Results of Proficiency Test Biodiesel 100% FAME (B100) May 2017

Transcription

1 Results of Proficiency Test Biodiesel 1% FAME (B1) May 217 Organised by: Author: Correctors: Report no.: Spijkenisse, the Netherlands ing. R.J. Starink dr. R.G. Visser & ing. G.A. Oosterlaken-Buijs iis17g2astm July 217

2 Spijkenisse, July 217 CONTENTS 1 INTRODUCTION SET UP ACCREDITATION PROTOCOL CONFIDENTIALITY STATEMENT SAMPLES STABILITY OF THE SAMPLES ANALYSES RESULTS STATISTICS GRAPHICS Z-SCORES EVALUATION EVALUATION PER SAMPLE AND PER TEST PERFORMANCE EVALUATION FOR THE GROUP OF LABORATORIES COMPARISON OF THE PROFICIENCY TEST OF MAY 217 WITH PREVIOUS PTS Appendices: 1 Data and statistical results Number of participants per country Abbreviations and literature Page 2 of 51 Biodiesel B1: iis17g2astm

3 Spijkenisse, July INTRODUCTION Since 1991, the organises every year proficiency tests (PT) for Fatty Acid Methyl Esters (FAME) used as Biodiesel B1. In the annual proficiency testing program of 216/217, it was decided to continue the May proficiency tests on Biodiesel B1 in accordance with the latest applicable version of ASTM D6751 specification and additional tests (e.g. EN14214:212+A1:214/AC:214). In these interlaboratory studies, in total, 44 laboratories from 23 different countries registered for participation. See appendix 2 for a list of number of participants per study and per country. In this report the results of the 217 Biodiesel B1 ASTM proficiency test are presented and discussed. This report is also electronically available through the iis website 2 SET UP In this proficiency test on Biodiesel B1, a sample of Rapeseed methyl ester was used. Sample analyses for fit-for-use and homogeneity testing were subcontracted to an ISO/IEC 1725 accredited laboratory. In this proficiency test, the participants received, depending on the registration, from one up to five different samples of Biodiesel B1, see table below. Samples Amount in L Purpose Spiked # For regular analysis -- # Cetane Number &DCN -- # Analysis of Phosphorus, Potassium, Sodium and Calcium & Magnesium Phosphorus, Sodium, Calcium # Total Contamination test Arizona dust # Cold Soak Test / Filter Blocking -- Table 1: five different Biodiesel B1 samples used in iis17g2astm The participants were requested to report rounded and unrounded test results. The unrounded test results were preferably used for statistical evaluation. 2.1 ACCREDITATION The (iis) in Spijkenisse, the Netherlands, is accredited in agreement with ISO/IEC 1743:21 (R7), since January 2, by the Dutch Accreditation Council (Raad voor Accreditatie). These PTs fall under the accredited scope. This ensures strict adherence to protocols for sample preparation and statistical evaluation and 1% confidentiality of participant s data. Feedback from the participants on the reported data is encouraged and customer s satisfaction is measured on regular basis by sending out questionnaires. Biodiesel B1: iis17g2astm page 3 of 51

4 Spijkenisse, July PROTOCOL The protocol followed in the organisation of this proficiency test was the one as described for proficiency testing in the report iis Interlaboratory Studies: Protocol for the Organisation, Statistics and Evaluation of March 217 (iis-protocol, version 3.4). This protocol is electronically available through the iis website from the FAQ page. 2.3 CONFIDENTIALITY STATEMENT All data presented in this report must be regarded as confidential and for use by the participating companies only. Disclosure of the information in this report is only allowed by means of the entire report. Use of the contents of this report for third parties is only allowed by written permission of the. Disclosure of the identity of one or more of the participating companies will be done only after receipt of a written agreement of the companies involved. 2.4 SAMPLES The necessary bulk material, 2 drums, with in total approximately 4 L of Biodiesel (1% RME) for this PT was obtained from an European producer. Biodiesel B1 #1765 After fit-for-use testing and homogenisation of one drum, 64 amber glass bottles of 1L and 64 amber glass bottles of.5l, were filled, closed with inner and outer caps and labelled #1765.The homogeneity of the subsamples #1765 was checked by the determination of Density in accordance with ASTM D452 on 8 stratified randomly selected samples: Density at 15ºC in kg/m 3 sample # sample # sample # sample # sample # sample # sample # sample # Table 2: homogeneity test results of subsamples #1765 From the above test results, the calculated repeatability was calculated and compared with.3 times the reproducibilities (R) of the reference test method in agreement with the procedure of ISO13528, Annex B2 in the next table: Density at 15ºC in kg/m 3 r (observed).3 reference test method ISO12185:96.3 x R (ref. test method).15 Table 3: evaluation of the repeatability of subsamples #1765 Page 4 of 51 Biodiesel B1: iis17g2astm

