BS EN ISO 16591-2010 Petroleum products Determination of sulfur content Oxidative microcoulometry method《石油产品 硫含量测定 氧化微库仑分析法》.pdf

1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN ISO 16591:2010BS 2000-373:2010Petroleum products Determination of sulfur content Oxidative microcoulometry method (ISO 16591:2010)Licensed Copy: Wang Bin, ISO/EXCHANGE CHIN

2、A STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN ISO16591:2010.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/13, Petroleum Testing and Terminology.A li

3、st of organizations represented on this committee can beobtained on request to its secretary.Energy Institute, under the brand of IP, publishes and sells all Parts of BS 2000, and all BS EN petroleum test methods that would be Part of BS 2000, both in its annual publication “Standard methods for ana

4、lysis and testing of petroleum and related products and British Standard 2000 Parts” and individually.Further information is available from:Energy Institute, 61 New Cavendish Street, London W1G 7AR.Tel: 020 7467 7100. Fax: 020 7255 1472.This publication does not purport to include all the necessaryp

5、rovisions of a contract. Users are responsible for its correctapplication. BSI 2011 ISBN 978 0 580 63784 1 ICS 75.080 Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee

6、on 31 January 2011. Amendments issued since publicationDate Text affectedLicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 16591 December 2010 ICS 75.080 English Version Petroleum products - Det

7、ermination of sulfur content - Oxidative microcoulometry method (ISO 16591:2010) Produits ptroliers - Dosage du soufre - Mthode par microcoulomtrie oxydante (ISO 16591:2010) Minerallerzeugnisse - Bestimmung des Schwefelgehaltes - Oxidatives mikrocoulometrisches Verfahren (ISO 16591:2010) This Europe

8、an 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 Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references co

9、ncerning 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 (English, French, German). A version in any other language made by translation under the responsibility of a CEN member

10、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, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ir

11、eland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix

12、 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: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010 EN ISO 16591:2010 (E

13、) 3 Foreword This document (EN ISO 16591:2010) has been prepared by Technical Committee ISO/TC 28 “Petroleum products and lubricants” in collaboration with Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” the secr

14、etariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication 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

15、the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following cou

16、ntries are bound to implement this European Standard: Austria, Belgium, 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, Slo

17、venia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 16591:2010 has been approved by CEN as a EN ISO 16591:2010 without any modification. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010ISO

18、 16591:2010(E) ISO 2010 All rights reserved iiiContents Page Foreword iv 1 Scope1 2 Normative references1 3 Principle .2 4 Reagents and materials 2 5 Apparatus.3 6 Samples and sampling5 7 Apparatus preparation5 7.1 Titration cell .5 7.2 Microcoulometer and recorder 6 7.3 Heating tape .6 7.4 Typical

19、operating conditions .6 8 Apparatus verification and calibration curve construction 6 9 Procedure.7 10 Calculation .8 11 Expression of results8 12 Precision 8 12.1 General .8 12.2 Repeatability, r.9 12.3 Reproducibility, R 9 13 Test report9 Annex A (informative) Determination of sulfur contents belo

20、w 1 mg/kg Standby technique.10 Annex B (informative) Troubleshooting .11 Annex C (informative) Calculation of sulfur content from electrochemical data.13 Bibliography15 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010ISO 16591:20

21、10(E) iv ISO 2010 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body

22、interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotech

23、nical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by t

24、he technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent right

25、s. ISO shall not be held responsible for identifying any or all such patent rights. ISO 16591 was prepared by Technical Committee ISO/TC 28, Petroleum products and lubricants. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010INTER

26、NATIONAL STANDARD ISO 16591:2010(E) ISO 2010 All rights reserved 1Petroleum products Determination of sulfur content Oxidative microcoulometry method WARNING The use of this International Standard may involve hazardous material, operations and equipment. This International Standard does not purport

27、to address all of the safety problems associated with its use. It is the 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 specifie

28、s a method for the determination of the sulfur content by oxidative microcoulometry 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

29、 100 mg/kg can be analysed after dilution with a suitable sulfur-free solvent. 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

30、the analysis at concentrations above 0,1 % (m/m), and chlorine interferes 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 a

31、pproximately 500 mg/kg. NOTE 1 The microcoulometric method is capable of 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 r

32、esult in the formation of carbonaceous deposits in the inlet portion of the 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

33、 purposes of this International Standard, the term “% (m/m)” is used to represent 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 refer

34、ences, the latest edition of the referenced document (including any amendments) 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 I

35、SO 3696, Water for analytical laboratory use Specification and test methods ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-tube method Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010ISO

36、16591:2010(E) 2 ISO 2010 All rights reserved3 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 a titration cell, where the sulfur dioxide reacts with tri-iodide ion present in the electrolyte. The tri-i

37、odide 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 SO3+ 3I + 2H+(1) 3I I3 + 2e (2) 4 Reagents and materials All reagents shall be of recognized analytical grade,

38、 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 ml of water in a 1 000 ml volumetric flask. Add 5 ml of glacial acetic acid (CH3COOH) and make up to the ma

39、rk 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. Crystalline sodium azide decomposes explosively under conditions of heat, shock, concussion and friction. E

40、nsure 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 grade, minimum purity of 99,995 %. 4.3 Carrier gas, of high-purity grade argon, helium or nitrogen, with a m

41、inimum 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 is essentially sulfur-free ( 0,5 mg/kg) or has an accurately known low ( 5 mg/kg) sulfur content, similar in

42、 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 solution 4.6.1 General A certified reference material (CRM), or a prepared stock solution with a sulfur conten

43、t 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 the boiling range and sulfur type expected to be present in the sample. Weigh, to the nearest 0,1 mg, a qua

44、ntity 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 exact sulfur content to the nearest 0,000 1 % (m/m) (1 mg/kg). Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA

45、STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010ISO 16591:2010(E) ISO 2010 All rights reserved 3NOTE 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) dibenzothi

46、ophene (DBT), 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 so

47、lution (4.6) 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 Appara

48、tus 5.1 Microcoulometric 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

49、 7 titration cell 4 outlet zone 8 pyrolysis furnace aOxygen, O2. bCarrier gas. Figure 1 General arrangement of microcoulometric apparatus Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 20/04/2011 09:09, Uncontrolled Copy, (c) BSIBS EN ISO 16591:2010ISO 16591:2010(E) 4 ISO 2010 All rights reserved5.1.2 Pyrolysis furnace, electrically powered, consisting of two or three independently controlled temperature zones. The first, or inlet, zone shall maintain a temperature sufficient to volatilize