Underpinning green energy: Traceable

reference standards and methods for the

measurement of total silicon in biogas
L. Culleton, A. Murugan
Gas and Particle Metrology Group, National Physical Laboratory (NPL), Teddington, UK
lucy.culleton@npl.co.uk

Introduction
Siloxane impurities within biogas can cause extensive damage to gas processing equipment if not removed effectively. A European specification is being
developed that will impose a maximum limit value on the total silicon content of biogas in order for it to be safely utilised [1, 2]. This requirement for accurate
measurements of total silicon at low amount fractions has driven advances in measurement methods as part of a European project [3].

Preparation
High accuracy, traceable gas
reference standards containing
L2, L3, D4, and D5 siloxanes
were prepared gravimetrically
through the use of transfer
vessels. The addition process
has been refined over five years
of research at NPL.

Name

ID

Molecular
Weight (g/mol)

Hexamethyldisiloxane

L2

162.4

Octamethyltrisiloxane

L3

236.5

Octamethylcyclotetrasiloxane

D4

296.6

Decamethylcyclopentasiloxane

D5

370.8

Stability
An internal standard of n-octane was added to a ppb-level siloxane mixture to
assess the stability of the individual components. The L3 component was found to
be the least stable in cylinders, with a relative amount fraction decrease of up to
70% measured after a period of 6 months.

Figure 1: Pure siloxane injected into transfer vessel

Figure 2: High accuracy weighing

Validation

Graph 1: Graph depicting the relative stability of ppb-level L2 , L3 , D4 and D5 siloxanes in a biogas matrix within a gas cylinder

6
3

28Si

The mixtures are validated using gas

chromatography with flame ionisation
detection and mass spectrometry (GCFID/MS), with k=2 uncertainties ranging
from 1-8% relative. Higher uncertainties
are typically associated with heavier
molecules and lower amount fractions.

92.223%

29Si

4.685%

30Si

3.092%

Figures 3 & 4: Capillary column GC and FID

chromatogram of L2, L3, D4 and D5 siloxanes

Total silicon method

NPL is developing a novel technique that will accurately measure the total silicon
content of a biogas sample at ppb-level amount fractions.

Figure 5: GC-ICP-MS
instrumentation and
siloxane gas standards

Figure 6: Relative abundances of silicon isotopes are used to measure total silicon after the
siloxanes are back flushed into the ICP-MS detector

Acknowledgements

Research funding provided by the European Metrology Research Programme and the
UK Government National Measurement Offices Chemistry and Biology Knowledge Base
Programme.

References

www.npl.co.uk

[1] prEN 16723-1 Natural gas and biomethane for use in transport and biomethane for injection in the natural gas
network Part 1: Specifications for biomethane for injection in the natural gas network, Draft after CD ballot, 2015
[2] prEN 16723-2 -- Natural gas and biomethane for use in transport and biomethane for injection in the natural gas
network Part 2: Automotive fuel specifications, Draft after CD ballot, 2015
[3] EMRP Metrology for Biogas project http://projects.npl.co.uk/metrology-for-biogas/

NPL Management Limited, 2016. 11659/0516

This is achieved
through use of a Gas
Chromatograph coupled
to an Inductively Coupled
Plasma Mass Spectrometer
(GC-ICP-MS). The lighter
biogas molecules are
removed with a GC
backflush mechanism,
allowing the siloxanes to
enter the ICP-MS as a single
packet.