5 Spijkenisse, July 217 Biodiesel B1 Cetane Number #1766 After fit-for-use testing and homogenisation of the second drum, 68 amber glass bottles of 1L were filled, closed with inner and outer caps and labelled #1766.The homogeneity of the subsamples #1766 was checked by the determination of Density in accordance with ASTM D452 on 8 stratified randomly selected samples: Density at 15ºC in kg/m 3 sample # sample # sample # sample # sample # sample # sample # sample # Table 4: homogeneity test results of subsamples #1766 From the above test results, the calculated repeatability was calculated and compared with.3 times the reproducibilities (R) of the reference test method in agreement with the procedure of ISO13528, Annex B2 in the next table: Density at 15ºC in kg/m 3 r (observed).1 reference test method ISO12185:96.3 x R (ref. test method).15 Table 5: evaluation of the repeatability of subsamples #1766 Metals in Biodiesel B1 #1767 From the remaining batch used for sample #1765, approx. 6 litres (5.3 kg) were spiked with Calcium (approx. 6 mg/kg), Phosphorus (approx. 9 mg/kg) and Sodium (approx. 6 mg/kg). After homogenisation, the material was subsequently divided over 59 HDPE bottles of.1l and labelled #1767. The homogeneity of the subsamples #1767 was checked by determination of Phosphorus in accordance with EN1417 and Sodium in accordance with EN14214 on 8 stratified randomly selected samples: Phosphorus in mg/kg Sodium in mg/kg sample # sample # sample # sample # sample # sample # sample # sample # Table 6: homogeneity test results of subsamples #1767 Biodiesel B1: iis17g2astm page 5 of 51

6 Spijkenisse, July 217 From the above test results, the calculated repeatability was calculated and compared with.3 times the reproducibilities (R) of the reference test method in agreement with the procedure of ISO13528, Annex B2 in the next table: Phosphorus in mg/kg Sodium in mg/kg r (observed).3.2 reference test method EN1417:3 EN14214:14.3 x R (ref. test method) Table 7: evaluation of the repeatability of subsamples #1767 Total Contamination #1768 Into 41 amber glass bottles 1 ml of a freshly prepared and ultrasonically homogenized 15 g/kg Arizona Dust in oil suspension was pipetted. The addition was checked by weighing each bottle before and after the addition of the oil suspension. Subsequently, each bottle with inner and outer caps was filled with one litre Biodiesel B1, coming from the remaining batch used for sample #1765. The bottles were labelled #1768. Cold Soak Test / Filter Blocking Tendency #1769 From the remaining batch used for the Cetane Number of Biodiesel, 25 litres were used to fill 48 bottles of.5 litre amber glass bottles and labelled #1769. The homogeneity of the subsamples was checked by the determination of density in accordance with ASTM D452 on 8 stratified randomly selected samples. Density at 15ºC in kg/m 3 sample # sample # sample # sample # sample # sample # sample # sample # Table 8: homogeneity test results of subsamples #1769 From the above test results, the calculated repeatability was calculated and compared with.3 times the reproducibilities (R) of the reference test method in agreement with the procedure of ISO13528, Annex B2 in the next table: Density at 15ºC in kg/m 3 r (observed).2 reference test method ISO12185:96.3 x R (ref. test method).15 Table 9: evaluation of the repeatability of subsamples #1769 The calculated repeatabilities for sample #1765, #1766, #1767, #1768 and #1769 were less than.3 times the corresponding reproducibility of the respective reference method. Therefore, homogeneity of the subsamples was assumed. Page 6 of 51 Biodiesel B1: iis17g2astm

