From ‘The Guardian’ (online, 13/10/14): Carney told a World Bank seminar on integratedreporting on Friday [10th October 2014] that the “vast majority of reserves are unburnable” ifglobal temperature rises are to be limited to below 2 °C (the target proposed in the UNCopenhagen Accord of 2009). This means two thirds of known fossil fuel reserves would bewritten off, losing the potential income from their combined sale price of $28 trillion/£17.5trillion (see www.businessweek.com/articles/2014-06-26/climate-change-and-the-two-thirds-imperative). By 2100 fossil fuel use (without carbon capture) should be phased out(see www.bbc.co.uk/news/science-environment-29855884).

The European Commission has proposed the ‘bio-economy’ as a strategy for long termsustainable growth (see ec.europa.eu/research/bioeconomy/pdf/official-strategy_en.pdf).They say “In order to cope with an increasing global population, rapid depletion of …resources, increasing environmental pressures and climate change, Europe needs to radicallychange its approach to production, consumption, processing, storage, recycling and disposalof biological resources”. The action plan involves investment in research and policy makingfor the development of the bio-based product market.

European efforts towards designing new standards, labelling and certification is presentlybeing undertaken in order to facilitate the growth of the European Bio-based market (seewww.kbbpps.eu and www.open-bio.eu for related research projects). These measures shouldimprove consistency and quality in the sector, reducing trade barriers and increasingcustomer confidence. A standard is essentially an agreed way of doing something, oftenpublished as a technical specification. This might be an agreed test method for thedetermination of boiling points for example, or the criteria used to define sustainability.

The model product is loosely based on theingredients of a vanilla scented shampoo. Shampooand domestic cleaning products are typically dilutesurfactant solutions. The example in this workshophas been designed to accentuate the outcomes ofthe choice of biomass and different certificationoptions. The quantities of each ingredient are notrealistic quantities, and the amounts are based ondry weight. Subsequent calculations are based on adry weight of 100 kg, representing one batch of theformulation. If this was an actual product, it wouldbe diluted in water and sold in bottles much smallerthan 100 kg!

The glycerol is assumed to be bio-based (as the by-product of bio-diesel production there tends to be asurplus), while the proportion of biomass in both thesurfactant sodium laureth sulphate and vanillin arechosen by you!

Biorefineries are not a new concept and in their current revival are developing with greatdiversity. The categories assigned are rarely clear cut and sometimes the products and theirquantity are flexible. ‘Generations of biomass’ is a concept usually applied to the resultingbiofuels (e.g. a second generation biofuel). Here the meaning is used to describe the biomassitself.

Biodiesel can be made on a small scale from virgin vegetable oil (1st generation biomass) orused cooking oil (2nd generation biomass). The major product is fatty acid methyl esters(FAME) and the byproduct is crude glycerol (glycerine). The biggest biodiesel biorefineries inthe UK are in Hull and Teesside (refer to ECOFYS “UK biofuel industry overview” report, seewww.gov.uk/government/uploads/system/uploads/attachment_data/file/308142/uk-biofuel-producer.pdf). Capacity for producing bio-ethanol is now larger than bio-diesel in theUK.

Roquette mostly manufacture starch and its derivatives (see www.roquette.com/raw-materials-potatoe-corn-wheat-pea-micro-algae), hence it has been labelled as a 2ndgeneration bio-refinery. Processes include hydrogenation (for isosorbide) and fermentation(bio-ethanol).

Chemopolis is a lignocellulose biorefinery, using tree wood to produce cellulosic bio-ethanolor paper depending on the market and economic advantage at any one time. Lignin isconverted to energy with a side-stream of fertiliser. Furfural and other small molecules arealso produced. Any lignocellulosic biomass is applicable, and this flexibility of feedstockmeans Chemopolis is a 3rd generation bio-refinery.

The wheat crop is 58% straw, which although not directly used for food is useful as insulationfor protecting root vegetable crops such as carrots and as animal feed. Total wheatproduction in the UK was 13 million metric tonnes in 2012 (see faostat.fao.org). Total strawproduction in the UK exceeds 11 millions tonnes per annum including other cereal andoilseed crops which represents a surplus (see ‘National and regional supply/demand balancefor agricultural straw in Great Britain’ by J. Copeland and D. Turley – ‘googleable’).

