Online Feature: Raman spectroscopy: The new standard in oil, gas and petrochemical laboratories
AUTHOR: Brian Marquardt, MarqMetrix, Seattle, Washington
Most large refineries, petrochemical plants and storage terminal complexes have an internal testing laboratory to manage the analysis of crude oil, distillates, petroleum feedstock, fuel additives and refined products. If this option is not available, operators can send samples to external, third-party labs for on-demand analysis. The analytical data is critical for operators to make informed decisions regarding product quality, infrastructure protection, regulatory compliance and other key factors that ultimately impact profitability.
To conduct tests, laboratories rely on various analytical tools and testing methodologies such as chromatography (gas, liquid, ion), spectroscopy (UV/Vis, FTIR), scanning electron microscopy, calorimetry, titration and other established techniques.
Many laboratories are counting solid-state Raman spectroscopy as an essential analytical tool to determine the composition and concentration of components in refined petroleum fuels, aromatics, petrochemicals, liquid petroleum gas (LPG), natural gas, lubricants, additives, feedstocks, intermediaries and other related hydrocarbon products.
Raman spectroscopy. Raman spectroscopy is a laser-based optical analysis technique used to measure composition through the vibrational properties of molecules. Samples are collected using a 785-nm excitation laser and a contact probe that produces a unique spectral fingerprint that identifies the chemical composition and molecular structure of an oil or gas. The distribution of the spectral peaks describes the molecule’s composition, while the signal intensity correlates linearly with concentration.
Since its discovery in the 1920s, Raman spectroscopy has revolutionized process analysis with its nondestructive mode of operation and capability to measure sample composition. However, the broader adoption of this technique is the result of advancements in the stability and portability of solid-state Raman systems and technological improvements in lasers, optics and detectors that have made the technique faster and more accessible.
Raman spectroscopy is a well-established technique that compliments everything else in the testing lab. Although its use in oil and gas analysis is relatively new, it has already proven to be a highly accurate, efficient and usable compositional measurement tool.
One promising application example for Raman in internal labs is to speed custody transfer at refineries, storage facilities, storage tanks and pipelines. Octane tests such as research octane number (RON) or motor octane number (MON) measure gasoline characteristics related to engine knocking. RON is determined by utilizing test methods specified by ASTM D2699 and MON as specified by ASTM D2700. To derive the octane rating, both tests involve increasing the compression ratio of a single cylinder, four-stroke cycle engine until it starts to knock.
However, fuel engine test can take several hours, delaying custody transfer. Although Raman testing does not replace fuel engine testing, ASTM D8340 establishes an approach to ensure a degree of confidence in analyzer predicted values in relation to the primary fuel engine testing. ASTM D8340 further stipulates that gasoline can be released based on those values.
With Raman testing, one lab technician can run multiple analysis in seconds, including octane, vapor pressure and API gravity. These values can be derived on a single instrument without requiring a dedicated specialist in the testing methodology. For example, at an eight-bay refinery rack, the tanker trucks often must wait while the lab runs a 2 hr–3 hr octane test to certify the RON and MON before loading can commence. With a quick scan using a Raman analyzer, the gasoline could be released while the fuel engine testing is finalized, the product certified and the documentation filled out.
The same would apply to other transactions as gasoline is loaded onto barges and ships, offloaded into shore tanks or distributed through pipelines.
Solid-state Raman. Today’s solid-state Raman systems have very few moving parts and are ideal for continuous process monitoring and routine lab analysis. As a result, these systems can be placed at any point of measurement including inline, at-line or offline.
A proprietary Raman systema has been created to produce identical and repeatable results from unit to unit, in a package 80% smaller than previous Raman instruments. Each device is nearly an exact copy, so common mathematical models can be applied across systems to produce consistent results.
The system works with a wide array of contact probes suitable for oil and gas applications that can be changed in seconds, without the need for recalibration. The immersion optic ball lens probes—that are widely used throughout the industry—enable users to achieve reproducible measurements of samples better than 1% accuracy.
The proprietary Raman systema can be used on any components that require Raman analysis, which provides labs with tremendous flexibility in what is measured and how it is operated.
Although the proprietary Raman system’sa equipment can be used to identify the components within approximately 15 min of unboxing, quantifying the concentrations of each component first requires creating a predictive model. For general laboratory use, the system’s manufacturer offers a library of pre-developed models that covers most common applications.
For refined fuels, for example, the system’s manufacturing company has built models for jet fuel, gasoline and diesel that come with the unit. The models are expanded to include additional properties and values, as needed.
Takeaway. Accurate measurement is more essential than ever in the oil and gas industry. Understanding the chemical composition of raw materials and the consistency of processed products is key to manage processes, reduce risks, and maximize outcomes.
With the advancements in applying Raman spectroscopy systems to sample measurements, laboratories now have a reliable and economical tool that produces accurate, fast results and complements existing testing methodologies.
a MarqMetrix’s All-in-One
Brian Marquardt, Ph.D, is the Founder and CEO of Seattle, Washington based MarqMetrix, founded in 2012 at the University of Washington, the company specializes in compositional analysis utilizing Raman spectroscopy and has pioneered advancements in Raman for use in process analysis.