7 Spijkenisse, July 217 Depending on the registration of the participant, one 1 litre bottle and.5 litre bottle both labelled #1765, two 1 litre bottles labelled #1766, a 1mL bottle labelled #1767, a 1 litre bottle labelled #1768 and/or a.5 litre bottle labelled #1769, were dispatched to each of the participating laboratories on April 12, STABILITY OF THE SAMPLES The stability of the Biodiesel B1, packed in the brown glass bottles, was checked. The material has been found sufficiently stable for the period of the proficiency test. 2.6 ANALYSES The tests methods to be used by the participating laboratories should be in accordance with the requirements of ASTM D6751:15 and additional tests (e.g. EN14214:12+A1:14/AC:14): Parameter ASTM D6751:15 Parameter EN14214:12 Acid Number ASTM D664 Acid Value *) EN1414 *) Carbon Residue on 1% FAME ASTM D453 CFPP EN116 Cloud Point ASTM D25 Copper Strip Corrosion ASTM D13 Copper Strip Corrosion ISO216 Density at 15 C ISO12185 Flash Point ASTM D93 Flash Point (Recc) *) ISO3679 *) Flash Point (PMcc) ISO2719 Iodine Value EN14111 Kin. Visc. at 4 C ASTM D445 Kin. Visc. at 4 C ISO314 Oxidation Stability EN15751 Oxidation Stability EN14112 Sulphated Ash ASTM D874 Sulphated Ash ISO3987 Sulphur ASTM D5453 Sulphur ISO2846 Water and Sediment ASTM D279 Water ISO12937 Calcium + Magnesium EN14538 Calcium + Magnesium EN14538 Phosphorus ASTM D4951 Phosphorus EN1417 Polyunsaturated esters *) EN15779 *) Potassium + Sodium EN14538 Potassium + Sodium EN1418/1419 Methanol EN1411 Methanol EN1411 mono-, di-, tri-glycerides EN1415 Free + Total Glycerin ASTM D6584 Free + Total Glycerol EN1415 Distillation; 9% recovered D116 FAME content *) EN1413 *) Linolenic Acid *) EN1413 *) Total Contamination D7321 Total Contamination EN12662 Cold Soak Filterability ASTM D751 Table 1: requirements and test methods acc. to specifications ASTM D6751:15 and EN14214:12+A1:14/AC:14 *) not evaluated in this ASTM based round robin It was explicitly requested to treat the samples as if they were routine samples. Therefore, each laboratory is advised to perform only those analyses that normally are done in daily routine (but the laboratories are allowed to do all analyses). Furthermore, it was requested to report the test results using the indicated units on the report form and not to round the test results, but report as much significant figures as possible. It was also requested not to Biodiesel B1: iis17g2astm page 7 of 51

8 Spijkenisse, July 217 report less than test results, which are above the detection limit, because such test results cannot be used for meaningful statistical evaluations. To get comparable test results, a detailed report form and a letter of instructions are prepared. On the report form the reporting units are given as well as the reference test methods that will be used during the evaluation. The detailed report form and the letter of instructions are both made available on the data entry portal The participating laboratories are also requested to confirm the sample receipt on this data entry portal. The letter of instructions can also be downloaded from the iis website 3 RESULTS During five weeks after sample dispatch, the test results of the individual laboratories were gathered via the data entry portal The reported test results are tabulated per determination in appendix 1 of this report. The laboratories are presented by their code numbers. Directly after the deadline, a reminder was sent to those laboratories that had not reported test results at that moment. Shortly after the deadline, the available test results were screened for suspect data. A test result was called suspect in case the Huber Elimination Rule (a robust outlier test) found it to be an outlier. The laboratories that produced these suspect data were asked to check the reported test results (no reanalysis). Additional or corrected test results are used for data analysis and original test results are placed under 'Remarks' in the test result tables in appendix 1. Test results that came in after the deadline were not taken into account in this screening for suspect data and thus these participants were not requested for checks. 3.1 STATISTICS The protocol followed in the organization of this proficiency test was the one as described for proficiency testing in the report iis Interlaboratory Studies: Protocol for the Organisation, Statistics and Evaluation of March 217 (iis-protocol, version 3.4). For the statistical evaluation the unrounded (when available) figures were used instead of the rounded test results. Test results reported as < or > were not used in the statistical evaluation. First, the normality of the distribution of the various data sets per determination was checked by means of the Lilliefors-test a variant of the Kolmogorov-Smirnov test and by the calculation of skewness and kurtosis. Evaluation of the three normality indicators in combination with the visual evaluation of the graphic Kernel density plot, lead to judgement of the normality being either unknown, OK, suspect or not OK. After removal of outliers, this check was repeated. If a data set does not have a normal distribution, the results of the statistical evaluation should be used with due care. Page 8 of 51 Biodiesel B1: iis17g2astm

