraction C12 fraction

% mol/mol 0.0121 0.0546 0.0309 0.0327 0.0002 0.0171 0.0339 0.0000 0.0056 0.0022 0.00026 2.6E-06 ND ND

Hydrocarbon dewpoint curve

100 80

Pressure (bar)

60 40 20 0 -30 -20 -10 0 10 20 30 Temperature (C)

Equation of state

Gas samples

Calculated gas composition

Calculated dewcurve

GC systems used:
Lab GC 1 Lab GC 2 Process GC 3 Process GC 4

Danalyser model 500 (up to C5) with HP 4890 GC (C5+) Danalyser model 500 (up to C5) with Varian 3400 GC (C5+) Danalyser model 700 (all species) Orbital all in one system based on Siemens Maxum GC
Calibrated using the same traceable, multi-component, reference gas standards Calibration gas also used to define GC retention times etc.

Use of equations of state

Hydrocarbon dewcurves were calculated using:

RKS (Redlich-Kwong-Soave) LRS (London Research Station; variant of RKS with different functional forms for some constants) 60 PR (Peng Robinson)
RKS

All three EoS are cubic

Pressure (bar)

50

LRS PR

40

30

20

10 -8 -6 -4 -2 0 2

Temperature (C)

Measurement techniques: Chilled mirror (manual and automatic)

Chandler model A-2 manual chilled mirror

Michell Instruments Condumax II automatic chilled mirror

(diameter of visible mirror approx 1 cm)

Dark spot optical principle

Collimated red light focussed on conical depression in optical surface - condensate reduces light intensity in dark spot

3.0 C 2.5 7.5 C 5.0 5.5 C 2.0 6.0 C 4.5 C 6.5 C 7.0 4.0 3.5 C No film visible Slight Film fully mark No film visible No film visible No film visible visible

Manual chilled mirror: Sensitivity

20 15 10 5 0 -5 -10 -15 0 100 200 300 400 500 600

Low 1 - Run 1 Low 1 - Run 2 Low 2 - Run 1 Low 2 - Run 2 Mid 1 - Run 1 Mid 1 - Run 2 Mid 2 - Run 1 Mid 2 - Run 2 High 1 - Run 1 High 1 - Run 2

Mirror temperature (degC)

Sensitivity setting of 275 mV equivalent to manual chilled mirror Adaptive trigger point correction under development.

Sensitivity (mV)

Instrument calibration

Pressure (psig)

Chilled mirror instruments Calibrated thermometers / temperature sensors Instruments validated by measurement of a gravimetric mixture of 10% n-butane in nitrogen

160 150 140 130 120 110 100 90 80 -14

Gravimetric composition Automatic chilled mirror Manual chilled mirror

-12

-10

-8

-6

-4

-2

Temperature (C)

Synthetic mixtures

Five synthetic Primary Reference Gas Mixtures prepared gravimetrically and verified by NPL
Mixtures contained n-isomers up to C10, benzene, toluene and cyclohexane Compositions chosen to encompass the range of hydrocarbon condensation rates found in gas fields around the British Isles
0.10 0.09 0.08
80 100

-3

Condensate / g.m

Pressure (bar)

0.07 0.06 0.05 0.04 0.03 0.02 0.01 0.00 0 1 2 3 4 5

Mid 1 Mid 2 High Low 1 Low 2

60
Mid 1

40

Mid 2 High Low 1 Low 2

20

0 -80 -60 -40 -20 0

Temperature below dewpoint / C

Temperature (C)

Calculated condensation rates

Calculated hydrocarbon dewcurves

Synthetic mixtures: Results (1)

Phase One - Mixture 'Mid 1'

100 80
60 50

Phase One - Mixture 'Mid 1'

Pressure (bar)

Pressure (bar)

60 40 20 0 -60 -50 -40 -30 -20 -10 0

40 30 20 10 -16 -14 -12 -10 -8 -6

Temperature (C)

Temperature (C)

Gravimetric data Lab GC 1 Automatic chilled mirror

Synthetic mixtures: Results (2)

Gravimetric data Lab GC 1 Automatic chilled mirror

Phase One - Mixture 'High'

70 60 60 50

Phase One - Mixture 'Mid 2'

Pressure (bar)

50 40 30 20 -12 -10 -8 -6 -4

Pressure (bar)

