Concawe REACH - Analytical Characterisation of Petroleum UVCB Substances
Concawe REACH - Analytical Characterisation of Petroleum UVCB Substances
Concawe REACH - Analytical Characterisation of Petroleum UVCB Substances
CONCAWE
ABSTRACT
The purpose of this report is to summarise the findings of the scientific and technical work undertaken by CONCAWE to assess the feasibility and potential benefit of characterising petroleum UVCB1 substances beyond the recommendations issued by CONCAWE for the substance identification of petroleum substances under REACH.
KEYWORDS
UVCB, petroleum substances, REACH, substance characterisation, substance identity, analytical techniques, ultra-violet spectroscopy, infra-red spectroscopy, nuclear magnetic resonance spectroscopy, mass spectroscopy, high-pressure liquid chromatography, gas chromatography.
INTERNET
This report is available as an Adobe pdf file on the CONCAWE website (www.concawe.org).
NOTE Considerable efforts have been made to assure the accuracy and reliability of the information contained in this publication. However, neither CONCAWE nor any company participating in CONCAWE can accept liability for any loss, damage or injury whatsoever resulting from the use of this information. This report does not necessarily represent the views of any company participating in CONCAWE.
1
II
CONTENTS
SUMMARY 1. REACH REQUIREMENTS FOR SUBSTANCE CHARACTERISATION 1.1. NATURE OF PETROLEUM UVCB SUBSTANCES 1.2. CONCAWE GUIDANCE ON SUBSTANCE IDENTIFICATION FOR REACH DESCRIPTION OF ANALYTICAL TECHNIQUES CONTAINED IN REACH REGULATION (EC) NO 1907/2006 ANNEX VI 2.1. SPECTROSCOPIC TECHNIQUES 2.1.1. Ultra-Violet (UV) Spectroscopy 2.1.2. Infra-Red (IR) Spectroscopy 2.1.3. Nuclear Magnetic Resonance (NMR) Spectroscopy 2.1.4. Mass Spectrometry (MS) 2.2. CHROMATOGRAPHIC TECHNIQUES 2.2.1. Gas Chromatography (GC) 2.2.2. Liquid Chromatography (LC) CASE STUDIES 3.1. CASE STUDY 1: LOW BOILING POINT NAPHTHAS 3.2. CASE STUDY 2: KEROSINES 3.3. CASE STUDY 3: HEAVY FUEL OIL COMPONENTS 3.4. CASE STUDY 4: OTHER LUBRICANT BASE OILS 3.5. CASE STUDY 5: RESIDUAL AROMATIC EXTRACTS 3.6. CASE STUDY 6: BITUMENS CONCLUSIONS AND RECOMMENDATIONS GLOSSARY REFERENCES
Page IV 1 1 2 5 5 5 6 7 8 9 9 11 13 13 15 16 17 18 18 20 22 25
2.
3.
4. 5. 6.
APPENDIX 1A: STANDARD METHODS ISSUED BY THE ENERGY INSTITUTE (EI) WITH CORRESPONDING BS 2000, EN, ISO AND ASTM METHODS APPENDIX 1B: APPENDIX 2: APPENDIX 3: APPENDIX 4: APPENDIX 5: APPENDIX 6: APPENDIX 7: STANDARD METHODS FOR THE CHARACTERISATION OF PETROLEUM UVCB SUBSTANCES ANALYTICAL DATA FOR CASE STUDY 1 ANALYTICAL DATA FOR CASE STUDY 2 ANALYTICAL DATA FOR CASE STUDY 3 ANALYTICAL DATA FOR CASE STUDY 4 ANALYTICAL DATA FOR CASE STUDY 5 ANALYTICAL DATA FOR CASE STUDY 6
26 45 51 72 82 87 94 103
III
SUMMARY
The purpose of this report is to summarise the findings of the scientific and technical work undertaken by CONCAWE to assess the feasibility and potential benefit of characterising petroleum UVCB substances beyond the recommendations issued by CONCAWE for the substance identification of petroleum substances under REACH. The report is based on Member Company experience of the chemical analysis of petroleum UVCB substances, including analysis in support of REACH registrations undertaken in 2010. This report is structured into four main sections, namely: Section 1: provides an introduction to the subject of petroleum UVCB substance identification including the purpose of the report, regulatory requirements, the nature of petroleum UVCB substances, and CONCAWEs guidance to Member Companies and other potential registrants. Section 2: provides a description of the capabilities of each of the analytical techniques described in REACH Regulation (EC) No 1907/2006 Annex VI item 2. This section also includes details on the type of analytical information obtained by each technique and an evaluation of what each technique can provide for the characterisation of petroleum UVCB substances. Section 3: provides a series of case studies for six petroleum substance categories (low boiling point naphthas, kerosines, heavy fuel oils, other lubricant base oils, residual aromatic extracts and bitumens) to illustrate the value of the information derived from each analytical procedure, and provide an explanation for why some techniques are not scientifically necessary. Section 4: provides a summary of the conclusions reached from the technical investigations undertaken by CONCAWE Member Companies, and summarising the recommendations issued by CONCAWE for the substance identification of petroleum substances, per substance category, under REACH.
IV
1.
The REACH regulation (Annex VI, item 2) states that "For each substance, the information given in this section shall be sufficient to enable each substance to be identified. If it is not technically possible or if it does not appear scientifically necessary to give information on one or more of the items below, the reasons shall be clearly stated." Annex VI item 2 lists some eighteen sub-items to be considered for the identification of a substance and refers to specific analytical information requirements, namely: Item 2.3.5. Spectral data (ultra-violet, infra-red, nuclear magnetic resonance or mass spectrum). Item 2.3.6. High-pressure liquid chromatogram, or gas chromatogram 1.
1.1.
According to the June 2011 guidance entitled Questions and answers on inquiry and substance identification (ECHA-11-QA-02-EN) registrants are guided to provide either a High Pressure Liquid Chromatogram or a Gas Chromatogram.
As shown in the figure below, the lightest petroleum substances, such as LPG, are composed of relatively few hydrocarbon components but with increasing carbon number the complexity increases exponentially such that naphthas (~C4-C12 range hydrocarbons) contain a few hundred individual compounds and kerosines (~C9-C16 range hydrocarbons) contain several thousand components. Gas oils contain hundreds of thousands of components and the heavier refinery products (e.g. lubricating oils; heavy fuel oils; bitumen) are considered to contain many millions of individual chemical compounds. The rapid increase in complexity with carbon number arises from the vast number of isomers encountered in hydrocarbon chemistry but increased carbon number can also lead to increased chemical functionality (e.g. the presence of aromatic species in molecules containing six or more carbon atoms), and the higher molecular weight components can even contain several different chemical functionalities (e.g. naphthenic, aromatic, paraffinic, etc.,).
Petroleum Substances
Possible Structures
101 102
C OO H HO O C N N HO S O N S O S O N HO C OO H HO O C S N S O S S S S S O S S S N H S N H S S N H S S S S O N H S N H N H N H N O N S O N S O N H O OC
104 106
S N H S
S S
1.2.
and customers because they provide a strong technical basis for confirming consistent product quality and assessing potential health, safety and environmental hazards associated with these materials. Appendix 1a illustrates the vast number and range of standard methods issued by the Energy Institute (formerly the Institute of Petroleum or IP), the UK professional body for the energy industry and one of several national or global organisations maintaining standard methods for petroleum substances. Many of these methods are harmonised with those of other organisations (e.g. ASTM, DIN, EN, ISO etc.) and methods are continually being developed, reviewed, updated or deleted depending on industry sector requirements and measurement technologies available. Appendix 1b lists the standard methods considered most relevant by CONCAWE for the characterisation of petroleum UVCB substances for REACH. The CONCAWE guidance confirmed that analytical data should be based on a spot sample of the production or imported substance to provide the following general information as required by Section 4.3.2.2 of the ECHA Guidance for identification and naming of substances under REACH [1]: Source/feedstock (IUCLID5 section 3.1 Technological process Methods of manufacture) Refining history (IUCLID5 section 3.1 Technological process Methods of manufacture) Boiling range (IUCLID5 section 1.4 Analytical information) Carbon number range (IUCLID5 section 1.4 Analytical information) Identification and concentration of any known constituents present at 10% or greater (IUCLID5 section 1.2 Composition) Identification and concentration of any constituents relevant for hazard classification (i.e. concentration of any marker constituents identified for the Category) (IUCLID5 section 1.2 Composition) Identification and concentration of any constituents relevant for PBT assessment (IUCLID5 section 1.2 Composition) Identification of any stabilising additives known to be present (IUCLID5 section 1.2 Composition) Unknown constituents identified by generic description of their chemical nature (IUCLID5 section 1.2 Composition) Chromatographic or spectral information, as appropriate, to substantiate the information reported on composition (IUCLID5 section 1.4 Analytical information). Flash point and viscosity measurements may also be necessary data for IUCLID5 section 1.4 on analytical information in order to ensure appropriate hazard classification for particular categories.
It was recognized that both the REACH regulation and the ECHA guidance allow for the possibility to waive data for the methods included in Annex VI to REACH on the basis of technical feasibility or scientific justification. CONCAWE guidance recommended the provision of analytical information considered sufficient to identify petroleum substances and ensure assignment within the appropriate Petroleum Substance Category, for the purposes of hazard classification and risk assessment. Registrants were recommended to enter in Subsection 1.4 of the IUCLID dossier a
waiving statement for the spectral or chromatographic methods not applied as they were not considered scientifically necessary to identify the substance.
2.
2.1. 2.1.1.
Absorbance intensity is particularly strong for components where the unsaturated bonds are conjugated, such as in aromatic hydrocarbons, and UV spectroscopy is therefore particularly sensitive for the measurement of these compounds. For relatively pure substances or multi-component substances where the component of interest has a particularly intense chromophore, the technique can be used for quantitative analysis and purity assessment. However, UV spectroscopy is more commonly used in a qualitative fashion to indicate the presence/absence of unsaturated compounds. UV spectroscopy is usually carried out using either a dilute solution of the sample in a suitable (non-absorbing) solvent, or directly on the sample using a short path-length measurement cell. Applicability of UV Spectroscopy to petroleum UVCB substances In the case of petroleum UVCB substances, UV spectroscopy yields limited information because the spectra obtained are somewhat similar for most products and typically show a strong absorbance at wavelengths below 250-300 nm. This arises from the very strong UV absorbance of aromatic and olefinic hydrocarbons,
so even petroleum substances containing very low concentrations (ppm levels) of these components will produce a spectrum showing a strong absorption band. Moreover, UV spectroscopy typically yields broad, unresolved bands owing to the various vibrational and rotational energy levels associated with each electronic transition state so the wavelength resolution is insufficient to differentiate between absorbances arising from aromatic or olefinic components present in the substance.
2.1.2.
The low-energy region of the spectrum (400-1500 cm-1) is known as the fingerprint region because it is particularly characteristic for each compound and can therefore be useful for assessing the purity of simple substances. As for UV spectroscopy, IR spectroscopy of liquid substances is usually carried out either as a dilute solution in a suitable (non-absorbing) solvent or directly using a short path-length measurement cell. Samples can also be examined directly by attenuated total reflectance measurements. Applicability of IR Spectroscopy to petroleum UVCB substances For petroleum substances, IR spectroscopy is mainly used in a qualitative fashion to indicate the presence or absence of specific hydrocarbon functionalities such as alkyl or aryl groups. However, as shown in Appendices 2.2, 3.2, 4.2, 5.2, 6.2 and 7.2, many different petroleum UVCB substances yield very similar IR spectra and, because the absorbance bands corresponding to unsaturated hydrocarbons are weaker than those associated with saturated hydrocarbons, it does not always provide a good estimate of the degree of aromaticity present in petroleum UVCB substances.
