1、BSI Standards Publication Bio-based products Overview of methods to determine the bio-based content PD CEN/TR 16721:2014National foreword This Published Document is the UK implementation of CEN/TR 16721:2014. The UK participation in its preparation was entrusted to Technical Committee MI/2, Bio-base
2、d products. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2014. Published
3、 by BSI Standards Limited 2014 ISBN 978 0 580 85558 0 ICS 13.020.60 Compliance with a British Standard cannot confer immunity from legal obligations. This Published Document was published under the authority of the Standards Policy and Strategy Committee on 30 September 2014. Amendments/corrigenda i
4、ssued since publication Date Text affected PUBLISHED DOCUMENT PD CEN/TR 16721:2014 TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16721 August 2014 ICS 13.020.60 English Version Bio-based products - Overview of methods to determine the bio- based content Produits biosourcs - Vue dense
5、mble des mthodes pour dterminer la teneur biosource Biobasierte Produkte - berblick ber verfgbare und mgliche Methoden und Techniken zur Bestimmung des gesamten biobasierten Gehaltes von Produkten This Technical Report was approved by CEN on 21 July 2014. It has been drawn up by the Technical Commit
6、tee CEN/TC 411. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands
7、, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of
8、 exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 16721:2014 E PD CEN/TR 16721:2014CEN/TR 16721:2014 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Terms and definitions .5 3 Method using the radiocarbon analysis and elemental analysi
9、s .5 3.1 Background 5 3.2 Principle 6 3.3 Basic rules 6 3.3.1 Oxygen, hydrogen and nitrogen elements 6 3.3.2 Chemical reactions 6 3.3.3 Natural products 7 3.4 Test methods 7 3.5 Products obtained by chemical synthesis (Group 1).7 3.5.1 General 7 3.5.2 Validation criteria .8 3.6 Formulated products (
10、Group 2) 9 3.6.1 General 9 3.6.2 Calculation of the bio-based content of a sample 9 3.6.3 Calculation of the bio-based carbon content of a sample . 10 3.6.4 Assessment of deviations of measured 14C values from theoretical values 11 4 Methods based on measurement of stable isotopic ratio 11 4.1 Gener
11、al . 11 4.1.1 Introduction . 11 4.1.2 Material and Methods . 12 4.2 13 C/ 12 C isotope ratio 14 4.3 18 O/ 16 O isotope ratio . 14 4.3.1 Isotopic measurement of water . 14 4.3.2 Isotopic measurements of organic samples 14 4.4 2 H/ 1 H isotope ratio. 15 4.5 15 N/ 14 N Isotope ratio 15 4.6 Isotopes S 1
12、5 4.7 Multi-isotopic determinations 15 5 Method based on material balance . 15 5.1 General . 15 5.2 Principle . 16 5.3 Examples . 16 5.3.1 Paint formulation 16 5.3.2 Flexible insulation panel made from wood fibres . 17 6 Applicability of the different methods 17 7 Recommendations 18 Annex A (informa
13、tive) Isotope ratio tables 19 Bibliography . 23 PD CEN/TR 16721:2014CEN/TR 16721:2014 (E) 3 Foreword This document (CEN/TR 16721:2014) has been prepared by Technical Committee CEN/TC 411 “Bio-based products”, the secretariat of which is held by NEN. Attention is drawn to the possibility that some of
14、 the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identifying any or all such patent rights. PD CEN/TR 16721:2014CEN/TR 16721:2014 (E) 4 Introduction Bio-based products from forestry and agriculture have a long history of application, such as p
15、aper, board and various chemicals and materials. The last decades have seen the emergence of new bio-based products in the market. Some of the reasons for the increased interest lie in the bio-based products benefits in relation to the depletion of fossil resources and climate change. Bio-based prod
16、ucts may also provide additional product functionalities. This has triggered a wave of innovation with the development of knowledge and technologies allowing new transformation processes and product development. Acknowledging the need for common standards for bio-based products, the European Commiss
17、ion issued mandate M/492 1 , resulting in a series of standards developed by CEN/TC 411, with a focus on bio-based products other than food, feed and biomass for energy applications. The standards of CEN/TC 411 “Bio-based products“ provide a common basis on the following aspects: Common terminology;
18、 Bio-based content determination; Life Cycle Assessment (LCA); Sustainability aspects; Declaration tools. It is important to understand what the term bio-based product covers and how it is being used. The term “bio- based“ means “derived from biomass“. Bio-based products (bottles, insulation materia
