BS EN 13752-2009 Products used for treatment of water intended for human consumption —Manganese dioxide.pdf

? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? BS EN 13752:2009 EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM EN 13752 March 2009 ICS 71.100.80Supersedes EN 13752:2003 English Version Products used for treatment of water intended for human consumption - Manganese dioxide Produits utilisés pour le traitement de l'eau destinée à la consommation humaine - Dioxyde de manganèse Produkte zur Aufbereitung von Wasser für den menschlichen Gebrauch - Mangandioxid This European Standard was approved by CEN on 1 February 2009. 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 concerning such national standards may be obtained on application to the CEN 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 into its own language and notified to the CEN Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, 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 COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels © 2009 CENAll rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 13752:2009: E BS EN 13752:2009 EN 13752:2009 (E) 2 Contents Foreword 3 1Scope 5 2Normative references 5 3Terms, definitions and symbols . 5 4Description . 5 4.1Identification . 5 4.2Commercial form . 6 5Physical properties 6 5.1Appearance 6 5.2Particle size distribution . 6 5.3Density 6 6Chemical properties 7 7Specific properties. 7 8Test methods 7 8.1Sampling . 7 8.2Analysis 7 9Labelling, transportation and storage . 9 9.1Means of delivery . 9 9.2Risk and safety labelling according to EU Directives . 9 9.3Transportation regulations and labelling 10 9.4Marking . 10 9.5Storage 10 Annex A (informative) General information on manganese dioxide 11 Annex B (normative) General rules relating for safety 14 Bibliography 15 ? BS EN 13752:2009 EN 13752:2009 (E) 3 Foreword This document (EN 13752:2009) 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 September 2009, and conflicting national standards shall be withdrawn at the latest by September 2009. 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 rights. This document supersedes EN 13752:2003. Differences between this edition and EN 13752:2003 are editorial to harmonize the text with other standards in this series. Annex A is informative and Annex B is normative. 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, 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 the United Kingdom. ? BS EN 13752:2009 EN 13752:2009 (E) 4 Introduction In respect of potential adverse effects on the quality of water intended for human consumption, caused by the product covered by this standard: a) this standard provides no information as to whether the product may be used without restriction in any of the Member States of the EU or EFTA; b) 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 Conformity with this standard does 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 European Standard is subject to regulation or control by National Authorities. ? BS EN 13752:2009 EN 13752:2009 (E) 5 1 Scope This European Standard is applicable to manganese dioxide used for treatment of water intended for human consumption. It describes the characteristics of manganese dioxide and specifies the requirements and the corresponding test methods for manganese dioxide. It gives information on its use in water treatment. This standard is not applicable to manganese dioxide with purity ranging from 85 % to 90 % and bulk density loose greater than 1850 kg/m3. 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 amendments) applies. EN 12901:1999, Products used for treatment of water intended for human consumption - Inorganic supporting and filtering materials - Definitions EN 12902, Products used for treatment of water intended for human consumption - Inorganic supporting and filtering materials - Methods of test EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696:1987) ISO 385, Laboratory glassware Burettes ISO 6333, Water quality - Determination of manganese - Formaldoxime spectrometric method 3 Terms, definitions and symbols For the purposes of this document, the terms, definitions and symbols given in EN 12901:1999 apply. 4 Description 4.1 Identification 4.1.1 Chemical name Manganese dioxide. 4.1.2 Synonym or common names Manganese(IV) oxide, pyrolusite. 4.1.3 Chemical formula MnO2. NOTE Manganese dioxide used as a catalytic filtering medium is a natural ore, usually pyrolusite. Manganese dioxide ores differ widely in their chemical composition depending on their origin. Most are composed of manganese dioxide together with silica, alumina, iron oxide and numerous other elements present in varying proportions. ? BS EN 13752:2009 EN 13752:2009 (E) 6 4.1.4 CAS Registry number 1) Manganese dioxide: 1313-13-9. 4.1.5 EINECS reference 2) Manganese oxides: 215-202-6. 4.2 Commercial form Manganese dioxide is a granular material usually available in two size ranges: 0,355 mm to 0,850 mm and 0,50 mm to 1,00 mm. 5 Physical properties 5.1 Appearance The product is a granular material varying in colour from dark brown to dark grey to black, depending upon its origin. It consists of amorphous grains which can be rounded or sub-angular. The product shall be generally homogeneous and shall be visibly free of extraneous matter. 5.2 Particle size distribution The particle size distribution shall be described by either: a) effective size: (d10) with a maximum deviation of ± 5 %; uniformity coefficient: (U) less than 1,5; minimum size: (d1) with a limit deviation of ± 5 %; NOTE 1 The particle size can decrease during transportation and handling. b) or, particle size range and mass fraction of oversize and undersize particles according to application. The maximum contents of oversize and undersize shall be a mass fraction of 5 % for application of the product in multimedia filters and a mass fraction of 10 % for use in single media filters. See A.2.3 for examples of available particle sizes that are used. NOTE 2 Other values can be necessary for certain applications. 