40 30 20 10 -12 -10 -8 -6 -4

Temperature (C)

Temperature (C)

Phase One - Mixture 'Low 1'

50 40 50 40

Phase One - Mixture 'Low 2'

Pressure (bar)

30 20 10 0 -10 -8 -6 -4 -2

Pressure (bar)

30 20 10 0 -8 -6 -4 -2 0

Temperature (C)

Temperature (C)

Synthetic mixtures: Results summary

Strong agreement between GC and gravimetric data

Average difference at cricondentherm of 0.3C

Good agreement between automatic chilled mirror and gravimetric data

Average difference at cricondentherm of 1.9C These differences are within the uncertainty of the measurement
The use of a different equation of state can lead to a difference in calculated dewpoint of more than 2C

Automatic chilled mirror results are always lower than the gravimetric data Closer agreement is observed when comparing the automatic chilled mirror data to an calculated dewpoint for 70 mg.m-3 of condensate

Synthetic mixtures: Dewpoint at 70 mg.m-3 of condensate

70 mg.m-3 is an empirical estimate of the amount of condensate required for detection by the automatic chilled mirror
Corresponds approximately to an automatic chilled mirror sensitivity of 275mV 70 mg.m-3 of condensate equivalent to approx 11ppm n-decane
55

Pressure (bar)

45

35

Average difference between the automatic chilled mirror and 70 mg.m-3 of condensate (calculated from gravimetric data) now 0.7C (was 1.9C for theoretical dewpoint)

25

15 -14 -12 -10 -8 -6 -4 -2

Temperature (C)
Low 1 Low 2 Mid 1 Mid 2 High Lines = automatic chilled mirror measurement Circles = calculated T for the formation of 70 mg.m-3 of condensate

Real natural gases: Outline

Seven samples of real natural gas

Sampled (following ISO 10715:2001) into evacuated 50 litre cylinders
5.0
Gas A Gas B Gas C Gas D Gas E Gas F Gas G

Condensate / g.m

-3

4.0

3.0

Calculated hydrocarbon condensation rates: (from GC analysis data)

2.0

1.0

0.0 0 1 2 3 4 5

Temperature below dewpoint / C

Analysis much more challenging than for synthetic mixtures due to the highly complex nature of the gases

Real natural gases: Analysis methods

GC
Lab GC 1 Lab GC 2 Process GC 3 Process GC 4 [Danalyser 500 + HP 4890 GC] [Danalyser 500 + Varian 3400 GC] [Danalyser 700] [Orbital all in one system:- Siemens Maxum GC]

Automatic chilled mirror

Standard sensitivity setting (275mV)

Manual chilled mirror Calculations

All hydrocarbon dewcurves calculated using RKS equation of state Water dewlines calculated using RKS equation of state with interaction parameters, Rij = 0.5.

Real natural gases: Gas A results

Lab GC 1 Lab GC 2 Process GC 3 Process GC 4

Manual chilled mirror Automatic chilled mirror Water dewline

Highest dewpoint; second highest condensation rate

Gas A
100 80

Gas A
70 60

Pressure (bar)

Pressure (bar)
-50 -40 -30 -20 -10 0 10 20

60 40 20 0

50 40 30 20 0 2 4 6 8 10

Temperature (C)

Temperature (C)

Very good agreement between GC methods 1, 2 & 3

Gas A has the highest dewpoint, a high C6 to C7 content and a low C8+ content easy to analyse

Process GC 4 results are lower than lab GCs (but close to manual chilled mirror)
May be due to the automatic allocation of boiling points by the process GC or choice of equation of state (under investigation)

Real natural gases: Gas C results

Lab GC 1 Lab GC 2 Process GC 3 Process GC 4

Manual chilled mirror Automatic chilled mirror Water dewline

Second lowest condensation rate; high aromatic content; highest C8 to C12 content
Gas C
100 80
60 50

Gas C

Pressure (bar)

60 40 20 0 -60 -50 -40 -30 -20 -10 0 10

Pressure (bar)

40 30 20 10 -7 -5 -3 -1 1 3

Temperature (C)

Temperature (C)

Relatively large difference between manual and automatic chilled mirrors

Gas has the longest hydrocarbon tail Difference may be due to sampling issues, or other factors related to the operation of the instrument (cooling rate, sensitivity, etc.)