19、ls, wood and wood products, paper, solvents, chemical intermediates, composite materials, et cetera.) are products which are wholly or partly derived from biomass. It is essential to characterize the amount of biomass contained in the product by for instance its bio-based content or bio-based carbon
20、 content. The bio-based content of a product does not provide information on its environmental impact or sustainability, which may be assessed through LCA and sustainability criteria. In addition, transparent and unambiguous communication within bio-based value chains is facilitated by a harmonized
21、framework for certification and declaration. The purpose of this Technical Report is provide an overview of methods for the determination of the bio-based content of solid, liquid and gaseous products. The ability to determine the bio-based content of a product is an obvious prerequisite for develop
22、ing the market for bio-based products. Currently, the bio-based content is usually derived from the determination of the bio-based carbon content by means of 14 C measurement (as described in ASTM D6866-12 1).This methodology is used because 14 C is measurable. However, results based on the 14 C met
23、hodology are expressed as a fraction of bio-based carbon on the total (organic) carbon content of the sample. In some cases the bio-based content of a product can differ substantially from the bio-based carbon content. For example, for products in which a fraction of the raw materials has been repla
24、ced by bio-based materials/constituents containing other elements such as oxygen, nitrogen or hydrogen (e.g. carbohydrate-based products), the bio-based carbon content may be substantially lower than the fraction of the product that is derived from biomass. This Technical Report describes three diff
25、erent methodologies to determine the bio-based content in a product and proposes the development of standards. It should be noted that the quantification of the bio-based content is not a measure of sustainability of a bio-based product. 1A Mandate is a standardization task embedded in European trad
26、e laws. M/492 Mandate is addressed to the European Standardization bodies, CEN, CENELEC and ETSI, for the development of horizontal European Standards for bio-based products. PD CEN/TR 16721:2014CEN/TR 16721:2014 (E) 5 1 Scope This Technical Report gives an overview of methods which can be used for
27、the determination of the bio-based content of solid, liquid and gaseous products. It describes more specifically: a) a method using the radiocarbon analysis and elemental analysis: this method is based on a statement and a verification of the composition of the products; b) methods based on measurem
28、ent of stable isotopic ratio; and c) a method based on the material balance. This Technical Report gives guidance on the applicability of the different methods. This Technical Report also gives recommendations for the further development of European Standards for the determination of the bio-based c
29、ontent. 2 Terms and definitions For the purposes of this document, the terms and definitions given in FprEN 16575:2014 2 and the following apply. 2.1 formulated product product obtained by mixing of different constituents 2.2 material balance comparison of physical quantities of inputs, outputs and
30、inventory changes in a quantity centre over a specified time period SOURCE: ISO 14051:2011, 3.1 3 Method using the radiocarbon analysis and elemental analysis 3.1 Background Element carbon, C, has an isotope, 14 C, which allows for a clear distinction between carbon based substances derived from bio
31、mass and carbon based substances from fossil sources. The 14 C present in chemicals originates from recent atmospheric CO 2 . Due to its radioactive decay, it is almost absent from fossil products older than 20 000 years to 30 000 years. The 14 C content may thus be considered as a tracer of chemica
32、ls recently synthesized from atmospheric CO 2and particularly of recently produced products. The approach based on isotopic measurements to determine the bio-based content of a sample can be used for carbon but not for other elements, such as oxygen, nitrogen or hydrogen. However the content of each
33、 element can be determined by an elemental analysis which leads to the total content of each element, but does not differentiate the elements according to their origin from bio-based resources or fossil resources. Therefore, the combination of the 14 C content determination and an elemental analysis
34、 does not give the bio-based content of a sample. To circumvent this difficulty, the method as given in 3.2 is proposed. NOTE The bio-based content of a product can be derived from the bio-based carbon content if the composition of the biomass used is unchanged. Even for derivatives the bio-based ca