The wax can be extracted from the straw using solvents (including supercritical carbondioxide which is also used for the decaffeination of coffee). The wax is less than 2% of thestraw mass but contains fatty acids and fatty alcohols suitable for producing surfactants. Thedewaxed straw can then be used in a variety of applications. It can be burnt as a fuel and thesilicates recovered for use as composite binders, or potentially serve as the feedstock forcellulosic ethanol bio-refineries.

From the ECOFYS UK biofuel report (see www.gov.uk/government/uploads/system/uploads/attachment_data/file/308142/uk-biofuel-producer.pdf):“British Sugar opened the UK’s first bioethanol plant in 2007 at Wissington, Norfolk. The plantproduces up to 55 ktonne (70 million litres) of bioethanol per year, and uses around 650ktonne of sugar beet (equivalent to around 110 ktonne of sugar) as the feedstock. TheWissington biofuel plant is co-located next to an existing sugar plant which supplies 400ktonne of sugar and 100 ktonne of dry animal feed per year, as well as a variety of otherproducts (including top soil and lime). The plant also captures the carbon dioxide from thesugar fermentation which is sold to the food and drink sector. The site employs 240 people intotal, of which around 30 are directly involved in the biofuel plant”.

Bigger still is the ‘Vivergo’ plant in Hull, which uses wheat straw for bioethanol production(yearly 420 million litre capacity, see www.vivergofuels.com/process).

Sugar beet (sugar cane in more exotic places) is a high yielding sugar crop. The sugar can beused in fermentation to produce bio-ethanol. However it is 1st generation biomass. Thewaste streams from food sugar production can be useful feedstocks too, and have beenshown to be viable materials for producing plastics (e.g. PHA from molasses, seewww.dw.de/italian-company-makes-plastic-from-sugar-beet-waste/a-15438369). All thesugar beet crop waste can be put to use in a 3rd generation biorefinery, creating a number ofopportunities.

The bio-ethanol produced from sugar fermentation can also be used in the plastics industry.The Brazilian company Braskem are producing a premium poly(ethylene) by dehydrating bio-ethanol to ethylene, and polymerising. This bio-ethylene could see use in a huge number ofadditional chemical manufacturing processes. For the purpose of making the hydrophobictail of the surfactant sodium laureth sulphate, the oligomer of ethylene, dodecene, can behydrated to 1-dodecanol. This is analogous to the conventional petrochemical procedure.Bio-ethanol from any source could be used to produce 1-dodecanol in this way.

The 2009 EU Directive 2009/28/EC states 10% of transport fuel must be renewable by 2020(see ec.europa.eu/energy/renewables/biofuels/land_use_change_en.htm). As of 2013 theactual value is 4.7%. Furthermore, it was ruled in 2011 that biofuels contributing to Europeanrenewable energy targets must be certified sustainable. This must apply to the actual biofueland not by the transfer of certificates to unsustainable biomass (i.e. book and claim method,see www.rspo.org/file/FAQ%20on%20RSPO-RED_7March(1).pdf for an example).

The recent drop in biofuel use has been blamed on Spain (and Germany to a lesser extent),with biodiesel use elsewhere in Europe generally steady or increasing. The slowdown inbiofuel use in Europe has been attributed to policy disagreements regarding the use of 1st

generation biomass and the ‘indirect land use change impacts’ regarding greenhouse gasemissions (moving beyond the classic ‘food vs. fuel’ debate). “On 17th October 2012, the ECpublished a proposal to limit global land conversion for biofuel production, and raise theclimate benefits of biofuels used in the EU. The use of food-based biofuels to meet the 10%renewable [transport] energy target of the Renewable Energy Directive will be limited to 5%”(see ec.europa.eu/energy/renewables/biofuels/land_use_change_en.htm).

The current total renewable energy target for Europe is 20% by the year 2020 (12.7% wasachieved in 2010, 14.1% in 2012) although with respect to biofuels (not wind power etc.)adoption was considered too slow (see ec.europa.eu/energy/renewables/reports/reports_en.htm). A new target of 27% renewable energy use at EU level by 2030 wasagreed on 23rd October 2014 (see www.european-council.europa.eu/council-meetings?meeting=f02588fd-757c-4697-a2cc-8af00f65ff7c&lang=en&type=EuropeanCouncil). Nice pictures and graphs on this topic are available aten.wikipedia.org/wiki/Renewable_energy_in_the_European_Union#Renewable_energy_targets (note the UK and the Netherlands are doing pretty crap!)

