Portable Analytical Instrumentation for Instantaneous Real-Time Measurement of Chemical Elements in Raw Petroleum and Refinery Products
We have successfully completed Phases I, II and IIB of research and development effort that resulted in the development of an advanced prototype based on laser induced breakdown spectroscopy (LIBS) technology for the analysis of liquid samples. The experiments with the crude oils resulted in a scientific paper and a patent. The flexibility of the apparatus allows for the analysis of both oils and aqueous solutions. The LIBS analyzer requires about 750 µl of liquid sample, 1 liter of N2 gas, and 10 s of the analysis time to record 100 spectra. The limits of detection are as low as 0.01–0.04 ppm for Li, Mg, and Cu. They increase for the difficult elements, such as Pb and Hg (7-10 ppm), Cl (250 ppm), and S (~0.7%). The relative standard deviation of measuring 100 ppm vanadium in both oil and aqueous solution was 1.5%. The LIBS detection limits and repeatability are better than that required for the analysis of lubricating oils by ICP-OES according to the standard method ASTM D5185. Several petroleum samples were analyzed by LIBS and the quantitative results for V, Ni, and Fe showed a good agreement with the ICP-OES data. Light crude oils can be analyzed directly but medium crude oils require at least a dilution in 1:1 ratio, otherwise errors of determination become large. Presumably, utilization of the internal standard and chemometrics can be useful to correct for the matrix effects. LIBS offer instantaneous real-time measurements of a multitude of chemical elements and their ratios, such as H/C and O/C, at atmospheric pressure. In addition to the trace element analysis, LIBS can also be used to quantify the major constituents without dilution. One such application was the direct analysis of brine for the quantification of B, Mg, Ca, Li, Na and K. The concentration of the elements ranged from a few hundred ppm to 10 wt% and is not possible to analyze with ICP-OES unless diluted to at least 1:100 ratio. The advance prototype was developed in close collaboration with a geothermal solutions company who specializes in the extraction of Li from brine. The main goal for this entire project was the development of a multi-purpose compact LIBS instrument capable of instantly analyzing both solid and liquid samples of any viscosity. This instrument is intended as a cost-effective tool for general test analysis at petroleum refineries. A single LIBS instrument can rapidly analyze any materials such as crude oils, LPG, gasoline, naphtha, intermediate products, residues, used motor oils, lubricants, asphaltenes, catalysts, petrochemical products, shale rocks, and various deposits inside the refinery lines. Eventually, LIBS can be used for real-time continuous monitoring of the refining processes and can be moved around the factory and pipelines for the expedient use at various locations of need, including exploration fields. Presently, the multi-element analysis is performed by inductively coupled plasma–optical emission spectrometry (ICP-OES) operating in the vacuum ultraviolet spectral region and providing detection limits for Cl and Br of approximately 200 ppm, and sub-ppm for metals. However, ICP-OES requires acid digestion of samples, an evacuated spectrometer with a pump, a flow of high-purity argon, quartz/glassware, and other costly consumables. For digestion of high-silica catalysts, HF acid is necessary that is very dangerous and requires personnel training, drills, and emergency procedures. Hazardous chemical waste must be disposed after the ICP measurement. Lengthy sample handling, high power consumption (~3 kW) and large equipment sizes impede the use of ICP-OES for rapid measurement of species in fuel sources, especially on the floor of industrial premises. LIBS enable rapid chemical analysis and requires no or minimum sample preparation and consumables. It generates no waste in the case of solid analysis and significantly less waste in liquid analysis compared to ICP-OES. The speed of LIBS analysis cannot be matched by any other available technology. The instrument is especially valuable to those applications where field deployment or in-situ analysis is necessary such as in refineries and mining industries.
- Research Organization:
- Applied Spectra, Inc
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- SC0015804
- OSTI ID:
- 1835655
- Type / Phase:
- SBIR (Phase IIB)
- Report Number(s):
- DOE-ASI-15804
- Country of Publication:
- United States
- Language:
- English
Similar Records
Rapid Analysis of Inorganic Species in Herbaceous Materials Using Laser-Induced Breakdown Spectroscopy [plus supplemental information]
Utilizing rare earth elements as tracers in high TDS reservoir brines in CCS applications