9 Spijkenisse, July 217 According to ISO 5725 the original test results per determination were submitted to Dixon s, Grubbs and/or Rosner s outlier tests. Outliers are marked by D(.1) for the Dixon s test, by G(.1) or DG(.1) for the Grubbs test and by R(.1) for the Rosner s test. Stragglers are marked by D(.5) for the Dixon s test, by G(.5) or DG(.5) for the Grubbs test and by R(.5) for the Rosner s test. Both outliers and stragglers were not included in the calculations of averages and standard deviations. For each assigned value the uncertainty was determined in accordance with ISO Subsequently the calculated uncertainty was evaluated against the respective requirement based on the target reproducibility in accordance with ISO When the uncertainty passed the evaluation, no remarks are made in the report. However, when the uncertainty failed the evaluation it is mentioned in the report and it will have consequences for the evaluation of the test results. Finally, the reproducibilities were calculated from the standard deviations by multiplying them with a factor of GRAPHICS In order to visualize the data against the reproducibilities from literature, Gauss plots were made, using the sorted data for one determination (see appendix 1). On the Y-axis the reported test results are plotted. The corresponding laboratory numbers are on the X-axis. The straight horizontal line presents the consensus value (a trimmed mean). The four striped lines, parallel to the consensus value line, are the +3s, +2s, -2s and -3s target reproducibility limits of the selected reference test method. Outliers and other data, which were excluded from the calculations, are represented as a cross. Accepted data are represented as a triangle. Furthermore, Kernel Density Graphs were made. This is a method for producing a smooth density approximation to a set of data that avoids some problems associated with histograms. Also a normal Gauss curve was projected over the Kernel Density Graph for reference. 3.3 Z-SCORES To evaluate the performance of the participating laboratories the z-scores were calculated. As it was decided to evaluate the performance of the participants in this proficiency test (PT) against the literature requirements, e.g. ASTM or IP reproducibilities, the z-scores were calculated using a target standard deviation. This results in an evaluation independent of the variation of this interlaboratory study. The target standard deviation was calculated from the literature reproducibility by division with 2.8. In case no literature reproducibility was available, other targets values were used. In some cases a reproducibility based on former iis proficiency tests could be used. When a laboratory did use a test method with a reproducibility that is significantly different from the reproducibility of the reference test method used in this report, it is strongly advised to recalculate the z-score, while using the reproducibility of the actual test method used, this in order to evaluate whether the reported test result is fit-for-use. Biodiesel B1: iis17g2astm page 9 of 51

10 Spijkenisse, July 217 The z-scores were calculated according to: z (target) = (test result - average of PT) / target standard deviation The z (target) scores are listed in the test result tables in appendix 1. Absolute values for z<2 are very common and absolute values for z>3 are very rare. The usual interpretation of z-scores is as follows: z < 1 good 1 < z < 2 satisfactory 2 < z < 3 questionable 3 < z unsatisfactory 4 EVALUATION In this proficiency test several problems were encountered during the execution. For the regular Biodiesel PT (#1765): 3 participants reported test results after the final reporting date and 3 other participant did not report any test results at all. For the Cetane Number PT (#1766): 1 participant reported test results after the final reporting date and 3 other participant did not report any test results at all. For the Total Contamination PT: 2 participants reported the test result after the final reporting date and 3 participants did not report any test results at all. For the Metals in Biodiesel PT: 1 participant reported the test results after the final reporting date and 4 participants did not report any test results at all. For the Filter Blocking PT: 1 participant reported a result after the final reporting date and 6 participants did not report any test results at all. Finally, in total 449 numerical test results were reported by the participants. Observed were 11 outlying results, which is 2.5%. In proficiency studies, outlier percentages of 3% - 7.5% are quite normal. 4.1 EVALUATION PER SAMPLE AND PER TEST In this section, the reported test results are discussed per sample and per test. The specified test methods and requirements ASTM D6751:15 and additional tests (e.g. EN14214:12+A1:14/AC:14) which were used by the various laboratories were taken into account for explaining the observed differences when possible and applicable. These methods are also in the tables together with the reported data. The abbreviations, used in these tables, are listed in appendix 3. Not all original data sets proved to have a normal Gaussian distribution. These are referred to as not OK or suspect. The statistical evaluation of these data sets should be used with due care, see also paragraph 3.1. In the iis PT reports, ASTM methods are referred to with a number (e.g. D6371) and an added designation for the year that the method was adopted or revised (e.g. D6371:5). If applicable, a designation in parentheses is added to designate the year of reapproval (e.g. Page 1 of 51 Biodiesel B1: iis17g2astm