2.1.3.
C NMR Chemical shift 9-60 ppm 14 ppm 19 ppm 23 ppm 30 ppm 32 ppm 35-45 ppm 100-130 ppm 130-150 ppm
Carbon type Environment alkyl terminal methyl CH3-CH2-CH2-CH2internal methyl -CH2-CH(CH3)-CH2methylene CH3-CH2-CH2-CH2methylene CH3-CH2-CH2-(CH2)nmethylene CH3-CH2-CH2-CH2branched and cyclic aromatic (tertiary) and olefinic (tertiary and secondary) aromatic and olefinic (quaternary)
Other nuclei which generate signals include 19F, 29Si and 31P although these have little relevance for characterising petroleum UVCB substances which consist predominantly of hydrocarbons. In addition to providing detailed structural information, including discriminating between certain isomers, NMR provides quantitative information on the different types of nuclei present (e.g. CH, CH2 and CH3 protons) and is therefore also employed for assessing the purity of simple substances. A range of signal enhancement techniques can also be used to provide greater discrimination and more structural information about the substance under investigation. The majority of NMR measurements are carried out on solutions of the test substance in a deuterated (2H) solvent such as deuterochloroform. Modern high-field instruments (e.g. 500 MHz) enable most proton NMR spectra to be
obtained within a few minutes whereas it may take several hours to obtain a carbon NMR spectrum owing to the relatively small quantity of 13C present in the sample. Although interpretation of complex NMR spectra requires considerable expertise, extensive libraries of reference spectra and predictive computer programs facilitate the routine identification of simple substances. Applicability of NMR Spectroscopy to petroleum UVCB substances NMR cannot discriminate between different constituents in a petroleum UVCB substance and the information obtained, whether qualitative or quantitative, therefore refers to the bulk sample. Moreover, the complexity of these substances is such that it is not possible to resolve all the signals in the NMR spectrum nor assign them to specific nuclear resonances and couplings and, as shown in Appendices 2.3, 3.3, 4.3, 5.3, 6.3 and 7.3, many different petroleum UVCB substances yield very similar NMR spectra. However, some signals can be assigned to specific groups of 1 H and 13C nuclei present and, although this information does not permit identification of individual constituents present in the sample, it provides accurate quantitative information on the total quantities of some chemical functionalities present. For example and as described in Case Studies 2 and 4, the values for total aromatic content of the kerosine and base oil samples determined by 13C NMR and HPLC are in good agreement when the NMR value for aromatic carbon content is adjusted to reflect the carbon number distribution of the constituents present in these samples.
2.1.4.
Applicability of MS to petroleum UVCB substances As indicated above, MS data obtained by direct analysis of a petroleum UVCB substance, in which all constituents are ionised and fragmented simultaneously, would be too complex to allow meaningful interpretation. Spectral libraries typically contain MS data obtained on single constituent or relatively pure simple substances and therefore have little value for characterising UVCB substances unless it is possible to separate the constituents present before generating the spectroscopic data, which can sometimes be achieved by GC-MS or HPLC-MS. In addition to the complexity of the spectra obtained for petroleum UVCB substances, the relatively poor molecular ionisation of many hydrocarbon constituents limits the value of MS for the comprehensive characterisation of these materials. Moreover the degree of ionisation can differ considerably depending on the chemical functionalities present in the substances (e.g. aromatic species are more readily ionised than saturated constituents), and with the relative molecular mass of a particular class of constituents. It is also unable to discriminate between hydrocarbon isomers and can therefore only provide limited information on constituents typically found in petroleum UVCB substances.
2.2. 2.2.1.
chromatographic peaks rather than by using a vast number of individual calibration standards. The lighter petroleum UVCB substances like naphthas and gasoline, which typically contain a few hundred individual constituents in the ~C4-C12 range, can be comprehensively characterised by Detailed Hydrocarbon Analysis (DHA) GC or Reformulyzer-GC analysis. DHA uses temperature-programmed, high-resolution, capillary column GC analysis to resolve all the hydrocarbons present such that each individual constituent can be identified (by retention matching) and quantified. Reformulyzer-GC analysis is a multi-dimensional chromatographic technique in which a series of special column-coupling and column-switching procedures are employed to separate the constituents into different hydrocarbon groups (e.g. nalkanes; iso-alkanes; cyclo-alkanes/naphthenes; aromatics) prior to final resolution of the individual constituents. By modifications to the instrument configuration and operating conditions it is possible to optimise the separation depending on the specific characteristics of the petroleum substance under investigation. DHA-GC and Reformulyzer-GC are unable to resolve the many thousands of constituents present in the heavier middle-distillate petroleum substances, such as kerosine (~C9-C16 range hydrocarbons) and diesel fuel (~C11-C25 range hydrocarbons). The more recently developed technique of comprehensive two-dimensional GC (GCxGC) can provide detailed compositional information on these more complex petroleum substances although it should be noted that even this technique cannot provide total separation of all the constituents present. GCxGC involves separation using two GC columns, each having different properties. The constituents eluting from the first column are repeatedly trapped and introduced onto the second column so the whole sample is subjected to two independent (orthogonal) GC separations, which gives greatly enhanced separation of the numerous constituents present. For petroleum substances the first-dimension separation is usually based on the relative volatility of the constituents present (i.e. carbon number) and the second dimension separation on their relative polarity (i.e. chemical functionality), so it is possible to provide quantitative information on the different hydrocarbon types (e.g. alkanes, naphthenes, aromatics, naphthenic-aromatics etc) for each carbon number present. GCxGC can therefore provide detailed compositional analysis information on middle-distillate petroleum UVCB substances but the upper temperature limit of the second column used for the polarity separation currently limits its application to substances containing <C30-35 hydrocarbons. Although GCxGC is capable of separating highly complex mixtures, considerable effort and expertise is required to develop GCxGC methodologies for specific substances. At present there are no petroleum industry standard methods which employ GCxGC and most petroleum analysis laboratories do not currently have this capability. Simulated Distillation (SIMDIS) GC is a specific type of GC frequently used to screen middle-distillate and heavier petroleum substances and provide information of their boiling range and carbon number distribution. In essence the technique involves analysing a sample by temperature-programmed GC on a hightemperature, non-polar separation column which basically separates constituents in order of their relative volatility. The system is calibrated by analysing a mixture of nalkane standards, with known boiling points, on the same column under the same operating conditions and relative carbon numbers can then be obtained for the hydrocarbon constituents present in the petroleum UVCB substance. Although the technique is unable to resolve the multitude of individual constituents present in most UVCB petroleum substances, SIMDIS-GC provides a good estimate of the boiling range and carbon number distribution.
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2.2.2.
carbon dioxide facilitates the use of FID, an excellent universal hydrocarbon detector, which is not possible with HPLC. Although SFC is little used by European petroleum analysis laboratories, in which HPLC is the preferred technique for the measurement of aromatic hydrocarbons in middle distillate fuels, it is widely employed in the USA, as illustrated by the existence of an industry standard method for this analysis 2.
ASTM D5186-03(2009) : Standard Test Method for Determination of Aromatic Content and Polynuclear Aromatic Content of Diesel Fuels and Aviation Turbine Fuels by Supercritical Fluid Chromatography.
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3.
CASE STUDIES
In general, characterisation of petroleum substances has focused on the measurement of physico-chemical properties and specific chemical constituents or markers (e.g. benzene, PAHs, etc.,) which are critical to the performance and safe use of the materials. As described in Section 2, detailed characterisation of the lighter petroleum UVCB substances (e.g. LPG, naphthas) is possible using GC, but similar characterisation of the heavier substances (e.g. lubricating base oils; heavy fuel oils; bitumen) is not currently possible by any of the techniques described. Consequently most of the analytical information which can be generated on these heavier materials relates to the concentrations of particular classes of constituents present (e.g. olefins; di-aromatics etc) rather than to individual constituents. As shown in the CONCAWE guidance paper entitled Guidance on analytical requirements for petroleum UVCB substances [1], many industry standard methods have been developed for this purpose. Characterisation of many petroleum substances relies on obtaining complementary information from different analytical techniques. Some techniques provide a considerable amount of information while other approaches yield little, if any, further information. CONCAWE therefore proposes that a structured approach to chemical characterisation be employed depending on the specific petroleum UVCB substance under investigation rather than examining all substances using a standard suite of analytical techniques, such as those listed in Annex VI of the REACH Regulation. To illustrate the value of such an approach and show why some of the analytical techniques listed in Annex VI of the REACH Regulation are not scientifically necessary, case studies are presented below for six specific petroleum UVCB substance categories (low boiling point naphthas; kerosines; heavy fuel oil components; other lubricant base oils; residual aromatic extracts; bitumen). Although only six categories are addressed in this report, the evidence presented is also applicable to the other categories of petroleum UVCB substances.
3.1.
13
DHA-GC therefore enables us to provide a comprehensive qualitative and quantitative description of the composition of this naphtha sample which, despite being the simplest petroleum UVCB substance in the case studies presented here, still contains 231 individual constituents. None of the other analytical techniques described below provide additional information to that obtained by DHA-GC and it is therefore recommended that GC alone is sufficient for the analytical characterisation of substances in the naphtha category. The UV/Visible spectrum shows that the sample contains aromatic and/or olefinic hydrocarbons on account of the strong absorbance bands at wavelengths below ~250 nm. This sample was heavily diluted with hexane to give a sample concentration of ~10 ppm prior to measurement. Given that DHA-GC shows this sample contains 7.7% (m/m) aromatics and 0.6% (m/m) olefins, it can be assumed that the UV absorbance results from ~1 ppm aromatic/olefinic hydrocarbons. It is not therefore surprising that virtually every petroleum UVCB substance yields a UV spectrum showing very strong absorbance at wavelengths below ~250 nm. Moreover, this absorbance cannot be attributed to a single chemical constituent but is likely to have resulted from several constituents, possibly with widely varying extinction coefficients, and it is therefore impossible to make any accurate quantitative measurement from the UV spectrum obtained on the naphtha sample. The IR spectrum provides slightly more information than that obtained by UV spectroscopy in that absorbance bands corresponding to the presence of both saturated and aromatic/olefinic bonds are present. However, as with UV spectroscopy, these bands cannot be attributed to individual constituents and arise from the gross chemical functionalities present in this UVCB substance. Consequently it is not feasible to use IR spectroscopy to obtain information on the type and concentration of hydrocarbon constituents present in this naphtha sample. DHA-GC shows that this sample contains 7.7% (m/m) aromatics, 29.0% (m/m) n-paraffins, 32.5% (m/m) iso-paraffins, 29.9% (m/m) naphthenes and 0.6% (m/m) olefins, but IR spectroscopy can only confirm the presence of saturated and aromatic/olefinic components. The 1H NMR spectrum provides more information on the composition of the naphtha sample than IR spectroscopy. NMR confirms the presence of saturated, aromatic and olefinic moieties and therefore has the advantage over IR that it can discriminate between aromatic and olefinic functionalities present in a sample. Moreover, NMR is an accurate quantitative technique and the integrated spectrum shows that the vast majority of the measured signal (0.2-2 ppm chemical shift) arises from protons associated with saturated bonds but there is also a low percentage of protons associated with aromatic nuclei (2-4.5 ppm and 6-8 ppm chemical shift) and a trace of olefinic protons (4.5-6 ppm chemical shift). These results therefore do not contribute further to the information obtained on this sample by DHA-GC. Furthermore, care must be taken when interpreting quantitative NMR data because in this case the value for aromatic protons (6-8 ppm chemical shift) refers only to the percentage of hydrogen atoms in the aromatic rings of the molecules present relative to the total hydrogen content of the substance, the hydrogen atoms present in the substituent side chains of the aromatic rings not being included in this chemical shift region.