Rapeseed is a major UK and international crop. It is produced for its vegetable (triglyceride)oil, which in addition to a foodstuff is the feedstock for biodiesel production. Hydrolysisyields the fatty acids, which in turn may be hydrogenated and applied in the synthesis ofanionic surfactants such as sodium laureth sulphate. The infrastructure for producingchemicals from vegetable oil is already in place because of biodiesel biorefineries.

Lauric acid (for sodium laureth sulphate production) is only abundant as part of thetriglycerides of coconut oil (~50%). It is not prevalent in rapeseed oil. The liberated fatty acidsof coconut oil have been used to make bio-based surfactants, typically featuring coco- in thename, e.g. sodium coco sulphate and cocamidopropyl betaine). For more information onsurfactants based on renewable feedstocks, seeeu.wiley.com/WileyCDA/WileyTitle/productCd-0470760419.html# where the relevantchapter of the book, ‘Surfactants from Renewable Resources’, is available to download forfree (true as of 27/10/14). We will (incorrectly) assume for the purpose of this workshop thatall the fatty acid groups of vegetable oils are suitable for producing surfactants with.

This is a very much simplified schematic of a biorefinery process using vegetable oil toreplace the ethylene previously required to make 1-dodecanol. Other biomass feedstocks(wheat straw, sugar beet, etc.) that yield bio-ethanol are not too dissimilar to theconventional process requiring ethylene. Ethylene from naphtha is still used to produce theethylene oxide intermediate. The width of the arrows is proportional to the material flow(known as a Sankey diagram). Feedstocks are blue, by-products and wastes green,intermediates orange, and the product is red. The material masses indicated are for theproduction of 50 kg of sodium laureth sulphate (dry mass).

The substitution of petrochemicals can be incomplete, and it can vary seasonally oraccording to economic favourability. This is called a non-dedicated biorefinery. Harvest timevaries depending on the country and the crop. For an example of biomass price variance,rapeseed oil price peaked this year (2014) in March and has been declining since (seewww.nesteoil.com/default.asp?path=1,41,538,2035,14053).

Now you can choose a number to go in the first box on your answer sheet. Imagine you operate a biorefineryproducing sodium laureth sulphate partially made from a biomass feedstock, as was shown on the previousslide. Due to price competition (and maybe plant capacity limitations too) you cannot change over to acompletely bio-based feedstock. In order to produce the hydrophobic part of the surfactant, you have abiomass feedstock budget of ‘6 credits’. However the price of the biomass varies seasonally (the blue bars onthe graph). It is cheapest in the autumn just after the harvest with 1 credit needed to purchase all the biomassyou need to maintain production of sodium laureth sulphate. The price increases steadily into the winter andspring as reserves are depleted by demand. Storage costs will also accumulate. In the summer the price goesdown in reaction to the market holding out until the new harvest. You can choose one option from thefollowing 4 scenarios. When making your choice remember the final shampoo product (containing 50 kg ofsodium laureth sulphate in every 100 kg) is produced by a formulator after purchasing each ingredient fromdifferent suppliers. The sodium laureth sulphate will be certified before formulation. Then that information isused in turn to certify the final shampoo formulation as sustainable, bio-based, etc.

Option 1: You can use a 100% biomass feedstock to produce the hydrophobic part of the surfactant all the timeexcept for in spring when the price is highest. On average biomass utilisation is high (75% of the maximum) butfor a quarter of the year the surfactant contains no biomass and could be misleading to consumers (althoughbear in mind the glycerol and vanillin within the final shampoo formulation will impart some bio-based contentall year round).

Option 2: You can use biomass until the budget runs out, which means full biomass use in the autumn andwinter and for ¾ of the spring. Across the year the average is about two thirds of the maximum but again forpart of the year no biomass is incorporated into the sodium laureth sulphate.

Option 3: You can attempt to maximise biomass use while also ensuring a decent amount of a renewablefeedstock is used at all times. This means allowing for more biomass when it is cheap but reserving funds to usea lower proportion of biomass when the feedstock is more expensive. With this option biomass feedstockutilisation never drops below 50%. The end result is a marginally lower biomass use than ‘option 2’.