11 Spijkenisse, July 217 D6371:5(21)). In the results tables of Appendix 1 only the method number and year of adoption or revision e.g. D6371:5 will be used. For Biodiesel B1 sample #1765 Acid Number: (ASTM) This determination was not problematic. One statistical outlier was observed. However, the calculated reproducibility after rejection of the statistical outlier is in full agreement with the requirements of ASTM D664:11ae1 (method B). Cloud Point: This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in full agreement with the requirements of ASTM D25:16b. CFPP: This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ASTM D6371:16. Carbon Residue on 1%: All reported results were near or below the applicable lower limit of D453:15 (.1%M/M). Therefore no significant conclusions were drawn. Copper Strip Corrosion: No problems have been observed. All participants agreed on a test result of 1. Density at 15 C This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ISO12185:96. Flash Point PMcc: This determination was not problematic. No statistical outliers were observed, but three test results were excluded from statistical calculations as the used test method is not comparable with ASTM D93. However, the calculated reproducibility after rejection of the suspect data is in agreement with the requirements of ASTM D93C:15. Iodine Value: This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of EN14111:3. Kin.Visco. at 4 C: The determination was not problematic. One statistical outlier was observed. However, the calculated reproducibility after rejection of the statistical outlier is in good agreement with the requirements of ASTM D445:17. Oxidation Stability: This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in good agreement with the requirements of EN15751:14. Biodiesel B1: iis17g2astm page 11 of 51

12 Spijkenisse, July 217 Sulphated Ash: Sulphur: Water: All reported results were near or below the applicable lower limit of ASTM D874:13a and/or ISO3987:1 (.5% M/M). Therefore no significant conclusions were drawn. This determination was problematic at a low level of 1.6 mg/kg. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of ASTM D5453:16e1. This determination was not problematic. Three statistical outliers were observed. However the calculated reproducibility after rejection of the statistical outliers is in good agreement with the requirements of ASTM D634:16e1. Water and Sediment: All reported results were near or below the applicable lower limit of ASTM D279:96(211). Therefore no significant conclusions were drawn. Distillation: Methanol: mono-glycerides: di-glycerides: tri-glycerides: Free Glycerine: Total Glycerine: Only three laboratories reported test results, therefore no significant conclusions were drawn. This determination was problematic for a number of laboratories. Three statistical outliers were observed. However, the calculated reproducibility after rejection of the statistical outliers is in agreement with the requirements of EN1411:3. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ASTM D6584:13. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ASTM D6584:13. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ASTM D6584:13. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ASTM D6584:13. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of ASTM D6584:13. Page 12 of 51 Biodiesel B1: iis17g2astm

13 Spijkenisse, July 217 For Biodiesel B1 sample #1766: Cetane Number Cetane Number: This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in full agreement with the requirements of ASTM D613:16a. Derived Cetane Number: In total only three laboratories reported test results, therefore no significant conclusions were drawn. For Biodiesel B1 sample #1767: Metals Calcium and Magnesium: This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of EN14538:6. Phosphorus Potassium Sodium This determination was problematic. Two statistical outliers were observed. The calculated reproducibility after rejection of the statistical outliers is not in agreement with the requirements of EN1417:3. The samples were spiked with Phosphorus. The average recovery of Phosphorus (theoretical increment of 8.99 mg/kg) may be excellent: less than 1%. The actual blank concentration for Phosphorus is unknown. All reported results were near or below the applicable lower limit of EN14214:14. Therefore no significant conclusions were drawn. This determination was not problematic. No statistical outliers were observed. The calculated reproducibility is in agreement with the requirements of EN14214:12+A1:214/AC:214 and with the requirements of EN1418:3. The samples were spiked with Sodium. The average recovery of Sodium (theoretical increment of 5.99 mg/kg) may be satisfactory: less than 79%. The actual blank concentration for Sodium is unknown. Potassium and Sodium: This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of EN14538:6. For Biodiesel B1 sample #1768: Particulate Contamination Total Contamination: As this proficiency test was ASTM based, the intention was to evaluate the Total contamination against ASTM D7321. Regretfully, the majority of the laboratories reported to have used EN12662 as test method. Therefore it was decided to evaluate the test results for ASTM D7321 and EN12662 separately, which have significant differences and may produce different test results. ASTM D7321: This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of ASTM D7321:14. Biodiesel B1: iis17g2astm page 13 of 51

14 Spijkenisse, July 217 EN12662: This determination was very problematic. One statistical outlier was observed. The calculated reproducibility after rejection of the statistical outlier is not at all in agreement with the requirements of EN12662:98. The test results vary over a large range: < mg/kg. For Biodiesel B1 sample #1769: CSFT&FBT Filter Blocking Potential by Cold Soak test: This determination was problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of ASTM D751:12a. The test results vary over a large range: mg/kg. Filter Blocking Tendency: This determination may be problematic. No statistical outliers were observed. However, the calculated reproducibility is not in agreement with the requirements of ASTM D268:14 (or IP387-B, which is identical). The low number of reported test results may partly explain the large variation. Page 14 of 51 Biodiesel B1: iis17g2astm

