EN 12671-2016 en Chemicals used for treatment of water intended for human consumption - Chlorine dioxide generated in situ《处理人类生活用水的化学物质-原位生成二氧化氯》.pdf

1、BS EN 12671:2016Chemicals used for treatmentof water intended for humanconsumption Chlorinedioxide generated in situBSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN 12671:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN

2、12671:2016.It supersedes BS EN 12671:2009 which is withdrawn. The UK participation in its preparation was entrusted to TechnicalCommittee CII/59, Chemicals for drinking water treatment.A list of organizations represented on this committee can beobtained on request to its secretary.This publication d

3、oes not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 86572 5ICS 13.060.20; 71.100.80Compliance with a British Standard cannot confer immunit

4、y fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 August 2016.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS EN 12671:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 12671 May 201

5、6 ICS 71.100.80 Supersedes EN 12671:2009English Version Chemicals used for treatment of water intended for human consumption - Chlorine dioxide generated in situ Produits chimiques utiliss pour le traitement de leau destine la consommation humaine - Dioxyde de chlore gnr in situ Produkte zur Aufbere

6、itung von Wasser fr den menschlichen Gebrauch - Vor Ort erzeugtes Chlordioxid This European Standard was approved by CEN on 18 March 2016. 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 nation

7、al 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 (English, French, German). A versi

8、on 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, Bulgaria, Croatia, Cyprus, Cz

9、ech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.

10、EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 12671:2016 E

11、BS EN 12671:2016EN 12671:2016 (E) 2 Contents Page European foreword . 4 Introduction 5 1 Scope 6 2 Normative references 6 3 Description 6 3.1 Identification 6 3.1.1 Chemical name . 6 3.1.2 Synonym or common name . 6 3.1.3 Relative molecular mass . 6 3.1.4 Empirical formula . 6 3.1.5 Chemical formula

12、 6 3.1.6 CAS Registry Number 6 3.1.7 EINECS reference 6 3.2 Presentation form . 7 3.3 Physical properties . 7 3.3.1 Appearance 7 3.3.2 Density 7 3.3.3 Solubility in water . 7 3.3.4 Vapour pressure 7 3.3.5 Boiling point at 101,3 kPa . 8 3.3.6 Crystallization point . 8 3.3.7 Specific heat 8 3.3.8 Visc

13、osity (dynamic) 8 3.3.9 Critical temperature 8 3.3.10 Critical pressure 8 3.3.11 Physical hardness . 8 3.3.12 Dissolution heat . 8 3.4 Chemical properties . 8 4 Purity criteria . 9 4.1 General 9 4.2 Composition of in situ generated product 9 4.3 Impurities and main by-products . 9 4.4 Chemical param

14、eters . 9 5 Test methods . 10 5.1 Sampling 10 5.2 Determination of chlorine dioxide and chlorite concentrations 10 5.2.1 General . 10 5.2.2 Principle 10 5.2.3 Reagents 11 5.2.4 Apparatus 12 5.2.5 Procedure 12 5.2.6 Expression of results . 13 6 Labelling, distribution and storage . 13 6.1 Labelling a

15、ccording to the EU legislation . 13 BS EN 12671:2016EN 12671:2016 (E) 3 6.2 Means of distribution 15 6.3 Storage, stability . 15 Annex A (informative) General information on chlorine dioxide 16 A.1 Origin 16 A.1.1 Raw materials 16 A.1.2 Manufacturing process . 16 A.2 Use 17 A.2.1 Function . 17 A.2.2

16、 Form in which it is used 17 A.2.3 Treatment dose . 17 A.2.4 Means of application 17 A.2.5 Secondary effects 17 A.2.6 Removal of excess product 17 A.3 Spectrometric method for specific determination of CIO217 A.3.1 Principle . 17 A.3.2 Reagents . 18 A.3.3 Apparatus 18 A.3.4 Procedure 19 A.3.5 Precis

17、ion 20 A.3.6 Specificity 20 A.4 Determination of chlorite and chlorate ions contents in aqueous chlorine dioxide as produced by the reactors . 20 A.4.1 General . 20 A.4.2 Sample collection and preparation 20 A.4.3 Principle . 20 A.4.4 Reagents . 20 A.4.5 Apparatus 21 A.4.6 Procedure 21 A.4.7 Express

