1、 ISO 2014 Solid mineral fuels Determination of Chlorine content Combustibles minraux solides Dosage de la teneur en chlore TECHNICAL SPECIFICATION ISO/TS 18806 Reference number ISO/TS 18806:2014(E) First edition 2014-12-15 ISO/TS 18806:2014(E)ii ISO 2014 All rights reserved COPYRIGHT PROTECTED DOCUM
2、ENT ISO 2014 All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can
3、 be requested from either ISO at the address below or ISOs member body in the country of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ISO/TS 18806:2014(E)Contents Pa
4、ge Foreword iv 1 Scope . 1 2 Normative references 1 3 T erms and definitions . 1 4 Principle 1 4.1 Method A High temperature combustion in oxygen . 1 4.2 Method B Bomb combustion . 1 5 Reagent . 2 5.1 Method A 2 5.2 Method B 2 6 Apparatus . 2 6.1 Method A 2 6.2 Method B 4 7 Preparation of sample 4 8
5、 Procedure. 5 8.1 Blank Value Determination 5 8.2 Method A 5 8.3 Method B Bomb Combustion. 5 9 Determination of dissolved chloride . 6 9.1 General . 6 9.2 Determination by ion chromatography . 6 10 Calculation and expression of results . 7 11 Test report . 7 Annex A (normative) Quality control . 8 A
6、nnex B (Informative)Results of the German Interlaboratory comparison 2009 for DIN 51727:2011 “Solid fuels-Determination of the chlorine content” 9 Bibliography .11 ISO 2014 All rights reserved iii ISO/TS 18806:2014(E) Foreword ISO (the International Organization for Standardization) is a worldwide f
7、ederation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that co
8、mmittee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. The procedures used to develop this document
9、 and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives,
10、Part 2 (see www.iso.org/directives). Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development o
11、f the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents). Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement. For an explanation on the meaning of ISO specifi
12、c terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT), see the following URL: Foreword Supplementary information. The committee responsible for this document is ISO/TC 27, Solid mineral fue
13、ls, Subcommittee SC 5, Methods of Analysis.iv ISO 2014 All rights reserved Solid mineral fuels Determination of Chlorine content 1 Scope This Technical Specification specifies two methods (high temperature combustion and bomb combustion) for the determination of chlorine in solid mineral fuels. It i
14、s applicable to hard coals, brown coals, coke, and tailings. The chlorine in the digestion solution can be determined using different methods, e.g. an ion-selective electrode, coulometric or potentiometric titration, spectrophotometry, or ion chromatography. In this Technical Specification, the ion
15、chromatographic separation with conductivity detection is described. The method is applicable to determine the chlorine content higher than 0,005 per cent mass fraction. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispens
16、able for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 687, Solid mineral fuels Coke Determination of moisture in the general analysis test sample ISO 1170, Coal and
17、 coke Calculation of analyses to different bases ISO 1213-2, Solid mineral fuels Vocabulary Part 2: Terms relating to sampling, testing and analysis ISO 5068-2, Brown coals and lignites Determination of moisture content Part 2: Indirect gravimetric method for moisture in the analysis sample ISO 5725
18、-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method ISO 11722, Solid mineral fuels Hard coal Determination of moisture in the general analysis test sample by drying i