15 Spijkenisse, July PERFORMANCE EVALUATION FOR THE GROUP OF LABORATORIES A comparison has been made between the reproducibility as declared by the relevant standard and the reproducibility as found for the group of laboratories that participated. The reproducibilities derived from literature standards (in casu the ASTM, EN, ISO and IP standards) and the calculated reproducibilities of the samples (see appendix 1) are compared in the next table. Parameter unit n average R (Calc.) R (lit) Acid Number (D664-B) mg KOH/g Cloud Point C Cold Filter Plugging Point C Carbon Residue on 1% FAME %M/M 15 <.1 n.a. n.a. Copper Strip Corrosion 22 1 n.a. n..a Density at 15 C kg/m Flash Point (PMcc) ASTM C Iodine Value g I 2 /1g Kin. Viscosity at 4 C mm 2 /s Oxidation Stability EN15751 hours Sulphated Ash %M/M 12 <.5 n.a. n.a. Sulphur mg/kg Water mg/kg Water and Sediment %V/V 11 <.5 n.a. n.a. Distillation at 1mm Hg 8% recovered C 3 (353.5) (1.4) (4.6) 9% recovered C 3 (355.2) (1.9) (4.6) 95% recovered C 3 (359.7) (8.) (4.6) Methanol %M/M mono-glycerides %M/M di-glycerides %M/M tri-glycerides %M/M Free Glycerine %M/M Total Glycerine %M/M Table 11: comparison of the observed and target reproducibilities of Biodiesel B1 sample #1765 (results between brackets are for information only) Parameter unit n average R (Calc.) R (lit) Cetane Number DCN (D7668) 1 n.a. n.a. n.a. DCN (D689) n.a. n.a. Table 12: comparison of the observed and target reproducibilities of Biodiesel B1 sample #1766 Parameter unit n average R (Calc.) R (lit) sum Calcium and Magnesium mg/kg Phosphorus mg/kg Potassium mg/kg 9 <1 n.a. n.a. Sodium mg/kg Sum Potassium and Sodium mg/kg Table 13: comparison of the observed and target reproducibilities of Biodiesel B1 sample #1767 Biodiesel B1: iis17g2astm page 15 of 51

16 Spijkenisse, July 217 Parameter Unit n average R (Calc.) R (lit) Particulate Contamination (D7321) mg/l Total Contamination (EN12662) mg/kg Table 14: comparison of the observed and target reproducibilities of Biodiesel B1 sample #1768 Parameter Unit n average R (Calc.) R (lit) Filter Blocking Potential by CST s Filter Blocking Tendency Table 15: comparison of the observed and target reproducibilities of Biodiesel B1 sample #1769 Without further statistical calculations it can be concluded that for many tests there is a good compliance of the group of participating laboratories with the relevant standards. The problematic tests have been discussed in paragraph COMPARISON OF THE PROFICIENCY TEST OF MAY 217 WITH PREVIOUS PTS May 217 May 216 October 215 April 215 Type of FAME Rapeseed Rapeseed Rapeseed Rapeseed Number of reporting labs Number of results reported Number of statistical outliers Percentage statistical outliers 2.5% 4.2% 2.4% 2.4% Table 16: comparison with previous proficiency tests In proficiency tests, outlier percentages of 3% - 7.5% are quite normal. The performance of the determinations of the proficiency tests was compared against the requirements of the respective standards. The conclusions are given the following table: Determination May 217 May 216 October 215 April 215 Acid Number (D664-B) +/ Cloud Point +/ Cold Filter Plugging Point /- Carbon Residue on 1% FAME n.e. n.e. (-) n.e. Density at15 C /- Flash Point PMcc ASTM +/- +/- - + Iodine Value - +/- + +/- Kin. Viscosity at 4 C /- - Oxidation Stability Sulphated Ash n.e. n.e. n.e. (--) Sulphur Water Distillation (8, 9 and 95% rec.) (+) - n.e. n.e. Methanol mono-glycerides di-glycerides /- +/- tri-glycerides Free Glycerine Total Glycerine Table 17 : comparison of group performances against the standard requirements Page 16 of 51 Biodiesel B1: iis17g2astm

