Contents. Purpose. 1.Measurement Condition. 2.Sample. 3.Standard Requirement. 4.Contents of evaluation. 5.Result. 6.Conclusion. 7.Notices.

Transcription

1 ASTM D4294 :Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry ISO8754 :Petroleum products Determination of sulfur content Energy-dispersive X-ray fluorescence spectrometry Compliance check by EDX-7000 SHIMADZU Corp.

2 Contents Purpose 1.Measurement Condition 2.Sample 3.Standard Requirement 4.Contents of evaluation 5.Result 6.Conclusion 7.Notices Appendix

3 Purpose Verify and confirm that the EDX-7000 meets the requirements of ASTM D Verify and confirm that the EDX-7000 meets the requirements of ISO8754

4 1.Measurement Condition Instrument: EDX-7000 Factor Required Standard Requirement (ASTM D4249 ISO8754) Actual Condition Temperature Not specified. Room Temperature (25 ) Humidity Not specified. Normal ambient condition (50%) Changing Air Presser Warming-up Time Film Atmosphere Counting Time Not specified. ASTM: Not specified. ISO: Shall be continuously switched on. 6µm Polyester, Polypropylene, Polycarbonate, Polyimide ASTM: Air and Helium ISO: Not specified ASTM: 1 to 5minute ISO: Not specified Normal ambient condition. 15 minutes or more 5µm Polypropylene film ASTM: Air and Helium ISO: Air ASTM: 200sec and 100sec ISO: Same as ASTM D 4294

5 2.Sample Calibration Sample Contents of Sulfur Catalog Number Analytical Service 0, 20, 50, 100, 200, 400, 500, 600, 800, 1000ppm SMO Analytical Service 0, 0.1, 0.2, 0.5, 0.75, 1, 2, 3, 4, 5wt% SMO(HL) Measurement Sample Contents of Sulfur Catalog Number Japan Petroleum Institute(JPI) 0.00wt% S0316 JPI 0.2wt% S0245 JPI 0.5wt% S0225 JPI 1.0wt% S0226 JPI 4.0wt% S0317 SPEX 50ppm DSS8-AY SPEX 100ppm DSS8-1Y SPEX 300ppm DSS8-CY SPEX 500ppm DSS8-1AY SPEX(Diesel) 100ppm SDSF-100-Y

6 3.Standard Requirement S:Sulfur standard value Standard Number Request items Request content Standard criterion Repeatability The difference between results obtained by the same operator with the same apparatus under constant operating conditions on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty Base oil: r= S ppm Diesel: r= S ppm ASTM D4294 Reproducibility The difference two single and independent test results obtained by different operators working in different laboratories on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty. Base oil: R= S ppm Diesel: R= S ppm Blank Be performed before the measurement is preferably blank calibration, the value is less than 2.0ppm. 2.0ppm or less ISO8754 Repeatability Reproducibility The difference between two test results obtained by the same operator with the same apparatus under constant operating conditions on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty. The difference two single and independent test results obtained by different operators working in different laboratories on identical test material would in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty. Concentration range (0.03<S<0.05)wt% r=0.045(s+0.05) wt% Concentration range (S>0.05)wt% r=0.0215(s+0.15) wt% Concentration range (0.03<S<0.05)wt% R=0.1781(S+0.05)wt% Concentration range (S>0.05)wt% R=0.0812(S+0.15)wt%

7 4. Contents of evaluation S:Sulfur standard value Standard number Test contents Contents of evaluation Standard criterion Repeatability Compare the standard criterion and the range of the measurement value through the performance of 20 times measurement with the same operator, apparatus and sample in the same laboratory. Base oil r= S ppm Diesel r= S ppm ASTM D4294 Reproducibility Compare the standard criterion and the range of the measurement value through the performance of 20 times measurement with the different operator, apparatus and same sample in the different laboratory. Base oil R= S ppm Diesel R= S ppm Blank Performs 20 measurements of sample sulfur content 0.0ppm, to obtain an maximum value. 2.0ppm or less ISO8754 Repeatability Reproducibility Compare the standard criterion and the range of the measurement value through the performance of 2 sets of 20 times measurement with the same operator, apparatus and sample in the same laboratory. Prepare the new sample and cell each set of measurement. Compare the standard criterion and the range of the measurement value through the performance of 20 times measurement with the different operator, apparatus and same sample in the different laboratory. Concentration range (0.03<S<0.05)wt% r=0.045(s+0.05) wt% Concentration range (S>0.05)wt% r=0.0215(s+0.15) wt% Concentration range (0.03<S<0.05)wt% R=0.1781(S+0.05)wt% Concentration range (S>0.05)wt% R=0.0812(S+0.15)wt%