5.3 Density 5.3.1 Bulk density loose The bulk density loose shall be in the range of 1 750 kg/m3 to 1 850 kg/m3. 1) Chemical Abstracts Service Registry Number. 2) European Inventory of Existing Commercial Chemical Substances. ? BS EN 13752:2009 EN 13752:2009 (E) 7 5.3.2 Bulk density packed The bulk density packed shall be in the range of 1 950 kg/m3 to 2 050 kg/m3. 6 Chemical properties For the composition of the commercial product, see A.2.1. NOTE 1 After filling, washing and commissioning of a filter system producing drinking water, manganese dioxide should not increase the concentrations of chemical parameters above the regulated values (see 1). NOTE 2 Water extractable substances, determined in accordance with the method for granular materials given in EN 12902, can be used to estimate the leaching of the chemicals specified in EN 12902. NOTE 3 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, contents of other impurities and additives used in the products not stated in the product standard. 7 Specific properties The oxidation capacity of manganese dioxide shall be at least 500 bed volumes when tested according to the method described in 8.2.4. 8 Test methods 8.1 Sampling Prepare the laboratory sample(s) required by the relevant procedure described in EN 12902. 8.2 Analysis 8.2.1 Particle size distribution The particle size distribution shall be determined on samples taken at the point of manufacture using the method of test given in EN 12902. 8.2.2 Bulk density loose The bulk density loose shall be determined in accordance with EN 12902. 8.2.3 Bulk density packed The bulk density packed shall be determined in accordance with EN 12902. 8.2.4 Oxidation capacity 8.2.4.1 Principle A solution of manganese sulphate is passed through a bed of “ regenerated” manganese dioxide. Portions of the effluent are analysed for manganese and the cumulative volume, until breakthrough of manganese, is determined. ? BS EN 13752:2009 EN 13752:2009 (E) 8 8.2.4.2 Reagents 8.2.4.2.1 General All reagents shall be of a recognized analytical grade and the water used shall conform to grade 2 in accordance with EN ISO 3696. 8.2.4.2.2 Manganese sulphate stock solution, 5 mg/l Dissolve 1,00 g of sodium hydrogen carbonate (NaHCO3) in water and add 0,1538 g of manganese sulphate monohydrate (MnSO4·H2O). Dilute to 10 l with water and adjust the pH to 7,0 ± 0,5 using dilute sulphuric acid or sodium hydroxide solution as required. 8.2.4.2.3 Manganese sulphate test solution, 1 mg/l Dilute 2 l of the manganese sulphate stock solution (8.2.4.2.2) to 10 l with water and adjust the pH to 7,0 ± 0,5 using dilute sulphuric acid or sodium hydroxide solution as required. 8.2.4.2.4 Sodium hypochlorite solution, approximately 1 200 mg/l Cl2 Dilute 10 ml of sodium hypochlorite solution, available chlorine concentration approximately 120 g/l, to 1 l with water. 8.2.4.3 Apparatus Ordinary laboratory apparatus and glassware together with the following. 8.2.4.3.1 Glass burette of 50 ml capacity conforming to the requirements of ISO 385. 8.2.4.3.2 Graduated measuring cylinder, 200 ml capacity. 8.2.4.3.3 Borosilicate glass bottle, 10 l capacity. 8.2.4.4 Preparation of test sample Take approximately 100 g of the manganese dioxide and sieve to obtain that fraction of the material sized between 0,355 mm and 0,850 mm, using the procedure for determination of particle size described in EN 12902. Use this fraction for the determination. Take approximately 20 g of the manganese dioxide (0,355 mm to 0,850 mm), place in a 250 ml beaker and gently wash with successive portions of water until all adherent fines have been removed. Dry the beaker and contents to constant mass at (100 ± 5) °C. Place a loose plug of glass wool in the bottom of the burette (8.2.4.3.1) and add the manganese dioxide to a depth of approximately 50 mm. Connect the nozzle of the burette to a cold water tap by means of suitable rubber tubing and backwash the manganese dioxide in the burette vigorously ensuring complete fluidisation of the bed in order to remove any ultra-fine material not previously removed. When any remaining fines have been washed off, turn off the tap and drain down the water in the burette to just above the surface of the manganese dioxide bed. To avoid entrapment of air, ensure the water level does not fall below the top of the manganese dioxide bed. Tap the burette gently with a glass rod fitted with a rubber policeman to compact the manganese dioxide and measure the depth of the bed of manganese dioxide and the internal diameter of the burette and calculate the volume of the bed of manganese dioxide in litres. Add sodium hypochlorite solution (8.2.4.2.4) to the burette and allow to drain out drop wise until the manganese dioxide has been in contact with the sodium hypochlorite solution for 10 min. Drain the sodium hypochlorite solution until the liquid level is just above the surface of the manganese dioxide bed. Fill the burette with water, open the tap fully and rinse the manganese dioxide for about 10 min to remove residual sodium hypochlorite solution. ? BS EN 13752:2009 EN 13752:2009 (E) 9 8.2.4.5 Procedure Pass water through the burette and adjust the setting of the tap to give a flow rate of 16 ml/min. NOTE This corresponds to a velocity of 2,77 mm/s. Drain the water to just above the surface of the manganese dioxide bed and, leaving the tap at the same setting, pass the manganese sulphate solution (8.2.4.2.2) through the burette at the same flow rate. Collect the effluent in 200 ml aliquots in the measuring cylinder (8.2.4.3.2) and analyse for manganese content in accordance with ISO 6333. When the concentration of manganese in the effluent reaches 0,05 mg/l, stop the flow of manganese sulphate solution. Reject the aliquot having a manganese concentration greater than 0,05