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Crude Oil and NIRS Analysis

With the scarcity of crude oil supplies these days which reflects itself as the sharp increase in gas prices, it is increasingly important to do better quality control on the existing crude oil supplies. The composition of crude oil varies with natural origin, transport and storage conditions (Reference 1). Physio-chemical properties of crude which are of importance are specific gravity (also called API gravity), true boiling point curve and viscosity (Reference 1). API gravity is short for American Petroleum Institute gravity which is an inverse measure the weight of petroleum liquids in comparison to water. If a liquid has API gravity of more than 10, it will be considered as a light oil that floats on water.

 Analytical methods of quality control for crude oil are very time consuming, expensive and require sample preparation. Near IR Spectroscopy (NIRS) is a rapid, inexpensive method that does not require any sample preparation and can be used for in-situ measurements of crude oil’s physio-chemical properties onsite. Bonds such as CH, NH and SH are target absorption bonds which NIRS can identify. Figure 1 shows the NIRS spectrum of crude oil in a wide range. Allied Scientific Pro offers T1 and T11 portable near IR spectrometers with cuvette which can measure part of the NIR spectrum as shown in figure 1.


Figure 1: NIRS spectrum of crude oil. The blue and red boxes show spectral ranges of Allied Scientific Pro’s spectrometers T1 and T11.

For more information about these transmittance spectrometers, please refer to https://www.alliedscientificpro.com/nirvascan

The sulfur content of the crude oil is also quite important to quantify because downstream processes such as catalytic cracking and refining are affected adversely by high sulfur content. Catalytic cracking is an important process in the oil industry where petroleum vapour passes through a low-density bed of catalyst, which causes the heavier fractions to crack and causing lighter and more values products to be produced. The sulfhydryl group represented by the SH bond shown in figure 2 can be detected by a Near IR spectrometer at 1750 nm.



Figure 2: Sulfhydryl group (SH bond) can be detected using the T11 spectrometer at 1750 

Partial Least Square modelling was used in a study to model 153 crude oil samples (Reference 1). First derivative and Savitzky Golay (SG) filter were applied to the collected and prediction were made on 30 spectra in a testing set which were subjected to first derivative and the same SG filter. The API range for the samples were 20-43° and the sulfur content was 0.3-3.8%. nm. The PLS regression model had an accuracy of 2.73%  for API gravity and 4.46% for sulfur content which are reasonable accuracies. 

In another study that was conducted at Allied Scientific Pro, several samples of crude oil were supplied for testing with the T1 spectrometer which has a range between 900-1700 nm. The samples were all sealed and apparently had varying viscosity. Because the crude oil samples are generally very viscos and have dark colors a nominal 1 cm cuvette for a transmittance spectrometer is not suitable to measure their transmission. For this reason,  a 1 mm thick cuvette was  provided. Figure 3 shows the crude oil sample in a 1 mm thick cuvette.


Figure 3: Crude oil sample in a 1 mm thick cuvette

The cuvette was placed in the transmittance spectrometer as shown in figure 2 and the transmission of it over the range 900-1700 was measured.


Figure 4: 1 mm cuvette filled with crude oil was placed inside the cuvette holder of T1 spectrometer


Several samples were tested and their absorption plot is shown in figure 5.



Figure 5: The absorption plots of crude oil samples

Although this was just a qualitative study and no PLS modelling were performed on these samples, it was noticed that the more viscous samples had a sharp rise in absorption at the short wavelength region of the absorption plot. The viscous nature of the samples was assessed visually while pouring the samples inside the cuvette based on the residual adhesion of the samples to the cuvette once the samples were removed.

In conclusion, hand-held NIR spectrometers are ideal devices for field testing of crude oil products and can provide information on physio-chemical properties of crude oil. Allied Scientific Pro also offers the Nirvacloud platform where the users can upload their spectral profiles, do pre-processing and create Partial Least Square (PLS) models to quantify ingredients in their crude oil samples. For more information, refer to the following link:  https://nirvacloud.ai/

References:

    1-  Rapid crude oil analysis using near-infrared reflectance spectroscopy, J     Long et.al, Petrolium science and technology, vol 37, no 3, 2019.

    2-  Sulfur content. The science of Victorian brown coal, science direct 1991.


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