Laser-Driven Calorimetry and Chemometric Quantification of Standard Reference Material Diesel/Biodiesel Fuel Blends

Werickson Fortunato de Carvalho Rocha; Cary Presser; Shannon Bernier; Ashot Nazarian; David A Sheen

doi:10.1016/j.fuel.2020.118720

Laser-Driven Calorimetry and Chemometric Quantification of Standard Reference Material Diesel/Biodiesel Fuel Blends

Fuel (Lond). 2020:281:10.1016/j.fuel.2020.118720. doi: 10.1016/j.fuel.2020.118720.

Authors

Werickson Fortunato de Carvalho Rocha¹, Cary Presser², Shannon Bernier³, Ashot Nazarian⁴, David A Sheen²

Affiliations

¹ NIST Associate, National Institute of Metrology, Quality and Technology (Inmetro), 25250-020 Duque de Caxias, RJ, Brazil.
² Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.
³ NIST SURF Student, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.
⁴ NIST Associate, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA.

Abstract

Requirements for blends of drop-in petroleum/bio-derived fuels with specific thermophysical and thermochemical properties highlights the need for chemometric models that can predict these properties. Multivariate calibration methods were evaluated using the measured thermograms (i.e., change in temperature with time) of 11 diesel/biodiesel fuel blends (including four repeated runs for each fuel blend). Two National Institute of Standards and Technology Standard Reference Material^® (SRM^®) pure fuels were blended by serial dilution to produce fuels having diesel/biodiesel volumetric fractions between (0 to 100) %. The fuels were evaluated for the prepared fuel-blend volume fraction and total specific energy release (heating value), using a laser-driven calorimetry technique, termed 'laser-driven thermal reactor'. The experimental apparatus consists of a copper sphere-shaped reactor (mounted at the center of a stainless-steel chamber) that is heated by a high-power continuous wave Nd:YAG laser. Prior to heating by the laser, liquid sample is injected onto a copper pan substrate that rests near the center of the reactor and is in contact with a fine-wire thermocouple. A second thermocouple is in contact with the sphere-reactor inner surface. The thermograms are then used to evaluate for the thermochemical characteristic of interest. Partial least squares (PLS) and support vector machine (SVM) models were constructed and evaluated for SRM-fuel-blend quantification, and determination of prepared fuel-blend volume fraction and heating value. Quantification of the fuel-blend thermograms by the SVM method was found to better correlate with the experimental results than PLS. The combination of laser-driven calorimetry and multivariate calibration methods has demonstrated the potential application of using thermograms for fuels quantification and analysis of fuel-blend properties.

Keywords: Chemometric analysis; chemometric quantification; diesel fuel blends; laser-driven calorimetry; multivariate calibration methods; standard reference materials.

Grants and funding

9999-NIST/ImNIST/Intramural NIST DOC/United States