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Declining European natural gas resources and increasing legislation mean that diversification towards ‘non-conventional gases’ is essential. Accurate and traceable measurements of the composition of non- conventional gases are required to ensure gases can be transported in existing pipeline networks, and used with existing appliances. The EMRP ‘Characterisation of energy gases’ project is successfully developing a metrology infrastructure to underpin these measurements. New standards and methods have been developed for biogas composition, biogas impurities, coal mine gases, refinery gases and environmentally-friendly odorants. The project is set to conclude in 2013 with the challenging analysis of a series of real non-conventional gas samples.
Comparison of traceable methods for determining the calorific value of non-conventional fuel gases
(2016)
Energy-content measurements by direct methods (such as calorimetry) are used to validate the indirect method (from gas composition obtained by gas chromatography) which is generally adopted by grid operators for on-site gas control. A primary reference gas calorimeter and three field calorimeters were used for the first time to measure accurately the energy content of non-conventional gases (biogas and coal mine methane). The gas mixtures for this study were prepared by gravimetry and comprised three binary mixtures containing carbon dioxide and (up to 80 mol-%) methane, three ternary mixtures containing carbon dioxide, (up to 70 mol-%) methane and (up to 0.3 mol-%) hydrogen sulphide as well as a ten-component mixture with a methane content of approximately 64 mol-% which represents a typical coal mine methane. Associated uncertainty calculations were developed for each instrument and are presented here. Traceability of the measurements to the SI units is ensured in reference calorimetry, as calibration is accomplished by electrical simulation based on the Joule effect in order to obtain the heat capacity of the entire system. The results obtained with the four calorimeters are compared with each other and also with results calculated from the indirect method that is based on gas chromatography. Uncertainties (k = 2) between 0.07 and 0.49% for the reference gases were obtained with the reference calorimeter, while uncertainties for the field calorimeters range between 0.18 and 2.48% for the same mixtures. Compared to the usual standard deviation observed by gas chromatography for a multicomponent gas mixture of about 1%, it is demonstrated that the calorimetric method, although rarely used for non-conventional gases before, is appropriate for energy-content measurements of gases originating from renewable energy sources.
Analysis of natural gas by gas chromatography Reduction of correlated uncertainties by normalisation
(2004)
The results of gas chromatographic analysis of natural gas mixtures reveal strong correlations (Pearson correlation coefficient of >0.96) between the uncertainty of each component and variations in the ambient pressure. Although correction for ambient pressure variations can reduce this variability, normalisation of the results of each analysis using the assumption that the sum of all component amount fractions is unity provides significantly greater reductions in the uncertainty of each measured component. We show that the uncertainty in normalised components can be estimated approximately using the correlation coefficient as a measure of the correlation present in the measurements, or exactly using a full calculation of the variance/covariance (V/C) structure of the data.