DIN EN ISO 16591-2011 Petroleum products - Determination of sulfur content - Oxidative microcoulometry method (ISO 16591 2010) German version EN ISO 16591 2010《石油产品 硫含量测定 氧化微库仑分析法(.pdf

1、April 2011 Translation by DIN-Sprachendienst.English price group 12No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS

2、75.080!$nb+“1756308www.din.deDDIN EN ISO 16591Petroleum products Determination of sulfur content Oxidative microcoulometry method (ISO 16591:2010)English translation of DIN EN ISO 16591:2011-04Minerallerzeugnisse Bestimmung des Schwefelgehaltes Oxidatives mikrocoulometrisches Verfahren (ISO 16591:20

3、10)Englische bersetzung von DIN EN ISO 16591:2011-04Produits ptroliers Dosage du soufre Mthode par microcoulomtrie oxydante (ISO 16591:2010)Traduction anglaise de DIN EN ISO 16591:2011-04www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritat

4、ive.2003.11 DIN EN ISO 16591:2011-04 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee ISO/TC 28 “Petroleum products and lubricants” (Secretariat: ANSI, USA) in collaboration with Technical Committee CEN/TC 19 “Gaseous and liquid fuels, l

5、ubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-70 AA Spiegelausschuss zu

6、 ISO/TC 28 Minerallerzeugnisse und Schmierstoffe of the Fachausschuss Minerall- und Brennstoffnormung. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 91-1 DIN ISO 91-1 ISO 3170 DIN EN ISO 3170 ISO 3171 DIN EN ISO 3171 ISO 3675 DIN EN I

7、SO 3675 ISO 3696 DIN ISO 3696 ISO 4259 DIN EN ISO 4259 ISO 4260 DIN EN 24260 ISO 12185 DIN EN ISO 12185 National Annex NA (informative) Bibliography DIN ISO 91-1, Petroleum measurement tables Part 1: Tables based on reference temperatures of 15 C and 60 F DIN EN ISO 3170, Petroleum liquids Manual sa

8、mpling DIN EN ISO 3171, Petroleum liquids Automatic pipeline sampling DIN EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method DIN ISO 3696, Water for analytical laboratory use Specification and test methods DIN EN ISO 4259, Petroleum produ

9、cts Determination and application of precision data in relation to methods of test DIN EN 24260, Petroleum products and hydrocarbons Determination of sulfur content Wickbold combustion method DIN EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method

10、2 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 16591 December 2010 ICS 75.080 English Version Petroleum products Determination of sulfur content Oxidative microcoulometry method (ISO 16591:2010) Produits ptroliers Dosage du soufre Mthode par microcoulomtrie oxydante (ISO 16591:2010) Mine

11、rallerzeugnisse Bestimmung des Schwefelgehaltes Oxidatives mikrocoulometrisches Verfahren (ISO 16591:2010) This European Standard was approved by CEN on 10 December 2010. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European

12、Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (En

13、glish, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium

14、, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTE

15、E FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2010 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 16591:2010: EContents Page Foreword .

16、3 1 Scope4 2 Normative references4 3 Principle .5 4 Reagents and materials 5 5 Apparatus.6 6 Samples and sampling8 7 Apparatus preparation8 7.1 Titration cell .8 7.2 Microcoulometer and recorder 9 7.3 Heating tape .9 7.4 Typical operating conditions .9 8 Apparatus verification and calibration curve

17、construction 9 9 Procedure.10 10 Calculation .11 11 Expression of results11 12 Precision 11 12.1 General .11 12.2 Repeatability, r.12 12.3 Reproducibility, R 12 13 Test report12 Annex A (informative) Determination of sulfur contents below 1 mg/kg Standby technique.13 Annex B (informative) Troublesho

18、oting .14 Annex C (informative) Calculation of sulfur content from electrochemical data.16 Bibliography18 EN ISO 16591:2010 (E) DIN EN ISO 16591:2011-04 2EN ISO 16591:2010 (E) 3 Foreword This document (EN ISO 16591:2010) has been prepared by Technical Committee ISO/TC 28 “Petroleum products and lubr