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3.2.
15
In summary, the chromatographic techniques (HPLC and SIMDIS-GC) provide some degree of separation of the several thousand individual constituents present in the kerosine sample, and provide for the quantification of aromatic classes and saturated aliphatic hydrocarbons. In contrast, spectral data (UV, IR, NMR) provide only gross chemical functionalities and no information on individual constituents present in the kerosine. None of the spectroscopic techniques provide any additional information beyond that provided by HPLC. There are no individual constituents in kerosine defined for hazard classification (markers). In order to identify and quantify the hydrocarbon constituents of petroleum UVCB substances in the middle distillate range and heavier, more advanced analytical techniques are required, beyond those in routine use within the petroleum industry and, in our view, beyond those specified in Annex VI to the REACH regulation. In the case of middle distillate UVCB substances like kerosine, GCxGC analysis with a universal hydrocarbon detector such as FID can provide detailed and comprehensive quantitative information on the chemical composition and has been used to provide input for environmental risk assessments.
3.3.
16
3.4.
17
3.5.
3.6.
18
by separation as the raffinate from a residual oil in a deasphalting or decarbonization process. Information on the boiling range of Sample A was obtained by distillation which showed that the sample has an initial boiling point (atmospheric equivalent temperature) of 380C and that just over 5% (m/m) of the components present in the sample had distilled over at the final temperature of 511C (atmospheric equivalent temperature). Sample B was examined by SIMDIS-GC which showed it to contain constituents in the C25 to >C100 carbon number range and with initial and final boiling points of 439C and >750C respectively. Open-column LC on Sample A provided quantitative information on the major classes of compounds present and indicated that the sample contains 50.3% (m/m) aromatic components and 27.8% (m/m) saturated components together with 21.9% (m/m) polar material (i.e. resins and asphaltenes). Sample B was examined by TLCFID which showed it to contain 65.4% (m/m) aromatic and 10.6% (m/m) saturated hydrocarbons together with 11.9% (m/m) resins and 12.1% (m/m) asphaltenes. The proton NMR spectrum obtained on Sample A confirms the presence of aliphatic and aromatic moieties and indicates that no significant concentration of olefinic protons are present. In this case no integration of the signals was made due to severe peak overlaps, which is indicative of the very high complexity of substances such as bitumen. UV spectroscopy on the same sample shows that it contains aromatic and/or olefinic hydrocarbons on account of the strong absorbance band at ~240 nm and, in common with the other substances examined by this technique, the sample had to be very heavily diluted with chloroform (sample concentration 40 ppm) to provide an on-scale spectrum. The IR spectrum of this sample indicates the presence of both saturated and aromatic bonds. Bitumen is the heaviest and most chemically complex of the petroleum UVCB substance categories containing many millions of individual hydrocarbon constituents. Distillation enables us to determine the boiling range of this substance whereas SIMDIS-GC provides information on the carbon number distribution and boiling range. Quantitative information on the basic chemical classes present in bitumen, such as saturates, aromatics and polar materials, can be obtained by LC or TLC-FID although, given the great complexity of this substance, it should be noted that some individual components contain more than one chemical functionality. NMR is the most useful of the three spectroscopic techniques applied in this examination with no additional useful information being provided by UV or IR spectroscopy.
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4.
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Table 1
CONCAWE recommendations for the substance identification of petroleum substances under REACH
Comments
(i) Full characterisation of components (i) Full characterisation of components (i) Carbon number range and/or boiling range (ii) Aromatic classes (i) Carbon number range and/or boiling range (ii) Aromatic classes (HPLC) or total aromatics (LC)
Kerosines
Swedish Mk1 Diesel Fuel, Straight-Run Gas Oils, Cracked Gas Oils, Vacuum and Hydrocracked Gas Oils and Distillate Fuels, Other Gas Oils Heavy Fuel Oil Components, Highly Refined Base Oils
(i) Carbon number and boiling ranges (ii) Aromatic classes (HPLC) or total aromatics (LC or NMR) (i) Carbon number and boiling ranges (ii) Total aromatics
Unrefined/Acid Treated Oils, Foots Oils, Paraffin and Hydrocarbon Waxes, Slack Waxes, Petrolatums, Untreated Distillate Aromatic Extracts, Residual Aromatic Extracts Other Lubricant Base Oils
(i) Carbon number and boiling ranges (ii) Total aromatics (i) Carbon number and boiling ranges (ii) Saturates, aromatics and polars (LC) or saturates, aromatics, resins and asphaltenes (TLC-FID)
Bitumens
Note: In addition to the Annex VI techniques listed above, IP 346 is used for Foots Oils, Other Lubricant Base Oils and Treated Distillate Aromatic Extracts as a classification marker for the determination of carcinogenicity. Similarly, ASTM E 1687-04 is used as a classification marker for the determination of carcinogenicity for Residual Aromatic Extracts.
21
5.
Analyte Asphaltenes
GLOSSARY
The substance that is being analysed. Components of crude oil that are insoluble in n-pentane (at a specific dilution ratio) and re-dissolve in toluene. They consist primarily of carbon, hydrogen, nitrogen, oxygen and sulfur, and have molecular masses in the 400-1500 range. American Society for Testing and Materials Carbon-13 nuclei used in nuclear magnetic resonance spectroscoy. Chemical Abstracts Service A specific group of petroleum UVCB substances with similar properties and chemical composition (e.g. kerosines). A group of atoms and bonds in a chemical compound that are responsible for the colour of the compound. A group containing compounds with the same chemical functionality. Single molecular species A conjugated system is a system of connected p-orbitals with delocalised electrons in compounds with alternating single and multiple bonds. The compound may be cyclic or acyclic. The property that is being measured by the analytical method (e.g. monoaromatic content) Detailed Hydrocarbon Analysis Deutsches Institut fr Normung European Commission European Chemicals Agency European Inventory of Existing Commercial Chemical Substances European Norm Value indicating the extent to which a substance absorbs electromagnetic radiation (e.g. UV or IR radiation). Flame ionisation detector Gas Chromatography Comprehensive Two-dimensional Gas Chromatography Gas Chromatography Flame Ionisation Detector
ASTM
13
Determinant
22
GC-MS
1
Gas Chromatography - Mass Spectrometry Hydrogen-1 nuclei used in nuclear magnetic resonance spectroscopy In organic chemistry a heteroatom is any atom other than carbon or hydrogen. The term is usually employed to indicate that non-carbon atoms have replaced carbon in the backbone of the molecular structure. Typical heteroatoms are nitrogen, oxygen, sulfur, phosphorus, chlorine, bromine and iodine. High-performance liquid chromatography. High-performance liquid chromatography - Mass spectrometry. 'Water loving'. Having an affinity for, tending to combine with, or capable of dissolving in water or other polar solvents. A chemical property associated with specific compounds (e.g. aromatic). Infra-Red International Organization for Standardization Compounds having the same type and number of atoms but in different molecular arrangements. International Uniform ChemicaL Information Database Liquid Chromatography Liquefied Petroleum Gas. 'Fat loving'. Having an affinity for, tending to combine with, or capable of dissolving in lipids or other apolar solvents. Types of chemical functionality. Nanometer. Nuclear Magnetic Resonance. Mass Spectrometry. Polycyclic aromatic hydrocarbons Persistent, Bioaccumulative and Toxic Parts per million. Registration, Evaluation, Authorisation and Restriction of Chemical substances Components of crude oil that are insoluble in propane but not in n-heptane.
Heteroatom
Resins
23
Cyclic or acyclic hydrocarbon species composed entirely of single bonds and saturated with hydrogen. Supercritical fluid chromatography. Substance Information Exchange Forum. Simulated Distillation Simulated Distillation - Gas Chromatography The material registered in REACH and described by a specific CAS or EINECS number. Thin-layer chromatography United States of America Ultra-Violet Substances of Unknown or Variable Composition, Complex reaction products or Biological materials.
24
6.
1.
REFERENCES
ECHA (2012) Guidance for identification and naming of substances under REACH. Helsinki: European Chemicals Agency (http://guidance.echa.europe.eu/) CEN (2008) Automotive fuels unleaded petrol requirements and test methods. EN 228:2008. Brussels: Comit Europen de Normalisation CEN (2009) Automotive fuels diesel - requirements and test methods. EN 590:2009. Brussels: Comit Europen de Normalisation Ministry of Defence (2008) Turbine fuel, aviation kerosine type, Jet A-1. NATO Code: F-35. Joint Service Designation: AVTUR. Def Stan 91-91. Issue 6. Glasgow: UK Ministry of Defence IP (1993) Determination of polycyclic aromatics in unused lubricating base oils and asphaltene free petroleum fractions dimethyl sulphoxide extraction refractive index method. IP 346/92. In: Standard methods for analysis and testing of petroleum and related products. Vol 2. Chichester: John Wiley and Sons
2.
3.
4.
5.