Option 4: The amount of biomass is constant throughout the year. This would require you to plan carefully inadvance to avoid going over budget! The total biomass utilisation is the lowest of the 4 options at 60%.

Now choose the second number for your answer sheet. Broadly speaking there are two typesof certification that relate to biomass in bio-based products. The first type concerns thebiomass feedstock (is it sustainable? how much fossil resource is displaced?) and the otherrelates to the proportion of biomass contained within the final article (claims of bio-basedcontent). In reality they can be used in combination but you are only allowed to chose one!

ISCC is one of many third party organisations offering biomass sustainability certification (forbiofuel sustainability schemes including one offered by ISCC, seeec.europa.eu/energy/renewables/biofuels/sustainability_schemes_en.htm). The list ofcriteria listed here have been proposed for an upcoming standard describing sustainable bio-based products (prEN 16751). Certification is applied to the product, but is derived from thesustainability of the biomass feedstock. The sustainability criteria do not apply to anypetrochemical or mineral feedstocks.

The amount of biomass incorporated into a bio-based product is not considered. This hasbeen the subject of heated debate (see bio-based.eu/news/can-issc-plus-certification-misleading-bio-based-share-labelled). Only if the sustainability certification is used as part ofa greater requirement (e.g. in combination with the bio-based solvent standard FprCEN/TS16766 which demands a minimum of 25% bio-based carbon content) does the proportion ofbiomass in the product become relevant.

The use of renewable resources in the production of bio-based products can be accountedfor in many different ways. This this hypothetical example, 30% (by mass) of the feedstock isbiomass. The biomass is distributed across the numerous products in a way that might notbe well understood and vary with time. With allocation methods of bio-based content, thatbiomass fraction can be assigned to whichever product (output) is deemed suitable as longas the biomass content does not exceed the biorefinery input. Sometimes the certificationrules are more strict than this, bound by chemical reactivity rules. In this case for a non-dedicated biorefinery the amount of bio-based content in a given product could not exceedthe maximum feasible value. The result can be expressed as the amount of fossil resourcesdisplaced from the manufacturing process (e.g. 30%).

The certification scheme developed by BASF and TÜV SÜD (see www.tuv-sud.com/news-media/news-archive/tuev-sued-develops-standard-for-renewable-raw-materials) takes thisallocation approach one step further and performs the calculation using the calorific value ofthe feedstocks, not their mass. The claimed fossil resource saving is therefore not directlyrelated to the mass of petrochemicals displaced. This can be demonstrated with the exampleof sodium laureth sulphate made with the maximum amount of vegetable oil required toproduce the intermediate 1-dodecanol without using petrochemical ethylene and assumingno losses throughout the process. The mass of biomass utilised is 68% of the organicfeedstock but only 37% of the total feedstock including water, oxygen sodium chloride andhydrogen sulphide. The bio-based content that can be attributed to the sodium laurethsulphate according to this method is 70%.

The method of ‘book and claim’ is exemplified in this workshop with the certification offeredby the ‘Roundtable on Sustainable Palm Oil’ (RSPO) (see www.rspo.org/en/document_supply_chain_certification). Although only applicable to palm oil it is fairly representative of theprocess generally. If a chemical manufacturer is in possession of a certain quantity ofuncertified palm oil, they may purchase the certificates from an equal volume of palm oilthat has been certified as sustainable. The certificates are swapped and the palm oil that wasactually produced by sustainable methods is no longer considered as such. The sameprocedure can be applied to other chemical feedstocks, and feasibly for a wider range oftransposed characteristics such as bio-based content.

RSPO has a variety of other ways it will certify palm oil as sustainable. These do not form partof this workshop but are reviewed here briefly for completeness. The ‘conventional supplychain’ of sustainable palm oil, from plantation to end product, can be certified if completelytraceable. The quantity of palm oil at the end of the supply chain is sustainable with nocontact having been made with uncertified palm oil.

