SIST EN 15039:2006
(Main)Chemicals used for treatment of water intended for human consumption - Antiscalants for membranes - Polycarboxilic acids and salts
Chemicals used for treatment of water intended for human consumption - Antiscalants for membranes - Polycarboxilic acids and salts
This European Standard is applicable to polycarboxylic acids and salts used as antiscalants for membranes for the treatment of water intended for human consumption. It describes the characteristics and specifies the requirements and the corresponding analytical methods for polycarboxylic acids and salts. It gives information on their use as antiscalants for membranes in water treatment.
Produkte zur Aufbereitung von Wasser für den menschlichen Gebrauch - Antiscalants für Membranen - Polycarbonsäuren und deren Salze
Diese Europäische Norm gilt für Polycarbonsäuren und deren Salze (Polycarboxylate), die als Antiscalants (Kesselsteingegenmittel) für Membranen zur Aufbereitung von Wasser für den menschlichen Gebrauch bestimmt sind. Sie beschreibt die Eigenschaften und legt die Anforderungen sowie die entsprechenden Analysenverfahren für Polycarbonsäuren und Polycarboxylate fest. Sie gibt Informationen über deren Verwendung als Antiscalants für Membranen in der Wasseraufbereitung.
Produits chimiques pour le traitement de l'eau destinée a la consommation humaine - Produits antitartres pour membranes - Acides polycarboxyliques et leurs sels
La présente Norme européenne s’applique aux acides polycarboxyliques et leurs sels utilisés comme antitartres pour membranes dans le traitement de l’eau destinée a la consommation humaine. Elle décrit les caractéristiques des acides polycarboxyliques et spécifie les exigences et les méthodes d'analyse correspondantes pour les acides polycarboxyliques et leurs sels. Elle donne des informations pour leur emploi comme produits antitartres pour membranes dans le traitement de l’eau.
Kemikalije, ki se uporabljajo za pripravo pitne vode - Sredstva proti apnencu na membranah - Polikarboksilne kisline in soli
General Information
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Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Kemikalije, ki se uporabljajo za pripravo pitne vode - Sredstva proti apnencu na membranah - Polikarboksilne kisline in soliProdukte zur Aufbereitung von Wasser für den menschlichen Gebrauch - Antiscalants für Membranen - Polycarbonsäuren und deren SalzeProduits chimiques pour le traitement de l'eau destinée a la consommation humaine - Produits antitartres pour membranes - Acides polycarboxyliques et leurs selsChemicals used for treatment of water intended for human consumption - Antiscalants for membranes - Polycarboxilic acids and salts71.100.80Chemicals for purification of water13.060.20Pitna vodaDrinking waterICS:Ta slovenski standard je istoveten z:EN 15039:2006SIST EN 15039:2006en,fr,de01-oktober-2006SIST EN 15039:2006SLOVENSKI
STANDARD
SIST EN 15039:2006
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15039July 2006ICS 71.100.80 English VersionChemicals used for treatment of water intended for humanconsumption - Antiscalants for membranes - Polycarboxilic acidsand saltsProduits chimiques pour le traitement de l'eau destinée à laconsommation humaine - Produits antitartres pourmembranes - Acides polycarboxiliques et selsProdukte zur Aufbereitung von Wasser für denmenschlichen Gebrauch - Antiscalants für Membranen -Polycarbonsäuren und deren SalzeThis European Standard was approved by CEN on 5 June 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, 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 STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2006 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15039:2006: ESIST EN 15039:2006
EN 15039:2006 (E) 2 Contents Page Foreword.3 Introduction.4 1 Scope.5 2 Normative references.5 3 Description.6 4 Purity criteria.9 5 Test methods.10 6 Labelling - Transportation - Storage.15 Annex A (informative)
General information on polycarboxylic acids and salts.17 Annex B (normative)
Analytical methods for polycarboxylic acids and salts.19 Annex C (informative) Environmental, health and safety precautions within chemical laboratory.24 Bibliography.25
SIST EN 15039:2006
EN 15039:2006 (E) 3 Foreword This document (EN 15039:2006) 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 January 2007, and conflicting national standards shall be withdrawn at the latest by January 2007. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, 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. SIST EN 15039:2006