8 4. Contents of evaluation Verification other items Contents of evaluation Accuracy of Calibration Curve Lower limit of detection (LLD) The content of the evaluation Evaluate the accuracy of the calibration curve. Calculate Lower limit detection from the obtained calibration curve. Lower limit of detection calculation equation L. L. D. = 3 C NET BG T A NET:Fluorescent X-ray intensity of S [cps/µa] BG:Background intensity of S[cps/µA] C:Sulfur concentration in oil[ppm] T:Integration time[sec] A:Current value[µa]

9 4. Contents of evaluation Standard Requirement for Criterion Standard Number Test contents Standard value Standard Criterion [ppm] ASTM D4294 ISO 8754 Standard criterion and sulfur content of the sample used in this testing. Repeatability Reproducibility 50ppm 100ppm 500ppm 0.5wt% 4.0wt% 50ppm 500ppm 4.0wt% Repeatability (Diesel) 100ppm 7.8 Reproducibility (Diesel) 100ppm 41 Blank 0.0ppm 2.0ppm or less Repeatability Reproducibility 300ppm 500ppm 0.2wt 1.0wt 4.0wt% 500ppm 4.0wt%

10 5.Result 5.1 Measurement result(astm D 4294) (Judgment)<(Standard criterion) Note)Standard scope range is in colored cell, otherwise is stricter than scope range Test content Measurement time (sec) Standard criterion (ppm) Air [ppm] Judgment Result He [ppm] Judgment Repeatability Base oil 50ppm OK Repeatability Base oil 100ppm OK Repeatability Base oil 500ppm OK 12 OK Repeatability Base oil 0.5wt% OK 44 OK Repeatability Base oil 4.0wt% OK 159 OK Repeatability diesel 100ppm OK Repeatability Base oil 500ppm OK 14 OK Repeatability Base oil 0.5wt% OK 41 OK Repeatability Base oil 4.0wt% OK 91 OK Reproducibility Base oil 50ppm OK Reproducibility Base oil 500ppm OK 12 OK Reproducibility Base oil 4.0wt% OK 667 OK Reproducibility Diesel 100ppm OK Blank OK

11 5.Result 5.2 Measurement result(iso8754) (Judgment)<(Standard criterion) Test content Measurement time [sec] Standard criterion [ppm] Measurement results Air[ppm] Judgment Repeatability 0.03wt% OK Repeatability 0.05wt% OK Repeatability 0.2wt% OK Repeatability 1.0wt% OK Repeatability 4.0wt% OK Reproducibility 0.03wt% OK Reproducibility 4.0wt% OK

12 5.Result 5.3 Verification other results Spectrum at air and He condition Calibration curve at He condition Air He X-ray intensity[cps/µa] Accuracy of calibration curve at ppm range and LLD Standard value[ppm] Accuracy LLD(200sec) Air 8.66 [ppm] 5.61 [ppm] He 5.31 [ppm] 2.49 [ppm]

13 5.Result 5.4 Typical measured results 20 times measurements at ASTM:500ppm Air He ppm_Air 500ppm_He