When a known amount of certified sustainable palm oil is combined with a known amount ofuncertified palm oil, the end mixture may be divided into portions that reflect the originalinput of sustainable palm oil. For example, 20 tonnes of sustainable palm oil might be mixedwith 80 tonnes of uncertified palm oil for transportation convenience. The mixture itselfcannot be claimed as sustainable or even as ‘20% sustainable’. Then 20 tonnes of the palmoil mixture may be partitioned from the bulk and that aliquot designated as the sustainablepalm oil. This is the ‘allocated mass balance’ method and bears a resemblance to theprevious certification approach that also uses an allocation method.

If you chose to certify the feedstock for your second answer you now have the choice ofthese three certification scheme types with which to fill in the third box on your answersheet (if you chose to certify the product for your second answer wait for now). Forclarification the options are as follows.

Sustainability: The biomass you use in the production of the surfactant must meet a long listof sustainability criteria. There is no minimum amount of biomass required to validate thecertification.

Renewable resource use: The proportion of fossil resources displaced by biomass isaccounted for, and can be expressed as a percentage of the total feedstock requirement.However this value will not represent a mass of biomass used in the process or the bio-basedcontent of the product.

Book and claim: Your unsustainable biomass is redeemed by purchasing certificatesbelonging to an equal volume of sustainably produced biomass. In doing so sustainablepractice is both funded and encouraged.

Previously the sustainability criteria and fossil resource savings have attributed qualities to abio-based product derived from the biomass feedstock. However it is possible to analyse thefinished product and produce a value for the bio-based content of that article. The premiermethod of bio-based content analysis is radiocarbon analysis. If the ratio of 14C/12C isotopesmatches atmospheric levels all the carbon in the sample is bio-based. Intermediate valuesbetween the modern radiocarbon abundance and that found in fossil reserves indicatepartially bio-based products. The precise bio-based carbon content of the sample can thenbe calculated.

The presence of carbonate fillers in composite materials effects the determination of bio-based carbon content. In the US standard test method (ASTM D6866) the carbon is removedwith an acid pre-treatment before radiocarbon analysis. In the European equivalent (CEN/TS16640) it is not and so there an be a discrepancy between the two approaches depending oncomposition of the test material. These test methods, one off measurements, only apply toproducts with a fixed quantity of bio-based carbon (products of dedicated bio-refineries). Ifthe proportion of biomass feedstock changes over time the product cannot be certified andlabelled with a specific bio-based carbon content.

The most accurate apparatus with which to determine carbon isotopic ratios is acceleratormass spectrometry (AMS) which is able to detect parts per trillion quantities of 14C.Remember that carbon is not the only element in bio-based products. It is however the onlyelement that has a precise analytical method for determining whether it is fossil derived orbio-based. Furthermore, in replacing fossil resources, consisting mainly of hydrocarbons,displacing the petrochemical carbon with renewable carbon is most the battle.

The analysis of bio-based carbon content was discussed previously in the workshop. Theresults of the radiocarbon analysis can be extended to the other elements in a bio-basedchemical. As demonstrated for sodium laureth sulphate, the atoms chemically bonded tobio-based carbons (in green) can also be described as bio-based (framed in green squares)under the rules of ‘atom connectivity’ (entitled “allocation of total bio-based content” on theslide). Deciding which carbons are bio-derived must be done on the basis of known reactionchemistry pathways and an understanding of the feedstocks used, as is true when aheteroatom is bound to both bio-based and fossil derived carbons. This methodology wasproposed by ACDV (see www.chimieduvegetal.com/pageLibre000110dd.asp). It does notaccount for mineral derived atoms or the true origin of the non-carbon atoms. A true massbalance (called ‘material balance’ here to distinguish it from other protocols) can incorporatemineral derived atoms (framed in grey boxes).

The disparity between each approach is quite noticeable, with only the material balanceoffering a true reflection of the actual bio-based content. However its calculation iscomplicated and the result is not appealing when compared to the other methods. It is notverified by analysis as the other two methods are, leaving it susceptible to errors, but it isadvantageous when the biomass input into a (non-dedicated) biorefinery fluctuates overtime as the product can still be certified as bio-based, as long as it always remains above 0%.

For formulations, the individual components, each bearing there own certification, arecombined and the weighted sum of their bio-based content is used to produce a value forthe final article. If an ingredient is not certified it is assumed to be fossil derived.