EN 15039:2006 (E) 4 Introduction In respect of potential adverse effects on the quality of water intended for human consumption, caused by the products covered by this European Standard: a) this European Standard provides no information as to whether the products 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 these products remain in force. NOTE Conformity with this European Standard does not confer or imply acceptance or approval of the products in any of the Member States of the EU or EFTA. The use of the products covered by this European Standard is subject to regulation or control by National Authorities. SIST EN 15039:2006
EN 15039:2006 (E) 5 1 Scope This European Standard is applicable to polycarboxylic acids and salts used as antiscalants for membranes for the treatment of water intended for human consumption. It describes the characteristics and specifies the requirements and the corresponding analytical methods for polycarboxylic acids and salts. It gives information on their use as antiscalants for membranes in water treatment. 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 1483, Water quality — Determination of mercury EN ISO 3696, Water for analytical laboratory use — Specification and test methods (ISO 3696:1987) EN ISO 5961, Water quality — Determination of cadmium by atomic absorption spectrometry (ISO 5961:1994) EN ISO 11885, Water quality — Determination of 33 elements by inductively coupled plasma atomic emission spectroscopy (ISO 11885:1996) EN ISO 11969, Water quality — Determination of arsenic — Atomic absorption spectrometric method (hydride technique) (ISO 11969:1996) ISO 3165, Sampling of chemical products for industrial use — Safety in sampling ISO 6206, Chemical products for industrial use — Sampling — Vocabulary ISO 6703-1, Water quality — Determination of cyanide — Part 1: Determination of total cyanide ISO 8213, Chemical products for industrial use — Sampling techniques — Solid chemical products in the form of particles varying from powders to coarse lumps ISO 8288:1986, Water quality — Determination of cobalt, nickel, copper, zinc, cadmium and lead — Flame atomic absorption spectrometric methods ISO 9174, Water quality — Determination of chromium — Atomic absorption spectrometric methods ISO 9965, Water quality — Determination of selenium — Atomic absorption spectrometric method (hydride technique) SIST EN 15039:2006
EN 15039:2006 (E) 6 3 Description 3.1 Identification 3.1.1 Chemical name Homopolymers:
a) polyacrylic acid;
b) polymethacrylic acid;
c) poly maleic acid;
d) poly aspartic acid. These acids can also be used as sodium, potassium, and ammonium salts. Copolymers of acrylic acid, methacrylic acid, maleic acid, vinylsulfonic acid, allyl sulfonic acid, methylallyl sulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, vinyl phosphonic acid and acrylamide. The acid monomers can also be used as sodium, potassium, and ammonium salts. Monomers:
e) benzene sulfonic acid, 4-[(2-methyl-2-propenyl)oxy]-, sodium salt;
f) benzene sulfonic acid, 4-vinyl-, sodium salt;
g) 1-propanesulfonic acid, 2-hydroxy-3-(2-propenyloxy)-, monosodium salt. 3.1.2 Synonym or common names Nil. 3.1.3 Relative molecular mass < 100 000 g/mol. 3.1.4 Empirical formula Nil. 3.1.5 Chemical formula Homopolymers: a) (C2H3COOH)n; b) (C3H5COOH)n; c) (HOOCC2H2COOH)n; d) (C4H5NO4)n. SIST EN 15039:2006
EN 15039:2006 (E) 7 Monomers for the copolymers: C2H3COOH, C3H5COOH, HOOCC2H2COOH, C2H4O3S, C3H6O3S, C4H8O3S, C7H13NO4S, C2H4O3P, C3H5NO. Monomers: e) C10 H12 O4 S Na; f) C8 H8 O3 S Na; g) C6 H12 O5 S Na. 3.1.6 CAS Registry Number1) Homopolymers (acids): a) 9003-01-4; b) 25087-26-7 ; c) 26099-09-2; d) 25608-40-6. Table 1 — Salts
Na+ K+ NH4+ Acrylic acid 9003-04-7
(part. neutralized)
25549-84-2 25608-12-2 9003-03-6
(part. neutralized)
28214-57-6 Methacrylic acid 54193-36-1 29297-93-6 28805-15-4 Maleic acid 30915-61-8
Copolymers : Poly acrylic acid-acrylamide: 9003-06-9; Acrylic acid-methacrylic acid: 25751-21-7; Acrylic acid-itaconic acid: 258948-33-8; Acrylic acid-maleic acid: 29132-58-9. Monomers:
Benzene sulfonic acid, 4-[(2-methyl-2-propenyl)oxy]-, sodium salt : 1208-67-9
1) Chemical Abstracts Service Registry Number. SIST EN 15039:2006
EN 15039:2006 (E) 8
Benzene sulfonic acid, 4-ethenyl-, sodium salt: 2695-37-6