17 Spijkenisse, July 217 Determination May 217 May 216 October 215 April 215 Cetane Number +/- n.e. n.e. n.e. DCN n.e. n.e. n.e. n.e. Sum of Calcium and Magnesium - +/- - - Phosphorus Potassium n.e Sodium Sum of Potassium and Sodium - -- n.e. n.e. Particle contamination -- n.e. n.e. n.e. Total Contamination Filter Blocking Potential by CST -- +/- n.e. n.e. Filter Blocking Tendency - - n.e. n.e. Table 18 : comparison of group performances against the standard requirements * Signs between brackets are for assigned values below the application range of the respective reference test method and therefore should be used with due care The performance of the determinations against the requirements of the respective standards is listed in the above table. The following performance categories were used: ++: group performed much better than the standard + : group performed better than the standard +/-: group performance equals the standard - : group performed worse than the standard -- : group performed much worse than the standard n.e.: not evaluated Biodiesel B1: iis17g2astm page 17 of 51

18 Spijkenisse, July 217 APPENDIX 1 Determination of Acid Number total conform ASTM spec. on sample #1765; results in mg KOH/g lab method value mark z(targ) remarks 62 D664-B D664-B D664-B EN EN D R(.1) D664-B D D664-B D664-B D664-B D664-B EN EN D664-B D664-B D664-B D664-B D D664-B D664-A EN D664-B D664-B normality OK n 23 outliers 1 mean (n) st.dev. (n) R(calc.).1712 R(D664B:11ae1) Kernel Density Page 18 of 51 Biodiesel B1: iis17g2astm

19 Spijkenisse, July 217 Determination of Cloud Point on sample #1765; results in C lab method Value mark z(targ) remarks 62 D25-5. C.64 First reported D D D EN D D D EN D D D D D D D D D ISO EN IP D D EN D D EN D normality OK n 28 outliers mean (n) st.dev. (n) R(calc.) 5.9 R(D25:16b) 5 Compare R(EN2315/ISO315) = Kernel Density Biodiesel B1: iis17g2astm page 19 of 51

20 Spijkenisse, July 217 Determination of Cold Filter Plugging Point on sample #1765; results in C lab method value mark z(targ) remarks 62 D C.22 First reported D D D EN D D EN EN D IP D D D IP EN EN EN EN D EN IP EN normality OK n 23 outliers mean (n) st.dev. (n) R(calc.) 4.18 R(D6371:16) 4.73 Compare R(EN14241:12) = Kernel Density Page 2 of 51 Biodiesel B1: iis17g2astm

21 Spijkenisse, July 217 Determination of Carbon Residue on 1% FAME on sample #1765; results in %M/M lab method value mark z(targ) remarks 62 D453 < D453 < D453 < EN137 < D D D D453 < D453 L EN ISO137 < D453 < D D D normality unknown n 15 outliers mean (n) <.1 st.dev. (n) n.a. R(calc.) n.a. R(D453:15) n.a. Application range:.1.3%m/m Biodiesel B1: iis17g2astm page 21 of 51

22 Spijkenisse, July 217 Determination of Copper Strip Corrosion 3 hrs/5 C on sample #1765 lab method value mark z(targ) remarks 62 D13 1b D13 1a D13 1a D13 1A D13 1b D D13 1A D13 1a D13 1A D13 1A D13 1a D13 1a D13 1A IP154 1b ISO216 1a ISO216 1A D13 1A ISO216 1a D13 1b IP154 1A D13 1a ISO216 1a normality n.a. n 22 outliers n.a. mean (n) 1 st.dev. (n) n.a. R(calc.) n.a. R(lit) n.a. Page 22 of 51 Biodiesel B1: iis17g2astm

23 Spijkenisse, July 217 Determination of Density at 15 C on sample #1765; results in kg/m 3 lab method value mark z(targ) remarks 62 D D D D D D D D D ISO D D C.25 First reported.882 kg/m3 556 D D D D D D D D IP ISO ISO IP ISO D ISO D IP D ISO D ISO D D normality suspect n 35 outliers mean (n) st.dev. (n).1358 R(calc.).38 R(ISO12185:96) Kernel Density Biodiesel B1: iis17g2astm page 23 of 51