If you chose to certify the product for your second answer pick one of the three bio-basedcontent methodologies for your third answer. Refer back to the question summary for thecorrect numbers to use.

Cosmetics and personal care products can be certified ‘Organic’ by the USDA if the >95% of the ingredientsmeet the criteria (excluding water and salt). Although certification and labelling exist for food productsgenerally (organic, fairtrade, etc.), differentiation between natural and ‘unnatural’ products is not the basis of aspecial label. Guidelines are in place however for the use of the word natural on packaging, and changes tothese rules are persuading food producers to abandon ‘natural’ claims on processed foods (seeonline.wsj.com/articles/SB10001424052702304470504579163933732367084).

Depending on how you perceive the added-value of these labels and claims, chose between natural vanillin andsynthetic vanillin options for your final answer.

The majority of vanillin is produced synthetically (99% in fact, see cen.acs.org/articles/92/i6/Following-Routes-Naturally-Derived-Vanillin.html). The known processes are varied, using wholly petrochemicals (guaiacol),lignin, or clove oil (which contains eugenol). A historical synthesis of vanillin used natural guaiacol and isanalogous to the contemporary petrochemical synthesis. Guaiacol is obtained from pine wood tar (seewww.chm.bris.ac.uk/motm/vanillin/vanillinh.htm). The reaction of guaiacol with glyoxylic acid (made frompetrochemical ethylene) results in vanillin that is 81% bio-based (88% bio-based carbon).

Because of its premium price, food applications of natural vanilla are at risk of adulteration with cheapersynthetic vanillin. A routine check is available using stable isotope ratios. Natural vanillin from vanilla beans hasan enrichment of 13C compared to synthetic products, even those using biomass feedstocks. Thus moreinformation is gained than radiocarbon analysis alone. Stable isotope ratios vary for a number of reasons. Theprimary cause for differentiation in stable carbon isotopes is photosynthesis. Different plants have one of twomechanisms for photosynthesis (C3 or C4). Natural vanillin is characteristic as coming from a C4 plant(sugarcane is another C4 plant). In some cases another stable isotope ratio might be needed. Petroleum comesfrom ancient plants all using C3-type photosynthesis (C4 is newer in evolutionary terms). Stable hydrogenisotopic analysis can be used to help distinguish between petrochemical products and C3 plant (e.g. wheat) bio-based products.

The blue bars are the volume of material required just to produce the hydrophobic group for 50 kg ofsurfactant (scale to the left). The price (green bars, scale to the right) increases going from the biomass(sugarcane or wheat straw) to the intermediate bio-ethylene because of processing costs (fermentation etc.).My apologies for the rubbish estimates I have created using minimal data. The estimated cellulosic bio-ethyleneprice is particularly spurious and not commercially available anyway. It is unlikely to fall beneath the 10% priceincrease that at least 50% of consumers are willing to pay (McKinsey Green Chemicals Survey – ‘googleable’).The cost of producing the intermediate compound 1-dodecanol from rapeseed oil has not been estimated asthe lauric acid content of the triglycerides is negligible, and although using coconut oil is viable the necessarydata was not found.

A separate sheet with the answers summarised is available. It should be distributed at theend of the workshop and will also be available online, along with a more detailed break-down of the relevant calculations.

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James Sherwoodjames.sherwood@york.ac.uk

Calculation results (1/6)

? XXX Bio-based content of sodium laureth sulphate

? = 1 ? = 2 ? = 3 ? = 4

Biomass feedstock utilisation(for hydrophobic group)

75% 68.8% 67.5% 60%

Average fossil resource savings53% 48% 48% 42%

Applicable Y Y Y Y

Average bio-based carbon content 50% 46% 45% 40%

Applicable(i.e. does not vary with time)

N N N Y

Average total bio-based content (atom connectivity)

43% 39% 39% 34%

Applicable(i.e. never varies in a dedicatedfacility)

N N N Y

Average total bio-based content (material balance)

31% 29% 28% 25%

Applicable(i.e. never drops to zero)

N N Y Y

? X21

? X62

? X52

? X42

Sodium laureth sulphate is 50% of the mass of the formulation so the valuesabove should be weighted appropriately to obtain their contribution to theformulation. Sodium laureth sulphate is 51% carbon by mass.