19、n nitrogen EN ISO 10304-1, Water quality Determination of dissolved anions by liquid chromatography of ions Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate 3 T erms a nd definiti ons For the purposes of this document, the terms and definitions given in I
20、SO 1213-2 apply. 4 Principle 4.1 Method A High temperature combustion in oxygen The sample is combusted at high temperature in an oxygen atmosphere. The gaseous combustion products including the formed chloride are collected in a trap filled with water, in which they are dissolved. 4.2 Method B Bomb
21、 combustion The sample is combusted in a high pressure bomb in an oxygen atmosphere. The formed chloride is collected in an absorption solution inside the bomb. TECHNICAL SPECIFICATION ISO/TS 18806:2014(E) ISO 2014 All rights reserved 1 ISO/TS 18806:2014(E) 5 Reagent 5.1 Method A 5.1.1 Oxygen, pure,
22、 with an assay of at least 99,5 % volume fraction. 5.1.2 Combustion aid (optional), spectroscopic carbon or iron phosphate (FePO 4 ). 5.2 Method B 5.2.1 Oxygen, pure, with an assay of at least 99,5 % volume fraction. 5.2.2 Combustion aid (optional), paraffin, benzoic acid, polyethylene combustion ba
23、gs, acetobutyrate capsules, or other suitable materials. 5.2.3 Fuse, ignition wire (e.g. platinum) and cotton fuse (optional). Note A possible contribution of the cotton fuse to the chlorine content should be considered. 5.2.4 Absorption solution, either eluent used for ion chromatographic determina
24、tion, or alkaline solution (e.g. 0,2 mol/l KOH or 0,1 mol/l NaOH), or deionised water. 6 Apparatus 6.1 Method A 6.1.1 Fused silica combustion tube, absorber , and headpiece, the sintered glass discs in the absorber and the headpiece shall have a pore size of 90 m to 150 m (see Figure 1).2 ISO 2014 A
25、ll rights reserved ISO/TS 18806:2014(E) 39 55 34 22 820 25 154 102 12 106 124 84 428 1 2 3 7 8 546 Key 1 headpiece 2 sintered glass disc 3 V45/50 conical ground joint (ISO 383) 4 combustion tube 5 VS 13 spherical joint (ISO 641) 6 oxygen inlet 7 absorber 8 sintered glass disc Figure 1 Apparatus for
26、Method A 6.1.2 Porcelain combustion boat, with handle, e.g. 70 mm long, 10 mm wide, and 7 mm deep. 6.1.3 Silica pusher, with iron inlay (see Figure 2). ISO 2014 All rights reserved 3 ISO/TS 18806:2014(E) 25 275 5 15 1 2 Key 1 silica pusher 2 iron inlay Figure 2 Silica pusher 6.1.4 Magnet. 6.1.5 Elec
27、trical tube furnace, about 300 mm long, capable of being heated to at least 1 300 C and maintained at (1 250 25) C. 6.1.6 Flow meter. 6.1.7 Oxygen inlet, consisting of a pierced silicon stopper with a glass tube. 6.2 Method B 6.2.1 Digestion unit 6.2.1.1 Digestion bomb, with inner surface that is re
28、sistant to corrosion by acidic gases formed or emitted during combustion. 6.2.1.2 Pressure regulator, to control the filling of the bomb with oxygen and discharging afterwards. 6.2.1.3 Pressure gauge, with relieve valve operating at 3,5 MPa. 6.2.1.4 Ignition circuit. If appropriate, the equipment fo
29、r determination of calorific value according to ISO 1928 can be used simultaneously for chlorine determination. Attention is drawn to the fact that deionised water should be used as absorption solution and that 10 ml instead of 1 ml (as in ISO 1928) are used. 6.2.2 Crucible, of silica, nickel-chromi
30、um, platinum, or similar non-reactive material that is resistant to corrosion by acidic gases formed or emitted during combustion. 7 Preparation of sample The coal or coke used for the determination of the chlorine content is the general analysis test sample ground to pass a sieve of 212 m aperture.