35、rbon content can be used if the chemistry behind the conversion is well known and constant. PD CEN/TR 16721:2014CEN/TR 16721:2014 (E) 6 3.2 Principle NOTE 1 This method is under development and at the end of experiment phase the results will be taken into account when drafting the European Standard
36、dealing with this method. This method, supported by rules described in 3.3, consists of the statement of the bio-based content and of the elemental content of the sample obtained by calculation. This statement is validated by means of a comparison with the same kind of data resulting from the 14 C a
37、nalysis and the elemental analysis of the sample. NOTE 2 The “statement“ in the sense of this document is not to be confused with the “declaration“ of the bio-based content, based on the results of this method. Products can be classified into two groups, chemicals and formulated products depending o
38、n the type of analyses to be carried out: a) Group 1: products obtained by chemical synthesis. A representative sample is analysed on the following criteria: 14 C content determination and elemental analysis of carbon, hydrogen, oxygen and/or nitrogen. If other elements are present, they may also be
39、 analysed. The validation process uses common rules of stoichiometry for these products. See 3.5; b) Group 2: formulated products. A representative sample is analysed with the 14 C method only, if the bio- based content of the constituents (Group 1) of the product are analysed according to this meth
40、od. The validation process uses a calculation by mass for these products. See 3.6. NOTE 3 Since Group 2 formulated products can be made from several constituents, even in a large number, the complete method described for Group 1 may be difficult to implement. This is the reason why a simplified meth
41、od was developed for the formulated products of Group 2. 3.3 Basic rules 3.3.1 Oxygen, hydrogen and nitrogen elements As it is not possible to make a distinction between bio-based and non-bio-based elements such as oxygen, hydrogen or nitrogen, for the application of this method in this Technical Re
42、port, the following convention applies: If oxygen (O) and/or hydrogen (H) and/or nitrogen (N) element(s) is(are) bound to a biomass carbon structure, it(they) is(are) considered to be part(s) of the bio-based content. 3.3.2 Chemical reactions For products/constituents of products obtained by chemica
43、l synthesis, the following guidance is proposed: a) in case that the chemical reaction occurs without release of by-products: 1) if the reactants are exclusively derived from biomass, the bio-based content of the product/constituent of the product is 100 %; if none of the reactants is derived from b
44、iomass, the bio- based content of the product/constituent of the product is 0 %; 2) if the reactants are derived from both biomass and fossil resource, the final product has a bio-based content proportional to the bio-based content of each reactant; b) in case that the chemical reaction leads to the
45、 release of a molecule which is not part of the main product, the allocation of the main elements of the reactants follows the basic chemical rules. EXAMPLE Esterification leads to the release of a water molecule, in which the oxygen will be considered as coming from the acid according to the usual
46、chemical rules. PD CEN/TR 16721:2014CEN/TR 16721:2014 (E) 7 3.3.3 Natural products The bio-based carbon content and the bio-based content of natural products e.g. wood (including pulp), flax, hemp, bamboo are each equal to 100 %. Therefore, it is not necessary to determine these contents by analytic
47、al methods. 3.4 Test methods The bio-based carbon content of a sample can be determined according to FprCEN/TS 16640 3, Method C (AMS). Alternatively, the bio-based carbon content can be determined according to EN 15440 4 or CEN/TS 16137 5, Method C, and declared according to CEN/TS 16295 6 or ASTM
48、D6866-12 1 and the results can be reported according to ASTM D7026-04 7. NOTE CEN/TS 16137 is applicable to plastic material and products, but the test methods can be in principle applied to any other product. For the elemental analysis, standard analytical methods should be used. 3.5 Products obtai
49、ned by chemical synthesis (Group 1) 3.5.1 General The statement (see 3.2) should include a detailed elemental composition of the bio-based part and the fossil part of the product, as well as the bio-based content. EXAMPLE 1 Bio-ethyl acetate obtained by esterification between bio-ethanol from fermentation of sugar and acetic acid from fossil resources: Fraction C % H % O % Total % Fossil fraction (from acetic acid) 27,3 3,4 18,2 48,9 Bio-based fraction (from ethanol) 27,2 5,7 18,2 51,1 Total 54,5 9,1 36,4 100,0 Then, the data of the statem