Calculation results (2/6)

X X?1 Sustainability certification

? = 1 ? = 3

Biomass certificationSustainability criteria

Book and claim

Applicable to biomass asfeedstock

Y (e.g. RSPO) Y (e.g. RSPO)

Applicable to European bio-fuels Y N

Sustainability applicable to all parts of a bio-based product

N (only the biomass)

N (only the biomass)

All the biomass must be sustainable and then the product is classifiable asmade from sustainable biomass. The proportion of biomass is not a factoralthough if used in conjunction with other standards that can be applied tospecific products (bio-based solvents, etc.) minimum bio-based contentthresholds apply.

The ‘book-and-claim’ variety of sustainable biomass certification is notalways applicable. It is not allowed for bio-fuels within Europe, and atpresent it is not included within draft standards addressing mass balanceclaims for bio-based products. Therefore ‘book-and-claim’ sustainablebiomass may not be a viable route to certifying bio-based products.

Calculation results (3/6)

Fossil resource savings can be calculated by assuming units of methaneequivalents for each calorific feedstock. This value is the lower heatingvalue of methane (50 MJ/kg) divided by that of the feedstock. The productis assigned ‘allocation units’ by adding the individual feedstock massesmultiplied by their own methane equivalent values (*44 for sodium laurethsulphate made from vegetable oil, the worked example is given below).

Total bio-based content is derived from the mass and calorific value of thebiomass feedstock(s). This can be applied to the individual ingredients of aformulation, in turn to give a bio-based content for the complete article.

Contribution Bio-based content

IngredientMass /kg

CH4

eq.Materialbalance

Allocation (CH4 eq.)**

Sodium laureth sulphate (bio-based hydrophobic tail)

<50 44.36* 42% 70%

Vegetable oil 25 1.23

Methane 2 1.00

Ethylene (naphtha) 10 1.13

Sodium laureth sulphate (petrochemical)

<50 0% 0%

Vanillin (natural) <20 100% 100%

Vanillin (synthetic) <20 81% 37%

Glycerol 15 97% 94%

Sodium chloride 10 0% 0%

Other stuff 5 0% 0%

**Total bio-based content by allocation using units of methane equivalentsis the proportion of biomass feedstock(s) contributing to the assignedmethane equivalents of the intended product.

X X21 Sustainability certification

Calculation results (4/6)

X ?XX Vanillin source

? = 1 ? = 2

Vanillin origin NaturalSynthetic(guaiacol)

Average fossil resource savings 100% 37%

Applicable Y Y

Average bio-based carbon content 100% 88%

Applicable(i.e. does not vary with time)

Y Y

Average total bio-based content (atom connectivity)

100% 81%

Applicable(i.e. never varies in a dedicated facility)

Y Y

Average total bio-based content (material balance)

100% 81%

Applicable(i.e. never drops to zero)

Y Y

Vanillin is 20% of the mass of the formulation so the values above should beweighted appropriately to obtain their contribution to the formulation.Vanillin is 63% carbon by mass.

Calculation results (5/6)

Other formulation ingredients

GlycerolSodium chloride

‘Other things’

Average fossil resource savings

94% 0% 0%

Applicable Y Y Y

Average bio-based carbon content (total carbon content)

100% (39%) 0% (0%) 0% (84%)

Applicable(i.e. does not vary with time)

Y Y Y

Average total bio-based content (atom connectivity)

100% 0% 0%

Applicable(i.e. never varies in a dedicated facility)

Y Y Y

Average total bio-based content (material balance)

97% 0% 0%

Applicable(i.e. never drops to zero)

Y Y Y

Calculation results (6/6)

Bio-based carbon content:The bio-based carbon content is obtained by analysis of the radiocarbon

isotope ratio. Knowledge of the chemical synthesis and the choice offeedstocks is usually enough in order to be able to reach a good estimate ofthe analytical result.

Atom connectivity methodology:From the bio-based carbon content, the bio-based carbon atoms are

assigned within the structure of the compound using knowledge of thesynthesis.

Heteroatoms (limited to hydrogen, nitrogen, and oxygen) bonded to thebio-based carbon atoms are also considered bio-based. When multiplecarbon atoms are bonded to a heteroatom a knowledge of the syntheticroute is required to attribute the correct source to the heteroatom. Otheratoms (S, Na, Cl, etc.) are considered as bio-based.