14 6.Conclusion Compliant contents For Repeatability of ASTM D4294 [Base Oil] It was confirmed that EDX-7000 can comply with ASTM D4294 at sulfur concentration of 500ppm or more under the Air condition. In the He condition, EDX-7000 can also comply with ASTM D4294 at low sulfur concentration range of 50ppm. It was confirmed that EDX-7000 can comply with ASTM D4294 even if the measurement time is shorter (50sec) than the required condition. [Diesel Oil] It was confirmed that EDX-7000 can comply with ASTM D4259 at sulfur concentration of 100ppm or more under the He condition. For Reproducibility of ASTM D4294 [Base Oil] It was confirmed that EDX-7000 can comply with ASTM D4294 at sulfur concentration of 500ppm or more under the Air and He conditions. [Diesel Oil] It was confirmed that EDX-7000 can comply with ASTM D4259 at sulfur concentration of 100ppm or more under the He condition. For ISO8754 It was confirmed that EDX-7000 can comply with ISO8754 at all concentration range. ASTM D4294 Air condition ASTM D4294 He condition ISO8754 Air condition Repeatability Base oil 500ppm or more 50ppm or more All concentration range Reproducibility Base oil 500ppm or more 50ppm or more All concentration range Repeatability Diesel 100ppm or more Reproducibility Diesel 100ppm or more

15 7.Notices Due to the influence of the wrinkles in the film to be used, may affect the measurement result. Please measure to double check the status of the film. In particular, PET film(mylar film) is more stable than polypropylene film in the measurement of the high concentration sample. It is possible that the mylar film was suitable for measurement at long term in same sample. However, mylar film must be careful in the analysis for diffraction line is overlapped with the peak of sulfur. Effect of the film was increased by measurement under using the turret, it is following results, however it is pass the standard criterion. Base oil Stand by time until measurement Without turret With turret Standard criterion 5000ppm 3 hours 44ppm 80ppm 102 4wt% 4 hours 159ppm 314ppm 405

16 Appendix Certified reference material information No. S0316 S0245 S0225 S0226 Name Concentrate(wt %) Reference Materials of sulfur Reference Materials of sulfur Reference Materials of sulfur 0.5wt% equivalent Reference Materials of sulfur Uncertainty Density(g/cm3) C/H No. Name Concentrate(wt %) S0317 Reference Materials of sulfur 4.0wt% equivalent 4.01 Uncertainty 0.03 Density(g/cm3) C/H 8.1

17 Appendix Certified reference material information No. DSS8-AY DSS8-1Y DSS8-CY DSS8-1AY Description Sulfur Oil Standard Sulfur Oil Standard Sulfur Oil Standard Sulfur Oil Standard Matrix Base Oil 20 Base Oil 20 Base Oil 20 Base Oil 20 Concentrate [ppm] Uncertainty ±1% ±1% ±1% ±1% Density(g/cm3) 0.802g/mL 0.802g/mL 0.802g/mL 0.802g/mL No. Description SDSF-100-Y Sulfur Oil Standard Matrix Concentrate (ppm) #2 Diesel Fuel 100 Uncertainty ±1% Density(g/cm3) 0.822g/mL

18 Appendix ASTM: Repeatability Base oil Data in air Sample Base oil Base oil Measurement time (sec) Concentration[ppm] Number of times Average Standard deviation Maximum Minimum Range Criterion Judgment OK OK OK OK OK OK

19 Appendix ASTM: Reproducibility Base oil Data in air Sample Base oil A B A B Measurement time[sec] Concentration[ppm] Number of times Average Standard deviation Maximum Minimum Range Criterion Judgment OK OK

20 Appendix Base oil Diesel Base oil Blank Measurement time[sec] Concentration [ppm] Number of times Average Standard deviation Maximum Minimum Range (Max when Bkank) ASTM: Repeatability Data in He Criterion Judgment OK OK OK OK OK OK OK OK OK OK OK OK OK

21 Appendix ASTM: Reproducibility Data in He Sample Base oil Diesel A B A B A B A B Measurement time[sec] Concentration[ppm] Number of times Average Standard deviation Maximum Minimum Range Criterion Judgment OK OK OK OK

22 Appendix ISO: Repeatability Base oil Data in air Sample Base oil Measurement time[sec] Concentration[ppm] set 2set 1set 2set 1set 2set 1set 2set 1set 2set Number of times Average Standard deviation Maximum Minimum Range Criterion Judgment OK OK OK OK OK

23 Appendix ISO: Reproducibility Base oil Data in air Base oil Measurement time[sec] Concentration[ppm] A B A B Number of times Average Standard deviation Maximum Minimum Range Criterion Judgment OK OK