18、ion of results . 22 A.4.8 Detection limit . 22 Annex B (normative) General rules relating to safety 23 B.1 Rules for safe handling and use . 23 B.2 Emergency procedures . 23 B.2.1 First aid 23 B.2.2 Spillage . 23 B.2.3 Fire . 23 Bibliography . 24 BS EN 12671:2016EN 12671:2016 (E) 4 European foreword

19、 This document (EN 12671:2016) has been prepared by Technical Committee CEN/TC 164 “Water supply”, the secretariat of which is held by AFNOR. 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 Novemb

20、er 2016, and conflicting national standards shall be withdrawn at the latest by November 2016. 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 be held responsible for identifying any or all such patent

21、 rights. This document supersedes EN 12671:2009. Significant technical differences between this edition and EN 12671:2009 are as follows: a) deletion of reference to EU Directive 67/548/EEC of June 27, 1967 in order to take into account the latest Regulation in force (see 3); b) Subclause 6.2 updati

22、ng of risk and safety labelling according to EU Regulation 3 and its latest Adaptations to Technical Progress). 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

23、, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey

24、 and the United Kingdom. BS EN 12671:2016EN 12671:2016 (E) 5 Introduction In respect of potential adverse effects on the quality of water intended for human consumption, caused by the product covered by this document: 1) this document provides no information as to whether the product may be used wit

25、hout restriction in any of the Member States of the EU or EFTA; 2) it should be noted that, while awaiting the adoption of verifiable European criteria, existing national regulations concerning the use and/or the characteristics of this product remain in force. NOTE 1 Conformity with this standard d

26、oes not confer or imply acceptance or approval of the product in any of the Member States of the EU or EFTA. The use of the product covered by this document is subject to regulation or control by National Authorities. NOTE 2 This product is a biocide and needs to comply with the relevant legislation

27、 in force. In the European Union, at the time of publication, this legislation is REGULATION (EU) No 528/2012 2). BS EN 12671:2016EN 12671:2016 (E) 6 1 Scope This European Standard is applicable to chlorine dioxide generated on site for treatment of water intended for human consumption. It describes

28、 the characteristics for chlorine dioxide and specifies the composition and the corresponding test methods for chlorine dioxide. It gives information on its use in water treatment. It also determines the rules relating to safe handling and use of chlorine dioxide generated on site (see Annex B). 2 N

29、ormative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendmen

30、ts) applies. EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696) ISO 3165, Sampling of chemical products for industrial use Safety in sampling ISO 6206, Chemical products for industrial use Sampling Vocabulary 3 Description 3.1 Identification 3.1.1 Chemical nam

31、e Chlorine dioxide. 3.1.2 Synonym or common name None. 3.1.3 Relative molecular mass 67,46. 3.1.4 Empirical formula ClO2. 3.1.5 Chemical formula _O Cl O (resonance structure). 3.1.6 CAS Registry Number 1)10049-04-4. 3.1.7 EINECS reference 2)233-162-8. 1) Chemical Abstracts Service Registry Number. 2

32、) European Inventory of Existing Commercial Chemical Substances. BS EN 12671:2016EN 12671:2016 (E) 7 3.2 Presentation form For water treatment, chlorine dioxide is generated in situ as an aqueous solution on or near the site of use and transferred to the site of use. 3.3 Physical properties 3.3.1 Ap

33、pearance The pure product is an orange gas or liquid, which forms a yellow solution in water. NOTE If the solution becomes red-brown, it is a sign of decomposition. 3.3.2 Density Gas: 3,09 g/l, (2,4 g/l relative, air = 1) at 273 K and 101,3 kPa 3). Liquid: 1,64 g/ml at 20 C. 3.3.3 Solubility in wate

34、r In Table 1 the solubility values (S) for chlorine dioxide are given in grams per cubic meter (g/m3) water at a pressure of 101,3 kPa for different temperatures: Table 1 Solubility values Temperature of water C S (323g/mHOg / m gas) 0 70 0,7 5 (60,3) 10 (53,7) 15 45 20 (42,7) 25 (33) 30 (30,1) 35 2

35、6,5 0,8 NOTE 1 S is a ratio, not an absolute value of concentration. NOTE 2 The S values are directly measured values except those in brackets which are extrapolated data. 3.3.4 Vapour pressure The vapour pressure of pure chlorine dioxide as a function of temperature is given in Table 2. 3) 100 kPa