25
APPENDIX 1A: STANDARD METHODS ISSUED BY THE ENERGY INSTITUTE ((,) WITH CORRESPONDING BS 2000, EN, ISO AND ASTM METHODS
IP Reference Appendix A:08 Appendix B Appendix C Appendix D Appendix E Appendix F Appendix G Appendix H Appendix I Appendix J 1/94(04) 2/98(04)* 3 4/05* 5 6 7 8 9 10/94(10) 11 12/79(01) 13/94(03) 14/94(04)* 15/95(04)* 16/08* 17/10 18 19/03 20 21 Acidity Aniline and mixed aniline point obsolete Ash obsolete superseded by IP 143 superseded by IP 143 obsolete superseded by IP 129, 130 Kerosine 24 h burning obsolete Specific energy Conradson carbon residue Ramsbottom carbon residue Pour point Freezing point of aviation fuels Colour Lovibond tintometer obsolete Demulsibility characteristics of lubricating oil superseded by IP 295 obsolete SC-C-4 19:03 SC-B-2 SC-B-10 SC-C-4 SC-C-4 SC-B-7 SC-B-10 12.93 13.94 14.94 15.95 6615:93 4262:93 3016:94 524-03 97-02 2386-05 SC-B-10 10:95 SC-G-3 4:02 ISO 6245:02 6245:01 482-03 Method Title Specifications - IP standard thermometers Specifications - IP standard liquids Physical constants obsolete superseded by IP 367 Temperature conversions Density of water Density of ambient air Barometric pressure corrections for Hg barometers TMS Density Density TMS TMS, SCs and Panels SC-C-4 SC-B-10 1:95 2:98 2977:97 611-01 0.4:96 Panel SC-L-4 TMS TMS BS 2000 0:Section 0.1:08 0:Section 0.2:96 EN ISO ASTM D
26
IP Reference 22 23/2000* 24 25 26 27 28 29 30/07 31 32 33 34/03* 35/63(01) 36/02 37/04(10) 38 39 40/97(04)* 41/99* 42 43 44 45 46 47/07e 48/97(11) 49/07e 50/88(07)* 51 52 53/2000* 54 55/77(01)* 56 57/95(03)* 58/07e 59
Method Title obsolete Gasoline engine crankcase oil fuel dilution obsolete obsolete superseded by IP 123 superseded by IP 525 superseded by IP 123 superseded by IP 123 Doctor test superseded by IP 132 obsolete obsolete Pensky-Martens closed flash point Pensky-Martens open flash and fire point Cleveland open flash and fire point Acidity and alkalinity of lubricating grease obsolete obsolete Oxidation stability of gasoline induction period Cetane number engine obsolete superseded by IP 150 superseded by IP 236 superseded by IP 506 obsolete Solubility of bituminous binders Oxidation characteristics of lubricating oil Needle penetration of bituminous material Cone penetration of lubricating grease obsolete superseded by IP 136 Sediment by extraction obsolete Melting point of wax obsolete Smoke point Softening point of bitumen ring and ball obsolete
Panel
BS 2000
EN
ISO
ASTM D
SC-C-4
322-97(02)
SC-B-10
ISO 2719:02
2719:02:00
93-02
ISO 2592:01
2592:00:00
SC-B-8 SC-B-1
40:96 41:98
7536:94 5165:98
525-01 613-01
SC-E
12592:07
1426:07:00 217-02(07)
SC-B-3
53:99
ISO 3735:99
3735:99
473-02
SC-C-7
SC-B-10 SC-E
3014:93
27
IP Reference 60 61/99(08)* 62 63 64 65 66 67 68 69/01(08) 70 71 S1/97* 71 S2/95(04)* 72 73 74/2000* 75 76/70(04)* 77/72(04) 78 79 80/07e 81 82 83 84 85 86 87 88 89 90 91/09e 92 93 94
Method Title obsolete Sulfur high pressure combustion superseded by IP 107 obsolete superseded by IP 154 obsolete superseded by IP 61 obsolete obsolete Reid vapour pressure obsolete Kinematic viscosity and calculation of dynamic viscosity Kinematic viscometers specifications superseded by IP 502 superseded by IP 226 Water by distillation petroleum products obsolete Congealing point of waxes and petrolatum Salt content crude oil and products obsolete obsolete Fraass breaking point of bitumen obsolete obsolete obsolete obsolete obsolete obsolete obsolete obsolete obsolete obsolete Residue on sieving bitumen emulsions and storage stability obsolete obsolete obsolete
Panel
BS 2000
EN
ISO
ASTM D
SC-G-5
61:99
129-00(05)
SC-B-9
69:01:00
3007:99
SC-C-3 SC-C-3
ISO 3104:96
3104:94 3105:94
445-03 446-00
SC-B-3
74:00:00
3733:99
95-99
SC-C-7 SC-G-3
76:93
938-92(98)
SC-E
80:07:00
12593:07
SC-G-2
SC-E
91:09:00
1429:09:00
28
IP Reference 95 96 97 98 99 100 101 102 103/88(01) 104 105 106 107/86(01)* 108 109 110/82(01) 111/82(01) 112/05 113 114 115 116 117 118 119/96(08)* 120 121/11 122 123/01 124 125/08 126 127 128 129/03(10) 130/98(04)* 131/99 132 133/79(01)*
Method Title obsolete obsolete superseded by IP 131 obsolete superseded by IP 136 superseded by IP 213 obsolete obsolete Hydrogen sulphide in LPG and light distillates obsolete obsolete obsolete Lamp sulphur obsolete obsolete obsolete obsolete Copper corrosion grease
Panel
BS 2000
EN
ISO
ASTM D
SC-G-5
SC-G-5
107:93
126698(03)
SC-G-3 SC-G-3 SC-C-6 obsolete obsolete superseded by IP 149 obsolete obsolete obsolete 112:05:00
Supercharge knock rating obsolete Grease oil separation obsolete Distillation of petroleum products obsolete Cast iron corrosion petroleum products superseded by IP 237 obsolete obsolete Bromine number colour indicator titration Bromine number electrometric titration Gum content of light and middle distillate fuels obsolete Drop melting point of wax and petroleum
SC-B-1
909-01
SC-C-6
121:05:00
SC-B-9
123:01:00
ISO 3405:00
3405:00:00
SC-C-5
SC-C-7
133:93
127-87(99)
29
IP Reference 134 135/06* 136 S1/98(06)* 136 S2/99(06)* 137/82(04) 138/02(08)* 139/98(04)* 140 141 142/85(10)* 143/04* 144 145 146/10* 147 148 149/93(03)* 150 151 152 153 154/2000* 155 156/08 157/96(11)
Method Title obsolete Rust preventing characteristics of steam turbine oil Saponification number colour indicator titration Saponification number potentiometric titration Oil content of water mix metalworking fluids Oxidation stability of aviation fuel Acid or base number colour indicator titration obsolete obsolete Oxidation stability of lubricating grease Asphaltenes (heptane insolubles) obsolete obsolete Foaming characteristics of lubricating oils obsolete obsolete Phosphorus in lubricating oils and additives superseded by IP 236 obsolete obsolete obsolete Copper corrosion obsolete Hydrocarbon types by FIA Oxidation stability of inhibited mineral oils (TOST test) Oil content of waxes gravimetric obsolete Hydrometer density superseded by IP 410 obsolete Sulphated ash of lubricating oils and additives obsolete obsolete
Panel
BS 2000
EN
ISO
ASTM D
SC-C-4 SC-G-2 SC-G-2 SC-C-5 SC-B-8 SC-C-4 136:98 S1 136:99 S2 137:93 138:02:00 139:98 6618:96 6293-1:96 6293-2:98
873-02(07) 974-02
942-02(07) 6560-00
SC-C-4
892-06e1
SC-G-3
149:93
4265:86
404700(05)
SC-B-10
154:99
2160:98
130-94(00)
SC-G-2 SC-C-2
156:07:00
SC-C-7
721-02
Density
160:98
ISO 3675:98
3675:98
129899(05)
SC-G-3
163:96
3987:94
30
IP Reference 166 167 168/08 169 170/09 171 172 173 174 177/10* 178 179/79(04)* 180 181 182/06 183/08 184 185/65(04)* 186/93(10) 187 188 189/05 190/05 191 192 193 194 195/98(09) 196/97(04)* 197 198 199 200/08* 212/92(04)
Method Title obsolete obsolete Rolling bearing performance of lubricating grease superseded by IP 264 Flash pointAbel closed-cup obsolete superseded by IP 237 obsolete obsolete Weak and strong acid number potentiometric titration obsolete Cone penetration of petrolatum obsolete obsolete Inorganic acidity colour indicator titration Evaporation loss of lubricating grease superseded by IP 264 Odour of petroleum wax Low temperature torque of lubricating grease obsolete obsolete Pyknometer density Pyknometer density incorporated into IP 123 as Group 0 superseded by IP 160 obsolete obsolete Distillation volatile organic liquids ASTM colour obsolete obsolete obsolete Petroleum measurement tables (published separately) Viscosity of bitumen road emulsions
Panel
BS 2000
EN
ISO
ASTM D
SC-C-6
SC-B-4
170:08:00
ISO13736:08
13736:08
SC-C-4
664-07
SC-C-7
179:93
937-97(02)
SC-C-4 SC-C-6
182:06:00
SC-C-7 SC-C-6
183387(07)
Density Density
189/190:04 189/190:04
3838:04:00 3838:04:00
SC-B-9 SC-B-10
1250-07 SC-E
31
IP Reference 213/82(04) 214 215/08 216/05* 217 218 219/94(04) 220/07 221 222/07e 223/68(04) 224/02 225/76(03) 226/04* 227 228/72(04) 229/93(04) 230 231/69(01) 232 233 234 235/86(04) 236/09* 237/06* 238/82(88)a 239/07 240/84(04) 241 242 243/94(04)
Method Title Neutralization value of bitumen colour indicator titration obsolete Water washout characteristics of lubricating grease Particulate contaminant of aviation turbine fuels obsolete obsolete Cloud point Rust prevention characteristics of lubricating greases obsolete Absolute viscosity of bitumen capillary viscometer Ash of petroleum products containing mineral matter Lead content of light petroleum distillates Copper in light petroleum distillates spectrophotometric Calculation of viscosity index obsolete Lead content of gasoline xray spectrometry Oxidation stability of steam turbine oils obsolete Engine cleanliness obsolete obsolete obsolete Pressure hydrometer density Motor octane number Research octane number obsolete Extreme pressure/antiwear properties of lubricants and greases four ball Extreme pressure properties of lubricants Timken obsolete obsolete Sulfur Wickbold combustion
Panel SC-E
BS 2000 213:93
EN
ISO
ASTM D
SC-B-7 SC-C-6
219:94
23015:94
3015:92
222:07:00 223:93
12596:07
226:02:00
2909:02:00
227093(98)
SC-G-3 SC-C-2
TMS
Density SC-B-1 SC-B-1 SC-B-1 SC-C-1 SC-C-1 236.05 IC March 08 237.05 ISO 5163:05 ISO 5164:05 5163:05:00 5164:05:00 2700-01 2699-01
SC-G-5
243:94
24260:94
4260:87
32
IP Reference 244 245 247/69(01) 248 249/79(04) 250 261 262 263 264/72(07) 265/01(04) 266/93(10) 267 268 269 270/96(04) 271/70(04) 272/2000 273 274/09* 275 276/95(04)* 277 278 280/11 281 282 283 284/04 285/79(04) 286 287/08 288 289/06 290 291/00e
Method Title obsolete obsolete Engine cleanliness and wear obsolete Bingham pyknometer density obsolete obsolete obsolete superseded by IP 580 LPG and propylene concentrates GC Salts content of crude oils conductivity Bearing greases churning tendency obsolete obsolete obsolete Lead content of Gasoline ICl Barium in lubricating oil additive concentrates acid oxidation Mercaptan sulfur and H2S in LPG electrometric titration obsolete Electrical conductivity of aviation and distillate fuels obsolete Base number perchloric acid potentiometric titration obsolete obsolete Oxidation stability of inhibited mineral turbine Oils obsolete obsolete obsolete Saponifiable and unsaponifiable matter in oils, fats and waxes Nickel and vanadium spectrophotometric obsolete Rust prevention characteristics of water mix metal working fluids Use IP 470 instead Water reaction of aviation fuels obsolete Water by distillation bitumen emulsions
Panel
BS 2000
EN
ISO
ASTM D
TMS
Density
270:96
ISO 3830:95
3830:93
272:00:00
SC-B-8
2624-07a
276:96 3771:94
SC-C-4
2896-01
SC-C-2
280:99
7624:97
SC-G-2 SC-G-3
284:04:00
SC-C-5
SC-B-11
SC-E
291:00:00
1428:99
33
IP Reference 292/09e 293 294 295/83(05) 296 297 298/92(06) 299/03* 300 301 302 303 Part 1/01 303 Part 2/01 304 Part 1 304 Part 2 305 306/94(11) 307 308/85(04) 309/99 310/84(10)* 311 312 313/01 314 315/98(04)* 316/93(05) 317/95(02)* 318/75(04) 319/07e 320 321 322 323/11 324 325
Method Title Particle charge of bitumen emulsions obsolete obsolete Electric strength of insulating oils obsolete obsolete Quinizarin extraction spectrophotometric Bromine index electrometric titration obsolete This number not used This number not used Replaced by IP 523 Replaced by IP 524 Replaced by IP 492 Replaced by IP 491 obsolete Oxidation stability of straight mineral oil obsolete Ba, Ca, Mg and Zn in unused lubricating oils AAS CFPP of diesel and domestic heating fuels Quarter and half cone penetration of grease superseded by IP 580 superseded by IP 580 Air release value of hydraulic, turbine and lubricating oils obsolete Copper corrosion electrical insulating oils Solids in used engine oils LPG residue at 38 C Characterization of pollutants GC Kinematic viscosity of bitumens obsolete obsolete obsolete JFTOT thermal oxidation stability of gas turbine fuels obsolete Obsolete