The total bio-based content is reached by adding together the atomicmasses of the bio-based atoms as a percentage of the full molecular weight.This can be applied to the individual ingredients of a formulation to give atotal bio-based content for the complete article.

Material balance:Feedstocks are designated as either biomass, fossil derived or

mineral/inorganic. The proportion of each feedstock present in the finalarticle after reaction and processing losses contributes to the total mass ofthe final product. The mass of the combined feedstocks must equal theoutput of the process (product, by-products, and losses).

The proportion of biomass present in the final product gives the total bio-based content (see the worked example for 15 kg of glycerol, 97% bio-based,made from the transesterfication of vegetable oils with methanol).

Whereas the two methods above only apply to dedicated biorefineryproducts, for material balance an average (time-weighted) bio-basedcontent is permissible but the bio-based content may never drop to 0%.

Material balance: Feedstocks for glycerol

Mass /kg Origin% present in product

Vegetable oil 104 Biomass 14% (14.5 kg)

Natural gas (for methanol) 8 Fossil 4% (0.3 kg)

Water (for methanol) 9 Inorganic 2% (0.2 kg)

AnswerBio-based

carbon content

Total bio-based

content (atom

connectivity)

Total bio-based

content (material balance)

Sustainablebiomass?

Fossil resource

saving (by allocation)

Natural?

1 1 1 1 38% 35% 35% Yes 60% Yes1 1 1 2 35% 31% 31% Yes 48% No1 1 2 1 38% 35% 35% No 60% Yes1 1 2 2 35% 31% 31% No 48% No1 1 3 1 38% 35% 35% Yes 60% Yes1 1 3 2 35% 31% 31% Yes 48% No1 2 4 1 38% 35% 35% No 60% Yes1 2 4 2 35% 31% 31% No 48% No1 2 5 1 38% 35% 35% No 60% Yes1 2 5 2 35% 31% 31% No 48% No1 2 6 1 38% 35% 35% No 60% Yes1 2 6 2 35% 31% 31% No 48% No2 1 1 1 38% 35% 35% Yes 58% Yes2 1 1 2 35% 31% 31% Yes 46% No2 1 2 1 38% 35% 35% No 58% Yes2 1 2 2 35% 31% 31% No 46% No2 1 3 1 38% 35% 35% Yes 58% Yes2 1 3 2 35% 31% 31% Yes 46% No2 2 4 1 38% 35% 35% No 58% Yes2 2 4 2 35% 31% 31% No 46% No2 2 5 1 38% 35% 35% No 58% Yes2 2 5 2 35% 31% 31% No 46% No2 2 6 1 38% 35% 35% No 58% Yes2 2 6 2 35% 31% 31% No 46% No3 1 1 1 38% 35% 49% Yes 58% Yes3 1 1 2 35% 31% 45% Yes 45% No3 1 2 1 38% 35% 49% No 58% Yes3 1 2 2 35% 31% 45% No 45% No3 1 3 1 38% 35% 49% Yes 58% Yes3 1 3 2 35% 31% 45% Yes 45% No3 2 4 1 38% 35% 49% No 58% Yes3 2 4 2 35% 31% 45% No 45% No3 2 5 1 38% 35% 49% No 58% Yes3 2 5 2 35% 31% 45% No 45% No3 2 6 1 38% 35% 49% No 58% Yes

3 2 6 2 35% 31% 45% No 45% No4 1 1 1 59% 52% 47% Yes 55% Yes4 1 1 2 56% 48% 43% Yes 43% No4 1 2 1 59% 52% 47% No 55% Yes4 1 2 2 56% 48% 43% No 43% No4 1 3 1 59% 52% 47% Yes 55% Yes4 1 3 2 56% 48% 43% Yes 43% No4 2 4 1 59% 52% 47% No 55% Yes4 2 4 2 56% 48% 43% No 43% No4 2 5 1 59% 52% 47% No 55% Yes4 2 5 2 56% 48% 43% No 43% No4 2 6 1 59% 52% 47% No 55% Yes4 2 6 2 56% 48% 43% No 43% No

Results in black are in response to the choices made in the workshop. Thosein grey are applicable but not a consequence of the choices made.

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James Sherwoodjames.sherwood@york.ac.uk