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TWO critical measurements ONE push of a button ZERO hassle
INTRODUCTION
With the high volatility in crude prices leading to uncertainty in budgets, refi ners are seeking new, innovative ways to respond to the industry’s dynamic landscape. Refi neries are facing many new challenges, including complying with new regulations, protecting against chlorine-induced corrosion, and the costs associated with both.
• Globally, adoption of regulations like Euro VI and Tier 3 continue to lower the required sulfur level in automotive fuels. With these changes come challenges, and it is more important than ever to seek out the most precise and reliable solution to produce the best data.
• Refi nery corrosion is a critical and very expensive problem. Leading refi ners have found that by lowering the chloride content of desalted crude oil and process streams, they can signifi cantly extend time between turnarounds, lower the costs of corrosion, and decrease related safety hazards. In order to do so, they must implement a process to monitor chlorine levels.
What if you could get two critical measurements with one push of a button and zero hassle?
INTRODUCING SINDIE +CL
Sindie +Cl delivers both sulfur and chlorine trace analysis with one push of a button and zero hassle. Samples are measured directly, which means it can analyze even the heaviest of hydrocarbons, like crude oil or coker residuals, without the hassle of boats, injectors, furnaces, or changing detectors. Sindie +Cl utilizes a technique known as Monochromatic Wavelength Dispersive X-ray Fluorescence (MWDXRF) delivering exceptional reproducibility.
Method Compliance
• ASTM D2622, D7039, D7536 • ISO 20884 • SH / T 0842
APPLICATION STUDY 1. Certifying Sulfur in Automotive Fuels
MWDXRF has long been in the petroleum industry for certifi cation of sulfur levels in diesel and gasoline blends. To study the performance of Sindie +Cl, ten repeat measurements were performed on commercially-available diesel and gasoline standards with 10 ppm and 9 ppm sulfur respectively. Ten separate aliquots of each of the diesel and gasoline samples were measured for fi ve minutes each using ASTM D7039 methodology. The result of ten measurements on a 10 ppm sulfur in diesel standard was an average value of 9.59 ppm sulfur, with a standard deviation of 0.44 ppm, and a relative standard deviation (RSD) of 4.62%. The results of the ten measurements on the 9 ppm sulfur in gasoline standard was an average of 8.62 ppm, 0.41 ppm standard deviation, and 4.71% RSD. Additionally, as outlined in the ASTM D7039 method, if the repeats are paired (i.e. 1 and 2, 3 and 4, etc.), each paired repeat is within the method’s repeatability standard. The measurement data for this study can be seen in Table 1.
Table 3: Effect of Sulfur Correction on Coker Residual Chlorine Sulfur Correction Off
Chlorine (ppm) 1.25
Sulfur (wt%) 1.91
Sulfur Correction On
Chlorine (ppm) 1.7
Sulfur (wt%) 1.91
2. Chlorine Monitoring for Corrosion Mitigation
In an effort to mitigate the multi-billion dollar costs of corrosion in global refi neries, the regular monitoring of chlorine in desalted crude oil is becoming more critical. To assess the performance of Sindie +Cl for this application, ten repeat measurements were performed on a commercially available 10 ppm chlorine in crude oil standard. The sulfur content of this standard was unknown. Ten separate aliquots of the crude oil were measured simultaneously for chlorine and sulfur using a fi ve-minute measurement time. A modifi ed D7536 procedure was used for chlorine measurements, which included a 0-500 ppm chlorine in mineral oil calibration for the measurement of crude oil. Results of the ten chlorine measurements averaged 10.13 ppm chlorine, with a standard deviation of 0.30 ppm, and a 2.95% RSD. Despite the modifi ed chlorine procedure, if the repeats are paired (i.e. 1 and 2, 3 and 4, etc.), each paired repeat is within D7536 repeatability. For the sulfur values, results averaged 443.33 ppm, with a standard deviation of 1.42
ppm, and an RSD of 0.32%. Paired repeat measurements exhibit precision within ASTM D2622 repeatability. The measurement data for this study can be seen in Table 2.
3. Automatic Sulfur Correction
Many heavy samples, like crude oil, VGO or coker residual, may have percent-level sulfur present while chlorine may be as low as a few parts per million. High sulfur levels will typically depress the chlorine measurement result during XRF analysis. Sindie +Cl is able to measure the sulfur and chlorine concentrations simultaneously and then automatically correct the chlorine measurement. To illustrate this issue, a coker residual sample was fi rst analyzed for chlorine and sulfur with the automatic sulfur correction disabled, and then the sample was reanalyzed with the automatic sulfur correction enabled to demonstrate this capability. This comparison can be seen in Table 3, where the use of automatic sulfur correction will assist in the prevention of reporting falsely low measurement results.
Repeats 1 2 3 4 5 6 7 8 9
10 Average
Standard Deviation
%RSD
Table 1: Trace Sulfur (ppm) in Fuels Diesel Results 9.59 9.49 9.53 9.26 9.75 9.00 9.82 9.03
10.49 9.89 9.59
0.443 4.62
Gasoline Results 8.88 8.15 7.79 8.64 8.51 8.86 8.48 9.17 8.83 8.88 8.62
0.405 4.71
Table 2: Chlorine & Sulfur (ppm) in Crude Oil Chlorine Results 10.09 10.56 9.83 9.97
Repeats 1 2 3 4 5 6 7 8 9
10 Average
Standard Deviation
%RSD
10.26 10.63 10.20 9.94
10.17 9.69
10.13 0.299 2.95
Sulfur Results 441.91 443.63 442.06 441.07 443.75 445.93 442.72 444.09 443.62 444.48 443.33
1.419 0.32
CONCLUSION
The results of this application study demonstrate that Sindie +Cl is an ideal solution for multiple applications where precision, ease-of-use, and fl exibility is needed. Get Sindie +Cl to certify low sulfur level fuels for regulatory purposes, and monitor chlorine in desalted crudes and other process streams to identify potential sources of corrosion.
Sindie +Cl delivers two critical measurements with one push of a button and zero hassle.
To learn more about Sindie +Cl, please visit
XOS.COM/SINDIEplusCL ANNUAL BUYERS GUIDE 2017 •
WWW.PETRO-ONLINE.COM
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