Panel SC-E
BS 2000 292:09:00
EN 1430:09:00
ISO
ASTM D
SC-C-4
SC-B-4 SC-B-4
SC-C-2
306:94
SC-C-4
313:01:00
3427-02
315:98
5662:97
1275-96a
317:95
2158-02
319:07:00
12595:07
SC-B-8
3241-07
34
IP Reference 326/05 327 328 329 330 331 332 333 334 335 336/04 337/78(10) 338 339 342/2000* 343/01(06) 344/88(10) 345 346/92(04) 350 351 352/2007 354/09* 355/01 356/99* 357 358/97(03) 359 360/96a* 361/82(88)a* 362/93(03) 363 364 365/97(04) 366 367/07
Method Title Extreme pressure properties of grease Timken obsolete obsolete obsolete obsolete obsolete obsolete obsolete obsolete use CEC L-07-A obsolete Sulfur by EDXRF Composition of nonassociated natural gas obsolete obsolete Mercaptan sulfur in distillate fuels potentiometric 24M6B in AVTUR HPLC Light hydrocarbons in stabilized crude oils GC obsolete PCAs in petroleum fractions obsolete obsolete Lead content gasoline EDXRF Acidity of AVTUR colour indicator titration Calculation of net specific energy of AVTUR Water in crude oil potentiometric Karl Fischer obsolete Water by distillation crude oils obsolete RON and MON on-line analysers obsolete Lead content of gasoline AAS obsolete obsolete Oscillating U-tube density obsolete Application of precision data
Panel SC-C-1
BS 2000
EN
ISO
ASTM D 2509-03
SC-G-5 SC-G-6
336:03:00
ISO 8754:03
8754:03:00
342:00:00
3012:99
3227-02
SC-G-2
346:96
SC-G-3 SC-B-11 SC-B-2 SC-B-3 355:01:00 356:99 15911:00 10336:97 437700(06) 3242-08
SC- B-3
358:97
ISO 9029:95
9029:90 288595(99)
Density
365:96
ISO12185:96
12185:96
TMS
367:06:00
ISO4259:06
4259:06:00
35
IP Reference 368/01(06) 369/84(06)* 370 371/85(04) 372/85(09) 373/99 374/01(06) 375/99* 376/86(04) 377/95(03) 378/87(01)* 379/88(01)* 380/08 381/97(04)* 382/88(03) 383 384 385/99 386/99* 387/11 388/97(04)* 389/93(04) 390/94(04) 391/07 392/90(08) 393/96(04) 394/08 395/98(04)*
Method Title Hydrocarbon types in lubricating oil basestocks HPLC Composition of oil soluble petroleum sulphonates LC obsolete Drop point of petrolatum Carbon number distribution of paraffin wax GC Sulphur microcoulometry Coumarin fluorimetric and HPLC Sediment in residual fuel oils and distillate blends filtration Needle penetration of petroleum wax Al and Si in fuel oil ICPES and AAS Storage stability at 43 C of distillate fuel Organically bound trace nitrogen Calculation of cetane index Estimation of net specific energy of aviation fuels obsolete obsolete obsolete Viable aerobic microbial content of fuels and fuel components Water in crude oil coulometric Karl Fischer Filter blocking tendency of gas oils and distillate diesel fuels Oxidation stability of middledistillate fuels WATof middle distillate fuels DTA or DSC Thermal and chemical ageing of residual fuel Oils Aromatic hydrocarbon types in diesel fuels and distillates HPLC Aromatic hydrogen and carbon contents NMR Volatility of automotive lubricating oils Air saturated vapour pressure Valve freeze dryness of propane
BS 2000
EN
ISO
ASTM D
371291(00)
SC-C-7 SC-G-6 SC-G-5 SC-G-2 SC-B-5 SC-C-7 SC-G-3 SC-B-5 SC-G-5 SC-B-2 SC-B-2 SC-G-6 380:07:00 381:97 ISO 4264:07 4264:07:00 3648:94 4529-02 377:95 10478:94 462592(98) 4629-02 375:99 +TC1:97 103071:93 4870-99
Microbiology SC-B-3 SC-B-5 SC-B-5 SC-G-9 SC-B-5 SC-G-2 SC-G-4 SC-G-9 SC-B-9 SC-B-5 394:07:00 395:97 13016-1:07 ISO13758:96 13758:96 271391(01) 390:94 391:06:00 12916: 06 103072:93 388:96 ISO12205:96 12205:95 2274-03 386:99 10337:97 492800(05)
36
IP Reference 396/02 397 398/96(04) 399/10 400/01 401/95(04) 402 403 404 405/94(09) 406/06* 407/95(04) 408/98(09) 409/08 410/99(08) 411/99(07) 412/96(04) 413/96(03) 414/96(04) 415/07* 416/96(04) 417/96(04) 418/96(04) 419/03 420 421 422/96(11) 423/10* 424/96(10) 425/01(07) 426/98(04) 427/97(04)
Method Title Automatic dropping point of lubricating grease obsolete Carbon residue (micro method) Hydrogen sulfide in fuel oils Base number conductimetric titration Hydrogen sulfide in LPG lead acetate obsolete obsolete obsolete Propane and butane analysis by GC Boiling range of products GC method Ba, Ca, P, S and Zn by WDXRF Oxygenates and total oxygen in unleaded petrol GC, O-FID Absolute vapour pressure of gasoline at 40 C and 100 C Gauge vapour pressure of LPG Copper corrosion LPG Water separability of petroleum oils and synthetic fluids Low levels V flameless AAS Cooling characteristics industrial quenching oils Particulate content of middle distillate fuels laboratory filtration Sulfate and nitrate in diesel particulate filters Base number potentiometric titration Relative volatility of automotive lubricating oils obsolete Superseded by IP 432 obsolete Filter flow of aviation turbine fuels Particulate contaminant of AVTUR laboratory filtration FSII in AVTUR by HPLC Benzene content GC Oil content of effluent water Oily residues hightemperature
Panel SC-C-6
BS 2000
EN
ISO
ASTM D
398:96
ISO10370:95
10370:93
401:95
ISO 8819:95
8819:93
SC-G-6 SC-G-6 SC-G-3 SC-G-6 SC-B-9 SC-B-9 SC-B-10 SC-C-4 SC-G-3 SC-C-5 SC-B-5 SC-G-10 SC-C-4 SC-G-9 SC-B-7
405:94
27941:93
7941:88 2887-02
1601:97 13016-2:07 ISO 4256:98 ISO 6251:98 4256:96 6251:96 6614:94 8691:94 9950:95 621798(03)
SC-B-7 SC-B-11 SC-G-2 SC-G-6 SC-G-4 SC-B-5 427:96 ISO13757:96 13757:96 425:00:00 12177:00 5452-08
37
IP Reference 428/06(10) 429/04 430/98(10) 431/98(04) 432/00 433/00(10) 434 435/08 436/11 437/98(04) 438/01 439/01 440/08 441/99(04)* 442/99 443/99 444/09* 445/09* 446/09* 447/08 448S2 449/00 450/00 451/00(05) 452 453/10* 454/00
Method Title Low lead content of petrol AAS Benzene content of petrol IR Alkyl nitrate in diesel fuels Acid number semi-micro colour indicator titration LPG calculated density and vapour pressure Vanadium and nickel content WDXRF Replaced by IP 528 Freezing point of aviation turbine fuels automatic phase transition Aromatic in aviation fuels and distillates HPLC RI Elements in unused lubricating oils and additive packages ICPAES Water content products coulometric Karl Fischer Water content products potentiometric Karl Fischer Contamination in middle distillates Pour point of crude oils Fuel and oil-derived hydrocarbons in diesel particulates GC SOF of diesel particulates soxhlet extraction gravimetric Cloud point automatic stepped cooling Cloud point automatic linear cooling rate Cloud point automatic constant cooling rate Sulphur content WDXRF now only published as BS ISO 13357:2 Acid number non-aqueous potentiometric titration Lubricity of diesel fuel HFRR Aromatic carbon content of lubricant mineral base oils IR obsolete High temperature foaming characteristics of lubricating oils Phosphorus in gasoline spectrophotometric
Panel SC-G-3 SC-G-4 SC-G-2 SC-C-4 SC-B-2 SC-G-3 SC-B-7 SC-B-7 SC-G-2 SC-G-3 SC-B-3 SC-B-3 SC-B-5 SC-B-7 SC-G-10 SC-G-10 SC-B-7 SC-B-7 SC-B-7 SC-G-5 SC-C-4 SC-C-4 TMS SC-G-4
ISO
ASTM D
13759:96 7537:97
ISO8973:99 ISO14597:99
8973:97 14597:97
6379-99
ISO12937:00
585395(00)
449:98 450:00:00
12634:98 (12156)
6082-06
38
IP Reference 455/01 456/00 457/00e 458/09e 459 Part 1/07e 459 Part 2/00e 460 Part 1/07e 460 Part 2/07e 460 Part 3/07e 461/07e 462-1/01 462-2/02 462-3/08 463/02* 464/01(10) 465/01(10) 466/01(07) 467/01* 468 469/01(06) 470/05 471/06 472/02 473/02(09) 474/05 475/05 476/02
Method Title Manganese in gasoline AAS Potassium in gasoline AAS Bitumen characterisation of perceptible properties Recovered binder and oil from bitumen emulsions by distillation Bitumen paraffin wax content by distillation Bitumen paraffin wax content by extraction Bitumen resistance to hardening RTFOT Bitumen resistance to hardening TFOT Bitumen resistance to hardening RFT Bitumen preparation of test samples PCBs separation by GC ECD PCBs and related products PCBs and related products, determination and quantification Potential instability of middle distillates Sodium by AAS Nickel and vanadium by AAS Oxygenates and organically bound oxygen GC High temperature stability of middle distillate fuels obsolete Saturated, aromatic and polar compounds TLC FID Metals in fuel oil by AAS Water content of fuel oil Karl Fischer potentiometric Fungal fragments content of fuels boiling below 390C Composition of LP GC Bitumen sampling Manual sampling Automatic pipeline sampling
Panel SC-G-3 SC-G-3 SC-E SC-E SC-E SC-E SC-E SC-E SC-E SC-E SC-G SC-G SC-G SC-B-5 SC-G-3 SC-G-3 SC-G-6 SC-B-5
BS 2000 455:01:00 456:00:00 457:00:00 458:09:00 459:07 Part 1 459:00 Part 2 460:07 Part 1 460:07 Part 2 460:07 Part 3 461:07:00 462.1:01 462.2:01 462.3:04
EN
ISO
ASTM D
1425:99 1431:09 12606-1:07 12606-2:99 12607-1:07 12607-2:07 12607-3:07 12594:07 12766-1:00 12766-2:01 12766-3:04
6748-02
464:01:00 465:01:00 466:01:00 241:00:00 13131:00 13132:00
6468-99
SC-G-2 SC-G-3 SC-B-3 Microbiology SC-G-6 PTI/13/-/3 PTI/13/-/3 PTI/13/-/3 474:04:00 475:04:00 476:02:00 58:04:00 ISO 3170:04 ISO 3171:99 3170:04:00 3171:88
39
IP Reference 477/02 478/02(09) 479/02 480/07 481/03(09) 482/02 483/02 484/03e 485/09e 486/09e 487/09e 488/09e 489/03(10) 490/05 491/03 492/03 493/03e
Method Title Liquefied petroleum gas sampling Copper in AVTUR Wet and dry oil density Boiling range distribution of distillates and lubricants GC Air saturated vapour pressure (ASVP) of crude oil obsolete Sediment in crude oil membrane filtration Efflux time of bitumen emulsions Settling tendency of bitumen emulsions Mixing stability with cement of bitumen emulsions Penetration power of bitumen emulsions pH bitumen emulsions Low lead in gasolines WDXRF Sulfur petroleum products UV Flash/no flash closed cup equilibrium Flash point closed cup equilibrium Recovery of binder from bitumen emulsions by evaporation Breaking behaviour cationic bitumen emulsions mineral filler Breaking behaviour cationic bitumen emulsions fines mixing time Sulfur in automotive fuels EDXRF Sulfur in automotive fuels WDXRF Derived cetane number IQT Aromatic carbon 13C NMR spectroscopy Phosphorus in residual fuels UV Al, Si, V, Ni, Fe, Na, Ca, Zn and P in residual fuel oil ICPES Viscosity of cutback and fluxed bitumens Chlorine and bromine WDXRF Staining tendancy of bitumen Viscosity of bitumen rotating spindle Loss in mass on heating bitumen
Panel PTI/13/-3 SC-G-3 Density SC-G-6 SC-B-9 SC-B-8 SC-B-3 SC-E SC-E SC-E SC-E SC-E SC-G-3 SC-G-5 SC-B-4 SC-B-4 SC-E
BS 2000 477:01:00
EN ISO 4257:01
ISO 4257:01:00
ASTM D
480:06:00
15199-1:06
484:03:00 485:09:00 486:09:00 487:09:00 488:09:00 489:02:00 490:04:00 491:02:00 492:02:00 493:02:00
12846:02 12847:09 12848:09 12849:09 12850:09 13723:02 ISO 20846:04 ISO 1516:02 ISO 1523:02 13074:02 20846:04 1516:02:00 1523:02:00
494/09e 495/09e 496/05 497/05 498/08 499/11 500/03 501/05 502/03e 503/04 504/10e 505/10e 506/09e
SC-E SC-E SC-G-5 SC-G-5 SC-B-13 SC-G-4 SC-G-3 SC-G-3 SC-E SC-G-3 SC-E SC-E SC-E
40
IP Reference 507/07 508/04 509/04 510/04(10) 511/04 512/04 513/10e 514/04e 515/04e 516/10e 517/10e 518/10e 519/10e 520/08e 521/05e 522/08e 523/05 524/05 525/10e 526/05 527/05 528/08 529/08* 530/06 531/10* 532/10* 533/05e 534/06