Close agreement between manual chilled mirror and process GC data

Real natural gases: Discussion (1)

GC methods: process GC v laboratory GC

For six out of seven real gases the measured dewpoints are in the order: Lab GC 1 > Lab GC 2 > Process GCs
Order demonstrates sensitivity of instruments to detect higher hydrocarbons The outstanding has a low hydrocarbon dewpoint measurements in this temperature region are not crucial to legislators

Results for Process GCs show more variability. Due to:

Automated assignment of boiling points by process GC instrument? Sampling issues? Sensitivity to equation of state? Under investigation

Real natural gases: Discussion (2)

Dewpoint instruments: manual chilled mirror v automatic chilled mirror

For all real gases, the measured dewpoints are in the order
Automatic chilled mirror > Manual chilled mirror

Difference in measured dewpoint ranges from 1.7C (Gas E) to 9C (Gas F)

Differences larger than expected

For some gases, closer agreement obtained when using the adaptive trigger method
Replicates retrograde behaviour of calculated dewcurves Method still under development

Automatic chilled mirror adaptive trigger method

Gas B
60 50

Pressure (bar)

An adaptive trigger point correction can be applied to account for variations in the amount of gas in the cell with changing pressure
Standard (275 mV) sensitivity Adaptive trigger method
Gas C
60

40 30 20 10 -15 -13 -11 -9 -7 -5

Temperature (C)

Gas F
65

50

55

Pressure (bar)

40

Pressure (bar)
-7 -5 -3 -1 1 3

45

30 20

35 25

10

15 -30 -28 -26 -24 -22 -20

Temperature (C)

Temperature (C)

Real natural gases: Discussion (3)

Process methods: process GC v automatic chilled mirror

Real gases: Automatic chilled mirror > Process GCs
Difference would be more pronounced if the GC data was used to calculate the dewpoint at 70 mg.m-3 of condensate In complex gas mixtures, GCs may undermeasure, not detect or misidentify higher hydrocarbons and unexpected components Butthe manual chilled mirror measures dewpoints that are lower than those measured by the GCs.

Synthetic mixtures: Process GCs > Automatic chilled mirror

Simple gas mixtures. Measurement by GC relatively is straightforward GC results agree very well with the gravimetric data

Real natural gases: Discussion (4)

Role of synthetic gas mixtures

Essential for the calibration of laboratory and process GCs Role in the calibration of chilled mirror instruments may be limited Calibration using an n-butane in nitrogen standard is straightforward and inexpensive, but the mixture does not form a typical hydrocarbon film

What is the true value of hydrocarbon dewpoint?

What is the true value of hydrocarbon dewpoint?

Methods agree to within a reasonable estimate of their uncertainties None of the methods can be said to definitively measure the true hydrocarbon dewpoint
GCs may not measure trace quantities of higher hydrocarbons, or unexpected components (e.g. heavy oils, glycols, etc.) Chilled mirror instruments are dependent on detection of a liquid film, and other operational and instrumental factors

Reported hydrocarbon dewpoint should be appended with the method used and any assumptions made

Conclusions

Comprehensive study of hydrocarbon dewpoint measurement of synthetic and real natural gases Close agreement for measurement of synthetic natural gases Measurement of real natural gases more difficult. Methods agree to within a reasonable estimate of their uncertainties True value of hydrocarbon dewpoint difficult to define Data from the project available at:
www.npl.co.uk/environment/hydrocarbondewpoint.html

Contributions of project partners

Laboratory gas chromatography Process gas chromatography

Automatic chilled mirror

Manual chilled mirror Process gas chromatography Facilitated collection of real gas samples Owner and operator of Great Britains national gas transmission system Preparation and certification of highaccuracy natural gas standards

What is hydrocarbon dewpoint?

ISO 14532:2005 (Natural gas Vocabulary) definition:

The temperature above which no condensation of hydrocarbons occurs at a specified pressure.

Theoretical dewpoint cannot be measured in practice requires the detection of the first molecule of liquid condensate
Discussions on-going within ISO/TC193/SC1 to redefine as a technical or measurable dewpoint e.g. define the amount of hydrocarbon liquid formed for a given gas at a given temperature and pressure Alternative approach would be to define a technique-specific correction factor and include suspected error in the uncertainty budget

Hydrocarbon dewpoint often not well defined in legislation

Term should be appended with, e.g. the method of determination or a maximum permissible error