19、icants” in collaboration with Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publicatio

20、n of an identical text or by endorsement, at the latest by June 2011, and conflicting national standards shall be withdrawn at the latest by June 2011. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not b

21、e held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Es

22、tonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 16591:2010 has been approved by C

23、EN as a EN ISO 16591:2010 without any modification. DIN EN ISO 16591:2011-04 WARNING The use of this International Standard may involve hazardous material, operations and equipment. This International Standard does not purport to address all of the safety problems associated with its use. It is the

24、responsibility of the user of this International Standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. 1 Scope This International Standard specifies a method for the determination of the sulfur content by oxidative micro

25、coulometry of petroleum light and middle distillates with a final boiling point not higher than 400 C. It is applicable to materials with sulfur contents in the range of 1 mg/kg to 100 mg/kg. Products with sulfur contents above 100 mg/kg can be analysed after dilution with a suitable sulfur-free sol

26、vent. Products with sulfur contents below 1 mg/kg can also be analysed by a modified technique described in Annex A. The precision quoted only applies to measurements in the 1 mg/kg to 100 mg/kg range. Nitrogen interferes with the analysis at concentrations above 0,1 % (m/m), and chlorine interferes

27、 at concentrations above 1,0 % (m/m), but these interferences are overcome by the addition of sodium azide to the cell electrolyte. Bromine and organometallic compounds also interfere with the analysis at concentrations above approximately 500 mg/kg. NOTE 1 The microcoulometric method is capable of

28、analysing light liquid hydrocarbons boiling in the range from 26 C to 274 C (for example, naphtha and MS samples) that undergo pyrolysis at 900 C to 1 200 C. The combustion of high boiling components (for example, diesel) can result in the formation of carbonaceous deposits in the inlet portion of t

29、he combustion tube, which need to be removed frequently. NOTE 2 The results obtained using this International Standard on light and light-middle distillates generally approximate to those obtained using ISO 4260. NOTE 3 For the purposes of this International Standard, the term “% (m/m)” is used to r

30、epresent the mass fraction of a material. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amend

31、ments) applies. ISO 3170, Petroleum liquids Manual sampling ISO 3171, Petroleum liquids Automatic pipeline sampling ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method ISO 3696, Water for analytical laboratory use Specification and test metho

32、ds ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method EN ISO 16591:2010 (E) DIN EN ISO 16591:2011-04 43 Principle A test portion is burned in a combustion tube under a flowing stream of oxygen plus an inert gas. The combustion products are swept into

33、 a titration cell, where the sulfur dioxide reacts with tri-iodide ion present in the electrolyte. The tri-iodide ions that are consumed are coulometrically replaced, and the current required for replacement is a direct measure of the sulfur content of the sample. The reactions are: I3 + SO2+ H2O SO

34、3+ 3I + 2H+(1) 3I I3 + 2e (2) 4 Reagents and materials All reagents shall be of recognized analytical grade, and water shall conform to the requirements of Grade 3 of ISO 3696. 4.1 Electrolyte Dissolve 0,5 g 0,01 g of potassium iodide (KI) and 0,6 g 0,01 g of sodium azide (NaN3) in approximately 500

35、 ml of water in a 1 000 ml volumetric flask. Add 5 ml of glacial acetic acid (CH3COOH) and make up to the mark with water. Store in a dark glass bottle or in a dark place. CAUTION Sodium azide is highly toxic in contact with the skin. Wear protective clothing at all times when handling sodium azide.