Method Title SIMDIST residues Fuel quality monitoring Sampling for fuel quality monitoring Organic halogens Carbonyls in dilute exhaust Test portion preparation - N2 purge Bitumen dynamic viscosity cone and plate Superseded by IP 505/10e Bitumen deformation energy Bitumen elastic recovery Bitumen storage stability Bitumen polymer dispension Bitumen tensile properties Bitumen force ductility Bitumen emulsion adhesivity water immersion Bitumen cohesion pendulum test Flash point rapid equilibrium Flash/no flash rapid equilibrium Cutback bitumen distillation Hydrocarbon types and oxygenates MDGC Grease cold temperature cone penetration AVTUR freezing point fibre optic AVTUR freezing point automatic laser Density of grease Sulfur content proportional counting EDXRF Sulfur content polarized XRF Bitumen flexural creep, bending beam rheometer Flash point small scale ramp
Panel SC-G-6 PTI/2 TMS SC-G-5 SC-G-10 SC-G-10 SC-E SC-E SC-E SC-E SC-E SC-E SC-E SC-E SC-E SC-E SC-B-4 SC-B-4 SC-E SC-G-6 SC-C-6 SC-B-7 SC-B-7 SC-C-6 SC-G-5 SC-G-5 SC-E SC-B-4
ISO
ASTM D
512:04:00 513:10:00 514:03:00 515:03:00 516:10:00 517:10:00 518:10:00 519:10:00 520:08:00 521:04:00 522:08:00 523:04:00 524:04:00 525:10:00 526:04:00 527:04:00
ISO 20764:03 13702-1:10 13702-2:03 13703:03 13398:10 13399:10 13632:10 13587:10 13589:08 13614:04 13588:08 ISO 3679:04 ISO 3680:04 13358:10 14517:04
20764:03
3679:04:00 3680:04:00
13737:04
7153-05
41
IP Reference 535/05e 536/05e 537/06 538/08 539/08 540/08 541/06 542/06e 543/10 544/07 545/09 546/07e 547/07 548/07* 549/09e 550/08 551/07e 552/08 553/08 554/08 555/08 556/08 557/08 558/07* 559/08 560/08 561/08 562/09
Method Title Bitumen accelerated ageing, pressure vessel Bitumen shear, modular and phase angle Purity of heptane and methylcyclohexane GC Total acidity of ethanol Water content of ethanol Gum content of AVTUR Ignition quality of marine fuel oils (FIA) Stabilisation of binder Dynamic viscosity Metal corrosion grease Crude oil boiling range GC Superseded by IP 505/10e FAME Ca K Mg and Na Aromatics in distillates HPLC Bitumen density and specific gravity Sulfated ash of burner fuels from waste mineral oils Bitumen ageing RCAT Ethanol chloride Ethanol sulfur WDXRF Ethanol sulfur UV Ethanol phosphorus Ethanol copper Ethanol pHe X-ray code of practice Hand held density meter Metals in used greases WDXRF Metals in used greases ICPAES Metalworking fluids foam test
Panel SC-E SC-E SC-G-6 SC-G-2 SC-B-3 SC-B-8 SC-B-14 SC-E SC-C-3 SC-C-6 SC-G-6 SC-E SC-G-3 SC-G-2 SC-E SC-G-3 SC-E SC-G-3 SC-G-5 SC-G-5 SC-G-3 SC-G-3 SC-G-2 SC-G-3 Density SC-G-3 SC-G-3 SC-C-5
EN 14769:05 14770:05
ISO
ASTM D
538:07:00 539:07:00
15491:07 15489:07
542:06:00
14895:06
549/A1:09
15326:07+A1
42
IP Reference 563/08 564/11 565/11 566/09 567/09 568/11* 569/09 570/11 571/09 572/09 573/09 574/09 575/09e 576/09 577/11 578/10 579/10
Method Title Ethanol inorganic chloride and sulfate IC AVTUR cleanliness LAPC AVTUR cleanliness PAPC Hydrocarbon types and oxygenatesMDGC DCN of middle distillate fuelsConstant volume combustion chamber SDA in AVTUR and middle distillate fuels Lovibond colourAutomatic Hydrogen sulfide in fuel oils rapid phase extraction Ethanol higher alcohols, methanol and volatile impurities GC Ethanol water Karl Fischer potentiometric titration Ethanol visual appearance FAME stability to accelerated oxidation Bitumen adhesivity water immersion Ethanol dry residue gravimetric AVTUR cleanliness APC light extinction FAME PUFA GC Determination of FAME in middle distillates - Infrared spectrometry method Water mix metal working fluids thermal and emulsion stability and foaming characteristics Determination of P, Cu and S content by ICP-OES Determination of boiling range distribution, GC method FAME in AVTUR - FTIR rapid screening method Determination of the fracture toughness temperature by a three point bending test on a notched specimen FAME in AVTUR-GC-MS Ethanol blending component and ethanol (E85) automotive fuel - Electrical conductivity not yet published
Panel SC-G-3 SC-B-11 SC-B-11 SC-G-6 SC-B-13 SC-G-2 SC-B-10 SC-G-5 SC-G-6 SC-B-3 SC-M SC-M SC-E SC-M SC-B-11 SC-G-6 SC-G-4
BS 2000 563:08:00
EN 15492:08
ISO
ASTM D
566:08:00
ISO 22854:08
22854:08
7524-10
578:09:00 579:09:00
15779:09 14078:09
SC-C-5 SC-G-3 SC-G-6 SC-G-4 SC-E SC-G-6 SC-B-8 586:10:00 15938:10 584:10:00 15963:10 581:09:00 582:10:00 15837:09 ISO 3924:10 3924:10:00
43
Method Title not yet published not yet published FAME in aviation turbine fuel HPLC method not yet published Determination of Pb, Ni, Cr, Cu, Zn, As, Cd, Tl, Sb, Co, Mn and V in burner fuels by ICPMS method Determination of Pb, Ni, Cr, Cu, Zn, As, Cd, Tl, Sb, Co, Mn and V in burner fuels by WDXRF method Determination of Hg in burner fuels - combustion, amalgamation, CVAAS method
Panel
BS 2000
EN
ISO
ASTM D
SC-G-2
SC-G-3
593/11
SC-G-3
594/11
SC-G-3
44
Method
DISTILLATION
Title
Analyte(s)
Scope
Comments
IBP, FBP and specific temperatures at which 2%, 5%, light/middle distillates; IBP >0 C; 10%, 20% ..... 95% of sample FBP <400 C recovered
GAS ANALYSIS BY GC
Commercial propane and butane Analysis saturated and unsaturated C2, C3, C4 and C5 hydrocarbons by gas chromatography
ASTM D5134
hydrocarbon components of individual components <151 C; petroleum naphthas (including suitable for samples containing n-hexane and BTEX) <2% olefins
APPENDIX 1B: STANDARD METHODS FOR THE CHARACTERISATION OF PETROLEUM UVCB SUBSTANCES
45
46
ASTM D6729
Determination of Individual Components in Spark Ignition Engine Fuels by 100 Metre Capillary High Resolution Gas Chromatography
hydrocarbon components individual components <225 C; (including n-hexane and BTEX) suitable for samples containing and oxygenates (e.g. MeOH, <25% olefins EtOH, BuOH, MTBE, ETBE, TAME)
ASTM D6730
Determination of Individual Components in Spark Ignition Engine Fuels by 100Metre Capillary (with Precolumn) High-Resolution Gas Chromatography
hydrocarbon components individual components <225 C; (including n-hexane and BTEX) suitable for samples containing and oxygenates (e.g. MeOH, <25% olefins EtOH, BuOH, MTBE, ETBE, TAME)
Liquid petroleum products Determination of hydrocarbon types and EN 22854 / ISO 22854 / oxygenates in automotive-motor gasoline ASTM D6839 Multidimensional gas chromatography method
SIMULATED DISTILLATION BY GC
EN 15199-1 / IP 480
Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils
IBP, FBP and specific temperatures representing 5%, IBP >100 C; FBP <750 C 10%, 20% ..... 95% sample recovery
EN 15199-2 / IP 507
Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 2: Heavy distillates and residual fuels IBP >100 C; FBP >750 C
IBP and recovery at selected final elution temperature of 720 C or 750 C; specific temperatures representing defined percentage recovery values IBP and recovery at selected calibration against n-alkane standards covering boiling range up to 720 C (C100) or 750 C (C120) calibration against n-alkane standards covering boiling range up to 720 C (C100) or 750 C (C120)
final elution temperature of Petroleum products - Determination of 720 C or 750 C; specific IBP <100 C; FBP >750 C boiling range distribution by gas temperatures representing chromatography method - Part 3: Crude oil defined percentage recovery values IBP, FBP and specific Boiling Range Distribution of Petroleum temperatures representing 5%, FBP <538 C; unsuitable for Fractions by Gas Chromatography 10%, 20% ..... 95% sample gasoline and components recovery
ASTM D3710
specific temperatures Boiling Range Distribution of Gasoline and representing 1% ... 99% sample FBP <260 C Gasoline Fractions by Gas Chromatography recovery and 0.5% (IBP) and 99.5% (FBP)
ASTM D7096
Determination of the Boiling Range Distribution of Gasoline by Wide-Bore Capillary Gas Chromatography
specific temperatures representing 1% ... 99% sample FBP <280 C recovery and 0.5% (IBP) and 99.5% (FBP)
47
48
ASTM D2007
Characteristic Groups in Rubber Extender and Processing Oils and Other PetroleumDerived Oils by the Clay-Gel Absorption Chromatographic Method saturate, aromatic and polar hydrocarbons IBP >260 C
gravimetric measurement of analytes; aromatics measured by difference or desorption from second column
Determination of aromatic hydrocarbon types in aviation fuels and petroleum distillates High performance liquid chromatography method with refractive index detection mono- and di-aromatic hydrocarbons boiling range 50-300 C; suitable for samples containing 0-75% mono-aromatics and 0-25% diaromatics
samples with FBP >300C can contain tri-aromatic and heavier hydrocarbons and should be analysed by IP 391
IP 391 / EN 12916
Petroleum products - Determination of aromatic hydrocarbon types in middle distillates High performance liquid chromatography method with refractive index detection mono-, di- and tri+ aromatic hydrocarbons boiling range 150-400 C
Determination of aromatic hydrocarbon types in middle distillates High performance liquid chromatography method with refractive index detection mono-, di- and tri+ aromatic hydrocarbons
IP 368
Determination of hydrocarbon types in lubricating oil basestocks Preparative high saturate and aromatic performance liquid chromatography hydrocarbons method
IBP >270 C
ASTM D7419
Determination of Total Aromatics and Total Saturates in Lube Basestocks by High saturate and aromatic hydrocarbons Performance Liquid Chromatography (HPLC) with Refractive Index Detection suitable for samples containing 0.2-46% aromatics backflush method
IP 469
Determination of saturated, aromatic and polar compounds in petroleum products by saturate, aromatic and polar hydrocarbons thin layer chromatography and flame ionisation detection IBP >300 C (5% recovered sample)
IP 392
Determination of aromatic hydrogen and carbon content High resolution nuclear magnetic resonance spectroscopy method mole percent aromatic hydrogen or aromatic carbon
hydrocarbon oils including kerosines, gas oils, lube oils and coal liquids
ASTM D5292
Aromatic Carbon Contents of Hydrocarbon mole percent aromatic Oils by High Resolution Nuclear Magnetic hydrogen or aromatic carbon Resonance Spectroscopy
hydrocarbon oils including kerosines, gas oils, lube oils and coal liquids
ASTM D2008
absorbance at specified Ultraviolet Absorbance and Absorptivity of wavelength in 220-400 nm Petroleum Products range
typically used to measure absorbance of white mineral oil, refined petroleum wax and petrolatum
49
50
IP 346
Determination of polycyclic aromatics in unused lubricating base oils and asphaltene polycyclic aromatic free petroleum fractions Dimethyl hydrocarbons (three or more sulfoxide extraction refractive index fused rings) method IBP >300 C (5% recovered sample); suitable for samples containing 1-15% polycyclic aromatics
gravimetric measurement of analyte; correlation between IP 346 results and in-vitro mutagenicity measurements (Ames Test)
VISCOSITY MEASUREMENT
Petroleum products - Transparent and opaque liquids - Determination of kinematic kinematic viscosity viscosity and calculation of dynamic viscosity
liquid petroleum products dynamic viscosity calculated including base oils, formulated from kinematic viscosity and oils, petroleum wax and residual density fuel oils
DENSITY MEASUREMENT
crude petroleum and related products 600-1100 kg/m3 range
Crude petroleum and petroleum products Determination of density - Oscillating Udensity tube method
2.1.