31、 Expose the sample in a thin layer for the minimum time required for the moisture content to reach approximate equilibrium with the laboratory atmosphere. Before commencing the determination, mix the air-dried sample.4 ISO 2014 All rights reserved ISO/TS 18806:2014(E) After weighing the test portion
32、 (see 8.2.2 or 8.3.2), determine the moisture content using a further portion of the test sample by the method described in ISO 687, ISO 5068-2, or ISO 11722, as appropriate. 8 Procedure 8.1 Blank Value Determination Blank values shall be measured by performing a complete analysis (method A or metho
33、d B, whatever used for analysis of samples) without sample but including combustion aid, if used. Blank values should be measured on a daily basis or when series of analyses are started. 8.2 Method A 8.2.1 Preparation Adjust the tube furnace to ensure a temperature of (1 250 25) C in the combustion
34、zone. Place the combustion tube in the furnace so that its projecting vertical section with the spherical ground joint is as near as possible to the hottest zone to prevent any condensation of combustion products. Adjust the oxygen flow to (1 0,1) l/min. Mix samples having more than 30 % mass fracti
35、on ash with 0,1 g to 0,2 g of combustion aid to achieve uniform combustion. 8.2.2 Combustion procedure Weigh, to an accuracy of 0,1 mg, about 50 mg to 1 000 mg (depending on the chlorine concentration) of the sample prepared according to Clause 7 into a combustion boat. Push the boat into the combus
36、tion tube using the silica pusher until the tube can be closed with the oxygen inlet. NOTE Carefully place the front end of the pusher into the handle of the combustion boat. Otherwise problems to remove the boat after test might occur. Fill the absorber with 150 ml deionised water. After starting t
37、he oxygen flow, mount the headpiece on the absorber and fill it with 20 ml deionised water. To prevent deflagration, initially use the magnet to move the pusher together with the combustion boat containing the sample into the combustion zone so far only, that the front section of the sample is ignit
38、ed only. After the sample has reached red heat (approximately one minute after ignition), push it into the combustion zone to burn it completely. High temperature coke samples can be pushed into the combustion zone directly. Combustion time is depending on the ash of the sample. It is about 20 mins
39、for coals having 10 % to 20 % mass fraction ash. After combustion has been terminated, transfer the absorption liquid from headpiece and absorber into a 250 ml volumetric flask. Rinse headpiece and absorber with deionised water and add to the flask. Fill up to the mark with deionised water (V D ). 8
40、.3 Method B Bomb Combustion 8.3.1 Preparation Bomb parts shall be inspected regularly for wear and corrosion; particular attention shall be paid to the condition of the threads of the main closure. Manufacturers instructions and any local regulations regarding the safe handling and use of the bomb s
41、hall be observed. Before starting a test ensure that no gas leakage occurs. NOTE Gas leakage can be checked easily by complete immersing the pressurized bomb in cold water. ISO 2014 All rights reserved 5 ISO/TS 18806:2014(E) 8.3.2 Combustion procedure Weigh, to an accuracy of 0,1 mg, about 50 mg to
42、1 000 mg (depending on the chlorine concentration) of the sample prepared according to Clause 7 into a crucible. Note If appropriate, chlorine can be determined simultaneously with calorific value according to ISO 1928 (for details see 6.2.1). If not easily combusting samples are to be analysed, wei
43、gh into e.g. acetobutyrate capsules or use a combustion aid, e.g. benzoic acid. Fill 10 ml of the absorption solution (5.2.4) into the bomb and wet the inner surface of the bomb, e.g. by carefully rotating it. Select an absorption solution that is capable to absorb the acidic combustion products com
44、pletely. Place the crucible in its support and fix it. Attach the ignition wire and assemble the bomb. Charge the bomb slowly with oxygen to a pressure of maximum (3,0 0,2) MPa. Initiate the combustion by firing the fuse. After the combustion is completed let the bomb cool down to ambient temperatur
45、e. Release the pressure at a moderate rate and dismantle the bomb carefully. Transfer the chlorine absorbed solution into a volumetric flask by either Addition of, e.g. 40 ml absorption solution (5.2.4) to the bomb, closing and shaking the bomb in such a manner as to rinse all interior surfaces of t
46、he bomb, the combustion crucible, and the pressure release valve with absorbing solution; and/or Rinsing all interior surfaces of the bomb, the combustion crucible, and the pressure release valve with absorbing solution (5.2.4). Transfer all solutions into a volumetric flask (e.g. 100 ml or 50 ml, d
47、epending on the chlorine content) and fill up to the mark (V D ) with absorption solution (5.2.4). If appropriate, take an aliquot (V A ), transfer it to another volumetric flask and fill up to the mark (V M ). with absorption solution (5.2.4). NOTE Before injecting the sample into the ion chromatog
48、raph, an aliquot of the sample solution can be filtered through an, e.g. 0,45 m disposable filter in order to protect the column. 9 Determination of dissolved chloride 9.1 General The chloride content in the digestion solution can be determined using different methods, e.g. an ion- selective electro
49、de, coulometric or potentiometric titration, spectrophotometry, or ion chromatography. In this Technical Specification, the ion chromatographic separation with conductivity detection is described in detail. 9.2 Determination by ion chromatography 9.2.1 General The ion chromatographic separation with conductivity detection is performed according to EN ISO 10304-1. As the chromatograms, especially retention times depend on concentrations and matrix, a calibration on the basis of matri