1-Propanesulfonic acid, 2-hydroxy-3-(2-propenyloxy)-, monosodium salt : 52556-42-0 3.1.7 EINECS reference2) The EINECS-declarations for all mentioned polymers are: POLYMER (All used monomers are listed on the EINECS inventory). 3.2 Commercial forms The polycarboxylic acids and polyacrylates are available as aqueous solutions and as in granular and powder form. All concentrations mentioned refer to the active matter and shall be calculated accordingly. 3.3 Physical properties 3.3.1 Appearance The products in solution are a colourless to amber solution and in solid form are white to yellow particles. 3.3.2 Density The density of solid in granular and powder form has typical values between 400 g/dm3 to 600 g/dm3. The density of solution is 1,00 g/ml to 1,40 g/ml for a product concentration from mass fraction 20 % to 50 % of active matter at 20 °C. 3.3.3 Solubility in water Solid: it is soluble in all portions of water; Liquid: it is miscible in all proportions of water. 3.3.4 Vapour pressure Not applicable. 3.3.5 Boiling point at 100 kPa3) Solid: not applicable; Liquid: approximately 100 °C . 3.3.6 Melting point Solid: not applicable; Liquid: within –25 °C and 0 °C (aqueous product solution). 3.3.7 Specific heat Not known.
2) European Inventory of Existing Commercial Chemical Substances. 3) 100 kPa = 1 bar. SIST EN 15039:2006
EN 15039:2006 (E) 9 3.3.8 Viscosity (dynamic) For the liquid the viscosity is equal from 1 mPa.s to 25 mPa.s for a product concentration of 50 g/l. 3.3.9 Critical temperature Not applicable. 3.3.10 Critical pressure Not applicable. 3.3.11 Physical hardness Not applicable. 3.4 Chemical properties The polycarboxylic acids and solutions of polycarboxylic acid salts have acidic to alkaline reactions. The pH value of an aqueous solution of a mass fraction of 1 % is approximately between 2 to 11. 4 Purity criteria 4.1 General This European Standard specifies the minimum purity requirements for polycarboxylic acids and salts used as antiscalants for the membranes in the treatment of water intended for human consumption. Limits are given for impurities commonly present in the products. 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 relevant authorities. NOTE Users of these products 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 the products not stated in this product standard. Limits have been given for impurities and chemicals 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 quantities of impurities, by-products or additives being present, this shall be notified to the user. 4.2 Composition of commercial product The product in solid form shall have a polymer content in mass fraction between 85 % to 100%. The product in aqueous solution shall conform to the following requirements on a dry mass basis : polymer content : mass fraction of (20 to 50) %. NOTE If additional requirements are agreed between the customer and the manufacturer/supplier, the latter should provide the necessary test methods, if requested, so that the customer can carry out his own quality checks. A certificate of analysis should be provided by the manufacturer/supplier if requested. 4.3 Impurities and main by-products The content of acrylic acid in polycarboxylic acids and salts shall not exceed 1 500 mg/kg of dry product. SIST EN 15039:2006
EN 15039:2006 (E) 10 4.4 Chemical parameters Content of various metals depends on the origin of the raw materials, most of these elements are present only as traces. The product shall conform to the requirements specified in Table 2. Table 2 — Chemical parameters Parameter
Limit
mg/kg of dry product Antimony (Sb) max. 3 Arsenic (As) max. 3 Cadmium (Cd) max. 3 Chromium (Cr) max. 10 Cyanide (CN) max. 5 Lead (Pb) max. 10 Mercury (Hg) max. 1 Nickel (Ni) max. 10 Selenium (Se) max. 3 NOTE Pesticides and polycyclic aromatic hydrocarbons are not relevant in these products. For other parameters see [1] 5 Test methods 5.1 Sampling 5.1.1 General Observe the recommendations of ISO 3165 and take into account ISO 6206. 5.1.2 Solid Prepare the laboratory sample(s) required by the relevant procedure described in ISO 8213. 5.1.3 Liquid 5.1.3.1 Sampling from drums and bottles 5.1.3.1.1 General 5.1.3.1.1.1 Mix the contents of each container to be sampled by shaking the container, by rolling it or by rocking it from side to side, taking care not to damage the container or spill any of the liquid. 5.1.3.1.1.2 If the design of the container is such (for example, a narrow-necked bottle) that it is impracticable to use a sampling implement, take a sample by pouring after the contents have been thoroughly mixed. Otherwise, proceed as described in 5.1.3.1.1.3. 5.1.3.1.1.3 Examine the surface of the liquid. If there are signs of surface contamination, take samples from the surface as described in 5.1.3.1.2; otherwise, take samples as described in 5.1.3.1.3. SIST EN 15039:2006