UV/Visible Spectroscopy
Thermo Scientific Evolution 600 UV-VIS Spectrophotometer 3 ml in UV-Cuvette (Fisher brand) 1 cm 1 cm 190-900 nm Hexane 0.00115 g/100 mL Hexane (11.5 pppm) 20 C 600 nm/min 1 1.5 nm, Data interval: 2 nm
Instrument: Cell type: Slit width: Path length: Range: Solvent: Concentration: Test temperature: Scanning speed: Number of cycles: Slit - Band width:
51
2.2.
IR Spectroscopy
Thermo Nicolet Magna 550 FTIR Instrument with ATR accessory 64 4 cm-1
0.10
0.09
0.08
0.07
0.06
Abs orbance
0.05
0.04
0.03
0.02
Vibration assignment SP CH stretch SP antisymm CH stretch SP symm CH stretch C=C stretch CH3 antisymm. Deformation/CH2 bend CH3 bending CH out of plane bend
3 3 2
52
2.3.
NMR Spectroscopy
Varian Mercury Plus 300 NMR Spectrometer 300 MHz Deuterochloroform 30% 25 C Tetramethylsilane (chemical shift 0.0 ppm)
7.297 2.336 2.299 2.250 1.686 1.676 1.672 1.668 1.649 1.634 1.555 1.522 1.459 1.449 1.437 1.360 1.353 1.335 1.314 1.293 1.267 1.257 1.241 1.232 1.217 1.201 1.194 1.188 1.181 1.171 1.165 1.150 1.001 0.996 0.975 0.957 0.954 0.945 0.924 0.920 0.903 0.897 0.887 0.882 0.875 0.866 0.855 0.848 0.841 0.838 0.831 0.019
12
10
PPM
Assignment CH polyaromatic (internal) CH aromatic CH, CH2 olefinic CH, CH2, CH3 alpha to aromatic CH, CH2 aliphatic CH3 aliphatic (chain end)
53
2.4.
DHA-Gas Chromatography
J&W DB-1, 40m x 0.1mm I.D. x 0.2m film thickness Hydrogen 75 psi Split/splitless 250C 0.1 L 30C (initial) programmed at 10C/min to 50C; held for 3.30 mins; programmed at 6C to 220C; held for 5.37 mins Flame ionisation 325C
Column: Carrier gas: Inlet pressure: Injector: Inlet temperature: Injection volume: Oven temperature: Detector: Detector temperature:
54
55
56
57
58
59
60
61
Sample Chromatogram
62
Sample Chromatogram
63
Sample Chromatogram
64
Sample Chromatogram
65
Sample Chromatogram
66
Sample Chromatogram
Continuation of chromatogram from previous page - no peaks detected in this section of the chromatogram
67
Sample Chromatogram
Continuation of chromatogram from previous page - no peaks detected in this section of the chromatogram
68
Sample Chromatogram
Continuation of chromatogram from previous page - no peaks detected in this section of the chromatogram
69
Sample Chromatogram
Continuation of chromatogram from previous page - no peaks detected in this section of the chromatogram
70
Sample Chromatogram
Continuation of chromatogram from previous page - no peaks detected in this section of the chromatogram
71
Kerosines
3.1.
UV/Visible Spectroscopy
Perkin Elmer Lambda XLS+ UV/Visible Spectrophotometer 200-950 nm 1 cm quartz cell
3.0
2.5
2.0
Absorbance (A)
1.5
1.0
0.5
0.0
200.0 300.0 400.0 500.0 600.0 700.0 800.0 900.0
-0.5
Wavelength (nm)
The UV/Visible spectrum shows that the kerosine sample contains aromatic components.
72
3.2.
IR Spectroscopy
Bruker Vertex 80 FTIR Spectrophotometer Potassium bromide plates 4000-400 cm-1 32 4 cm-1 Thin film formed between potassium bromide plates
IR Spectral Band (cm-1) 2925, 2855 (s) 1607 (w) 1460 (m) 1378 (m) 724 (w)
Assignment CH stretching alkyl Aromatic ring stretching CH bending alkyl CH bending (symmetrical CH3) (CH2)n rocking
73
3.3.
NMR Spectroscopy
Bruker Avance 400 NMR Spectrometer H - 400 MHz; 13C - 100 MHz Deuterochloroform Tetramethylsilane (TMS) (1H, 13C chemical shift 0 ppm).
1
Spectrum
7.21 7.11 7.08 7.05 6.99 2.31 2.28 2.27 2.26 2.22 1.26 0.88 0.88 0.87 0.86 0.85
8.0
7.5
4.02
7.0
ppm
11
10
8
4.02
3
95.98
ppm
Chemical Shift (ppm relative to TMS) 0.5-1.0 1.0-1.4 1.4-2.0 2.0-4.0 6.7-8.0 7.3
Assignment Methyl groups Methylene groups Methine groups Groups adjacent to aromatic rings Aromatic protons Residual CHCl3 in solvent
74
13
C Spectrum
150
140
12.44
130
120
ppm
170
160
150
140
12.44
130
120
110
100
90
80
70
60
Assignment Methyl groups CH3-CH2-CH2CH3-CH2-CH2Mid chain methylene groups CH3-CH2-CH2Branched carbons CDCl3 (solvent) Aromatic carbon
The NMR spectra show that the kerosine sample is comprised of saturated and aromatic hydrocarbon components and contains 4.0% aromatic hydrogen (protons in the aromatic ring as a percentage of total proton content) and 12.4% aromatic carbon (carbons in the aromatic ring as a percentage of total carbon content). These values refer only to those nuclei within the aromatic rings of components present in the sample and do not include the nuclei present in substituent side chains.
87.56
39.69 34.72 32.61 32.29 30.09 30.04 29.99 29.78 29.75 29.69 28.26 23.34 23.00 22.84 22.79 22.75 20.43 19.32 14.53 14.29
50
40
30
20
10 ppm
75
3.4.
SIMDIS-Gas Chromatography
SIMDIS-GC analysis was carried out according to IP 480/07. The sample was dissolved in carbon disulphide and analysed by temperature programmed GC with flame ionisation detection using a non-polar separation column. The resulting chromatogram was compared with a calibration chromatogram obtained under identical conditions using n-alkanes spanning the elution range of the hydrocarbons present in the sample. The boiling range distribution of the components present was determined from these data.
76
SIMDIS GC analysis shows that the kerosine sample contains components distributed over the C7-18 carbon number and 99-295C boiling ranges.
77
3.5.
The sample was examined directly by GCxGC using the following operating conditions: Instrument Injector : : Agilent Technologies 6890 Series GC Optic II PTV Split mode Packed injection port liner Initial temperature 45 C Initial time 0 min Ramp 8 C/sec Final temperature 200 C Final time 174 min Carrier gas pressure 250 kPa Split flow 150 mL/min Agilent ALS Injection volume 0.1 L Cryogenic modulator, single jet loop type (ZOEX Corporation) Modulation time 7.5 sec Pulse width 400 ms Nitrogen flowrate ~5 L/min (optimised to modulate n-C5) Flame-ionisation Temperature 350 C Make-up gas Helium Make-up flow 20 mL/min Hydrogen flow 35 mL/min Air flow 350 mL/min 10 m x 0.25 mm i.d. dimethylpolysiloxane (DB-1) 0.25 m film thickness 2 m x 0.10 mm i.d deactivated fused silica (1 m in loop) 2 m x 0.10 mm i.d. polysilphenylene-siloxane (BPX-50) 0.10 m film thickness 0.3 m x 0.10 mm i.d. deactivated fused silica
Sample injection :
Modulator
Detector
Column 1
78
Carrier gas
Helium 40 C (5 min isothermal) then 1.0 C/min to 200 C (10 min isothermal) 65 C offset from first-dimension: 105 C (5 min isothermal) then 1.0 C/min to 265 C (10 min isothermal) 50 C offset from first-dimension: 90 C (5 min isothermal) then 1.0 C/min to 250 C (10 min isothermal)
Main (1st Dim) : oven temperature Aux (2nd Dim) : oven temperature
The individual components found by GCxGC were grouped both on the basis of carbon number (C5 to C25) and the following chemical functionalities: normal paraffins iso-paraffins mono-naphthenics di-naphthenics mono-aromatics naphthenic mono-aromatics di-aromatics naphthenic di-aromatics
JET A-1 ex Rheinland Nord (166) 7.5
5.0
2.5
79
80
3.6.
HPLC analysis (IP 391 method) shows that the kerosine sample contains 19.1% (m/m) mono-aromatic, 1.5% (m/m) di-aromatic and <0.1% (m/m) tri+aromatic hydrocarbons.
81
4.1.
UV/Visible Spectroscopy
Thermo Scientific Evolution 600 UV-VIS Spectrophotometer 3 ml in UV-Cuvette (Fisher brand) 1 cm 1 cm 190-900 nm Toluene 0.00217 g/50 mL Toluene 20 C 600 nm/min 1 1.5 nm, Data interval: 2 nm
Instrument: Cell type: Slit width: Path length: Range: Solvent: Concentration: Test temperature: Scanning speed: Number of cycles: Slit - Band width:
82
4.2.