36、= 1 bar. BS EN 12671:2016EN 12671:2016 (E) 8 Table 2 Vapour pressure of pure chlorine dioxide Temperature C Vapour pressure kPa 0 82,3 5 90,4 10 98,8 11 100,5 20 116,5 (extrapolated) 25 125,8 (extrapolated) 30 135,3 (extrapolated) 35 145,1 (extrapolated) 40 155,0 (extrapolated) 3.3.5 Boiling point a

37、t 101,3 kPa 4)11 C (for pure chlorine dioxide). 3.3.6 Crystallization point - 59 C (for pure chlorine dioxide). 3.3.7 Specific heat The specific heat of solutions of chlorine dioxide is very similar to that of pure water. 3.3.8 Viscosity (dynamic) The dynamic viscosity of solutions of chlorine dioxi

38、de is very similar to that of pure water. 3.3.9 Critical temperature 153 C (for pure chlorine dioxide). 3.3.10 Critical pressure Not applicable. 3.3.11 Physical hardness Not applicable. 3.3.12 Dissolution heat The heat of the dissolution in water is 26,8 kJ/mol (exothermic). 3.4 Chemical properties

39、Chlorine dioxide is a molecule containing an unpaired electron and has the characteristics of a “molecule-free-radical”. Relevant Redox potentials of chlorine dioxide and related molecules are (Eovalues at 25 C in volts): 4) 100 kPa = 1 bar. BS EN 12671:2016EN 12671:2016 (E) 9 HCIO2+ 3H+ 4e- CI-+ 2H

40、2O E0= 1,57 V CIO2(dissolved gas) + 1e- CIO2-E0= 1,15 V CIO3-+ 1e-+ 2H+ ClO2+ H2O E0= 1,15 V ClO2(dissolved liquid) + 1e- CIO2-E0= 0,95 V CIO2-+ 4e-+ 4 H+ CI-+ 2H2O E0= 0,78 V 4 Purity criteria 4.1 General This European Standard specifies the minimum purity requirements for chlorine dioxide generate

41、d in situ used for the treatment of water intended for human consumption. Limits are given for impurities commonly present in the product. Depending on the raw material and the manufacturing process, other impurities may be present and, if so, this shall be notified to the user and when necessary to

42、 relevant authorities. Users of this product should check the national regulations in order to clarify whether it is of appropriate purity for treatment of water intended for human consumption, taking into account raw water quality, required dosage, contents of other impurities and additives used in

43、 the product not stated in this product standard. Limits have been given for impurities and chemical parameters where these are likely to be present in significant quantities from the current production process and raw materials. If the production process or raw materials lead to significant quantit

44、ies of impurities, by-products or additives being present, this shall be notified to the user. 4.2 Composition of in situ generated product Chlorine dioxide (ClO2) is produced as aqueous solution on or near the site of use. For safety reasons the aqueous ClO2solution without intermediate storage in

45、a storage tank (i.e. without headspace) shall not exceed a concentration of 20 g/l. The concentration of the aqueous ClO2solution with intermediate storage in a storage tank (i.e. with headspace) should not exceed a concentration of 3 g/l, to ensure an adequate distance to the explosion limit (see B

46、.1). 4.3 Impurities and main by-products Impurities and main by-products of the starting products used for the generation (indicated in A.1.1) can be found in the in situ generated product in respective proportional concentrations. Inadequate design, operation and maintenance of reactors can give ri

47、se to the formation of chlorine and traces of chlorate ion and, eventually, the presence of unreacted chlorite, chlorate and/or chlorine (see 6); for analysis see 5.2 and A.4. 4.4 Chemical parameters NOTE For the purpose of this standard, “chemical parameters“ are those defined in the EU Directive 9

48、8/83/EC of 3 November 1998 (see 1). Limits of chemical parameters being potentially present in chlorine dioxide solution have been specified in the corresponding EN standards of the starting products (indicated in A.1.1). BS EN 12671:2016EN 12671:2016 (E) 10 5 Test methods 5.1 Sampling Sampling of c

49、hlorine dioxide solutions shall avoid photochemical decompositions, losses by evaporation of the product and consumption by the glassware and dilution water. Samples shall be taken at the exit of the reactor or from the storage tank with a sampling tube and the analytical procedures started as fast as possible. In order to achieve these objectives the following step by step procedure shall be adopted: sampling shall be made in accordance with the general requirements given in ISO 3165 and take ISO 6206 into account;