24 Spijkenisse, July 217 Determination of Flash Point (PMcc) conform ASTM spec. on sample #1765; results in C lab method value mark z(targ) remarks 62 D93-C D93-C D93-C D93-C D93-C D93-C D93-C D93-C ISO2719-C D93-C D93-C D93-C NBR C First reported D93-C D93-C D93-A D93-C D93-C D93-C D93-C ISO2719-A ISO ex 2.23 Result excluded, test method is not comparable with D ISO3679 > D93-A ISO ex 2.89 Result excluded, test method is not comparable with D D93-A D93-C D93-A D93-C D93-C ISO ex 1.75 Result excluded, test method is not comparable with D normality OK n 27 outliers (+3excl) mean (n) st.dev. (n) R(calc.) R(D93C:15) 14.7 Compare R(ISO2719C:16) = Kernel Density Page 24 of 51 Biodiesel B1: iis17g2astm

25 Spijkenisse, July 217 Determination of Iodine Value conform EN spec. on sample #1765; results in g I 2 /1g lab method value mark z(targ) remarks EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN normality suspect n 18 outliers mean (n) st.dev. (n) R(calc.) 6.76 R(EN14111:3) Kernel Density Biodiesel B1: iis17g2astm page 25 of 51

26 Spijkenisse, July 217 Determination of Kinematic Viscosity at 4 C on sample #1765; results in mm 2 /s lab method value mark z(targ) remarks 62 D D R(.5) D D C -.7 First reported ISO D D D D D D D D D D ISO ISO IP ISO D D D D D D D ISO D D normality OK n 28 outliers 1 mean (n) st.dev. (n) R(calc.).4983 R(D445:17).9935 Compare R(EN14214:12) = Kernel Density Page 26 of 51 Biodiesel B1: iis17g2astm

27 Spijkenisse, July 217 Determination of Oxidation Stability Induction period on sample #1765; results in hours lab method value mark z(targ) remarks EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN EN normality OK n 18 outliers mean (n) st.dev. (n).4496 R(calc.) R(EN15751:14) Compare R(EN14114:3) = Kernel Density Biodiesel B1: iis17g2astm page 27 of 51

28 Spijkenisse, July 217 Determination of Sulphated Ash on sample #1765; results in %M/M lab method value mark z(targ) remarks D874 < D874 < ISO D D874 < D D D D874 < D ISO3987 <, ISO3987 < ISO3987 <, ISO3987 < normality unknown n 12 outliers n.a. mean (n) <.5 st.dev. (n) n.a. R(calc.) n.a. R(D874:13a) n.a. Page 28 of 51 Biodiesel B1: iis17g2astm

29 Spijkenisse, July 217 Determination of Sulphur on sample #1765; results in mg/kg lab method value mark z(targ) remarks 62 D D D D D D ISO D D ISO D D D C 1.34 First reported D D D D ISO ISO2846 < D ISO ISO2884 < D ISO8754 < compare normality OK n 21 outliers mean (n) st.dev. (n).4675 R(calc.) 1.39 R(D5453:16e1).84 Application range: 1 8 mg/kg R(ISO2846:11) 1.34 Application range: 3 5 mg/kg Kernel Density Biodiesel B1: iis17g2astm page 29 of 51

30 Spijkenisse, July 217 Determination of Water content by KF on sample #1765; results in mg/kg lab method value mark z(targ) remarks 62 D634-A D634-A D634-A 469 R(.5) ISO ISO ISO D634-A ISO D634-A R(.5) D D634-A D634-A D634-A D634-B 19.7 R(.1) D634-A D634-A D634-A IP ISO ISO IP ISO ISO D634-A ISO E IP ISO ISO ISO ISO E ISO normality suspect n 3 outliers 3 mean (n) st.dev. (n) R(calc.) 87.3 R(D634:16e1) Kernel Density Page 3 of 51 Biodiesel B1: iis17g2astm

31 Spijkenisse, July 217 Determination of Water and sediment on sample #1765; results in %V/V lab method value mark z(targ) remarks 62 D279 < D279 < D D D279 < D279 < D279 < D279 < D279 < D D normality n.a. n 11 outliers n.a. mean (n) <.5 st.dev. (n) n.a. R(calc.) n.a. R(D279:16) n.a. Biodiesel B1: iis17g2astm page 31 of 51

32 Spijkenisse, July 217 Determination of Distillation at 1 mm Hg, % recovered as AET on sample #1765; results in C lab method 8% rec mark z(targ) 9% rec mark z(targ) 95% rec mark z(targ) D D D normality unknown unknown unknown n outliers n.a. n.a. n.a. mean (n) (353.51) (355.24) (359.65) st.dev. (n) (.5) (.677) (2.852) R(calc.) (1.4) (1.89) (7.99) R(D116:15) (4.64) (4.64) (4.64) Page 32 of 51 Biodiesel B1: iis17g2astm