IR Spectroscopy
Thermo Nicolet Magna 550 FTIR Instrument with ATR accessory 32 4 cm-1
83
4.3.
NMR Spectroscopy
Varian Mercury Plus 300 NMR Spectrometer 300 MHz Deuterochloroform 30% 25 C Tetramethylsilane (chemical shift 0.0 ppm)
84
4.4.
SIMDIS-Gas Chromatography
85
4.5.
86
5.1.
UV/Visible Spectroscopy
Perkin Elmer Lambda XLS+ UV/Visible Spectrophotometer 200-950 nm 1 cm quartz cell
3.0
2.5
2.0
Absorbance (A)
1.5
1.0
0.5
-0.5
Wavelength (nm)
The UV/Visible spectrum shows that the sample contains aromatic components.
87
5.2.
IR Spectroscopy
Bruker Vertex 80 FTIR Spectrophotometer Potassium bromide plates 4000-400 cm-1 32 4 cm-1 Thin film formed between potassium bromide plates
IR Spectral Band (cm-1) 2924, 2854 (s) 1606 (w) 1460 (s) 1377 (m) 900-700 (w)
Assignment CH stretching alkyl Aromatic ring C-C stretching CH bending alkyl CH bending (symmetrical CH3) Aromatic C-H bending
88
5.3.
NMR Spectroscopy
Bruker Avance 400 NMR Spectrometer H - 400 MHz; 13C - 100 MHz Deuterochloroform Tetramethylsilane (TMS) (1H, 13C chemical shift 0 ppm).
1
2H L
Spectrum
7.20 7.10 6.96 2.32 2.28 2.18 2.17 1.71 1.52 1.51 1.49 1.48 1.26 1.16 1.08 0.96 0.94 0.88 0.87
8.5
8.0
7.5
2.59
7.0
ppm
11
10
8
2.59
3
97.41
ppm
Chemical Shift (ppm relative to TMS) 0.5-1.0 1.0-1.4 1.4-2.0 2.0-3.5 6.5-8.0 7.2
Assignment Methyl groups Methylene groups Methine groups Groups adjacent to aromatic rings Aromatic protons Residual CHCl3 in solvent
89
13
ppm
170
160
150
140
130
9.17
120
110
100
90
80
70
60
50
Assignment Methyl groups CH3-CH2-CH2CH3-CH2-CH2Mid chain methylene groups CH3-CH2-CH2Branched carbons CDCl3 (solvent) Aromatic carbon
The NMR spectra show that the base oil sample is comprised of saturated and aromatic hydrocarbon components and contains 2.6% aromatic hydrogen (protons in the aromatic ring as a percentage of total proton content) and 9.2% aromatic carbon (carbons in the aromatic ring as a percentage of total carbon content). These values refer only to those nuclei within the aromatic rings of components present in the sample and do not include the nuclei present in substituent side chains.
90
90.83
37.51 37.23 34.47 32.84 32.39 32.06 30.19 29.87 29.52 28.04 26.87 22.81 22.72 19.75 14.49
C NMR spectrum
40
30
20
10 ppm
5.4.
SIMDIS-Gas Chromatography
SIMDIS-GC analysis was carried out according to IP 480/07. The sample was dissolved in carbon disulphide and analysed by temperature programmed GC with flame ionisation detection using a non-polar separation column. The resulting chromatogram was compared with a calibration chromatogram obtained under identical conditions using n-alkanes spanning the elution range of the hydrocarbons present in the sample. The boiling range distribution of the components present was determined from these data.
91
SIMDIS-GC analysis showed that the sample contains hydrocarbons covering the C15 to C31 range corresponding with initial and final boiling points of 304C and 436C respectively. The boiling point distribution plot and table showing the boiling point for each 5% mass fraction of the sample are shown below.
92
5.5.
HPLC analysis was carried out using a slightly modified version of IP 368/01 in which pentane rather than hexane was used as the mobile phase. A solution of the sample in pentane was separated into saturated and aromatic hydrocarbon fractions using normalphase HPLC with refractive index detection. Following emergence of the saturated hydrocarbons from the column a backflush valve was activated and the aromatic hydrocarbons collected by reverse-elution. The pentane mobile phase was evaporated from the two fractions and the hydrocarbon types determined gravimetrically. HPLC analysis of the sample showed that it contains 65.4% (m/m) saturated hydrocarbons and 33.4% (m/m) aromatic hydrocarbons, corresponding to a sample recovery of 98.8% (m/m) from the chromatographic fractionation.
93
6.1.
UV/Visible Spectroscopy
Perkin Elmer Lambda XLS+ UV/Visible Spectrophotometer 200-950 nm 0.1 cm quartz cell Dichloromethane 2% (m/m)
2.5
2.0
Absorbance (A)
1.5
1.0
0.5
-0.5
Wavelength (nm)
94
6.2.
IR Spectroscopy
Bruker Vertex 80 FTIR Spectrophotometer Potassium bromide plates 4000-400 cm-1 32 4 cm-1 Thin film formed between potassium bromide plates
IR Spectral Band (cm-1) 2923, 2853 (s) 1602 (w) 1461 (m) 1377 (m) 723 (w)
Assignment CH stretching alkyl C=C aromatic ring stretching CH bending alkyl CH bending (symmetrical CH3) (CH2)n rocking
95
6.3.
NMR Spectroscopy
Bruker Avance 400 NMR Spectrometer H - 400 MHz; 13C - 100 MHz Deuterochloroform Tetramethylsilane (TMS) (1H, 13C chemical shift 0 ppm).
1
H Spectrum
7.24
8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4
6.65
ppm
9.5
9.0
8.5
8.0
7.5
6.65
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
93.35
2.0
Chemical Shift (ppm relative to TMS) 0.5-1.0 1.0-1.4 1.4-2.0 2.0-3.5 6.7-8.8 7.2
Assignment Methyl groups Methylene groups Methine groups Groups adjacent to aromatic rings Aromatic protons Residual CHCl3 in solvent
96
13
C Spectrum
150
140
130
26.12
120
110
ppm
170
160
150
140
130
26.12
120
110
100
90
80
70
60
50
37.39 37.13 32.75 31.98 30.10 29.44 27.14 22.74 19.72 14.17
40
73.88
30
20
10 ppm
Quantitative analysis of the NMR signals showed that the sample contains 6.6% aromatic hydrogen (protons in the aromatic ring as a percentage of total proton content), and 26.1% aromatic carbon (carbons in the aromatic ring as a percentage of total carbon content). These values refer only to those nuclei within the aromatic rings of components present in the sample and do not include the nuclei present in substituent side chains.
97
6.4a.
SIMDIS-Gas Chromatography
SIMDIS-GC analysis was carried out according to IP 480/07. The sample was dissolved in carbon disulphide and analysed by temperature programmed GC with flame ionisation detection using a non-polar separation column. The resulting chromatogram was compared with a calibration chromatogram obtained under identical conditions using n-alkanes spanning the elution range of the hydrocarbons present in the sample. The boiling range distribution of the components present was determined from these data.
98
SIMDIS-GC analysis showed that the sample contains hydrocarbons covering the C25 to C95 range corresponding with initial and final boiling points of 423C and 691C respectively. The boiling point distribution plot and boiling point distribution table for the sample are shown below.
99
SAMPLE B
6.4b. SIMDIS-Gas Chromatography
SIMDIS-GC was carried out on a solution of the sample dissolved in carbon disulphide. This was analysed by temperature programmed GC with flame ionisation detection using a nonpolar separation column, and the resulting chromatogram was compared with a calibration chromatogram obtained under identical conditions using n-alkanes spanning the elution range of the hydrocarbons present in the sample. The boiling range distribution of the components present was determined from these data.
100
SIMDIS-GC analysis showed that the sample contains hydrocarbons covering the 403C to >750C boiling range, although 98% of the sample had a boiling range of 403C to 702C. The boiling point distribution table for the sample is shown below.
101
6.5.
Liquid Chromatography
102
Bitumen
7.1.
UV/Visible Spectroscopy
Varian Cary 1E Spectrophotometer 190-700 nm 1 nm 1 cm quartz cell Chloroform 40 ppm (mg/L)
103
7.2.
IR Spectroscopy
Instrument: Perkin Elmer Spectrum-1000 Spectrophotometer Cell: ATR sample cell with zinc selenide crystal Range: 4000-650 cm-1 cm-1 Range: 4000-650 Number of scans: 20 20 Number of scans: -1 Spectral resolution: 2 cm2 Spectral resolution: cm-1 Sample: Thin Thin film formed on crystal by introducing the sample dissolved in in Sample: film formed on crystal by introducing the sample dissolved chloroform and subsequent evaporation of solvent chloroform and subsequent evaporation of solvent
104
7.3.
NMR Spectroscopy
Bruker AMX500 NMR Spectrometer
Instrument:
Solvent:
Deuterochloroform
105
7.4a.
Distillation
ASTM D 1160 (Standard Test Method for Distillation of Petroleum Products at Reduced Pressure) Herzog HDV 632 0.13-6.7 kPa (1-50 mm Hg) Controlled to ensure uniform distillate recovery of 6-8 mL/min achieved after first 10% of distillate recovered Vapour temperature, time and pressure recorded and used to calculate equivalent temperature at atmospheric pressure (AET)
106
7.5a.
Liquid Chromatography
Known mass of sample (0.1g) charged to top of glass chromatographic column packed with activated alumina and silica gel:
Column eluted with: (i) 20 mL n-heptane to elute saturates (ii) 35 mL n-heptane + dichloromethane (1:2.5 v/v) to elute aromatics (iii) 30 mL dichloromethane + tetrahydrofuran (1:3 v/v) to elute resins + asphaltenes Solvents removed by rotary evaporation (60C; 120/357 mbar) and saturates, aromatics and polar (resins + asphaltenes) fractions determined gravimetrically.
107
7.4b.
SIMDIS-Gas Chromatography
SIMDIS-GC analysis was carried out according to IP 480/07. The sample was dissolved in carbon disulphide and analysed by temperature programmed GC with flame ionisation detection using a non-polar separation column. The resulting chromatogram was compared with a calibration chromatogram obtained under identical conditions using n-alkanes spanning the elution range of the hydrocarbons present in the sample. The boiling range distribution of the components present was determined from these data.
SIMDIS-GC analysis showed that the sample contains hydrocarbons covering the C25 to >C100 range corresponding with initial and final boiling points of 439C and >750C respectively. The boiling point distribution table for the sample is shown below.
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IBP 5% 10% 15% 20% 25% 30% 35% 40% 45% 439.0 491.0 509.5 523.5 535.5 547.0 558.0 569.0 580.5 592.0
50% 55% 60% 65% 70% 75% 80% 85% 90% 91% 604.5 617.0 631.0 645.5 662.0 680.0 700.0 720.0 742.0 750.0
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7.5b.
TLC-FID analysis of the sample was carried out according to IP 469/01(2). The sample was dissolved in dichloromethane and separated by TLC using silica rods and three successive developments with the following mobile phases: (i) (ii) (iii) heptane toluene:heptane (80:20 v/v) dichloromethane:methanol (95:5 v/v)
Following evaporation of the final mobile phase, the rods were examined using an Iatroscan Mark V TLC-FID Analyser and the quantities of saturates, aromatics, resins and asphaltenes in the sample determined by internal normalisation of the resulting chromatogram.
The TLC-FID chromatogram has been annotated to show the peaks corresponding to the saturates, aromatics, resins and asphaltenes present. Normalisation of these peaks showed that the sample contains 10.6% (m/m) saturates, 65.4% (m/m) aromatics, 11.9% (m/m) resins and 12.1% (m/m) asphaltenes.
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