International Point of View on Natural Gas, Liquefied Natural Gas and Liquefied Petroleum Gas Adriaan M.H

International point of view on Natural Gas, Liquefied Natural Gas and Liquefied Petroleum Gas Adriaan M.H. van der Veen, G. Nieuwenkamp, E.T. Zalewska, A. Baldan International Awareness Forum on Environment, Energy and Public Health Santiago de Querétaro, Qro. Mexico, 11 October 2018 Metrology for LNG

. Economic way of transporting natural gas . Composition as for natural gas, without − Helium − Carbon dioxide

− C6+ hydrocarbons . Temperature -161 °C . Pressure up to 4 bar

11-10-2018 NIST-OAS Forum 2 Flow rate measurement: primary standard

. Reference: gravimetry . Up to 25 m3/h Partly undefined direction of flow . Up to 5 bar during switch over

. Uncertainty 0.08 % Supplying tank (for MUT 0.12 %) Weighing tank Fixed connection causing non- constant forces on scale

Uncertainty in mass Pump Reference for collected between Flow meter to be calibrated calibrations MUT and Reference

11-10-2018 NIST-OAS Forum 3 Calibration and testing facility

Designing, building and validating a mid-scale LNG mass and volume flow calibration facility

11-10-2018 NIST-OAS Forum 4 Composition standard Aims: . Produce an accurate, lab-based sampling and analysis reference method to test and calibrate commercially available sampling/ composition measurement systems . Develop methods to sample and vaporize LNG in a representative and homogeneous fashion . Validate Raman spectroscopy methods for composition analysis and compare the results obtained to those from GC methods . Study the effects of long-term storage on LNG composition

11-10-2018 NIST-OAS Forum 5 Application of the LNG sampling and composition measurement reference standard

Reference Sampler &Vaporizer LNG based calibration gases

LNG loop Measurement 1 (Reference)

Measurement 2 (Result)

Service

Commercial Quantity (unit) Quantity Sampler &Vaporizer

Reference Result 11-10-2018 Presentation at GAS2017, 13-15 JuneNIST-2017,OAS ForumWTC Rotterdam 6 LNG Density

. Conversion between mass and volume . Specifications (RU Bochum) − T-range: 90 K to 300 K − p-range: 0.05 MPa to 12 MPa − Homogeneous + saturated liquid (incl. vapor pressure), hom. gas − Δρ/ρ < 0.05 % (incl. mix. unc.)

11-10-2018 NIST-OAS Forum 7 Natural gas substitutes: refinery, synthesis and coke oven gas

. Growing demand of new energy sources Syngas Biosyngas Refinery gas Coke oven gas − flexibility of refining process causes varying composition of refinery gas Hydrogen − alternative methods producing synthesis gas or biosyngas Carbon dioxide . For fiscal purposes and to provide compliance

to carbon emissions required by the European Carbon monoxide Emissions Trading Scheme.

. Challenging and maybe not perfect but worth Nitrogen to improve cost-effectiveness of the measurement Methane

0 10 20 30 40 50 60 70 80 . Development of a universal analytical method amount of substance fraction (%) for refinery and synthesis gas-type mixtures . Preparation of a suite of primary standard gas mixtures

11-10-2018 NIST-OAS Forum 8 Experimental

FID1 A, Front Signal (2012\20120914\120914 2012-09-14 11-29-07\005F0502.D) TCD2 B, Back Signal (2012\20120914\120914 2012-09-14 11-29-07\005F0502.D) TCD3 C, Aux Signal (2012\20120914\120914 2012-09-14 11-29-07\005F0502.D) pA . Agilent 7890A Series GC CH4 250 . Four micro packed GC columns, two capillary 200 columns, three six port rotary valves, two ten port rotary valves, a split/splitless inlet, a flame 150

ionization detector (FID) and two thermal 100

50 conductivity detectors (TCD). CO

. Equipped with three channels: 0

1. Aluminiumoxide plot ‘S’ column 25 m × 0.32mm × 8mm; FID, higher 5.2 5.4 5.6 5.8 6 6.2 min FID1 A, Front Signal (2012\20120914\120914 2012-09-14 11-29-07\012F1206.D) hydrocarbons. TCD2 B, Back Signal (2012\20120914\120914 2012-09-14 11-29-07\012F1206.D) TCD3 C, Aux Signal (2012\20120914\120914 2012-09-14 11-29-07\012F1206.D) pA 2. HayeSep Q (80/100 mesh) 0.25 m × 1/16'‘column (trapped higher

hydrocarbons) + Hayesep N (80/100 mesh) 1 m × 1/16'' column 2000 H2

(CO2, C2H6, C2H4,H2S) + Molsieve 13X, 2 m × 1/16'' column,

1500 CO2 TCD (O2, N2, CH4, CO).

3. Combined HayeSepQ/Molsieve 5A column (1 m/2 m, 1/16'') TCD, 1000 N2

N carrier gas (He, H ). 500 CO

2 2 C2H4

CH4

CH4 C2H6 0 iso-Buteen

-500

-1000

1 2 3 4 5 6 min

11-10-2018 NIST-OAS Forum 9 Results (full ranges)

. Calibration function 2nd order polynomial . Uncertainties similar as for CCQM-K77 . Combination of high fraction methane and low fraction carbon monoxide problematic . For most compositions, method performs sufficiently well and is a low(er)-cost alternative to dedicated methods

calibration range [%] Sr CMC component model low high low high low high Hydrogen parabola 5 46 0.06 0.01 0.08% 0.03% Methane parabola 1 40 0.2 0.09 0.20% 0.12% Nitrogen parabola 2 71 0.25 0.04 0.31% 0.04% Carbon monoxide parabola 1 70 2.1 0.03 1.73% 0.04% Carbon monoxide parabola 2.5 70 0.32 0.03 0.35% 0.04% Carbon dioxide parabola 0.2 37 0.19 0.07 0.24% 0.10% Ethene parabola 2 16 0.07 0.06 0.10% 0.07% Ethane parabola 0.2 20 0.09 0.04 0.28% 0.05%

11-10-2018 NIST-OAS Forum 10 Liquefied petroleum gas

. Reference standards: − Gravimetric preparation, largely based on ISO 6142-1 − Verification done using ISO 6143, ISO 6974 − Challenge to keep the entire mixture in one phase (liquid, vapour) . At the brink of gas metrology and petroleum chemistry . One key comparison organized (CCQM-K119) − Most results agreed within ± 1 % − Expanded uncertainty typically 1 % or larger

11-10-2018 NIST-OAS Forum 11 Hydrogen-enriched natural gas

. Development of a suite of reference gas mixtures for hydrogen in natural gas (3% - 20%) . Validation of the extension of the scope of ISO 6974 for this application . Expanded uncertainty in the order of 0.12 % on the natural gas analyser, 0.20 % on the refinery gas analyser . Results published in Int. J. Hydrogen Energy 40(46) (2015), pp. 15877-15884

11-10-2018 NIST-OAS Forum 12 European Metrology Network (EMN) for Energy Gases . European knowledge and metrological service centre for energy gases . Facilitate energy transition, with focus on metering of energy gases . Conventional fluids and fluids related to (emerging) renewable/ sustainable energy sources . Cross-cutting character: gas analysis, flow, humidity, pressure, density, material data and testing . Under EURAMET

11-10-2018 NIST-OAS Forum 13 Questions?