EN 15039:2006 (E) 11 5.1.3.1.2 Surface sampling Take a sample using a suitable ladle. Lower the ladle into the liquid until the rim is just below the surface, so that the surface layer runs into it. Withdraw the ladle just before it fills completely and allow any liquid adhering to the ladle to drain off. If necessary, repeat this operation so that, when the other selected containers have been sampled in a similar manner, the total volume of sample required for subsequent analysis is obtained. 5.1.3.1.3 Bottom sampling Take a sample using an open sampling tube, or a bottom-valve sampling tube, suited to the size of container and the viscosity of the liquid. When using an open sampling tube, close it at the top and then lower the bottom end to the bottom of the container. Open the tube and move it rapidly so that the bottom of the tube traverses the bottom of the container before the tube is filled. Close the tube, withdraw it from the container and allow any liquid adhering to the outside of the tube to drain off. When using a bottom-valve sampling tube, close the valve before lowering the tube into the container and then proceed in a similar manner to that when using an open sampling tube. 5.1.3.2 Sampling from tanks and tankers From each access point, take samples as follows: a) from the surface of the liquid, using a ladle as described in 5.1.3.1.2; b) from the bottom of the tank or tanker, using a sampling tube as described in 5.1.3.1.3 or using a specially designed bottom-sampling apparatus; c) from one or more positions, depending on the overall depth, between the bottom and the surface using a weighted sampling can. 5.2 Analyses 5.2.1 Polymer content (main product) 5.2.1.1 General The concentration of polymer (polycarboxilic acid) shall be determined by potentiometric titration. 5.2.1.2 Principle Determination of the amount of polycarboxilic acid by potentiometric titration where the total amount of carboxylic groups is measured, whether they are acidic or neutralized. Dilution of the polymer and the solution is brought back to a pH value below or equal to 0,9 with hydrochloric acid. Titration of this dilution by sodium hydroxide gives the total amount of carboxylic groups available. If the polymer is titrated directly by sodium hydroxide without prior addition of hydrochloric acid, only the un-neutralised carboxylic groups will be measured. The titration is preferably realised with an automatic titrator that can detect pH jumps. 5.2.1.3 Reagents 5.2.1.3.1
General All the reagents shall be of a recognized analytical grade. SIST EN 15039:2006
EN 15039:2006 (E) 12 5.2.1.3.2 Deionized water The water shall have conductivity below 1 µS. 5.2.1.3.3 Sodium hydroxide standard volumetric solution, c(NaOH) = 1 mol/l. When prepared, the exact concentration of the solution is determined by titration with potassium hydrogen phthalate. 5.2.1.3.4 Hydrochloric acid standard volumetric solution, c(HCl) = 1 mol/l. When prepared, the exact concentration of the solution is determined by titration with the sodium hydroxide solution (5.2.1.3.3). 5.2.1.3.5 Buffer solutions Standard buffer solutions at pH values of 4, 7 and 10 are used for the calibration of the pH electrode. 5.2.1.4 Apparatus Ordinary laboratory apparatus and: 5.2.1.4.1 Automatic titrator capable of detecting potentiometric jumps. 5.2.1.4.2 pH electrode for aqueous measurements. 5.2.1.5 Procedure 5.2.1.5.1 Test solution Weigh, to the nearest 0,001 g, approximately 1 g (m) of polymer as dry product (2 g of commercial polymer if its solids content is of 50 %) into a 100 ml flask. Add between 10 ml and 50 ml of water (5.2.1.3.2) and mix. 5.2.1.5.2 Calibration Since the titration will be done over a large range of pH values (1 to 12), the pH value of electrode shall be calibrated with a three points method using the 4, 7 and 10 buffer solutions at pH values 4, 7 and 10. 5.2.1.5.3 Determination Immerse the pH electrode (5.2.1.4.2) connected to the titrator (5.2.1.4.1) into the test solution (5.2.1.5.1), stir and add the hydrochloric acid standard volumetric solution (5.2.1.3.4) (V3) to reach a pH value of 0,9 or less. Then titrate with the so
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