36、 Crystalline sodium azide decomposes explosively under conditions of heat, shock, concussion and friction. Ensure adequate precautions are taken to prevent these conditions occurring. NOTE The shelf life of bulk electrolyte has been found to be approximately three months. 4.2 Oxygen, of high-purity

37、grade, minimum purity of 99,995 %. 4.3 Carrier gas, of high-purity grade argon, helium or nitrogen, with a minimum purity of 99,995 %. If nitrogen is used, it should be tested in the apparatus for baseline stability. 4.4 Iodine, resublimed. 4.5 Sulfur-free solvent, preferably a sulfur solvent which

38、is essentially sulfur-free ( 0,5 mg/kg) or has an accurately known low ( 5 mg/kg) sulfur content, similar in characteristics to the sample being analysed. Alternatively, a high-purity grade of cyclohexane, 2,2,4-trimethylpentane, toluene or hexadecane is suitable, as appropriate. 4.6 Sulfur stock so

39、lution 4.6.1 General A certified reference material (CRM), or a prepared stock solution with a sulfur content in the range 200 mg/kg to 500 mg/kg. 4.6.2 Preparation Select a solvent-soluble sulfur compound (see the note in this subclause) of accurately known sulfur content, preferably appropriate to

40、 the boiling range and sulfur type expected to be present in the sample. Weigh, to the nearest 0,1 mg, a quantity of this compound into a weighed 100 ml volumetric flask. Add solvent (4.5), swirl to ensure dissolution, make up to the mark with solvent and reweigh to the nearest 0,1 mg. Calculate the

41、 exact sulfur content to the nearest 0,000 1 % (m/m) (1 mg/kg). EN ISO 16591:2010 (E) DIN EN ISO 16591:2011-04 5NOTE Suitable sulfur compounds include: a) thiophene, of nominal sulfur content 38,103 % (m/m); b) dibutyl sulfide (DBS), of nominal sulfur content 21,915 % (m/m); c) dibenzothiophene (DBT

42、), of nominal sulfur content 17,399 % (m/m); d) thionaphthene (TNA), of nominal sulfur content 23,89 % (m/m). 4.7 Sulfur standard solutions Prepare a range of sulfur standard solutions to cover the range of concentrations expected in the samples being analysed, by dilution of the stock solution (4.6

43、) with solvent (4.5) calculated on the basis of mass fraction. At least three standard solutions are required for each concentration level, or a range of not less than five standard solutions to cover a set of sample analyses within the total scope of this International Standard. 5 Apparatus 5.1 Mic

44、rocoulometric apparatus 5.1.1 General The microcoulometer and associated apparatus are described in 5.1.2 to 5.1.7, and the general arrangement is shown in Figure 1. ab12345678Key 1 sample injection septum 5 mirocoulometer 2 inlet zone 6 potentiometric recorder 3 oxidizing combustion zone 7 titratio

45、n cell 4 outlet zone 8 pyrolysis furnace aOxygen, O2. bCarrier gas. Figure 1 General arrangement of microcoulometric apparatus EN ISO 16591:2010 (E) DIN EN ISO 16591:2011-04 65.1.2 Pyrolysis furnace, electrically powered, consisting of two or three independently controlled temperature zones. The fir

46、st, or inlet, zone shall maintain a temperature sufficient to volatilize the entire organic sample. The second zone, or oxidizing combustion zone, shall maintain a temperature sufficient to pyrolize the organic matrix and oxidize all the organically bound sulfur. The third, or outlet, zone for furth

47、er pyrolysis, is optional. The manufacturers instructions should be consulted for optimum temperatures. 5.1.3 Pyrolysis tube, of quartz, constructed in such a way that the test portion is completely vaporized in an inert gas atmosphere in the inlet section and swept into the oxidation zone, where it

48、 mixes with oxygen and is burned. The inlet end of the tube shall hold a septum for syringe introduction of the test portion, and side arms for the admission of oxygen and carrier gas. The oxidizing combustion zone(s) shall be of sufficient volume to ensure complete pyrolysis of the test portion. The outlet section of the tube may be closed by a 20 mm length of quartz-wool if desired. Typical designs of pyrolysis tube are shown in Figure 2. Some manufacturers r